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Sample records for adsorbable organic halogens

  1. Adsorbable organic halogens generation and reduction during degradation of phenol by UV radiation/sodium hypochlorite.

    PubMed

    Zeng, Qing-Fu; Fu, Jie; Shi, Yin-Tao; Xia, Dong-Sheng; Zhu, Hai-Liang

    2009-02-01

    The degradation of phenol by UV radiation/sodium hypochlorite (UV/NaClO) was investigated. The degradation processes were analyzed by a UV-visible spectrometer, total organic carbon analyzer, and gas chromatography-mass spectroscopy. The experimental results indicate that phenol can be photodegraded by UV/NaClO effectively. However, adsorbable organic halogens (AOX) were produced during the degradation process. Analysis of the mechanism of degradation indicates that the decrease in pH value would increase the formation of AOX. Also, dissolved oxygen greatly increased the rate of phenol degradation and reduced the formation of AOX. Therefore, appropriate conditions could increase degradation and inhibit chlorination. Adjusting the pH value and increasing the amount of oxygen were effective methods.

  2. Sense or no-sense of the sum parameter for water soluble "adsorbable organic halogens" (AOX) and "absorbed organic halogens" (AOX-S18) for the assessment of organohalogens in sludges and sediments.

    PubMed

    Müller, German

    2003-07-01

    "AOX" is the abbreviation of the sum parameter for water soluble "adsorbable organic halogens" in which 'A' stands for adsorbable, 'O' for organic and 'X' for the halogens chlorine, bromine and iodine. After the introduction of the AOX in 1976, this parameter has been correctly used for "real" AOX constituents (DDT and its metabolites, PCBs, etc.) but also misused for non-adsorbable adsorbed OX-compounds, mostly high molecular organohalogens in plants and even to inorganic compounds being neither organic nor adsorbable. The question of natural "Adsorbable Organic Halogens" (AOX) formed by living organisms and/or during natural abiogenic processes has been definitively solved by the known existence of already more than 3650 organohalogen compounds, amongst them the highly reactive, cancerogenic vinyl chloride (VC). The extension of the AOX to AOX-S18 for Sludges and Sediments, in which A stands for adsorbed (not for adsorbable) is questionable. It includes the most important water insoluble technical organochlorine product: polyvinyl chloride, PVC. In addition to organic halogens it also includes inorganic, mineralogenic halides, incorporated mainly in the crystal lattice of fine grained phyllosilicates, the typical clay minerals (kaolinite, montmorillonite, illite and chlorite) which are main constituents of sediments and sedimentary rocks representing the major part of the sedimentary cover of the earth. Other phyllosilicates, biotite and muscovite, major constituents of granites and many metamorphic rocks (gneiss and mica schist) will also contribute to the AOX-S18 especially in soils as result of weathering processes. Since chlorine is incorporated into the mineral structure and, as a consequence, not soluble by the nitric acid analytical step (pH 0.5) of the S18 determination, it will account to the AOX-S18 in the final charcoal combustion step at temperatures >950 degrees C. After heavy rainfalls sewage sludge composition is strongly influenced by

  3. Sense or no-sense of the sum parameter for water soluble "adsorbable organic halogens" (AOX) and "absorbed organic halogens" (AOX-S18) for the assessment of organohalogens in sludges and sediments.

    PubMed

    Müller, German

    2003-07-01

    "AOX" is the abbreviation of the sum parameter for water soluble "adsorbable organic halogens" in which 'A' stands for adsorbable, 'O' for organic and 'X' for the halogens chlorine, bromine and iodine. After the introduction of the AOX in 1976, this parameter has been correctly used for "real" AOX constituents (DDT and its metabolites, PCBs, etc.) but also misused for non-adsorbable adsorbed OX-compounds, mostly high molecular organohalogens in plants and even to inorganic compounds being neither organic nor adsorbable. The question of natural "Adsorbable Organic Halogens" (AOX) formed by living organisms and/or during natural abiogenic processes has been definitively solved by the known existence of already more than 3650 organohalogen compounds, amongst them the highly reactive, cancerogenic vinyl chloride (VC). The extension of the AOX to AOX-S18 for Sludges and Sediments, in which A stands for adsorbed (not for adsorbable) is questionable. It includes the most important water insoluble technical organochlorine product: polyvinyl chloride, PVC. In addition to organic halogens it also includes inorganic, mineralogenic halides, incorporated mainly in the crystal lattice of fine grained phyllosilicates, the typical clay minerals (kaolinite, montmorillonite, illite and chlorite) which are main constituents of sediments and sedimentary rocks representing the major part of the sedimentary cover of the earth. Other phyllosilicates, biotite and muscovite, major constituents of granites and many metamorphic rocks (gneiss and mica schist) will also contribute to the AOX-S18 especially in soils as result of weathering processes. Since chlorine is incorporated into the mineral structure and, as a consequence, not soluble by the nitric acid analytical step (pH 0.5) of the S18 determination, it will account to the AOX-S18 in the final charcoal combustion step at temperatures >950 degrees C. After heavy rainfalls sewage sludge composition is strongly influenced by

  4. Halogen Bonding in Organic Synthesis and Organocatalysis.

    PubMed

    Bulfield, David; Huber, Stefan M

    2016-10-01

    Halogen bonding is a noncovalent interaction similar to hydrogen bonding, which is based on electrophilic halogen substituents. Hydrogen-bonding-based organocatalysis is a well-established strategy which has found numerous applications in recent years. In light of this, halogen bonding has recently been introduced as a key interaction for the design of activators or organocatalysts that is complementary to hydrogen bonding. This Concept features a discussion on the history and electronic origin of halogen bonding, summarizes all relevant examples of its application in organocatalysis, and provides an overview on the use of cationic or polyfluorinated halogen-bond donors in halide abstraction reactions or in the activation of neutral organic substrates.

  5. Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms

    NASA Astrophysics Data System (ADS)

    Ofner, J.; Balzer, N.; Buxmann, J.; Grothe, H.; Schmitt-Kopplin, P.; Platt, U.; Zetzsch, C.

    2012-01-01

    Reactive halogen species (RHS), such as X·, X2 and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA) and organic aerosol derived from biomass-burning (BBOA) has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols. Model SOA from α-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS released from simulated natural halogen sources like salt pans. Subsequently the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which result in new functional groups, changed UV/VIS absorption, or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance.

  6. Fractionation of halogenated organic matter present in rain and snow

    PubMed

    Laniewski; Boren; Grimvall

    1999-01-01

    Organic matter in samples of rain and snow from Sweden, Poland, Germany and the Republic of Ireland was fractionated by employing a series of filtration, purging, evaporation and extraction steps. Determinations of the group parameter AOX (adsorbable organic halogens) in aqueous phases and EOX (extractable organic halogens) in organic phases showed that halogenated organic matter present in bulk precipitation is composed of several different groups of compounds. The largest amounts of organically bound halogens were found in fractions of relatively polar and non-volatile to semivolatile compounds. In particular, a significant part of the AOX could be attributed to alkaline-labile organic bases. Gas chromatographic analysis of different organic extracts in the chlorine channel of an atomic emission detector (AED) resulted in chromatograms with few distinct peaks, and analysis in the bromine channel did not produce any distinct peaks. Chlorinated acetic acids were the most abundant halogenated organic acids, and chlorinated alkyl phosphates were normally responsible for the largest peaks in the chlorine chromatogram of neutral, hexane-extractable compounds. When analysing volatiles, 1,4-dichlorobenzene and a thus far unidentified chloroorganic compound often caused the largest response in the chlorine channel of the AED system.

  7. Screening of organic halogens and identification of chlorinated benzoic acids in carbonaceous meteorites.

    PubMed

    Schöler, Heinz F; Nkusi, Gerard; Niedan, Volker W; Müller, German; Spitthoff, Bianca

    2005-09-01

    The occurrence of halogenated organic compounds measured as a sum parameter and the evidence of chlorinated benzoic acids in four carbonaceous meteorites (Cold Bokkeveld, Murray, Murchison and Orgueil) from four independent fall events is reported. After AOX (Adsorbable organic halogen) and EOX (Extractable organic halogen) screening to quantify organically bound halogens, chlorinated organic compounds were analyzed by gas chromatography. AOX concentrations varying from 124 to 209 microg Cl/g d.w. were observed in carbonaceous meteorites. Ion chromatographic analysis of the distribution of organically bound halogens performed on the Cold Bokkeveld meteorite revealed that chlorinated and brominated organic compounds were extractable, up to 70%, whereas only trace amounts of organofluorines could be extracted. Chlorinated benzoic acids have been identified in carbonaceous meteorite extracts. Their presence and concentrations raise the question concerning the origin of halogenated, especially chlorinated, organic compounds in primitive planetary matter.

  8. Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms

    NASA Astrophysics Data System (ADS)

    Ofner, J.; Balzer, N.; Buxmann, J.; Grothe, H.; Schmitt-Kopplin, Ph.; Platt, U.; Zetzsch, C.

    2012-07-01

    Reactive halogen species (RHS), such as X·, X2 and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA) and organic aerosol derived from biomass-burning (BBOA) has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols. Model SOA from α-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS, released from simulated natural halogen sources like salt pans. Subsequently, the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which results in new functional groups (FTIR spectroscopy), changes UV/VIS absorption, chemical composition (ultrahigh resolution mass spectroscopy (ICR-FT/MS)), or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance.

  9. Biodegradation of halogenated organic compounds.

    PubMed Central

    Chaudhry, G R; Chapalamadugu, S

    1991-01-01

    In this review we discuss the degradation of chlorinated hydrocarbons by microorganisms, emphasizing the physiological, biochemical, and genetic basis of the biodegradation of aliphatic, aromatic, and polycyclic compounds. Many environmentally important xenobiotics are halogenated, especially chlorinated. These compounds are manufactured and used as pesticides, plasticizers, paint and printing-ink components, adhesives, flame retardants, hydraulic and heat transfer fluids, refrigerants, solvents, additives for cutting oils, and textile auxiliaries. The hazardous chemicals enter the environment through production, commercial application, and waste. As a result of bioaccumulation in the food chain and groundwater contamination, they pose public health problems because many of them are toxic, mutagenic, or carcinogenic. Although synthetic chemicals are usually recalcitrant to biodegradation, microorganisms have evolved an extensive range of enzymes, pathways, and control mechanisms that are responsible for catabolism of a wide variety of such compounds. Thus, such biological degradation can be exploited to alleviate environmental pollution problems. The pathways by which a given compound is degraded are determined by the physical, chemical, and microbiological aspects of a particular environment. By understanding the genetic basis of catabolism of xenobiotics, it is possible to improve the efficacy of naturally occurring microorganisms or construct new microorganisms capable of degrading pollutants in soil and aquatic environments more efficiently. Recently a number of genes whose enzyme products have a broader substrate specificity for the degradation of aromatic compounds have been cloned and attempts have been made to construct gene cassettes or synthetic operons comprising these degradative genes. Such gene cassettes or operons can be transferred into suitable microbial hosts for extending and custom designing the pathways for rapid degradation of recalcitrant

  10. Biodegradation of halogenated organic compounds.

    PubMed

    Chaudhry, G R; Chapalamadugu, S

    1991-03-01

    In this review we discuss the degradation of chlorinated hydrocarbons by microorganisms, emphasizing the physiological, biochemical, and genetic basis of the biodegradation of aliphatic, aromatic, and polycyclic compounds. Many environmentally important xenobiotics are halogenated, especially chlorinated. These compounds are manufactured and used as pesticides, plasticizers, paint and printing-ink components, adhesives, flame retardants, hydraulic and heat transfer fluids, refrigerants, solvents, additives for cutting oils, and textile auxiliaries. The hazardous chemicals enter the environment through production, commercial application, and waste. As a result of bioaccumulation in the food chain and groundwater contamination, they pose public health problems because many of them are toxic, mutagenic, or carcinogenic. Although synthetic chemicals are usually recalcitrant to biodegradation, microorganisms have evolved an extensive range of enzymes, pathways, and control mechanisms that are responsible for catabolism of a wide variety of such compounds. Thus, such biological degradation can be exploited to alleviate environmental pollution problems. The pathways by which a given compound is degraded are determined by the physical, chemical, and microbiological aspects of a particular environment. By understanding the genetic basis of catabolism of xenobiotics, it is possible to improve the efficacy of naturally occurring microorganisms or construct new microorganisms capable of degrading pollutants in soil and aquatic environments more efficiently. Recently a number of genes whose enzyme products have a broader substrate specificity for the degradation of aromatic compounds have been cloned and attempts have been made to construct gene cassettes or synthetic operons comprising these degradative genes. Such gene cassettes or operons can be transferred into suitable microbial hosts for extending and custom designing the pathways for rapid degradation of recalcitrant

  11. FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS

    SciTech Connect

    John F. Schabron; Joseph F. Rovani, Jr.; Theresa M. Bomstad

    2003-07-01

    Western Research Institute (WRI) is continuing work toward the development of new screening methodology and a test kit to measure halogenated volatile organic compounds (VOCs) in the field. Heated diode and corona discharge sensors are commonly used to detect leaks of refrigerants from air conditioners, freezers, and refrigerators. They are both selective to the presence of halogens. In prior work, the devices were tested for response to carbon tetrachloride, heptane, toluene, and water vapors. In the current work, sensor response was evaluated with sixteen halogenated VOCs relative to carbon tetrachloride. The results show that the response of the various chlorinated VOCs is within an order of magnitude of the response to carbon tetrachloride for each of the sensors. Thus, for field screening a single response factor can be used. Both types of leak detectors are being further modified to provide an on-board LCD signal readout, which is related to VOC concentration. The units will be fully portable and will operate with 115-V line or battery power. Signal background, noise level, and response data on the Bacharach heated diode detector and the TIF corona discharge detector show that when the response curves are plotted against the log of concentration, the plot is linear to the upper limit for the particular unit, with some curvature at lower levels. When response is plotted directly against concentration, the response is linear at the low end and is curved at the high end. The dynamic ranges for carbon tetrachloride of the two devices from the lower detection limit (S/N=2) to signal saturation are 4-850 vapor parts per million (vppm) for the corona discharge unit and 0.01-70 vppm for the heated diode unit. Additional circuit modifications are being made to lower the detection limit and increase the dynamic response range of the corona discharge unit. The results indicate that both devices show potential utility for future analytical method development work toward

  12. Desorption Induced by Excited Electrons from Semiconductor Surfaces (I)
    —Desorption Induced by Electron-/hole-injection into Halogen-adsorbed Silicon Surfaces—

    NASA Astrophysics Data System (ADS)

    Shudo, Kenichi; Tanaka, Masatoshi

    We review excited-electron-induced desorption from halogen-adsorbed semiconductor surfaces, focusing on desorption processes associated with electron-beam irradiation using an electron gun and hole-injection using a scanning tunneling microscope. Recent studies on halogen-adsorbed silicon surfaces, i.e., typical etching systems, are described from the viewpoint of desorption induced by electronic transitions (DIET).

  13. The heterogeneous interaction of HOCl with solid KBr substrates: the catalytic role of adsorbed halogens.

    PubMed

    Santschi, Ch; Rossi, M J

    2005-07-01

    The heterogeneous reactivity of HOCl on solid KBr at ambient temperature has been studied using a Knudsen flow reactor. On solid KBr steady-state uptake experiments reveal the formation of Br- and Cl-containing reaction products formed in secondary reactions such as Br(2), BrCl, HOBr, BrOCl, Cl(2) and Cl(2)O with the latter two predominating in the late stages of the reaction. The uptake coefficient gamma spanning a range between 0.15 and 1 x 10(-3) and product yields of HOCl strongly depend on the nature of the solid sample, whether grain, ground grain or thin sprayed film, as well as on sample processing such as pumping and/or heating. Furthermore, the presence of adsorbed halogen species such as Br(2)(a) are crucial for the kinetics of the reaction of HOCl with solid KBr substrates. The presence of surface-adsorbed water (SAW) leads to deactivation of KBr whereas mechanical stress such as grinding leads to the formation of surface defects that become reaction centers. Desorption of SAW at T > 620 K induces high reactivity of the KBr sample at ambient temperature. A reaction mechanism encompassing all significant observations including unusual autocatalytic activity is given as there is no direct reaction of HOCl with solid KBr. It stresses the importance of adsorbed Br-containing species such as Br(2)(a) and HBr(a) that initiate the heterogeneous chemistry of HOCl on solid KBr in the presence of SAW. The role of surface acidity and SAW for the extent of reaction is emphasized.

  14. Hydrophobic Porous Material Adsorbs Small Organic Molecules

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K.; Hickey, Gregory S.

    1994-01-01

    Composite molecular-sieve material has pore structure designed specifically for preferential adsorption of organic molecules for sizes ranging from 3 to 6 angstrom. Design based on principle that contaminant molecules become strongly bound to surface of adsorbent when size of contaminant molecules is nearly same as that of pores in adsorbent. Material used to remove small organic contaminant molecules from vacuum systems or from enclosed gaseous environments like closed-loop life-support systems.

  15. Mechanochemical destruction of halogenated organic pollutants: A critical review.

    PubMed

    Cagnetta, Giovanni; Robertson, John; Huang, Jun; Zhang, Kunlun; Yu, Gang

    2016-08-01

    Many tons of intentionally produced obsolete halogenated persistent organic pollutants (POPs), are stored worldwide in stockpiles, often in an unsafe manner. These are a serious threat to the environment and to human health due to their ability to migrate and accumulate in the biosphere. New technologies, alternatives to combustion, are required to destroy these substances, hopefully to their complete mineralization. In the last 20 years mechanochemical destruction has shown potential to achieve pollutant degradation, both of the pure substances and in contaminated soils. This capability has been tested for many halogenated pollutants, with various reagents, and under different milling conditions. In the present paper, a review of the published work in this field is followed by a critique of the state of the art of POPs mechanochemical destruction and its applicability to full-scale halogenated waste treatment.

  16. Primary cells utilize halogen-organic charge transfer complex

    NASA Technical Reports Server (NTRS)

    Gutmann, F.; Hermann, A. M.; Rembaum, A.

    1966-01-01

    Electrochemical cells with solid state components employ charge transfer complexes or donor-acceptor complexes in which the donor component is an organic compound and the acceptor component is a halogen. A minor proportion of graphite added to these composition helps reduce the resistivity.

  17. Size selective hydrophobic adsorbent for organic molecules

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K. (Inventor); Hickey, Gregory S. (Inventor)

    1997-01-01

    The present invention relates to an adsorbent formed by the pyrolysis of a hydrophobic silica with a pore size greater than 5 .ANG., such as SILICALITE.TM., with a molecular sieving polymer precursor such as polyfurfuryl alcohol, polyacrylonitrile, polyvinylidene chloride, phenol-formaldehyde resin, polyvinylidene difluoride and mixtures thereof. Polyfurfuryl alcohol is the most preferred. The adsorbent produced by the pyrolysis has a silicon to carbon mole ratio of between about 10:1 and 1:3, and preferably about 2:1 to 1:2, most preferably 1:1. The pyrolysis is performed as a ramped temperature program between about 100.degree. and 800.degree. C., and preferably between about 100.degree. and 600.degree. C. The present invention also relates to a method for selectively adsorbing organic molecules having a molecular size (mean molecular diameter) of between about 3 and 6 .ANG. comprising contacting a vapor containing the small organic molecules to be adsorbed with the adsorbent composition of the present invention.

  18. Determination of gaseous semi- and low-volatile organic halogen compounds by barrier-discharge atomic emission spectrometry.

    PubMed

    Sun, Yifei; Watanabe, Nobuhisa; Wang, Wei; Zhu, Tianle

    2013-01-01

    A group parameter approach using "total organic halogen" is effective for monitoring gaseous organic halogen compounds, including fluorine, chlorine, and bromine compounds, generated from combustion. We described the use of barrier-discharge radiofrequency-helium-plasma/atomic emission spectrometry, for the detection of semi- and low-volatile organic halogen compounds (SLVOXs), which can be collected by Carbotrap adsorbents and analyzed using thermal desorption. The optimal carrier gas flow rates at the injection and desorption lines were established to be 100 mL/min. The detection range for SLVOXs in the gaseous samples was from 10 ng to tens of micrograms. Measuring F was more difficult than measuring C1 or Br, because the wavelength of F is close to that of air. The barrier-discharge radiofrequency-helium-plasma/atomic emission spectrometry measured from 85% to 103% of the SLVOXs in the gas sample. It has been found that Carbotrap B is appropriate for high-boiling-point compounds, and Carbotrap C is suitable for the determination of organic halogen compounds with lower boiling points, in the range 200-2300C. Under optimal analysis conditions, a chlorine-containing plastic was destroyed using different oxygen concentrations. Lower oxygen concentrations resulted in the production of lower amounts of organic halogen compounds. PMID:23586317

  19. Determination of gaseous semi- and low-volatile organic halogen compounds by barrier-discharge atomic emission spectrometry.

    PubMed

    Sun, Yifei; Watanabe, Nobuhisa; Wang, Wei; Zhu, Tianle

    2013-01-01

    A group parameter approach using "total organic halogen" is effective for monitoring gaseous organic halogen compounds, including fluorine, chlorine, and bromine compounds, generated from combustion. We described the use of barrier-discharge radiofrequency-helium-plasma/atomic emission spectrometry, for the detection of semi- and low-volatile organic halogen compounds (SLVOXs), which can be collected by Carbotrap adsorbents and analyzed using thermal desorption. The optimal carrier gas flow rates at the injection and desorption lines were established to be 100 mL/min. The detection range for SLVOXs in the gaseous samples was from 10 ng to tens of micrograms. Measuring F was more difficult than measuring C1 or Br, because the wavelength of F is close to that of air. The barrier-discharge radiofrequency-helium-plasma/atomic emission spectrometry measured from 85% to 103% of the SLVOXs in the gas sample. It has been found that Carbotrap B is appropriate for high-boiling-point compounds, and Carbotrap C is suitable for the determination of organic halogen compounds with lower boiling points, in the range 200-2300C. Under optimal analysis conditions, a chlorine-containing plastic was destroyed using different oxygen concentrations. Lower oxygen concentrations resulted in the production of lower amounts of organic halogen compounds.

  20. Supramolecular chemistry of halogens: complementary features of inorganic (M-X) and organic (C-X') halogens applied to M-X...X'-C halogen bond formation.

    PubMed

    Zordan, Fiorenzo; Brammer, Lee; Sherwood, Paul

    2005-04-27

    Electronic differences between inorganic (M-X) and organic (C-X) halogens in conjunction with the anisotropic charge distribution associated with terminal halogens have been exploited in supramolecular synthesis based upon intermolecular M-X...X'-C halogen bonds. The synthesis and crystal structures of a family of compounds trans-[MCl(2)(NC(5)H(4)X-3)(2)] (M = Pd(II), Pt(II); X = F, Cl, Br, I; NC(5)H(4)X-3 = 3-halopyridine) are reported. With the exception of the fluoropyridine compounds, network structures propagated by M-Cl...X-C halogen bonds are adopted and involve all M-Cl and all C-X groups. M-Cl...X-C interactions show Cl...X separations shorter than van der Waals values, shorter distances being observed for heavier halogens (X). Geometries with near linear Cl...X-C angles (155-172 degrees ) and markedly bent M-Cl...X angles (92-137 degrees ) are consistently observed. DFT calculations on the model dimers {trans-[MCl(2)(NH(3))(NC(5)H(4)X-3)]}(2) show association through M-Cl...X-C (X not equal F) interactions with geometries similar to experimental values. DFT calculations of the electrostatic potential distributions for the compounds trans-[PdCl(2)(NC(5)H(4)X-3)(2)] (X = F, Cl, Br, I) demonstrate the effectiveness of the strategy to activate C-X groups toward halogen bond formation by enhancing their electrophilicity, and explain the absence of M-Cl...F-C interactions. The M-Cl...X-C halogen bonds described here can be viewed unambiguously as nucleophile-electrophile interactions that involve an attractive electrostatic contribution. This contrasts with some types of halogen-halogen interactions previously described and suggests that M-Cl...X-C halogen bonds could provide a valuable new synthon for supramolecular chemists.

  1. Formation of halogen-induced secondary organic aerosol (XOA)

    NASA Astrophysics Data System (ADS)

    Kamilli, Katharina; Ofner, Johannes; Zetzsch, Cornelius; Held, Andreas

    2013-04-01

    Reactive halogen species (RHS) are very important due to their potential of stratospheric ozone depletion and surface ozone destruction. RHS seem to interact with precursors of secondary organic aerosol (SOA) similarly to common atmospheric oxidants like OH radicals and ozone. The potential interaction of RHS with preformed SOA has recently been studied (Ofner et al., 2012). Although aerosol formation from reaction of RHS with typical SOA precursors was previously studied (e.g. Cai et al., 2006), no data are available on bromine-induced aerosol formation from organic precursors yet. An aerosol smog-chamber was used to examine the halogen-induced secondary organic aerosol (XOA) formation under atmospheric conditions using simulated sunlight. With a concentration of 10 ppb for the organic precursor, 2 ppb for molecular chlorine, and 10 ppb for molecular bromine, the experimental setup is close to ambient conditions. By combined measurements of the aerosol size distribution, ozone and NOx mixing ratios, as well as the decay of the organic precursor, aerosol yields and aerosol growth rates were determined. The decay of the organic precursor was analyzed by capillary gas chromatography coupled with flame-ionization detection (GC-FID) and the aerosol size distribution was measured using a Scanning Mobility Particle Sizer (SMPS). Additionally, with the decay rate of the precursor and the calculated photolysis rates of molecular halogen species, based on the well-known spectrum of the solar simulator, mechanistic details on the XOA formation pathways can be determined. We observed XOA formation even at very low precursor and RHS concentrations with a diameter mode at 10-20 nm and a number concentration up to 1000000 particles cm-3. While the XOA formation from chlorine is very rapid, the interaction of bromine with the organic precursors is about five times slower. The aerosol yield reached maximum values of 0.01 for the reaction of chlorine with α-pinene and 0.0004 for

  2. Impact of bromide on halogen incorporation into organic moieties in chlorinated drinking water treatment and distribution systems.

    PubMed

    Tan, J; Allard, S; Gruchlik, Y; McDonald, S; Joll, C A; Heitz, A

    2016-01-15

    The impact of elevated bromide concentrations (399 to 750 μg/L) on the formation of halogenated disinfection by-products (DBPs), namely trihalomethanes, haloacetic acids, haloacetonitriles, and adsorbable organic halogen (AOX), in two drinking water systems was investigated. Bromine was the main halogen incorporated into all of the DBP classes and into organic carbon, even though chlorine was present in large excess to maintain a disinfectant residual. Due to the higher reactivity of bromine compared to chlorine, brominated DBPs were rapidly formed, followed by a slower increase in chlorinated DBPs. Higher bromine substitution and incorporation factors for individual DBP classes were observed for the chlorinated water from the groundwater source (lower concentration of dissolved organic carbon (DOC)), which contained a higher concentration of bromide, than for the surface water source (higher DOC). The molar distribution of adsorbable organic bromine to chlorine (AOBr/AOCl) for AOX in the groundwater distribution system was 1.5:1 and almost 1:1 for the surface water system. The measured (regulated) DBPs only accounted for 16 to 33% of the total organic halogen, demonstrating that AOX measurements are essential to provide a full understanding of the formation of halogenated DBPs in drinking waters. In addition, the study demonstrated that a significant proportion (up to 94%) of the bromide in source waters can be converted AOBr. An evaluation of AOBr and AOCl through a second groundwater treatment plant that uses conventional treatment processes for DOC removal produced 70% of AOX as AOBr, with 69% of the initial source water bromide converted to AOBr. Exposure to organobromine compounds is suspected to result in greater adverse health consequences than their chlorinated analogues. Therefore, this study highlights the need for improved methods to selectively reduce the bromide content in source waters.

  3. Nonbonding interactions of organic halogens in biological systems: implications for drug discovery and biomolecular design.

    PubMed

    Lu, Yunxiang; Wang, Yong; Zhu, Weiliang

    2010-05-14

    Halogenation is an important approach in lead optimization for drug development and about half of the molecules used in high-throughput screening are halogenated. However, there is neither a suitable theoretical algorithm for evaluating the interaction between the halogen atoms of a ligand and its target protein nor a detailed understanding of how a halogen atom interacts with electron-rich atoms or groups of the residues in the binding pocket. In this Perspective, we concentrate on nonbonding interactions of halogens from both crystallographic data and theoretical viewpoints. It is found that organic halogen atoms are favorably involved in a wide variety of noncovalent protein-ligand interactions, such as halogen bonds C-X...O and hydrogen bonds C-X...H, that show remarkable differences in terms of the geometrical and energetic features. In biological molecules, heavier halogens prefer to form linear interactions with oxygen atoms and aromatic pi systems as compared to N or S, while the mean intermolecular distances for these types of halogen bonds increase with the radius or polarizability of halogen atoms, viz., Cl < Br < I. Furthermore, F...H interactions in protein-ligand complexes exhibit disparate behavior relative to X...H (X = Cl, Br, I) counterparts. These observed tendencies of the interactions involving halogens are subsequently rationalized by means of ab initio calculations using small model systems. The results presented herein should be of great use in the rational design of halogenated ligands as inhibitors and drugs as well as in biological engineering.

  4. Likelihood of atom–atom contacts in crystal structures of halogenated organic compounds

    PubMed Central

    Jelsch, Christian; Soudani, Sarra; Ben Nasr, Cherif

    2015-01-01

    The likelihood of occurrence of intermolecular contacts in crystals of halogenated organic compounds has been analysed statistically using tools based on the Hirshfeld surface. Several families of small halogenated molecules (containing organic F, Cl, Br or I atoms) were analysed, based on chemical composition and aromatic or aliphatic character. The behaviour of crystal contacts was also probed for molecules containing O or N. So-called halogen bonding (a halogen making short interactions with O or N, or a π interaction with C) is generally disfavoured, except when H is scarce on the molecular surface. Similarly, halogen⋯halogen contacts are more rare than expected, except for molecules that are poor in H. In general, the H atom is found to be the preferred partner of organic halogen atoms in crystal structures. On the other hand, C⋯C interactions in parallel π-stacking have a high propensity to occur in halogenated aromatic molecules. The behaviour of the four different halogen species (F, Cl, Br, I) is compared in several chemical composition contexts. The analysis tool can be refined by distinguishing several types for a given chemical species, such as H atoms bound to O or C. Such distinction shows, for instance, that C—H⋯Cl and O—H⋯O are the preferred interactions in compounds containing both O and Cl. PMID:25995842

  5. Likelihood of atom-atom contacts in crystal structures of halogenated organic compounds.

    PubMed

    Jelsch, Christian; Soudani, Sarra; Ben Nasr, Cherif

    2015-05-01

    The likelihood of occurrence of intermolecular contacts in crystals of halogenated organic compounds has been analysed statistically using tools based on the Hirshfeld surface. Several families of small halogenated molecules (containing organic F, Cl, Br or I atoms) were analysed, based on chemical composition and aromatic or aliphatic character. The behaviour of crystal contacts was also probed for molecules containing O or N. So-called halogen bonding (a halogen making short interactions with O or N, or a π interaction with C) is generally disfavoured, except when H is scarce on the molecular surface. Similarly, halogen⋯halogen contacts are more rare than expected, except for molecules that are poor in H. In general, the H atom is found to be the preferred partner of organic halogen atoms in crystal structures. On the other hand, C⋯C interactions in parallel π-stacking have a high propensity to occur in halogenated aromatic molecules. The behaviour of the four different halogen species (F, Cl, Br, I) is compared in several chemical composition contexts. The analysis tool can be refined by distinguishing several types for a given chemical species, such as H atoms bound to O or C. Such distinction shows, for instance, that C-H⋯Cl and O-H⋯O are the preferred interactions in compounds containing both O and Cl.

  6. 40 CFR Appendix III to Part 268 - List of Halogenated Organic Compounds Regulated Under § 268.32

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 26 2010-07-01 2010-07-01 false List of Halogenated Organic Compounds... Part 268—List of Halogenated Organic Compounds Regulated Under § 268.32 In determining the... defined the HOCs that must be included in a calculation as any compounds having a carbon-halogen...

  7. PATTERN RECOGNITION STUDIES OF HALOGENATED ORGANIC COMPOUNDS USING CONDUCTING POLYMER SENSOR ARRAYS. (R825323)

    EPA Science Inventory

    Direct measurement of volatile and semivolatile halogenated organic compounds of environmental interest was carried out using arrays of conducting polymer sensors. Mathematical expressions of the sensor arrays using microscopic polymer network model is described. A classical, non...

  8. [Source emission characteristics and impact factors of volatile halogenated organic compounds from wastewater treatment plant].

    PubMed

    He, Jie; Wang, Bo-Guang; Liu, Shu-Le; Zhao, De-Jun; Tang, Xiao-Dong; Zou, Yu

    2011-12-01

    A low enrichment method of using Tenax as absorbent and liquid nitrogen as refrigerant has been established to sample the volatile halogenated organic compounds in Guangzhou Liede municipal wastewater treatment plant as well as its ambient air. The composition and concentration of target halogenated hydrocarbons were analyzed by combined thermal desorption/GC-MS to explore its sources profile and impact factors. The result showed that 19 halogenated organic compounds were detected, including 11 halogenated alkanets, 3 halogenated alkenes, 3 halogenated aromatic hydrocarbons and 2 haloesters, with their total concentrations ranged from 34.91 microg x m(-3) to 127.74 microg x m(-3) and mean concentrations ranged from n.d. to 33.39 microg x m(-3). Main pollutants of the studied plant were CH2Cl2, CHCl3, CFC-12, C2H4Cl2, CFC-11, C2HCl3 and C2Cl4, they came from the wastewater by volatilization. Among the six processing units, the dehydration room showed the highest level of halogenated organic compounds, followed by pumping station, while the sludge thickener was the lowest. The emissions from pumping station, aeration tank and biochemical pool were significantly affected by temperature and humidity of environment.

  9. Magnesium silicates adsorbents of organic compounds

    NASA Astrophysics Data System (ADS)

    Ciesielczyk, Filip; Krysztafkiewicz, Andrzej; Jesionowski, Teofil

    2007-08-01

    Studies were presented on production of highly dispersed magnesium silicate at a pilote scale. The process of silicate adsorbent production involved precipitation reaction using water glass (sodium metasilicate) solution and appropriate magnesium salt, preceded by an appropriate optimization stage. Samples of best physicochemical parameters were in addition modified (in order to introduce to silica surface of several functional groups) using the dry technique and various amounts of 3-isocyanatepropyltrimethoxysilane, 3-thiocyanatepropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane. The so prepared samples were subjected to a comprehensive physicochemical analysis. At the terminal stage of studies attempts were made to adsorb phenol from its aqueous solutions on the surface of unmodified and modified magnesium silicates. Particle size distributions were determined using the ZetaSizer Nano ZS apparatus. In order to define adsorptive properties of studied magnesium silicates isotherms of nitrogen adsorption/desorption on their surfaces were established. Efficiency of phenol adsorption was tested employing analysis of post-adsorption solution.

  10. Complexation of trace metals by adsorbed natural organic matter

    USGS Publications Warehouse

    Davis, J.A.

    1984-01-01

    The adsorption behavior and solution speciation of Cu(II) and Cd(II) were studied in model systems containing colloidal alumina particles and dissolved natural organic matter. At equilibrium a significant fraction of the alumina surface was covered by adsorbed organic matter. Cu(II) was partitioned primarily between the surface-bound organic matter and dissolved Cu-organic complexes in the aqueous phase. Complexation of Cu2+ with the functional groups of adsorbed organic matter was stronger than complexation with uncovered alumina surface hydroxyls. It is shown that the complexation of Cu(II) by adsorbed organic matter can be described by an apparent stability constant approximately equal to the value found for solution phase equilibria. In contrast, Cd(II) adsorption was not significantly affected by the presence of organic matter at the surface, due to weak complex formation with the organic ligands. The results demonstrate that general models of trace element partitioning in natural waters must consider the presence of adsorbed organic matter. ?? 1984.

  11. Organic colloid as a mode of transport for toxic halogenated organic compounds in the Mississippi river

    SciTech Connect

    Rostad, C.E.

    1995-12-01

    Suspended material was isolated from water samples from sixteen sites on the Mississippi River and its major tributaries from Minneapolis, Minn., to New Orleans, La., during the summer and fall of 1991 and the spring of 1992. The suspended material was separated into silt and colloid fractions in order to determine the proportion of associated toxic hydrophobic halogenated organic compounds transported on the colloid. The silt fraction (63 {mu}m to 1 {mu}m in diameter) was isolated first by centrifugation, then the colloidal fraction (1 {mu}m to 0.005 {mu}m in diameter) was isolated by tangential-flow ultrafiltration. The colloid averaged about 10 percent by weight of the total suspended material. Organic carbon content of the colloid ranged from 7 to 30 percent by weight. Silt organic carbon content ranged from 2 to 5 percent by weight. The proportion of suspended organic carbon transport in the river associated with the colloids averaged 35 percent of the total suspended organic carbon transport. Toxic halogenated organic compounds associated with both fractions included PCBs, chlordane, DCPA, hexachlorobenzene, and trifluralin. In some cases, transport of these compounds by the colloid fraction in the Mississippi River was greater than by the silt fraction.

  12. AQUATIC PHOTOLYSIS OF OXY-ORGANIC COMPOUNDS ADSORBED ON GOETHITE.

    USGS Publications Warehouse

    Goldberg, Marvin C.

    1985-01-01

    Organic materials that will not absorb light at wavelengths longer than 295 nanometers (the solar wavelength cutoff) may nevertheless, undergo electron transfer reactions initiated by light. These reactions occur when the organic materials are adsorbed as ligand complexes to the surface of iron oxy-hydroxide (goethite). The adsorbed materials can be either inner or outer coordination sphere complexes. Goethite was chosen as the iron oxyhydroxide surface because it has the highest thermodynamic stability of any of the oxyhydroxides in water and it can be synthesized easily, with high purity.

  13. Interactions of organic contaminants with mineral-adsorbed surfactants

    USGS Publications Warehouse

    Zhu, L.; Chen, B.; Tao, S.; Chiou, C.T.

    2003-01-01

    Sorption of organic contaminants (phenol, p-nitrophenol, and naphthalene) to natural solids (soils and bentonite) with and without myristylpyridinium bromide (MPB) cationic surfactant was studied to provide novel insight to interactions of contaminants with the mineral-adsorbed surfactant. Contaminant sorption coefficients with mineral-adsorbed surfactants, Kss, show a strong dependence on surfactant loading in the solid. At low surfactant levels, the Kss values increased with increasing sorbed surfactant mass, reached a maximum, and then decreased with increasing surfactant loading. The Kss values for contaminants were always higher than respective partition coefficients with surfactant micelles (Kmc) and natural organic matter (Koc). At examined MPB concentrations in water the three organic contaminants showed little solubility enhancement by MPB. At low sorbed-surfactant levels, the resulting mineral-adsorbed surfactant via the cation-exchange process appears to form a thin organic film, which effectively "adsorbs" the contaminants, resulting in very high Kss values. At high surfactant levels, the sorbed surfactant on minerals appears to form a bulklike medium that behaves essentially as a partition phase (rather than an adsorptive surface), with the resulting Kss being significantly decreased and less dependent on the MPB loading. The results provide a reference to the use of surfactants for remediation of contaminated soils/sediments or groundwater in engineered surfactant-enhanced washing.

  14. DESIGNING FIXED-BED ADSORBERS TO REMOVE MIXTURES OF ORGANICS.

    EPA Science Inventory

    A liquid-phase granular activated carbon (GAC) pilot plant and a full-scale GAC adsorber were designed, built, and operated in order to evaluate their performance for treating a groundwater contaminated with several volatile and synthetic organic chemicals. Several empty bed con...

  15. Interactions of organic contaminants with mineral-adsorbed surfactants.

    PubMed

    Zhu, Lizhong; Chen, Baoliang; Tao, Shu; Chiou, Cary T

    2003-09-01

    Sorption of organic contaminants (phenol, p-nitrophenol, and naphthalene) to natural solids (soils and bentonite) with and without myristylpyridinium bromide (MPB) cationic surfactant was studied to provide novel insightto interactions of contaminants with the mineral-adsorbed surfactant. Contaminant sorption coefficients with mineral-adsorbed surfactants, Kss, show a strong dependence on surfactant loading in the solid. At low surfactant levels, the Kss values increased with increasing sorbed surfactant mass, reached a maximum, and then decreased with increasing surfactant loading. The Kss values for contaminants were always higher than respective partition coefficients with surfactant micelles (Kmc) and natural organic matter (Koc). At examined MPB concentrations in water the three organic contaminants showed little solubility enhancement by MPB. At low sorbed-surfactant levels, the resulting mineral-adsorbed surfactant via the cation-exchange process appears to form a thin organic film, which effectively "adsorbs" the contaminants, resulting in very high Kss values. At high surfactant levels, the sorbed surfactant on minerals appears to form a bulklike medium that behaves essentially as a partition phase (rather than an adsorptive surface), with the resulting Kss being significantly decreased and less dependent on the MPB loading. The results provide a reference to the use of surfactants for remediation of contaminated soils/sediments or groundwater in engineered surfactant-enhanced washing.

  16. 40 CFR Appendix III to Part 268 - List of Halogenated Organic Compounds Regulated Under § 268.32

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 27 2011-07-01 2011-07-01 false List of Halogenated Organic Compounds Regulated Under § 268.32 III Appendix III to Part 268 Protection of Environment ENVIRONMENTAL PROTECTION... Part 268—List of Halogenated Organic Compounds Regulated Under § 268.32 In determining...

  17. 40 CFR Appendix III to Part 268 - List of Halogenated Organic Compounds Regulated Under § 268.32

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 27 2014-07-01 2014-07-01 false List of Halogenated Organic Compounds Regulated Under § 268.32 III Appendix III to Part 268 Protection of Environment ENVIRONMENTAL PROTECTION... Part 268—List of Halogenated Organic Compounds Regulated Under § 268.32 In determining...

  18. 40 CFR Appendix III to Part 268 - List of Halogenated Organic Compounds Regulated Under § 268.32

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 28 2013-07-01 2013-07-01 false List of Halogenated Organic Compounds Regulated Under § 268.32 III Appendix III to Part 268 Protection of Environment ENVIRONMENTAL PROTECTION... Part 268—List of Halogenated Organic Compounds Regulated Under § 268.32 In determining...

  19. 40 CFR Appendix III to Part 268 - List of Halogenated Organic Compounds Regulated Under § 268.32

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 28 2012-07-01 2012-07-01 false List of Halogenated Organic Compounds Regulated Under § 268.32 III Appendix III to Part 268 Protection of Environment ENVIRONMENTAL PROTECTION... Part 268—List of Halogenated Organic Compounds Regulated Under § 268.32 In determining...

  20. Legacy and emerging halogenated organic pollutants in marine organisms from the Pearl River Estuary, South China.

    PubMed

    Sun, Run-Xia; Luo, Xiao-Jun; Tan, Xiao-Xin; Tang, Bin; Li, Zong-Rui; Mai, Bi-Xian

    2015-11-01

    A suite of legacy and emerging halogenated organic pollutants (HOPs) were measured in marine organisms (coastal fish and invertebrates) from the Pearl River Estuary, South China, to investigate the current contamination status after the Stockholm Convention was implemented in China. Dichlorodiphenyltrichloroethane and its metabolites (DDTs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) were detected in all samples at concentrations of 54-1500, 16-700, and 0.56-59ng/g lipid weight, respectively. Dechlorane Plus (DP), decabromodiphenyl ethane (DBDPE), 2,3,5,6-tetrabromo-p-xylene (pTBX), and pentabromotoluene (PBT) were also found at concentrations of ND (non-detectable) to 37ng/g lipid weight. The concentrations of these investigated contaminants in the present study were at moderate levels, as compared with those reported in other regions. Significant interspecies differences were found in the levels of DDTs, PCBs, PBDEs and the alternative halogenated flame retardants (AHFRs). DDTs were the predominant HOPs in those species and represented >50% of the total HOPs, followed by PCBs, PBDEs, and AHFRs. The total estimated daily intakes (EDIs) of DDTs, PCBs, PBDEs, and AHFRs were 28, 12, 1.0, and 0.18 (ng/kg)/d, respectively, via seafood consumption. These concentrations are not expected to pose health risks to humans. PMID:26318119

  1. Legacy and emerging halogenated organic pollutants in marine organisms from the Pearl River Estuary, South China.

    PubMed

    Sun, Run-Xia; Luo, Xiao-Jun; Tan, Xiao-Xin; Tang, Bin; Li, Zong-Rui; Mai, Bi-Xian

    2015-11-01

    A suite of legacy and emerging halogenated organic pollutants (HOPs) were measured in marine organisms (coastal fish and invertebrates) from the Pearl River Estuary, South China, to investigate the current contamination status after the Stockholm Convention was implemented in China. Dichlorodiphenyltrichloroethane and its metabolites (DDTs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) were detected in all samples at concentrations of 54-1500, 16-700, and 0.56-59ng/g lipid weight, respectively. Dechlorane Plus (DP), decabromodiphenyl ethane (DBDPE), 2,3,5,6-tetrabromo-p-xylene (pTBX), and pentabromotoluene (PBT) were also found at concentrations of ND (non-detectable) to 37ng/g lipid weight. The concentrations of these investigated contaminants in the present study were at moderate levels, as compared with those reported in other regions. Significant interspecies differences were found in the levels of DDTs, PCBs, PBDEs and the alternative halogenated flame retardants (AHFRs). DDTs were the predominant HOPs in those species and represented >50% of the total HOPs, followed by PCBs, PBDEs, and AHFRs. The total estimated daily intakes (EDIs) of DDTs, PCBs, PBDEs, and AHFRs were 28, 12, 1.0, and 0.18 (ng/kg)/d, respectively, via seafood consumption. These concentrations are not expected to pose health risks to humans.

  2. Toxicity of halogenated organic compounds. (Latest citations from the NTIS bibliographic database). Published Search

    SciTech Connect

    Not Available

    1993-09-01

    The bibliography contains citations concerning health and environmental effects of halogenated organic compounds. Topics include laboratory and field investigations regarding bioaccumulation and concentration, metabolic aspects, and specific site studies in industrial and commercial operations. Pesticides, solvents, and a variety of industrial compounds are discussed. (Contains 250 citations and includes a subject term index and title list.)

  3. Spectroscopic investigations of organic aerosol and its reaction with halogens, released by sea-salt activation

    NASA Astrophysics Data System (ADS)

    Ofner, J.; Zetzsch, C.

    2009-04-01

    The release of reactive halogen species from sea-salt aerosol offers a class of reactants for heterogeneous reactions of utmost importance. These heterogeneous reactions have been overlooked so far, although they may occur with internal and external mixtures of sea-salt aerosol and organic aerosol or organic matter. Such reactions might constitute sources of gaseous organohalogen compounds or halogenated organic aerosol in the atmospheric boundary layer. Infrared and UV/VIS spectroscopy provide an insight into chemical processes at reactive sites of the organic phase on a molecular level. Model studies of heterogeneous reactions of halogens with different kinds of (secondary) organic aerosols and organic matter were performed using a 700L smog chamber with a solar simulator. The model compounds alpha-pinene, catechol and humic acid have been chosen as precursors/material for the condensed, organic phase of the aerosol. After formation of the secondary organic aerosol or preparation of the organic material and the sea-salt solution the reaction was carried out using molecular chlorine and bromine in the presence of simulated sunlight. Chemical transformation of the organic material was studied using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) on a ZnSe crystal and diffuse reflectance UV/VIS spectroscopy. An electrostatic precipitator was developed to deposit the aerosol particles on the ATR crystal as a thin film. On the other hand, longpath-FTIR spectroscopy with a 40m White-cell allows us to monitor both the condensed and gas phase of the aerosol in situ in the smog chamber directly. These spectroscopic techniques enable us to characterize different organic aerosol particles and their functional groups at reactive sites on these particles as well as to study aerosol formation and transformation directly. The heterogeneous reaction of reactive halogen species with organic material at atmospheric conditions leads to small reactive

  4. Organo-halogenated contaminants (OHCs) in the sediments from the Soan River, Pakistan: OHCs(adsorbed TOC) burial flux, status and risk assessment.

    PubMed

    Malik, Riffat Naseem; Mehboob, Fouzia; Ali, Usman; Katsoyiannis, Athanasios; Schuster, Jasmin K; Moeckel, Claudia; Jones, Kevin C

    2014-05-15

    In this study, regression analysis revealed that TOC is the principal factor in controlling the fate of organo-halogenated contaminants (OHCs: PCBs, PBDEs, OCPs) in Soan River, Pakistan. The OHCs(adsorbed TOC) burial flux (OHCs(adsorbed TOC)Bf; mg/cm(2)·yr) was calculated in the following ranges: ∑PCBs (0.07-0.31), ∑PBDEs (0.005-0.029), ∑HCHs (0.015-0.046) and ∑DDTs (0.007-0.039). Apart from OHCs(adsorbed TOC)Bf, the levels of OHCs were in the following order: PCBs>DDTs>PBDEs>HCH>Chlordane>HCB. PBDEs and PCB congener patterns showed following order respectively: BDE-149>-153>-18>-138>-44 and PCB-149>-153>-18>-138>-44. DDT isomers and metabolites' pattern were p,p'-DDT>p,p'-DDD>p,p'-DDE>o,p'-DDT>o,p'-DDD>o,p'-DDE and HCHs were β-HCH>α-HCH>γ-HCH>δ-HCH. PBDE composition had similarities to penta-BDE and DE-71 mixtures and PCBs with commercial products Aroclor-1254 and -1260. (DDE+DDD)/∑DDTs and p,p'-DDT/p,p'-DDE suggested the recent input of DDTs in sediments while α/γ-HCH indicated past usage of lindane and technical mixtures. Risk assessment suggested that Soan River and its tributaries are potentially at risk against most of the OHCs.

  5. Optimization of dynamic headspace extraction system for measurement of halogenated volatile organic compounds in liquid or viscous samples

    NASA Astrophysics Data System (ADS)

    Taniai, G.; Oda, H.; Kurihara, M.; Hashimoto, S.

    2010-12-01

    Halogenated volatile organic compounds (HVOCs) produced in the marine environment are thought to play a key role in atmospheric reactions, particularly those involved in the global radiation budget and the depression of tropospheric and stratospheric ozone. To evaluate HVOCs concentrations in the various natural samples, we developed an automated dynamic headspace extraction method for the determination of 15 HVOCs, such as chloromethane, bromomethane, bromoethane, iodomethane, iodoethane, bromochloromethane, 1-iodopropane, 2-iodopropane, dibromomethane, bromodichloromethane, chloroiodomethane, chlorodibromomethane, bromoiodomethane, tribromomethane, and diiodomethane. Dynamic headspace system (GERSTEL DHS) was used to purge the gas phase above samples and to trap HVOCs on the adsorbent column from the purge gas. We measured the HVOCs concentrations in the adsorbent column with gas chromatograph (Agilent 6890N)- mass spectrometer (Agilent 5975C). In dynamic headspace system, an glass tube containing Tenax TA or Tenax GR was used as adsorbent column for the collection of 15 HVOCs. The parameters for purge and trap extraction, such as purge flow rate (ml/min), purge volume (ml), incubation time (min), and agitator speed (rpm), were optimized. The detection limits of HVOCs in water samples were 1270 pM (chloromethane), 103 pM (bromomethane), 42.1 pM (iodomethane), and 1.4 to 10.2 pM (other HVOCs). The repeatability (relative standard deviation) for 15 HVOCs were < 9 % except chloromethane (16.2 %) and bromomethane (11.0 %). On the basis of the measurements for various samples, we concluded that this analytical method is useful for the determination of wide range of HVOCs with boiling points between - 24°C (chloromethane) and 181°C (diiodomethane) for the liquid or viscous samples.

  6. Organic halogenated contaminants in mother-fetus pairs of harbor seals (Phoca vitulina richardii) from Alaska, 2000-2002

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Environmental stressors may interfere with foraging, survival and reproduction of marine mammals resulting in marine mammal population decline. In this study, organic halogenated pollutants [OHs, including organochlorine pesticides, polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCN...

  7. Measurements of halogenated organic compounds near the tropical tropopause

    NASA Technical Reports Server (NTRS)

    Schauffler, S. M.; Heidt, L. E.; Pollock, W. H.; Gilpin, T. M.; Vedder, J. F.; Solomon, S.; Lueb, R. A.; Atlas, E. L.

    1993-01-01

    The amount of organic chlorine and bromine entering the stratosphere have a direct influence on the magnitude of chlorine and bromine catalyzed ozone losses. Twelve organic chlorine species and five organic bromine species were measured from 12 samples collected near the tropopause between 23.8 deg N and 25.3 deg N during AASE 2. The average mixing ratios of total organic chlorine and total organic bromine were 3.50 +/- 0.06 ppbv and 21.1 +/- 0.8 pptv, respectively. CH3Cl represented 15.1% of the total organic chlorine, with CFC 11 (CCl3F) and CFC 12 (CCl2F2) accounting for 22.6% and 28.2%, respectively, with the remaining 34.1% primarily from CCl4, CH3CCl3, and CFC 113 (CCl2FCClF2). CH3Br represented 54% of the total organic bromine. The 95% confidence intervals of the mixing ratios of all but four of the individual compounds were within the range observed in low and mid-latitude mid-troposphere samples. The four compounds with significantly lower mixing ratios at the tropopause were CHCl3, CH2Cl2, CH2Br2, and CH3CCl3. The lower mixing ratios may be due to entrainment of southern hemisphere air during vertical transport in the tropical region and/or to exchange of air across the tropopause between the lower stratosphere and upper troposphere.

  8. Measurements of Halogenated Organic Compounds near the Tropical Tropopause

    NASA Technical Reports Server (NTRS)

    Schauffler, S. M.; Heidt, L. E.; Pollock, W. H.; Gilpin, T. M.; Vedder, J. F.; Solomon, S.; Leub, R. A.; Atlas, E. L.

    1993-01-01

    The amount of organic chlorine and bromine entering the stratosphere have a direct influence on the magnitude of chlorine and bromine catalyzed ozone losses. Twelve organic chlorine species and five organic bromine species were measured from 12 samples collected near the tropopause between 23.8 deg N and 25.3 deg N during AASE 2. The average mixing ratios of total organic chlorine and total organic bromine were 3.50 +/- 0.06 ppbv and 21.1 +/- 0.8 pptv, respectively. CH3Cl represented 15.1% of the total organic chlorine, with CFC 11 (CCl3F) and CFC 12 (CCl2F2) accounting for 22.6% and 28.2%, respectively, with the remaining 34.1% primarily from CCl4, CH3CCl3, and CFC 113 (CCl2FCClF2). CH3Br represented 54% of the total organic bromine. The 95% confidence intervals of the mixing ratios of all but four of the individual compounds were within the range observed in low and mid-latitude midtroposphere samples. The four compounds with significantly lower mixing ratios at the tropopause were CHCl3, CH2Cl2, CH2Br2, and CH3CCl3. The lower mixing ratios may be due to entrainment of southern hemisphere air during vertical transport in the tropical region and/or to exchange of air across the tropopause between the lower stratosphere and upper troposphere.

  9. Organic Halogen and Related Trace Gases in the Tropical Atmosphere: Results from Recent Airborne Campaigns Over the Pacific

    NASA Astrophysics Data System (ADS)

    Atlas, E. L.; Navarro, M. A.; Donets, V.; Schauffler, S.; Lueb, R.; Hendershot, R.; Gabbard, S.; Hornbrook, R. S.; Apel, E. C.; Riemer, D. D.; Pan, L.; Salawitch, R. J.; Nicely, J. M.; Montzka, S. A.; Miller, B.; Moore, F. L.; Elkins, J. W.; Hintsa, E. J.; Campos, T. L.; Quack, B.; Zhu, X.; Pope, L.

    2014-12-01

    Organic halogen gases, especially containing bromine and iodine, play a significant role as precursors to active halogen chemistry and ozone catalytic loss. Much of the reactive organic halogen originates from biological processes in the surface ocean, which can be quite variable by season and location. The tropics and coastal margins are potentially important sources that are being examined. The recent coordinated CONTRAST/ATTREX/CAST missions were conducted in the Western Tropical Pacific, a region that is a major transport pathway for tropospheric air entering the stratosphere. One of the goals of the missions was to identify sources, distributions, and transport of organic halogens from the ocean surface into the tropical lower stratosphere. The missions were conducted during the NH winter season, Jan-Feb, 2014. In this presentation, we will discuss the distributions and variability of organic halogen gases in the study region and will examine the input of organic halogen species into the Tropical Tropopause Layer (TTL). Comparison with other tracers, such as methyl nitrate and NMHC, will help identify source regions for these gases. We will focus on the measurements obtained in the CONTRAST and ATTREX missions with data from in-situ GC/MS measurements and whole air samples collected on the NSF GV and NASA Global Hawk aircraft. Comparisons with other recent airborne campaigns, such as HIPPO and TC4, and with several ship-based studies will provide an additional context for evaluating the variability of organic halogen species in the tropical atmosphere and their role in transporting reactive halogen compounds into the UT/LS.

  10. Designing fixed-bed adsorbers to remove mixtures of organics

    SciTech Connect

    Hand, D.W.; Crittenden, J.C.; Arora, H.; Miller, J.M.; Lykins, B.W.

    1989-01-01

    A liquid-phase granular activated carbon (GAC) pilot plant and a full-scale GAC adsorber were designed, built, and operated in order to evaluate their performance for treating a groundwater contaminated with several volatile and synthetic organic chemicals. Several empty bed contact times (EBCTs) ranging from 1 to 30 min were used during the pilot-plant study, and a simple method for evaluating the GAC use rate as a function of the EBCT was developed and demonstrated for dichloroethene and trichloroethene (TCE). Pilot-plant data were compared with the pore surface diffusion model, which considers external and internal mass transfer mechanisms of pore and surface diffusion. Natural organic matter in the water was found to decrease GAC capacity and kinetics for TCE.

  11. Nucleophilic reactivity and electrocatalytic reduction of halogenated organic compounds by nickel o-phenylenedioxamidate complexes.

    PubMed

    Das, Siva Prasad; Ganguly, Rakesh; Li, Yongxin; Soo, Han Sen

    2016-09-14

    A growing number of halogenated organic compounds have been identified as hazardous pollutants. Although numerous advanced oxidative processes have been developed to degrade organohalide compounds, reductive and nucleophilic molecular approaches to dehalogenate organic compounds have rarely been reported. In this manuscript, we employ nickel(ii)-ate complexes bearing the o-phenylenebis(N-methyloxamide) (Me2opba) tetraanionic ligand as nucleophilic reagents that can react with alkyl halides (methyl up to the bulky isobutyl) by O-alkylation to give their respective imidate products. Four new nickel(ii) complexes have been characterized by X-ray crystallography, and the salient structural parameters and FT-IR vibrational bands (∼1655 cm(-1)) concur with their assignment as the imidate tautomeric form. To the best of our knowledge, this is the first report on the nucleophilic reactivity of Ni(II)(Me2opba) with halogenated organic compounds. The parent nickel(ii) Me2opba complex exhibits reversible electrochemical oxidation and reduction behavior. As a proof of concept, Ni(II)(Me2opba) and its alkylated congeners were utilized for the electrocatalytic reduction of chloroform, as a representative, simple polyhalogenated organic molecule that could arise from the oxidative treatment of organic compounds by chlorination. Modest turnover numbers of up to 6 were recorded, with dichloromethane identified as one of the possible products. Future efforts are directed towards bulkier -ate complexes that possess metal-centered instead of ligand-centered nucleophilic activity to create more effective electrocatalysts for the reduction of halogenated organic compounds. PMID:27506275

  12. Nucleophilic reactivity and electrocatalytic reduction of halogenated organic compounds by nickel o-phenylenedioxamidate complexes.

    PubMed

    Das, Siva Prasad; Ganguly, Rakesh; Li, Yongxin; Soo, Han Sen

    2016-09-14

    A growing number of halogenated organic compounds have been identified as hazardous pollutants. Although numerous advanced oxidative processes have been developed to degrade organohalide compounds, reductive and nucleophilic molecular approaches to dehalogenate organic compounds have rarely been reported. In this manuscript, we employ nickel(ii)-ate complexes bearing the o-phenylenebis(N-methyloxamide) (Me2opba) tetraanionic ligand as nucleophilic reagents that can react with alkyl halides (methyl up to the bulky isobutyl) by O-alkylation to give their respective imidate products. Four new nickel(ii) complexes have been characterized by X-ray crystallography, and the salient structural parameters and FT-IR vibrational bands (∼1655 cm(-1)) concur with their assignment as the imidate tautomeric form. To the best of our knowledge, this is the first report on the nucleophilic reactivity of Ni(II)(Me2opba) with halogenated organic compounds. The parent nickel(ii) Me2opba complex exhibits reversible electrochemical oxidation and reduction behavior. As a proof of concept, Ni(II)(Me2opba) and its alkylated congeners were utilized for the electrocatalytic reduction of chloroform, as a representative, simple polyhalogenated organic molecule that could arise from the oxidative treatment of organic compounds by chlorination. Modest turnover numbers of up to 6 were recorded, with dichloromethane identified as one of the possible products. Future efforts are directed towards bulkier -ate complexes that possess metal-centered instead of ligand-centered nucleophilic activity to create more effective electrocatalysts for the reduction of halogenated organic compounds.

  13. Low-Level detections of halogenated volatile organic compounds in groundwater: Use in vulnerability assessments

    USGS Publications Warehouse

    Plummer, L.N.; Busenberg, E.; Eberts, S.M.; Bexfield, L.M.; Brown, C.J.; Fahlquist, L.S.; Katz, B.G.; Landon, M.K.

    2008-01-01

    Concentrations of halogenated volatile organic compounds (VOCs) were determined by gas chromatography (GC) with an electron-capture detector (GC-ECD) and by gas chromatography with mass spectrometry (GC-MS) in 109 groundwater samples from five study areas in the United States. In each case, the untreated water sample was used for drinking-water purposes or was from a monitoring well in an area near a drinking-water source. The minimum detection levels (MDLs) for 25 VOCs that were identified in GC-ECD chromatograms, typically, were two to more than four orders of magnitude below the GC-MS MDLs. At least six halogenated VOCs were detected in all of the water samples analyzed by GC-ECD, although one or more VOCs were detected in only 43% of the water samples analyzed by GC-MS. In nearly all of the samples, VOC concentrations were very low and presented no known health risk. Most of the low-level VOC detections indicated post-1940s recharge, or mixtures of recharge that contained a fraction of post-1940s water. Concentrations of selected halogenated VOCs in groundwater from natural and anthropogenic atmospheric sources were estimated and used to recognize water samples that are being impacted by nonatmospheric sources. A classification is presented to perform vulnerability assessments at the scale of individual wells using the number of halogenated VOC detections and total dissolved VOC concentrations in samples of untreated drinking water. The low-level VOC detections are useful in vulnerability assessments, particularly for samples in which no VOCs are detected by GC-MS analysis. ?? ASCE 2008.

  14. Halogenated volatile organic compounds in chlorine-bleach-containing household products and implications for their use

    NASA Astrophysics Data System (ADS)

    Odabasi, Mustafa; Elbir, Tolga; Dumanoglu, Yetkin; Sofuoglu, Sait C.

    2014-08-01

    It was recently shown that substantial amounts of halogenated volatile organic compounds (VOCs) are formed in chlorine-bleach-containing household products as a result of reactions of sodium hypochlorite with organic product components. Use of these household products results in elevated indoor air halogenated VOC concentrations. Halogenated VOCs in several chlorine-bleach-containing household products (plain, n = 9; fragranced, n = 4; and surfactant-added, n = 29) from Europe and North America were measured in the present study. Chloroform and carbon tetrachloride were the dominating compounds having average concentrations of 9.5 ± 29.0 (average ± SD) and 23.2 ± 44.3 (average ± SD) mg L-1, respectively. Halogenated VOC concentrations were the lowest in plain bleach, slightly higher in fragranced products and the highest in the surfactant-added products. Investigation of the relationship between the halogenated VOCs and several product ingredients indicated that chlorinated VOC formation is closely related to product composition. Indoor air concentrations from the household use of bleach products (i.e., bathroom, kitchen, and hallway cleaning) were estimated for the two dominating VOCs (chloroform and carbon tetrachloride). Estimated indoor concentrations ranged between 0.5 and 1030 (34 ± 123, average ± SD) μg m-3 and 0.3-1124 (82 ± 194, average ± SD) μg m-3 for chloroform and carbon tetrachloride, respectively, indicating substantial increases compared to background. Results indicated that indoor air concentrations from surfactant-added products were significantly higher (p < 0.01) than other categories. The highest concentrations were from the use of surfactant-added bleach products for bathroom cleaning (92 ± 228 and 224 ± 334 μg m-3, average ± SD for chloroform and carbon tetrachloride, respectively). Associated carcinogenic risks from the use of these products were also estimated. The risk levels may reach to considerably high levels for a

  15. Halogen-induced organic aerosol (XOA) formation and decarboxylation of carboxylic acids by reactive halogen species - a time-resolved aerosol flow-reactor study

    NASA Astrophysics Data System (ADS)

    Ofner, Johannes; Zetzsch, Cornelius

    2013-04-01

    Reactive halogen species (RHS) are released to the atmosphere from various sources like photo-activated sea-salt aerosol and salt lakes. Recent studies (Cai et al., 2006 and 2008, Ofner et al., 2012) indicate that RHS are able to interact with SOA precursors similarly to common atmospheric oxidizing gases like OH radicals and ozone. The reaction of RHS with SOA precursors like terpenes forms so-called halogen-induced organic aerosol (XOA). On the other hand, RHS are also able to change the composition of functional groups, e.g. to initiate the decarboxylation of carboxylic acids (Ofner et al., 2012). The present study uses a 50 cm aerosol flow-reactor, equipped with a solar simulator to investigate the time-resolved evolution and transformation of vibrational features in the mid-infrared region. The aerosol flow-reactor is coupled to a home-made multi-reflection cell (Ofner et al., 2010), integrated into a Bruker IFS 113v FTIR spectrometer. The reactor is operated with an inlet feed (organic compound) and a surrounding feed (reactive halogen species). The moveable inlet of the flow reactor allows us to vary reaction times between a few seconds and up to about 3 minutes. Saturated vapours of different SOA precursors and carboxylic acids were fed into the flow reactor using the moveable inlet. The surrounding feed inside the flow reactor was a mixture of zero air with molecular chlorine as the precursor for the formation of reactive halogen species. Using this setup, the formation of halogen-induced organic aerosol could be monitored with a high time resolution using FTIR spectroscopy. XOA formation is characterized by hydrogen-atom abstraction, carbon-chlorine bond formation and later, even formation of carboxylic acids. Several changes of the entire structure of the organic precursor, caused by the reaction of RHS, are visible. While XOA formation is a very fast process, the decarboxylation of carboxylic acids, induced by RHS is rather slow. However, XOA formation

  16. Determination of total organic halogen (TOX) in humic acids after microwave-induced combustion.

    PubMed

    Pereira, Juliana S F; Moreira, Clarissa M; Albers, Christian N; Jacobsen, Ole S; Flores, Erico M M

    2011-04-01

    Chemically chlorinated organic matter as well as natural background humic acids contain significant amounts of organically bound halogens that must be determined for assessment of environmental pollution. In this work the use of ion chromatography (IC) and inductively coupled plasma mass spectrometry (ICP-MS) is proposed for the determination of total organic Cl, Br and I concentration in humic acids extracted from various forest soil horizons after a single digestion by microwave-induced combustion (MIC). Samples were pressed as pellets and combusted using 20 bar of oxygen and ammonium nitrate solution as igniter. Analytes were absorbed in diluted alkaline solution (50mM (NH(4))(2)CO(3)) and a reflux step was applied after combustion to improve analyte recoveries (5 min, microwave power of 1400W). The accuracy was evaluated using certified reference materials (CRM) and spiked samples. Using MIC the agreement with CRM values and spike recoveries was higher than 97% for all analytes. As an advantage over conventional procedures, using MIC it was possible to digest up to eight samples in only 25 min, obtaining a single solution suitable for all halogens determination in humic acids samples by different techniques (IC and ICP-MS). The limit of detection (3σ) for Cl, Br and I obtained by IC was 1.2, 2.5 and 4.3μgg(-1) and by ICP-MS it was 1.4, 0.03 and 0.002μgg(-1), respectively.

  17. Identifying Bioaccumulative Halogenated Organic Compounds Using a Nontargeted Analytical Approach: Seabirds as Sentinels

    PubMed Central

    Millow, Christopher J.; Mackintosh, Susan A.; Lewison, Rebecca L.; Dodder, Nathan G.; Hoh, Eunha

    2015-01-01

    Persistent organic pollutants (POPs) are typically monitored via targeted mass spectrometry, which potentially identifies only a fraction of the contaminants actually present in environmental samples. With new anthropogenic compounds continuously introduced to the environment, novel and proactive approaches that provide a comprehensive alternative to targeted methods are needed in order to more completely characterize the diversity of known and unknown compounds likely to cause adverse effects. Nontargeted mass spectrometry attempts to extensively screen for compounds, providing a feasible approach for identifying contaminants that warrant future monitoring. We employed a nontargeted analytical method using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC/TOF-MS) to characterize halogenated organic compounds (HOCs) in California Black skimmer (Rynchops niger) eggs. Our study identified 111 HOCs; 84 of these compounds were regularly detected via targeted approaches, while 27 were classified as typically unmonitored or unknown. Typically unmonitored compounds of note in bird eggs included tris(4-chlorophenyl)methane (TCPM), tris(4-chlorophenyl)methanol (TCPMOH), triclosan, permethrin, heptachloro-1'-methyl-1,2'-bipyrrole (MBP), as well as four halogenated unknown compounds that could not be identified through database searching or the literature. The presence of these compounds in Black skimmer eggs suggests they are persistent, bioaccumulative, potentially biomagnifying, and maternally transferring. Our results highlight the utility and importance of employing nontargeted analytical tools to assess true contaminant burdens in organisms, as well as to demonstrate the value in using environmental sentinels to proactively identify novel contaminants. PMID:26020245

  18. Natural Organic Matter Exposed to Sulfate Radicals Increases Its Potential to Form Halogenated Disinfection Byproducts.

    PubMed

    Lu, Junhe; Dong, Wei; Ji, Yuefei; Kong, Deyang; Huang, Qingguo

    2016-05-17

    Sulfate radical-based advanced oxidation processes (SR-AOPs) are considered as viable technologies to degrade a variety of recalcitrant organic pollutants. This study demonstrates that o-phthalic acid (PA) could lead to the formation of brominated disinfection byproducts (DBPs) in SR-AOPs in the presence of bromide. However, PA does not generate DBPs in conventional halogenation processes. We found that this was attributed to the formation of phenolic intermediates susceptible to halogenation, such as salicylic acid through the oxidation of PA by SO4(•-). In addition, reactive bromine species could be generated from Br(-) oxidation by SO4(•-). Similar in situ generation of phenolic functionalities likely occurred by converting carboxylic substituents on aromatics to hydroxyl when natural organic matter (NOM) was exposed to trace level SO4(•-). It was found that such structural reconfiguration led to a great increase in the reactivity of NOM toward free halogen and, thus, its DBP formation potential. After a surface water sample was treated with 0.1 μM persulfate for 48 h, its potential to form chloroform, trichloroacetic acid, and dichloroacetic acid increased from 197.8, 54.3, and 27.6 to 236.2, 86.6, and 57.6 μg/L, respectively. This is the first report on possible NOM reconfiguration upon exposure to low-level SO4(•-) that has an implication in DBP formation. The findings highlight potential risks associated with SO4(•-)-based oxidation processes and help to avoid such risks in design and operation. PMID:27077814

  19. Process for the solvent extraction for the radiolysis and dehalogenation of halogenated organic compounds in soils, sludges, sediments and slurries

    DOEpatents

    Golden, Jeffry

    2007-02-13

    A process of extracting halogenated organic compounds, and particularly PCBs, from soil, sediment, slurry, sludge and dehalogenating the compounds contacts a contaminated soil sample with an extraction medium of a mixture of an alkane and a water miscible alcohol. The organic compounds dissolve in the extraction medium which is separated from the soil by passing water upwardly through the soil. The extraction medium floats to the surface of the water and is separated. Thereafter, the extraction medium containing the halogenated organic contaminants is subjected to ionizing radiation to radiolytically dehalogenate the compounds.

