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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. Development of an element-selective monitoring system for adsorbable organic halogens (AOX) with plasma emission spectrometric detection for quasi-continuous waste-water analysis.

    PubMed

    Twiehaus, T; Evers, S; Buscher, W; Cammann, K

    2001-11-01

    An automated quasi-continuously-operating monitor has been developed for element-selective analysis of adsorbable organic halogens (AOX) in water. After extensive optimization the automatic method was applied to the analysis of standard solutions and real waste water samples to prove its analytical applicability. The new instrument is based on the element-selective analysis of halogens by means of a spectroscopic detection system consisting of a microwave-induced helium plasma excitation source (TM010-type; developed in this laboratory) and the plasma emission detector (PED) which operates with oscillating narrow-band interference filters. After enriching the organic components on activated charcoal and pyrolysis in an oxygen stream at 950 degrees C, in accordance with DIN/EN 38409,H14/1485, interfering CO2 and H2O gas generated during combustion is removed from the analytes in the so-called ELSA-system (element-selective AOX-analyzer). For focused injection into the plasma excitation source the analytes (hydrogen halides) are trapped in a deactivated fused silica capillary at -180 degrees C; this is followed by identification and quantification on the basis of element-specific emission of radiation in the VIS and NIR-region (chlorine 837.6 nm, fluorine 685.6 nm). Bromine and iodine could not be detected with satisfactory inter-element selectivity, because of spectral interferences caused by matrix elements, and so results from the respective single-element investigations for determination of AOBr and AOI are not presented. The procedure has been validated and the analytical performance has been examined by calibration with p-chlorophenol and p-fluorophenol. The limit of detection was 1.1 microg (absolute) for chlorine and 6.6 microg (absolute) for fluorine.

  4. Halogen Bonding in Organic Synthesis and Organocatalysis.

    PubMed

    Bulfield, David; Huber, Stefan M

    2016-10-04

    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. 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.

  6. Halogen bonds in organic synthesis and organocatalysis.

    PubMed

    Schindler, S; Huber, Stefan M

    2015-01-01

    In contrast to hydrogen bonding, halogen bonding has so far found very little use in organic synthesis and organocatalysis. Although there are multiple reports on the use of elemental iodine in a wide range of organic reactions, the understanding of the actual mode of activation in these cases is very rudimentary. Recently, first proof-of-principle reactions have been established towards the use of carbon-based halogen-bond donors as activators or organocatalysts. These halogen-based Lewis acids offer more structural variety and potential than elemental iodine itself, and the mode of activation is better understood. Yet, the reported cases still only cover simple benchmark reactions, and there is a clear need for further and more complex applications.

  7. 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

  8. 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

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

    PubMed

    Santschi, Ch; Rossi, M J

    2005-07-07

    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.

  10. 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.

  11. 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.

  12. Completely automated system for determining halogenated organic compounds by multisyringe flow injection analysis.

    PubMed

    Maya, Fernando; Estela, José Manuel; Cerdà, Víctor

    2008-08-01

    A new, multisyringe flow injection setup was designed to develop the first completely automated flow methodology for the expeditious, accurate in-line determination of halogenated organic compounds (HOCs) in water. The target compounds are preconcentrated and isolated by solid-phase extraction. Following elution, previously organically bound halogens are released as free hydrogen halides by the combined action of UV light and a chemical oxidant for their subsequent spectrophotometric determination by reaction with Hg(SCN) 2 and Fe(3+). Optimizing the major hydrodynamic and chemical variables resulted in improved performance. Recovery of various HOCs was assessed, and potential interferents were examined. Under the selected operating conditions, the proposed method exhibits variable analytical performance depending on the particular sample volume used (e.g., a sample volume of 5 mL provides a linear working range of 140-2000 microg L(-1), a LOD of 100 microg L(-1), and a throughput of 9 samples h(-1)). The method was successfully used to determine total adsorbable organic halogens (AOX) in well water and leachates, and the results validated against an AOX reference method. The role of the proposed system in the environmental analytical field is critically discussed.

  13. 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.

  14. 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.

  15. Halogenated organic species over the tropical rainforest

    NASA Astrophysics Data System (ADS)

    Gebhardt, S.; Colomb, A.; Hofmann, R.; Williams, J.; Lelieveld, J.

    2008-01-01

    Airborne measurements of the halogenated trace gases methyl chloride, methyl bromide and chloroform were conducted over the Atlantic Ocean and 1000 km of pristine tropical rainforest in Suriname and French Guyana (3-6° N, 51-59° W) in October 2005. In the boundary layer (0-1.4 km), maritime air masses initially low in forest hydrocarbons, advected over the forest by southeasterly trade winds, were measured at various distances from the coast. Since the organohalogens presented here have relatively long atmospheric lifetimes (0.4-1.0 years) in comparison to the transport times (1-2 days), emissions will accumulate in air traversing the rainforest. The distributions of methyl chloride, methyl bromide and chloroform were analyzed as a function of forest contact time and the respective relationship used to determine fluxes from the rainforest during the long dry season. Emission fluxes have been calculated for methyl chloride and chloroform as 9.4 (±4.0 2σ) and 0.34 (0.14± 2σ) μg m-2 h-1, respectively. No significant flux from the rainforest was observed for methyl bromide within the limits of these measurements. The flux of methyl chloride was in general agreement with the flux measured over the same region in March 1998 during the LBA Claire project using a different analytical system. This confirms that the rainforest is a strong source for methyl chloride and suggests that this emission is relatively uniform throughout the year. In contrast the chloroform flux derived here is a factor of three less than previous measurements made in March 1998 suggesting a pronounced ecosystem variation. The differences in chloroform fluxes could not be attributed to either temperature or rainfall changes. The global extrapolation of the derived fluxes led to 1.5 (±0.6 2σ) Tg yr-1 for methyl chloride, which is in the range of the missing source postulated by previous model studies and 55 (±22 2σ) Gg yr-1 for chloroform.

  16. 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

  17. 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.

  18. 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.

  19. Halogen Atom Ratios in the Springtime Arctic Troposphere as Determined From Measurements of Halogenated Volatile Organic Compounds

    NASA Astrophysics Data System (ADS)

    Keil, A.; Shepson, P. B.

    2005-12-01

    The concentrations of a suite of halogenated volatile organic compounds (HVOCs) were measured near Barrow, Alaska from January to April 2005. The HVOCs are produced from the reaction of ethene and propene with bromine and chlorine atoms, which are important atmospheric oxidants in the Arctic troposphere. Chlorine atom oxidation is responsible for significant decreases in non-methane hydrocarbons and bromine atoms are thought to be responsible for the catalytic destruction of tropospheric ozone and mercury. The HVOC concentrations are used to probe the sources of these halogen atoms and their relative ambient concentrations. We find evidence for local production of the halogen atom precursors, and determine [Br]/[Cl] to be between 20 and 300, somewhat lower than those determined by VOC decay methods.

  20. Reversible Capture and Release of Elemental Halogens with a Redox-Active Metal-Organic Framework.

    PubMed

    Tulchinsky, Yuri; Hendon, Christopher H; Lomachenko, Kirill A; Borfecchia, Elisa; Melot, Brent C; Hudson, Matthew R; Tarver, Jacob D; Korzynski, Maciej D; Stubbs, Amanda W; Kagan, Jacob J; Lamberti, Carlo; Brown, Craig M; Dinca, Mircea

    2017-03-28

    Extreme toxicity, corrosiveness, and volatility pose serious challenges for the safe storage and transportation of elemental chlorine and bromine, which play critical roles in the chemical industry. Solid materials capable of forming stable non-volatile compounds upon reaction with elemental halogens may partially mitigate these challenges by allowing safe halogen release on demand. Here, we demonstrate that elemental halogens quantitatively oxidize coordinatively unsaturated Co(II) ions in a robust azolate metal-organic framework (MOF) to produce an air-stable and safe-to-handle Co(III) material featuring terminal Co(III)-halogen bonds. Thermal treatment of the oxidized MOF causes homolytic cleavage of the Co(III)-halogen bonds, reduction to Co(II), and concomitant release of elemental halogens. Remarkably, the reversible chemical storage and thermal release of elemental halogens occur with no significant losses of structural integrity, the parent cobaltous MOF retaining crystallinity and porosity even after three oxidation/reduction cycles. These results highlight a material operating via redox mechanism that may find utility in the storage and capture of other noxious and corrosive gases.

  1. 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.

  2. Halogenated volatile organic compounds from the use of chlorine-bleach-containing household products.

    PubMed

    Odabasi, Mustafa

    2008-03-01

    Sodium hypochlorite (NaOCl) and many organic chemicals contained in household cleaning products may react to generate halogenated volatile organic compounds (VOCs). Halogenated VOC emissions from eight different chlorine bleach containing household products (pure and diluted) were investigated by headspace experiments. Chloroform and carbon tetrachloride were the leading compounds along with several halogenated compounds in the headspace of chlorine bleach products. One of the most surprising results was the presence of carbon tetrachloride (a probable human carcinogen and a powerful greenhouse gas that was banned for household use by the U.S. Food and Drug Administration) in very high concentrations (up to 101 mg m(-3)). By mixing surfactants or soap with NaOCl, it was shown that the formation of carbon tetrachloride and several other halogenated VOCs is possible. In addition to quantitatively determined halogenated VOCs (n = 15), several nitrogen-containing (n = 4), chlorinated (n = 10), oxygenated compounds (n = 22), and hydrocarbons (n = 14) were identified in the headspace of bleach products. Among these, 1,1-dichlorobutane and 2-chloro-2-nitropropane were the most abundant chlorinated VOCs, whereas trichloronitromethane and hexachloroethane were the most frequently detected ones. Indoor air halogenated VOC concentrations resulting from the use of four selected household products were also measured before, during, and 30 min after bathroom, kitchen, and floor cleaning applications. Chloroform (2.9-24.6 microg m(-3)) and carbon tetrachloride (0.25-459 microg m(-3)) concentrations significantly increased during the use of bleach containing products. During/ before concentration ratios ranged between 8 and 52 (25 +/- 14, average +/- SD) for chloroform and 1-1170 (146 +/- 367, average +/- SD) for carbon tetrachloride, respectively. These results indicated that the bleach use can be important in terms of inhalation exposure to carbon tetrachloride, chloroform and

  3. 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...

  4. 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...

  5. 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 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...

  6. 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...

  7. 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.

  8. 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.

  9. The destruction of halogenated organic chemicals by plasma pyrolysis.

    PubMed

    Barton, T G; Mordy, J A

    1984-08-01

    Very high destruction efficiencies for halogenated chemicals have been achieved by plasma pyrolysis. Destruction efficiencies exceeded 99.9999999% for tests with polychlorinated biphenyls (PCBs). Preliminary tests with tetrachloromethane have obtained destruction efficiencies exceeding 99.99%. The plasma pyrolysis process involved the creation of a 250-kW plasma with a temperature in excess of 25 000 degrees C. The toxic material was injected into the plasma zone at a rate between 1 and 2 L/min. Thermochemical and photochemical dissociation of the toxic materials produced atoms and ions which recombined to form primarily H2, CO, HCl, and particulate carbon. The HCl was neutralized by NaOH. The flaring of the H2 and CO should destroy to a high degree any trace residuals. The application of plasma pyrolysis for the ultimate disposal of toxicological waste was also investigated. Rat carcasses containing mean lethal dosage of PCB were pyrolyzed.

  10. 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.

  11. Chiral switching by spontaneous conformational change in adsorbed organic molecules.

    PubMed

    Weigelt, Sigrid; Busse, Carsten; Petersen, Lars; Rauls, Eva; Hammer, Bjørk; Gothelf, Kurt V; Besenbacher, Flemming; Linderoth, Trolle R

    2006-02-01

    Self-assembly of adsorbed organic molecules is a promising route towards functional surface nano-architectures, and our understanding of associated dynamic processes has been significantly advanced by several scanning tunnelling microscopy (STM) investigations. Intramolecular degrees of freedom are widely accepted to influence ordering of complex adsorbates, but although molecular conformation has been identified and even manipulated by STM, the detailed dynamics of spontaneous conformational change in adsorbed molecules has hitherto not been addressed. Molecular surface structures often show important stereochemical effects as, aside from truly chiral molecules, a large class of so-called prochiral molecules become chiral once confined on a surface with an associated loss of symmetry. Here, we investigate a model system in which adsorbed molecules surprisingly switch between enantiomeric forms as they undergo thermally induced conformational changes. The associated kinetic parameters are quantified from time-resolved STM data whereas mechanistic insight is obtained from theoretical modelling. The chiral switching is demonstrated to enable an efficient channel towards formation of extended homochiral surface domains. Our results imply that appropriate prochiral molecules may be induced (for example, by seeding) to assume only one enantiomeric form in surface assemblies, which is of relevance for chiral amplification and asymmetric heterogenous catalysis.

  12. Halogenated organic species over the tropical South American rainforest

    NASA Astrophysics Data System (ADS)

    Gebhardt, S.; Colomb, A.; Hofmann, R.; Williams, J.; Lelieveld, J.

    2008-06-01

    Airborne measurements of the halogenated trace gases methyl chloride, methyl bromide and chloroform were conducted over the Atlantic Ocean and about 1000 km of pristine tropical rainforest in Suriname and French Guyana (3 6° N, 51 59° W) in October 2005. In the boundary layer (0 1.4 km), maritime air masses, advected over the forest by southeasterly trade winds, were measured at various distances from the coast. Since the organohalogens presented here have relatively long atmospheric lifetimes (0.4 1.0 years) in comparison to the advection times from the coast (1 2 days), emissions will accumulate in air traversing the rainforest. The distributions of methyl chloride, methyl bromide and chloroform were analyzed as a function of time the air spent over land and the respective relationship used to determine net fluxes from the rainforest for one week within the long dry season. Net fluxes from the rainforest ecosystem have been calculated for methyl chloride and chloroform as 9.5 (±3.8 2σ) and 0.35 (±0.15 2σ)μg m-2 h-1, respectively. No significant flux was observed for methyl bromide within the limits of these measurements. The global budget of methyl chloride contains large uncertainties, in particular with regard to a possible source from tropical vegetation. Our measurements are used in a large-scale approach to determine the net flux from a tropical ecosystem to the planetary boundary layer. The obtained global net flux of 1.5 (±0.6 2σ) Tg yr-1 for methyl chloride is at the lower end of current estimates for tropical vegetation sources, which helps to constrain the range of tropical sources and sinks (0.82 to 8.2 Tg yr-1 from tropical plants, 0.03 to 2.5 Tg yr-1 from senescent/dead leaves and a sink of 0.1 to 1.6 Tg yr-1 by soil uptake). Nevertheless, these results show that the contribution of the rainforest ecosystem is the major source in the global budget of methyl chloride. For chloroform, the extrapolated global net flux from tropical ecosystems

  13. 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.

  14. Contribution of sea ice in the Southern Ocean to the cycling of volatile halogenated organic compounds

    NASA Astrophysics Data System (ADS)

    Granfors, Anna; Karlsson, Anders; Mattsson, Erik; Smith, Walker O.; Abrahamsson, Katarina

    2013-08-01

    The contribution of sea ice to the flux of biogenic volatile halogenated organic compounds to the atmosphere in the Southern Ocean is currently not known. To approach this question, we measured halocarbons in sea ice, sea ice brine, and surface water of the Amundsen and Ross Seas. Concentrations in sea ice of these compounds, normalized to seawater salinity, ranged from 0.2 to 810 pmol L-1. Salinity-normalized chlorophyll a concentrations in the ice ranged from 3.5 to 190 µg L-1. Our results suggest biological production of halocarbons in sea ice, with maxima of halogenated organics and chlorophyll a commonly found in the interior of the ice cores. Iodinated VHOCs were found to be more enriched in sea ice than brominated ones. Furthermore, depth distributions indicated a transport of halocarbons from sea ice to air and underlying water.

  15. 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...

  16. 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.

  17. 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.

  18. 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.

  19. Controlling the magnetism of adsorbed metal-organic molecules

    NASA Astrophysics Data System (ADS)

    Kuch, Wolfgang; Bernien, Matthias

    2017-01-01

    Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule’s magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

  20. Controlling the magnetism of adsorbed metal-organic molecules.

    PubMed

    Kuch, Wolfgang; Bernien, Matthias

    2017-01-18

    Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule's magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

  1. 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.

  2. Comparison of chlorination and ozonation in treatment of waste water effluents: effects on selected halogenated organic compounds

    SciTech Connect

    Chang, H.

    1983-01-01

    The formation of halogenated hydrocarbons is considered a major drawback in disinfection of waste water using chlorine. The behavior of ozone as an alternative treatment agent was studied by monitoring the generation or destruction of twenty-one volatile halogenated organic compounds that were either proved or suspected products during the chlorination of waste water. The results demonstrated that ozone is preferable to chlorine. While chlorination most of the time resulted in an increase of halogenated compound concentration, ozonation usually diminished the levels of these compounds. Only in one case did ozonation give moderately high production of halogenated organics (tetrachloroethylene). It was found that the behaviors of these oxidizing agents were considerably different in waste water than in carbon filtered water; the chemical reactivities of oxidizing agents may be reinforced in the waste water by certain inorganic species such as trivalent iron.

  3. 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.

  4. Effect of halogenated impurities on lifetime of organic light emitting diode

    NASA Astrophysics Data System (ADS)

    Yamawaki, Hayato; Suzuki, Kunihiko; Kubota, Tomohiro; Watabe, Takeyoshi; Ishigaki, Ayumi; Nakamura, Rina; Inoue, Hideko; Nakashima, Harue; Horikoshi, Nozomi; Nowatari, Hiromi; Kataishi, Riho; Hamada, Toshiki; Sasaki, Toshiki; Suzuki, Tsunenori; Seo, Satoshi

    2016-09-01

    We investigated a correlation between lifetime and the halogen element concentration in an organic light-emitting diode (OLED) and conducted experiments and simulations to discuss degradation mechanisms due to the halogen. OELD is generally formed of high-purity materials. Since the synthesis of high-purity materials takes time and cost, quantitative understanding of the kind, amount, and influence of impurities in OLED devices is expected. The results of combustion ion chromatography show that, if the chlorine concentration in the host material is more than several parts per million, the lifetime of the device is drastically reduced. The chlorine element, which is derived from the chlorinated by-product of the host material, is found to be transferred from the chloride to other materials (e.g., an emissive dopant) according to the results of LC-MS analysis. In addition, the electron transport layer including such impurities is also found to adversely affect the lifetime. The results of TOF-SIMS analysis suggest that the dissociated chlorine element diffuse to the light-emitting layer side when the device is driven. The results of simulations (Gaussian 09) and electrochemical analyses (cyclic voltammetry and electrolysis) reveal that the halogen element is easy to dissociate from halide by excitation or reduction. The halogen element can repeat reactions with the peripheral materials by excitation or reduction and cause damages, e.g., generate radicals or further reaction products due to the radicals. The results of simulation suggest that, such compounds have low energy level and become quenchers.

  5. 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

  6. Fluorescence spectroscopy for monitoring reduction of natural organic matter and halogenated furanone precursors by biofiltration.

    PubMed

    Peleato, Nicolás M; McKie, Michael; Taylor-Edmonds, Lizbeth; Andrews, Susan A; Legge, Raymond L; Andrews, Robert C

    2016-06-01

    The application of fluorescence spectroscopy to monitor natural organic matter (NOM) reduction as a function of biofiltration performance was investigated. This study was conducted at pilot-scale where a conventional media filter was compared to six biofilters employing varying enhancement strategies. Overall reductions of NOM were identified by measuring dissolved organic carbon (DOC), and UV absorbance at 254 nm, as well as characterization of organic sub-fractions by liquid chromatography-organic carbon detection (LC-OCD) and parallel factors analysis (PARAFAC) of fluorescence excitation-emission matrices (FEEM). The biofilter using granular activated carbon media, with exhausted absorptive capacity, was found to provide the highest removal of all identified PARAFAC components. A microbial or processed humic-like component was found to be most amenable to biodegradation by biofilters and removal by conventional treatment. One refractory humic-like component, detectable only by FEEM-PARAFAC, was not well removed by biofiltration or conventional treatment. All biofilters removed protein-like material to a high degree relative to conventional treatment. The formation potential of two halogenated furanones, 3-chloro-4(dichloromethyl)-2(5H)-furanone (MX) and mucochloric acid (MCA), as well as overall treated water genotoxicity are also reported. Using the organic characterization results possible halogenated furanone and genotoxicity precursors are identified. Comparison of FEEM-PARAFAC and LC-OCD results revealed polysaccharides as potential MX/MCA precursors.

  7. 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

  8. 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

  9. 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.

  10. The formation of halogen-specific TOX from chlorination and chloramination of natural organic matter isolates.

    PubMed

    Kristiana, Ina; Gallard, Hervé; Joll, Cynthia; Croué, Jean-Philippe

    2009-09-01

    The formation of disinfection by-products (DBPs) is a public health concern. An important way to evaluate the presence of DBPs is in terms of the total organic halogen (TOX), which can be further specified into total organic chlorine (TOCl), bromine (TOBr), and iodine (TOI). The formation and distribution of halogen-specific TOX during chlorination and chloramination of natural organic matter (NOM) isolates in the presence of bromide and iodide ions were studied. As expected, chloramination produced significantly less TOX than chlorination. TOCl was the dominant species formed in both chlorination and chloramination. TOI was always produced in chloramination, but not in chlorination when high chlorine dose was used, due to the limited presence of HOI in chlorination as a result of the oxidation of iodide to iodate in the presence of excess chlorine. The formation of TOI during chloramination increased as the initial iodide ion concentration increased, with a maximum of approximately 60% of the initial iodide ion becoming incorporated into NOM. Iodine incorporation in NOM was consistently higher than bromine incorporation, demonstrating that the competitive reactions between bromine and iodine species in chloramination favoured the formation of HOI and thus TOI, rather than TOBr. Correlations between the aromatic character of the NOM isolates (SUVA(254) and % aromatic C) and the concentrations of overall TOX and halogen-specific TOX in chloramination were observed. This indicates that the aromatic moieties in NOM, as indicated by SUVA(254) and % aromatic C, play an important role in the formation of overall TOX and halogen-specific TOX in chloramination. THMs comprised only a fraction of TOX, up to 7% in chloramination and up to 47% in chlorination. Although chloramine produces less TOX than chlorine, it formed proportionally more non-THM DBPs than chlorine. These non-THM DBPs are mostly unknown, corresponding to unknown health risks. Considering the higher

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. The Effects of Organic Adsorbates on the Underpotential Deposition of Silver on Pt(111) Electrodes

    DTIC Science & Technology

    1993-01-01

    CV) The Effects of Organic Adsorbates on the Underpotential Deposition W.0 of Silver on Pt(111) Electrodes _• D. L. Taylor and H. D. Abruxla* D TIC...to determine the effects of competing organic adsorbates on the underpotential deposition of silver on Pt(111). The adsorbates studied are known to...hcis )n appive tor pubic release and sal Its distribution is unlimited. fu .. 93-12456 INTRODUCTION The process of underpotential deposition (UPD) of

  16. Halogen Chemistry in the CMAQ Model

    EPA Science Inventory

    Halogens (iodine and bromine) emitted from oceans alter atmospheric chemistry and influence atmospheric ozone mixing ratio. We previously incorporated a representation of detailed halogen chemistry and emissions of organic and inorganic halogen species into the hemispheric Commun...

  17. 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…

  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 AGENCY (CONTINUED) SOLID WASTES (CONTINUED) LAND DISPOSAL RESTRICTIONS Pt. 268, App. III Appendix III...

  19. How the inclusion of treated water in beverages influences the appearance of halogenated volatile organic compounds.

    PubMed

    Montesinos, Isabel; Gallego, Mercedes

    2014-10-22

    A simple, robust, and reliable headspace gas chromatography method has been developed for the determination of 14 halogenated volatile organic compounds, including iodinated trihalomethanes (THMs), at nanogram per liter levels in beverages. The main source of the presence of THMs in reconstituted fruit juices, nectars, and soft drinks is the treated water included as an ingredient; the concentration and speciation depend on the volume and disinfection process of the treated water either from the distribution network or from water directly disinfected by the food factory. Chloroform appears at concentrations below 1 μg/L in natural juices and soft drinks prepared with mineral water due to contamination from the chlorinated sanitizers usually employed in the food industry. However, the beverages manufactured with treated water contain, in addition to chloroform, brominated THMs and dichloroiodomethane (detected in beverages for the first time), which can be used as indicators of the presence of treated water.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. Crystal structure prediction and isostructurality of three small organic halogen compounds.

    PubMed

    Asmadi, Aldi; Kendrick, John; Leusen, Frank J J

    2010-08-14

    A theoretical investigation of the packing stabilities of three small organic halogen compounds is presented based on a crystal structure prediction (CSP) study. Each compound has four identical halogen atoms (fluorine, chlorine, and bromine) and a four-membered ring consisting of carbon and sulfur atoms arranged alternately. Two halogen atoms are attached to each carbon and two oxygen atoms are attached to each sulfur forming SO(2) functional groups. The crystal structures of these compounds have been determined experimentally and show distinct packing arrangements. Utilising the computational approaches implemented in the GRACE software package, each compound is subjected to a full CSP study using a force field specific for each molecule (called the tailor-made force field or TMFF) and a dispersion corrected solid-state density functional method (or DFT(d) method). Energetically feasible crystal structures are generated in all 230 space groups restricted to a single molecule in the crystallographic asymmetric unit (Z' = 1) using the TMFF of each molecule. Next, a selection of structures with low TMFF lattice energies are further refined with the DFT(d) method. The CSP results show that the experimental crystal structures of the molecules containing fluorine and chlorine are well described energetically and geometrically by their TMFFs and the DFT(d) method. Both approaches locate their experimental lattices as the most stable structures. For the molecule containing bromine, a crystal structure corresponding to the force field optimised experimental structure is located as the second structure in the list of force field predicted structures, ranked by calculated lattice energy. Despite the structural similarity of the predicted and experimental structures, close examination of the DFT(d) optimisation results of the experimental structure reveals a slightly lower energy structure than that found by the CSP simulations. Furthermore, minimisation of the force field

  5. 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.

  6. 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.

  7. Novel enhancement of thin-form-factor galvanic cells: Probing halogenated organic oxidizers and metal anodes

    NASA Astrophysics Data System (ADS)

    Cardenas-Valencia, Andres M.; Adornato, Lori; Short, R. Timothy; Langebrake, Larry

    The work reported herein demonstrates a novel method to improve the overall performance of thin-form-factor galvanic cells, fabricated via micro-electromechanical systems (MEMS) processes. Use of solid, low cost, cyclic-halogenated, organic catholyte materials permits water activation of cells consisting of metal anode and catalytic platinum positive electrodes. Similar cells, employing aluminum and zinc anodes, have been activated using sodium hypochlorite (NaClO) solutions, i.e. bleach, in the past. The oxidizers chosen for this study (bromo-, chloro- and iodo-succinimides, and sodium dichloroisocyanuric acid) supply the cathode's oxy-halogenated ions when in contact with water. Zinc, magnesium and aluminum anodes are utilized to fabricate galvanic cells. A comparison between these anodes, coupled with various oxidizers, is included herein. Results using aluminum anode cells show that, even though the utilization efficiency of the catholyte reagents is low (faradic efficiencies between 16 and 19%), the performance of the new water-activated cells (6 cm × 6 cm × 0.25 cm) is superior when compared to those activated with bleach. For instance, operational lives of 6 h (activation with 10% NaClO solution) increase to more than 30 h using the new approach, with a 100-ohm-load. It is also shown that specific energies of 90-110 Wh kg -1 (calculated to include both reagent and packaging mass) could be obtained using the described approach with current draws between 10 and 20 mA. The specific energies obtained suggest that novel MEMS-type cells could have much broader application than low-current, bleach-activated cells.

  8. Determination of volatile halogenated organic compounds in the tropical terrestrial ecosystem

    SciTech Connect

    Quintana, A.; Lopez-Garriga, J.

    1995-12-01

    Volatile Halogenated Organic Compounds are discharged into our biosphere by plants, marine organisms, fungi and by other natural processes. Due to the high rate of evaporation of the tropical terrestrial ecosystem, the production of VHOC by fungi, higher plants and other organisms may be one of the most important sources of the total amount of VHOC released to the atmosphere from biogenic origin. The main goal of this research was to determine the VHOC`s released to the surroundings from biogenic origin in the tropical terrestrial ecosystem. Using vacuum distillation with cryogenic trapping and a thermal desorption unit coupled to a GC-ECD, we found that samples of air, water and soil contains 36.418 ng/L, 0.222 ng/mL and 9.156 ng/g (wet) of chloroform. Microorganisms such as the Actinomycetes and Halobacterium salinarium were also analyzed for VHOC`S contents. Carbontetrachloride, 1,1-dichloroethene, dichlorodifluoromethane, trichlorofluoromethane and other VHOC`S of environmental importance were determined. This is the first time that the presence of VHOC`S is reported in pure cultured bacteria.

