Sample records for acenaphthene

  1. Degradation of Acenaphthene by Ozone


    Objective To investigate the oxidation of acenaphthene (Ace), a polycyclic aromatic hydrocarbon (PAH) with a saturated C-C bond by ozone and to characterize the intermediate products of ozonation. Methods Ozone was generated from filtered dry oxygen by an ozone generator and continually bubbled into a reactor containing 1g/L Ace dissolved in an acetonitrile/water solvent mixture (90/10, v/v) at a rate of 0.5 mg/s. HPLC was used to analyze the Ace concentration. Total organic carbon (TOC) was used to measure the amount of water soluble organic compounds. GC-MS was used to identify the ozonized products. Oxygen uptake rate (OUR) of activated sludge was used to characterize the biodegradability of ozonized products. Results During the ozonation process, Ace was degraded, new organic compounds were produced and these intermediate products were difficult mineralize by ozone, with increasing TOC of soluble organics. The ozonized products were degraded by activated sludge more easily than Ace. Conclusion Ozonation decomposes the Ace and improves its biodegradability. The ozonation combined with biological treatment is probably an efficient and economical way to mineralize acenaphthene in wastewater.

  2. Naphthalene and acenaphthene decomposition by electron beam generated plasma application

    Ostapczuk, A.; Hakoda, T.; Shimada, A.; Kojima, T. [Institute for Nuclear Chemistry and Technology, Warsaw (Poland)


    The application of non-thermal plasma generated by electron beam (EB) was investigated in laboratory scale to study decomposition of polycyclic aromatic hydrocarbons like naphthalene and acenaphthene in flue gas. PAH compounds were treated by EB with the dose up to 8 kGy in dry and humid base gas mixtures. Experimentally established G-values gained 1.66 and 3.72 mol/100 eV for NL and AC at the dose of 1 kGy. NL and AC removal was observed in dry base gas mixtures showing that the reaction with OH radical is not exclusive pathway to initialize PAH decomposition; however in the presence of water remarkably higher decomposition efficiency was observed. As by-products of NL decomposition were identified compounds containing one aromatic ring and oxygen atoms besides CO and CO{sub 2}. It led to the conclusion that PAH decomposition process in humid flue gas can be regarded as multi-step oxidative de-aromatization analogical to its atmospheric chemistry.

  3. Gas- and particle-phase products from the photooxidation of acenaphthene and acenaphthylene by OH radicals

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


    This work is focused on the gas-phase oxidation of acenaphthylene and acenaphthene by OH radicals and associated secondary organic aerosol (SOA) formation under low and high-NOx conditions. Experiments were carried out in an atmospheric simulation chamber using a proton transfer reaction time-of-flight-mass spectrometer (PTR-TOF-MS) and an aerosol time-of-flight-mass spectrometer (ATOFMS) to chemically characterize the gas- and particle-phase products, respectively. Due to the structures of these two aromatic compounds, the proposed chemical mechanisms exhibit some differences. In the case of acenaphthene, H-atom abstraction from the saturated cyclopenta-fused ring was found to be competitive with the OH-addition to the aromatic rings. During the photooxidation of acenaphthene using nitrous acid (HONO), aromatic ring-opening products such as indanone and indanone carbaldehyde, generated through OH addition to the aromatic ring, were formed in higher yields compared to low-NOx conditions. In the case of acenaphthylene, OH addition to the unsaturated cyclopenta-fused ring was strongly favored. Hence, ring-retaining species such as acenaphthenone and acenaphthenequinone, were identified as the main reaction products in both gas- and particle-phases, especially under high-NOx conditions. Subsequent SOA formation was observed in all experiments and SOA yields were determined under low/high-NOx conditions to be 0.61/0.46 and 0.68/0.55 from the OH-initiated oxidation of acenaphthylene and acenaphthene, respectively.

  4. Isolation and Identification of Carcinogen Acenaphthene-Degrading Endemic Bacteria from Crude Oil Contaminated Soils around Abadan Refinery

    Farshid Kafilzadeh


    Full Text Available Background and Objective: PAHs are non-polar organic compounds consisting of two or more fused benzene multi-rings. Among these compounds, acenaphthene is a multi-ring hydrocarbon that occurs abundantly in nature. Use of microorganisms to clean the contaminations of soil can be cheap and effective. The most important acenaphthene-degrading bacteria are pseudomonas, micrococcus, and Bacillus. The goal of this study was to isolate and identify the bacteria which degrade acenaphthene in soils around Abadan Refinery and to investigate the relation between the levels of environmental pollution with acenaphthene. Materials and Methods: Soil samples were collected from three areas around Abadan Refinery. The number of the bacteria was counted on the nutrient agar culture with and without acenaphthene. Isolation of the bacteria was done by culturing the samples on acenaphthene broth with a mineral-salt medium, and on an acenaphthene agar medium. Then, the bacteria were identified via biochemical diagnostic tests. Results: The logarithm average of the bacteria was 4.786 ± 0.073 at a medium with acenaphthene, which was 6.671 ± 0.073 less than that of the control medium. The maximum number of degrading bacteria was 7.089 ± 0.089 at Station C, and the minimum number of the degrading bacteria was 4.485 ± 0.089 at Station B. In this study, Bacillus sp, Micrococcus Luteus, Corynebacterium sp, Staphylococcus epidermidis, and Pseudomonas sp bacteria were isolated and identified in terms of frequency, respectively. Conclusion: The results of this study showed that the soil around Abadan Refinery contained a great number of acenaphthene degrading bacteria, especially Bacillus and Micrococcus.

  5. Thermal kinetic and dielectric parameters of acenaphthene crystal grown by vertical Bridgman technique

    Karuppusamy, S.; Dinesh Babu, K.; Nirmal Kumar, V.; Gopalakrishnan, R.


    The bulk acenaphthene crystal was grown in a single-wall ampoule by vertical Bridgman technique. X-ray diffraction analysis confirmed the orthorhombic crystal system of title compound with space group Pcm21. Thermal behavior of compound was studied using thermogravimetry—differential scanning calorimetry analysis. Thermal kinetic parameters like activation energy, frequency factor, Avrami exponent, reaction rate and degree of conversion were calculated using Kissingers and Ozawa methods under non-isothermal condition for acenaphthene crystal and reported for the first time. The calculated thermal kinetic parameters are presented. Dielectric studies were performed to calculate the dielectric parameters such as dielectric constant, dielectric loss, AC conductivity, and activation energy from Arrhenius plot.

  6. 1,2-Bis(imino)acenaphthene complexes of molybdenum and nickel.

    Fedushkin, Igor L; Skatova, Alexandra A; Lukoyanov, Anton N; Khvoinova, Nalalie M; Piskunov, Alexander V; Nikipelov, Alexander S; Fukin, Georgy K; Lysenko, Konstantin A; Irran, Elisabeth; Schumann, Herbert


    Molybdenum hexacarbonyl reacts with 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (, dpp-BIAN) and 1,2-bis[(trimethylsilyl)imino]acenaphthene (, tms-BIAN) in toluene to produce (dpp-BIAN)Mo(CO)(4) () and (tms-BIAN)Mo(CO)(4) (), respectively. The reaction of [CpNi(CO)](2) with yields (dpp-BIAN)NiCp (). Metathesis between Li(2)(tms-BIAN) and NiCl(2)(dppe) affords the Ni(0) complex (tms-BIAN)Ni(dppe) (). The diamagnetic compounds , and have been characterized by (1)H, (29)Si and (31)P NMR spectroscopy, IR spectroscopy and elemental analysis. The ESR spectrum of the paramagnetic compound indicates the presence of Ni(i) coordinated by Cp and a neutral dpp-BIAN ligand. The molecular structures of have been determined by single-crystal X-ray analysis.

  7. Effect of concentration, temperature, and freezing rate on the phosphorescence parameters of acenaphthene in n-hexane matrices

    Zhdanova, N. V.; Deryabin, M. I.


    The effect of the concentration, temperature, and freezing rate on the spectra, kinetics, and intensity of phosphorescence of acenaphthene in polycrystalline n-hexane matrices has been studied. The specific features of the transformation of quasi-lines in the phosphorescence spectrum of molecules embedded in an n-hexane crystal lattice into broad molecular bands at high concentrations of the solution (~10‒1 mol/L) have been considered. It has been demonstrated that a distortion of the n-hexane crystal lattice at a high concentration of embedded acenaphthene molecules can be a cause of the observed transformation of the quasi-line spectrum.

  8. X-ray, Hirshfeld surface analysis, spectroscopic and DFT studies of polycyclic aromatic hydrocarbons: Fluoranthene and acenaphthene

    Śmiszek-Lindert Wioleta


    Full Text Available The X-ray structure, theoretical calculation, Hirshfeld surfaces analysis, IR and Raman spectra of fluoranthene and acenaphthene were reported. Acenaphthene crystallizes in the orthorhombic crystal system and space group P21ma, with crystal parameters a = 7.2053 (9 Å, b = 13.9800 (15 Å, c = 8.2638 (8 Å, Z = 4 and V = 832.41 (16 Å3. In turn, the grown crystals of fluoranthene are in monoclinic system with space group P21/n. The unit cell parameters are a = 18.3490 (2 Å, b = 6.2273 (5 Å, c = 19.8610 (2 Å, β = 109.787 (13°, Z = 8 and unit cell volume is 2135.50 (4 Å3. Theoretical calculations of the title compounds isolated molecule have been carried out using DFT at the B3LYP level. The intermolecular interactions in the crystal structure, for both the title PAHs, were analyzed using Hirshfeld surfaces computational method.

  9. Impact of dissolved humic acid on the bioavailability of acenaphthene and chrysene assessed by membrane-based passive samplers


    Dissolved organic carbon (DOC) is known to reduce the bioavailability of hydrophobic organic compounds (HOCs) in aqueous environments. This reduction occurs as a result of adsorption to DOC, apparently reducing the freely dissolved concentration of HOCs. In the present study, triolein-embedded cellulose acetate membrane (TECAM) and Japanese medaka (Oryzias latipes) were used to measure the uptake of acenaphthene and chrysene in the presence of commercial humic acid (HA) at different concentrations (0―15 mg C·L-1) under controlled laboratory conditions. Apparent uptake rate constants for PAHs in TECAM and medaka were compared and DOC-water partition coefficients (KDOCs) of two PAHs were calculated with different sampling methods by model fit. Results showed that HA present in water significantly reduced the uptake of PAHs in TECAM and medaka. The obtained values of log KDOC of acenaphthene and chrysene measured by TECAM were 4.63 and 5.83, respectively, whereas biologically determined values were 4.52 and 5.76, respectively. These log KDOC values were comparable to earlier published KDOCs toward commercial HA, thereby indicating that TECAM accumulated only the freely dissolved fraction of chemicals and uptake PAHs in a manner similar to that of fish. All these results suggested that the TECAM method can provide a good means for assessing the impact of DOC on bioavailability of PAHs in the aqueous environment.

  10. Bioremediation of polycyclic aromatic hydrocarbon (PAH) compounds: (acenaphthene and fluorene) in water using indigenous bacterial species isolated from the Diep and Plankenburg rivers, Western Cape, South Africa.

    Alegbeleye, Oluwadara Oluwaseun; Opeolu, Beatrice Olutoyin; Jackson, Vanessa


    This study was conducted to investigate the occurrence of PAH degrading microorganisms in two river systems in the Western Cape, South Africa and their ability to degrade two PAH compounds: acenaphthene and fluorene. A total of 19 bacterial isolates were obtained from the Diep and Plankenburg rivers among which four were identified as acenaphthene and fluorene degrading isolates. In simulated batch scale experiments, the optimum temperature for efficient degradation of both compounds was determined in a shaking incubator after 14 days, testing at 25°C, 30°C, 35°C, 37°C, 38°C, 40°C and 45°C followed by experiments in a Stirred Tank Bioreactor using optimum temperature profiles from the batch experiment results. All experiments were run without the addition of supplements, bulking agents, biosurfactants or any other form of biostimulants. Results showed that Raoultella ornithinolytica, Serratia marcescens, Bacillus megaterium and Aeromonas hydrophila efficiently degraded both compounds at 37°C, 37°C, 30°C and 35°C respectively. The degradation of fluorene was more efficient and rapid compared to that of acenaphthene and degradation at Stirred Tank Bioreactor scale was more efficient for all treatments. Raoultella ornithinolytica, Serratia marcescens, Bacillus megaterium and Aeromonas hydrophila degraded a mean total of 98.60%, 95.70%, 90.20% and 99.90% acenaphthene, respectively and 99.90%, 97.90%, 98.40% and 99.50% fluorene, respectively. The PAH degrading microorganisms isolated during this study significantly reduced the concentrations of acenaphthene and fluorene and may be used on a larger, commercial scale to bioremediate PAH contaminated river systems.

  11. An efficient synthesis of 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one catalyzed by recyclable solid superacid SO42-/TiO2under grinding condition

    Guo Liang Feng


    An efficient synthesis of symmetrical 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one is achieved via a reaction of acenaphthe-nequinone and indoles catalyzed by solid superacid SO42-/TiO2 under solvent-free conditions at room temperature by grinding,which provides an efficient route to the synthesis of symmetrical 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one.This procedure offers several advantages including solvent-free conditions,excellent yields of products,simple work-up as well as reuse of catalysts which makes it a useful and attractive protocol for the synthesis of these compounds.

  12. Thermal, spectroscopic, and solvent influence studies on mixed-ligand copper(II) complexes containing the bulky ligand: Bis[ N-( p-tolyl)imino]acenaphthene

    El-Ayaan, Usama; Gabr, I. M.


    Four mixed-ligand copper(II) complexes containing the rigid bidentate nitrogen ligand bis[ N-( p-tolyl)imino]acenaphthene (abb. p-Tol-BIAN) ligand are reported. These complexes, namely [Cu( p-Tol-BIAN) 2](ClO 4) 21, [Cu( p-Tol-BIAN)(acac)](ClO 4) 2, [Cu( p-Tol-BIAN)Cl 2] 3 and [Cu( p-Tol-BIAN)(AcOH) 2](ClO 4) 24 (where acac, acetylacetonate and AcOH, acetic acid) have been prepared and characterized by elemental analysis, spectroscopic, magnetic and molar conductance measurements. ESR spectra suggest a square planar geometry for complexes 1 and 2. In complexes 3 and 4, a distorted tetrahedral arrangement around copper(II) centre was suggested. Solvatochromic behavior of all studied complexes indicates strong solvatochromism of their solutions. The observed solvatochromism is mainly due to the solute-solvent interaction between the chelate cation and the solvent molecules. Thermal properties and decomposition kinetics of all complexes are investigated. The kinetic parameters ( E, A, Δ H, Δ S and Δ G) of all thermal decomposition stages have been calculated using the Coats-Redfern and other standard equations.

  13. Molecular structures and thermodynamic properties of polybrominated acenaphthene compounds%多溴苊化合物的分子结构和热力学性质

    曾小兰; 于永生


    Polybrominated acenaphthene (PBACE) compounds are one type of latent chemical pollutants. In this article, molecular geometric structures of 35 PBACE compounds were optimized using density functional theory (DFT) at the B3LYP/6-311G** level and some thermodynamic properties of them in the ideal gas state were calculated. The relations of these thermodynamic properties with the number and position of bromine atoms were also explored, from which the relative stability of PBACE congeners was theoretically proposed according to the magnitude of the relative standard Gibbs free energy of formation (△r,fGe). The computed results show that atoms other than four H are in the same plane in most PBACE isomers. The values of △fHe and △fGe of both most stable and least stable PBACE isomers increase with increasing the number of bromine atoms. The values of △fHe and △fGe for PBACE isomers with the same number of bromine atoms show a strong dependence on the position of bromine atoms and the relative stability of PBACE congeners are mainly determined by intramolecular adjacent Br-Br nuclear repulsive interaction between Br atoms at two different six-membered rings. All of PBACE congeners are more difficult to form thermodynamically than their parent compound.%多溴苊是一类潜在的有机污染物.本文采用密度泛函理论在B3LYP/6-311G**水平上优化35个多溴苊化合物的分子几何结构,并获得它们在理想气态的一些热力学性质的数值,研究这些性质与取代的溴原子数目和位置的关系,根据各异构体的标准生成Gibbs自由能的相对大小,求得它们的热力学稳定性顺序.计算结果表明:在大部分多溴苊分子中,除4个氢原子外的其他原子在同一平面上.多溴苊最稳定及最不稳定异构体的△fHθ及△fGθ,都随Br原子数目增加而逐渐增加.溴原子数目相同的多溴苊异构体的△fHθ和△fGθ与溴原子的取代位置有很大的关系,其相对稳定性主要

  14. Synthesis, structural and solvent influence studies on solvatochromic mixed-ligand copper(II) complexes with the rigid nitrogen ligand: bis[ N-(2,4,6-trimethylphenyl)imino]acenaphthene

    El-Ayaan, Usama; Murata, Fumiko; El-Derby, Soheir; Fukuda, Yutaka


    Three mixed-ligand copper (II) complexes containing the rigid bidentate nitrogen ligand bis[ N-(2,4,6-trimethylphenyl)imino]acenaphthene (abbr. 2,4,6-Me 3C 6H 2-BIAN) and β-diketonate (dike) ligands are reported and characterized. These complexes namely, [Cu(dike)(2,4,6-Me 3C 6H 2-BIAN)]ClO 4 {where dike=acac (acetylacetonate), bzac (benzoylacetonate) or (dibm) dibenzoylmethanate}have been synthesized and characterized by elemental analysis, spectroscopic, magnetic and molar conductance measurements. In addition to their high solubility in various organic solvents, these three complexes show a color change on going from one solvent to another, that is, strong solvatochromism of their solutions. The observed solvatochromism is mainly due to the solute-solvent interaction between the chelate cation and the solvent molecules. Reported also are the X-ray crystal structures of the free 2,4,6-Me 3C 6H 2-BIAN ligand and the [Cu(acac)(2,4,6-Me 3C 6H 2-BIAN)]ClO 4 complex.

  15. An experimental and theoretical investigation of Acenaphthene-5-boronic acid: conformational study, NBO and NLO analysis, molecular structure and FT-IR, FT-Raman, NMR and UV spectra.

    Karabacak, Mehmet; Sinha, Leena; Prasad, Onkar; Asiri, Abdullah M; Cinar, Mehmet


    The solid state Fourier transform infrared (FT-IR) and FT-Raman spectra of Acenaphthene-5-boronic acid (AN-5-BA), have been recorded in the range 4000-400cm(-1) and 4000-10cm(-1), respectively. Density functional theory (DFT), with the B3LYP functional was used for the optimization of the ground state geometry and simulation of the infrared and Raman spectra of the molecule. The vibrational wave numbers and their assignments were examined theoretically using the Gaussian 09 set of quantum chemistry codes and the normal modes were assigned by a scaled quantum mechanical (SQM) force field approach. Hydrogen-bonded dimer of AN-5-BA, optimized by counterpoise correction, has also been studied by B3LYP at the 6-311++G(d,p) level and the effects of molecular association through O-H⋯O hydrogen bonding have been discussed. The (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by Gauge-Including Atomic Orbital (GIAO) method. Natural bond orbital (NBO) analysis has been applied to study stability of the molecule arising from charge delocalization. UV spectrum of the title compound was also recorded and the electronic properties, such as frontier orbitals, and band gap energies were measured by TD-DFT approach. The first order hyperpolarizability 〈β〉, its components and associated properties such as average polarizability and anisotropy of the polarizability (α and Δα) of AN-5-BA was calculated using the finite-field approach.

  16. Synthesis, crystal structure and luminescence properties of acenaphthene benzohydrazide based ligand and its zinc(II) complex

    Kumar, Mukesh; Roy, Soumyabrata; Faizi, Md. Serajul Haque; Kumar, Santosh; Singh, Mantu Kumar; Kishor, Shyam; Peter, Sebastian C.; John, Rohith P.


    The complex compound of zinc(II) supported by (Z)-2-hydroxy-N‧-(1-oxoacenaphthylen-2(1H) ylidene)benzohydrazide ligand (H2L1) has been reported and discussed. The reaction of zinc acetate with H2L1 ligand leads to the formation of a mononuclear zinc(ii) complex, [Zn(HL1)2H2O]. The ligand, H2L1 has been characterized by elemental analysis, 1H, 13C and 1Hsbnd COSY -NMR, IR and ESI-MS, while the complex was characterized by elemental analysis, IR, and ESI-MS. The crystal structures of the free ligand H2L1 and the complex have also been determined by single crystal X-ray diffraction. The ligand chelates with metal centre with a nitrogen atom of imino moiety and an oxygen atom of enolic group. The complex shows distorted trigonal bipyramidal geometry around the metal centre with oxygen atoms lying in the equatorial plane and imino nitrogen atoms along the axial direction. The DFT/TD-DFT calculations were performed on both the ligand and its zinc complex to get insight into the structural, electronic and optical properties. The photoluminescence, fluorescence properties of the complex have been investigated.

  17. The ligand redox behavior and role in 1,2-bis[(2,6-diisopropylphenyl)imino]-acenaphthene nickel-TMA(MAO) systems for ethylene polymerization.

    Gao, Wei; Xin, Lan; Hao, Zhiqiang; Li, Guodong; Su, Ji-Hu; Zhou, Lijing; Mu, Ying


    The BIAN ligands in Brookhart catalysts were proved to be redox-active during the catalyst activation with alkylaluminum or MAO, and the neutral catalytically active species with a radical anionic BIAN rather than the cationic ones with a neutral BIAN ligand were confirmed to be formed in the catalytic system.

  18. 40 CFR 464.21 - Specialized definitions.


    ...) Casting Quench (§ 464.25(a) and § 464.26(a)): 23. chloroform (trichloromethane) 64. pentachlorophenol 66....26(c)): 1. acenaphthene 22. para-chloro meta-cresol 23. chloroform (trichloromethane) 34. 2,4... § 464.26(e)): 1. acenaphthene 22. para-chloro meta-cresol 23. chloroform (trichloromethane) 34....

  19. Comparison of PCBs and PAHs levels in European coastal waters using mussels from the

    Olenycz, M.; Sokolowski, A.; Niewinska, A.; Niewinska, M.; Namiesnik, J.; Hummel, H.; Jansen, J.


    Mussels from the Mytilus edulis complex were used as biomonitors for two groups of organic pollutants: polychlorinated biphenyls (PCBs, congeners: 28, 52, 101, 118, 138, 153 and 180) and polycyclic aromatic hydrocarbons (PAHs, naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthra

  20. Differential immunomodulatory responses to nine polycyclic aromatic hydrocarbons applied by passive dosing

    Oostingh, Gertie J.; Smith, Kilian E. C.; Tischler, Ulrike


    (a)antracene and benzo(a)pyrene. Cytokine promoter expression was then studied in dose response experiments with acenaphthene, phenanthrene and benzo(a)anthracene. The strongest induction was observed for benzo(a)anthracene. Cell viability analysis was performed and showed that none of the PAHs induced cytotoxicity...

  1. Adaptive behavior of a redox-active gallium carbenoid in complexes with molybdenum.

    Fedushkin, Igor L; Sokolov, Vladimir G; Piskunov, Alexander V; Makarov, Valentine M; Baranov, Eugeny V; Abakumov, Gleb A


    A gallium(I) carbenoid derived from redox-active diimine 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) in complexes with molybdenum may serve either as a neutral [(dpp-bian)Ga:] or an anionic [(dpp-bian)Ga:](-) two-electron donor depending on the electronic state of the transition metal.

  2. Toxicity of xenobiotics during sulfate, iron, and nitrate reduction in primary sewage sludge suspensions

    Elsgaard, Lars


    The effect and persistence of six organic xenobiotics was tested under sulfate-, iron-, and nitrate-reducing conditions in primary sewage sludge suspensions. The xenobiotics tested were acenaphthene, phenanthrene, di(2-ethylhexyl)phthalate (DEHP), 4-nonylphenol (4-NP), linear alkylbenzene sulfonate...

  3. Partition of polycyclic aromatic hydrocarbons on organobentonites


    A series of organobentonites synthesized by exchanging organiccation such as dodecyltri-methylammonium (DTMA),benzyldimethyltetradecylammonium (BDTDA), cetyltrimethyl-ammonium (CTMA), octodeyltrimethylammonium (OTMA) on bentonite. The optimal condition, properties and mechanisms for the organobentonites to sorb phenanthrene, anthracene, naphthalene, acenaphthene in water were investigated in detail. The partition behavior was determined for four polycyclic aromatic hydrocarbons (PAHs), such as naphthalene, phenanthrene, anthracene and acenaphthene, from water to a series of organobentonites. The interlayer spacings and organic carbon contents of organobentonites, removal rate and sorption capacities for organobentonites to treat phenanthrene,anthracene, naphthalene, acenaphthene were correlated to the length of alkyl chains and the amounts of cation surfactant exchanged on Foundation item: the bentonite. Phenanthrene, anthracene, naphthalene, and acenaphthene sorption to organobentonites were characterized by linear isotherms, indicating solute partition between water and the organic phase composed of the large alkyl functional groups of quaternary ammonium cations. PAHs distribution coefficients (Kd)between organobentonites and water were proportional to the organic carbon contents of organobentonites. However, the partition coefficients (Koc) were nearly constants for PAHs in the system of organobentonite-water. The Koc of phenanthrene, anthracene,naphthalene, acenaphthene were 2.621x105, 2.106x105, 2.247x104,5.085x104, respectively. The means Koc values on the organobentonites are about ten to twenty times larger than the values on the soils/sediments, what is significant prerequisite for organobentonite to apply to remediation of pollution soil and groundwater. The sorption mechanism was also evaluated from octanol-water partition coefficients and aqueous solubility of PAHs. The correlations between lgKoc and 1gkow, 1gKoc and 1gS for PAHs in the system of water

  4. 40 CFR 464.41 - Specialized definitions.


    .... tetrachloroethylene (2) Die Casting (§ 465.45(b) and § 464.46(b)): 1. acenaphthene 21. 2,4,6-trichlorophenol 22. para.... tetrachloroethylene 86. toluene 87. trichloroethylene (3) Melting Furnace Scrubber (§ 464.45(c) and § 464.46(c)): 31.... tetrachloroethylene 86. toluene 87. trichloroethylene (4) Mold Cooling (§ 464.45(d) and § 464.46(d)): 21....

  5. Intrinsic biodegradation potential of aromatic hydrocarbons in an alluvial aquifer--potentials and limits of signature metabolite analysis and two stable isotope-based techniques.

    Morasch, Barbara; Hunkeler, Daniel; Zopfi, Jakob; Temime, Brice; Höhener, Patrick


    Three independent techniques were used to assess the biodegradation of monoaromatic hydrocarbons and low-molecular weight polyaromatic hydrocarbons in the alluvial aquifer at the site of a former cokery (Flémalle, Belgium). Firstly, a stable carbon isotope-based field method allowed quantifying biodegradation of monoaromatic compounds in situ and confirmed the degradation of naphthalene. No evidence could be deduced from stable isotope shifts for the intrinsic biodegradation of larger molecules such as methylnaphthalenes or acenaphthene. Secondly, using signature metabolite analysis, various intermediates of the anaerobic degradation of (poly-) aromatic and heterocyclic compounds were identified. The discovery of a novel metabolite of acenaphthene in groundwater samples permitted deeper insights into the anaerobic biodegradation of almost persistent environmental contaminants. A third method, microcosm incubations with 13C-labeled compounds under in situ-like conditions, complemented techniques one and two by providing quantitative information on contaminant biodegradation independent of molecule size and sorption properties. Thanks to stable isotope labels, the sensitivity of this method was much higher compared to classical microcosm studies. The 13C-microcosm approach allowed the determination of first-order rate constants for 13C-labeled benzene, naphthalene, or acenaphthene even in cases when degradation activities were only small. The plausibility of the third method was checked by comparing 13C-microcosm-derived rates to field-derived rates of the first approach. Further advantage of the use of 13C-labels in microcosms is that novel metabolites can be linked more easily to specific mother compounds even in complex systems. This was achieved using alluvial sediments where 13C-acenaphthyl methylsuccinate was identified as transformation product of the anaerobic degradation of acenaphthene.

  6. Risk assessment of Xenobiotics in stormwater discharged to Harrestrup Å, Denmark

    Eriksson, Eva; Baun, Anders; Mikkelsen, Peter Steen


    Surface waters are highly manipulated in many cities in Europe, and the flow is largely impacted by discharges of stormwater and combined sewer overflow. Toxicity tests shown adverse effects in some of these recipients due to the presence of xenobiotic organic carbons (XOCs). Harrestrup Å, situat...... option to be implemented in order to improve the water quality. These are five pesticides (diuron, glyphosate, isoproturon, MCPA, terbutylazine), 4 PAHs (acenaphthene, fluoranthene, fluorene, pyrene), 3 others (LAS, nonylphenol and dinitro-o-cresol)....

  7. Reactions of 1-naphthyl radicals with ethylene. Single pulse shock tube experiments, quantum chemical, transition state theory, and multiwell calculations.

    Lifshitz, Assa; Tamburu, Carmen; Dubnikova, Faina


    The reactions of 1-naphthyl radicals with ethylene were studied behind reflected shock waves in a single pulse shock tube, covering the temperature range 950-1200 K at overall densities behind the reflected shocks of approximately 2.5 x 10(-5) mol/cm3. 1-Iodonaphthalene served as the source for 1-naphthyl radicals as its C-I bond dissociation energy is relatively small. It is only approximately 65 kcal/mol as compared to the C-H bond strength in naphthalene which is approximately 112 kcal/mol and can thus produce naphthyl radicals at rather low reflected shock temperatures. The [ethylene]/[1-iodo-naphthalene] ratio in all of the experiments was approximately 100 in order to channel the free radicals into reactions with ethylene rather than iodonaphthalene. Four products resulting from the reactions of 1-naphthyl radicals with ethylene were found in the post shock samples. They were vinyl naphthalene, acenaphthene, acenaphthylene, and naphthalene. Some low molecular weight aliphatic products at rather low concentrations, resulting from the attack of various free radicals on ethylene were also found in the shocked samples. In view of the relatively low temperatures employed in the present experiments, the unimolecular decomposition rate of ethylene is negligible. Three potential energy surfaces describing the production of vinyl naphthalene, acenaphthene, and acenaphthylene were calculated using quantum chemical methods and rate constants for the elementary steps on the surfaces were calculated using transition state theory. Naphthalene is not part of the reactions on the surfaces. Acenaphthylene is obtained only from acenaphthene. A kinetics scheme containing 27 elementary steps most of which were obtained from the potential energy surfaces was constructed and computer modeling was performed. An excellent agreement between the experimental yields of the four major products and the calculated yields was obtained.

  8. Pollution characteristics of polycyclic aromatic hydrocarbons (PAHs) in oily sludge from the Zhongyuan Oilfield and its peripheral soils

    KUANG Shaoping; XU Zhong


    The purpose of this study is to determine the degree of contamination caused by polycyclic aromatic hydrocarbons (PAHs) in oily sludge and soils around it in the Zhongyuan Oilfield. The contents of polycyclic aromatic hydrocarbons in oily sludge samples were determined with HPLC. The contents of PAHs of oily sludge from three different oil production plants vary from high to low in the order of the Wenming oily sludge dumping site of No. 3 Oil Production Plant (3W)>the Mazhai oily sludge dumping site of No. 3 Oil Production Plant (3M)>the Wen'er oily sludge dumping site of No. 4 Oil Production Plant (4W). Naphthalene, acenaphthylene, acenaphthene, fluorine and phenanthrene are the major pollutants of PAHs in oily sludge. The contents of PAHs in soil samples around the oily sludge dumping sites vary widely from 434.49 to 2408.8 ng/g. Naphthalene, acenaphthene, fluorine, phenanthrene and pyrene are the characteristic factors of PAHs in soil samples of 3M and 3W, and naphthalene, acenaphthene, fluorine and phenanthrene are the characteristic factors of PAHs in soil samples of 4W. According to these data and the ratios of Fl/Py, PAHs in oily sludge samples come mainly from petrogenic sources, and soil samples are divided into petrogenic soil samples and mixed-source soil samples, and both petrogenic and pyrogenic soil samples in terms of the sources of PAHs. The classification by Nemero index P indicates that soils around the oily sludge dumping sites have been seriously polluted.

  9. Investigating silver coordination to mixed chalcogen ligands.

    Knight, Fergus R; Randall, Rebecca A M; Wakefield, Lucy; Slawin, Alexandra M Z; Woollins, J Derek


    Six silver(I) coordination complexes have been prepared and structurally characterised. Mixed chalcogen-donor acenaphthene ligands L1-L3 [Acenap(EPh)(E'Ph)] (Acenap = acenaphthene-5,6-diyl; E/E' = S, Se, Te) were independently treated with silver(I) salts (AgBF₄/AgOTf). In order to keep the number of variables to a minimum, all reactions were carried out using a 1:1 ratio of Ag/L and run in dichloromethane. The nature of the donor atoms, the coordinating ability of the respective counter-anion and the type of solvent used in recrystallisation, all affect the structural architecture of the final silver(I) complex, generating monomeric, silver(I) complexes {[AgBF₄(L)₂] (1 L = L1; 2 L = L2; 3 L = L3), [AgOTf(L)₃] (4 L = L1; 5 L = L3), [AgBF₄(L)₃] (2a L = L1; 3a L = L3)} and a 1D polymeric chain {[AgOTf(L3)](n) 6}. The organic acenaphthene ligands L1-L3 adopt a number of ligation modes (bis-monodentate μ₂-η²-bridging, quasi-chelating combining monodentate and η⁶-E(phenyl)-Ag(I) and classical monodentate coordination) with the central silver atom at the centre of a tetrahedral or trigonal planar coordination geometry in each case. The importance of weak interactions in the formation of metal-organic structures is also highlighted by the number of short non-covalent contacts present within each complex.

  10. Investigating Silver Coordination to Mixed Chalcogen Ligands

    J. Derek Woollins


    Full Text Available Six silver(I coordination complexes have been prepared and structurally characterised. Mixed chalcogen-donor acenaphthene ligands L1–L3 [Acenap(EPh(E'Ph] (Acenap = acenaphthene-5,6-diyl; E/E' = S, Se, Te were independently treated with silver(I salts (AgBF4/AgOTf. In order to keep the number of variables to a minimum, all reactions were carried out using a 1:1 ratio of Ag/L and run in dichloromethane. The nature of the donor atoms, the coordinating ability of the respective counter-anion and the type of solvent used in recrystallisation, all affect the structural architecture of the final silver(I complex, generating monomeric, silver(I complexes {[AgBF4(L2] (1 L = L1; 2 L = L2; 3 L = L3, [AgOTf(L3] (4 L = L1; 5 L = L3, [AgBF4(L3] (2a L = L1; 3a L = L3} and a 1D polymeric chain {[AgOTf(L3]n 6}. The organic acenaphthene ligands L1-L3 adopt a number of ligation modes (bis-monodentate μ2-η2-bridging, quasi-chelating combining monodentate and η6-E(phenyl-Ag(I and classical monodentate coordination with the central silver atom at the centre of a tetrahedral or trigonal planar coordination geometry in each case. The importance of weak interactions in the formation of metal-organic structures is also highlighted by the number of short non-covalent contacts present within each complex.

  11. Analysis of the organic contaminants in the condensate produced in the in situ underground coal gasification process.

    Smoliński, Adam; Stańczyk, Krzysztof; Kapusta, Krzysztof; Howaniec, Natalia


    Addressing the environmental risks related to contamination of groundwater with the phenolics, benzene, toluene, ethyl benzene, xylene (BTEX) and polycyclic aromatic hydrocarbons (PAHs), which might be potentially released from the underground coal gasification (UCG) under adverse hydrogeological and/or operational conditions, is crucial in terms of wider implementation of the process. The aim of this study was to determine the main organic pollutants present in the process condensate generated during the UCG trial performed on hard coal seam in the Experimental Mine 'Barbara', Poland; 8,933 L of condensate was produced in 813 h of experiment duration (including 456 h of the post-process stage) with average phenolics, BTEX and PAH concentrations of 576,000, 42.3 and 1,400.5 μg/L, respectively. The Hierarchical Clustering Analysis was used to explore the differences and similarities between the samples. The sample collected during the first 48 h of the process duration was characterized by the lowest phenanthrene, anthracene, fluoranthene and pyrene contents, high xylene content and the highest concentrations of phenolics, benzene, toluene and ethyl benzene. The samples collected during the stable operation of the UCG process were characterized by higher concentrations of naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, while in the samples acquired in the post-process stage the lowest concentrations of benzene, toluene, naphthalene, acenaphthene and fluorene were observed.