  20. Process for the solvent extraction for the radiolysis and dehalogenation of halogenated organic compounds in soils, sludges, sediments and slurries

    DOEpatents

    Mincher, Bruce J.; Curry, Randy Dale; Clevenger, Thomas E.; Golden, Jeffry

    2000-01-01

    A process of extracting halogenated organic compounds, and particularly PCBs, from soil, sediment, slurry, sludge and dehalogenating the compounds contacting a contaminated soil sample with an extraction medium of a mixture of an alkane and a water miscible alcohol. The organic compounds dissolve in the extraction medium which is separated from the soil by passing water upwardly through the soil. The extraction medium floats to the surface of the water and is separated. Thereafter, the extraction medium containing the halogenated organic contaminants is subjected to ionizing radiation to radiolytically dehalogenate the compounds.

  1. Process for the solvent extraction for the radiolysis and dehalogenation of halogenated organic compounds in soils, sludges, sediments and slurries

    DOEpatents

    Mincher, Bruce J.; Curry, Randy Dale; Clevenger, Thomas E.; Golden, Jeffry

    2003-05-27

    A process of extracting halogenated organic compounds, and particularly PCBs, from soil, sediment, slurry, sludge and dehalogenating the compounds contacts a contaminated soil sample with an extraction medium of a mixture of an alkane and a water miscible alcohol. The organic compounds dissolve in the extraction medium which is separated from the soil by passing water upwardly through the soil. The extraction medium floats to the surface of the water and is separated. Thereafter, the extraction medium containing the halogenated organic contaminants is subjected to ionizing radiation to radiolytically dehalogenate the compounds.

  2. Atomic resolution ADF-STEM imaging of organic molecular crystal of halogenated copper phthalocyanine.

    PubMed

    Haruta, Mitsutaka; Yoshida, Kaname; Kurata, Hiroki; Isoda, Seiji

    2008-05-01

    Annular dark-field (ADF) scanning transmission electron microscopy (STEM) measurements are demonstrated for the first time to be applicable for acquiring Z-contrast images of organic molecules at atomic resolution. High-angle ADF imaging by STEM is a new technique that provides incoherent high-resolution Z-contrast images for organic molecules. In the present study, low-angle ADF-STEM is successfully employed to image the molecular crystal structure of hexadecachloro-Cu-phthalocyanine (Cl16-CuPc), an organic molecule. The structures of CuPc derivatives (polyhalogenated CuPc with Br and Cl) are determined quantitatively using the same technique to determine the occupancy of halogens at each chemical site. By comparing the image contrasts of atomic columns, the occupancy of Br is found to be ca. 56% at the inner position, slightly higher than that for random substitution and in good agreement with previous TEM results.

  3. Relationship between nine haloacetic acids with total organic halogens in different experimental conditions.

    PubMed

    Pourmoghadas, Hossein; Kinman, Riley N

    2013-04-03

    The effects of pH and bromide ion concentration on the formation of nine haloacetic acids (HAAs) and total organic halogens (TOX) in chlorinated drinking water have been evaluated. In an extensive study, the relationships of nine HAAs with TOX have been investigated. Honesty Significant Differences test (HSD) and ANOVA tests were used for the statistical analyses. The study determined the concentration range of nine HAAs as of a percentage of TOX at varying experimental conditions. Statistical analyses showed that the parameters pH and Br had significant effects on the formation of nine HAAs and TOX. This study also showed that brominated and mixed species of HAAs would be dominant in the presence of high bromide ion concentration which contributes a high percentage of the TOX. The results of this study could be used to set up a maximum contaminant level of TOX as a water quality standard for chlorination by-products.

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

    DOEpatents

    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.

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

    DOEpatents

    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.

  6. Headspace GC-MS Analysis of Halogenated Volatile Organic Compounds in Aqueous Samples: An Experiment for General Chemistry Laboratory

    ERIC Educational Resources Information Center

    Keller, John W.; Fabbri, Cindy E.

    2012-01-01

    Analysis of halogenated volatile organic compounds (HVOCs) by GC-MS demonstrates the use of instrumentation in the environmental analysis of pollutant molecules and enhances student understanding of stable isotopes in nature. In this experiment, students separated and identified several HVOCs that have been implicated as industrial groundwater…

  7. Interactions between volatile organic compounds and reactive halogen in the tropical marine atmosphere using WRF-Chem

    NASA Astrophysics Data System (ADS)

    Badia, Alba; Reeves, Claire E.; Baker, Alex; Volkamer, Rainer; von Glasow, Roland

    2016-04-01

    Halogen species (chlorine, bromine and iodine) are known to play an important role in the chemistry and oxidizing capacity of the troposphere, particularly in the marine boundary layer (MBL). Reactive halogens cause ozone (O3) destruction, change the HOx and NOX partitioning, affect the oxidation of volatile organic compounds (VOCs) and mercury, reduce the lifetime of methane, and take part in new particle formation. Numerical models predicted that reactive halogen compounds account for 30% of O3 destruction in the MBL and 5-20% globally. There are indications that the chemistry of reactive halogens and oxygenated VOCs (OVOCs) in the tropics are inter-related. Moreover, the presence of aldehydes, such as glyoxal (CHOCHO), has a potential impact on radical cycling and secondary organic aerosol (SOA) formation in the MBL and free troposphere (FT). Model calculations suggest aldehydes to be an important sink for bromine atoms and hence competition for their reaction with O3 forming BrO and so illustrating a link between the cycles of halogens and OVOCs in the marine atmosphere. The main objective of this contribution is to investigate the atmospheric chemistry in the tropical East Pacific with a focus on reactive halogens and OVOCs and their links using the latest version of the Weather Research and Forecasting (WRF) model coupled with Chemistry (WRF-Chem) and field data from the TORERO campaign. WRF-Chem is a highly flexible community model for atmospheric research where aerosol-radiation-cloud feedback processes are taken into account. Our current reaction mechanism in WRF-Chem is based on the MOZART mechanism and has been extended to include bromine, chlorine and iodine chemistry. The MOZART mechanism includes detailed gas-phase chemistry of CHOCHO formation as well as state-of-the-science pathways to form SOA. Oceanic emissions of aldehydes, including CHOCHO, and of organic halogens based on measurements from the TORERO campaign have been added into the model. Sea

  8. RADIOLYSIS OF ORGANIC COMPOUNDS IN THE ADSORBED STATE

    DOEpatents

    Sutherland, J.W.; Allen, A.O.

    1961-10-01

    >A method of forming branch chained hydrocarbons by means of energetic penetrating radiation is described. A solid zeolite substrate is admixed with a cobalt ion and is irradiated with a hydrocarbon adsorbed therein. Upon irradiation with gamma rays, there is an increased yield of branched and lower molecular straight chain compounds. (AEC)

  9. Abiotic source of reactive organic halogens in the sub-arctic atmosphere?

    PubMed

    Carpenter, Lucy J; Hopkins, James R; Jones, Charlotte E; Lewis, Alastair C; Parthipan, Rajendran; Wevill, David J; Poissant, Laurier; Pilote, Martin; Constant, Philippe

    2005-11-15

    Recent theoretical studies indicate that reactive organic iodocarbons such as CH2I2 would be extremely effective agents for tropospheric Arctic ozone depletion and that iodine compounds added to a Br2/BrCl mixture have a significantly greater ozone (and mercury) depletion effect than additional Br2 and BrCl molecules. Here we report the first observations of CH2I2, CH2IBr, and CH2ICl in Arctic air, as well as other reactive halocarbons including CHBr3, during spring at Kuujjuarapik, Hudson Bay. The organoiodine compounds were present atthe highest levels yet reported in air. The occurrence of the halocarbons was associated with northwesterly winds from the frozen bay, and, in the case of CHBr3, was anticorrelated with ozone and total gaseous mercury (TGM), suggesting a link between inorganic and organic halogens. The absence of local leads coupled with the extremely short atmospheric lifetime of CH2I2 indicates that production occurred in the surface of the sea-ice/overlying snowpack over the bay. We propose an abiotic mechanism for the production of polyhalogenated iodo- and bromocarbons, via reaction of HOI and/or HOBr with organic material on the quasi-liquid layer above sea-ice/snowpack, and report laboratory data to support this mechanism. CH2I2, CH2IBr, and other organic iodine compounds may therefore be a ubiquitous component of air above sea ice where they will increase the efficiency of bromine-initiated ozone and mercury depletion.

  10. FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS: THE NEW X-WAND HVOC SCREENING DEVICE

    SciTech Connect

    John F. Schabron; Susan S. Sorini; Joseph F. Rovani Jr

    2006-03-01

    Western Research Institute (WRI) has developed new methodology and a test kit to screen soil or water samples for halogenated volatile organic compounds (HVOCs) in the field. The technology has been designated the X-Wand{trademark} screening tool. The new device uses a heated diode sensor that is commonly used to detect leaks of refrigerants from air conditioners, freezers, and refrigerators. This sensor is selective to halogens. It does not respond to volatile aromatic hydrocarbons, such as those in gasoline, and it is not affected by high humidity. In the current work, the heated diode leak detectors were modified further to provide units with rapid response and enhanced sensitivity. The limit of detection for trichloroethylene TCE in air is 0.1 mg/m{sup 3} (S/N = 2). The response to other HVOCS relative to TCE is similar. Variability between sensors and changes in a particular sensor over time can be compensated for by normalizing sensor readings to a maximum sensor reading at 1,000 mg/m{sup 3} TCE. The soil TCE screening method was expanded to include application to water samples. Assuming complete vaporization, the detection limit for TCE in soil is about 1 ug/kg (ppb) for a 25-g sample in an 8-oz jar. The detection limit for TCE in water is about 1 ug/L (ppb) for a 25-mL sample in an 8-oz jar. This is comparable to quantitation limits of EPA GC/MS laboratory methods. A draft ASTM method for screening TCE contaminated soils using a heated diode sensor was successfully submitted for concurrent main committee and subcommittee balloting in ASTM Committee D 34 on Waste Management. The method was approved as ASTM D 7203-05, Standard Test Method for Screening Trichloroethylene (TCE)-Contaminated Soil Using a Heated Diode Sensor.

  11. Toxicity of gaseous halogenated organic compounds. (Latest citations from the NTIS bibliographic database). Published Search

    SciTech Connect

    1997-02-01

    The bibliography contains citations concerning the toxicology of halogenated hydrocarbons and their health effects. Topics cover halogenated gases used as industrial chemicals, fire extinguishers, anesthetics, solvents, pesticides, and aerosol propellants. (Contains 50-250 citations and includes a subject term index and title list.) (Copyright NERAC, Inc. 1995)

  12. EVALUATION OF SOLID ADSORBENTS FOR THE COLLECTION AND ANALYSES OF AMBIENT BIOGENIC VOLATILE ORGANICS

    EPA Science Inventory

    Micrometeorological flux measurements of biogenic volatile organic compounds (BVOCs) usually require that large volumes of air be collected (whole air samples) or focused during the sampling process (cryogenic trapping or gas-solid partitioning on adsorbents) in order to achiev...

  13. Inhomogeneous distribution of organic molecules adsorbed in sol gel glasses

    NASA Astrophysics Data System (ADS)

    Meneses-Nava, M. A.; Chávez-Cerda, S.; Sánchez-Villicaña, V.; Sánchez-Mondragón, J. J.; King, T. A.

    1999-09-01

    The effects of the porous matrix upon the radiative characteristics of quinine sulphate doped sol-gel glasses are investigated. The broadenings of the absorption and fluorescence spectra are explained by the attachment of the molecules on distorted sites or in a non-planar fashion, creating an inhomogeneous distribution of adsorbed molecules. For this reason, each emitting center relaxes with its own characteristics. This inhomogeneous distribution is also supported by the non-exponential and the wavelength dependence of the fluorescence decay.

  14. Halogenated methanesulfonic acids: A new class of organic micropollutants in the water cycle.

    PubMed

    Zahn, Daniel; Frömel, Tobias; Knepper, Thomas P

    2016-09-15

    Mobile and persistent organic micropollutants may impact raw and drinking waters and are thus of concern for human health. To identify such possible substances of concern nineteen water samples from five European countries (France, Switzerland, The Netherlands, Spain and Germany) and different compartments of the water cycle (urban effluent, surface water, ground water and drinking water) were enriched with mixed-mode solid phase extraction. Hydrophilic interaction liquid chromatography - high resolution mass spectrometry non-target screening of these samples led to the detection and structural elucidation of seven novel organic micropollutants. One structure could already be confirmed by a reference standard (trifluoromethanesulfonic acid) and six were tentatively identified based on experimental evidence (chloromethanesulfonic acid, dichloromethanesulfonic acid, trichloromethanesulfonic acid, bromomethanesulfonic acid, dibromomethanesulfonic acid and bromochloromethanesulfonic acid). Approximated concentrations for these substances show that trifluoromethanesulfonic acid, a chemical registered under the European Union regulation REACH with a production volume of more than 100 t/a, is able to spread along the water cycle and may be present in concentrations up to the μg/L range. Chlorinated and brominated methanesulfonic acids were predominantly detected together which indicates a common source and first experimental evidence points towards water disinfection as a potential origin. Halogenated methanesulfonic acids were detected in drinking waters and thus may be new substances of concern. PMID:27267477

  15. Halogenated methanesulfonic acids: A new class of organic micropollutants in the water cycle.

    PubMed

    Zahn, Daniel; Frömel, Tobias; Knepper, Thomas P

    2016-09-15

    Mobile and persistent organic micropollutants may impact raw and drinking waters and are thus of concern for human health. To identify such possible substances of concern nineteen water samples from five European countries (France, Switzerland, The Netherlands, Spain and Germany) and different compartments of the water cycle (urban effluent, surface water, ground water and drinking water) were enriched with mixed-mode solid phase extraction. Hydrophilic interaction liquid chromatography - high resolution mass spectrometry non-target screening of these samples led to the detection and structural elucidation of seven novel organic micropollutants. One structure could already be confirmed by a reference standard (trifluoromethanesulfonic acid) and six were tentatively identified based on experimental evidence (chloromethanesulfonic acid, dichloromethanesulfonic acid, trichloromethanesulfonic acid, bromomethanesulfonic acid, dibromomethanesulfonic acid and bromochloromethanesulfonic acid). Approximated concentrations for these substances show that trifluoromethanesulfonic acid, a chemical registered under the European Union regulation REACH with a production volume of more than 100 t/a, is able to spread along the water cycle and may be present in concentrations up to the μg/L range. Chlorinated and brominated methanesulfonic acids were predominantly detected together which indicates a common source and first experimental evidence points towards water disinfection as a potential origin. Halogenated methanesulfonic acids were detected in drinking waters and thus may be new substances of concern.

  16. Scandium-Triflate/Metal-Organic Frameworks: Remarkable Adsorbents for Desulfurization and Denitrogenation.

    PubMed

    Khan, Nazmul Abedin; Jhung, Sung Hwa

    2015-12-01

    Scandium-triflate (Sc(OTf)3) was introduced for the first time on metal-organic frameworks (MOFs), to utilize acidic Sc(OTf)3 for adsorptive desulfurization and denitrogenation of fuel containing benzothiophene (BT), dibenzothiophene (DBT), quinoline (QUI), and indole (IND). A remarkable improvement in the adsorption capacity (about 65% based on the weight of adsorbents; 90% based on the surface area of the adsorbents) was observed with the Sc(OTf)3/MOFs as compared to the virgin MOFs for the adsorption of BT from liquid fuel. The basic QUI was also adsorbed preferentially onto the acidic Sc(OTf)3/MOFs. However, nonsupported Sc(OTf)3 showed negligible adsorption capacities. The improved adsorptive performance for BT, DBT, and QUI might be derived from acid-base interactions between the acidic Sc(OTf)3 and basic adsorbates. On the other hand, the Sc(OTf)3, loaded on MOFs, reduced the adsorption capacity for neutral IND due to lack of interaction between the neutral adsorbate and acidic adsorbent and the reduced porosities of the modified adsorbents. The reusability of the adsorbents was found satisfactory up to the fourth run. On the basis of the result, it is suggested that metal-triflates, such as Sc(OTf)3, can be prospective materials for adsorptive desulfurization/denitrogenation of fuels when supported on porous materials such as MOFs.

  17. Scandium-Triflate/Metal-Organic Frameworks: Remarkable Adsorbents for Desulfurization and Denitrogenation.

    PubMed

    Khan, Nazmul Abedin; Jhung, Sung Hwa

    2015-12-01

    Scandium-triflate (Sc(OTf)3) was introduced for the first time on metal-organic frameworks (MOFs), to utilize acidic Sc(OTf)3 for adsorptive desulfurization and denitrogenation of fuel containing benzothiophene (BT), dibenzothiophene (DBT), quinoline (QUI), and indole (IND). A remarkable improvement in the adsorption capacity (about 65% based on the weight of adsorbents; 90% based on the surface area of the adsorbents) was observed with the Sc(OTf)3/MOFs as compared to the virgin MOFs for the adsorption of BT from liquid fuel. The basic QUI was also adsorbed preferentially onto the acidic Sc(OTf)3/MOFs. However, nonsupported Sc(OTf)3 showed negligible adsorption capacities. The improved adsorptive performance for BT, DBT, and QUI might be derived from acid-base interactions between the acidic Sc(OTf)3 and basic adsorbates. On the other hand, the Sc(OTf)3, loaded on MOFs, reduced the adsorption capacity for neutral IND due to lack of interaction between the neutral adsorbate and acidic adsorbent and the reduced porosities of the modified adsorbents. The reusability of the adsorbents was found satisfactory up to the fourth run. On the basis of the result, it is suggested that metal-triflates, such as Sc(OTf)3, can be prospective materials for adsorptive desulfurization/denitrogenation of fuels when supported on porous materials such as MOFs. PMID:26575418

  18. Formation of halogenated organic byproducts during medium-pressure UV and chlorine coexposure of model compounds, NOM and bromide.

    PubMed

    Zhao, Quan; Shang, Chii; Zhang, Xiangru; Ding, Guoyu; Yang, Xin

    2011-12-01

    When chlorine is applied before or during UV disinfection of bromide-containing water, interactions between chlorine, bromide and UV light are inevitable. Formation of halogenated organic byproducts was studied during medium-pressure UV (MPUV) and chlorine coexposure of phenol, nitrobenzene and benzoic acid and maleic acid, chosen to represent electron-donating aromatics, electron-withdrawing aromatics, and aliphatic structures in natural organic matter (NOM), respectively. All were evaluated in the presence and absence of bromide. MPUV and chlorine coexposure of phenol produced less total organic halogen (TOX, a collective parameter for halogenated organic byproducts) than chlorination in the dark, and more haloacetic acids instead of halophenols. Increases in TOX were found in the coexposure of nitrobenzene and benzoic acid, but maleic acid was rather inert during coexposure. The presence of bromide increased the formation of brominated TOX but did not significantly affect total TOX formation, in spite of the fact that it reduced hydroxyl radical levels. MPUV and chlorine coexposure of NOM gave a higher differential UV absorbance of NOM and a larger shift to lower molecular weight compounds than chlorination in the dark. However, TOX formation with NOM remained similar to that observed from dark chlorination.

  19. Halogen-induced organic aerosol (XOA): a study on ultra-fine particle formation and time-resolved chemical characterization.

    PubMed

    Ofner, Johannes; Kamilli, Katharina A; Held, Andreas; Lendl, Bernhard; Zetzsch, Cornelius

    2013-01-01

    The concurrent presence of high values of organic SOA precursors and reactive halogen species (RHS) at very low ozone concentrations allows the formation of halogen-induced organic aerosol, so-called XOA, in maritime areas where high concentrations of RHS are present, especially at sunrise. The present study combines aerosol smog-chamber and aerosol flow-reactor experiments for the characterization of XOA. XOA formation yields from alpha-pinene at low and high concentrations of chlorine as reactive halogen species (RHS) were determined using a 700 L aerosol smog-chamber with a solar simulator. The chemical transformation of the organic precursor during the aerosol formation process and chemical aging was studied using an aerosol flow-reactor coupled to an FTIR spectrometer. The FTIR dataset was analysed using 2D correlation spectroscopy. Chlorine induced homogeneous XOA formation takes place at even 2.5 ppb of molecular chlorine, which was photolysed by the solar simulator. The chemical pathway of XOA formation is characterized by the addition of chlorine and abstraction of hydrogen atoms, causing simultaneous carbon-chlorine bond formation. During further steps of the formation process, carboxylic acids are formed, which cause a SOA-like appearance of XOA. During the ozone-free formation of secondary organic aerosol with RHS a special kind of particulate matter (XOA) is formed, which is afterwards transformed to SOA by atmospheric aging or degradation pathways.

  20. Assessing California groundwater susceptibility using trace concentrations of halogenated volatile organic compounds

    USGS Publications Warehouse

    Deeds, Daniel A.; Kulongoski, Justin T.; Belitz, Kenneth

    2012-01-01

    Twenty-four halogenated volatile organic compounds (hVOCs) and SF6 were measured in groundwater samples collected from 312 wells across California at concentrations as low as 10–12 grams per kilogram groundwater. The hVOCs detected are predominately anthropogenic (i.e., “ahVOCs”) and as such their distribution delineates where groundwaters are impacted and susceptible to human activity. ahVOC detections were broadly consistent with air-saturated water concentrations in equilibrium with a combination of industrial-era global and regional hVOC atmospheric abundances. However, detection of ahVOCs in nearly all of the samples collected, including ancient groundwaters, suggests the presence of a sampling or analytical artifact that confounds interpretation of the very-low concentration ahVOC data. To increase our confidence in ahVOC detections we establish screening levels based on ahVOC concentrations in deep wells drawing ancient groundwater in Owens Valley. Concentrations of ahVOCs below the Owens Valley screening levels account for a large number of the detections in prenuclear groundwater across California without significant loss of ahVOC detections in shallow, recently recharged groundwaters. Over 80% of the groundwaters in this study contain at least one ahVOC after screening, indicating that the footprint of human industry is nearly ubiquitous and that most California groundwaters are vulnerable to contamination from land-surface activities.

  1. Contamination of estuarine water, biota, and sediment by halogenated organic compounds: A field study

    USGS Publications Warehouse

    Pereira, W.E.; Rostad, C.E.; Chiou, C.T.; Brinton, T.I.; Barber, L.B.; Demcheck, D.K.; Demas, C.R.

    1988-01-01

    Studies conducted in the vicinity of an industrial outfall in the Calcasieu River estuary, Louisiana, have shown that water, bottom and suspended sediment, and four different species of biota are contaminated with halogenated organic compounds (HOC) including haloarenes. A "salting-out" effect in the estuary moderately enhanced the partitioning tendency of the contaminants into biota and sediments. Contaminant concentrations in water, suspended sediments, and biota were found to be far below the values predicted on the basis of the assumption of phase equilibria with respect to concentrations in bottom sediment. Relative concentration factors of HOC between biota (catfish) and bottom sediment increased with increasing octanol/estuarine water partition coefficients (Kow*), maximizing at log Kow* of about 5, although these ratios were considerably less than equilibrium values. In contrast, contaminant concentrations in water, biota, and suspended sediments were much closer to equilibrium values. Bioconcentration factors of HOC determined on the basis of lipid content for four different biotic species correlated reasonably well with equilibrium triolein/water partition coefficients (Ktw).

  2. Organic halogens in the environment: Studies of environmental biodegradability and human exposure

    SciTech Connect

    Salkinoja-Salonen, M.; Uotila, J.; Jokela, J.; Laine, M.; Saski, E.

    1995-06-01

    Organic halogens from chlorobleaching of kraft pulp were not as biorecalcitrant as has been assumed. Fifty percent were removed during biotreatment of wastewater, and 50% of the remaining organolhalogens faded in fresh water ecosystems in 200 to 400 days. Molecular size seemed not to hinder biodegradation up to sizes of approximately 2000 daltons. Anoxic biodegradation was of prime importance for halomineralization of pulp bleaching organohalogens but could also lead to toxic metabolites such as vinyl chloride from tri- and tetrachloroethene in anoxic soil. Indigenous soil microbes were unable to clean old organohalogen pollution but had converted chlorophenols into polymeric substances, chlorohumus, which were found bioaccumulable by earthworms in spite of the large (up to 5000 g/mole) molecular sizes. Because of the danger of formation of toxic metabolites, the biochemistry of the xenobiotic degradation must be elucidated before active bioremediation is practiced on polluted soil or water. Groundwater pollution by chlorophenols led to increased disease among the exposed population in one well-studied case. Two further cases of potential environmental health impact are described. 40 refs., 10 figs., 1 tab.

  3. Assessing California groundwater susceptibility using trace concentrations of halogenated volatile organic compounds.

    PubMed

    Deeds, Daniel A; Kulongoski, Justin T; Belitz, Kenneth

    2012-12-18

    Twenty-four halogenated volatile organic compounds (hVOCs) and SF₆ were measured in groundwater samples collected from 312 wells across California at concentrations as low as 10⁻¹² grams per kilogram groundwater. The hVOCs detected are predominately anthropogenic (i.e., "ahVOCs") and as such their distribution delineates where groundwaters are impacted and susceptible to human activity. ahVOC detections were broadly consistent with air-saturated water concentrations in equilibrium with a combination of industrial-era global and regional hVOC atmospheric abundances. However, detection of ahVOCs in nearly all of the samples collected, including ancient groundwaters, suggests the presence of a sampling or analytical artifact that confounds interpretation of the very-low concentration ahVOC data. To increase our confidence in ahVOC detections we establish screening levels based on ahVOC concentrations in deep wells drawing ancient groundwater in Owens Valley. Concentrations of ahVOCs below the Owens Valley screening levels account for a large number of the detections in prenuclear groundwater across California without significant loss of ahVOC detections in shallow, recently recharged groundwaters. Over 80% of the groundwaters in this study contain at least one ahVOC after screening, indicating that the footprint of human industry is nearly ubiquitous and that most California groundwaters are vulnerable to contamination from land-surface activities.

  4. Extra adsorption and adsorbate superlattice formation in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Sung Cho, Hae; Deng, Hexiang; Miyasaka, Keiichi; Dong, Zhiyue; Cho, Minhyung; Neimark, Alexander V.; Ku Kang, Jeung; Yaghi, Omar M.; Terasaki, Osamu

    2015-11-01

    Metal-organic frameworks (MOFs) have a high internal surface area and widely tunable composition, which make them useful for applications involving adsorption, such as hydrogen, methane or carbon dioxide storage. The selectivity and uptake capacity of the adsorption process are determined by interactions involving the adsorbates and their porous host materials. But, although the interactions of adsorbate molecules with the internal MOF surface and also amongst themselves within individual pores have been extensively studied, adsorbate-adsorbate interactions across pore walls have not been explored. Here we show that local strain in the MOF, induced by pore filling, can give rise to collective and long-range adsorbate-adsorbate interactions and the formation of adsorbate superlattices that extend beyond an original MOF unit cell. Specifically, we use in situ small-angle X-ray scattering to track and map the distribution and ordering of adsorbate molecules in five members of the mesoporous MOF-74 series along entire adsorption-desorption isotherms. We find in all cases that the capillary condensation that fills the pores gives rise to the formation of ‘extra adsorption domains’—that is, domains spanning several neighbouring pores, which have a higher adsorbate density than non-domain pores. In the case of one MOF, IRMOF-74-V-hex, these domains form a superlattice structure that is difficult to reconcile with the prevailing view of pore-filling as a stochastic process. The visualization of the adsorption process provided by our data, with clear evidence for initial adsorbate aggregation in distinct domains and ordering before an even distribution is finally reached, should help to improve our understanding of this process and may thereby improve our ability to exploit it practically.

  5. Extra adsorption and adsorbate superlattice formation in metal-organic frameworks.

    PubMed

    Sung Cho, Hae; Deng, Hexiang; Miyasaka, Keiichi; Dong, Zhiyue; Cho, Minhyung; Neimark, Alexander V; Ku Kang, Jeung; Yaghi, Omar M; Terasaki, Osamu

    2015-11-26

    Metal-organic frameworks (MOFs) have a high internal surface area and widely tunable composition, which make them useful for applications involving adsorption, such as hydrogen, methane or carbon dioxide storage. The selectivity and uptake capacity of the adsorption process are determined by interactions involving the adsorbates and their porous host materials. But, although the interactions of adsorbate molecules with the internal MOF surface and also amongst themselves within individual pores have been extensively studied, adsorbate-adsorbate interactions across pore walls have not been explored. Here we show that local strain in the MOF, induced by pore filling, can give rise to collective and long-range adsorbate-adsorbate interactions and the formation of adsorbate superlattices that extend beyond an original MOF unit cell. Specifically, we use in situ small-angle X-ray scattering to track and map the distribution and ordering of adsorbate molecules in five members of the mesoporous MOF-74 series along entire adsorption-desorption isotherms. We find in all cases that the capillary condensation that fills the pores gives rise to the formation of 'extra adsorption domains'-that is, domains spanning several neighbouring pores, which have a higher adsorbate density than non-domain pores. In the case of one MOF, IRMOF-74-V-hex, these domains form a superlattice structure that is difficult to reconcile with the prevailing view of pore-filling as a stochastic process. The visualization of the adsorption process provided by our data, with clear evidence for initial adsorbate aggregation in distinct domains and ordering before an even distribution is finally reached, should help to improve our understanding of this process and may thereby improve our ability to exploit it practically. PMID:26550825

  6. Molecular separations with breathing metal-organic frameworks: modelling packed bed adsorbers.

    PubMed

    Van Assche, Tom R C; Baron, Gino V; Denayer, Joeri F M

    2016-03-14

    Various metal-organic framework (MOFs) adsorbents show peculiar adsorption behaviour as they can adopt different crystal phases, each phase with its own adsorption characteristics. Besides external stimuli such as temperature or light, different species of guest adsorbate can trigger a transition (breathing) of the host structure at a different pressure. Such phase transitions also occur during dynamic separations on a packed bed of adsorbent, where the concentrations of the adsorbates vary throughout axial column distance and time. This work presents a general strategy to model the adsorption behavior of such phase changing adsorbents during column separations and focuses on remarkable model predictions for pure components and binary mixtures in diluted and non-diluted conditions. During binary breakthrough experiments, the behaviour of flexible adsorbents is quite complex. A succession of complete or even partial phase transformations (resulting in phase coexistence) can occur during the adsorption process. A variety of unusual breakthrough profiles is observed for diluted binary mixtures. Simulations reveal at least five types of breakthrough profiles to emerge. The occurrence of these cases can be rationalized by the hodograph technique, combined with the phase diagram of the adsorbent. The remarkable experimental breakthrough profiles observed for ortho-xylene/ethylbenzene (diluted) and CO2/CH4 (non-diluted) separation on the flexible MIL-53 framework can be rationalized by application of the proposed model strategy. PMID:26885972

  7. Environmental health sciences center task force review on halogenated organics in drinking water

    PubMed Central

    Deinzer, M.; Schaumburg, F.; Klein, E.

    1978-01-01

    The disinfection of drinking water by chlorination has in recent years come under closer scrutiny because of the potential hazards associated with the production of stable chlorinated organic chemicals. Organic chemical contaminants are common to all water supplies and it is now well-established that chlorinated by-products are obtained under conditions of disinfection, or during tertiary treatment of sewage whose products can ultimately find their way into drinking water supplies. Naturally occurring humic substances which are invariably present in drinking waters are probably the source of chloroform and other halogenated methanes, and chloroform has shown up in every water supply investigated thus far. The Environmental Protection Agency is charged with the responsibility of assessing the public health effects resulting from the consumption of contaminated drinking water. It has specifically undertaken the task of determining whether organic contaminants or their chlorinated derivatives have a special impact, and if so, what alternatives there are to protect the consumer against bacterial and viral diseases that are transmitted through infected drinking waters. The impetus to look at these chemicals is not entirely without some prima facie evidence of potential trouble. Epidemiological studies suggested a higher incidence of cancer along the lower Mississippi River where the contamination from organic chemicals is particularly high. The conclusions from these studies have, to be sure, not gone unchallenged. The task of assessing the effects of chemicals in the drinking water is a difficult one. It includes many variables, including differences in water supplies and the temporal relationship between contamination and consumption of the finished product. It must also take into account the relative importance of the effects from these chemicals in comparison to those from occupational exposure, ingestion of contaminated foods, inhalation of polluted air, and many

  8. Development of a New Thermal HF Plasma Reactor for the Destruction of Radioactive Organic Halogen Liquid Wastes

    SciTech Connect

    Bournonville, B.; Meillot, E.; Girold, C.

    2006-07-01

    A newly patented process employing thermal plasma for destruction of radioactive organic halogen liquid wastes is proposed. This studied safe system can destroy a great variety of wastes, even mixed together, using plasma torch as high temperature source. At the exit of the process, only non-toxic products are formed as atmospheric gases, liquid water and halogen sodium salt. The process has been built with the help of thermodynamic and kinetic simulations. A good atomic stoichiometry is necessary for avoiding the formation of solid carbon (soot) or toxic COCl{sub 2}. That why liquid water is added to the waste in the plasma flow. Then, an introduction of air cools and dilutes the formed gases and adds oxidant agent achieving oxidation of explosive H{sub 2} and toxic CO. Due to the high concentration of hydrochloric acid, an efficient wet treatment using soda traps it. Subsequently, the exhaust gases are only composed of Ar, O{sub 2}, N{sub 2}, CO{sub 2} and H{sub 2}O. In the first experimental step, pure organic molecules, mixed or not, without halogen have been destroyed. The experimental results show that all the compounds have been completely destroyed and only CO{sub 2} and H{sub 2}O have been formed without formation of any toxic compound or soot. After these encouraging results, chlorinated compounds as dichloromethane or chloroform have been destroyed by the process. In this case, the results are close to the previous one with an important formation of hydrochloric acid, as expected, which was well trapped by the soda to respect the French norm of rejection. A specific parameter study has been done with dichloromethane for optimising the operating condition to experimentally observe the influence of different parameters of the process as the stoichiometry ratio between waste and water, the air addition flow, the waste flow. The final aim of this study is to develop a clean process for treatment of radioactive organic halogen compounds. A small scale reactor

  9. Halogenated persistent organic pollutants in deep water fish from waters to the west of Scotland.

    PubMed

    Webster, Lynda; Walsham, Pam; Russell, Marie; Hussy, Ines; Neat, Francis; Dalgarno, Eric; Packer, Gill; Scurfield, Judith A; Moffat, Colin F

    2011-04-01

    Halogenated persistent organic pollutants [polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)] along with total lipid, were measured in the liver and muscle of three species of deep water fish (black scabbard, black dogfish (liver only) and roundnose grenadier) collected from the Rockall fishing area, to the west of Scotland, between 2006 and 2008. Both contaminant groups were detected in the muscle and liver, with concentrations of PCBs being higher than PBDEs. There were no significant differences in the PCB or PBDE concentrations between the three species, or different sampling locations in the Rockall fishing area. PCB concentrations (ΣICES (International Council for the Exploration of the Sea)7 PCBs) greater than 500 μg kg(-1) lipid weight were found in 26 of the 106 liver samples. PCB concentrations were compared to OSPAR assessment criteria, concentrations were above background but below Environmental Assessment Criteria. Estimated Toxic Equivalent (TEQ) concentrations, calculated using published models, in the fish muscle and liver indicated that consumption of deep water fish is unlikely to represent a risk to human health. The high squalene content in some of the black dogfish liver necessitated an additional clean-up step, involving gel permeation chromatography, when analyzing for PBDEs. Concentrations of PBDEs were low with many congeners being below detection limits, particularly in the muscle. There are currently no assessment criteria available for PBDEs. Furthermore, there is only very limited data on PBDEs in deep water fish. However, the concentrations observed in this study were similar to the concentrations recently reported in Mediterranean deep water fish. PMID:21421255

  10. Halogenated persistent organic pollutants in deep water fish from waters to the west of Scotland.

    PubMed

    Webster, Lynda; Walsham, Pam; Russell, Marie; Hussy, Ines; Neat, Francis; Dalgarno, Eric; Packer, Gill; Scurfield, Judith A; Moffat, Colin F

    2011-04-01

    Halogenated persistent organic pollutants [polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)] along with total lipid, were measured in the liver and muscle of three species of deep water fish (black scabbard, black dogfish (liver only) and roundnose grenadier) collected from the Rockall fishing area, to the west of Scotland, between 2006 and 2008. Both contaminant groups were detected in the muscle and liver, with concentrations of PCBs being higher than PBDEs. There were no significant differences in the PCB or PBDE concentrations between the three species, or different sampling locations in the Rockall fishing area. PCB concentrations (ΣICES (International Council for the Exploration of the Sea)7 PCBs) greater than 500 μg kg(-1) lipid weight were found in 26 of the 106 liver samples. PCB concentrations were compared to OSPAR assessment criteria, concentrations were above background but below Environmental Assessment Criteria. Estimated Toxic Equivalent (TEQ) concentrations, calculated using published models, in the fish muscle and liver indicated that consumption of deep water fish is unlikely to represent a risk to human health. The high squalene content in some of the black dogfish liver necessitated an additional clean-up step, involving gel permeation chromatography, when analyzing for PBDEs. Concentrations of PBDEs were low with many congeners being below detection limits, particularly in the muscle. There are currently no assessment criteria available for PBDEs. Furthermore, there is only very limited data on PBDEs in deep water fish. However, the concentrations observed in this study were similar to the concentrations recently reported in Mediterranean deep water fish.

  11. Reactive and organic halogen species in three different European coastal environments

    NASA Astrophysics Data System (ADS)

    Peters, C.; Pechtl, S.; Stutz, J.; Hebestreit, K.; Hönninger, G.; Heumann, K. G.; Schwarz, A.; Winterlik, J.; Platt, U.

    2005-12-01

    We present results of three field campaigns using active longpath DOAS (Differential Optical Absorption Spectroscopy) for the study of reactive halogen species (RHS) BrO, IO, OIO and I2. Two recent field campaigns took place in Spring 2002 in Dagebüll at the German North Sea Coast and in Spring 2003 in Lilia at the French Atlantic Coast of Brittany. In addition, data from a campaign in Mace Head, Ireland in 1998 was partly re-evaluated. During the recent field campaigns volatile halogenated organic compounds (VHOCs) were determined by a capillary gas chromatograph coupled with an electron capture detector and an inductively coupled plasma mass spectrometer (GC/ECD-ICPMS) in air and water. Due to the inhomogeneous distribution of macroalgae at the German North Sea Coast we found a clear connection between elevated levels of VHOCs and the appearance of macroalgae. Extraordinarily high concentrations of several VHOCs, especially CH3I and CH3Br of up to 1830 pptv and 875 pptv, respectively, were observed at the coast of Brittany, demonstrating the outstanding level of bioactivity there. We found CH2I2 at levels of up to 20 pptv, and a clear anti-correlation with the appearance of IO. The IO mixing ratio reached up to 7.7±0.5 ppt(pmol/mol) during the day, in reasonable agreement with model studies designed to represent the meteorological and chemical conditions in Brittany. For the two recent campaigns the DOAS spectra were evaluated for BrO, OIO and I2, but none of these species could be clearly identified (average detection limits around 2 ppt, 3 ppt, 20 ppt, resp., significantly higher in individual cases). Only in the Mace Head spectra evidence was found for the presence of OIO. Since macroalgae under oxidative stress are suggested to be a further source for I2 in the marine boundary layer, we re-analyzed spectra in the 500-600 nm range taken during the 1998 PARFORCE campaign in Mace Head, Ireland, which had not previously been analyzed for I2. We identified

  12. Covalent organic frameworks: Potential adsorbent for carbon dioxide adsorption

    NASA Astrophysics Data System (ADS)

    Xie, Yinhuan

    A series of covalent organic frameworks (COFs) based on propeller shaped hexaphenylbenzene derivatives were obtained under solvothermal conditions via Schiff base reaction. The relationship between the geometry parameters of monomers and gas absorption behaviors of planar COFs was investigated. The FT-IR spectroscopy confirms the formation of imine double bond in the obtained COFs by showing a peak around 1620 cm-1. The resulting frameworks have high BET surface areas approaching 700 m2/g and CO2 uptake up to 14% at 273 K and 1 bar, which are better than most of the 2-D porous aromatic frameworks. The thermogravimetric analysis shows those frameworks are stable until 773 K, allowing for the practical application of the post-combustion CO2 technology. Moreover, a novel synthetic strategy for the trigonal pyramidal hydrozide monomers was established. It provides an efficient way to synthesize the hydrozide monomers at multi-gram scale, promising for the synthesis of hydrozane porous organic cages.

  13. Graphene nanosheets and graphite oxide as promising adsorbents for removal of organic contaminants from aqueous solution.

    PubMed

    Ji, Liangliang; Chen, Wei; Xu, Zhaoyi; Zheng, Shourong; Zhu, Dongqiang

    2013-01-01

    Graphenes are an emerging class of carbon nanomaterials whose adsorption properties toward organic compounds have not been well understood. In the present study, graphene nanosheets were prepared by reoxidation and abrupt heating of graphite oxide, which was prepared by sequential chemical oxidation of commercial nonporous graphite powder. Adsorption properties of three aromatic compounds (naphthalene, 2-naphthol, and 1-naphthylamine) and one pharmaceutical compound (tylosin) on graphene nanosheets and graphite oxide were examined to explore the potential of these two adsorbents for the removal of organic contaminants from aqueous solutions. Compared with the literature data of adsorption on carbon nanotubes, adsorption of bulky, flexible tylosin on graphene nanosheets exhibited markedly faster adsorption kinetics, which can be attributed to their opened-up layer structure. Graphene nanosheets and graphite oxide showed similar sequences of adsorption affinity: 1-naphthylamine > 2-naphthol > tylosin > naphthalene (with much larger differences observed on graphite oxide). It was proposed that the strong adsorption of the three aromatic compounds was mainly due to π-π electron donor-acceptor interactions with the graphitic surfaces of adsorbents. Additionally, Lewis acid-base interaction was likely an important factor contributing to the strong adsorption of 1-naphthylamine and tylosin, especially for the O-functionality-abundant graphite oxide. After being normalized on the basis of adsorbent surface area, adsorption affinities of all four tested adsorbates on graphene nanosheets were very close to those on nonporous graphite powder, reflecting complete accessibility of the adsorbent surface area in adsorption.

  14. Quantum Mechanical Calculations to Interpret Vibrational and NMR Spectra of Organic Compounds Adsorbed onto Mineral Surfaces

    NASA Astrophysics Data System (ADS)

    Kubicki, J. D.

    2008-12-01

    Vibrational (e.g., ATR FTIR and Raman) and nuclear magnetic resonance (NMR) spectroscopies provide excellent information on the bonding and atomic environment of adsorbed organic compounds. However, interpretation of observed spectra collected for organic compounds adsorbed onto mineral surfaces can be complicated by the lack of comparable analogs of known structure and uncertainties about the mineral surface structure. Quantum mechanical calculations provide a method for testing interpretations of observed spectra because models can be built to mimic predicted structures, and the results are independent of experimental parameters (i.e., no fitting to data is necessary). In this talk, methodologies for modeling vibrational frequencies and NMR chemical shifts of adsorbed organic compounds are discussed. Examples included salicylic acid (as an analog for important binding functional groups in humic acids) adsorbed onto aluminum oxides, organic phosphoryl compounds that represent herbicides and bacterial extracellular polymeric substances (EPS), and ofloxacin (a common agricultural antibiotic). The combination of the ability of quantum mechanical calculations to predict structures, spectroscopic parameters and energetics of adsorption with experimental data on these same properties allows for more definitive construction of surface complex models.

  15. Influences of Dilute Organic Adsorbates on the Hydration of Low-Surface-Area Silicates.

    PubMed

    Sangodkar, Rahul P; Smith, Benjamin J; Gajan, David; Rossini, Aaron J; Roberts, Lawrence R; Funkhouser, Gary P; Lesage, Anne; Emsley, Lyndon; Chmelka, Bradley F

    2015-07-01

    Competitive adsorption of dilute quantities of certain organic molecules and water at silicate surfaces strongly influence the rates of silicate dissolution, hydration, and crystallization. Here, we determine the molecular-level structures, compositions, and site-specific interactions of adsorbed organic molecules at low absolute bulk concentrations on heterogeneous silicate particle surfaces at early stages of hydration. Specifically, dilute quantities (∼0.1% by weight of solids) of the disaccharide sucrose or industrially important phosphonic acid species slow dramatically the hydration of low-surface-area (∼1 m(2)/g) silicate particles. Here, the physicochemically distinct adsorption interactions of these organic species are established by using dynamic nuclear polarization (DNP) surface-enhanced solid-state NMR techniques. These measurements provide significantly improved signal sensitivity for near-surface species that is crucial for the detection and analysis of dilute adsorbed organic molecules and silicate species on low-surface-area particles, which until now have been infeasible to characterize. DNP-enhanced 2D (29)Si{(1)H}, (13)C{(1)H}, and (31)P{(1)H} heteronuclear correlation and 1D (29)Si{(13)C} rotational-echo double-resonance NMR measurements establish hydrogen-bond-mediated adsorption of sucrose at distinct nonhydrated and hydrated silicate surface sites and electrostatic interactions with surface Ca(2+) cations. By comparison, phosphonic acid molecules are found to adsorb electrostatically at or near cationic calcium surface sites to form Ca(2+)-phosphonate complexes. Although dilute quantities of both types of organic molecules effectively inhibit hydration, they do so by adsorbing in distinct ways that depend on their specific architectures and physicochemical interactions. The results demonstrate the feasibility of using DNP-enhanced NMR techniques to measure and assess dilute adsorbed molecules and their molecular interactions on low

  16. Structural features of polymer adsorbent LiChrolut EN and interfacial behavior of water and water/organic mixtures.

    PubMed

    Gun'ko, V M; Turov, V V; Zarko, V I; Nychiporuk, Y M; Goncharuk, E V; Pakhlov, E M; Yurchenko, G R; Kulik, T V; Palyanytsya, B B; Borodavka, T V; Krupskaya, T V; Leboda, R; Skubiszewska-Zieba, J; Osovskii, V D; Ptushinskii, Y G; Turov, A V

    2008-07-01

    The structural and adsorption characteristics of polymer adsorbent LiChrolut EN and the behavior of adsorbed water and water/organic mixtures were studied using adsorption, microcalorimetry, transmission and scanning electron microscopy, mass spectrometry, infrared spectroscopy, 1H NMR spectroscopy with layer-by-layer freezing-out of liquids (190-273 K), and thermally stimulated depolarization current method (90-265 K). This adsorbent is characterized by large specific surface area (approximately 1500 m2/g) and pore volume (0.83 cm3/g) with a major contribution of narrow pores (R<10 nm) of a complicated shape (long hysteresis loop is in nitrogen adsorption-desorption isotherm). The adsorbent includes aromatic and aliphatic structures and oxygen-containing functionalities and can effectively adsorb organics and water/organic mixtures. On co-adsorption of water and organics (dimethyl sulfoxide, chloroform, methane), there is a weak influence of one on another adsorbate due to their poor mixing in pores. Weakly polar chloroform displaces a fraction of water from narrow pores. These effects can explain high efficiency of the adsorbent in solid-phase extraction of organics from aqueous solutions. The influence of structural features of several carbon and polymer adsorbents on adsorbed nitrogen, water and water/organics is compared on the basis of the adsorption and 1H NMR data. PMID:18440015

  17. Effects of acceptors on halogenated organic compound biotransformations in a biofilm column

    SciTech Connect

    Cobb, G.D.; Bouwer, E.J. )

    1991-06-01

    The transformability of trihalomethanes, carbon tetrachloride, 1,1,1-trichlorethane, 1,2-dibromomethane, tetrachlorethylene, dibromochloropropane, and chlorinated benzenes was evaluated by a biofilm utilizing a mixture of primary electron acceptors (oxygen, nitrate, and sulfate). These compounds at concentrations commonly found in groundwater were continuously administered for 4 years to a biofilm column reactor that resembled polluted groundwater environments. Acetate was the primary substrate to support microbial growth. Sequential biofilm zones or aerobic respiration, denitrification, and sulfate reduction developed within the column. Transformation of the halogenated aliphatic compounds coincided with the onset of sulfate in the column feed decreased the steady-state removals for several of the halogenated aliphatic compounds. These results suggest that sulfate was an important primary electron acceptor. Aerobic transformations of the chlorinated benzenes were incomplete due to the rapid depletion of oxygen and limited aerobic zone at the column inlet.

  18. Halogens in the atmosphere

    NASA Technical Reports Server (NTRS)

    Cicerone, R. J.

    1981-01-01

    Atmospheric halogen measurement data are presented for: (1) inorganic and organic gaseous compounds of chlorine, fluorine, bromine and iodine; and (2) chloride, fluoride, bromide and iodine in particulate form and in precipitation. The roles that these data and other, unavailable data play in the determination of the global cycles of the halogens are discussed. It is found that the speciation of the halogen gases in the troposphere is uncertain, with the only inorganic species detected by species-specific methods being HC1 and SF6. It is shown that heterogeneous reactions, both gas-to-particle and particle-to-gas processes, precipitation removal, and sea-salt aerosol generation and fractionation processes, need quantitative investigation to allow progress in estimating halogen sources and sinks. Where practical, quantitative comparisons are made between measured and predicted concentrations.

  19. Multiple Noncovalent Bonding in Halogen Complexes with Oxygen Organics. I. Tertiary Amides.

    PubMed

    Suponitsky, Kyrill Yu; Burakov, N I; Kanibolotsky, Alexander L; Mikhailov, Vasilii A

    2016-06-23

    The present work describes the structure and binding of adducts of N,N'-diacetylpiperazine with halogens and interhalogens based on combination of different experimental methods and quantum chemical calculations. On the basis of conductometric and spectro-photometric experimental results, behavior of complexes in the acetonitrile solution was described. The iodine adduct with N,N'-diacetylpiperazine fully degrades into components. Adducts of interhalogens I-X (X = Cl or Br) with N,N'-diacetylpiperazine in acetonitrile partially dissociate to anionic [X-I-X](-) and cationic species. In the solid state, molecules are connected via C═O···I, C-H···I, and Cl···Cl attractive interactions. N,N'-diacetylpiperazine···dihalogen complex is stabilized by simultaneous C═O···I and C-H···I interactions. Such binding mode allows to explain the problems of the direct halogenation of acetyl-containing compounds with molecular halogens as reagents. We believe that the observed binding pattern can be used as prototypical for future design of halogeno complexes. PMID:27228362

  20. Removal of malachite green dye from wastewater by different organic acid-modified natural adsorbent: kinetics, equilibriums, mechanisms, practical application, and disposal of dye-loaded adsorbent.

    PubMed

    Wang, Hou; Yuan, Xingzhong; Zeng, Guangming; Leng, Lijian; Peng, Xin; Liao, Kailingli; Peng, Lijuan; Xiao, Zhihua

    2014-10-01

    Natural adsorbent (Cinnamomum camphora sawdust) modified by organic acid (oxalic acid, citric acid, and tartaric acid) was investigated as a potential adsorbent for the removal of hazardous malachite green (MG) dye in aqueous media in a batch process. The extent of MG adsorption onto modified sawdust increased with increasing organic acid concentrations, pH, contact time, and temperature but decreased with increasing adsorbent dosage and ionic strength. Kinetic study indicated that the pseudo-second-order kinetic model could best describe the adsorption kinetics of MG. Equilibrium data were found to fit well with the Langmuir model, and the maximum adsorption capacity of the three kinds of organic acid-modified sawdust was 280.3, 222.8, and 157.5 mg/g, respectively. Thermodynamic parameters suggested that the sorption of MG was an endothermic process. The adsorption mechanism, the application of adsorbents in practical wastewater, the prediction of single-stage batch adsorption system, and the disposal of depleted adsorbents were also discussed.

  1. Organic Halogen and Hydrocarbon Distributions During SEAC4RS Measured from the ER-2 and DC-8.

    NASA Astrophysics Data System (ADS)

    Schauffler, S.; Atlas, E. L.; Navarro, M. A.; Pan, L.; Blake, D. R.; Blake, N. J.; Kinnison, D. E.; Meinardi, S.; Lueb, R.; Zhu, X.; Pope, L.

    2014-12-01

    Organic halogens and hydrocarbons are important contributors to chemical processes in the upper troposphere/lower stratosphere (UTLS) region and hydrocarbons are well known contributors to chemical processes throughout the troposphere. Whole Air Sampler systems (WAS) were deployed during Studies of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys (SEAC4RS) on the NASA ER-2 (Univ. of Miami WAS) and the NASA DC-8 (Univ. of California, Irvine WAS). Both systems measured a wide variety of organic halogen and hydrocarbon species in the samples collected. For this presentation we show the vertical distributions of select chemical species from the surface to the lower stratosphere and compare those distributions to the Community Atmosphere Model with Chemistry (CAM-Chem) in order to evaluate their representation in the global model. We also show a comparison of measurements taken during SEAC4RS (2013) with those taken in the same region during the Stratosphere-Troposphere Analysis of Regional Transport 2008 (START08) campaign. The Univ. of Miami WAS system was flown on the NSF/NCAR GV during START08. The two campaigns were conducted in different seasons and different stratosphere/troposphere exchange regimes, allowing evaluation of how the North American Monsoon convection influences the transport time scale in the UTLS (during SEAC4RS) relative to the pre-monsoon regime observed during START08.

  2. INVESTIGATION OF THE TOTAL ORGANIC HALOGEN ANALYTICAL METHOD AT THE WASTE SAMPLING CHARACTERIZATION FACILITY (WSCF)

    SciTech Connect

    DOUGLAS JG; MEZNARICH HD, PHD; OLSEN JR; ROSS GA; STAUFFER M

    2008-09-30

    Total organic halogen (TOX) is used as a parameter to screen groundwater samples at the Hanford Site. Trending is done for each groundwater well, and changes in TOX and other screening parameters can lead to costly changes in the monitoring protocol. The Waste Sampling and Characterization Facility (WSCF) analyzes groundwater samples for TOX using the United States Environmental Protection Agency (EPA) SW-846 method 9020B (EPA 1996a). Samples from the Soil and Groundwater Remediation Project (S&GRP) are submitted to the WSCF for analysis without information regarding the source of the sample; each sample is in essence a 'blind' sample to the laboratory. Feedback from the S&GRP indicated that some of the WSCF-generated TOX data from groundwater wells had a number of outlier values based on the historical trends (Anastos 2008a). Additionally, analysts at WSCF observed inconsistent TOX results among field sample replicates. Therefore, the WSCF lab performed an investigation of the TOX analysis to determine the cause of the outlier data points. Two causes were found that contributed to generating out-of-trend TOX data: (1) The presence of inorganic chloride in the groundwater samples: at inorganic chloride concentrations greater than about 10 parts per million (ppm), apparent TOX values increase with increasing chloride concentration. A parallel observation is the increase in apparent breakthrough of TOX from the first to the second activated-carbon adsorption tubes with increasing inorganic chloride concentration. (2) During the sample preparation step, excessive purging of the adsorption tubes with oxygen pressurization gas after sample loading may cause channeling in the activated-carbon bed. This channeling leads to poor removal of inorganic chloride during the subsequent wash step with aqueous potassium nitrate. The presence of this residual inorganic chloride then produces erroneously high TOX values. Changes in sample preparation were studied to more effectively

  3. Direct Measurement of Adsorbed Gas Redistribution in Metal–Organic Frameworks

    SciTech Connect

    Chen, Ying-Pin; Liu, Yangyang; Liu, Dahuan; Bosch, Mathieu; Zhou, Hong-Cai

    2015-03-04

    Knowledge about the interactions between gas molecules and adsorption sites is essential to customize metal-organic frameworks (MOFs) as adsorbents. The dynamic interactions occurring during adsorption/desorption working cycles with several states are especially complicated. Even so, the gas dynamics based upon experimental observations and the distribution of guest molecules under various conditions in MOFs have not been extensively studied yet. In this work, a direct time-resolved diffraction structure envelope (TRDSE) method using sequential measurements by in situ synchrotron powder X-ray diffraction has been developed to monitor several gas dynamic processes taking place in MOFs: infusion, desorption, and gas redistribution upon temperature change. The electron density maps indicate that gas molecules prefer to redistribute over heterogeneous types of sites rather than to exclusively occupy the primary binding sites. We found that the gas molecules are entropically driven from open metal sites to larger neighboring spaces during the gas infusion period, matching the localized-to-mobile mechanism. In addition, the partitioning ratio of molecules adsorbed at each site varies with different temperatures, as opposed to an invariant distribution mode. Equally important, the gas adsorption in MOFs is intensely influenced by the gas–gas interactions, which might induce more molecules to be accommodated in an orderly compact arrangement. This sequential TRDSE method is generally applicable to most crystalline adsorbents, yielding information on distribution ratios of adsorbates at each type of site.

  4. Efficient adsorbents of nanoporous aluminosilicate monoliths for organic dyes from aqueous solution.

    PubMed

    El-Safty, Sherif A; Shahat, Ahmed; Awual, Md Rabiul

    2011-07-01

    Growing public awareness on the potential risk to humans of toxic chemicals in the environment has generated demand for new and improved methods for toxicity assessment and removal, rational means for health risk estimation. With the aim of controlling nanoscale adsorbents for functionality in molecular sieving of organic pollutants, we fabricated cubic Im3m mesocages with uniform entrance and large cavity pores of aluminosilicates as highly promising candidates for the colorimetric monitoring of organic dyes in an aqueous solution. However, a feasible control over engineering of three-dimensional (3D) mesopore cage structures with uniform entrance (~5 nm) and large cavity (~10 nm) allowed the development of nanoadsorbent membranes as a powerful tool for large-quantity and high-speed (in minutes) adsorption/removal of bulk molecules such as organic dyes. Incorporation of high aluminum contents (Si/Al=1) into 3D cubic Im3m cage mesoporous silica monoliths resulted in small, easy-to-use optical adsorbent strips. In such adsorption systems, natural surfaces of active acid sites of aluminosilicate strips strongly induced both physical adsorption of chemically responsive dyes and intraparticle diffusion into cubic Im3m mesocage monoliths. Results likewise indicated that although aluminosilicate strips with low Si/Al ratios exhibit distortion in pore ordering and decrease in surface area and pore volume, enhancement of both molecular converges and intraparticle diffusion onto the network surfaces and into the pore architectures of adsorbent membranes was achieved. Moreover, 3D mesopore cage adsorbents are reversible, offering potential for multiple adsorption assays.

  5. INVESTIGATION OF THE TOTAL ORGANIC HALOGEN ANALYTICAL METHOD AT THE WASTE SAMPLING AND CHARACTERIZATION FACILITY

    SciTech Connect

    JG DOUGLAS; HK MEZNARICH, PHD; JR OLSEN; GA ROSS PHD; M STAUFFER

    2009-02-13

    Total organic halogen (TOX) is used as a parameter to screen groundwater samples at the Hanford Site. Trending is done for each groundwater well, and changes in TOX and other screening parameters can lead to costly changes in the monitoring protocol. The Waste Sampling and Characterization Facility (WSCF) analyzes groundwater samples for TOX using the United States Environmental Protection Agency (EPA) SW-S46 method 9020B (EPA 1996a). Samples from the Soil and Groundwater Remediation Project (SGRP) are submitted to the WSCF for analysis without information regarding the source of the sample; each sample is in essence a ''blind'' sample to the laboratory. Feedback from the SGRP indicated that some of the WSCF-generated TOX data from groundwater wells had a number of outlier values based on the historical trends (Anastos 200Sa). Additionally, analysts at WSCF observed inconsistent TOX results among field sample replicates. Therefore, the WSCF lab performed an investigation of the TOX analysis to determine the cause of the outlier data points. Two causes were found that contributed to generating out-of-trend TOX data: (1) The presence of inorganic chloride in the groundwater samples: at inorganic chloride concentrations greater than about 10 parts per million (ppm), apparent TOX values increase with increasing chloride concentration. A parallel observation is the increase in apparent breakthrough of TOX from the first to the second activated-carbon adsorption tubes with increasing inorganic chloride concentration. (2) During the sample preparation step, excessive purging of the adsorption tubes with oxygen pressurization gas after sample loading may cause channeling in the activated carbon bed. This channeling leads to poor removal of inorganic chloride during the subsequent wash step with aqueous potassium nitrate. The presence of this residual inorganic chloride then produces erroneously high TOX values. Changes in sample preparation were studied to more effectively

  6. A reconnaissance study of halogenated organic compounds in catfish from the lower Mississippi river and its major tributaries

    USGS Publications Warehouse

    Leiker, T.J.; Rostad, C.E.; Barnes, C.R.; Pereira, W.E.

    1991-01-01

    Blue catfish, (Ictarurus furcatus), black bullhead catfish, (Ictalurus melas), channel catfish (Ictalurus punctatus), and flathead catfish (Pylodictus olivaris), were collected along a 1200 mile river reach of the Mississippi River and its major tributaries. Tissue samples were extracted and analyzed by fused silica capillary gas chromatography/mass spectrometry (GC/MS) to determine the concentrations of hydrophobic organic halogenated contaminants that have bioconcentrated within the tissues. The compounds identified in the tissue include chlordane, polychlorinated biphenyls (PCBs), DDT and its metabolites along with several other chlorinated pesticides. The data indicates that the southern reach of the river system appears to be more contaminated than the middle and upper reaches of the study area.

  7. Tunable crossover between one- and three-dimensional magnetic dynamics in C oII single-chain magnets organized by halogen bonding

    NASA Astrophysics Data System (ADS)

    Amjad, A.; Clemente-Juan, J. M.; Coronado, E.; Luis, F.; Evangelisti, M.; Espallargas, G. Mínguez; del Barco, E.

    2016-06-01

    Low-temperature magnetometry, ac susceptibility, and calorimetry have been employed to study Co-based single-chain magnets (SCMs) organized through halogen bonding. Magnetic hysteresis and maxima in the dc and ac susceptibilities, respectively, confirm the SCM behavior of the system. Several characteristic magnetic relaxation regimes are observed at different temperatures, which can be associated with both intra- and interchain exchange interactions. Remarkably, tweaking the rate at which an external magnetic field is swept along the axis of the chains enables a controlled transition between the one- and three-dimensional dynamics. Experiments on an isostructural Co-based SCM system crystallized with different halogens do not show three-dimensional dynamics, illustrating the importance of halogen bonding on the control of interchain interactions.

  8. Validation of thermodesorption method for analysis of semi-volatile organic compounds adsorbed on wafer surface.

    PubMed

    Hayeck, Nathalie; Gligorovski, Sasho; Poulet, Irène; Wortham, Henri

    2014-05-01

    To prevent the degradation of the device characteristics it is important to detect the organic contaminants adsorbed on the wafers. In this respect, a reliable qualitative and quantitative analytical method for analysis of semi-volatile organic compounds which can adsorb on wafer surfaces is of paramount importance. Here, we present a new analytical method based on Wafer Outgassing System (WOS) coupled to Automated Thermal Desorber-Gas chromatography-Mass spectrometry (ATD-GC-MS) to identify and quantify volatile and semi-volatile organic compounds from 6", 8" and 12" wafers. WOS technique allows the desorption of organic compounds from one side of the wafers. This method was tested on three important airborne contaminants in cleanroom i.e. tris-(2-chloroethyl) phosphate (TCEP), tris-(2-chloroisopropyl) phosphate (TCPP) and diethyl phthalate (DEP). In addition, we validated this method for the analysis and quantification of DEP, TCEP and TCPP and we estimated the backside organic contamination which may contribute to the front side of the contaminated wafers. We are demonstrating that WOS/ATD-GC-MS is a suitable and highly efficient technique for desorption and quantitative analysis of organophosphorous compounds and phthalate ester which could be found on the wafer surface.

  9. Mechanistic Insights to the Influence of Adsorbed Organic Macromolecules on Nanoparticle Attachment Efficiency in Porous Media

    NASA Astrophysics Data System (ADS)

    Phenrat, T.; Song, J.; Cisneros, C. M.; Schoenfelder, D. P.; Illangasekare, T. H.; Tilton, R. D.; Lowry, G. V.

    2009-12-01

    Assessing the potential risks of natural or engineered nanoparticles to the environment and human health requires the ability to predict their mobility in porous media such as groundwater aquifers or sand filters used in water treatment. Semi-empirical correlations to predict the collision efficiency of electrostatically stabilized nanoparticles are available; however, they are not applicable to nanoparticles coated with natural organic matter (NOM) or polymeric surface coatings because the existing correlations do not account the electrosteric repulsions and lubrication afforded by coatings that inhibit or reverse nanoparticle attachment to surfaces. Regression analysis of published data on the collision efficiency of NOM-coated latex and hematite particles, and on new data collected for poly(styrene sulfonate)-, carboxy methyl cellulose, and polyaspartate-coated hematite and titanium dioxide nanoparticles was used to develop an empirical correlation of the collision efficiency of NOM- and polymer-coated nanomaterials and dimensionless parameters including the adsorbed layer-electrokinetic parameter (NLEK) representing electrosteric repulsions and lubrication afforded by adsorbed NOM or polyelectrolyte. An empirical correlation with three dimensionless parameters can predict the measured collision efficiency on coated metal oxide nanoparticles over a wide dynamic range in particle type, coating type, and solution conditions (~80 data points). This study indicates that including the adsorbed NOM and polymer layer properties of the properties is essential for understanding the transport and fate of NOM- and polymer-coated natural and manufactured nanomaterials in porous media.

  10. Development of adsorbent for the simultaneous removal of organic and inorganic contaminants from aqueous solution.

    PubMed

    Choi, J W; Chung, S G; Hong, S W; Kim, D J; Lee, S H

    2011-01-01

    In this study, a modified adsorbent, alginate complex beads, was prepared and applied to the removal of mixed contaminants from wastewater. The alginate complex beads were generated by the immobilization of powdered activated carbon and synthetic zeolites onto alginate gel beads, which were then dried at 110 °C for 20 h until the diameter had been reduced to 1 mm. This dry technique increased the hardness of the adsorbent to assure its durability and application. The adsorption onto the alginate complex beads of organic and inorganic compounds, as target contaminants, was investigated by performing both equilibrium and kinetic batch experiments. From the adsorption isotherms, according to the Langmuir equation, the alginate complex bead was capable of effectively removing benzene, toluene, zinc and cadmium. From kinetic batch experiments, the removal efficiencies of benzene, toluene, zinc and cadmium were found to be 66.5, 92.4, 74.1 and 76.7%, respectively, for initial solution concentrations of 100 mg L(-1). The results indicated that the adsorbent developed in this study has the potential to be a promising material for the removal of mixed pollutants from industrial wastewater or contaminated groundwater. PMID:22020474

  11. Occurrence of halogenated alkaloids.

    PubMed

    Gribble, Gordon W

    2012-01-01

    blubber. Given the fact that of the 500,000 estimated marine organisms--which are the source of most halogenated alkaloids--only a small percentage have been investigated for their chemical content, it is certain that myriad new halogenated alkaloids are awaiting discovery. For example, it is estimated that nearly 4000 species of bryozoans have not been examined for their chemical content. The few species that have been studied contain some extraordinary halogenated alkaloids, such as hinckdentine A (610) and the chartellines (611-613). Of the estimated 1.5 million species of fungi, secondary metabolites have been characterized from only 5000 species. The future seems bright for the collector of halogenated alkaloids! PMID:23189746

  12. The effects of adsorbing organic pollutants from super heavy oil wastewater by lignite activated coke.

    PubMed

    Tong, Kun; Lin, Aiguo; Ji, Guodong; Wang, Dong; Wang, Xinghui

    2016-05-01

    The adsorption of organic pollutants from super heavy oil wastewater (SHOW) by lignite activated coke (LAC) was investigated. Specifically, the effects of LAC adsorption on pH, BOD5/COD(Cr)(B/C), and the main pollutants before and after adsorption were examined. The removed organic pollutants were characterized by Fourier transform infrared spectroscopy (FTIR), Boehm titrations, gas chromatography-mass spectrometry (GC-MS), and liquid chromatography with organic carbon detection (LC-OCD). FTIR spectra indicated that organic pollutants containing -COOH and -NH2 functional groups were adsorbed from the SHOW. Boehm titrations further demonstrated that carboxyl, phenolic hydroxyl, and lactonic groups on the surface of the LAC increased. GC-MS showed that the removed main organic compounds are difficult to be degraded or extremely toxics to aquatic organisms. According to the results of LC-OCD, 30.37 mg/L of dissolved organic carbons were removed by LAC adsorption. Among these, hydrophobic organic contaminants accounted for 25.03 mg/L. Furthermore, LAC adsorption was found to increase pH and B/C ratio of the SHOW. The mechanisms of adsorption were found to involve between the hydrogen bonding and the functional groups of carboxylic, phenolic, and lactonic on the LAC surface. In summary, all these results demonstrated that LAC adsorption can remove bio-refractory DOCs, which is beneficial for biodegradation.

  13. The effects of adsorbing organic pollutants from super heavy oil wastewater by lignite activated coke.

    PubMed

    Tong, Kun; Lin, Aiguo; Ji, Guodong; Wang, Dong; Wang, Xinghui

    2016-05-01

    The adsorption of organic pollutants from super heavy oil wastewater (SHOW) by lignite activated coke (LAC) was investigated. Specifically, the effects of LAC adsorption on pH, BOD5/COD(Cr)(B/C), and the main pollutants before and after adsorption were examined. The removed organic pollutants were characterized by Fourier transform infrared spectroscopy (FTIR), Boehm titrations, gas chromatography-mass spectrometry (GC-MS), and liquid chromatography with organic carbon detection (LC-OCD). FTIR spectra indicated that organic pollutants containing -COOH and -NH2 functional groups were adsorbed from the SHOW. Boehm titrations further demonstrated that carboxyl, phenolic hydroxyl, and lactonic groups on the surface of the LAC increased. GC-MS showed that the removed main organic compounds are difficult to be degraded or extremely toxics to aquatic organisms. According to the results of LC-OCD, 30.37 mg/L of dissolved organic carbons were removed by LAC adsorption. Among these, hydrophobic organic contaminants accounted for 25.03 mg/L. Furthermore, LAC adsorption was found to increase pH and B/C ratio of the SHOW. The mechanisms of adsorption were found to involve between the hydrogen bonding and the functional groups of carboxylic, phenolic, and lactonic on the LAC surface. In summary, all these results demonstrated that LAC adsorption can remove bio-refractory DOCs, which is beneficial for biodegradation. PMID:26808249

  14. Heterogeneous and Photochemical Reactions Involving Surface Adsorbed Organics: Common Lignin Pyrolysis Products With Nitrogen Dioxide.

    NASA Astrophysics Data System (ADS)

    Hinrichs, R. Z.; Nichols, B. R.; Rapa, C.; Costa, V.

    2009-05-01

    Solid-air interfaces, such as airborne particulate matter and ground level surfaces, provide unique supports for tropospheric heterogeneous chemistry. These interfaces commonly contain surface adsorbed organics, such as lignin pyrolysis products, that can significantly alter their physical and chemical properties. Attenuated total reflectance infrared spectroscopy (ATR-FTIR) provides an ideal tool for monitoring chemical changes in thin organic films during heterogeneous and photochemical reactions. Phenolic compounds, with and without co- adsorbed photosensitizers, were exposed to NO2 concentrations in the parts-per-billion range at 300 K and 20% relative humidity. Catechol, when mixed with benzophenone or dicyclohexylketone, formed 4- nitrocatechol as the dominant product under dark conditions. Deuterating the catechol alcohol groups caused the initial rate of reaction to decrease by a factor of 3.3±0.5, consistent with formation of the ortho- semiquinone radical as the rate determining step. The rate of 4-nitrocatechol formation did not increase under illuminated conditions, even with the presence of benzophenone a well known photosensitizer. UV-A/visible radiation did, however, initiate a photochemical reaction between benzophenone and 4-nitrocatechol, likely forming high molecular weight polymerization products. In contrast, 2-ethoxyphenol displayed no reactivity with NO2, even under illuminated conditions with a photosensitizer. Implications for the fate of lignin pyrolysis products, which are prevalent in biomass combustion smoke, will be discussed.