  9. 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)

  10. 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...

  11. 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.

  12. Vapor Pressure Isotope Effects in Halogenated Organic Compounds and Alcohols Dissolved in Water.

    PubMed

    Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

    2016-12-20

    Volatilization causes changes in the isotopic composition of organic compounds as a result of different vapor pressures of molecules containing heavy and light isotopes. Both normal and inverse vapor pressure isotope effects (VPIE) have been observed, depending on molecular interactions in the liquid phase and the investigated element. Previous studies have focused mostly on pure compound volatilization or on compounds dissolved in organic liquids. Environmentally relevant scenarios, such as isotope fractionation during volatilization of organics from open water surfaces, have largely been neglected. In the current study, open-system volatilization experiments (focusing thereby on kinetic/-nonequilibrium effects) were carried out at ambient temperatures for trichloromethane, trichloroethene, trichlorofluoromethane, trichlorotrifluoroethane, methanol, and ethanol dissolved in water and, if not previously reported in the literature for these compounds, for volatilization from pure liquids. Stable carbon isotopic signatures were measured using continuous flow isotope ratio mass spectrometry. The results demonstrate that volatilization of the four halogenated compounds from water does not cause a measurable change in the carbon isotopic composition, whereas for pure-phase evaporation, significant inverse isotope effects are consistently observed (+0.3 ‰< ε < + 1.7 ‰). In contrast, methanol and ethanol showed normal isotope effects for evaporation of pure organic liquids (-3.9 ‰ and -1.9 ‰) and for volatilization of compounds dissolved in water (-4.4 ‰ and -2.9 ‰), respectively. This absence of measurable carbon isotope fractionation considerably facilitates the application of isotopic techniques for extraction of field samples and preconcentration of organohalogens-known to be important pollutants in groundwater and in the atmosphere.

  13. 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).

  14. 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.

  15. 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.

  16. 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.

  17. A computer modelling study of the interaction of organic adsorbates with fluorapatite surfaces

    NASA Astrophysics Data System (ADS)

    Mkhonto, Donald; Ngoepe, Phuti E.; Cooper, Timothy G.; de Leeuw, Nora H.

    2006-08-01

    Computer modelling techniques were employed to investigate the adsorption of a selection of organic surfactant molecules to a range of fluorapatite surfaces, and new interatomic potential models for the apatite/adsorbate interactions are presented. The adsorbates coordinate mainly to the surfaces through interaction between their oxygen (or nitrogen) atoms to surface calcium ions, followed by hydrogen-bonded interactions to surface oxygen ions and, to a much lesser extent, surface fluorides. Bridging between two surface calcium ions is the preferred mode of adsorption, when the geometry of the adsorbates allows it, and multiple interactions between surfaces and adsorbate molecules lead to the largest adsorption energies. All adsorbates containing carbonyl and hydroxy groups interact strongly with the surfaces, releasing energies between approximately 100 and 215 kJ mol-1, but methylamine containing only the NH2 functional group adsorbs to the surfaces to a much lesser extent (25 95 kJ mol-1). Both hydroxy methanamide and hydroxy ethanal prefer to adsorb to some surfaces in an eclipsed conformation, which is a requisite for these functional groups. Sorption of the organic material by replacement of pre-adsorbed water at different surface features is calculated to be mainly exothermic for methanoic acid, hydroxy methanamide and hydroxy ethanal molecules, whereas methyl amine would not replace pre-adsorbed water at the fluorapatite surfaces. The efficacy of the surfactant molecules is calculated to be hydroxy aldehydes > alkyl hydroxamates > carboxylic acids ≫ alkyl amines. The results from this study suggest that computer simulations may provide a route to the identification or even design of particular organic surfactants for use in mineral separation by flotation.

  18. 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

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. Transient magnetization of core excited organic molecules adsorbed on graphene

    NASA Astrophysics Data System (ADS)

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

    This work presents a density functional theory based computational investigation of electronic and magnetic properties of physisorbed and chemisorbed organic molecules on graphene in the ground state and core excited one at low molecular coverage. 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, it is found 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 contrary, when graphene is covalently functionalized, the system is magnetic in the ground state presenting 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. This project has received funding from the European Union Seventh Framework Programme under grant agreement n∘ 607232 [THINFACE].

  9. The Use of Amberlite Adsorbents for Green Chromatography Determination of Volatile Organic Compounds in Air

    PubMed Central

    Juan-Peiró, Luis; Bernhammer, Anne; Pastor, Agustin; de la Guardia, Miguel

    2012-01-01

    Passive samplers have been widely used for volatile organic compounds determination. Following the green chemistry tendency of the direct determination of adsorbed compounds in membrane-based devices through using head space direct chromatography analysis, this work has evaluated the use of Amberlite XAD-2, XAD-4, and XAD-16 adsorbents as a filling material for passive samplers. Direct analysis of the membranes by HS-GC-MS involves a solvent-free method avoiding any sample treatment. For exposed membranes, recoveries ranged from 10% to 203%, depending on the compound and adsorbent used. The limit of the detection values ranged from 1 to 140 ng per sampler. Acceptable precision and sensitivity levels were obtained for the XAD resins assayed. PMID:22848870

  10. 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

  11. Low cost adsorbents for the removal of organic pollutants from wastewater.

    PubMed

    Ali, Imran; Asim, Mohd; Khan, Tabrez A

    2012-12-30

    Water pollution due to organic contaminants is a serious issue because of acute toxicities and carcinogenic nature of the pollutants. Among various water treatment methods, adsorption is supposed as the best one due to its inexpensiveness, universal nature and ease of operation. Many waste materials used include fruit wastes, coconut shell, scrap tyres, bark and other tannin-rich materials, sawdust and other wood type materials, rice husk, petroleum wastes, fertilizer wastes, fly ash, sugar industry wastes blast furnace slag, chitosan and seafood processing wastes, seaweed and algae, peat moss, clays, red mud, zeolites, sediment and soil, ore minerals etc. These adsorbents have been found to remove various organic pollutants ranging from 80 to 99.9%. The present article describes the conversion of waste products into effective adsorbents and their application for water treatment. The possible mechanism of adsorption on these adsorbents has also been included in this article. Besides, attempts have been made to discuss the future perspectives of low cost adsorbents in water treatment.

  12. Direct measurement of adsorbed gas redistribution in metal-organic frameworks.

    PubMed

    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.

  13. 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.

  14. Persistent halogenated organic contaminants and mercury in northern fulmars (Fulmarus glacialis) from the Canadian Arctic.

    PubMed

    Braune, Birgit M; Mallory, Mark L; Butt, Craig M; Mabury, Scott A; Muir, Derek C G

    2010-12-01

    Northern fulmars from two breeding colonies in the Canadian Arctic, Cape Vera and Prince Leopold Island, were analyzed for organochlorine pesticides, PCBs, perfluorinated compounds (PFCs) and total mercury (Hg). Hepatic concentrations of organochlorines and Hg were highest in the male fulmars from Cape Vera. Perfluorooctane sulfonate (PFOS) concentrations did not vary significantly between sexes or colonies. However, concentrations of the perfluorinated carboxylates (PFCAs) were higher in fulmars from Cape Vera than Prince Leopold Island. The C(11)-C(15) PFCAs averaged 90% of the PFCA profile at both colonies. Polychorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and non-ortho PCBs (NO-PCBs) were measured only in birds from Prince Leopold Island. Concentrations of PCDDs, PCDFs, NO-PCBs and Toxic Equivalents (TEQs) did not differ significantly between sexes. ΣTEQ was comprised mainly of ΣTEQ(PCDF). Concentrations of Hg and the persistent halogenated compounds reported in this study were below published toxicological threshold values for wild birds.

  15. 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.

  16. Halogenated organic pollutants in marine biota from the Xuande Atoll, South China Sea: Levels, biomagnification and dietary exposure.

    PubMed

    Sun, Yu-Xin; Hu, Yong-Xia; Zhang, Zai-Wang; Xu, Xiang-Rong; Li, Heng-Xiang; Zuo, Lin-Zi; Zhong, Yi; Sun, Hong; Mai, Bi-Xian

    2017-03-11

    Six marine biota species were collected from the Xuande Atoll, South China Sea to investigate the bioaccumulation of dichlorodiphenyltrichloroethane (DDT), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane (DBDPE) and dechlorane plus (DP). Pike conger (Muraenesox talabonoides) had the highest concentrations of halogenated organic pollutants (HOPs) among the six marine biota species. DDTs were the predominant HOPs, followed by PCBs and PBDEs, with minor contributions of DBDPE and DP. Twenty-one percent of samples had ratios of (DDE+DDD)/ΣDDTs lower than 0.5, implying the presence of fresh DDT inputs in the environment of the Xuande Atoll. The biomagnification factor values for DDTs, PCBs, PBDEs and DP were higher than 1, suggesting biomagnification of these contaminants in the marine food chains. Consumption of seafood from the Xuande Atoll might not subject local residents in the coastal areas of South China to health risks as far as HOPs are concerned.

  17. 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

  18. Near-infrared spectroscopy study for determination of adsorbed acetochlor in the organic and inorganic bentonites.

    PubMed

    Tomić, Zorica P; Ašanin, Darko; Đurović, Rada; Đorđević, Aleksandar; Makreski, Petre

    2012-12-01

    NIR spectroscopy is used to determine acetochlor herbicide adsorption on Na-montmorillonite (NaP) and organically modified montmorillonite (NaOM). Both montmorillonites NIR spectra shows bands at 7061 and 6791 cm(-1). Organo-montmorillonite is characterised by two emphasized bands at 5871 and 5667 cm(-1) that are attributed to the fundamental overtones of the mid-IR bands at 2916 and 2850 cm(-1). Bands at 6017 and 6013 cm(-1) are attributed to acetochlor adsorbed to organo-montmorillonite and Na-montmorillonite, which is confirmed by X-ray powder diffraction (XRPD). Greater quantity of acetochlor is adsorbed to organo-clays compared to non-modified montmorillonite. Acetochlor poses high risk to environmental contamination. Organo-clays are the most useful for removing acetochlor from water and soil.

  19. 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!

  20. 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.

  1. Formation of Adsorbed Oxygen Radicals on Minerals at the Martian Surface and the Decomposition of Organic Molecules

    NASA Technical Reports Server (NTRS)

    Yen, A. S.; Kim, S. S.; Freeman, B. A.; Hecht, M. H.

    2000-01-01

    We present experimental evidence that superoxide ions form on mineral grains at the martian surface and show that these adsorbates can explain the unusual reactivity of the soil as well as the apparent absence of organic molecules.

  2. Halogenated pyrrolopyrimidine analogues of adenosine from marine organisms: pharmacological activities and potent inhibition of adenosine kinase.

    PubMed

    Davies, L P; Jamieson, D D; Baird-Lambert, J A; Kazlauskas, R

    1984-02-01

    Two novel halogenated pyrrolopyrimidine analogues of adenosine, isolated from marine sources, have been examined for pharmacological and biochemical activities. 4-Amino-5-bromo-pyrrolo[2,3-d]pyrimidine, from a sponge of the genus Echinodictyum, had bronchodilator activity at least as potent as theophylline but with a different biochemical profile; unlike theophylline it had no antagonist activity at CNS adenosine receptors and it was quite a potent inhibitor of adenosine uptake and adenosine kinase in brain tissue. 5'-Deoxy-5-iodotubercidin, isolated from the red alga Hypnea valentiae, caused potent muscle relaxation and hypothermia when injected into mice. This compound was a very potent inhibitor of adenosine uptake into rat and guinea-pig brain slices and an extremely potent inhibitor of adenosine kinase from guinea-pig brain and rat brain and liver. Neither of these two pyrrolopyrimidine analogues was a substrate for, or an inhibitor of, adenosine deaminase. Neither compound appeared to have any direct agonist activity on guinea-pig brain adenosine-stimulated adenylate cyclase (A2 adenosine receptors). 5'-Deoxy-5-iodotubercidin is unique in two respects: it appears to be the first naturally-occurring example of a 5'-deoxyribosyl nucleoside and is the first example of a specifically iodinated nucleoside from natural sources. It may be the most potent adenosine kinase inhibitor yet described and, by virtue of its structure, may prove to be the most specific.

  3. 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.

  4. Radiolytic and thermal dechlorination of organic chlorides adsorbed on molecular sieve 13X.

    PubMed

    Yamamoto, Y; Tagawa, S

    2001-05-15

    Reductive dechlorination of chlorobenzene (PhCl), trichloroethylene (TCE), tetrachloroethylene (PCE), 1- and 2-chlorobutanes, chloroform, carbon tetrachloride, and 1,1,1- and 1,1,2-trichloroethanes adsorbed on molecular sieve 13X was investigated. The molecular sieve adsorbing the organic chlorides was irradiated with gamma-rays, heated, or allowed to stand at room temperature in a sealed ampule and was then soaked in water. The dechlorination yields were determined from the Cl- concentrations of the supernatant aqueous solutions. It was found that the chlorinated alkanes adsorbed on the molecular sieve are readily dechlorinated on standing at room temperature. The dechlorination at room temperature was limited for TCE and PCE. PhCl was quite stable even at 200 degrees C. gamma-Radiolysis was examined for PhCl, TCE, and PCE at room temperature. The radiation chemical yields of the dechlorination, G(Cl-), were 1.9, 40, and 30 for PhCl, TCE, and PCE, respectively. After 5 h of heating at 200 degrees C, the dechlorination yields for TCE and PCE were 24.5 and 4.3%, respectively. TCE is much more reactive than PCE in the thermal dechlorination, whereas their radiolytic dechlorination yields are comparable. The pH of the supernatant solutions decreased along with the dechlorination.

  5. EVALUATION OF A NOVEL CARBON ADSORBENT FOR FRACTIONATION AND TREATMENT OF HALOGENATED ORGANIC WASTES. (R825549C011)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  6. Xylanase and laccase based enzymatic kraft pulp bleaching reduces adsorbable organic halogen (AOX) in bleach effluents: a pilot scale study.

    PubMed

    Sharma, Abha; Thakur, Vasanta Vadde; Shrivastava, Anita; Jain, Rakesh Kumar; Mathur, Rajeev Mohan; Gupta, Rishi; Kuhad, Ramesh Chander

    2014-10-01

    In present study, xylanase and laccase were produced in a cost-effective manner up to 10 kg substrate level and evaluated in elemental chlorine free bleaching of Eucalyptus kraft pulp. Compared to the pulp pre-bleached with xylanase (15%) or laccase (25%) individually, the ClO2 savings were higher with sequential treatment of xylanase followed by laccase (35%) at laboratory scale. The sequential enzyme treatment when applied at pilot scale (50 kg pulp), resulted in improved pulp properties (50% reduced post color number, 15.71% increased tear index) and reduced AOX levels (34%) in bleach effluents. The decreased AOX level in effluents will help to meet AOX discharge limits, while improved pulp properties will be value addition to the paper.

  7. Release of Reactive Halogen Species from Sea-Salt Aerosols under Tropospheric Conditions with/without the Influence of Organic Matter in Smog-Chamber Experiments

    NASA Astrophysics Data System (ADS)

    Balzer, N.; Behnke, W.; Bleicher, S.; Krueger, H.; Ofner, J.; Siekmann, F.; Zetzsch, C.

    2008-12-01

    Experiments to investigate the release of reactive halogen species from sea-salt aerosol and the influence of organic matter were performed in an aerosol smog-chamber (3500 l), made of Teflon film (FEP 200A, Dupont). Smog chamber facilities at lowered temperature (coolable down to -25°C) enable us to simulate these reactions under polar, tropospheric conditions. First experiments were performed to investigate the production of atomic Br and Cl without the impact of organic aerosol. Br and Cl play an important role in atmospheric ozone depletion, particularly regarding ozone depletion events (bromine explosion) during polar spring. In these studies, the aerosol was generated by atomizing salt solutions containing the typical Br/Cl ratio of 1/660 in seawater by an ultrasonic nebulizer and increasing the Br content up to sixfold. To ensure the aqueous surface of the aerosol, the experiments were performed at relative humidities above 76%. We determined the atomic Cl and OH-radical concentrations from the simultaneous consumption of four reference hydrocarbons. The Br-radical concentration was calculated on the basis of ozone depletion. Organic aerosol may take part in these reaction cycles by halogenation and production of volatile organic halogens. Further experiments are planned to add organic aerosol for mechanistic and kinetic studies on the influence of secondary organic aerosols (SOA) and humic-like substances (HULIS) on bromine explosion. The formation of the secondary organic aerosol and the determination of possible halogenated gaseous and solid organic products will be studied using longpath-FTIR, DRIFTS, ATR-FTIR, GC-FID, GC-ECD, GC-MS, TPD-MS and DMA-CNC.

  8. Occurrence of legacy and emerging halogenated organic contaminants in marine shellfish along French coasts.

    PubMed

    Munschy, C; Olivier, N; Veyrand, B; Marchand, P

    2015-01-01

    Current contamination levels of selected legacy, currently-used and emerging halogenated contaminants were monitored in marine shellfish along French coastlines. The studied contaminants included polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenylethane (DBDPE), hexabromobenzene (HBB), 2,2′,4,4′,5,5′-hexabromobiphenyl (BB-153) and perfluorinated compounds (PFCs).BDE-47, BDE-209, BTBPE, HBB and α-HBCDD were detected in 100% of the analyzed samples, whereas BB-153, DBDPE and PFOS were detected at frequencies of 97%, 90% and 55%, respectively. Concentrations were in the pg g−1 ww range and varied as follows: PFOS > BDE-47 ∼ α-HBCDD > BDE-209 > BTBPE ∼ DBDPE > HBB ∼ BB-153. Overall, non-PBDE Brominated Flame Retardants (BFRs) revealed concentrations between 3 and 59 times lower than those of PBDEs.PBDE pattern was dominated by BDE-47, followed by BDE-99 > BDE-100 > BDE-49 > BDE-209 > BDE-154; these 6 congeners represented 94% of the summed ten PBDEs. PFC pattern determination revealed PFOS as the predominant PFC in samples from the English Channel and Atlantic, whereas perfluorocarboxylic acids (PFCAs) prevailed in Mediterranean samples. Temporal trend investigations on archived samples from the Mediterranean coast collected between 1981 and 2012 showed a prevalence of PFOS until 1998; PFCAs subsequently increased and became more abundant than PFOS. High levels of PFCAs were observed until 2008, followed by a decrease and stabilization in 2010–2012. Amongst PFCAs, perfluorotridecanoic acid (PFTrDA) and perfluoroundecanoic acid (PFUnA) were predominant and exhibited similar time trends, suggesting similar sources at the investigated site, home to major industrial activity.

  9. From the 1988 drought to the 1993 flood: Transport of halogenated organic compounds with the Mississippi river suspended sediment at Thebes, Illinois

    USGS Publications Warehouse

    Rostad, C.E.

    1997-01-01

    Suspended sediment was isolated from water samples collected from the Mississippi River at Thebes, IL, eight times over a 5-year period from May 1988 through September 1993 in order to evaluate the transport of lipophilic halogenated organic compounds associated with the suspended sediment. Two hydrologic extremes were included-the 1988 drought and the 1993 flood. Halogenated organic compounds included polychlorinated biphenyls (PCBs), hexachlorobenzene, pentachloroanisole, DCPA (dacthal), trifluralin, aldrin, dieldrin, and chlordane components. Sediment transport of most of these organic compounds was substantially higher during the 1993 flood then at other sampling times. The extreme transports during the flood were due to unusually high concentrations of some contaminants on the suspended sediment, low to average concentrations of suspended sediment being transported, and unusually high water discharges.

  10. 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.

  11. 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

    2016-05-05

    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.

  12. Chemical characterization of organic carbon dissolved in natural waters using inorganic adsorbents.

    PubMed

    Sugiyama, Y; Kumagai, T

    2001-01-01

    Dissolved organic carbon (DOC) in water samples from Lake Biwa was chemically characterized by two inorganic adsorbents with completely different surface characteristics. The two adsorbents were HIO (hydrous iron oxide) and SG (silica gel). Solutions of reference standard materials were analyzed concerning their adsorption behavior to HIO and SG for bovine serum albumin (BSA), fulvic acid extracted from the bottom sediments of Lake Biwa, phthalic acid, and starch. The adsorption of DOC to HIO was mainly controlled by ligand exchange and electrostatic interaction; that of SG was by electrostatic interaction. It was found that in a weak acid solution of around pH 5, BSA adsorbs to both HIO and SG, but that fulvic acid, phthalic acid and starch only show adsorption to HIO. Using these characteristics, DOC samples in natural water samples were characterized into pro-DOC, which adsorbs to both HIO and SG at pH 5, and car-DOC, which only adsorbs to HIO at pH 5. The DOC samples in Lake Biwa on October 7, 1997, at sampling sites Nb-2 and Nb-5 (south basin of Lake Biwa, the depths were about 2 and 4 m), and Ie-1 (north basin of Lake Biwa, the depth was about 75 m) were characterized. The pro-DOC has different values, depending on their sampling sites and depths, and had the maximum value of 0.42 mg C l(-1) at the surface water of Ie-1, and had the lowest values at middle to deeper water depths (0.18-0.27 mg C l(-1)). The car-DOC showed a relatively stable value at Ie-1 regardless of the depth (0.63-0.83 mg C l(-1)), and the maximum value was observed in Nb-2 and Nb-5 (1.2 and 1.3 mg C l(-1)). The ratios between car-DOC and pro-DOC concentrations were 0.2-0.5, and had different values for different sampling sites and depths. The ratios were significantly different for surface water samples where the biological activities are high and for bottom water samples where decomposition predominates.

  13. Investigation of organic, inorganic and synthetic adsorbents for the pretreatment of landfill leachate.

    PubMed

    Shahriari, H; Fernandes, L; Tezel, F H

    2008-05-01

    An investigation into the use of organic, inorganic and synthetic adsorbents for the pretreatment of landfill leachate, generated by the City of Ottawa Trail Road Landfill, was carried out. The purpose of this project was to reduce the concentration of contaminants in order to meet the local Sewer Use By-Laws, prior to transporting the leachate from the generating site to the local municipal sewage treatment plant, and thereby reducing the disposal fees. Peat moss, compost, clinoptilolite, basalt and two types of activated carbon (DSR-A and F400) were investigated to determine the adsorption capacity for contaminants from leachate. Kinetic studies were also performed. The results based on batch adsorption isotherms show that peat moss has the highest adsorption capacity for boron (B) and barium (Ba), compared with the other adsorbents. Also peat moss has good removals of Total Kjeldahl Nitrogen (TKN), Total Organic Carbon (TOC), and benzene, toluene, ethylbenzene and xylene (BTEX), but these are lower than the removals obtained with activated carbon. Because of its relatively low cost and higher adsorption of B and Ba, peat moss was selected as the filter media for the column studies. The treated leachate was tested for B, Ba, TKN, carbonaceous biological oxygen demand (CBOD5) and hydrogen sulfide (H2S). The breakthrough curves for B and Ba showed the effectiveness of peat moss in removing these contaminants.

  14. Methyl red removal from water by iron based metal-organic frameworks loaded onto iron oxide nanoparticle adsorbent

    NASA Astrophysics Data System (ADS)

    Dadfarnia, S.; Haji Shabani, A. M.; Moradi, S. E.; Emami, S.

    2015-03-01

    The objective followed by this research is the synthesis of iron based metal organic framework loaded on iron oxide nanoparticles (Fe3O4@MIL-100(Fe)) and the study of its capability for the removal of methyl red. Effective parameters in the selection of a new adsorbent, i.e. adsorption capacity, thermodynamics, and kinetics were investigated. All the studies were carried out in batch experiments. Removal of methyl red from aqueous solutions varied with the amount of adsorbent, methyl red contact time, initial concentration of dye, adsorbent dosage, and solution pH. The capability of the synthesized adsorbent in the removal of methyl red was compared with the metal organic framework (MIL-100(Fe)) and iron oxide nanoparticles. The results show that Fe3O4@MIL-100(Fe) nanocomposite exhibits an enhanced adsorption capacity.

  15. Live microbial cells adsorb Mg2+ more effectively than lifeless organic matter

    NASA Astrophysics Data System (ADS)

    Qiu, Xuan; Yao, Yanchen; Wang, Hongmei; Duan, Yong

    2017-03-01

    The Mg2+ content is essential in determining different Mg-CaCO3 minerals. It has been demonstrated that both microbes and the organic matter secreted by microbes are capable of allocating Mg2+ and Ca2+ during the formation of Mg-CaCO3, yet detailed scenarios remain unclear. To investigate the mechanism that microbes and microbial organic matter potentially use to mediate the allocation of Mg2+ and Ca2+ in inoculating systems, microbial mats and four marine bacterial strains (Synechococcus elongatus, Staphylococcus sp., Bacillus sp., and Desulfovibrio vulgaris) were incubated in artificial seawater media with Mg/Ca ratios ranging from 0.5 to 10.0. At the end of the incubation, the morphology of the microbial mats and the elements adsorbed on them were analyzed using scanning electronic microscopy (SEM) and energy diffraction spectra (EDS), respectively. The content of Mg2+ and Ca2+ adsorbed by the extracellular polysaccharide substances (EPS) and cells of the bacterial strains were analyzed with atomic adsorption spectroscopy (AAS). The functional groups on the surface of the cells and EPS of S. elongatus were estimated using automatic potentiometric titration combined with a chemical equilibrium model. The results show that live microbial mats generally adsorb larger amounts of Mg2+ than Ca2+, while this rarely is the case for autoclaved microbial mats. A similar phenomenon was also observed for the bacterial strains. The living cells adsorb more Mg2+ than Ca2+, yet a reversed trend was observed for EPS. The functional group analysis indicates that the cell surface of S. elongatus contains more basic functional groups (87.24%), while the EPS has more acidic and neutral functional groups (83.08%). These features may be responsible for the different adsorption behavior of Mg2+ and Ca2+ by microbial cells and EPS. Our work confirms the differential Mg2+ and Ca2+ mediation by microbial cells and EPS, which may provide insight into the processes that microbes use to

  16. Gem-Difluoroallyllithium: Preparation by Lithium-Halogen Exchange and Utilization in Organosilicon and Organic Synthesis.

    DTIC Science & Technology

    1983-03-23

    EXCHANGE AND UTILIZATION IN ORGANOSILICON AND ORGANIC SYNTHESIS by Dietmar Seyferth, Robert M. Simon Dennis J. Sepelak, and Helmut A. Klein Prepared for...and Utilization in Organosilicon and Organic Synthesis . 6. PERFORMING ORG. REPORT NUMBER 7. AUTHOR(*) S. CONTRACT OR GRANT NUMBER(&) D. Seyferth, R. M...aide if necessary and Identify by block number) organo lithium organofluorine 4 organic synthesis 20. ABST-kCT (Continue on reverse side it necessary

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. Determination of volatile halogenated organic compounds in soils by purge-and-trap capillary gas chromatography with atomic emission detection.

    PubMed

    Campillo, Natalia; Viñas, Pilar; López-García, Ignacio; Aguinaga, Nerea; Hernández-Córdoba, Manuel

    2004-10-20

    Nine volatile halogenated organic compounds (VHOCs), including four trihalomethanes (THMs), were determined in soils by capillary gas chromatography with microwave induced-plasma atomic emission spectrometry (GC-AED), using a purge-and-trap system (PT) for sample preconcentration. Analytes were previously extracted from the soil sample in methanol and the extract was preconcentrated before being chromatographed. Element-specific detection and quantification were carried out monitoring two wavelength emission lines, corresponding to chlorine (479nm) and bromine (478nm). Each chromatographic run took 21min, including the purge step. The method showed a precision of 1.1-7.2% (R.S.D.) depending on the compound. Detection limits ranged from 0.05 to 0.55ngml(-1), for chloroform and dichloromethane, respectively, corresponding to 3.3 and 36.0ngg(-1) in the soil samples. The chromatographic profiles obtained showed no interference from co-extracted compounds. Low levels of dichloromethane and chloroform ranging from 0.04 to 1.13mugg(-1) were found in samples obtained from small gardens irrigated with tap water. The method is reliable and can be used for routine monitoring in soil samples.

  2. Analysis of organochlorine compounds and extractable organic halogen in three subspecies of ringed seal from northeast Europe

    SciTech Connect

    Kostamo, A.; Medvedev, N.; Pellinen, J.; Hyvaerinen, H.; Kukkonen, J.V.K.