  12. Enhanced solubilisation of six PAHs by three synthetic cyclodextrins for remediation applications: molecular modelling of the inclusion complexes.

    Esmeralda Morillo

    Full Text Available Solubilisation of six polycyclic aromatic hydrocarbons (PAHs (acenaphthene, anthracene, fluoranthene, fluorene, phenanthrene and pyrene by three synthetic cyclodextrins (CDs (2-hydroxypropyl-β-CD, hydroxypropyl-γ-CD and randomly methylated-β-CD was investigated in order to select the CD which presents the greatest increase in solubility and better complexation parameters for its use in contaminated scenarios. The presence of the three cyclodextrins greatly enhanced the apparent water solubility of all the PAHs through the formation of inclusion complexes of 1:1 stoichiometry. Anthracene, fluoranthene, fluorene and phenanthrene clearly presented a higher solubility when β-CD derivatives were used, and especially the complexes with the randomly methylated-β-CD were favoured. On the contrary, pyrene presented its best solubility results when using 2-hydroxypropyl-γ-CD, but for acenaphthene the use of any of the three CDs gave the same results. Complementary to experimental phase-solubility studies, a more in-depth estimation of the inclusion process for the different complexes was carried out using molecular modelling in order to find a correlation between the degree of solubilisation and the fit of PAH molecules within the cavity of the different CDs and to know the predominant driving forces of the complexation.

  13. Biodegradation of high concentrations of mixed polycyclic aromatic hydrocarbons by indigenous bacteria from a river sediment: a microcosm study and bacterial community analysis.

    Muangchinda, Chanokporn; Yamazoe, Atsushi; Polrit, Duangporn; Thoetkiattikul, Honglada; Mhuantong, Wuttichai; Champreda, Verawat; Pinyakong, Onruthai


    This study assessed the biodegradation of mixtures of polycyclic aromatic hydrocarbons (PAHs) by indigenous bacteria in river sediment. Microcosms were constructed from sediment from the Chao Phraya River (the main river in Thailand) by supplementation with high concentrations of fluorene, phenanthrene, pyrene (300 mg kg(-1) of each PAH), and acenaphthene (600 mg kg(-1)). Fluorene and phenanthrene were completely degraded, whereas 50% of the pyrene and acenaphthene were removed at the end of the incubation period (70 days). Community analyses revealed the dynamics of the bacterial profiles in the PAH-degrading microcosms after PAH exposure. Actinobacteria predominated and became significantly more abundant in the microcosms after 14 days of incubation at room temperature under aerobic conditions. Furthermore, the remaining PAHs and alpha diversity were positively correlated. The sequencing of clone libraries of the PAH-RHDα genes also revealed that the dioxygenase genes of Mycobacterium sp. comprised 100% of the PAH-RHDα library at the end of the microcosm setup. Moreover, two PAH-degrading Actinobacteria (Arthrobacter sp. and Rhodococcus ruber) were isolated from the original sediment sample and showed high activity in the degradation of phenanthrene and fluorene in liquid cultivation. This study reveals that indigenous bacteria had the ability to degrade high concentrations of mixed PAHs and provide clear evidence that Actinobacteria may be potential candidates to play a major role in PAH degradation in the river sediment.


    CHEN Min; CHEN Xiaonong; YUAN Xinhua; ZHANG Yan; ZHANG Chunyan; LIU Hua; DAI Qixun


    To obtain new functional aromatic polymer material. 3.3'-biacenophthene. which is used as macrotnolecule intermediate of function aromatic polymer material. was synthesized through the coupling reaction of acenaphthene catalyzing by ionic liquid (/bmim/Cl/FeCl3) at mild reaction condition. Pure 3,3' -biacenaphthene was obtained by recrystalling and column chromatography from the reaction mixture, and was determined by GC/MS. 1HNMR and FTIR analysis. The influence of various reaction conditions on the yield of 3,3'-biacenaphthene were studied by GC analysis. The result shows that the optimun synthesis conditions of the coupling reaction are as following: the molar ratio of FeCl3 to [Bmim]Cl being 3. the mole ratio of FeCl3 in [Bmim]Cl/FeCl3 to acenaphthene being 4. the reaction temperature being 20 ℃, the reaction time being 4h and the solvent of the reaction system being PhNO2. Under those conditions, the yield of the 3,3'-biacenaphthene will be 48.71% and selectivity of that will be 78.56 %. Further more.[bmim ]Cl/FeCl3 has no pollution to environments and can be reused.

  15. Evidence of polycyclic aromatic hydrocarbon biodegradation in a contaminated aquifer by combined application of in situ and laboratory microcosms using (13)C-labelled target compounds.

    Bahr, Arne; Fischer, Anko; Vogt, Carsten; Bombach, Petra


    The number of approaches to evaluate the biodegradation of polycyclic aromatic hydrocarbons (PAHs) within contaminated aquifers is limited. Here, we demonstrate the applicability of a novel method based on the combination of in situ and laboratory microcosms using (13)C-labelled PAHs as tracer compounds. The biodegradation of four PAHs (naphthalene, fluorene, phenanthrene, and acenaphthene) was investigated in an oxic aquifer at the site of a former gas plant. In situ biodegradation of naphthalene and fluorene was demonstrated using in situ microcosms (BACTRAP(®)s). BACTRAP(®)s amended with either [(13)C6]-naphthalene or [(13)C5/(13)C6]-fluorene (50:50) were incubated for a period of over two months in two groundwater wells located at the contaminant source and plume fringe, respectively. Amino acids extracted from BACTRAP(®)-grown cells showed significant (13)C-enrichments with (13)C-fractions of up to 30.4% for naphthalene and 3.8% for fluorene, thus providing evidence for the in situ biodegradation and assimilation of those PAHs at the field site. To quantify the mineralisation of PAHs, laboratory microcosms were set up with BACTRAP(®)-grown cells and groundwater. Naphthalene, fluorene, phenanthrene, or acenaphthene were added as (13)C-labelled substrates. (13)C-enrichment of the produced CO2 revealed mineralisation of between 5.9% and 19.7% for fluorene, between 11.1% and 35.1% for acenaphthene, between 14.2% and 33.1% for phenanthrene, and up to 37.0% for naphthalene over a period of 62 days. Observed PAH mineralisation rates ranged between 17 μg L(-1) d(-1) and 1639 μg L(-1) d(-1). The novel approach combining in situ and laboratory microcosms allowed a comprehensive evaluation of PAH biodegradation at the investigated field site, revealing the method's potential for the assessment of PAH degradation within contaminated aquifers.

  16. Photoelectron spectroscopy of cluster anions of naphthalene and related aromatic hydrocarbons

    Ando, Naoto; Mitsui, Masaaki; Nakajima, Atsushi


    The electronic structures and structural morphologies of naphthalene cluster anions, (naphthalene)n- (n=3-150), and its related aromatic cluster anions, (acenaphthene)n- (n=4-100) and (azulene)n- (n=1-100), are studied using anion photoelectron spectroscopy. For (naphthalene)n- clusters, two isomers coexist over a wide size range: isomers I and II-1 (28⩽n⩽60) or isomers I and II-2 (n⩾˜60). Their contributions to the photoelectron spectra can be separated using an anion beam hole-burning technique. In contrast, such an isomer coexistence is not observed for (acenaphthene)n- and (azulene)n- clusters, where isomer I is exclusively formed throughout the whole size range. The vertical detachment energies (VDEs) of isomer I (7⩽n⩽100) in all the anionic clusters depend linearly on n-1/3 and their size-dependent energetics are quite similar to one another. On the other hand, the VDEs of isomers II-1 and II-2 produced in (naphthalene)n- clusters with n ⩾˜30 remain constant at 0.84 and 0.99eV, respectively, 0.4-0.6eV lower than those of isomer I. Based upon the ion source condition dependence and the hole-burning photoelectron spectra experiments for each isomer, the energetics and characteristics of isomers I, II-1, and II-2 are discussed: isomer I is an internalized anion state accompanied by a large change in its cluster geometry after electron attachment, while isomers II-1 and II-2 are crystal-like states with little structural relaxation. The nonappearance of isomers II-1 and II-2 for (acenaphthene)n- and (azulene)n- and a comparison with other aromatic cluster anions indicate that a highly anisotropic and symmetric π-conjugated molecular framework, such as found in the linear oligoacenes, is an essential factor for the formation of the crystal-like ordered forms (isomers II-1 and II-2). On the other hand, lowering the molecular symmetry makes their production unfavorable.

  17. Description of adsorption equilibrium of PAHs on hypercrosslinked polymeric adsorbent using Polanyi potential theory

    LONG Chao; LI AiMin; HU DaBo; LIU FuQiang; ZHANG QuanXing


    In this research, static adsorption of three polycyclic aromatic hydrocarbons (PAHs), naphthalene, acenaphthene, and fluorene, from aqueous solutions onto hypercrosslinked polymeric adsorbent within the temperature range of 288-308 K is investigated. Several isotherm equations are correlated with the equilibrium data, and the experimental data is found to fit the Polanyi-Dubinin-Manes model best within the entire range of concentrations, providing evidence that pore-filling is the dominating sorption mechanism for PAHs. The study shows that the molecular size of adsorbates has distinct in-fluence on adsorption capacity of hypercrosslinked polymeric adsorbent for the PAHs; the larger the adsorbate molecular size, the lower the adsorption equilibrium capacity. Based on the Polanyi-Dubinin-Manes model, the molecular size of adsorbates was introduced to adjust the adsorbate molar volume. Plots of qv vs. (σε/Vs) are collapsed to a single correlation curve for different adsorbates on hypercrosslinked polymeric resin.

  18. [Pt(mesBIAN)(tda)]: a near-infrared emitter and singlet oxygen sensitizer.

    Rachford, Aaron A; Hua, Fei; Adams, Christopher J; Castellano, Felix N


    The synthesis and subsequent photophysical investigation of [Pt(mesBIAN)(tda)], where mesBIAN is bis(mesitylimino)acenaphthene and tda is tolan-2,2'-diacetylide, reveal excited-state characteristics best described as triplet charge transfer ((3)CT) in nature upon visible light excitation. Large ground-state dipole moments are apparent as the absorption spectrum dramatically red-shifts with decreasing solvent polarity. The (3)CT excited state is significantly lower in energy than the ligand-centered (3)tda excited-state, as confirmed by steady-state and time-resolved techniques. Singlet oxygen sensitization studies demonstrate that (1)O(2) production occurs by diffusive quenching from the photo-excited (3)CT state (Phi(Delta) = 0.24, lambda(max) approximately 1270 nm) in oxygen-saturated dichloromethane.

  19. Sorption of polycyclic aromatic hydrocarbons (PAHs) to lignin: effects of hydrophobicity and temperature.

    Zhang, Ming; Ahmad, Mahtab; Lee, Sang Soo; Xu, Li Heng; Ok, Yong Sik


    The study of the sorption of contaminants to lignin is significant for understanding the migration of contaminants in the environment as well as developing low cost sorbent. In this study, sorption of three polycyclic aromatic hydrocarbons (PAHs), naphthalene, acenaphthene and phenanthrene, to lignin was investigated. Sorption isotherms were well described by both linear and Freundlich sorption models. Sorption coefficients of PAHs to lignin from water obtained from regression of both linear model (K d) and Freundlich model (K f) were highly positively correlated with hydrophobicity of PAHs. The amorphous structure of lignin provided sufficient sorption domain for partitioning of PAHs, and the attraction between PAHs molecules and aromatic fractions in lignin via π-π electron-donor-acceptor (π-π EDA) interaction is hypothesized to provide a strong sorption force. Thermodynamic modeling revealed that sorption of PAHs to lignin was a spontaneous and exothermic process.

  20. Single-walled carbon nanotube release affects the microbial enzyme-catalyzed oxidation processes of organic pollutants and lignin model compounds in nature.

    Chen, Ming; Qin, Xiaosheng; Zeng, Guangming


    The question how microbial enzyme-catalyzed oxidation processes of organic pollutants and lignin model compounds (LMCs) are affected by the release of single-walled carbon nanotube (SWCNT) into the environment remains to be addressed at the molecular level. We have, therefore concentrated the effects of SWCNT on some important properties associated with enzyme activity and function during microbial oxidation of polycyclic aromatic hydrocarbons (benzo(a)pyrene, acenaphthene and anthracene), LMCs (2,6-dimethoxyphenol, guaiacol and veratryl alcohol) and β-hexachlorocyclohexane, including the behaviour of water molecules, hydrogen bonds (HBs) and hydrophobic interactions (HYs) between ligand and the enzyme, and conformational dynamics in N- and C-terminus. Our study revealed that SWCNT significantly affected the behaviour of water molecules within 5 Å of both these substrates and their respective enzymes during oxidation (p microbial enzyme-catalyzed processes of organic pollutants and LMCs in nature.

  1. Polycyclic aromatic hydrocarbons (PAHs) in bio-crudes from induction-heating pyrolysis of biomass wastes.

    Tsai, Wen-Tien; Mi, Hsiao-Hsuan; Chang, Yuan-Ming; Yang, Shyh-Yu; Chang, Jeng-Hung


    The aim of this work was to prepare the bio-crudes from agricultural wastes (i.e., rice straw, rice husk, sugarcane bagasse and coconut shell) by using induction-heating pyrolysis at specified conditions. The quantitative analysis of 21 priority pollutant polycyclic aromatic hydrocarbons (PAHs) in bio-crudes examined using gas chromatography/mass spectrometry (GC/MS) revealed that the PAHs in bio-crudes were primarily dominant in the low molecular weight (LMW) PAHs, including naphthalene (1.10-2.45 mg/L) and acenaphthene (0.72-7.61 mg/L). However, by considering carcinogenic potency, the bio-crudes from rice husk and sugarcane bagasse contained higher contents of benzo[a]pyrene (BaP) (0.52 and 0.92 mg/L, respectively) as compared to those from rice straw and coconut shell.

  2. Comparison of PCBs and PAHs levels in European coastal waters using mussels from the Mytilus edulis complex as biomonitors

    Michał Olenycz


    Full Text Available Mussels from the Mytilus edulis complex were used as biomonitors for two groups of organic pollutants: polychlorinated biphenyls (PCBs, congeners: 28, 52, 101, 118, 138, 153 and 180 and polycyclic aromatic hydrocarbons (PAHs, naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz(aanthracene, chrysene, benzo(bfluoranthene, benzo(kfluoranthene, benzo(apyrene, indeno(1,2,3-cdpyrene, dibenz(a,hanthracene, benzo(g,h,iperylene at 17 sampling sites to assess their relative bioavailabilities in coastal waters around Europe. Because of the temporal differences in PCBs and PAHs concentrations, data were adjusted using Seasonal Variation Coefficients (SVC before making large-scale spatial comparisons. The highest concentrations of PCBs were found near estuaries of large rivers flowing through urban areas and industrial regions. Elevated bioavailabilities of PAHs occurred in the vicinity of large harbors, urban areas, and regions affected by petroleum pollution as well as in some remote locations, which indicated long-range atmospheric deposition.

  3. Adsorption of Polycyclic Aromatic Hydrocarbons (PAHS from Aqueous Solutions on Different Sorbents

    Smol Marzena


    Full Text Available This paper presents the results of the possibility and effectiveness of PAHs removal from a model aqueous solution, during the sorption on the selected sorbents. Six PAHs (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene listed by EPA for the analysis in the environmental samples were determined. Model aqueous solution was prepared with RESTEK 610 mix PAHs standard. After the sorption process, decrease in the concentration of individual hydrocarbons was observed. The removal percentage was dependent on the type of sorbent (quartz sand, mineral sorbent, activated carbon. The highest efficiency (98.1% was observed for activated carbon.. The results shows that the sorption processes can be used in aqueous solutions treatment procedures.

  4. Comparison of passive and standard dosing of polycyclic aromatic hydrocarbons to the marine algae Phaeodactylum tricornutum

    Witt, G.; Niehus, N. C.; Konopka, K.


    to speed up the release from the O-rings. The toxicity of the individual PAHs was investigated at controlled concentrations up to their aqueous solubility in artificial seawater. The concentration-dependent growth inhibition of Phaeodactylum tricornutum was then compared for passive dosing and standard...... concentrations and eliminates spiking with cosolvents. Passive dosing using silicone Orings as donor and PAHs as test substances (fluoranthene, naphthalene, phenanthrene, acenaphthene, fluorene, benzo[a]pyrene, anthracene and pyrene) were applied in the marine algal growth inhibition test with Phaeodactylum...... tricornutum (based on ISO EN 10253) in 24-well microtiter plates. The O-rings were loaded by partitioning from methanol solutions or suspensions of the respective PAHs (1), and these loaded O-rings were added to the wells in test media before the beginning of the test. Agitation of the plates was used...

  5. Evaluation of toxicity to the biological treatment and removal of recalcitrant organic compounds from oil refineries wastewaters; Avaliacao da toxicidade ao tratamento biologico e remocao de compostos organicos recalcitrantes existentes em efluentes de refinarias de petroleo

    Barros Junior, Laerte M.; Macedo, Gorete R.; Bezerra, Marcio S.; Pereira, Franklin M.S. [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil). Dept. de Engenharia Quimica; Schmidell, Willibaldo [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil)


    Oil industry waste water usually contains recalcitrant chemical compounds, like phenol, benzene, toluene, xylene, naphthalene and acenaphthene. The respirometry, determination of respiration rate of an active biomass, is an adequate methodology for quantification of aerobic activity biological. This study aims evaluate the inhibition effect of phenol in the oxidation capacity of an industrial sludge. This work also intends to study the phenol removal through biological and photochemical-biological processes. The respirometry was carried out with synthetic solution, using sludge from an oil processing industry. The phenol degradation experiments were carried out in an activated sludge unit and in a photochemical reactor. This work suggests the potential of photochemical-biological treatment use, in relation to the biological process with a no-acclimated sludge, in the removal of refractory organic compounds from oil industry wastewaters. The characterization of biomass using the respirometry methodology showed which is a useful tool in evaluation of phenol toxicity to biological treatment. (author)

  6. Removal of polycyclic aromatic hydrocarbons from aqueous solution by raw and modified plant residue materials as biosorbents.

    Xi, Zemin; Chen, Baoliang


    Removal of polycyclic aromatic hydrocarbons (PAHs), e.g., naphthalene, acenaphthene, phenanthrene and pyrene, from aqueous solution by raw and modified plant residues was investigated to develop low cost biosorbents for organic pollutant abatement. Bamboo wood, pine wood, pine needles and pine bark were selected as plant residues, and acid hydrolysis was used as an easily modification method. The raw and modified biosorbents were characterized by elemental analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. The sorption isotherms of PAHs to raw biosorbents were apparently linear, and were dominated by a partitioning process. In comparison, the isotherms of the hydrolyzed biosorbents displayed nonlinearity, which was controlled by partitioning and the specific interaction mechanism. The sorption kinetic curves of PAHs to the raw and modified plant residues fit well with the pseudo second-order kinetics model. The sorption rates were faster for the raw biosorbents than the corresponding hydrolyzed biosorbents, which was attributed to the latter having more condensed domains (i.e., exposed aromatic core). By the consumption of the amorphous cellulose component under acid hydrolysis, the sorption capability of the hydrolyzed biosorbents was notably enhanced, i.e., 6-18 fold for phenanthrene, 6-8 fold for naphthalene and pyrene and 5-8 fold for acenaphthene. The sorption coefficients (Kd) were negatively correlated with the polarity index [(O+N)/C], and positively correlated with the aromaticity of the biosorbents. For a given biosorbent, a positive linear correlation between logKoc and logKow for different PAHs was observed. Interestingly, the linear plots of logKoc-logKow were parallel for different biosorbents. These observations suggest that the raw and modified plant residues have great potential as biosorbents to remove PAHs from wastewater. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of

  7. Polycyclic Aromatic Hydrocarbon Metabolism by White Rot Fungi and Oxidation by Coriolopsis gallica UAMH 8260 Laccase

    Pickard, Michael A.; Roman, Rosa; Tinoco, Raunel; Vazquez-Duhalt, Rafael


    We studied the metabolism of polycyclic aromatic hydrocarbons (PAHs) by using white rot fungi previously identified as organisms that metabolize polychlorinated biphenyls. Bran flakes medium, which has been shown to support production of high levels of laccase and manganese peroxidase, was used as the growth medium. Ten fungi grown for 5 days in this medium in the presence of anthracene, pyrene, or phenanthrene, each at a concentration of 5 μg/ml could metabolize these PAHs. We studied the oxidation of 10 PAHs by using laccase purified from Coriolopsis gallica. The reaction mixtures contained 20 μM PAH, 15% acetonitrile in 60 mM phosphate buffer (pH 6), 1 mM 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulfonate) (ABTS), and 5 U of laccase. Laccase exhibited 91% of its maximum activity in the absence of acetonitrile. The following seven PAHs were oxidized by laccase: benzo[a]pyrene, 9-methylanthracene, 2-methylanthracene, anthracene, biphenylene, acenaphthene, and phenanthrene. There was no clear relationship between the ionization potential of the substrate and the first-order rate constant (k) for substrate loss in vitro in the presence of ABTS. The effects of mediating substrates were examined further by using anthracene as the substrate. Hydroxybenzotriazole (HBT) (1 mM) supported approximately one-half the anthracene oxidation rate (k = 2.4 h−1) that ABTS (1 mM) supported (k = 5.2 h−1), but 1 mM HBT plus 1 mM ABTS increased the oxidation rate ninefold compared with the oxidation rate in the presence of ABTS, to 45 h−1. Laccase purified from Pleurotus ostreatus had an activity similar to that of C. gallica laccase with HBT alone, with ABTS alone, and with 1 mM HBT plus 1 mM ABTS. Mass spectra of products obtained from oxidation of anthracene and acenaphthene revealed that the dione derivatives of these compounds were present. PMID:10473379

  8. Microbial degradation of acenapthene and napthalene under denitrification conditions in soil--water systems: Annual report, October 1987

    Mihelcic, J.R.; Luthy, R.G.


    This study examined the microbial degradation of acenaphthene and naphthalene under denitrification conditions at soil-to-water ratios of 1:25 and 1:50 with soil containing approximately 10/sup 5/ denitrifying organisms per gram of soil. Under nitrate-excess conditions, both acenaphthene and naphthalene were degraded microbially from initial aqueous-phase concentrations of about one and several mg/l, respectively, to nondetectable levels (<0.01 mg/l) in time periods less than 9 weeks. Acclimation periods of 12 to 36 days were observed prior to the onset of microbial degradation in tests with soil not previously exposed to PAH, while acclimation periods were absent in tests with soil reserved from prior PAH degradation tests. It was judged that the apparent acclimation period resulted from the time for a small population of organisms capable of PAH degradation to attain sufficient densities to exhibit detectable PAH reduction. About 0.9 percent of the naturally occurring soil organic carbon could be mineralized under denitrification conditions, and this accounted for the greater proportion of the nitrate depletion. The mineralization of the labile fraction of the soil organic carbon via microbial denitrification occurred without an observed acclimation period, and was rapid compared to PAH degradation. Under nitrate-limiting conditions the PAH compounds were stable owing to the depletion of nitrate via the more rapid process of soil organic carbon mineralization. The microbial degradation of the PAH compound depends on the interrelationships between: the desorption kinetics and the reversibility of desorption of sorbed compound from the soil, the concentration of PAH-degrading microorganisms, and the competing reaction for nitrate utilization via mineralization of the labile fraction of naturally occurring soil organic carbon. 44 refs., 10 figs.

  9. [Emim]Cl-AlCl3离子液体中5-苯甲酰基苊的合成%Synthesis of 5-benzoylacenaphthene in presence of ionic liquid[Emim]Cl-AlCl3

    刘华; 程晓农; 袁新华; 罗颖; 黄立静; 陈敏


    To obtain new fine chemical and macromolecule intermediate, the Friedel-Craft acylation of acenaphthene with benzoyl chloride catalysed by [ Emim ] C1 - AICI3 ionic liquid to synthesize 5 - benzoylacenaphthene was investigated and 5 - benzoylacenaphthene was determined by CC/MS analysis. According to orthogonal experiments, the optimum technological conditions were obtained as follows: n(acenaphthene): n (benzoyl chloride): n ([ Emim ]CI -AICI3 ) = 1: 2: 1, temperature 35 ℃ and time 45 min. The yield of 5 -benzoylacenaphthene was 88. 6% under such conditions. Furthermore, the yield of 5 -benzoylacenaphthene changed a little after the catalyst was reused for five times. Pure 5 benzoylacenaphthene was prepared by extraction and recrystaling and the structure of 5 -benzoylacenaphthene was identified by measuration of melting point, CC/MS, FT - IR and 1 H NMR analyses.%为合成新型精细化工产品和功能高分子中间体,研究了氯代1-乙基3-甲基咪唑-三氯化铝([Emim]Cl-AlCl3)离子液体催化下,苊与苯甲酰氯的Friedel-Craft酰基化反应,GC-MS分析发现生成了5-苯甲酰基苊.通过正交试验,得到该酰基化反应的最优条件为∶n(苊)∶n(苯甲酰氯)∶n([Emim]Cl-AlCl3)=1∶2∶1,反应温度35℃,反应时间45 min.此条件下,5-苯甲酰基苊的收率可达88.6%.[Emim]Cl-AlCl3离子液体5次循环使用后,5-苯甲酰基苊的收率变化很小.经萃取、重结晶等方法得到了5-苯甲酰基苊纯产品,并通过mp测定、GC/MS、FT-IR和1H NMR对该产物进行了定性和定量分析.

  10. PAHs in leachates from thermal power plant wastes and ash-based construction materials.

    Irha, Natalya; Reinik, Janek; Jefimova, Jekaterina; Koroljova, Arina; Raado, Lembi-Merike; Hain, Tiina; Uibu, Mai; Kuusik, Rein


    The focus of the current study is to characterise the leaching behaviour of polycyclic aromatic hydrocarbons (PAHs) from oil shale ashes (OSAs) of pulverised firing (PF) and circulating fluidised-bed (CFB) boilers from Estonian Thermal Power Plant (Estonia) as well as from mortars and concrete based on OSAs. The target substances were 16 PAHs from the EPA priority pollutant list. OSA samples and OSA-based mortars were tested for leaching, according to European standard EN 12457-2 (2002). European standard CEN/TC 15862(2012) for monolithic matter was used for OSA-based concrete. Water extracts were analysed by GC-MS for the concentration of PAHs. Naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene were detected. Still, the release of PAHs was below the threshold limit value for inert waste. The amount of the finest fraction (particle size <0.045 mm), the content of the Al-Si glass phase and the surface characteristics were the main factors, which could affect the accessibility of PAHs for leaching. The mobility of PAHs from OSA of CFB and PF boilers was 20.2 and 9.9%, respectively. Hardening of OSA-based materials did not lead to the immobilisation of soluble PAHs. Release of PAHs from the monolith samples did not exceed 0.5 μg/m(2). In terms of leaching of PAHs, OSA is safe to be used for construction purposes.

  11. Development of Multi-Membrane Near-Infrared Diode Mass Spectrometer for Field Analysis of Aromatic Hydrocarbons

    Mach, Phillip M.; Wright, Kenneth C.; Verbeck, Guido F.


    Membrane Inlet Mass Spectrometry (MIMS) is a technique that incorporates a semi-permeable membrane selective for differing organic molecules and chemistries. This eliminates the need for time-consuming sample preparation and facilitates near instantaneous analysis. This study will examine how the front end of MIMS incorporates three dual inlet ports, allowing for differing MIMS materials and selectivity for specific environments. Polydimethylsiloxane (PDMS) membranes have proven to be selective of benzene, toluene, and xylene (BTX) as well as aromatic hydrocarbons that are common in petroleum products while remaining selective against the aliphatic chains. PDMS has proven to be a successful choice of membrane with high permeability in atmospheric environments. In addition, polycyclic aromatic hydrocarbons (PAHs) such as acenaphthene, acenapthylene, naphthalene, and fluorene have recently been detected to the 5 ppb level in a nitrogen atmosphere with our current configuration. This preliminary work provides proof of concept using near-infrared laser diodes that act upon the membrane to increase its permeability and provide higher sensitivity of aromatic samples.

  12. Concentration Levels and Ecological Risks of Persistent Organic Pollutants in the Surface Sediments of Tianjin Coastal Area, China

    Lu, Xiaoxia; Chen, Chaoqi; Zhang, Shu; Hou, Zhen; Yang, Junjun


    Sediments were sampled from different surface water bodies in Tianjin coastal area, China, and persistent organic pollutants (POPs) including polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) were measured using GC/MS or GC/ECD. The purposes were to investigate the concentration levels of the POPs and to assess their ecological risks. The results showed that all the 16 priority PAHs were detected from the 10 sediments sampled with the total concentrations of the 16 PAHs ranging from 274.06 μg/kg to 2656.65 μg/kg, while the concentrations of the halogenated POPs were generally low except in the Dagu waste discharging river where the total concentrations of 24 OCPs, 35 PCBs, and 14 PBDEs were 3103.36 μg/kg, 87.31 μg/kg, and 13.88 μg/kg, respectively. In the studied sediments, PAHs exhibited risks to benthonic organisms; particularly the concentrations of naphthalene and/or acenaphthene exceeded their probable effect concentrations in several locations. In comparison, only in the Dagu waste discharging river, OCPs exhibited risks with the concentrations of heptachlor epoxide and lindane exceeding their probable effect concentrations. PCBs and PBDEs posed rare risks in the studied area. PMID:23401668

  13. Concentration Levels and Ecological Risks of Persistent Organic Pollutants in the Surface Sediments of Tianjin Coastal Area, China

    Xiaoxia Lu


    Full Text Available Sediments were sampled from different surface water bodies in Tianjin coastal area, China, and persistent organic pollutants (POPs including polycyclic aromatic hydrocarbons (PAHs, organochlorine pesticides (OCPs, polychlorinated biphenyls (PCBs, and polybrominated diphenyl ethers (PBDEs were measured using GC/MS or GC/ECD. The purposes were to investigate the concentration levels of the POPs and to assess their ecological risks. The results showed that all the 16 priority PAHs were detected from the 10 sediments sampled with the total concentrations of the 16 PAHs ranging from 274.06 μg/kg to 2656.65 μg/kg, while the concentrations of the halogenated POPs were generally low except in the Dagu waste discharging river where the total concentrations of 24 OCPs, 35 PCBs, and 14 PBDEs were 3103.36 μg/kg, 87.31 μg/kg, and 13.88 μg/kg, respectively. In the studied sediments, PAHs exhibited risks to benthonic organisms; particularly the concentrations of naphthalene and/or acenaphthene exceeded their probable effect concentrations in several locations. In comparison, only in the Dagu waste discharging river, OCPs exhibited risks with the concentrations of heptachlor epoxide and lindane exceeding their probable effect concentrations. PCBs and PBDEs posed rare risks in the studied area.

  14. Polycyclic Aromatic Hydrocarbon Residues in Serum Samples of Autopsied Individuals from Tennessee

    Aramandla Ramesh


    Full Text Available This study reports the concentrations of Polycyclic Aromatic Hydrocarbons (PAHs in human blood sera samples (n = 650 obtained at autopsy from individuals who died of drug abuse, alcohol toxicity, homicide, suicide and other unknown causes. The analyzed samples from decedents revealed the presence of PAHs of which B(aP was the most predominant one, followed by benzo(bfluoranthene and benzo(kfluoranthene. The other PAHs detected sporadically and measured were benzo(g,h,iperylene, acenaphthene, anthracene, phenanthrene, and fluoranthene The mean concentrations of PAHs were greater in the twenties to fifties age groups compared to others. The PAH residue levels detected were high in African Americans compared to Caucasians, Asians, and Hispanics. It appears that environmental exposure, dietary intake and in some cases occupational exposure may have contributed to the PAH body burden. While the PAH residue concentrations measured fall within the range of those reported for healthy adults elsewhere, in isolated cases, the concentrations detected were high, calling the need for a reduction in PAH emissions and human biomonitoring studies for purposes of risk assessment.

  15. Identification and quantification of organic pollutants in the air of the city of Astana using solid phase microextraction

    Dina Orazbayeva


    Full Text Available Solid-phase microextraction in combination with gas chromatography and mass-spectrometry (GC-MS was used for determination of benzene, toluene, ethylbenzene and o-xylene (BTEX, polycyclic aromatic hydrocarbons (PAH, and for identification of volatile organic compounds (VOCs in ambient air of the city of Astana, Kazakhstan. The screening of the samples showed the presence of mono- and polycyclic aromatic hydrocarbons, alkanes, alkenes, phenols, and benzaldehydes. The concentrations of naphthalene were 5-7 times higher than the permissible value, it was detected in all studied air samples. Average concentration of naphthalene was 18.4 μg/m3, acenaphthylene – 0.54 μg/m3, acenaphthene – 1.63 μg/m3, fluorene – 0.79 μg/m3, anthracene – 3.27 μg/m3, phenanthrene – 0.22 μg/m3, fluorantene – 0.74 μg/m3, pyrene – 0.73 μg/m3. Average concentrations of BTEX in the studied samples were 31.1, 84.9, 10.8 and 11.6 μg/m3, respectively. Based on the statistical analysis of the concentrations of BTEX and PAH, the main source of city air pollution with them was assumed to be vehicle emissions.

  16. Characterization of polycyclic aromatic hydrocarbons in fugitive PM10 emissions from an integrated iron and steel plant.

    Khaparde, V V; Bhanarkar, A D; Majumdar, Deepanjan; Rao, C V Chalapati


    Fugitive emissions of PM10 (particles blast furnace and steel manufacturing unit in an integrated iron and steel plant situated in India. Concentrations of PM10, PM10-bound total PAHs, benzo (a) pyrene, carcinogenic PAHs and combustion PAHs were found to be highest around the sintering unit. Concentrations of 3-ring and 4-ring PAHs were recorded to be highest in the coking unit whereas 5-and 6-ring PAHs were found to be highest in other units. The following indicatory PAHs were identified: indeno (1,2,3-cd) pyrene, dibenzo (a,h) anthracene, benzo (k) fluoranthene in blast furnace unit; indeno (1,2,3-cd) pyrene, dibenzo (a,h) anthracene, chrysene in sintering unit; Anthracene, fluoranthene, chrysene in coking unit and acenaphthene, fluoranthene, fluorene in steel making unit. Total-BaP-TEQ (Total BaP toxic equivalent quotient) and BaP-MEQ (Total BaP mutagenic equivalent quotient) concentration levels ranged from 2.4 to 231.7ng/m(3) and 1.9 to 175.8ng/m(3), respectively. BaP and DbA (dibenzo (a,h) anthracene) contribution to total-BaP-TEQ was found to be the highest.

  17. Wastewater Irrigation: Persistent Organic Pollutans in Soil and Product

    Mehmet Emin AYDIN


    Full Text Available Treated or untreated wastewaters, used for irrigation purpose, contain various persistent organic pollutants. The long use of these waters for irrigation purpose results in deposition of the pollutants in soil, contaminates products and has adverse health affect on the human through food chain, and biologic activity of flora and fauna. The wastewaters of Konya were conveyed to the Salt Lake through the main drainage channel without any treatment until 2010.  During the arid period, the wastewater in the main drainage channel was used for irrigation and the products were cultivated. In this work, persistent organic pollutants i.e., polychlorinated biphenyls (PCB 28, 52, 101, 138, 153, 180 and polycyclic aromatic hydrocarbons (naphthalene, acenaphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene are determined in wastewater irrigated agricultural soil samples and the wheat samples cultivated in the region. High alkaline properties and clay structure of Konya soil were determined. These properties of soil result in the accumulation of contaminants in top soil layer used for agricultural production. On the other hand, PCB and PAH compounds were determined in comparable concentrations in well water irrigated reference soils with wastewater irrigated soils. PCB and PAH sources other than wastewater irrigation was evidenced for the study field.