  15. Bioaccumulation of emerging organic compounds (perfluoroalkyl substances and halogenated flame retardants) by earthworm in biosolid amended soils.

    PubMed

    Navarro, Irene; de la Torre, Adrián; Sanz, Paloma; Pro, Javier; Carbonell, Gregoria; Martínez, María de Los Ángeles

    2016-08-01

    In the present work, the bioaccumulation behavior of 49 target emerging organic compounds (20 perfluoroalkyl substances, PFASs, and 29 halogenated flame retardants, HFRs) was studied in soil invertebrates (Eisenia andrei). Multi species soil systems (MS·3) were used to assess the fate and the effects associated with the application of four biosolids in agricultural soil on terrestrial soil organisms. Biosolid amendment increased concentrations 1.5-14-fold for PFASs, 1.1-2.4-fold for polybrominated diphenyl ethers, PBDEs, and 1.1-3.6-fold for chlorinated flame retardants, CFRs. Perfluorooctanesulfonate, PFOS, (25%) and BDE-209 (60%) were the predominant PFAS and HFR compounds, respectively, in biosolids-amended soils. Total concentrations (ng/g dry weight) in earthworms from biosolid-amended soils ranged from 9.9 to 101 for PFASs, from 45 to 76 for PBDEs and 0.3-32 for CFRs. Bioaccumulation factors (BAFs) were calculated to evaluate the degree of exposure of pollutants in earthworms. The mean BAF ranged from 2.2 to 198 for PFASs, 0.6-17 for PBDEs and 0.5-20 for CFRs. The relationship of PFAS and PBDE BAFs in earthworms and their log Kow were compared: PFAS BAFs increased while PBDE BAFs declined with increasing log Kow values. The effect of the aging (21 days) on the bioavailability of the pollutants in amended soils was also assessed: the residence time affected differently to the compounds studied. PMID:27174781

  16. Polycyclic aromatic hydrocarbons and halogenated persistent organic pollutants in canned fish and seafood products: smoked versus non-smoked products.

    PubMed

    Drabova, Lucie; Pulkrabova, Jana; Kalachova, Kamila; Tomaniova, Monika; Kocourek, Vladimir; Hajslova, Jana

    2013-01-01

    In this study, levels of several groups of environmental contaminants represented by PAHs, PCBs, organochlorine pesticides and polybrominated diphenyl ethers were determined in various types of canned smoked and non-smoked fish and seafood products (54 samples) obtained from the Czech market. PAHs were detected in all of the studied samples, and at least one of the target halogenated persistent organic pollutants was present above the LOQ in 85% of the samples. The levels of PAHs, PCBs, organochlorine pesticides (mainly DDTs) and polybrominated diphenyl ethers found in the canned products varied in the range of 1.4-116 µg kg(-1), 0.6-59.6 µg kg(-1), 0.6-82.7 µg kg(-1) and 0.1-2.1 µg kg(-1) can content, respectively. Smoked sprats were the most contaminated fish product (n = 12) in which the highest levels of both PAHs and persistent organic pollutants were found. In 67% of the samples of smoked sprats in oil, the level of benzo[a]pyrene exceeded the maximum level of 5 µg kg(-1) established for smoked fish by European Union legislation. The distribution of target analytes between oil and fish fractions was also assessed. Significantly higher levels of PAHs were measured in the oil fraction. PMID:23339715

  17. Typical halogenated persistent organic pollutants in indoor dust and the associations with childhood asthma in Shanghai, China.

    PubMed

    Meng, Ge; Nie, Zhiqing; Feng, Yan; Wu, Xiaomeng; Yin, Yong; Wang, Yan

    2016-04-01

    Halogenated persistent organic pollutants (Hal-POPs) are significant contaminants in the indoor environment that are related to many human diseases. Ingestion of indoor dust is considered the major pathway of Hal-POP exposures, especially for children aged 3-6 years. Alongside a retrospective study on the associations between typical Hal-POP exposure and childhood asthma in Shanghai, indoor dust samples from asthmatic and non-asthmatic children's homes (n = 60, each) were collected. Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were measured by GC-MS. BDE-209, PCB-8 and p,p'-DDE were the predominant components in each chemical category. The concentrations of most Hal-POPs were significantly higher in the asthmatic families. The associations between Hal-POP exposure and asthma occurrence were examined by calculating the odds ratios (ORs) using a logistic regression model. A positive association was found between p,p'-DDE in indoor dust and childhood asthma (OR = 1.825, 95%CI: 1.004, 3.317; p = 0.048). The average daily doses of Hal-POP intake were calculated using the method provided by the USEPA. Non-carcinogenic health risks were preliminarily assessed. Our study indicated that exposure to p,p'-DDE via indoor dust may contribute to childhood asthma occurrence. Non-carcinogenic health risks were not found with the intake of Hal-POPs via the ingestion of indoor dust.

  18. Effect of reduced food intake on toxicokinetics of halogenated organic contaminants in herring gull (Larus argentatus) chicks.

    PubMed

    Routti, Heli; Helgason, Lisa Bjørnsdatter; Arukwe, Augustine; Wolkers, Hans; Heimstad, Eldbjørg Sofie; Harju, Mikael; Berg, Vidar; Gabrielsen, Geir Wing

    2013-01-01

    The aim of the present study was to investigate how contaminant exposure and reduced food intake affect tissue distribution and biotransformation of halogenated organic contaminants (HOCs) in Arctic seabirds using herring gull (Larus argentatus) as a model species. Herring gull chicks were exposed for 44 d to cod liver oil containing a typical mixture of contaminants. Following exposure, food intake was reduced for a one-week period in a subgroup of the chicks. Polyclorinated biphenyls, organochlorine pesticides, and brominated flame retardants, as well as a wide range of hydroxy, methyl sulfone, and methoxy compounds were measured in liver, brain, and plasma samples. Additionally, phase I biotransformation enzyme activities and phase I and II messenger ribonucleic acid (mRNA) expression were investigated in the liver, brain, or both. Both contaminant exposure and reduced food intake had an increasing effect on the concentrations of HOCs and their metabolites. The HOC exposure and reduced food intake also led to increased 7-ethoxyresorufin-O-deethylation (EROD) activity, whereas mRNA expression of the biotransformation enzymes increased only following the reduced food intake. Tissue distribution of HOCs and their metabolites was not affected by either contaminant exposure or reduced food intake. In conclusion, the results indicate that biotransformation capacity and formation of HOC metabolites increase during reduced food intake. This finding supports the hypothesis that reduced food intake increases the susceptibility of Arctic animals to the effects of lipophilic HOCs.

  19. Effect of reduced food intake on toxicokinetics of halogenated organic contaminants in herring gull (Larus argentatus) chicks.

    PubMed

    Routti, Heli; Helgason, Lisa Bjørnsdatter; Arukwe, Augustine; Wolkers, Hans; Heimstad, Eldbjørg Sofie; Harju, Mikael; Berg, Vidar; Gabrielsen, Geir Wing

    2013-01-01

    The aim of the present study was to investigate how contaminant exposure and reduced food intake affect tissue distribution and biotransformation of halogenated organic contaminants (HOCs) in Arctic seabirds using herring gull (Larus argentatus) as a model species. Herring gull chicks were exposed for 44 d to cod liver oil containing a typical mixture of contaminants. Following exposure, food intake was reduced for a one-week period in a subgroup of the chicks. Polyclorinated biphenyls, organochlorine pesticides, and brominated flame retardants, as well as a wide range of hydroxy, methyl sulfone, and methoxy compounds were measured in liver, brain, and plasma samples. Additionally, phase I biotransformation enzyme activities and phase I and II messenger ribonucleic acid (mRNA) expression were investigated in the liver, brain, or both. Both contaminant exposure and reduced food intake had an increasing effect on the concentrations of HOCs and their metabolites. The HOC exposure and reduced food intake also led to increased 7-ethoxyresorufin-O-deethylation (EROD) activity, whereas mRNA expression of the biotransformation enzymes increased only following the reduced food intake. Tissue distribution of HOCs and their metabolites was not affected by either contaminant exposure or reduced food intake. In conclusion, the results indicate that biotransformation capacity and formation of HOC metabolites increase during reduced food intake. This finding supports the hypothesis that reduced food intake increases the susceptibility of Arctic animals to the effects of lipophilic HOCs. PMID:23060285

  20. Molecular mechanism of metal-independent decomposition of organic hydroperoxides by halogenated quinoid carcinogens and the potential biological implications.

    PubMed

    Huang, Chun-Hua; Ren, Fu-Rong; Shan, Guo-Qiang; Qin, Hao; Mao, Li; Zhu, Ben-Zhan

    2015-05-18

    Halogenated quinones (XQ) are a class of carcinogenic intermediates and newly identified chlorination disinfection byproducts in drinking water. Organic hydroperoxides (ROOH) can be produced both by free radical reactions and enzymatic oxidation of polyunsaturated fatty acids. ROOH have been shown to decompose to alkoxyl radicals via catalysis by transition metal ions, which may initiate lipid peroxidation or transform further to the reactive aldehydes. However, it is not clear whether XQ react with ROOH in a similar manner to generate alkoxyl radicals metal-independently. By complementary applications of ESR spin-trapping, HPLC/high resolution mass spectrometric and other analytical methods, we found that 2,5-dichloro-1,4-benzoquinone (DCBQ) could significantly enhance the decomposition of a model ROOH tert-butylhydroperoxide, resulting in the formation of t-butoxyl radicals independent of transition metals. On the basis of the above findings, we detected and identified, for the first time, an unprecedented C-centered quinone ketoxy radical. Then, we extended our study to the more physiologically relevant endogenous ROOH 13-hydroperoxy-9,11-octadecadienoic acid and found that DCBQ could also markedly enhance its decomposition to generate the reactive lipid alkyl radicals and the genotoxic 4-hydroxy-2-nonenal (HNE). Similar results were observed with other XQ. In summary, these findings demonstrated that XQ can facilitate ROOH decomposition to produce reactive alkoxyl, quinone ketoxy, lipid alkyl radicals, and genotoxic HNE via a novel metal-independent mechanism, which may explain partly their potential genotoxicity and carcinogenicity.

  1. Nontargeted Biomonitoring of Halogenated Organic Compounds in Two Ecotypes of Bottlenose Dolphins (Tursiops truncatus) from the Southern California Bight

    PubMed Central

    2015-01-01

    Targeted environmental monitoring reveals contamination by known chemicals, but may exclude potentially pervasive but unknown compounds. Marine mammals are sentinels of persistent and bioaccumulative contaminants due to their longevity and high trophic position. Using nontargeted analysis, we constructed a mass spectral library of 327 persistent and bioaccumulative compounds identified in blubber from two ecotypes of common bottlenose dolphins (Tursiops truncatus) sampled in the Southern California Bight. This library of halogenated organic compounds (HOCs) consisted of 180 anthropogenic contaminants, 41 natural products, 4 with mixed sources, 8 with unknown sources, and 94 with partial structural characterization and unknown sources. The abundance of compounds whose structures could not be fully elucidated highlights the prevalence of undiscovered HOCs accumulating in marine food webs. Eighty-six percent of the identified compounds are not currently monitored, including 133 known anthropogenic chemicals. Compounds related to dichlorodiphenyltrichloroethane (DDT) were the most abundant. Natural products were, in some cases, detected at abundances similar to anthropogenic compounds. The profile of naturally occurring HOCs differed between ecotypes, suggesting more abundant offshore sources of these compounds. This nontargeted analytical framework provided a comprehensive list of HOCs that may be characteristic of the region, and its application within monitoring surveys may suggest new chemicals for evaluation. PMID:25526519

  2. Nontargeted biomonitoring of halogenated organic compounds in two ecotypes of bottlenose dolphins (Tursiops truncatus) from the Southern California Bight.

    PubMed

    Shaul, Nellie J; Dodder, Nathan G; Aluwihare, Lihini I; Mackintosh, Susan A; Maruya, Keith A; Chivers, Susan J; Danil, Kerri; Weller, David W; Hoh, Eunha

    2015-02-01

    Targeted environmental monitoring reveals contamination by known chemicals, but may exclude potentially pervasive but unknown compounds. Marine mammals are sentinels of persistent and bioaccumulative contaminants due to their longevity and high trophic position. Using nontargeted analysis, we constructed a mass spectral library of 327 persistent and bioaccumulative compounds identified in blubber from two ecotypes of common bottlenose dolphins (Tursiops truncatus) sampled in the Southern California Bight. This library of halogenated organic compounds (HOCs) consisted of 180 anthropogenic contaminants, 41 natural products, 4 with mixed sources, 8 with unknown sources, and 94 with partial structural characterization and unknown sources. The abundance of compounds whose structures could not be fully elucidated highlights the prevalence of undiscovered HOCs accumulating in marine food webs. Eighty-six percent of the identified compounds are not currently monitored, including 133 known anthropogenic chemicals. Compounds related to dichlorodiphenyltrichloroethane (DDT) were the most abundant. Natural products were, in some cases, detected at abundances similar to anthropogenic compounds. The profile of naturally occurring HOCs differed between ecotypes, suggesting more abundant offshore sources of these compounds. This nontargeted analytical framework provided a comprehensive list of HOCs that may be characteristic of the region, and its application within monitoring surveys may suggest new chemicals for evaluation. PMID:25526519

  3. Influence of season, location, and feeding strategy on bioaccumulation of halogenated organic contaminants in Arctic marine zooplankton.

    PubMed

    Hallanger, Ingeborg G; Ruus, Anders; Herzke, Dorte; Warner, Nicholas A; Evenset, Anita; Heimstad, Eldbjørg S; Gabrielsen, Geir W; Borgå, Katrine

    2011-01-01

    The influence of season, location, feeding strategy, and trophic position on concentration, compositional pattern, and bioaccumulation factors (BAFs) of halogenated organic contaminants (HOCs; polychlorinated biphenyls, chlorinated pesticides, and brominated flame retardants) was investigated within an Arctic zooplankton food web. Water (dissolved fraction) and seven Arctic marine pelagic zooplankton species (including herbivores, omnivores, and predators) were sampled in May, July, and October 2007 at two stations in Kongsfjorden, Svalbard, Norway. The HOC concentrations in both water and zooplankton generally decreased from May to October. The HOC concentrations and patterns among zooplankton species were explained by their feeding strategies, roughly categorized as herbivores, omnivores, and predators, and not stable isotope-derived trophic position. Field-derived BAFs varied greatly, with higher BAFs in May compared with July and October. Furthermore, BAFs differed among the species according to their feeding strategies. The relationship between BAFs from the different seasons and K(OW) (octanol:water partitioning coefficient) showed comparable intercepts and different slopes between May and October, with all relationships diverging from the assumed 1:1 relationship between BAF and K(OW). Differences in HOC concentrations and BAFs from herbivores to predators showed that biomagnification occurred in zooplankton. The results suggest that concentrations and patterns of HOCs in zooplankton species are influenced not only by equilibrium partitioning with water but also by feeding strategy.

  4. Influence of season, location, and feeding strategy on bioaccumulation of halogenated organic contaminants in Arctic marine zooplankton.

    PubMed

    Hallanger, Ingeborg G; Ruus, Anders; Herzke, Dorte; Warner, Nicholas A; Evenset, Anita; Heimstad, Eldbjørg S; Gabrielsen, Geir W; Borgå, Katrine

    2011-01-01

    The influence of season, location, feeding strategy, and trophic position on concentration, compositional pattern, and bioaccumulation factors (BAFs) of halogenated organic contaminants (HOCs; polychlorinated biphenyls, chlorinated pesticides, and brominated flame retardants) was investigated within an Arctic zooplankton food web. Water (dissolved fraction) and seven Arctic marine pelagic zooplankton species (including herbivores, omnivores, and predators) were sampled in May, July, and October 2007 at two stations in Kongsfjorden, Svalbard, Norway. The HOC concentrations in both water and zooplankton generally decreased from May to October. The HOC concentrations and patterns among zooplankton species were explained by their feeding strategies, roughly categorized as herbivores, omnivores, and predators, and not stable isotope-derived trophic position. Field-derived BAFs varied greatly, with higher BAFs in May compared with July and October. Furthermore, BAFs differed among the species according to their feeding strategies. The relationship between BAFs from the different seasons and K(OW) (octanol:water partitioning coefficient) showed comparable intercepts and different slopes between May and October, with all relationships diverging from the assumed 1:1 relationship between BAF and K(OW). Differences in HOC concentrations and BAFs from herbivores to predators showed that biomagnification occurred in zooplankton. The results suggest that concentrations and patterns of HOCs in zooplankton species are influenced not only by equilibrium partitioning with water but also by feeding strategy. PMID:20853452

  5. Process for removal of hydrogen halides or halogens from incinerator gas

    DOEpatents

    Huang, Hann S.; Sather, Norman F.

    1988-01-01

    A process for reducing the amount of halogens and halogen acids in high temperature combustion gases and through their removal, the formation of halogenated organics at lower temperatures, with the reduction being carried out electrochemically by contacting the combustion gas with the negative electrode of an electrochemical cell and with the halogen and/or halogen acid being recovered at the positive electrode.

  6. Process for removal of hydrogen halides or halogens from incinerator gas

    DOEpatents

    Huang, H.S.; Sather, N.F.

    1987-08-21

    A process for reducing the amount of halogens and halogen acids in high temperature combustion gas and through their removal, the formation of halogenated organics at lower temperatures, with the reduction being carried out electrochemically by contacting the combustion gas with the negative electrode of an electrochemical cell and with the halogen and/or halogen acid being recovered at the positive electrode.

  7. Anion transport with halogen bonds.

    PubMed

    Jentzsch, Andreas Vargas; Matile, Stefan

    2015-01-01

    This review covers the application of halogen bonds to transport anions across lipid bilayer membranes. The introduction provides a brief description of biological and synthetic transport systems. Emphasis is on examples that explore interactions beyond the coordination with lone pairs or hydrogen bonds for the recognition of cations and anions, particularly cation-π and anion-π interactions, and on structural motifs that are relevant for transport studies with halogen bonds. Section 2 summarizes the use of macrocyclic scaffolds to achieve transport with halogen bonds, focusing on cyclic arrays of halogen-bond donors of different strengths on top of calixarene scaffolds. This section also introduces methods to study anion binding in solution and anion transport in fluorogenic vesicles. In Sect. 3, transport studies with monomeric halogen bond-donors are summarized. This includes the smallest possible organic anion transporter, trifluoroiodomethane, a gas that can be bubbled through a suspension of vesicles to turn on transport. Anion transport with a gas nicely illustrates the power of halogen bonds for anion transport. Like hydrogen bonds, they are directional and strong, but compared to hydrogen-bond donors, halogen-bond donors are more lipophilic. Section 3 also offers a concise introduction to the measurement of ion selectivity in fluorogenic vesicles and conductance experiments in planar bilayer membranes. Section 4 introduces the formal unrolling of cyclic scaffolds into linear scaffolds that can span lipid bilayers. As privileged transmembrane scaffolds, the importance of hydrophobically matching fluorescent p-oligophenyl rods is fully confirmed. The first formal synthetic ion channel that operates by cooperative multiion hopping along transmembrane halogen-bonding cascades is described. Compared to homologs for anion-π interactions, transport with halogen bonds is clearly more powerful.

  8. Control of volatile organic chemical emissions by adsorption onto hydrophobic and organophilic adsorbents

    NASA Astrophysics Data System (ADS)

    Yee, Lee Lai

    With the advent of the Environmental Protection Act 1990, the control of volatile organic chemical (VOC) emissions has become necessary. Complying with regulations may result in additional costs, but these may be alleviated if solvent recovery by means of low pressure drop monoliths is considered. Monoliths, in comparison with traditional packed beds, have a very low pressure drop and high surface areas. The principal aims of the research were to determine the effectiveness of high silica zeolites as adsorbents for the recovery of VOCs and to utilise the zeolites in the monolithic configuration. Silicalite and ZSM-5 were selected as the adsorbents and propane, ethanol and methylene chloride were selected as representative VOCs. The project was divided into two phases. The first was concerned with optimising the chemical formulation of pastes containing a high percentage of silicalite such that they can be extruded to form monolith structures. The second phase of the project involved comparing the equilibrium and kinetic performances of the manufactured monoliths with the performance of an equivalent packed bed containing commercially available silicalite pellets. Multichannel monoliths containing up to 90 % silicalite and with cell densities up to 29 cells/cm and adsorbent wall thicknesses down to 0.6 mm were produced. A square channel monolith having a channel size of 1.0 mm, a wall thickness of 1.0 mm and a cell density of 25 cells/cm was selected for further study due to its relatively high mechanical strength, ease of fabrication, and to the fact that its overall dimensions were comparable with those of an equivalent packed bed. The single component adsorption of VOCs onto high silica zeolites is highly favourable and isotherms of rectangular shape were obtained. The equilibrium capacities for the VOCs were found to be broadly similar for the two adsorbent forms whilst, in their favour for air pollution control applications, the manufactured monoliths were

  9. Metal-organic framework@microporous organic network: hydrophobic adsorbents with a crystalline inner porosity.

    PubMed

    Chun, Jiseul; Kang, Sungah; Park, Nojin; Park, Eun Ji; Jin, Xing; Kim, Kwang-Dae; Seo, Hyun Ook; Lee, Sang Moon; Kim, Hae Jin; Kwon, Woo Hyun; Park, Young-Kwon; Kim, Ji Man; Kim, Young Dok; Son, Seung Uk

    2014-05-14

    This work reports the synthesis and application of metal-organic framework (MOF)@microporous organic network (MON) hybrid materials. Coating a MOF, UiO-66-NH2, with MONs forms hybrid microporous materials with hydrophobic surfaces. The original UiO-66-NH2 shows good wettability in water. In comparison, the MOF@MON hybrid materials float on water and show excellent performance for adsorption of a model organic compound, toluene, in water. Chemical etching of the MOF results in the formation of hollow MON materials. PMID:24786337

  10. Evaluation of adsorbent sampling tube materials and Tenax-TA for analysis of volatile biogenic organic compounds

    NASA Astrophysics Data System (ADS)

    Arnts, Robert R.

    2010-04-01

    Adsorbent tube materials, bed retainers and Tenax-TA were evaluated for their respective roles in adsorbing biogenic volatile organic compounds from air and their tendencies to cause chemical transformation of analytes upon thermal desorption. Stainless steel, Silcosteel ® and Sulfinert ® treated stainless steel tubes exhibited varying degrees of adsorption and reactivity towards some analytes. However, the typical short exposure of the sample stream to wall material before entering an adsorbent bed, minimizes the effect of these properties. Three forms of silica wool (untreated glass wool and siloxane-treated glass and fused silica wool), often used as adsorbent bed retainers, were evaluated and found to function as an adsorbent bed especially for oxygenated monoterpenes and sesquiterpenes. Tenax-TA was evaluated in stainless steel tubes (untreated and treated) with a 2 μm mesh woven wire disk (also untreated and treated) to circumvent the effects of using a silica wool bed retainer. Tenax-TA adsorbent in stainless steel, Silcosteel and Sulfinert tubes yielded equivalent results when compared with direct (cryogenic) pre-concentration analysis of a multi-component mixture of n-alkanes and selected biogenic VOC. Tenax-TA tubes that had been used for 15-20 bake out-sample-desorption cycles (field and laboratory sampling) were compared with freshly packed tubes and found to give equivalent results.

  11. Activated boron nitride as an effective adsorbent for metal ions and organic pollutants.

    PubMed

    Li, Jie; Xiao, Xing; Xu, Xuewen; Lin, Jing; Huang, Yang; Xue, Yanming; Jin, Peng; Zou, Jin; Tang, Chengchun

    2013-01-01

    Novel activated boron nitride (BN) as an effective adsorbent for pollutants in water and air has been reported in the present work. The activated BN was synthesized by a simple structure-directed method that enabled us to control the surface area, pore volume, crystal defects and surface groups. The obtained BN exhibits an super high surface area of 2078 m(2)/g, a large pore volume of 1.66 cm(3)/g and a special multimodal microporous/mesoporous structure located at ~ 1.3, ~ 2.7, and ~ 3.9 nm, respectively. More importantly, the novel activated BN exhibits an excellent adsorption performance for various metal ions (Cr(3+), Co(2+), Ni(2+), Ce(3+), Pb(2+)) and organic pollutants (tetracycline, methyl orange and congo red) in water, as well as volatile organic compounds (benzene) in air. The excellent reusability of the activated BN has also been confirmed. All the features render the activated BN a promising material suitable for environmental remediation. PMID:24220570

  12. Activated carbon prepared from coffee pulp: potential adsorbent of organic contaminants in aqueous solution.

    PubMed

    Gonçalves, Maraisa; Guerreiro, Mário César; Ramos, Paulize Honorato; de Oliveira, Luiz Carlos Alves; Sapag, Karim

    2013-01-01

    The processing of coffee beans generates large amounts of solid and liquid residues. The solid residues (pulp, husk and parchment) represent a serious environmental problem and do not have an adequate disposal mechanism. In this work, activated carbons (ACs) for adsorption of organic compounds were prepared from coffee pulp by controlled temperature at different pulp/Na2HPO4 ratios (4:1, 2:1, 5:4 and 1:1). The N2 adsorption/desorption isotherms showed ACs with high quantities of mesopores and micropores and specific surface areas of 140, 150, 450 and 440 m(2)g(-1) for AC 4:1, AC 2:1, AC 5:4 and AC 1:1, respectively. The prepared material AC 5:4 showed a higher removal capacity of the organic contaminants methylene blue (MB), direct red (DR) and phenol than did a Merck AC. The maximum capacities for this AC are approximately 150, 120 and 120 mg g(-1) for MB, DR and phenol, respectively. Thus, a good adsorbent was obtained from coffee pulp, an abundant Brazilian residue.

  13. Activated boron nitride as an effective adsorbent for metal ions and organic pollutants

    PubMed Central

    Li, Jie; Xiao, Xing; Xu, Xuewen; Lin, Jing; Huang, Yang; Xue, Yanming; Jin, Peng; Zou, Jin; Tang, Chengchun

    2013-01-01

    Novel activated boron nitride (BN) as an effective adsorbent for pollutants in water and air has been reported in the present work. The activated BN was synthesized by a simple structure-directed method that enabled us to control the surface area, pore volume, crystal defects and surface groups. The obtained BN exhibits an super high surface area of 2078 m2/g, a large pore volume of 1.66 cm3/g and a special multimodal microporous/mesoporous structure located at ~ 1.3, ~ 2.7, and ~ 3.9 nm, respectively. More importantly, the novel activated BN exhibits an excellent adsorption performance for various metal ions (Cr3+, Co2+, Ni2+, Ce3+, Pb2+) and organic pollutants (tetracycline, methyl orange and congo red) in water, as well as volatile organic compounds (benzene) in air. The excellent reusability of the activated BN has also been confirmed. All the features render the activated BN a promising material suitable for environmental remediation. PMID:24220570

  14. Halogenated persistent organic pollutants in relation to trophic level in deep sea fish.

    PubMed

    Webster, Lynda; Russell, Marie; Walsham, Pam; Hussy, Ines; Lacaze, Jean-Pierre; Phillips, Lesley; Dalgarno, Eric; Packer, Gill; Neat, Francis; Moffat, Colin F

    2014-11-15

    The bioaccumulation of persistent organic pollutants (POPs) in deep sea fish from the Rockall fishing area was investigated. Predator and prey species were analysed for stable isotopes, fatty acids, polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). δ(15)N indicated that black scabbard was at the highest trophic level and the prey the lowest. The fatty acid signatures indicated that black scabbard and black dogfish fed at a higher trophic level compared to the roundnose grenadier. PCBs and PBDEs were detected in the liver of all three predator species. PCB concentrations were significantly higher in the roundnose grenadier, possibly due to their longer life span. PCB concentrations were compared to OSPAR assessment criteria, concentrations were above background but below Environmental Assessment Criteria for all but one congener. PCB concentrations were below food safety levels in the flesh, but exceeded the limit for liver in the roundnose grenadier and black dogfish.

  15. Reactive and recoverable sorbents for halogenated organic compound remediation in sediments

    NASA Astrophysics Data System (ADS)

    Werner, David; Taggalou, Villy; Kordulis, Christos; Dolfing, Jan; Karapanagioti, Hrissi K.

    2013-04-01

    Activated carbon (AC) has been proposed as a sediment amendment for aquatic systems polluted with hydrophobic organic compounds. AC acts as a strong binding agent that lowers the pollutant concentration and thus, its toxicity. A draw back of this in-situ remediation method is that although the pollutant will remain non-bioavailable for many years being sorbed into AC, it actually stays in the system. A reactive sorbent, a sorbent that would, at the same time, facilitate the degradation of the pollutant, would be better accepted by the public or the regulators than AC amendment. So far, catalysts supported on AC with zero valent iron and a reactive metal have been proposed for the dechlorination of chlorinated organic compounds. These reactive metals are usually expensive or toxic and thus, their addition to the environment is not desirable. In the present study, activated carbon modified with reduced iron(AC/Fe) is tested in batch systems in the presence of sediment and DDT sorbed on polyethylene sheets. The batch systems are equilibrated for different contact times. Then, the DDT remaining in the polyethylene sheets is quantified along with DDD produced due to the dechlorination of DDT. A small percentage of DDT is degraded to DDD in the systems containing the AC/Fe material. No degradation of DDT is observed in the control systems containing the pollutant and the sediment or the pollutant, the sediment and AC. Thus, the addition of AC/Fe to the sediment with the DDT is enough to cause the dechlorination of DDT. At the end of the experiments, a magnet rod is used to recover the AC/Fe material from the batches with the sediment. An average recovery of 83% is achieved. This is a high percentage suggesting that the material can be easily recovered. Some drawbacks of the material preparation method are identified after the composite material characterization. For example, the AC/Fe surface area is decreased with the material preparation compared to the initial surface

  16. HYDRODEHALOGENATION OF 1- TO 3-CARBON HALOGENATED ORGANIC COMPOUNDS IN WATER USING A PALLADIUM CATALYST AND HYDROGEN GAS. (R825421)

    EPA Science Inventory

    Supported palladium (Pd) metal catalysts along with H2 gas show
    significant potential as a technology which can provide rapid, on-site
    destruction of halogenated groundwater contaminants. Pd catalyzes the rapid
    hydrodehalogenation of nine 1- to 3-carbon ...

  17. What’s New in Enzymatic Halogenations

    PubMed Central

    Fujimori, Danica Galoniæ; Walsh, Christopher T.

    2007-01-01

    Summary The halogenation of thousands of natural products occurs during biosynthesis and often confers important functional properties. While haloperoxidases had been the default paradigm for enzymatic incorporation of halogens, via X+ equivalents into organic scaffolds, a combination of microbial genome sequencing, enzymatic studies and structural biology have provided deep new insights into enzymatic transfer of halide equivalents in three oxidation states. These are: (1) the halide ions (X−) abundant in nature, (2) halogen atoms (X•), and (3) the X+ equivalents. The mechanism of halogen incorporation is tailored to the electronic demands of specific substrates and involves enzymes with distinct redox coenzyme requirements. PMID:17881282

  18. Sunlight-driven photochemical halogenation of dissolved organic matter in seawater: a natural abiotic source of organobromine and organoiodine.

    PubMed

    Méndez-Díaz, José Diego; Shimabuku, Kyle K; Ma, Jing; Enumah, Zachary O; Pignatello, Joseph J; Mitch, William A; Dodd, Michael C

    2014-07-01

    Reactions of dissolved organic matter (DOM) with photochemically generated reactive halogen species (RHS) may represent an important natural source of organohalogens within surface seawaters. However, investigation of such processes has been limited by difficulties in quantifying low dissolved organohalogen concentrations in the presence of background inorganic halides. In this work, sequential solid phase extraction (SPE) and silver-form cation exchange filtration were utilized to desalt and preconcentrate seawater DOM prior to nonspecific organohalogen analysis by ICP-MS. Using this approach, native organobromine and organoiodine contents were found to range from 3.2-6.4 × 10(-4) mol Br/mol C and 1.1-3.8 × 10(-4) mol I/mol C (or 19-160 nmol Br L(-1) and 6-36 nmol I L(-1)) within a wide variety of natural seawater samples, compared with 0.6-1.2 × 10(-4) mol Br/mol C and 0.6-1.1 × 10(-5) mol I/mol C in terrestrial natural organic matter (NOM) isolates. Together with a chemical probe method specific for RHS, the SPE+ICP-MS approach was also employed to demonstrate formation of nanomolar levels of organobromine and organoiodine during simulated and natural solar irradiation of DOM in artificial and natural seawaters. In a typical experiment, the organobromine content of 2.1 × 10(-4) mol C L(-1) (2.5 mg C L(-1)) of Suwannee River NOM in artificial seawater increased by 69% (from 5.9 × 10(-5) to 1.0 × 10(-4) mol Br/mol C) during exposure to 24 h of simulated sunlight. Increasing I(-) concentrations (up to 2.0 × 10(-7) mol L(-1)) promoted increases of up to 460% in organoiodine content (from 8.5 × 10(-6) to 4.8 × 10(-5) mol I/mol C) at the expense of organobromine formation under the same conditions. The results reported herein suggest that sunlight-driven reactions of RHS with DOM may play a significant role in marine bromine and iodine cycling.

  19. Sunlight-driven photochemical halogenation of dissolved organic matter in seawater: a natural abiotic source of organobromine and organoiodine.

    PubMed

    Méndez-Díaz, José Diego; Shimabuku, Kyle K; Ma, Jing; Enumah, Zachary O; Pignatello, Joseph J; Mitch, William A; Dodd, Michael C

    2014-07-01

    Reactions of dissolved organic matter (DOM) with photochemically generated reactive halogen species (RHS) may represent an important natural source of organohalogens within surface seawaters. However, investigation of such processes has been limited by difficulties in quantifying low dissolved organohalogen concentrations in the presence of background inorganic halides. In this work, sequential solid phase extraction (SPE) and silver-form cation exchange filtration were utilized to desalt and preconcentrate seawater DOM prior to nonspecific organohalogen analysis by ICP-MS. Using this approach, native organobromine and organoiodine contents were found to range from 3.2-6.4 × 10(-4) mol Br/mol C and 1.1-3.8 × 10(-4) mol I/mol C (or 19-160 nmol Br L(-1) and 6-36 nmol I L(-1)) within a wide variety of natural seawater samples, compared with 0.6-1.2 × 10(-4) mol Br/mol C and 0.6-1.1 × 10(-5) mol I/mol C in terrestrial natural organic matter (NOM) isolates. Together with a chemical probe method specific for RHS, the SPE+ICP-MS approach was also employed to demonstrate formation of nanomolar levels of organobromine and organoiodine during simulated and natural solar irradiation of DOM in artificial and natural seawaters. In a typical experiment, the organobromine content of 2.1 × 10(-4) mol C L(-1) (2.5 mg C L(-1)) of Suwannee River NOM in artificial seawater increased by 69% (from 5.9 × 10(-5) to 1.0 × 10(-4) mol Br/mol C) during exposure to 24 h of simulated sunlight. Increasing I(-) concentrations (up to 2.0 × 10(-7) mol L(-1)) promoted increases of up to 460% in organoiodine content (from 8.5 × 10(-6) to 4.8 × 10(-5) mol I/mol C) at the expense of organobromine formation under the same conditions. The results reported herein suggest that sunlight-driven reactions of RHS with DOM may play a significant role in marine bromine and iodine cycling. PMID:24933183

  20. Aquatic photolysis: photolytic redox reactions between goethite and adsorbed organic acids in aqueous solutions

    USGS Publications Warehouse

    Goldberg, M.C.; Cunningham, K.M.; Weiner, Eugene R.

    1993-01-01

    Photolysis of mono and di-carboxylic acids that are adsorbed onto the surface of the iron oxyhydroxide (goethite) results in an oxidation of the organic material and a reduction from Fe(III) to Fe(II) in the iron complex. There is a subsequent release of Fe2+ ions into solution. At constant light flux and constant solution light absorption, the factors responsible for the degree of photolytic reaction include: the number of lattice sites that are bonded by the organic acid; the rate of acid readsorption to the surface during photolysis; the conformation and structure of the organic acid; the degree of oxidation of the organic acid; the presence or absence of an ??-hydroxy group on the acid, the number of carbons in the di-acid chain and the conformation of the di-acid. The ability to liberate Fe(III) at pH 6.5 from the geothite lattice is described by the lyotropic series: tartrate>citrate> oxalate > glycolate > maleate > succinate > formate > fumarate > malonate > glutarate > benzoate = butanoate = control. Although a larger amount of iron is liberated, the series is almost the same at pH 5.5 except that oxalate > citrate and succinate > maleate. A set of rate equations are given that describe the release of iron from the goethite lattice. It was observed that the pH of the solution increases during photolysis if the solutions are not buffered. There is evidence to suggest the primary mechanism for all these reactions is an electron transfer from the organic ligand to the Fe(III) in the complex. Of all the iron-oxyhydroxide materials, crystalline goethite is the least soluble in water; yet, this study indicates that in an aqueous suspension, iron can be liberated from the goethite lattice. Further, it has been shown that photolysis can occur in a multiphase system at the sediment- water interface which results in an oxidation of the organic species and release of Fe2+ to solution where it becomes available for further reaction. ?? 1993.

  1. Raman spectroscopy of organic dyes adsorbed on pulsed laser deposited silver thin films

    NASA Astrophysics Data System (ADS)

    Fazio, E.; Neri, F.; Valenti, A.; Ossi, P. M.; Trusso, S.; Ponterio, R. C.

    2013-08-01

    The results of a surface-enhanced Raman scattering (SERS) study performed on representative organic and inorganic dyes adsorbed on silver nanostructured thin films are presented and discussed. Silver thin films were deposited on glass slides by focusing the beam from a KrF excimer laser (wavelength 248 nm, pulse duration 25 ns) on a silver target and performing the deposition in a controlled Ar atmosphere. Clear Raman spectra were acquired for dyes such as carmine lake, garanza lake and brazilwood overcoming their fluorescence and weak Raman scattering drawbacks. UV-visible absorption spectroscopy measurements were not able to discriminate among the different chromophores usually referred as carmine lake (carminic, kermesic and laccaic acid), as brazilwood (brazilin and brazilein) and as garanza lake (alizarin and purpurin). SERS measurements showed that the analyzed samples are composed of a mixture of different chromophores: brazilin and brazilein in brazilwood, kermesic and carminic acid in carmine lake, alizarin and purpurin in garanza lake. Detection at concentration level as low as 10-7 M in aqueous solutions was achieved. Higher Raman intensities were observed using the excitation line of 632.8 nm wavelength with respect to the 785 nm, probably due to a pre-resonant effect with the molecular electronic transitions of the dyes.

  2. Organic silicon compounds anf hydrogen sulfide removal from biogas by mineral and adsorbent

    NASA Astrophysics Data System (ADS)

    Choi, J.

    2015-12-01

    Biogas utilized for energy production needs to be free from organic silicon compounds and hydrogen sulfide , as their burning has damaging effects on utilities and humans; organic silicon compounds and hydrogen sulfide can be found in biogas produced from biomass wastes, due to their massive industrial use in synthetic product,such as cosmetics, detergents and paints.Siloxanes and hydrogen sulfide removal from biogas can be carried out by various methods (Ajhar et al., 2010); aim of the present work is to find a single practical andeconomic way to drastically and simultaneously reduce both hydrogen sulfide and the siloxanes concentration to less than 1 ppm. Some commercial activated carbons previously selected (Monteleoneet al., 2011) as being effective in hydrogen sulfide up taking have been tested in an adsorption measurement apparatus, by flowing both hydrogen sulphide and volatile siloxane (Decamethycyclopentasiloxane or D5) in a nitrogen stream,typically 25-300 ppm D5 over N2, through an clay minerals, Fe oxides and Silica; the adsorption process was analyzed by varying some experimental parameters (concentration, grain size, bed height). The best silica shows an adsorption capacity of 0.2 g D5 per gram of silica. The next thermo gravimetric analysis (TGA) confirms the capacity data obtained experimentally by the breakthrough curve tests.The capacity results depend on D5 and hydrogen sulphide concentrations. A regenerative silica process is then carried out byheating the silica bed up to 200 ° C and flushing out the adsorbed D5 and hydrogen sulphide samples in a nitrogen stream in athree step heating procedure up to 200 ° C. The adsorption capacity is observed to degrade after cyclingthe samples through several adsorption-desorption cycles.

  3. On-Surface Synthesis of Two-Dimensional Covalent Organic Structures versus Halogen-Bonded Self-Assembly: Competing Formation of Organic Nanoarchitectures.

    PubMed

    Peyrot, David; Silly, Fabien

    2016-05-24

    The competition between the on-surface synthesis of covalent nanoarchitectures and the self-assembly of star-shaped 1,3,5-Tris(4-iodophenyl)benzene molecules on Au(111) in vacuum is investigated using scanning tunneling microscopy above room temperature. The molecules form covalent polygonal nanoachitectures at the gold surface step edges and at the elbows of the gold reconstruction at low coverage. With coverage increasing two-dimensional halogen-bonded structures appear and grow on the surface terraces. Two different halogen-bonded nanoarchitectures are coexisting on the surface and hybrid covalent-halogen bonded structures are locally observed. At high coverage covalent nanoarchitectures are squeezed at the domain boundary of the halogen-bonded structures. The competitive growth between the covalent and halogen-bonded nanoarchitectures leads to formation of a two-layer film above one monolayer deposition. For this coverage, the covalent nanoarchitectures are propelled on top of the halogen-bonded first layer. These observations open up new opportunities for decoupling covalent nanoarchitectures from catalytically active and metal surfaces in vacuum. PMID:27158901

  4. On-Surface Synthesis of Two-Dimensional Covalent Organic Structures versus Halogen-Bonded Self-Assembly: Competing Formation of Organic Nanoarchitectures.

    PubMed

    Peyrot, David; Silly, Fabien

    2016-05-24

    The competition between the on-surface synthesis of covalent nanoarchitectures and the self-assembly of star-shaped 1,3,5-Tris(4-iodophenyl)benzene molecules on Au(111) in vacuum is investigated using scanning tunneling microscopy above room temperature. The molecules form covalent polygonal nanoachitectures at the gold surface step edges and at the elbows of the gold reconstruction at low coverage. With coverage increasing two-dimensional halogen-bonded structures appear and grow on the surface terraces. Two different halogen-bonded nanoarchitectures are coexisting on the surface and hybrid covalent-halogen bonded structures are locally observed. At high coverage covalent nanoarchitectures are squeezed at the domain boundary of the halogen-bonded structures. The competitive growth between the covalent and halogen-bonded nanoarchitectures leads to formation of a two-layer film above one monolayer deposition. For this coverage, the covalent nanoarchitectures are propelled on top of the halogen-bonded first layer. These observations open up new opportunities for decoupling covalent nanoarchitectures from catalytically active and metal surfaces in vacuum.

  5. Thermodynamics of the adsorption of organic compounds from the gas phase over a monolayer of liquid crystal formed on the surface of a carbon adsorbent

    NASA Astrophysics Data System (ADS)

    Kopytin, K. A.; Bykov, E. S.; Onuchak, L. A.; Kudryashov, S. Yu.; Kuvshinova, S. A.; Burmistrov, V. A.

    2015-04-01

    Inverse gas-solid chromatography is used to study the adsorption of vapors of organic compounds with different structures and polarities on a carbon adsorbent modified with a monolayer of 4-(3-hydroxypropyloxy)-4'-formylazobenzene (HPOFAB) polar LIQUID crystal. The resulting thermodynamic characteristics of adsorption on the original and modified adsorbents are compared. The effect the nature and structure of adsorbate molecules and the liquid crystal modifier have on the thermodynamic characteristics of adsorption is considered.

  6. Nonequilibrium Molecular Dynamics Simulations of Organic Friction Modifiers Adsorbed on Iron Oxide Surfaces.

    PubMed

    Ewen, James P; Gattinoni, Chiara; Morgan, Neal; Spikes, Hugh A; Dini, Daniele

    2016-05-10

    For the successful development and application of lubricants, a full understanding of the nanoscale behavior of complex tribological systems is required, but this is difficult to obtain experimentally. In this study, we use nonequilibrium molecular dynamics (NEMD) simulations to examine the atomistic structure and friction properties of commercially relevant organic friction modifier (OFM) monolayers adsorbed on iron oxide surfaces and lubricated by a thin, separating layer of hexadecane. Specifically, acid, amide, and glyceride OFMs, with saturated and Z-unsaturated hydrocarbon tail groups, are simulated at various surface coverages and sliding velocities. At low and medium coverage, the OFMs form liquidlike and amorphous monolayers, respectively, which are significantly interdigitated with the hexadecane lubricant, resulting in relatively high friction coefficients. At high coverage, solidlike monolayers are formed for all of the OFMs, which, during sliding, results in slip planes between well-defined OFM and hexadecane layers, yielding a marked reduction in the friction coefficient. When present at equal surface coverage, OFMs with saturated and Z-unsaturated tail groups are found to yield similar structure and friction behavior. OFMs with glyceride head groups yield significantly lower friction coefficients than amide and particularly carboxylic acid head groups. For all of the OFMs and coverages simulated, the friction coefficient is found to increase linearly with the logarithm of sliding velocity; however, the gradient of this increase depends on the coverage. The structure and friction details obtained from these simulations agree well with experimental results and also shed light on the relative tribological performance of these OFMs through nanoscale structural variations. This has important implications in terms of the applicability of NEMD to aid the development of new formulations to control friction.

  7. Dietary exposure to, and internal organ transfer of, selected halogenated organic compounds in birds eating fish from the Southern Baltic.

    PubMed

    Falkowska, Lucyna; Reindl, Andrzej R

    2015-01-01

    The aim of this study was to assess the effect of a marine diet on the accumulation, magnification, maternal transfer and detoxification of chlorinated organic pollutants on the highest trophic level in the Baltic Sea. Results showed that birds eating whole herring received the highest doses of herbicides > pesticides > fungicides > polychlorinated dibenzofurans (PCDFs) > polychlorinated dibenzo-para-dioxins (PCDDs). The toxicity of PCDD/Fs in a penguin's 24-h alimentary exposure was estimated at 7.77 ng TEQ-WHO2005. Among pesticides, the highest concentrations--both in fish and penguin tissue--were those of the pp-DDE isomer. In terms of herbicides, simazine and terbutrine were predominant. The majority of Persistent Organic Pollutants (POPs) underwent accumulation and magnification, and these factors were observed to increase with the birds' age. Guano was found to be an effective means of elimination for all of the studied xenobiotics. Maternal transfer of PCDD/Fs into eggs from internal tissues was most prominent for highly chlorinated dioxins and low chlorinated furans. PMID:26121018

  8. Development and characterization of activated hydrochars from orange peels as potential adsorbents for emerging organic contaminants.

    PubMed

    Fernandez, M E; Ledesma, B; Román, S; Bonelli, P R; Cukierman, A L

    2015-05-01

    Activated hydrochars obtained from the hydrothermal carbonization of orange peels (Citrus sinensis) followed by various thermochemical processing were assessed as adsorbents for emerging contaminants in water. Thermal activation under flows of CO2 or air as well as chemical activation with phosphoric acid were applied to the hydrochars. Their characteristics were analyzed and related to their ability to uptake three pharmaceuticals (diclofenac sodium, salicylic acid and flurbiprofen) considered as emerging contaminants. The hydrothermal carbonization and subsequent activations promoted substantial chemical transformations which affected the surface properties of the activated hydrochars; they exhibited specific surface areas ranging from 300 to ∼620 m(2)/g. Morphological characterization showed the development of coral-like microspheres dominating the surface of most hydrochars. Their ability to adsorb the three pharmaceuticals selected was found largely dependent on whether the molecules were ionized or in their neutral form and on the porosity developed by the new adsorbents. PMID:25742754

  9. Halogenation of microcapsule walls

    NASA Technical Reports Server (NTRS)

    Davis, T. R.; Schaab, C. K.; Scott, J. C.

    1972-01-01

    Procedure for halogenation of confining walls of both gelatin and gelatin-phenolic resin capsules is similar to that used for microencapsulation. Ten percent halogen content renders capsule wall nonburning; any higher content enhances flame-retardant properties of selected internal phase material. Halogenation decreases permeability of wall material to encapsulated materials.

  10. Inorganic-organic phase arrangement as a factor affecting gas-phase desulfurization on catalytic carbonaceous adsorbents.

    PubMed

    Ansari, Adil; Bandosz, Teresa J

    2005-08-15

    Dried sewage sludge was physically mixed with waste paper (paper-to-sludge ratios from 25% to 75%). To increase the catalytic activity, from 1% to 6% calcium hydroxide was added to the mixtures. Then the precursors were carbonized at 950 degrees C. The performance of materials as H2S adsorbents was tested using a home-developed dynamic breakthrough test. The samples, before and after the adsorption process, were characterized by adsorption of nitrogen, potentiometric titration, thermal analysis, XRF, and SEM. Differences in the performance were linked to the surface properties. Itwas found that mixing paper with sludge increases the amount of H2S adsorbed/oxidized in comparison with that adsorbed/oxidized by the adsorbents obtained from pure precursors (sludge or waste paper) and the capacity is comparable to those of the best activated carbons existing on the market. Although both sewage sludge and waste paper provide the catalytic centers for hydrogen sulfide oxidation, the dispersion of the catalyst and its location within accessible pores is an important factor. The presence of cellulose in the precursor mixture leads to the formation of a light macroporous char whose particles physically separate the inorganic catalytic phase of the sewage sludge origin, decreasing the density of the adsorbent and thus providing more space for storage of oxidation products. This, along with calcium, contributes to a significant increase in the capacity of the materials as hydrogen sulfide adsorbents. On their surface about 30 wt % H2S can be adsorbed, mainly as elemental sulfur or sulfates. The results demonstrate the importance of the composition and arrangement of inorganic/ organic phases for the removal of hydrogen sulfide. The interesting finding is that although some microporosity is necessary to increase the storage area for oxidation products, the carbonaceous phase does not need to be highly microporous. It is important that it provides space for deposition of sulfur

  11. Using specialized adsorbents for remediation

    SciTech Connect

    Hochmuth, D.P.; Grant, A.

    1995-11-01

    This paper describes two remediation case studies in which specialized adsorbents were used. In one case, the adsorbents were used to treat effluent from a soil vapor extraction system. In the other case, the adsorbents were used to treat air from a groundwater air stripper. The specialized adsorbents effectively removed volatile organic compounds from each air stream.

  12. Halogen lamp experiment, HALEX

    NASA Technical Reports Server (NTRS)

    Schmitt, G.; Stapelmann, J.

    1986-01-01

    The main purpose of the Halogen Lamp Experiment (HALEX) was to investigate the operation of a halogen lamp during an extended period in a microgravity environment and to prove its behavior in space. The Mirror Heating Facilities for Crystal Growth and Material Science Experiments in space relies on one or two halogen lamps as a furnace to melt the specimens. The HALEX aim is to verify: full power operation of a halogen lamp for a period of about 60 hours; achievement of about 10% of its terrestrial life span; and operation of the halogen lamp under conditions similar to furnace operation.

  13. Halogen bond involving hypervalent halogen: CSD search and theoretical study.

    PubMed

    Wang, Weizhou

    2011-08-25

    The Cambridge Structure Database search shows that there are over seventy crystal structures containing halogen bonds in which hypervalent halogens, not monovalent halogens as usual, behave as acceptors of electron density. The nature of the halogen bond involving hypervalent halogen has been investigated by using several theoretical methods with different basis sets. The HF calculations for the complexes studied cover most of their binding energies, which indicates the electrostatic nature of the halogen bond involving hypervalent halogen. The MP2 methods with medium basis sets fail to predict the relative strength of the halogen bond involving hypervalent halogen and the corresponding halogen bond involving monovalent halogen. Accurate computational results show that the halogen bond involving hypervalent halogen may be weaker than the corresponding halogen bond involving monovalent halogen even in the case that the hypervalent halogen is more positively charged than the monovalent halogen, the reasons of which were discussed in some detail. In comparison with the halogen bond involving monovalent halogen, the bonding characteristic and electron-density transfer of the halogen bond involving hypervalent halogen were also analyzed with the "atoms in molecules" theory and the natural bond orbital theory.

  14. Scanning tunneling microscopy studies of organic monolayers adsorbed on the rhodium(111) crystal surface

    SciTech Connect

    Cernota, Paul D.

    1999-08-01

    Scanning Tunneling Microscopy studies were carried out on ordered overlayers on the (111) surface of rhodium. These adsorbates include carbon monoxide (CO), cyclohexane, cyclohexene, 1,4-cyclohexadiene, para-xylene, and meta-xylene. Coadsorbate systems included: CO with ethylidyne, CO with para- and meta-xylene, and para-xylene with meta-xylene. In the case of CO, the structure of the low coverage (2x2) overlayer has been observed. The symmetry of the unit cell in this layer suggests that the CO is adsorbed in the 3-fold hollow sites. There were also two higher coverage surface structures with ({radical}7x{radical}7) unit cells. One of these is composed of trimers of CO and has three CO molecules in each unit cell. The other structure has an additional CO molecule, making a total of four. This extra CO sits on a top site.

  15. Analysis of halogen-specific TOX revisited: Method improvement and application.

    PubMed

    Kristiana, Ina; McDonald, Suzanne; Tan, Jace; Joll, Cynthia; Heitz, Anna

    2015-07-01

    A method was optimised and evaluated for the analysis of total organic halogen (TOX) in drinking water samples. It involved adsorption of organic halogen onto activated carbon, followed by combustion of the activated carbon and adsorbed material, absorption of the resulting hydrogen halide gases in an absorbing solution, and analysis of halide ions in the solution using an on-line ion chromatograph. Careful optimisation and validation of the method resulted in significant improvements compared to previously reported methods. Method detection limits were 5µgL(-1) for TOCl (as Cl(-)), 2µgL(-1) for TOBr (as Br(-)), and 2µgL(-1) for TOI (as I(-)). Interferences with TOI measurement occurred when iodide or iodate was present in the sample at concentrations at or above 100µgL(-1) and 500µgL(-1), respectively. In general, excellent method recoveries were determined for a wide range of model compounds. The method was used to investigate the formation of halogen-specific TOX through a water treatment plant and in laboratory-scale disinfection experiments. Up to 70% of bromide in the water was converted to TOBr following disinfection at the plant. In the disinfection experiments, TOI was preferentially formed in chloraminated samples, and trihalomethanes only constituted a small fraction (≤20%) of TOX, highlighting the significant proportion of halogenated organic DBPs that are not measured regularly. This is the first report of a comprehensive assessment of the key parameters influencing the efficiency and reliability of the analysis of halogen-specific TOX in drinking water with demonstration of its applications.

  16. Group additivity values for estimating the enthalpy of formation of organic compounds: an update and reappraisal. 2. C, H, N, O, S, and halogens.

    PubMed

    Holmes, John L; Aubry, Christiane

    2012-07-01

    This study extends a previous publication on group additivity values (GAVs) for the elements C, H, and O, to include the elements nitrogen, sulfur, and the halogens. The present state and utility of the Benson additivity schemes for estimating the enthalpy of formation (Δ(f)H(0)) of organic compounds are again described, extending them to include more elements. Old and new GAVs for a wide variety of compounds are provided and are revised where necessary. When new terms are proposed, or old ones are significantly altered, the rationale for so doing is presented. GAV derived ring strain values for benzene and pyridine indicate that the aromatic stabilization of each is essentially the same. As before, the thermochemical consequences of replacing one functional group by another are also shown, thus permitting quick shortcuts to the estimation of new Δ(f)H(0) values.

  17. Method for halogenating or radiohalogenating a chemical compound

    DOEpatents

    Kabalka, George W.

    2006-05-09

    A method for obtaining a halogenated organic compound, whereby an organotrifluoroborate compound is reacted with a halide ion in the presence of an oxidizing agent to produce the corresponding halogenated organic compound. The method may be used for producing radiohalogenated organic compounds.

  18. The Halogen Bond.

    PubMed

    Cavallo, Gabriella; Metrangolo, Pierangelo; Milani, Roberto; Pilati, Tullio; Priimagi, Arri; Resnati, Giuseppe; Terraneo, Giancarlo

    2016-02-24

    The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design. PMID:26812185

  19. The Halogen Bond

    PubMed Central

    2016-01-01

    The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design. PMID:26812185

  20. Qualitative analysis of halogenated organic contaminants in American eel by gas chromatography/time-of-flight mass spectrometry.

    PubMed

    Byer, Jonathan D; Pacepavicius, Grazina; Lebeuf, Michel; Brown, R Stephen; Backus, Sean; Hodson, Peter V; Alaee, Mehran

    2014-12-01

    Target compound analysis with scanning mass spectrometers such as quadrupole or magnetic sector instruments is used extensively in environmental chemistry because of the selectivity, sensitivity, and robustness. Yet, target compound analysis selectively ignores the majority of compounds present in a sample, especially in complex matrices like fish. In this study, time-of-flight mass spectrometry was used to screen for and identify halogenated compounds in American eels (Anguilla rostrata). Individual and then pooled eel samples were analysed using electron ionization and electron capture negative ionization (ECNI) modes. Eels were differentiated by principal component analysis of chemical profiles and were grouped corresponding to their capture location, all with a single instrument injection per sample. Bromine containing compounds were further investigated by taking advantage of the selectivity of ECNI by utilizing the Br(-) ion m/z 79 and 81. A total of 51 brominated compounds were detected and their identities were attempted by authentic standards, library searching, and/or chemical formula prediction based on accurate mass measurements. Several PBDEs were identified in the samples, and the majority of the non-PBDEs identified were bromophenols, bromoanisoles, and bromobenzenes. These classes of compounds are synthesized for use in flame retardant production either as intermediates or as final products. However, their occurrence in eels was most likely the result of metabolism or break-down products of high production volume flame retardants like polybrominated diphenyl ethers and bromophenoxy compounds.

  1. Influence of molecular structure and adsorbent properties on sorption of organic compounds to a temperature series of wood chars.

    PubMed

    Lattao, Charisma; Cao, Xiaoyan; Mao, Jingdong; Schmidt-Rohr, Klaus; Pignatello, Joseph J

    2014-05-01

    Chars from wildfires and soil amendments (biochars) are strong adsorbents that can impact the fate of organic compounds in soil, yet the effects of solute and adsorbent properties on sorption are poorly understood. We studied sorption of benzene, naphthalene, and 1,4-dinitrobenzene from water to a series of wood chars made anaerobically at different heat treatment temperatures (HTT) from 300 to 700 °C, and to graphite as a nonporous, unfunctionalized reference adsorbent. Peak suppression in the NMR spectrum by sorption of the paramagnetic relaxation probe TEMPO indicated that only a small fraction of char C atoms lie near sorption sites. Sorption intensity for all solutes maximized with the 500 °C char, but failed to trend regularly with N2 or CO2 surface area, micropore volume, mesopore volume, H/C ratio, O/C ratio, aromatic fused ring size, or HTT. A model relating sorption intensity to a weighted sum of microporosity and mesoporosity was more successful. Sorption isotherm linearity declined progressively with carbonization of the char. Application of a thermodynamic model incorporating solvent-water and char-graphite partition coefficients permitted for the first time quantification of steric (size exclusion in pores) and π-π electron donor-acceptor (EDA) free energy contributions, relative to benzene. Steric hindrance for naphthalene increases exponentially from 9 to 16 kJ/mol (∼ 1.6-2.9 log units of sorption coefficient) with the fraction of porosity in small micropores. π-π EDA interactions of dinitrobenzene contribute -17 to -19 kJ/mol (3-3.4 log units of sorption coefficient) to sorption on graphite, but less on chars. π-π EDA interaction of naphthalene on graphite is small (-2 to 2 kJ/mol). The results show that sorption is a complex function of char properties and solute molecular structure, and not very predictable on the basis of readily determined char properties.

  2. Influence of molecular structure and adsorbent properties on sorption of organic compounds to a temperature series of wood chars.

    PubMed

    Lattao, Charisma; Cao, Xiaoyan; Mao, Jingdong; Schmidt-Rohr, Klaus; Pignatello, Joseph J

    2014-05-01

    Chars from wildfires and soil amendments (biochars) are strong adsorbents that can impact the fate of organic compounds in soil, yet the effects of solute and adsorbent properties on sorption are poorly understood. We studied sorption of benzene, naphthalene, and 1,4-dinitrobenzene from water to a series of wood chars made anaerobically at different heat treatment temperatures (HTT) from 300 to 700 °C, and to graphite as a nonporous, unfunctionalized reference adsorbent. Peak suppression in the NMR spectrum by sorption of the paramagnetic relaxation probe TEMPO indicated that only a small fraction of char C atoms lie near sorption sites. Sorption intensity for all solutes maximized with the 500 °C char, but failed to trend regularly with N2 or CO2 surface area, micropore volume, mesopore volume, H/C ratio, O/C ratio, aromatic fused ring size, or HTT. A model relating sorption intensity to a weighted sum of microporosity and mesoporosity was more successful. Sorption isotherm linearity declined progressively with carbonization of the char. Application of a thermodynamic model incorporating solvent-water and char-graphite partition coefficients permitted for the first time quantification of steric (size exclusion in pores) and π-π electron donor-acceptor (EDA) free energy contributions, relative to benzene. Steric hindrance for naphthalene increases exponentially from 9 to 16 kJ/mol (∼ 1.6-2.9 log units of sorption coefficient) with the fraction of porosity in small micropores. π-π EDA interactions of dinitrobenzene contribute -17 to -19 kJ/mol (3-3.4 log units of sorption coefficient) to sorption on graphite, but less on chars. π-π EDA interaction of naphthalene on graphite is small (-2 to 2 kJ/mol). The results show that sorption is a complex function of char properties and solute molecular structure, and not very predictable on the basis of readily determined char properties. PMID:24758543

  3. A model to predict the adsorber thermal behavior during treatment of volatile organic compounds onto wet activated carbon.

    PubMed

    Pré, P; Delage, F; Le Cloirec, P

    2002-11-01

    A model for adsorption of volatile organic compounds (VOCs) onto a wet activated carbon bed was proposed in this study. This model accounts for temperature changes induced by the reversed and coupled mass-transfer processes of both organic species adsorption and water desorption. Indeed, it was experimentally pointed out that temperature rises, which result from the exothermal nature of the energetic interactions between the organic molecule and the activated carbon surface, are notably reduced when the adsorbent contains an initial moisture of approximately 10% in weight. Moreover, it was shown that water rate desorption was enhanced in the presence of organic vapor. This phenomenon may be explained by the displacement of sorbed water bythe organic molecules, owing to more intensive interactions with the activated carbon surface. The model proposed was elaborated from a previous comprehensive analysis of the diffusion mechanisms governing VOC adsorption at high concentrations onto a dry activated carbon bed. In a similar way, a theoretical approach was developed to model water desorption during drying of a wet activated carbon bed under pure flowing air. At last, a theoretical depiction of both competitive and reverse processes was outlined. The final model fits reasonably with experimental data relative to both breakthrough curves and thermal wave shape along the bed, even if local temperature change calculation may require some further improvement.

  4. Resin pellets from beaches of the Portuguese coast and adsorbed persistent organic pollutants

    NASA Astrophysics Data System (ADS)

    Antunes, J. C.; Frias, J. G. L.; Micaelo, A. C.; Sobral, P.

    2013-09-01

    The occurrence of stranded plastic marine debris along the Portuguese coastline was investigated. Number of items m-2 and size range of resin pellets were recorded, corresponding to 53% of total marine debris collected items. In addition, concentrations of adsorbed persistent bioaccumulative and toxic chemicals (PBTC) were determined, PAH - polycyclic aromatic hydrocarbons; PCB - polychlorinated biphenyls and DDT - dichlorodiphenyltrichloroethane. Matosinhos (Mt) and Vieira de Leiria (VL) presented the highest number of items m-2 (362 and 332, respectively). Resin pellets with 4 mm diameter were the most abundant (50%). Contaminants concentration was variable. PAH concentrations recorded values between 53 and 44800 ng g-1, PCB ranged from 2 to 223 ng g-1 and DDT between 0.42 and 41 ng g-1. In general, aged and black pellets recorded higher concentrations for all contaminants. Matosinhos (Mt), Vieira de Leiria (VL) and Sines (Si), near industrial areas and port facilities, were the most contaminated beaches. Research efforts are needed to assess the points of entry of industrial plastic pellets in order to take action and minimize impacts on the ecosystems, in particular, points of transfer during transportation from plastic manufacturers to plastic converters should be identified and controlled so that virgin pellets are contained and will not enter rivers and be carried to the oceans where they can remain for a long time and travel great distances.

  5. Preparation of magnetic metal organic frameworks adsorbent modified with mercapto groups for the extraction and analysis of lead in food samples by flame atomic absorption spectrometry.

    PubMed

    Wang, Yang; Chen, Huanhuan; Tang, Jie; Ye, Guiqin; Ge, Huali; Hu, Xiaoya

    2015-08-15

    A novel magnetic metal organic frameworks adsorbent modified with mercapto groups was synthesized and developed for extraction and spectrophotometric determination of trace lead. The adsorbent was characterized by Fourier transforms infrared spectrometer, X-ray diffraction, scanning electron microscopy and vibrating sample magnetometry. The results indicated the adsorbents exhibited high adsorption capacities for lead due to the chelation mechanism between metal cations and mercapto groups. Meanwhile, the lead sorption onto the adsorbents could be easily separated from aqueous solution using a magnetic separation method. Under the optimal conditions, a linear calibration curve in the range from 1 to 20 μg L(-1) was achieved with an enrichment factor of 100. The limits of detection and quantitation for lead were found to be 0.29 and 0.97 μg L(-1), respectively. The developed method was successfully applied to the determination of trace amounts of lead in food samples and certified reference material with satisfactory results. PMID:25794739

  6. Preparation of magnetic metal organic frameworks adsorbent modified with mercapto groups for the extraction and analysis of lead in food samples by flame atomic absorption spectrometry.

    PubMed

    Wang, Yang; Chen, Huanhuan; Tang, Jie; Ye, Guiqin; Ge, Huali; Hu, Xiaoya

    2015-08-15

    A novel magnetic metal organic frameworks adsorbent modified with mercapto groups was synthesized and developed for extraction and spectrophotometric determination of trace lead. The adsorbent was characterized by Fourier transforms infrared spectrometer, X-ray diffraction, scanning electron microscopy and vibrating sample magnetometry. The results indicated the adsorbents exhibited high adsorption capacities for lead due to the chelation mechanism between metal cations and mercapto groups. Meanwhile, the lead sorption onto the adsorbents could be easily separated from aqueous solution using a magnetic separation method. Under the optimal conditions, a linear calibration curve in the range from 1 to 20 μg L(-1) was achieved with an enrichment factor of 100. The limits of detection and quantitation for lead were found to be 0.29 and 0.97 μg L(-1), respectively. The developed method was successfully applied to the determination of trace amounts of lead in food samples and certified reference material with satisfactory results.

  7. Comparison of nutshell granular activated carbons to commercial adsorbents for the purge-and-trap gas chromatographic analysis of volatile organic compounds.

    PubMed

    Wartelle, L H; Marshall, W E; Toles, C A; Johns, M M

    2000-05-26

    Granular activated carbons (GACs) made from agricultural by-products were investigated as adsorbents for short path thermal desorption gas chromatographic analysis of selected polar and nonpolar organic compounds. GACs made from macadamia nut, black walnut and hazelnut shells were compared to four commercially available adsorbents, namely, Tenax TA, Carboxen 569, Carbosieve SIII and coconut charcoal for their properties in purge-and-trap analysis. Adsorption values and breakthrough volumes were calculated for compounds from C3 and C6-C10. GACs derived from macadamia nut shells were found to adsorb and desorb between 80% (benzene) and 277% (ethylbenzene) more acetone (C3), benzene (C6), toluene (C7), ethyl- (C8), n-propyl- (C9), or sec.-butylbenzenes (C10) purged from water at the 100 ppb level than the commercial adsorbents tested. PMID:10893033

  8. Removal of hexenuronic acid by xylanase to reduce adsorbable organic halides formation in chlorine dioxide bleaching of bagasse pulp.

    PubMed

    Nie, Shuangxi; Wang, Shuangfei; Qin, Chengrong; Yao, Shuangquan; Ebonka, Johnbull Friday; Song, Xueping; Li, Kecheng

    2015-11-01

    Xylanase-aided chlorine dioxide bleaching of bagasse pulp was investigated. The pulp was pretreated with xylanase and followed a chlorine dioxide bleaching stage. The ATR-FTIR and XPS were employed to determine the surface chemistry of the control pulp, xylanase treated and chlorine dioxide treated pulps. The hexenuronic acid (HexA) could obviously be reduced after xylanase pretreatment, and the adsorbable organic halides (AOX) were reduced after chlorine dioxide bleaching. Compared to the control pulp, AOX could be reduced by 21.4-26.6% with xylanase treatment. Chlorine dioxide demand could be reduced by 12.5-22% to achieve the same brightness. The ATR-FTIR and XPS results showed that lignin and hemicellulose (mainly HexA) were the main source for AOX formation. Xylanase pretreatment could remove HexA and expose more lignin, which decreased the chlorine dioxide demand and thus reduced formation of AOX. PMID:26263004

  9. Prediction of capacity factors for aqueous organic solutes adsorbed on a porous acrylic resin

    USGS Publications Warehouse

    Thurman, E.M.

    1978-01-01

    The capacity factors of 20 aromatic, allphatic, and allcycllc organic solutes with carboxyl, hydroxyl, amine, and methyl functional groups were determined on Amberlite XAD-8, a porous acrylic resin. The logarithm of the capacity factor, k???, correlated inversely with the logarithm of the aqueous molar solubility with significance of less than 0.001. The log k???-log solubility relationship may be used to predict the capacity of any organic solute for XAD-8 using only the solubility of the solute. The prediction is useful as a guide for determining the proper ratio of sample to column size In the preconcentration of organic solutes from water. The inverse relationship of solubility and capacity is due to the unfavorable entropy of solution of organic solutes which affects both solubility and sorption.

  10. Selective pressurized liquid extraction technique for halogenated organic pollutants in marine mammal blubber: a lipid-rich matrix.

    PubMed

    Robinson, E M; Jia, M; Trumble, S J; Usenko, S

    2015-03-13

    Analytical methods for unique and rare samples, such as marine mammal tissue, strive to reduce opportunities for analyte loss and contamination. Historically, analytical methodologies for marine mammal tissues required an extraction followed by multiple cleanup and concentration steps. These steps increase the opportunity for analyte loss and sample contamination. Selective pressurized liquid extractions (SPLE; an analytical technique that combines PLE with in-cell adsorbent cleanup) have the potential to reduce and/or eliminate the number of steps. A SPLE method was developed for the simultaneous extraction of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) from bowhead whale blubber. This SPLE utilized acidic silica with a fat-to-fat retainer ratio of 0.02 as well as eliminated post-extraction cleanup steps, such as size-exclusion chromatography step. In addition, neutral silica was placed beneath the acidic silica as an acid buffer, thereby preventing acid from contaminating the extraction system. Analysis was performed using gas chromatography/mass spectrometry in electron capture negative ionization mode. PBDE, PCB and OCP triplicate recoveries averaged 84±1%, 83±3%, and 76±11%, respectively. Overall, measurements of NIST Whale Blubber SRM 1945 were within±30% of certified values. PBDEs were measured for the first time in bowhead whale blubber; average concentrations ranged from 0.2 to 1.4 ng g(-1) wet weight (ww). Average OCPs and PCBs concentrations ranged from 0.4 to 37 ng g(-1)ww and 0.1 to 3.0 ng g(-1)ww, respectively, which were within one order of magnitude lower than those previously reported in bowhead whale blubber.

  11. AMBIENT LEVEL VOLATILE ORGANIC COMPOUND (VOC) MONITORING USING SOLID ADSORBANTS - RECENT U.S. EPA STUDIES

    EPA Science Inventory

    Ambient air spiked with 1-10 ppbv concentrations of 41 toxic volatile organic compounds (VOCs) listed in U.S. Environmental Protection Agency (EPA) Compendium Method TO-14A was monitored using solid sorbents for sample collection and a Varian Saturn 2000 ion trap mass spectrome...