    2000-04-01

    Organochlorine compounds in blubber samples of the ringed seal (Phoca hispida saimensis, P. H. ladogensis, and P. h. hispida) were analyzed in order to estimate the state of pollution in three different water areas in Northeast Europe, namely, Lake Saimaa in Finland, Lake Lodoga, and the White Sea in Russia. Geographic differences in concentrations and in relative concentrations of tri- and tetrachlorocymenes, hexachlorobenzene, {alpha}-HCH, {beta}-HCH, {gamma}-HCH (Lindane), seven polychlorinated biphenyl (PCB) congeners, and p,p{prime}-DDT and its metabolites in ringed seals were compared. Concentrations of chlorinated hydrocarbons varied between the water areas. The highest concentrations were found in Saimaa ringed seals, followed by Lodaga ringed seals, and the lowest concentrations were detected in ringed seals from the White Sea. Extractable organic halogen (EOX) concentrations in blubber were also analyzed. The concentrations showed a geographic trend similar to those for the individual compounds identified. In Lakes Ladoga and Saimaa, the concentrations of EOX and chlorinated hydrocarbons in the blubber were dependent on the age and sex of the seals, but no such relationship was observed in samples from the White Sea.

  3. 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.

  4. Characteristics of adsorbents made from biological, chemical and hybrid sludges and their effect on organics removal in wastewater treatment.

    PubMed

    Pan, Zhi-hui; Tian, Jia-yu; Xu, Guo-ren; Li, Jun-jing; Li, Gui-bai

    2011-01-01

    Meso-macropore adsorbents were prepared from biological sludge, chemical sludge and hybrid sludge of biological and chemical sludges, by chemically activating with 18.0 M H(2)SO(4) in the mass ratio of 1:3, and then pyrolyzing at 550 °C for 1 h in anoxic atmosphere. The physical and chemical characteristics of the sludge-based adsorbents were examined in terms of surface physical morphology, specific surface area and pore size distribution, aluminum and iron contents, surface functional groups and crystal structure. Furthermore, the adsorption effect of these adsorbents on the organic substances in wastewater was also investigated. The results indicated that the adsorption capacities of the sludge-based adsorbents for UV(254) were lower than that of commercial activated carbon (AC), whereas the adsorption capacities of the adsorbents prepared from hybrid sludge (HA) and chemical sludge (CA) for soluble COD(Cr) (SCOD(Cr)) were comparable or even higher than that of the commercial AC. The reasons might be that the HA and CA possessed well-developed mesopore and macropore structure, as well as abundant acidic surface functional groups. However, the lowest adsorption efficiency was observed for the biological sludge-based adsorbent, which might be due to the lowest metal content and overabundance of surface acidic functional groups in this adsorbent.

  5. Determination of molar absorption coefficients of organic compounds adsorbed in porous media.

    PubMed

    Ciani, Andrea; Goss, Kai-Uwe; Schwarzenbach, René P

    2005-12-01

    The kinetics of direct photochemical transformations of organic compounds in light absorbing and scattering media has been sparsely investigated. This is mostly due to the experimental difficulties to assess the major parameters: light intensity in porous media, the reaction quantum yield and the molar absorption coefficient of the adsorbed compound, epsilon(i) (lambda). Here, we propose a method for the determination of the molar absorption coefficient of compounds adsorbed to air-dry surfaces using the Kubelka-Munk model for the description of radiative transfer. To illustrate the method, the molar absorption coefficients of three compounds, i.e. 4-nitroanisole (PNA), the herbicide trifluralin and the flame retardant decabromodiphenyl ether (DecaBDE), were determined on air-dry kaolinite. The measured diffuse reflectance spectra were evaluated with the Kubelka-Munk model and with previously determined Kubelka-Munk absorption and scattering coefficients (k and s), for kaolinite. For all compounds the maximum absorption band was found to be red shifted and the corresponding epsilon(i) (lambda) values were significantly greater than those determined in solvents. Together with the absorption and scattering coefficient of the medium, the measured epsilon(i) (lambda) can be used to determine the quantum yield of the photochemical reaction in this medium from experimentally determined reaction kinetics.

  6. Influence of structural fluctuations on lifetimes of adsorbate states at hybrid organic-semiconductor interfaces

    NASA Astrophysics Data System (ADS)

    Müller, M.; Sánchez-Portal, D.; Lin, H.; Fratesi, G.; Brivio, G. P.; Selloni, A.

    On the road towards a more realistic description of charge transfer processes at hybrid organic-semiconductor interfaces for photovoltaic applications we extend our first-principles scheme for the extraction of elastic linewidths to include the effects of structural fluctuations. Based on snapshots obtained from Car-Parinello molecular dynamics simulations at room temperature, we set up geometries in which dye molecules at interfaces are attached to a semi-infinite TiO2 substrate. The elastic linewidths are computed using a Green's function method. This effectively introduces the coupling to a continuum of states in the substrate. In particular we investigate catechol and isonicotinic acid on rutile(110) and anatase(101) at the level of semi-local density functional theory. We perform multiple calculations of linewidths and peak-positions associated with the adsorbate's frontier orbitals for different geometric configurations to obtain a time-averaged analysis of such physical properties. We compare the results from the considered systems to understand the effects of dynamics onto interfacial charge transfer and systematically assess the dependence of the extracted elastic lifetimes on the relative alignment between adsorbate and substrate states. This project has received funding from the European Union Seventh Framework Programme under Grant Agreement No. 607323 [THINFACE].

  7. Controlling the spatial arrangement of organic magnetic anions adsorbed on epitaxial graphene on Ru(0001).

    PubMed

    Stradi, Daniele; Garnica, Manuela; Díaz, Cristina; Calleja, Fabián; Barja, Sara; Martín, Nazario; Alcamí, Manuel; Vazquez de Parga, Amadeo L; Miranda, Rodolfo; Martín, Fernando

    2014-12-21

    Achieving control over the self-organization of functional molecules on graphene is critical for the development of graphene technology in organic electronic and spintronic. Here, by using a scanning tunneling microscope (STM), we show that the electron acceptor molecule 7,7',8,8'-tetracyano-p-quinodimethane (TCNQ) and its fluorinated derivative 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyano-p-quinodimethane (F4-TCNQ), co-deposited on the surface of epitaxial graphene on Ru(0001), transform spontaneously into their corresponding magnetic anions and self-organize in two remarkably different structures. TCNQ forms densely packed linear magnetic arrays, while F4-TCNQ molecules remain as isolated non interacting magnets. With the help of density functional theory (DFT) calculations, we trace back the origin of this behavior in the competition between the intermolecular repulsion experienced by the individual charged anions, which tends to separate the molecules, and the delocalization of the electrons transferred from the surface to the molecules, which promotes the formation of molecular oligomers. Our results demonstrate that it is possible to control the spatial arrangement of organic magnetic anions co-adsorbed on a surface by means of chemical substitution, paving the way for the design of two-dimensional fully organic magnetic structures on graphene and on other surfaces.

  8. A comparison of chlorinated organic material produced by chlorine and chlorine dioxide bleaching

    SciTech Connect

    McKaque, A.B.; Reeve, D.W.

    1995-12-31

    Chlorine and chlorine dioxide react differently with pulp during bleaching and produce different types of organic by-products. The main differences are the large reduction in the amount of AOX (adsorbable organic halogen) in the effluent and EOX (extractable organic halogen) in the pulp. This talk reviews the differences in the amounts and types of chlorinated organic by-products produced by the two different bleaching agents.

  9. Anaerobic degradation of adsorbable organic halides (AOX) from pulp and paper industry wastewater.

    PubMed

    Savant, D V; Abdul-Rahman, R; Ranade, D R

    2006-06-01

    Adsorbable organic halides (AOX) are generated in the pulp and paper industry during the bleaching process. These compounds are formed as a result of reaction between residual lignin from wood fibres and chlorine/chlorine compounds used for bleaching. Many of these compounds are recalcitrant and have long half-life periods. Some of them show a tendency to bioaccumulate while some are proven carcinogens and mutagens. Hence, it is necessary to remove or degrade these compounds from wastewater. Physical, chemical and electrochemical methods reported to remove AOX compounds are not economically viable. Different types of aerobic, anaerobic and combined biological treatment processes have been developed for treatment of pulp and paper industry wastewater. Maximum dechlorination is found to occur under anaerobic conditions. However, as these processes are designed specifically for reducing COD and BOD of wastewater, they do not ensure complete removal of AOX. This paper reviews the anaerobic biological treatments developed for pulp and paper industry wastewater and also reviews the specific micro-organisms reported to degrade AOX compounds under anaerobic conditions, their nutritional and biochemical requirements. It is imperative to consider these specific micro-organisms while designing an anaerobic treatment for efficient removal of AOX.

  10. Temperature dependence of infinite dilution activity coefficients in octanol and octanol/water partition coefficients of some volatile halogenated organic compounds

    SciTech Connect

    Bhatai, S.R.; Sandler, S.I.

    1995-11-01

    The study of the fate and transport of volatile halogenated organic compounds in the environment is of interest as these chemicals, many of which have been classified as pollutants, are widely used as industrial solvents and are now appearing in water supplies. Infinite dilution activity coefficients and Henry`s law coefficients have been measured for 11 halogenated C{sub 1} to C{sub 3} compounds in 1-octanol above room temperature using a gas-liquid chromatographic measurement method. Then, using their earlier data for these substances in water and a correlation relating the limiting activity coefficients of a substance in pure water and in pure 1-octanol to their octanol/water partition coefficients, these latter quantities have been computed. One conclusion from these measurements is that the limiting activity coefficients in octanol and the octanol/water partition coefficients of the halogenated compounds studied are only weakly dependent on temperature over the range from 25 to 50 C. Also, from these and their earlier data, have estimated the infinite dilution partial molar excess enthalpies and excess entropies of these compounds in both 1-octanol and water.

  11. 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

  12. 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 ...

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    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.

  15. Pore distribution effect of activated carbon in adsorbing organic micropollutants from natural water.

    PubMed

    Ebie, K; Li, F; Azuma, Y; Yuasa, A; Hagishita, T

    2001-01-01

    Adsorption isotherms of organic micropollutants in coexistence with natural organic matter (NOM) were analyzed to evaluate the impacts of pore size distribution of activated carbon (AC) on the competition effects of the NOM. Single solute adsorption experiments and simultaneous adsorption experiments with NOM contained in a coagulation-pretreated surface water were performed for four agricultural chemicals and three coal-based activated carbons (ACs) having different pore distributions. The results showed that, for all the carbons used, the adsorption capacity of the chemicals was reduced distinctly in the presence of NOM. Such a reduction was more apparent for AC with a larger portion of small pores suitable for the adsorption of small organic molecules and for the agricultural chemicals with a more hydrophilic nature. Ideal adsorbed solution theory (IAST) incorporated with the Freundlich isotherm expression (IAST-Freundlich model) could not interpret the impact of NOM on the adsorption capacity of the chemicals unless a pore blockage effect caused by the adsorption of NOM was also considered. By taking into account this effect, the adsorption isotherm of the chemicals in the presence of NOM was well described, and the capacity reduction caused by the NOM was quantitatively assessed from the viewpoints of the site competition and the pore blockage. Analytical results clearly indicated that pore blockage was an important competition mechanism that contributed to 10-99% of the total capacity reductions of the chemicals, the level depended greatly on the ACs, the chemicals and the equilibrium concentrations, and could possibly be alleviated by broadening the pore size distributions of the ACs to provide a large volume percentage for pores with sizes above 30 A.

  16. 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.

  17. 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.

  18. 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.

  19. Screening Metal-Organic Frameworks by Analysis of Transient Breakthrough of Gas Mixtures in a Fixed Bed Adsorber

    SciTech Connect

    Krishna, Rajamani; Long, Jeffrey R.

    2011-07-07

    Metal–organic frameworks (MOFs) offer considerable potential for separating a variety of mixtures that are important in applications such as CO₂ capture and H₂ purification. In view of the vast number of MOFs that have been synthesized, there is a need for a reliable procedure for comparing screening and ranking MOFs with regard to their anticipated performance in pressure swing adsorption (PSA) units. For this purpose, the most commonly used metrics are the adsorption selectivity and the working capacity. Here, we suggest an additional metric for comparing MOFs that is based on the analysis of the transient response of an adsorber to a step input of a gaseous mixture. For a chosen purity of the gaseous mixture exiting from the adsorber, a dimensionless breakthrough time τ{sub break} can be defined and determined; this metric determines the frequency of required regeneration and influences the productivity of a PSA unit. The values of τ{sub break} are dictated both by selectivity and by capacity metrics .By performing transient adsorber calculations for separation of CO₂/H₂, CO₂/CH₄, CH₄/H₂, and CO₂/CH₄/H₂ mixtures, we compare the values of τbreak to highlight some important advantages of MOFs over conventionally used adsorbents such as zeolite NaX. For a given separation duty, such comparisons provide a more realistic ranking of MOFs than afforded by either selectivity or capacity metrics alone. We conclude that breakthrough calculations can provide an essential tool for screening MOFs.

  20. The Effects of Organic Adsorbates on the Underpotential and Bulk Deposition of Silver on Polycrystalline Platinum Electrodes

    DTIC Science & Technology

    1994-03-14

    the Underpotential and Bulk Deposition of Silver on Polycrystalline Platinum Electrodes S.H. Harford, D.L. Taylor, and H.D. Abrufia Department of...Arlington, VA 22217 i1 iTITLE (Irlude Security Cla$slficatIon) The Effects of Organic Adsorbates on the Underpotential and Bulk Deposition of Silver on...through a nitrogen hetero-atom significantly hinder both the silver underpotential (UPD) and bulk deposition processes. The existence of a Pt/Ag

  1. 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.

  2. 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.

  3. 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.

  4. Evaluation of different adsorbents for large-volume pre-concentration for analyzing atmospheric persistent organic pollutants at trace levels.

    PubMed

    Avino, Pasquale; Cinelli, Giuseppe; Notardonato, Ivan; Russo, Mario Vincenzo

    2011-07-01

    This paper investigates the performance of some adsorbents, Carbopack B, Tenax-GC, and XAD-2, in a SPE and GC analytical method for sampling and determining some persistent organic pollutants such as benzene, toluene, o-, m-, and p-xylenes, naphthalene, anthracene, fluorene, fluoranthene, benzo(i,k)fluorene, pyrene and benzo(a)pyrene, aldrin, dieldrin, endrin, endosulfan, and PCB congeners (nos. 1, 15, 44, 77, and 209). Adsorbents evaluated in this study are Carbopack B, Tenax-GC, and XAD-2. Before applying the analytical method to air samples, it was widely investigated in laboratory: the sampler is constituted by a glass pyrex vial home-filled with 300 mg (sampling section) and 50 mg of adsorbent material (backup section). The re-extraction is performed by CS(2) (1-2 mL) and analysis is performed by GC-FID and GC-ECD. The evaluation of breakthrough volumes and desorption efficiencies shows the XAD-2 performance in the enrichment of different organic species present in atmosphere at trace levels (ppt) to be more advantageous than the other two materials in terms of analytical and technical parameters. One of the advantages is the high volume of sampled air with high concentration factor and limited loss of analytes (breakthrough volumes are higher than 5,000 L g(-1) for high-boiling compounds and higher than 400 L g(-1) for low-boiling solutes). Another advantage is the possibility of easy and speed re-extraction of analytes using small volumes of solvent (a few milliliters). The recoveries are about 100% with a RSD ≤ 2.3 for low-boiling compounds, and between 77% and 109% with a RSD ≤ 5.7% for high-boiling species. The XAD-2 adsorbent was applied to real air samples collected in different polluted areas (urban, industrial, rural, and remote locations) demonstrating the wide application of such methodology in various environmental situation.

  5. Blue emitting halogen-phenoxy substituted 1,8-naphthalimides for potential organic light emitting diode applications

    NASA Astrophysics Data System (ADS)

    Ulla, Hidayath; Raveendra Kiran, M.; Garudachari, B.; Satyanarayan, M. N.; Umesh, G.; Isloor, A. M.

    2014-11-01

    In this paper, we report the synthesis and characterization of six 1,8-naphthalimides [4a-4c and 5a-5c] obtained by the substitution of electron donating halogen-phenoxy groups at the C-4 position. The derivatives were characterized using 1H NMR, 13C NMR, mass spectra, FT-IR, single crystal XRD; photo-physical, thermal, surface morphological and electrochemical properties were also investigated. The derivatives exhibit deep blue photoluminescence in the range 414-423 nm (in CHCl3) and 457-466 nm (in thin film state) on UV excitation with high Stokes' shifts and good chromaticity. The TGA and DSC analysis showed that the derivatives possess good thermal stability (271-284 °C) and melting points (138-201 °C). The HOMO and LUMO energy levels estimated by cyclic voltammetry are in the range 6.21-6.34 eV and 3.31-3.41 eV respectively corresponding to energy band gaps of 2.98-3.15 eV. These energy values are relatively higher than the commonly used electron transporting materials. The optical and electronic properties of the derivatives were tuned by the introduction of different electron donating halogen-phenoxy groups through C-4 position of the naphthalimide moiety. The emissive and electron-transporting properties of the naphthalimide derivative 4a were studied by fabricating a bi-layer and tri-layer devices. Further a phosphorescent device with 4a as electron transport layer (ETL) exhibited superior performance than the device without any ETL and was comparable with the device using standard Alq3 as ETL. These results indicate that the synthesized naphthalimide derivatives could play an important role in the development of OLEDs.

  6. 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

    2012-07-05

    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.

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

    SciTech Connect

    Cernota, Paul Davis

    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 (√7x√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.

  8. 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.

  9. Sorption of organic molecules on surfaces of a microporous polymer adsorbent modified with different quantities of uracil

    NASA Astrophysics Data System (ADS)

    Gus'kov, V. Yu.; Ganieva, A. G.; Kudasheva, F. Kh.

    2016-11-01

    The sorption of organic molecules on the surfaces of a number of adsorbents based on a microporous copolymer of styrene and divinylbenzene modified with different quantities of uracil is studied by means of inverse gas chromatography at infinite dilution. Samples containing 10-6, 10-5, 10-4, 10-3, 10-2, and 0.5 × 10‒1 weight parts of uracil (the pC of uracil ranges from 1.3 to 6) are studied. The contributions from different intermolecular interactions to the Helmholtz energy of sorption are calculated via the linear free energy relationship. It is found that as the concentration of uracil on the surface of the polymer adsorbent grows, the contributions from different intermolecular interactions and the conventional polarity of the surface have a bend at pC = 3, due probably to the formation of a supramolecular structure of uracil. Based on the obtained results, it is concluded that the formation of the supramolecular structure of uracil on the surface of the polymer adsorbent starts when pC < 3.

  10. Novel adsorbent based on multi-walled carbon nanotubes bonding on the external surface of porous silica gel particulates for trapping volatile organic compounds.

    PubMed

    Wang, Li; Liu, Jiemin; Zhao, Peng; Ning, Zhanwu; Fan, Huili

    2010-09-10

    A novel adsorbent, 3-amino-propylsilica gel-multi-walled carbon nanotubes (APSG-MW), was prepared by chemical bonding multi-walled carbon nanotubes on silica gel. The surface area of APSG-MW was 98 m(2)/g, and the particle size was between 60 and 80 mesh with the average size of 215.0 microm. The adsorption capability of the new adsorbent to volatile organic compounds (VOCs) was measured. The effect of water to the adsorbent and its stability during storage were also investigated. Duplicate precision (DP) and distributed volume pair (DVP) on the basis of the EPA TO-17 criteria were estimated. The results showed that the sampling precision of the adsorbent was more superior compared to the MWCNTs because of the better air permeability. The new adsorbent was successfully applied in the determination of VOCs in ambient indoor air.

  11. 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.

  12. 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

  13. 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.

  14. A novel adsorbent obtained by inserting carbon nanotubes into cavities of diatomite and applications for organic dye elimination from contaminated water.

    PubMed

    Yu, Hongwen; Fugetsu, Bunshi

    2010-05-15

    A novel approach is described for establishing adsorbents for elimination of water-soluble organic dyes by using multi-walled carbon nanotubes (MWCNTs) as the adsorptive sites. Agglomerates of MWCNTs were dispersed into individual tubes (dispersed-MWCNTs) using sodium n-dodecyl itaconate mixed with 3-(N,N-dimethylmyristylammonio)-propanesulfonate as the dispersants. The resultant dispersed-MWCNTs were inserted into cavities of diatomite to form composites of diatomite/MWCNTs. These composites were finally immobilized onto the cell walls of flexible polyurethane foams (PUF) through an in situ PUF formation process to produce the foam-like CNT-based adsorbent. Ethidium bromide, acridine orange, methylene blue, eosin B, and eosin Y were chosen to represent typical water-soluble organic dyes for studying the adsorptive capabilities of the foam-like CNT-based adsorbent. For comparisons, adsorptive experiments were also carried out by using agglomerates of the sole MWCNTs as adsorbents. The foam-like CNT-based adsorbents were found to have higher adsorptive capacities than the CNT agglomerates for all five dyes; in addition, they are macro-sized, durable, flexible, hydrophilic and easy to use. Adsorption isotherms plotted based on the Langmuir equation gave linear results, suggesting that the foam-like CNT-based adsorbent functioned in the Langmuir adsorption manner. The foam-like CNT-based adsorbents are reusable after regeneration with aqueous ethanol solution.

  15. Control of the dipole layer of polar organic molecules adsorbed on metal surfaces via different charge-transfer channels

    NASA Astrophysics Data System (ADS)

    Lin, Meng-Kai; Nakayama, Yasuo; Zhuang, Ying-Jie; Su, Kai-Jun; Wang, Chin-Yung; Pi, Tun-Wen; Metz, Sebastian; Papadopoulos, Theodoros A.; Chiang, T.-C.; Ishii, Hisao; Tang, S.-J.

    2017-02-01

    Organic molecules with a permanent electric dipole moment have been widely used as a template for further growth of molecular layers in device structures. Key properties of the resulting organic films such as energy level alignment (ELA), work function, and injection/collection barrier are linked to the magnitude and direction of the dipole moment at the interface. Using angle-resolved photoemission spectroscopy (ARPES), we have systematically investigated the coverage-dependent work function and spectral line shapes of occupied molecular energy states (MESs) of chloroaluminium-phthalocyanine (ClAlPc) grown on Ag(111). We demonstrate that the dipole orientation of the first ClAlPc layer can be controlled by adjusting the deposition rate and postannealing conditions, and we find that the ELA at the interface differs by ˜0.4 eV between the Cl up and down configurations of the adsorbed ClAlPc molecules. These observations are rationalized by density functional theory (DFT) calculations based on a realistic model of the ClAlPc/Ag(111) interface, which reveal that the different orientations of the ClAlPc dipole layer lead to different charge-transfer channels between the adsorbed ClAlPc and Ag(111) substrate. Our findings provide a useful framework toward method development for ELA tuning.

  16. Simulating the performance of fixed-bed granular activated carbon adsorbers: removal of synthetic organic chemicals in the presence of background organic matter.

    PubMed

    Jarvie, Michelle Edith; Hand, David W; Bhuvendralingam, Shanmugalingam; Crittenden, John C; Hokanson, Dave R

    2005-06-01

    Granular activated carbon (GAC) adsorption is an effective treatment technology for the removal of synthetic organic chemicals (SOCs) from drinking water supplies. This treatment process can be expensive if not properly designed. Application of mathematical models is an attractive method to evaluate the impact of process variables on process design and performance. Practical guidelines were developed to select an appropriate model framework and to estimate site-specific model parameters to predict GAC adsorber performance. Pilot plant and field-scale data from 11 different studies were utilized to investigate the effectiveness of this approach in predicting adsorber performance in the presence of background organic batter (BOM). These data represent surface and ground water sources from four different countries. The modeling approach was able to adequately describe fixed-bed adsorber performance for the purpose of determining the carbon usage rate and process design variables. This approach is more accurate at predicting bed life in the presence of BOM than the current methods commonly used by practicing engineers.

  17. Rechargeable zinc halogen battery

    SciTech Connect

    Spaziante, P.M.; Nidola, A.

    1980-01-01

    A rechargeable zinc halogen battery has an aqueous electrolyte containing ions of zinc and halogen and an amount of polysaccharide and/or sorbitol sufficient to prevent zinc dendrite formation during recharging. The electrolyte may also contain trace amounts of metals such as tungsten, molybdenum, and lead. 7 tables.

  18. Quantum transport simulation scheme including strong correlations and its application to organic radicals adsorbed on gold

    NASA Astrophysics Data System (ADS)

    Droghetti, Andrea; Rungger, Ivan

    2017-02-01

    We present a computational method to quantitatively describe the linear-response conductance of nanoscale devices in the Kondo regime. This method relies on a projection scheme to extract an Anderson impurity model from the results of density functional theory and nonequilibrium Green's functions calculations. The Anderson impurity model is then solved by continuous-time quantum Monte Carlo. The developed formalism allows us to separate the different contributions to the transport, including coherent or noncoherent transport channels, and also the quantum interference between impurity and background transmission. We apply the method to a scanning tunneling microscope setup for the 1,3,5-triphenyl-6-oxoverdazyl (TOV) stable radical molecule adsorbed on gold. The TOV molecule has one unpaired electron, which when brought in contact with metal electrodes behaves like a prototypical single Anderson impurity. We evaluate the Kondo temperature, the finite-temperature spectral function, and transport properties, finding good agreement with published experimental results.

  19. Effect of the adsorbate kinetic diameter on the accuracy of the Dubinin-Radushkevich equation for modeling adsorption of organic vapors on activated carbon.

    PubMed

    Jahandar Lashaki, Masoud; Fayaz, Mohammadreza; Niknaddaf, Saeid; Hashisho, Zaher

    2012-11-30

    This paper investigates the effect of the kinetic diameter (KD) of the reference adsorbate on the accuracy of the Dubinin-Radushkevich (D-R) equation for predicting the adsorption isotherms of organic vapors on microporous activated carbon. Adsorption isotherms for 13 organic compounds on microporous beaded activated carbon were experimentally measured, and predicted using the D-R model and affinity coefficients. The affinity coefficients calculated based on molar volumes, molecular polarizabilities, and molecular parachors were used to predict the isotherms based on four reference compounds (4.3≤KD≤6.8 Å). The results show that the affinity coefficients are independent of the calculation method if the reference and test adsorbates are from the same organic group. Choosing a reference adsorbate with a KD similar to that of the test adsorbate results in better prediction of the adsorption isotherm. The relative error between the predicted and the measured adsorption isotherms increases as the absolute difference in the kinetic diameters of the reference and test adsorbates increases. Finally, the proposed hypothesis was used to explain reports of inconsistent findings among published articles. The results from this study are important because they allow a more accurate prediction of adsorption capacities of adsorbents which allow for better design of adsorption systems.

  20. Removing organic contaminants with bifunctional iron modified rectorite as efficient adsorbent and visible light photo-Fenton catalyst.

    PubMed

    Zhao, Xiaorong; Zhu, Lihua; Zhang, Yingying; Yan, Jingchun; Lu, Xiaohua; Huang, Yingping; Tang, Heqing

    2012-05-15

    Iron-modified rectorite (FeR) was prepared as both adsorbent and catalyst. The iron modification increased layer-to-layer spacing and surface area of rectorite, leading to much increased adsorption of Rhodamine B (RhB) on rectorite. The maximum adsorption capacity of RhB on FeR reached 101mgg(-1) at pH 4.5, being 11 folds of that on the unmodified one. The iron modification also enabled rectorite to have efficient visible light photocatalytic ability. The apparent rate constant for the degradation of RhB (80μM) at 298K and pH 4.5 in the presence of H(2)O(2) (6.0mM) and FeR (0.4gL(-1)) was evaluated to be 0.0413min(-1) under visible light and 0.122min(-1) under sunlight, respectively. The analysis with electron spin resonance spin-trapping technique supported that the iron modified rectorite effectively catalyzed the decomposition of H(2)O(2) into hydroxyl radicals. On the basis of the characterization and analysis, the new bifunctional material was well clarified as both adsorbent and photocatalyst in the removing of organic pollutants.

  1. 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.

  2. 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.

  3. Relationship between persistent halogenated organic contaminants and TCDD-toxic equivalents on EROD activity and retinoid and thyroid hormone status in northern fulmars.