  18. Polycyclic aromatic hydrocarbons in surface sediments of the Zhelin Bay in the South China Sea

    DONG Qiaoxiang; HUANG Hong; HUANG Changjiang


    This study examined the concentrations of polycyclic aromatic hydrocarbons (PAHs) in surface sediments collected in July 2004 from eight stations in the Zhelin Bay, one of the most important bays for large-scale mariculture in Guangdong Province. Thirteen individual parent PAH compounds were identified using high performance liquid chromatography with UV detection. The overall average concentration of total PAHs was 477.0 ng/g, ranging from 146.1 to 928.8 ng/g. Low molecular mass PAHs with two to three rings (e.g., acenaphthene) were dominant in each sample. The PAH concentration varied among sampling stations, with the highest concentration observed at bay outlets and the lowest found at stations outside the bay. Ratios of low to high molecular mass PAHs and fluoranthene to pyrene were used to determine the origin of PAHs, and results indicated mainly petroleum-derived contamination. Compared with other bays and harbors around the world, the total concentrations of PAHs in surface sediments at the Zhelin Bay are moderate, but this does not exclude the possibility of potential impact on human consumers because some strong carcinogenic PAHs with high molecular mass were found at the station with a nearby caged-fish and oyster farm. Long-term monitoring of PAH contamination in the Zhelin Bay is recommended to reduce the potential toxicological effects on aquatic: organisms and humans.

  19. Response of microbial activities and diversity to PAHs contamination at coal tar contaminated land

    Zhao, Xiaohui; Sun, Yujiao; Ding, Aizhong; Zhang, Dan; Zhang, Dayi


    Coal tar is one of the most hazardous and concerned organic pollutants and the main hazards are polycyclic aromatic hydrocarbons (PAHs). The indigenous microorganisms in soils are capable to degrade PAHs, with essential roles in biochemical process for PAHs natural attenuation. This study investigated 48 soil samples (from 8 depths of 6 boreholes) in Beijing coking and chemistry plant (China) and revealed the correlation between PAHs contamination, soil enzyme activities and microbial community structure, by 16S rRNA denaturing gradient gel electrophoresis (DGGE). At the site, the key contaminants were identified as naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene and anthracene, and the total PAHs concentration ranged from 0.1 to 923.9 mg/kg dry soil. The total PAHs contamination level was positively correlated (psoil), showing the significant response of microbial population and degrading functions to the organic contamination in soils. The PAHs contamination stimulated the PAHs degrading microbes and promoted their biochemical roles in situ. The positive relationship between bacteria count and dehydrogenase activities (psoil microbial functions at the PAHs heavily contaminated sites, offering deeper understanding on the roles of indigenous microbial community in natural attenuation process.

  20. Using sediment microbial fuel cells (SMFCs) for bioremediation of polycyclic aromatic hydrocarbons (PAHs).

    Sherafatmand, Mohammad; Ng, How Yong


    In this study, a sediment microbial fuel cell (SMFC) was explored to bioremediate polycyclic aromatic hydrocarbons (PAHs) in water originated from soil. The results showed consistent power generations of 6.02±0.34 and 3.63±0.37 mW/m(2) under an external resistance of 1500 Ω by the aerobic and anaerobic SMFC, respectively. Although the power generations were low, they had relatively low internal resistances (i.e., 436.6±69.4 and 522.1±1.8 Ω for the aerobic and anaerobic SMFC, respectively) in comparison with the literature. Nevertheless, the significant benefit of this system was its bioremediation capabilities, achieving 41.7%, 31.4% and 36.2% removal of naphthalene, acenaphthene and phenanthrene, respectively, in the aerobic environment and 76.9%, 52.5% and 36.8%, respectively, in the anaerobic environment. These results demonstrated the ability of SMFCs in stimulating microorganisms for bioremediation of complex and recalcitrant PAHs.

  1. Chemometric Study of the Ex Situ Underground Coal Gasification Wastewater Experimental Data.

    Smoliński, Adam; Stańczyk, Krzysztof; Kapusta, Krzysztof; Howaniec, Natalia


    The main goal of the study was the analysis of the parameters of wastewater generated during the ex situ underground coal gasification (UCG) experiments on lignite from Belchatow, and hard coal from Ziemowit and Bobrek coal mines, simulated in the ex situ reactor. The UCG wastewater may pose a potential threat to the groundwater since it contains high concentrations of inorganic (i.e., ammonia nitrogen, nitrites, chlorides, free and bound cyanides, sulfates and trace elements: As, B, Cr, Zn, Al, Cd, Co, Mn, Cu, Mo, Ni, Pb, Hg, Se, Ti, Fe) and organic (i.e., phenolics, benzene and their alkyl derivatives, and polycyclic aromatic hydrocarbons) contaminants. The principal component analysis and hierarchical clustering analysis enabled to effectively explore the similarities and dissimilarities between the samples generated in lignite and hard coal oxygen gasification process in terms of the amounts and concentrations of particular components. The total amount of wastewater produced in lignite gasification process was higher than the amount generated in hard coal gasification experiments. The lignite gasification wastewater was also characterized by the highest contents of acenaphthene, phenanthrene, anthracene, fluoranthene, and pyrene, whereas hard coal gasification wastewater was characterized by relatively higher concentrations of nitrites, As, Cr, Cu, benzene, toluene, xylene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, and benzo(a)pyrene.

  2. Hot foam for weed control-Do alkyl polyglucoside surfactants used as foaming agents affect the mobility of organic contaminants in soil?

    Cederlund, H; Börjesson, E


    Use of alkyl polyglucosides (APGs) as a foaming agent during hot water weed control may influence the environmental fate of organic contaminants in soil. We studied the effects of the APG-based foaming agent NCC Spuma (C8-C10) on leaching of diuron, glyphosate, and polycyclic aromatic hydrocarbons (PAHs) in sand columns. We also examined how APG concentration affected the apparent water solubility and adsorption of the herbicides and of the PAHs acenaphthene, acenaphthylene and fluorene. Application of APGs at the recommended concentration of 0.3% did not significantly affect leaching of any of the compounds studied. However, at a concentration of 1.5%, leaching of both diuron and glyphosate was significantly increased. The increased leaching corresponded to an increase in apparent water solubility of diuron and a decrease in glyphosate adsorption to the sand. However, APG addition did not significantly affect the mobility of PAHs even though their apparent water solubility was increased. These results suggest that application of APG-based foam during hot water weed control does not significantly affect the mobility of organic contaminants in soil if used according to recommendations. Moreover, they suggest that APGs could be useful for soil bioremediation purposes if higher concentrations are used.

  3. Treatment of rainwater runoff in recovery and recycling companies: Lab and pilot-scale testing.

    Chys, M; Depuydt, V; Boeckaert, C; Van Hulle, S W H


    Wastewater released from the storage and/or processing of recycling and materials recovery can be characterised as rainwater runoff. Recuperation and recycling companies are confronted with wastewater that has a very fluctuating flow rate and composition. The flow rate mainly depends on the amount of rainfall while the composition additionally depends on what is currently stored on site. An analysis of possible physical-chemical treatment (coagulation/flocculation, sand filtration, activated carbon filtration and sedimentation) methods was performed at two different recycling companies in order to find a robust and economical feasible water treatment system that meets the discharge limits at all times. A violation of some measurement values (Cd, Cr, Ni and acenaphthene) after coagulation/flocculation occurred, which could be further reduced by using sand filtration. Good removal is achieved for common parameters as for mono- and poly-aromatic hydrocarbons (MAH and PAH) and polychlorinated biphenyls (PCB). Applying a coupled sand- and activated carbon filtration on runoff resulted in a removal of over 80% of several measurement values (suspended solids, heavy metals). This clearly indicates the applicability of the physical-chemical treatment techniques.

  4. Identification and quantification of phencyclidine pyrolysis products formed during smoking

    Lue, L.P.; Scimeca, J.A.; Thomas, B.F.; Martin, B.R.

    As a result of frequent phencyclidine (PCP) abuse, pyrolysis studies were conducted to further investigate its fate during smoking. Marijuana placebo cigarettes were impregnated with /sup 3/H-PCP HCl and burned under conditions simulating smoking. Mainstream smoke was passed through glass wool filters as well as acidic and basic traps. Approximately 90% of the starting material could be accounted for in the first glass wool trap and cigarette holder. HPLC and GC/MS analysis of methanol extracts of these glass wool traps revealed the presence of 1-phenyl-1-cyclohexene (47% of the starting material) > PCP (40%) > piperidine (15%) > N-acetylpiperidine (9%). It was not possible to fully account for the remainder of the piperidine moiety. It has been reported that at high temperatures PCP is converted to numerous polynuclear aromatic compounds which include styrene, ..cap alpha..-methylstyrene, naphthalene, 2-methyl-naphthalene, 1-methylnaphthalene, biphenyl, cyclohexylbenzene, acenaphthene, phenanthrene, and anthracene. These compounds were not formed from PCP under smoking conditions.


    朱亚先; 张勇; 庄一廷; Ka-FaiPoon; MichaelH.W.Lam; 洪华生; RudolfS.S.Wu


    A new mimic biological Semi-permeable Membrane Device (SPMD) introduced for sampling organic pollutants yielded satisfactory results when it was frrst used as a passive sampler to concentrate and determine 16 kinds of polynuclear aromatic hydrocarbons (PAHs) by means of capillary GC on an HP 5890 GC-FID in coastal sediment perewater. The concentration of PAHs in sediment porewater for naphthalene(N), acenaphthlene(AL), acenaphthene (AE), fluorene (F), phenaphthene(P), anthracene(A), fluoranthene(FA), pyrene(Py), benzo[a]anthracene(B[a]A), chrysene(Chr), benzo[b] fluor- anthene(B[b]F), benzo[k]fluoranthene(B[k]F), benzo[a]pyrene(B[a]P),indeno[1,2,3,-cd]-Pyrene(I[123]P), dibenz[a,h]anthracene(D[ab]A) and benzo[g,h,i] perylene(B[ghi]P) were:50.36, under detection limits(UD), 18.19, 8.41, 8.40, 1.44, UD, 8.01, 524.15, 168.47, 50.13,123.66, 63.48, 27.40, 82.04 and 58,81 ng/L, respectively.



    A new mimic biological Semi-permeable Membrane Device (SPMD) introduced for sampling organic pollutants yielded satisfactory results when it was first used as a passive sampler to concentrate and determine 16 kinds of polynuclear aromatic hydrocarbons (PAHs) by means of capillary GC on an HP 5890 GC-FID in coastal sediment porewater. The concentration of PAHs in sediment porewater for naphthalene(N), acenaphthlene(AL), acenaphthene(AE), fluorene(F), phenaphthene(P), anthracene(A), fluoranthene(FA), pyrene(Py), benzo[ a] anthracene( B [a] A), chrysene(Chr), benzo[b]fluor- anthene ( B [ b ] F ), benzo[ k ] fluoranthene ( B [ k ] F ), benzo[ a ] pyrene ( B [ a ] P), indeno [ 1,2,3,-cd]-Pyrene(I[123]P), dibenz[a,h]anthracene(D[ah]A) and benzo[g,h,i] perylene(B[ghi]P) were:50.36, under detection limits( UD), 18.19, 8.41, 8.40, 1.44, UD, 8.01, 524.15, 168.47, 50.13,123.66, 63.48, 27.40, 82.04 and 58,81 ng/L, respectively.

  7. Biodegradation of Various Aromatic Compounds by Enriched Bacterial Cultures: Part A-Monocyclic and Polycyclic Aromatic Hydrocarbons.

    Oberoi, Akashdeep Singh; Philip, Ligy; Bhallamudi, S Murty


    Present study focused on the screening of bacterial consortium for biodegradation of monocyclic aromatic hydrocarbon (MAH) and polycyclic aromatic hydrocarbons (PAHs). Target compounds in the present study were naphthalene, acenaphthene, phenanthrene (PAHs), and benzene (MAH). Microbial consortia enriched with the above target compounds were used in screening experiments. Naphthalene-enriched consortium was found to be the most efficient consortium, based on its substrate degradation rate and its ability to degrade other aromatic pollutants with significantly high efficiency. Substrate degradation rate with naphthalene-enriched culture followed the order benzene > naphthalene > acenaphthene > phenanthrene. Chryseobacterium and Rhodobacter were discerned as the predominant species in naphthalene-enriched culture. They are closely associated to the type strain Chryseobacterium arthrosphaerae and Rhodobacter maris, respectively. Single substrate biodegradation studies with naphthalene (PAH) and benzene (MAH) were carried out using naphthalene-enriched microbial consortium (NAPH). Phenol and 2-hydroxybenzaldehyde were identified as the predominant intermediates during benzene and naphthalene degradation, respectively. Biodegradation of toluene, ethyl benzene, xylene, phenol, and indole by NAPH was also investigated. Monod inhibition model was able to simulate biodegradation kinetics for benzene, whereas multiple substrate biodegradation model was able to simulate biodegradation kinetics for naphthalene.

  8. Multisubstrate kinetics of PAH mixture biodegradation: analysis in the double-logarithmic plot.

    Baboshin, Mikhail; Golovleva, Ludmila


    The proposed method of kinetic analysis of aqueous-phase biodegradation of polycyclic aromatic hydrocarbons (PAH) mixture presupposes representation of kinetic curves for each pair of mixture components, S(x) and S(y), in double-logarithmic coordinates (ln S(x); ln S(y)). If PAH mixture conversion corresponds to the multisubstrate model with a common active site, then the graphs in double-logarithmic coordinates are straight lines with the angular coefficients equal to the ratio of respective first-order rate constants k(y)(x)= V(y)K(x)/K(y)V(x), where K(x) and K(y) are half-saturation constants, V(x) and V( y ) are the maximum conversion rates for substrates S(x) and S(y); the graph slope does not depend on any concentrations and remains constant during the change of reaction rates as a result of inhibition, induction/inactivation of enzymes or biomass growth. The formulated method has been used to analyze PAH mixture conversion by the culture of Sphingomonas sp. VKM B-2434. It has been shown that this process does not satisfy the multisubstrate model with a single active site. The results suggest that the strain VKM B-2434 contains at least two dioxygenases of different substrate specificity: one enzyme converts phenanthrene and fluoranthene and the other converts acenaphthene and acenaphthylene. The ratios of first-order rate constants have been obtained for these pairs of substrates.

  9. Heavy metals and polycyclic hydrocarbon compounds in benthic organisms of the Upper Gulf of Thailand

    Hungspreugs, M.; Silpipat, S.; Tonapong, C.; Lee, R.F.; Windom, H.L.; Tenore, K.R.


    Concentrations of heavy metals and polycyclic aromatic hydrocarbons (PAHs) were measured in bivalves collected in the Upper Gulf of Thailand. PAHs detected included acenaphthene, acenaphthylene, benzo(a)pyrene, fluoranthene, methylphenanthrene, phenanthrene and triphenylene. Benzol(a)pyrene was detected in all species at concentrations varying from 1.0 to 8.2 ng.g/sup -1/. Concentrations of cadmium, cobalt, copper, lead, and nickel were significantly lower in bivalves from the Gulf than in green mussels collected from the mouth of the Chao Phraya River. No correlation was found between metal concentrations in animals and sediment, with the exception of copper. Copper concentrations in polychaetes and clams appeared to correlate with the copper:iron ratio of sediments. High rates of degradation were observed when radiolabelled chlorobenzene, phenanthrene and chrysene were added to water and sediment of the Chao Phraya River. Rates were lower in the waters and sediment of the Gulf of Thailand. The calculated half-lives of chlorobenzene in the Gulf of Thailand and the Chao Phraya River were about 130 and 68 days, respectively. 32 references, 3 figures, 3 tables.

  10. Description of adsorption equilibrium of PAHs on hypercrosslinked polymeric adsorbent using Polanyi potential theory


    In this research,static adsorption of three polycyclic aromatic hydrocarbons(PAHs),naphthalene,acenaphthene,and fluorene,from aqueous solutions onto hypercrosslinked polymeric adsorbent within the temperature range of 288-308 K is investigated.Several isotherm equations are correlated with the equilibrium data,and the experimental data is found to fit the Polanyi-Dubinin-Manes model best within the entire range of concentrations,providing evidence that pore-filling is the dominating sorption mechanism for PAHs.The study shows that the molecular size of adsorbates has distinct in-fluence on adsorption capacity of hypercrosslinked polymeric adsorbent for the PAHs;the larger the adsorbate molecular size,the lower the adsorption equilibrium capacity.Based on the Polanyi-Dubinin-Manes model,the molecular size of adsorbates was introduced to adjust the adsorbate molar volume.Plots of qv vs.(σε /Vs) are collapsed to a single correlation curve for different adsorbates on hypercrosslinked polymeric resin.

  11. Differential immunomodulatory responses to nine polycyclic aromatic hydrocarbons applied by passive dosing.

    Oostingh, Gertie J; Smith, Kilian E C; Tischler, Ulrike; Radauer-Preiml, Isabella; Mayer, Philipp


    Studying the effects of hydrophobic chemicals using in vitro cell based methods is hindered by the difficulty in bringing and keeping these chemicals in solution. Their effective concentrations are often lower than their nominal concentrations. Passive dosing is one approach that provides defined and stable dissolved concentrations during in vitro testing, and was applied to control and maintain freely dissolved concentrations of polycyclic aromatic hydrocarbons (PAHs) at levels up to their aqueous solubility limit. The immunomodulatory effects of 9 different PAHs at aqueous solubility on human bronchial epithelial cells were determined by analysing the cytokine promoter expression of 4 different inflammatory cytokines using stably transfected recombinant A549 cell lines. Diverse immunomodulatory responses were found with the highest induction observed for the most hydrophobic PAHs chrysene, benzo(a)antracene and benzo(a)pyrene. Cytokine promoter expression was then studied in dose response experiments with acenaphthene, phenanthrene and benzo(a)anthracene. The strongest induction was observed for benzo(a)anthracene. Cell viability analysis was performed and showed that none of the PAHs induced cytotoxicity at any of the concentrations tested. Overall, this study shows that (1) immunomodulatory effects of PAHs can be studied in vitro at controlled freely dissolved concentrations, (2) the most hydrophobic PAHs were the strongest inducers and (3) induction was often higher at lower exposure levels and decreased then with concentration despite the apparent absence of cytotoxicity.

  12. Crystal structure of 8-[7,8-bis-(4-chloro-benzo-yl)-7H-cyclo-penta-[a]ace-naphthylen-9-yl]naphthalene-1-carb-oxy-lic acid.

    Jacob, Jomon P; Sithambaresan, M; Kunjachan, Christy; Kurup, M R Prathapachandra


    The title compound, C40H22Cl2O4, was formed by a Michael-Aldol domino reaction sequence, which coupled acenaphthene-quinone with 4-chloro-aceto-phenone in the presence of KOH in methanol. The dihedral angles between the central cyclo-penta-[a]ace-naphthyl-ene fused-ring system (r.m.s. deviation = 0.066 Å) and the 4-chloro-benzoyl rings are 62.25 (10) and 70.19 (10)°. The dihedral angle between the central ring system and the naphthoic acid grouping is 62.46 (7)°. This twisting of the pendant rings facilitates the formation of an intra-molecular aromatic π-π stacking inter-action between the 4-chloro-benzoyl and naphthoic acid rings, with centroid-centroid distances of 3.4533 (16) and 3.5311 (16) Å, and a C-H⋯π inter-action between one of the H atoms of the central moiety and the 4-chloro-benzoyl ring with an H⋯π distance of 2.57 Å. In the crystal, carb-oxy-lic acid inversion dimers generate R 2 (2)(8) loops. The dimers are linked by weak C-H⋯O and C-H⋯Cl hydrogen bonds and C-H⋯π inter-actions, generating a three-dimensional architecture.

  13. Modelling of an enhanced PAH attenuation experiment and associated biogeochemical changes at a former gasworks site in southern Germany

    Herold, Maria; Greskowiak, Janek; Ptak, Thomas; Prommer, Henning


    Former manufactured gas plant sites often form a widespread contaminant source in the subsurface, leading to large plumes that contain a wide variety of tar-oil related compounds. Although most of these compounds eventually degrade naturally, the relevant processes tend to be slow and inefficient, often leaving active remediation as the only viable option to eliminate the risks of toxic substances to reach potential receptors such as surface waters or drinking water wells. In this study we use a reactive transport model to analyse the fate of a contaminant plume containing acenaphthene, methylbenzofurans and dimethylbenzofurans (i) prior to the installation of an active remediation scheme and (ii) for an enhanced remediation experiment during which O 2 and H 2O 2 were added to the contaminated groundwater through a recirculation well. The numerical model developed for this study considers the primary contaminant degradation reactions (i.e., microbially mediated redox reactions) as well as secondary and competing mineral precipitation/dissolution reactions that affect the site's hydrochemistry and/or contaminant fate. The model was calibrated using a variety of constraints to test the uncertainty on model predictions resulting from the undocumented presence of reductants such as pyrite. The results highlight the important role of reactive transport modelling for the development of a comprehensive process understanding.

  14. Colonization on root surface by a phenanthrene-degrading endophytic bacterium and its application for reducing plant phenanthrene contamination.

    Juan Liu

    Full Text Available A phenanthrene-degrading endophytic bacterium, Pn2, was isolated from Alopecurus aequalis Sobol grown in soils contaminated with polycyclic aromatic hydrocarbons (PAHs. Based on morphology, physiological characteristics and the 16S rRNA gene sequence, it was identified as Massilia sp. Strain Pn2 could degrade more than 95% of the phenanthrene (150 mg · L(-1 in a minimal salts medium (MSM within 48 hours at an initial pH of 7.0 and a temperature of 30 °C. Pn2 could grow well on the MSM plates with a series of other PAHs, including naphthalene, acenaphthene, anthracene and pyrene, and degrade them to different degrees. Pn2 could also colonize the root surface of ryegrass (Lolium multiflorum Lam, invade its internal root tissues and translocate into the plant shoot. When treated with the endophyte Pn2 under hydroponic growth conditions with 2 mg · L(-1 of phenanthrene in the Hoagland solution, the phenanthrene concentrations in ryegrass roots and shoots were reduced by 54% and 57%, respectively, compared with the endophyte-free treatment. Strain Pn2 could be a novel and useful bacterial resource for eliminating plant PAH contamination in polluted environments by degrading the PAHs inside plants. Furthermore, we provide new perspectives on the control of the plant uptake of PAHs via endophytic bacteria.


    M. Àngels Olivella


    Full Text Available Quercus cerris is an important oak species extended in large areas of Eastern Europe and Minor Asia that has a thick bark which is not utilized at all. The sorption performance of cork from Quercus cerris bark with four polycyclic aromatic hydrocarbons (PAHs (acenaphthene, fluorene, phenanthrene, and anthracene was investigated. Quercus cerris cork was characterized for elemental analysis, acidic groups, and summative chemical composition, and the results were compared with Quercus suber cork. A Microtox® test was carried out to test for the release of any toxic compounds into the solution. All isotherms fit the Freundlich model and displayed linear n values. Quercus cerris exhibited a high efficiency for sorption of PAHs for the studied concentrations (5 to 50 µg/L with 80-96% removal, while the desorption isotherms showed a very low release of the adsorbed PAHs (<2%. In relation to Quercus suber cork, KF values of Quercus cerris cork are about three times lower. The quantity of Quercus cerris cork required to reduce water pollution by PAHs was estimated to be less than twice the quantity of other adsorbents such as aspen wood and leonardite. Toxicity tests indicated that non-toxic compounds were released into the solution by the Quercus cerris and Quercus suber cork samples. Overall the results indicate the potential use of Quercus cerris cork and of Quercus suber cork as effective and economical biosorbents for the treatment of PAH-contaminated waters.

  16. Triacontyl modified silica gel as a sorbent for the preconcentration of polycyclic aromatic hydrocarbons in aqueous samples prior to gas chromatographic-mass spectrometry determination



    Triacontyl modified silica gel as a sorbent coupled with gas chromatography-mass spectrometry (GC-MS) was developed to determine EPA prior 16 polycyclic aromatic hydrocarbons (PAHs) in water samples. Various parameters of solid-phase extraction such as organic modifier solvent, eluent, sample flow rate and volume were optimized. The developed method was found to yield a linear calibration curve in the concentration range of 0.05-8 μg/L with respect to naphthalene, acenaphthylene, acenaphthene and 0.01-8μg/L for dibenz[a,h]anthracene and 0.05-14 μg/L for fluorene, phenanthrene, anthracene and 0.01-14 μg/L for the rest of analytes. Furthermore, the good accuracy and repeatability of the method made sure the requirements for achieving reliable analysis of PAHs in the environmental water samples, and the recoveries of optimal method were in the range of 80-120% except to higher volatility PAHs. C30-bonded silica was proved to be an efficient sorbent for extraction of high molecular weight PAHs.

  17. Sample preparation of sewage sludge and soil samples for the determination of polycyclic aromatic hydrocarbons based on one-pot microwave-assisted saponification and extraction.

    Pena, M Teresa; Pensado, Luis; Casais, M Carmen; Mejuto, M Carmen; Cela, Rafael


    A microwave-assisted sample preparation (MASP) procedure was developed for the analysis of polycyclic aromatic hydrocarbons (PAHs) in sewage sludge and soil samples. The procedure involved the simultaneous microwave-assisted extraction of PAHs with n-hexane and the hydrolysis of samples with methanolic potassium hydroxide. Because of the complex nature of the samples, the extracts were submitted to further cleaning with silica and Florisil solid-phase extraction cartridges connected in series. Naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[e]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-cd]pyrene, were considered in the study. Quantification limits obtained for all of these compounds (between 0.4 and 14.8 microg kg(-1) dry mass) were well below of the limits recommended in the USA and EU. Overall recovery values ranged from 60 to 100%, with most losses being due to evaporation in the solvent exchange stages of the procedure, although excellent extraction recoveries were obtained. Validation of the accuracy was carried out with BCR-088 (sewage sludge) and BCR-524 (contaminated industrial soil) reference materials.

  18. Lignin Peroxidase Oxidation of Aromatic Compounds in Systems Containing Organic Solvents

    Vazquez-Duhalt, Rafael; Westlake, Donald W. S.; Fedorak, Phillip M.


    Lignin peroxidase from Phanerochaete chrysosporium was used to study the oxidation of aromatic compounds, including polycyclic aromatic hydrocarbons and heterocyclic compounds, that are models of moieties of asphaltene molecules. The oxidations were done in systems containing water-miscible organic solvents, including methanol, isopropanol, N, N-dimethylformamide, acetonitrile, and tetrahydrofuran. Of the 20 aromatic compounds tested, 9 were oxidized by lignin peroxidase in the presence of hydrogen peroxide. These included anthracene, 1-, 2-, and 9-methylanthracenes, acenaphthene, fluoranthene, pyrene, carbazole, and dibenzothiophene. Of the compounds studied, lignin peroxidase was able to oxidize those with ionization potentials of <8 eV (measured by electron impact). The reaction products contain hydroxyl and keto groups. In one case, carbon-carbon bond cleavage, yielding anthraquinone from 9-methylanthracene, was detected. Kinetic constants and stability characteristics of lignin peroxidase were determined by using pyrene as the substrate in systems containing different amounts of organic solvent. Benzyl alkylation of lignin peroxidase improved its activity in a system containing water-miscible organic solvent but did not increase its resistance to inactivation at high solvent concentrations. PMID:16349176

  19. Characterization and biodegradation of polycyclic aromatic hydrocarbons in radioactive wastewater

    Tikilili, Phumza V. [Water Utilisation Division, Department of Chemical Engineering, University of Pretoria, Pretoria 0002 (South Africa); Nkhalambayausi-Chirwa, Evans M., E-mail: [Water Utilisation Division, Department of Chemical Engineering, University of Pretoria, Pretoria 0002 (South Africa)


    Highlights: {yields} Biodegradation of recalcitrant toxic organics under radioactive conditions. {yields} Biodegradation of PAHs of varying size and complexity in mixed waste streams. {yields} Validation of radiation-tolerance and performance of the isolated organisms. - Abstract: PAH degrading Pseudomonad and Alcaligenes species were isolated from landfill soil and mine drainage in South Africa. The isolated organisms were mildly radiation tolerant and were able to degrade PAHs in simulated nuclear wastewater. The radiation in the simulated wastewater, at 0.677 Bq/{mu}L, was compatible to measured values in wastewater from a local radioisotope manufacturing facility, and was enough to inhibit metabolic activity of known PAH degraders from soil such as Pseudomonas putida GMP-1. The organic constituents in the original radioactive waste stream consisted of the full range of PAHs except fluoranthene. Among the observed PAHs in the nuclear wastewater from the radioisotope manufacturing facility, acenaphthene and chrysene predominated-measured at 25.1 and 14.2 mg/L, respectively. Up to sixteen U.S.EPA priority PAHs were detected at levels higher than allowable limits in drinking water. The biodegradation of the PAHs was limited by the solubility of the compounds. This contributed to the observed faster degradation rates in low molecular weight (LMW) compounds than in high molecular weight compounds.

  20. Sample preparation of sewage sludge and soil samples for the determination of polycyclic aromatic hydrocarbons based on one-pot microwave-assisted saponification and extraction

    Pena, M.T.; Pensado, Luis; Casais, M.C.; Mejuto, M.C.; Cela, Rafael [Universidad de Santiago de Compostela, Dpto. Quimica Analitica, Nutricion y Bromatologia. Instituto de Investigacion y Analisis Alimentario, Santiago de Compostela (Spain)


    A microwave-assisted sample preparation (MASP) procedure was developed for the analysis of polycyclic aromatic hydrocarbons (PAHs) in sewage sludge and soil samples. The procedure involved the simultaneous microwave-assisted extraction of PAHs with n-hexane and the hydrolysis of samples with methanolic potassium hydroxide. Because of the complex nature of the samples, the extracts were submitted to further cleaning with silica and Florisil solid-phase extraction cartridges connected in series. Naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[e]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-cd]pyrene, were considered in the study. Quantification limits obtained for all of these compounds (between 0.4 and 14.8 {mu}g kg{sup -1} dry mass) were well below of the limits recommended in the USA and EU. Overall recovery values ranged from 60 to 100%, with most losses being due to evaporation in the solvent exchange stages of the procedure, although excellent extraction recoveries were obtained. Validation of the accuracy was carried out with BCR-088 (sewage sludge) and BCR-524 (contaminated industrial soil) reference materials. (orig.)

  1. Comparison of polycyclic aromatic hydrocarbons level between suspended solid and sediment samples of Pengkalan Chepa River, Kelantan state, Malaysia

    Muslim, Noor Zuhartini Md; Babaheidari, Seyedreza Hashemi; Zakaria, Mohamad Pauzi


    Sixteen type of common Polycyclic Aromatic Hydrocarbons (PAHs) which consist of naphthalene, acenaphthene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, benzo[ghi]-perylene, indeno[1,2,3-cd]-pyrene and dibenz[a,h]-anthracene in suspended solid and sediment samples of Pengkalan Chepa River, Kelantan state, Malaysia were investigated. The analysis samples were taken from six different sites of Pengkalan Chepa River during sunny day. The samples were subjected to a series of pre-treatment before the level of PAHs can be determined. A Gas Chromatography-Mass Spectrometry (GC-MS) was the prime method for the analysis of PAHs level. A total of 16 PAHs concentration in suspended solid of the whole Pengkalan Chepa River was found to be 2144.6 ng/g dry weights. This concentration was about eight times more than 16 PAHs concentration in sediment which found to be 266.5 ng/g dry weights.

  2. 青岛浴场表层海水正构烷烃和芳烃组成分布特征研究%Distributions and Source Analysis of Alkanes and Aromatics in Surface Seawater of Qingdao Offshore

    张璐; 马启敏


    The compositions and sources of n-alkanes and polycyclic aromatic hydrocarbons (PAHs)in the surface seawater samples collected from 4 sites in Qingdao offshore (the First Beach,the Second Beach,Golden Beach and the May Fourth Square)were analyzed by gas chromatography-mass spec-trometry method (GC-MS).The results showed that the concentrations of ∑n-alk were between 1.14 and 25.47μg/L.The n-alkanes in all four sites’seawater showed bimodal patterns,but the dominant peak and parity advantage were different.The concentrations of ∑PAHs changed between 201.01 and 314.30μg/L.Naphthalene with two or three benzene rings,acenaphthene,acenaphthene,fluorene, phenanthrene,and fluoranthene were the dominant components.N-ankanes in the First Beach,the Sec-ond Beach,and the May Fourth Square mainly came from anthropogenic incomplete combustions of crude oil and fossil fuel,while N-alkanes in Golden Beach came from plankton such as diatoms and bac-teria.PAHs in seawater samples of the First Beach,the Second Beach,and Golden Beach were all mainly from petroleum pollution and fossil fuel combustions,while PAHs in the May Fourth Square were mainly from petroleum pollutions.Diagnostic ratios (CP,OEP and Pr/Ph)showed that all the four sites’seawater surfers from petroleum pollution.%对青岛浴场表层海水中正构烷烃和多环芳烃组成、分布及来源进行分析。分别在第一海水浴场(以下简称一浴)、第二海洋浴场(以下简称二浴)、黄岛金沙滩海水浴场和五四广场4个站位采集表层海水,经萃取、浓缩后用气质联用法(GC-MS)进行测定。结果表明,各站位海水中正构烷烃谱图均为双峰型,主峰碳和奇偶优势各不相同,正构烷烃(∑n-alk)含量为1.14-25.47μg/L;多环芳烃(∑PAHs)含量为201.01-314.30 ng/L,以二、三环的萘、苊、二氢苊、芴、菲、荧蒽为优势组分;一浴、二浴和五四广场海水正构烷烃以石油、化石燃料的不完全燃烧等人类活动

  3. Preparation Method of Stalk Environmental Biomaterial and Its Sorption Ability for Polycyclic Aromatic Hydrocarbons in Water%秸秆生物质环境材料的制备及对水中多环芳烃的处理性能

    何娇; 孔火良; 韩进; 高彦征


    300~700℃下热解炭化黄豆、芝麻、玉米秸秆8h,制备了秸秆生物质环境材料,测定了秸秆生物质环境材料的BET比表面积及其对亚甲基蓝和碘的吸附能力.以多环芳烃(PAHs)为目标污染物,探讨了生物质环境材料对水中单一和复合PAHs的吸附性能.结果表明,随热解温度升高,秸秆生物质环境材料比表面积增大,其对亚甲基蓝、碘的吸附能力增强.所制备的生物质环境材料吸附水中PAHs的能力强,以700℃下制备的黄豆秸秆生物质环境材料为例,0.01 g材料对32 mL水中萘、苊、菲的去除率分别高达91.28%、89.01%和99.66%;生物质环境材料对水中3种PAHs的去除率大小顺序为菲>萘>苊.不同秸秆制备的生物质环境材料对水中萘和苊的去除能力大小为玉米>黄豆>芝麻,而对菲的去除能力则为黄豆>玉米>芝麻.研究结果可为农作物秸秆的资源化利用、制备经济高效的生物质环境材料等提供依据.%The soybean, sesame and corn stalks were pyrolyzed and charred for 8 h at 300-700℃ to obtain stalk environmental biomaterials. The BET specific surface areas, methylene blue, and iodine adsorption capacity of the stalk environmental biomaterials were determined. The sorption efficiency of these materials on single polycyclic aromatic hydrocarbon(PAH) and mixing PAHs were investigated. The BET specific surface areas of stalk biomaterials enlarged, and the sorption ability on methylene blue and iodine enhanced with increasing the treatment temperature. The obtained stalk biomaterials could effectively remove the PAHs from water. For instance, 91.28%, 89.01% and 99.66% of naphthalene, aeenaphthene, and phenanthrene in 32 mL water were removed by 0.01 g biomaterials obtained by soybean stalk at 700℃. The removal efficiencies of biomaterials for mixed PAHs in water were in the order of phenanthrene > naphthalene > acenaphthene. However, the sorption ability of produced stalk

  4. Comparison of Polycyclic Aromatic Hydrocarbon (PAHs concentrations in urban and natural forest soils in the Atlantic Forest (São Paulo State

    Christine Bourotte


    Full Text Available Studies about pollution by Polycyclic Aromatic Hydrocarbons (PAHs in tropical soils and Brazil are scarce. A study was performed to examine the PAHs composition, concentrations and sources in red-yellow Oxisols of remnant Atlantic Forest of the São Paulo State. Sampling areas were located in an urban site (PEFI and in a natural one (CUNHA.The granulometric composition, pH, organic matter content and mineralogical composition were determined in samples of superficial soils. The sum of PAHs (ΣHPAs was 4.5 times higher in the urban area than in the natural one. Acenaphthylene, acenaphthene, fluorene, phenanthrene and fluoranthene have been detected in the soils of both areas and presented similar concentrations. Acenaphthene and fluorene were the most abundant compounds. Pyrene was twice more abundant in the soils of natural area (15 µ than of the urban area and fluoranthene was the dominant compound (203 µ in urban area (6.8 times higher than in the natural area. Some compounds of higher molecular weight, which are tracers of vehicular emissions showed significant concentrations in urban soils. Pyrene represented 79% of ΣPAHs whereas it has not been detected in natural soils. The results showed that forest soils in urban area are characterized by the accumulation of high molecular weight compounds of industrial and vehicular origin.Estudos sobre a poluição por Hidrocarbonetos Policíclicos Aromáticos (HPAs são escassos em solos tropicais e no Brasil. Um estudo foi realizado para examinar a composição, as concentrações e fontes de HPAs encontrados em Latossolos vermelho-amarelo (Oxissolos, remanescentes de Mata Atlântica no Estado de São Paulo. As áreas de estudos localizaram-se em um sítio urbano (PEFI e um natural (CUNHA. A composição granulométrica, pH, teor de matéria orgânica e composição mineralógica foram determinados em amostras de solo superficial. A soma dos HPAs analisados (ΣHPAs foi 4,5 vezes mais

  5. [An investigation of the formation of] polycyclic aromatic hydrocarbon (PAH) emissions when firing pulverized coal in a bench-scale drop tube reactor

    Pisupati, S.V.; Wasco, R.S.; Scaroni, A.W. [Pennsylvania State Univ., University Park, PA (United States). Combustion Lab.