  12. Liquid chromatography enantioseparations of halogenated compounds on polysaccharide-based chiral stationary phases: role of halogen substituents in molecular recognition.

    PubMed

    Peluso, Paola; Mamane, Victor; Cossu, Sergio

    2015-10-01

    Halogenated chiral molecules have become important in several fields of science, industry, and society as drugs, natural compounds, agrochemicals, environmental pollutants, synthetic products, and chiral supports. Meanwhile, the perception of the halogen moiety in organic compounds and its role in recognition processes changed. Indeed, the recognition of the halogen bond as an intermolecular interaction occurring when the halogen acts as a Lewis acid had a strong impact, particularly in crystal engineering and medicinal chemistry. Due to this renewed interest in the potentialities of chiral organohalogens, here we focus on selected recent applications dealing with enantioseparations of halogenated compounds on polysaccharide-based chiral stationary phases (CSPs), widely used in liquid chromatography (LC). In particular, recently the first case of halogen bonding-driven high-performance LC (HPLC) enantioseparation was reported on a cellulose-based CSP. Along with enantioseparations performed under conventional HPLC, representative applications using supercritical fluid chromatography (SFC) are reported.

  13. Biomolecular halogen bonds.

    PubMed

    Ho, P Shing

    2015-01-01

    Halogens are atypical elements in biology, but are common as substituents in ligands, including thyroid hormones and inhibitors, which bind specifically to proteins and nucleic acids. The short-range, stabilizing interactions of halogens - now seen as relatively common in biology - conform generally to halogen bonds characterized in small molecule systems and as described by the σ-hole model. The unique properties of biomolecular halogen bonds (BXBs), particularly in their geometric and energetic relationship to classic hydrogen bonds, make them potentially powerful tools for inhibitor design and molecular engineering. This chapter reviews the current research on BXBs, focusing on experimental studies on their structure-energy relationships, how these studies inform the development of computational methods to model BXBs, and considers how BXBs can be applied to the rational design of more effective inhibitors against therapeutic targets and of new biological-based materials.

  14. Fluorous Metal Organic Frameworks as Superhydrophobic Adsorbents for Oil Spill Cleanup and Hydrocarbons Storage

    SciTech Connect

    Yang, Chi; Mather, Qian; Wang, Xiaoping; Kaipa, Ushasree; Nesterov, Vladimir; Venero, Augustin; Omary, Mohammad A

    2011-01-01

    We demonstrate that fluorous metal-organic frameworks (FMOFs) are highly hydrophobic porous materials with a high capacity and affinity to C{sub 6}-C{sub 8} hydrocarbons of oil components. FMOF-1 exhibits reversible adsorption with a high capacity for n-hexane, cyclohexane, benzene, toluene, and p-xylene, with no detectable water adsorption even at near 100% relative humidity, drastically outperforming activated carbon and zeolite porous materials. FMOF-2, obtained from annealing FMOF-1, shows enlarged cages and channels with double toluene adsorption vs FMOF-1 based on crystal structures. The results suggest great promise for FMOFs in applications such as removal of organic pollutants from oil spills or ambient humid air, hydrocarbon storage and transportation, water purification, etc. under practical working conditions.

  15. Halogens in the troposphere.

    PubMed

    Finlayson-Pitts, Barbara J

    2010-02-01

    Although inorganic halogen gases are believed to play key roles in the chemistry of the lower atmosphere, many of them have not yet been detected or measured in ambient air. This article describes some of the current techniques and future needs for inorganic halogens in air. (To listen to a podcast about this feature, please go to the Analytical Chemistry multimedia page at pubs.acs.org/page/ancham/audio/index.html.).

  16. Parametrization of the SCC-DFTB Method for Halogens.

    PubMed

    Kubař, Tomáš; Bodrog, Zoltán; Gaus, Michael; Köhler, Christof; Aradi, Bálint; Frauenheim, Thomas; Elstner, Marcus

    2013-07-01

    Parametrization of the approximative DFT method SCC-DFTB for halogen elements is presented. The new parameter set is intended to describe halogenated organic as well as inorganic molecules, and it is compatible with the established parametrization of SCC-DFTB for carbon, hydrogen, oxygen, and nitrogen. The performance of the parameter set is tested on a representative set of molecules and discussed.

  17. Reduction of ferrihydrite with adsorbed and coprecipitated organic matter: microbial reduction by Geobacter bremensis vs. abiotic reduction by Na-dithionite

    NASA Astrophysics Data System (ADS)

    Eusterhues, K.; Hädrich, A.; Neidhardt, J.; Küsel, K.; Keller, T. F.; Jandt, K. D.; Totsche, K. U.

    2014-09-01

    Ferrihydrite is a widespread poorly crystalline Fe oxide which becomes easily coated by natural organic matter in the environment. This mineral-bound organic matter entirely changes the mineral surface properties and therefore the reactivity of the original mineral. Here, we investigated 2-line ferrihydrite, ferrihydrite with adsorbed organic matter, and ferrihydrite coprecipitated with organic matter for microbial and abiotic reduction of Fe(III). Ferrihydrite-organic matter associations with different organic matter loadings were reduced either by Geobacter bremensis or abiotically by Na-dithionite. Both types of experiments showed decreasing initial Fe-reduction rates and decreasing degrees of reduction with increasing amounts of mineral-bound organic matter. At similar organic matter loadings, coprecipitated ferrihydrites were more reactive than ferrihydrites with adsorbed organic matter. The difference can be explained by the smaller crystal size and poor crystallinity of such coprecipitates. At small organic matter loadings the poor crystallinity of coprecipitates led to even faster Fe-reduction rates than found for pure ferrihydrite. The amount of mineral-bound organic matter also affected the formation of secondary minerals: goethite was only found after reduction of organic matter-free ferrihydrite and siderite was only detected when ferrihydrites with relatively low amounts of mineral-bound organic matter were reduced. We conclude that direct contact of G. bremensis to the Fe oxide mineral surface was inhibited by attached organic matter. Consequently, mineral-bound organic matter shall be taken into account as a factor in slowing down reductive dissolution.

  18. Recycling of Organic Waste Sludge by Hydrothermal Dry Steam Aiming for Adsorbent

    NASA Astrophysics Data System (ADS)

    Hoshikawa, Hisahiro; Hayakawa, Tomoki; Yamasaki, Nakamichi

    2006-05-01

    Global warming becomes more serious problem today. We have to develop new technology for new energy or fixation of carbon dioxide. Biomass is considered to be one of new energies. Methane fermentation is a method to make methane from biomass, such as garbage and fecal of farm animals, by methane fermentation bacteria. It has a problem, however, that bacteria are deactivated due to ammonia, which is made by itself. And much methane fermentation residue is incinerated. Therefore recycling methane fermentation residue is important for effective use of biomass. We research hydrothermal process. Dry steam means unsaturated vapor, we call. It demands a temperature less than 400 °C. And it is expected to accelerate dehydration effect, decompose and extract the organic matter, and make porous material. Thus, we try to apply the dry steam to recycling of organic waste sludge aiming for absorbent. Experiments were conducted at 250-350 °C in nitrogen atmosphere. The carbon products are analyzed by CHNS elemental analysis, and Thermogravimetry. The extractives are analyzed by gas chromatograph.

  19. Impact of Molecular Organization on Exciton Diffusion in Photosensitive Single-Crystal Halogenated Perylenediimides Charge Transfer Interfaces.

    PubMed

    Pinto, Rui M; Gouveia, Wilson; Maçôas, Ermelinda M S; Santos, Isabel C; Raja, Sebastian; Baleizão, Carlos; Alves, Helena

    2015-12-23

    The efficiency of organic photodetectors and optoelectronic devices is strongly limited by exciton diffusion, in particular for acceptor materials. Although mechanisms for exciton diffusion are well established, their correlation to molecular organization in real systems has received far less attention. In this report, organic single-crystals interfaces were probed with wavelength-dependent photocurrent spectroscopy and their crystal structure resolved using X-ray diffraction. All systems present a dynamic photoresponse, faster than 500 ms, up to 650 nm. A relationship between molecular organization and favorable exciton diffusion in substituted butyl-perylenediimides (PDIB) is established. This is demonstrated by a set of PDIBs with different intra- and interstack distances and short contacts and their impact on photoresponse. Given the short packing distances between PDIs cores along the same stacking direction (3.4-3.7 Å), and across parallel stacks (2.5 Å), singlet exciton in these PDIBs can follow both Förster and Dexter exciton diffusion, with the Dexter-type mechanism assuming special relevance for interstack exciton diffusion. Yet, the response is maximized in substituted PDIBs, where a 2D percolation network is formed through strong interstack contacts, allowing for PDIBs primary excitons to reach with great efficiency the splitting interface with crystalline rubrene. The importance of short contacts and molecular distances, which is often overlooked as a parameter to consider and optimize when choosing materials for excitonic devices, is emphasized. PMID:26599347

  20. Femtomagnetism in graphene induced by core level excitation of organic adsorbates

    PubMed Central

    Ravikumar, Abhilash; Baby, Anu; Lin, He; Brivio, Gian Paolo; Fratesi, Guido

    2016-01-01

    We predict the induction or suppression of magnetism in the valence shell of physisorbed and chemisorbed organic molecules on graphene occurring on the femtosecond time scale as a result of core level excitations. For physisorbed molecules, where the interaction with graphene is dominated by van der Waals forces and the system is non-magnetic in the ground state, numerical simulations based on density functional theory show that the valence electrons relax towards a spin polarized configuration upon excitation of a core-level electron. The magnetism depends on efficient electron transfer from graphene on the femtosecond time scale. On the other hand, when graphene is covalently functionalized, the system is magnetic in the ground state showing two spin dependent mid gap states localized around the adsorption site. At variance with the physisorbed case upon core-level excitation, the LUMO of the molecule and the mid gap states of graphene hybridize and the relaxed valence shell is not magnetic anymore. PMID:27089847

  1. A Water-Stable Cationic Metal-Organic Framework as a Dual Adsorbent of Oxoanion Pollutants.

    PubMed

    Desai, Aamod V; Manna, Biplab; Karmakar, Avishek; Sahu, Amit; Ghosh, Sujit K

    2016-06-27

    A three-dimensional water-stable cationic metal-organic framework (MOF) pillared by a neutral ligand and with Ni(II)  metal nodes has been synthesized employing a rational design approach. Owing to the ordered arrangement of the uncoordinated tetrahedral sulfate (SO4 (2-) ) ions in the channels, the compound has been employed for aqueous-phase ion-exchange applications. The compound exhibits rapid and colorimetric aqueous-phase capture of environmentally toxic oxoanions (with similar geometries) in a selective manner. This system is the first example of a MOF-based system which absorbs both dichromate (Cr2 O7 (2-) ) and permanganate (MnO4 (-) ) ions, with the latter acting as a model for the radioactive contaminant pertechnetate (TcO4 (-) ). PMID:26855323

  2. Aluminium fumarate metal-organic framework: A super adsorbent for fluoride from water.

    PubMed

    Karmakar, Sankha; Dechnik, Janina; Janiak, Christoph; De, Sirshendu

    2016-02-13

    Potential of aluminium fumarate metal organic framework (MOF) for fluoride removal from groundwater has been explored in this work. The laboratory produced MOF exhibited characteristics similar to the commercial version. MOF was found to be micro-porous with surface area of 1156 m(2)/g and average pore size 17Å. Scanning electron micrograph of the AlFu MOF showed minute pores and texture was completely different from either of the parent materials. Change in the composition of AlFu MOF after fluoride adsorption was evident from powder X-ray diffraction analysis. Thermal stability of the AlFu MOF up to 700K was established by thermo-gravimetric analysis. Incorporation of fluoride phase after adsorption was confirmed by X-ray fluorescence analysis. As observed from FTIR study, hydroxyl ions in AlFu MOF were substituted by fluoride. 0.75 g/l AlFu MOF was good enough for complete removal of 30 mg/l fluoride concentration in feed solution. The maximum adsorption capacity for fluoride was 600, 550, 504 and 431 mg/g, respectively, at 293, 303, 313 and 333K. PMID:26513559

  3. Volatile halogenated hydrocarbons in foods

    SciTech Connect

    Miyahara, Makoto; Toyoda, Masatake; Saito, Yukio

    1995-02-01

    Volatile halogenated organic compounds were determined in foods. Statistical treatment of the data for 13 sampled from 20 families living in suburban Tokyo (Saitama prefecture) indicated that the foods were contaminated by water pollution and/or substances introduced by the process of food production. Butter and margarine were contaminated by chlorinated ethylene, ethane, and related compounds released by dry cleaning and other operations. Soybean sprouts and tofu (soybean curd) contained chloroform and related trihalomethanes absorbed during the production process. 27 refs., 6 figs., 5 tabs.

  4. Adsorbent phosphates

    NASA Technical Reports Server (NTRS)

    Watanabe, S.

    1983-01-01

    An adsorbent which uses as its primary ingredient phosphoric acid salts of zirconium or titanium is presented. Production methods are discussed and several examples are detailed. Measurements of separating characteristics of some gases using the salts are given.

  5. Speciation of trace metals in natural waters: the influence of an adsorbed layer of natural organic matter (NOM) on voltammetric behaviour of copper.

    PubMed

    Louis, Yoann; Cmuk, Petra; Omanović, Dario; Garnier, Cédric; Lenoble, Véronique; Mounier, Stéphane; Pizeta, Ivanka

    2008-01-01

    The influence of an adsorbed layer of the natural organic matter (NOM) on voltammetric behaviour of copper on a mercury drop electrode in natural water samples was studied. The adsorption of NOM strongly affects the differential pulse anodic stripping voltammogram (DPASV) of copper, leading to its distortion. Phase sensitive ac voltammetry confirmed that desorption of adsorbed NOM occurs in general at accumulation potentials more negative than -1.4V. Accordingly, an application of negative potential (-1.6V) for a very short time at the end of the accumulation time (1% of total accumulation time) to remove the adsorbed NOM was introduced in the measuring procedure. Using this protocol, a well-resolved peak without interferences was obtained. It was shown that stripping chronopotentiogram of copper (SCP) in the depletive mode is influenced by the adsorbed layer in the same manner as DPASV. The influence of the adsorbed NOM on pseudopolarographic measurements of copper and on determination of copper complexing capacity (CuCC) was demonstrated. A shift of the peak potential and the change of the half-peak width on the accumulation potential (for pseudopolarography) and on copper concentration in solution (for CuCC) were observed. By applying a desorption step these effects vanished, yielding different final results.

  6. Degradation of halogenated aliphatic compounds by Xanthobacter autotrophicus GJ10.

    PubMed Central

    Janssen, D B; Scheper, A; Dijkhuizen, L; Witholt, B

    1985-01-01

    A bacterium that is able to utilize a number of halogenated short-chain hydrocarbons and halogenated carboxylic acids as sole carbon source for growth was identified as a strain of Xanthobacter autotrophicus. The organism constitutively produces two different dehalogenases. One enzyme is specific for halogenated alkanes, whereas the other, which is more heat stable and has a higher pH optimum, is specific for halogenated carboxylic acids. Haloalkanes were hydrolyzed in cell extracts to produce alcohols and halide ions, and a route for the metabolism of 1,2-dichlorethane is proposed. Both dehalogenases show a broad substrate specificity, allowing the degradation of bromine- and chlorine-substituted organic compounds. The results show that X. autotrophicus may play a role in the degradation of organochlorine compounds and that hydrolytic dehalogenases may be involved in the microbial metabolism of short-chain halogenated hydrocarbons in microorganisms. Images PMID:3994371

  7. Distribution of selected halogenated organic compounds among suspended particulate, colloid, and aqueous phases in the Mississippi River and major tributaries

    USGS Publications Warehouse

    Rostad, C.E.; Daniel, S.R.

    2007-01-01

    Suspended particulate, colloid, and aqueous phases were separated and analyzed to determine spatial variation of specific organic compound transport associated with each phase in a dynamic river system. Sixteen sites along the Mississippi River and its major tributaries were sampled at low-flow conditions to maximize the possibility of equilibrium. Across the solubility range studied, the proportion transported by each phase depended on the compound solubility, with more water-soluble compounds (dacthal, trifluralin) transported predominantly in the aqueous phase and less-water soluble compounds (polychlorinated biphenyls, chlordane-related compounds) transported predominantly in the particulate and colloid phases. ?? 2007 Springer Science+Business Media, LLC.

  8. Preparation of a new adsorbent from activated carbon and carbon nanofiber (AC/CNF) for manufacturing organic-vacbpour respirator cartridge.

    PubMed

    Jahangiri, Mehdi; Adl, Javad; Shahtaheri, Seyyed Jamaleddin; Rashidi, Alimorad; Ghorbanali, Amir; Kakooe, Hossein; Forushani, Abbas Rahimi; Ganjali, Mohammad Reza

    2013-01-26

    In this study a composite of activated carbon and carbon nanofiber (AC/CNF) was prepared to improve the performance of activated carbon (AC) for adsorption of volatile organic compounds (VOCs) and its utilization for respirator cartridges. Activated carbon was impregnated with a nickel nitrate catalyst precursor and carbon nanofibers (CNF) were deposited directly on the AC surface using catalytic chemical vapor deposition. Deposited CNFs on catalyst particles in AC micropores, were activated by CO2 to recover the surface area and micropores. Surface and textural characterizations of the prepared composites were investigated using Brunauer, Emmett and Teller's (BET) technique and electron microscopy respectively. Prepared composite adsorbent was tested for benzene, toluene and xylene (BTX) adsorption and then employed in an organic respirator cartridge in granular form. Adsorption studies were conducted by passing air samples through the adsorbents in a glass column at an adjustable flow rate. Finally, any adsorbed species not retained by the adsorbents in the column were trapped in a charcoal sorbent tube and analyzed by gas chromatography. CNFs with a very thin diameter of about 10-20 nm were formed uniformly on the AC/CNF. The breakthrough time for cartridges prepared with CO2 activated AC/CNF was 117 minutes which are significantly longer than for those cartridges prepared with walnut shell- based activated carbon with the same weight of adsorbents. This study showed that a granular form CO2 activated AC/CNF composite could be a very effective alternate adsorbent for respirator cartridges due to its larger adsorption capacities and lower weight.

  9. Preparation of a new adsorbent from activated carbon and carbon nanofiber (AC/CNF) for manufacturing organic-vacbpour respirator cartridge

    PubMed Central

    2013-01-01

    In this study a composite of activated carbon and carbon nanofiber (AC/CNF) was prepared to improve the performance of activated carbon (AC) for adsorption of volatile organic compounds (VOCs) and its utilization for respirator cartridges. Activated carbon was impregnated with a nickel nitrate catalyst precursor and carbon nanofibers (CNF) were deposited directly on the AC surface using catalytic chemical vapor deposition. Deposited CNFs on catalyst particles in AC micropores, were activated by CO2 to recover the surface area and micropores. Surface and textural characterizations of the prepared composites were investigated using Brunauer, Emmett and Teller’s (BET) technique and electron microscopy respectively. Prepared composite adsorbent was tested for benzene, toluene and xylene (BTX) adsorption and then employed in an organic respirator cartridge in granular form. Adsorption studies were conducted by passing air samples through the adsorbents in a glass column at an adjustable flow rate. Finally, any adsorbed species not retained by the adsorbents in the column were trapped in a charcoal sorbent tube and analyzed by gas chromatography. CNFs with a very thin diameter of about 10-20 nm were formed uniformly on the AC/CNF. The breakthrough time for cartridges prepared with CO2 activated AC/CNF was 117 minutes which are significantly longer than for those cartridges prepared with walnut shell- based activated carbon with the same weight of adsorbents. This study showed that a granular form CO2 activated AC/CNF composite could be a very effective alternate adsorbent for respirator cartridges due to its larger adsorption capacities and lower weight. PMID:23369424

  10. Organic halogenated contaminants in mother-fetus pairs of harbor seals (Phoca vitulina richardii) from Alaska, 2000–2002

    PubMed Central

    Wang, Dongli; Atkinson, Shannon; Hoover-Miller, Anne; Shelver, Weilin L.; Li, Qing X.

    2012-01-01

    This study measured organochlorine pesticides (OCPs) including hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB), heptachlor and dichlorodiphenyltrichloroethanes (DDTs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs) and polybrominated diphenyl ethers (PBDEs) in tissues of six mother–fetus pairs of harbor seals that were hunted for subsistence in Alaska waters of the Northern Pacific Ocean. These data suggest that significant amounts of these contaminants were transferred from mother harbor seals to fetuses during pregnancy and distributed among fetal organs. The tissue distribution depended on the chemical groups, the specific compounds in the groups and the target organs. Concentration profiles of ΣOCPs, ΣPCBs, ΣPCNs and ΣPBDEs were remarkably similar among maternal blubber, liver, and placenta, fetal blubber, and liver (except for HCHs), possibly indicating that the placenta did not serve as a barrier for all of the compounds analyzed. DDTs, HCB, HCHs, PCBs and PBDEs could penetrate the placenta and accumulate in the blubber of the fetus in utero, while HCHs, PCBs and PBDEs penetrated the placenta and accumulated more preferentially in the fetal liver than in the fetal brain in comparison with DDTs and HCB. Heptachlor and PCNs penetrated the placenta and accumulated in the fetal liver and brain instead of fetal blubber. Similar maternal transfer trends for OCPs, PCBs, PCNs and PBDEs were shown by fetal to maternal (FM) blubber ratios and FM liver ratios. Prenatal transfer of these toxic contaminants from mothers to fetus presumably through the placenta may pose health risks to the fetus during development. PMID:22579763

  11. Use of industrial by-products and natural media to adsorb nutrients, metals and organic carbon from drinking water.

    PubMed

    Grace, Maebh A; Healy, Mark G; Clifford, Eoghan

    2015-06-15

    Filtration technology is well established in the water sector but is limited by inability to remove targeted contaminants, found in surface and groundwater, which can be damaging to human health. This study optimises the design of filters by examining the efficacy of seven media (fly ash, bottom ash, Bayer residue, granular blast furnace slag (GBS), pyritic fill, granular activated carbon (GAC) and zeolite), to adsorb nitrate, ammonium, total organic carbon (TOC), aluminium, copper (Cu) and phosphorus. Each medium and contaminant was modelled to a Langmuir, Freundlich or Temkin adsorption isotherm, and the impact of pH and temperature (ranging from 10 °C to 29 °C) on their performance was quantified. As retention time within water filters is important in contaminant removal, kinetic studies were carried out to observe the adsorption behaviour over a 24h period. Fly ash and Bayer residue had good TOC, nutrient and Cu adsorption capacity. Granular blast furnace slag and pyritic fill, previously un-investigated in water treatment, showed adsorption potential for all contaminants. In general, pH or temperature adjustment was not necessary to achieve effective adsorption. Kinetic studies showed that at least 60% of adsorption had occurred after 8h for all media. These media show potential for use in a multifunctional water treatment unit for the targeted treatment of specific contaminants.

  12. Preparation and characterization of humic acid-carbon hybrid materials as adsorbents for organic micro-pollutants.

    PubMed

    Radwan, Emad K; Abdel Ghafar, Hany H; Moursy, Ahmed S; Langford, Cooper H; Bedair, Ahmed H; Achari, Gopal

    2015-08-01

    The present work involves the preparation of novel adsorbent materials by the insolubilization and hybridization of humic acid (HA) with carbon. The prepared materials were characterized by N2 adsorption, elemental analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, solid-state (13)C cross polarization magic angle spinning nuclear magnetic resonance, and low-field nuclear magnetic resonance (NMR) relaxometry on wetted samples. The water solubility of these materials and the lack of effect of oxidants were also confirmed. With this background, the adsorption capacities toward phenol, 2,4,6-tricholrophenol, and atrazine were evaluated, using these as model compounds for organic micropollutants of concern in water. Experimental results show that the prepared materials are mesoporous and have a higher surface area than humic acid and even than the porous carbon in the case of carbon coating. They retain the basic features of the starting materials with lowered functional group content. Moreover, there are interesting new features. NMR relaxometry shows that equilibration of water uptake is very fast, making use in water simple. They have higher adsorption capacities than the pure materials, and they can be applied under a wide range of environmental conditions. PMID:25874433

  13. EFFECTS OF COVAPORS ON ADSORPTION RATE COEFFICIENTS OF ORGANIC VAPORS ADSORBED ONTO ACTIVATED CARBON FROM FLOWING AIR

    SciTech Connect

    G. WOOD

    2000-12-01

    Published breakthrough time, adsorption rate, and capacity data for components of organic vapor mixtures adsorbed from flows through fixed activated carbon beds have been analyzed. Capacities (as stoichiometric centers of constant pattern breakthrough curves) yielded stoichiometric times {tau}, which are useful for determining elution orders of mixture components. We also calculated adsorption rate coefficients k{sub v} of the Wheeler (or, more general Reaction Kinetic) breakthrough curve equation, when not reported, from breakthrough times and {tau}. Ninety-five k{sub v} (in mixture)/ k{sub v} (single vapor) ratios at similar vapor concentrations were calculated and averaged for elution order categories. For 43 first-eluting vapors the average ratio (1.07) was statistically no different (0.21 standard deviation) than unity, so that we recommend using the single-vapor k{sub v} for such. Forty-seven second-eluting vapor ratios averaged 0.85 (0.24 standard deviation), also not significantly different from unity; however, other evidence and considerations lead us recommend using k{sub v} (in mixture) = 0.85 k{sub v} (single vapor). Five third- and fourth-eluting vapors gave an average of 0.56 (0.16 standard deviation) for a recommended k{sub v} (in mixture) = 0.56 k{sub v} (single vapor) for such.

  14. Preparation and characterization of humic acid-carbon hybrid materials as adsorbents for organic micro-pollutants.

    PubMed

    Radwan, Emad K; Abdel Ghafar, Hany H; Moursy, Ahmed S; Langford, Cooper H; Bedair, Ahmed H; Achari, Gopal

    2015-08-01

    The present work involves the preparation of novel adsorbent materials by the insolubilization and hybridization of humic acid (HA) with carbon. The prepared materials were characterized by N2 adsorption, elemental analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, solid-state (13)C cross polarization magic angle spinning nuclear magnetic resonance, and low-field nuclear magnetic resonance (NMR) relaxometry on wetted samples. The water solubility of these materials and the lack of effect of oxidants were also confirmed. With this background, the adsorption capacities toward phenol, 2,4,6-tricholrophenol, and atrazine were evaluated, using these as model compounds for organic micropollutants of concern in water. Experimental results show that the prepared materials are mesoporous and have a higher surface area than humic acid and even than the porous carbon in the case of carbon coating. They retain the basic features of the starting materials with lowered functional group content. Moreover, there are interesting new features. NMR relaxometry shows that equilibration of water uptake is very fast, making use in water simple. They have higher adsorption capacities than the pure materials, and they can be applied under a wide range of environmental conditions.

  15. Determination of benzenic and halogenated volatile organic compounds in animal-derived food products by one-dimensional and comprehensive two-dimensional gas chromatography-mass spectrometry.

    PubMed

    Ratel, Jérémy; Engel, Erwan

    2009-11-01

    Animal-derived products are particularly vulnerable to contamination by volatile organic compounds (VOCs). These lipophilic substances, which are generated by an increasing number of sources, are easily transferred to the atmosphere, water, soil, and plants. They are ingested by livestock and become trapped in the fat fraction of edible animal tissues. The aim of this work was to determine the occurrence, risk for human health and entryways of benzenic and halogenated VOCs (BHVOCs) in meat products, milks and sea foods using gas chromatography- mass spectrometry (GC-MS) techniques. In the first part, the occurrence and levels of the BHVOCs in animal products were studied. One muscle and three fat tissues were analysed by GC-Quad/MS in 16 lambs. Of 52 BHVOCs identified, 46 were found in the three fat tissues and 29 in all four tissues, confirming that VOCs are widely disseminated in the body. Twenty-six BHVOCs were quantified in fat tissues, and risk for consumer health was assessed for six of these compounds regulated by the US Environmental Protection Agency (EPA). The BHVOC content was found to be consistent with previous reports and was below the maximum contaminant levels set by the EPA. In the second part, the performance of GCxGC-TOF/MS for comprehensively detecting BHVOCs and showing their entryways in animal-derived food chains was assessed. Meat, milk and oysters were analysed by GC-Quad/MS and GCxGC-TOF/MS. For all these products, at least a 7-fold increase in the contaminants detected was achieved with the GCxGC-TOF/MS technique. The results showed that the production surroundings, through animal feeding or geographical location, were key determinants of BHVOC composition in the animal products. PMID:19782373

  16. Formation of Bromate and Halogenated Disinfection Byproducts during Chlorination of Bromide-Containing Waters in the Presence of Dissolved Organic Matter and CuO.

    PubMed

    Liu, Chao; Croué, Jean-Philippe

    2016-01-01

    Previous studies showed that significant bromate (BrO3(-)) can be formed via the CuO-catalyzed disproportionation of hypobromous acid (HOBr) pathway. In this study, the influence of CuO on the formation of BrO3(-) and halogenated disinfection byproducts (DBPs) (e.g., trihalomethanes, THMs and haloacetic acids, HAAs) during chlorination of six dissolved organic matter (DOM) isolates was investigated. Only in the presence of slow reacting DOM (from treated Colorado River water, i.e., CRW-BF-HPO), significant BrO3(-) formation is observed, which competes with bromination of DOM (i.e., THM and HAA formation). Reactions between HOBr and 12 model compounds in the presence of CuO indicates that CuO-catalyzed HOBr disproportionation is completely inhibited by fast reacting phenols, while it predominates in the presence of practically unreactive compounds (acetone, butanol, propionic, and butyric acids). In the presence of slow reacting di- and tricarboxylic acids (oxalic, malonic, succinic, and citric acids), BrO3(-) formation varies, depending on its competition with bromoform and dibromoacetic acid formation (i.e., bromination pathway). The latter pathway can be enhanced by CuO due to the activation of HOBr. Therefore, increasing CuO dose (0-0.2 g L(-1)) in a reaction system containing chlorine, bromide, and CRW-BF-HPO enhances the formation of BrO3(-), total THMs and HAAs. Factors including pH and initial reactant concentrations influence the DBP formation. These novel findings have implications for elevated DBP formation during transportation of chlorinated waters in copper-containing distribution systems.

  17. Formation of Bromate and Halogenated Disinfection Byproducts during Chlorination of Bromide-Containing Waters in the Presence of Dissolved Organic Matter and CuO.

    PubMed

    Liu, Chao; Croué, Jean-Philippe

    2016-01-01

    Previous studies showed that significant bromate (BrO3(-)) can be formed via the CuO-catalyzed disproportionation of hypobromous acid (HOBr) pathway. In this study, the influence of CuO on the formation of BrO3(-) and halogenated disinfection byproducts (DBPs) (e.g., trihalomethanes, THMs and haloacetic acids, HAAs) during chlorination of six dissolved organic matter (DOM) isolates was investigated. Only in the presence of slow reacting DOM (from treated Colorado River water, i.e., CRW-BF-HPO), significant BrO3(-) formation is observed, which competes with bromination of DOM (i.e., THM and HAA formation). Reactions between HOBr and 12 model compounds in the presence of CuO indicates that CuO-catalyzed HOBr disproportionation is completely inhibited by fast reacting phenols, while it predominates in the presence of practically unreactive compounds (acetone, butanol, propionic, and butyric acids). In the presence of slow reacting di- and tricarboxylic acids (oxalic, malonic, succinic, and citric acids), BrO3(-) formation varies, depending on its competition with bromoform and dibromoacetic acid formation (i.e., bromination pathway). The latter pathway can be enhanced by CuO due to the activation of HOBr. Therefore, increasing CuO dose (0-0.2 g L(-1)) in a reaction system containing chlorine, bromide, and CRW-BF-HPO enhances the formation of BrO3(-), total THMs and HAAs. Factors including pH and initial reactant concentrations influence the DBP formation. These novel findings have implications for elevated DBP formation during transportation of chlorinated waters in copper-containing distribution systems. PMID:26630351

  18. Modern and historical fluxes of halogenated organic contaminants to a lake in the Canadian arctic, as determined from annually laminated sediment cores.

    PubMed

    Stern, G A; Braekevelt, E; Helm, P A; Bidleman, T F; Outridge, P M; Lockhart, W L; McNeeley, R; Rosenberg, B; Ikonomou, M G; Hamilton, P; Tomy, G T; Wilkinson, P

    2005-04-15

    Two annually laminated cores collected from Lake DV09 on Devon Island in May 1999 were dated using 210Pb and 137Cs, and analyzed for a variety of halogenated organic contaminants (HOCs), including polychlorinated biphenyls (PCBs), organochlorine pesticides, short-chain polychlorinated n-alkanes (sPCAs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and polybrominated diphenyl ethers (PBDEs). Dry weight HOC concentrations in Lake DV09 sediments were generally similar to other remote Arctic lakes. Maximum HOC fluxes often agreed well with production maxima, although many compound groups exhibited maxima at or near the sediment surface, much later than peak production. The lower than expected HOC concentrations in older sediment slices may be due to anaerobic degradation and possibly to dilution resulting from a temporary increase in sedimentation rate observed between the mid-1960s and 1970s. Indeed, temporal trends were more readily apparent for those compound classes when anaerobic metabolites were also analyzed, such as for DDT and toxaphene. However, it is postulated here for the first time that the maximum or increasing HOC surface fluxes observed for many of the major compound classes in DV09 sediments may be influenced by climate variation and the resulting increase in algal primary productivity which could drive an increasing rate of HOC scavenging from the water column. Both the fraction (F(TC)) and enantiomer fraction (EF) of trans-chlordane (TC) decreased significantly between 1957 and 1997, suggesting that recent inputs to the lake are from weathered chlordane sources. PCDD/Fs showed a change in sources from pentachlorophenol (PeCP) in the 1950s and 1960s to combustion sources into the 1990s. Improvements in combustion technology may be responsible for the reducing the proportion of TCDF relative to OCDD in the most recent slice.

  19. Halogenated solvent remediation

    DOEpatents

    Sorenson, Kent S.

    2004-08-31

    Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. A preferred method includes adding a composition to the ground water wherein the composition is an electron donor for microbe-mediated reductive dehalogenation of the halogenated solvents and enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative compositions effective in these methods include surfactants such as C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof. Especially preferred compositions for use in these methods include lactic acid, salts of lactic acid, such as sodium lactate, lactate esters, and mixtures thereof. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the composition.

  20. Halogenated solvent remediation

    DOEpatents

    Sorenson, Jr., Kent S.

    2008-11-11

    Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. An illustrative method includes adding an electron donor for microbe-mediated anaerobic reductive dehalogenation of the halogenated solvents, which electron donor enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative electron donors include C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof, of which lactic acid, salts of lactic acid--such as sodium lactate, lactate esters, and mixtures thereof are particularly illustrative. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the electron donor.

  1. Mechanism of formation of humus coatings on mineral surfaces 3. Composition of adsorbed organic acids from compost leachate on alumina by solid-state 13C NMR

    USGS Publications Warehouse

    Wershaw, R. L.; Llaguno, E.C.; Leenheer, J.A.

    1996-01-01

    The adsorption of compost leachate DOC on alumina is used as a model for elucidation of the mechanism of formation of natural organic coatings on hydrous metal oxide surfaces in soils and sediments. Compost leachate DOC is composed mainly of organic acid molecules. The solid-state 13C NMR spectra of these organic acids indicate that they are very similar in composition to aquatic humic substances. Changes in the solid-state 13C NMR spectra of compost leachate DOC fractions adsorbed on alumina indicate that the DOC molecules are most likely adsorbed on metal oxide surfaces through a combination of polar and hydrophobic interaction mechanisms. This combination of polar and hydrophobic mechanism leads to the formation of bilayer coatings of the leachate molecules on the oxide surfaces.

  2. Cytotoxicity of halogenated graphenes

    NASA Astrophysics Data System (ADS)

    Teo, Wei Zhe; Khim Chng, Elaine Lay; Sofer, Zdeněk; Pumera, Martin

    2013-12-01

    Graphene and its family of derivatives possess unique and remarkable physicochemical properties which make them valuable materials for applications in many areas like electronics, energy storage and biomedicine. In response to the possibility of its large-scale manufacturing as commercial products in the future, an investigation was conducted to determine the cytotoxicity of one particular family of graphene derivatives, the halogenated graphenes, for the first time. Halogenated graphenes were prepared through thermal exfoliation of graphite oxide in gaseous chlorine, bromine or iodine atmospheres to yield chlorine- (TRGO-Cl), bromine- (TRGO-Br) and iodine-doped graphene (TRGO-I) respectively. 24 h exposure of human lung carcinoma epithelial cells (A549) to the three halogenated graphenes and subsequent cell viability assessments using methylthiazolyldiphenyl-tetrazolium bromide (MTT) and water-soluble tetrazolium salt (WST-8) assays revealed that all the halogenated graphenes examined are rather cytotoxic at the concentrations tested (3.125 μg mL-1 to 200 μg mL-1) and the effects are dose-dependent, with TRGO-Cl reducing the cell viability to as low as 25.7% at the maximum concentration of 200 μg mL-1. Their levels of cytotoxicity can be arranged in the order of TRGO-Cl > TRGO-Br > TRGO-I, and it is suggested that the amount of halogen present in the graphene material is the determining factor for the observed trend. Control experiments were carried out to test for possible nanomaterial-induced interference as a consequence of reaction between the halogenated graphenes and the viability markers (MTT/WST-8 reagent) or binding of the formazan products under cell-free conditions. The data obtained eliminate the probability of significant influence by these interferents as the change in the normalized percentage of formazan formed is relatively small and thorough washings were performed prior to the viability assessments to reduce the amount of halogenated

  3. Cytotoxicity of halogenated graphenes.

    PubMed

    Teo, Wei Zhe; Chng, Elaine Lay Khim; Sofer, Zdeněk; Pumera, Martin

    2014-01-21

    Graphene and its family of derivatives possess unique and remarkable physicochemical properties which make them valuable materials for applications in many areas like electronics, energy storage and biomedicine. In response to the possibility of its large-scale manufacturing as commercial products in the future, an investigation was conducted to determine the cytotoxicity of one particular family of graphene derivatives, the halogenated graphenes, for the first time. Halogenated graphenes were prepared through thermal exfoliation of graphite oxide in gaseous chlorine, bromine or iodine atmospheres to yield chlorine- (TRGO-Cl), bromine- (TRGO-Br) and iodine-doped graphene (TRGO-I) respectively. 24 h exposure of human lung carcinoma epithelial cells (A549) to the three halogenated graphenes and subsequent cell viability assessments using methylthiazolyldiphenyl-tetrazolium bromide (MTT) and water-soluble tetrazolium salt (WST-8) assays revealed that all the halogenated graphenes examined are rather cytotoxic at the concentrations tested (3.125 μg mL(-1) to 200 μg mL(-1)) and the effects are dose-dependent, with TRGO-Cl reducing the cell viability to as low as 25.7% at the maximum concentration of 200 μg mL(-1). Their levels of cytotoxicity can be arranged in the order of TRGO-Cl > TRGO-Br > TRGO-I, and it is suggested that the amount of halogen present in the graphene material is the determining factor for the observed trend. Control experiments were carried out to test for possible nanomaterial-induced interference as a consequence of reaction between the halogenated graphenes and the viability markers (MTT/WST-8 reagent) or binding of the formazan products under cell-free conditions. The data obtained eliminate the probability of significant influence by these interferents as the change in the normalized percentage of formazan formed is relatively small and thorough washings were performed prior to the viability assessments to reduce the amount of halogenated

  4. Halogen bonds in crystal engineering: like hydrogen bonds yet different.

    PubMed

    Mukherjee, Arijit; Tothadi, Srinu; Desiraju, Gautam R

    2014-08-19

    used in the design of ternary cocrystals. Structural modularity in which an entire crystal structure is defined as a combination of modules is rationalized on the basis of the intermediate strength of a halogen bond. The specific directionality of the halogen bond makes it a good tool to achieve orthogonality in molecular crystals. Mechanical properties can be tuned systematically by varying these orthogonally oriented halogen···halogen interactions. In a further development, halogen bonds are shown to play a systematic role in organization of LSAMs (long range synthon aufbau module), which are bigger structural units containing multiple synthons. With a formal definition in place, this may be the right time to look at differences between halogen bonds and hydrogen bonds and exploit them in more subtle ways in crystal engineering.

  5. Evaluation and Application of a Solid Adsorbent Method for Monitoring Exposure to Volatile Organic Compounds from Oil and Gas Operations.

    NASA Astrophysics Data System (ADS)

    Smith, K. R.; Helmig, D.; Thompson, C. R.; Wang, W.; Terrell, R. M.; Lewis, A. C.

    2014-12-01

    Residential communities are being increasingly impacted by emissions from oil and gas development and this has driven the need for simple, effective, and low-cost methods for air quality monitoring. Primary emissions from oil and gas production consist of volatile organic compounds (VOCs) ranging from the short chain alkanes and alkenes to aromatic and semi-volatile species; many of these are a concern from both an air quality and public health viewpoint, as they can lead to local ozone pollution and increased risk of cancer or respiratory illness. The fate of hydrocarbons once in the atmosphere is ultimately oxidation through to CO2 and water, adding to the greenhouse gas burden. Measurement techniques that are capable of identifying and quantifying the full range of primary emissions of concern are required to assess community exposure to air toxics and to better inform residents, as well as local and state legislators. Here, we present evaluation of a low-cost air monitoring technique using stainless steel diffusion cartridges containing multiple solid adsorbents. Over the course of a three-month period in summer of 2014, cartridges were deployed at five monitoring sites located around Boulder County in the Northern Colorado Front Range, and exposed to ambient air for periods of up to four days along with concurrent sampling using stainless steel SUMMA canisters. Samples collected with both methods were subsequently analyzed for VOCs by GC-FID and the results were compared to determine the accuracy and precision of the diffusion cartridge method. Results of this evaluation show that the diffusion cartridge method has the potential to be a simple and low-cost solution for widespread exposure monitoring in communities near oil and gas development regions. Such measurements may also provide supporting evidence on wider effects on greenhouse gas emissions from oil and gas development operations.

  6. Halogenation of cobalt dicarbollide

    DOEpatents

    Hurlburt, P.K.; Abney, K.D.; Kinkead, S.A.

    1997-05-20

    A method for selectively adding chlorine, bromine, or iodine to cobalt dicarbollide anions by means of electrophilic substitution reactions. Halogens are added only to the B10 and B10{prime} positions of the anion. The process involves use of hypohalous acid or N-halosuccinimide or gaseous chlorine in the presence of iron. 1 fig.

  7. Halogenation of cobalt dicarbollide

    DOEpatents

    Hurlburt, Paul K.; Abney, Kent D.; Kinkead, Scott A.

    1997-01-01

    A method for selectively adding chlorine, bromine, or iodine to cobalt dicarbollide anions by means of electrophilic substitution reactions. Halogens are added only to the B10 and B10' positions of the anion. The process involves use of hypohalous acid or N-halosuccinimide or gaseous chlorine in the presence of iron.

  8. Halogens in CM Chondrites

    NASA Astrophysics Data System (ADS)

    Menard, J. M.; Caron, B.; Jambon, A.; Michel, A.; Villemant, B.

    2013-09-01

    We set up an extraction line of halogens (fluorine, chlorine) by pyrohydrolysis with 50 mg of rock. We analyzed 7 CM2 chondrites found in Antarctica and found that the Cl content of meteorites with an intact fusion crust is higher than those without.

  9. Species-specific bioaccumulation of halogenated organic pollutants and their metabolites in fish serum from an e-waste site, South China.

    PubMed

    Zeng, Yan-Hong; Luo, Xiao-Jun; Zheng, Xiao-Bo; Tang, Bin; Wu, Jiang-Ping; Mai, Bi-Xian

    2014-10-01

    Halogenated organic pollutants (HOPs)-including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenylethers (PBDEs), polybromobiphenyls (PBBs), dechlorane plus (DP), tetrabromobisphenol A (TBBPA), and hexabromocyclododecanes (HBCDs) as well as PCB metabolites (methylsulfone [MeSO2-]) and hydroxylated (OH-) PCBs and OH-PBDEs-were determined in the serum of mud carp and northern snakehead from an electronic-waste (e-waste) site in South China. The average concentrations (mean ± SD) of ΣPCBs, ΣPBDEs, ΣOCPs, ΣPBBs, ΣTBBPA, ΣHBCDs, and ΣDP were 1410 ± 324, 70 ± 20, 3.0 ± 0.4, 2.8 ± 0.8, 1.6 ± 0.4, 1.0 ± 0.2, and 0.3 ± 0.03 ng/g wet weight (ww) in mud carp and 6430 ± 781, 468 ± 49, 22.4 ± 1.1, 7.0 ± 0.6, 2.9 ± 2.3, 5.5 ± 1.1, and 4.6 ± 0.6 ng/g ww in northern snakehead, respectively. MeSO2-PCBs, OH-PCBs, and OH-PBDEs were detected at a total concentration of 0.44 ± 0.03 and 9.7 ± 0.3 ng/g ww in mud carp and northern snakehead, respectively. The congener profiles of PCBs, PBDEs, OH/MeSO2-PCBs, and OH-PBDEs were found to be significantly different between the two fish species, possibly as a result of species-specific bioaccumulation and/or metabolism of the HOPs. Chirality of ten PCB congeners and α-HBCD, as well as the f anti values of DP in the serum samples, supported the species-specific biotransformation of HOPs. Furthermore, the presence of covaried and counter-varied enantiomeric fractions of PCBs between the two fish species indicated species- and congener-specific enantiomer enrichment of PCBs. PMID:24859045

  10. Historical trends in occurrence and atmospheric inputs of halogenated volatile organic compounds in untreated ground water used as a source of drinking water.

    PubMed

    Shapiro, Stephanie Dunkle; Busenberg, Eurybiades; Focazio, Michael J; Plummer, L Niel

    2004-04-01

    Analyses of samples of untreated ground water from 413 community-, non-community- (such as restaurants), and domestic-supply wells throughout the US were used to determine the frequency of detection of halogenated volatile organic compounds (VOCs) in drinking-water sources. The VOC data were compiled from archived chromatograms of samples analyzed originally for chlorofluorocarbons (CFCs) by purge-and-trap gas chromatography with an electron-capture detector (GC-ECD). Concentrations of the VOCs could not be ascertained because standards were not routinely analyzed for VOCs other than trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113). Nevertheless, the peak areas associated with the elution times of other VOCs on the chromatograms can be classified qualitatively to assess concentrations at a detection limit on the order of parts per quadrillion. Three or more VOCs were detected in 100% (percent) of the chromatograms, and 77.2% of the samples contained 10 or more VOCs. The maximum number of VOCs detected in any sample was 24. Modeled ground-water residence times, determined from concentrations of CFC-12, were used to assess historical trends in the cumulative occurrence of all VOCs detected in this analysis, as well as the occurrence of individual VOCs, such as CFC-11, carbon tetrachloride (CCl(4)), chloroform and tetrachloroethene (PCE). The detection frequency for all of the VOCs detected has remained relatively constant from approximately 1940 to 2000; however, the magnitude of the peak areas on the chromatograms for the VOCs in the water samples has increased from 1940 to 2000. For CFC-11, CCl(4), chloroform and PCE, small peaks decrease from 1940 to 2000, and large peaks increase from 1940 to 2000. The increase in peak areas on the chromatograms from analyses of more recently recharged water is consistent with reported increases in atmospheric concentrations of the VOCs. Approximately 44

  11. Species-specific bioaccumulation of halogenated organic pollutants and their metabolites in fish serum from an e-waste site, South China.

    PubMed

    Zeng, Yan-Hong; Luo, Xiao-Jun; Zheng, Xiao-Bo; Tang, Bin; Wu, Jiang-Ping; Mai, Bi-Xian

    2014-10-01

    Halogenated organic pollutants (HOPs)-including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenylethers (PBDEs), polybromobiphenyls (PBBs), dechlorane plus (DP), tetrabromobisphenol A (TBBPA), and hexabromocyclododecanes (HBCDs) as well as PCB metabolites (methylsulfone [MeSO2-]) and hydroxylated (OH-) PCBs and OH-PBDEs-were determined in the serum of mud carp and northern snakehead from an electronic-waste (e-waste) site in South China. The average concentrations (mean ± SD) of ΣPCBs, ΣPBDEs, ΣOCPs, ΣPBBs, ΣTBBPA, ΣHBCDs, and ΣDP were 1410 ± 324, 70 ± 20, 3.0 ± 0.4, 2.8 ± 0.8, 1.6 ± 0.4, 1.0 ± 0.2, and 0.3 ± 0.03 ng/g wet weight (ww) in mud carp and 6430 ± 781, 468 ± 49, 22.4 ± 1.1, 7.0 ± 0.6, 2.9 ± 2.3, 5.5 ± 1.1, and 4.6 ± 0.6 ng/g ww in northern snakehead, respectively. MeSO2-PCBs, OH-PCBs, and OH-PBDEs were detected at a total concentration of 0.44 ± 0.03 and 9.7 ± 0.3 ng/g ww in mud carp and northern snakehead, respectively. The congener profiles of PCBs, PBDEs, OH/MeSO2-PCBs, and OH-PBDEs were found to be significantly different between the two fish species, possibly as a result of species-specific bioaccumulation and/or metabolism of the HOPs. Chirality of ten PCB congeners and α-HBCD, as well as the f anti values of DP in the serum samples, supported the species-specific biotransformation of HOPs. Furthermore, the presence of covaried and counter-varied enantiomeric fractions of PCBs between the two fish species indicated species- and congener-specific enantiomer enrichment of PCBs.

  12. Adsorption of halogenated aliphatic contaminants by graphene nanomaterials.

    PubMed

    Zhou, Yang; Apul, Onur Guven; Karanfil, Tanju

    2015-08-01

    In this study, adsorption of ten environmentally halogenated aliphatic synthetic organic compounds (SOCs) by a pristine graphene nanosheet (GNS) and a reduced graphene oxide (rGO) was examined, and their adsorption behaviors were compared with those of a single-walled carbon nanotube (SWCNT) and a granular activated carbon (GAC). In addition, the impacts of background water components (i.e., natural organic matter (NOM), ionic strength (IS) and pH) on the SOC adsorption behavior were investigated. The results indicated HD3000 and SWCNT with higher microporous volumes exhibited higher adsorption capacities for the selected aliphatic SOCs than graphenes, demonstrating microporosity of carbonaceous adsorbents played an important role in the adsorption. Analysis of adsorption isotherms demonstrated that hydrophobic interactions were the dominant contributor to the adsorption of aliphatic SOCs by graphenes. However, π-π electron donor-acceptor and van der Waals interactions are likely the additional mechanisms contributing to the adsorption of aliphatic SOCs on graphenes. Among the three background solution components examined, NOM showed the most influential effect on adsorption of the selected aliphatic SOCs, while pH and ionic strength had a negligible effects. The NOM competition on aliphatic adsorption was less pronounced on graphenes than SWCNT. Overall, in terms of adsorption capacities, graphenes tested in this study did not exhibit a major advantage over SWCNT and GAC for the adsorption of aliphatic SOCs.

  13. Tropospheric Halogen Chemistry

    NASA Astrophysics Data System (ADS)

    von Glasow, R.; Crutzen, P. J.

    2003-12-01

    Halogens are very reactive chemicals that are known to play an important role in anthropogenic stratospheric ozone depletion chemistry, first recognized by Molina and Rowland (1974). However, they also affect the chemistry of the troposphere. They are of special interest because they are involved in many reaction cycles that can affect the oxidation power of the atmosphere indirectly by influencing the main oxidants O3 and its photolysis product OH and directly, e.g., by reactions of the Cl radical with hydrocarbons (e.g., CH4).Already by the middle of the nineteenth century, Marchand (1852) reported the presence of bromine and iodine in rain and other natural waters. He also mentions the benefits of iodine in drinking water through the prevention of goitres and cretinism. In a prophetic monograph "Air and Rain: The Beginnings of a Chemical Climatology," Smith (1872) describes measurements of chloride in rain water, which he states to originate partly from the oceans by a process that he compares with the bursting of "soap bubbles" which produces "small vehicles" that transfer small spray droplets of seawater to the air. From deviations of the sulfate-to-chloride ratio in coastal rain compared to seawater, Smith concluded that chemical processes occur once the particles are airborne.For almost a century thereafter, however, atmospheric halogens received little attention. One exception was the work by Cauer (1939), who reported that iodine pollution has been significant in Western and Central Europe due to the inefficient burning of seaweed, causing mean gas phase atmospheric concentrations as high as or greater than 0.5 μg m-3. In his classical textbook Air Chemistry and Radioactivity, Junge (1963) devoted less than three pages to halogen gas phase chemistry, discussing chlorine and iodine. As reviewed by Eriksson (1959a, b), the main atmospheric source of halogens is sea salt, derived from the bursting of bubbles of air which are produced by ocean waves and other

  14. Remediation of Organic and Inorganic Arsenic Contaminated Groundwater using a Nonocrystalline TiO2 Based Adsorbent

    SciTech Connect

    Jing, C.; Meng, X; Calvache, E; Jiang, G

    2009-01-01

    A nanocrystalline TiO2-based adsorbent was evaluated for the simultaneous removal of As(V), As(III), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) in contaminated groundwater. Batch experimental results show that As adsorption followed pseudo-second order rate kinetics. The competitive adsorption was described with the charge distribution multi-site surface complexation model (CD-MUSIC). The groundwater containing an average of 329 ?g L-1 As(III), 246 ?g L-1 As(V), 151 ?g L-1 MMA, and 202 ?g L-1 DMA was continuously passed through a TiO2 filter at an empty bed contact time of 6 min for 4 months. Approximately 11 000, 14 000, and 9900 bed volumes of water had been treated before the As(III), As(V), and MMA concentration in the effluent increased to 10 ?g L-1. However, very little DMA was removed. The EXAFS results demonstrate the existence of a bidentate binuclear As(V) surface complex on spent adsorbent, indicating the oxidation of adsorbed As(III). A nanocrystalline TiO2-based adsorbent could be used for the simultaneous removal of As(V), As(III), MMA, and DMA in contaminated groundwater.

  15. [Halogens: discoveries of pharmacists].

    PubMed

    Rabiant, J

    2008-01-01

    The discovery of four halogens is due to pharmacists. Chlorine was isolated by Carl Wilhem Scheele, a Swedish who was first an assistant to a pharmacist, then a pharmacist himself. Bernard Courtois, a pharmacist under the First Empire, the son of a saltpetre worker isolated iodine in I811, after a modification of the ancestral production protocol of potassium nitrate, which is the major component of the gunpowder: he replaced wood ashes by varech ashes which are less expensive. Antoine Jerôme Balard was still an assistant in chemistry and physics when he discovered bromine in the residues of the salt marshes. He became soon after a pharmacist and started a famous career as then he became Professor in the College de France and General Inspector of Higher Education. The last halogen: fluorine was isolated by Henri Moissan who received the Nobel Prize of Chemistry. The discovery will be the subject of our next communication.

  16. Reference spectra of important adsorbed organic and inorganic phosphate binding forms for soil P speciation using synchrotron-based K-edge XANES spectroscopy.

    PubMed

    Prietzel, Jörg; Harrington, Gertraud; Häusler, Werner; Heister, Katja; Werner, Florian; Klysubun, Wantana

    2016-03-01

    Direct speciation of soil phosphorus (P) by linear combination fitting (LCF) of P K-edge XANES spectra requires a standard set of spectra representing all major P species supposed to be present in the investigated soil. Here, available spectra of free- and cation-bound inositol hexakisphosphate (IHP), representing organic P, and of Fe, Al and Ca phosphate minerals are supplemented with spectra of adsorbed P binding forms. First, various soil constituents assumed to be potentially relevant for P sorption were compared with respect to their retention efficiency for orthophosphate and IHP at P levels typical for soils. Then, P K-edge XANES spectra for orthophosphate and IHP retained by the most relevant constituents were acquired. The spectra were compared with each other as well as with spectra of Ca, Al or Fe orthophosphate and IHP precipitates. Orthophosphate and IHP were retained particularly efficiently by ferrihydrite, boehmite, Al-saturated montmorillonite and Al-saturated soil organic matter (SOM), but far less efficiently by hematite, Ca-saturated montmorillonite and Ca-saturated SOM. P retention by dolomite was negligible. Calcite retained a large portion of the applied IHP, but no orthophosphate. The respective P K-edge XANES spectra of orthophosphate and IHP adsorbed to ferrihydrite, boehmite, Al-saturated montmorillonite and Al-saturated SOM differ from each other. They also are different from the spectra of amorphous FePO4, amorphous or crystalline AlPO4, Ca phosphates and free IHP. Inclusion of reference spectra of orthophosphate as well as IHP adsorbed to P-retaining soil minerals in addition to spectra of free or cation-bound IHP, AlPO4, FePO4 and Ca phosphate minerals in linear combination fitting exercises results in improved fit quality and a more realistic soil P speciation. A standard set of P K-edge XANES spectra of the most relevant adsorbed P binding forms in soils is presented. PMID:26917141

  17. Iron Catalyzed Halogenation Processes in Saline Soils

    NASA Astrophysics Data System (ADS)

    Tubbesing, C.; Lippe, S.; Kullik, V.; Hauck, L.; Krause, T.; Keppler, F.; Schoeler, H. F.

    2014-12-01

    Within upcoming years the extent of salt deserts and salt lakes will probably increase due to climate change. It is known that volatile organic halogens (VOX) are released from saline soils and thus higher emissions from these environments are likely expected in the future. The origin of some organohalogens is not reasonably constrained by established natural halogenation processes. Therefore detailed biogeochemical investigations of these environments are necessary to identify the specific halogenation pathways. Redox-sensitive metals like iron are already known as triggers of chemical reactions via so called Fenton and Fenton-like reactions requiring H2O2 which is photochemically produced in water. In this study we collected soil samples from several salt lakes in Western Australia with pH values ranging from 2 to 8. The high pH variability was considered useful to study the impact of iron mobility and availability on halogenation processes. Iron was found to mainly occur as oxides and sulfides within the alkaline soils and acidic soils, respectively. All soil samples were lyophilised and finely ground prior to incubation at 40 °C for 24 h in aqueous solutions. Formation of volatile organic compounds (VOC) and VOX from these soils was observed using GC-FID and GC-MS. When H2O2 was added to the samples much higher concentrations of VOC and VOX were observed. Furthermore, when the pH of the soils was changed towards lower values higher emissions of VOC were also observed. Based on C-H activation processes we delineate a halide containing iron complex as a provider of anions reacting with previously generated hydrocarbon radicals. We suggest iron sulfate derivatives as those complexes which are generated if the above-mentioned natural H2O2 addition to iron sulfates and sulfides occurs. The origin of these complexes is able to explain the halogenation of chemically unreactive alkanes.

  18. Aerosol-halogen interaction: Change of physico-chemical properties of SOA by naturally released halogen species

    NASA Astrophysics Data System (ADS)

    Ofner, J.; Balzer, N.; Buxmann, J.; Grothe, H.; Krüger, H.; Platt, U.; Schmitt-Kopplin, P.; Zetzsch, C.

    2011-12-01

    Reactive halogen species are released by various sources like photo-activated sea-salt aerosol or salt pans and salt lakes. These heterogeneous release mechanisms have been overlooked so far, although their potential of interaction with organic aerosols like Secondary Organic Aerosol (SOA), Biomass Burning Organic Aerosol (BBOA) or Atmospheric Humic LIke Substances (HULIS) is completely unknown. Such reactions can constitute sources of gaseous organo-halogen compounds or halogenated organic particles in the atmospheric boundary layer. To study the interaction of organic aerosols with reactive halogen species (RHS), SOA was produced from α-pinene, catechol and guaiacol using an aerosol smog-chamber. The model SOAs were characterized in detail using a variety of physico-chemical methods (Ofner et al., 2011). Those aerosols were exposed to molecular halogens in the presence of UV/VIS irradiation and to halogens, released from simulated natural halogen sources like salt pans, in order to study the complex aerosol-halogen interaction. The heterogeneous reaction of RHS with those model aerosols leads to different gaseous species like CO2, CO and small reactive/toxic molecules like phosgene (COCl2). Hydrogen containing groups on the aerosol particles are destroyed to form HCl or HBr, and a significant formation of C-Br bonds could be verified in the particle phase. Carbonyl containing functional groups of the aerosol are strongly affected by the halogenation process. While changes of functional groups and gaseous species were visible using FTIR spectroscopy, optical properties were studied using Diffuse Reflectance UV/VIS spectroscopy. Overall, the optical properties of the processed organic aerosols are significantly changed. While chlorine causes a "bleaching" of the aerosol particles, bromine shifts the maximum of UV/VIS absorption to the red end of the UV/VIS spectrum. Further physico-chemical changes were recognized according to the aerosol size-distributions or the

  19. Historical trends in occurrence and atmospheric inputs of halogenated volatile organic compounds in untreated ground water used as a source of drinking water

    USGS Publications Warehouse

    Shapiro, S.D.; Busenberg, E.; Focazio, M.J.; Plummer, L.N.

    2004-01-01

    Analyses of samples of untreated ground water from 413 community-, non-community- (such as restaurants), and domestic-supply wells throughout the US were used to determine the frequency of detection of halogenated volatile organic compounds (VOCs) in drinking-water sources. The VOC data were compiled from archived chromatograms of samples analyzed originally for chlorofluorocarbons (CFCs) by purge-and-trap gas chromatography with an electron-capture detector (GC-ECD). Concentrations of the VOCs could not be ascertained because standards were not routinely analyzed for VOCs other than trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113). Nevertheless, the peak areas associated with the elution times of other VOCs on the chromatograms can be classified qualitatively to assess concentrations at a detection limit on the order of parts per quadrillion. Three or more VOCs were detected in 100% (percent) of the chromatograms, and 77.2% of the samples contained 10 or more VOCs. The maximum number of VOCs detected in any sample was 24. Modeled ground-water residence times, determined from concentrations of CFC-12, were used to assess historical trends in the cumulative occurrence of all VOCs detected in this analysis, as well as the occurrence of individual VOCs, such as CFC-11, carbon tetrachloride (CCl4), chloroform and tetrachloroethene (PCE). The detection frequency for all of the VOCs detected has remained relatively constant from approximately 1940 to 2000; however, the magnitude of the peak areas on the chromatograms for the VOCs in the water samples has increased from 1940 to 2000. For CFC-11, CCl4, chloroform and PCE, small peaks decrease from 1940 to 2000, and large peaks increase from 1940 to 2000. The increase in peak areas on the chromatograms from analyses of more recently recharged water is consistent with reported increases in atmospheric concentrations of the VOCs. Approximately 44% and 6

  20. Remediation of organic and inorganic arsenic contaminated groundwater using a nanocrystalline TiO2-based adsorbent.

    PubMed

    Jing, Chuanyong; Meng, Xiaoguang; Calvache, Edwin; Jiang, Guibin

    2009-01-01

    A nanocrystalline TiO2-based adsorbent was evaluated for the simultaneous removal of As(V), As(III), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) in contaminated groundwater. Batch experimental results show that As adsorption followed pseudo-second order rate kinetics. The competitive adsorption was described with the charge distribution multi-site surface complexation model (CD-MUSIC). The groundwater containing an average of 329 microg L(-1) As(III), 246 microg L(-1) As(V), 151 microg L(-1) MMA, and 202 microg L(-1) DMA was continuously passed through a TiO2 filter at an empty bed contact time of 6 min for 4 months. Approximately 11,000, 14,000, and 9900 bed volumes of water had been treated before the As(III), As(V), and MMA concentration in the effluent increased to 10 microg L(-1). However, very little DMA was removed. The EXAFS results demonstrate the existence of a bidentate binuclear As(V) surface complex on spent adsorbent, indicating the oxidation of adsorbed As(III).

  1. Adsorptive Removal of Pharmaceuticals and Personal Care Products from Water with Functionalized Metal-organic Frameworks: Remarkable Adsorbents with Hydrogen-bonding Abilities

    PubMed Central

    Seo, Pill Won; Bhadra, Biswa Nath; Ahmed, Imteaz; Khan, Nazmul Abedin; Jhung, Sung Hwa

    2016-01-01

    Adsorption of typical pharmaceuticals and personal care products (PPCPs) (such as naproxen, ibuprofen and oxybenzone) from aqueous solutions was studied by using the highly porous metal-organic framework (MOF) MIL-101 with and without functionalization. Adsorption results showed that MIL-101s with H-donor functional groups such as –OH and –NH2 were very effective for naproxen adsorption, despite a decrease in porosity, probably because of H-bonding between O atoms on naproxen and H atoms on the adsorbent. For this reason, MIL-101 with two functional groups capable of H-bonding (MIL-101-(OH)2) exhibited remarkable adsorption capacity based on adsorbent surface area. The favorable contributions of –OH and –(OH)2 on MIL-101 in the increased adsorption of ibuprofen and oxybenzone (especially based on porosity) confirmed again the importance of H-bonding mechanism. The adsorbent with the highest adsorption capacity, MIL-101-OH, was very competitive when compared with carbonaceous materials, mesoporous materials, and pristine MIL-101. Moreover, the MIL-101-OH could be recycled several times by simply washing with ethanol, suggesting potential application in the adsorptive removal of PPCPs from water. PMID:27695005

  2. Adsorptive Removal of Pharmaceuticals and Personal Care Products from Water with Functionalized Metal-organic Frameworks: Remarkable Adsorbents with Hydrogen-bonding Abilities

    NASA Astrophysics Data System (ADS)

    Seo, Pill Won; Bhadra, Biswa Nath; Ahmed, Imteaz; Khan, Nazmul Abedin; Jhung, Sung Hwa

    2016-10-01

    Adsorption of typical pharmaceuticals and personal care products (PPCPs) (such as naproxen, ibuprofen and oxybenzone) from aqueous solutions was studied by using the highly porous metal-organic framework (MOF) MIL-101 with and without functionalization. Adsorption results showed that MIL-101s with H-donor functional groups such as –OH and –NH2 were very effective for naproxen adsorption, despite a decrease in porosity, probably because of H-bonding between O atoms on naproxen and H atoms on the adsorbent. For this reason, MIL-101 with two functional groups capable of H-bonding (MIL-101-(OH)2) exhibited remarkable adsorption capacity based on adsorbent surface area. The favorable contributions of –OH and –(OH)2 on MIL-101 in the increased adsorption of ibuprofen and oxybenzone (especially based on porosity) confirmed again the importance of H-bonding mechanism. The adsorbent with the highest adsorption capacity, MIL-101-OH, was very competitive when compared with carbonaceous materials, mesoporous materials, and pristine MIL-101. Moreover, the MIL-101-OH could be recycled several times by simply washing with ethanol, suggesting potential application in the adsorptive removal of PPCPs from water.

  3. A Halogen-Bond-Induced Triple Helicate Encapsulates Iodide.

    PubMed

    Massena, Casey J; Wageling, Nicholas B; Decato, Daniel A; Martin Rodriguez, Enrique; Rose, Ariana M; Berryman, Orion B

    2016-09-26

    The self-assembly of higher-order anion helicates in solution remains an elusive goal. Herein, we present the first triple helicate to encapsulate iodide in organic and aqueous media as well as the solid state. The triple helicate self-assembles from three tricationic arylethynyl strands and resembles a tubular anion channel lined with nine halogen bond donors. Eight strong iodine⋅⋅⋅iodide halogen bonds and numerous buried π-surfaces endow the triplex with remarkable stability, even at elevated temperatures. We suggest that the natural rise of a single-strand helix renders its linear halogen-bond donors non-convergent. Thus, the stringent linearity of halogen bonding is a powerful tool for the synthesis of multi-strand anion helicates. PMID:27411932

  4. Interpretation of the excess adsorption isotherms of organic eluent components on the surface of reversed-phase adsorbents. Effect on the analyte retention.

    PubMed

    Kazakevich, Y V; LoBrutto, R; Chan, F; Patel, T

    2001-04-13

    The excess adsorption isotherms of acetonitrile, methanol and tetrahydrofuran from water on reversed-phase packings were studied, using 10 different columns packed with C1-C6, C8, C10, C12, and C18 monomeric phases, bonded on the same type of silica. The interpretation of isotherms on the basis of the theory of excess adsorption shows significant accumulation of the organic eluent component on the adsorbent surface on the top of "collapsed" bonded layer. The accumulated amount was shown to be practically independent of the length of alkyl chains bonded to the silica surface. A model that describes analyte retention on a reversed-phase column from a binary mobile phase is developed. The retention mechanism involves a combination of analyte distribution between the eluent and organic adsorbed layer, followed by analyte adsorption on the surface of the bonded phase. A general retention equation for the model is derived and methods for independent measurements of the involved parameters are suggested. The theory was tested by direct measurement of analyte retention from the eluents of varied composition and comparison of the values obtained with those theoretically calculated values. Experimental and theoretically calculated values are in good agreement.

  5. Halogenating activities detected in Antarctic macroalgae

    SciTech Connect

    Laturnus, F.; Adams, F.C.; Gomez, I.; Mehrtens, G.

    1997-03-01

    Halogenating activities were determined in samples of 18 cultivated species of brown, red and green macroalgae from the Antarctic. Activities for the halogenating organic compounds with bromide, iodide and chloride were found. Investigated red algae (rhodophytes) showed higher brominating and iodinating activities compared to brown (phaeophytes) and green (chlorophytes) algae. The highest brominating and iodinating activities were measured in the red algae Plocamium cartilagineum (1.11 {+-} 0.01 U g{sup -1} wet algal weight and 0.18 U g{sup -1} wet algal weight, respectively) and Myriogramme mangini (3.62 {+-} 0.17 U g{sup -1} wet algal weight and 4.5 U g{sup -1} wet algal weight, respectively). Chlorinating activities were detected in the red alga Plocamium cartilagineum only (0.086 U g{sup -1} wet algal weight). 30 refs., 2 figs., 1 tab.

  6. A rapid microwave-assisted synthesis of a sodium-cadmium metal-organic framework having improved performance as a CO2 adsorbent for CCS.

    PubMed

    Palomino Cabello, Carlos; Arean, Carlos Otero; Parra, José B; Ania, Conchi O; Rumori, P; Turnes Palomino, G

    2015-06-01

    We report on a facile and rapid microwave-assisted method for preparing a sodium-cadmium metal-organic framework (having coordinatively unsaturated sodium ions) that considerably shortens the conventional synthesis time from 5 days to 1 hour. The obtained (Na,Cd)-MOF showed an excellent volumetric CO2 adsorption capacity (5.2 mmol cm(-3) at 298 K and 1 bar) and better CO2 adsorption properties than those shown by the same metal-organic framework when synthesized following a more conventional procedure. Moreover, the newly prepared material was found to display high selectivity for adsorption of carbon dioxide over nitrogen, and good regenerability and stability during repeated CO2 adsorption-desorption cycles, which are the required properties for any adsorbent intended for carbon dioxide capture and sequestration (CSS) from the post-combustion flue gas of fossil fuelled power stations.

  7. Use of chloroflurocarbons as internal standards for the measurement of atmospheric non-methane volatile organic compounds sampled onto solid adsorbent cartridges.