    PubMed

    Helgason, Lisa B; Verreault, Jonathan; Braune, Birgit M; Borgå, Katrine; Primicerio, Raul; Jenssen, Bjørn M; Gabrielsen, Geir W

    2010-11-15

    We investigated whether the hepatic cytochrome P450 1A activity (measured as 7-ethoxyresorufin-O-deethylase (EROD)) and plasma thyroid hormone and liver retinoid concentrations were explained by liver and blood levels of halogenated organic contaminants (HOCs) in free-ranging breeding northern fulmars (Fulmarus glacialis) from Bjørnøya in the Norwegian Arctic. Hepatic EROD activity and liver levels of 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs) were positively correlated, suggesting that hepatic EROD activity is a good indicator for dioxin and dioxin-like HOC exposure in breeding northern fulmars. There were not found other strong relationships between HOC concentrations and hepatic EROD activity, plasma thyroid or liver retinoid concentrations in the breeding northern fulmars. It is suggested that the HOC levels found in the breeding northern fulmars sampled on Bjørnøya were too low to affect plasma concentrations of thyroid hormones and liver levels of retinol and retinyl palmitate, and that hepatic EROD activity is a poor indicator of polychlorinated biphenyl (PCB) and pesticide exposure.

  4. 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.

  5. 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.

  6. The Study and Development of Metal Oxide Reactive Adsorbents for the Destruction of Toxic Organic Compounds

    DTIC Science & Technology

    2008-04-15

    exposure of personnel and systems to chemical warfare agents and other toxic organic compounds. The research program that was developed built upon earlier...TASK NUMBER 5f. WORK UNIT NUMBER 5c. PROGRAM ELEMENT NUMBER 5b. GRANT NUMBER 5a. CONTRACT NUMBER W911NF-04-1-0377 406038 Form Approved OMB NO. 0704...of the exposure of personnel and systems to chemical warfare agents and other toxic organic compounds. The research program that was developed

  7. Inorganic Halogen Oxidizer Research

    DTIC Science & Technology

    1975-02-26

    KEY WORDS (Continue on reverse aide il necesxary and identity by block number) Synthesis, Novel Oxidizers, Perchlorates, Fluorination , Halogen...C. J. Schack, R. D. Wilson, and E. C. Curtis, 5th European Fluorine Symposium, Avie.nore, Scotland (September 1974) 20. "New Energetic Halogen...elimination lasers. For NF-, no evidence for protonation was found at tempera- tures as low as -78 C. Furthermore, attempts to fluorinate NH. AsF

  8. 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.).

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

    PubMed

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

    2013-07-09

    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.

  10. Composition of Organic Compounds Adsorbed on PM10 in the Air Above Maribor.

    PubMed

    Miuc, Alen; Vončina, Ernest; Lečnik, Uroš

    2015-01-01

    Organic compounds in atmospheric particulate matterabove Maribor were analysed in 120 samples of PM10 sampled according to the EN 12341:2014 reference method. Organic compounds compositions were investigated together with the primary and secondary sources of air pollution. Silylation as derivatisation method was used for the GC/MS determination of volatile and semi-volatile polar organic compounds. Distribution of fatty acids, n-alkanes and iso-alkanes, phthalate esters, siloxanes, different sterols, various sugars and sugar alcohols, compounds of lignin and resin acids, dicarboxylic acids from photochemical reactions, PAHs, organic nitrogen compounds and products from secondary oxidation of monoterpenes were determined. The use of silicone grease for the purpose of lubricating the impact surface of the air sampler caused higher values of gravimetric determination. Solid particles may have been bounced from the surface of a greasy impact plate and re-entrained within the air stream and then collected on a sample filter. The carryover of siloxanes was at least from 5% up to 15% of the accumulated particles weight, depending on ambient temperature. This was the reason that the gravimetric results for determination of PM10 according to the standard EN 12341:2014 were overestimated.

  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. 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.

  13. 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.

  14. Evaluating topologically diverse metal–organic frameworks for cryo-adsorbed hydrogen storage

    SciTech Connect

    Gómez-Gualdrón, Diego A.; Colón, Yamil J.; Zhang, Xu; Wang, Timothy C.; Chen, Yu-Sheng; Hupp, Joseph T.; Yildirim, Taner; Farha, Omar K.; Zhang, Jian; Snurr, Randall Q.

    2016-01-01

    Metal–organic frameworks (MOFs) are porous materials synthesized by combining inorganic and organic molecular building blocks into crystalline networks of distinct topologies. Due to the combinatorial possibilities, there are millions of possible MOF structures. Aiming to exploit their exceptional tunability, surface areas and pore volumes, researchers have investigated MOFs for storage of gaseous fuels such as hydrogen for over a decade, but a suitable MOF to store hydrogen at ambient conditions has not yet been found. Here, we sought to rapidly determine the viability of using MOFs for hydrogen storage at recently proposed, cryogenic operating conditions. We constructed a large and structurally diverse set of 13 512 potential MOF structures based on 41 different topologies and used molecular simulation to determine MOF hydrogen deliverable capacities between 100 bar/77 K and 5 bar/160 K. The highest volumetric deliverable capacity was 57 g L-1 of MOF, which surpasses the 37 g L-1 of tank of the incumbent technology (compressing hydrogen to 700 bar at ambient temperature). To validate our in silico MOF construction method, we synthesized a new isoreticular family of MOFs (she-MOF-x series) based on the she topology, which is extremely rare among MOFs. To validate our hydrogen storage predictions, we activated and measured hydrogen adsorption on she-MOF-1 and NU-1103. The latter MOF showed outstanding stability and a good combination of volumetric and gravimetric performance, presenting 43.2 g L-1 of MOF and 12.6 wt% volumetric and gravimetric deliverable capacities, respectively.

  15. 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.

  16. 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.

  17. 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

  18. 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

    2016-01-05

    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.

  19. Study of IR laser photoacoustic spectra of organic molecules adsorbed on metal surface

    NASA Astrophysics Data System (ADS)

    Lu, Huizong; Chen, Kaitai; Wang, Zhaoyong

    1987-06-01

    Using a branch-tuning CW CO2 laser in the range of 0.2 to 10.8 microns, the IR photoacoustic spectra of organic molecules absorbed on a silver surface were studied. The absorbed molecular spectra of four layers of arachidic acid and cellulose diacetate with different surface densities was studied. No peak shift was found in a comparison between IR photoacoustic spectra of solid arachidic acid near 944/cm and the corresponding IR Fourier spectra of solid archidic acid. The IR photoacoustic spectra of cellulose diacetate with sigma sub 1 = 14,000/sq cm and sigma sub 1 = 5.5 x 10 to the 15th/sq cm respectively was compared with the corresponding transmission spectra of solid cellulose diacetate. It was found that the peak of the former near 1054/cm had a red shift of about 5/cm while the peak of the latter had no obvious shift within the range of accuracy of the experiment.

  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. 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.

  2. 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.

  3. 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

  4. What is the real effect of halogen atoms? electronic and packing properties of organic semiconductors (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Pei, Jian; Wang, Jie-Yu; Shi, Ke; Zheng, Yu-Qing

    2016-11-01

    N-type semiconductor is a necessary component for high speed and low power dissipation complementary circuits. However, n-type organic field-effect transistors (OFETs) with both high electron mobility and good ambient stability are rare. In this contribution, we develop a strong electron-deficient small molecule, tetrafluorine benzodifurandione-based oligo(p-phenylenevinylene) (4F-BDOPV), for n-type OFETs. 4F-BDOPV has a low LUMO level down to -4.44 eV and a cofacial packing structure in single crystal. These fea-tures provide 4F-BDOPV with good ambient stability and large charge transfer integrals leading to a high electron mobility of up to 12.6 cm2 V-1 s-1 in air, which is among the highest values for n-type OFETs. This work demonstrates a new molecule system for high-performance air-stable n-type OFETs, which is highly promising for single crystal based electronics.

  5. 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

  6. A simple QSPR model for the prediction of the adsorbability of organic compounds onto activated carbon cloth.

    PubMed

    Xu, J; Zhu, L; Fang, D; Liu, L; Bai, Z; Wang, L; Xu, W

    2013-01-01

    A quantitative structure-property relationship (QSPR) model was proposed between the molecular descriptors representing the molecular structure and the Freundlich adsorbability parameter (K) for a set of 55 organic compounds onto activated carbon cloth. The best linear model was composed of three descriptors, which were selected by stepwise multiple linear regression (MLR) analysis. The statistical parameters provided by the linear model were r² = 0.7744, r²(adj) = 0.7551, s = 0.169 for the training set; and r² = 0.6725, r²(adj) = 0.6316, s = 0.196 for the external test set, respectively. The stability and predictive power of the proposed model were further verified using Y-randomization tests, five-fold cross-validation and leave-many-out cross-validation. The model may give some insight into the main structural features that affect the adsorption of the investigated compounds onto activated carbon cloth.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

    2004-04-05

    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

  14. Preparation of organic sulfur adsorbent from coal for adsorption of dibenzothiophene-type compounds in diesel fuel

    SciTech Connect

    Cigdem Shalaby; Xiaoliang Ma; Anning Zhou; Chunshan Song

    2009-05-15

    High-performance organic sulfur adsorbents (OSA) have been prepared from coal by chemical activation for selective adsorption of the refractory sulfur compounds, such as 4-methyl dibenzothiophene and 4,6-dimethyldibenzothiophene, in diesel fuel. The performance of the prepared OSAs for adsorptive desulfurization (ADS) was evaluated in batch and flow adsorption systems at room temperature using a model diesel fuel. It was found that coal rank and preparation conditions, including activation agents (NaOH, KOH, and NaOH + KOH) and their ratio to coal, activation temperature, and time have significant impacts on the yield and ADS performance of the OSAs. The high-performance OSAs can be prepared from different ranks of coal by using NaOH + KOH as an activation agent with an activating-agent-to-coal ratio of 3.5. The yield of OSA increased in the order of lignite < high volatile bituminous coal < medium volatile bituminous coal < anthracite. The OSA-A, which was derived from an anthracite with the highest yield (68 wt %) by the activation at 650{sup o}C for 1 h, gave the best ADS performance among the OSAs from all coal samples tested. The sulfur adsorption capacity of OSA-A reached 0.281 mmol-S/g-A at an equilibrium sulfur concentration of 50 ppmw in the model diesel fuel, which was 155% higher than a commercial coal-derived activated carbon and 35% higher than the best commercial activated carbon among all commercial activated carbons examined in our laboratory. The higher ADS capacity of OSA-A can be attributed to its significantly higher density (2.77 {mu}mol/m{sup 2}) of the adsorption sites on the surface as determined by Langmuir adsorption isotherm, which is related to its oxygen-containing functional groups on the carbonaceous surface as revealed by temperature-programmed desorption analysis. 57 refs., 10 figs., 6 tabs.

  15. 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.

  16. 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.

  17. Application of near infrared spectroscopy for the determination of adsorbed p-nitrophenol on HDTMA organoclay--implications for the removal of organic pollutants from water.

    PubMed

    Zhou, Qin; Xi, Yunfei; He, Hongping; Frost, Ray L

    2008-03-01

    NIR spectroscopy has been used to measure the adsorption of p-nitrophenol on untreated montmorillonite and surfactant exchanged montmorillonite. p-Nitrophenol is characterised by an intense NIR band at 8890 cm(-1) which shifts to 8840 cm(-1) upon adsorption on organoclay. The band was not observed for p-nitrophenol adsorbed on untreated montmorillonite. Both the montmorillonite and the surfactant modified montmorillonite are characterised by NIR bands at 7061 and 6791 cm(-1). The organoclay is characterised by two prominent bands at 5871 and 5667 cm(-1) assigned to the fundamental overtones of the mid-IR bands at 2916 and 2850 cm(-1). A band at 6017 cm(-1) is attributed to the p-nitrophenol adsorbed on the organoclay. The band is not observed for the montmorillonite with adsorbed p-nitrophenol. It is concluded that p-nitrophenol is adsorbed to significantly greater amounts on the organoclay compared with the untreated montmorillonite. The implication is that organoclays are most useful for removing organic molecules from water through adsorption.

  18. Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse.

    PubMed

    Agarwal, Vinayak; Miles, Zachary D; Winter, Jaclyn M; Eustáquio, Alessandra S; El Gamal, Abrahim A; Moore, Bradley S

    2017-01-20

    Naturally produced halogenated compounds are ubiquitous across all domains of life where they perform a multitude of biological functions and adopt a diversity of chemical structures. Accordingly, a diverse collection of enzyme catalysts to install and remove halogens from organic scaffolds has evolved in nature. Accounting for the different chemical properties of the four halogen atoms (fluorine, chlorine, bromine, and iodine) and the diversity and chemical reactivity of their organic substrates, enzymes performing biosynthetic and degradative halogenation chemistry utilize numerous mechanistic strategies involving oxidation, reduction, and substitution. Biosynthetic halogenation reactions range from simple aromatic substitutions to stereoselective C-H functionalizations on remote carbon centers and can initiate the formation of simple to complex ring structures. Dehalogenating enzymes, on the other hand, are best known for removing halogen atoms from man-made organohalogens, yet also function naturally, albeit rarely, in metabolic pathways. This review details the scope and mechanism of nature's halogenation and dehalogenation enzymatic strategies, highlights gaps in our understanding, and posits where new advances in the field might arise in the near future.

  19. 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

  20. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 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...

  1. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 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...

  2. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 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...

  3. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 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...

  4. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 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...

  5. [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.

  6. 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.

  7. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 16 2013-07-01 2013-07-01 false Halogen scrubbers and other halogen... Routing to a Fuel Gas System or a Process § 65.154 Halogen scrubbers and other halogen reduction devices. (a) Halogen scrubber and other halogen reduction device equipment and operating requirements. (1)...

  8. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 15 2010-07-01 2010-07-01 false Halogen scrubbers and other halogen... Routing to a Fuel Gas System or a Process § 65.154 Halogen scrubbers and other halogen reduction devices. (a) Halogen scrubber and other halogen reduction device equipment and operating requirements. (1)...

  9. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 16 2012-07-01 2012-07-01 false Halogen scrubbers and other halogen... Routing to a Fuel Gas System or a Process § 65.154 Halogen scrubbers and other halogen reduction devices. (a) Halogen scrubber and other halogen reduction device equipment and operating requirements. (1)...

  10. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 16 2014-07-01 2014-07-01 false Halogen scrubbers and other halogen... Routing to a Fuel Gas System or a Process § 65.154 Halogen scrubbers and other halogen reduction devices. (a) Halogen scrubber and other halogen reduction device equipment and operating requirements. (1)...

  11. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 15 2011-07-01 2011-07-01 false Halogen scrubbers and other halogen... Routing to a Fuel Gas System or a Process § 65.154 Halogen scrubbers and other halogen reduction devices. (a) Halogen scrubber and other halogen reduction device equipment and operating requirements. (1)...

  12. 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

  13. 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.

  14. An adsorbent performance indicator as a first step evaluation of novel sorbents for gas separations: application to metal-organic frameworks.

    PubMed

    Wiersum, Andrew D; Chang, Jong-San; Serre, Christian; Llewellyn, Philip L

    2013-03-12

    An adsorbent performance indicator (API) is proposed in an effort to initially highlight porous materials of potential interest for PSA separation processes. This expression takes into account working capacities, selectivities, and adsorption energies and additionally uses weighting factors to reflect the specific requirements of a given process. To demonstrate the applicability of the API, we have performed the adsorption of carbon dioxide and methane at room temperature on a number of metal-organic frameworks, a zeolite and a molecular sieve carbon. The API is calculated for two different CO2/CH4 separation case scenarios: "bulk separation" and "natural gas purification". This comparison highlights how the API can be more versatile than previously proposed comparison factors for an initial indication of potential adsorbent performance.

  15. 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

  16. Crystal engineering through halogen bonding

    NASA Astrophysics Data System (ADS)

    Walsh, Rosa Daneen Bailey

    Crystal engineering has been defined as "the understanding of intermolecular interactions in the context of crystal packing and in the utilization of such understanding in the design of new solids with desired physical and chemical properties." The field of crystal engineering is growing rapidly and is generally centered on the use of hydrogen bonding or coordination polymers in the design and synthesis of new materials. Other interactions, such as halogen bonding also lend themselves to crystal design. In halogen-bonding, donation of a lone pair of electrons into the sigma and sigma* orbitals of an acceptor molecule, like elemental iodine or bromine, allows for relatively strong and highly directional interactions. Charge-transfer interactions involving aromatic nitrogen heterocycles and diiodine (I 2) will be discussed. With weaker donors, such as pyrazine, we have prepared target complexes with infinite chain structures consisting of alternating donor and acceptor molecules. But with stronger donors, such as 4,4 '-bipyridine, only simple adducts are formed. Strong donation at one end of the I2 reduces the Lewis acid character at the other end and extended interactions do not form. With some strong donors, reduction in Lewis acidity occurs to the point that the I2 exhibits amphoteric behavior. In these systems, the non-complexed end serves as a Lewis base to a second-bridging I2 molecule to form neutral polyiodine systems. To reduce electronic communication between the two iodine atoms, organoiodides, in which an organic spacer has been inserted between the two iodine atoms, have been employed. The organic spacer also offers a manifold for adjusting the Lewis acidity of the acceptors in these compounds. Acceptors involving more than two iodines provide the possibility of multidirectional extended interactions leading to interesting layered or network solids. Useful acceptors include 1,4-diiodobenzene, 4,4'-diiodobiphenyl, 1,4-diiodotetraflurobenzene, and

  17. Optimization of operating parameters of novel composite adsorbent for organic pollutants removal from POME using response surface methodology.

    PubMed

    Adeleke, A O; Latiff, Ab Aziz Ab; Al-Gheethi, A A; Daud, Zawawi

    2017-05-01

    The present work aimed to develop a novel composite material made up of activated cow bone powder (CBP) as a starting material for reducing chemical oxygen demand (COD) and ammonia-nitrogen (NH3N) from palm oil mill effluent (POME). The optimization of the reduction efficiency was investigated using response surface methodology (RSM). Six independent variables used in the optimization experiments include pH (4-10), speed (0.27-9.66 rcf), contact time (2-24 h), particle size (1-4.35 mm), dilution factor (100-500) and adsorbent dosage (65-125 g/L). The chemical functional groups were determined using Fourier transform irradiation (FTIR). The elemental composition were detected using SEM-EDX, while thermal decomposition was investigated using thermo gravimetric analysis (TGA) in order to determine the effects of carbonization temperature on the adsorbent. The results revealed that the optimal reduction of COD and NH3N from raw POME was observed at pH 10, 50 rpm, within 2 h and 3 mm of particle size as well as at dilution factor of 500 and 125 g L(-1) of adsorbent dosage, the observed and predicted reduction were 89.60 vs. 85.01 and 75.61 vs. 74.04%, respectively for COD and NH3N. The main functional groups in the adsorbent were OH, NH, CO, CC, COC, COH, and CH. The SEM-EDX analysis revealed that the CBP-composite has a smooth surface with high contents of carbon. The activated CBP has very stable temperature profile with no significant weight loss (9.85%). In conclusion, the CBP-composite investigated here has characteristics high potential for the remediation of COD and NH3N from raw POME.

  18. 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).

  19. Novel zwitterionic inorganic-organic hybrids: synthesis of hybrid adsorbents and their applications for Cu2+ removal.

    PubMed

    Dong, Qiang; Liu, Junsheng; Song, Long; Shao, Guoquan

    2011-02-28

    A series of zwitterionic hybrid adsorbents were prepared via the ring-opening polymerization of pyromellitic acid dianhydride (PMDA) and N-[3-(trimethoxysilyl)propyl] ethylene diamine (TMSPEDA), and a subsequent zwitterionic process as well as sol-gel reaction. Their applications for Cu(2+) removal by adsorption were performed. FTIR spectra confirmed the step products. TGA revealed that the initial decomposition temperature (IDT) of these zwitterionic hybrid adsorbents could arrive at near 150°C. DSC showed that T(g) values decreased with an increase in PMDA content in the hybrid matrix. Ion-change capacity (IEC) revealed that the cation-exchange capacities (CIECs) and anion-exchange capacities (AIECs) of these hybrid adsorbents were within the range of 9.13-11.49 and 4.97-6.28 mmol g(-1), respectively. Meanwhile, the CIECs and AIECs exhibit an opposite change trend as PMDA content increases. Adsorption experiment indicated that their adsorptions for Cu(2+) ions followed Lagergren second-order kinetic model, surface adsorption and intraparticle diffusion mechanisms might be the major process. These findings demonstrated that they are promising absorbents for the separation and recovery of Cu(2+) ions from contaminated water.

  20. 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

  1. 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.

  2. Effects of dissolved organic matter on adsorbed Fe(II) reactivity for the reduction of 2-nitrophenol in TiO2 suspensions.

    PubMed

    Zhu, Zhenke; Tao, Liang; Li, Fangbai

    2013-09-01

    Dissolved organic matter (DOM) is widespread in aquatic and terrestrial environments. Iron is the most abundant transition metal in the Earth's crust. The biogeochemistry of iron and the strength of Fe(II) as a reducing agent while adsorbed on minerals are affected by DOM. This study investigated the effects of Fe(II)/DOM interactions on the reduction of 2-nitrophenol (2-NP) in TiO2 suspensions. Kinetic measurements demonstrated that rates (k) of 2-NP reduction by adsorbed Fe(II) species are affected by adding DOM (denoted O-DOM), and the obtained k values under the impact of the Fe(II)/DOM interaction with different molecular weight DOM fractions [including MW<3500Da (L-DOM), 350014000Da (H-DOM)] showed significant differences. The enhanced rates of 2-NP reduction contributed to increases in the amount of adsorbed Fe(II) species and negative shifts in peak oxidation potential values (EP) in CV tests. For different molecular weight DOM fractions, increases in k (O-DOMadsorbed Fe(II) and the lower EP values. In addition, the ETC values were slightly higher in the TiO2 suspension containing the H-DOM fraction as compared the other two DOM fractions, which would further enhance the reduction rate of 2-NP. These findings promote a general understanding of Fe(II)/DOM interactions and their impact on the fate of contaminants in actual subsurface environments.

  3. Ethene/ethane and propene/propane separation via the olefin and paraffin selective metal-organic framework adsorbents CPO-27 and ZIF-8.

    PubMed

    Böhme, Ulrike; Barth, Benjamin; Paula, Carolin; Kuhnt, Andreas; Schwieger, Wilhelm; Mundstock, Alexander; Caro, Jürgen; Hartmann, Martin

    2013-07-09

    Two types of metal-organic frameworks (MOFs) have been synthesized and evaluated in the separation of C2 and C3 olefins and paraffins. Whereas Co2(dhtp) (=Co-CPO-27 = Co-MOF-74) and Mg2(dhtp) show an adsorption selectivity for the olefins ethene and propene over the paraffins ethane and propane, the zeolitic imidazolate framework ZIF-8 behaves in the opposite way and preferentially adsorbs the alkane. Consequently, in breakthrough experiments, the olefins or paraffins, respectively, can be separated.

  4. 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.

  5. Halogen substituted quinolylsalicylaldimines: Four halogens three structural types

    NASA Astrophysics Data System (ADS)

    Sirirak, Jitnapa; Phonsri, Wasinee; Harding, David J.; Harding, Phimphaka; Phommon, Pimonrat; Chaoprasa, Wannapa; Hendry, Rebecca M.; Roseveare, Thomas M.; Adams, Harry

    2013-03-01

    A series of halogen substituted 5-X-N-(8-quinolyl)salicylaldimines (HqsalX, X = F 1, Cl 2, Br 3 and I 4) have been prepared, characterized and the crystal structures of all four are reported. The compounds form stacks, in most cases held together either by π-π or lone pair(N)-π interactions. All compounds exhibit an intramolecular Osbnd H⋯N hydrogen bond with 2 also displaying an intermolecular Osbnd H⋯O hydrogen bonding square. Additional Csbnd H⋯N/O and Csbnd H⋯π interactions serve to link neighbouring HqsalX molecules with 3 and 4 forming narcissistic dimers. While the halogen has a profound effect on the structure it is not involved in either hydrogen or halogen bonding in any of the structures. DFT calculations suggest that the conformational preference is dependent on the halogen.

  6. 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.

  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. RESIDUAL RISK ASSESSMENT: HALOGENATED SOLVENTS

    EPA Science Inventory

    This source category previously subjected to a technology-based standard will be examined to determine if health or ecological risks are significant enough to warrant further regulation for Halogenated Solvent Degreasing Facilities. These assessments utilize existing models and d...

  9. 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.

  10. The physiological and ecological roles of volatile halogen production by marine diatoms

    NASA Astrophysics Data System (ADS)

    Hughes, Claire; Sun, Shuo

    2015-04-01

    Sea-to-air halogen flux is known to have a major impact on catalytic ozone cycling and aerosol formation in the troposphere. The biological production of volatile organic (e.g. bromoform, diiodomethane) and reactive inorganic halogens (e.g. molecular iodine) is believed to play an important role in mediating halogen emissions from the marine environment. Marine diatoms in particular are known to produce the organic and inorganic volatile halogens at high rates in pelagic waters and sea-ice systems. The climate-induced changes in diatom communities that have already been observed and are expected to occur throughout the world's oceans as warming progresses are likely to alter sea-to-air halogen flux. However, we currently have insufficient understanding of the physiological and ecological functions of volatile halogen production to develop modelling tools that can predict the nature and magnitude of the impact. The results of a series of laboratory studies aimed at establishing the physiological and ecological role of volatile halogen production in two marine polar diatoms (Thalassiosira antarctica and Porosira glacialis) will be described in this presentation. We will focus on our work investigating how the activity of the haloperoxidases, a group of enzymes known to be involved in halogenation reactions in marine organisms, is altered by environmental conditions. This will involve exploring the antioxidative defence role proposed for marine haloperoxidases by showing specifically how halogenating activity varies with photosynthetic rate and changes in the ambient light conditions in the two model marine diatoms. We will also present results from our experiments designed to investigate how volatile halogen production is impacted by and influences diatom-bacterial interactions. We will discuss how improved mechanistic understanding like this could pave the way for future volatile halogen-ecosystem model development.

  11. 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.

  12. The halogen bond in the design of functional supramolecular materials: recent advances.

    PubMed

    Priimagi, Arri; Cavallo, Gabriella; Metrangolo, Pierangelo; Resnati, Giuseppe

    2013-11-19

    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

  13. 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.

  14. 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.

  15. Reactive halogen chemistry in the troposphere.

    PubMed

    Saiz-Lopez, Alfonso; von Glasow, Roland

    2012-10-07

    Halogen chemistry is well known for ozone destruction in the stratosphere, however reactive halogens also play an important role in the chemistry of the troposphere. In the last two decades, an increasing number of reactive halogen species have been detected in a wide range of environmental conditions from the polar to the tropical troposphere. Growing observational evidence suggests a regional to global relevance of reactive halogens for the oxidising capacity of the troposphere. This critical review summarises our current understanding and uncertainties of the main halogen photochemistry processes, including the current knowledge of the atmospheric impact of halogen chemistry as well as open questions and future research needs.

  16. 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.

  17. 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

  18. Halogenated compounds from marine algae.

    PubMed

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

    2010-08-09

    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.

  19. 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.

  20. MTBE adsorption on alternative adsorbents and packed bed adsorber performance.

    PubMed

    Rossner, Alfred; Knappe, Detlef R U

    2008-04-01

    Widespread use of the fuel additive methyl tertiary-butyl ether (MTBE) has led to frequent MTBE detections in North American and European drinking water sources. The overall objective of this research was to evaluate the effectiveness of a silicalite zeolite, a carbonaceous resin, and a coconut-shell-based granular activated carbon (GAC) for the removal of MTBE from water. Isotherm and short bed adsorber tests were conducted in ultrapure water and river water to obtain parameters describing MTBE adsorption equilibria and kinetics and to quantify the effect of natural organic matter (NOM) on MTBE adsorption. Both the silicalite zeolite and the carbonaceous resin exhibited larger MTBE adsorption uptakes than the tested GAC. Surface diffusion coefficients describing intraparticle MTBE mass transfer rates were largest for the GAC and smallest for the carbonaceous resin. Pilot tests were conducted to verify MTBE breakthrough curve predictions obtained with the homogeneous surface diffusion model and to evaluate the effect of NOM preloading on packed bed adsorber performance. Results showed that GAC was the most cost-competitive adsorbent when considering adsorbent usage rate only; however, the useful life of an adsorber containing silicalite zeolite was predicted to be approximately 5-6 times longer than that of an equally sized adsorber containing GAC. Pilot column results also showed that NOM preloading did not impair the MTBE removal efficiency of the silicalite zeolite. Thus, it may be possible to regenerate spent silicalite with less energy-intensive methods than those required to regenerate GAC.

  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. Thermochemical properties and phase behavior of halogenated polycyclic aromatic hydrocarbons.

    PubMed

    Fu, Jinxia; Suuberg, Eric M

    2012-03-01

    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), 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 with parent compounds but does not necessarily increase the enthalpy of sublimation. Furthermore, 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 with single halogen-substituted polycyclic aromatic hydrocarbons. In addition, the enthalpy of fusion and melting temperature of these 12 PACs were determined using differential scanning calorimetry and melting point analysis.