    The Clean Air Act Amendments (CAAA) of 1990 contain provisions which will set standards for the allowable emissions of 188 analytes designated as hazardous air pollutants (HAPs). This list of HAPs was used to establish an initial list of source categories for which EPA would be required to establish technology-based emission standards, which would result in regulated sources sharply reducing routine emissions of toxic air pollutants. Polycyclic organic matter (POM) has also been referred to as polynuclear or polycyclic aromatic compounds (PACs). Nine major categories of POM have been defined by EPA. The study of organic compounds from coal combustion is complex and the results obtained so far are inconclusive with respect to emission factors. The most common organic compounds in the flue gas of coal-fired power plants are polycyclic aromatic hydrocarbons (PAHs). Furthermore, EPA has specified 16 PAH compounds as priority pollutants. These are naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benz[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, benzo[ghi]perylene, and dibenz[ah]anthracene. Penn State`s Combustion Laboratory is equipped to collect and analyze the HAPs in the flue gas from fossil fuels combustion. The overall objective of this study was to examine the effect of unit temperature on PAH emissions. A Modified Method 5 sampling train was used to isokinetically collect samples at desired locations in flue gas streams. The collected sample can be separated into solid, condensed liquid and gaseous phases. The PAHs of interest are extracted from the collected sample, concentrated, then separated and quantified by gas chromatography/mass spectrometry (GC/MS). This study was conducted using a bench-scale drop-tube reactor (DTR). The fuel selected for this study was a Middle Kittanning seam coal pulverized to 80% passing US Standard 200 mesh (commonly

  6. An investigation on polycyclic aromatic hydrocarbon emissions from pulverized coal combustion systems

    Pisupati; Wasco; Scaroni


    Results from a series of tests conducted to study the emission of polynuclear or polycyclic aromatic hydrocarbons (PAHs) from bench-scale and small industrial, water-tube boiler are discussed. A Middle Kittanning, and Upper Freeport seam coals were used in the study. Samples were extracted from the reactor outlet and from the inlet and outlet sides of the research boiler's (RB) baghouse using EPA promulgated methods.Only acenaphthene and fluoranthene were detected in down-fired combustor (DFC) samples. In addition to these two, naphthalene was detected in the RB samples. Emission factors ranged from 80 to 320 &mgr;g/kg of fuel fired. Although there were minor trends in the emissions' data, given the reproducibility limits for PAH compounds, no significant differences were found in the emissions with respect to the fuel type or form (pulverized coal (PC) vs. coal-water slurry fuel (CWSF), and raw vs. cleaned coal) and firing conditions (high and low excess air). The PAH emissions showed a decrease with increase in the firing rate.A bench-scale drop-tube reactor (DTR) was used to study the effects of temperature and residence time on PAH formation. The results revealed near constant PAH concentrations in the solid-phase samples, while the PAH concentrations in the vapor-phase samples increased as a function of temperature. At a temperature of around 1300 degrees C, the rate of PAH formation was exceeded by the rate of PAH oxidation, and PAH concentrations in the vapor phase began to decrease.

  7. Atmospheric processes of organic pollutants over a remote lake on the central Tibetan Plateau: implications for regional cycling

    Ren, Jiao; Wang, Xiaoping; Wang, Chuanfei; Gong, Ping; Yao, Tandong


    Atmospheric processes (air-surface exchange, and atmospheric deposition and degradation) are crucial for understanding the global cycling and fate of organic pollutants (OPs). However, such assessments over the Tibetan Plateau (TP) remain uncertain. More than 50 % of Chinese lakes are located on the TP, which exerts a remarkable influence on the regional water, energy, and chemical cycling. In this study, air and water samples were simultaneously collected in Nam Co, a large lake on the TP, to test whether the lake is a secondary source or sink of OPs. Lower concentrations of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) were observed in the atmosphere and lake water of Nam Co, while the levels of polycyclic aromatic hydrocarbons (PAHs) were relatively higher. Results of fugacity ratios and chiral signatures both suggest that the lake acted as the net sink of atmospheric hexachlorocyclohexanes (HCHs), following their long-range transport driven by the Indian monsoon. Different behaviours were observed in the PAHs, which primarily originated from local biomass burning. Acenaphthylene, acenaphthene, and fluorene showed volatilization from the lake to the atmosphere, while other PAHs were deposited into the lake due to the integrated deposition process (wet/dry and air-water gas deposition) and limited atmospheric degradation. As the dominant PAH compound, phenanthrene exhibited a seasonal reversal of air-water gas exchange, which was likely related to the melting of the lake ice in May. The annual input of HCHs from the air to the entire lake area (2015 km2) was estimated as 1.9 kg yr-1, while input estimated for ∑ 15PAHs can potentially reach up to 550 kg yr-1. This study highlights the significance of PAH deposition on the regional carbon cycling in the oligotrophic lakes of the TP.

  8. Polycyclic Aromatic Hydrocarbons In Edible Mushrooms from Niger Delta, Nigeria: Carcinogenic and Non-Carcinogenic Health Risk Assessment

    Igbiri, Sorbari; Udowelle, Nnaemeka Arinze; Ekhator, Osazuwa Clinton; Asomugha, Rose Ngozi; Igweze, Zelinjo Nkeiruka; Orisakwe, Orish Ebere


    In the oil-rich Niger Delta, hydrocarbon pollution and oil spillages, gas flaring and sundry anthropogenic activities constitute sources of polycyclic aromatic hydrocarbons (PAHs), with food contamination playing a major role in human exposure. In this study we assessed PAH levels in wild and cultivated edible mushroom species consumed by the general population from the oil producing Niger Delta, Nigeria. The concentrations of USEPA-16 PAHs were determined by gas chromatography and carcinogenic and non-carcinogenic health risks were calculated. The concentrations of USEPA-16 PAHs ranged from 0.02 mg/kg – 3.37 mg/kg. The dietary intake of carcinogenic and non-carcinogenic USEPA-16 PAHs (Naphthalene, Acenaphthylene, Acenaphthene, Anthracene, Phenanthrene, Flourene, Flouranthene, Pyrene, Benzo[a]Anthracene, Chrysene, Benzo[a]Pyrene, Benzo[b]Flouranthene, Benzo[K]Flouranthene, Benzo[g,h,i] Perylene, Dibenz[a,h]Anthracene and Ideno[1,2,3-cd]Pyrene) for adults, adolescents and seniors ranged from 0.00 – 0.05 mg/kg/day, 0.00 – 0.06 mg/kg/day and 0.00 – 0.07 mg/kg/day. The BaPeq ranged from 0.02 – 2.76 with margin of exposure MOE values of BaP ranging from 3,500,000 to 700,000, 3,500,000 and 3,500,000 to 7,000,000 for adults, adolescents and seniors indicating very insignificant health risk. The incremental lifetime cancer risk was within the safe range of 1.56x10-8 – 1.73x10-6 with the highest calculated risk found for wild Pleurotus ostreatus mushroom species from the study area. Creative Commons Attribution License

  9. Temporal occurrence and sources of persistent organic pollutants in suspended particulate matter from the most heavily polluted river mouth of Lake Chaohu, China.

    Liu, Cheng; Zhang, Lei; Fan, Chengxin; Xu, Fuliu; Chen, Kaining; Gu, Xiaozhi


    The Nanfei River is by many measures the most heavily polluted tributary to Lake Chaohu. In this study, the temporal occurrence and sources of four classes of persistent organic pollutants (POPs), including polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs), in suspended particulate matter (SPM) from the river mouth were investigated monthly during 2014. Results show that concentrations of all four POPs in SPM were higher than those in the sediment of Lake Chaohu. PBDEs (26.7 ng g(-1) dry weight (dw)) were originated mainly from commercial deca-BDE mixtures. PCB concentrations (1.336 ng g(-1) dw) were lower than those of sediments in many other water bodies worldwide. PAHs (2597 ng g(-1) dw) and OCPs (57.38 ng g(-1) dw) were the most common POPs. PAHs mainly had high molecular weights and originated from pyrolytic sources, with a small proportion of petrogenic origin. The predominant OCPs were DDTs, heptachlorepoxides, dieldrin, hexachlorocyclohexanes, hexachlorobenzene, and chlordanes. Most OCPs originated from historical use, except lindane. Generally, of all the POPs studied, those of primary ecological concern should be acenaphthene, fluorene, DDTs, and chlordanes. Higher concentrations of POPs were detected during winter and spring than in summer and autumn, probably because of the high river flow during the rainy season. The high concentration of POPs in the riverine SPM and the fractionation of POPs in the water and SPM of the river should be a focal point in the future study of Lake Chaohu. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Oligomerization of Ethylene to Produce Linear α-Olefins Using Heterogeneous Catalyst Prepared by Immobilization of α-Diiminenickel(II Complex into Fluorotetrasilicic Mica Interlayer

    Hideki Kurokawa


    Full Text Available Heterogeneous catalysts for production of linear α-olefins from ethylene were prepared by the direct reaction of the α-diimine ligand [L: R-N=C(R'-C(R'=N-R; R' = Me and R = 2,6-Me2Ph (L5, 2,5-Me2Ph (L1, 2-MePh (L2, or Ph (L3; R' = 1,8-naphth-diyl and R = Ph (L4] and Ni2+ ion-exchanged fluorotetrasilicic mica. Only high molecular weight polyethylene was obtained in the reaction using the L5/Ni2+-Mica procatalyst activated by AlEt3 (TEA as an activator, whereas the TEA-activated L1- and L2/Ni2+-Mica procatalysts afforded a mixture of a large amount of low-molecular weight polyethylene and a small amount of oligomers having 4-22 carbons. The procatalyst consisting of Ni2+-Mica and the L3 ligand that possesses non-substituted phenyl groups on the iminonitrogen atoms effectively promoted the oligomerization of ethylene after its activation with TEA, resulting in the fact that the ethylene oligomers were produced with a moderate catalytic activity (101 g-ethylene g-cat−1 h−1 at 0.7 MPa-ethylene in the presence of TEA. When the backbone was varied from the butane moiety (L3 to acenaphthene (L4, the solid product dramatically increased. The weight percentage of the oligomers in the total products increased with the increasing reaction temperature; however, an insignificant increase in the oligomers was observed when the ethylene pressure was decreased.

  11. Usefulness of oxidative stress biomarkers evaluated in the snout scraping, serum and Peripheral Blood Cells of Crocodylus moreletii from Southeast Campeche for assessment of the toxic impact of PAHs, metals and total phenols.

    Dzul-Caamal, Ricardo; Hernández-López, Abigail; Gonzalez-Jáuregui, Mauricio; Padilla, Sergio E; Girón-Pérez, Manuel Ivan; Vega-López, Armando


    In this study, we assessed the effects of inorganic and organic pollutants [As, Cu, Fe, Mn, Pb, Zn, PAHs (11 compounds) and total phenols] from a panel of biomarkers [O2, H2O2, thiobarbituric acid reactive substances (TBARS), carbonyl proteins (RCO), superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx) and total cytochrome P450 activities] evaluated in the Snout Scraping (SS), Serum (S) and Peripheral Blood Cells (PBC) of the Morelet's crocodile (Crocodylus moreletii) inhabiting the reference locality (Lake Mocu) and polluted locality (Champoton River) using Principal Component Analysis (PCA). In male crocodiles from the reference site, only H2O2 in PBC was related to levels of fluoranthene on the Keel of Caudal Scales (KCS), but, in females, no association was detected. In contrast, a sex-linked response was detected in specimens from the polluted locality. Levels of benzo[a]pyrene, benzo[a]anthracene, chrysene, pyrene, phenanthrene, acenaphthene, Zn, Cu, and Pb in KCS of the female crocodil were related to the oxidative stress biomarkers on PBC, incluing the total CYP450 activity and levels of O2, H2O2 in serum. However, in male crocodiles, the oxidative stress in SS and in the serum (TBARS, RCO, CAT, GPx), and SOD in PBC was related to As, Pb, Cu, Fe, and benzo[a]pyrene water concentrations and to the burdens of As, Fe, Mn, indeno[1,2,3cd]pyrene in KCS. These results confirm the usefulness of minimal or non-invasive methods of evaluating the oxidative stress response for the environmental monitoring program on the wild Morelet's crocodile that is subject to special protection in Mexican guidelines. Copyright © 2016 Elsevier Inc. All rights reserved.

  12. Atmospheric concentrations and air–soil gas exchange of polycyclic aromatic hydrocarbons (PAHs) in remote, rural village and urban areas of Beijing–Tianjin region, North China

    Wang, Wentao; Simonich, Staci; Giri, Basant; Chang, Ying; Zhang, Yuguang; Jia, Yuling; Tao, Shu; Wang, Rong; Wang, Bin; Li, Wei; Cao, Jun; Lu, Xiaoxia


    Forty passive air samplers were deployed to study the occurrence of gas and particulate phase PAHs in remote, rural village and urban areas of Beijing–Tianjin region, North China for four seasons (spring, summer, fall and winter) from 2007 to 2008. The influence of emissions on the spatial distribution pattern of air PAH concentrations was addressed. In addition, the air–soil gas exchange of PAHs was studied using fugacity calculations. The median gaseous and particulate phase PAH concentrations were 222 ng/m3 and 114 ng/m3, respectively, with a median total PAH concentration of 349 ng/m3. Higher PAH concentrations were measured in winter than in other seasons. Air PAH concentrations measured at the rural villages and urban sites in the northern mountain region were significantly lower than those measured at sites in the southern plain during all seasons. However, there was no significant difference in PAH concentrations between the rural villages and urban sites in the northern and southern areas. This urban–rural PAH distribution pattern was related to the location of PAH emission sources and the population distribution. The location of PAH emission sources explained 56%–77% of the spatial variation in ambient air PAH concentrations. The annual median air–soil gas exchange flux of PAHs was 42.2 ng/m2/day from soil to air. Among the 15 PAHs measured, acenaphthylene (ACY) and acenaphthene (ACE) contributed to more than half of the total exchange flux. Furthermore, the air–soil gas exchange fluxes of PAHs at the urban sites were higher than those at the remote and rural sites. In summer, more gaseous PAHs volatilized from soil to air because of higher temperatures and increased rainfall. However, in winter, more gaseous PAHs deposited from air to soil due to higher PAH emissions and lower temperatures. The soil TOC concentration had no significant influence on the air–soil gas exchange of PAHs. PMID:21669328

  13. Diversity and distribution of bacterial community in the coastal sediments of Bohai Bay, China

    WANG Liping; ZHENG Binghui; LEI Kun


    In order to understand the diversity and distribution of the bacterial community in the coastal sediment of the Bohai Bay, China, high-throughput barcoded pyrosequencing of the 16S rRNA gene was used. Metagenomic DNA was extracted from the sediment samples, and was sequenced using a 454 GS FLX Titanium system. At 97%similarity, the sequences were assigned to 22 884 operational taxonomic units (OTUs) which belonged to 41 phyla, 84 classes, 268 genera and 789 species. At the different taxonomic levels, both the dominants and their distribution varied significantly among the six coastal sediments. Proteobacteria was the first dominant phylum across all the six coastal sediments, representing 57.52%, 60.66%, 45.10%, 60.92%, 56.63% and 56.59%, respectively. Bacteroidetes was the second dominant phylum at Stas S1, S2 and S4, while Chloroflexi was the second dominant phylum at Stas S3, S5 and S6. At class level,γ-Proteobacteria was the first dominant class at Stas S1, S2, S4 and S6, whileδ-Proteobacteria became the first dominant class at Stas S3 and S5. In addition, a large proportion of unclassified representatives have distributed at the different taxonomic levels. Canonical correspondence analysis (CCA) results indicated that the sediment texture, water depth (D), dissolved oxygen (DO), total nitrogen (TN) and nine EPA priority control polycyclic aromatic hydrocarbons (PAHs) including naphthalene, acenaphthylene, acenaphthene, fluorine, phenanthrene, fluoranthene, pyrene, benzo[a]anthracene and indeno[1,2,3-cd]pyrene were the important factors in regulating the bacterial community composition. Those results are very important to further understand the roles of bacterial community in the coastal biogeochemical cycles.

  14. Generation and distribution of PAHs in the process of medical waste incineration.

    Chen, Ying; Zhao, Rongzhi; Xue, Jun; Li, Jinhui


    After the deadly earthquake on May 12, 2008 in Wenchuan county of China, several different incineration approaches were used for medical waste disposal. This paper investigates the generation properties of polycyclic aromatic hydrocarbons (PAHs) during the incineration. Samples were collected from the bottom ash in an open burning slash site, surface soil at the open burning site, bottom ash from a simple incinerator, bottom ash generated from the municipal solid waste (MSW) incinerator used for medical waste disposal, and bottom ash and fly ash from an incinerator exclusively used for medical waste. The species of PAHs were analyzed, and the toxicity equivalency quantities (TEQs) of samples calculated. Analysis results indicate that the content of total PAHs in fly ash was 1.8×10(3) times higher than that in bottom ash, and that the strongly carcinogenic PAHs with four or more rings accumulated sensitively in fly ash. The test results of samples gathered from open burning site demonstrate that Acenaphthylene (ACY), Acenaphthene (ACE), Fluorene (FLU), Phenanthrene (PHE), Anthracene (ANT) and other PAHs were inclined to migrate into surrounding environment along air and surface watershed corridors, while 4- to 6-ring PAHs accumulated more likely in soil. Being consistent with other studies, it has also been confirmed that increases in both free oxygen molecules and combustion temperatures could promote the decomposition of polycyclic PAHs. In addition, without the influence of combustion conditions, there is a positive correlation between total PCDD/Fs and total PAHs, although no such relationship has been found for TEQ. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Wall modified photonic crystal fibre capillaries as porous layer open tubular columns for in-capillary micro-extraction and capillary chromatography.

    Kazarian, Artaches A; Sanz Rodriguez, Estrella; Deverell, Jeremy A; McCord, James; Muddiman, David C; Paull, Brett


    Wall modified photonic crystal fibre capillary columns for in-capillary micro-extraction and liquid chromatographic separations is presented. Columns contained 126 internal parallel 4 μm channels, each containing a wall bonded porous monolithic type polystyrene-divinylbenzene layer in open tubular column format (PLOT). Modification longitudinal homogeneity was monitored using scanning contactless conductivity detection and scanning electron microscopy. The multichannel open tubular capillary column showed channel diameter and polymer layer consistency of 4.2 ± 0.1 μm and 0.26 ± 0.02 μm respectively, and modification of 100% of the parallel channels with the monolithic polymer. The modified multi-channel capillaries were applied to the in-capillary micro-extraction of water samples. 500 μL of water samples containing single μg L(-1) levels of polyaromatic hydrocarbons were extracted at a flow rate of 10 μL min(-1), and eluted in 50 μL of acetonitrile for analysis using HPLC with fluorescence detection. HPLC LODs were 0.08, 0.02 and 0.05 μg L(-1) for acenaphthene, anthracene and pyrene, respectively, with extraction recoveries of between 77 and 103%. The modified capillaries were also investigated briefly for direct application to liquid chromatographic separations, with the retention and elution of a standard protein (cytochrome c) under isocratic conditions demonstrated, proving chromatographic potential of the new column format, with run-to-run retention time reproducibility of below 1%.

  16. Wall modified photonic crystal fibre capillaries as porous layer open tubular columns for in-capillary micro-extraction and capillary chromatography

    Kazarian, Artaches A. [Australian Centre for Research on Separation Science, School of Physical Sciences, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001 (Australia); W.M. Keck FT-ICR-MS Laboratory, Department of Chemistry, North Carolina State University, Raleigh, NC (United States); Sanz Rodriguez, Estrella; Deverell, Jeremy A. [Australian Centre for Research on Separation Science, School of Physical Sciences, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001 (Australia); McCord, James; Muddiman, David C. [W.M. Keck FT-ICR-MS Laboratory, Department of Chemistry, North Carolina State University, Raleigh, NC (United States); Paull, Brett, E-mail: [Australian Centre for Research on Separation Science, School of Physical Sciences, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001 (Australia); ARC Centre of Excellence for Electromaterials Science, School of Physical Sciences, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001 (Australia)


    Wall modified photonic crystal fibre capillary columns for in-capillary micro-extraction and liquid chromatographic separations is presented. Columns contained 126 internal parallel 4 μm channels, each containing a wall bonded porous monolithic type polystyrene-divinylbenzene layer in open tubular column format (PLOT). Modification longitudinal homogeneity was monitored using scanning contactless conductivity detection and scanning electron microscopy. The multichannel open tubular capillary column showed channel diameter and polymer layer consistency of 4.2 ± 0.1 μm and 0.26 ± 0.02 μm respectively, and modification of 100% of the parallel channels with the monolithic polymer. The modified multi-channel capillaries were applied to the in-capillary micro-extraction of water samples. 500 μL of water samples containing single μg L{sup −1} levels of polyaromatic hydrocarbons were extracted at a flow rate of 10 μL min{sup −1}, and eluted in 50 μL of acetonitrile for analysis using HPLC with fluorescence detection. HPLC LODs were 0.08, 0.02 and 0.05 μg L{sup −1} for acenaphthene, anthracene and pyrene, respectively, with extraction recoveries of between 77 and 103%. The modified capillaries were also investigated briefly for direct application to liquid chromatographic separations, with the retention and elution of a standard protein (cytochrome c) under isocratic conditions demonstrated, proving chromatographic potential of the new column format, with run-to-run retention time reproducibility of below 1%. - Highlights: • Novel PS-DVB modified photonic crystal fibres for in-capillary micro-extraction. • New method for micro-extraction of PAHs and HPLC-FL detection at sub-ppb levels. • Demonstration of PS-DVB modified photonic crystal fibres for capillary bioseparations.

  17. Biological monitoring of exposure to polycyclic aromatic hydrocarbons by determination of unmetabolized compounds in urine.

    Campo, Laura; Addario, Liliana; Buratti, Marina; Scibetta, Licia; Longhi, Omar; Valla, Carla; Cirla, Piero E; Martinotti, Irene; Foà, Vito; Fustinoni, Silvia


    In this paper we evaluated the possibility to assess occupational exposure to polycyclic aromatic hydrocarbons (PAHs) measuring unmetabolized PAHs in urine. With this aim, 24 road paving (RP) workers, exposed to bitumen fumes, and 6 road construction workers (CW), exposed to diesel exhausts, were investigated. Median personal exposure to low boiling PAHs (from naphthalene to pyrene) during the work shift ranged from 0.5 to 369 ng/m(3), with naphthalene as the most abundant compound. Three urine samples were collected for each worker: baseline (after 2 days of vacation), before- and end-shift samples (in the second part of the work week). The following urinary compounds were measured by headspace-solid phase microextraction GC/MS: naphthalene (U-NAP), acenaphthylene (U-ACY), acenaphthene (U-ACE), fluorene (U-FLE), phenanthrene (U-PHE), anthracene (U-ANT), fluoranthene (U-FLU), pyrene (U-PYR). Urinary PAHs were detected in almost all samples. Median levels for U-NAP, U-PHE, U-PYR and U-FLE in end-shift samples were 82, 48, 54 and 21 ng/L in RP and 69, 14, 24 and 15 ng/L in CW, respectively. Significant differences in the levels of U-PHE, U-FLU and U-PYR were found between RP and CW (p<0.05). Moreover in RP samples the urinary excretion of most analytes increased during the work shift (p<0.05). These results suggest that urinary PAHs may be useful biomarkers of occupational exposure.

  18. Biosorption and biodegradation of polycyclic aromatic hydrocarbons in aqueous solutions by a consortium of white-rot fungi.

    Chen, Baoliang; Wang, Yinshan; Hu, Dingfei


    Bioremediation is a popular approach used to abate polycyclic aromatic hydrocarbons (PAHs) in the environment. A consortium of white-rot fungi (CW-1) isolated from wood pieces was used for studying their potential of bioremediation of PAHs. Biosorption and biodegradation of PAHs by live and heat-killed white-rot fungi (CW-1) were investigated to elucidate the bio-dissipation mechanisms of PAHs. Sorption isotherms of naphthalene, acenaphthene, fluorene, phenanthrene and pyrene to heat-killed fungal biomass were linear and non-competitive, indicating the primary mechanism of biosorption to be by partition. The carbon-normalized partition coefficients (K(oc)) were linearly correlated with octanol-water partition coefficients (K(ow)), i.e., log K(oc)=1.13 log K(ow)-0.84 (n=5, r(2)=0.996). Biosorption and biodegradation of phenanthrene and pyrene by live white-rot fungi were quantified. In 1 week, the removal efficiency of phenanthrene (70-80%) and pyrene (90%) by live fungi from aqueous solution were comparable to those by heat-killed fungi. However, approximately 40-65% of phenanthrene and 60-85% of pyrene were still stored in organismal bodies. Biosorption might restrict biodegradation while nutrient limitation and presence of a PAH mixture might stimulate biodegradation. The apparent partition coefficients (K(d)(*)) in live fungal systems and the K(d) of heat-killed fungi without biodegradation were compared, and then the K(d)(*)/K(d) ratios were employed to illustrate the relative contributions of biosorption and biodegradation under different nutrient conditions.

  19. Pseudomonads rule degradation of polyaromatic hydrocarbons in aerated sediment

    Jiri eWald


    Full Text Available Given that the degradation of aromatic pollutants in anaerobic environments such as sediment is generally very slow, aeration could be an efficient bioremediation option. Using stable isotope probing (SIP coupled with pyrosequencing analysis of 16S rRNA genes, we identified naphthalene-utilizing populations in aerated polyaromatic hydrocarbon (PAH-polluted sediment. The results showed that naphthalene was metabolized at both 10°C and 20°C following oxygen delivery, with increased degradation at 20°C as compared to 10°C – a temperature more similar to that found in situ. Naphthalene-derived 13C was primarily assimilated by pseudomonads. Additionally, Stenotrophomonas, Acidovorax, Comamonas and other minor taxa were determined to incorporate 13C throughout the measured time course. The majority of SIP-detected bacteria were also isolated in pure cultures, which facilitated more reliable identification of naphthalene-utilizing populations as well as proper differentiation between primary consumers and cross-feeders. The pseudomonads acquiring the majority of carbon were identified as Pseudomonas veronii and P. gessardii. Stenotrophomonads and Acidovorax defluvii, however, were identified as cross-feeders unable to directly utilize naphthalene as a growth substrate. PAH degradation assays with the isolated bacteria revealed that all pseudomonads as well as Comamonas testosteroni degraded acenaphthene, fluorene and phenanthrene in addition to naphthalene. Furthermore, P. veronii and C. testosteroni were capable of transforming anthracene, fluoranthene and pyrene. Screening of isolates for naphthalene dioxygenase genes using a set of in-house designed primers for Gram-negative bacteria revealed the presence of such genes in pseudomonads and Comamonas testosteroni. Overall, our results indicated an apparent dominance of pseudomonads in the sequestration of carbon from naphthalene and potential degradation of other PAHs upon aeration of the

  20. Long-term simulation of in situ biostimulation of polycyclic aromatic hydrocarbon-contaminated soil.

    Richardson, Stephen D; Jones, Maiysha D; Singleton, David R; Aitken, Michael D


    A continuous-flow column study was conducted to evaluate the long-term effects of in situ biostimulation on the biodegradation of polycyclic aromatic hydrocarbons (PAHs) in soil from a manufactured gas plant site. Simulated groundwater amended with oxygen and inorganic nutrients was introduced into one column, while a second column receiving unamended groundwater served as a control. PAH and dissolved oxygen (DO) concentrations, as well as microbial community profiles, were monitored along the column length immediately before and at selected intervals up to 534 days after biostimulation commenced. Biostimulation resulted in significantly greater PAH removal than in the control condition (73% of total measured PAHs vs. 34%, respectively), with dissolution accounting for a minor amount of the total mass loss (~6%) in both columns. Dissolution was most significant for naphthalene, acenaphthene, and fluorene, accounting for >20% of the total mass removed for each. A known group of PAH-degrading bacteria, 'Pyrene Group 2' (PG2), was identified as a dominant member of the microbial community and responded favorably to biostimulation. Spatial and temporal variations in soil PAH concentration and PG2 abundance were strongly correlated to DO advancement, although there appeared to be transport of PG2 organisms ahead of the oxygen front. At an estimated oxygen demand of 6.2 mg O(2)/g dry soil and a porewater velocity of 0.8 m/day, it took between 374 and 466 days for oxygen breakthrough from the 1-m soil bed in the biostimulated column. This study demonstrated that the presence of oxygen was the limiting factor in PAH removal, as opposed to the abundance and/or activity of PAH-degrading bacteria once oxygen reached a previously anoxic zone.

  1. Isolation of marine polycyclic aromatic hydrocarbon (PAH)-degrading Cycloclasticus strains from the Gulf of Mexico and comparison of their PAH degradation ability with that of Puget Sound Cycloclasticus strains

    Geiselbrecht, A.D.; Hedlund, B.P.; Tichi, M.A.; Staley, J.T. [Univ. of Washington, Seattle, WA (United States). Dept. of Microbiology


    Phenanthrene- and naphthalene-degrading bacteria were isolated from four offshore and nearshore locations in the Gulf of Mexico by using a modified most-probable-number technique. The concentrations of these bacteria ranged from 10{sup 2} to 10{sup 6} cells per ml of wet surficial sediment in mildly contaminated and noncontaminated sediments. A total of 23 strains of polycyclic aromatic hydrocarbon (PAH)-degrading bacteria were obtained. Based on partial 16S ribosomal DNA sequences and Phenotypic characteristics, these 23 strains are members of the genus Cycloclasticus. Three representatives were chosen for a complete phylogenetic analysis, which confirmed the close relationship of these isolates to type strain Cycloclasticus pugetii PS-1, which was isolated from Puget Sound. PAH substrate utilization tests which included high-molecular-weight PAHs revealed that these isolates had similar, broad substrate ranges which included naphthalene, substituted naphthalenes, phenanthrene, biphenyl, anthracene, acenaphthene, and fluorene. Degradation of pyrene and fluoranthene occurred only when the strains were incubated with phenanthrene. Two distinct partial PAH dioxygenase iron sulfur protein (ISP) gene sequences were PCR amplified from Puget Sound and Gulf of Mexico Cycloclasticus strains. Phylogenetic analyses of these sequences revealed that one ISP type is related to the bph type of ISP sequences, while the other ISP type is related to the nah type of ISP sequences. The predicted ISP amino acid sequences for the Gulf of Mexico and Puget Sound strains are identical, which supports the hypothesis that these geographically separated isolates are closely related phylogentically. Cycloclasticus species appear to be numerically important and widespread PAH-degrading bacteria in both Puget Sound and the Gulf of Mexico.

  2. Modeling of experimental data on trace elements and organic compounds content in industrial waste dumps.

    Smoliński, Adam; Drobek, Leszek; Dombek, Václav; Bąk, Andrzej


    The main objective of the study presented was to investigate the differences between 20 mine waste dumps located in the Silesian Region of Poland and Czech Republic, in terms of trace elements and polycyclic aromatic hydrocarbons contents. The Principal Component Analysis and Hierarchical Clustering Analysis were applied in exploration of the studied data. Since the data set was affected by outlying objects, the employment of a relevant analysis strategy was necessary. The final PCA model was constructed with the use of the Expectation-Maximization iterative approach preceded by a correct identification of outliers. The analysis of the experimental data indicated that three mine waste dumps located in Poland were characterized by the highest concentrations of dibenzo(g,h,i)anthracene and benzo(g,h,i)perylene, and six objects located in Czech Republic and three objects in Poland were distinguished by high concentrations of chrysene and indeno (1.2.3-cd) pyrene. Three of studied mine waste dumps, one located in Czech Republic and two in Poland, were characterized by low concentrations of Cr, Ni, V, naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthen, benzo(a)anthracene, chrysene, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo(a)pyrene, dibenzo(g,h,i)anthracene, benzo(g,h,i)perylene and indeno (1.2.3-cd) pyrene in comparison with the remaining ones. The analysis contributes to the assessment and prognosis of ecological and health risks related to the emission of trace elements and organic compounds (PAHs) from the waste dumps examined. No previous research of similar scope and aims has been reported for the area concerned.

  3. Vanadyl cationic complexes as catalysts in olefin oxidation.

    Nunes, Carla D; Vaz, Pedro D; Félix, Vítor; Veiros, Luis F; Moniz, Tânia; Rangel, Maria; Realista, Sara; Mourato, Ana C; Calhorda, Maria José


    Three new mononuclear oxovanadium(IV) complexes [VO(acac)(R-BIAN)]Cl (BIAN = 1,2-bis{(R-phenyl)imino}acenaphthene, R = H, 1; CH3, 2; Cl, 3) were prepared and characterized. They promoted the catalytic oxidation of olefins such as cyclohexene, cis-cyclooctene, and styrene with both tbhp (tert-butylhydroperoxide) and H2O2, and of enantiopure olefins (S(-)- and R(+)-pinene, and S(-)- and R(+)-limonene) selectively to their epoxides, with tbhp as the oxidant. The TOFs for styrene epoxidation promoted by complex 3 with H2O2 (290 mol mol(-1)V h(-1)) and for cis-cyclooctene epoxidation by 2 with tbhp (248 mol mol(-1)V h(-1)) are particularly good. Conversions reached 90% for several systems with tbhp, and were lower with H2O2. A preference for the internal C=C bond, rather than the terminal one, was found for limonene. Kinetic data indicate an associative process as the first step of the reaction and complex [VO(acac)(H-BIAN)](+) (1(+)) was isolated in an FTICR cell after adding tbhp to 1. EPR studies provide evidence for the presence of a V(IV) species in solution, until at least 48 hours after the addition of tbhp and cis-cyclooctene, and cyclic voltammetry studies revealed an oxidation potential above 1 V for complex 1. DFT calculations suggest that a [VO(H-BIAN)(MeOO)](+) complex is the likely active V(IV) species in the catalytic cycle from which two competitive mechanisms for the reaction proceed, an outer sphere path with an external attack of the olefin at the coordinated peroxide, and an inner sphere mechanism starting with a complex with the olefin coordinated to vanadium.

  4. Biological monitoring as a useful tool for the detection of a coal-tar contamination in bitumen-exposed workers

    Raulf-Heimsoth, M.; Angerer, J.; Pesch, B.; Marczynski, B.; Hahn, J.U.; Spickenheuer, A.; Preuss, R.; Ruhl, R.; Rode, P.; Bruning, T. [Institute at the Ruhr University of Bochum, Bochum (Germany)


    In our research project entitled 'Chemical irritative and/or genotoxic effect of fumes of bitumen under high processing temperatures on the airways,' 73 mastic asphalt workers exposed to fumes of bitumen and 49 construction nonexposed workers were analyzed and compared with respect to polycyclic aromatic hydrocarbons (PAHs) exposure and exposure-related health effects. In order to assess the internal exposure the monohydroxylated metabolites of pyrene, 1-hydroxypyrene (1-OHP), and phenanthrene, 1-, 2- and 9-, and 3- and 4-hydroxyphenanthrene (OHPH) were determined in pre- and post-shift urinary samples. Significantly higher concentrations 1-OHP and OHPH were detected in the post-shift urine samples of 7 mastic asphalt workers working on the same construction site compared to the reference workers and all other 66 mastic asphalt workers. The adjusted mean OHPH in the reference, 66 mastic worker, and 7 worker subgroups was 1022, 1544, and 12919 ng/g creatinine (crn) respectively, indicating a marked rise in the 7 worker subgroup. In addition, there was a more than 12-fold increase of PAH metabolites from pre- to post-shift in these 7 workers, whereas in the other mastic asphalt workers there was only a twofold rise in PAH-metabolite concentration between pre- and post-shift values. The analysis of a drilling core from the construction site of the seven workers led to the detection of the source for this marked PAH exposure during the working shift as being coal tar plates, which were, without knowledge of the workers and coordinators, the underground material of the mastic asphalt layer. The evaluation of the stationary workplace concentration showed enhanced levels of phenanthrene, pyrene, fluorene, anthracene, and acenaphthene during working shifts at the construction site of these seven workers. Our study shows that biological monitoring is also a useful tool for the detection of unrecognized sources with high PAH concentrations.