    PubMed

    Karbiwnyk, Christine M; Mills, Craig S; Helmig, Detlev; Birks, John W

    2003-03-01

    Solid adsorbents have proven useful for determining the vertical profiles of volatile organic compounds (VOCs) using sampling platforms such as balloons, kites, and light aircraft, and those profiles provide valuable information about the sources, sinks, transformations, and transport of atmospheric VOCs. One of the largest contributions to error in VOC concentrations is the estimation of the volume of air sampled on the adsorbent cartridge. These errors arise from different sources, such as variations in pumping flow rates from changes in ambient temperature and pressure with altitude, and decrease in the sampling pump battery power. Another significant source for sampling rate variations are differences in the flow resistance of individual sampling cartridges. To improve the accuracy and precision of VOC measurements, the use of ambient chlorofluorocarbons (CFCs) as internal standards was investigated. A multibed solid adsorbent, AirToxic (Supelco), was chosen for its wide sampling range (C3-C12). Analysis was accomplished by thermal desorption and dual detection GC/FID/ECD, resulting in sensitive and selective detection of both VOCs and CFCs in the same sample. Long-lived chlorinated compounds (CFC-11, CFC-12, CFC-113, CCl4 and CH3CCl3) banned by the Montreal Protocol and subsequent amendments were studied for their ability to predict sample volumes using both ground-based and vertical profiling platforms through the boundary layer and free troposphere. Of these compounds, CFC-113 and CCl4 were found to yield the greatest accuracy and precision for sampling volume determination. Use of ambient CFC-113 and CCl4 as internal standards resulted in accuracy and precision of generally better than 10% for the prediction of sample volumes in ground-, balloon-, and aircraft-based measurements. Consequently, use of CFCs as reference compounds can yield a significant improvement of accuracy and precision for ambient VOC measurements in situations where accurate flow

  8. Use of chloroflurocarbons as internal standards for the measurement of atmospheric non-methane volatile organic compounds sampled onto solid adsorbent cartridges.

    PubMed

    Karbiwnyk, Christine M; Mills, Craig S; Helmig, Detlev; Birks, John W

    2003-03-01

    Solid adsorbents have proven useful for determining the vertical profiles of volatile organic compounds (VOCs) using sampling platforms such as balloons, kites, and light aircraft, and those profiles provide valuable information about the sources, sinks, transformations, and transport of atmospheric VOCs. One of the largest contributions to error in VOC concentrations is the estimation of the volume of air sampled on the adsorbent cartridge. These errors arise from different sources, such as variations in pumping flow rates from changes in ambient temperature and pressure with altitude, and decrease in the sampling pump battery power. Another significant source for sampling rate variations are differences in the flow resistance of individual sampling cartridges. To improve the accuracy and precision of VOC measurements, the use of ambient chlorofluorocarbons (CFCs) as internal standards was investigated. A multibed solid adsorbent, AirToxic (Supelco), was chosen for its wide sampling range (C3-C12). Analysis was accomplished by thermal desorption and dual detection GC/FID/ECD, resulting in sensitive and selective detection of both VOCs and CFCs in the same sample. Long-lived chlorinated compounds (CFC-11, CFC-12, CFC-113, CCl4 and CH3CCl3) banned by the Montreal Protocol and subsequent amendments were studied for their ability to predict sample volumes using both ground-based and vertical profiling platforms through the boundary layer and free troposphere. Of these compounds, CFC-113 and CCl4 were found to yield the greatest accuracy and precision for sampling volume determination. Use of ambient CFC-113 and CCl4 as internal standards resulted in accuracy and precision of generally better than 10% for the prediction of sample volumes in ground-, balloon-, and aircraft-based measurements. Consequently, use of CFCs as reference compounds can yield a significant improvement of accuracy and precision for ambient VOC measurements in situations where accurate flow

  9. Halogenated arsenenes as Dirac materials

    NASA Astrophysics Data System (ADS)

    Tang, Wencheng; Sun, Minglei; Ren, Qingqiang; Wang, Sake; Yu, Jin

    2016-07-01

    Arsenene is the graphene-like arsenic nanosheet, which has been predicted very recently [S. Zhang, Z. Yan, Y. Li, Z. Chen, and H. Zeng, Angewandte Chemie, 127 (2015) 3155-3158]. Using first-principles calculations, we systematically investigate the structures and electronic properties of fully-halogenated arsenenes. Formation energy analysis reveals that all the fully-halogenated arsenenes except iodinated arsenene are energetically favorable and could be synthesized. We have revealed the presence of Dirac cone in fully-halogenated arsenene compounds. They may have great potential applications in next generation of high-performance devices.

  10. Magnetic metal-organic framework-titanium dioxide nanocomposite as adsorbent in the magnetic solid-phase extraction of fungicides from environmental water samples.

    PubMed

    Su, Hao; Lin, Yunliang; Wang, Zhenhua; Wong, Y-L Elaine; Chen, Xiangfeng; Chan, T-W Dominic

    2016-09-30

    In this work, a core-shell Fe3O4@SiO2@MOF/TiO2 nanocomposite was synthesized and used to as adsorbent for magnetic solid-phase extraction (MSPE) of triazole fungicides from environmental water samples. Five triazole fungicides, namely, triadimenol, hexaconazole, diniconazole, myclobutanil, and tebuconazole, were selected as target analytes for MSPE. These analytes were quantitatively adsorbed on microspheres, and the sorbents were separated from the solution by using a magnet. The analytes were desorbed by methanol and determined through liquid-chromatography coupled with tandem mass spectrometry. The extraction parameters affecting the extraction efficiency were optimized through response surface methodology. The limits of detection and limits of quantification for the selected fungicides were 0.19-1.20ngL(-1) and 0.61-3.62ngL(-1), respectively. The proposed method was applied to determine the concentration of fungicides in actual environmental water samples. The accuracy of the proposed method was evaluated by measuring the recovery of the spiked samples. The satisfying recoveries of the four water samples ranged from 90.2% to 104.2%. Therefore, the magnetic metal-organic framework/TiO2 nanocomposite based MSPE is a potential approach to analyze fungicides in actual water samples. PMID:27592609

  11. Reduction of halogenated ethanes by green rust.

    SciTech Connect

    O'Loughlin, E. J.; Burris, D. R.; Environmental Research; Air Force Research Lab.; Integrated Science and Technology, Inc.

    2004-01-01

    Green rusts, mixed Fe{sup II}/Fe{sup III} hydroxide minerals present in many suboxic environments, have been shown to reduce a number of organic and inorganic contaminants. The reduction of halogenated ethanes was examined in aqueous suspensions of green rust, both alone and with the addition of Ag{sup I} (AgGR) and Cu{sup II} (CuGR). Hexachloroethane (HCA), pentachloroethane (PCA), 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA), 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA), 1,1,1-trichloroethane (1,1,1-TCA), 1,1,2-trichloroethane (1,1,2-TCA), 1,1-dichloroethane (1,1-DCA), and 1,2-dibromoethane were reduced in the presence of green rust alone, AgGR, or CuGR; only 1,2-dichloroethane and chloroethane were nonreactive. The reduction was generally more rapid for more highly substituted ethanes than for ethanes having fewer halogen groups (HCA > PCA > 1,1,1,2-TeCA > 1,1,1-TCA > 1,1,2,2-TeCA > 1,1,2-TCA > 1,1-DCA), and isomers with the more asymmetric distributions of halogen groups were more rapidly reduced than the isomer with greater symmetry (e.g., 1,1,1-TCA > 1,1,2-TCA). The addition of Ag{sup I} or Cu{sup II} to green rust suspensions resulted in a substantial increase in the rate of halogenated ethane reduction as well as significant differences in the product distributions with respect to green rust alone.

  12. Quantitation of persistent organic pollutants adsorbed on plastic debris from the Northern Pacific Gyre's "eastern garbage patch".

    PubMed

    Rios, Lorena M; Jones, Patrick R; Moore, Charles; Narayan, Urja V

    2010-12-01

    Floating marine plastic debris was found to function as solid-phase extraction media, adsorbing and concentrating pollutants out of the water column. Plastic debris was collected in the North Pacific Gyre, extracted, and analyzed for 36 individual PCB congeners, 17 organochlorine pesticides, and 16 EPA priority PAHs. Over 50% contained PCBs, 40% contained pesticides, and nearly 80% contained PAHs. The PAHs included 2, 3 and 4 ring congeners. The PCBs were primarily CB-11, 28, 44, 52, 66, and 101. The pesticides detected were primarily p,p-DDTs and its metabolite, o,p-DDD, as well as BHC (a,b,g and d). The concentrations of pollutants found ranged from a few ppb to thousands of ppb. The types of PCBs and PAHs found were similar to those found in marine sediments. However, these plastic particles were mostly polyethylene which is resistant to degradation and although functioning similarly to sediments in accumulating pollutants, these had remained on or near the ocean surface. Particles collected included intact plastic items as well as many pieces less than 5 mm in size. PMID:21042605

  13. Modern halogen leak detectors /Review/

    NASA Astrophysics Data System (ADS)

    Evlampiev, A. I.; Karpov, V. I.; Levina, L. E.

    1981-04-01

    The halogen method is one of the basic techniques of leak detection for monitoring airtightness in such objects as refrigeration equipment and aerosol containers. Sensitivity has been improved by heated platinum emitters which stabilize background currents. Methods for protecting the region in which the gas is selected include placing the sensitive element in a new flow gauge and keeping the chamber at a certain distance from the tested surface. Chromatograph separating columns both increase sensitivity and distinguish test materials on a background of extraneous halogen-containing materials. Solid-state platinum diodes have been used as the sensitive elements of halogen leak detectors. Leak detectors based on electron-capture practically eliminate the effect of contamination of the surrounding atmosphere on leak detector sensitivity. A technique of vacuum testing is based on the high affinity of halogen-containing materials for electrons.

  14. Modern halogen leak detectors /Review/

    NASA Astrophysics Data System (ADS)

    Evlampiev, A. I.; Karpov, V. I.; Levina, L. E.

    1980-09-01

    The halogen method is one of the basic techniques of leak detection for monitoring airtightness in such objects as refrigeration equipment and aerosol containers. Sensitivity has been improved by heated platinum emitters which stabilize background currents. Methods for protecting the region in which the gas is selected include placing the sensitive element in a new flow gauge and keeping the chamber at a certain distance from the tested surface. Chromatograph separating columns both increase sensitivity and distinguish test materials on a background of extraneous halogen-containing materials. Solid-state platinum diodes have been used as the sensitive elements of halogen leak detectors. Leak detectors based on electron-capture practically eliminate the effect of contamination of the surrounding atmosphere on leak detector sensitivity. A technique of vacuum testing is based on the high affinity of halogen-containing materials for electrons.

  15. Potential halogenated industrial carcinogenic and mutagenic chemicals. IV. Halogenated aryl derivatives.

    PubMed

    Fishbein, L

    1979-04-01

    A variety of halogenated aryl derivatives possess significant activity as solvents for pesticides, heat transfer agents, pesticide intermediates, additives for rubber products, intermediates in organic synthesis and as insect repellants and deodorants. Ortho- and para-dichlorobenzenes; 1,2,4-trichloro- and hexachlorobenzene, as well as bromobenzenes and benzylchloride were reviewed principally in terms of their synthesis, areas of utility, stability, distribution, reactivity, levels of exposure, populations at risk, metabolism, carcinogenicity and mutagenicity.

  16. The interaction of organic adsorbate vibrations with substrate lattice waves in methyl-Si(111)-(1 Ã-- 1)

    NASA Astrophysics Data System (ADS)

    Brown, Ryan D.; Hund, Zachary M.; Campi, Davide; O'Leary, Leslie E.; Lewis, Nathan S.; Bernasconi, M.; Benedek, G.; Sibener, S. J.

    2014-07-01

    A combined helium atom scattering and density functional perturbation theory study has been performed to elucidate the surface phonon dispersion relations for both the CH3-Si(111)-(1 × 1) and CD3-Si(111)-(1 × 1) surfaces. The combination of experimental and theoretical methods has allowed characterization of the interactions between the low energy vibrations of the adsorbate and the lattice waves of the underlying substrate, as well as characterization of the interactions between neighboring methyl groups, across the entire wavevector resolved vibrational energy spectrum of each system. The Rayleigh wave was found to hybridize with the surface rocking libration near the surface Brillouin zone edge at both the {bar M}-point and {bar K}-point. The calculations indicated that the range of possible energies for the potential barrier to the methyl rotation about the Si-C axis is sufficient to prevent the free rotation of the methyl groups at a room temperature interface. The density functional perturbation theory calculations revealed several other surface phonons that experienced mode-splitting arising from the mutual interaction of adjacent methyl groups. The theory identified a Lucas pair that exists just below the silicon optical bands. For both the CH3- and CD3-terminated Si(111) surfaces, the deformations of the methyl groups were examined and compared to previous experimental and theoretical work on the nature of the surface vibrations. The calculations indicated a splitting of the asymmetric deformation of the methyl group near the zone edges due to steric interactions of adjacent methyl groups. The observed shifts in vibrational energies of the -CD3 groups were consistent with the expected effect of isotopic substitution in this system.

  17. Mutagenicity of organic pollutants adsorbed on suspended particulate matter in the center of Wrocław (Poland)

    NASA Astrophysics Data System (ADS)

    Bełcik, Maciej; Trusz-Zdybek, Agnieszka; Galas, Ewa; Piekarska, Katarzyna

    2014-10-01

    Mutagenicity of pollutants adsorbed on suspended dust of the PM10 fraction, collected in winter and summer season alike over the Wrocław city centre (Poland) was studied using the standard Salmonella assay (plate-incorporation) and the Kado modified assay (microsuspension method). The dust was collected using Staplex high volume air sampler. Further on it was extracted with dichloromethane in a Soxhlet apparatus. PAH content in extracts was determined by the high performance liquid chromatography technique using fluorescence detection, whereas the nitro-PAH content- by the gas chromatography using mass detection. Two Salmonella typhimurium strains, TA98 and YG1041, were used in the assays. The assays were conducted with and without a metabolic activation. Investigated air pollution extracts differed against each other with regard to a total content as well as to a percentage of individual compounds, depending on the sampling season. Both the total PAH content and the nitro-PAH content in the tested samples, and their spectrum as well, were found the highest in winter season. Higher mutagenic effect was noted for the dust extract from samples collected in wintertime than from those collected in summer. Pollutants directly affecting the genetic material and those showing such indirect action were present in the examined samples. The YG1041 strain turned out to be the most sensitive, which was the sign that large amounts of nitro-aromatic compounds were present in the tested samples. Obtained results proved that the Kado modified Salmonella assay would be useful for the atmospheric air pollution monitoring in urban agglomerations. Mutagenic effect in assays conducted according to the Kado procedure was obtained by using in the assays lower concentrations of tested extracts, compared to the classical assay.

  18. Halogen poisoning effect of Pt-TiO2 for formaldehyde catalytic oxidation performance at room temperature

    NASA Astrophysics Data System (ADS)

    Zhu, Xiaofeng; Cheng, Bei; Yu, Jiaguo; Ho, Wingkei

    2016-02-01

    Catalytic decomposition of formaldehyde (HCHO) at room temperature is an important method for HCHO removal. Pt-based catalysts are the optimal catalyst for HCHO decomposition at room temperature. However, the stability of this catalyst remains unexplored. In this study, Pt-TiO2 (Pt-P25) catalysts with and without adsorbed halogen ions (including F-, Cl-, Br-, and I-) were prepared through impregnation and ion modification. Pt-TiO2 samples with adsorbed halogen ions exhibited reduced catalytic activity for formaldehyde decomposition at room temperature compared with the Pt-TiO2 sample; the catalytic activity followed the order of F-Pt-P25, Cl-Pt-P25, Br-Pt-P25, and I-Pt-P25. Characterization results (including XRD, TEM, HRTEM, BET, XPS, and metal dispersion) showed that the adsorbed halogen ions can poison Pt nanoparticles (NPs), thereby reducing the HCHO oxidation activity of Pt-TiO2. The poison mechanism is due to the strong adsorption of halogen ions on the surface of Pt NPs. The adsorbed ions form coordination bonds with surface Pt atoms by transferring surplus electrons into the unoccupied 5d orbit of the Pt atom, thereby inhibiting oxygen adsorption and activation of the Pt NP surface. Moreover, deactivation rate increases with increasing diameter of halogen ions. This study provides new insights into the fabrication of high-performance Pt-based catalysts for indoor air purification.

  19. The Halogen Bond in the Design of Functional Supramolecular Materials: Recent Advances

    PubMed Central

    2013-01-01

    Halogen bonding is an emerging noncovalent interaction for constructing supramolecular assemblies. Though similar to the more familiar hydrogen bonding, four primary differences between these two interactions make halogen bonding a unique tool for molecular recognition and the design of functional materials. First, halogen bonds tend to be much more directional than (single) hydrogen bonds. Second, the interaction strength scales with the polarizability of the bond-donor atom, a feature that researchers can tune through single-atom mutation. In addition, halogen bonds are hydrophobic whereas hydrogen bonds are hydrophilic. Lastly, the size of the bond-donor atom (halogen) is significantly larger than hydrogen. As a result, halogen bonding provides supramolecular chemists with design tools that cannot be easily met with other types of noncovalent interactions and opens up unprecedented possibilities in the design of smart functional materials. This Account highlights the recent advances in the design of halogen-bond-based functional materials. Each of the unique features of halogen bonding, directionality, tunable interaction strength, hydrophobicity, and large donor atom size, makes a difference. Taking advantage of the hydrophobicity, researchers have designed small-size ion transporters. The large halogen atom size provided a platform for constructing all-organic light-emitting crystals that efficiently generate triplet electrons and have a high phosphorescence quantum yield. The tunable interaction strengths provide tools for understanding light-induced macroscopic motions in photoresponsive azobenzene-containing polymers, and the directionality renders halogen bonding useful in the design on functional supramolecular liquid crystals and gel-phase materials. Although halogen bond based functional materials design is still in its infancy, we foresee a bright future for this field. We expect that materials designed based on halogen bonding could lead to

  20. The Halogen Occultation Experiment

    NASA Technical Reports Server (NTRS)

    Russell, James M., III; Gordley, Larry L.; Park, Jae H.; Drayson, S. R.; Hesketh, W. D.; Cicerone, Ralph J.; Tuck, Adrian F.; Frederick, John E.; Harries, John E.; Crutzen, Paul J.

    1993-01-01

    The Halogen Occultation Experiment (HALOE) uses solar occultation to measure vertical profiles of O3, HCl, HF, CH4, H2O, NO, NO2, aerosol extinction, and temperature versus pressure with an instantaneous vertical field of view of 1.6 km at the earth limb. Latitudinal coverage is from 80 deg S to 80 deg N over the course of 1 year and includes extensive observations of the Antarctic region during spring. The altitude range of the measurements extends from about 15 km to about 60-130 km, depending on channel. Experiment operations have been essentially flawless, and all performance criteria either meet or exceed specifications. Internal data consistency checks, comparisons with correlative measurements, and qualitative comparisons with 1985 atmospheric trace molecule spectroscopy (ATMOS) results are in good agreement. Examples of pressure versus latitude cross sections and a global orthographic projection for the September 21 to October 15, 1992, period show the utility of CH4, HF, and H2O as tracers, the occurrence of dehydration in the Antarctic lower stratosphere, the presence of the water vapor hygropause in the tropics, evidence of Antarctic air in the tropics, the influence of Hadley tropical upwelling, and the first global distribution of HCl, HF, and NO throughout the stratosphere. Nitric oxide measurements extend through the lower thermosphere.

  1. QSAR models for removal rates of organic pollutants adsorbed by in situ formed manganese dioxide under acid condition.

    PubMed

    Su, Pingru; Zhu, Huicen; Shen, Zhemin

    2016-02-01

    Manganese dioxide formed in oxidation process by potassium permanganate exhibits promising adsorptive capacity which can be utilized to remove organic pollutants in wastewater. However, the structure variances of organic molecules lead to wide difference of adsorption efficiency. Therefore, it is of great significance to find a general relationship between removal rate of organic compounds and their quantum parameters. This study focused on building up quantitative structure activity relationship (QSAR) models based on experimental removal rate (r(exp)) of 25 organic compounds and 17 quantum parameters of each organic compounds computed by Gaussian 09 and Material Studio 6.1. The recommended model is rpre = -0.502-7.742 f(+)x + 0.107 E HOMO + 0.959 q(H(+)) + 1.388 BOx. Both internal and external validations of the recommended model are satisfied, suggesting optimum stability and predictive ability. The definition of applicability domain and the Y-randomization test indicate all the prediction is reliable and no possibility of chance correlation. The recommended model contains four variables, which are closely related to adsorption mechanism. f(+)x reveals the degree of affinity for nucleophilic attack. E HOMO represents the difficulty of electron loss. q(H(+)) reflect the distribution of partial charge between carbon and hydrogen atom. BO x shows the stability of a molecule.

  2. Influence of organic acids on kinetic release of chromium in soil contaminated with leather factory waste in the presence of some adsorbents.

    PubMed

    Taghipour, Marzieh; Jalali, Mohsen

    2016-07-01

    In this study, batch experiments were conducted to investigate the effects of nanoparticles (NPs) (MgO, ZnO, TiO2) and clay minerals (bentonite, zeolite) on the release of chromium (Cr) from leather factory waste (LFW) and LFW treated soil using organic acids. Chromium release from all treatments was studied in the presence of citric acid, oxalic acid and CaCl2 solutions. The results showed that, in all treatments, organic acids released more Cr than inorganic salt (CaCl2). The release of Cr by citric acid was higher than that by oxalic acid. In LFW treated soil and LFW, the release of Cr from the all treatments with NPs was less than that from the clay mineral treatments. On the other hand, in the presence of organic acids, Cr release by NPs and clay minerals decreased. Two kinetic models including pseudo-first- and pseudo-second-order model were tested to describe the time dependent Cr release data. Among the kinetic models used, the pseudo-second-order model generally gave the best fits to experimental data. Before and after release experiments, Cr in LFW, treated LFW, control soil and LFW treated soils were fractionated. In all treatments, the greatest amounts of Cr were found in the residual fraction (RES). The organic acids were effective in reducing the exchangeable (EXC), bound to organic matter (OM) and bound to carbonate (CAR) fractions of Cr in all treatments, whereas, after release of Cr from treated soils, Cr remained mainly in the RES fraction. The application of NPs and clay minerals in soil led to a significant transformation of Cr from mobile fractions to the RES fraction. Therefore, organic ligands played a dominant role in mobility and bioavailability of Cr and the removal of Cr by adsorbents.

  3. Influence of organic acids on kinetic release of chromium in soil contaminated with leather factory waste in the presence of some adsorbents.

    PubMed

    Taghipour, Marzieh; Jalali, Mohsen

    2016-07-01

    In this study, batch experiments were conducted to investigate the effects of nanoparticles (NPs) (MgO, ZnO, TiO2) and clay minerals (bentonite, zeolite) on the release of chromium (Cr) from leather factory waste (LFW) and LFW treated soil using organic acids. Chromium release from all treatments was studied in the presence of citric acid, oxalic acid and CaCl2 solutions. The results showed that, in all treatments, organic acids released more Cr than inorganic salt (CaCl2). The release of Cr by citric acid was higher than that by oxalic acid. In LFW treated soil and LFW, the release of Cr from the all treatments with NPs was less than that from the clay mineral treatments. On the other hand, in the presence of organic acids, Cr release by NPs and clay minerals decreased. Two kinetic models including pseudo-first- and pseudo-second-order model were tested to describe the time dependent Cr release data. Among the kinetic models used, the pseudo-second-order model generally gave the best fits to experimental data. Before and after release experiments, Cr in LFW, treated LFW, control soil and LFW treated soils were fractionated. In all treatments, the greatest amounts of Cr were found in the residual fraction (RES). The organic acids were effective in reducing the exchangeable (EXC), bound to organic matter (OM) and bound to carbonate (CAR) fractions of Cr in all treatments, whereas, after release of Cr from treated soils, Cr remained mainly in the RES fraction. The application of NPs and clay minerals in soil led to a significant transformation of Cr from mobile fractions to the RES fraction. Therefore, organic ligands played a dominant role in mobility and bioavailability of Cr and the removal of Cr by adsorbents. PMID:27139119

  4. Simultaneous removal of multiple pesticides from water: effect of organically modified clays as coagulant aid and adsorbent in coagulation-flocculation process.

    PubMed

    Shabeer, T P Ahammed; Saha, Ajoy; Gajbhiye, V T; Gupta, Suman; Manjaiah, K M; Varghese, Eldho

    2014-01-01

    Contamination of drinking water sources with agrochemical residues became a major concern in the twenty-first century. Coagulation-flocculation is the most widely used water-treatment process, but the efficiency to remove pesticides and other organic pollutants are limited compared to adsorption process. Thus, simultaneous action of adsorption on normal bentonite or organo-modified montmorillonite clays [modified with octadecylamine (ODA-M) and octadecylamine + amino-propyltriethoxysilane (ODAAPS-M)] followed by coagulation-flocculation by alum and poly aluminium chloride has been evaluated for removal of 10 different pesticides, namely atrazine, lindane, metribuzin, aldrin, chlorpyriphos, pendimethalin, alpha-endosulphan, beta-endosulphan, p,p'-DDT, cypermethrin and two of its metabolites, endosulphan sulphate and p,p'-DDE, from water. The coagulation without integration of adsorption was less effective (removal % varies from 12 to 49) than the adsorption-coagulation integrated system (removal % varies from 71 to 100). Further, coagulation integrated with adsorption was more effective when organically modified montmorillonite was used as adsorbent compared to normal bentonite. The removal efficiency of organic clay depends upon the concentration of pesticides, doses of clay minerals, and efficiency was more for ODAAPS-M as compared to ODA-M. The combination of ODAAPS-M-clay with coagulants was also used efficiently for the removal of pesticides from natural and fortified natural water collected and the results exhibit the usefulness of this remediation technique for application in water decontamination and in treatment of industrial and agricultural waste waters.

  5. REUSABLE ADSORBENTS FOR DILUTE SOLUTIONS SEPARATION. 5: PHOTODEGRADATION OF ORGANIC COMPOUNDS ON SURFACTANT-MODIFIED TITANIA. (R828598C753)

    EPA Science Inventory

    A semiconductor titania (TiO2) surface was modified by surfactant adsorption to make it more hydrophobic and to increase the adsorption of hydrophobic organic compounds (HOCs) and their photodegradation rates under UV irradiation. Photocatalytic experiments using Ti...

  6. A routine accredited method for the analysis of polychlorinated biphenyls, organochlorine pesticides, chlorobenzenes and screening of other halogenated organics in soil, sediment and sludge by GCxGC-μECD.

    PubMed

    Muscalu, Alina M; Reiner, Eric J; Liss, Steven N; Chen, Tony; Ladwig, Gerry; Morse, David

    2011-11-01

    The analysis of persistent organic pollutants is a real challenge due to the large number of compounds with varying chemical and physical properties. Gas chromatography with electron capture detection or mass spectrometry has been the method of choice for the past 50 years. Comprehensive two-dimensional gas chromatography (GCxGC) coupled with micro-electron capture detector (μECD) is a new method that can analyze polychlorinated biphenyls (PCBs), organochlorine pesticides (OCs) and chlorobenzenes (CBz) in a single analytical run with enhanced selectivity and sensitivity over single column methods and can also be used to screen for other halogenated organics in environmental samples. An accredited routine method using commercially available LECO GCxGC-μECD and a column combination DB-1 × Rtx-PCB has been developed to analyse PCBs/OCs/CBz in soils, sediments and sludges. The method provides quantification of Aroclors and Aroclor mixtures to within 15% of target values and sub-nanogrammes per gramme detection limits.

  7. Reduction of ferrihydrite with adsorbed and coprecipitated organic matter: microbial reduction by Geobacter bremensis vs. abiotic reduction by Na-dithionite

    NASA Astrophysics Data System (ADS)

    Eusterhues, K.; Hädrich, A.; Neidhardt, J.; Küsel, K.; Keller, T. F.; Jandt, K. D.; Totsche, K. U.

    2014-04-01

    Ferrihydrite (Fh) is a widespread poorly crystalline Fe oxide which becomes easily coated by natural organic matter (OM) in the environment. This mineral-bound OM entirely changes the mineral surface properties and therefore the reactivity of the original mineral. Here, we investigated the reactivity of 2-line Fh, Fh with adsorbed OM and Fh coprecipitated with OM towards microbial and abiotic reduction of Fe(III). As a surrogate for dissolved soil OM we used a water extract of a Podzol forest floor. Fh-OM associations with different OM-loadings were reduced either by Geobacter bremensis or abiotically by Na-dithionite. Both types of experiments showed decreasing initial Fe reduction rates and decreasing degrees of reduction with increasing amounts of mineral-bound OM. At similar OM-loadings, coprecipitated Fhs were more reactive than Fhs with adsorbed OM. The difference can be explained by the smaller crystal size and poor crystallinity of such coprecipitates. At small OM loadings this led to even faster Fe reduction rates than found for pure Fh. The amount of mineral-bound OM also affected the formation of secondary minerals: goethite was only found after reduction of OM-free Fh and siderite was only detected when Fhs with relatively low amounts of mineral-bound OM were reduced. We conclude that direct contact of G. bremensis to the Fe oxide mineral surface was inhibited when blocked by OM. Consequently, mineral-bound OM shall be taken into account besides Fe(II) accumulation as a further widespread mechanism to slow down reductive dissolution.

  8. Evidence for Interfacial Halogen Bonding.

    PubMed

    Swords, Wesley B; Simon, Sarah J C; Parlane, Fraser G L; Dean, Rebecca K; Kellett, Cameron W; Hu, Ke; Meyer, Gerald J; Berlinguette, Curtis P

    2016-05-10

    A homologous series of donor-π-acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye-X (X=F, Cl, Br, and I) was immobilized on a TiO2 surface to investigate how the halogen substituents affect the reaction between the light-induced charge-separated state, TiO2 (e(-) )/Dye-X(+) , with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye-F < Dye-Cl < Dye-Br < Dye-I. Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ-hole on the heavier halogens, the differences in dye regeneration kinetics for Dye-Cl, Dye-Br, and Dye-I are ascribed to the extent of halogen bonding with the nucleophilic solution species. PMID:27060916

  9. Halogenated Compounds from Marine Algae

    PubMed Central

    Cabrita, Maria Teresa; Vale, Carlos; Rauter, Amélia Pilar

    2010-01-01

    Marine algae produce a cocktail of halogenated metabolites with potential commercial value. Structures exhibited by these compounds go from acyclic entities with a linear chain to complex polycyclic molecules. Their medical and pharmaceutical application has been investigated for a few decades, however other properties, such as antifouling, are not to be discarded. Many compounds were discovered in the last years, although the need for new drugs keeps this field open as many algal species are poorly screened. The ecological role of marine algal halogenated metabolites has somehow been overlooked. This new research field will provide valuable and novel insight into the marine ecosystem dynamics as well as a new approach to comprehending biodiversity. Furthermore, understanding interactions between halogenated compound production by algae and the environment, including anthropogenic or global climate changes, is a challenging target for the coming years. Research of halogenated metabolites has been more focused on macroalgae than on phytoplankton. However, phytoplankton could be a very promising material since it is the base of the marine food chain with quick adaptation to environmental changes, which undoubtedly has consequences on secondary metabolism. This paper reviews recent progress on this field and presents trends on the role of marine algae as producers of halogenated compounds. PMID:20948909

  10. Thermochemical Properties and Phase Behavior of Halogenated Polycyclic Aromatic Hydrocarbons

    PubMed Central

    Suuberg, Eric M.

    2013-01-01

    Knowledge of vapor pressure of organic pollutants is essential in predicting their fate and transport in the environment. In the present study, the vapor pressures of 12 halogenated polycyclic aromatic compounds (PACs), i.e. 9-chlorofluorene, 2,7-dichlorofluorene, 2-bromofluorene, 9-bromofluorene, 2,7-dibromofluorene, 2-bromoanthracene, 9-chlorophenanthrene, 9-bromophenanthrene, 9,10-dibromophenanthrene, 1-chloropyrene, 7-bromobenz[a]anthracene and 6,12-dibromochrysene, were measured using the Knudsen effusion method over the temperature range of 301 to 464 K. Enthalpies and entropies of sublimation of these compounds were determined via application of the Clausius–Clapeyron equation. The data were also compared with earlier published literature values to study the influence of halogen substitution on vapor pressure of PACs. As expected, the halogen substitution decreases vapor pressure compared to parent compounds, but does not necessarily increase the enthalpy of sublimation. Moreover, the decrease of vapor pressure also depends on the substitution position and the substituted halogen, and the di-substitution of chlorine and/or bromine decreases the vapor pressure compared to single halogen substituted polycyclic aromatic hydrocarbons. Additionally, the enthalpy of fusion and melting temperature of these 12 PACs were determined using differential scanning calorimetry and melting point analysis. PMID:22139714

  11. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... is subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the... halogen scrubber or other halogen reduction technique used to reduce the vent stream halogen atom mass... subpart shall determine the halogen atom mass emission rate prior to the combustion device according...

  12. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... is subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the... halogen scrubber or other halogen reduction technique used to reduce the vent stream halogen atom mass... subpart shall determine the halogen atom mass emission rate prior to the combustion device according...

  13. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... is subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the... halogen scrubber or other halogen reduction technique used to reduce the vent stream halogen atom mass... subpart shall determine the halogen atom mass emission rate prior to the combustion device according...

  14. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... is subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the... halogen scrubber or other halogen reduction technique used to reduce the vent stream halogen atom mass... subpart shall determine the halogen atom mass emission rate prior to the combustion device according...

  15. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... is subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the... halogen scrubber or other halogen reduction technique used to reduce the vent stream halogen atom mass... subpart shall determine the halogen atom mass emission rate prior to the combustion device according...

  16. Biodegradation of Trihalomethanes and Other Halogenated Aliphatic Compounds

    NASA Technical Reports Server (NTRS)

    Smith, G. B.

    1996-01-01

    The biological dehalogenation of common water pollutants such as trichloromethane (chloroform) and other halogenated aliphatic compounds was the subject of this project. Samples from diverse water environments such as from groundwater contaminated with halogenated compounds and wastewaters from regional treatment plants were studied to identify conditions that favor certain dehalogenation reactions over others. Gene probe analyses of DNA extracted from the dichlormethane-degrading wastewater indicated the presence of the gene coding for dichloromethane dehalogenase, indicating the genetic basis for the dechlorination activity observed. These studies indicate that methanogenic bacteria are the organisms responsible for the chloroform dechlorination. Dechlorination of a common chlorofluorocarbon (CFC-11) was identified in samples taken from a regional aquifer contaminated with halogenated aliphatic compounds.

  17. 40 CFR 721.329 - Halogenated benzyl ester acrylate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halogenated benzyl ester acrylate (generic). 721.329 Section 721.329 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... substance may cause internal organ effects (kidney and blood). The requirements of this section do not...

  18. 40 CFR 721.329 - Halogenated benzyl ester acrylate (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halogenated benzyl ester acrylate (generic). 721.329 Section 721.329 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... substance may cause internal organ effects (kidney and blood). The requirements of this section do not...

  19. 40 CFR 721.329 - Halogenated benzyl ester acrylate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogenated benzyl ester acrylate (generic). 721.329 Section 721.329 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... substance may cause internal organ effects (kidney and blood). The requirements of this section do not...

  20. 40 CFR 721.329 - Halogenated benzyl ester acrylate (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated benzyl ester acrylate (generic). 721.329 Section 721.329 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... substance may cause internal organ effects (kidney and blood). The requirements of this section do not...

  1. 40 CFR 721.329 - Halogenated benzyl ester acrylate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halogenated benzyl ester acrylate (generic). 721.329 Section 721.329 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... substance may cause internal organ effects (kidney and blood). The requirements of this section do not...

  2. Halogen radicals contribute to photooxidation in coastal and estuarine waters

    NASA Astrophysics Data System (ADS)

    Parker, Kimberly M.; Mitch, William A.

    2016-05-01

    Although halogen radicals are recognized to form as products of hydroxyl radical (•OH) scavenging by halides, their contribution to the phototransformation of marine organic compounds has received little attention. We demonstrate that, relative to freshwater conditions, seawater halides can increase photodegradation rates of domoic acid, a marine algal toxin, and dimethyl sulfide, a volatile precursor to cloud condensation nuclei, up to fivefold. Using synthetic seawater solutions, we show that the increased photodegradation is specific to dissolved organic matter (DOM) and halides, rather than other seawater salt constituents (e.g., carbonates) or photoactive species (e.g., iron and nitrate). Experiments in synthetic and natural coastal and estuarine water samples demonstrate that the halide-specific increase in photodegradation could be attributed to photochemically generated halogen radicals rather than other photoproduced reactive intermediates [e.g., excited-state triplet DOM (3DOM*), reactive oxygen species]. Computational kinetic modeling indicates that seawater halogen radical concentrations are two to three orders of magnitude greater than freshwater •OH concentrations and sufficient to account for the observed halide-specific increase in photodegradation. Dark •OH generation by gamma radiolysis demonstrates that halogen radical production via •OH scavenging by halides is insufficient to explain the observed effect. Using sensitizer models for DOM chromophores, we show that halogen radicals are formed predominantly by direct oxidation of Cl‑ and Br‑ by 3DOM*, an •OH-independent pathway. Our results indicate that halogen radicals significantly contribute to the phototransformation of algal products in coastal or estuarine surface waters.

  3. Halogen radicals contribute to photooxidation in coastal and estuarine waters.

    PubMed

    Parker, Kimberly M; Mitch, William A

    2016-05-24

    Although halogen radicals are recognized to form as products of hydroxyl radical ((•)OH) scavenging by halides, their contribution to the phototransformation of marine organic compounds has received little attention. We demonstrate that, relative to freshwater conditions, seawater halides can increase photodegradation rates of domoic acid, a marine algal toxin, and dimethyl sulfide, a volatile precursor to cloud condensation nuclei, up to fivefold. Using synthetic seawater solutions, we show that the increased photodegradation is specific to dissolved organic matter (DOM) and halides, rather than other seawater salt constituents (e.g., carbonates) or photoactive species (e.g., iron and nitrate). Experiments in synthetic and natural coastal and estuarine water samples demonstrate that the halide-specific increase in photodegradation could be attributed to photochemically generated halogen radicals rather than other photoproduced reactive intermediates [e.g., excited-state triplet DOM ((3)DOM*), reactive oxygen species]. Computational kinetic modeling indicates that seawater halogen radical concentrations are two to three orders of magnitude greater than freshwater (•)OH concentrations and sufficient to account for the observed halide-specific increase in photodegradation. Dark (•)OH generation by gamma radiolysis demonstrates that halogen radical production via (•)OH scavenging by halides is insufficient to explain the observed effect. Using sensitizer models for DOM chromophores, we show that halogen radicals are formed predominantly by direct oxidation of Cl(-) and Br(-) by (3)DOM*, an (•)OH-independent pathway. Our results indicate that halogen radicals significantly contribute to the phototransformation of algal products in coastal or estuarine surface waters. PMID:27162335

  4. Halogen radicals contribute to photooxidation in coastal and estuarine waters

    NASA Astrophysics Data System (ADS)

    Parker, Kimberly M.; Mitch, William A.

    2016-05-01

    Although halogen radicals are recognized to form as products of hydroxyl radical (•OH) scavenging by halides, their contribution to the phototransformation of marine organic compounds has received little attention. We demonstrate that, relative to freshwater conditions, seawater halides can increase photodegradation rates of domoic acid, a marine algal toxin, and dimethyl sulfide, a volatile precursor to cloud condensation nuclei, up to fivefold. Using synthetic seawater solutions, we show that the increased photodegradation is specific to dissolved organic matter (DOM) and halides, rather than other seawater salt constituents (e.g., carbonates) or photoactive species (e.g., iron and nitrate). Experiments in synthetic and natural coastal and estuarine water samples demonstrate that the halide-specific increase in photodegradation could be attributed to photochemically generated halogen radicals rather than other photoproduced reactive intermediates [e.g., excited-state triplet DOM (3DOM*), reactive oxygen species]. Computational kinetic modeling indicates that seawater halogen radical concentrations are two to three orders of magnitude greater than freshwater •OH concentrations and sufficient to account for the observed halide-specific increase in photodegradation. Dark •OH generation by gamma radiolysis demonstrates that halogen radical production via •OH scavenging by halides is insufficient to explain the observed effect. Using sensitizer models for DOM chromophores, we show that halogen radicals are formed predominantly by direct oxidation of Cl- and Br- by 3DOM*, an •OH-independent pathway. Our results indicate that halogen radicals significantly contribute to the phototransformation of algal products in coastal or estuarine surface waters.

  5. Fabrication of Isolated Metal-Organic Polyhedra in Confined Cavities: Adsorbents/Catalysts with Unusual Dispersity and Activity.

    PubMed

    Kang, Ying-Hu; Liu, Xiao-Dan; Yan, Ni; Jiang, Yao; Liu, Xiao-Qin; Sun, Lin-Bing; Li, Jian-Rong

    2016-05-18

    Metal-organic polyhedra (MOPs) have attracted great attention due to their intriguing structure. However, the applications of MOPs are severely hindered by two shortcomings, namely low dispersity and poor stability. Here we report the introduction of four MOPs (constructed from dicopper and carboxylates) to cavity-structured mesoporous silica SBA-16 via a double-solvent strategy to overcome both shortcomings simultaneously. By judicious design, the dimension of MOPs is just between the size of cavities and entrances of SBA-16, MOP molecules are thus confined in the cavities. This leads to the formation of isolated MOPs with unusual dispersion, making the active sites highly accessible. Hence, the adsorption capacity on carbon dioxide and propene as well as catalytic performance on ring opening are much superior to bulk MOPs. More importantly, the structure and catalytic activity of MOPs in confined cavities are well preserved after exposure to humid atmosphere, whereas those of bulk MOPs are degraded seriously. PMID:27049737

  6. EMERGING TECHNOLOGY SUMMARY: DEMONSTRATION OF AMBERSORB 563 ADSORBENT TECHNOLOGY

    EPA Science Inventory

    A field pilot study was conducted to demonstrate the technical feasibility and cost-effectiveness of Ambersorb® 5631 carbonaceous adsorbent for remediating groundwater contaminated with volatile organic compounds (VOCs). The Ambersorb adsorbent technology demonstration consist...

  7. Halogen derivatives of benzo- and dibenzocrown ethers: synthesis, structure, properties and application

    NASA Astrophysics Data System (ADS)

    Pluzhnik-Gladyr, S. M.

    2016-02-01

    Methods of synthesis of halogenated benzo- and dibenzocrown ether derivatives are surveyed: halogenation of benzo- and dibenzocrown ethers with molecular halogens, N-halosuccinimides in the solid phase and different media (water, ethanol, halohydrocarbons) and hypohalites in water, as well as the 'assembly' method. Reactions of these compounds are considered: synthesis of phosphorus-containing crown ethers, organometallic synthesis, the Heck and Sonogashira reactions, synthesis of acetylene derivatives and other reactions. Special attention is focused on the complexing properties of halogenated benzocrown ethers with respect to ionic guests and neutral organic molecules. The possibility of synthesis of complexes of such compounds in the solid phase is demonstrated. The extraction and sorption properties of halogenated benzo- and dibenzocrown ethers are considered. Examples of practical use of these compounds are presented. The bibliography includes 203 references.

  8. Effects of surface water on gas sorption capacities of gravimetric sensing layers analyzed by molecular descriptors of organic adsorbates.

    PubMed

    Sugimoto, Iwao; Mitsui, Kouta; Nakamura, Masayuki; Seyama, Michiko

    2011-02-01

    The gas sorption capacities of sputtered carbonaceous films are evaluated with quartz crystal resonators. These films are sensitive to 20 ppm organic vapors and exhibit structure-dependent responses. Films derived from synthetic polymers are hydrophobic, whereas films derived from biomaterials are amphiphilic or hydrophilic. Polyethylene (PE) film has an extremely high sorption capacity for a wide range of vapors. Transient sorption responses are investigated using a humidified carrier by employing carboxylic acid esters, whose aliphatic groups are systematically changed. Small esters with a higher affinity to water induce negative U-shaped responses from amphiphilic films derived from biomaterials. On the other hand, polymeric films exhibit positive exponential response curves. Even if the concentrations are decreased, the response intensities are enhanced with the incremental expansion of carbon chains of aliphatic groups. Only fluoropolymer film shows the opposite tendency. The modeling of quantitative structure property relationships has indicated that the sorption capacities of the PE film to the carboxylic acid esters are fundamentally governed by electrostatic interactions. The intermolecular attractive forces are basically attributable to interactions between the positively polarized sites in esters and the negatively polarized/charged sites in PE film.

  9. Hybrid functional calculated optical and electronic structures of thin anatase TiO2 nanowires with organic dye adsorbates

    NASA Astrophysics Data System (ADS)

    Ünal, Hatice; Gunceler, Deniz; Gülseren, Oğuz; Ellialtıoğlu, Şinasi; Mete, Ersen

    2015-11-01

    The electronic and optical properties of thin anatase TiO2 (1 0 1) and (0 0 1) nanowires have been investigated using the screened Coulomb hybrid density functional calculations. For the bare nanowires with sub-nanometer diameters, the calculated band gaps are larger relative to the bulk values due to size effects. The role of organic light harvesting sensitizers on the absorption characteristics of the anatase nanowires has been examined using the hybrid density functional method incorporating partial exact exchange with range separation. For the lowest lying excitations, directional charge redistribution of tetrahydroquinoline (C2-1) dye shows a remarkably different profile in comparison to a simple molecule which is chosen as the coumarin skeleton. The binding modes and the adsorption energies of C2-1 dye and coumarin core on the anatase nanowires have been studied including non-linear solvation effetcs. The calculated optical and electronic properties of the nanowires with these two different types of sensitizers have been interpreted in terms of their electron-hole generation, charge carrier injection and recombination characteristics.

  10. Influence of surface chemistry on the structural organization of monomolecular protein layers adsorbed to functionalized aqueous interfaces.

    PubMed Central

    Lösche, M; Piepenstock, M; Diederich, A; Grünewald, T; Kjaer, K; Vaknin, D

    1993-01-01

    The molecular organization of streptavidin (SA) bound to aqueous surface monolayers of biotin-functionalized lipids and binary lipid mixtures has been investigated with neutron reflectivity and electron and fluorescence microscopy. The substitution of deuterons (2H) for protons (1H), both in subphase water molecules and in the alkyl chains of the lipid surface monolayer, was utilized to determine the interface structure on the molecular length scale. In all cases studied, the protein forms monomolecular layers underneath the interface with thickness values of approximately 40 A. A systematic dependence of the structural properties of such self-assembled SA monolayers on the surface chemistry was observed: the lateral protein density depends on the length of the spacer connecting the biotin moiety and its hydrophobic anchor. The hydration of the lipid head groups in the protein-bound state depends on the dipole moment density at the interface. Images FIGURE 1 FIGURE 2 FIGURE 3 FIGURE 5 FIGURE 11 FIGURE 12 FIGURE A1 PMID:8298041

  11. Hybrid inorganic/organic alumina adsorbents-functionalized-purpurogallin for removal and preconcentration of Cr(III), Fe(III), Cu(II), Cd(II) and Pb(II) from underground water.

    PubMed

    Mahmoud, Mohamed E; Hafez, Osama F; Osman, Maher M; Yakout, Amr A; Alrefaay, Ahmed

    2010-04-15

    Metal pollution is well recognized as one of the major environmental problems that must be imperatively addressed and solved. In this study, three types of alumina adsorbents (I-III) were physically immobilized with purporogallin as a chelating ion exchangers. These were found to exhibit strong capability and selectivity characters for a series of heavy metal ions. Surface modification of hybrid alumina was characterized and identified from the determination of surface coverage and infrared analysis. Hybrid alumina adsorbents were identified for their strong resistivity to acid leaching in pH>2-7 as well as their high thermal stability up to 350 degrees C. The ability of newly synthesized hybrid inorganic/organic alumina adsorbents (I-III) to bind and extract various metal ions was examined and evaluated in various buffer solutions (pH 1.0-7.0) via determination of the metal adsorption capacity values. These were identified as high as 420-560, 500-580 and 500-590 micromol g(-1) for alumina adsorbents (I), (II) and (III), respectively in the case of high concentration levels of Cr(III), Fe(III) and Cu(II). The influence of alumina matrices were highly characterized when low concentration levels (microg ml(-1) and ng ml(-1)) of metal ions were used. Hybrid alumina adsorbents were successfully applied for selective extraction, removal and preconcentration of various heavy metals from underground water samples with percentage recovery values of 92-100+/-1-3%. PMID:20031308

  12. Hybrid inorganic/organic alumina adsorbents-functionalized-purpurogallin for removal and preconcentration of Cr(III), Fe(III), Cu(II), Cd(II) and Pb(II) from underground water.

    PubMed

    Mahmoud, Mohamed E; Hafez, Osama F; Osman, Maher M; Yakout, Amr A; Alrefaay, Ahmed

    2010-04-15

    Metal pollution is well recognized as one of the major environmental problems that must be imperatively addressed and solved. In this study, three types of alumina adsorbents (I-III) were physically immobilized with purporogallin as a chelating ion exchangers. These were found to exhibit strong capability and selectivity characters for a series of heavy metal ions. Surface modification of hybrid alumina was characterized and identified from the determination of surface coverage and infrared analysis. Hybrid alumina adsorbents were identified for their strong resistivity to acid leaching in pH>2-7 as well as their high thermal stability up to 350 degrees C. The ability of newly synthesized hybrid inorganic/organic alumina adsorbents (I-III) to bind and extract various metal ions was examined and evaluated in various buffer solutions (pH 1.0-7.0) via determination of the metal adsorption capacity values. These were identified as high as 420-560, 500-580 and 500-590 micromol g(-1) for alumina adsorbents (I), (II) and (III), respectively in the case of high concentration levels of Cr(III), Fe(III) and Cu(II). The influence of alumina matrices were highly characterized when low concentration levels (microg ml(-1) and ng ml(-1)) of metal ions were used. Hybrid alumina adsorbents were successfully applied for selective extraction, removal and preconcentration of various heavy metals from underground water samples with percentage recovery values of 92-100+/-1-3%.

  13. Halogen bonding in solution: thermodynamics and applications.

    PubMed

    Beale, Thomas M; Chudzinski, Michael G; Sarwar, Mohammed G; Taylor, Mark S

    2013-02-21

    Halogen bonds are noncovalent interactions in which covalently bound halogens act as electrophilic species. The utility of halogen bonding for controlling self-assembly in the solid state is evident from a broad spectrum of applications in crystal engineering and materials science. Until recently, it has been less clear whether, and to what extent, halogen bonding could be employed to influence conformation, binding or reactivity in the solution phase. This tutorial review summarizes and interprets solution-phase thermodynamic data for halogen bonding interactions obtained over the past six decades and highlights emerging applications in molecular recognition, medicinal chemistry and catalysis.

  14. A novel dispersive solid-phase extraction method using metal-organic framework MIL-101 as the adsorbent for the analysis of benzophenones in toner.

    PubMed

    Li, Ning; Zhu, Quanfei; Yang, Yang; Huang, Jianlin; Dang, Xueping; Chen, Huaixia

    2015-01-01

    Metal-organic frameworks (MOFs) have been paid widespread attention in the field of adsorption and separation materials due to its porosity, large specific surface area, unsaturated metal-ligand sites and structural diversity. In this study, the green powder MIL-101 was synthesized and used for the extraction of benzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxy-benzophenone from toner samples for the first time. The synthesized MIL-101 was characterized by X-ray diffraction, scanning electron microscopy, thermogravimetry and nitrogen adsorption porosimetry. The MIL-101 was applied as the dispersive solid phase extraction (DSPE) adsorbent for the extraction and preconcentration of benzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxy-benzophenone from toner samples. The extraction conditions were investigated. Under the optimized conditions, a DSPE-HPLC method for the determination of benzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxy-benzophenone was developed. The method yielded a linear calibration curve in the concentration ranges from 4.0 to 3500 μg L(-1) for the three analytes in toner samples with regression coefficients (r(2)) of 0.9992, 0.9999 and 0.9990, respectively. Limits of detection were 1.2, 1.2 and 0.9 μg L(-1), respectively. Both the intra-day and inter-day precisions (RSDs) were <10%. PMID:25476369

  15. Fluorescence dynamics of microsphere-adsorbed sunscreens

    NASA Astrophysics Data System (ADS)

    Krishnan, R.

    2005-03-01

    Sunscreens are generally oily substances which are prepared in organic solvents, emulsions or dispersions with micro- or nanoparticles. These molecules adsorb to and integrate into skin cells. In order to understand the photophysical properties of the sunscreen, we compare steady-state and time-resolved fluorescence in organic solvent of varying dielectric constant ɛ and adsorbed to polystyrene microspheres and dispersed in water. Steady-state fluorescence is highest and average fluorescence lifetime longest in toluene, the solvent of lowest ɛ. However, there is no uniform dependence on ɛ. Sunscreens PABA and padimate-O show complex emission spectra. Microsphere-adsorbed sunscreens exhibit highly non-exponential decay, illustrative of multiple environments of the adsorbed molecule. The heterogeneous fluorescence dynamics likely characterizes sunscreen adsorbed to cells.

  16. Structural Perspective on Enzymatic Halogenation

    PubMed Central

    2008-01-01

    Simple halogen substituents frequently afford key structural features that account for the potency and selectivity of natural products, including antibiotics and hormones. For example, when a single chlorine atom on the antibiotic vancomycin is replaced by hydrogen, the resulting antibacterial activity decreases by up to 70% (HarrisC. M.; KannanR.; KopeckaH.; HarrisT. M.J. Am. Chem. Soc.1985, 107, 6652−6658). This Account analyzes how structure underlies mechanism in halogenases, the molecular machines designed by nature to incorporate halogens into diverse substrates. Traditional synthetic methods of integrating halogens into complex molecules are often complicated by a lack of specificity and regioselectivity. Nature, however, has developed a variety of elegant mechanisms for halogenating specific substrates with both regio- and stereoselectivity. An improved understanding of the biological routes toward halogenation could lead to the development of novel synthetic methods for the creation of new compounds with enhanced functions. Already, researchers have co-opted a fluorinase from the microorganism Streptomyces cattleya to produce 18F-labeled molecules for use in positron emission tomography (PET) (DengH.; CobbS. L.; GeeA. D.; LockhartA.; MartarelloL.; McGlincheyR. P.; O’HaganD.; OnegaM.Chem. Commun.2006, 652−654). Therefore, the discovery and characterization of naturally occurring enzymatic halogenation mechanisms has become an active area of research. The catalogue of known halogenating enzymes has expanded from the familiar haloperoxidases to include oxygen-dependent enzymes and fluorinases. Recently, the discovery of a nucleophilic halogenase that catalyzes chlorinations has expanded the repertoire of biological halogenation chemistry (DongC.; HuangF.; DengH.; SchaffrathC.; SpencerJ. B.; O’HaganD.; NaismithJ. H.Nature2004, 427, 561−56514765200). Structural characterization has provided a basis toward a mechanistic understanding of the specificity

  17. Noncovalent interactions in halogenated ionic liquids: theoretical study and crystallographic implications.

    PubMed

    Li, Haiying; Lu, Yunxiang; Wu, Weihong; Liu, Yingtao; Peng, Changjun; Liu, Honglai; Zhu, Weiliang

    2013-03-28

    In recent years, several specific imidazolium-based ionic liquids with halogen substituents on the imidazole ring as well as on the alkyl chains have been reported. In this work, noncovalent interactions in four halogenated ionic liquids, i.e. 2-bromo-/iodo- and 4,5-dibromo-/diiodo-1,3-dimethylimidazolium trifluoromethanesulfonates, were systematically investigated using density functional theory calculations. The structural and energetic properties of the ion pairs for such ionic liquids have been fully examined and compared with the non-halogenated ones. It was found that C-X···O halogen bonds, C-H···O hydrogen bonds, and electrostatic interactions with the anion located over the imidazole ring in the ion pairs. In addition, the structures and energetics of two ion pairs for such ionic liquids were also explored to reproduce experimental observations. The halogen-bonded ring structures and the conformers with the concurrent C-H···O and C-X···O contacts were predicted, consistent with the X-ray crystal structures of corresponding organic salts. Finally, the implications of the observed structural and energetic features of ion pairs on the design of halogen-bonding ionic liquids were discussed. The results presented herein should provide useful information in the development of novel halogenated ionic liquids used for specific tasks ranging from organic synthesis to gas absorption.

  18. PERVAPORATION USING ADSORBENT-FILLED MEMBRANES

    EPA Science Inventory

    Membranes containing selective fillers, such as zeolites and activated carbon, can improve the separation by pervaporation. Applications of adsorbent-filled membranes in pervaporation have been demonstrated by a number of studies. These applications include removal of organic co...

  19. Modeling adsorption: Investigating adsorbate and adsorbent properties

    NASA Astrophysics Data System (ADS)

    Webster, Charles Edwin

    1999-12-01

    Surface catalyzed reactions play a major role in current chemical production technology. Currently, 90% of all chemicals are produced by heterogeneously catalyzed reactions. Most of these catalyzed reactions involve adsorption, concentrating the substrate(s) (the adsorbate) on the surface of the solid (the adsorbent). Pore volumes, accessible surface areas, and the thermodynamics of adsorption are essential in the understanding of solid surface characteristics fundamental to catalyst and adsorbent screening and selection. Molecular properties such as molecular volumes and projected molecular areas are needed in order to convert moles adsorbed to surface volumes and areas. Generally, these molecular properties have been estimated from bulk properties, but many assumptions are required. As a result, different literature values are employed for these essential molecular properties. Calculated molar volumes and excluded molecular areas are determined and tabulated for a variety of molecules. Molecular dimensions of molecules are important in the understanding of molecular exclusion as well as size and shape selectivity, diffusion, and adsorbent selection. Molecular dimensions can also be used in the determination of the effective catalytic pore size of a catalyst. Adsorption isotherms, on zeolites, (crystalline mineral oxides) and amorphous solids, can be analyzed with the Multiple Equilibrium Analysis (MEA) description of adsorption. The MEA produces equilibrium constants (Ki), capacities (ni), and thermodynamic parameters (enthalpies, ΔHi, and entropies, ΔSi) of adsorption for each process. Pore volumes and accessible surface areas are calculated from the process capacities. Adsorption isotherms can also be predicted for existing and new adsorbate-adsorbent systems with the MEA. The results show that MEA has the potential of becoming a standard characterization method for microporous solids that will lead to an increased understanding of their behavior in gas

  20. Contribution of selected perfluoroalkyl and polyfluoroalkyl substances to the adsorbable organically bound fluorine in German rivers and in a highly contaminated groundwater.

    PubMed

    Willach, Sarah; Brauch, Heinz-Jürgen; Lange, Frank T

    2016-02-01

    Due to the lack of analytical standards the application of surrogate parameters for organofluorine detection in the aquatic environment is a complementary approach to single compound target analysis of perfluoroalkyl and polyfluoroalkyl chemicals (PFASs). The recently developed method adsorbable organically bound fluorine (AOF) is based on adsorption of organofluorine chemicals to activated carbon followed by combustion ion chromatography. This AOF method was further simplified to enable measurement of larger series of environmental samples. The limit of quantification (LOQ) was 0.77 μg/L F. The modified protocol was applied to 22 samples from German rivers, a municipal wastewater treatment plant (WWTP) effluent, and four groundwater samples from a fire-fighting training site. The WWTP effluent (AOF = 1.98 μg/L F) and only three river water samples (AOF between 0.88 μg/L F and 1.47 μg/L F) exceeded the LOQ. The AOF levels in a PFASs plume at a heavily contaminated site were in the range of 162 ± 3 μg/L F to 782 ± 43 μg/L F. In addition to AOF 17 PFASs were analyzed by high performance liquid chromatography-tandem mass spectrometry. 32-51% of AOF in the contaminated groundwater samples were explained by individual PFASs wheras in the surface waters more than 95% remained unknown. Organofluorine of two fluorinated pesticides, one pesticide metabolite and three fluorinated pharmaceuticals was recovered as AOF by >50% from all four tested water matrices. It is suggested that in the diffusely contaminated water bodies such fluorinated chemicals and not monitored PFASs contribute significantly to AOF.

  1. Quantification of the effects of organic and carbonate buffers on arsenate and phosphate adsorption on a goethite-based granular porous adsorbent.

    PubMed

    Kanematsu, Masakazu; Young, Thomas M; Fukushi, Keisuke; Sverjensky, Dimitri A; Green, Peter G; Darby, Jeannie L

    2011-01-15

    Interest in the development of oxide-based materials for arsenate removal has led to a variety of experimental methods and conditions for determining arsenate adsorption isotherms, which hinders comparative evaluation of their adsorptive capacities. Here, we systematically investigate the effects of buffer (HEPES or carbonate), adsorbent dose, and solution pH on arsenate and phosphate adsorption isotherms for a previously well characterized goethite-based adsorbent (Bayoxide E33 (E33)). All adsorption isotherms obtained at different adsorbate/adsorbent concentrations were identical when 1 mM of HEPES (96 mg C/L) was used as a buffer. At low aqueous arsenate and phosphate concentration (∼1.3 μM), however, adsorption isotherms obtained using 10 mM of NaHCO(3) buffer, which is a reasonable carbonate concentration in groundwater, are significantly different from those obtained without buffer or with HEPES. The carbonate competitive effects were analyzed using the extended triple layer model (ETLM) with the adsorption equilibrium constant of carbonate calibrated using independent published carbonate adsorption data for pure goethite taking into consideration the different surface properties. The successful ETLM calculations of arsenate adsorption isotherms for E33 under various conditions allowed quantitative comparison of the arsenate adsorption capacity between E33 and other major adsorbents initially tested under varied experimental conditions in the literature.

  2. Theoretical study of stability and charge-transport properties of coronene molecule and some of its halogenated derivatives: A path to ambipolar organic-based materials?

    SciTech Connect

    Sancho-García, J. C. Pérez-Jiménez, A. J.

    2014-10-07

    We have carefully investigated the structural and electronic properties of coronene and some of its fluorinated and chlorinated derivatives, including full periphery substitution, as well as the preferred orientation of the non-covalent dimer structures subsequently formed. We have paid particular attention to a set of methodological details, to first obtain single-molecule magnitudes as accurately as possible, including next the use of modern dispersion-corrected methods to tackle the corresponding non-covalently bound dimers. Generally speaking, this class of compounds is expected to self-assembly in neighboring π-stacks with dimer stabilization energies ranging from –20 to –30 kcal mol{sup −1} at close distances around 3.0–3.3 Å. Then, in a further step, we have also calculated hole and electron transfer rates of some suitable candidates for ambipolar materials, and corresponding charge mobility values, which are known to critically depend on the supramolecular organization of the samples. For coronene and per-fluorinated coronene, we have found high values for their hopping rates, although slightly smaller for the latter due to an increase (decrease) of the reorganization energies (electronic couplings)

  3. Theoretical study of stability and charge-transport properties of coronene molecule and some of its halogenated derivatives: a path to ambipolar organic-based materials?

    PubMed

    Sancho-García, J C; Pérez-Jiménez, A J

    2014-10-01

    We have carefully investigated the structural and electronic properties of coronene and some of its fluorinated and chlorinated derivatives, including full periphery substitution, as well as the preferred orientation of the non-covalent dimer structures subsequently formed. We have paid particular attention to a set of methodological details, to first obtain single-molecule magnitudes as accurately as possible, including next the use of modern dispersion-corrected methods to tackle the corresponding non-covalently bound dimers. Generally speaking, this class of compounds is expected to self-assembly in neighboring π-stacks with dimer stabilization energies ranging from -20 to -30 kcal mol(-1) at close distances around 3.0-3.3 Å. Then, in a further step, we have also calculated hole and electron transfer rates of some suitable candidates for ambipolar materials, and corresponding charge mobility values, which are known to critically depend on the supramolecular organization of the samples. For coronene and per-fluorinated coronene, we have found high values for their hopping rates, although slightly smaller for the latter due to an increase (decrease) of the reorganization energies (electronic couplings). PMID:25296829

  4. Halogenated DOPA in a Marine Adhesive Protein

    PubMed Central

    Sun, Cheng Jun; Srivastava, Aasheesh; Reifert, Jack R.; Waite, J. Herbert

    2009-01-01

    The sandcastle worm Phragmatopoma californica, a marine polychaete, constructs a tube-like shelter by cementing together sand grains using a glue secreted from the building organ in its thorax. The glue is a mixture of post-translationally modified proteins, notably the cement proteins Pc-1 and Pc-2 with the amino acid, 3,4-dihydroxyphenyl-L-alanine (DOPA). Significant amounts of a halogenated derivative of DOPA were isolated from the worm cement following partial acid hydrolysis and capture of catecholic amino acids by phenylboronate affinity chromatography. Analysis by tandem mass spectrometry and 1H NMR indicates the DOPA derivative to be 2-chloro-4, 5-dihydroxyphenyl-L-alanine. The potential roles of 2-chloro-DOPA in chemical defense and underwater adhesion are considered. PMID:20126508

  5. Insights into enzymatic halogenation from computational studies

    PubMed Central

    Senn, Hans M.

    2014-01-01

    The halogenases are a group of enzymes that have only come to the fore over the last 10 years thanks to the discovery and characterization of several novel representatives. They have revealed the fascinating variety of distinct chemical mechanisms that nature utilizes to activate halogens and introduce them into organic substrates. Computational studies using a range of approaches have already elucidated many details of the mechanisms of these enzymes, often in synergistic combination with experiment. This Review summarizes the main insights gained from these studies. It also seeks to identify open questions that are amenable to computational investigations. The studies discussed herein serve to illustrate some of the limitations of the current computational approaches and the challenges encountered in computational mechanistic enzymology. PMID:25426489

  6. Insights into enzymatic halogenation from computational studies

    NASA Astrophysics Data System (ADS)

    Senn, Hans

    2014-11-01

    The halogenases are a group of enzymes that have only come to the fore over the last ten years thanks to the discovery and characterization of several of novel representatives. They have re-vealed the fascinating variety of distinct chemical mechanisms that nature utilizes to activate and introduce halogens into organic substrates. Computational studies using a range of approaches have already elucidated many details of the mechanisms of these enzymes, often in synergistic combination with experiment. This Review summarizes the main insights gained from these stud-ies. It also seeks to identify open questions that are amenable to computational investigations. The studies discussed herein also serve to illustrate some of the limitations of the current computa-tional approaches and the challenges encountered in computational mechanistic enzymology.

  7. Halogenated DOPA in a Marine Adhesive Protein.

    PubMed

    Sun, Cheng Jun; Srivastava, Aasheesh; Reifert, Jack R; Waite, J Herbert

    2009-02-01

    The sandcastle worm Phragmatopoma californica, a marine polychaete, constructs a tube-like shelter by cementing together sand grains using a glue secreted from the building organ in its thorax. The glue is a mixture of post-translationally modified proteins, notably the cement proteins Pc-1 and Pc-2 with the amino acid, 3,4-dihydroxyphenyl-L-alanine (DOPA). Significant amounts of a halogenated derivative of DOPA were isolated from the worm cement following partial acid hydrolysis and capture of catecholic amino acids by phenylboronate affinity chromatography. Analysis by tandem mass spectrometry and (1)H NMR indicates the DOPA derivative to be 2-chloro-4, 5-dihydroxyphenyl-L-alanine. The potential roles of 2-chloro-DOPA in chemical defense and underwater adhesion are considered.

  8. A new 68Ge/68Ga generator system using an organic polymer containing N-methylglucamine groups as adsorbent for 68Ge.

    PubMed

    Nakayama, M; Haratake, M; Ono, M; Koiso, T; Harada, K; Nakayama, H; Yahara, S; Ohmomo, Y; Arano, Y

    2003-01-01

    A macroporous styrene-divinylbenzene copolymer containing N-methylglucamine groups was selected for a new 68Ge/68Ga generator system. This resin packed into a column effectively adsorbed the parent nuclide 68Ge. The daughter 68Ga was eluted from the resin with a solution of a low-affinity gallium chelating ligand such as citric or phosphoric acid. The 68Ge leakage was less than 0.0004% of the 68Ge adsorbed on the resin. By simple mixing of transferrin and desferoxamine conjugated HSA and IgG with the eluate from the column, 68Ga-labeling was completed in high yield. PMID:12485657

  9. [The mutagenicity of organic microcontamination in the environment. II. The mutagenicity of volatile organic halogens in the Salmonella microsome test (Ames Test) with regard to the contamination of groundwater and drinking water].

    PubMed

    Mersch-Sundermann, V

    1989-02-01

    To determine the sensitivity and specificity of microbial shortterm-tests for the registration of the mutagenic potency of halogenated hydrocarbons (OHV) 18 pure substances out of the groups of halomethanes, -ethanes and -ethylenes were examined with different laboratory methods (classical Ames-Test, Spot-Testing, Preincubation-Procedure) of the Salmonella-Microsome-Test (Ames-Test). The Salmonella typhimurium- strains TA97, TA98, TA100 und TA102 were used with and without metabolic activation of Arochlor 1254 induced rat-liver microsomes. Mutagenicity with one or several procedures shows 1,1,2,2-tetrachloroethane, hexachloroethane, trichloroethylene, bromdichloromethane and bromoform without metabolic activation and dichloromethane, tetrachloromethane, 1,1,2,2-tetrachloroethane, hexachloroethane, 1,1-dichloroethylene, trans-1,2-dichloroethylene, tetrachloroethylene and bromdichloromethane with metabolic activation. The range of sensitivity amounted from microgram to nanogram values of OHV's per plate, so that the Ames-test can be a sensitive screening method sufficient for detection of mutagenic effects by several OHV's in high contaminated environmental samples even without extraction procedures.

  10. METHOD FOR PRODUCING ISOTOPIC METHANES AND PARTIALLY HALOGENATED DERIVATIVES THEROF

    DOEpatents

    Frazer, J.W.

    1959-08-18

    A method is given for producing isotopic methanes and/ or partially halogenated derivatives. Lithium hydride, deuteride, or tritide is reacted with a halogenated methane or with a halogenated methane in combination with free halogen. The process is conveniently carried out by passing a halogenated methane preferably at low pressures or in an admixture with an inert gas through a fixed bed of finely divided lithium hydride heated initially to temperatures of 100 to 200 deg C depending upon the halogenated methane used.

  11. VERUCLAY – a new type of photo-adsorbent active in the visible light range: modification of montmorillonite surface with organic surfactant

    EPA Science Inventory

    Montmorillonite K10 was treated with VeruSOL-3, a biodegradable and food-grade surfactant mixture of coconut oil, castor oil and citrus extracts, to manufacture a benign catalytic adsorbent that is active in the visible light. Veruclay was characterized by SEM, XRD, TGA, UVDRS, a...

  12. Determination of adsorbable organic fluorine from aqueous environmental samples by adsorption to polystyrene-divinylbenzene based activated carbon and combustion ion chromatography.

    PubMed

    Wagner, Andrea; Raue, Brigitte; Brauch, Heinz-Jürgen; Worch, Eckhard; Lange, Frank T

    2013-06-21

    A new method for the determination of trace levels of adsorbable organic fluorine (AOF) in water is presented. Even if the individual contributing target compounds are widely unknown, this surrogate parameter is suited to identify typical organofluorine contaminations, such as with polyfluorinated chemicals (PFCs), and represents a lower boundary of the organofluorine concentration in water bodies. It consists of the adsorption of organofluorine chemicals on a commercially available synthetic polystyrene-divinylbenzene based activated carbon (AC) followed by analysis of the loaded AC by hydropyrolysis combustion ion chromatography (CIC). Inorganic fluorine is displaced by excess nitrate during the extraction step and by washing the loaded activated carbon with an acidic sodium nitrate solution. Due to its high purity the synthetic AC had a very low and reproducible fluorine blank (0.3 μg/g) compared to natural ACs (up to approximately 9 μg/g). Using this AC, fluoride and the internal standard phosphate could be detected free of chromatographic interferences. With a sample volume of 100 mL and 2× 100 mg of AC packed into two extraction columns combined in series, a limit of quantification (LOQ), derived according to the German standard method DIN 32645, of 0.3 μg/L was achieved. The recoveries of six model PFCs were determined from tap water and a municipal wastewater treatment plant (WWTP) effluent. Except for the extremely polar perfluoroacetic acid (recovery of approximately 10%) the model substances showed fairly good (50% for perfluorobutanoic acid (PFBA)) to very good fluorine recoveries (100±20% for perfluorooctanoic acid (PFOA), perfluorobutanesulfonate (PFBS), 6:2 fluorotelomersulfonate (6:2 FTS)), both from tap water and wastewater matrix. This new analytical protocol was exemplarily applied to several surface water and groundwater samples. The obtained AOF values were compared to the fluorine content of 19 target PFCs analyzed by high performance

  13. 40 CFR 721.8675 - Halogenated pyridines.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8675 Halogenated pyridines. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated pyridine (PMN P-83-1163)...