  3. Effect of halogenated fluorescent compounds on bioluminescent reactions.

    PubMed

    Kirillova, Tamara N; Gerasimova, Marina A; Nemtseva, Elena V; Kudryasheva, Nadezhda S

    2011-04-01

    The paper investigates an application of luminescent bioassays to monitor the toxicity of organic halides. Effects of xanthene dyes (fluorescein, eosin Y, and erythrosin B), used as model compounds, on bioluminescent reactions of firefly Luciola mingrelica, marine bacteria Photobacterium leiognathi, and hydroid polyp Obelia longissima were studied. Dependence of bioluminescence quenching constants on the atomic weight of halogen substituents in dye molecules was demonstrated. Bacterial bioluminescence was shown to be most sensitive to heavy halogen atoms involved in molecular structure; hence, it is suitable for construction of sensors to monitor toxicity of halogenated compounds. Mechanisms of bioluminescence quenching--energy transfer processes, collisional interactions, and enzyme-dye binding--were considered. Changes of bioluminescence (BL) spectra in the presence of the dyes were analyzed. Interactions of the dyes with enzymes were studied using fluorescence characteristics of the dyes in steady-state and time-resolved experiments. The dependences of fluorescence anisotropy of enzyme-bound dyes, the average fluorescence lifetime, and the number of exponential components in fluorescence decay on the atomic weight of halogen substituents were demonstrated. The results are discussed in terms of "dark effect of heavy halogen atom" in the process of enzyme-dye binding; hydrophobic interactions were assumed to be responsible for the effect.

  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. Removal of Intermediate Aromatic Halogenated DBPs by Activated Carbon Adsorption: A New Approach to Controlling Halogenated DBPs in Chlorinated Drinking Water.

    PubMed

    Jiang, Jingyi; Zhang, Xiangru; Zhu, Xiaohu; Li, Yu

    2017-03-21

    During chlorine disinfection of drinking water, chlorine may react with natural organic matter (NOM) and bromide ion in raw water to generate halogenated disinfection byproducts (DBPs). To mitigate adverse effects from DBP exposure, granular activated carbon (GAC) adsorption has been considered as one of the best available technologies for removing NOM (DBP precursor) in drinking water treatment. Recently, we have found that many aromatic halogenated DBPs form in chlorination, and they act as intermediate DBPs to decompose and form commonly known DBPs including trihalomethanes and haloacetic acids. In this work, we proposed a new approach to controlling drinking water halogenated DBPs by GAC adsorption of intermediate aromatic halogenated DBPs during chlorination, rather than by GAC adsorption of NOM prior to chlorination (i.e., traditional approach). Rapid small-scale column tests were used to simulate GAC adsorption in the new and traditional approaches. Significant reductions of aromatic halogenated DBPs were observed in the effluents with the new approach; the removals of total organic halogen, trihalomethanes, and haloacetic acids by the new approach always exceeded those by the traditional approach; and the effluents with the new approach were considerably less developmentally toxic than those with the traditional approach. Our findings indicate that the new approach is substantially more effective in controlling halogenated DBPs than the traditional approach.

  6. 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.

  7. 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...

  8. 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.

  9. 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.

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

    PubMed Central

    Parker, Kimberly M.; Mitch, William A.

    2016-01-01

    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. PMID:27162335

  11. Measurement of laser activated electron tunneling from semiconductor zinc oxide to adsorbed organic molecules by a matrix assisted laser desorption ionization mass spectrometer.

    PubMed

    Zhong, Hongying; Fu, Jieying; Wang, Xiaoli; Zheng, Shi

    2012-06-04

    Measurement of light induced heterogeneous electron transfer is important for understanding of fundamental processes involved in chemistry, physics and biology, which is still challenging by current techniques. Laser activated electron tunneling (LAET) from semiconductor metal oxides was observed and characterized by a MALDI (matrix assisted laser desorption ionization) mass spectrometer in this work. Nanoparticles of ZnO were placed on a MALDI sample plate. Free fatty acids and derivatives were used as models of organic compounds and directly deposited on the surface of ZnO nanoparticles. Irradiation of UV laser (λ=355 nm) with energy more than the band gap of ZnO produces ions that can be detected in negative mode. When TiO(2) nanoparticles with similar band gap but much lower electron mobility were used, these ions were not observed unless the voltage on the sample plate was increased. The experimental results indicate that laser induced electron tunneling is dependent on the electron mobility and the strength of the electric field. Capture of low energy electrons by charge-deficient atoms of adsorbed organic molecules causes unpaired electron-directed cleavages of chemical bonds in a nonergodic pathway. In positive detection mode, electron tunneling cannot be observed due to the reverse moving direction of electrons. It should be able to expect that laser desorption ionization mass spectrometry is a new technique capable of probing the dynamics of electron tunneling. LAET offers advantages as a new ionization dissociation method for mass spectrometry.

  12. Risk assessment for halogenated solvents

    SciTech Connect

    Travis, C.C.

    1988-01-01

    A recent development in the cancer risk area is the advent of biologically based pharmacokinetic and pharmacodynamic models. These models allow for the incorporation of biological and mechanistic data into the risk assessment process. These advances will not only improve the risk assessment process for halogenated solvents but will stimulate and guide basic research in the biological area.

  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. 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...

  15. 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.

  16. Upflow anaerobic filter for the degradation of adsorbable organic halides (AOX) from bleach composite wastewater of pulp and paper industry.

    PubMed

    Deshmukh, N S; Lapsiya, K L; Savant, D V; Chiplonkar, S A; Yeole, T Y; Dhakephalkar, P K; Ranade, D R

    2009-05-01

    The removal of AOX from bleach plant effluent of pulp and paper industry was studied using upflow anaerobic filter. In this paper biodegradation of AOX at different concentrations and effect of electron donors like acetate and glucose thereon in an upflow anaerobic filter at 20 d HRT is described. Results showed significant improvement in AOX degradation when electron donors such as acetate and glucose were supplemented to the influent. AOX degradation was 88% at 28 mg AOX L(-1) and 28% at 42 mg AOX L(-1). The percent degradation efficiency was enhanced to 90.7, 90.2, and 93.0 at 28 mg AOX L(-1) when the influent was supplemented with glucose, acetate and both glucose and acetate, respectively. Similarly, the efficiency was 57, 56.6 and 79.6 at 42 mg AOX L(-1) when the influent was supplemented with glucose, acetate and both glucose and acetate, respectively. The GC-MS analysis data indicated that supplementation of the influent with electron donor increased the biodegradability of number of chlorinated organic compounds.

  17. Excited-state potential-energy surfaces of metal-adsorbed organic molecules from linear expansion Δ-self-consistent field density-functional theory (ΔSCF-DFT)

    NASA Astrophysics Data System (ADS)

    Maurer, Reinhard J.; Reuter, Karsten

    2013-07-01

    Accurate and efficient simulation of excited state properties is an important and much aspired cornerstone in the study of adsorbate dynamics on metal surfaces. To this end, the recently proposed linear expansion Δ-self-consistent field method by Gavnholt et al. [Phys. Rev. B 78, 075441 (2008)], 10.1103/PhysRevB.78.075441 presents an efficient alternative to time consuming quasi-particle calculations. In this method, the standard Kohn-Sham equations of density-functional theory are solved with the constraint of a non-equilibrium occupation in a region of Hilbert-space resembling gas-phase orbitals of the adsorbate. In this work, we discuss the applicability of this method for the excited-state dynamics of metal-surface mounted organic adsorbates, specifically in the context of molecular switching. We present necessary advancements to allow for a consistent quality description of excited-state potential-energy surfaces (PESs), and illustrate the concept with the application to Azobenzene adsorbed on Ag(111) and Au(111) surfaces. We find that the explicit inclusion of substrate electronic states modifies the topologies of intra-molecular excited-state PESs of the molecule due to image charge and hybridization effects. While the molecule in gas phase shows a clear energetic separation of resonances that induce isomerization and backreaction, the surface-adsorbed molecule does not. The concomitant possibly simultaneous induction of both processes would lead to a significantly reduced switching efficiency of such a mechanism.

  18. 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

  19. High-Quality Metal–Organic Framework ZIF-8 Membrane Supported on Electrodeposited ZnO/2-methylimidazole Nanocomposite: Efficient Adsorbent for the Enrichment of Acidic Drugs

    PubMed Central

    Wu, Mian; Ye, Huili; Zhao, Faqiong; Zeng, Baizhao

    2017-01-01

    Metal–organic framework (MOF) membranes have received increasing attention as adsorbents, yet the defects in most membrane structures greatly thwart their capacity performance. In this work, we fabricated a novel ZnO/2-methylimidazole nanocomposite with multiple morphology by electrochemical method. The nanocomposite provided sufficient and strong anchorages for the zeolitic imidazolate frameworks-8 (ZIF-8) membrane. Thus, a crack-free and uniform MOF membrane with high performance was successfully obtained. In this case, 2-methylimidazole was believed to react with ZnO to form uniform ZIF nuclei, which induced and guided the growth of ZIF-8 membrane. The as-prepared ZIF-8 membrane had large surface area and good thermal stability. As expected, it displayed high adsorption capacity for acidic drugs (e.g., ibuprofen, ketoprofen and acetylsalicylic acid) as they could interact through hydrophobic, hydrogen bonding and π-π stacking interaction. Accordingly, by coupling with gas chromatography the ZIF-8 membrane was successfully applied to the real-time dynamic monitoring of ibuprofen in patient’s urine. PMID:28051129

  20. High-Quality Metal–Organic Framework ZIF-8 Membrane Supported on Electrodeposited ZnO/2-methylimidazole Nanocomposite: Efficient Adsorbent for the Enrichment of Acidic Drugs

    NASA Astrophysics Data System (ADS)

    Wu, Mian; Ye, Huili; Zhao, Faqiong; Zeng, Baizhao

    2017-01-01

    Metal–organic framework (MOF) membranes have received increasing attention as adsorbents, yet the defects in most membrane structures greatly thwart their capacity performance. In this work, we fabricated a novel ZnO/2-methylimidazole nanocomposite with multiple morphology by electrochemical method. The nanocomposite provided sufficient and strong anchorages for the zeolitic imidazolate frameworks-8 (ZIF-8) membrane. Thus, a crack-free and uniform MOF membrane with high performance was successfully obtained. In this case, 2-methylimidazole was believed to react with ZnO to form uniform ZIF nuclei, which induced and guided the growth of ZIF-8 membrane. The as-prepared ZIF-8 membrane had large surface area and good thermal stability. As expected, it displayed high adsorption capacity for acidic drugs (e.g., ibuprofen, ketoprofen and acetylsalicylic acid) as they could interact through hydrophobic, hydrogen bonding and π-π stacking interaction. Accordingly, by coupling with gas chromatography the ZIF-8 membrane was successfully applied to the real-time dynamic monitoring of ibuprofen in patient’s urine.

  1. Magnetic metal-organic nanotubes: An adsorbent for magnetic solid-phase extraction of polychlorinated biphenyls from environmental and biological samples.

    PubMed

    Li, Qiu-Lin; Wang, Lei-Lei; Wang, Xia; Wang, Ming-Lin; Zhao, Ru-Song

    2016-06-03

    A new type of three-dimensional, echinus-like magnetic Fe3O4 @ cobalt(Ⅱ)-based metal-organic nanotube (Fe3O4 @ Co-MONT) yolk-shell microspheres, have been designed and synthesized for the first time. Fe3O4 @ Co-MONTs yolk-shell microspheres were characterized by scanning electron micrographs, transmission electron microscopy, Fourier transform infrared spectra, X-ray diffraction, and vibrating sample magnetometry. The feasibility of the new material for use as an absorbent was investigated for magnetic solid phase-extraction (MSPE) of polychlorinated biphenyls (PCBs) from environmental water samples and biological samples. The Plackett-Burman design and Box-Behnken design were used to determine and optimize the extraction parameters influencing the extraction efficiency through response surface methodology. Under the optimized conditions, the developed method showed good linearity within the range of 5-1000ngL(-1), low limits of detection (0.31-0.49ngL(-1)), and good reproducibility (RSD<10%). The proposed method was successfully applied for the analysis of PCBs in real environmental water samples. These results demonstrated that Fe3O4 @ Co-MONTs is a promising adsorbent material for the MSPE of PCBs at trace levels from environmental water samples and biological samples.

  2. Development of a novel polystyrene/metal-organic framework-199 electrospun nanofiber adsorbent for thin film microextraction of aldehydes in human urine.

    PubMed

    Liu, Feilong; Xu, Hui

    2017-01-01

    In this work, electrospun polystyrene/metal-organic frameworks-199 (PS/MOF-199) nanofiber film was synthesized and investigated as a novel adsorbent for thin film microextraction (TFME) of aldehydes in human urine. Some properties of the prepared PS/MOF-199 nanofiber film, including morphology, structure, wettability, solvent stability and extraction performance were studied systematically. Porous fibrous structure, large surface area, good stability, strong hydrophobicity and excellent extraction efficiency were obtained for the film. Based on the PS/MOF-199 film, a thin film microextraction-high performance liquid chromatography (TFME-HPLC) method was developed, and the experimental parameters that affected the extraction and desorption were optimized. Under the optimal conditions, the limits of detection (LODs) were in the range of 4.2-17.3nmolL(-1) for the analysis of six aldehydes. Good linearity was achieved with correlation coefficients (R(2)) being lager than 0.9943. Satisfactory recovery (82-112%) and acceptable reproducibility (relative standard deviation: 2.1-13.3%) were also obtained for the method. The developed TFME-HPLC method has been successfully applied to the analysis of aldehyde metabolites in the urine samples of lung cancer patients and healthy people. The method possesses the advantages of simplicity, rapidity, cost-effective, sensitivity and non-invasion, it provides an alternative tool for the determination of aldehydes in complex sample matrices.

  3. Fine-Tuning of the Carbon Dioxide Capture Capability of Diamine-Grafted Metal-Organic Framework Adsorbents Through Amine Functionalization.

    PubMed

    Jo, Hyuna; Lee, Woo Ram; Kim, Nam Woo; Jung, Hyun; Lim, Kwang Soo; Kim, Jeong Eun; Kang, Dong Won; Lee, Hanyeong; Hiremath, Vishwanath; Seo, Jeong Gil; Jin, Hailian; Moon, Dohyun; Han, Sang Soo; Hong, Chang Seop

    2017-02-08

    A combined sonication and microwave irradiation procedure provides the most effective functionalization of ethylenediamine (en) and branched primary diamines of 1-methylethylenediamine (men) and 1,1-dimethylethylenediamine (den) onto the open metal sites of Mg2 (dobpdc) (1). The CO2 capacities of the advanced adsorbents 1-en and 1-men under simulated flue gas conditions are 19 wt % and 17.4 wt %, respectively, which are the highest values reported among amine-functionalized metal-organic frameworks (MOFs) to date. Moreover, 1-den exhibits both a significant working capacity (12.2 wt %) and superb CO2 uptake (11 wt %) at 3 % CO2 . Additionally, this framework showcases the superior recyclability; ultrahigh stability after exposure to O2 , moisture, and SO2 ; and exceptional CO2 adsorption capacity under humid conditions, which are unprecedented among MOFs. We also elucidate that the performance of CO2 adsorption can be controlled by the structure of the diamine ligands grafted such as the number of amine end groups or the presence of side groups, which provides the first systematic and comprehensive demonstration of fine-tuning of CO2 uptake capability using different amines.

  4. 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%.

  5. 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.

  6. 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.

  7. Influence of saponins on the biodegradation of halogenated phenols.

    PubMed

    Kaczorek, Ewa; Smułek, Wojciech; Zdarta, Agata; Sawczuk, Agata; Zgoła-Grześkowiak, Agnieszka

    2016-09-01

    Biotransformation of aromatic compounds is a challenge due to their low aqueous solubility and sorptive losses. The main obstacle in this process is binding of organic pollutants to the microbial cell surface. To overcome these, we applied saponins from plant extract to the microbial culture, to increase pollutants solubility and enhance diffusive massive transfer. This study investigated the efficiency of Quillaja saponaria and Sapindus mukorossi saponins-rich extracts on biodegradation of halogenated phenols by Raoultella planticola WS2 and Pseudomonas sp. OS2, as an effect of cell surface modification of tested strains. Both strains display changes in inner membrane permeability and cell surface hydrophobicity in the presence of saponins during the process of halogenated phenols biotransformation. This allows them to more efficient pollutants removal from the environment. However, only in case of the Pseudomonas sp. OS2 the addition of surfactants to the culture improved effectiveness of bromo-, chloro- and fluorophenols biodegradation. Also introduction of surfactant allowed higher biodegradability of halogenated phenols and can shorten the process. Therefore this suggests that usage of plant saponins can indicate more successful halogenated phenols biodegradation for selected strains.

  8. Halogenated carbazoles induce cardiotoxicity in developing zebrafish (Danio rerio) embryos.

    PubMed

    Fang, Mingliang; Guo, Jiehong; Chen, Da; Li, An; Hinton, David E; Dong, Wu

    2016-10-01

    Halogenated carbazoles are increasingly identified as a novel class of environmental contaminants. However, no in vivo acute toxicity information on those compounds was available. In the present study, an in vivo zebrafish embryonic model (Danio rerio) was used to investigate the developmental toxicity of those halogenated carbazoles. The results suggested that acute toxicity was structure-dependent. Two of the 6 tested carbazoles, 2,7-dibromocarbazole (27-DBCZ) and 2,3,6,7-tetrachlorocarbazole, showed obvious developmental toxicity at nanomolar levels. The typical phenotypes were similar to dioxin-induced cardiotoxicity, including swollen yolk sac, pericardial sac edema, elongated and unlooped heart, and lower jaw shortening. During embryonic development 27-DBCZ also induced a unique pigmentation decrease. Gene expression and protein staining of cytochrome P4501A (CYP1A) showed that both halogenated carbazoles could induce CYP1A expression at the micromolar level and primarily in the heart area, which was similar to dioxin activity. Further, aryl hydrocarbon receptor-(AhR)2 gene knockdown with morpholino confirmed that the acute cardiotoxicity is AhR-dependent. In conclusion, the results demonstrate that halogenated carbazoles represent yet another class of persistent organic pollutants with dioxin-like activity in an in vivo animal model. Environ Toxicol Chem 2016;35:2523-2529. © 2016 SETAC.

  9. 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...

  10. 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

  11. 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)

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

    NASA Astrophysics Data System (ADS)

    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).

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Stereoselective Halogenation in Natural Product Synthesis.

    PubMed

    Chung, Won-jin; Vanderwal, Christopher D

    2016-03-24

    At last count, nearly 5000 halogenated natural products have been discovered. In approximately half of these compounds, the carbon atom to which the halogen is bound is sp(3) -hybridized; therefore, there are an enormous number of natural products for which stereocontrolled halogenation must be a critical component of any synthesis strategy. In this Review, we critically discuss the methods and strategies used for stereoselective introduction of halogen atoms in the context of natural product synthesis. Using the successes of the past, we also attempt to identify gaps in our synthesis technology that would aid the synthesis of halogenated natural products, as well as existing methods that have not yet seen application in complex molecule synthesis. The chemistry described herein demonstrates yet again how natural products continue to provide the inspiration for critical advances in chemical synthesis.

  19. 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...

  20. 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

  1. 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.

  2. Bacterial dehalogenation of halogenated alkanes and fatty acids.

    PubMed Central

    Omori, T; Alexander, M

    1978-01-01

    Sewage samples dehalogenated 1,9-dichloronane, 1-chloroheptane, and 6-bromohexanoate, but an organism able to use 1,9-dichlorononane as the sole carbon source could not be isolated from these samples. Resting cells of Pseudomonas sp. grown on n-undecane, but not cells grown on glycerol, dehalogenated 1,9-dichlorononane in the presence of chloramphenicol. Resting cells of five other n-undecane-utilizing bacteria cleaved the halogen from dichlorononane and 6-bromohexanoate, and four dehalogenated 1-chloroheptane; however, none of these organisms used 1,9-dichlorononane for growth. By contrast, four benzoate-utilizing bacteria removed bromine from 6-bromohexanoate but had little or no activity on the chlorinated hydrocarbons. Incubation of sewage with 1,9-dichlorononane increased its subsequent capacity to dehalogenate 1,9-dichlorononane and 6-bromohexanoate but not 1-chloroheptane. A soil isolate could dehalogenate several dichloralkanes, three halogenated heptanes, and halogen-containing fatty acids. An enzyme preparation from this bacterium released chloride from 1,9-dichlorononane. PMID:655703

  3. Insights into halogen bond-driven enantioseparations.

    PubMed

    Peluso, Paola; Mamane, Victor; Aubert, Emmanuel; Dessì, Alessandro; Dallocchio, Roberto; Dore, Antonio; Pale, Patrick; Cossu, Sergio

    2016-10-07

    Although the halogen bond (XB) has been so far mainly studied in silico and in the solid state, its potential impact in solution is yet to be fully understood. In this study, we describe the first systematic investigation on the halogen bond in solvated environment by high-performance liquid chromatography (HPLC). Thirty three atropisomeric polyhalogenated-4,4'-bipyridines (HBipys), containing Cl, Br and I as substituents, were selected and used as potential XB donors (XBDs) on two cellulose-based chiral stationary phases (CSPs) containing potential XB acceptors (XBAs). The impact of the halogens on the enantiodiscrimination mechanism was investigated and iodine showed a pivotal role on the enantioseparation in non-polar medium. Electrostatic potentials (EPs) were computed to understand the electrostatic component of CSP-analyte interaction. Moreover, van't Hoff studies for ten HBipys were performed and the thermodynamic parameters governing the halogen-dependent enantioseparations are discussed. Finally, a molecular dynamic (MD) simulation is proposed to model halogen bond in polysaccharide-analyte complexes by inclusion of a charged extra point to represent the positive 'σ-hole' on the halogen atom. On the basis of both experimental results and theoretical data, we have profiled the halogen bond as a chemo-, regio-, site- and stereoselective interaction which can work in HPLC environment besides other known interactions based on the complementarity between selector and selectand.

  4. Chemical reactivity of polycyclic organic compounds adsorbed on coal fly ash and related solid surfaces. Progress report, May 1985-April 1986

    SciTech Connect

    Mamantov, G.; Wehry, E.L.

    1986-04-01

    The fundamental objectives of this research are to characterize and understand the photochemical and nonphotochemical reactivity of polycyclic aromatic hydrocarbons (PAHs) and their derivatives as adsorbates on the surface of coal fly ash and related particulate solids. Specific efforts undertaken and results obtained during this period are summarized with detailed discussions presented in the form of Appendices. Results are tabulated from a thorough examination of the photochemistry of pyrene, benzo(a)pyrene (BaP), anthracene, phenanthrene, and benz(a)anthracene (BaA) as adsorbates on eight coal stack ashes. A procedure was developed to separate coal ashes into carbon and iron contents. Attempts to measure heats of absorption of PAHs on various coal ashes were made. Pyrene nitration occurred only when NO/sub 2/ was contaminated with nitric acid.

  5. 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.

  6. 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.

  7. 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.

  8. Organic waste destruction by indirect electrooxidation

    SciTech Connect

    Leffrang, U.; Ebert, K.; Flory, K.

    1995-04-01

    The destruction of organic model substances by indirect electrooxidation was investigated. The oxidation agent Co(III) was used because of the high redox potential of the Co(III)/Co(II) redox couple (E{sub O}=1.808 V). Experiments were performed in a batch and in a continuous electrolytic cell by using various model substances (especially phenol and different chlorophenols). Intermediate and final products of the oxidation were identified and quantified. Organic carbon is ultimately transformed to CO{sub 2} and to small amounts of CO. The residual carbon in the process solution was determined by TOC measurement to be about 20 ppm. Organic chlorine is oxidized via chlorate to perchlorate. The remaining amount of adsorbable organic halogens (AOX) was less than 3 ppm. Based on these results, a pilot plant was constructed and is presently in operation.

  9. 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

  10. Cross-reactivity of Halogenated Platinum Salts

    EPA Science Inventory

    Halogenated platinum (Pt) salts are well-known respiratory sensitizers associated with the development of asthma. People may be exposed to a variety of platinum compounds in different contexts (e.g. occupationally, automobile exhaust). Published reports suggest that sensitizati...

  11. Energy efficient alternatives to halogen torchieres

    SciTech Connect

    Siminovitch, M.; Marr, L.; Mitchell, J.; Page, E.

    1997-03-01

    A series of novel energy efficient torchiere systems have been developed using compact fluorescent lamps (CFLs). These systems were studied photometrically and compared with the performance of traditional commercially available tungsten halogen sources. Gonio-photometric data and power assessments indicate that significant lighting energy savings can be obtained by utilizing CFL sources instead of standard tungsten halogen sources. This energy savings is jointly due to the higher source efficacy of the CFLs and the surprisingly poor performance of the imported 300 Watt halogen lamps. Experimental data shows that a 50 to 60 Watt CFL will effectively lumen match a variety of 300 Watt tungsten halogen sources with 5 to 10 times the efficacy. CFL torchieres have additional benefits of higher power quality and cooler lamp operating temperature, making them safer fixtures.

  12. Latest generation of halogen-containing pesticides.

    PubMed

    Jeschke, Peter

    2017-02-01

    Agriculture is confronted with enormous challenges, from production of enough high-quality food to water use, environmental impacts and issues combined with a continually growing world population. Modern agricultural chemistry has to support farmers by providing innovative agrichemicals, used in applied agriculture. In this context, the introduction of halogen atoms into an active ingredient is still an important tool to modulate the properties of new crop protection compounds. Since 2010, around 96% of the launched products (herbicides, fungicides, insecticides/acaricides and nematicides) contain halogen atoms. The launched nematicides contain the largest number of halogen atoms, followed by insecticides/acaricides, herbicides and fungicides. In this context, fungicides and herbicides contain in most cases fluorine atoms, whereas nematicides and insecticides contain in most cases 'mixed' halogen atoms, for example chlorine and fluorine. This review gives an overview of the latest generation of halogen-containing pesticides launched over the past 6 years and describes current halogen-containing development candidates. © 2017 Society of Chemical Industry.

  13. Application of the CAPRAM Halogen Module 2.0 in mixed urban and maritime coastal areas

    NASA Astrophysics Data System (ADS)

    Bräuer, Peter; Tilgner, Andreas; Wolke, Ralf; Herrmann, Hartmut

    2013-04-01

    Approximately 20% of the earth's surface is covered with coastal regions. About one half of the world's population live in these areas (Gelpke and Visbeck, 2010). Therefore, there is a great interest to understand interactions of marine and continental air masses in coastal areas. A comprehensive halogen multiphase chemical mechanism, the CAPRAM Halogen Module 2.0 (HM2), together with the multiphase chemical mechanism RACM-MIM2ext/CAPRAM 3.0n has been used to investigate the tropospheric multiphase chemistry in coastal areas, where clean marine air masses mix with urban air masses. While marine air masses are strongly influenced by halogen chemistry expressed in the HM2, urban air masses are affected by organic chemistry (implemented in CAPRAM 3.0). An innovation of the HM2 is the linkage of organic and halogen chemistry in an explicit chemical mechanism. Two different scenarios have been used to investigate the interactions of halogens with organic and inorganic systems. In the first scenario, a maritime air mass moves over an urban area while in the second scenario, a polluted air mass passes the coastal ocean. Both scenarios include non-permanent clouds with 8 cloud passages of the air parcel, which allows the investigation of the influence of clouds on the halogen multiphase chemistry. As an advantage of this scenario not only the chemistry under non- and in-cloud conditions can be investigated, but under cloud formation and evaporation conditions as well. Furthermore, modifications of the air parcel after cloud passages are noticeable. Besides investigations of the concentration-time profiles of important halogen and non-halogen species, detailed time-resolved flux analyses have been performed to determine the most important chemical cycles and to understand the time evolution of the concentration profiles. The simulations have shown that the influence of the origin of the air mass is significant only on the first day. Thereafter, the emissions of the new

  14. 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.

  15. 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

    2016-09-06

    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.

  16. 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.

  17. 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.

  18. 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.