  5. Hard Cap Espresso Machines in Analytical Chemistry: What Else?

    Armenta, Sergio; de la Guardia, Miguel; Esteve-Turrillas, Francesc A


    A hard cap espresso machine has been used in combination with liquid chromatography with molecular fluorescence detection for the determination of polycyclic aromatic hydrocarbons (PAHs) from contaminated soils and sediments providing appropriate extraction efficiencies and quantitative results. Naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benz[b]fluoranthene, benz[k]fluoranthene, benz[a]pyrene, dibenz[a,h]anthracene, benz[ghi]perylene, and indeno[1,2,3-cd]pyrene were used as target compounds. It should be mentioned that the pairs benz[a]anthracene-chrysene and dibenz[a,h]anthracene-benz[ghi]perylene peaks coelute under the employed chromatographic conditions; thus, those compounds were determined together. PAHs were extracted from 5.0 g of soil, previously homogenized, freeze-dried, and sieved to 250 μm, with 50 mL of 40% (v/v) acetonitrile in water at a temperature of 72 ± 3 °C. The proposed procedure is really fast, with an extraction time of 11 s, and it reduces the required amount of organic solvent to do the sample preparation. The obtained limit of detection for the evaluated PAHs was from 1 to 38 μg kg(-1). Recoveries were calculated using clean soils spiked with 100, 500, 1000, and 2000 μg kg(-1) PAHs with values ranging from 81 to 121% and good precision with relative standard deviation values lower than 30%. The method was validated using soil and sediment certified reference materials and also using real samples by comparison with ultrasound-assisted extraction, as reference methodology, obtaining statistically comparable results. Thus, the use of hard cap espresso machines in the analytical laboratories offers tremendous possibilities as low cost extraction units for the extraction of solid samples.

  6. Distribution pattern of polycyclic aromatic hydrocarbons in particle-size fractions of coking plant soils from different depth.

    Liao, Xiaoyong; Ma, Dong; Yan, Xiulan; Yang, Linsheng


    The concentrations of 16 priority polycyclic aromatic hydrocarbons (PAHs) in four size fractions (200 μm) in soils at different depth from a heavily contaminated crude benzol production facility of a coking plant were determined using GC-MS. Vertically, elevated total PAHs concentrations were observed in the soils at 3.0-4.5 m (layer B) and 6.0-7.5 m (layer C), relatively lower at 1.5-3.0 m (layer A) and 10.5-12.0 m (layer D). At all sampling sites, the silt (2-20 μm) contained the highest PAHs concentration (ranged from 726 to 2,711 mg/kg). Despite the substantial change in PAHs concentrations in soils with different particle sizes and lithologies, PAHs composition was similarly dominated by 2-3 ring species (86.5-98.3 %), including acenaphthene, fluorene, and phenanthrene. For the contribution of PAHs mass in each fraction to the bulk soil, the 20-200 μm size fraction had the greatest accumulation of PAHs in loamy sand layers at 1.0-7.5 m, increasing with depth; while in deeper sand layer at 10.5-12.0 m, the >200 μm size fraction showed highest percentages and contributed 81 % of total PAHs mass. For individual PAH distribution, the 2-3 ring PAHs were highly concentrated in the small size fraction (PAHs showed the highest concentrations in the 2-20 μm size fraction, increasing with depth. The distribution of PAHs was primarily determined by the sorption on soil organic matter and the characteristics of PAHs. This research should have significant contribution to PAH migration study and remediation design for PAHs-contaminated sites.

  7. A comparison of physicochemical methods for the remediation of porous medium systems contaminated with tar

    Hauswirth, Scott C.; Miller, Cass T.


    The remediation of former manufactured gas plant (FMGP) sites contaminated with tar DNAPLs (dense non-aqueous phase liquids) presents a significant challenge. The tars are viscous mixtures of thousands of individual compounds, including known and suspected carcinogens. This work investigates the use of combinations of mobilization, solubilization, and chemical oxidation approaches to remove and degrade tars and tar components in porous medium systems. Column experiments were conducted using several flushing solutions, including an alkaline-polymer (AP) solution containing NaOH and xanthan gum (XG), a surfactant-polymer (SP) solution containing Triton X-100 surfactant (TX100) and XG, an alkaline-surfactant-polymer (ASP) solution containing NaOH, TX100, and XG, and base-activated sodium persulfate both with and without added TX100. The effectiveness of the flushing solutions was assessed based on both removal of polycyclic aromatic hydrocarbon (PAH) mass and on the reduction of dissolved-phase PAH concentrations. SP flushes of 6.6 to 20.9 PV removed over 99% of residual PAH mass and reduced dissolved-phase concentrations by up to two orders of magnitude. ASP flushing efficiently removed 95-96% of residual PAH mass within about 2 PV, and significantly reduced dissolved-phase concentrations of several low molar mass compounds, including naphthalene, acenaphthene, fluorene, and phenanthrene. AP flushing removed a large portion of the residual tar (77%), but was considerably less effective than SP and ASP in terms of the effect on dissolved PAH concentrations. Persulfate was shown to oxidize tar components, primarily those with low molar mass, however, the overall degradation was relatively low (30-50% in columns with low initial tar saturations), and the impact on dissolved-phase concentrations was minimal.

  8. Analysis of polycyclic aromatic hydrocarbons in street soil dust in Kumasi Metropolis of Ghana.

    Essumang, D K; Dodoo, D K; Obiri, S; Oduro, A K


    Concentrations of polycyclic aromatic hydrocarbons (PAHs) in street soil dust from streets in Kumasi Metropolis in the Ashanti Region of the Republic of Ghana have been measured in this study. The concentrations of the various types of PAHs identified in this study are as follows: Naphthalene (m/e 128) - 41,700 microg/kg, Acenaphthylene (m/e 152) - 99,300 microg/kg, Acenaphthene (m/e 154) - 111,200 microg/kg, Fluorene (m/e 166) - 8,900 microg/kg, Carbazole (m/e 167) - 3,500 microg/kg, phenathrene (m/e 178) - 12,900 microg/kg, Anthracene (m/e 178) - 5,400 microg/kg, Fluoranthene (m/e 202) - 16,200 microg/kg, Pyrene (m/e 202) - 15,000 microg/kg, Benzo[a]anthracene (m/e 228) - 13,800 microg/kg, Chrysene (m/e 228) - 33,600 microg/kg, Benzo[k]fluoranthene (m/e 252) - 45,700 microg/kg, Benzo[a]pyrene (m/e 252) - 27,900 microg/kg, Perylene (m/e 252) - 57,200 microg/kg and Benzo[g, h, i]perylene (m/e 276) - 47,000 microg/kg. The results of the study shows that road users, like resident living in buildings within these areas, those engaged in commercial activities like hawking, and the general public are at risk of exposure to the toxic effects of the various types of PAHs from the exhaust of vehicles into the environment. According to these results, there is the potential for exposure to high levels of PAHs for road users and those living in urban environments or along highways.

  9. Assessment of cancer and noncancer health risks from exposure to PAHs in street dust in the Tamale Metropolis, Ghana.

    Obiri, Samuel; Cobbina, Samuel J; Armah, Frederick A; Luginaah, Isaac


    This study is part of a broader initiative to characterize, quantify and assess the human health risk associated with exposure to polycyclic aromatic hydrocarbons (PAHs) in street dust along the Trans-ECOWAS highway in West Africa. In the first part, PAHs were characterized and quantified in low- and high-traffic zones. In this study, cancer and noncancer human health risks from exposure to (PAHs) in street dust in the Tamale metropolis, Ghana were assessed in accordance with the USEPA risk assessment guidelines. The results of the study as obtained from inhalation of benzo [a] anthracene (BaA), benzo [a] pyrene (BaP), benzo [k] fluoranthene (BkF) and chrysene via central tendency exposure parameters (CTE) by trespassers (street hawkers including children and adults) in street dust within low traffic zones in the Tamale metropolis are 1.6E-02, 4.7E-02, 1.8E-03, and 1.6E-04 respectively. For reasonable maximum exposure parameters (RME), risk values of 1.2E-01, 3.5E-01, 1.3E-02 and 1.2E-03 respectively were obtained for benzo [a] anthracene, benzo [a] pyrene, benzo [k] fluoranthene and chrysene. Hazard index for acenaphthene, anthracene, fluoranthene, fluorine, naphthalene and pyrene in the CTE and RME scenarios were 2.2, 3.E-01, 2.6, 2.6, 100, 38 and 12, 1.7,15, 14, 550, 210 respectively. Generally, the cancer health risk associated with inhalation of benzo [a] anthracene, benzo [a] pyrene, benzo [k] fluoranthene and chrysene revealed that resident adults and children in the Tamale metropolis are at risk from exposure to these chemicals. The results of this preliminary assessment that quantified PAH related health risks along this part of the Trans-ECOWAS highway revealed that, there is the need for regulatory agencies to put in comprehensive measures to mitigate the risks posed to these categories of human receptors.

  10. Polycyclic aromatic hydrocarbon levels in European catfish from the upper Po River basin.

    Squadrone, Stefania; Favaro, Livio; Abete, Maria Cesarina; Vivaldi, Barbara; Prearo, Marino


    Polycyclic aromatic hydrocarbons (PAHs) are a major concern in environmental studies as many of them have been labeled as probable carcinogens by the International Agency for Research on Cancer (IARC 1983). Due to their lipophilic properties and resistance to degradation, PAHs can accumulate in organic tissue. As a consequence, alarming concentrations of these compounds have been found in many aquatic species. The European catfish (Silurus glanis) is a top food chain predator that is considered to be a reliable bio-indicator of environmental pollution. From 2009 to 2011, 54 specimens of S. glanis were captured from four different sites covering the area of the Po River basin (Northern Italy). Fish muscles were analyzed in the laboratory to determine the levels of nine PAHs, namely naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, pyrene, benz[a]anthracene, chrysene, and benz[a]pyrene (BaP), which were detected by high-performance liquid chromatography (HPLC). The total average concentration of PAHs was 26.90 ± 49.50 ng g(-1) (min 0.60, max 275.75 ng g(-1)). Analysis showed that 9.20% of the fish muscles exceeded the maximum levels of 2 ng g(-1) set for BaP by European regulations (Commission Regulation (EC), 2006). Values measured for benz[a]pyrene ranged from 0.05 to 8.20 ng g(-1) (mean 1.07 ± 1.58 ng g(-1)). Chrysene and benz[a]anthracene, both considered potential human carcinogens (PAH2), were found at levels of 4.40 and 0.05 ng g(-1) (mean values), respectively. The highest mean concentration was recorded for anthracene (12.92 ng g(-1)), which has been recently included in the list of substances of very high concern (SVHC) as reported by the European Chemicals Agency (ECHA 1-9, 2009).

  11. Miniscale Liquid-Liquid Extraction Coupled with Full Evaporation Dynamic Headspace Extraction for the Gas Chromatography/Mass Spectrometric Analysis of Polycyclic Aromatic Hydrocarbons with 4000-to-14 000-fold Enrichment.

    Liew, Christina Shu Min; Li, Xiao; Lee, Hian Kee


    A new sample preparation approach of combining a miniscale version of liquid-liquid extraction (LLE), termed miniscale-LLE (msLLE), with automated full evaporation dynamic headspace extraction (FEDHS) was developed. Its applicability was demonstrated in the extraction of several polycyclic aromatic hydrocarbons (PAHs) (acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, and pyrene) from aqueous samples. In the first step, msLLE was conducted with 1.75 mL of n-hexane, and all of the extract was vaporized through a Tenax TA sorbent tube via a nitrogen gas flow, in the FEDHS step. Due to the stronger π-π interaction between the Tenax TA polymer and PAHs, only the latter, and not n-hexane, was adsorbed by the sorbent. This selectivity by the Tenax TA polymer allowed an effective concentration of PAHs while eliminating n-hexane by the FEDHS process. After that, thermal desorption was applied to the PAHs to channel them into a gas chromatography/mass spectrometric (GC/MS) system for analysis. Experimental parameters affecting msLLE (solvent volume and mixing duration) and FEDHS (temperature and duration) were optimized. The obtained results achieved low limits of detection (1.85-3.63 ng/L) with good linearity (r(2) > 0.9989) and high enrichment factors ranging from 4200 to 14 100. The optimized settings were applied to the analysis of canal water sampled from an industrial area and tap water, and this methodology was compared to stir-bar sorptive extraction (SBSE). This innovative combined extraction-concentration approach proved to be fast, effective, and efficient in determining low concentrations of PAHs in aqueous samples.

  12. Prioritization of chemicals according to the degree of hazard in the aquatic environment

    Branson, Dean R.


    Chemicals designated as “priority pollutants” or “toxics” have received special attention recently because the discharge of these compounds into public water is to be restricted to the maximum possible with little regard to water quality or economics. The selection of many of the 129 priority cemicals was not based on an objective scientific assessment of the exposure and effect data. In fact, for some compounds, including acenaphthene and 4-chlorophenyl-phenyl ether, the necessary data for listing were non-existent. As an alternative to arbitrarily listing or delisting chemicals for the purpose of prioity control, this paper suggests a promising scientific approach to selecting priority chemicals based on the principles of hazard assessment for chemicals in the aquatic environment. According o the hypothesis, the highest priority chemicals are those with the least margin of safety, defined as the gap between the no-observable-effect concentrations and the ambient exposure concentrations. The no-observable-effect concenrations are based on the results of chronic or sensitive life stage tests with aquatic organisms and the acceptable daily intake rate for fish eates. The ambient exposure concentrations are levels either measured in fish and water, or roughly estimated from a simple nomogram that requires only two of the following three factors: environmental release rate, ratio of dissipation to bioconcentration potential, or ambient residues in fish. The chemicals studied to illustrate this approach to prioritizing chemicals based on hazard assessment are: polychlorinated biphenyls, di-2-ethylhexyl phthalate, linear alkylbenzene sulfonate, and pentachlorophenol. PMID:6771128

  13. Biological monitoring as a useful tool for the detection of a coal-tar contamination in bitumen-exposed workers.

    Raulf-Heimsoth, Monika; Angerer, Jürgen; Pesch, Beate; Marczynski, Boleslaw; Hahn, Jens Uwe; Spickenheuer, Anne; Preuss, Ralf; Rühl, Reinhold; Rode, Peter; Brüning, Thomas


    In our research project entitled "Chemical irritative and/or genotoxic effect of fumes of bitumen under high processing temperatures on the airways," 73 mastic asphalt workers exposed to fumes of bitumen and 49 construction nonexposed workers were analyzed and compared with respect to polycyclic aromatic hydrocarbons (PAHs) exposure and exposure-related health effects. In order to assess the internal exposure the monohydroxylated metabolites of pyrene, 1- hydroxypyrene (1-OHP), and phenanthrene, 1-, 2- and 9-, and 3- and 4-hydroxyphenanthrene (OHPH) were determined in pre- and post-shift urinary samples. Significantly higher concentrations 1-OHP and OHPH were detected in the post-shift urine samples of 7 mastic asphalt workers working on the same construction site compared to the reference workers and all other 66 mastic asphalt workers. The adjusted mean OHPH in the reference, 66 mastic worker, and 7 worker subgroups was 1022, 1544, and 12919 ng/g creatinine (crn) respectively, indicating a marked rise in the 7 worker subgroup. In addition, there was a more than 12-fold increase of PAH metabolites from pre- to post-shift in these 7 workers, whereas in the other mastic asphalt workers there was only a twofold rise in PAH-metabolite concentration between pre- and post-shift values. The analysis of a drilling core from the construction site of the seven workers led to the detection of the source for this marked PAH exposure during the working shift as being coal tar plates, which were, without knowledge of the workers and coordinators, the underground material of the mastic asphalt layer. The evaluation of the stationary workplace concentration showed enhanced levels of phenanthrene, pyrene, fluorene, anthracene, and acenaphthene during working shifts at the construction site of these seven workers. Our study shows that biological monitoring is also a useful tool for the detection of unrecognized sources with high PAH concentrations.

  14. Application of GC-FID and GC-MS for assessing PAHs in suspended dust.

    Weglarz, A; Skrok, R


    The social concern about polycyclic aromatic hydrocarbons (PAHs) is due to the awareness that several of them are carcinogens and are present in polluted air. Several epidemiological investigations have tried to assess the influence of air pollution on the incidence in the population (1). Some authors have suggest that 1-10% of the incidence of lung cancer is caused by air pollution (2, 3). Several sources, e.g. traffic, oil heating, wood stoves, industry may contribute PAHs to the air pollution. Therefore continuous air pollution control applying selective and precise analytical procedures is needed. The submitted work presents results of examination of sixteen polycyclic aromatic hydrocarbons [naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, dibenzo(a, h)anthracene, benzo(ghi)perylene] settled on particles of 10 microns fractions of ashes, emitted from industrial and communication sources. Samples of suspended dust were collected at twelve measuring points, from May to June 1998, in 24-hour cycles, in accordance with US EPA methodology. PAHs were extracted from suspended dust in a Soxhlet apparatus and then exposed to extraction in a liquid-solid system (solid extraction-SPE) to eliminate redundant pollution, which may interfere with compounds by determined analysis. Samples were then analyzed using by capillary gas chromatographs "Varian" model 3400 with FID and MS detectors. Results of analysis make it possible to determine the influence of industry and traffic on atmospheric pollution, to compare results of two analytical methods (GC-FID and GC-MS).

  15. A new multimedia contaminant fate model for China: how important are environmental parameters in influencing chemical persistence and long-range transport potential?

    Zhu, Ying; Price, Oliver R; Tao, Shu; Jones, Kevin C; Sweetman, Andy J


    We present a new multimedia chemical fate model (SESAMe) which was developed to assess chemical fate and behaviour across China. We apply the model to quantify the influence of environmental parameters on chemical overall persistence (POV) and long-range transport potential (LRTP) in China, which has extreme diversity in environmental conditions. Sobol sensitivity analysis was used to identify the relative importance of input parameters. Physicochemical properties were identified as more influential than environmental parameters on model output. Interactive effects of environmental parameters on POV and LRTP occur mainly in combination with chemical properties. Hypothetical chemicals and emission data were used to model POV and LRTP for neutral and acidic chemicals with different KOW/DOW, vapour pressure and pKa under different precipitation, wind speed, temperature and soil organic carbon contents (fOC). Generally for POV, precipitation was more influential than the other environmental parameters, whilst temperature and wind speed did not contribute significantly to POV variation; for LRTP, wind speed was more influential than the other environmental parameters, whilst the effects of other environmental parameters relied on specific chemical properties. fOC had a slight effect on POV and LRTP, and higher fOC always increased POV and decreased LRTP. Example case studies were performed on real test chemicals using SESAMe to explore the spatial variability of model output and how environmental properties affect POV and LRTP. Dibenzofuran released to multiple media had higher POV in northwest of Xinjiang, part of Gansu, northeast of Inner Mongolia, Heilongjiang and Jilin. Benzo[a]pyrene released to the air had higher LRTP in south Xinjiang and west Inner Mongolia, whilst acenaphthene had higher LRTP in Tibet and west Inner Mongolia. TCS released into water had higher LRTP in Yellow River and Yangtze River catchments. The initial case studies demonstrated that SESAMe

  16. Heat and PAHs Emissions in Indoor Kitchen Air and Its Impact on Kidney Dysfunctions among Kitchen Workers in Lucknow, North India.

    Amarnath Singh

    Full Text Available Indoor air quality and heat exposure have become an important occupational health and safety concern in several workplaces including kitchens of hotels. This study investigated the heat, particulate matter (PM, total volatile organic compounds (TVOCs and polycyclic aromatic hydrocarbons (PAHs emissions in indoor air of commercial kitchen and its association with kidney dysfunctions among kitchen workers. A cross sectional study was conducted on 94 kitchen workers employed at commercial kitchen in Lucknow city, North India. A questionnaire-based survey was conducted to collect the personal and occupational history of the kitchen workers. The urine analysis for specific gravity and microalbuminuria was conducted among the study subjects. Indoor air temperature, humidity, wet/ dry bulb temperature and humidex heat stress was monitored during cooking activities at the kitchen. Particulate matter (PM for 1 and 2.5 microns were monitored in kitchen during working hours using Hazdust. PAHS in indoor air was analysed using UHPLC. Urinary hydroxy-PAHs in kitchen workers were measured using GC/MS-MS. Higher indoor air temperature, relative humidity, PM1 and PM2.5 (p<0.001 was observed in the kitchen due to cooking process. Indoor air PAHs identified are Napthalene, fluorine, acenaphthene, phenanthrene, pyrene, chrysene and indeno [1,2,3-cd pyrene. Concentrations of all PAHs identified in kitchen were above the permissible OSHA norms for indoor air. Specific gravity of urine was significantly higher among the kitchen workers (p<0.001 as compared to the control group. Also, the prevalence of microalbuminuria was higher (p<0.001 among kitchen workers. Urinary PAH metabolites detected among kitchen workers were 1-NAP, 9-HF, 3-HF, 9-PHN and 1-OHP. Continuous heat exposure in kitchens due to cooking can alter kidney functions viz., high specific gravity of urine in kitchen workers. Exposure to PM, VOCs and PAHs in indoor air and presence of urinary PAHs

  17. Heat and PAHs Emissions in Indoor Kitchen Air and Its Impact on Kidney Dysfunctions among Kitchen Workers in Lucknow, North India

    Singh, Amarnath; Kamal, Ritul; Mudiam, Mohana Krishna Reddy; Gupta, Manoj Kumar; Satyanarayana, Gubbala Naga Venkata; Bihari, Vipin; Shukla, Nishi; Khan, Altaf Hussain; Kesavachandran, Chandrasekharan Nair


    Indoor air quality and heat exposure have become an important occupational health and safety concern in several workplaces including kitchens of hotels. This study investigated the heat, particulate matter (PM), total volatile organic compounds (TVOCs) and polycyclic aromatic hydrocarbons (PAHs) emissions in indoor air of commercial kitchen and its association with kidney dysfunctions among kitchen workers. A cross sectional study was conducted on 94 kitchen workers employed at commercial kitchen in Lucknow city, North India. A questionnaire-based survey was conducted to collect the personal and occupational history of the kitchen workers. The urine analysis for specific gravity and microalbuminuria was conducted among the study subjects. Indoor air temperature, humidity, wet/ dry bulb temperature and humidex heat stress was monitored during cooking activities at the kitchen. Particulate matter (PM) for 1 and 2.5 microns were monitored in kitchen during working hours using Hazdust. PAHS in indoor air was analysed using UHPLC. Urinary hydroxy-PAHs in kitchen workers were measured using GC/MS-MS. Higher indoor air temperature, relative humidity, PM1 and PM2.5 (p<0.001) was observed in the kitchen due to cooking process. Indoor air PAHs identified are Napthalene, fluorine, acenaphthene, phenanthrene, pyrene, chrysene and indeno [1,2,3-cd) pyrene. Concentrations of all PAHs identified in kitchen were above the permissible OSHA norms for indoor air. Specific gravity of urine was significantly higher among the kitchen workers (p<0.001) as compared to the control group. Also, the prevalence of microalbuminuria was higher (p<0.001) among kitchen workers. Urinary PAH metabolites detected among kitchen workers were 1-NAP, 9-HF, 3-HF, 9-PHN and 1-OHP. Continuous heat exposure in kitchens due to cooking can alter kidney functions viz., high specific gravity of urine in kitchen workers. Exposure to PM, VOCs and PAHs in indoor air and presence of urinary PAHs metabolites may

  18. Mass transfer kinetic mechanism in monolithic columns and application to the characterization of new research monolithic samples with different average pore sizes.

    Gritti, Fabrice; Guiochon, Georges


    A general reduced HETP (height equivalent to a theoretical plate) equation is proposed that accounts for the mass transfer of a wide range of molecular weight compounds in monolithic columns. The detailed derivatization of each one of the individual and independent mass transfer contributions (longitudinal diffusion, eddy dispersion, film mass transfer resistance, and trans-skeleton mass transfer resistance) is discussed. The reduced HETPs of a series of small molecules (phenol, toluene, acenaphthene, and amylbenzene) and of a larger molecule, insulin, were measured on three research grade monolithic columns (M150, M225, M350) having different average pore size (approximately 150, 225, and 350 A, respectively) but the same dimension (100 mm x 4.6 mm). The first and second central moments of 2 muL samples were measured and corrected for the extra-column contributions. The h data were fitted to the new HETP equation in order to identify which contribution controls the band broadening in monolithic columns. The contribution of the B-term was found to be negligible compared to that of the A-term, even at very low reduced velocities (numass transfer across the column. Experimental chromatograms exhibited variable degrees of systematic peak fronting, depending on the column studied. The heterogeneity of the distribution of eluent velocities from the column center to its wall (average 5%) is the source of this peak fronting. At high reduced velocities (nu>5), the C-term of the monolithic columns is controlled by film mass transfer resistance between the eluent circulating in the large throughpores and the eluent stagnant inside the thin porous skeleton. The experimental Sherwood number measured on the monolith columns increases from 0.05 to 0.22 while the adsorption energy increases by nearly 6 kJ/mol. Stronger adsorption leads to an increase in the value of the estimated film mass transfer coefficient when a first order film mass transfer rate is assumed (j proportional

  19. Validación de un método de análisis para la determinación de hidrocarburos aromáticos policíclicos por cromatografía líquida de alta eficiencia en partículas PM10 Y PM2,5 Validation of an analytical method for the determination of polycyclic aromatic hydrocarbons by high efficiency liquid chromatography in PM10 and PM2, 5

    Jorge Herrera Murillo


    Full Text Available Se validó un método analítico para la determinación de hidrocarburos aromáticos policíclicos presentes en partículas PM10 y PM 2,5 recolectadas en el aire mediante cromatografía líquida de alta resolución (CLAR. Los HPA incluidos en la metodología comprenden: Naftaleno, Acenaftileno, Fluoreno, Acenafteno, Fenantreno, Antraceno, Fluoranteno, Pireno, Benzo (aantraceno, Criseno, Benzo (bfluoranteno, Benzo (kfluoranteno, Benzo (apireno, Dibenzo (a,h antraceno, Benzo (g,h,iperileno y Indeno (1,2,3- C.D pireno. Para estos compuestos, los límites de detección y cuantificación estuvieron entre 0,02 y 0,1 mg/l utilizando un equipo marca Dionex modelo ICS- 3000, el cual consta de dos detectores en serie, un ultravioleta modelo VWD-1 y un detector de fluorescencia modelo RF-2000, permitiendo diferenciar las distintas señales de absorción y emisión para la debida identificación de los distintos compuestos. Para todos los compuestos analizados, el factor de recuperación resultó no ser significativamente diferente de uno y la repetibilidad y reproducibilidad resultó ser adecuada para un método analítico, especialmente para los HPA más ligeros.An analytical method for polycyclic aromatic hydrocarbons in PM10 and PM 2.5 par ticles collected from air by high performance liquid chromatography (HPLC was validated. The PAHs analyzed in the methodology include: Naphthalene, Acenaphthylene, Fluorene, Acenaphthene, Phenanthrene, Anthracene, fluoranthene,pyrene,Benzo(aanthracene,Chrysene, Benzo (bfluoranthene, Benzo (kfluoranthene, Benzo (apyrene Dibenzo (a, hanthracene, Benzo (g, h, iperylene and Indeno (1,2,3-CDpyrene. For these compounds, the detection limit and quantification limit were between 0,02 and 0,1 mg/l using a DIONEX ICS 3000 model cromatograph, that has two in serie detectors: UV/Vis and Fluorescense, separating the different absorption and emission signals for proper identification of individual compounds. For all the compounds

  20. Characterization of used lubricating oil by spectrometric techniques

    Souza, Andressa Moreira de, E-mail: [Embrapa Agroindustria de Alimentos, Guaratiba, Rio de Janeiro, RJ (Brazil); Correa, Sergio Machado [Faculdade de Engenharia. Universidade do Estado do Rio de Janeiro (UERJ), Resende, RJ (Brazil); Silva, Glauco Correa da [Instituto de Engenharia Nuclear (IEN/CNEN-RJ), Rio de Janeiro, RJ (Brazil)


    Using GC/FID, USEPA METHOD 8021B - Aromatic and halogenated volatiles by gas chromatography using photoionization and/or electrolytic conductivity detectors e USEPA METHOD 8270C - Semivolatile organic compounds by gas chromatography/mass spectrometry (GC/MS), to identify: Total Petroleum Hydrocarbons (TPH); polyaromatic hydrocarbons (PAHs) - naphthalene, acenaphthylene, acenaphthene , fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benze[a]anthracene and chrysene; benzene, toluene, ethylbenzene and xylenes (BTEX). After characterization of the engine lubricating oil after use allows us to evaluate engine wear and determine oil change interval. (author)

  1. Pressurised hot water extraction of n-alkanes and polyaromatic hydrocarbons in soil and sediment from the oil shale industry district in Estonia

    Kronholm, J.; Kettunen, J.; Hartonen, K.; Riekkola, M.L. [Lab. of Analytical Chemistry, Dept. of Chemistry, Univ. of Helsinki (Finland)


    general, recoveries for short-chain n-alkanes (C10-C16) and PAHs with two benzene rings (i.e. naphthalene, acenaphthylene, acenaphthene and fluorene) were better with PHWE at 350 C than with Soxhlet extraction. These compounds are relatively volatile and may be lost during Soxhlet extraction. For longer chain n-alkanes, recoveries were better with Soxhlet extraction than with PHWE. The longer chain compounds are less polar than the shorter chain compounds and not so easily recovered by PHWE. For PAHs with more than two benzene rings, PHWE at 350 C produced roughly similar recoveries as Soxhlet extraction. (orig.)

  2. ENA of heterocyclic hydrocarbons by adding hydrogen peroxide in groundwater circulation wells - a field-based study on a large physical model scale

    Sagner, A.; Tiehm, A. [Technologiezentrum Wasser, Karlsruhe (Germany); Trotschler, O.; Haslwimmer, Th.; Koschitzky, H.P. [Stuttgart Univ., VEGAS, Institut fur Wasserbau (Germany)


    hydraulically separated filter sections. Field monitoring at TFS showed the degradation of all PAH along the plume, except for acenaphthene. The NSO-HET are still present in the plume due to anaerobic conditions. In a second step, the technology is to be applied in a field trial of about one year's duration.

  3. Gradient distribution of persistent organic contaminants along northern slope of central-Himalayas, China.

    Wang, Xiao-Ping; Yao, Tan-Dong; Cong, Zhi-Yuan; Yan, Xing-Liang; Kang, Shi-Chang; Zhang, Yong


    High mountains may serve as condenser for persistent organic pollutants (POPs) and the vegetation in remote areas has been used as a means to characterized atmospheric concentrations of air pollutants. In this study, organochlorine pesticides (OCPs) and polycyclic aromatic hydrocarbons (PAHs) in Himalayan spruce needle samples from Zhangmu-Nyalam region (central-Himalayas) were analyzed and the altitudinal gradient of these pollutants was investigated. Total HCHs and DDTs concentration in needles were in the range of 1.3-2.9 ng g(-1) dry weight and 1.7-11 ng g(-1) dry weight, which were lower than concentrations reported in spruce needles from Alps, however higher than concentrations in conifer needles from mountain areas of Alberta. Total Himalayan spruce needle PAHs was below 600 ng g(-1) and fluorene, phenanthrene and acenaphthene were abundant individual compounds measured. The ratios of alpha-HCH/gamma-HCH in pine needles were similar with the usual values for technical HCH, implying technical HCHs might be used in this region. The high ratios of o-p'-DDT/p-p'-DDT and no p-p'-DDE measured in this study led to the suspicion that a new source of o-p'-DDT and/or p-p'-DDT existed in this region. In addition, higher ratios of low molecular weight-/high molecular weight-PAHs in this region indicated that petroleum combustion, vehicle emission and low-temperature combustion might be the major contributions of PAH source. To examine the POPs distillation, the analyte concentrations were correlated with altitude. The more volatile OCPs, alpha-HCH, gamma-HCH, aldrin and alpha-endosulfan positively correlated with altitude, however, less volatile OCPs (DDT and DDD) inversely related with elevation. Almost all PAHs detected in this area showed positive correlations with altitude. It is worthy to note that heavy PAHs (Benzo[k] fluoranthene and Benzo[a]anthracene) displayed positive correlation, which implied the sources of PAHs were near the sampling sites. The

  4. Ice phase as an important factor on the seasonal variation of polycyclic aromatic hydrocarbons in the Tumen River, Northeastern of China.

    Cong, Linlin; Fang, Yingyu; He, Miao; Wang, Xinshun; Kannan, Narayanan; Li, Donghao


    The climatic characteristic is a major parameter affecting on the distribution variation of organic pollutants such as polycyclic aromatic hydrocarbons (PAHs). The Tumen River is located in Northeastern of China. The winter era lasts for more than 5 months in a year, and the river water was frozen and covered by ice phase. Coal combustion is an essential heating source in the Tumen River Basin. The objective of this research is to study ice phase effect on the seasonal variation of PAHs in the Tumen River environment. Samples were collected from 13 sites along the River in March, July, October, and December of 2008. In addition, the ice sample, under ice water and air particulate were also collected in winter. The samples were analyzed for 16 PAHs (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, beazo[a]anthene, chrysene, beazo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno(1,2,3-cd)pyrene, dibenz(a,h)anthracene, and benzo(ghi)perylene). The compounds were extracted from the water samples and solid samples using LLE and Soxhlet extraction technique, respectively, and it is determined by gas chromatography-mass spectrometry. Among 16 PAHs, fluorene, phenanthrene, and pyrene were found to be present in high concentrations and at high detection frequencies. The total concentration of PAHs in the water, particulate, sediment and ice phase ranged from 35.1-1.05 x 10(3) ng L(-1), 25.4-817 ng L(-1), 117-562 ng g(-1)and 62.8-136 ng g(-1), respectively. The levels of PAHs were generally higher in spring than other seasons. The ice phase in winter acts like a major reservoir of the pollutants and it is major contributor on the seasonal variation of PAHs in Tumen River. The PAHs found in water, particulate, and sediment in the Tumen River were possibly derived from similar pollution sources a proposition based on the compositions and isomer ratios of PAHs. The distribution of PAHs was showed clear seasonal

  5. Ligand "Brackets" for Ga-Ga Bond.

    Fedushkin, Igor L; Skatova, Alexandra A; Dodonov, Vladimir A; Yang, Xiao-Juan; Chudakova, Valentina A; Piskunov, Alexander V; Demeshko, Serhiy; Baranov, Evgeny V


    The reactivity of digallane (dpp-Bian)Ga-Ga(dpp-Bian) (1) (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) toward acenaphthenequinone (AcQ), sulfur dioxide, and azobenzene was investigated. The reaction of 1 with AcQ in 1:1 molar ratio proceeds via two-electron reduction of AcQ to give (dpp-Bian)Ga(μ2-AcQ)Ga(dpp-Bian) (2), in which diolate [AcQ](2-) acts as "bracket" for the Ga-Ga bond. The interaction of 1 with AcQ in 1:2 molar ratio proceeds with an oxidation of the both dpp-Bian ligands as well as of the Ga-Ga bond to give (dpp-Bian)Ga(μ2-AcQ)2Ga(dpp-Bian) (3). At 330 K in toluene complex 2 decomposes to give compounds 3 and 1. The reaction of complex 2 with atmospheric oxygen results in oxidation of a Ga-Ga bond and affords (dpp-Bian)Ga(μ2-AcQ)(μ2-O)Ga(dpp-Bian) (4). The reaction of digallane 1 with SO2 produces, depending on the ratio (1:2 or 1:4), dithionites (dpp-Bian)Ga(μ2-O2S-SO2)Ga(dpp-Bian) (5) and (dpp-Bian)Ga(μ2-O2S-SO2)2Ga(dpp-Bian) (6). In compound 5 the Ga-Ga bond is preserved and supported by dithionite dianionic bracket. In compound 6 the gallium centers are bridged by two dithionite ligands. Both 5 and 6 consist of dpp-Bian radical anionic ligands. Four-electron reduction of azobenzene with 1 mol equiv of digallane 1 leads to complex (dpp-Bian)Ga(μ2-NPh)2Ga(dpp-Bian) (7). Paramagnetic compounds 2-7 were characterized by electron spin resonance spectroscopy, and their molecular structures were established by single-crystal X-ray analysis. Magnetic behavior of compounds 2, 5, and 6 was investigated by superconducting quantum interference device technique in the range of 2-295 K.