  14. 40 CFR 721.505 - Halogenated acrylonitrile.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.505 Halogenated acrylonitrile. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated acrylonitrile, (PMN P-90-299)...

  15. 40 CFR 721.505 - Halogenated acrylonitrile.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.505 Halogenated acrylonitrile. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated acrylonitrile, (PMN P-90-299)...

  16. Halogen-bonded mesogens direct polymer self-assemblies up to millimetre length scale

    PubMed Central

    Houbenov, Nikolay; Milani, Roberto; Poutanen, Mikko; Haataja, Johannes; Dichiarante, Valentina; Sainio, Jani; Ruokolainen, Janne; Resnati, Giuseppe; Metrangolo, Pierangelo; Ikkala, Olli

    2014-01-01

    Aligning polymeric nanostructures up to macroscale in facile ways remains a challenge in materials science and technology. Here we show polymeric self-assemblies where nanoscale organization guides the macroscopic alignment up to millimetre scale. The concept is shown by halogen bonding mesogenic 1-iodoperfluoroalkanes to a star-shaped ethyleneglycol-based polymer, having chloride end-groups. The mesogens segregate and stack parallel into aligned domains. This leads to layers at ~10 nm periodicity. Combination of directionality of halogen bonding, mesogen parallel stacking and minimization of interfacial curvature translates into an overall alignment in bulk and films up to millimetre scale. Upon heating, novel supramolecular halogen-bonded polymeric liquid crystallinity is also shown. As many polymers present sites capable of receiving halogen bonding, we suggest generic potential of this strategy for aligning polymer self-assemblies. PMID:24893843

  17. Reactions of halogens with surfaces stimulated by VUV light

    NASA Astrophysics Data System (ADS)

    Ney, Verena; Schwentner, Nikolaus

    2006-08-01

    Reactions of halogens (Cl2,XeF2) with metals (Cu) and semiconductors (Si, GaAs) are investigated. The main focus is put on light induced reactions, stimulated by synchrotron radiation in the spectral range from 200 to 50 nm, in comparison with the dark reaction. Growth of reaction products on the surface and the desorption of volatile compounds are studied. A set-up with a quartz microbalance was adopted to determine reaction rates in situ. The rates are very sensitive to sample preparation. In the system Cu/Cl2, oxygen was found to especially slow down the reaction and much higher reaction rates than reported previously were observed for pure samples. Measurements with masks show the possibility of using desorption (also called light induced dry etching) to microstructure materials. Analysis of the irradiations with different wavelengths reveals a high spectral dependence of the reactions, which can therefore be controlled. The efficiency of the light induced non-selective reaction follows the gas phase absorption of the etching gases, whereas selective reactions, which are used to structure the materials, are induced in adsorbed halogens at different wavelengths. High efficiencies of single-photon events, due to chain reactions, with multiplication factors of the order of 105, are observed. The resulting pit size has to be contrasted with the intended spatial resolution.

  18. Selective Halogenation Using an Aniline Catalyst.

    PubMed

    Samanta, Ramesh C; Yamamoto, Hisashi

    2015-08-17

    Electrophilic halogenation is used to produce a wide variety of halogenated compounds. Previously reported methods have been developed mainly using a reagent-based approach. Unfortunately, a suitable "catalytic" process for halogen transfer reactions has yet to be achieved. In this study, arylamines have been found to generate an N-halo arylamine intermediate, which acts as a highly reactive but selective catalytic electrophilic halogen source. A wide variety of heteroaromatic and aromatic compounds are halogenated using commercially available N-halosuccinimides, for example, NCS, NBS, and NIS, with good to excellent yields and with very high selectivity. In the case of unactivated double bonds, allylic chlorides are obtained under chlorination conditions, whereas bromocyclization occurs for polyolefin. The reactivity of the catalyst can be tuned by varying the electronic properties of the arene moiety of catalyst.

  19. Halogen Chemistry on Catalytic Surfaces.

    PubMed

    Moser, Maximilian; Pérez-Ramírez, Javier

    2016-01-01

    Halogens are key building blocks for the manufacture of high-value products such as chemicals, plastics, and pharmaceuticals. The catalytic oxidation of HCl and HBr is an attractive route to recover chlorine and bromine in order to ensure the sustainability of the production processes. Very few materials withstand the high corrosiveness and the strong exothermicity of the reactions and among them RuO2 and CeO2-based catalysts have been successfully applied in HCl oxidation. The search for efficient systems for HBr oxidation was initiated by extrapolating the results of HCl oxidation based on the chemical similarity of these reactions. Interestingly, despite its inactivity in HCl oxidation, TiO2 was found to be an outstanding HBr oxidation catalyst, which highlighted that the latter reaction is more complex than previously assumed. Herein, we discuss the results of recent comparative studies of HCl and HBr oxidation on both rutile-type (RuO2, IrO2, and TiO2) and ceria-based catalysts using a combination of advanced experimental and theoretical methods to provide deeper molecular-level understanding of the reactions. This knowledge aids the design of the next-generation catalysts for halogen recycling. PMID:27131113

  20. Effects of halogen doping on nanocarbon catalysts synthesized by a solution plasma process for the oxygen reduction reaction.

    PubMed

    Ishizaki, Takahiro; Wada, Yuta; Chiba, Satoshi; Kumagai, Sou; Lee, Hoonseung; Serizawa, Ai; Li, Oi Lun; Panomsuwan, Gasidit

    2016-08-01

    Halogen-doped carbon nanoparticles (CNPs) were synthesized by a simple one-step solution plasma process at room temperature using a mixture of benzene (C6H6) and organics containing halogen atoms as the precursors (i.e., hexafluorobenzene (C6F6), hexachlorobenzene (C6Cl6), and hexabromobenzene (C6Br6)). The experimental results demonstrated that halogen doping, especially F and Cl, could lead to more efficient removal of residual hydrogen compared to carbon synthesized with pure benzene. This phenomenon was related to the different binding energies between hydrogen and halogens to form hydrogen halides. Their crystallinity and morphology did not change and remained the same as non-doped carbon. The electrochemical evaluation of oxygen reduction reaction (ORR) activity in an alkaline solution revealed that halogen doping did not play a significant role in shifting the onset potential for the ORR, while a slight enhancement in diffusion limited current density was observed at high overpotentials. Moreover, the electron transfer number involved in the ORR process determined from the Koutecky-Levich plot at -0.6 V was found to increase for halogen-doped carbons in the following order: F-CNPs > Br-CNPs > Cl-CNPs > CNPs. The improved ORR performance of F-CNPs could reasonably be attributed to the synergistic effects of specific bonding states between the halogen and carbon, structural defects and surface functional groups. Our results confirmed the validity of using halogen doping to improve the ORR catalytic activity of CNPs. PMID:27435811

  1. Ion mobility mass spectrometry enables the efficient detection and identification of halogenated natural products from cyanobacteria with minimal sample preparation.

    PubMed

    Esquenazi, Eduardo; Daly, Michael; Bahrainwala, Tasneem; Gerwick, William H; Dorrestein, Pieter C

    2011-11-15

    Direct observation of halogenated natural products produced by different strains of marine cyanobacteria was accomplished by electrospray ionization and matrix assisted laser desorption ionization and gas phase separation via ion mobility mass spectrometry of extracts as well as intact organisms.

  2. Molecular Adsorber Coating

    NASA Technical Reports Server (NTRS)

    Straka, Sharon; Peters, Wanda; Hasegawa, Mark; Hedgeland, Randy; Petro, John; Novo-Gradac, Kevin; Wong, Alfred; Triolo, Jack; Miller, Cory

    2011-01-01

    A document discusses a zeolite-based sprayable molecular adsorber coating that has been developed to alleviate the size and weight issues of current ceramic puck-based technology, while providing a configuration that more projects can use to protect against degradation from outgassed materials within a spacecraft, particularly contamination-sensitive instruments. This coating system demonstrates five times the adsorption capacity of previously developed adsorber coating slurries. The molecular adsorber formulation was developed and refined, and a procedure for spray application was developed. Samples were spray-coated and tested for capacity, thermal optical/radiative properties, coating adhesion, and thermal cycling. Work performed during this study indicates that the molecular adsorber formulation can be applied to aluminum, stainless steel, or other metal substrates that can accept silicate-based coatings. The coating can also function as a thermal- control coating. This adsorber will dramatically reduce the mass and volume restrictions, and is less expensive than the currently used molecular adsorber puck design.

  3. Halogen Bonding in Hypervalent Iodine Compounds.

    PubMed

    Catalano, Luca; Cavallo, Gabriella; Metrangolo, Pierangelo; Resnati, Giuseppe; Terraneo, Giancarlo

    2016-01-01

    Halogen bonds occur when electrophilic halogens (Lewis acids) attractively interact with donors of electron density (Lewis bases). This term is commonly used for interactions undertaken by monovalent halogen derivatives. The aim of this chapter is to show that the geometric features of the bonding pattern around iodine in its hypervalent derivatives justify the understanding of some of the longer bonds as halogen bonds. We suggest that interactions directionality in ionic and neutral λ(3)-iodane derivatives is evidence that the electron density distribution around iodine atoms is anisotropic, a region of most positive electrostatic potential exists on the extensions of the covalent bonds formed by iodine, and these positive caps affect, or even determine, the crystal packing of these derivatives. For instance, the short cation-anion contacts in ionic λ(3)-iodane and λ(5)-iodane derivatives fully match the halogen bond definition and geometrical prerequisites. The same holds for the short contacts the cation of ionic λ(3)-iodanes forms with lone-pair donors or the short contacts given by neutral λ(3)-iodanes with incoming nucleophiles. The longer and weaker bonds formed by iodine in hypervalent compounds are usually called secondary bondings and we propose that the term halogen bond can also be used. Compared to the term secondary bond, halogen bond may possibly be more descriptive of some bonding features, e.g., its directionality and the relationships between structure of interacting groups and interaction strength. PMID:26809623

  4. Regioselective Halogenation of 1,4-Benzodiazepinones via CH Activation

    PubMed Central

    Abdelkafi, Hajer; Cintrat, Jean-Christophe

    2015-01-01

    This article reports an efficient CH activation process for regioselective halogenation of 1,4-benzodiazepinones. Direct halogenation with NXS (X = Br, I) affords halogenated benzodiazepinones on the central aromatic ring whereas catalyst (Pd(OAc)2) controlled CH activation furnishes regioselectively ortho halogenated benzodiazepinones on the phenyl side chain. PMID:26179245

  5. Does fluorine participate in halogen bonding?

    PubMed

    Eskandari, Kiamars; Lesani, Mina

    2015-03-16

    When R is sufficiently electron withdrawing, the fluorine in the R-F molecules could interact with electron donors (e.g., ammonia) and form a noncovalent bond (F⋅⋅⋅N). Although these interactions are usually categorized as halogen bonding, our studies show that there are fundamental differences between these interactions and halogen bonds. Although the anisotropic distribution of electronic charge around a halogen is responsible for halogen bond formations, the electronic charge around the fluorine in these molecules is spherical. According to source function analysis, F is the sink of electron density at the F⋅⋅⋅N BCP, whereas other halogens are the source. In contrast to halogen bonds, the F⋅⋅⋅N interactions cannot be regarded as lump-hole interactions; there is no hole in the valence shell charge concentration (VSCC) of fluorine. Although the quadruple moment of Cl and Br is mainly responsible for the existence of σ-holes, it is negligibly small in the fluorine. Here, the atomic dipole moment of F plays a stabilizing role in the formation of F⋅⋅⋅N bonds. Interacting quantum atoms (IQA) analysis indicates that the interaction between halogen and nitrogen in the halogen bonds is attractive, whereas it is repulsive in the F⋅⋅⋅N interactions. Virial-based atomic energies show that the fluorine, in contrast to Cl and Br, stabilize upon complex formation. According to these differences, it seems that the F⋅⋅⋅N interactions should be referred to as "fluorine bond" instead of halogen bond.

  6. Halogen bond: a long overlooked interaction.

    PubMed

    Cavallo, Gabriella; Metrangolo, Pierangelo; Pilati, Tullio; Resnati, Giuseppe; Terraneo, Giancarlo

    2015-01-01

    Because of their high electronegativity, halogen atoms are typically considered, in most of their derivatives, as sites of high electron density and it is commonly accepted that they can form attractive interactions by functioning as the electron donor site (nucleophilic site). This is the case when they work as hydrogen bond acceptor sites. However, the electron density in covalently bound halogens is anisotropically distributed. There is a region of higher electron density, accounting for the ability of halogens to function as electron donor sites in attractive interactions, and a region of lower electron density where the electrostatic potential is frequently positive (mainly in the heavier halogens). This latter region is responsible for the ability of halogen atoms to function as the electron-acceptor site (electrophilic site) in attractive interactions formed with a variety of lone pair-possessing atoms, anions, and π-systems. This ability is quite general and is shown by a wide diversity of halogenated compounds (e.g., organohalogen derivatives and dihalogens). According to the definition proposed by the International Union of Pure and Applied Chemistry, any attractive interactions wherein the halogen atom is the electrophile is named halogen bond (XB). In this chapter, it is discussed how the practice and the concept of XB developed and a brief history of the interaction is presented. Papers (either from the primary or secondary literature) which have reported major experimental findings in the field or which have given important theoretical contributions for the development of the concept are recollected in order to trace how a unifying and comprehensive categorization emerged encompassing all interactions wherein halogen atoms function as the electrophilic site.

  7. Impact of Enhanced Ozone Deposition and Halogen Chemistry on Tropospheric Ozone over the Northern Hemisphere.

    PubMed

    Sarwar, Golam; Gantt, Brett; Schwede, Donna; Foley, Kristen; Mathur, Rohit; Saiz-Lopez, Alfonso

    2015-08-01

    Fate of ozone in marine environments has been receiving increased attention due to the tightening of ambient air quality standards. The role of deposition and halogen chemistry is examined through incorporation of an enhanced ozone deposition algorithm and inclusion of halogen chemistry in a comprehensive atmospheric modeling system. The enhanced ozone deposition treatment accounts for the interaction of iodide in seawater with ozone and increases deposition velocities by 1 order of magnitude. Halogen chemistry includes detailed chemical reactions of organic and inorganic bromine and iodine species. Two different simulations are completed with the halogen chemistry: without and with photochemical reactions of higher iodine oxides. Enhanced deposition reduces mean summer-time surface ozone by ∼3% over marine regions in the Northern Hemisphere. Halogen chemistry without the photochemical reactions of higher iodine oxides reduces surface ozone by ∼15% whereas simulations with the photochemical reactions of higher iodine oxides indicate ozone reductions of ∼48%. The model without these processes overpredicts ozone compared to observations whereas the inclusion of these processes improves predictions. The inclusion of photochemical reactions for higher iodine oxides leads to ozone predictions that are lower than observations, underscoring the need for further refinement of the halogen emissions and chemistry scheme in the model.

  8. Impact of Enhanced Ozone Deposition and Halogen Chemistry on Tropospheric Ozone over the Northern Hemisphere.

    PubMed

    Sarwar, Golam; Gantt, Brett; Schwede, Donna; Foley, Kristen; Mathur, Rohit; Saiz-Lopez, Alfonso

    2015-08-01

    Fate of ozone in marine environments has been receiving increased attention due to the tightening of ambient air quality standards. The role of deposition and halogen chemistry is examined through incorporation of an enhanced ozone deposition algorithm and inclusion of halogen chemistry in a comprehensive atmospheric modeling system. The enhanced ozone deposition treatment accounts for the interaction of iodide in seawater with ozone and increases deposition velocities by 1 order of magnitude. Halogen chemistry includes detailed chemical reactions of organic and inorganic bromine and iodine species. Two different simulations are completed with the halogen chemistry: without and with photochemical reactions of higher iodine oxides. Enhanced deposition reduces mean summer-time surface ozone by ∼3% over marine regions in the Northern Hemisphere. Halogen chemistry without the photochemical reactions of higher iodine oxides reduces surface ozone by ∼15% whereas simulations with the photochemical reactions of higher iodine oxides indicate ozone reductions of ∼48%. The model without these processes overpredicts ozone compared to observations whereas the inclusion of these processes improves predictions. The inclusion of photochemical reactions for higher iodine oxides leads to ozone predictions that are lower than observations, underscoring the need for further refinement of the halogen emissions and chemistry scheme in the model. PMID:26151227

  9. Halogen Cycle Operation Test under Microgravity Conditions Using Sounding Rocket

    NASA Astrophysics Data System (ADS)

    Yamamoto, Fumio; Mizutani, Takayuki; Yokota, Takao; Saito, Masatoshi; Kanbayashi, Akio; Nakahata, Yoshihiro; Sawaoka, Akira

    1984-02-01

    Effect of halogen cycle under microgravity conditions was determined by using halogen lamp equipment on board sounding rocket TT-500 A #12 launched by the National Space Development Agency of Japan. Results show that the halogen lamp halogen cycle under microgravity conditions behaves the same as on the ground. From this result, it is foreseeable that there will be no reduction halogen cycle effect in the lamp in the image furnace on board the Space Shuttle Spacelab.

  10. Investigation of Halogenated Components Formed from Chlorination of Natural Waters: Preliminary Studies

    SciTech Connect

    Bean, R. M.; Riley, R. G.

    1980-11-01

    Chlorination of power plant cooling water is extensively used as a means of controlling biofouling. This practice presents the potential for formation of halogenated organic compounds hazardous to man and his environment. Accordingly, the organic composition resulting from the chlorination of natural waters (northern Olympic Penn1sula sea water and the Columbia River in Washington State} has been investigated. Nonpolar lipophilic organic halogens were extracted by passing large volumes of water over columns of XAD-2 macroreticular resins. Examination of ether extracts from the resin columns using capillary gas chromatography revealed the presence of halogenated methanes, as well as other electron-capturing components~ that were not found when unchlorinated water was sampled. Examination of the chlorinated water extracts using gas chromatography/mass spectrometry revealed complex mixtures which generally were not separable into individual components~ even when high efficiency WCOT capillary columns were used. The samples were separated into fractions of increasing polarity using a water-deactivated silica gel column. Fractions were thus obtained which were more amenable to GC/MS investigation. Haloforms were identified as the major halogenated product from chlorination of the waters studied. Other halogenated products were found at much lower concentrations.

  11. Iron Mineral Catalyzed C-H Activation As a Potential Pathway for Halogenation Processes

    NASA Astrophysics Data System (ADS)

    Tubbesing, C.; Schoeler, H. F.; Benzing, K.; Krause, T.; Lippe, S.; Rudloff, M.

    2014-12-01

    Due to increasing drinking water demand of mankind and an expected climate change the impact of salt lakes and salt deserts will increase within the next decades. Furthermore, a rising sea level influences coastal areas like salt marshes and abets processes which will lead to elevated organohalogen formation. An additional increase of the global warming potential, of particle formation and stratospheric ozone depletion is expected. Understanding these multifaceted processes is essential for mankind to be prepared for these alterations of the atmosphere. For example, Keppler et al. (2000) described the production of volatile halogenated organic compounds via oxidation of organic matter driven by ferric iron. However, the formation of long-chained alkyl halides in salt lakes is yet undisclosed. Despite the relative "inertness" of alkanes a direct halogenation of these compounds might be envisaged. In 2005 Vaillancourt et al. discovered a nonheme iron enzyme which is able to halogenate organic compounds via generating the high valent ferryl cation as reaction center. Based on various publications about C-H activation (Bergman, 2007) we postulate a halogenation process in which an iron containing minerals catalyse the C-H bond cleavage of organic compounds in soils. The generated organic radicals are highly reactive towards halides connected to the iron complex. We suggest that next to diagenetically altered iron containing enzymes, minerals such as oxides, hydroxides and sulfides are involved in abiotic halogenation processes. We applied the amino acid methionine as organic model compound and soluble iron species as reactants. All samples were incubated in aqueous phases containing various NaCl concentrations. As a result various halogenated ethanes and ethenes were identified as reaction products. References Bergman, R. G. (2007) Nature, 446(7134) 391-393 Keppler, F., et al. (2000) Nature, 403(6767) 298-301 Vaillancourt, F. H., et al. (2005) Nature, 436(7054) 1191-1194

  12. Regenerative adsorbent heat pump

    NASA Technical Reports Server (NTRS)

    Jones, Jack A. (Inventor)

    1991-01-01

    A regenerative adsorbent heat pump process and system is provided which can regenerate a high percentage of the sensible heat of the system and at least a portion of the heat of adsorption. A series of at least four compressors containing an adsorbent is provided. A large amount of heat is transferred from compressor to compressor so that heat is regenerated. The process and system are useful for air conditioning rooms, providing room heat in the winter or for hot water heating throughout the year, and, in general, for pumping heat from a lower temperature to a higher temperature.

  13. Comparative ecotoxicology of halogenated hydrocarbon residues.

    PubMed

    Winteringham, F P

    1977-12-01

    The term ecotoxicology is adopted in the sense of a comparative and integrated study of the undesirable effects of trace contaminants on the range of fauna and flora of an "ecosystem" or of a defined part or unit thereof. The importance of population changes over long periods of time is stressed. Sources, usage, and global trends of representative halogenated hydrocarbon (HHC) residues which appear as trace contaminants of environment, food, and living organisms are briefly compared: industrial solvents and intermediates, chlorofluoromethanes as an atmospheric pollutant, methyl bromide as a food and soil residue, HCH (hexachlorobenzene) as a fungicide residue, DDT, lindane (gamma-hexachlorocyclohexane), and dieldrin as insecticide residues, and polychlorinated biphenyls (PCBs) as industrial contaminants. A simple mathematical approach to the problem of relating inputs, persistence, and steady-state residue levels is explained. Persistence and biodegradation of representative compounds are compared. Attention is drawn to the persistence of hexachlorobenzene, the p,p'-dichlorodiphenyl- and hexachlorocyclopentadiene-derived moities of HHC residues. Ecotoxicological effects and their implications are discussed comparatively under the indirect effects of atmospheric pollutants and direct and indirect effects of trace contaminants of soil and aquatic ecosystems. Some conclusions related to research and "impact monitoring" are drawn.

  14. Halogen production from aqueous tropospheric particles.

    PubMed

    Herrmann, H; Majdik, Z; Ervens, B; Weise, D

    2003-07-01

    Box model studies have been performed to study the role of aqueous phase chemistry with regard to halogen activation for marine and urban clouds and the marine aerosol as well. Different chemical pathways leading to halogen activation in diluted cloud droplets and highly concentrated sea salt aerosol particles are investigated. The concentration of halides in cloud droplets is significantly smaller than in sea-salt particles, and hence different reaction sequences control the overall chemical conversions. In diluted droplets radical chemistry involving OH, NO(3), Cl/Cl(2)(-)/ClOH(-), and Br/Br(2)(-)/BrOH(-) gains in importance and pH independent pathways lead to the release of halogens from the particle phase whereas the chemistry in aerosol particles with high electrolyte concentrations is controlled by non-radical reactions at high ionic strengths and relatively low pH values. For the simulation of halogen activation in tropospheric clouds and aqueous aerosol particles in different environments a halogen module was developed including both gas and aqueous phase processes of halogen containing species. This module is coupled to a base mechanism consisting of RACM (Regional Atmospheric Chemistry Mechanism) and the Chemical Aqueous Phase Radical Mechanism CAPRAM 2.4 (MODAC-mechanism). Phase exchange is described by the resistance model by Chemistry of Multiphase Atmospheric Systems, NATO ASI Series, 1986. It can be shown that under cloud conditions the bromine atom is mainly produced by OH initiated reactions, i.e. its concentration maximum is reached at noon. In contrast, the concentration level of chlorine atoms is linked to NO(3) radical chemistry leading to a smaller amplitude between day and night time concentrations. The contribution of radical processes to halogen atom formation in the particle phase is evident, e.g. by halogen atoms which undergo direct phase transfer. Furthermore, the application of the multiphase model for initial concentrations for sea

  15. Halogens, OVOC and H2O Distributions over the Eastern Pacific Ocean during TORERO

    NASA Astrophysics Data System (ADS)

    Dix, B. K.; Apel, E. C.; Baidar, S.; Zondlo, M. A.; Volkamer, R.

    2013-12-01

    As part of the Tropical Ocean tRoposphere Exchange of Reactive halogen species and Oxygenated VOC (TORERO) field project 17 research flights were conducted with the NSF/NCAR GV aircraft over the Eastern Tropical Pacific Ocean (42S to 14N Lat.; 70W to 105W Long). Equipped with a combination of chemical in-situ sensors and remote sensing instruments, a broad spectrum of reactive halogen species, oxygenated hydrocarbons, and aerosols were measured over different ocean environments. Using optical remote sensing (airborne Multi Axis DOAS), we measured iodine monoxide (IO), bromine monoxide (BrO), glyoxal (CHOCHO) and water vapor among others. A newly developed parameterization method allowed us to directly convert the measured slant column densities into mixing ratios along the whole flight track. Atmospheric reactive halogen species and organic carbon are important, because they modify HOx radical abundances, influence the reactive chemistry and lifetime of climate active gases (e.g., ozone, methane, dimethyl sulfide), modify aerosol-cloud interactions and halogen radicals can also oxidize atmospheric mercury. Here we summarize and evaluate the spatial distribution of IO, BrO and glyoxal over the TORERO study area. For select case studies we present comparisons to halogen precursors and OVOCs measured in-situ by on-line mass spectrometry (trace organic gas analyzer). The correlation of remotely observed water vapor to in-situ measurements further allows us to conclude on the homogeneity of spatial scales covered by both remote and in-situ sensors.

  16. Two-Dimensional Inorganic Cationic Network of Thorium Iodate Chloride with Unique Halogen-Halogen Bonds.

    PubMed

    Lu, Huangjie; Wang, Yaxing; Wang, Congzhi; Chen, Lanhua; Shi, Weiqun; Diwu, Juan; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

    2016-09-01

    A unique two-dimensional inorganic cationic network with the formula [Th3O2(IO3)5(OH)2]Cl was synthesized hydrothermally. Its crystal structure can best be described as positively charged slabs built with hexanuclear thorium clusters connected by iodate trigonal pyramids. Additional chloride anions are present in the interlayer spaces but surprisingly are not exchangeable, as demonstrated by a series of CrO4(2-) uptake experiments. This is because all chloride anions are trapped by multiple strong halogen-halogen interactions with short Cl-I bond lengths ranging from 3.134 to 3.333 Å, forming a special Cl-centered trigonal-pyramidal polyhedron as a newly observed coordination mode for halogen bonds. Density functional theory calculations clarified that electrons transformed from central Cl atoms to I atoms, generating a halogen-halogen interaction energy with a value of about -8.3 kcal mol(-1) per Cl···I pair as well as providing a total value of -57.9 kcal mol(-1) among delocalized halogen-halogen bonds, which is a new record value reported for a single halogen atom. Additional hydrogen-bonding interaction is also present between Cl and OH, and the interaction energy is predicted to be -8.1 kcal mol(-1), confirming the strong total interaction to lock the interlayer Cl anions. PMID:27494285

  17. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the liquid to... reduce the overall emissions of hydrogen halides and halogens by 99 percent, or reduce the outlet mass of total hydrogen halides and halogens to less than 0.45 kilograms per hour (0.99 pound per hour)...

  18. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the liquid to... reduce the overall emissions of hydrogen halides and halogens by 99 percent, or reduce the outlet mass of total hydrogen halides and halogens to less than 0.45 kilograms per hour (0.99 pound per hour)...

  19. Adsorbent and adsorbent bed for materials capture and separation processes

    SciTech Connect

    Liu, Wei

    2011-01-25

    A method device and material for performing adsorption wherein a fluid mixture is passed through a channel in a structured adsorbent bed having a solid adsorbent comprised of adsorbent particles having a general diameter less than 100 um, loaded in a porous support matrix defining at least one straight flow channel. The adsorbent bed is configured to allow passage of a fluid through said channel and diffusion of a target material into said adsorbent under a pressure gradient driving force. The targeted molecular species in the fluid mixture diffuses across the porous support retaining layer, contacts the adsorbent, and adsorbs on the adsorbent, while the remaining species in the fluid mixture flows out of the channel.

  20. Treatment System for Removing Halogenated Compounds from Contaminated Sources

    NASA Technical Reports Server (NTRS)

    Quinn, Jacqueline W. (Inventor); Clausen, Christian A. (Inventor); Yestrebsky, Cherie L. (Inventor)

    2015-01-01

    A treatment system and a method for removal of at least one halogenated compound, such as PCBs, found in contaminated systems are provided. The treatment system includes a polymer blanket for receiving at least one non-polar solvent. The halogenated compound permeates into or through a wall of the polymer blanket where it is solubilized with at least one non-polar solvent received by said polymer blanket forming a halogenated solvent mixture. This treatment system and method provides for the in situ removal of halogenated compounds from the contaminated system. In one embodiment, the halogenated solvent mixture is subjected to subsequent processes which destroy and/or degrade the halogenated compound.

  1. The Halogen's History of the Early Earth

    NASA Astrophysics Data System (ADS)

    Bureau, H.; Raepsaet, C.; Munsch, P.; Auzende, A.; Testemale, D.; Mezouar, M.; Kubsky, S.; Carriere, M.; Ricolleau, A.; Fiquet, G.

    2012-12-01

    The halogen elements are important in Earth Sciences because, thanks to their unique ability to exist as gazes, liquids and solids, they are perfect tracers and actors for geochemical processes. The cycling of halogens in the Earth is still the matter of controversy because whereas atmosphere, crust and upper mantle are more or less characterized with respect to these elements, a real miss of knowledge is observed concerning the possible role and presence of halogen elements in the deep Earth. In this study we focus on halogen element behaviors during the Earth's differentiation at the Hadean magma ocean stage. We combined synchrotron X-Ray Fluorescence analysis with diamond anvil cells (DAC) experiments at the beam lines Id27 and FAME from ESRF and DiffAbs from SOLEIL. DAC were used as reactors to simulate pressure and temperature conditions relevant for a magma ocean. Experimental monitoring of Br [Bureau et al., 2010, CGA 74, 3839-3850] and I degassing from high pressure hydrous melts was performed in situ in DAC by measuring their partitioning between aqueous fluids and melts during decompression. Results show a stronger affinity of Br and I for the aqueous phase during decompression. Both of them are degassing with water and are totally washout from the melt. Assuming that Br and I are good analogues for F and Cl, and that halogen elements cycle is linked to the Earth's water cycle, this suggests that halogen elements may have been efficiently degassed with water during the early stages of an oxidized magma ocean. We propose that degassing during the Earth's differentiation is one of the first and dominant processes that may have distributed halogen elements between the early Earth's reservoirs.

  2. Boiling of simulated tap water: effect on polar brominated disinfection byproducts, halogen speciation, and cytotoxicity.

    PubMed

    Pan, Yang; Zhang, Xiangru; Wagner, Elizabeth D; Osiol, Jennifer; Plewa, Michael J

    2014-01-01

    Tap water typically contains numerous halogenated disinfection byproducts (DBPs) as a result of disinfection, especially of chlorination. Among halogenated DBPs, brominated ones are generally significantly more toxic than their chlorinated analogues. In this study, with the aid of ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry by setting precursor ion scans of m/z 79/81, whole spectra of polar brominated DBPs in simulated tap water samples without and with boiling were revealed. Most polar brominated DBPs were thermally unstable and their levels were substantially reduced after boiling via decarboxylation or hydrolysis; the levels of a few aromatic brominated DBPs increased after boiling through decarboxylation of their precursors. A novel adsorption unit for volatile total organic halogen was designed, which enabled the evaluation of halogen speciation and mass balances in the simulated tap water samples during boiling. After boiling for 5 min, the overall level of brominated DBPs was reduced by 62.8%, of which 39.8% was volatilized and 23.0% was converted to bromide; the overall level of chlorinated DBPs was reduced by 61.1%, of which 44.4% was volatilized and 16.7% was converted to chloride; the overall level of halogenated DBPs was reduced by 62.3%. The simulated tap water sample without boiling was cytotoxic in a chronic (72 h) exposure to mammalian cells; this cytotoxicity was reduced by 76.9% after boiling for 5 min. The reduction in cytotoxicity corresponded with the reduction in overall halogenated DBPs. Thus, boiling of tap water can be regarded as a "detoxification" process and may reduce human exposure to halogenated DBPs through tap water ingestion.

  3. Boiling of simulated tap water: effect on polar brominated disinfection byproducts, halogen speciation, and cytotoxicity.

    PubMed

    Pan, Yang; Zhang, Xiangru; Wagner, Elizabeth D; Osiol, Jennifer; Plewa, Michael J

    2014-01-01

    Tap water typically contains numerous halogenated disinfection byproducts (DBPs) as a result of disinfection, especially of chlorination. Among halogenated DBPs, brominated ones are generally significantly more toxic than their chlorinated analogues. In this study, with the aid of ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry by setting precursor ion scans of m/z 79/81, whole spectra of polar brominated DBPs in simulated tap water samples without and with boiling were revealed. Most polar brominated DBPs were thermally unstable and their levels were substantially reduced after boiling via decarboxylation or hydrolysis; the levels of a few aromatic brominated DBPs increased after boiling through decarboxylation of their precursors. A novel adsorption unit for volatile total organic halogen was designed, which enabled the evaluation of halogen speciation and mass balances in the simulated tap water samples during boiling. After boiling for 5 min, the overall level of brominated DBPs was reduced by 62.8%, of which 39.8% was volatilized and 23.0% was converted to bromide; the overall level of chlorinated DBPs was reduced by 61.1%, of which 44.4% was volatilized and 16.7% was converted to chloride; the overall level of halogenated DBPs was reduced by 62.3%. The simulated tap water sample without boiling was cytotoxic in a chronic (72 h) exposure to mammalian cells; this cytotoxicity was reduced by 76.9% after boiling for 5 min. The reduction in cytotoxicity corresponded with the reduction in overall halogenated DBPs. Thus, boiling of tap water can be regarded as a "detoxification" process and may reduce human exposure to halogenated DBPs through tap water ingestion. PMID:24308807

  4. A QTAIM exploration of the competition between hydrogen and halogen bonding in halogenated 1-methyluracil: Water systems

    NASA Astrophysics Data System (ADS)

    Huan, Guo; Xu, Tianlv; Momen, Roya; Wang, Lingling; Ping, Yang; Kirk, Steven R.; Jenkins, Samantha; van Mourik, Tanja

    2016-10-01

    Using QTAIM we show that the hydrogen bonding complexes of 5-halogenated-1-methyluracil (XmU; X = F, Cl, Br, I or At) with a water molecule were always stronger than the corresponding halogen bonds. The strength of the hydrogen bond decreased with increasing halogen size. The hydrogen bonds displayed an admixture of covalent character but all the halogen bonds were purely electrostatic in nature. An F---O halogen bond was found and was facilitated by an intermediate F---H bonding interaction. The metallicity ξ(rb) of the C = O bonds neighboring the hydrogen bonds and of the C-X bonds contiguous with the halogen bonds was explored.

  5. Chloramination of nitrogenous contaminants (pharmaceuticals and pesticides): NDMA and halogenated DBPs formation.

    PubMed

    Le Roux, Julien; Gallard, Hervé; Croué, Jean-Philippe

    2011-05-01

    Disinfection with chloramines is often used to reduce the production of regulated disinfection by-products (DBPs) such as trihalomethanes (THMs) and haloacetic acids (HAAs). However, chloramination can lead to the formation of N-nitrosamines, including N-nitrosodimethylamine (NDMA), a probable human carcinogen. Previous research used dimethylamine (DMA) as a model precursor of NDMA, but certain widely used tertiary dimethylamines (e.g. the pharmaceutical ranitidine) show much higher conversion rates to NDMA than DMA. This study investigates the NDMA formation potential of several tertiary amines including pharmaceuticals and herbicides. The reactivity of these molecules with monochloramine (NH(2)Cl) is studied through the formation of NDMA, and other halogenated DBPs such as haloacetonitriles (HANs) and AOX (Adsorbable Organic Halides). Several compounds investigated formed NDMA in greater amounts than DMA, revealing the importance of structural characteristics of tertiary amines for NDMA formation. Among these compounds, the pharmaceutical ranitidine showed the highest molar conversion to NDMA. The pH and dissolved oxygen content of the solution were found to play a major role for the formation of NDMA from ranitidine. NDMA was formed in higher amounts at pH around pH 8 and a lower concentration of dissolved oxygen dramatically decreased NDMA yields. These findings seem to indicate that dichloramine (NHCl(2)) is not the major oxidant involved in the formation of NDMA from ranitidine, results in contradiction with the reaction mechanisms proposed in the literature. Dissolved oxygen was also found to influence the formation of other oxygen-containing DBPs (i.e. trichloronitromethane and haloketones). The results of this study identify several anthropogenic precursors of NDMA, indicating that chloramination of waters impacted by these tertiary amines could lead to the formation of significant amounts of NDMA and other non-regulated DBPs of potential health concern (e

  6. Halogen Radical Chemistry at Aqueous Interfaces.

    PubMed

    Enami, Shinichi; Hoffmann, Michael R; Colussi, A J

    2016-08-11

    Halogens play key roles in the chemical composition of marine boundary layers, the free troposphere and the stratosphere. Atmospheric halogen chemistry is dominated by reactions between gas-phase and aqueous species on the surfaces of the ocean and marine aerosol. The mechanisms of interfacial halogen radical/halide reactions, however, are not fully understood, partly due to the dearth of techniques for in situ monitoring of the products and intermediates of fast interfacial halogen radical reactions. Here, we report the online electrospray mass spectrometric identification of the species produced on the surface of aqueous Br(-) and I(-) microjets collided by I(•)(g) pulses generated from the 266 nm laser photolysis of CH3I/O2/N2 gas mixtures. Mass-specific identification of intermediates and products in D2O and H2(18)O solutions and their dependences on I(•)(g) fluxes let us outline mechanisms of formation. We found that the uptake of I(•)(g) on the surface of Br(-) and I(-) microjets (effective uptake coefficient γeff ≥ 2 × 10(-4)) yields IBr(•)(-)/I2(•)(-) radical intermediates, which rapidly react with additional I(•) to produce trihalides I2Br(-)/IBr2(-)/I3(-) plus I3On(-) (n = 1, 2) species within ∼10 μs. Our findings point to a new halogen activation pathway initiated by photogenerated I(•). PMID:27414750

  7. Charge transfer during alkali-surface adsorbate collisions

    NASA Astrophysics Data System (ADS)

    Yang, Ye

    The study of charge transfer process between atomic particles and surface adsorbates is important, from both fundamental and practical points of view. Resonant charge transfer (RCT) process during the scattering of low-energy alkali ions from surfaces is proven to depend on the surface local electrostatic potential (LEP). This dissertation investigates the surface electronic environment around halogen and hydrogen adatoms on transition metal and silicon surfaces by using alkali ion scattering. Charge transfer in 7Li+ scattering from clean Si surfaces was shown to involve RCT between the Li 2s level and the Si dangling bonds. Hydrogen adsorption decreases the neutralization because it ties up the dangling bonds. The neutral fractions in 7Li + scattering from Cs/Si are also determined primarily by the dangling bond states, so that the surface LEP cannot be directly probed. Hydrogen adsorption on Cs/Si ties up the dangling bonds, thereby revealing the local potentials. The neutralization probabilities of Li+ backscattered from the hydrogen- and iodine-covered Ni(100) surface were measured. The neutral fraction does not change significantly on H-adsorbed surface. For iodine adsorption, however, unexpected high neutralization probabilities were found for Li scattered directly from iodine sites. Similar behavior were observed for Li+ scattering from I- and Br-covered Fe(100) and Fe(110). The neutralization of Li+ was measured as a function of the incident energy, adatom charge and coverage, and exit angle. It was found that the larger neutral fractions of Li scattered from the halogen sites are caused by a lower potential directly above the adatoms due to internal polarization. As the exit beam moves off-normal, the neutral fraction of Li scattered from iodine decreases. This is in contrast to Cs and Ag adsorbates where the neutral fractions increase for glancing exit trajectories. These angular-dependences are verified by a semi-quantitative theoretical analysis. To

  8. Non-conventional gas phase remediation of volatile halogenated compounds by dehydrated bacteria.

    PubMed

    Erable, Benjamin; Goubet, Isabelle; Seltana, Amira; Maugard, Thierry

    2009-06-01

    Traditional biological removal processes are limited by the low solubility of halogenated compounds in aqueous media. A new technology appears very suitable for the remediation of these volatile organic compounds (VOCs). Solid/gas bio-catalysis applied in VOC remediation can transform halogenated compounds directly in the gas phase using dehydrated cells as a bio-catalyst. The hydrolysis of volatile halogenated substrates into the corresponding alcohol was studied in a solid/gas biofilter where lyophilised bacterial cultures were used as the catalyst. Four strains containing dehalogenase enzymes were tested for the hydrolysis of 1-chlorobutane. The highest removal yield was obtained using the dhaA-containing strains, the maximal reaction rate of 0.8 micromol min(-1)g(-1) being observed with Escherichia coli BL21(DE3)(dhaA). Various treatments such as cell disruption by lysozyme or alkaline gas addition in the bio-filter could stabilise the dehalogenase activity of the bacteria. A pre-treatment of the dehydrated bacterial cells by ammonia vapour improved the stability of the catalyst and a removal activity of 0.9 micromol min(-1)g(-1) was then obtained for 60h. Finally, the process was extended to a range of halogenated substrates including bromo- and chloro-substrates. It was shown that the removal capacity for long halogenated compounds (C(5)-C(6)) was greatly increased relative to traditional biological processes.

  9. Seaonal Sea Ice as a source of organo-halogens during Polar night

    NASA Astrophysics Data System (ADS)

    Abrahamsson, Katarina; Granfors, Anna; Ahnoff, Martin

    2016-04-01

    The release of bromine from snow and sea ice surfaces has mainly been attributed to the reaction of hypobromous acid with bromide at acidic conditions to form Br2. Little attention has been given to the role of volatile halogenated organic compounds (organo-halogens) in the formation of reactive halogen species in the atmosphere during bromine explosion events. The load of organo-halogens was studied during a winter expedition to the Weddell Sea in June to August 2013. These compounds are emitted from the different compartments of the cryosphere to the atmosphere where they are photolysed to BrO and IO, which are involved in the degradation of ozone. We will present results that show the importance of organo-halogens formed during polar winter. In newly formed ice, in contrast to summer sea ice, the concentration of organo-bromine was found at levels as high as nM. These high concentrations were reflected both in frost flowers and in the sea-snow interface. Moreover, air measurements revealed high loads of organo-bromine over the sea ice. The situation was similar for iodinated compounds. Interestingly, the precursers of IO, mainly diiodomethane, could be measured in sea ice and snow, most probably due to the low light levels.

  10. Electroluminescence of Halogen Complexes with Monovalent Copper: OLED Devices and DFT Modeling

    NASA Astrophysics Data System (ADS)

    Valiev, R. R.; Minaev, B. F.; Gadirov, R. M.; Nikonova, E. N.; Solodova, T. A.; Nikonov, S. Yu.; Bushuev, M. B.; Kopylova, T. N.

    2016-01-01

    Spectroscopic characteristics of complexes of Cu[I] ion with halogens synthesized by the TDDFT/CAM-B3LYP method are studied. It is shown that S0 → S1 and S0 → T1 electronic transitions are excitations with charge transfer. In this case, the electronic transitions proceed from the HOMO, HOMO-1 and HOMO-2 localized on halogen atoms to the LUMO localized on a ligand. The matrix elements of spin-orbit interaction are calculated using the single-electron operator (HSO). Based on these compounds, the organic light emitting diodes have been created. Their current-voltage and current-brightness characteristics are investigated.

  11. Evaluation of Halogenated Coumarins for Antimosquito Properties

    PubMed Central

    Narayanaswamy, Venugopala K.; Gleiser, Raquel M.; Kasumbwe, Kabange; Aldhubiab, Bandar E.; Attimarad, Mahesh V.; Odhav, Bharti

    2014-01-01

    Mosquitoes are the major vectors of parasites and pathogens affecting humans and domestic animals. The widespread development of insecticide resistance and negative environmental effects of most synthetic compounds support an interest in finding and developing alternative products against mosquitoes. Natural coumarins and synthetic coumarin analogues are known for their several pharmacological properties, including being insecticidal. In the present study halogenated coumarins (3-mono/dibromo acetyl, 6-halogenated coumarin analogues) were screened for larvicidal, adulticidal, and repellent properties against Anopheles arabiensis, a zoophilic mosquito that is one of the dominant vectors of malaria in Africa. Five compounds exerted 100% larval mortality within 24 h of exposure. All coumarins and halogenated coumarins reversibly knocked down adult mosquitoes but did not kill them after 24 h of exposure. Repellent properties could not be evidenced. Five compounds were considered potential larvicidal agents for further research and development, while adulticidal activity was considered only mild to moderate. PMID:25610898

  12. Evaluation of halogenated coumarins for antimosquito properties.

    PubMed

    Narayanaswamy, Venugopala K; Gleiser, Raquel M; Kasumbwe, Kabange; Aldhubiab, Bandar E; Attimarad, Mahesh V; Odhav, Bharti

    2014-01-01

    Mosquitoes are the major vectors of parasites and pathogens affecting humans and domestic animals. The widespread development of insecticide resistance and negative environmental effects of most synthetic compounds support an interest in finding and developing alternative products against mosquitoes. Natural coumarins and synthetic coumarin analogues are known for their several pharmacological properties, including being insecticidal. In the present study halogenated coumarins (3-mono/dibromo acetyl, 6-halogenated coumarin analogues) were screened for larvicidal, adulticidal, and repellent properties against Anopheles arabiensis, a zoophilic mosquito that is one of the dominant vectors of malaria in Africa. Five compounds exerted 100% larval mortality within 24 h of exposure. All coumarins and halogenated coumarins reversibly knocked down adult mosquitoes but did not kill them after 24 h of exposure. Repellent properties could not be evidenced. Five compounds were considered potential larvicidal agents for further research and development, while adulticidal activity was considered only mild to moderate. PMID:25610898

  13. The interaction of organic adsorbate vibrations with substrate lattice waves in methyl-Si(111)-(1 × 1).

    PubMed

    Brown, Ryan D; Hund, Zachary M; Campi, Davide; O'Leary, Leslie E; Lewis, Nathan S; Bernasconi, M; Benedek, G; Sibener, S J

    2014-07-14

    A combined helium atom scattering and density functional perturbation theory study has been performed to elucidate the surface phonon dispersion relations for both the CH3-Si(111)-(1 × 1) and CD3-Si(111)-(1 × 1) surfaces. The combination of experimental and theoretical methods has allowed characterization of the interactions between the low energy vibrations of the adsorbate and the lattice waves of the underlying substrate, as well as characterization of the interactions between neighboring methyl groups, across the entire wavevector resolved vibrational energy spectrum of each system. The Rayleigh wave was found to hybridize with the surface rocking libration near the surface Brillouin zone edge at both the M̄-point and K̄-point. The calculations indicated that the range of possible energies for the potential barrier to the methyl rotation about the Si-C axis is sufficient to prevent the free rotation of the methyl groups at a room temperature interface. The density functional perturbation theory calculations revealed several other surface phonons that experienced mode-splitting arising from the mutual interaction of adjacent methyl groups. The theory identified a Lucas pair that exists just below the silicon optical bands. For both the CH3- and CD3-terminated Si(111) surfaces, the deformations of the methyl groups were examined and compared to previous experimental and theoretical work on the nature of the surface vibrations. The calculations indicated a splitting of the asymmetric deformation of the methyl group near the zone edges due to steric interactions of adjacent methyl groups. The observed shifts in vibrational energies of the -CD3 groups were consistent with the expected effect of isotopic substitution in this system.

  14. The interaction of organic adsorbate vibrations with substrate lattice waves in methyl-Si(111)-(1 × 1)

    SciTech Connect

    Brown, Ryan D.; Hund, Zachary M.; Sibener, S. J.; Campi, Davide; Bernasconi, M.; O’Leary, Leslie E.; Lewis, Nathan S.; Benedek, G.

    2014-07-14

    A combined helium atom scattering and density functional perturbation theory study has been performed to elucidate the surface phonon dispersion relations for both the CH{sub 3}-Si(111)-(1 × 1) and CD{sub 3}-Si(111)-(1 × 1) surfaces. The combination of experimental and theoretical methods has allowed characterization of the interactions between the low energy vibrations of the adsorbate and the lattice waves of the underlying substrate, as well as characterization of the interactions between neighboring methyl groups, across the entire wavevector resolved vibrational energy spectrum of each system. The Rayleigh wave was found to hybridize with the surface rocking libration near the surface Brillouin zone edge at both the M{sup ¯}-point and K{sup ¯}-point. The calculations indicated that the range of possible energies for the potential barrier to the methyl rotation about the Si-C axis is sufficient to prevent the free rotation of the methyl groups at a room temperature interface. The density functional perturbation theory calculations revealed several other surface phonons that experienced mode-splitting arising from the mutual interaction of adjacent methyl groups. The theory identified a Lucas pair that exists just below the silicon optical bands. For both the CH{sub 3}- and CD{sub 3}-terminated Si(111) surfaces, the deformations of the methyl groups were examined and compared to previous experimental and theoretical work on the nature of the surface vibrations. The calculations indicated a splitting of the asymmetric deformation of the methyl group near the zone edges due to steric interactions of adjacent methyl groups. The observed shifts in vibrational energies of the -CD{sub 3} groups were consistent with the expected effect of isotopic substitution in this system.

  15. The interaction of organic adsorbate vibrations with substrate lattice waves in methyl-Si(111)-(1 × 1).

    PubMed

    Brown, Ryan D; Hund, Zachary M; Campi, Davide; O'Leary, Leslie E; Lewis, Nathan S; Bernasconi, M; Benedek, G; Sibener, S J

    2014-07-14

    A combined helium atom scattering and density functional perturbation theory study has been performed to elucidate the surface phonon dispersion relations for both the CH3-Si(111)-(1 × 1) and CD3-Si(111)-(1 × 1) surfaces. The combination of experimental and theoretical methods has allowed characterization of the interactions between the low energy vibrations of the adsorbate and the lattice waves of the underlying substrate, as well as characterization of the interactions between neighboring methyl groups, across the entire wavevector resolved vibrational energy spectrum of each system. The Rayleigh wave was found to hybridize with the surface rocking libration near the surface Brillouin zone edge at both the M̄-point and K̄-point. The calculations indicated that the range of possible energies for the potential barrier to the methyl rotation about the Si-C axis is sufficient to prevent the free rotation of the methyl groups at a room temperature interface. The density functional perturbation theory calculations revealed several other surface phonons that experienced mode-splitting arising from the mutual interaction of adjacent methyl groups. The theory identified a Lucas pair that exists just below the silicon optical bands. For both the CH3- and CD3-terminated Si(111) surfaces, the deformations of the methyl groups were examined and compared to previous experimental and theoretical work on the nature of the surface vibrations. The calculations indicated a splitting of the asymmetric deformation of the methyl group near the zone edges due to steric interactions of adjacent methyl groups. The observed shifts in vibrational energies of the -CD3 groups were consistent with the expected effect of isotopic substitution in this system. PMID:25028033

  16. Use of flavins as catalyst for the remediation of halogenated compounds.

    PubMed

    Rathore, Deepshikha; Singh, Ram; Geetanjali; Srivastava, Richa

    2014-10-01

    Flavin-containing monooxygenases (FMOs) are an important monooxygenase system present in living organisms starting from eukaryotes to human beings. They are involved in catalysing wide variety of oxygenation reactions including bioremediation process. The central reaction in these enzymes is always the formation of a peroxyflavin intermediate by reaction of reduced flavin with molecular oxygen. The microenvironment of the peroxyflavin regulates the reactive character of the peroxyflavin. Utilizing this aspect of the biology, chemremediation of aromatic halogenated phenols have been initiated and achieved using flavinium perchlorate salt as catalyst in 38 % yield. The flavinium perchlorate during the reaction gets converted to peroxyflavin with H2O2. This method will be useful in the removal of halogens from aromatic halogenated phenols.

  17. Impact of enhanced ozone deposition and halogen chemistry on model performance

    EPA Science Inventory

    In this study, an enhanced ozone deposition scheme due to the interaction of iodide in sea-water and atmospheric ozone and the detailed chemical reactions of organic and inorganic halogen species are incorporated into the hemispheric Community Multiscale Air Quality model. Prelim...

  18. Plasma-chemical technology of treatment of halogen-containing waste including polychlorinated biphenyls

    NASA Astrophysics Data System (ADS)

    Gusarov, E. E.; Malkov, Yu. P.; Stepanov, S. G.; Troshchinenko, G. A.; Zasypkin, I. M.

    2010-12-01

    We consider the developed plasma-chemical technology of halogen-containing substances treatment. The paper contains the experimental plant schematic and the positive results obtained after the treatment of tetrafluoromethane, ozone-damaging freon 12, polychlorinated biphenyls (PCB), the waste containing fluoride and chloride organics. The technology is proposed for industrial application.

  19. Method and apparatus for low temperature destruction of halogenated hydrocarbons

    DOEpatents

    Reagen, William Kevin; Janikowski, Stuart Kevin

    1999-01-01

    A method and apparatus for decomposing halogenated hydrocarbons are provided. The halogenated hydrocarbon is mixed with solvating agents and maintained in a predetermined atmosphere and at a predetermined temperature. The mixture is contacted with recyclable reactive material for chemically reacting with the recyclable material to create dehalogenated hydrocarbons and halogenated inorganic compounds. A feature of the invention is that the process enables low temperature destruction of halogenated hydrocarbons.

  20. Halogen chemistry in the marine boundary layer

    NASA Astrophysics Data System (ADS)

    Plane, J. M. C.; Gomez Martin, J. C.; Kumar, R.; Mahajan, A. S.; Oetjen, H.; Saunders, R. W.

    2009-04-01

    Important atmospheric sources of iodine include the air-sea exchange of biogenic iodocarbons, and the emission of I2 from macro-algae. The major source of bromine is the release of bromide ions from sea-salt aerosol. The subsequent atmospheric chemistry of these halogens (1), changes the oxidizing capacity of the marine boundary layer by destroying ozone and changing the hydroxyl radical concentration; (2), reacts efficiently with dimethyl sulphide and mercury (in the polar regions); and (3), leads to the formation of ultra-fine particles which may contribute to cloud condensation nuclei (CCN) and hence affect climate. This paper will report observations of IO, BrO, OIO and I2 made by the technique of differential optical absorption spectroscopy, in several contrasting marine environments: the equatorial mid-Atlantic (Cape Verde); mid-latitude clean coastal (Mace Head, Ireland); polluted coastal (Roscoff, France); and the polar marine boundary layer (Hudson Bay, Canada). Both IO and BrO are observed in all these locations at significant concentrations (> 1 pptv), and so have a major impact on (1) and (2) above. To complement the field campaigns we have also carried out wide-ranging laboratory investigation. A new study of OIO photochemistry shows that absorption in the visible bands between 490 and 630 nm leads to I atom production with a quantum yield of unity, which now means that iodine is a particularly powerful ozone-depleting agent. We have also studied the formation and growth kinetics of iodine oxide nano-particles, and their uptake of water, sulphuric acid and di-carboxylic organic acids, in order to model their growth to a size where they can act as CCN. Their ice-nucleating properties will also be reported.

  1. Boundary layer halogens in coastal Antarctica.

    PubMed

    Saiz-Lopez, Alfonso; Mahajan, Anoop S; Salmon, Rhian A; Bauguitte, Stephane J-B; Jones, Anna E; Roscoe, Howard K; Plane, John M C

    2007-07-20

    Halogens influence the oxidizing capacity of Earth's troposphere, and iodine oxides form ultrafine aerosols, which may have an impact on climate. We report year-round measurements of boundary layer iodine oxide and bromine oxide at the near-coastal site of Halley Station, Antarctica. Surprisingly, both species are present throughout the sunlit period and exhibit similar seasonal cycles and concentrations. The springtime peak of iodine oxide (20 parts per trillion) is the highest concentration recorded anywhere in the atmosphere. These levels of halogens cause substantial ozone depletion, as well as the rapid oxidation of dimethyl sulfide and mercury in the Antarctic boundary layer.

  2. Halogenated silanes, radicals, and cations

    NASA Astrophysics Data System (ADS)

    Wang, Liming; He, Yi-Liang

    2008-09-01

    Quantum chemistry study has been carried out on the structure and energetics of halogenated silanes, radicals, and cations (SiHxXy0,+1, X = F, Cl, Br; x + y = 1-4). The geometries are optimized at B3LYP/6-31+G(2df,p) level. The adiabatic ionization energiess (IEas), relative energetics of cations, proton affinities (PAs) of silanes, and the enthalpies of formation are predicted using G3(CC) model chemistry. Non-classical ion complex structures are found for hydrogenated cations and transition states connecting classical and non-classical structures are also located. The most stable cations for silylene and silyl radicals have their classical divalent and trivalent structures, and those for silanes have non-classical structures except for SiH3Br+ and SiH2Br2+. The non-classical structures for halosilane cations imply difficulty in experimentally measurement of the adiabatic ionization energies using photoionization or photoelectron studies. For SiH3X, SiH2X2, and SiHX3, the G3(CC) adiabatic IEas to classical ionic structures closest to their neutrals agree better with the photoelectron spectroscopic measurements. The transition states between classical and non-classical structures also hamper the photoionization determination of the appearance energies for silylene cations from silanes. The G3(CC) results for SiHx0,+1 agree excellently with the photoionization mass spectrometric study, and the results for fluorinated and chlorinated species also agree with the previous theoretical predictions at correlation levels from BAC-MP4 to CCSD(T)/CBS. The predicted enthalpy differences between SiH2Cl+, SiHCl2+, and SiCl3+ are also in accordance with previous kinetics study. The G3(CC) results show large discrepancies to the collision-induced charge transfer and/or dissociation reactions involving SiFx+ and SiClx+ ions, for which the G3(CC) enthalpies of formation are also significantly differed from the previous theoretical predictions, especially on SiFx+ (x = 2-4). The G3

  3. 40 CFR 721.10259 - Halogenated aromatic hydrocarbon (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halogenated aromatic hydrocarbon... Specific Chemical Substances § 721.10259 Halogenated aromatic hydrocarbon (generic). (a) Chemical substance... halogenated aromatic hydrocarbon (PMN P-09-540) is subject to reporting under this section for the...

  4. 40 CFR 721.10259 - Halogenated aromatic hydrocarbon (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halogenated aromatic hydrocarbon... Specific Chemical Substances § 721.10259 Halogenated aromatic hydrocarbon (generic). (a) Chemical substance... halogenated aromatic hydrocarbon (PMN P-09-540) is subject to reporting under this section for the...

  5. 40 CFR 721.10259 - Halogenated aromatic hydrocarbon (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogenated aromatic hydrocarbon... Specific Chemical Substances § 721.10259 Halogenated aromatic hydrocarbon (generic). (a) Chemical substance... halogenated aromatic hydrocarbon (PMN P-09-540) is subject to reporting under this section for the...

  6. Halogenases: A Biotechnological Alternative for the Synthesis of Halogenated Pharmaceuticals.

    PubMed

    Ayala, Marcela; Segovia, Lorenzo; Torres, Eduardo

    2016-01-01

    The role of halogen atoms in pharmaceutical compounds has been recently revised, due to the weak interaction through the so called "halogen bond" between small molecules and proteins or other biomacromolecules, which could be fundamental for binding at a particular site within the macromolecule. Moreover, thousands of natural halogenated compounds have been described to date, pointing to a functional role of halogen atoms in these compounds, as well as a diversity of halogenating enzymes involved in the synthesis of these halogenated metabolites. In this mini-review the different halogenases described to date are presented, particularly those catalyzing halogenation reactions with potential applications in the pharmaceutical field. Oxidative halogenases following an electrophilic halogenation mechanism are the oldest and best characterized halogenases; however, novel halogenases following a nucleophilic halogenation mechanism have been recently described. The catalytic properties as well as the selectivity of some of these enzymes can be modulated through protein engineering, both by single point mutations or by directed evolution; on the other hand, metabolic pathway engineering has been used to improve the production of halogenated metabolites, as well as to produce novel halogenated compounds, potentially important in the pharmaceutical field. Recent advances and prospective on the field of enzymatic halogenation are covered.

  7. 40 CFR 721.8700 - Halogenated alkyl pyridine.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogenated alkyl pyridine. 721.8700... Substances § 721.8700 Halogenated alkyl pyridine. Link to an amendment published at 79 FR 34638, June 18... identified generically as halogenated alkyl pyridine (PMN P-83-237) is subject to reporting under...

  8. 40 CFR 721.8700 - Halogenated alkyl pyridine.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halogenated alkyl pyridine. 721.8700... Substances § 721.8700 Halogenated alkyl pyridine. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated alkyl pyridine (PMN P-83-237)...

  9. 40 CFR 721.5546 - Halogen substituted oxetanes (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogen substituted oxetanes (generic... Substances § 721.5546 Halogen substituted oxetanes (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as halogen substituted...

  10. 40 CFR 721.5546 - Halogen substituted oxetanes (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogen substituted oxetanes (generic... Substances § 721.5546 Halogen substituted oxetanes (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as halogen substituted...

  11. 40 CFR 721.5546 - Halogen substituted oxetanes (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halogen substituted oxetanes (generic... Substances § 721.5546 Halogen substituted oxetanes (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as halogen substituted...

  12. 40 CFR 721.5546 - Halogen substituted oxetanes (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halogen substituted oxetanes (generic... Substances § 721.5546 Halogen substituted oxetanes (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as halogen substituted...

  13. 40 CFR 721.5546 - Halogen substituted oxetanes (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halogen substituted oxetanes (generic... Substances § 721.5546 Halogen substituted oxetanes (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as halogen substituted...

  14. Passivation of quartz for halogen-containing light sources

    DOEpatents

    Falkenstein, Zoran

    1999-01-01

    Lifetime of halogen containing VUV, UV, visible or IR light sources can be extended by passivating the quartz or glass gas containers with halogens prior to filling the quartz with the halogen and rare gas mixtures used to produce the light.

  15. Natural Transformation of Azotobacter vinelandii by Adsorbed Chromosomal DNA: Role of Adsorbed DNA Conformation

    NASA Astrophysics Data System (ADS)

    Lv, N.; Zilles, J.; Nguyen, H.

    2008-12-01

    Recent increases in antibiotic resistance among pathogenic microorganisms and the accompanying public health concerns result both from the widespread use of antibiotics and from the transfer of antibiotic resistance genes among microorganisms. To understand the transfer of antibiotic resistance genes and identify efficient measures to minimize these transfers, an interdisciplinary approach was used to identify physical and chemical factors that control the fate and biological availability of extracellular DNA. Quartz crystal microbalance with dissipation (QCM-D) was used to study extracellular DNA adsorption and the conformation of the adsorbed DNA on silica and natural organic matter (NOM) surfaces. Solution chemistry was varied systematically to investigate the role of adsorbed DNA conformation on transformation. Gene transfer was assessed under the same conditions using natural transformation of chromosomal DNA into the soil bacteria Azotobacter vinelandii. DNA adsorbed to both silica and NOM surfaces has a more compact and rigid conformation in the presence of Ca2+ compared to Na+. Extracellular DNA adsorbed on silica and NOM surfaces transformed A. vinelandii. The transformation efficiency of adsorbed DNA was up to 4 orders of magnitude lower than that of dissolved DNA. Preliminary results suggest that the presence of Ca2+ in groundwater (e.g. hardness) reduces the availability of adsorbed DNA for transformation.

  16. Measurements of halogen oxides in the Western Pacific

    NASA Astrophysics Data System (ADS)

    Wittrock, Folkard; Walker, Hannah; Heard, Dwayne; Ingham, Trevor; Lampel, Johannes; Horbanski, Martin; Großmann, Katja; Bracher, Astrid; Sentian, Justin; Vrekoussis, Mihalis; Huang, Ru-Jin; Peters, Enno; Schönhardt, Anja; Richter, Andreas; Burrows, John P.

    2013-04-01

    Reactive halogens such as iodine, bromine and their oxides have received growing attention in the past years owing to their strong impact on tropospheric composition. In particular, reactive halogens deplete ozone and alter the HOx and NOx ratios, consequently changing the oxidizing capacity of the troposphere. The halogen oxides iodine monoxide (IO) and bromine monoxide (BrO), generated from the reaction of atomic I and Br with ozone, play a central role in these processes. Iodine atoms may be released by photolysis of precursor substances such as I2 or volatile iodocarbons emitted from the marine biosphere. Inorganic release processes are also being considered, but they are so far uncertain. Bromine precursors include organic as well as inorganic sources. Here we report on measurements of IO and BrO during and related to the SHIVA field campaign, which has been carried out in November 2011 in the Western Pacific around Borneo. Different techniques have been applied in order to detect the trace gases: cavity-enhanced differential optical absorption spectroscopy (CE-DOAS), multi axis (MAX)-DOAS, airborne multi axis (AMAX)-DOAS and laser induced fluorescence (LIF, discussed in detail in Heard et al.). While for BrO no clear signal above the detection limit was found, IO levels up to 2.5 ppt were found in the open Sulu Sea and similar levels up to 2 ppt close to seaweed farms around Semporna, Malaysia. In this area both MAX-DOAS and AMAX-DOAS observations gave indication for the presence of uplifted layers of IO. These results are discussed and interpreted by using complementary observations of the main precursor substances. In addition correlation studies taking into account meteorological and oceanic parameters have been carried out to identify possible source processes. Finally the ground-based IO observations have been compared to satellite observations and a reasonable agreement was found.

  17. Nanopore reactive adsorbents for the high-efficiency removal of waste species

    DOEpatents

    Yang, Arthur Jing-Min; Zhang, Yuehua

    2005-01-04

    A nanoporous reactive adsorbent incorporates a relatively small number of relatively larger reactant, e.g., metal, enzyme, etc., particles (10) forming a discontinuous or continuous phase interspersed among and surrounded by a continuous phase of smaller adsorbent particles (12) and connected interstitial pores (14) therebetween. The reactive adsorbent can effectively remove inorganic or organic impurities in a liquid by causing the liquid to flow through the adsorbent. For example, silver ions may be adsorbed by the adsorbent particles (12) and reduced to metallic silver by reducing metal, such as ions, as the reactant particles (10). The column can be regenerated by backwashing with the liquid effluent containing, for example, acetic acid.

  18. Skin Sensitizing Potency of Halogenated Platinum Salts.

    EPA Science Inventory

    The relationship between occupational exposure to halogenated platinum (Pt) salts and Pt-specific allergic sensitization is well-established. Although human case reports and clinical studies demonstrate that Pt salts are potent skin sensitizers, no studies have been published tha...

  19. The halogen bond: an interim perspective.

    PubMed

    Legon, Anthony C

    2010-07-28

    There has been an upsurge of interest in the halogen bond during the last decade. This non-covalent interaction is less familiar than the hydrogen bond, but is similar to it in several respects. In this article, we first discuss the nature of the halogen bond in the gas phase, as established by systematic investigations of the rotational spectra of complexes B...XY, where B is a simple Lewis base and XY is a dihalogen molecule. The geometry of a given B...XY is found to be isomorphic with that of the corresponding hydrogen-bonded system B...HX, an observation that leads an interim definition of the halogen bond similar to that recently proposed for the hydrogen bond. Selected novel applications of the halogen bond made in the last decade in various areas of chemistry/materials (namely crystal engineering, liquid crystals, nano-materials, polymer chemistry and inorganic chemistry) are then reviewed. These applications generally involve molecules of the type XR (where R is an electron-withdrawing group) acting as the electron donor, rather than dihalogens XY.

  20. Reactions of halogen-pyridine systems

    SciTech Connect

    Coury, A.J.; Cahalan, P.T.

    1980-01-01

    The combination of halogens (acceptors) with pyridine derivatives (donors) produces, initially, charge transfer complexes with conductivities useful as depolarizers in lithium-halogen power cell cathodes. The complex most often employed in pacemaker batteries is I/sub 2//P2VP. Pyridines and halogens undergo additional reactions of consequence to cell performance. Such side reactions include: Alkyl group substitution, ring coupling, polymer molecular weight degradation, olefin addition and ring substitution. Instrumental analysis of model systems and the commercial iodine/poly-2-vinylpyridine (I/sub 2//P2VP) system provided evidence for alkyl group substitution, coupling and molecular weight degradation. The addition reaction was inferred from the presence of the needed reactants and their facile reactivity. Halogenation of the pyridine ring was not found. Side reactions cause reduced cathode capacity. Hydrogen halides generated by such side reactions may cause corrosion, but may enhance conductivity properties. Deleterious pressure buidup or dimensional changes may result from side reactions occurring within sealed battery cans. 7 refs.

  1. Retention of Halogens in Waste Glass

    SciTech Connect

    Hrma, Pavel R.

    2010-05-01

    In spite of their potential roles as melting rate accelerators and foam breakers, halogens are generally viewed as troublesome components for glass processing. Of five halogens, F, Cl, Br, I, and At, all but At may occur in nuclear waste. A nuclear waste feed may contain up to 10 g of F, 4 g of Cl, and ≤100 mg of Br and I per kg of glass. The main concern is halogen volatility, producing hazardous fumes and particulates, and the radioactive iodine 129 isotope of 1.7x10^7-year half life. Because F and Cl are soluble in oxide glasses and tend to precipitate on cooling, they can be retained in the waste glass in the form of dissolved constituents or as dispersed crystalline inclusions. This report compiles known halogen-retention data in both high-level waste (HLW) and low-activity waste (LAW) glasses. Because of its radioactivity, the main focus is on I. Available data on F and Cl were compiled for comparison. Though Br is present in nuclear wastes, it is usually ignored; no data on Br retention were found.

  2. High-temperature corrosion in halogen environments

    SciTech Connect

    McNallan, M. )

    1994-09-01

    Halogen contaminants, particularly chlorine and fluorine, cause accelerated corrosion in such high-temperature systems as waste incinerators and waste heat recuperators on metallurgical furnaces. The mechanisms by which these phenomena occur are reviewed and discussed with the goal of identifying appropriate corrosion control strategies for materials that operate in these environments.

  3. Halogenated Indole Alkaloids from Marine Invertebrates

    PubMed Central

    Pauletti, Patrícia Mendonça; Cintra, Lucas Silva; Braguine, Caio Guedes; da Silva Filho, Ademar Alves; Silva, Márcio Luís Andrade e; Cunha, Wilson Roberto; Januário, Ana Helena

    2010-01-01

    This review discusses the isolation, structural elucidation, and biological activities of halogenated indole alkaloids obtained from marine invertebrates. Meridianins and related compounds (variolins, psammopemmins, and aplicyanins), as well as aplysinopsins and leptoclinidamines, are focused on. A compilation of the 13C-NMR spectral data of these selected natural indole alkaloids is also provided. PMID:20559487

  4. Preparation, characterization, and activity of fluorinated aluminas for halogen exchange

    SciTech Connect

    Hegde, R.I.; Barteau, M.A. )

    1989-12-01

    Fluorinated aluminas with {alpha}-AlF{sub 3} contents up to 90+% were prepared by treatment with the fluoroalkanes CHF{sub 3} or C{sub 2}HF{sub 5} at 773 K. XPS results suggest that nearly complete fluorination of the surface occurs even at low extents of bulk fluorination. Neither {gamma}-Al{sub 2}O{sub 3} nor {alpha}-AlF{sub 3} exhibits significant activity for reaction of CHF{sub 3} following adsorption at 300 K and subsequent temperature-programmed desorption. In contrast, partially fluorinated aluminas strongly adsorb CHF{sub 3}, CHClF{sub 2}, and CHCl{sub 2}F. TPD experiments indicate that all three C{sub 1}-HCFCs desorb from partially fluorinated alumina above 500 K; all react to liberate HF and CO{sub 2}, and the chlorine-containing species undergo fluorine-for-chlorine exchange to produce CHF{sub 3}. These results suggest that halogen-exchange reactions of HCFCs can be carried out with materials resembling conventional fluorination catalysts.