  19. Volume reduction of nonaqueous media contaminated with a highly halogenated model compound using superoxide.

    PubMed

    Furman, Olha S; Teel, Amy L; Watts, Richard J

    2010-02-10

    Highly halogenated organic compounds, which include polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins (PCDDs) formed during the synthesis of pentachlorophenol and chlorophenoxy herbicides, are often found as contaminants in less toxic nonaqueous media, such as waste oil, oily sludges, or biosolids. Superoxide is highly reactive with halogenated compounds when both are dissolved in nonaqueous media; however, superoxide is most economically generated in water, where it is unreactive with most organic compounds. Superoxide reactivity was investigated in organic solvent-water systems as a basis for treating halogenated contaminants in less toxic nonaqueous media. Such a process could potentially render a contaminated oil or sludge nonhazardous, providing a mechanism for waste volume reduction. Increasing amounts of water added to acetone and dimethyl sulfoxide systems decreased the activity of superoxide in the solvent, but enough activity remained for effective treatment. Superoxide was then generated in the aqueous phase of two-phase water-organic solvent systems, and significant superoxide activity was achieved in the organic media with the addition of phase transfer catalysts (PTCs) to transfer superoxide into the nonaqueous phase. The results of this research demonstrate that superoxide, which can be generated in water electrochemically or through the catalytic decomposition of peroxygens, has the potential to be transferred to oils, sludges, and other less toxic nonaqueous media to destroy highly refractory contaminants such as PCBs, PCDDs, and other halogenated contaminants.

  20. 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

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

    DOEpatents

    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.

  2. 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.

  3. 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

  4. The effect of halogenated hydantoins on biofilms

    SciTech Connect

    Ludyanskiy, M.L.; Himpler, F.J.

    1997-12-01

    The biocidal efficacy of halogenated hydantoins against laboratory-prepared biofilms was compared to the free halogen donors NaOCl and NaOBr. Higher biocide concentrations were required to control a filamentous biofilm than to control free floating planktonic bacteria. Control of a biocide-resistant S. antans biofilm was best obtained with a repeated slug+3 hour continuous treatment procedure or with conventional continuous biocide treatment. A bromine, methylethylhydantoin-containing oxidizing biocide (BrMEH) was found to be more efficacious than either free chlorine or free bromine in controlling filamentous biofilms. Previous studies indicating the inability of free chlorine to penetrate biofilms were supported as the combination of free and combined halogen was demonstrated to be more effective than free chlorine or bromine alone against attached bacteria.

  5. 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.

  6. 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...

  7. 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.

  8. Effects of feed-borne Fusarium mycotoxins and an organic mycotoxin adsorbent on immune cell dynamics in the jejunum of chickens infected with Eimeria maxima.

    PubMed

    Girgis, George N; Barta, John R; Girish, Channarayapatna K; Karrow, Niel A; Boermans, Herman J; Smith, Trevor K

    2010-12-01

    An experiment was conducted to explore the effects of Fusarium mycotoxins, common animal feed contaminants, on intestinal immune responses to coccidia (Eimeria) in chickens. Effects of feed-borne Fusarium mycotoxins and a polymeric glucomannan mycotoxin adsorbent (GMA) on immune cell populations were studied in the jejunum of broiler breeder pullets using an Eimeria maxima infection model. Birds were fed a control diet, a diet naturally contaminated with Fusarium mycotoxins, contaminated diet plus 0.2% GMA, or control diet plus 0.2% GMA. Contaminated diets contained up to 6.5μg/g deoxynivalenol (DON), 0.47μg/g 15-acetyl-DON and 0.73μg/g zearalenone. Birds received a primary oral inoculation (1000 oocysts/bird) with E. maxima USDA strain 68 at 2 weeks of age and a secondary oral inoculation (30,000 oocysts/bird) with the same strain at 4 weeks of age. Diet-related differences in CD4(+) cell, CD8(+) cell and macrophage recruitment pattern into the jejunum were observed following both the primary and secondary infections. It was concluded that feed-borne Fusarium mycotoxins and GMA have the potential to modulate immune response to coccidial infections.

  9. Graphene oxide/Fe3O4/chitosan nanocomposite: a recoverable and recyclable adsorbent for organic dyes removal. Application to methylene blue

    NASA Astrophysics Data System (ADS)

    Tran, Hoang V.; Bui, Lieu T.; Dinh, Thuy T.; Le, Dang H.; Huynh, Chinh D.; Trinh, Anh X.

    2017-03-01

    In this research, the potential of chitosan/Fe3O4/graphene oxide (CS/Fe3O4/GO) nanocomposite for efficient removal of methylene blue (MB) as a cationic dye from aqueous solutions was investigated. For this purpose, first, graphene oxide (GO) was prepared from pencil’s graphite by Hummer’s method, then after, CS/Fe3O4/GO was synthesized via chemical co-precipitation method from a mixture solution of GO, Fe3+, Fe2+ and chitosan. The synthesized CS/Fe3O4/GO was characterized by XRD, VSM and SEM techniques. Also, the various parameters affecting dye removal were investigated. Dye adsorption equilibrium data were fitted well to the Langmuir isotherm rather than Freundlich isotherm. The maximum monolayer capacity (q max), was calculated from the Langmuir as 30.10 mg · g‑1. The results show that, CS/Fe3O4/GO nanocomposite, can be used as a cheap and efficient adsorbent for removal of cationic dyes from aqueous solutions.

  10. Halogen-enriched fragment libraries as chemical probes for harnessing halogen bonding in fragment-based lead discovery.

    PubMed

    Zimmermann, Markus O; Lange, Andreas; Wilcken, Rainer; Cieslik, Markus B; Exner, Thomas E; Joerger, Andreas C; Koch, Pierre; Boeckler, Frank M

    2014-04-01

    Halogen bonding has recently experienced a renaissance, gaining increased recognition as a useful molecular interaction in the life sciences. Halogen bonds are favorable, fairly directional interactions between an electropositive region on the halogen (the σ-hole) and a number of different nucleophilic interaction partners. Some aspects of halogen bonding are not yet understood well enough to take full advantage of its potential in drug discovery. We describe and present the concept of halogen-enriched fragment libraries. These libraries consist of unique chemical probes, facilitating the identification of favorable halogen bonds by sharing the advantages of classical fragment-based screening. Besides providing insights into the nature and applicability of halogen bonding, halogen-enriched fragment libraries provide smart starting points for hit-to-lead evolution.

  11. 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... Specific Chemical Substances § 721.329 Halogenated benzyl ester acrylate (generic). (a) Chemical substance... halogenated benzyl ester acrylate (PMN P-90-1527) is subject to reporting under this section for...

  12. 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... Specific Chemical Substances § 721.329 Halogenated benzyl ester acrylate (generic). (a) Chemical substance... halogenated benzyl ester acrylate (PMN P-90-1527) is subject to reporting under this section for...

  13. 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... Specific Chemical Substances § 721.329 Halogenated benzyl ester acrylate (generic). (a) Chemical substance... halogenated benzyl ester acrylate (PMN P-90-1527) is subject to reporting under this section for...

  14. 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... Specific Chemical Substances § 721.329 Halogenated benzyl ester acrylate (generic). (a) Chemical substance... halogenated benzyl ester acrylate (PMN P-90-1527) is subject to reporting under this section for...

  15. 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... Specific Chemical Substances § 721.329 Halogenated benzyl ester acrylate (generic). (a) Chemical substance... halogenated benzyl ester acrylate (PMN P-90-1527) is subject to reporting under this section for...

  16. 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.

  17. 40 CFR 721.536 - Halogenated phenyl alkane.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated phenyl alkane. 721.536... 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)...

  18. 40 CFR 721.535 - Halogenated alkane (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkane (generic). 721.535... 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...

  19. 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...

  20. 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...

  1. 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...

  2. 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...

  3. 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...

  4. 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...

  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. 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...

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. Mouse Model of Halogenated Platinum Salt Hypersensitivity

    EPA Science Inventory

    Occupational exposure to halogenated platinum salts can trigger the development of asthma. Concern for increased asthma risk exists for the general population due to the use of platinum (Pt) in catalytic converters and its emerging use as a diesel fuel additive. To investigate a...

  12. 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...

  13. Genotoxic activity of halogenated phenylglycine derivatives.

    PubMed

    Boto, Alicia; Gallardo, Juan A; Hernández, Rosendo; Ledo, Francisco; Muñoz, Ana; Murguía, José R; Menacho-Márquez, Mauricio; Orjales, Aurelio; Saavedra, Carlos J

    2006-12-01

    The discovery of genotoxic amino acids derived from phenylglycine, and possessing halogen substituents, is described. The utility of hypervalent iodine reagents in the synthesis of this class of compounds is highlighted. The mechanism of action of the (haloaryl)glycines was studied in Saccharomyces cerevisiae.

  14. 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.

  15. 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.

  16. Gas-phase reactions of halogen species of atmospheric importance

    NASA Astrophysics Data System (ADS)

    Heard, Anne C.

    A low-pressure discharge-flow technique, with various optical detection methods, has been used to determine bimolecular rate coefficients for a number of reactions in the gas-phase between OH radicals and organic halogen-containing molecules and between NO3 radicals and the iodine species I2 and I. These experiments have shown that: (1) the reaction of methyl iodide with OH accounts for approximately 2 percent of the removal of CH3I from the troposphere as compared with photolysis; (2) abstraction of I-atoms from a C-I bond by OH is probable in the gas-phase; (3) the halogen-containing anaesthetic substances halothane CF3CClBrH, enflurane CF2HOCF2CFClH, isoflurane CF2HOCClHCF3 and sevoflurane (CF3)2CHOCFH2 have significantly shorter tropospheric lifetimes than the fully halogenated CFCs and halons because of reaction with the OH radical and are thus unlikely to be transported up to the stratosphere where they could contribute to the depletion of ozone. Data obtained for reactions between OH and some 'CFC alternatives' along with measurements of the integrated absorption cross-sections of the compounds in the spectral region 800-1200 cm(exp -1) were used to calculate ozone depletion potentials (ODP) and greenhouse warming potentials relative to CFCl3 for each compound. The study of the reactions between OH and CF3CFBrH and CF2BrH was used to provide a useful first estimate of the environmental acceptability of these compounds in the context of their possible use as replacements for the conventional CFCs. A method was developed to provide a first estimate of the ODP of a halogenated alkane without use of a complicated (and expensive) computer modeling scheme. A reaction between molecular iodine and the nitrate radical in the gas-phase was discovered and the kinetics of this reaction have been studied. No temperature or pressure dependence was observed for the rate of reaction, the rate constant of which was found to be (1.5 +/- 0.5) x 10(exp -12)/cu cm

  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. 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

  19. Inter-layer charge disproportionation in the dual-layer organic metal (tTTF-I)2ClO4 with unsymmetrical I···O halogen bond interactions.

    PubMed

    Shin, Kyoung-Soon; Jeannin, Olivier; Brezgunova, Mariya; Dahaoui, Slimane; Aubert, Emmanuel; Espinosa, Enrique; Auban-Senzier, Pascale; Świetlik, Roman; Frąckowiak, Arkadiusz; Fourmigué, Marc

    2014-04-14

    A mixed-valence salt of tTTF-I with ClO4(-), formulated as (tTTF-I)2ClO4, is characterized by the presence of two crystallographically independent donor molecules, segregated in different layers and linked together through I···O interactions with the ClO4(-) anion disordered at room temperature. The tTTF-I donor molecule was prepared by metallation of tTTF (trimethylene tetrathiafulvalene) followed by reaction with iodine to afford the mono and diiodo derivatives tTTF-I and tTTFI2, respectively. The crystal structure of the latter neutral tTTFI2 shows the occurrence of strong type II, II halogen bond interactions. Band structure calculations of the dual-layer structure of the 2 : 1 salt (tTTF-I)2ClO4 show co-existence of both 1D open and 2D closed Fermi surfaces. The salt undergoes a metal-insulator phase transition at T(MI) = 90 K, associated with an electronic dimensionality decrease, since already at 100 K, the 2D part of the Fermi surface transforms into 1D corrugated planes. High resolution X-ray investigations performed at 100 K, combined with multipolar refinements, indicate an approximately equivalent +0.5e charge in both donor molecules, as also deduced from the intramolecular bond distances. On the other hand, Raman spectroscopic investigations show that at ambient temperature the charge is actually distributed non-uniformly in conducting layers of tTTF-I molecules, with the identification of molecules with charges +1, +0.5, 0e, while at low temperature the charge distribution becomes essentially uniform (+0.5e), as confirmed from the X-ray high resolution data. These apparently contradictory behaviors are actually a consequence of a partial electron transfer between the two independent slabs to reach a common Fermi level in the metallic phase.

  20. Rediscovery of halogen bonds in protein-ligand complexes.

    PubMed

    Zhou, P; Tian, F; Zou, J; Shang, Z

    2010-04-01

    Although the halogen bond has attracted much interest in chemistry and material science communities, its implications for drug design are just now coming to light. The protein-ligand interactions through short halogen-oxygen/nitrogen/sulfur contacts have been observed in crystal structures for a long time, but only in recent years, with the experimental and theoretical progress in weak biological interactions, especially the pioneering works contributed by Ho and co-workers (Auffinger, P.; Hays, F. A.; Westhof, E.; Ho, P. S. Proc. Natl. Acad. Sci. USA 2004, 101, 16789-16794), these short contacts involving halogens in biomolecules were rediscovered and re-recognized as halogen bonds to stress their shared similarities with hydrogen bonds in strength and directionality. Crystal structure determinations of protein complexes with halogenated ligands preliminarily unveiled the functionality of halogen bonds in protein-ligand recogni-tion. Database surveys further revealed a considerable number of short halogen-oxygen contacts between proteins and halogenated ligands. Theoretical calculations on model and real systems eventually gave a quantitative pronouncement for the substantial contribution of halogen bonds to ligand binding. All of these works forebode that the halogen bond can be exploited as a new and versatile tool for rational drug design and bio-crystal engineering.

  1. 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.

  2. 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.

  3. 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%.

  4. 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.

  5. Halogen bonding origin properties and applications

    NASA Astrophysics Data System (ADS)

    Hobza, Pavel

    2015-12-01

    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.

  6. 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.

  7. 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.

  8. 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.

  9. Study of the Vertical Scale of Halogen Chemistry at Sunrise at Barrow, AK

    NASA Astrophysics Data System (ADS)

    Tackett, P.; Cavender, A.; Morin, S.; Savarino, J.; Deary, J.; Bottenheim, J.; Steffen, A.; Shepson, P.

    2005-12-01

    The vertical extent of halogen chemistry in the Arctic springtime was investigated through the measurement of several atmospheric chemical components. Various chemical species that are modified by halogen chemistry were measured during late March through mid-April 2005, including VOCs, ozone, and mercury. Airborne volatile organic compounds were sampled through ambient air samples and collected onto Tenax-TA sorbent material. GEM (gaseous elemental mercury) was sampled through a Teflon inlet leading to a ground-based cold vapor atomic fluorescence mercury analyzer, and ambient ozone concentrations were determined using a 2B ozone spectrometer. The sampling apparatus was suspended beneath a tethered balloon that allowed collection at multiple altitudes extending up to 300 meters. The Tenax sample tubes were analyzed via cryo-concentrated thermal desorption/GC, and detected by FID (flame ionization detection). Species will be presented and discussed in a vertical profile format to enable analysis of the vertical extent of halogen chemistry in the halogen-rich lower atmosphere occurring during polar sunrise.

  10. 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.

  11. Adsorbed Water Illustration

    NASA Technical Reports Server (NTRS)

    2008-01-01

    The Thermal and Electrical Conductivity Probe on NASA's Phoenix Mars Lander detected small and variable amounts of water in the Martian soil.

    In this schematic illustration, water molecules are represented in red and white; soil minerals are represented in green and blue. The water, neither liquid, vapor, nor solid, adheres in very thin films of molecules to the surfaces of soil minerals. The left half illustrates an interpretation of less water being adsorbed onto the soil-particle surface during a period when the tilt, or obliquity, of Mars' rotation axis is small, as it is in the present. The right half illustrates a thicker film of water during a time when the obliquity is greater, as it is during cycles on time scales of hundreds of thousands of years. As the humidity of the atmosphere increases, more water accumulates on mineral surfaces. Thicker films behave increasingly like liquid water.

    The Phoenix Mission is led by the University of Arizona, Tucson, on behalf of NASA. Project management of the mission is by NASA's Jet Propulsion Laboratory, Pasadena, Calif. Spacecraft development is by Lockheed Martin Space Systems, Denver.

  12. Sand consolidation methods using adsorbable catalysts

    SciTech Connect

    Friedman, R. H.

    1985-04-23

    Methods are provided for selectively consolidating sand grains within a subterranean formation. First an acidic zirconium salt catalyst, such as ZrOCl/sub 2/, Zr(SO/sub 4/)/sub 2/, or ZrCl/sub 4/, is injected into the subterranean formation, wherein the acidic salt catalyst is adsorbed to the surface of the sand grains. Next a polymerizable resin composition such as furfuryl alcohol oligomer is introduced into the well formation. Polymerization of the resin occurs upon exposure to the elevated well temperatures and contact with the acid salt catalyst adsorbed to the sand grains. The polymerized resin serves to consolidate the surfaces of the sand grains while retaining permeability through the pore spaces. An ester of a weak organic acid is included with the resin compositions to control the extent of a polymerization by consuming the water by-product formed during the polymerization reaction.

  13. Effectiveness of Halogen-Based Disinfectants Against Acinetobacter Baumannii: Wound Care and Environmental Decontamination

    DTIC Science & Technology

    2006-11-01

    contaminated hands. Although all agents were found to be effective, 70% ethyl alcohol and 10% povidone - iodine removed significantly more bacteria from... compared the bacteriostatic and bactericidal activities of five commercially available U.S. halogen- based disinfectants against A. baumannii, along with...a standard E. coli comparator , in a novel bacterial culture system that incorporated a three log range of organic growth media concentrations. We

  14. Biodehalogenation: The kinetics and rates of the microbial cleavage of carbon-halogen bonds

    SciTech Connect

    Castro, C.E. . Nematology Dept.)

    1993-09-01

    Specific rate constants associated with defined molecular paths of carbon-halogen bond cleavage from a variety of alkyl halide substrates by six soil organisms are presented. Five aerobes (three pseudomonads, one methylotroph, and one flavobacterium) and one anaerobe (a methanogen) are compared. The rate constants were obtained with resting cells in phosphate buffer at pH 7.4 in the absence of nutrients or other substances. The observed general rate law is d(X[sup [minus

  15. Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer–chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS)

    USGS Publications Warehouse

    Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B.; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A.; Schimmelmann, Arndt

    2017-01-01

    Conclusions: The optimized EA-Cr/HTC reactor design can be implemented in existing analytical equipment using commercially available material and is universally applicable for both heteroelement-bearing and heteroelement-free organic-compound classes. The sensitivity and simplicity of the on-line EA-Cr/HTC-IRMS technique provide a much needed tool for routine hydrogen-isotope source tracing of organic contaminants in the environment. Copyright © 2016 John Wiley & Sons, Ltd.

  16. 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

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. 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...

  2. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., 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...

  3. 40 CFR 721.10015 - Halogenated benzimidazole (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 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...

  4. 40 CFR 721.10015 - Halogenated benzimidazole (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 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...

  5. 40 CFR 721.10015 - Halogenated benzimidazole (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 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...

  6. 40 CFR 721.10015 - Halogenated benzimidazole (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 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...

  7. 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...

  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. 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.

  10. 40 CFR 721.8750 - Halogenated substituted pyridine.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 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...

  11. 40 CFR 721.8750 - Halogenated substituted pyridine.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 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...

  12. 40 CFR 721.8750 - Halogenated substituted pyridine.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 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...

  13. 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...

  14. 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...

  15. 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...

  16. 40 CFR 721.8750 - Halogenated substituted pyridine.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 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...

  17. 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

  18. 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.

  19. Gas-Phase Reactions of Halogen Species of Atmospheric Importance.

    NASA Astrophysics Data System (ADS)

    Heard, Anne C.

    Available from UMI in association with The British Library. Requires signed TDF. A low-pressure discharge-flow technique, with various optical detection methods, has been used to determine bimolecular rate coefficients for a number of reactions in the gas-phase between OH radicals and organic halogen -containing molecules and between NO_3 radicals and the iodine species I_2 and I. These experiments have shown that: (i) the reaction of methyl iodide with OH accounts for approximately 2% of the removal of CH_3I from the troposphere as compared with photolysis; (ii) abstraction of I-atoms from a C-I bond by OH is probable in the gas -phase; (iii) the halogen-containing anaesthetic substances halothane CF_3CCl BrH, enflurane CF_2HOCF _2CFClH, isoflurane CF_2HOCClHCF _3 and sevoflurane (CF_3) _2CHOCFH_2 have significantly shorter tropospheric lifetimes than the fully halogenated CFCs and halons because of reaction with the OH radical and are thus unlikely to be transported up to the stratosphere where they could contribute to the depletion of ozone. Data obtained for reactions between OH and some 'CFC alternatives' along with measurements of the integrated absorption cross -sections of the compounds in the spectral region 800-1200 cm^{-1} were used to calculate ozone depletion potentials (ODP) and greenhouse warming potentials relative to CFCl_3 for each compound. The study of the reactions between OH and CF_3CFBrH and CF _2BrH was used to provide a useful first estimate of the environmental acceptability of these compounds in the context of their possible use as replacements for the conventional CFCs. A method was developed to provide a first estimate of the ODP of a halogenated alkane without use of a complicated (and expensive) computer modeling scheme. A reaction between molecular iodine and the nitrate radical in the gas-phase was discovered and the kinetics of this reaction have been studied. No temperature or pressure dependence was observed for the rate of

  20. [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.

  1. 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}.

  2. Polyacrylate adsorbents for the selective adsorption of cholesterol-rich lipoproteins from plasma or blood

    PubMed Central

    Heuck, Claus-Chr.

    2011-01-01

    Polyacrylate (PAA) adsorbents selectively bind low density lipoproteins (LDL) from human plasma and blood, whereas very low density lipoproteins (VLDL) are only minimally adsorbed. The adsorption of cholesterol-rich lipoproteins to PAA adsorbents is related to the molecular weight (mw) of the polyanion ligand. Ca++ and Mg++ inhibit the binding of LDL to PAA adsorbents. The chemical composition of the organic hardgels of the adsorbents does not have an influence on adsorption. The selective adsorption of LDL to PAA adsorbents can be explained to result from their low negative surface charge density and the specific colloid-chemical properties of the surface-bound PAA, which do not prevent LDL from binding to charge-like domains of the ligand. By contrast, VLDL and high density lipoproteins (HDL) are repelled from the adsorbents due to their higher negative surface charge density. PMID:21289994

  3. Polyacrylate adsorbents for the selective adsorption of cholesterol-rich lipoproteins from plasma or blood.

    PubMed

    Heuck, Claus-Chr

    2011-01-24

    Polyacrylate (PAA) adsorbents selectively bind low density lipoproteins (LDL) from human plasma and blood, whereas very low density lipoproteins (VLDL) are only minimally adsorbed. The adsorption of cholesterol-rich lipoproteins to PAA adsorbents is related to the molecular weight (mw) of the polyanion ligand. Ca(++) and Mg(++) inhibit the binding of LDL to PAA adsorbents. The chemical composition of the organic hardgels of the adsorbents does not have an influence on adsorption. The selective adsorption of LDL to PAA adsorbents can be explained to result from their low negative surface charge density and the specific colloid-chemical properties of the surface-bound PAA, which do not prevent LDL from binding to charge-like domains of the ligand. By contrast, VLDL and high density lipoproteins (HDL) are repelled from the adsorbents due to their higher negative surface charge density.

  4. 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

  5. Rotary adsorbers for continuous bulk separations

    DOEpatents

    Baker, Frederick S [Oak Ridge, TN

    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.

  6. 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

  7. 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.

  8. 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.

  9. Prediction of Thermodynamic Properties for Halogenated Hydrocarbon

    NASA Astrophysics Data System (ADS)

    Higashi, Yukihiro

    The predictive methods of thermodynamic properties are discussed with respect to the halogenated hydrocarbons using as working fluids for refrigeration and heat pump cycles. The methods introduced into this paper can be calculated by the limited information; critical properties, normal boiling point and acentric factor. The results of prediction are compared with the experimental values of PVT property, vapor pressure and saturated liquid density. On the basis of these comparisons, Lydersen's method for predicting the critical properties, the generalized vapor pressure correlation by Ashizawa et, al., and Hankinson-Thomson's method for predicting saturated liquid density can be recommended. With respect to the equation of state, either Soave equation or Peng-Robinson equation is effective in calculating the thermodynamic properties except high density region.

  10. 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.

  11. 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

  12. Uremic toxins and oral adsorbents.

    PubMed

    Goto, Shunsuke; Yoshiya, Kunihiko; Kita, Tomoyuki; Fujii, Hideki; Fukagawa, Masafumi

    2011-04-01

    Uremic toxins are associated with various disorders in patients with end-stage renal disease and it is difficult to remove some of these toxins by dialysis. Since some uremic toxins are generated by bacterial metabolites in the colon, oral adsorbents that interfere with the absorption of uremic toxins or their precursors are believed to prevent their accumulation in the body. AST-120 adsorbs various uremic retention solutes in the gastrointestinal system and has potential for providing clinical benefit. Sevelamer hydrochloride binds some harmful compounds in addition to phosphate and seems to have pleiotropic effects that include lowering serum LDL cholesterol levels and reduction of inflammation. The effect of sevelamer hydrochloride on indoxyl sulfate and p-cresol has been shown in an in vitro study; however, in vivo studies in mice or humans did not demonstrate this effect on protein-binding uremic toxins. Oral adsorbents are thus one of the important modalities in the treatment of uremic syndrome.

  13. 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.

  14. Conformational changes of adsorbed proteins

    NASA Astrophysics Data System (ADS)

    Allen, Scott

    2005-03-01

    The adsorption of bovine serum albumin (BSA) and pepsin to gold surfaces has been studied using surface plasmon resonance (SPR). Proteins are adsorbed from solution onto a gold surface and changes in the conformation of the adsorbed proteins are induced by changing the buffer solution. We selected pH and ionic strength values for the buffer solutions that are known from our circular dichroism measurements to cause conformational changes of the proteins in bulk solution. We find that for both BSA and pepsin the changes in conformation are impeded by the interaction of the protein with the gold surface.

  15. 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

  16. Storage stability of ketones on carbon adsorbents.

    PubMed

    Prado, C; Alcaraz, M J; Fuentes, A; Garrido, J; Periago, J F

    2006-09-29

    Activated coconut carbon constitutes the more widely used sorbent for preconcentration of volatile organic compounds in sampling workplace air. Water vapour is always present in the air and its adsorption on the activated carbon surface is a serious drawback, mainly when sampling polar organic compounds, such as ketones. In this case, the recovery of the compounds diminishes; moreover, ketones can be decomposed during storage. Synthetic carbons contain less inorganic impurities and have a lower capacity for water adsorption than coconut charcoal. The aim of this work was to evaluate the storage stability of various ketones (acetone, 2-butanone, 4-methyl-2-pentanone and cyclohexanone) on different activated carbons and to study the effect of adsorbed water vapour under different storage conditions. The effect of storage temperature on extraction efficiencies was significant for each ketone in all the studied sorbents. Recovery was higher when samples were stored at 4 degrees C. The results obtained for storage stability of the studied ketones showed that the performance of synthetic carbons was better than for the coconut charcoals. The water adsorption and the ash content of the carbons can be a measure of the reactive sites that may chemisorb ketones or catalize their decomposition. Anasorb 747 showed good ketone stability at least for 7 days, except for cyclohexanone. After 30-days storage, the stability of the studied ketones was excellent on Carboxen 564. This sorbent had a nearly negligible ash content and the adsorbed water was much lower than for the other sorbents tested.

  17. 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

    2004-05-03

    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.

  18. 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.

  19. 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...

  20. 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.

  1. 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.

  2. Occurrence and concentrations of selected trace elements, halogenated organic compounds, and polycyclic aromatic hydrocarbons in streambed sediments and results of water-toxicity testing in Westside Creeks and the San Antonio River, San Antonio, Texas, 2014

    USGS Publications Warehouse

    Crow, Cassi L.; Wilson, Jennifer T.; Kunz, James L.

    2016-12-01

    Sediment samples and samples for water-toxicity testing were collected during 2014 from several streams in San Antonio, Texas, known locally as the Westside Creeks (Alazán, Apache, Martínez, and San Pedro Creeks) and from the San Antonio River. Samples were collected during base flow and after periods of stormwater runoff (poststorm conditions) to determine baseline sediment- and water-quality conditions. Streambed-sediment samples were analyzed for selected constituents, including trace elements and organic contaminants such as pesticides, polychlorinated biphenyls (PCBs), brominated flame retardants, and polycyclic aromatic hydrocarbons (PAHs). Potential risks of contaminants in sediment were evaluated by comparing concentrations of contaminants in sediment to two effects-based sediment-quality guidelines: (1) a lower level, called the threshold effect concentration, below which, harmful effects to benthic biota are not expected, and (2) a higher level, the probable effect concentration (PEC), above which harmful effects are expected to occur frequently. Samples for water-toxicity testing were collected from each stream to provide information about fish toxicity in the study area. The trace metal lead was detected at potentially toxic concentrations greater than the PEC in both the base-flow and poststorm samples collected at two sites sampled on San Pedro Creek. The PECs for the pesticides dichlorodiphenyldichloroethane, dichlorodiphenyldichloroethylene, dichlorodiphenyltrichloroethane, and chlordane were exceeded in some of the samples at the same two sites on San Pedro Creek. Brominated flame retardants and polybrominated diphenyl ether (PBDE) 85, 153, and 154 were found in all streambed-sediment samples. Federal Environmental Quality Guidelines established by Environment Canada for PBDE 99 and PBDE 100 were exceeded in all samples in which PBDE 99 was detected and in a majority of the samples in which PBDE 100 was detected; the greatest concentrations

  3. Adsorption of organic matter at mineral/water interfaces: I. ATR-FTIR spectroscopic and quantum chemical study of oxalate adsorbed at boehmite/water and corundum/water interfaces

    NASA Astrophysics Data System (ADS)

    Yoon, Tae Hyun; Johnson, Stephen B.; Musgrave, Charles B.; Brown, Gordon E.