  6. Digallane with redox-active diimine ligand: dualism of electron-transfer reactions.

    Fedushkin, Igor L; Skatova, Alexandra A; Dodonov, Vladimir A; Chudakova, Valentina A; Bazyakina, Natalia L; Piskunov, Alexander V; Demeshko, Serhiy V; Fukin, Georgy K


    The reactivity of digallane (dpp-Bian)Ga-Ga(dpp-Bian) (1), which consists of redox-active ligand 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-Bian), has been studied. The reaction of 1 with I2 proceeds via one-electron oxidation of each of two dpp-Bian ligands to a radical-anionic state and affords complex (dpp-Bian)IGa-GaI(dpp-Bian) (2). Dissolution of complex 2 in pyridine (Py) gives monomeric compound (dpp-Bian)GaI(Py) (3) as a result of a solvent-induced intramolecular electron transfer from the metal-metal bond to the dpp-Bian ligands. Treatment of compound 3 with B(C6F5)3 leads to removal of pyridine and restores compound 2. The reaction of compound 1 with 3,6-di-tert-butyl-ortho-benzoquinone (3,6-Q) proceeds with oxidation of all the redox-active centers in 1 (the Ga-Ga bond and two dpp-Bian dianions) and results in mononuclear catecholate (dpp-Bian)Ga(Cat) (4) (Cat = [3,6-Q](2-)). Treatment of 4 with AgBF4 gives a mixture of [(dpp-Bian)2Ag][BF4] (5) and (dpp-Bian)GaF(Cat) (6), which both consist of neutral dpp-Bian ligands. The reduction of benzylideneacetone (BA) with 1 generates the BA radical-anions, which dimerize, affording (dpp-Bian)Ga-(BA-BA)-Ga(dpp-Bian) (7). In this case the Ga-Ga bond remains unchanged. Within 10 min at 95 °C in solution compound 7 undergoes transformation to paramagnetic complex (dpp-Bian)Ga(BA-BA) (8) and metal-free compound C36H40N2 (9). The latter is a product of intramolecular addition of the C-H bond of one of the iPr groups to the C═N bond in dpp-Bian. Diamagnetic compounds 3, 5, 6, and 9 have been characterized by NMR spectroscopy, and paramagnetic complexes 2, 4, 7, and 8 by ESR spectroscopy. Molecular structures of 2-7 and 9 have been established by single-crystal X-ray analysis.

  7. Tunable Electrochemical and Catalytic Features of BIAN- and BIAO-Derived Ruthenium Complexes.

    Hazari, Arijit Singha; Das, Ankita; Ray, Ritwika; Agarwala, Hemlata; Maji, Somnath; Mobin, Shaikh M; Lahiri, Goutam Kumar


    This article deals with a class of ruthenium-BIAN-derived complexes, [Ru(II)(tpm)(R-BIAN)Cl]ClO4 (tpm = tris(1-pyrazolyl)methane, R-BIAN = bis(arylimino)acenaphthene, R = 4-OMe ([1a]ClO4), 4-F ([1b]ClO4), 4-Cl ([1c]ClO4), 4-NO2 ([1d]ClO4)) and [Ru(II)(tpm)(OMe-BIAN)H2O](2+) ([3a](ClO4)2). The R-BIAN framework with R = H, however, leads to the selective formation of partially hydrolyzed BIAO ([N-(phenyl)imino]acenapthenone)-derived complex [Ru(II)(tpm)(BIAO)Cl]ClO4 ([2]ClO4). The redox-sensitive bond parameters involving -N═C-C═N- or -N═C-C═O of BIAN or BIAO in the crystals of representative [1a]ClO4, [3a](PF6)2, or [2]ClO4 establish its unreduced form. The chloro derivatives 1a(+)-1d(+) and 2(+) exhibit one oxidation and successive reduction processes in CH3CN within the potential limit of ±2.0 V versus SCE, and the redox potentials follow the order 1a(+) oxidation and primarily BIAN- or BIAO-based successive reduction processes. The aqua complex 3a(2+) undergoes two proton-coupled redox processes at 0.56 and 0.85 V versus SCE in phosphate buffer (pH 7) corresponding to {Ru(II)-H2O}/{Ru(III)-OH} and {Ru(III)-OH}/{Ru(IV)═O}, respectively. The chloro (1a(+)-1d(+)) and aqua (3a(2+)) derivatives are found to be equally active in functioning as efficient precatalysts toward the epoxidation of a wide variety of alkenes in the presence of PhI(OAc)2 as oxidant in CH2Cl2 at 298 K, though the analogous 2(+) remains virtually inactive. The detailed experimental analysis with the representative precatalyst 1a(+) suggests the involvement of the active {Ru(IV)═O} species in the catalytic cycle, and the reaction proceeds through the radical mechanism, as also supported by the DFT calculations.

  8. Bioaccumulation surveillance in Milford Haven Waterway.

    Langston, W J; O'Hara, S; Pope, N D; Davey, M; Shortridge, E; Imamura, M; Harino, H; Kim, A; Vane, C H


    Biomonitoring of contaminants (metals, organotins, polyaromatic hydrocarbons (PAHs), PCBs) was undertaken in Milford Haven Waterway (MHW) and a reference site in the Tywi Estuary (St Ishmael/Ferryside) during 2007-2008. Bioindicator species encompassed various uptake routes-Fucus vesiculosus (dissolved contaminants); Littorina littorea (grazer); Mytilus edulis and Cerastoderma edule (suspension feeders); and Hediste (=Nereis) diversicolor (sediments). Differences in feeding and habitat preference have subtle implications for bioaccumulation trends though, with few exceptions, contaminant burdens in MHW were higher than the Tywi reference site, reflecting inputs. Elevated metal concentrations were observed at some MHW sites, whilst As and Se (molluscs and seaweed) were consistently at the higher end of the UK range. However, for most metals, distributions in MH biota were not exceptional. Several metal-species combinations indicated increases in bioavailability upstream, which may reflect the influence of geogenic/land-based sources-perhaps enhanced by lower salinity. TBT levels in MH mussels were below OSPAR toxicity thresholds and in the Tywi were close to zero. Phenyltins were not accumulated appreciably in M. edulis, whereas some H. diversicolor populations appear subjected to localized (historical) sources. PAHs in H. diversicolor were distributed evenly across most of MHW, although acenaphthene, fluoranthene, pyrene, benzo(a)anthracene and chrysene were highest at one site near the mouth; naphthalenes in H. diversicolor were enriched in the mid-upper Haven (a pattern seen in M. edulis for most PAHs). Whilst PAH (and PCB) concentrations in MH mussels were mostly above reference and OSPAR backgrounds, they are unlikely to exceed ecotoxicological thresholds. Bivalve Condition indices (CI) were highest at the Tywi reference site and at the seaward end of MH, decreasing upstream-giving rise to several significant (negative) relationships between CI and body burdens

  9. Hidrocarbonetos policíclicos aromáticos (HPAs em aguardentes PHAs in spirits

    S. M. Bettin


    Full Text Available A presença de hidrocarbonetos aromáticos polinucleares (HPAs em aguardentes foi investigada por cromatografia líquida (CLAE após sua prévia extração em fase sólida (SPE. A separação foi realizada em uma coluna Supelco, LCPAH-octadecil silano (25cm x 4,6mm x 5mm com gradiente acetonitrila/água e a quantificação utilizando detector de fluorescência. Os HPAs (naftaleno; acenaftaleno; fluoreno; fenantreno; antraceno; fluoranteno; pireno; 1,2- benzo(epireno; criseno; benzo(epireno; 2,3-benzo(aantraceno; 1,2-benzo(bfluoranteno; benzo(kfluoranteno; dibenzo(a,hantraceno; benzo(apireno; benzo(ghipirileno foram identificados e quantificados em vinte e oito amostras de aguardentes de cana. Os resultados experimentais para as amostras de aguardentes (cachaças são analisados em termos de análises de componentes principais (PCA objetivando a diferenciação entre o perfil das aguardentes produzidas a partir de cana-de-açúcar queimada e não-queimada.The presence of PHAs (polycyclic aromatic hydrocabons in spirits has been investigated using high performance liquid chromatography (HPLC after solid phase extraction (SPE. The separation was achieved with a Supelco LCPAH-octadecil silane column [25cm x 4,6mm x 5mm] and acetonitrile/water elution gradient and the quantification using a fluorescence detector. The PHAs (naphthalene; acenaphthene; fluorene; phenantrene; anthracene; phuorantene; pyrene; 1,2-benzo(epyrene; chrysene; benzo(epyrene; 2,3-benzo(aanthracene; 1,2-benzo(bphluoranthene; benzo(kfluoranthene; dibenzo(a,hanthracene; benzo(apyreno; benzo(ghipyrilene were quantifed in twenty eight samples of sugar cane spirits. All the experimental data for sugar cane spirit have been analyzed through principal components analysis (PCA aiming to compare the chemical profile of beverages produced from burned and not burned sugar cane.

  10. A comparative evaluation of passive and active samplers for measurements of gaseous semi-volatile organic compounds in the tropical atmosphere

    He, Jun; Balasubramanian, Rajasekhar


    The polyurethane foam (PUF) disk-based passive air samplers (PAS), mounted inside two aluminium bowls to buffer the air flow to the disk and to shield it from precipitation and sunlight, were used for the collection of atmospheric SVOCs in Singapore during April 2008-June 2008. Data obtained from PAS measurements are compared to those from active high-volume air sampling (AAS). Single factor ANOVA tests show that there were no significant differences in chemical distribution profiles between actively and passively collected samples (PAHs, F = 3.38 × 10 -8 0.05; OCPs, F = 2.71 × 10 -8 0.05). The average air-side mass transfer coefficient ( k A) for PAS, determined from the loss of depuration compounds such as 13C 6 - HCB (1000 ng), 13C 12 - 4,4' DDT (1000 ng) and 13C 12 - PCB 101 (1000 ng)spiked on the disks prior to deployment, was 0.12 ± 0.04 m s -1. These values are comparable to those reported previously in the literature. The average sampling rate was 3.78 ± 1.83 m 3 d -1 for the 365 cm 2 PUF disk. Throughout the entire sampling period (˜68 d), most of the PAHs and all OCPs exhibited a linear uptake trend on PAS, while naphthalene, acenaphthylene, acenaphthene and fluorene reached the curvilinear phase after the first ˜30 d exposure. Theoretically estimated times to equilibrium ( t eq) ranged from around one month for Acy to hundreds of years for DB(ah)A. Sampling rates, based on the time integrated active sampling-derived concentrations and masses collected by PUF disks during the linear uptake phase, were determined for all target compounds with the average values of 2.50 m 3 d -1 and 3.43 m 3 d -1 for PAHs and OCPs, respectively. More variations were observed as compared to those from the depuration study. These variation were most likely due to the difference of physicochemical properties of individual species. Lastly, multiple linear regression models were developed to estimate the log-transformed gaseous concentration of an individual compound in

  11. Distribution of Polycyclic Aromatic Hydrocarbons in Soil Profiles in Southeast Suburb of Beijing Wastewater Irrigation Area%北京东南郊污灌区PAHs垂向分布规律

    何江涛; 金爱芳; 陈素暖; 魏永霞


    3 borehole profiles samples were collected using Eijkelkamp soil sampler from the wastewater irrigation area of Beijing Southeast suburb. The soil samples were collected from surface to 5.5 m underground every 0.5 m. Physical-chemical properties of the samples such as clay content,total amount of clay minerals,cation exchange capacity (CEC),total organic compounds (TOC),etc. were analyzed. 16 polycyclic aromatic hydrocarbons (PAHs) defined by the U.S.EPA were also analyzed with gas chromatography-mass spectrometry (GC-MS). Results show that 14 PAHs were detected in the surface soil samples. The concentrations of PAHs range from 4 μg/kg to 428 μg/kg. Under the surface,both species and concentrations of PAHs in soil samples drop very fast. Only 2 rings and 3 rings PAHs were detected,which were naphthalene,phenanthrene,fluorene,acenaphthylene,acenaphthene,and fluoranthene. Clay content,total amount of clay minerals,CEC and TOC have significant correlations at 0.05 level between each other. Under the surface,clay contents also have a relationship with low-rings PAHs concentration. Where the layers have higher clay contents,the PAHs have higher concentrations. The contents of PAHs changing along the profiles also show that,low-rings PAHs are easier to migrate than high-rings PAHs. The sequence of the migration capabilities of low-ring PAHs is acenaphthene>fluorene>naphthalene>phenanthrene>acenaphthylene>fluoranthene. However,high-ring PAHs were only detected in surface soil samples. That means low-rings PAHs can reach the deep layers of the vertical profiles under long-term wastewater irrigation. Therefore,the shallow groundwater has the possibility to be contaminated.%采用Eijkelkamp土壤采样器对北京东南郊污灌区进行了3个钻孔剖面采样,分析了土壤样品的理化参数,并且采用气相色谱-质谱联用仪对土壤样品的多环芳烃(PAHs)进行了定量分析,研究了土壤理化参数和16种PAHs从表层到5.5 m深的范围内垂向

  12. Remediation of Wheat-Straw-Biochar on Petroleum-Polluted Soil%小麦秸秆生物炭对石油烃污染土壤的修复作用

    朱文英; 唐景春


    Biochar was made from wheat straw at 300℃for 3, 6, 8 hours respectively. The productivity, pH, ash content and C, H, N content of these biochar were compared. The surface morphology of the 300 ℃-6 h biochar was characterized, and it was used to remediate the petroleum-polluted soil of Dagang oil field. Results showed that, as the extension of pyrolisis time, the productivity of biochar decreased, pH increased, ash content increased, H/C decreased. But productivity, pH, ash content and H/C changed significantly from 3 h to 6 h, unsignifi-cantly from 6 h to 8 h. C content showed a downward trend after the first rise. After remediation of biochar for 14 and 28 days, the TPH degra-dation rate were 45.48%and 46.88%respectively, higher than control group. After 14 days remediation, content of naphthalene, acenaph-thene, Benzo [a] anthracene, chrysene, Benzo [b] fluoranthene, Benzo [k] fluoranthene, Benzo [a] pyrene, Indene and [1,2,3-CD] pyrene were decreased to various degrees, with the Benzo [a] pyrene content decreased by 98.18%, and the degradation rate of other PAH higher than con-trol group. After 28 days remediation however, content of these PAH showed a rising trend. It suggested that pyrolisis time had influence on biochar’s characteristics, and 300℃-6 h biochar could be used to remediate petroleum-polluted soil.%以小麦秸秆为原材料,在300℃下缺氧裂解3、6、8 h制备生物炭,比较了3种生物炭的产率、pH值、灰分以及C、H、N元素含量,表征了300℃、6 h生物炭的表面形态,并用其作为修复材料,对大港油田的石油污染土壤进行修复。结果表明,随裂解时间的延长,生物炭产率下降,pH值升高,灰分含量增加,H/C值下降,但产率、pH值、灰分和H/C值都是从3h到6h差异显著,6h到8h差异不显著。C元素含量先升高后下降。石油污染土壤经生物炭修复14 d和28 d后,总石油烃降解率分别为45.48%和46.88%,均

  13. Amelioration of soil PAH and heavy metals by combined application of fly ash and biochar

    Masto, Reginald; George, Joshy; Ansari, Md; Ram, Lal


    Generation of electricity through coal combustion produces huge quantities of fly ash. Sustainable disposal and utilization of these fly ash is a major challenge. Fly ash along with other amendments like biochar could be used for amelioration of soil. In this study, fly ash and biochar were used together for amelioration of polycyclic aromatic hydrocarbon (PAH) contaminated soil. Field experiment was conducted to investigate the effects of fly ash and biochar on the amelioration of soil PAH, and the yield of Zea mays. The treatments were control, biochar (4 t/ha), fly ash (4 t/ha), ash + biochar ( 2 + 2 t/ha). Soil samples were collected after the harvest of maize crop and analysed for chemical and biological parameters. Thirteen PAHs were analysed in the postharvest soil samples. Soil PAHs were extracted in a microwave oven at 120 °C using hexane : acetone (1:1) mixture. The extracted solutions were concentrated, cleaned and the 13 PAHs [Acenaphthene (Ace), fluorene (Flr), phenanthrene (Phn), anthracene(Ant), pyrene(Pyr), benz(a)anthracene (BaA), chrysene (Chy), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene, benzo(g,h,i)perylene (BghiP), dibenzo(a,h)anthracene, and indeno(1,2,3-cd)pyrene)(Inp)] were analysed using GC-MS. The mean pH increased from 6.09 in control to 6.64 and 6.58 at biochar and fly ash treated soils, respectively. N content was not affected, whereas addition of biochar alone and in combination with fly ash, has significantly increased the soil organic carbon content. P content was almost double in combined (9.06 mg/kg) treatment as compared to control (4.32 mg/kg). The increase in K due to biochar was 118%, whereas char + ash increased soil K by 64%. Soil heavy metals were decreased: Zn (-48.4%), Ni (-41.4%), Co (-36.9%), Cu (-35.7%), Mn (-34.3%), Cd (-33.2%), and Pb (-30.4%). Soil dehydrogenase activity was significantly increased by ash and biochar treatments and the maximum activity was observed for the combined

  14. Distribution, Sources and Risk Assessment of Polycyclic Aromatic Hydrocarbons in Surface Sediments from Typical Coastal Areas of the Shandong Peninsula%山东半岛典型海岸带多环芳烃分布特征、来源解析及风险评价

    张道来; 刘娜; 朱志刚; 路晶芳; 林学辉; 侯国华; 印萍


    by the effects range-low (ERL)and the effects range-median (ERM)indicates little negative effect from surface sediments on the coast of the Shandong peninsula. However,acenaphthene and fluorenein in the sites of Laizhou Bay,Weihai and the Qingdao coast may pose a potential risk to the environment.In conclusion,the negative effects of 16 PAHs in the surface sediments from the Shandong peninsula were weak and easily controlled.

  15. Polycyclic aromatic hydrocarbons pollution effect on soil biological activity in the anthropogenic contaminated area

    Batukaev, Abdulmalik; Sushkova, Svetlana; Minkina, Tatiana; Antonenko, Elena; Salamova, Anzhelika; Gimp, Alina; Deryabkina, Irina


    in the monitoring plots situated through the prevailing wind direction from NPs. Level of dehydrogenases has high positive correlation with technogenic accumulated biphenyl, acenaphthene and negative correlation with anthracene content in studied soil. The lowmolecular PAHs content of soil influenced activity of dehydrogenases positively. Urease activity of monitoring plots has a high positive correlation with 12 PAHs exclude biphenyl, benzo(a)anthracene, naphthalene. Negative dependence of urease activity was observed for lowmolecular PAHs. The abundance of soil bacteria has a negative correlation with PAHs level. Anthracene has no correlations with abundance of soil bacteria and negatively influences on dehydrogenase, urease. Thus, the most subjected to technogenic pollution in 2015 were monitoring plots situated through the prevailing wind direction from NPs. It was established that ratio of low- and highmolecular PAHs content in soils of monitoring plots is the indicator of technogenic pollution soils. Contamination by PAHs in the affected zone has negative influence at the abundance of soil bacteria. The most number of PAHs has positive correlation with biological activity parameters of soil. This work was supported by grant of the Russian Scientific Foundation № 16-14-10217.

  16. Concentrations of polynuclear aromatic hydrocarbons and inorganic constituents in ambient surface soils, Chicago, Illinois, 2001-02

    Kay, Robert T.; Arnold, Terri L.; Cannon, William F.; Graham, David; Morton, Eric; Bienert, Raymond


    Polynuclear aromatic hydrocarbon (PAH) compounds are ubiquitous in ambient surface soils in the city of Chicago, Illinois. PAH concentrations in samples collected in June 2001 and January 2002 were typically in the following order from highest to lowest: fluoranthene, pyrene, benzo(b)fluoranthene, phenanthrene, benzo(a)pyrene, chrysene, benzo(a)anthracene, benzo(k)fluoranthene, indeno(1,2,3-cd)pyrene, benzo(g,h,i)perylene, dibenzo(a,h)anthracene, and anthracene. Naphthalene, acenaphthene, acenaphthylene, and fluorene were consistently at the lowest concentrations in each sample. Concentrations of the PAH compounds showed variable correlation. Concentrations of PAH compounds with higher molecular weights typically show a higher degree of correlation with other PAH compounds of higher molecular weight, whereas PAH compounds with lower molecular weights tended to show a lower degree of correlation with all other PAH compounds. These differences indicate that high and low molecular-weight PAHs behave differentl y once released into the environment. Concentrations of individual PAH compounds in soils typically varied by at least three orders of magnitude across the city and varied by more than an order of magnitude over a distance of about 1,000 feet. Concentrations of a given PAH in ambient surface soils are affected by a variety of site-specific factors, and may be affected by proximity to industrial areas. Concentrations of a given PAH in ambient surface soils did not appear to be affected the organic carbon content of the soil, proximity to non-industrial land use, or proximity to a roadway. The concentration of the different PAH compounds in ambient surface soils appears to be affected by the propensity for the PAH compound to be in the vapor or particulate phase in the atmosphere. Lower molecular-weight PAH compounds, which are primarily in the vapor phase in the atmosphere, were detected in lower concentrations in the surface soils. Higher molecular-weight PAH

  17. New tetradentate N,N,N,N-chelating α-diimine ligands and their corresponding zinc and nickel complexes: synthesis, characterisation and testing as olefin polymerisation catalysts.

    Li, Lidong; Gomes, Clara S B; Gomes, Pedro T; Duarte, M Teresa; Fan, Zhiqiang


    A series of zinc complexes of the general formula {[ZnCl(ArN=C(An)-C(An)=NAr)](+)}(2)[Zn(2)Cl(6)](2-) (where Ar = 2-(1-benzyl-1H-1,2,3-triazol-4-yl)phenyl 2a, 2-(1-(1-phenylethyl)-1H-1,2,3-triazol-4-yl)phenyl 2b, 2-(1-phenyl-1H-1,2,3-triazol-4-yl)phenyl 2c; An = acenaphthene backbone) were prepared by the condensation of acenaphthenequinone with the corresponding o-triazolyl-substituted anilines (2-(1-benzyl-1H-1,2,3-triazol-4-yl)aniline 1a, 2-(1-(1-phenylethyl)-1H-1,2,3-triazol-4-yl)aniline 1b, 2-(1-phenyl-1H-1,2,3-triazol-4-yl)aniline 1c) which were formed by the copper(I)-catalyzed Huisgen[3+2] dipolar cycloaddition between 2-ethynylaniline and the corresponding azides in high yields, using anhydrous ZnCl(2) as the metal template, in boiling glacial acetic acid. Zinc complexes of the type [ZnCl(ArN=C(An)-C(An)=NAr)](+)[ZnCl(3)(NCCH(3))](-) (4a-c) were synthesized by crystallisation of the corresponding complexes 2a-c in acetonitrile, at -20 °C. After removal of zinc dichloride from complexes 2a-c by the addition of potassium oxalate, in dichloromethane, the tetradentate N,N,N,N-chelating α-diimine ligands of the type ArN=C(An)-C(An)=NAr (5a-c) were obtained. The new ligand precursors and zinc complexes were characterised by elemental analysis, (1)H and (13)C{(1)H} NMR spectroscopy, two-dimensional NMR spectroscopy, and X-ray diffraction. Reaction of the ligand precursors 5a-c with [NiBr(2)(DME)], in dichloromethane, gave nickel complexes of the type [NiBr(2)(ArN=C(An)-C(An)=NAr)] (6a-c). The results of single crystal X-ray diffraction characterisation and magnetic susceptibility measurements demonstrated that nickel complexes 6a-c possess octahedral geometries around the nickel atoms with variable configurations, the Br atoms of which can be ionized when dissolved in methanol. In preliminary catalytic tests, complexes 6a-c revealed to be active as catalysts for the polymerisation of norbornene and styrene, when activated by cocatalyst MAO. The characterisation

  18. Vieillissement du polyamide 11 utilisé dans les conduites flexibles : influence de la composition du fluide transporté Influence of the Chemical Nature of the Environment on the Aging of Polyamide 11 Used for Offshore Flexible Pipes

    Ubrich E.


    hydrocarbons absorbed preferentially, and having a pasticating role, was determined. These are two-cycle aromatics (alkylnaphthalenes, acenaphthenes, diphenyls, acenaphthylenes, fluorenes and sulfur-containing aromatics (benzothiophenes and dibenzothiophenes. The different results led to the conclusion that the principal phenomenon involved in aging is a hydrolysis caused by the presence of absorbed water in the material, which leads to the cutting of the macromolecular chains and embrittlement of the polymer. Lastly, the model created with gas-oil cuts was applied to a case of aging of a crude oil, and this led to the satisfactory prediction of how the mechanical and physicochernical properties of the polymer evolve in such an environment.