  5. Characterization and Biological Potency of Mono- to Tetra-Halogenated Carbazoles.

    PubMed

    Riddell, Nicole; Jin, Un-Ho; Safe, Stephen; Cheng, Yating; Chittim, Brock; Konstantinov, Alex; Parette, Robert; Pena-Abaurrea, Miren; Reiner, Eric J; Poirier, David; Stefanac, Tomislav; McAlees, Alan J; McCrindle, Robert

    2015-09-01

    This paper deals with the characterization and aryl hydrocarbon receptor (AhR) agonist activities of a series of chlorinated, brominated, and mixed bromo/chlorocarbazoles, some of which have been identified in various environmental samples. Attention is directed here to the possibility that halogenated carbazoles may currently be emitted into the environment as a result of the production of carbazole-containing polymers present in a wide variety of electronic devices. We have found that any carbazole that is not substituted in the 1,3,6,8 positions may be lost during cleanup of environmental extracts if a multilayer column is utilized, as is common practice for polychlorinated dibenzo-p-dioxin (dioxin) and related compounds. In the present study, (1)H NMR spectral shift data for 11 relevant halogenated carbazoles are reported, along with their gas chromatographic separation and analysis by mass spectrometry. These characterization data allow for confident structural assignments and the derivation of possible correlations between structure and toxicity based on the halogenation patterns of the isomers investigated. Some halogenated carbazoles exhibit characteristics of persistent organic pollutants and their potential dioxin-like activity was further investigated. The structure-dependent induction of CYP1A1 and CYP1B1 gene expression in Ah-responsive MDA-MB-468 breast cancer cells by these carbazoles was similar to that observed for other dioxin-like compounds, and the magnitude of the fold induction responses for the most active halogenated carbazoles was similar to that observed for 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). 2,3,6,7-Tetrachlorocarbazole was one of the most active halogenated carbazoles and, like TCDD, contains 4 lateral substituents; however, the estimated relative effect potency for this compound (compared to TCDD) was 0.0001 and 0.0032, based on induction of CYP1A1 and CYP1B1 mRNA, respectively.

  6. Halogen Radicals Promote the Photodegradation of Microcystins in Estuarine Systems.

    PubMed

    Parker, Kimberly M; Reichwaldt, Elke S; Ghadouani, Anas; Mitch, William A

    2016-08-16

    The transport of microcystin, a hepatotoxin produced by cyanobacteria (e.g., Microcystis aeruginosa), to estuaries can adversely affect estuarine and coastal ecosystems. We evaluated whether halogen radicals (i.e., reactive halogen species (RHS)) could significantly contribute to microcystin photodegradation during transport within estuaries. Experiments in synthetic and natural water samples demonstrated that the presence of seawater halides increased quantum yields for microcystin indirect photodegradation by factors of 3-6. Additional experiments indicated that photoproduced RHS were responsible for this effect. Despite the fact that dissolved organic matter (DOM) concentrations decreased in more saline waters, the calculated photochemical half-life of microcystin decreased 6-fold with increasing salinity along a freshwater-estuarine transect due to the halide-associated increase in quantum yield. Modeling of microcystin photodegradation along this transect indicated that the time scale for RHS-mediated microcystin photodegradation is comparable to the time scale of transport. Microcystin concentrations decline by ∼98% along the transect when considering photodegradation by RHS, but only by ∼54% if this pathway were ignored. These results suggest the importance of considering RHS-mediated photodegradation in future models of microcystin fate in freshwater-estuarine systems. PMID:27447196

  7. The Brenner Moor - A saline bog as a source for halogenated and non-halogenated volatile compounds

    NASA Astrophysics Data System (ADS)

    Krause, T.; Studenroth, S.; Furchner, M.; Hoffman, A.; Lippe, S.; Kotte, K.; Schöler, H. F.

    2012-04-01

    The Brenner Moor is a small bog in the catchment area of the river Trave located in Schleswig-Holstein, North Germany, between Baltic and North Sea. The bog is fed by several saline springs with chloride concentrations up to 15 g/L. The high chloride concentrations and the high organic content of the peat make the Brenner Moor an ideal source for the abiotic formation of volatile organic halogenated compounds (VOX). VOX play an important role in the photochemical processes of the lower atmosphere and information on the atmospheric input from saline soils like the Brenner Moor will help to understand the global fluxes of VOX. Soil samples were taken in spring 2011 from several locations and depths in the vicinity of the Brenner Moor. The samples were freeze-dried, ground and incubated in water emphasising an abiotic character for the formation of volatile organic compounds. 1,2-dichloroethane and trichloromethane are the main halogenated compounds emitted from soils of the Brenner Moor. The abiotic formation of trichloromethane as well as other trihalomethanes has been part of intensive studies. A well known source is the decarboxylation of trichloroacetic acid and trichloroacetyl-containing compounds to trichloromethane [1]. Huber et al. discovered another pathway in which catechol, as a model compound for organic substances, is oxidised under Fenton-like conditions with iron(III), hydrogen peroxide and halides to form trihalomethanes [2]. Besides the halogenated compounds, the formation of sulphur compounds such as dimethyl sulfide and dimethyl disulfide and several furan derivatives could be detected which also have an impact on atmospheric chemistry, especially particle formation of clouds. Furan, methylfuran and dimethylfuran are compounds that can be obtained under Fenton-like oxidation from catechol, methyl- and dimethylcatechol and are known to be produced in natural soils [3]. A novel class of furan derivatives that are formed under abiotic conditions from

  8. Mercury adsorption properties of sulfur-impregnated adsorbents

    USGS Publications Warehouse

    Hsi, N.-C.; Rood, M.J.; Rostam-Abadi, M.; Chen, S.; Chang, R.

    2002-01-01

    Carbonaceous and noncarbonaceous adsorbents were impregnated with elemental sulfur to evaluate the chemical and physical properties of the adsorbents and their equilibrium mercury adsorption capacities. Simulated coal combustion flue gas conditions were used to determine the equilibrium adsorption capacities for Hg0 and HgCl2 gases to better understand how to remove mercury from gas streams generated by coal-fired utility power plants. Sulfur was deposited onto the adsorbents by monolayer surface deposition or volume pore filling. Sulfur impregnation increased the total sulfur content and decreased the total and micropore surface areas and pore volumes for all of the adsorbents tested. Adsorbents with sufficient amounts of active adsorption sites and sufficient microporous structure had mercury adsorption capacities up to 4,509 ??g Hg/g adsorbent. Elemental sulfur, organic sulfur, and sulfate were formed on the adsorbents during sulfur impregnation. Correlations were established with R2>0.92 between the equilibrium Hg0/HgCl2 adsorption capacities and the mass concentrations of elemental and organic sulfur. This result indicates that elemental and organic sulfur are important active adsorption sites for Hg0 and HgCl2.

  9. Lipase from Solvent-Tolerant Pseudomonas sp. DMVR46 Strain Adsorb on Multiwalled Carbon Nanotubes: Application for Enzymatic Biotransformation in Organic Solvents.

    PubMed

    Vrutika, Patel; Datta, Madamwar

    2015-11-01

    Immobilization of biocatalysts onto particulate carriers has been widely explored for recycling of biocatalyst. However, surface properties often affect the amount of biocatalysts immobilized, their bioactivity and stability, hampering their wide applications. The aim of this work was to elucidate the importance of nanoimmobilization system in organic synthesis. The surface of multiwalled carbon nanotubes (MWCNTs) was functionalized with a mixture of concentrated acids to create an interface for enzyme immobilization. Successful functionalization and enzyme immobilization was structurally evidenced by transmision electron microscopy analysis and Fourier-transform infrared spectroscopy analysis. Furthermore, immobilized enzyme was exploited for the synthesis of flavoured ester ethyl butyrate in the presence of n-heptane. Optimized conditions for enhanced ester synthesis was found to be 8.5 pH, 40 °C, 150 rpm, 0.15:0.2 M substrate molar ratio (ethanol/butyric acid) and n-heptane as reaction medium. Utmost 81% of ester synthesis was obtained using immobilized lipase quite higher in comparison to that of free lipase. The activation energy indicated a lower energy requirement for immobilization of lipase on the surface of functionalized MWCNTs. In summary, immobilization of lipase on functionalized MWCNTs by simple adsorption method displayed excellent properties for enzyme stability and reusability, indicating its potential for application in organic synthesis.

  10. Microchip electrophoresis with background electrolyte containing polyacrylic acid and high content organic solvent in cyclic olefin copolymer microchips for easily adsorbed dyes.

    PubMed

    Wei, Xuan; Sun, Ping; Yang, Shenghong; Zhao, Lei; Wu, Jing; Li, Fengyun; Pu, Qiaosheng

    2016-07-29

    Plastic microchips can significantly reduce the fabrication cost but the adsorption of some analytes limits their application. In this work, background electrolyte containing ionic polymer and high content of organic solvent was adopted to eliminate the analyte adsorption and achieve highly efficient separation in microchip electrophoresis. Two dyes, rhodamine 6G (Rh6G) and rhodamine B (RhB) were used as the model analytes. By using methanol as the organic solvent and polyacrylic acid (PAA) as a multifunctional additive, successful separation of the two dyes within 75μm id. microchannels was realized. The role of PAA is multiple, including viscosity regulator, selectivity modifier and active additive for counteracting analyte adsorption on the microchannel surface. The number of theoretical plate of 7.0×10(5)/m was attained within an effective separation distance of 2cm using background electrolyte consisting 80% methanol, 0.36% PAA and 30mmol/L phosphate at pH 5.0. Under optimized conditions, relative standard deviations of Rh6G and RhB detection (n=5) were no more than 1.5% for migration time and 2.0% for peak area, respectively. The limit of detection (S/N=3) was 0.1nmol/L for Rh6G. The proposed technique was applied in the determination of both Rh6G and RhB in chilli powder and lipstick samples with satisfactory recoveries of 81.3-103.7%. PMID:27371017

  11. Microchip electrophoresis with background electrolyte containing polyacrylic acid and high content organic solvent in cyclic olefin copolymer microchips for easily adsorbed dyes.

    PubMed

    Wei, Xuan; Sun, Ping; Yang, Shenghong; Zhao, Lei; Wu, Jing; Li, Fengyun; Pu, Qiaosheng

    2016-07-29

    Plastic microchips can significantly reduce the fabrication cost but the adsorption of some analytes limits their application. In this work, background electrolyte containing ionic polymer and high content of organic solvent was adopted to eliminate the analyte adsorption and achieve highly efficient separation in microchip electrophoresis. Two dyes, rhodamine 6G (Rh6G) and rhodamine B (RhB) were used as the model analytes. By using methanol as the organic solvent and polyacrylic acid (PAA) as a multifunctional additive, successful separation of the two dyes within 75μm id. microchannels was realized. The role of PAA is multiple, including viscosity regulator, selectivity modifier and active additive for counteracting analyte adsorption on the microchannel surface. The number of theoretical plate of 7.0×10(5)/m was attained within an effective separation distance of 2cm using background electrolyte consisting 80% methanol, 0.36% PAA and 30mmol/L phosphate at pH 5.0. Under optimized conditions, relative standard deviations of Rh6G and RhB detection (n=5) were no more than 1.5% for migration time and 2.0% for peak area, respectively. The limit of detection (S/N=3) was 0.1nmol/L for Rh6G. The proposed technique was applied in the determination of both Rh6G and RhB in chilli powder and lipstick samples with satisfactory recoveries of 81.3-103.7%.

  12. C–H bond halogenation catalyzed or mediated by copper: an overview

    PubMed Central

    Hao, Wenyan

    2015-01-01

    Summary Carbon–halogen (C–X) bonds are amongst the most fundamental groups in organic synthesis, they are frequently and widely employed in the synthesis of numerous organic products. The generation of a C–X bond, therefore, constitutes an issue of universal interest. Herein, the research advances on the copper-catalyzed and mediated C–X (X = F, Cl, Br, I) bond formation via direct C–H bond transformation is reviewed. PMID:26664634

  13. I. Fundamental Practicum: Temperature Measurements of Falling Droplets, July, 1989. II. Industrial Practicum: Interaction and Effect of Adsorbed Organics on Reference Clays and Reservoir Rock, April, 1988. III. Apprenticeship Practicum: Studies of Group XIII Metal Inclusion Complexes, March, 1987

    NASA Astrophysics Data System (ADS)

    Wells, Mark Richard

    The temperature of 225 μm decane droplets falling through a hot, quiescent, oxygen -free environment were measured using laser-induced exciplex fluorescence thermometry. The temperature of the droplets was found to increase approximately 0.42^ circC/^circC increase in the environment temperature as the environment temperature was increased to 250^circ C. Less than 10% evaporation of the droplets was observed at the highest environment temperatures. This represents one of the first successful applications of a remote-sensing technique for the temperature determination of droplets in a dynamic system. Industrial practicum. The industrial practicum report, entitled "Interaction and Effect of Adsorbed Organics on Reference Clays and Reservoir Rock," is a discussion of the measurement of the effect adsorbed organic material, especially from crude petroleum, has on the surface area, cation exchange capacity, and zeta potential of reference clay material and reservoir rock. In addition, the energetics of adsorption of a petroleum extract onto several reference clays and reservoir rock were measured using both flow and batch microcalorimetry. These results are very important in evaluating and understanding the wettability of reservoir rock and its impact on the recovery of crude oil from a petroleum reservoir. Apprenticeship practicum. "Studies of Group XIII Metal Inclusion Complexes" investigates the structure and dynamics of liquid inclusion complexes having the general formula (R_4N) (Al_2 Me_6I) cdot (C_6H_6) _{rm x}. ^1H and ^{13}C spin-lattice relaxation times, nuclear Overhauser enhancements, and molecular correlation times were measured as well as diffusion coefficients of the various species in solution. The dynamics of transfer between "guest" and free solvent molecules were measured using a variety of techniques. The inherent structure of liquid inclusion complexes as an ordered medium for homogeneous catalysis was studied using hydrogenation catalyzed by

  14. Effect of bromine and chlorine positioning in the induction of renal and testicular toxicity by halogenated propanes.

    PubMed

    Låg, M; Søderlund, E J; Omichinski, J G; Brunborg, G; Holme, J A; Dahl, J E; Nelson, S D; Dybing, E

    1991-01-01

    A series of halogenated propanes were studied for renal and testicular necrogenic effects in the rat and correlated to their ability to induce in vivo renal and testicular DNA damage and in vitro testicular DNA damage. 1,2-Dibromo-3-chloropropane (DBCP) and 1,2,3-tribromopropane were most potent in causing organ damage in both kidney and testes. Extensive necrosis was evident at 85 mumol/kg in kidney and at 170 mumol/kg in testis. The dibromomonochlorinated analogue 1,3-dibromo-2-chloropropane was less organ toxic than DBCP and 1,2,3-tribromopropane, but induced more organ damage than the dichloromonobrominated analogues 1-bromo-2,3-dichloropropane and 1,3-dichloro-2-bromopropane. Dihalogenated propanes were even less necrogenic. These observed differences in toxic potency between the halogenated propanes could not be explained by relative differences in tissue concentrations. The ability of the halogenated propanes to induce DNA damage in vivo correlated well with their ability to induce organ damage. However, DNA damage occurred at lower doses and at a shorter period of exposure than organ necrosis. This indicates that DNA damage might be an initial event in the development of organ necrosis by halogenated propanes in general. Further, testicular DNA damage induced by the halogenated propanes in vivo correlated well with the DNA damage observed in isolated testicular cells in vitro, showing that toxicity was due to in situ activation. The numbers, positions, and the types of halogen substituents appear to be important determinants in causing DNA damage and necrogenic effects.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:1793801

  15. Periodic density-functional calculations on work-function change induced by adsorption of halogens on Cu(111).

    PubMed

    Roman, Tanglaw; Groß, Axel

    2013-04-12

    Using periodic density-functional theory calculations, we address the work-function change induced by the adsorption of chlorine and iodine on Cu(111) which are shown to change the work function in opposite ways, contrary to what one may expect for these two electron acceptors. In contrast to previous studies, we demonstrate that substrate effects play only a minor role in work-function changes brought about by halogen adsorption on metals. Instead, polarization on the adsorbate not only explains the sign of the work-function change as a contributor to a positive surface dipole moment, but it is also the decisive factor in the dependence of adsorption-induced work-function changes on the coverage of halogens on metal surfaces.

  16. Synthesis, characterization, antimicrobial activity and applications of polyanilineTi(IV)arsenophosphate adsorbent for the analysis of organic and inorganic pollutants.

    PubMed

    Bushra, Rani; Shahadat, Mohammad; Ahmad, Anees; Nabi, S A; Umar, Khalid; Oves, M; Raeissi, A S; Muneer, M

    2014-01-15

    A novel polyaniline based composite cation exchange material has been synthesized by simple chemical route and characterized on the basis of sophisticated techniques. XRD and SEM analyses reveal the amorphous morphology of the material. The partition coefficient studies of different metal ions on the material were performed in DMW and diverse concentrations of HClO4 solutions. On the basis of high Kd values some significant separations of heavy toxic metal ions were achieved from synthetic mixtures as well as tap water samples by using columns of this exchanger. For the optimum adsorption of dye on the material, the effect of various parameters along with Langmuir and Freundlich adsorption isotherm were examined. The observed result of conducting measurement indicates that the material covers semiconductor range. The photochemical degradation of industrial dyes and antimicrobial activity were also investigated which show significant results than some of the known antibiotics. On the basis of good ion exchange capacity along with photochemical degradation and microbial activity, polyanilineTi(IV)arsenophosphate can be considered as an excellent conducting material for the treatment metal ions and degradation of organic pollutants. PMID:24238807

  17. Systematic Investigation of Nanoscale Adsorbate Effects at Organic Light-Emitting diode Interfaces. Interfacial Structure-Charge Injection-Luminance Relationships

    SciTech Connect

    Huang,Q.; Li, J.; Evmenenko, G.; Dutta, P.; Marks, T.

    2006-01-01

    Molecule-scale structure effects at indium tin oxide (ITO) anode-hole transport layer (HTL) interfaces in organic light-emitting diode (OLED) heterostructures are systematically probed via a self-assembly approach. A series of ITO anode-linked silyltriarylamine precursors differing in aryl group and linker density are synthesized for this purpose and used to probe the relationship between nanoscale interfacial chemical structure and charge-injection/electroluminescence properties. These precursors form conformal and largely pinhole-free self-assembled monolayers (SAMs) on the ITO anode surface with angstrom-level thickness control. Deposition of a HTL on top of the SAMs places the probe molecules precisely at the anode-HTL interface. OLEDs containing ITO/SAM/HTL configurations have dramatically varied hole-injection magnitudes and OLED responses. These can be correlated with the probe molecular structures and electrochemically derived heterogeneous electron-transfer rates for such triarylamine fragments. The large observed interfacial molecular structure effects offer an approach to tuning OLED hole-injection flux over 1-2 orders of magnitude, resulting in up to 3-fold variations in OLED brightness at identical bias and up to a 2 V driving voltage reduction at identical brightness. Very bright and efficient ({approx}70 000 cd/m{sup 2}, {approx}2.5% forward external quantum efficiency, {approx}11 lm/W power efficiency) Alq (tris(8-hydroxyquinolinato)aluminum(III))-based OLEDs can thereby be fabricated.

  18. The influence of sediment particle size on the properties of adsorbed dissolved organic matter in the Yangtze Estuary and its interactions with As/Sb.

    PubMed

    Wang, Ying; Zhang, Manman; Zhang, Di; Shen, Zhenyao

    2016-04-15

    The characteristics of dissolved organic matter (DOM) extracted from sediments with four particle sizes (<25, 63-25, 200-63 and >200μm) in the Yangtze Estuary were compared. The differences in their binding capacities for individual fluorescent components with As/Sb were studied using fluorescence-quenching titrations combined with excitation-emission matrix (EEM) spectra. The results indicated that the particle size influenced the quality and quantity of extracted DOM. With increasing particle size, the extracted DOM content, value of UV280 and acidic functional group content of the DOM decreased. Three protein-like components (C2, C3 and C4) and one humic-like component (C1) were identified using the parallel factor analysis (PARAFAC) model. Wherein, protein-like material dominated in DOM on different particle-size fractions and possessed a stronger complex capacity with As/Sb. A significant positive correlation between the complexation capacity of extracted DOM from samples, as well as with the acidic functional group content, was observed.

  19. Synthesis, characterization, antimicrobial activity and applications of polyanilineTi(IV)arsenophosphate adsorbent for the analysis of organic and inorganic pollutants.

    PubMed

    Bushra, Rani; Shahadat, Mohammad; Ahmad, Anees; Nabi, S A; Umar, Khalid; Oves, M; Raeissi, A S; Muneer, M

    2014-01-15

    A novel polyaniline based composite cation exchange material has been synthesized by simple chemical route and characterized on the basis of sophisticated techniques. XRD and SEM analyses reveal the amorphous morphology of the material. The partition coefficient studies of different metal ions on the material were performed in DMW and diverse concentrations of HClO4 solutions. On the basis of high Kd values some significant separations of heavy toxic metal ions were achieved from synthetic mixtures as well as tap water samples by using columns of this exchanger. For the optimum adsorption of dye on the material, the effect of various parameters along with Langmuir and Freundlich adsorption isotherm were examined. The observed result of conducting measurement indicates that the material covers semiconductor range. The photochemical degradation of industrial dyes and antimicrobial activity were also investigated which show significant results than some of the known antibiotics. On the basis of good ion exchange capacity along with photochemical degradation and microbial activity, polyanilineTi(IV)arsenophosphate can be considered as an excellent conducting material for the treatment metal ions and degradation of organic pollutants.

  20. Boiling points of halogenated ethanes: an explanatory model implicating weak intermolecular hydrogen-halogen bonding.

    PubMed

    Beauchamp, Guy

    2008-10-23

    This study explores via structural clues the influence of weak intermolecular hydrogen-halogen bonds on the boiling point of halogenated ethanes. The plot of boiling points of 86 halogenated ethanes versus the molar refraction (linked to polarizability) reveals a series of straight lines, each corresponding to one of nine possible arrangements of hydrogen and halogen atoms on the two-carbon skeleton. A multiple linear regression model of the boiling points could be designed based on molar refraction and subgroup structure as independent variables (R(2) = 0.995, standard error of boiling point 4.2 degrees C). The model is discussed in view of the fact that molar refraction can account for approximately 83.0% of the observed variation in boiling point, while 16.5% could be ascribed to weak C-X...H-C intermolecular interactions. The difference in the observed boiling point of molecules having similar molar refraction values but differing in hydrogen-halogen intermolecular bonds can reach as much as 90 degrees C.

  1. Halogen bonding origin properties and applications

    SciTech Connect

    Hobza, Pavel

    2015-12-31

    σ-hole bonding represents an unusual and novel type of noncovalent interactions in which atom with σ- hole interacts with Lewis base such as an electronegative atom (oxygen, nitrogen, …) or aromatic systems. This bonding is of electrostatic nature since the σ-hole bears a positive charge. Dispersion energy forms equally important energy term what is due to the fact that two heavy atoms (e.g. halogen and oxygen) having high polarizability lie close together (the respective distance is typically shorter than the sum of van der Waals radii). Among different types of σ-hole bondings the halogen bonding is by far the most known but chalcogen and pnictogen bondings are important as well.

  2. Method and apparatus for detecting halogenated hydrocarbons

    DOEpatents

    Monagle, Matthew; Coogan, John J.

    1997-01-01

    A halogenated hydrocarbon (HHC) detector is formed from a silent discharge (also called a dielectric barrier discharge) plasma generator. A silent discharge plasma device receives a gas sample that may contain one or more HHCs and produces free radicals and excited electrons for oxidizing the HHCs in the gas sample to produce water, carbon dioxide, and an acid including halogens in the HHCs. A detector is used to sensitively detect the presence of the acid. A conductivity cell detector combines the oxidation products with a solvent where dissociation of the acid increases the conductivity of the solvent. The conductivity cell output signal is then functionally related to the presence of HHCs in the gas sample. Other detectors include electrochemical cells, infrared spectrometers, and negative ion mobility spectrometers.

  3. Oxidation of hydrogen halides to elemental halogens

    DOEpatents

    Rohrmann, Charles A.; Fullam, Harold T.

    1985-01-01

    A process for oxidizing hydrogen halides having substantially no sulfur impurities by means of a catalytically active molten salt is disclosed. A mixture of the subject hydrogen halide and an oxygen bearing gas is contacted with a molten salt containing an oxidizing catalyst and alkali metal normal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen and substantially free of sulfur oxide gases.

  4. Predictive Models for Halogen-bond Basicity of Binding Sites of Polyfunctional Molecules.

    PubMed

    Glavatskikh, Marta; Madzhidov, Timur; Solov'ev, Vitaly; Marcou, Gilles; Horvath, Dragos; Graton, Jérôme; Le Questel, Jean-Yves; Varnek, Alexandre

    2016-02-01

    Halogen bonding (XB) strength assesses the ability of an electron-enriched group to be involved in complexes with polarizable electrophilic halogenated or diatomic halogen molecules. Here, we report QSPR models of XB of particular relevance for an efficient screening of large sets of compounds. The basicity is described by pKBI2 , the decimal logarithm of the experimental 1 : 1 (B : I2 ) complexation constant K of organic compounds (B) with diiodine (I2 ) as a reference halogen-bond donor in alkanes at 298 K. Modeling involved ISIDA fragment descriptors, using SVM and MLR methods on a set of 598 organic compounds. Developed models were then challenged to make predictions for an external test set of 11 polyfunctional compounds for which unambiguous assignment of the measured effective complexation constant to specific groups out of the putative acceptor sites is not granted. At this stage, developed models were used to predict pKBI2 of all putative acceptor sites, followed by an estimation of the predicted effective complexation constant using the ChemEqui program. The best consensus models perform well both in cross-validation (root mean squared error RMSE=0.39-0.47 logKBI2 units) and external predictions (RMSE=0.49). The SVM models are implemented on our website (http://infochim.u-strasbg.fr/webserv/VSEngine.html) together with the estimation of their applicability domain and an automatic detection of potential halogen-bond acceptor atoms. PMID:27491792

  5. Mechanism of action of toxic halogenated aromatics.

    PubMed Central

    Vickers, A E; Sloop, T C; Lucier, G W

    1985-01-01

    2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) and related halogenated aromatic hydrocarbons are a highly toxic class of environmental contaminants, as evidenced by numerous cases of accidental poisonings of human and animal populations and their extreme toxic potency in laboratory animals. The proposed model for the mechanism of action of TCDD and related compounds is analogous to that of the steroid hormones, which modulate gene expression through a receptor mechanism. In the steroid receptor model, the compound enters the cell cytoplasm where it acts as a specific ligand, binding selectively to a high affinity receptor protein. Bound to the appropriate ligand, the receptor concentrates in the nucleus where its increased association with chromatin leads to altered gene expression. This model has been useful in characterizing the Ah receptor; however, it does not provide a unifying hypothesis for all biochemical and toxic effects associated with exposure to halogenated aromatic hydrocarbons. Several findings suggest that a primary factor in determining TCDD toxicity might be tissue and species specific factors that control the actions of Ah receptor(s) in target tissues. Furthermore, numerous mechanisms might be involved. Clarifying the mechanism(s) for TCDD toxicity would enhance our ability to predict human health consequences to toxic halogenated aromatic hydrocarbons and would provide a more rational basis for risk analysis. PMID:2985378

  6. Performance of stabilized halogen biocides in cooling water

    SciTech Connect

    Dallmier, A.W.; Martens, J.D.; McCoy, W.F.

    1997-12-01

    Halogen-based biocides have been used for many years in cooling water to control microbial fouling. Potential problems associated with the misapplication of halogen-based biocides in cooling water are increased corrosion, degradation of scale and corrosion inhibitors, and poor storage stability. Advances and innovations in this field have led to products in which the oxidizing effects and degradative properties of the halogen are stabilized. This provides much more effective control of the microbial fouling process in cooling water shile being less aggressive towards other system components. Methods used to measure increased effectiveness of stabilized halogen biocides are presented and discussed in this paper. Laboratory and field experiments of a stabilized halogen antimicrobial control program are detailed. Performance of this stabilized halogen program for Legionella pneumophila control is also discussed.

  7. Computational Tools To Model Halogen Bonds in Medicinal Chemistry.

    PubMed

    Ford, Melissa Coates; Ho, P Shing

    2016-03-10

    The use of halogens in therapeutics dates back to the earliest days of medicine when seaweed was used as a source of iodine to treat goiters. The incorporation of halogens to improve the potency of drugs is now fairly standard in medicinal chemistry. In the past decade, halogens have been recognized as direct participants in defining the affinity of inhibitors through a noncovalent interaction called the halogen bond or X-bond. Incorporating X-bonding into structure-based drug design requires computational models for the anisotropic distribution of charge and the nonspherical shape of halogens, which lead to their highly directional geometries and stabilizing energies. We review here current successes and challenges in developing computational methods to introduce X-bonding into lead compound discovery and optimization during drug development. This fast-growing field will push further development of more accurate and efficient computational tools to accelerate the exploitation of halogens in medicinal chemistry.

  8. Direct conversion of halogen-containing wastes to borosilicate glass

    SciTech Connect

    Forsberg, C.W.; Beahm, E.C.; Rudolph, J.C.

    1996-12-09

    Glass has become a preferred waste form worldwide for radioactive wastes: however, there are limitations. Halogen-containing wastes can not be converted to glass because halogens form poor-quality waste glasses. Furthermore, halides in glass melters often form second phases that create operating problems. A new waste vitrification process, the Glass Material Oxidation and dissolution System (GMODS), removes these limitations by converting halogen-containing wastes into borosilicate glass and a secondary, clean, sodium-halide stream.

  9. Source of Cooperativity in Halogen-Bonded Haloamine Tetramers.

    PubMed

    Dominikowska, Justyna; Bickelhaupt, F Matthias; Palusiak, Marcin; Fonseca Guerra, Célia

    2016-02-16

    Inspired by the isostructural motif in α-bromoacetophenone oxime crystals, we investigated halogen-halogen bonding in haloamine quartets. Our Kohn-Sham molecular orbital and energy decomposition analysis reveal a synergy that can be traced to a charge-transfer interaction in the halogen-bonded tetramers. The halogen lone-pair orbital on one monomer donates electrons into the unoccupied σ*N-X orbital on the perpendicular N-X bond of the neighboring monomer. This interaction has local σ symmetry. Interestingly, we discovered a second, somewhat weaker donor-acceptor interaction of local π symmetry, which partially counteracts the aforementioned regular σ-symmetric halogen-bonding orbital interaction. The halogen-halogen interaction in haloamines is the first known example of a halogen bond in which back donation takes place. We also find that this cooperativity in halogen bonds results from the reduction of the donor-acceptor orbital-energy gap that occurs every time a monomer is added to the aggregate. PMID:26732989

  10. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the liquid to... which it is part, as specified in 40 CFR 63.100(k) (if the referencing subpart is 40 CFR part 63... 40 Protection of Environment 16 2012-07-01 2012-07-01 false Halogen scrubbers and other...

  11. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the liquid to... which it is part, as specified in 40 CFR 63.100(k) (if the referencing subpart is 40 CFR part 63... 40 Protection of Environment 16 2014-07-01 2014-07-01 false Halogen scrubbers and other...

  12. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the liquid to... which it is part, as specified in 40 CFR 63.100(k) (if the referencing subpart is 40 CFR part 63... 40 Protection of Environment 15 2010-07-01 2010-07-01 false Halogen scrubbers and other...

  13. The entropies of adsorbed molecules.

    PubMed

    Campbell, Charles T; Sellers, Jason R V

    2012-10-31

    Adsorbed molecules are involved in many reactions on solid surface that are of great technological importance. As such, there has been tremendous effort worldwide to learn how to predict reaction rates and equilibrium constants for reactions involving adsorbed molecules. Theoretical calculation of both the rate and equilibrium constants for such reactions requires knowing the entropy and enthalpy of the adsorbed molecule. While much effort has been devoted to measuring and calculating the enthalpies of well-defined adsorbates, few measurements of the entropies of adsorbates have been reported. We present here a new way to determine the standard entropies of adsorbed molecules (S(ad)(0)) on single crystal surfaces from temperature programmed desorption data, prove its accuracy by comparison to entropies measured by equilibrium methods, and apply it to published data to extract new entropies. Most importantly, when combined with reported entropies, we find that at high coverage, they linearly track the entropy of the gas-phase molecule at the same temperature (T), such that S(ad)(0)(T) = 0.70 S(gas)(0)(T) - 3.3R (R = the gas constant), with a standard deviation of only 2R over a range of 50R. These entropies, which are ~2/3 of the gas, are huge compared to most theoretical predictions. This result can be extended to reliably predict prefactors in the Arrhenius rate constant for surface reactions involving such species, as proven here for desorption. PMID:23033909

  14. Dehalogenation of halogenated fumigants by polysulfide salts.

    PubMed

    Bondarenko, S; Zheng, W; Yates, S R; Gan, J

    2006-07-26

    Halogenated fumigants are among the most heavily used pesticides in agriculture. Because of their high mobility and toxicological characteristics, the contamination of air or groundwater by these compounds has been a great environmental concern. In this study, we investigated dehalogenation of several halogenated fumigants by polysulfides. The reaction of polysulfides and methyl iodide (MeI), 1,3-dichloropropene (1,3-D), and chloropicrin (CP) was very rapid. When the initial fumigant and polysulfide concentrations were both 0.2 mM, the observed 50% disappearance time values (DT50) of MeI, cis-1,3-D, and trans-1,3-D were 27.2, 29.6, and 102 h, respectively. When the initial polysulfide concentration was 1.0 mM, the corresponding DT50 values were only 2.2, 1.6, and 3.8 h. Under similar conditions, the reaction with CP was even more rapid than with the other fumigants. In 0.2 mM polysulfide solution, more than 90% of the spiked CP disappeared in 1 h after the initiation of the reaction. The reaction between fumigants and polysulfides also progressed at enhanced rates when the polysulfide solution was initially purged with nitrogen. Analysis of reaction kinetics and initial products suggests that the reaction is SN2 nucleophilic substitution for MeI and 1,3-D but likely reductive dehalogenation for CP. Given the high reactivity of polysulfide salts toward halogenated fumigants, this reaction may be used as a pollution mitigation strategy, such as for disposal of fumigant wastes, treatment of fumigant-containing wastewater, and cleanup of fumigant residues in environmental media.

  15. Mercury and halogens in coal: Chapter 2

    USGS Publications Warehouse

    Kolker, Allan; Quick, Jeffrey C.; Granite, Evan J.; Pennline, Henry W.; Senior, Constance L.

    2014-01-01

    Apart from mercury itself, coal rank and halogen content are among the most important factors inherent in coal that determine the proportion of mercury captured by conventional controls during coal combustion. This chapter reviews how mercury in coal occurs, gives available concentration data for mercury in U.S. and international commercial coals, and provides an overview of the natural variation in halogens that influence mercury capture. Three databases, the U.S. Geological Survey coal quality (USGS COALQUAL) database for in-ground coals, and the 1999 and 2010 U.S. Environmental Protection Agency (EPA) Information Collection Request (ICR) databases for coals delivered to power stations, provide extensive results for mercury and other parameters that are compared in this chapter. In addition to the United States, detailed characterization of mercury is available on a nationwide basis for China, whose mean values in recent compilations are very similar to the United States in-ground mean of 0.17 ppm mercury. Available data for the next five largest producers (India, Australia, South Africa, the Russian Federation, and Indonesia) are more limited and with the possible exceptions of Australia and the Russian Federation, do not allow nationwide means for mercury in coal to be calculated. Chlorine in coal varies as a function of rank and correspondingly, depth of burial. As discussed elsewhere in this volume, on a proportional basis, bromine is more effective than chlorine in promoting mercury oxidation in flue gas and capture by conventional controls. The ratio of bromine to chlorine in coal is indicative of the proportion of halogens present in formation waters within a coal basin. This ratio is relatively constant except in coals that have interacted with deep-basin brines that have reached halite saturation, enriching residual fluids in bromine. Results presented here help optimize mercury capture by conventional controls and provide a starting point for

  16. Retrieval Algorithms for the Halogen Occultation Experiment

    NASA Technical Reports Server (NTRS)

    Thompson, Robert E.; Gordley, Larry L.

    2009-01-01

    The Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite (UARS) provided high quality measurements of key middle atmosphere constituents, aerosol characteristics, and temperature for 14 years (1991-2005). This report is an outline of the Level 2 retrieval algorithms, and it also describes the great care that was taken in characterizing the instrument prior to launch and throughout its mission life. It represents an historical record of the techniques used to analyze the data and of the steps that must be considered for the development of a similar experiment for future satellite missions.

  17. Boiling Heat Transfer to Halogenated Hydrocarbon Refrigerants

    NASA Astrophysics Data System (ADS)

    Yoshida, Suguru; Fujita, Yasunobu

    The current state of knowledge on heat transfer to boiling refrigerants (halogenated hydrocarbons) in a pool and flowing inside a horizontal tube is reviewed with an emphasis on information relevant to the design of refrigerant evaporators, and some recommendations are made for future research. The review covers two-phase flow pattern, heat transfer characteristics, correlation of heat transfer coefficient, influence of oil, heat transfer augmentation, boiling from tube-bundle, influence of return bend, burnout heat flux, film boiling, dryout and post-dryout heat transfer.

  18. Laboratory Investigations of Stratospheric Halogen Chemistry

    NASA Technical Reports Server (NTRS)

    Wine, Paul H.; Nicovich, J. Michael; Stickel, Robert E.; Hynes, Anthony J.

    1997-01-01

    A final report for the NASA-supported project on laboratory investigations of stratospheric halogen chemistry is presented. In recent years, this project has focused on three areas of research: (1) kinetic, mechanistic, and thermochemical studies of reactions which produce weakly bound chemical species of atmospheric interest; (2) development of flash photolysis schemes for studying radical-radical reactions of stratospheric interest; and (3) photochemistry studies of interest for understanding stratospheric chemistry. The first section of this paper contains a discussion of work which has not yet been published. All subsequent chapters contain reprints of published papers that acknowledge support from this grant.

  19. A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer

    NASA Astrophysics Data System (ADS)

    Toyota, K.; Kanaya, Y.; Takahashi, M.; Akimoto, H.

    2003-09-01

    A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry) to investigate photochemical interactions between volatile organic compounds (VOCs) and reactive halogen species in the marine boundary layer (MBL). Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit treatment of oxidative degradation of up to C3-hydrocarbons CH4, C2H6, C3H8, C2H4, C3H6, and C2H2) initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in the formation of halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO) and alkenes (especially C3H6) are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. On the other hand, the reaction between Br atoms and C2H2 is unimportant for determining the degree of bromine activation in the remote MBL. It is suggested that peroxyacetic acid formed via CH3CHO oxidation is one of the important chemical agents for triggering autocatalytic halogen release from sea-salt aerosols. These results imply that

  20. Modern Transition-Metal-Catalyzed Carbon-Halogen Bond Formation.

    PubMed

    Petrone, David A; Ye, Juntao; Lautens, Mark

    2016-07-27

    The high utility of halogenated organic compounds has prompted the development of a vast number of transformations which install the carbon-halogen motif. Traditional routes to these building blocks have commonly involved multiple steps, harsh reaction conditions, and the use of stoichiometric and/or toxic reagents. In this regard, using transition metals to catalyze the synthesis of organohalides has become a mature field in itself, and applying these technologies has allowed for a decrease in the production of waste, higher levels of regio- and stereoselectivity, and the ability to produce enantioenriched target compounds. Furthermore, transition metals offer the distinct advantage of possessing a diverse spectrum of mechanistic possibilities which translate to the capability to apply new substrate classes and afford novel and difficult-to-access structures. This Review provides comprehensive coverage of modern transition metal-catalyzed syntheses of organohalides via a diverse array of mechanisms. Attention is given to the seminal stoichiometric organometallic studies which led to the corresponding catalytic processes being realized. By breaking this field down into the synthesis of aryl, vinyl, and alkyl halides, it becomes clear which methods have surfaced as most favored for each individual class. In general, a pronounced shift toward the use of C-H bonds as key functional groups, in addition to methods which proceed by catalytic, radical-based mechanisms has occurred. Although always evolving, this field appears to be heading in the direction of using starting materials with a significantly lower degree of prefunctionalization in addition to less expensive and abundant metal catalysts. PMID:27341176

  1. Orbital tomography for highly symmetric adsorbate systems

    NASA Astrophysics Data System (ADS)

    Stadtmüller, B.; Willenbockel, M.; Reinisch, E. M.; Ules, T.; Bocquet, F. C.; Soubatch, S.; Puschnig, P.; Koller, G.; Ramsey, M. G.; Tautz, F. S.; Kumpf, C.

    2012-10-01

    Orbital tomography is a new and very powerful tool to analyze the angular distribution of a photoemission spectroscopy experiment. It was successfully used for organic adsorbate systems to identify (and consequently deconvolute) the contributions of specific molecular orbitals to the photoemission data. The technique was so far limited to surfaces with low symmetry like fcc(110) oriented surfaces, owing to the small number of rotational domains that occur on such surfaces. In this letter we overcome this limitation and present an orbital tomography study of a 3,4,9,10-perylene-tetra-carboxylic-dianhydride (PTCDA) monolayer film adsorbed on Ag(111). Although this system exhibits twelve differently oriented molecules, the angular resolved photoemission data still allow a meaningful analysis of the different local density of states and reveal different electronic structures for symmetrically inequivalent molecules. We also discuss the precision of the orbital tomography technique in terms of counting statistics and linear regression fitting algorithm. Our results demonstrate that orbital tomography is not limited to low-symmetry surfaces, a finding which makes a broad field of complex adsorbate systems accessible to this powerful technique.

  2. New insights into perfluorinated adsorbents for analytical and bioanalytical applications.

    PubMed

    Marchetti, Nicola; Guzzinati, Roberta; Catani, Martina; Massi, Alessandro; Pasti, Luisa; Cavazzini, Alberto

    2015-01-01

    Perfluorinated (F-) adsorbents are generally prepared by bonding perfluoro-functionalized silanes to silica gels. They have been employed for a long time essentially as media for solid-phase extraction of F-molecules or F-tagged molecules in organic chemistry and heterogeneous catalysis. More recently, this approach has been extended to proteomics and metabolomics. Owing to their unique physicochemical properties, namely fluorophilicity and proteinophilicity, and a better understanding of some fundamental aspects of their behavior, new applications of F-adsorbents in the field of environmental science and bio-affinity studies can be envisaged. In this article, we revisit the most important features of F-adsorbents by focusing, in particular, on some basic information that has been recently obtained through (nonlinear) chromatographic studies. Finally, we try to envisage new applications and possibilities that F-adsorbents will allow in the near future. PMID:25358910

  3. Halogen Bonding and Chalcogen Bonding in 4,7-Dibromo-5,6-dinitro-2,1,3-benzothiadiazole.

    PubMed

    Pavan, Mysore S; Jana, Ajay Kumar; Natarajan, S; Guru Row, Tayur N

    2015-08-27

    An organic solid, 4,7-dibromo-5,6-dinitro-2,1,3-benzothiadiazole, has been designed to serve as an illustrative example to quantitatively evaluate the relative merits of halogen and chalcogen bonding in terms of charge density features. The compound displays two polymorphic modifications, one crystallizing in a non-centrosymmetric space group (Z' = 1) and the other in a centrosymmetric space group with two molecules in the asymmetric unit (Z' = 2). Topological analysis based on QTAIM clearly brings out the dominance of the chalcogen bond over the halogen bond along with an indication that halogen bonds are more directional compared to chalcogen bonds. The cohesive energies calculated with the absence of both strong and weak hydrogen bonds as well as stacking interaction are indicative of the stabilities associated with the polymorphic forms.

  4. 40 CFR 721.4484 - Halogenated indane (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halogenated indane (generic name). 721.4484 Section 721.4484 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Substances § 721.4484 Halogenated indane (generic name). (a) Chemical substance and significant new...

  5. 40 CFR 721.4484 - Halogenated indane (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated indane (generic name). 721.4484 Section 721.4484 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Substances § 721.4484 Halogenated indane (generic name). (a) Chemical substance and significant new...

  6. 40 CFR 721.8700 - Halogenated alkyl pyridine.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8700 Halogenated alkyl pyridine. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated alkyl pyridine (PMN P-83-237)...

  7. 40 CFR 721.8750 - Halogenated substituted pyridine.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8750 Halogenated substituted pyridine. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated...

  8. Field-Reversal Source for Negative Halogen Ions

    NASA Technical Reports Server (NTRS)

    Chutjian, A.; Orient, O. J.; Aladzhadzhyan, S. H.

    1987-01-01

    Large zero-energy electron-attachment cross sections result in intense ion beams. Concept for producing negative halogen ions takes advantage of large cross sections at zero kinetic energy for dissociative attachment of electrons to such halogen-containing gases as SF6, CFCI3, and CCI4.

  9. 40 CFR 721.10015 - Halogenated benzimidazole (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated benzimidazole (generic... Specific Chemical Substances § 721.10015 Halogenated benzimidazole (generic). (a) Chemical substance and... benzimidazole (PMN P-01-110) is subject to reporting under this section for the significant new uses...

  10. 40 CFR 721.3480 - Halogenated biphenyl glycidyl ethers.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halogenated biphenyl glycidyl ethers... Substances § 721.3480 Halogenated biphenyl glycidyl ethers. (a) Chemical substance and significant new uses... ethers (PMNs P-90-1844, P-90-1845, and P-90-1846) are subject to reporting under this section for...

  11. 40 CFR 721.3480 - Halogenated biphenyl glycidyl ethers.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated biphenyl glycidyl ethers... Substances § 721.3480 Halogenated biphenyl glycidyl ethers. (a) Chemical substance and significant new uses... ethers (PMNs P-90-1844, P-90-1845, and P-90-1846) are subject to reporting under this section for...

  12. 40 CFR 721.4484 - Halogenated indane (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogenated indane (generic name). 721.4484 Section 721.4484 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4484 Halogenated...

  13. 40 CFR 721.536 - Halogenated phenyl alkane.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogenated phenyl alkane. 721.536 Section 721.536 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.536 Halogenated phenyl alkane....

  14. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject...

  15. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject...

  16. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject...

  17. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject...

  18. Scientific conferences: A big hello to halogen bonding

    NASA Astrophysics Data System (ADS)

    Erdelyi, Mate

    2014-09-01

    Halogen bonding connects a wide range of subjects -- from materials science to structural biology, from computation to crystal engineering, and from synthesis to spectroscopy. The 1st International Symposium on Halogen Bonding explored the state of the art in this fast-growing field of research.

  19. 40 CFR 721.535 - Halogenated alkane (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.535 Halogenated alkane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated alkane (PMN P-01-433) is...

  20. 40 CFR 721.535 - Halogenated alkane (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.535 Halogenated alkane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated alkane (PMN P-01-433) is...

  1. 40 CFR 721.536 - Halogenated phenyl alkane.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.536 Halogenated phenyl alkane. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated phenyl alkane (PMN P-89-867)...

  2. 40 CFR 721.536 - Halogenated phenyl alkane.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.536 Halogenated phenyl alkane. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated phenyl alkane (PMN P-89-867)...

  3. Kinetic smog-chamber studies on halogen activation from a simulated salt pan, using dry and wet NaCl/NaBr surfaces

    NASA Astrophysics Data System (ADS)

    Bleicher, Sergej; Balzer, Natalja; Zetzsch, Cornelius; Buxmann, Joelle; Platt, Ulrich

    2010-05-01

    Field experiments and laboratory studies have shown that atomic Br and Cl are released from sea-salt aerosol and saline soils. This halogen release is based on the uptake of gaseous HOX by aqueous, acidified salt surfaces. Br and Cl play an important role in atmospheric ozone depletion and the destruction of hydrocarbons. Furthermore, Secondary Organic Aerosol (SOA) and HUmic LIke Substances (HULIS) may take part in these reaction cycles by halogenation and production of volatile organic halogen compounds. Aerosol smog-chamber facilities (coolable to -25°C) enable us to simulate the halogen release mechanism under arctic tropospheric conditions. Mechanistic and kinetic studies are carried out to investigate the influence of SOA and HULIS on halogen cycles and to determine halogenated gaseous and solid organic products. The present laboratory measurements study halogen activation from salt surfaces, which are similar to typical salt pan environments. In these experiments we placed different artificial salt mixtures with NaCl/NaBr ratios up to 300:1 on a Teflon pan located in a Teflon chamber with a volume of 3.5 m3. Under clean air conditions we inject ozone and a mixture of non-methane hydrocarbons with well-known reactivities against OH and Cl and irradiated the chamber with a solar simulator. Beside the usual observing instruments like an ozone monitor and a gas chromatograph we used Differential Optical Absorption Spectroscopy (DOAS) in a White cell with a light path up to 320 m to observe various gas-phase species including BrO radicals. A dry air / dry salt pan environment showed no ozone depletion and no halogen activation. At relative humidity above 50%, a rapid ozone depletion (4.7 h half-life) was observed, which is much faster than for pure NaCl under the same conditions (77 h). Furthermore, the mixed salt was acidified with H2SO4 to a pH value of 4.3, no difference in ozone depletion and halogen activation was observed at this point. The DOAS

  4. Electrogenerative cell for the oxidation or halogenation of hydrocarbons

    SciTech Connect

    McIntyre, J.M.

    1988-03-15

    A process for producing electric power by the electrogenerative halogenation or oxidation of at least one unsaturated hydrocarbon in an electrochemical cell having an anode and cathode separated by a permselective membrane or electrolyte permeable diaphragm is described comprising: (A) flowing a first liquid electrolyte and the unsaturated hydrocarbon to an anolyte compartment of the cell containing a porous anode; (B) flowing a second liquid electrolyte and a halogen or oxygen gas to a catholyte compartment of the cell containing a porous cathode; (C) reacting the unsaturated hydrocarbon with the halogen or the oxygen at ambient or elevated temperatures and pressures; (D) recovering a halogenated or oxygenated hydrocarbon; (E) recycling the electrolytes, unsaturated hydrocarbon, and halogen or oxygen gas to the cell.

  5. Crystal structures of four δ-keto esters and a Cambridge Structural Database analysis of cyano-halogen interactions.

    PubMed

    Kamal, Kulsoom; Maurya, Hardesh K; Gupta, Atul; Vasudev, Prema G

    2015-10-01

    The revived interest in halogen bonding as a tool in pharmaceutical cocrystals and drug design has indicated that cyano-halogen interactions could play an important role. The crystal structures of four closely related δ-keto esters, which differ only in the substitution at a single C atom (by H, OMe, Cl and Br), are compared, namely ethyl 2-cyano-5-oxo-5-phenyl-3-(piperidin-1-yl)pent-2-enoate, C19H22N2O3, (1), ethyl 2-cyano-5-(4-methoxyphenyl)-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C20H24N2O4, (2), ethyl 5-(4-chlorophenyl)-2-cyano-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C19H21ClN2O3, (3), and the previously published ethyl 5-(4-bromophenyl)-2-cyano-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C19H21BrN2O3, (4) [Maurya, Vasudev & Gupta (2013). RSC Adv. 3, 12955-12962]. The molecular conformations are very similar, while there are differences in the molecular assemblies. Intermolecular C-H...O hydrogen bonds are found to be the primary interactions in the crystal packing and are present in all four structures. The halogenated derivatives have additional aromatic-aromatic interactions and cyano-halogen interactions, further stabilizing the molecular packing. A database analysis of cyano-halogen interactions using the Cambridge Structural Database [CSD; Groom & Allen (2014). Angew. Chem. Int. Ed. 53, 662-671] revealed that about 13% of the organic molecular crystals containing both cyano and halogen groups have cyano-halogen interactions in their packing. Three geometric parameters for the C-X...N[triple-bond]C interaction (X = F, Cl, Br or I), viz. the N...X distance and the C-X...N and C-N...X angles, were analysed. The results indicate that all the short cyano-halogen contacts in the CSD can be classified as halogen bonds, which are directional noncovalent interactions.

  6. Crystal structures of four δ-keto esters and a Cambridge Structural Database analysis of cyano-halogen interactions.

    PubMed

    Kamal, Kulsoom; Maurya, Hardesh K; Gupta, Atul; Vasudev, Prema G

    2015-10-01

    The revived interest in halogen bonding as a tool in pharmaceutical cocrystals and drug design has indicated that cyano-halogen interactions could play an important role. The crystal structures of four closely related δ-keto esters, which differ only in the substitution at a single C atom (by H, OMe, Cl and Br), are compared, namely ethyl 2-cyano-5-oxo-5-phenyl-3-(piperidin-1-yl)pent-2-enoate, C19H22N2O3, (1), ethyl 2-cyano-5-(4-methoxyphenyl)-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C20H24N2O4, (2), ethyl 5-(4-chlorophenyl)-2-cyano-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C19H21ClN2O3, (3), and the previously published ethyl 5-(4-bromophenyl)-2-cyano-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C19H21BrN2O3, (4) [Maurya, Vasudev & Gupta (2013). RSC Adv. 3, 12955-12962]. The molecular conformations are very similar, while there are differences in the molecular assemblies. Intermolecular C-H...O hydrogen bonds are found to be the primary interactions in the crystal packing and are present in all four structures. The halogenated derivatives have additional aromatic-aromatic interactions and cyano-halogen interactions, further stabilizing the molecular packing. A database analysis of cyano-halogen interactions using the Cambridge Structural Database [CSD; Groom & Allen (2014). Angew. Chem. Int. Ed. 53, 662-671] revealed that about 13% of the organic molecular crystals containing both cyano and halogen groups have cyano-halogen interactions in their packing. Three geometric parameters for the C-X...N[triple-bond]C interaction (X = F, Cl, Br or I), viz. the N...X distance and the C-X...N and C-N...X angles, were analysed. The results indicate that all the short cyano-halogen contacts in the CSD can be classified as halogen bonds, which are directional noncovalent interactions. PMID:26422224

  7. [Near infrared light irradiator using halogen lamp].

    PubMed

    Ide, Yasuo

    2012-07-01

    The practical electric light bulb was invented by Thomas Alva Edison in 1879. Halogen lamp is the toughest and brightest electric light bulb. With light filter, it is used as a source of near infrared light. Super Lizer and Alphabeam are made as near infrared light irradiator using halogen lamp. The light emmited by Super Lizer is linear polarized near infrared light. The wave length is from 600 to 1,600 nm and strongest at about 1,000 nm. Concerning Super Lizer, there is evidence of analgesic effects and normalization of the sympathetic nervous system. Super Lizer has four types of probes. SG type is used for stellate ganglion irradiation. B type is used for narrow area irradiation. C and D types are for broad area irradiation. The output of Alphabeam is not polarized. The wave length is from 700 to 1,600 nm and the strongest length is about 1,000nm. Standard attachment is used for spot irradiation. Small attachment is used for stellate ganglion irradiation. Wide attachment is used for broad area irradiation. The effects of Alphabeam are thought to be similar to that of Super Lizer.

  8. The halogen analogs of thiolated gold nanoclusters

    SciTech Connect

    Jiang, Deen; Walter, Michael

    2012-01-01

    Is it possible to replace all the thiolates in a thiolated gold nanocluster with halogens while still maintaining the geometry and the electronic structure? In this work, we show from density functional theory that such halogen analogs of thiolated gold nanoclusters are highly likely. Using Au{sub 25}X{sub 18}{sup -} as an example, where X = F, Cl, Br, or I replaces -SR, we find that Au{sub 25}Cl{sub 18}{sup -} demonstrates a high similarity to Au{sub 25}(SR){sub 18}{sup -} by showing Au-Cl distances, Cl-Au-Cl angles, band gap, and frontier orbitals similar to those in Au{sub 25}(SR){sub 18}{sup -}. DFT-based global minimization also indicates the energetic preference of staple formation for the Au{sub 25}Cl{sub 18}{sup -} cluster. The similarity between Au{sub m}(SR){sub n} and Au{sub m}X{sub n} could be exploited to make viable Au{sub m}X{sub n} clusters and to predict structures for Au{sub m}(SR){sub n}.

  9. [Interaction of soda lime and halogenated anesthetics].

    PubMed

    Torri, G; Montani, C; Tommasino, C

    1997-05-01

    The increased use of soda lime for low flow anaesthesia leads to some problems related to the interaction with halogenated agents. These agents may be absorbed by soda lime or degradated according to their water content. Halothane and enflurane, in contact with soda lime, produce some metabolites, but their concentration is low when compared to their own lethal concentration. Sevoflurane degradates to four compounds. Compound A may reach a value between 13.3-42.1 ppm in the inspired fraction: these values are 50-100 times lower than the toxic concentrations. Isoflurane and desflurane are degradable at very low extent. Some case reports of unexpected high carboxyhemoglobin levels during anaesthesia indicate the possibility of CO production from soda lime and baralyme when halogenated agents are used. This reaction occurs only with anaesthetics containing CHF2-moiety (isoflurane, enflurane and desflurane) and when some specific factors make soda lime or baralyme completely dry. Low flow anaesthesia preserves the moisture content of the soda lime and protects from carbon monoxide production, by increasing water content in the circle.

  10. On The Nature of the Halogen Bond.

    PubMed

    Wang, Changwei; Danovich, David; Mo, Yirong; Shaik, Sason

    2014-09-01

    The wide-ranging applications of the halogen bond (X-bond), notably in self-assembling materials and medicinal chemistry, have placed this weak intermolecular interaction in a center of great deal of attention. There is a need to elucidate the physical nature of the halogen bond for better understanding of its similarity and differences vis-à-vis other weak intermolecular interactions, for example, hydrogen bond, as well as for developing improved force-fields to simulate nano- and biomaterials involving X-bonds. This understanding is the focus of the present study that combines the insights of a bottom-up approach based on ab initio valence bond (VB) theory and the block-localized wave function (BLW) theory that uses monomers to reconstruct the wave function of a complex. To this end and with an aim of unification, we studied the nature of X-bonds in 55 complexes using the combination of VB and BLW theories. Our conclusion is clear-cut; most of the X-bonds are held by charge transfer interactions (i.e., intermolecular hyperconjugation) as envisioned more than 60 years ago by Mulliken. This is consistent with the experimental and computational findings that X-bonds are more directional than H-bonds. Furthermore, the good linear correlation between charge transfer energies and total interaction energies partially accounts for the success of simple force fields in the simulation of large systems involving X-bonds. PMID:26588518

  11. Study on the volatility of halogenated fluorenes.

    PubMed

    Oliveira, Juliana A S A; Oliveira, Tânia S M; Gaspar, Alexandra; Borges, Fernanda; Ribeiro da Silva, Maria D M C; Monte, Manuel J S

    2016-08-01

    This work reports the experimental determination of relevant thermophysical properties of five halogenated fluorenes. The vapor pressures of the compounds studied were measured at different temperatures using two different experimental techniques. The static method was used for studying 2-fluorofluorene (liquid and crystal vapor pressures between 321.04 K and 411.88 K), 2-iodofluorene (liquid and crystal vapor pressures between 362.63 K and 413.86 K), and 2,7-dichlorofluorene (crystal vapor pressures between 364.64 K and 394.22 K). The Knudsen effusion method was employed to determine the vapor pressures of 2,7-difluorofluorene (crystal vapor pressures between 299.17 K and 321.19 K), 2,7-diiodofluorene (crystal vapor pressures between 393.19 K and 415.14 K), and (again) 2-iodofluorene (crystal vapor pressures between 341.16 K and 361.12 K). The temperatures and the molar enthalpies of fusion of the five compounds were determined using differential scanning calorimetry. The application to halogenated fluorenes of recently developed methods for predicting vapor pressures and enthalpies of sublimation and vaporization of substituted benzenes is also discussed. PMID:27206270

  12. [Near infrared light irradiator using halogen lamp].

    PubMed

    Ide, Yasuo

    2012-07-01

    The practical electric light bulb was invented by Thomas Alva Edison in 1879. Halogen lamp is the toughest and brightest electric light bulb. With light filter, it is used as a source of near infrared light. Super Lizer and Alphabeam are made as near infrared light irradiator using halogen lamp. The light emmited by Super Lizer is linear polarized near infrared light. The wave length is from 600 to 1,600 nm and strongest at about 1,000 nm. Concerning Super Lizer, there is evidence of analgesic effects and normalization of the sympathetic nervous system. Super Lizer has four types of probes. SG type is used for stellate ganglion irradiation. B type is used for narrow area irradiation. C and D types are for broad area irradiation. The output of Alphabeam is not polarized. The wave length is from 700 to 1,600 nm and the strongest length is about 1,000nm. Standard attachment is used for spot irradiation. Small attachment is used for stellate ganglion irradiation. Wide attachment is used for broad area irradiation. The effects of Alphabeam are thought to be similar to that of Super Lizer. PMID:22860296

  13. Hydrogen bond and halogen bond inside the carbon nanotube

    NASA Astrophysics Data System (ADS)

    Wang, Weizhou; Wang, Donglai; Zhang, Yu; Ji, Baoming; Tian, Anmin

    2011-02-01

    The hydrogen bond and halogen bond inside the open-ended single-walled carbon nanotubes have been investigated theoretically employing the newly developed density functional M06 with the suitable basis set and the natural bond orbital analysis. Comparing with the hydrogen or halogen bond in the gas phase, we find that the strength of the hydrogen or halogen bond inside the carbon nanotube will become weaker if there is a larger intramolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom donor to the antibonding orbital of the X-H or X-Hal bond involved in the formation of the hydrogen or halogen bond and will become stronger if there is a larger intermolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom acceptor to the antibonding orbital of the X-H or X-Hal bond. According to the analysis of the molecular electrostatic potential of the carbon nanotube, the driving force for the electron-density transfer is found to be the negative electric field formed in the carbon nanotube inner phase. Our results also show that the X-H bond involved in the formation of the hydrogen bond and the X-Hal bond involved in the formation of the halogen bond are all elongated when encapsulating the hydrogen bond and halogen bond within the carbon nanotube, so the carbon nanotube confinement may change the blue-shifting hydrogen bond and the blue-shifting halogen bond into the red-shifting hydrogen bond and the red-shifting halogen bond. The possibility to replace the all electron nanotube-confined calculation by the simple polarizable continuum model is also evaluated.

  14. Rotary adsorbers for continuous bulk separations

    DOEpatents

    Baker, Frederick S.

    2011-11-08

    A rotary adsorber for continuous bulk separations is disclosed. The rotary adsorber includes an adsorption zone in fluid communication with an influent adsorption fluid stream, and a desorption zone in fluid communication with a desorption fluid stream. The fluid streams may be gas streams or liquid streams. The rotary adsorber includes one or more adsorption blocks including adsorbent structure(s). The adsorbent structure adsorbs the target species that is to be separated from the influent fluid stream. The apparatus includes a rotary wheel for moving each adsorption block through the adsorption zone and the desorption zone. A desorption circuit passes an electrical current through the adsorbent structure in the desorption zone to desorb the species from the adsorbent structure. The adsorbent structure may include porous activated carbon fibers aligned with their longitudinal axis essentially parallel to the flow direction of the desorption fluid stream. The adsorbent structure may be an inherently electrically-conductive honeycomb structure.

  15. Friction of iron lubricated with aliphatic and aromatic hydrocarbons and halogenated analogs

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1976-01-01

    The influence of oxygen and various organic molecules on the reduction of the friction of an iron (011) single crystal surface was investigated. A comparison was made between aliphatic and aromatic structures, all of which contained six carbon atoms, and among various halogen atoms. Results of the investigation indicate that hexane and benzene give similar friction coefficients over a range of loads except at very light loads. At light loads, the friction decreased with an increase in the load where the halogens fluorine and chlorine are incorporated into the benzene molecular structure; however, over the same load range when bromine and iodine were present, the friction was relatively unchanged. The aliphatic compound chlorohexane exhibited lower friction coefficients than the aromatic structure chlorobenzene at very light loads. With the brominated benzene structures, however, friction was essentially the same. Oxygen was more effective in reducing friction than were the simple hydrocarbons.

  16. Control of acid gases using a fluidized bed adsorber.

    PubMed

    Chiang, Bo-Chin; Wey, Ming-Yen; Yeh, Chia-Lin

    2003-08-01

    During incineration, secondary pollutants such as acid gases, organic compounds, heavy metals and particulates are generated. Among these pollutants, the acid gases, including sulfur oxides (SO(x)) and hydrogen chloride (HCl), can cause corrosion of the incinerator piping and can generate acid rain after being emitted to the atmosphere. To address this problem, the present study used a novel combination of air pollution control devices (APCDs), composed of a fluidized bed adsorber integrated with a fabric filter. The major objective of the work is to demonstrate the performance of a fluidized bed adsorber for removal of acid gases from flue gas of an incinerator. The adsorbents added in the fluidized bed adsorber were mainly granular activated carbon (AC; with or without chemical treatment) and with calcium oxide used as an additive. The advantages of a fluidized bed reactor for high mass transfer and high gas-solid contact can enhance the removal of acid gases when using a dry method. On the other hand, because the fluidized bed can filter particles, fine particles prior to and after passing through the fluidized bed adsorber were investigated. The competing adsorption on activated carbon between different characteristics of pollutants was also given preliminary discussion. The results indicate that the removal efficiencies of the investigated acid gases, SO(2) and HCl, are higher than 94 and 87%, respectively. Thus, a fluidized bed adsorber integrated with a fabric filter has the potential to replace conventional APCDs, even when there are other pollutants at the same time.

  17. Evaluation of a cesium adsorbent grafted with ammonium 12-molybdophosphate

    NASA Astrophysics Data System (ADS)

    Shibata, Takuya; Seko, Noriaki; Amada, Haruyo; Kasai, Noboru; Saiki, Seiichi; Hoshina, Hiroyuki; Ueki, Yuji

    2016-02-01

    A fibrous cesium (Cs) adsorbent was developed using radiation-induced graft polymerization with a cross-linked structure containing a highly stable adsorption ligand. The ligand, ammonium 12-molybdophosphate (AMP), was successfully introduced onto the fibrous polyethylene trunk material. The resulting Cs adsorbent contained 36% nonwoven fabric polyethylene (NFPE), 1% AMP, 2% triallyl isocyanurate (TAIC) and 61% glycidyl methacrylate (GMA). The adsorbent's Cs adsorption capacity was evaluated using batch and column tests. It was determined that the adsorbent could be used in a wide pH range. The amount of desorbed molybdenum, which can be used as an estimate for AMP stability on the Cs adsorbent, was minimized at the standard drinking water pH range of 5.8-8.6. Based from the inspection on the adherence of these results to the requirements set forth by the Food Sanitation Act by a third party organization, it can be concluded that the developed Cs adsorbent can be safely utilized for drinking water.

  18. Independent Evolution of Six Families of Halogenating Enzymes

    PubMed Central

    Xu, Gangming; Wang, Bin-Gui

    2016-01-01

    Halogenated natural products are widespread in the environment, and the halogen atoms are typically vital to their bioactivities. Thus far, six families of halogenating enzymes have been identified: cofactor-free haloperoxidases (HPO), vanadium-dependent haloperoxidases (V-HPO), heme iron-dependent haloperoxidases (HI-HPO), non-heme iron-dependent halogenases (NI-HG), flavin-dependent halogenases (F-HG), and S-adenosyl-L-methionine (SAM)-dependent halogenases (S-HG). However, these halogenating enzymes with similar biological functions but distinct structures might have evolved independently. Phylogenetic and structural analyses suggest that the HPO, V-HPO, HI-HPO, NI-HG, F-HG, and S-HG enzyme families may have evolutionary relationships to the α/β hydrolases, acid phosphatases, peroxidases, chemotaxis phosphatases, oxidoreductases, and SAM hydroxide adenosyltransferases, respectively. These halogenating enzymes have established sequence homology, structural conservation, and mechanistic features within each family. Understanding the distinct evolutionary history of these halogenating enzymes will provide further insights into the study of their catalytic mechanisms and halogenation specificity. PMID:27153321

  19. Mechanistic aspects regarding the direct aqueous environmental photochemistry of phenol and its simple halogenated derivatives. A review.

    PubMed

    Rayne, Sierra; Forest, Kaya; Friesen, Ken J

    2009-02-01

    We have reviewed the mechanistic aspects regarding the direct aqueous phase environmental photochemistry of phenol and its simple halogenated derivatives. These compounds are important industrial and natural products, are ubiquitous in aquatic systems, and their acute and chronic toxicity makes their environmental fate of interest. Work over the past two decades has unified the photochemistry of phenol and its simple halogenated derivatives. In general, three photochemical pathways dominate in aqueous solution depending on the nature of the substrate: (1) photoionization, (2) photochemical aryl-halogen bond homolysis, and (3) photochemical aryl-halogen bond heterolysis. Photoionization typically results in an array of biaryl radical coupling products which are only relevant for highly concentrated waste streams. Photolytic aryl-halogen bond homolysis will primarily give photoreduction products where reducing agents such as dissolved organic matter or reduced metal cations are present, and radical coupling products in highly concentrated waste streams. The 2- and 4-substituted halophenols may undergo photochemical aryl-halogen bond heterolysis upon irradiation to give an aryl cation. The aryl cation can be attacked by water to give the corresponding hydroxylated derivative, or may deprotonate to generate alpha- and gamma-ketocarbenes, respectively. Following their formation, the singlet alpha-ketocarbenes may undergo Wolff rearrangements to cyclopentadiene-ketenes that are subsequently hydrolyzed to cyclopentadiene carboxylic acids. The triplet alpha- and gamma-ketocarbenes are attacked by oxygen and hydrolyzed to give benzoquinones, directly hydrolyzed to yield hydroquinones, reduced to give phenols, or could take part in coupling reactions in highly concentrated waste streams to give dimers and hydroxybiaryl complexes. Additional studies in natural water samples are required to assess the relative importance of these direct irradiation mechanisms relative to

  20. Metal halogen battery construction with improved technique for producing halogen hydrate

    DOEpatents

    Fong, Walter L.; Catherino, Henry A.; Kotch, Richard J.

    1983-01-01

    An improved electrical energy storage system comprising, at least one cell having a positive electrode and a negative electrode separated by aqueous electrolyte, a store means wherein halogen hydrate is formed and stored as part of an aqueous material having a liquid level near the upper part of the store, means for circulating electrolyte through the cell, conduit means for transmitting halogen gas formed in the cell to a hydrate forming apparatus associated with the store, said hydrate forming apparatus including, a pump to which there is introduced quantities of the halogen gas and chilled water, said pump being located in the store and an outlet conduit leading from the pump and being substantially straight and generally vertically disposed and having an exit discharge into the gas space above the liquid level in the store, and wherein said hydrate forming apparatus is highly efficient and very resistant to plugging or jamming. The disclosure also relates to an improved method for producing chlorine hydrate in zinc chlorine batteries.

  1. Molecular halogen elimination from halogen-containing compounds in the atmosphere.

    PubMed

    Lin, King-Chuen; Tsai, Po-Yu

    2014-04-28

    Atmospheric halogen chemistry has drawn much attention, because the halogen atom (X) playing a catalytic role may cause severe stratospheric ozone depletion. Atomic X elimination from X-containing hydrocarbons is recognized as the major primary dissociation process upon UV-light irradiation, whereas direct elimination of the X2 product has been seldom discussed or remained a controversial issue. This account is intended to review the detection of X2 primary products using cavity ring-down absorption spectroscopy in the photolysis at 248 nm of a variety of X-containing compounds, focusing on bromomethanes (CH2Br2, CF2Br2, CHBr2Cl, and CHBr3), dibromoethanes (1,1-C2H4Br2 and 1,2-C2H4Br2) and dibromoethylenes (1,1-C2H2Br2 and 1,2-C2H2Br2), diiodomethane (CH2I2), thionyl chloride (SOCl2), and sulfuryl chloride (SO2Cl2), along with a brief discussion on acyl bromides (BrCOCOBr and CH2BrCOBr). The optical spectra, quantum yields, and vibrational population distributions of the X2 fragments have been characterized, especially for Br2 and I2. With the aid of ab initio calculations of potential energies and rate constants, the detailed photodissociation mechanisms may be comprehended. Such studies are fundamentally important to gain insight into the dissociation dynamics and may also practically help to assess the halogen-related environmental variation. PMID:24622955

  2. Four groups of new aromatic halogenated disinfection byproducts: effect of bromide concentration on their formation and speciation in chlorinated drinking water.