    2004-11-01

    The types and structures of adsorption complexes formed by oxalate at boehmite (γ-AlOOH)/water and corundum (α-Al 2O 3)/water interfaces were determined using in situ attenuated total reflectance fourier transform infrared (ATR-FTIR) spectroscopy and quantum chemical simulation methods. At pH 5.1, at least four different oxalate species were found at or near the boehmite/water interface for oxalate surface coverages (Γ ox) ranging from 0.25 to 16.44 μmol/m 2. At relatively low coverages (Γ ox < 2.47), strongly adsorbed inner-sphere oxalate species (IR peaks at 1286, 1418, 1700, and 1720 cm -1) replace weakly adsorbed carbonate species, and a small proportion of oxalate anions are adsorbed in an outer-sphere mode (IR peaks at 1314 and 1591 cm -1). IR peaks indicative of inner-sphere adsorbed oxalate are also observed for oxalate at the corundum/water interface at Γ ox = 1.4 μmol/m 2. With increasing oxalate concentration (Γ ox > 2.47 μmol/m 2), the boehmite surface binding sites for inner-sphere adsorbed oxalate become saturated, and excess oxalate ions are present dominantly as aqueous species (IR peaks at 1309 and 1571 cm -1). In addition to these adsorption processes, oxalate-promoted dissolution of boehmite following inner-sphere oxalate adsorption becomes increasingly pronounced with increasing Γ ox and results in an aqueous Al(III)-oxalate species, as indicated by shifted IR peaks (1286 → 1297 cm -1 and 1418 → 1408 cm -1). At pH 2.5, no outer-sphere adsorbed oxalate or aqueous oxalate species were observed. The similarity of adsorbed oxalate spectral features at pH 2.5 and 5.1 implies that the adsorption mechanism of aqueous HOx - species involves loss of protons from this species during the ligand-exchange reaction. As a consequence, adsorbed inner-sphere oxalate and aqueous Al(III)-oxalate complexes formed at pH 2.5 have coordination geometries very similar to those formed at pH 5.1. The coordination geometry of inner-sphere adsorbed oxalate

  4. 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

  5. Halogen chemistry reduces tropospheric O3 radiative forcing

    NASA Astrophysics Data System (ADS)

    Sherwen, Tomás; Evans, Mat J.; Carpenter, Lucy J.; Schmidt, Johan A.; Mickley, Loretta J.

    2017-01-01

    Tropospheric ozone (O3) is a global warming gas, but the lack of a firm observational record since the preindustrial period means that estimates of its radiative forcing (RFTO3) rely on model calculations. Recent observational evidence shows that halogens are pervasive in the troposphere and need to be represented in chemistry-transport models for an accurate simulation of present-day O3. Using the GEOS-Chem model we show that tropospheric halogen chemistry is likely more active in the present day than in the preindustrial. This is due to increased oceanic iodine emissions driven by increased surface O3, higher anthropogenic emissions of bromo-carbons, and an increased flux of bromine from the stratosphere. We calculate preindustrial to present-day increases in the tropospheric O3 burden of 113 Tg without halogens but only 90 Tg with, leading to a reduction in RFTO3 from 0.43 to 0.35 Wm-2. We attribute ˜ 50 % of this reduction to increased bromine flux from the stratosphere, ˜ 35 % to the ocean-atmosphere iodine feedback, and ˜ 15 % to increased tropospheric sources of anthropogenic halogens. This reduction of tropospheric O3 radiative forcing due to halogens (0.087 Wm-2) is greater than that from the radiative forcing of stratospheric O3 (˜ 0.05 Wm-2). Estimates of RFTO3 that fail to consider halogen chemistry are likely overestimates (˜ 25 %).

  6. 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.

  7. 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.

  8. 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.

  9. Halogenated MOF-5 variants show new configuration, tunable band gaps and enhanced optical response in the visible and near infrared.

    PubMed

    Yang, Li-Ming; Fang, Guo-Yong; Ma, Jing; Pushpa, Raghani; Ganz, Eric

    2016-11-30

    Inspired by recent experimental fabrication of mono-halogenated versions of Metal-Organic Framework MOF-5 (i.e., X-MOF-5, X = F to I) and some experimentally known fully halogenated MOF compounds, we systematically studied frameworks incorporating full halogenation of the BDC linkers of the prototypical Iso-Reticular Metal-Organic Framework (IRMOF) series, exemplified by MOF-5. Using quantum chemistry calculations, we find that halogenation leads to a 90° rotation of the aryl group, which is mainly ascribed to overcrowding between halogen atoms and the carboxyl and benzene ring and strong repulsion among in-plane atoms/groups. The 90° configuration decreases the repulsion, and maximizes the stabilization energy, and is therefore more stable than 0° configuration. We find that the band gap can be tuned from 4.1 to 1.5 eV as we go from F, Cl, Br, to I. This extends the optical response of these experimentally accessible materials through the visible and infrared region. We have also considered a broader range of new materials that substitute various metals for Zn. Totally, 70 materials were systematically examined computationally including (M4O)(BDC-Z4)3 (M = Zn, Cd, Be, Mg, Ca, Sr, Ba; Z = H, F, Cl, Br, I). For the full range of materials, we calculate band gaps of 4.2 to 1.0 eV, corresponding to a threshold of absorption of 290-1240 nm. Four selected materials were tested for stability using short 5 ps molecular dynamics simulations up to 600 K. The new materials with the smallest band gaps could potentially be used in near-infrared (NIR) light-emitting devices. Other properties, e.g., bulk moduli, formation energy, chemical bonding, and optical properties, were also investigated. The present results may provide new materials for use as novel photocatalysts, photoactive materials for photovoltaic cells, or functional devices in nanoelectronics and optoelectronics.

  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. 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.

  12. Structure-activity relationship of ochratoxin A and synthesized derivatives: importance of amino acid and halogen moiety for cytotoxicity.

    PubMed

    Rottkord, Ulrike; Röhl, Christopher; Ferse, Ines; Schulz, Marie-Christin; Rückschloss, Uwe; Gekle, Michael; Schwerdt, Gerald; Humpf, Hans-Ulrich

    2017-03-01

    The enigma why the mycotoxin ochratoxin A (OTA) impairs cell and organ function is still not solved. However, an interaction with target molecules is a prerequisite for any observed adverse effect. This interaction depends on characteristics of the target molecule as well as on the OTA molecule itself. OTA has different structural moieties which may be relevant for these interrelations including a halogen (chlorine) and an amino acid group (phenylalanine). To test their importance for the impact of OTA, detailed structure-activity studies with various OTA derivatives were performed. For this, 23 OTA derivatives were available, which were modified by either an exchange of the halogen moiety against another halogen (fluorine, iodine or bromine) or by the amino acid moiety against another one (tyrosine or alanine) or a combination of both. Additionally, the configuration of the 3R carbon atom was changed to 3S. These derivatives were tested in human renal cells for their ability to induce cell death (cytotoxicity, apoptosis, necrosis), their impact on collagen protein secretion and for their influence on gene expression. It turned out that the substitution of the amino acid moiety against tyrosine or alanine almost completely prevented the adverse effects of OTA. The exchange of the halogen moiety had minor effects and the inversion of the stereochemistry at C3 did not prevent the effects of OTA. Therefore, we conclude that the amino acid moiety of OTA is indispensable for the interaction of OTA with its target molecules.

  13. Synthesis of Soluble Halogenated Polyphenylenes. Mechanism for the Coupling Halogenated Lithiobenzenes

    DTIC Science & Technology

    1993-11-22

    the halogen content in these polymers was lowered using larger amounts of tert- butyllithium. TGA analysis (N2 , 20C/rmin) of I1 showed a 10% weight...iodide for every three aryl rings. DSC analysis (N2 , 20°C/min) for 1 8 showed no transitions on either the first or second heating scans to 230"C. TGA ... analysis (N2. 20C/rmin) showed a 10% weight loss at 3220C and char yields of 46% at 900"C. Visual analysis of the charred material did indicate that

  14. The relative roles of electrostatics and dispersion in the stabilization of halogen bonds.

    PubMed

    Riley, Kevin E; Hobza, Pavel

    2013-11-07

    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.

  15. Mouse Model of Halogenated Platinum Salt Hypersensitivity ...

    EPA Pesticide Factsheets

    Occupational exposure to halogenated platinum salts can trigger the development of asthma. Concern for increased asthma risk exists for the general population due to the use of platinum (Pt) in catalytic converters and its emerging use as a diesel fuel additive. To investigate airway responses to Pt, we developed a mouse model of Pt hypersensitivity. Previously, we confirmed the dermal sensitizing potency of ammonium hexachloroplatinate (AHCP) using an ex vivo [3H]methyl thymidine labeling version of the local lymph node assay in BALB/c mice. Here, we investigated the ability of AHCP to induce airway responses in mice sensitized by the dermal route. Mice were sensitized through application of 100 µL 1% AHCP in DMSO to the shaved back on days 0, 5 and 19, and 25 µl to each ear on days 10, 11 and 12. Unsensitized mice received vehicle. On day 24, mice were challenged by oropharyngeal aspiration (OPA) with 0 or 100 µg AHCP in saline. Before and immediately after challenge, airway responses were assessed using whole body plethysmography (WBP). On day 26, changes in ventilatory responses to methacholine (Mch) aerosol were assessed by WBP; dose-dependent increases in Mch responsiveness occurred in sensitized mice. Bronchoalveolar lavage fluid harvested from sensitized mice contained an average of 7.5% eosinophils compared to less than 0.5% in control mice (p < 0.05). This model will be useful for assessing both relative sensitizing potency and cross-reacti

  16. 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.

  17. 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.

  18. 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

  19. 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

    2015-08-04

    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.

  20. Evidence for halogen bond covalency in acyclic and interlocked halogen-bonding receptor anion recognition

    DOE PAGES

    Robinson, Sean W.; Mustoe, Chantal L.; White, Nicholas G.; ...

    2014-12-05

    The synthesis and anion binding properties of novel halogen-bonding (XB) bis-iodotriazole-pyridinium-containing acyclic and [2]catenane anion host systems are described. The XB acyclic receptor displays selectivity for acetate over halides with enhanced anion recognition properties compared to the analogous hydrogen-bonding (HB) acyclic receptor. A reversal in halide selectivity is observed in the XB [2]catenane, in comparison to the acyclic XB receptor, due to the interlocked host’s unique three-dimensional binding cavity, and no binding is observed for oxoanions. Notable halide anion association constant values determined for the [2]catenane in competitive organic–aqueous solvent mixtures demonstrate considerable enhancement of anion recognition as compared tomore » the HB catenane analogue. X-ray crystallographic analysis of a series of halide catenane complexes reveal strong XB interactions in the solid state. These interactions were studied using Cl and Br K-edge X-ray Absorption Spectroscopy (XAS) indicating intense pre-edge features characteristic of charge transfer from the halide to its bonding partner (σAX←X–* ← X1s), and providing a direct measure of the degree of covalency in the halogen bond(s). Lastly, the data reveal that the degree of covalency is similar to that which is observed in transition metal coordinate covalent bonds. These results are supported by DFT results, which correlate well with the experimental data.« less

  1. Evidence for halogen bond covalency in acyclic and interlocked halogen-bonding receptor anion recognition

    SciTech Connect

    Robinson, Sean W.; Mustoe, Chantal L.; White, Nicholas G.; Brown, Asha; Thompson, Amber L.; Kennepohl, Pierre; Beer, Paul D.

    2014-12-05

    The synthesis and anion binding properties of novel halogen-bonding (XB) bis-iodotriazole-pyridinium-containing acyclic and [2]catenane anion host systems are described. The XB acyclic receptor displays selectivity for acetate over halides with enhanced anion recognition properties compared to the analogous hydrogen-bonding (HB) acyclic receptor. A reversal in halide selectivity is observed in the XB [2]catenane, in comparison to the acyclic XB receptor, due to the interlocked host’s unique three-dimensional binding cavity, and no binding is observed for oxoanions. Notable halide anion association constant values determined for the [2]catenane in competitive organic–aqueous solvent mixtures demonstrate considerable enhancement of anion recognition as compared to the HB catenane analogue. X-ray crystallographic analysis of a series of halide catenane complexes reveal strong XB interactions in the solid state. These interactions were studied using Cl and Br K-edge X-ray Absorption Spectroscopy (XAS) indicating intense pre-edge features characteristic of charge transfer from the halide to its bonding partner (σAX←X–* ← X1s), and providing a direct measure of the degree of covalency in the halogen bond(s). Lastly, the data reveal that the degree of covalency is similar to that which is observed in transition metal coordinate covalent bonds. These results are supported by DFT results, which correlate well with the experimental data.

  2. Laboratory validation of vost and semivost for halogenated hydrocarbons from the Clean Air Act amendments list. Volume 2. Final report

    SciTech Connect

    Jackson, M.D.; Bursey, J.T.; Merrill, R.G.; McAllister, R.A.; McGaughey, J.F.

    1993-04-29

    The Clean Air Act Amendments of 1990, Title III, present a need for stationary source sampling and analytical methods for the list of 189 compounds. EPA has used Volatile Organic Sampling Train (VOST) and Semivolatile Organic Sampling Train (SemiVOST) sampling and analytical methods for the type of sampling of organic compounds in the past, but these methodologies have been completely validated for only a few of the organic compounds. In the study, the applicability of VOST and SemiVOST techniques to Clean Air Act halogenated compounds has been evaluated under laboratory conditions. The methods were evaluated first to determine whether the compounds could be analyzed successfully.

  3. 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.

  4. Investigating Planetary Volatile Accretion Mechanisms Using the Halogens

    NASA Astrophysics Data System (ADS)

    Ballentine, C. J.; Clay, P. L.; Burgess, R.; Busemann, H.; Ruzié, L.; Joachim, B.; Day, J. M.

    2014-12-01

    Depletion of the volatile elements in the Earth relative to the CI chondrites is roughly correlated with volatility, or decreasing condensation temperature. For the heavy halogen group elements (Cl, Br and I), volatility alone does not account for their apparent depletion, which early data has suggested is far greater than predicted [1-2]. Such depletion has been used to argue for the preferential loss of halogens by, amongst other processes, impact-driven erosive loss from Earth's surface [2]. Little consensus exists as to why the halogens should exhibit such preferential behavior during accretionary processes. Early efforts to constrain halogen abundance and understand their behavior in both Earth and planetary materials [3-6] have been hampered by their typically low abundance (ppb level) in most geologic materials. We present the results of halogen analysis of 23 chondrite samples, selected to represent diverse groups and petrologic type. Halogen abundances were measured by neutron irradiation noble gas mass spectrometry (NI-NGMS). Significant concentration heterogeneity is observed within some samples. However, a single Br/Cl and I/Cl ratio of 1.9 ± 0.2 (x 10-3) and 335 ± 10 (x 10-6) can be defined for carbonaceous chondrites with a good correlation between Br and Cl (R2 = 0.97) and between I and Cl (R2 = 0.84). Ratios of I/Cl overlap with terrestrial estimates of Bulk Silicate Earth and Mid Ocean Ridge Basalts. Similarly, good correlations are derived for enstatite (E) chondrites and a sulfide- and halogen- rich subset of E-chondrites. Chlorine abundances of CI (Orgueil) in this study are lower by factor of ~ 3 than the value of ~ 700 ppm Cl (compilation in [1]). Our results are similar to early discarded low values for Ivuna and Orgueil from [5,6] and agree more closely with values for CM chondrites. Halogens may not be as depleted in Earth as previously suggested, or a high degree of heterogeneity in the abundance of these volatile elements in

  5. 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.

  6. Multiphase halogen chemistry in the tropical Atlantic Ocean.

    PubMed

    Sommariva, Roberto; von Glasow, Roland

    2012-10-02

    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.

  7. A polarizable ellipsoidal force field for halogen bonds.

    PubMed

    Du, Likai; Gao, Jun; Bi, Fuzhen; Wang, Lili; Liu, Chengbu

    2013-09-05

    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.

  8. 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

  9. 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.

  10. 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.

  11. 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...

  12. 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

  13. First principles study of halogens adsorption on intermetallic surfaces

    NASA Astrophysics Data System (ADS)

    Zhu, Quanxi; Wang, Shao-qing

    2016-02-01

    Halides are often present at electrochemical environment, they can directly influence the electrode potential or zero charge potential through the induced work-function change. In this work, we focused in particular on the halogen-induced work function change as a function of the coverage of fluorine, chlorine, bromine and iodine on Al2Au and Al2Pt (110) surfaces. Results show that the real relation between work function change and dipole moment change for halogens adsorption on intermetallic surfaces is just a common linear relationship rather than a directly proportion. Besides, the different slopes between fitted lines and the theoretical slope employed in pure metal surfaces demonstrating that the halogens adsorption on intermetallic surfaces are more complicated. We also present a weight parameter β to describe different factors effect on work function shift and finally qualify which factor dominates the shift direction.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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

  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

    2012-03-06

    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. Behavior of halogens during the degassing of felsic magmas

    NASA Astrophysics Data System (ADS)

    Balcone-Boissard, H.; Villemant, B.; Boudon, G.

    2010-09-01

    Residual concentrations of halogens (F, Cl, Br, I) and H2O in glass (matrix glass and melt inclusions) have been determined in a series of volcanic clasts (pumice and lava-dome fragments) of plinian, vulcanian and lava dome-forming eruptions. Felsic magmas from calc-alkaline, trachytic and phonolitic systems have been investigated: Montagne Pelée and Soufrière Hills of Montserrat (Lesser Antilles), Santa Maria-Santiaguito (Guatemala), Fogo (Azores) and Vesuvius (Italy). The behavior of halogens during shallow H2O degassing primarily depends on their incompatible character and their partitioning between melt and exsolved H2O vapor. However, variations in pre-eruptive conditions, degassing kinetics, and syn-eruptive melt crystallization induce large variations in the efficiency of halogen extraction. In all systems studied, Cl, Br and I are not fractionated from each other by differentiation or by degassing processes. Cl/Br/I ratios in melt remain almost constant from the magma reservoir to the surface. The ratios measured in erupted clasts are thus characteristic of pre-eruptive magma compositions and may be used to trace deep magmatic processes. F behaves as an incompatible element and, unlike the other halogens, is never significantly extracted by degassing. Cl, Br and I are efficiently extracted from melts at high pressure by H2O-rich fluids exsolved from magmas or during slow effusive magma degassing, but not during rapid explosive degassing. Because H2O and halogen mobility depends on their speciation, which strongly varies with pressure in both silicate melts and exsolved fluids, we suggest that the rapid pressure decrease during highly explosive eruptions prevents complete equilibrium between the diverse species of the volatiles and consequently limits their degassing. Conversely, degassing in effusive eruptions is an equilibrium process and leads to significant halogen output in volcanic plumes.

  2. Halogen bonding: a study based on the electronic charge density.

    PubMed

    Amezaga, Nancy J Martinez; Pamies, Silvana C; Peruchena, Nélida M; Sosa, Gladis L

    2010-01-14

    Density functional theory (DFT) and atoms in molecules theory (AIM) were used to study the characteristic of the noncovalent interactions in complexes formed between Lewis bases (NH(3), H(2)O, and H(2)S) and Lewis acids (ClF, BrF, IF, BrCl, ICl, and IBr). In order to compare halogen and hydrogen bonds interactions, this study included hydrogen complexes formed by some Lewis bases and HF, HCl, and HBr Lewis acids. Ab initio, wave functions were generated at B3LYP/6-311++G(d,p) level with optimized structures at the same level. Criteria based on a topological analysis of the electron density were used in order to characterize the nature of halogen interactions in Lewis complexes. The main purpose of the present work is to provide an answer to the following questions: (a) why can electronegative atoms such as halogens act as bridges between two other electronegative atoms? Can a study based on the electron charge density answer this question? Considering this, we had performed a profound study of halogen complexes in the framework of the AIM theory. A good correlation between the density at the intermolecular bond critical point and the energy interaction was found. We had also explored the concentration and depletion of the charge density, displayed by the Laplacian topology, in the interaction zone and in the X-Y halogen donor bond. From the atomic properties, it was generally observed that the two halogen atoms gain electron population in response to its own intrinsic nature. Because of this fact, both atoms are energetically stabilized.

  3. Fine tuning of graphene properties by modification with aryl halogens

    NASA Astrophysics Data System (ADS)

    Bouša, D.; Pumera, M.; Sedmidubský, D.; Šturala, J.; Luxa, J.; Mazánek, V.; Sofer, Z.

    2016-01-01

    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.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. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06295k

  4. 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

  5. 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.

  6. Symmetric and asymmetric halogen-containing metallocarboranylporphyrins and uses thereof

    DOEpatents

    Miura, Michiko; Wu, Haitao

    2013-05-21

    The present invention is directed to low toxicity boronated compounds and methods for their use in the treatment, visualization, and diagnosis of tumors. More specifically, the present invention is directed to low toxicity halogenated, carborane-containing 5,10,15,20-tetraphenylporphyrin compounds and methods for their use particularly in boron neutron capture therapy (BNCT) and photodynamic therapy (PDT) for the treatment of tumors of the brain, head and neck, and surrounding tissue. The invention is also directed to using these halogenated, carborane-containing tetraphenylporphyrin compounds in methods of tumor imaging and/or diagnosis such as MRI, SPECT, or PET.

  7. Hydrogen/halogen fuel cell with improved water management system

    SciTech Connect

    Molter, T.M.; LaConti, A.B.

    1989-04-04

    This patent describes an improved method of operating a hydrogen/halogen fuel cell, comprising: a. introducing hydrogen fuel into the anode chamber of a fuel cell; b. introducing a halogen oxidant into the cathode chamber of a fuel cell; c. contacting the hydrogen fuel with the catalytic anode thereby catalytically disassociating the hydrogen into hydrogen ions and electrons; d. transporting the hydrogen ions through a solid polymer electrolyte membrane to the cathode electrode; e. passing the electrons through an external circuit to the cathode; and f. reacting the oxidant with the hydrogen ions in the presence of the catalytic cathode to produce an acid.

  8. Use of potassium dihydrogen phosphate and sawdust as adsorbents of ammoniacal nitrogen in aerobic composting process.

    PubMed

    Hu, Tian-Jue; Zeng, Guang-Ming; Huang, Dan-Lian; Yu, Hong-Yan; Jiang, Xiao-Yun; Dai, Fang; Huang, Guo-He

    2007-03-22

    Three kinds of adsorbents-potassium dihydrogen phosphate, sawdust and mixture of potassium dihydrogen phosphate and sawdust were added respectively into composting to investigate their adsorption effect on ammonia. The experimental results showed that all the adsorbents could restrain ammonia volatilizing, with the sorption of potassium dihydrogen phosphate adsorbents being the best of all, the sorption of mixture adsorbent with potassium dihydrogen phosphate and sawdust being the second and the sorption of sawdust adsorbent being the last. Therefore, the total nitrogen loss ratios respectively reduced from 38% to 13%, 15% and 21% after adding these three kinds of adsorbents into composting. However, potassium dihydrogen phosphate produced negative influence on composting properties as its supplemented amount exceeded a quantity basis equivalent to 18% of total nitrogen in the composting, for example: pH value had been lessened, microorganism activity reduced, which finally resulted in the reduction of biodegradation ratio of organic matter. But it did not result in these problems when using the mixture of potassium dihydrogen phosphate and sawdust as adsorbent, in which the amount of potassium dihydrogen phosphate was under a quantity basis equivalent to 6% of total nitrogen in the composting. Moreover, the mixture adsorbent produced better adsorption effect on ammonia, and raised biodegradation ratio of organic matter from 26% to 33%.

  9. ON DEVELOPING CLEANER ORGANIC UNIT PROCESSES

    EPA Science Inventory

    Organic waste products, potentially harmful to the human health and the environment, are primarily produced in the synthesis stage of manufacturing processes. Many such synthetic unit processes, such as halogenation, oxidation, alkylation, nitration, and sulfonation are common to...

  10. 40 CFR 721.275 - Halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated-N-(2-propenyl)-N... New Uses for Specific Chemical Substances § 721.275 Halogenated-N-(2-propenyl)-N-(substituted phenyl... identified generically as halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide (P-83-1085) is...

  11. 40 CFR 721.275 - Halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halogenated-N-(2-propenyl)-N... New Uses for Specific Chemical Substances § 721.275 Halogenated-N-(2-propenyl)-N-(substituted phenyl... identified generically as halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide (P-83-1085) is...

  12. 40 CFR 721.275 - Halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogenated-N-(2-propenyl)-N... New Uses for Specific Chemical Substances § 721.275 Halogenated-N-(2-propenyl)-N-(substituted phenyl... identified generically as halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide (P-83-1085) is...

  13. 40 CFR 721.275 - Halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halogenated-N-(2-propenyl)-N... New Uses for Specific Chemical Substances § 721.275 Halogenated-N-(2-propenyl)-N-(substituted phenyl... identified generically as halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide (P-83-1085) is...

  14. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  15. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  16. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  17. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  18. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  19. 40 CFR 721.275 - Halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halogenated-N-(2-propenyl)-N... New Uses for Specific Chemical Substances § 721.275 Halogenated-N-(2-propenyl)-N-(substituted phenyl... identified generically as halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide (P-83-1085) is...

  20. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting...

  1. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting...

  2. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting...

  3. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting...

  4. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting...

  5. 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.

  6. Shallow halogen vacancies in halide optoelectronic materials

    SciTech Connect

    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 VH 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.

  7. Assembling supramolecular networks by halogen bonding in coordination polymers driven by 5-bromonicotinic acid

    SciTech Connect

    Gu, Jin-Zhong; Wu, Jiang; Kirillov, Alexander M.; Lv, Dong-Yu; Tang, Yu; Wu, Jin-Cai

    2014-05-01

    A series of six coordination compounds ([Zn(5-Brnic){sub 2}]·1.5H{sub 2}O){sub n} (1), [Cd(5-Brnic){sub 2}]{sub n} (2), [Co(5-Brnic){sub 2}(H{sub 2}O){sub 2}]{sub n} (3), [Zn(5-Brnic){sub 2}(H{sub 2}biim)]{sub n} (4), ([Cd(5-Brnic){sub 2}(phen)]·H{sub 2}O){sub n} (5), and [Pb(5-Brnic){sub 2}(phen)] (6) have been generated by the hydrothermal method from the metal(II) nitrates, 5-bromonicotinic acid (5-BrnicH), and an optional ancillary 1,10-phenanthroline (phen) or 2,2′-biimidazole (H{sub 2}biim) ligand. All the products 1–6 have been characterized by IR spectroscopy, elemental, thermal, powder and single-crystal X-ray diffraction analyses. Their 5-bromonicotinate-driven structures vary from the 3D metal-organic framework with the seh-3,5-P21/c topology (in 2) and the 2D interdigitated layers with the sql topology (in 1 and 3), to the 1D chains (in 4 and 5) and the 0D discrete monomers (in 6). The 5-bromonicotinate moiety acts as a versatile building block and its tethered bromine atom plays a key role in reinforcing and extending the structures into diverse 3D supramolecular networks via the various halogen bonding Br⋯O, Br⋯Br, and Br⋯π interactions, as well as the N–H⋯O and C–H⋯O hydrogen bonds. The obtained results demonstrate a useful guideline toward engineering the supramolecular architectures in the coordination network assembly under the influence of various halogen bonding interactions. The luminescent (for 1, 2, 4, 5, and 6) and magnetic (for 3) properties have also been studied and discussed in detail. - Graphical abstract: Six coordination compounds driven by 5-bromonicotinic acid have been generated and structurally characterized, revealing diverse metal-organic networks that are further reinforced and extended via various halogen bonding interactions. - Highlights: • 5-Bromonicotinic acid is a versatile ligand for Zn, Cd, Co and Pb derivatives. • Careful selection of co-ligands and metals resulted in different network

  8. Core Halogenation as a Construction Principle in Tuning the Material Properties of Tetraazaperopyrenes.

    PubMed

    Hahn, Lena; Maass, Friedrich; Bleith, Tim; Zschieschang, Ute; Wadepohl, Hubert; Klauk, Hagen; Tegeder, Petra; Gade, Lutz H

    2015-12-01

    A detailed study on the effects of core halogenation of tetraazaperopyrene (TAPP) derivatives is presented. Its impact on the solid structure, as well as the photophysical and electrochemical properties, has been probed by the means of X-ray crystallography, UV/Vis and fluorescence spectroscopy, high-resolution electron energy loss spectroscopy (HREELS), cyclic voltammetry (CV), and DFT modeling. The aim was to assess the potential of this approach as a construction principle for organic electron-conducting materials of the type studied in this work. Although halogenation leads to a stabilization of the LUMOs compared to the unsubstituted parent compound, the nature of the halide barely affects the LUMO energy while strongly influencing the HOMO energies. In terms of band-gap engineering, it was demonstrated that the HOMO-LUMO gap is decreased by substitution of the TAPP core with halides, the effect being found to be most pronounced for the iodinated derivative. The performance of the recently reported core-fluorinated and core-iodinated TAPP derivatives in organic thin-film transistors (TFTs) was investigated on both a glass substrate, as well as on a flexible plastic substrate (PEN). Field-effect mobilities of up to 0.17 cm(2)  Vs(-1) and on/off current ratio of >10(6) were established.