  19. Chemistry%化学


    O612 01050129 具有微孔/大孔双孔道体系沸石材料的合成=Synthesis of Silicate Materials with Micro/Macroporous Bimodal Pore Systems[刊, 中]/王亚军(复旦大学),唐颐…∥高等学校化学学报.&2000, 21(7).&1013~1015 国家自然科学基金(29873011)资助 O612 01050130 一种新型磷酸钛大单晶的溶剂热法合成与结构研究=Studies on Solvothermal Synthesis and Structure of a New Titanium Phosphate Large Single Crystal[刊, 中]/郭阳虹(吉林大学),施展…∥高等学校化学学报.&2000, 21(7).&1010~1012 国家自然科学基金(29571011)资助 O613 01050131 一种氟气源的制备及热分解=Preparation and Thermal Decomposition of a Kind of Fluorine Source[刊, 中]/刘文元(西北核技术研究所),李辉…∥应用化学.&2000, 17(3).&300~303 国家"八六三”计划资助课题 O613 01050132 铒在HBTMPTP-正庚烷/水溶液间的传质动力学=Mass Transfer of Er(Ⅲ) between HBTMPTP Dissolved in n-Heptane and HAc-NaAc[刊, 中]/乐善堂(中科院长春应用化学所),马根祥…∥高等学校化学学报.&2000, 21(6).&832~835 在(30±0.5)℃下,用层流恒界面池研究了铒在HBTMPTP-正庚烷-0.2mol/L(H,Na)Ac萃取体系中的传质动力学.测定了该体系的界面张力,考察了水相酸度、萃取剂浓度、氯离子浓度、温度和比界面对萃取速率的影响.图6参16 国家自然科学基金(29771028,29801004)资助 O613 01050133 岩石中硼的提取分离及同位素组成的测定=Extraction and Separation of Boron in Rock Samples and lts lsotopic Determination by Thermal lonization Mass Spectrometry[刊, 中]/王刚(中科院青海盐湖所),王蕴慧…∥岩矿测试.&2000, 19(3).&169~172 介绍了一种用Na2CO3+K2CO3混合熔剂对岩石样品进行分解,用硼特效树脂和阴、阳混合离子交换树脂相结合进行岩石样品中硼的纯化分离的方法.采用该方法从岩石样品中提取、分离出来的硼能满足硼同位素质谱法测定的需要,不产生硼同位素分馏,硼同位素测定精度大多优于0.05%.表3参7 国家自然科学基金(29775028)资助 O614 01050134 有机/无机纳米杂化材料负载钛催化剂及聚合研究:Ⅰ.乙烯聚合=Study of Titanium Catalysts Supported on he Organic/Inorganic Hybrid and Polymerization Thereby:Ⅰ.Polymerization of Ethylene[刊, 中]/朱宁(中科院长春应用化学所),唐涛…∥应用化学.&2000, 17(3).&233~237 以苯乙烯与马来酸酐无规共聚物为有机组分,以正硅酸乙酯为无机组分,利用sol-gel方法制得纳米杂化材料,以此为载体合成了杂化材料载体钛系催化剂.图3表3参13 国家自然科学基金(29774028)资助 O614 01050135 硫酸锌与L-α-缬氨酸固体配合物的合成与表征=Synthesis and Characterization of Zinc Sulfate Complexes with L-α-Valine[刊, 中]/张晓玉(西北大学),杨旭武…∥应用化学.&2000, 17(3).&243~247 用半微量相平衡方法研究了ZnSO4-Val-H2O体系在25℃时的溶度图及饱和溶液折光率曲线.体系中未形成新化合物.合成了配合物Zn(Val)SO4*H2O、Zn(Val)2*H2O,并进行了表征.图2表3参13 国家自然科学基金(29871023)资助 O614 01050136 微乳液法制备超细包裹型铁粉=Preparation of Ultrafine Fe Particles by Microemulsion Method[刊, 中]/张朝平(贵州大学),邓伟…∥应用化学.&2000, 17(3).&248~251 应用W/O型微乳液法制备了纳米量级包裹型超细铁粉.由XRD、SEM、TEM和IR谱测试表明:它属于表面活性剂包裹型超细微粒.图3参9 国家自然科学基金(19872021)资助 O614 01050137 以12-钨(钼)磷杂多酸为掺杂剂的导电聚N,N-二甲基苯胺的合成与导电性=Synthesis and Conductivity of Conducting Poly N,N-Dimethaniline Doped by 12-Tungsto(Molybdo) Phosphoric Acid Used as Doping Agent[刊, 中]/张贞文(湖北大学),柳士忠…∥湖北大学学报(自然科学版).&2000, 22(3).&270~273 以12-钨(钼)磷杂多酸为掺杂剂,合成了聚N,N-二甲基苯胺.并利用ICP、元素分析、循环伏安、红外光谱及室温固体电导率的测定等手段进行了表征.结果表明,掺杂的PDMAn/PM12的室温导电率约为12-13 S/cm.图3参6 国家自然科学基金(29971010)资助 O614 01050138 Co(phen)2TATP3+与DNA在旋转金盘金环电极上的相互作用研究=Electrochemical Studies on the Interactions of the Complex of Co(phen)2TATP3+ with DNA at Rotating Au-Au Electrode[刊, 中]/李红(中山大学),蒋雄…∥高等学校化学学报.&2000, 21(7).&995~998 在pH=7.2的Tris缓冲溶液中,利用旋转环盘电极法研究了金电极上Co(phen)2TATP3+与DNA的相互作用,并根据扩散控制和电化学控制下得到的各种参数,对它们作用的模式进行了讨论.图3表2参13 国家自然科学基金(29871036)资助 O614 01050139 双金属杂原子分子筛CrCoBEA的合成、波谱及催化性能研究=Studies on the Synthesis, Spectroscopy and Catalytic Properties of CrCoBEA Metallosilicate[刊, 中]/王亚军(南开大学),唐祥海…∥高等学校化学学报.&2000, 21(7).&999~1004 采用水热晶化法首次合成出BEA结构含铬、钴双金属杂原子分子筛CrCoBEA,对晶化时间、晶化温度、成胶配比等合成条件进行了优化研究,测试其物相、波谱性质和催化性能.图6表1参15 国家自然科学基金重点项目(29733070)资助 O614 01050140 Ru(bpy)2+3在MCM-48中的组装及其发光性质=The Assembly of Tris(Bipyridine)Ruthenium(Ⅱ) in MCM-48 and Photoluminescent Properties of Assembly Products[刊, 中]/房铭(吉林大学),张萍…∥高等学校化学学报.&2000, 21(7).&1016~1017 国家自然科学基金(29771013,59795006)资助 O621 01050141 2-烯丙基-1,1-偕二金属环已烷的合成研究=Synthesis of 2-Allyl-1,1-Gemdimetallic Cyclohexane[刊, 中]/宋国强(江苏石油化工学院),王钒…∥合成化学.&2000, 8(3).&216~219 在无水乙醚中1-锂代环己烯和烯丙基溴化镁于无水溴化锌作用下发生金属化克兰荪重排反应,生成2-烯丙基-1,1-偕二金属环己烷.通过对温度、溶剂量和投料顺序等重排反应主要影响因素的考察和优化,可使2-烯丙基-1,1-偕二金属环己烷的收率达到65%.图2表3 国家自然科学基金(2947043)资助 O621 01050142 沙丘芦苇特有一小分子化合物及其对叶绿体的逆境保护效应[刊, 中]/浦铜良(兰州大学),程佑发…∥科学通报.&2000, 45(12).&1308~1313 用柱层析手段从沙漠地区沙丘芦苇叶片中分离得到一种为该生态型所特有的小分子物质,其化学特征与已报道的逆境胁迫诱导累积的溶质均不同,具多氨基芳香族强极性特征.其自然丰度与月平均气温和月极端高温值为指标的生境高温程度呈显著相关性.并主要存在于光合细胞器叶绿体中.该物质对离体叶绿体在高温下电子传递链的功能具有保护作用.图5表2参15 国家自然科学基金(39870062)资助 O621 01050143 亚胺氧自由基与酚类的反应=The Reaction of Iminoxy Radical with Phenols[刊, 中]/胡家欣(南京大学),吉民…∥高等学校化学学报.&2000, 21(7).&1045~1047 研究了亚胺氧自由基与酚类的反应,一步合成了取代苯并C023唑、萘并及喹啉并C023唑类衍生物,同时探讨了反应机理.表2参8 国家自然科学基金(29375052)资助 O621 01050144 新型磺酰胺类含氮手性配体的合成、晶体结构及催化苯乙酮的不对称氢转移反应=Studies on the Synthesis of New Sulfonylamide Ligand, Crystal Structure and Asymmetric Hydrogen Transfer Reaction of Acetophenone[刊, 中]/董春娥(中科院成都有机化学所),张俊龙…∥高等学校化学学报.&2000, 21(7).&1070~1072 国家自然科学基金(29973042)资助 O624 01050145 P+7原子团簇及其特殊配位=P+7 Clusters and Their Specical Coordinations[刊, 中]/陈明旦(厦门大学),罗海彬…∥厦门大学学报(自然科学版).&2000, 39(3).&341~346 在激光产生的磷原子团簇正离子的质谱图中,P+7具有最强的谱峰.使用分子图形软件设计出24种P+7的同分异构体,并进行分子力学、PM3半经验量子化学和ADF密度泛函优化.从各异构体成键能量的比较中可得知,最稳定的P+7构型是在最稳定的P6的双键位置增加1个磷原子所生成的结构.图2表2参23 国家自然科学基金资助 O626 01050146 硫醚双酐聚酰胺酸的合成及其热稳定性=The Synthesis and Thermal Stability of Thioether Dianhydride Poly(Amic Acid)[刊, 中]/王江洪(中科院感光化学所),沈玉全∥高等学校化学学报.&2000, 21(6).&879~883 合成了硫醚二酐和4-硝基-4′-[N,N-二(2-氨乙基)氨基]偶氮苯(二胺单体)及对应的硫醚聚酰胺酸,并对其结构进行表征.目前,这些聚合物在高敏感非线性光学材料方面显示着广泛的应用前景.图3参14 国家自然科学基金(69637010)资助 O626 01050147 具有光致变色和发光性能的有机化合物的合成及其性能研究=Synthesis and Characteristics of Compounds Having Both Photochromic and Fluorescent Character[刊, 中]/庞美丽(南开大学),王永梅…∥高等学校化学学报.&2000, 21(6).&903~907 以吲哚啉螺苯并吡喃与香豆素衍生物为原料.用DCC缩合酯化法在温和条件下合成了8种新的具有光致变色和发光性能的化合物.所得化合物同时具有光致变色和发荧光的双重特性.图2参15 国家自然科学基金(29872015)资助 O626 01050148 1,2,4-三唑并[3,2-d][1,5]-苯并氧氮杂C024化合物的合成=Synthesis of 1,2,4-Triazolo[3,2-d][1,5] Benzoxazepine Compounds[刊, 中]/刘现军(复旦大学),刘毅…∥高等学校化学学报.&2000, 21(7).&1052~1055 苯并二氢吡喃-4-酮的芳腙衍生的偶氮基碳正离子与腈发生1,3-偶极环加成反应,加成产物通过[1,2]-迁移扩环重排反应,形成新颖的三环系杂环化合物1,2,4-三唑并[3,2-d][1,5]-苯并氧氮杂C024化合物.图1表3参9 国家自然科学基金(A29872007)资助 O626 01050149 四(4-N-吡啶基)卟啉衍生物的合成及表征=Synthesis and Characterization of Meso-Tetrakis(4-Pyridyl) Porphyrin Derivatives[刊, 中]/刘淑清(吉林大学),孙浩然…∥应用化学.&2000, 17(3).&260~263 利用吡啶氮烷基化合成了一系列具有空间效应的水溶性和油溶性的四(4-N-吡啶基)卟啉衍生物及其对应的金属钴卟啉.表5参8 国家自然科学基金(29733090,29803003)资助 O627 01050150 η6-苯乙烯二羰基(三苯基膦)铬配合物的合成与聚合=Synthsis and Polymerization of η6-Styrenedicarbonyl (Triphenylphos- phine) Chromium Complexes[刊, 中]/田晓慧(华东理工大学),林嘉平…∥功能高分子学报.&2000, 13(4).&419~422 国家教委留学回国人员科研启动基金资助 O627 01050151 Schiff碱单核及双核配合物拟酶催化性能的研究=Studies on the Biomimetic Catalytic Character of New Schiff Base Mono-and Di-Nuclear Complexes[刊, 中]/陈新斌(湖南大学),朱申杰…∥高等学校化学学报.&2000, 21(7).&1048~1051 国家自然科学基金(29472055)资助 O627 01050152 Cp2TiCl2/BuiMgBr/THF体系还原二芳基二硒醚=Reduction of Diphenyldiselides with Cp2TiCl2/BuiMgBr/THF[刊, 中]/许新华(南开大学),黄宪∥高等学校化学学报.&2000, 21(7).&1073~1074 国家自然科学基金(29672008)资助 O629 01050153 环肽合成方法的研究进展=Progress in the Study on Synthetic Method of Cyclopeptide[刊, 中]/唐艳春(北京大学),田桂玲…∥高等学校化学学报.&2000, 21(7).&1056~1063 介绍了纯环肽与杂环肽合成的方法、策略及其优缺点,列举了一些常用缩合试剂,探讨了反应溶液浓度、线型肽前体化合物的结构及构象等因素对环化反应的影响.参64 国家自然科学基金(29772001)资助 O63 01050154 N-异丙基丙烯酰胺/N-乙烯基吡咯烷酮水凝胶的研究=Synthesis and Characterization of Copolymer Hydrogels of Poly(N-Isopropylacrylamide-co-N-Vinyl-2-Pyrrolidone)[刊, 中]/刘郁杨(西北工业大学),范晓东…∥功能高分子学报.&2000, 13(4).&380~384 陕西省自然科学基金资助 O63 01050155 组织工程细胞支架及其细胞亲和性改进研究进展=Cells Scaffold for Tissue Engineering and Improvement of Cells Affinity between the Cells and Cells Scaffold[刊, 中]/杨健(中科院化学所),贝建中…∥功能高分子学报.&2000, 13(4).&455~460 国家"973计划” O63 01050156 新型的乙烯聚合催化剂=Novel Catalysts for Ethylene Polymerization[刊, 中]/罗祥(中山大学),伍青∥功能高分子学报.&2000, 13(4).&481~486 广东省自然科学基金资助 O631 01050157 衣康酸对聚丙烯腈原丝结构和性能的影响=Effect of Itaconic Acid on the Structure and Properties of PAN Precursor[刊, 中]/张旺玺(山东工业大学)∥高分子学报.&2000, (3).&287~291 控制单体配比,采用丙烯腈与衣康酸自由基溶液共聚,以偶氮二异丁腈为引发剂在溶剂二甲基亚砜中合成了聚丙烯腈原丝纺丝溶液,并纺制了碳纤维前驱体聚丙烯腈原丝.通过元素分析、IR、DSC、13C-NMR等手段,讨论了共聚单体衣康酸对共聚反应及聚丙烯腈原丝结构和性能的影响.图3表3参11 国家自然科学基金(59783002)资助 O631 01050158 Cr(Ⅱ)与过氧化莰烷酮酰体系引发的活性自由基聚合反应研究=Study on "Living” Radical Polymerization Initiated by Aged Chronum (Ⅱ) Acetate and Ketopinyl Peroxide[刊, 中]/李增昌(中国科学技术大学),吴承佩…∥高分子学报.&2000, (3).&330~334 合成了过氧化莰烷酮酰(KPO),用它和Cr(Ac)2组成的氧化还原体系经陈化后,引发甲基丙烯酸甲酯,甲基丙烯酸β-羟乙酯和丙烯酸进行了聚合反应.其中甲基丙烯酸甲酯具有活性聚合特征.并有效引发含羟基单体如甲基丙烯酸β羟乙酯和丙烯酸进行聚合.图2表4参10 国家自然科学基金(29774027)资助 O631 01050159 MgCl2负载(dbm)2Ti(OPh)2催化乙烯聚合=Ethylene Polymerization with MgCl2-Supported(dbm)2Ti(OPh)2[刊, 中]/阎卫东(中科院化学所),洪瀚…∥高分子学报.&2000, (3).&358~360 报道了用MgCl2负载的二苯氧基二(二苯甲酰甲烷)钛铬合物(dbm)2Ti(OPh),以甲基铝氧烷为助催化剂,常压催化乙烯聚合的结果.图1表2参8 国家自然科学基金(29734141)重点资助 O631 01050160 单分散聚苯乙烯乳胶有序膜在二氧化硅多孔材料制备中的模板作用=Template Effects of the Ordered Film Formed from Monodispersed Polystyrene Latex[刊, 中]/杨振忠(中科院化学所),齐凯…∥高分子学报.&2000, (3).&364~367 以单分散聚苯乙烯乳胶室温形成的有序膜为模板,采用快速溶胶凝胶方法,制备了聚苯乙烯/二氧化硅杂化物,高温烧蚀除去有机物得到了二氧化硅有序孔材料,并讨论了聚苯乙烯有序膜的模板作用机理.图5参15 国家自然科学基金(29774038)资助 O631 01050161 新型含环氧端基聚芳醚酮的合成及表征=Synthesis and Characterization of a Novel Epoxy-Terminated Poly(Aryl Ether Ketoe)[刊, 中]/宣英男(大连理工大学),蹇锡高…∥高分子学报.&2000, (4).&407~410 国家"九五”攻关项目 O631 01050162 超支化聚(胺-酯)的分子设计及其制备=Synthesis and Characterization of Hyperbranched Poly(Amine-Ester)[刊, 中]/陆玉(中国科学技术大学),林德…∥高分子学报.&2000, (4).&411~414 国家自然科学基金(59673026)资助 O631 01050163 聚苯基单醚喹C023啉薄膜的性能与物理老化=The Relations between Properties and Physical Aging of Polyphenylquinoxaline Film[刊, 中]/刘万军(中科院化学所),沈静姝…∥高分子学报.&2000,(4).&415~419 国家科委基础性研究重大项目 O631 01050164 端基附壁模型聚合物环形链的构象统计理论=Configurational Statistics of Model Polymer Loop Chains Attached to a Surface[刊, 中]/廖琦(四川大学),吴大诚∥高分子学报.&2000,(4).&420~425 国家自然科学基金(29774016)资助 O631 01050165 拉格朗日-欧拉方法模拟高分子复杂流体平面收缩流动=The Lagrangian-Eulerian Method:Solutions for Planar Contraction Flow[刊, 中]/李险峰(中科院化学所),袁学锋…∥高分子学报.&2000,(4).&432~437 国家自然科学基金(29634030)资助 O631 01050166 气体膜分离用过渡金属有机络合物-聚酰亚胺杂化材料的研究=Study on Transitional Metal Organic Complex-Polyimide Hybrid Material for Gas Separation Membranes[刊, 中]/史德青(石油大学),孔瑛…∥高分子学报.&2000,(4).&457~461 科技部国家重点基础研究发展规划项目 O631 01050167 原子转移自由基聚合制备聚(丙二醇-g-苯乙烯)=Synthesis of Poly(Propylene Glycol-g-Styrene) from Atom Transfer Radical Polymerization[刊, 中]/黄昌国(华东理工大学),万小龙…∥高分子学报.&2000,(4).&467~471 国家自然科学基金(29634010)资助 O631 01050168 聚苯胺嵌入氧化石墨复合物的合成及表征=Synthesis and Characterization of Polyaniline Intercalated Graphite Oxide Composite[刊, 中]/刘平桂(北京航空材料研究院),龚克成∥高分子学报.&2000,(4).&492~495 国家自然科学基金(59836230)资助 O631 01050169 乙交酯/丙交酯共聚物的体内外降解行为及生物相容性研究=Study on the Biocompatibility and Degradation Behavior of Poly(l-Lactide-co-Glycolide) in vitro and in vivo[刊, 中]/蔡晴(中科院化学所),贝建中…∥功能高分子学报.&2000, 13(3).&249~254 国家重点基础研究发展规划(973)资助 O631 01050170 动态下HTDB/TDI体系凝胶化的研究=Study on the Gelation of Hydroxy-Teminated Polybutadiene/Diisocyanate Blends under Dynamic Condition[刊, 中]/邱方正(华东理工大学),陈建定∥功能高分子学报.&2000, 13(3).&289~292 国家教育部博士点基金资助 O631 01050171 含偶氮苯生色团的聚醚的合成与热致液晶性质=Synthesis and Thermotropic Liquid Crystalline Properties of Two Polyethers Containing Azobenzene Groups[刊, 中]/梁旭霞(中山大学),张灵志…∥功能高分子学报.&2000, 13(3).&277~284 广东省自然科学基金资助 O631 01050172 CoSalphen在壳聚糖上的固定化及对DOPA的催化氧化研究=CoSalphen Immobilized onto Chitosan and Its Activate in Catalytic Oxidation of DOPA[刊, 中]/马会宣(陕西师范大学),胡道道…∥功能高分子学报.&2000, 13(3).&301~305 陕西省自然科学基金资助 O631 01050173 环氧基活化凝胶的开环反应=Ring-Opening Reaction on Epoxy-Activated Resin[刊, 中]/查娟(生物反应器工程国家重点实验室),刘坐镇…∥功能高分子学报.&2000, 13(3).&321~324 由自制的乙酸乙烯酯-甲基丙烯酸缩水甘油酯-甲基丙烯酸烯丙酯大孔共聚物与氨水反应,实现了环氧基的开环反应.考查了不同的氨水浓度、反应温度和时间对胺化转化率的影响,并测定了形成的伯胺基的pKa值为6.9.图4表1参12 国家自然科学基金(29706002)资助 O631 01050174 纳米自组装聚电解质超薄多层膜=Polyelectrolyte Ultrathin Multilayer Films by Nano-Self-Assembly Process[刊, 中]/孙启龙(华南理工大学),王朝阳∥功能高分子学报.&2000, 13(3).&332~336 国家杰出青年科学基金(29725411)与国家自然科学基金(29804003)资助 O631 01050175 十二烷基硫酸钠减慢二苯胺-4-重氮盐及重氮树脂在水溶液中热分解反应的机理=The Mechanism of Thermal Decomposition of DDS and DR in Aqueous Solution Delayed by SDS[刊, 中]/杨伯C025(北京大学),曹维孝∥高等学校化学学报.&2000, 21(6).&969~975 国家自然科学基金(59633110及29774001)资助 O631 01050176 芘标记磺酸基聚电解质在水与DMSO中的荧光光谱=Fluorescence Spectra of Pyrene Labeled Polyelectrolytes with Sulfonate Groups in Water and DMSO[刊, 中]/高峰(华南理工大学),严宇…∥高等学校化学学报.&2000, 21(6).&976~979 国家自然科学基金(29804003)与国家杰出青年科学基金(29725411)资助 O631 01050177 尼龙1012的Brill转变=Brill Transition of Nylon 1012[刊, 中]/李勇进(上海交通大学),颜德岳…∥高等学校化学学报.&2000, 21(6).&983~984 国家自然科学基金(29974017)资助 O631 01050178 热致液晶含氯侧基聚芳醚酮的单晶状条带织构=The Single Crystal-Like Banded Textures in the Films of a Thermotropic Liquid Crystalline Poly(Aryl Ether Ketone) Containing a Lateral Chloro Group[刊, 中]/富露祥(中科院长春应用化学所),张善举…∥高等学校化学学报.&2000, 21(6).&988~990 国家自然科学基金(29974032)资助 O631 01050179 具有RAFT链转移过程的活性自由基聚合的Monte Carlo模拟=Monte Carlo Simulation on Living Radical Polymerization with RAFT Process[刊, 中]/李莉(复旦大学),何军坡…∥高等学校化学学报.&2000, 21(7).&1146~1148 国家自然科学基金资助 O631 01050180 C60-苯乙烯-顺丁烯二酸酐的三元自由基共聚=Free Radical Ternary Copolymerization of C60 with Styrene and Maleic Anhydride[刊, 中]/官文超(华中理工大学),雷洪…∥高等学校化学学报.&2000, 21(7).&1149~1150 国家自然科学基金(29674010)资助 O631 01050181 聚(苯乙烯-b-2-甲基-2-C023唑啉)嵌段共聚物的合成=Studies on Synthesis of P(S-b-Me-OXZ) Block Copolymers[刊, 中]/刘燕飞(华东理工大学),万小龙…∥高等学校化学学报.&2000, 21(7).&1157~1159 国家自然科学重点基金(29634010-2)资助 O631 01050182 乙丙共聚物接枝马来酸酐反应机理的模拟研究=Investigation of Reaction Mechanism of Maleic Anhydride Grafted onto Ethylene-Propylene Copolymer[刊, 中]/黄宏亮(中科院长春应用化学所),姚占海…∥应用化学.&2000, 17(3).&256~259 国家自然科学基金(59873022)资助 O631 01050183 稀土催化丁二烯-异戊二烯共聚合过程中的原位环化反应=In situ Cyclization in the Course of Butadiene Isoprene Copolymerization with Nd-Based Catalyst[刊, 中]/董为民(中科院长春应用化学所),逄束芬…∥应用化学.&2000, 17(3).&272~275 国家自然科学基金(29574179)资助 O631 01050184 计算机模式识别在颜料表面改性中的应用=Study on the Application of Pattern Recognition with a Computer in Surface Modification of Pigment[刊, 中]/严乐美(天津大学),杨桂琴…∥天津大学学报.&2000, 33(3).&344~347 国家自然科学基金(29376254)资助 O631 01050185 共混物中聚氯乙烯凝胶化度测试=Studies on Gelling Value of Polyvingyl Chloride in the Blend[刊, 中]/何本桥(湖北大学),张玉红…∥湖北大学学报(自然科学版).&2000, 22(4).&367~370 湖北省自然科学基金资助 O631 01050186 二氧化硅模板技术制备三维有序聚苯乙烯孔材料[刊, 中]/容建华(中科院化学所),杨振忠…∥科学通报.&2000, 45(15).&1627~1630 以单分散二氧化硅颗粒形成的有序结构为模板,制备了聚苯乙烯孔材料.通过扫描电子显微镜观察了模板、复合物及有序多孔聚苯乙烯的形态.结果表明,所合成的多孔材料中,孔大小均匀,空间排布高度有序,且结构与模板中二氧化硅小球自组装方式完全相同.图6参8 国家自然科学基金(20023003)资助 O631 01050187 光导性偶氮聚合物材料的设计[刊, 中]/周雪琴(浙江大学),陈红征…∥自然科学进展.&2000, 10(6).&543~548 以电荷转移理论为指导,对偶氮聚合物材料结构进行设计,获得了两类光导性偶氮聚合物材料,并对其结构和光导性进行了分析与讨论.图4表1参16 国家自然科学基金(59333071,69890230)资助 O631 01050188 聚合物复合材料中填料的摩擦学作用=Tribological Actions of Filiers in Polymer Composites[刊, 中]/薛群基(中科院兰州化学物理所),阎逢元∥中国科学基金.&2000, 14(4).&211~215 综述了就填料对聚合物复合材料的结构和摩擦学行为的影响,并对目前研究过程中所存在的问题进行了简要分析.图3参29 国家自然科学基金资助 O633 01050189 双马来酰亚胺树脂链结构对熔点和反应活性的影响=The Effect of Chain Structure of Bismaleimide Resins on Melting Point and Reactivity of Reaction[刊, 中]/刘润山(湖北省化学研究所),赵三平…∥功能高分子学报.&2000, 13(4).&487~493 湖北省自然科学基金资助 O636 01050190 高分子固体电解质材料研究进展=Advances in Material of Solid Polymer Electrolytes[刊, 中]/赵地顺(河北科技大学),孙凤霞…∥功能高分子学报.&2000, 13(4).&469~475 河北省自然科学基金资助 O64 01050191 Ru(bpy)2(NCS)2染料敏化CdS/Zn2+-TiO2复合半导体纳米多孔膜的光电化学=Photoelectrochemistry of CdS/Zn2+-TiO2 Composite Semiconductor Nanoporous Films Sensitized by Ru-(bpy)2(NCS)2 Dye[刊, 中]/张莉(北京大学),王艳芹…∥高等学校化学学报.&2000, 21(7).&1075~1079 国家自然科学基金(29773003)资助 O641 01050192 富勒烯笼结构的平面展示法[刊, 中]/叶大年(中科院地质与地球物理所),艾德生…∥科学通报.&2000, 45(16).&1781~1785 采用船式F5和F6与海燕式F5和F6分别表示富勒烯笼几何结构的两种平面图.这些平面图最大的优点是:(1)不破坏富勒烯笼的空间对称性;(2)可以非常清楚地展示出结构中F5和F6的配位形式.这为富勒烯笼的结构几何研究打下了基础.图3参17 国家自然科学基金(49872019)资助 O641 01050193 布朗扩散系数对胶体分形粒子簇扩散控制聚集动力学影响的Monte Carlo模拟=Monte Carlo Simulation to the Effect of Cluster Brownian Diffusion Coefficient on the Colloidal Fractal Cluster Aggregation Kinetics[刊, 中]/王惠(南开大学),王贵昌…∥高等学校化学学报.&2000, 21(6).&922~925 使用表征粒子簇结构的几何形状因子,通过对扩散控制聚集过程的模拟,从微观或介观层次研究了粒子簇结构对粒子簇增长速率和速率常数的影响规律,并与实验结果进行了对比分析.图4表1参15 国家自然科学基金(29573109)资助 O641 01050194 一些富勒烯C60双加成物稳定性的理论研究=Theoretical Studies on the Stabilities of Some C60 Bis-Adducts[刊, 中]/陈中方(南开大学),王贵昌…∥高等学校化学学报.&2000, 21(7).&1127~1129 国家自然科学基金(29773022)资助 O641 01050195 M(bpy)+32(M=Fe,Ru,Os)电子结构与相关性质=Electronic Structure and Related Chemical Properties of Complexes(M=Fe,Ru,Os)[刊, 中]/郑康成(中山大学),匡代彬…∥物理化学学报.&2000, 16(7).&608~612 报道了对配合物(M=Fe,Ru,Os)的量子化学密度泛函法研究的结果,探讨的电子结构特征及相关性质,特别是中心原子对配合物的配位键长、光谱性质、电荷布居及化学稳定性等的影响规律.图2表6参14 国家自然科学基金资助 O642 01050196 纳米HZSM-5分子筛的热稳定性=Thermostability of Nanosized HZSM-5 Zeolite[刊, 英]/张维萍(中科院大连化物所),包信和∥催化学报.&2000, 21(3).&195~196 科技部攀登计划项目 O642 01050197 微量热法研究硒对大肠杆菌生长代谢的作用=Microcalorimetric Study of the Action of Seleniumcontaining Complexes on Growth Metabolism of Escherichia coli[刊, 中]/李曦(武汉大学),刘义…∥物理化学学报.&2000, 16(6).&568~572 采用微量热法测定了Na2SeO3、吗啉、硒代吗啉和N,N'-亚基双硒代吗啉对大肠杆菌作用的热功率输出曲线,根据热功率输出曲线求算在这些药物作用下,大肠杆菌生长代谢的速率常数,并对它们的作用特征进行了比较.图2表1参7 国家自然科学基金资助 O642 01050198 反相气相色谱法测定溶剂在PBMA中的无限稀释活度系数=Measurement of Infinite Diluted Activity Coefficient of Solvent in PBMA by Inverse Gas Chromatography Method[刊, 中]/冯媛媛(华东理工大学),叶汝强…∥华东理工大学学报.&2000, 26(3).&305~308 用反相气相色谱方法测定了16种溶剂在聚甲基丙烯酸丁酯(PBMA)中343~433K范围内的无限稀释活度系数,并用周浩等的高分子溶液分子热力学模型对实验结果进行了关联,结果令人满意.图8表2参15 国家自然科学基金(29976011)资助 O643 01050199 海泡石对非晶态NiB合金催化剂的改性研究=Studies on the Modification of Sepiolite for Amorphous NiB Alloy Catalyst[刊, 中]/石秋杰(南昌大学),陈昭萍…∥物理化学学报.&2000, 16(6).&501~506 以常压气相苯加氢为探针反应,考察了酸改性前后海泡石的加入对非晶态NiB合金催化剂的加氢及抗硫性能的影响,用TPR、TPD表征了催化剂的表面性质,测定了酸改性前后海泡石的比表面及孔径分布,并与活性进行了关联.图3表3参12 国家自然科学基金资助 O643 01050200 F+NCO反应的机理和动力学=Mechanism and Kinetics of the F+NCO Reaction[刊, 中]/侯华(山东大学),王宝山…∥物理化学学报.&2000, 16(6).&517~521 高等学校博士学科点专项科研基金资助 O643 01050201 激光溅射下原子团簇生长的非平衡力学(Ⅱ)=Non-Equilibrium Kinetics of Clusters Growth under Laser Ablation(Ⅱ)[刊, 中]/曹玉群(厦门大学),黄荣彬…∥物理化学学报.&2000, 16(7).&621~626 国家自然科学基金(29890210,29773040)资助 O643 01050202 双(2,4-二甲基戊二烯基)氯化钆的合成及晶体结构=Synthesis and Structure of Bis(2,4-Dimethylpentadienyl)Gadolinium Chloride[刊, 中]/王建辉(吉林大学),母瀛…∥高等学校化学学报.&2000, 21(6).&829~831 国家自然科学基金(29672013,29754143)资助 O643 01050203 温控相转移催化&&水/有机两相催化新进展=Thermoregulated Phase-Transfer Catalysis&&Recent Advances in Water/Organic Biphasic Catalysis[刊, 中]/金子林(大连理工大学),梅建庭…∥高等学校化学学报.&2000, 21(6).&941~946 综述了"温控相转移催化”的原理,温控膦配体的设计、合成及其在水溶性极小的底物高碳烯烃的水/有机两相氢甲酰化反应中的应用效果.图4表5参35 国家自然科学基金(29792074)资助 O643 01050204 Cr-HMS合成、表征及其在催化氧化反应中的应用=Synthesis, Characterization of Cr-HMS and the Application in Catalytic Oxidation[刊, 中]/乐洪咏(复旦大学),华伟明…∥高等学校化学学报.&2000, 21(7).&1101~1104 合成了一系列不同Cr含量的Cr-HMS介孔分子筛,并对其物化性质进行了表征.结果表明,Cr的引入降低了介孔分子筛骨架结构的规整度和孔径的均一程度.Cr-HMS对苯羟基化和环己烷氧化反应均表现出良好的催化活性.并且随Cr含量的增加,催化活性呈火山型分布.图3表3参14 国家自然科学基金(29873011)资助 O643 01050205 新型甲烷无氧芳构化催化剂MoO3/MCM-49=A Novel Catalyst of MoO3/MCM-49 over Nonoxidative Aromatization of CH4[刊, 中]/许宁(吉林大学),阚秋斌…∥高等学校化学学报.&2000, 21(7).&1113~1114 国家自然科学基金(29973011)资助 O643 01050206 以TiCl4为钛源合成钛硅分子筛=Synthesis of Titanosilicalite Using Titanium Tetrachloride as Titanium Source[刊, 英]/张义华(大连理工大学),王祥生∥催化学报.&2000, 21(3).&197~198 以四丙基溴化铵为模板剂,以四氯化钛为钛源,研究了合成小晶粒钛硅分子筛(TS-1)的合成路线.合成的TS-1样品在丙烯环氧化反应中显示有较高的活性(96%)和选择性(95%),H2O2利用率高于95%.图3表1参8 国家自然科学基金(29792071)资助 O643 01050207 稀土氧化物在Fe1-xO基氨合成催化剂中的作用规律=Regular Effect of Rare Earth Oxide on Fe1-xO Catalyst for Ammonia Synthesis[刊, 中]/季德春(浙江工业大学),李小年∥催化学报.&2000, 21(3).&199~203 考察了稀土氧化物对Fe1-xO基催化剂性能的影响.结果表明,稀土氧化物与Fe1-xO作用生成一种复合氧化物REFeO3,从而促进了催化剂的还原,这种促进作用随稀土离子半径不同呈现规律性变化.图1表6参14 国家自然科学基金(29706011)资助 O643 01050208 光电催化降解磺基水杨酸的研究=Study of Photoelectrocatalytic Degradation of Sulfosalicylic Acid[刊, 中]/刘鸿(中科院大连化学物理所),冷文华∥催化学报, 21(3).&209~212 建立了以TiO2/Ni为工作电极、泡沫镍为对电极、饱和甘汞电极为参比电极的光电催化反应体系,研究了在磺基水杨酸(SSal)的光电催化降解过程中,外加电压和溶液pH值对降解速率的影响.图5表1参18 国家自然科学基金(29877024)资助 O643 01050209 多孔TiO2薄膜的表面微结构对甲基橙光催化脱色的影响=Effect of Surface Microstructure of Porous TiO2 Thin Films on Photocatalytic Decolorization of Methyl Orange[刊, 中]/余家国(武汉工业大学),赵修建∥催化学报.&2000, 21(3).&213~216 湖北省自然科学基金资助 O643 01050210 γ-Mo2N催化剂上的乙炔选择加氢=Selective Hydrogenation of Ethyne on γ-Mo2N[刊, 中]/郝志显(中科院大连化学物理所),魏昭彬∥催化学报.&2000, 21(3).&217~220 对γ-Mo2N催化剂上乙炔加氢反应进行了研究.在150℃的反应温度下,乙炔转化率为95%,乙烯选择性达80%,乙烷选择性为4%,丁烯选择性为10%.反应温度和空速对产物的选择性没有明显的影响.图4参17 国家自然科学基金(29625305)资助 O643 01050211 WO3/ZrO2固体强酸催化剂上异丁烷/丁烯的烷基化反应:Ⅱ.过渡金属的助催化作用=Study on Alkylation of Isobutane with Butene over WO3/ZrO2 Strong Solid Acid:Ⅱ. Promotions Effect of Transition Metal[刊, 中]/孙闻东(中科院长春应用化学所),吴越∥催化学报.&2000, 21(3).&229~233 制备了一系列用过渡金属活化的WO3/ZrO2固体强酸催化剂,并对其晶型结构、表面状态和酸量进行了表征.图7表2参22 国家自然科学基金(29792076)资助 O212 01050212 超细镍基催化剂上CH4-CO2重整反应的性能:Ⅰ.制备方法对催化剂结构和还原性能的影响=CH4 Reforming with CO2 over Superfine Ni-Based Catalysts:Ⅰ. Effects of Preparation Methods on Structure and TPR of Catalysts[刊, 中]/许峥(清华大学),张鎏∥催化学报.&2000, 21(3).&234~238 国家博士点基金资助 O643 01050213 SO2对Co3O4/Al2O3选择性催化氧化NO的影响=Effect of SO2 on Catalytic Oxidation of NO over Co3O4/Al2O3[刊, 中]/赵秀阁(华东理工大学),肖文德∥催化学报.&2000, 21(3).&239~242 采用流动态原位IR,TPD及XPS技术研究了NO及SO2在Co3O4/Al2O3金属氧化物催化剂表面上的吸附及脱附行为,并与该催化剂上模拟烟道气中NO的选择性催化氧化活性相关联,考察了SO2对该反应过程的影响及作用机理.图5参13 国家自然科学基金(29633030)资助 O643 01050214 Lewis酸对杂多酸催化异丁烷/丁烯烷基化反应的作用=Effect of Lewis Acid on Alkylation of Isobutane with Butene[刊, 中]/赵振波(中科院长春应用化学所),吴越∥催化学报.&2000, 21(3).&243~246 考察了SbCl5对杂多酸(HPA)催化异丁烷/丁烯烷基化反应的修饰作用,用Hammett指示剂测定了SbCl5/HPA催化剂的酸强度.结果表明,经SbCl5修饰的HPA的酸强度有所提高,SbCl5的加入量、反应温度及反应时间对烷基化油收率及产物分布均有不同的影响.图5表2参15 国家自然科学基金(29792076)资助 O643 01050215 微波固相法制备的ZnCl2/Y在α-蒎烯环氧化物重排反应中的催化性能=Catalytic Performance of ZnCl2/Y Catalyst Prepared by Solid-State Microwave Irradiation for Rearrangement Reaction of α-Pinene Oxide[刊, 中]/尹笃林(湖南师范大学),银董红∥催化学报.&2000, 21(3).&251~254 国家自然科学基金(29572042,29972011)资助 O643 01050216 Co-Mo/HZSM-5甲烷无氧芳构化催化剂上的积炭=Characterization of Coke on Co-Mo/HZSM-5 Catalyst for Methane Dehydro-Aromatization in the Absence of Oxygen[刊, 中]/田丙伦(中科院大连化学物理所),徐奕德∥催化学报.&2000, 21(3).&255~258 国家重点基础研究发展规划项目 O643 01050217 热处理改性的活性炭纤维的脱硫活性=Desulfurization Activity of Activated Carbon Fiber Modified by Heat Treatment[刊, 中]/李开喜(中科院山西煤炭化学所),凌立成∥催化学报.&2000, 21(3).&264~268 考察了在O2和水蒸气存在下高温热处理对活性炭纤维(ACF)催化转化SO2为H2SO4的活性的影响,关联了ACF表面含氧官能团的种类及数量与其脱硫活性之间的关系.图4表2参20 国家自然科学基金(29633030)资助 O643 01050218 制备方法对锶改性氧化铝的高温热稳定性的影响=The Influence of Preparation Methods on the Thermal Stability of Alumina Modified by Strontium[刊, 中]/刘勇(复旦大学),陈晓银∥催化学报.&2000, 21(3).&273~275 福特-中国研究与发展基金资助 O643 01050219 NO在氧化铝负载的Pd催化剂上吸附的TPD-MS研究=TPD-MS Study of NO Adsorption on Alumina Supported Pd Catalysts[刊, 中]/刘振林(中国科技大学),伏义路∥催化学报.&2000, 21(3).