    PubMed

    Pan, Yang; Zhang, Xiangru

    2013-02-01

    Bromide is naturally present in source waters worldwide. Chlorination of drinking water can generate a variety of chlorinated and brominated disinfection byproducts (DBPs). Although substantial efforts have been made to examine the effect of bromide concentration on the formation and speciation of halogenated DBPs, almost all previous studies have focused on trihalomethanes and haloacetic acids. Given that about 50% of total organic halogen formed in chlorination remains unknown, it is still unclear how bromide concentration affects the formation and speciation of the new/unknown halogenated DBPs. In this study, chlorinated drinking water samples with different bromide concentrations were prepared, and a novel approach-precursor ion scan using ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry-was adopted for the detection and identification of polar halogenated DBPs in these water samples. With this approach, 11 new putative aromatic halogenated DBPs were identified, and they were classified into four groups: dihalo-4-hydroxybenzaldehydes, dihalo-4-hydroxybenzoic acids, dihalo-salicylic acids, and trihalo-phenols. A mechanism for the formation of the four groups of new aromatic halogenated DBPs was proposed. It was found that increasing the bromide concentration shifted the entire polar halogenated DBPs as well as the four groups of new DBPs from being less brominated to being more brominated; these new aromatic halogenated DBPs might be important intermediate DBPs formed in drinking water chlorination. Moreover, the speciation of the four groups of new DBPs was modeled: the speciation patterns of the four groups of new DBPs well matched those determined from the model equations, and the reactivity differences between HOBr and HOCl in reactions forming the four groups of new DBPs were larger than those in reactions forming trihalomethanes and haloacetic acids.

  3. Halogen occultation experiment intergrated test plan

    NASA Technical Reports Server (NTRS)

    Mauldin, L. E., III; Butterfield, A. J.

    1986-01-01

    The test program plan is presented for the Halogen Occultation Experiment (HALOE) instrument, which is being developed in-house at the Langley Research Center for the Upper Atmosphere Research Satellite (UARS). This comprehensive test program was developed to demonstrate that the HALOE instrument meets its performance requirements and maintains integrity through UARS flight environments. Each component, subsystem, and system level test is described in sufficient detail to allow development of the necessary test setups and test procedures. Additionally, the management system for implementing this test program is given. The HALOE instrument is a gas correlation radiometer that measures vertical distribution of eight upper atmospheric constituents: O3, HC1, HF, NO, CH4, H2O, NO2, and CO2.

  4. Chalcogen bond: a sister noncovalent bond to halogen bond.

    PubMed

    Wang, Weizhou; Ji, Baoming; Zhang, Yu

    2009-07-16

    A sister noncovalent bond to halogen bond, termed chalcogen bond, is defined in this article. By selecting the complexes H(2)CS...Cl(-), F(2)CS...Cl(-), OCS...Cl(-), and SCS...Cl(-) as models, the bond-length change, interaction energy, topological property of the electron charge density and its Laplacian, and the charge transfer of the chalcogen bond have been investigated in detail theoretically. It was found that the similar misshaped electron clouds of the chalcogen atom and the halogen atom result in the similar properties of the chalcogen bond and the halogen bond. Experimental results are in good agreement with the theoretical predictions.

  5. Halogenated coumarin derivatives as novel seed protectants.

    PubMed

    Brooker, N; Windorski, J; Bluml, E

    2008-01-01

    Development of new and improved antifungal compounds that are target-specific is backed by a strong Federal, public and commercial mandate. Many plant-derived chemicals have proven fungicidal properties, including the coumarins (1,2-Benzopyrone) found in a variety of plants such as clover, sweet woodruff and grasses. Preliminary research has shown the coumarins to be a highly active group of molecules with a wide range of antimicrobial activity against both fungi and bacteria. It is believed that these cyclic compounds behave as natural pesticidal defence molecules for plants and they represent a starting point for the exploration of new derivative compounds possessing a range of improved antifungal activity. Within this study, derivatives of coumarin that were modified with halogenated side groups were screened for their antifungal activity against a range of soil-borne plant pathogenic fungi. Fungi included in this in vitro screen included Macrophomina phaseolina (charcoal rot), Phytophthora spp. (damping off and seedling rot), Rhizoctonia spp. (damping off and root rot) and Pythium spp. (seedling blight), four phylogenetically diverse and economically important plant pathogens. Studies indicate that these halogenated coumarin derivatives work very effectively in vitro to inhibit fungal growth and some coumarin derivatives have higher antifungal activity and stability as compared to the original coumarin compound alone. The highly active coumarin derivatives are brominated, iodinated and chlorinated compounds and results suggest that besides being highly active, very small amounts can be used to achieve LD100 rates. In addition to the in vitro fungal inhibition assays, results of polymer seed coating compatibility and phytotoxicity testing using these compounds as seed treatments will also be reported. These results support additional research in this area of natural pesticide development.

  6. A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer

    NASA Astrophysics Data System (ADS)

    Toyota, K.; Kanaya, Y.; Takahashi, M.; Akimoto, H.

    2004-09-01

    A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry) to investigate photochemical interactions between volatile organic compounds (VOCs) and reactive halogen species in the marine boundary layer (MBL). Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit description of oxidative degradation of up to C3-hydrocarbons (CH4, C2H6, C3H8, C2H4, C3H6, and C2H2) initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in forming halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO) and alkenes (especially C3H6) are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from a reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. The reaction between Br atoms and C2H2 is shown to be unimportant for determining the degree of bromine activation in the remote MBL. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl sulfide, NOx, and

  7. A novel evaluation method for extrapolated retention factor in determination of n-octanol/water partition coefficient of halogenated organic pollutants by reversed-phase high performance liquid chromatography.

    PubMed

    Han, Shu-ying; Liang, Chao; Qiao, Jun-qin; Lian, Hong-zhen; Ge, Xin; Chen, Hong-yuan

    2012-02-01

    The retention factor corresponding to pure water in reversed-phase high performance liquid chromatography (RP-HPLC), k(w), was commonly obtained by extrapolation of retention factor (k) in a mixture of organic modifier and water as mobile phase in tedious experiments. In this paper, a relationship between logk(w) and logk for directly determining k(w) has been proposed for the first time. With a satisfactory validation, the approach was confirmed to enable easy and accurate evaluation of k(w) for compounds in question with similar structure to model compounds. Eight PCB congeners with different degree of chlorination were selected as a training set for modeling the logk(w)-logk correlation on both silica-based C(8) and C(18) stationary phases to evaluate logk(w) of sample compounds including seven PCB, six PBB and eight PBDE congeners. These eight model PCBs were subsequently combined with seven structure-similar benzene derivatives possessing reliable experimental K(ow) values as a whole training set for logK(ow)-logk(w) regressions on the two stationary phases. Consequently, the evaluated logk(w) values of sample compounds were used to determine their logK(ow) by the derived logK(ow)-logk(w) models. The logK(ow) values obtained by these evaluated logk(w) were well comparable with those obtained by experimental-extrapolated logk(w), demonstrating that the proposed method for logk(w) evaluation in this present study could be an effective means in lipophilicity study of environmental contaminants with numerous congeners. As a result, logK(ow) data of many PCBs, PBBs and PBDEs could be offered. These contaminants are considered to widely exist in the environment, but there have been no reliable experimental K(ow) data available yet. PMID:22200319

  8. The Halogenated Metabolism of Brown Algae (Phaeophyta), Its Biological Importance and Its Environmental Significance

    PubMed Central

    La Barre, Stéphane; Potin, Philippe; Leblanc, Catherine; Delage, Ludovic

    2010-01-01

    Brown algae represent a major component of littoral and sublittoral zones in temperate and subtropical ecosystems. An essential adaptive feature of this independent eukaryotic lineage is the ability to couple oxidative reactions resulting from exposure to sunlight and air with the halogenations of various substrates, thereby addressing various biotic and abiotic stresses i.e., defense against predators, tissue repair, holdfast adhesion, and protection against reactive species generated by oxidative processes. Whereas marine organisms mainly make use of bromine to increase the biological activity of secondary metabolites, some orders of brown algae such as Laminariales have also developed a striking capability to accumulate and to use iodine in physiological adaptations to stress. We review selected aspects of the halogenated metabolism of macrophytic brown algae in the light of the most recent results, which point toward novel functions for iodide accumulation in kelps and the importance of bromination in cell wall modifications and adhesion properties of brown algal propagules. The importance of halogen speciation processes ranges from microbiology to biogeochemistry, through enzymology, cellular biology and ecotoxicology. PMID:20479964

  9. Cooperativity of halogen, chalcogen, and pnictogen bonds in infinite molecular chains by electronic structure theory.

    PubMed

    George, Janine; Deringer, Volker L; Dronskowski, Richard

    2014-05-01

    Halogen bonds (XBs) are intriguing noncovalent interactions that are frequently being exploited for crystal engineering. Recently, similar bonding mechanisms have been proposed for adjacent main-group elements, and noncovalent "chalcogen bonds" and "pnictogen bonds" have been identified in crystal structures. A fundamental question, largely unresolved thus far, is how XBs and related contacts interact with each other in crystals; similar to hydrogen bonding, one might expect "cooperativity" (bonds amplifying each other), but evidence has been sparse. Here, we explore the crucial step from gas-phase oligomers to truly infinite chains by means of quantum chemical computations. A periodic density functional theory (DFT) framework allows us to address polymeric chains of molecules avoiding the dreaded "cluster effects" as well as the arbitrariness of defining a "large enough" cluster. We focus on three types of molecular chains that we cut from crystal structures; furthermore, we explore reasonable substitutional variants in silico. We find evidence of cooperativity in chains of halogen cyanides and also in similar chalcogen- and pnictogen-bonded systems; the bonds, in the most extreme cases, are amplified through cooperative effects by 79% (I···N), 90% (Te···N), and 103% (Sb···N). Two experimentally known organic crystals, albeit with similar atomic connectivity and XB characteristics, show signs of cooperativity in one case but not in another. Finally, no cooperativity is observed in alternating halogen/acetone and halogen/1,4-dioxane chains; in fact, these XBs weaken each other by up to 26% compared to the respective gas-phase dimers.

  10. Adsorbent Alkali Conditioning for Uranium Adsorption from Seawater. Adsorbent Performance and Technology Cost Evaluation

    SciTech Connect

    Tsouris, Costas; Mayes, Richard T.; Janke, Christopher James; Dai, Sheng; Das, S.; Liao, W. -P.; Kuo, Li-Jung; Wood, Jordana; Gill, Gary; Byers, Maggie Flicker; Schneider, Eric

    2015-09-30

    natural seawater. Uptake of other metal ions such as V, Fe, and Cu follows the same trend as that of uranium. Also, the uptake of Ca, Mg, and Zn ions increased with increasing KOH conditioning time, probably due to formation of more carboxylates, which leads to conversion of uranium-selective binding sites to less selective sites. In the second part of the study, inorganic based reagents such as sodium hydroxide (NaOH), sodium carbonate (Na2CO3), cesium hydroxide (CsOH), as well as organic based reagents such as ammonium hydroxide (AOH), tetramethylammonium hydroxide (TMAOH), tetraethylammonium hydroxide (TEAOH), triethylmethylammonium hydroxide (TEMAOH), tetrapropylammonium hydroxide (TPAOH) and tetrabutylammonium hydroxide (TBAOH), in addition to KOH, were used for alkaline conditioning. NaOH has emerged as a better reagent for alkaline conditioning of amidoxime-based adsorbent because of higher uranium uptake capacity, higher uranium uptake selectivity ...

  11. EMERGING TECHNOLOGY REPORT: DEMONSTRATION OF AMBERSORB™ 563 ADSORBENT TECHNOLOGY

    EPA Science Inventory

    The Ambersorb™ (Rohm and Haas) Adsorbent technology demonstration was conducted over a 12-week period during the spring/summer of 1994 at Site 32/36 of the former Pease Air Force Base, Newington, N.H. The groundwater in this area is contaminated with a number of chlorinated organ...

  12. POSSIBLE MOLECULAR TARGETS OF HALOGENATED ARMOATIC HYDROCARBONS IN NEURONAL CELLS.

    EPA Science Inventory

    Halogenated aromatic hydrocarbons including polychlorinated biphenyls (PCBs) are persistent bioaccumulative toxicants. Due to these characteristics, there is considerable regulatory concern over the potential adverse health affects, especially to children, associated with exposur...

  13. Two-dimensional Supramolecular Structures by Hydrogen and Halogen Interactions

    NASA Astrophysics Data System (ADS)

    Keon Yoon, Jong; Kim, Howon; Huem Jeon, Jeong; Kahng, Se-Jong

    2010-03-01

    Supramolecualr ordering has been actively studied due to it's possible applications to the fabrication processes of nano-electronic devices. Van der Waals interaction and hydrogen bonding are frequently studied mechanisms for various molecular structures based on non-uniform charge distributions. Halogen atoms in molecules can have electrostatic interactions with similar strength. Big halogen atoms have strong non-uniform charge distributions. To study molecular orderings formed by hydrogen and halogen interactions, we chose a molecular system containing oxygen, hydrogen, and bromine atoms, a bromo-quinone. A two-dimensional molecular network was studied on Au(111) using a low-temperature scanning tunneling microscope. Bromo-quinone molecules form self-assembled square grids having windmill structures. Their molecular orderings, chiral structures, and defects are explained in terms of hydrogen and halogen interactions.

  14. Experimental measurement of noncovalent interactions between halogens and aromatic rings.

    PubMed

    Adams, Harry; Cockroft, Scott L; Guardigli, Claudio; Hunter, Christopher A; Lawson, Kevin R; Perkins, Julie; Spey, Sharon E; Urch, Christopher J; Ford, Rhonan

    2004-05-01

    Chemical double mutant cycles have been used to quantify the interactions of halogens with the faces of aromatic rings in chloroform. The halogens are forced over the face of an aromatic ring by an array of hydrogen-bonding interactions that lock the complexes in a single, well-defined conformation. These interactions can also be engineered into the crystal structures of simpler model compounds, but experiments in solution show that the halogen-aromatic interactions observed in the solid state are all unfavourable, regardless of whether the aromatic rings contain electron-withdrawing or electron-donating substituents. The halogen-aromatic interactions are repulsive by 1-3 kJ mol(-1). The interactions with fluorine are slightly less favourable than with chlorine and bromine.

  15. Halogen Bonding Promotes Higher Dye-Sensitized Solar Cell Photovoltages.

    PubMed

    Simon, Sarah J C; Parlane, Fraser G L; Swords, Wesley B; Kellett, Cameron W; Du, Chuan; Lam, Brian; Dean, Rebecca K; Hu, Ke; Meyer, Gerald J; Berlinguette, Curtis P

    2016-08-24

    We report here an enhancement in photovoltage for dye-sensitized solar cells (DSSCs) where halogen-bonding interactions exist between a nucleophilic electrolyte species (I(-)) and a photo-oxidized dye immobilized on a TiO2 surface. The triarylamine-based dyes under investigation showed larger rate constants for dye regeneration (kreg) by the nucleophilic electrolyte species when heavier halogen substituents were positioned on the dye. The open-circuit voltages (VOC) tracked these kreg values. This analysis of a homologous series of dyes that differ only in the identity of two halogen substituents provides compelling evidence that the DSSC photovoltage is sensitive to kreg. This study also provides the first direct evidence that halogen-bonding interactions between the dye and the electrolyte can bolster DSSC performance.

  16. Halogenated naphthyl methoxy piperidines for mapping serotonin transporter sites

    DOEpatents

    Goodman, Mark M.; Faraj, Bahjat

    1999-01-01

    Halogenated naphthyl methoxy piperidines having a strong affinity for the serotonin transporter are disclosed. Those compounds can be labeled with positron-emitting and/or gamma emitting halogen isotopes by a late step synthesis that maximizes the useable lifeterm of the label. The labeled compounds are useful for localizing serotonin transporter sites by positron emission tomography and/or single photon emission computed tomography.

  17. Halogenated naphthyl methoxy piperidines for mapping serotonin transporter sites

    DOEpatents

    Goodman, M.M.; Faraj, B.

    1999-07-06

    Halogenated naphthyl methoxy piperidines having a strong affinity for the serotonin transporter are disclosed. Those compounds can be labeled with positron-emitting and/or gamma emitting halogen isotopes by a late step synthesis that maximizes the useable lifeterm of the label. The labeled compounds are useful for localizing serotonin transporter sites by positron emission tomography and/or single photon emission computed tomography.

  18. The contribution of hydrothermally altered ocean crust to the mantle halogen and noble gas cycles

    NASA Astrophysics Data System (ADS)

    Chavrit, Déborah; Burgess, Ray; Sumino, Hirochika; Teagle, Damon A. H.; Droop, Giles; Shimizu, Aya; Ballentine, Chris J.

    2016-06-01

    Recent studies suggest that seawater-derived noble gases and halogens are recycled into the deep mantle by the subduction of oceanic crust. To understand the processes controlling the availability of halogens and noble gases for subduction, we determined the noble gas elemental and isotopic ratios and halogen (Cl, Br, I) concentrations in 28 igneous samples from the altered oceanic crust (AOC) from 5 ODP sites in the Eastern and Western Pacific Ocean. Crushing followed by heating experiments enabled determination of noble gases and halogens in fluid inclusions and mineral phases respectively. Except for He and Ar, Ne, Kr and Xe isotopic ratios were all air-like suggesting that primary MORB signatures have been completely overprinted by air and/or seawater interaction. In contrast, 3He/4He ratios obtained by crushing indicate that a mantle helium component is still preserved, and 40Ar/36Ar values are affected by radiogenic decay in the mineral phases. The 130Xe/36Ar and 84Kr/36Ar ratios are respectively up to 15 times and 5 times higher than those of seawater and the highest ratios are found in samples affected by low temperature alteration (shallower than 800-900 m sub-basement). We consider three possible processes: (i) adsorption onto the clays present in the samples; (ii) fluid inclusions with a marine pore fluid composition; and (iii) fractionation of seawater through phase separation caused by boiling. Ninety percent of the Cl, Br and I were released during the heating experiments, showing that halogens are dominantly held in mineral phases prior to subduction. I/Cl ratios vary by 4 orders of magnitude, from 3 × 10-6 to 2 × 10-2. The mean Br/Cl ratio is 30% lower than in MORB and seawater. I/Cl ratios lower than MORB values are attributed to Cl-rich amphibole formation caused by hydrothermal alteration at depths greater than 800-900 m sub-basement together with different extents of I loss during low and high temperature alteration. At shallower depths, I

  19. Synthesis of 4-vinylpyridine-divinylbenzene copolymer adsorbents for microwave-assisted desorption of benzene.

    PubMed

    Meng, Qing Bo; Yang, Go-Su; Lee, Youn-Sik

    2012-02-29

    Reports on the development of polymer adsorbents for microwave-assisted desorption of nonpolar volatile organic compounds (VOCs) are rare. In this study, we synthesized macroporous polymeric adsorbents with hydrophilic methyl pyridinium units for microwave-assisted desorption of nonpolar VOCs. The benzene adsorption and desorption properties of the adsorbents were investigated under both dry and humid conditions. Under humid conditions, as the content of the hydrophilic methyl pyridinium units in the adsorbents increased from 0 to 20%, the adsorption capacity of benzene decreased from about 21 to 7 mg/g, while the desorption efficiency of benzene increased significantly from 48 to 87%. The maximum concentration of desorbate also increased significantly as the content of the hydrophilic units was increased under humid conditions. We attributed the enhanced desorption efficiency mainly to more adsorbed moisture, which indirectly allowed heating of the polymer adsorbents to higher temperatures upon irradiation with 600 W microwaves. PMID:22236950

  20. Metal halogen battery system with multiple outlet nozzle for hydrate

    DOEpatents

    Bjorkman, Jr., Harry K.

    1983-06-21

    A metal halogen battery system, including at least one cell having a positive electrode and a negative electrode contacted by aqueous electrolyte containing the material of said metal and halogen, store means whereby halogen hydrate is formed and stored as part of an aqueous material, means for circulating electrolyte through the cell and to the store means, and conduit means for transmitting halogen gas formed in the cell to a hydrate former whereby the hydrate is formed in association with the store means, said store means being constructed in the form of a container which includes a filter means, said filter means being inoperative to separate the hydrate formed from the electrolyte, said system having, a hydrate former pump means associated with the store means and being operative to intermix halogen gas with aqueous electrolyte to form halogen hydrate, said hydrate former means including, multiple outlet nozzle means connected with the outlet side of said pump means and being operative to minimize plugging, said nozzle means being comprised of at least one divider means which is generally perpendicular to the rotational axes of gears within the pump means, said divider means acting to divide the flow from the pump means into multiple outlet flow paths.

  1. Treatment of halogen-containing waste and other waste materials

    DOEpatents

    Forsberg, Charles W.; Beahm, Edward C.; Parker, George W.

    1997-01-01

    A process for treating a halogen-containing waste material. The process provides a bath of molten glass containing a sacrificial metal oxide capable of reacting with a halogen in the waste material. The sacrificial metal oxide is present in the molten glass in at least a stoichiometric amount with respect to the halogen in the waste material. The waste material is introduced into the bath of molten glass to cause a reaction between the halogen in the waste material and the sacrificial metal oxide to yield a metal halide. The metal halide is a gas at the temperature of the molten glass. The gaseous metal halide is separated from the molten glass and contacted with an aqueous scrubber solution of an alkali metal hydroxide to yield a metal hydroxide or metal oxide-containing precipitate and a soluble alkali metal halide. The precipitate is then separated from the aqueous scrubber solution. The molten glass containing the treated waste material is removed from the bath as a waste glass. The process of the invention can be used to treat all types of waste material including radioactive wastes. The process is particularly suited for separating halogens from halogen-containing wastes.

  2. Treatment of halogen-containing waste and other waste materials

    DOEpatents

    Forsberg, C.W.; Beahm, E.C.; Parker, G.W.

    1997-03-18

    A process is described for treating a halogen-containing waste material. The process provides a bath of molten glass containing a sacrificial metal oxide capable of reacting with a halogen in the waste material. The sacrificial metal oxide is present in the molten glass in at least a stoichiometric amount with respect to the halogen in the waste material. The waste material is introduced into the bath of molten glass to cause a reaction between the halogen in the waste material and the sacrificial metal oxide to yield a metal halide. The metal halide is a gas at the temperature of the molten glass. The gaseous metal halide is separated from the molten glass and contacted with an aqueous scrubber solution of an alkali metal hydroxide to yield a metal hydroxide or metal oxide-containing precipitate and a soluble alkali metal halide. The precipitate is then separated from the aqueous scrubber solution. The molten glass containing the treated waste material is removed from the bath as a waste glass. The process of the invention can be used to treat all types of waste material including radioactive wastes. The process is particularly suited for separating halogens from halogen-containing wastes. 3 figs.

  3. Persistence, bioaccumulation, and toxicity of halogen-free flame retardants.

    PubMed

    Waaijers, Susanne L; Kong, Deguo; Hendriks, Hester S; de Wit, Cynthia A; Cousins, Ian T; Westerink, Remco H S; Leonards, Pim E G; Kraak, Michiel H S; Admiraal, Wim; de Voogt, Pim; Parsons, John R

    2013-01-01

    Polymers are synthetic organic materials having a high carbon and hydrogen content, which make them readily combustible. Polymers have many indoor uses and their flammability makes them a fire hazard. Therefore, flame retardants (FRs) are incorporated into these materials as a safety measure. Brominated flame retardants (BFRs), which accounted for about 21% of the total world market of FRs, have several unintended negative effects on the environment and human health. Hence, there is growing interest in finding appropriate alternative halogen-free flame retardants (HFFRs). Many of these HFFRs are marketed already, although their environ- mental behavior and toxicological properties are often only known to a limited extent, and their potential impact on the environment cannot yet be properly assessed. Therefore, we undertook this review to make an inventory of the available data that exists (up to September 2011) on the physical-chemical properties, pro- duction volumes, persistence, bioaccumulation, and toxicity (PBT) of a selection of HFFRs that are potential replacements for BFRs in polymers. Large data gaps were identified for the physical-chemical and the PBT properties of the reviewed HFFRs. Because these HFFRs are currently on the market, there is an urgent need to fill these data gaps. Enhanced transparency of methodology and data are needed to reevaluate certain test results that appear contradictory, and, if this does not provide new insights, further research should be performed. TPP has been studied quite extensively and it is clearly persistent, bioaccumulative, and toxic. So far, RDP and BDP have demonstrated low to high ecotoxicity and persistence. The compounds ATH and ZB exerted high toxicity to some species and ALPI appeared to be persistent and has low to moderate reported ecotoxicity. DOPO and MPP may be persistent, but this view is based merely on one or two studies, clearly indicating a lack of information. Many degradation studies have been

  4. Supercritical fluid regeneration of adsorbents

    NASA Astrophysics Data System (ADS)

    Defilippi, R. P.; Robey, R. J.

    1983-05-01

    The results of a program to perform studies supercritical (fluid) carbon dioxide (SCF CO2) regeneration of adsorbents, using samples of industrial wastewaters from manufacturing pesticides and synthetic solution, and to estimate the economics of the specific wastewater treatment regenerations, based on test data are given. Processing costs for regenerating granular activated carbon GAC) for treating industrial wastewaters depend on stream properties and regeneration throughput.

  5. Data for fire hazard assessment of selected non-halogenated and halogenated fire retardants: Report of Test FR 3983

    NASA Astrophysics Data System (ADS)

    Harris, R. H.; Babrauskas, V.; Levin, B. C.; Paabo, M.

    1991-10-01

    Five plastic materials, with and without fire retardants, were studied to compare the fire hazards of non-halogenated fire retardant additives with halogenated flame retardents. The plastic materials were identified by the sponsors as unsaturated polyesters, thermoplastic high density, low density and cross-linked low density polyethylenes, polypropylene, flexible and rigid poly(vinyl chlorides), and cross-linked and thermoplastic ethylene-vinyl acetate copolymers. The non-halogenated fire retardants tested were aluminum hydroxide, also known as alumina trihydrate, sodium alumino-carbonate, and magnesium hydroxide. The halogenated flame retardants were chlorine or bromine/antimony oxides. The plastics were studied using the Cone Calorimeter and the cup furnace smoke toxicity method (high density polyethylene only). The Cone Calorimeter provided data on mass consumed; time to ignition; peak rate and peak time of heat release; total heat release; effective heat of combustion; average yields of CO, CO2, HCl, and HBr; and average smoke obscuration. The concentrations of toxic gases generated in the cup furnace smoke toxicity method were used to predict the toxic potency of the mixed thermal decomposition products. The data from the Cone Calorimeter indicate that the non-halogenated fire retardants were, in most of the tested plastic formulations, more effective than the halogenated flame retardants in increasing the time to ignition. The non-halogenated fire retardants were also more effective in reducing the mass consumed, peak rate of heat release, total heat released, and effective smoke produced. The use of halogenated flame retardants increased smoke production and CO yields and, additionally, produced the known acid gases and toxic irritants, HCl and HBr, in measureable quantities.

  6. Ozonation of isoproturon adsorbed on silica particles under atmospheric conditions

    NASA Astrophysics Data System (ADS)

    Pflieger, Maryline; Grgić, Irena; Kitanovski, Zoran

    2012-12-01

    The results on heterogeneous ozonation of a phenylurea pesticide, isoproturon, under atmospheric conditions are presented for the first time in the present study. The study was carried out using an experimental device previously adopted and validated for the heterogeneous reactivity of organics toward ozone (Pflieger et al., 2011). Isoproturon was adsorbed on silica particles via a liquid-to-solid equilibrium with a load far below a monolayer (0.02% by weight/surface coverage of 0.5%). The rate constants were estimated by measuring the consumption of the organic (dark, T = 26 °C, RH < 1%). The experimental data were fitted by both the modified Langmuir-Hinshelwood and the Eley-Rideal patterns, resulting in atmospheric lifetimes of heterogeneous ozonation of 4 and 6 days, respectively (for 40 ppb of O3). Parameters, such as the number and the quantity of pesticides adsorbed on the solid support, which can significantly influence the heterogeneous kinetics, were investigated as well. The results obtained suggest that the organic compound is adsorbed in multilayer aggregates on the aerosol even though submonolayer coverage is assumed. The presence of a second herbicide, trifluralin, together with isoproturon on the aerosol surface does not affect the kinetics of ozonation, indicating that both compounds are adsorbed on different surface sites of silica particles.

  7. The relative roles of electrostatics and dispersion in the stabilization of halogen bonds.

    PubMed

    Riley, Kevin E; Hobza, Pavel

    2013-11-01

    In this work we highlight recent work aimed at the characterization of halogen bonds. Here we discuss the origins of the σ-hole, the modulation of halogen bond strength by changing of neighboring chemical groups (i.e. halogen bond tuning), the performance of various computational methods in treating halogen bonds, and the strength and character of the halogen bond, the dihalogen bond, and two hydrogen bonds in bromomethanol dimers (which serve as model complexes) are compared. Symmetry adapted perturbation theory analysis of halogen bonding complexes indicates that halogen bonds strongly depend on both dispersion and electrostatics. The electrostatic interaction that occurs between the halogen σ-hole and the electronegative halogen bond donor is responsible for the high degree of directionality exhibited by halogen bonds. Because these noncovalent interactions have a strong dispersion component, it is important that the computational method used to treat a halogen bonding system be chosen very carefully, with correlated methods (such as CCSD(T)) being optimal. It is also noted here that most forcefield-based molecular mechanics methods do not describe the halogen σ-hole, and thus are not suitable for treating systems with halogen bonds. Recent attempts to improve the molecular mechanics description of halogen bonds are also discussed.

  8. Compressed and saturated liquid densities for 18 halogenated organic compounds

    SciTech Connect

    Defibaugh, D.R.; Moldover, M.R.

    1997-01-01

    The pressure-density-temperature P({rho},T) behavior of 18 liquids that are potential working fluids in thermal machinery has been measured using a vibrating tube densimeter. For each liquid, the data were taken on isotherms spaced at intervals of 5 K to 10 K spanning the temperature range 245 K to 370 K. The pressures ranged from just above the vapor pressure (or the critical pressure) to 6500 kPa. The results of measurements at more than 12,000 thermodynamic points are summarized by correlating functions. Comparison with data from other laboratories indicates that the relative expanded uncertainty in the measured densities is less than 0.05%, except in the critical region. The repeatability of the vapor pressure to obtain the density of the liquid at the vapor pressure. The fluids studied (and their designations by the refrigeration industry) were trichlorofluoromethane (R11), chlorodifluoromethane (R22), 1,1-dichloro-2,2,2-trifluoroethane (R123), 1,2-dichloro-1,2,2-trifluoroethane (R123a), 1-chloro-1,2,2,2-tetrafluoroethane (R124), 1,1,2,2-tetrafluoroethane (R134), 1,1,1,2-tetrafluoroethane (R134a), 1,1-dichloro-1-fluoroethane (R141b), 1,1,1-trifluoroethane (R143), 1,1,2-trifluoroethane (R143a), pentafluorodimethyl ether (E125), 1,1-difluoroethane (R152a), octafluoropropane (R218), 1,1,1,2,3,3,3-heptafluoropropane (R227ea), 2-(difluoromethoxy)-1,1,1-trifluoroethane (E245), 1,1,1,2,2-pentafluoropropane (R245cb), 1,1,1,3,3-pentafluoropropane (R245fa), and propane (R290).

  9. Negative Halogen Ions for Fusion Applications

    SciTech Connect

    Grisham, L.R.; Kwan, J.W.; Hahto, S.K.; Hahto, S.T.; Leung, K.N.; Westenskow, G.

    2006-01-01

    Over the past quarter century, advances in hydrogen negative ion sources have extended the usable range of hydrogen isotope neutral beams to energies suitable for large magnetically confined fusion devices. Recently, drawing upon this experience, negative halogen ions have been proposed as an alternative to positive ions for heavy ion fusion drivers in inertial confinement fusion, because electron accumulation would be prevented in negative ion beams, and if desired, the beams could be photo-detached to neutrals. This paper reports the results of an experiment comparing the current density and beam emittance of Cl+ and Cl- extracted from substantially ion-ion plasmas with that of Ar+ extracted from an ordinary electron-ion plasma, all using the same source, extractor, and emittance scanner. At similar discharge conditions, the Cl- current was typically 85 – 90% of the positive chlorine current, with an e-/ Cl- ratio as low as seven without grid magnets. The Cl- was as much as 76% of the Ar+ current from a discharge with the same RF drive. The minimum normalized beam emittance and inferred ion temperatures of Cl+, Cl-, and Ar+ were all similar, so the current density and optical quality of Cl- appear as suitable for heavy ion fusion driver applications as a positive noble gas ion of similar mass. Since F, I, and Br should all behave similarly in an ion source, they should also be suitable as driver beams.

  10. Halogen Occultation Experiment (HALOE) optical filter characterization

    NASA Technical Reports Server (NTRS)

    Harvey, Gale A.

    1989-01-01

    The Halogen Occultation Experiment (HALOE) is a solar occultation experiment that will fly on the Upper Atmosphere Research Satellite to measure mixing ratio profiles of O3, H2O, NO2, NO, CH4, HCl, and HF. The inversion of the HALOE data will be critically dependent on a detailed knowledge of eight optical filters. A filter characterization program was undertaken to measure in-band transmissions, out-of-band transmissions, in-band transmission shifts with temperature, reflectivities, and age stability. Fourier Transform Infrared Spectrometers were used to perform measurements over the spectral interval 400/cm to 6300/cm (25 micrometers to 1.6 micrometers). Very high precision (0.1 percent T) in-band measurements and very high resolution (0.0001 percent T) out-of-band measurements have been made. The measurements revealed several conventional leaks at 0.01 percent transmission and greatly enhanced (1,000) leaks to the 2-element filters when placed in a Fabry-Perot cavity. Filter throughput changes by 5 percent for a 25 C change in filter temperature.

  11. Method And Apparatus For Regenerating Nox Adsorbers

    DOEpatents

    Driscoll, J. Joshua; Endicott, Dennis L.; Faulkner, Stephen A.; Verkiel, Maarten

    2006-03-28

    Methods and apparatuses for regenerating a NOx adsorber coupled with an exhaust of an engine. An actuator drives a throttle valve to a first position when regeneration of the NOx adsorber is desired. The first position is a position that causes the regeneration of the NOx adsorber. An actuator drives the throttle valve to a second position while regeneration of the NOx adsorber is still desired. The second position being a position that is more open than the first position and operable to regenerate a NOx adsorber.

  12. Methionine as a potential precursor for halogenated compounds by the reaction with iron minerals

    NASA Astrophysics Data System (ADS)

    Tubbesing, C.; Krause, T.; Mulder, I.; Kotte, K.; Schöler, H. F.

    2012-04-01

    Volatile halogenated compounds (VOX) play an important role in different photochemical reactions within the troposphere and the stratosphere. Soils and sediments seem to act as a major natural source for VOX, but investigations of the reaction mechanisms are rather scarce. To get further information on potential intermediates the reaction of the amino acid methionine with the ferrous and ferric iron minerals pyrite and ferrihydrite as well as solute ferrous sulfate was studied using a gas chromatography-flame ionization detector (GC-FID). Methionine is an important amino acid in the biosynthesis of plants used as a starting compound for the messenger ethene with aminocyclopropane carboxylic acid as an intermediate product. This pathway may also occur under abiotic conditions. Ethene is assumed as precursor for various halogenated C2-compounds like vinyl chloride and dichloroethene. Due to its ubiquity by an average concentration of 10 to 290 ng/g soil and its potential to regenerate in soils and organic litter by microorganisms, methionine may be an important educt for both abiotic and biotic terrestrial halogenation processes. In laboratory tests methionine was exposed to different iron species like pyrite, iron sulfate or ferrihydrite. The oxidant H2O2 was used to start the reaction. Production values of methyl chloride and other halogenated compounds are discussed in the context of methionine as their potential precursor and several Fe-minerals as soil-borne catalysers. Several possible intermediates for the production of VOX have been detected e.g. methane, ethene or propane. A formation of isobutylene is noteworthy for some cases. In addition to VOC the production of methyl chloride and dimethyl sulfide (DMS) was observed. Only the DMS bears upon a specific mineral. The samples containing pyrite reveal the highest concentrations. To get a better assessment of methionine, respectively VOC released from methionine as precursors for halogenated compounds

  13. Air stripper VOC treatment using specialized adsorbents

    SciTech Connect

    Craven, C.N.; Blystone, P.G.; Grant, A.

    1994-12-31

    Abatement of volatile organic compound (VOC) emissions is required by federal, state and local regulatory agencies. Sources of VOC emissions include air stripping processes at groundwater remediation and industrial wastewater operations. The Purus A2000 system is an innovative emission control system that utilizes specialized adsorbent resins, on-site regeneration and solvent recovery for abatement of VOCs. This paper describes two applications in which air stripper off-gas is treated by the Purus A2000 Adsorption System. The first is a groundwater remediation pump-and-treat operation in which the air stripper off-gas contains chlorinated solvents. At the second site, benzene and styrene emissions from an industrial wastewater air stripper operation were successfully treated. At both sites the recovered solvent was recycled. Capital and operating costs will be compared to other treatment methods.

  14. Halogenated Natural Products in Dolphins: Brain-Blubber Distribution and Comparison with Halogenated Flame Retardants.

    PubMed

    Barón, E; Hauler, C; Gallistl, C; Giménez, J; Gauffier, P; Castillo, J J; Fernández-Maldonado, C; de Stephanis, R; Vetter, W; Eljarrat, E; Barceló, D

    2015-08-01

    Halogenated natural products (MHC-1, TriBHD, TetraBHD, MeO-PBDEs, Q1, and related PMBPs) and halogenated flame retardants (PBDEs, HBB, Dec 602, Dec 603, and DP) in blubber and brain are reported from five Alboran Sea delphinids (Spain). Both HNPs and HFRs were detected in brain, implying that they are able to surpass the blood-brain barrier and reach the brain, which represents a new finding for some compounds, such as Q1 and PMBPs, MHC-1, TriBHD, TetraBHD, or Dec 603. Moreover, some compounds (TetraBHD, BDE-153, or HBB) presented higher levels in brain than in blubber. This study evidence the high concentrations of HNPs in the marine environment, especially in top predators. It shows the importance of further monitoring these natural compounds and evaluating their potential toxicity, when most studies focus on anthropogenic compounds only. While no bioaccumulation was found for ∑HNPs, ∑HFRs increased significantly with body size for both common and striped dolphins. Studies evaluating BBB permeation mechanisms of these compounds together with their potential neurotoxic effects in dolphins are recommended.

  15. Halogenated Natural Products in Dolphins: Brain-Blubber Distribution and Comparison with Halogenated Flame Retardants.

    PubMed

    Barón, E; Hauler, C; Gallistl, C; Giménez, J; Gauffier, P; Castillo, J J; Fernández-Maldonado, C; de Stephanis, R; Vetter, W; Eljarrat, E; Barceló, D

    2015-08-01

    Halogenated natural products (MHC-1, TriBHD, TetraBHD, MeO-PBDEs, Q1, and related PMBPs) and halogenated flame retardants (PBDEs, HBB, Dec 602, Dec 603, and DP) in blubber and brain are reported from five Alboran Sea delphinids (Spain). Both HNPs and HFRs were detected in brain, implying that they are able to surpass the blood-brain barrier and reach the brain, which represents a new finding for some compounds, such as Q1 and PMBPs, MHC-1, TriBHD, TetraBHD, or Dec 603. Moreover, some compounds (TetraBHD, BDE-153, or HBB) presented higher levels in brain than in blubber. This study evidence the high concentrations of HNPs in the marine environment, especially in top predators. It shows the importance of further monitoring these natural compounds and evaluating their potential toxicity, when most studies focus on anthropogenic compounds only. While no bioaccumulation was found for ∑HNPs, ∑HFRs increased significantly with body size for both common and striped dolphins. Studies evaluating BBB permeation mechanisms of these compounds together with their potential neurotoxic effects in dolphins are recommended. PMID:26148182

  16. Ultrasound-assisted construction of halogen-bonded nanosized cocrystals that exhibit thermosensitive luminescence.

    PubMed

    Yan, Dongpeng; Bučar, Dejan-Krešimir; Delori, Amit; Patel, Bhavnita; Lloyd, Gareth O; Jones, William; Duan, Xue

    2013-06-17

    Multi-component organic nanocrystals that are comprised of two or more supramolecular building blocks can be used to extend the design and assembly scope of solid molecular materials. Herein, we report the use of ultrasonication to prepare halogen-bonded stilbene-based nano-cocrystals that exhibit different photoemission properties, including one- and two-phonon emission and fluorescence lifetimes, relative to those of macrodimensional crystals. The structural transformation from nano-cocrystals into nanocrystals upon heating results in a luminescence red-shift from greenish blue to yellow. The temperature-dependent ratiometric luminescence may allow such nano-cocrystals to be used as fluorescent sensors and thermosensitive materials.

  17. Adsorbed polyelectrolyte coatings decrease Fe(0) nanoparticle reactivity with TCE in water: conceptual model and mechanisms.

    PubMed

    Phenrat, Tanapon; Liu, Yueqiang; Tilton, Robert D; Lowry, Gregory V

    2009-03-01

    The surfaces of reactive nanoscale zerovalent iron (NZVI) particles used for in situ groundwater remediation are modified with polymers or polyelectrolytes to enhance colloidal stability and mobility in the subsurface. However, surface modification decreases NZVI reactivity. Here, the TCE dechlorination rate and reaction products are measured as a function of adsorbed polyelectrolyte mass for three commercially available polyelectrolytes used for NZVI surface modification including poly(styrene sulfonate) (PSS), carboxymethyl cellulose (CMC), and polyaspartate (PAP). The adsorbed mass, extended layer thickness, and TCE-polyelectrolyte partition coefficient are measured and used to explain the effect of adsorbed polyelectrolyte on NZVI reactivity. For all modifiers, the dechlorination rate constant decreased nonlinearly with increasing surface excess, with a maximum of a 24-fold decrease in reactivity. The TCE dechlorination pathways were not affected. Consistent with Scheutjens-Fleer theory for homopolymer adsorption, the nonlinear relationship between the dechlorination rate and the surface excess of adsorbed polyelectrolyte suggests that adsorbed polyelectrolyte decreases reactivity primarily by blocking reactive surface sites at low surface excess where they adsorb relatively flat onto the NZVI surface, and by a combination of site blocking and decreasing the aqueous TCE concentration at the NZVI surface due to partitioning of TCE to adsorbed polyelectrolytes. This explanation is also consistent with the effect of adsorbed polyelectrolyte on acetylene formation. This conceptual model should apply to other medium and high molecular weight polymeric surface modifiers on nanoparticles, and potentially to adsorbed natural organic matter.

  18. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1979-February 14, 1980

    SciTech Connect

    Rack, E.P.

    1980-02-01

    The program consists of six interrelated areas: (1) Reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure, and liquid systems. Special attention was given to the reactivity of excited complex formation and structural effects of electrophilic iodine attack on various pi-bond systems. (2) The gas-to-condensed phase transition in halogen high energy chemistry. Current interest involves the study of caging effects of an ice lattice on recombination reactions involving neutron-irradiated frozen aqueous solutions of halogenated organic and biochemical solutes in order to learn more about kinetic energy effects, halogen size, solute molecule size, steric effects and hydrogen bonding within an ice lattice cage. (3) Systematics of halogen hot atom reactions. The reactions of /sup 80m/Br, /sup 80/Br, /sup 82m/Br + /sup 82/Br, /sup 82/Br, /sup 82/Br, /sup 128/I, /sup 130/I, and /sup 130m/I + /sup 130/I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators are currently being studied. (4) Mathematical and computer simulation studies of caging events within an ice lattice are being investigated. (5) At Brookhaven National Laboratory, cyclotron-produced chlorine and fluorine hot atoms substitution reactions with molecules possessing a single chiral center are under investigation to determine the role of hot atom kinetic energy, halogen atom, enantioner structure, steric effects and phase on the extent of substitution by retention of configuration or by Walden inversion. (6) The applications of high energy techniques and concepts to neutron activation analysis for trace element determinations in biological systems was continued.

  19. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1980-February 14, 1981

    SciTech Connect

    Not Available

    1981-02-01

    The stereochemistry of high energy /sup 18/F, /sup 34m/Cl, and /sup 76/Br substitution reactions involving enantiomeric molecules in the gas and condensed phase is studied. The gas to condensed state transition in halogen high energy chemistry, involving chlorine, bromine, and iodine activated by the (n,..gamma..) and (I.T.) processes in halomethanes, saturated and unsaturated hydrocarbons is being investigated in more detail. Special attention is given to defining the nature of the enhancement yields in the condensed phase. High energy halogen reactions in liquid and frozen aqueous solutions of organic and biomolecular solutes are studied in an attempt to learn more about these reactions. The applications of high energy chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Special attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as indicators of solute-solute interactions in liquid and frozen aqueous solutions of halogenated bases and nucleosides are being developed. Experiments are designed to explain the mechanisms of the radioprotection offered biomolecular solutes trapped within the frozen ice lattice. Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular solutes in liquid and frozen aqueous solutions are studied. The high energy reactions of iodine with the isomers of pentene have been studied in low pressure gaseous systems employing additives and rare gas moderators and liquid systems. Reactivity of excited complex formation and structural effects of electrophilic iodine attack on the pi-bond systems are studied.

  20. Gold nanoparticle-aluminum oxide adsorbent for efficient removal of mercury species from natural waters.

    PubMed

    Lo, Sut-I; Chen, Po-Cheng; Huang, Chih-Ching; Chang, Huan-Tsung

    2012-03-01

    We report a new adsorbent for removal of mercury species. By mixing Au nanoparticles (NPs) 13 nm in diameter with aluminum oxide (Al(2)O(3)) particles 50-200 μm in diameter, Au NP-Al(2)O(3) adsorbents are easily prepared. Three adsorbents, Al(2)O(3), Au NPs, and Au NP-Al(2)O(3), were tested for removal of mercury species [Hg(2+), methylmercury (MeHg(+)), ethylmercury (EtHg(+)), and phenylmercury (PhHg(+))]. The Au NP adsorbent has a higher binding affinity (dissociation constant; K(d) = 0.3 nM) for Hg(2+) ions than the Al(2)O(3) adsorbent (K(d) = 52.9 nM). The Au NP-Al(2)O(3) adsorbent has a higher affinity for mercury species and other tested metal ions than the Al(2)O(3) and Au NP adsorbents. The Au NP-Al(2)O(3) adsorbent provides a synergic effect and, thus, is effective for removal of most tested metal ions and organic mercury species. After preconcentration of mercury ions by an Au NP-Al(2)O(3) adsorbent, analysis of mercury ions down to the subppq level in aqueous solution was performed by inductively coupled plasma mass spectrometry (ICP-MS). The Au NP-Al(2)O(3) adsorbent allows effective removal of mercury species spiked in lake water, groundwater, and seawater with efficiencies greater than 97%. We also used Al(2)O(3) and Au NP-Al(2)O(3) adsorbents sequentially for selectively removing Hg(2+) and MeHg(+) ions from water. The low-cost, effective, and stable Au NP-Al(2)O(3) adsorbent shows great potential for economical removal of various mercury species.

  1. Comparative study of halogen- and hydrogen-bond interactions between benzene derivatives and dimethyl sulfoxide.

    PubMed

    Zheng, Yan-Zhen; Deng, Geng; Zhou, Yu; Sun, Hai-Yuan; Yu, Zhi-Wu

    2015-08-24

    The halogen bond, similar to the hydrogen bond, is an important noncovalent interaction and plays important roles in diverse chemistry-related fields. Herein, bromine- and iodine-based halogen-bonding interactions between two benzene derivatives (C6 F5 Br and C6 F5 I) and dimethyl sulfoxide (DMSO) are investigated by using IR and NMR spectroscopy and ab initio calculations. The results are compared with those of interactions between C6 F5 Cl/C6 F5 H and DMSO. First, the interaction energy of the hydrogen bond is stronger than those of bromine- and chlorine-based halogen bonds, but weaker than iodine-based halogen bond. Second, attractive energies depend on 1/r(n) , in which n is between three and four for both hydrogen and halogen bonds, whereas all repulsive energies are found to depend on 1/r(8.5) . Third, the directionality of halogen bonds is greater than that of the hydrogen bond. The bromine- and iodine-based halogen bonds are strict in this regard and the chlorine-based halogen bond only slightly deviates from 180°. The directional order is iodine-based halogen bond>bromine-based halogen bond>chlorine-based halogen bond>hydrogen bond. Fourth, upon the formation of hydrogen and halogen bonds, charge transfers from DMSO to the hydrogen- and halogen-bond donors. The CH3 group contributes positively to stabilization of the complexes.

  2. Multiphase halogen chemistry in the tropical Atlantic Ocean.

    PubMed

    Sommariva, Roberto; von Glasow, Roland

    2012-10-01

    We used a one-dimensional model to simulate the chemical evolution of air masses in the tropical Atlantic Ocean, with a focus on halogen chemistry. The model results were compared to the observations of inorganic halogen species made in this region. The model could largely reproduce the measurements of most chlorine species, especially under unpolluted conditions, but overestimated sea salt chloride, BrCl, and bromine species. Agreement with the measurements could be improved by taking into account the reactivity with aldehydes and the effects of dimethyl sulfide (DMS) and Saharan dust on aerosol pH; a hypothetical HOX → X(-) aqueous-phase reaction could also improve the agreement with measured Cl(2) and HOCl, especially under semipolluted conditions. The results also showed that halogens speciation and concentrations are very sensitive to cloud processing. The model was used to calculate the impact of the observed levels of halogens: Cl atoms accounted for 5.4-11.6% of total methane sinks and halogens (mostly bromine and iodine) accounted for 35-40% of total ozone destruction.

  3. A polarizable ellipsoidal force field for halogen bonds.

    PubMed

    Du, Likai; Gao, Jun; Bi, Fuzhen; Wang, Lili; Liu, Chengbu

    2013-09-01

    The anisotropic effects and short-range quantum effects are essential characters in the formation of halogen bonds. Since there are an array of applications of halogen bonds and much difficulty in modeling them in classical force fields, the current research reports solely the polarizable ellipsoidal force field (PEff) for halogen bonds. The anisotropic charge distribution was represented with the combination of a negative charged sphere and a positively charged ellipsoid. The polarization energy was incorporated by the induced dipole model. The resulting force field is "physically motivated," which includes separate, explicit terms to account for the electrostatic, repulsion/dispersion, and polarization interaction. Furthermore, it is largely compatible with existing, standard simulation packages. The fitted parameters are transferable and compatible with the general AMBER force field. This PEff model could correctly reproduces the potential energy surface of halogen bonds at MP2 level. Finally, the prediction of the halogen bond properties of human Cathepsin L (hcatL) has been found to be in excellent qualitative agreement with the cocrystal structures.

  4. Shallow halogen vacancies in halide optoelectronic materials

    NASA Astrophysics Data System (ADS)

    Shi, Hongliang; Du, Mao-Hua

    2014-11-01

    Halogen vacancies (VH ) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., C H3N H3Pb I3 and TlBr. Both C H3N H3Pb I3 and TlBr have been found to have shallow VH , in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., C H3N H3Pb I3 , C H3N H3Sn I3 (photovoltaic materials), TlBr, and CsPbB r3 (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VH is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of n s2 ions both play important roles in creating shallow VH in halides such as C H3N H3Pb I3 , C H3N H3Sn I3 , and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH , such as those with large cation-cation distances and low anion coordination numbers and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH . The results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.

  5. Shallow halogen vacancies in halide optoelectronic materials

    DOE PAGES

    Shi, Hongliang; Du, Mao -Hua

    2014-11-05

    Halogen vacancies (VH) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH3NH3PbI3 and TlBr. Both CH3NH3PbI3 and TlBr have been found to have shallow VH, in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., CH3NH3PbI3, CH3NH3SnI3 (photovoltaic materials), TlBr, and CsPbBr3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VHmore » is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns2 ions both play important roles in creating shallow VH in halides such as CH3NH3PbI3, CH3NH3SnI3, and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH, such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.« less

  6. Adsorbent selection for endosulfan removal from water environment.

    PubMed

    Sudhakar, Y; Dikshit, A K

    1999-01-01

    In the present study, an attempt was made to select a low cost adsorbing material for the removal of endosulfan [C,C'-(1,4,5,6,7,7-hexachloro-8,9,10- trinorborn-5-en-2,3-ylene)(dimethylsulphite)] from water. Various low cost adsorbents like wood charcoal, kimberlite tailings, silica, macro fungi sojar caju were tried with activated charcoal as reference material. The above materials were selected from various sources encompassing organic, inorganic, clayey, and biological sources. For the selection of suitable adsorbent for endosulfan uptake, maximum adsorption capacity (Qmax) was chosen as the parameter. Kinetic profiles of removal were generated for all the materials to assess the equilibrium time. Equilibrium studies were carried out for all materials to assess the adsorption equilibrium model that they followed. The model that gave the best correlation coefficient by linear regression analysis, was adopted for the calculation of Qmax of the corresponding adsorbent material. Using linearised forms of equilibrium models like Langmuir, BET, and Freundlich, maximum adsorptive capacities were determined. Activated charcoal showed the best adsorptive capacity with Qmax of 2.145 mg/g followed by wood charcoal 1.773 mg/g, sojar caju 1.575 mg/g, kimberlite tailings 0.8821 mg/g, and silica 0.3231 mg/g. Albeit activated charcoal gave better performance, it was not considered as a candidate material because of its high cost. Wood charcoal was the next best adsorbent with Qmax 1.773 mg/g. Therefore, wood charcoal was chosen as the best material for endosulfan removal. The study of physical and chemical characteristics of wood charcoal revealed that it is a potential adsorbent and can even be improved further.

  7. Adsorbent selection for endosulfan removal from water environment.

    PubMed

    Sudhakar, Y; Dikshit, A K

    1999-01-01

    In the present study, an attempt was made to select a low cost adsorbing material for the removal of endosulfan [C,C'-(1,4,5,6,7,7-hexachloro-8,9,10- trinorborn-5-en-2,3-ylene)(dimethylsulphite)] from water. Various low cost adsorbents like wood charcoal, kimberlite tailings, silica, macro fungi sojar caju were tried with activated charcoal as reference material. The above materials were selected from various sources encompassing organic, inorganic, clayey, and biological sources. For the selection of suitable adsorbent for endosulfan uptake, maximum adsorption capacity (Qmax) was chosen as the parameter. Kinetic profiles of removal were generated for all the materials to assess the equilibrium time. Equilibrium studies were carried out for all materials to assess the adsorption equilibrium model that they followed. The model that gave the best correlation coefficient by linear regression analysis, was adopted for the calculation of Qmax of the corresponding adsorbent material. Using linearised forms of equilibrium models like Langmuir, BET, and Freundlich, maximum adsorptive capacities were determined. Activated charcoal showed the best adsorptive capacity with Qmax of 2.145 mg/g followed by wood charcoal 1.773 mg/g, sojar caju 1.575 mg/g, kimberlite tailings 0.8821 mg/g, and silica 0.3231 mg/g. Albeit activated charcoal gave better performance, it was not considered as a candidate material because of its high cost. Wood charcoal was the next best adsorbent with Qmax 1.773 mg/g. Therefore, wood charcoal was chosen as the best material for endosulfan removal. The study of physical and chemical characteristics of wood charcoal revealed that it is a potential adsorbent and can even be improved further. PMID:10048207

  8. Effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds using a modified QSAR model.

    PubMed

    Lim, Seung Joo; Fox, Peter

    2014-02-01

    The effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds were investigated using a modified half life equation. The potential future pharmaceutical compounds investigated were approximately 2000 pharmaceutical drugs currently undergoing the United States Food and Drug Administration (US FDA) testing. EPI Suite (BIOWIN) model estimates the fates of compounds based on the biodegradability under aerobic conditions. While BIOWIN considered the biodegradability of a compound only, the half life equation used in this study was modified by biodegradability, sorption and cometabolic oxidation. It was possible that the potential future pharmaceutical compounds were more accurately estimated using the modified half life equation. The modified half life equation considered sorption and cometabolic oxidation of halogenated aromatic/aliphatics and nitrogen(N)-heterocyclic aromatics in the sub-surface, while EPI Suite (BIOWIN) did not. Halogenated aliphatics in chemicals were more persistent than halogenated aromatics in the sub-surface. In addition, in the sub-surface environment, the fates of organic chemicals were much more affected by halogenation in chemicals than by nitrogen(N)-heterocyclic aromatics.

  9. DESTRUCTION OF HALOGENATED HYDROCARBONS WITH SOLVATED ELECTRONS IN THE PRESENCE OF WATER. (R826180)

    EPA Science Inventory

    Model halogenated aromatic and aliphatic hydrocarbons and halogenated phenols were dehalogenated in seconds by solvated electrons generated from sodium in both anhydrous liquid ammonia and ammonia/water solutions. The minimum sodium required to completely dehalogenate these mo...

  10. Fine tuning of graphene properties by modification with aryl halogens.

    PubMed

    Bouša, D; Pumera, M; Sedmidubský, D; Šturala, J; Luxa, J; Mazánek, V; Sofer, Z

    2016-01-21

    Graphene and its derivatives belong to one of the most intensively studied materials. The radical reaction using halogen derivatives of arene-diazonium salts can be used for effective control of graphene's electronic properties. In our work we investigated the influence of halogen atoms (fluorine, chlorine, bromine and iodine) as well as their position on the benzene ring towards the electronic and electrochemical properties of modified graphenes. The electronegativity as well as the position of the halogen atoms on the benzene ring has crucial influence on graphene's properties due to the inductive and mesomeric effects. The results of resistivity measurement are in good agreement with the theoretical calculations of electron density within chemically modified graphene sheets. Such simple chemical modifications of graphene can be used for controllable and scalable synthesis of graphene with tunable transport properties.

  11. Loss of halogens from crystallized and glassy silicic volcanic rocks

    USGS Publications Warehouse

    Noble, D.C.; Smith, V.C.; Peck, L.C.

    1967-01-01

    One hundred and sixty-four F and Cl analyses of silicic welded tuffs and lavas and glass separates are presented. Comparison of the F and Cl contents of crystallized rocks with those of nonhydrated glass and hydrated glassy rocks from the same rock units shows that most of the halogens originally present were lost on crystallization. An average of about half of the F and four-fifths of the Cl originally present was lost. Analyses of hydrated natural glasses and of glassy rocks indicate that in some cases significant amounts of halogens may be removed from or added to hydrated glass through prolonged contact with ground water. The data show that the original halogen contents of the groundmass of a silicic volcanic rock can be reliably determined only from nonhydrated glass. ?? 1967.

  12. Halogenated graphenes: rapidly growing family of graphene derivatives.

    PubMed

    Karlický, František; Kumara Ramanatha Datta, Kasibhatta; Otyepka, Michal; Zbořil, Radek

    2013-08-27

    Graphene derivatives containing covalently bound halogens (graphene halides) represent promising two-dimensional systems having interesting physical and chemical properties. The attachment of halogen atoms to sp(2) carbons changes the hybridization state to sp(3), which has a principal impact on electronic properties and local structure of the material. The fully fluorinated graphene derivative, fluorographene (graphene fluoride, C1F1), is the thinnest insulator and the only stable stoichiometric graphene halide (C1X1). In this review, we discuss structural properties, syntheses, chemistry, stabilities, and electronic properties of fluorographene and other partially fluorinated, chlorinated, and brominated graphenes. Remarkable optical, mechanical, vibrational, thermodynamic, and conductivity properties of graphene halides are also explored as well as the properties of rare structures including multilayered fluorinated graphenes, iodine-doped graphene, and mixed graphene halides. Finally, patterned halogenation is presented as an interesting approach for generating materials with applications in the field of graphene-based electronic devices.

  13. Distribution of halogens during fluid-mediated apatite replacement

    NASA Astrophysics Data System (ADS)

    Kusebauch, Christof; John, Timm; Whitehouse, Martin J.

    2016-04-01

    Apatite (Ca5(PO4)3(F,Cl,OH)) is one the most abundant halogen containing minerals in the crust. It is present in many different rock types and stable up to P-T conditions of the mantle. Although probably not relevant for the halogen budget of the mantle, apatite is potentially a carrier phase of halogens into the mantle via subduction processes and therefore important for the global halogen cycle. Different partitioning behavior of the halogens between apatite and melt/fluids causes fractionation of these elements. In hydrothermal environments apatite reacts via a coupled dissolution-reprecipitation process that leads to apatite halogen compositions which are in (local) equilibrium with the hydrothermal fluid. This behavior enables apatite to be used as fluid probe and as a tool for tracking fluid evolution during fluid-rock interaction. Here, we present a combined experimental and field related study focused on replacement of apatite under hydrothermal conditions, to investigate the partitioning of halogens between apatite and fluids. Experiments were conducted in a cold seal pressure apparatus at 0.2 GPa and temperatures ranging from 400-700°C using halogen bearing solutions of different composition (KOH, NaF, NaCl, NaBr, NaI) to promote the replacement of Cl-apatite. The halogen composition of reacted apatite was analyzed by electron microprobe (EMPA) and secondary ion mass spectrometry (SIMS). The data was used to calculate partition coefficients of halogens between fluid and apatite. Our new partitioning data show that fluorine is the most compatible halogen followed by chlorine, bromine and iodine. Comparison between partition coefficients of the apatite-fluid system and coefficients derived in the apatite-melt system reveals values for F that are one to two orders of magnitude higher. In contrast, Cl and Br show a similar partition behavior in fluid and melt systems. Consequently, apatite that formed by fluid-rock interaction will fractionate F from Cl more

  14. GC-MS Study of Mono- and Bishaloethylphosphonates Related to Schedule 2.B.04 of the Chemical Weapons Convention: The Discovery of a New Intramolecular Halogen Transfer.

    PubMed

    Picazas-Márquez, Nerea; Sierra, María; Nova, Clara; Moreno, Juan Manuel; Aboitiz, Nuria; de Rivas, Gema; Sierra, Miguel A; Martínez-Álvarez, Roberto; Gómez-Caballero, Esther

    2016-09-01

    A new class of compounds, mono- and bis-haloethylphosphonates (HAPs and bisHAPs, respectively), listed in Schedule 2.B.04 of the Chemical Weapons Convention (CWC), has been synthesized and studied by GC-MS with two aims. First, to improve the identification of this type of chemicals by the Organization for the Prohibition of Chemical Weapons, (OPCW). Second, to study the synergistic effect of halogen and silicon atoms in molecules undergoing mass spectrometry. Fragmentation patterns of trimethylsilyl derivatives of HAPs were found to depend on the nature of the halogen atom; this was in agreement with DFT-calculations. The data suggest that a novel intramolecular halogen transfer takes place during the fragmentation process. Graphical Abstract ᅟ. PMID:27300717

  15. GC-MS Study of Mono- and Bishaloethylphosphonates Related to Schedule 2.B.04 of the Chemical Weapons Convention: The Discovery of a New Intramolecular Halogen Transfer.

    PubMed

    Picazas-Márquez, Nerea; Sierra, María; Nova, Clara; Moreno, Juan Manuel; Aboitiz, Nuria; de Rivas, Gema; Sierra, Miguel A; Martínez-Álvarez, Roberto; Gómez-Caballero, Esther

    2016-09-01

    A new class of compounds, mono- and bis-haloethylphosphonates (HAPs and bisHAPs, respectively), listed in Schedule 2.B.04 of the Chemical Weapons Convention (CWC), has been synthesized and studied by GC-MS with two aims. First, to improve the identification of this type of chemicals by the Organization for the Prohibition of Chemical Weapons, (OPCW). Second, to study the synergistic effect of halogen and silicon atoms in molecules undergoing mass spectrometry. Fragmentation patterns of trimethylsilyl derivatives of HAPs were found to depend on the nature of the halogen atom; this was in agreement with DFT-calculations. The data suggest that a novel intramolecular halogen transfer takes place during the fragmentation process. Graphical Abstract ᅟ.

  16. GC-MS Study of Mono- and Bishaloethylphosphonates Related to Schedule 2.B.04 of the Chemical Weapons Convention: The Discovery of a New Intramolecular Halogen Transfer

    NASA Astrophysics Data System (ADS)

    Picazas-Márquez, Nerea; Sierra, María; Nova, Clara; Moreno, Juan Manuel; Aboitiz, Nuria; de Rivas, Gema; Sierra, Miguel A.; Martínez-Álvarez, Roberto; Gómez-Caballero, Esther

    2016-09-01

    A new class of compounds, mono- and bis-haloethylphosphonates (HAPs and bisHAPs, respectively), listed in Schedule 2.B.04 of the Chemical Weapons Convention (CWC), has been synthesized and studied by GC-MS with two aims. First, to improve the identification of this type of chemicals by the Organization for the Prohibition of Chemical Weapons, (OPCW). Second, to study the synergistic effect of halogen and silicon atoms in molecules undergoing mass spectrometry. Fragmentation patterns of trimethylsilyl derivatives of HAPs were found to depend on the nature of the halogen atom; this was in agreement with DFT-calculations. The data suggest that a novel intramolecular halogen transfer takes place during the fragmentation process.

  17. Oceanic contributions from tropical upwelling systems to atmospheric halogens

    NASA Astrophysics Data System (ADS)

    Ziska, Franziska; Hepach, Helmke; Stemmler, Irene; Quack, Birgit; Atlas, Elliot; Fuhlbrügge, Steffen; Bracher, Astrid; Tegtmeier, Susann; Krüger, Kirstin

    2014-05-01

    Short lived halogenated substances (halocarbons) from the oceans contribute to atmospheric halogens, where they are involved in ozone depletion and aerosol formation. Oceanic regions that are characterized by high biological activity are often associated with increased halocarbon abundance of e.g. bromoform (CHBr3) and dibromomethane (CH2Br2), representing the main contributors to atmospheric organic bromine. Apart from biological production, photochemical pathways play an important role in the formation of methyl iodide (CH3I), the most abundant organoiodine in the marine atmosphere. Recently, the contribution of biogenic diiodomethane (CH2I2) and chloroiodomethane (CH2ClI) to atmospheric organic iodine has been estimated to be similarly significant as CH3I. In the tropics, rapid uplift of surface air can transport these short-lived compounds into the upper troposphere and into the stratosphere. Oceanic upwelling systems off Mauritania, Peru and in the equatorial Atlantic might therefore potentially contribute large amounts of halocarbons to the stratosphere. Concentrations and emissions of iodo- and bromocarbons from several SOPRAN campaigns in different tropical upwelling systems, the Mauritanian and the equatorial upwelling in the Atlantic, as well as the Peruvian upwelling in the Pacific, will be presented. Processes contributing to halocarbon occurrence in the water column, as well as biological and physical factors influencing their emission into the atmosphere are investigated (Fuhlbrügge, et al. 2013; Hepach et al., 2013). We will present the relative contribution of the upwelling systems to global air-sea fluxes from different modelling studies. The data based bottom-up emissions from Ziska et al. (2013) will be compared to model simulated halocarbons. The model is a global three-dimensional ocean general circulation model with an ecosystem model and halocarbon module embedded (MPIOM/HAMOCC). It resolves CH3I and CHBr3 production, degradation, and

  18. The role of halogen species in the troposphere.

    PubMed

    Platt, U; Hönninger, G

    2003-07-01

    While the role of reactive halogen species (e.g. Cl, Br) in the destruction of the stratospheric ozone layer is well known, their role in the troposphere was investigated only since their destructive effect on boundary layer ozone after polar sunrise became obvious. During these 'Polar Tropospheric Ozone Hole' events O(3) is completely destroyed in the lowest approximately 1000 m of the atmosphere on areas of several million square kilometres. Up to now it was assumed that these events were confined to the polar regions during springtime. However, during the last few years significant amounts of BrO and Cl-atoms were also found outside the Arctic and Antarctic boundary layer. Recently even higher BrO mixing ratios (up to 176 ppt) were detected by optical absorption spectroscopy (DOAS) in the Dead Sea basin during summer. In addition, evidence is accumulating that BrO (at levels around 1-2 ppt) is also occurring in the free troposphere at all latitudes. In contrast to the stratosphere, where halogens are released from species, which are very long lived in the troposphere, likely sources of boundary layer Br and Cl are autocatalytic oxidation of sea salt halides (the 'Bromine Explosion'), while precursors of free tropospheric BrO and coastal IO probably are short-lived organo-halogen species. At the levels suggested by the available measurements reactive halogen species have a profound effect on tropospheric chemistry: In the polar boundary layer during 'halogen events' ozone is usually completely lost within hours or days. In the free troposphere the effective O(3)-losses due to halogens could be comparable to the known photochemical O(3) destruction. Further interesting consequences include the increase of OH levels and (at low NO(X)) the decrease of the HO(2)/OH ratio in the free troposphere. PMID:12738256

  19. Substituent Effects on the [N–I–N]+ Halogen Bond

    PubMed Central

    2016-01-01

    We have investigated the influence of electron density on the three-center [N–I–N]+ halogen bond. A series of [bis(pyridine)iodine]+ and [1,2-bis((pyridine-2-ylethynyl)benzene)iodine]+ BF4– complexes substituted with electron withdrawing and donating functionalities in the para-position of their pyridine nitrogen were synthesized and studied by spectroscopic and computational methods. The systematic change of electron density of the pyridine nitrogens upon alteration of the para-substituent (NO2, CF3, H, F, Me, OMe, NMe2) was confirmed by 15N NMR and by computation of the natural atomic population and the π electron population of the nitrogen atoms. Formation of the [N–I–N]+ halogen bond resulted in >100 ppm 15N NMR coordination shifts. Substituent effects on the 15N NMR chemical shift are governed by the π population rather than the total electron population at the nitrogens. Isotopic perturbation of equilibrium NMR studies along with computation on the DFT level indicate that all studied systems possess static, symmetric [N–I–N]+ halogen bonds, independent of their electron density. This was further confirmed by single crystal X-ray diffraction data of 4-substituted [bis(pyridine)iodine]+ complexes. An increased electron density of the halogen bond acceptor stabilizes the [N···I···N]+ bond, whereas electron deficiency reduces the stability of the complexes, as demonstrated by UV-kinetics and computation. In contrast, the N–I bond length is virtually unaffected by changes of the electron density. The understanding of electronic effects on the [N–X–N]+ halogen bond is expected to provide a useful handle for the modulation of the reactivity of [bis(pyridine)halogen]+-type synthetic reagents. PMID:27265247

  20. The role of halogen species in the troposphere.

    PubMed

    Platt, U; Hönninger, G

    2003-07-01

    While the role of reactive halogen species (e.g. Cl, Br) in the destruction of the stratospheric ozone layer is well known, their role in the troposphere was investigated only since their destructive effect on boundary layer ozone after polar sunrise became obvious. During these 'Polar Tropospheric Ozone Hole' events O(3) is completely destroyed in the lowest approximately 1000 m of the atmosphere on areas of several million square kilometres. Up to now it was assumed that these events were confined to the polar regions during springtime. However, during the last few years significant amounts of BrO and Cl-atoms were also found outside the Arctic and Antarctic boundary layer. Recently even higher BrO mixing ratios (up to 176 ppt) were detected by optical absorption spectroscopy (DOAS) in the Dead Sea basin during summer. In addition, evidence is accumulating that BrO (at levels around 1-2 ppt) is also occurring in the free troposphere at all latitudes. In contrast to the stratosphere, where halogens are released from species, which are very long lived in the troposphere, likely sources of boundary layer Br and Cl are autocatalytic oxidation of sea salt halides (the 'Bromine Explosion'), while precursors of free tropospheric BrO and coastal IO probably are short-lived organo-halogen species. At the levels suggested by the available measurements reactive halogen species have a profound effect on tropospheric chemistry: In the polar boundary layer during 'halogen events' ozone is usually completely lost within hours or days. In the free troposphere the effective O(3)-losses due to halogens could be comparable to the known photochemical O(3) destruction. Further interesting consequences include the increase of OH levels and (at low NO(X)) the decrease of the HO(2)/OH ratio in the free troposphere.