  9. Molecular techniques in the biotechnological fight against halogenated compounds in anoxic environments

    PubMed Central

    Ding, Chang; He, Jianzhong

    2012-01-01

    Summary Microbial treatment of environmental contamination by anthropogenic halogenated organic compounds has become popular in recent decades, especially in the subsurface environments. Molecular techniques such as polymerase chain reaction‐based fingerprinting methods have been extensively used to closely monitor the presence and activities of dehalogenating microbes, which also lead to the discovery of new dehalogenating bacteria and novel functional genes. Nowadays, traditional molecular techniques are being further developed and optimized for higher sensitivity, specificity, and accuracy to better fit the contexts of dehalogenation. On the other hand, newly developed high throughput techniques, such as microarray and next‐generation sequencing, provide unsurpassed detection ability, which has enabled large‐scale comparative genomic and whole‐genome transcriptomic analysis. The aim of this review is to summarize applications of various molecular tools in the field of microbially mediated dehalogenation of various halogenated organic compounds. It is expected that traditional molecular techniques and nucleic‐acid‐based biomarkers will still be favoured in the foreseeable future because of relative low costs and high flexibility. Collective analyses of metagenomic sequencing data are still in need of information from individual dehalogenating strains and functional reductive dehalogenase genes in order to draw reliable conclusions. PMID:22070763

  10. Halogen and Cl isotopic systematics in Martian phosphates: Implications for the Cl cycle and surface halogen reservoirs on Mars

    NASA Astrophysics Data System (ADS)

    Bellucci, J. J.; Whitehouse, M. J.; John, T.; Nemchin, A. A.; Snape, J. F.; Bland, P. A.; Benedix, G. K.

    2017-01-01

    The Cl isotopic compositions and halogen (Cl, F, Br, and I) abundances in phosphates from eight Martian meteorites, spanning most rock types and ages currently available, have been measured in situ by Secondary Ion Mass Spectrometry (SIMS). Likewise, the distribution of halogens has been documented by x-ray mapping. Halogen concentrations range over several orders of magnitude up to some of the largest concentrations yet measured in Martian samples or on the Martian surface, and the inter-element ratios are highly variable. Similarly, Cl isotope compositions exhibit a larger range than all pristine terrestrial igneous rocks. Phosphates in ancient (>4 Ga) meteorites (orthopyroxenite ALH 84001 and breccia NWA 7533) have positive δ37Cl anomalies (+1.1 to + 2.5 ‰). These samples also exhibit explicit whole rock and grain scale evidence for hydrothermal or aqueous activity. In contrast, the phosphates in the younger basaltic Shergottite meteorites (<600 Ma) have negative δ37Cl anomalies (-0.2 to - 5.6 ‰). Phosphates with the largest negative δ37Cl anomalies display zonation in which the rims of the grains are enriched in all halogens and have significantly more negative δ37Cl anomalies suggestive of interaction with the surface of Mars during the latest stages of basalt crystallization. The phosphates with no textural, major element, or halogen enrichment evidence for mixing with this surface reservoir have an average δ37Cl of - 0.6 ‰, supporting a similar initial Cl isotope composition for Mars, the Earth, and the Moon. Oxidation and reduction of chlorine are the only processes known to strongly fractionate Cl isotopes, both positively and negatively, and perchlorate has been detected in weight percent concentrations on the Martian surface. The age range and obvious mixing history of the phosphates studied here suggest perchlorate formation and halogen cycling via brines, which have been documented on the Martian surface, has been active throughout Martian

  11. Noble gas isotopes and halogens in volatile-rich inclusions in diamonds

    NASA Technical Reports Server (NTRS)

    Burgess, Raymond; Turner, Grenville

    1994-01-01

    Application of the (40)Ar-(39)Ar method and noble gas studies to diamonds has increased our understanding of their age relationships to the host kimberlite or lamproite, and of the source and composition of volatile-rich fluids in the upper mantle. The properties of diamond (inert, high mechanical strength and low gas diffusivities) means they are especially useful samples for studying gases trapped deep within the earth (less than 150 km) as they are unlikely to have undergone loss or exchange of entrapped material since formation. Volatile-rich fluids (H2O-CO2) are important agents for metasomatic processes in the upper mantle, and the noble gases and halogens preferentially partition into this phase leading to a strong geochemical coherence between these groups of elements. The abundances of the halogens in the major reservoirs of the Earth shows a marked progression from chlorine, concentrated in the oceans, through to iodine which, through its affinity to organic material, is concentrated mainly in sediments. Abundances in the upper mantle are low. This is particularly true for iodine which is of special interest in view of its potential significance as an indicator of sediment recycling and by way of its link to (129)Xe amomalies in the mantle through the low extinct isotope (129)I. Extensions of the (40)Ar-(39)Ar technique enable measurements of halogens and other elements (K, Ca, Ba, U) by production of noble gas isotopes from these species during neutron irradiation. Samples analyzed in this way include 15 coated stones from an unknown source in Zaire, 3 boarts from the Jwaneng and 1 boart from the Orapa kimberlites, both in Botswana.

  12. 13C NMR study of halogen bonding of haloarenes: measurements of solvent effects and theoretical analysis.

    PubMed

    Glaser, Rainer; Chen, Naijun; Wu, Hong; Knotts, Nathan; Kaupp, Martin

    2004-04-07

    Solvent effects on the NMR spectra of symmetrical (X = F (1), X = Cl (2), X = Br (3), X = I (4), X = NO2 (5), X = CN (6)) and unsymmetrical (X = I, Y = MeO (7), Y = PhO (8)) para-disubstituted acetophenone azines X-C6H4-CMe=N-N=CMe-C6H4-Y and of models X-C6H4-CMe=N-Z (X = I, Z = H (9), Z = NH2 (10)), 4-iodoacetophenone (11), and iodobenzene (12) were measured in CDCl(3), DMSO, THF, pyridine, and benzene to address one intramolecular and one intermolecular issue. Solvent effects on the (13)C NMR spectra are generally small, and this finding firmly establishes that the azine bridge indeed functions as a "conjugation stopper," an important design concept in our polar materials research. Since intermolecular halogen bonding of haloarenes do occur in polar organic crystalline materials, the NMR solution data pose the question as to whether the absence of solvent shifts indicates the absence of strong halogen bonding in solution. This question was studied by the theoretical analysis of the DMSO complexes of iodoarenes 4, 9-12, and of iodoacetylene. DFT and MP2 computations show iodine bonding, and characteristic structural and electronic features are described. The nonrelativistic complexation shifts and the change in the spin-orbit induced heavy atom effect of iodine compensate each other, and iodine bonding thus has no apparent effect on Ci in the iodoarenes. For iodides, complexation by DMSO occurs and may or may not manifest itself in the NMR spectra. The absence of complexation shifts in the NMR spectra of halides does not exclude the occurrence of halogen bonding in solution.

  13. Anion-π interactions in complexes of proteins and halogen-containing amino acids.

    PubMed

    Borozan, Sunčica Z; Zlatović, Mario V; Stojanović, Srđan Đ

    2016-06-01

    We analyzed the potential influence of anion-π interactions on the stability of complexes of proteins and halogen-containing non-natural amino acids. Anion-π interactions are distance and orientation dependent and our ab initio calculations showed that their energy can be lower than -8 kcal mol(-1), while most of their interaction energies lie in the range from -1 to -4 kcal mol(-1). About 20 % of these interactions were found to be repulsive. We have observed that Tyr has the highest occurrence among the aromatic residues involved in anion-π interactions, while His made the least contribution. Furthermore, our study showed that 67 % of total interactions in the dataset are multiple anion-π interactions. Most of the amino acid residues involved in anion-π interactions tend to be buried in the solvent-excluded environment. The majority of the anion-π interacting residues are located in regions with helical secondary structure. Analysis of stabilization centers for these complexes showed that all of the six residues capable of anion-π interactions are important in locating one or more of such centers. We found that anion-π interacting residues are sometimes involved in simultaneous interactions with halogens as well. With all that in mind, we can conclude that the anion-π interactions can show significant influence on molecular organization and on the structural stability of the complexes of proteins and halogen-containing non-natural amino acids. Their influence should not be neglected in supramolecular chemistry and crystal engineering fields as well.

  14. A novel fiber-based adsorbent technology

    SciTech Connect

    Reynolds, T.A.

    1997-10-01

    In this Phase I Small Business Innovation Research program, Chemica Technologies, Inc. is developing an economical, robust, fiber-based adsorbent technology for removal of heavy metals from contaminated water. The key innovation is the development of regenerable adsorbent fibers and adsorbent fiber cloths that have high capacity and selectivity for heavy metals and are chemically robust. The process has the potential for widespread use at DOE facilities, mining operations, and the chemical process industry.

  15. Molecularly Imprinted Filtering Adsorbents for Odor Sensing

    PubMed Central

    Shinohara, Sho; Chiyomaru, You; Sassa, Fumihiro; Liu, Chuanjun; Hayashi, Kenshi

    2016-01-01

    Versatile odor sensors that can discriminate among huge numbers of environmental odorants are desired in many fields, including robotics, environmental monitoring, and food production. However, odor sensors comparable to an animal’s nose have not yet been developed. An animal’s olfactory system recognizes odor clusters with specific molecular properties and uses this combinatorial information in odor discrimination. This suggests that measurement and clustering of odor molecular properties (e.g., polarity, size) using an artificial sensor is a promising approach to odor sensing. Here, adsorbents composed of composite materials with molecular recognition properties were developed for odor sensing. The selectivity of the sensor depends on the adsorbent materials, so specific polymeric materials with particular solubility parameters were chosen to adsorb odorants with various properties. The adsorption properties of the adsorbents could be modified by mixing adsorbent materials. Moreover, a novel molecularly imprinted filtering adsorbent (MIFA), composed of an adsorbent substrate covered with a molecularly imprinted polymer (MIP) layer, was developed to improve the odor molecular recognition ability. The combination of the adsorbent and MIP layer provided a higher specificity toward target molecules. The MIFA thus provides a useful technique for the design and control of adsorbents with adsorption properties specific to particular odor molecules. PMID:27886070

  16. Thermodynamic formalism of water uptakes on solid porous adsorbents for adsorption cooling applications

    NASA Astrophysics Data System (ADS)

    Sun, Baichuan; Chakraborty, Anutosh

    2014-05-01

    This Letter presents a thermodynamic formulation to calculate the amount of water vapor uptakes on various adsorbents such as zeolites, metal organic frameworks, and silica gel for the development of an advanced adsorption chiller. This formalism is developed from the rigor of the partition distribution function of each water vapor adsorptive site on adsorbents and the condensation approximation of adsorptive water molecules and is validated with experimental data. An interesting and useful finding has been established that the proposed model is thermodynamically connected with the pore structures of adsorbent materials, and the water vapor uptake highly depends on the isosteric heat of adsorption at zero surface coverage and the adsorptive sites of the adsorbent materials. Employing the proposed model, the thermodynamic trends of water vapor uptakes on various adsorbents can be estimated.

  17. Biological Activity of Recently Discovered Halogenated Marine Natural Products

    PubMed Central

    Gribble, Gordon W.

    2015-01-01

    This review presents the biological activity—antibacterial, antifungal, anti-parasitic, antiviral, antitumor, antiinflammatory, antioxidant, and enzymatic activity—of halogenated marine natural products discovered in the past five years. Newly discovered examples that do not report biological activity are not included. PMID:26133553

  18. Process for oxidation of hydrogen halides to elemental halogens

    DOEpatents

    Lyke, Stephen E.

    1992-01-01

    An improved process for generating an elemental halogen selected from chlorine, bromine or iodine, from a corresponding hydrogen halide by absorbing a molten salt mixture, which includes sulfur, alkali metals and oxygen with a sulfur to metal molar ratio between 0.9 and 1.1 and includes a dissolved oxygen compound capable of reacting with hydrogen halide to produce elemental halogen, into a porous, relatively inert substrate to produce a substrate-supported salt mixture. Thereafter, the substrate-supported salt mixture is contacted (stage 1) with a hydrogen halide while maintaining the substrate-supported salt mixture during the contacting at an elevated temperature sufficient to sustain a reaction between the oxygen compound and the hydrogen halide to produce a gaseous elemental halogen product. This is followed by purging the substrate-supported salt mixture with steam (stage 2) thereby recovering any unreacted hydrogen halide and additional elemental halogen for recycle to stage 1. The dissolved oxygen compound is regenerated in a high temperature (stage 3) and an optical intermediate temperature stage (stage 4) by contacting the substrate-supported salt mixture with a gas containing oxygen whereby the dissolved oxygen compound in the substrate-supported salt mixture is regenerated by being oxidized to a higher valence state.

  19. Double Hole-Lump Interaction between Halogen Atoms.

    PubMed

    Duarte, Darío J R; Peruchena, Nélida M; Alkorta, Ibon

    2015-04-23

    In this paper a theoretical study has been carried out to investigate the nature of the unusual halogen-halogen contacts in the complexes R-X···X-R (with R = -H, -Cl, -F and X = Cl, Br, I). AIM, NBO, and MEP analyses have been used to characterize X···X interactions. Formation of the unusual X···X interactions leads to a significant increase of electron charge density in the bonding region between the two halogen atoms. The geometry and stability of these complexes is mainly due to electrostatic interactions lump(X1) → hole(X2) and lump(X2) → hole(X1) [or equivalently [VS,min(X1) → VS,max(X2) and VS,min(X2) → VS,max(X1)] and the charge transfers LP(X1) → σ*(R-X2) and LP(X2) → σ*(R-X1). In other words, these findings suggest that the electrostatic interactions and the charge transfer play a substantial role in determining the optimal geometry of these complexes, as in conventional halogen bonds, even though the dispersion term is the most important attractive term for all the complexes studied here, save one.

  20. Biochemical studies on the metabolic activation of halogenated alkanes.

    PubMed Central

    Cheeseman, K H; Albano, E F; Tomasi, A; Slater, T F

    1985-01-01

    This paper reviews recent investigations by Slater and colleagues into the metabolic activation of halogenated alkanes in general and carbon tetrachloride in particular. It is becoming increasingly accepted that free radical intermediates are involved in the toxicity of many such compounds through mechanisms including lipid peroxidation, covalent binding, and cofactor depletion. Here we describe the experimental approaches that are used to establish that halogenated alkanes are metabolized in animal tissues to reactive free radicals. Electron spin resonance spectroscopy is used to identify free-radical products, often using spin-trapping compounds. The generation of specific free radicals by radiolytic methods is useful in the determination of the precise reactivity of radical intermediates postulated to be injurious to the cell. The enzymic mechanism of the production of such free radicals and their subsequent reactions with biological molecules is studied with specific metabolic inhibitors and free-radical scavengers. These combined techniques provide considerable insight into the process of metabolic activation of halogenated compounds. It is readily apparent, for instance, that the local oxygen concentration at the site of activation is of crucial importance to the subsequent reactions; the formation of peroxy radical derivatives from the primary free-radical product is shown to be of great significance in relation to carbon tetrachloride and may be of general importance. However, while these studies have provided much information on the biochemical mechanisms of halogenated alkane toxicity, it is clear that many problems remain to be solved. PMID:3007102

  1. The halogens in Luna 16 and Luna 20 soils.

    NASA Technical Reports Server (NTRS)

    Reed, G. W., Jr.; Jovanovic, S.

    1973-01-01

    The halogens, uranium, and lithium contents found in Luna 16, Luna 20, and some Apollo lunar soil samples are discussed. Chlorine and phosphorus pentoxide do not appear to exhibit the same correlation in soils from the Luna 20 and possibly the Luna 16 sites as they do in samples from the Apollo 11-15 sites.

  2. Photoproduction of halogens using platinized TiO2

    NASA Technical Reports Server (NTRS)

    Reichman, B.; Byvik, C. E.

    1981-01-01

    Unlike electrolysis of halide salt solutions, technique using powdered titanium dioxide catalyst requires no external power other than ultraviolet radiation source. Semiconductor powders photocatalyze and photosynthesize many useful reactions; applications are production of halogen molecules, oxidation of hazardous materials in wastewater, and conversion of carbon monoxide to carbon dioxide.

  3. 40 CFR 721.8875 - Substituted halogenated pyridinol.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8875 Substituted halogenated pyridinol. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as substituted...

  4. 40 CFR 721.8850 - Disubstituted halogenated pyridinol.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8850 Disubstituted halogenated pyridinol. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted...

  5. 40 CFR 721.8850 - Disubstituted halogenated pyridinol.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8850 Disubstituted halogenated pyridinol. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted...

  6. 40 CFR 721.8850 - Disubstituted halogenated pyridinol.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8850 Disubstituted halogenated pyridinol. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted...

  7. 40 CFR 721.8875 - Substituted halogenated pyridinol.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8875 Substituted halogenated pyridinol. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as substituted...

  8. 40 CFR 721.8875 - Substituted halogenated pyridinol.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8875 Substituted halogenated pyridinol. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as substituted...

  9. 40 CFR 721.8700 - Halogenated alkyl pyridine.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8700 Halogenated alkyl pyridine. Link to an amendment published at 79 FR 34638, June 18, 2014. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical...

  10. 40 CFR 721.8850 - Disubstituted halogenated pyridinol.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8850 Disubstituted halogenated pyridinol. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted...

  11. 40 CFR 721.8875 - Substituted halogenated pyridinol.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8875 Substituted halogenated pyridinol. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as substituted...

  12. HALOGEN: a tool for fast generation of mock halo catalogues

    NASA Astrophysics Data System (ADS)

    Avila, Santiago; Murray, Steven G.; Knebe, Alexander; Power, Chris; Robotham, Aaron S. G.; Garcia-Bellido, Juan

    2015-06-01

    We present a simple method of generating approximate synthetic halo catalogues: HALOGEN. This method uses a combination of second-order Lagrangian Perturbation Theory (2LPT) in order to generate the large-scale matter distribution, analytical mass functions to generate halo masses, and a single-parameter stochastic model for halo bias to position haloes. HALOGEN represents a simplification of similar recently published methods. Our method is constrained to recover the two-point function at intermediate (10 h-1 Mpc < r < 50 h-1 Mpc) scales, which we show is successful to within 2 per cent. Larger scales (˜100 h-1 Mpc) are reproduced to within 15 per cent. We compare several other statistics (e.g. power spectrum, point distribution function, redshift space distortions) with results from N-body simulations to determine the validity of our method for different purposes. One of the benefits of HALOGEN is its flexibility, and we demonstrate this by showing how it can be adapted to varying cosmologies and simulation specifications. A driving motivation for the development of such approximate schemes is the need to compute covariance matrices and study the systematic errors for large galaxy surveys, which requires thousands of simulated realizations. We discuss the applicability of our method in this context, and conclude that it is well suited to mass production of appropriate halo catalogues. The code is publicly available at https://github.com/savila/halogen.

  13. Method for selective dehalogenation of halogenated polyaromatic compounds

    DOEpatents

    Farcasiu, Malvina; Petrosius, Steven C.

    1994-01-01

    A method for dehalogenating halogenated polyaromatic compounds is provided wherein the polyaromatic compounds are mixed with a hydrogen donor solvent and a carbon catalyst in predetermined proportions, the mixture is maintained at a predetermined pressure, and the mixture is heated to a predetermined temperature and for a predetermined time.

  14. Radiolysis of alanine adsorbed in a clay mineral

    SciTech Connect

    Aguilar-Ovando, Ellen Y.; Negron-Mendoza, Alicia

    2013-07-03

    Optical activity in molecules is a chemical characteristic of living beings. In this work, we examine the hypothesis of the influence of different mineral surfaces on the development of a specific chirality in organic molecules when subjected to conditions simulating the primitive Earth during the period of chemical evolution. By using X-ray diffraction techniques and HPLC/ELSD to analyze aqueous suspensions of amino acids adsorbed on minerals irradiated in different doses with a cobalt-60 gamma source, the experiments attempt to prove the hypothesis that some solid surfaces (like clays and meteorite rocks) may have a concentration capacity and protective role against external sources of ionizing radiation (specifically {gamma}-ray) for some organic compounds (like some amino acids) adsorbed on them. Preliminary results show a slight difference in the adsorption and radiolysis of the D-and L-alanine.

  15. The Important Role of Halogen Bond in Substrate Selectivity of Enzymatic Catalysis

    PubMed Central

    Jiang, Shuiqin; Zhang, Lujia; Cui, Dongbin; Yao, Zhiqiang; Gao, Bei; Lin, Jinping; Wei, Dongzhi

    2016-01-01

    The use of halogen bond is widespread in drug discovery, design, and clinical trials, but is overlooked in drug biosynthesis. Here, the role of halogen bond in the nitrilase-catalyzed synthesis of ortho-, meta-, and para-chlorophenylacetic acid was investigated. Different distributions of halogen bond induced changes of substrate binding conformation and affected substrate selectivity. By engineering the halogen interaction, the substrate selectivity of the enzyme changed, with the implication that halogen bond plays an important role in biosynthesis and should be used as an efficient and reliable tool in enzymatic drug synthesis. PMID:27708371

  16. The Important Role of Halogen Bond in Substrate Selectivity of Enzymatic Catalysis

    NASA Astrophysics Data System (ADS)

    Jiang, Shuiqin; Zhang, Lujia; Cui, Dongbin; Yao, Zhiqiang; Gao, Bei; Lin, Jinping; Wei, Dongzhi

    2016-10-01

    The use of halogen bond is widespread in drug discovery, design, and clinical trials, but is overlooked in drug biosynthesis. Here, the role of halogen bond in the nitrilase-catalyzed synthesis of ortho-, meta-, and para-chlorophenylacetic acid was investigated. Different distributions of halogen bond induced changes of substrate binding conformation and affected substrate selectivity. By engineering the halogen interaction, the substrate selectivity of the enzyme changed, with the implication that halogen bond plays an important role in biosynthesis and should be used as an efficient and reliable tool in enzymatic drug synthesis.

  17. Toxicity of Uranium Adsorbent Materials using the Microtox Toxicity Test

    SciTech Connect

    Park, Jiyeon; Jeters, Robert T.; Gill, Gary A.; Kuo, Li-Jung; Bonheyo, George T.

    2015-10-01

    The Marine Sciences Laboratory at the Pacific Northwest National Laboratory evaluated the toxicity of a diverse range of natural and synthetic materials used to extract uranium from seawater. The uranium adsorbent materials are being developed as part of the U. S. Department of Energy, Office of Nuclear Energy, Fuel Resources Program. The goal of this effort was to identify whether deployment of a farm of these materials into the marine environment would have any toxic effects on marine organisms.

  18. On the formation of tropical rings of atomic halogens: Causes and implications

    NASA Astrophysics Data System (ADS)

    Saiz-Lopez, Alfonso; Fernandez, Rafael P.

    2016-03-01

    Halogens produced by ocean biological and photochemical processes reach the tropical tropopause layer (TTL), where cold temperatures and the prevailing low ozone abundances favor the diurnal photochemical enhancement of halogen atoms. Under these conditions atomic bromine and iodine are modeled to be the dominant inorganic halogen species in the sunlit TTL, surpassing the abundance of the commonly targeted IO and BrO radicals. We suggest that due to the rapid photochemical equilibrium between halogen oxides and halogen atoms a natural atmospheric phenomenon evolves, which we have collectively termed "tropical rings of atomic halogens." We describe the main causes controlling the modeled appearance and variability of these superposed rings of bare bromine and iodine atoms that circle the tropics following the Sun. Some potential implications for atmospheric oxidizing capacity are also explored. Our model results suggest that if experimentally confirmed, the extent and intensity of the halogen rings would directly respond to changes in oceanic halocarbon emissions, their atmospheric transport, and photochemistry.

  19. F+ tunable laser activity and interaction of atomic halogens (F, Cl and Br) at the low coordinated surface sites of SrOAb initio and DFT calculations.

    PubMed

    Shalabi, Ahmed S

    2002-10-01

    The twofold potential of F+ color centers at the low coordinated surfaces of SrO for providing tunable laser activity and adsorption properties for atomic halogens (F, Cl and Br) has been investigated using ab initio electronic structure calculations. SrO clusters of variable sizes were embedded in simulated Coulomb fields that closely approximate the Madelung fields of the host surfaces and the nearest neighbor ions to F+ were allowed to relax to equilibrium. Based on Stokes shifted optical transition bands and horizontal shifts along the configuration coordinate diagrams, the F+ laser activity was found to decrease as the coordination number of the surface ions decreases from 5 (flat) to 4 (edge) to 3 (corner). An attempt has been made to explain this result in terms of Madelung potentials and optical-optical conversion efficiencies. All relaxed excited states are deep below the conduction bands of the perfect ground states, implying that F+ is a laser-suitable defect. The most laser active flat surface is the least probable for relaxed excited state orientational destruction of F+. The excited state at the edge has the highest energy, implying exciton (energy) transfer to the flat and edge sites. F+ relaxation and defect-formation energies increase with increasing surface coordination number. The Glasner-Tompkins relation between the fundamental optical absorption of F+ in solids and the fundamental absorption of the host crystals can be generalized to include the low coordinated surfaces of SrO. The F+ color center changes the nature of halogen-surface interaction (adsorption energies) from physical adsorption to chemical adsorption. The halogen-surface interactions increase with increasing electronegativity of the halogen. The calculated adsorption energies can be explained in terms of surface electrostatic potentials, and the covalent spin pairing mechanism plays a dominant role in determining adsorbate-substrate interactions.

  20. Comment on "Cosmic-ray-driven reaction and greenhouse effect of halogenated molecules: Culprits for atmospheric ozone depletion and global climate change"

    NASA Astrophysics Data System (ADS)

    Müller, Rolf; Grooß, Jens-Uwe

    2014-04-01

    Lu's "cosmic-ray-driven electron-induced reaction (CRE) theory" is based on the assumption that the CRE reaction of halogenated molecules (e.g., chlorofluorocarbons (CFCs), HCl, ClONO2) adsorbed or trapped in polar stratospheric clouds in the winter polar stratosphere is the key step in forming photoactive halogen species that are the cause of the springtime ozone hole. This theory has been extended to a warming theory of halogenated molecules for climate change. In this comment, we discuss the chemical and physical foundations of these theories and the conclusions derived from the theories. First, it is unclear whether the loss rates of halogenated molecules induced by dissociative electron attachment (DEA) observed in the laboratory can also be interpreted as atmospheric loss rates, but even if this were the case, the impact of DEA-induced reactions on polar chlorine activation and ozone loss in the stratosphere is limited. Second, we falsify several conclusions that are reported on the basis of the CRE theory: There is no polar ozone loss in darkness, there is no apparent 11-year periodicity in polar total ozone measurements, the age of air in the polar lower stratosphere is much older than 1-2 years, and the reported detection of a pronounced recovery (by about 20-25%) in Antarctic total ozone measurements by the year 2010 is in error. There are also conclusions about the future development of sea ice and global sea level which are fundamentally flawed because Archimedes' principle is neglected. Many elements of the CRE theory are based solely on correlations between certain datasets which are no substitute for providing physical and chemical mechanisms causing a particular behavior noticeable in observations. In summary, the CRE theory cannot be considered as an independent, alternative mechanism for polar stratospheric ozone loss and the conclusions on recent and future surface temperature and global sea level change do not have a physical basis.