&279~282 福特-中国研究与发基金资助项目 O643 01050220 不同焙烧气氛对氟化镁表面碱性的影响=The Effect of Different Calcination Atmosphere on the Surface Basicity of Magnesium Oxide[刊, 中]/孟明(中国科技大学),林培琰∥催化学报.&2000, 21(3).&286~288 在不同气氛中600℃下焙烧Mg(OH)2制得了MgO样品.结果表明,Mg(OH)2经焙烧后分解为MgO.样品的比表面积受焙烧气氛的影响,真空中制备的样品比表面积最大,而空气中制备的样品比表面积最小.真空中制备的样品具有最多的碱位和最强的碱性.图3表2参8 国家自然科学基金(29973037)资助 O643 01050221 Ni改性Cu/Mn/ZrO2催化剂上合成低碳混合醇的研究=Synthesis of Mixed Higher Alcohols by CO Hydrogenation over Ni-Modified Cu/Mn/ZrO2 Catalyst[刊, 中]/陈小平(中科院山西煤炭化学所),吴贵升∥催化学报.&2000, 21(4).&301~304 国家自然科学基金(29873064)资助 O643 01050222 超细镍基催化剂上CH4-CO2重整反应的性能:Ⅱ.制备方法对催化和抗积碳性能的影响=CH4 Reforming with CO2 over Superfine Ni-Based Catalysts:Ⅱ.Effects of Preparation Methods on Reactivity and Carbon Deposition over Catalysts[刊, 中]/许峥(清华大学),张鎏∥催化学报.&2000, 21(4).&309~313 国家博士点基金资助 O643 01050223 合成甲基叔丁基醚的分子筛催化剂研究=A Study of Zeolite Catalysts for Synthesis of Methyl tert-Butyl Ether[刊, 中]/李永红(天津大学),王莅∥催化学报.&2000, 21(4).&323~326 中国石油化工集团公司资助 O643 01050224 二苯并噻吩在CoMoNx催化剂上的加氢脱硫=Hydrodesulfurization of Dibenzothiophene over Cobalt-Promoted Molybdenum Nitride Catalysts[刊, 中]/柳云骐(石油大学),刘晨光∥催化学报.&2000, 21(4).&337~340 中国石油天然气集团公司资助 O643 01050225 锆助剂含量对钴基费-托合成催化剂的影响=Effect of ZrO2 Loadings on Catalytic Performance of Co/SiO2 for F-T Synthesis[刊, 中]/陈建刚(中科院山西煤炭化学所),相宏伟∥催化学报.&2000, 21(4).&359~362 国家重点基础研究发展规划项目 O643 01050226 一种天然气直接转化制乙烯的新过程=A Novel Process for Direct Conversion of Natural Gas to Ethylene[刊, 英]/朱爱民(中科院大连化物所),田志坚∥催化学报.&2000, 21(4).&395~396 国家科技部资助项目 O643 01050227 N,N-二甲基胺乙基膦酸-磷酸氢锆为载体的新型固体碱研究=Study on Solid Base Supported on Zirconium Dimethyl Aminoethylphosphonate-Phosphate[刊, 中]/龚成斌(中科院大连化学物理所),曾仁权…∥应用化学.&2000, 17(3).&264~267 国家自然科学基金资助 O643 01050228 丙烷在钒-磷混合氧化物催化剂上晶格氧氧化及其循环流化床工艺=Oxidation of Propane over Vanadium-Phosphorus Oxides Catalyst by Lattice Oxygen and Its Circulating Fluidized Bed Process[刊, 中]/王鉴(浙江大学),赵如松…∥应用化学.&2000, 17(3).&313~315 用脉冲色谱研究了丙烷在钒-磷混合氧化物催化剂上的选择氧化反应,并结合TPD和XRD表征结果,证明丙烷是与催化剂的晶格氧反应生成丙烯酸和乙酸.图2参5 国家自然科学基金(29676007)资助 O643 01050229 用以分解氟里昂-12的新型催化剂WO3/Al2O3=A Novel Catalyst WO3/Al2O3 for Decomposition of CFC-12[刊, 中]/马臻(复旦大学),华伟明…∥应用化学.&2000, 17(3).&319~321 国家科委攀登计划资助 O643 01050230 LaFeO3的光催化性=Photocatalytic Activity of LaFeO3[刊, 中]/白树林(天津大学),付希贤…∥应用化学.&2000, 17(3).&343~345 采用柠檬酸法和微乳液法制备纳米晶LaFeO3.结果表明,微乳液法较柠檬酸法制备的LaFeO3粒径小,表面积大,使LaFeO3吸附性增加,因此表现出较强的光催化活性.图2表1 国家自然科学基金(59772019)资助 O643 01050231 NiO/SiO2催化剂上CO氧化的反应机理研究=Mechanism of CO Oxidation on NiO/SiO2 Catalyst[刊, 中]/王远洋(宁夏大学),高荫本…∥宁夏大学学报(自然科学版).&2000, 21(2).&147~149 NiO/SiO2是优良的非贵金属型CO氧化催化剂,EXAFS和TPR表征表明其活性中心为NiO.在此基础上的Monte Carlo模拟表明,在NiO/SiO2上CO氧化遵循L-H机理.图5参11 国家自然科学基金(29803009)资助 O643 01050232 烯基取代的茂钛族络合物合成及应用于烯烃催化聚合的进展=Recent Advances in the Synthesis of Alkenyl Substituted Metallocene Complexes(Ti,Zr,Hf) and the Application of Its to α-Olefins Polymerization[刊, 中]/钱贤苗(华东理工大学),许胜…∥功能高分子学报.&2000, 13(3).&358~366 综述了含烯基取代基的茂钛族络合物的合成,取代基上双键的化学反应,以及在α-烯烃催化聚合上的最新进展.表2参45 国家自然科学基金(29871010)资助 O643 01050233 氧化态Co/γ-Al2O3催化剂的结构与反应性能研究:Ⅱ.钴物种微观结构的XAFS表征=Studies on the Structures and Catalytic Properties of Oxidized Co/γ-Al2O3 Catalysts:Ⅱ.XAFS Characterizations of the Micro-Structures of Co Species[刊, 中]/孟明(中国科学技术大学),林培琰…∥分子催化.&2000, 14(3).&161~165 采用X-射线吸收近边结构与扩展X-射线吸收精细结构技术,对用不同原料盐和不同焙烧温度制得的Co/γ-Al2O3催化剂中钴的微观结构进行了详细的表征.图5表1参8 国家自然科学基金(29973037)资助 O643 01050234 CuCl/γ-Al2O3上NO脱除过程研究=Reaction Mechanism of NO Conversion over CuCl/γ-Al2O3[刊, 中]/朱月香(北京大学),尉继英…∥分子催化.&2000, 14(3).&166~170 设计了一系列的对比实验,利用XRD、XPS、TPR、EXAFS等技术,系统研究了CuCl/γ-Al2O3上的NO脱除反应过程.图4表1参8 国家自然科学基金(29733080)资助 O643 01050235 以Au(PPh3)(NO3)为前体的Au/NiO催化剂的制备及其对CO的催化氧化=Preparation and Catalytic Performance of Au/NiO Catalyst Derived from Au(PPh3)(NO3) for CO Oxidation[刊, 中]/邹旭华(烟台大学),齐世学…∥分子催化.&2000, 14(3).&171~174 采用有机金属配合物固载法,将金的有机配合物Au(PPh3)(NO3)沉积于刚制备出的Ni(OH)2沉淀上.结果表明,以K2CO3作为制备Ni(OH)2的沉淀剂,金担载量为3%(质量分数)在焙烧温度为300℃的条件下,制备出的负载型金催化剂Au/NiO对CO的低温氧化有很高的催化活性.图2表3参15 国家自然科学基金(29873041)资助 O643 01050236 CexZr1-xO2复合氧化物负载PdO催化剂的CO和CH4氧化性能研究=CO and Methane Oxidation over CexZr1-xO2 Mixed Oxide Supported PdO Catalysts[刊, 中]/马磊(浙江大学),韩立峰…∥分子催化.&2000, 14(3).&175~178 浙江省自然科学基金资助 O643 01050237 溶胶-凝胶法镍基催化剂的研究&&Ti/Si原子比对NiO-TiO2-SiO2结构和苯加氢性能的影响=Study of the Nickel Catalysts Prepared by Sol-Gel Method&&The Effects of Si/Ti Atomic Ratios on the Structure and Catalytic Performance for Benzene Hydrogenation of NiO/TiO2-SiO2[刊, 中]/朱毅青(江苏石油化工学院),林西平…∥分子催化.&2000, 14(3).&184~190 中石化集团公司资助课题 O643 01050238 (NH4)15[La(PMo9V2O39)2]*6H2O杂多配合物对苯酚羟化的催化作用=Catalytic Activity of (NH4)15[La(PMo9V2O39)2]*6H2O Heteropoly Complex in Phenol Hydroxylation with Hydrogen Peroxide[刊, 中]/林深(福建师范大学),郑瑛…∥分子催化.&2000, 14(3).&191~194 福建省科委资助项目 O643 01050239 Co改性Mo/HZSM-5催化剂上甲烷无氧芳构化反应研究=Methane Dehydro-Aromatization over Cobalt Modified Mo/HZSM-5 Catalysts in the Absence of Oxygen[刊, 中]/田丙伦(中科院大连化学物理所),刘红梅…∥分子催化.&2000, 14(3).&200~204 国家重点基础研究发展规划项目 O643 01050240 甲醇催化氧化重整反应制氢的研究=Hydrogen Production by Catalytic Oxidation and Reforming of Methanol[刊, 中]/陈兵(华南理工大学),董新法…∥分子催化.&2000, 14(3).&205~208 广东省高教厅自然科学基金资助 O643 01050241 TiO2催化Cr(Ⅵ)-氯代苯酚共存体系中Cr(Ⅵ)的光致还原=Photo-Induced Cr(Ⅵ) Reduction in Cr(Ⅵ)-4CP Coexist Pollution System in the Presence of TiO2 Photocatalyst[刊, 中]/付宏祥(中科院兰州化学物理所),吕功煊…∥分子催化.&2000, 14(3).&214~218 中科院重大项目资助 O643 01050242 三磺化三苯基膦(TPPTS)制备方法的改进=Improvement of Synthesis Method of TPPTS[刊, 中]/张敬畅(北京化工大学),曹维良…∥分子催化.&2000, 14(3).&223~226 国家"九五”科技攻关项目 O644 01050243 预处理对TiO2表面超亲水性的影响=Effect of Pretreatment on Superhydrophilicity of TiO2 Films[刊, 中]/管自生(中科院化学所),马颖∥感光科学与光化学.&2000, 18(3).&204~207 在高温度环境下,应用紫外光辐射对溶胶-凝胶TiO2薄膜预处理,经过预处理的薄膜烧结后具有快速光致高度亲水特性和良好的光催化活性.超亲水的薄膜能够吸附大量的酸性品红,在光照下薄膜将吸附的酸性品红逐渐降解掉.图3参6 国家自然科学基金(59932040)重点资助 O644 01050244 荧光探针在测定N-异丙基丙烯酰胺共聚物最低临界溶液温度(LCST)时的扩散过程=The Diffusion Process of Fluorescence Probe in Measurement of LCST of Poly(N-Isopropylacrylamide-co-Acrylamide) Aqueous Solution[刊, 中]/李俊(中科院感光化学所),史向阳∥感光科学与光化学.&2000, 18(3).&208~213 合成了多种不同配比的N-异丙基丙烯酰胺(NIPAM)与丙烯酰胺(AM)的共聚物.研究了共聚物溶液在温度变化过程中发生的线团-胶粒转变,及荧光探针分子扩散进入疏水胶粒的动力学过程.图3表2参9 国家自然科学基金(29733100)资助 O644 01050245 蒽醌冠醚铕离子络合物分子内能量转移=Intramolecular Energy Transfer in Anthraquione Crown Ether-Eu3+ Complex[刊, 中]/江华(中科院感光化学所),许慧君∥感光科学与光化学.&2000, 18(3).&223~228 研究结果表明,选择性激发铕离子络合物中的蒽醌冠醚能发生分子内能量转移,观察到铕离子的发光.荧光衰减测试表明,由于冠醚的包络作用使得铕离子络合物的荧光寿命较未络合铕离子的寿命有所延长.图5表1参10 国家自然科学基金(29733100)资助 O644 01050246 有机染料光褪色机理及主要原因=The Mechanism and Main Reasons of Photofading of Organic Dyes[刊, 中]/于新瑞(大连理工大学),张淑芬∥感光科学与光化学.&2000, 18(3).&243~253 综述了有机染料光褪色机理的主要研究方法以及现有研究结论.对光氧化和光还原过程、影响因素、典型反应步聚、研究手段进行了系统的阐述,同时也对通过染料分子结构设计合成、通过添加剂的使用提高染料光牢度的方法进行了介绍.图4表3参29 国家自然科学基金重点基金(29836150)资助 O644 01050247 荧光分子开关的研究进展=The Progress of the Research on Fluorescent Molecular Switches[刊, 中]/甘家安(华东理工大学),陈孔常∥感光科学与光化学.&2000, 18(3).&254~262 根据开关动作完成的方式对近年来研究的各类荧光分子开关进行了简要的归类总结,并介绍了一些具有特殊功能的荧光分子开关器件.图8参33 国家自然科学基金(29836150)资助 O644 01050248 半花菁衍生物LB膜的光致荧光特性研究=Photoluminescence Characteristics of Hemicyanine Derivatives in Langmuir Blodgett Multilayers[刊, 中]/王文军(复旦大学),陆兴泽…∥物理化学学报.&2000, 16(6).&496~500 通过改变半花菁的亲水基团与硫水基团而得到了四种半花菁衍生物,利用稳态和时间分辨荧光研究了不同亲水基团与疏水基团对半花菁衍生物光学特性的影响.图1表3参7 国家自然科学基金重点基金(19834030)资助 O644 01050249 N-萘甲基多乙撑多胺类荧光化学敏感器=Fluorescence Chemical Sensor of Naphthylmethyl Polyethylenepolyamine[刊, 中]/梅明华(中科院感光化学所),吴世康∥物理化学学报.&2000, 16(6).&559~562 合成了一类带有萘甲基的多乙撑多胺化合物,对其在不同溶剂中作为FCS检测锌离子时的荧光光谱变化进行了研究.结果表明,两种不同锌盐化合物与配体相互作用时,其所带阴离子对络合物的组成和方式有很大的影响.图2表1参6 国家自然科学基金(29733100)资助 O644 01050250 三聚氰胺甲醛树脂的光学性质=Optical Properties of Melamine Formaldehyde Resin[刊, 中]/刘海波(复旦大学),侯占佳…∥物理化学学报.&2000, 16(6).&563~567 对三聚氰胺甲醛树脂的合成过程、波导制备条件及利用三聚氰胺甲醛树脂作为掺杂基质的非线性光学性质进行了研究.实验结果表明,三聚氰胺甲醛树脂是一种极具有应用前景的光学材料.图3参14 国家自然科学基金(69708005,69808001)资助 O644 01050251 紫菜两个光系统间激发能分配研究对光合进化的启示[刊, 中]/潘洁(中科院化学所),施定基…∥科学通报.&2000, 45(12).&1276~1279 选择两个不同发育阶段(孢子体和配子体)的条斑紫菜作为研究对象.对过多激发能在两个光系统间的分配进行了比较研究.图2参13 国家自然科学基金(39890390,29733100)资助 O644 01050252 非线性光学配合物的化学研究[刊, 中]/左景林(南京大学),游效曾∥科学通报.&2000, 45(14).&1457~1464 从化学角度出发,在分子水平上研究和探索新型分子基非线性光学材料是一个新的研究领域.总结了近年来在新型二阶、三阶极化率和光限制等非线性光学配合物的化学研究方面所取得的进展.图6表2参46 国家自然科学基金(29631040)资助 O644 01050253 螺旋共轭化合物1′,3′,3′-三甲基-6-羟基螺旋[2H-1-苯并吡喃-2,2′-二氢吲哚]的结构、光谱、非线性光学性质和光异构化过程的理论研究=Theoretical Study of the Structures, Spectra, Nonlinear Second-Order Optical Properties and Photoisomerization Process of the Spiroconjugated Compound 1′,3′,3′-Trimethyl-6-Hydroxyspiro[2H-1-Benzopyran-2,2′-Indoline][刊, 中]/孙秀云(吉林大学),封继康…∥高等学校化学学报.&2000, 21(7).&1080~1085 用AM1和ZINDO方法研究了螺旋共轭化合物1′,3′,3′-三甲基-6-羟基螺旋[2H-1-苯并吡喃-2,2′-二氢吲哚](HBPS)及其光导构化产物的结构和光谱性质,从理论上研究了HBPS的光异构化反应过程,并在此基础上,用自编的完全态求和公式(SOS)程序计算了非线性光学系数.图4表7参17 国家自然科学基金(29873016)资助 O644 01050254 Af型自由基均聚反应的固化理论(Ⅲ)&&高分子凝胶网络缺陷=The Curing Theory of Af Type Free Radical Homopolymerization(Ⅲ)&&The Defects of Polymer Gel Network[刊, 中]/王海军(河北大学),赵敏…∥高等学校化学学报.&2000, 21(7).&1138~1141 应用高分子反应统计理论,分析了高分子网络的形成过程,讨论了Af型自由基均聚反应凝胶网络中的缺陷&&悬吊环的数目及其形成几率.图4参22 国家自然科学基金(29673018)资助 O646 01050255 微过氧化物酶-11修饰电极对O2和H2O2的电催化还原=Electrocatalytic Reduction of O2 and H2O2 at the Glass Carbon Electrode Modified with Microperoxidase-11[刊, 中]/杨辉(南京师范大学),黄志忠…∥物理化学学报.&2000, 16(6).&527~532 运用电化学循环伏安法和旋转圆盘电极技术研究了O2和H2O2在Nafion膜固定的微过氧化物酶-11修饰的玻碳电极上的电化学还原.图6参16 国家自然科学基金资助 O646 01050256 电沉积Co-Cu颗粒膜的巨磁电阻效应=Giant Magnetoresistance in Electro-Deposited Co-Cu Granular Film[刊, 中]/李浩华(兰州大学),黎超…∥物理化学学报.&2000, 16(6).&573~576 用电化学沉积法制备了Co-Cu纳米颗粒膜,并对这种膜的结构、磁性、巨磁电阻效应作了较详细的研究.图6参7 国家自然科学基金资助 O646 01050257 磷酸溶液中铝恒压阳极氧化的研究=Investigation of Aluminum Anodizing in Phosphoric Acid Solution at Constant Voltage[刊, 中]/王为(天津大学),郭鹤桐…∥天津大学学报.&2000, 33(3).&341~343 结果表明,随着电解电压的升高,形成的氧化铝多孔膜的阻挡层增厚,多孔层的孔径和胞径均增加,其原因与离子迁移等密切相关.图6参6 国家自然科学基金(69601006)资助 O646 01050258 二次微分简易示波伏安法测定痕量镍=Determination of Trace Nickel by Second-Order Differential Simple Oscillographic Voltammetry[刊, 中]/傅业伟(西北大学),高敏…∥应用化学.&2000, 17(3).&296~299 国家自然科学基金(29775018)资助 O646 01050259 Ml(NiCuAlZn)5储氢合金粉末的包覆处理=Encapsulation of Ml(NiCuAlZn)5 Hydrogen Storage Alloy Powder[刊, 中]/王一菁(南开大学),赵东…∥应用化学.&2000, 17(3).&310~312 国家"八六三”计划资助项目 O646 01050260 和厚朴酚电化学还原机理的研究=Theoretical Study on the Mechanism of Electrochemical Reductions Reaction of Honokiol[刊, 中]/孙成科(曲靖师范高等专科学校),龚思源…∥高等学校化学学报.&2000, 21(6).&912~917 用量子化学AM1、PM3方法研究了和厚朴酚分子的电化学还原反应机理.结果表明,和厚朴酚分子电还原的基团为两个烯丙基的双键,其中邻位烯丙基优先被还原,对位次之,整个还原反应中和厚朴酚得到4e和4H+,使两个烯丙基饱和,计算结果较好地说明了实验事实.图2表7参12 国家自然科学基金(29773007)资助 O646 01050261 Fourier自去卷积示波计时电位法的研究=Oscillographic Chronopotentiometry with Fourier Self-Deconvolution[刊, 中]/郑建斌(西北大学),张红权…∥高等学校化学学报.&2000, 21(7).&1037~1039 国家自然科学基金(29775018)资助 O646 01050262 用规整膜板对砷化镓的三维微结构图形加工刻蚀=Three-Dimensional Microfabrication on GaAs Using a Regular Patterns Mold[刊, 中]/董海苟(厦门大学),孙建军…∥电化学.&2000, 6(3).&253~257 以微齿轮图形结构作为规整模板.用约束刻蚀剂层技术对GaAs样品表面进行了加工刻蚀.在有捕捉剂H3AsO3存在的情况下,规则微齿轮图形能够很好地在样品表面复制.图5参6 国家自然科学基金重点项目(29833070)资助 O646 01050263 混凝土中钢筋的腐蚀行为研究=Corrosion Behavior of Reinforcing Steel in Concrete[刊, 中]/林荣归(厦门大学),胡融刚…∥电化学.&2000, 6(3).&305~310 钢筋在混凝土中受到高碱性环境的保护,耐蚀性好,但随着介质pH的降低、Cl-含量的上升,钢筋腐蚀电流升高;动电位阳极极化曲线的测试表明,钢筋的维钝电流增大,击穿电位负移,混凝土中钢筋的耐蚀性下降.图4表1参6 国家自然科学基金(59871043)资助 O647 01050264 天冬氨酸在Cu(001)表面吸附的扫描隧道显微镜研究=Adsorption of Aspartic Acid on Cu(001) Studied by Scanning Tunneling Microscopy[刊, 中]/王浩(北京大学),赵学应…∥物理学报.&2000, 49(7).&1316~1320 国家自然科学基金(19634010)资助 O647 01050265 共聚高分子吸附的Monte Carlo模拟=Monta Carlo Simulation of Adsorption of Diblock Copolymer at Solid-Liquid Interface[刊, 中]/陈霆(华东理工大学),刘洪来…∥化工学报.&2000, 51(4).&512~518 用Monte Carlo方法对选择性溶剂中两嵌段共聚高分子在固液界面的吸附进行了模拟,获得了吸附等温线以及吸附层厚度、链附着率、表面覆盖率、链节浓度分布等表征吸附层结构的信息,同时模拟获得了固液界面区吸附构型大小及分布等表征高分子构型的微观信息.图12表1参10 国家自然科学基金(29736170)资助 O647 01050266 无规共聚高分子溶液相平衡的Monte Carlo模拟=Monte Carlo Simulations of Phase Equilibria of Random Copolymer Solutions[刊, 中]/陈霆(华东理工大学),刘洪来…∥化工学报.&2000, 51(4).&552~554 用构型偏倚蒸发Monte Carlo方法模拟研究了密堆积格子模型上A、B无规共聚高分子的相平衡问题,无规共聚高分子中链节A、B以不同的相互作用能来区别.模拟获得了链长直至200个链节的无规共聚高分子系统相平衡数据,同时计算获得了不同链长固定组成下无规共聚高分子系统相应的临界点.图2表1参12 国爱自然科学基金(29736170)资助 O648 01050267 Triton X-100/正癸醇/水层状液晶制备泡囊=Preparation of Vesicles from Lamellar Liquid Crystal in Triton X-100/n-C10H21OH/H2O System[刊, 中]/丁元华(扬州大学),刘天晴…∥物理化学学报.&2000, 16(6).&481~486 以Triton X-100/n-C10H21OH/H2O体系生成的层状液晶为介质制备泡囊,所得泡囊分布比较均匀,囊径在0.2~0.5 μm之间.研究了层状液晶组成、pH、超声振荡时间等因素对所制泡囊的电位及微极性的影响.图6表2参16 国家自然科学基金(29673035)资助 O648 01050268 表面波技术研究TBP对C12E8表面流变性质的影响=Influence of TBP on the Surface Rheological Properties of C12E8 Studied by Surface Wave Method[刊, 中]/韩国彬(厦门大学),吴金添…∥物理化学学报.&2000, 16(6).&507~511 利用表面波技术研究消泡剂TBP对起泡剂C12E8表面流变性质的影响,阐述泡沫的排液过程中液膜变形所产生的表面张力梯度修复机理以及液膜强度与表面膨胀模量、表面膨胀弹性和表面膨胀粘度的关系,并且探讨了消泡剂TBP的消泡机理.图4参6 国家自然科学基金(29973033)资助 O648 01050269 制备宽温区O/W微乳的新方法=Novel Method to Prepare O/W Microemulsions within a Wide Temperature Range[刊, 英]/梁文平(中科院化学所),Tharwat F Tadros∥物理化学学报.&2000, 16(6).&538~542 通过把一个带有羧基的离子表面活性剂镶嵌在微乳界面的单分子层中,在低pH值时,形成水包油微乳,然后用氢氧化钠中和使其表面离子化而形成一个较厚的双电层,从而得到的宽温区(0-90℃)水包油微乳.研究了油相浓度、pH以及微乳液滴的大小对体系的浊点的影响.图5参12 国家自然科学基金资助 O65 01050270 Triton X-100与牛血清白蛋白的相互作用=The Interaction between Triton X-100 and Bovine Serum Albumin[刊, 中]/魏晓芳(中科院化工冶金所),刘会洲∥分析化学.&2000, 28(6).&699~701 国家自然科学基金重点项目资助 O65 01050271 球形铜离子模板缩聚物的制备及其选择吸附性能=The Preparation of Globular Copper(Ⅱ) Template Condensation Polymer and Its Behavior of the Selective Adsorption[刊, 中]/王旭东(南开大学),何锡文…∥分析化学.&2000, 28(7).&805~809 以苯酚、甲醛、四乙烯五胺为反应单体,铜离子为模板,反相悬浮聚合制备出球形离子模板缩聚物.该模板缩聚物对铜离子的吸附性能显著优于相应的非模板缩聚物.图6参3 国家自然科学基金(29775011)资助 O65 01050272 杯芳烃银离子敏感场效应晶体管传感器=Silver Ion-Sensitive Field-Effect Transistor Based on Calixarene[刊, 中]/陈朗星(南开大学),牛文成…∥分析化学.&2000, 28(7).&815~819 报道了硫醚取代的杯[4]芳烃化合物的合成,以此化合物为敏感材料,研制了聚氯乙烯膜的银离子敏感场效应晶体管(Ag+-ISFET)传感器.Ag+-ISFET传感器对银离子表现出优良的能斯特响应,该传感器对碱金属、碱土金属及过渡金属离子有极高的选择性.图5表1参13 国家自然科学基金(29975014)资助 O65 01050273 电极扩散层内物质浓度及分布研究方法进展=Development of Research Method of Concentration Observation and Distribution in Electrode Diffusion Layer[刊, 中]/杨玉书(重庆大学),夏之宁…∥分析化学.&2000, 28(7).&897~903 评述了测试电极扩散层内物质浓度及分布的各种方法,分别从方法原理、实验装置、影响因素及其应用等方面加以论述,评价了各种方法的特点,并对发展方向进行了展望.参52 国家自然科学基金(29775035)资助 O657 01050274 甲烷氧化偶联Na-W-Mn/SiO2催化剂的喇曼光谱=Raman Spectroscopy Characterization of Na-W-Mn/SiO2 Catalyst for Oxidative Coupling of Methane[刊, 中]/陈宏善(中科院兰州化学物理所),牛建中…∥物理化学学报.&2000, 16(6).&543~546 研究了A16061/SiCp复合材料表面双层稀土转化膜的微观结构以及化学组成,并对稀土转化膜对抗腐蚀性能进行了评估.结果表明,稀土转化膜能显著提高耐蚀性.图2表3参10 国家自然科学基金资助 O657 01050275 12-钼磷酸-葡聚糖包合物的研究=Study on the Inclusion Compound of 12-Molybdenum Phosphoric Acid with Dextran[刊, 中]/程贤C026(福建师范大学),苏英草…∥物理化学学报.&2000, 16(7).&658~662 福建省教委基金资助 O657 01050276 O/W微乳液中制备甲基丙烯甲酯-苯乙烯共聚物超细颗粒=Preparation of Methyl Methacrylate and Styrene Copolymer Ultrafine Particles in the Oil-in-Water Microemulsions[刊, 中]/钱君律(同济大学),甘礼华…∥同济大学学报(自然科学版).&2000, 28(3).&320~323 在甲基丙烯酸甲酯(MMA)-苯乙烯-环己烷/十六烷基三甲基溴化铵/水体系的O/W微乳液中,制备了粒径约58 nm球状甲基丙烯酸甲酯-苯乙烯共聚物超细颗粒.研究了影响粒子形态和大小的因素.图4表1参12 国家自然科学基金(29673030)资助 O657 01050277 基于小波神经网络的新型算法用于化学信号处理=A Novel Algorithm Based on the Wavelet Neural Network for Processing Chemical Signals[刊, 中]/蔡文生(中国科技大学),于芳…∥高等学校化学学报.&2000, 21(6).&855~859 基于紧支集正交小波神经网络的构造思想,用具有紧支集的B-样条函数的伸缩和平移替代小波函数,提出了一种新型算法,并将其应用于化学信号的处理,实现了信号的压缩和滤噪,与自适应小波神经网络相比,学习速度得到了大幅度的提高.图4表2参9 国家自然科学基金(29775001)资助 O657 01050278 改进溶胶-凝胶法固定酶结构剖析及在苯酚光化学传感器中的应用=The Microstructure Analysis of Enzymes Immobilized by Sol-Gel Method and Its Application in Phenol Optical Chemical Sensor[刊, 中]/李军(湖南大学),王柯敏…∥高等学校化学学报.&2000, 21(7).&1018~1022 结果表明,酶固定于溶胶-凝胶中后,与在溶液中一样,呈均匀分布且不易流失.此敏感膜可用于制备基于化学发光强度减弱的苯酚光化学传感器;用竞争反应的原理讨论了响应机理.图3表1参20 国家自然科学基金(29675005)及国家杰出青年基金(29825110)资助 O657 01050279 一种用于电热蒸发-原子光谱的微型化固相萃取技术=A Miniaturization Solid-Phase Extraction Technique Designed for Electrothermal Vaporization-Atomic Emission Spectrometry Determination[刊, 中]/熊宏春(武汉大学),胡斌…∥高等学校化学学报.&2000, 21(7).&1035~1036 国家自然科学基金(29875022)资助 O657 01050280 多环芳烃芴、苊的无保护流体室温磷光性质研究=Studies on Non-Protected Fluid Room Temperature Phosphorescence of Polycyclic Aromatic Hydrocarbon of Fluoren and Acenaphthene[刊, 中]/李隆弟(清华大学),牟兰…∥高等学校化学学报.&2000, 21(7).&1040~1042 国家自然科学基金(29775013)资助 O657 01050281 高效液相色谱/大气压化学电离质谱快速分析水中痕量有机磷农药=Rapid Analysis of Trace Organophosphorous Pesticides in Water by High Performance Liquid Chromatography/Atmospheric Pressure Chemical Ionization Mass Spectrometry[刊, 中]/潘元海(中科院生态环境研究中心),金军…∥分析化学.&2000, 28(6).&661~671 用反相液谱短柱实现了6种有机磷农药(乙酰甲胺磷,甲基对硫磷、杀螟硫磷、喹硫磷、二嗪农、辛硫磷)的高效液相色谱/大气压化学电离质谱(HPLC/APCIMS)快速分析.此技术可以很好地实现水中痕量有机磷农药的测定,一次联机分析仅需10 min.图3表2参11 国家自然科学基金(29977023)资助 O657 01050282 氧氟沙星对映体的同步-导数荧光光谱法识别与测定=Recognition and Determination of Ofloxacin Enantiomers by Synchronization-Derivative Fluorimetry[刊, 中]/弓巧娟(山西大学),晋卫军…∥分析化学.&2000, 28(6).&672~677 控制pH=3,首次通过同步一阶导数荧光光谱技术,有效地识别和分辨氧氟沙星的R和S对映体,同时有效地消除尿样背景的干扰.据此建立了同时识别与测定两种旋光体的同步-导数荧光光谱法.图5表2参9 国家自然科学基金(29875016)资助 O657 01050283 一种新的重原子微扰剂氯代叔丁烷在亚硫酸钠化学除氧环糊精诱导室温磷光法中的应用研究=A Study of t-Butyl Chloride as Heavy Atom Perturber in Chemical Deoxygenation-Cyclodextrin Induced Room Temperature Phosphorimetry[刊, 中]/张淑珍(山西大学),魏雁声…∥分析化学.&2000, 28(6).&678~681 以氯代叔丁烷作重原子微扰剂采用亚硫酸钠化学除氧技术建立了菲、7,8-苯并喹啉、2-溴代萘在环糊精介质中的室温磷光分析法.图4表2参5 国家自然科学基金(29575204)资助 O657 01050284 小牛胸腺脱氧核糖核酸诱导中性红聚集的机理及其影响因素=The Aggregation of Neutral Red Encouraged by Deoxyribonucleic Acids and Its Depending Factors[刊, 中]/黄新华(西南师范大学),李原芳…∥分析化学.&2000, 28(6).&682~686 在pH7.6~7.8和低离子强度条件下,中性红与小牛脱氧核糖核酸(ctDNA)作用产生以535 nm为特征的共振光散射增强(ERLS)光谱.机理研究表明,这种ERLS是由于DNA诱导中性红的聚集所致.图6表1参11 国家自然科学基金(29875019)资助 O657 01050285 蛋白质样品的非竞争性毛细管电泳免疫分析激光诱导荧光检测=Noncompetitive Capillary Electrophoresis Based Immunoassay for Proteins with Laser Induced Fluorescence Detection[刊, 中]/王清刚(清华大学),罗国安…∥分析化学.&2000, 28(6).&687~691 国家自然科学基金重点资助 O657 01050286 亲和毛细管电泳测定孕酮与其单克隆抗体的结合常数=Determination of the Binding Constant between Progesterone and Its Monoclonal Antibody Using Affinity Capillary Electrophoresis[刊, 中]/王清刚(清华大学),王义明…∥分析化学.&2000, 28(6).&731~734 采用亲和毛细管电泳的配体分离模式,以激光诱导荧光作为检测手段,测定了荧光素标记的孕酮与孕酮单克隆抗体之间的结合常数,并研究了温育时间、电泳条件等因素对测定的影响.图3参5 国家自然科学基金重点资助 O657 01050287 钌(Ⅱ)-联吡啶-铈(Ⅳ)-戊二醛化学发光体系及其应用=Chemiluminescence System of Ru(bpy)2+3-Ce(Ⅳ)-Glutaraldehyde and Its Application[刊, 中]/韩鹤友(武汉大学),何治柯…∥分析化学.&2000, 28(6).&738~740 基于在硫酸介质中戊二醛增强铈(Ⅳ)氧化钌(Ⅱ)-联吡啶的化学发光强度.在优化后的条件下,方法的线性范围和检测限分别为2.5×10-6~2.5×10-3 mol/L和3.1×10-7 mol/L戊二醛.图1表1参6 国家自然科学基金(29605001)资助 O657 01050288 毛细管区带电泳法测定甲氧苄胺嘧啶和磺胺甲基异C023唑的离解常数及其在复方新诺明中的含量=Determination of Dissociation Constants of Trimethoprim and Sulfamethoxazole and Their concentrations in Co-Trimoxazole Tablets by Capillary Zone Electrophoresis[刊, 中]/李前锋(兰州大学),张红医…∥分析化学.&2000, 28(7).&793~797 国家自然科学基金(29475194和29675007)资助 O657 01050289 联用色谱数据的半自动解析法=Semiautomatic Deconvolution of Hyphenated Chromatographic Data[刊, 中]/甘峰(湖南大学),李晓宁…∥分析化学.&2000, 28(7).&833~836 采用正交投影法获得初始迭代光谱,继采用非负最小二乘法和常规最小二乘法进行交替迭代,最终获得纯光谱和纯色谱向量.图2参15 国家自然科学基金(29875007)资助 O657 01050290 陈皮挥发油的气相色谱/质谱分析=Determination of the Volatile Oil of Pericarpium Citri Reticulatae with Gas Chromatography/Mass Spectrometry[刊, 中]/龚范(湖南大学),梁逸曾…∥分析化学.&2000, 28(7).&860~864 用GC/MS分析复方制剂平胃散中的一种单味药材陈皮的挥发油化学成分及其相对含量.分离出53个组分,其中鉴定了34个组分,约占其挥发油总量的96.08%.图5表1参7 国家自然科学基金(29875007)资助 657 01050291 人工神经网络法鉴别红外光谱=Artificial Neural Network for the Identification of Infrared Spectra[刊, 中]/李燕(南京理工大学),王俊德…∥光谱学与光谱分析.&2000, 20(4).&477~479 将反向传播人工神经网络用于FTIR,鉴别未知化合物.结果表明,当训练集样本不含噪声时,纯光谱的预测结果很好.而当训练集样本有少量噪声干扰时,预测结果随预测集样本的不同,而得到了不同的改善.图3参6 国家自然科学基金资助 O657 01050292 苯丙氨酸桥联金属双卟啉的诱导圆二色光谱研究=The Study of Induced Circular Dichroism of Phenylalanine Bridged Metal Bis-Porphyrin[刊, 中]/刘海洋(华南理工大学),黄锦汪…∥光谱学与光谱分析.&2000, 20(4).&495~497 报道了邻位和对位桥联苯丙氨酸锌双卟啉的合成,考查了双卟啉的分子结构对诱导圆二色性的影响.结果表明,两个卟啉环之间的π-π堆积和手性激子偶合作用是影响此类双卟啉圆二色光谱的主要因素.图3参16 国家自然科学基金(29771034)资助 O657 01050293 砷和汞的顺序注射-蒸气发生原子吸收光谱测定=Sequential Injection Vapor Generation Atomic Absorption Spectrometric Determination of Mercury and Arsenic[刊, 中]/马泓冰(东北大学),徐淑坤…∥光谱学与光谱分析.&2000, 20(4).&529~532 建立了砷和汞的顺序注射-蒸气发生原子吸收光谱测定方法.在流动注射蒸气发生原子吸收光谱测定方法的基础上,采用汇流技术,通过两个微量注射泵和一个多位选择阀的计算机程控操作,实现待测组分与硼氢化钠间的强氧化还原反应及其气-液分离过程.图3表4参4 国家自然科学基金资助 O657 01050294 氢化物的气相富集及其在超痕量分析中的应用=The Gaseous Phase Enrichment Techniques in Hydride Generation (Review)[刊, 中]/郭旭明(厦门大学),黄本立…∥光谱学与光谱分析.&2000, 20(4).&533~536 从富集原理及其在光谱超痕量分析的应用方面分别对这几种氢化物发生后的气相富集技术进行了较详细地综述.这些气相富集方法包括液氮冷却捕集技术、气球收集技术、石墨炉原位捕集技术、吸收液吸收技术及固体吸附技术等.参63 国家自然科学基金资助 O657 01050295 pH诱导牛血清白蛋白芳香氨基酸残基微环境变化的光谱分析=Spectral Study of the Microenviroment Change of Aromatic Amino-Acid Residues in BSA Induced by pH[刊, 中]/魏晓芳(中科院化工冶金所),刘会洲…∥光谱学与光谱分析.&2000, 20(4).&556~559 用荧光光谱和紫外吸收光谱研究了pH=2.3~11.3范围内牛血清白蛋白芳香氨基酸残基微环境的变化,以此推断蛋白质构象的变化,并讨论蛋白质表面疏水性变化的趋势.图4表1参8 国家自然科学基金重点基金资助 O657 01050296 传感器几何结构对近红外组织氧合检测仪灵敏度的影响=The Influence of Probe Geometry on the Sensitivity of Tissue Oximeter Using Near Infra-Red Spectroscopy[刊, 中]/王峰(清华大学),丁海曙…∥光谱学与光谱分析.&2000, 20(4).&585~588 利用蒙特卡罗仿真方法对光在多层生物组织模型中的平均穿透深度、光子平均飞行距离和空间灵敏度分布进行了仿真,结果表明,传感器几何结构,即光源与光检测器之间的距离是影响灵敏度的重要因素,适当增加这一距离有助于深层组织生化信息的提取和测量灵敏度的提高,但是它又受到信噪比降低的限制.图8参3 国家自然科学基金资助 O657 01050297 精密气动液压伺服系统用于傅里叶变换光谱仪光谱测量=Spectral Measuring of Fourier Transform Spectrometer Using Pneumatic Hydraulic Servo System[刊, 中]/李志刚(中科院长春光学精密机械所),王淑荣…∥光谱学与光谱分析.&2000, 20(4).&589~591 讨论了傅里叶变换光谱仪动镜稳定平移的重要性,研制了以高压无氧氮气为动力源的精密气动液压系统用于推进在研傅里叶变换光谱仪"猫眼”动镜系统,并在此基础上测量了ZYGO干涉仪光源光谱图.图4参5 国家自然科学基金资助 O658 01050298 超临界流体色谱法分离手性化合物的进展=Advances in Chiral Separations by Supercritical Fluid Chromatography[刊, 中]/任其龙(浙江大学),苏宝根…∥分析化学.&2000, 28(6).&772~776 国家自然科学基金(29776040)资助 O658 01050299 长江口水体混合过程中溶解态稀土元素分布特征[刊, 中]/王中良(中科院地球化学所),刘丛强∥科学通报.&2000, 45(12).&1322~1326 采用液-液萃取与反萃取分离富集方法和ICP-MS测试技术,对长江河口南支盐度0.15~19 mg/g表层水体中溶解态稀土元素的浓度进行了测定.图2表1参17 国家杰出青年科学基金(49625304)资助 O658 01050300 分子烙印手性固定相分离过程热力学研究=Thermodynamic Study on Separation of Molecular Imprinting Chiral Stationary Phase[刊, 中]/王进防(中科院大连化学物理所),周良模…∥高等学校化学学报.&2000, 21(6).&930~933 结果表明,分子烙印手性固定相的分离过程为焓控制过程.随着温度的升高,样品的容量因子降低,手性选择因子α减小.样品与分子烙印固定相的作用力包括非特异作用力和特异作用力,只有特异作用力的差值才是手性分离的本质.表2参22 国家自然科学基金(29575212)资助 O658 01050301 十八烷基醚型高效液相反相色谱填料的制备=Synthesis and Characterization of Ether-Bond RP-Packing[刊, 中]/喻昕(中科院化学所),赵睿…∥高等学校化学学报.&2000, 21(7).&1043~1044 国家自然科学基金(29635010)资助