Transfert du trichloréthylène en milieu poreux à partir d'un panache de vapeursMass transfer of trichloroethylene in a porous medium from a vapor plume

A large scale experiment has been carried out on an experimental facility to study the mass transfer of trichloroethylene (TCE) in a partially saturated porous medium. 5 liters of TCE have been infiltrated in the vadose zone of the site. The mass transfer of TCE from the vapor plume in the unsaturated zone towards the top of groundwater was quantified based on an analytical and a numerical approach. The mass of the pollutant measured at the exit of the model is well represented by the two mathematical approaches. It is found that the transfer of TCE towards the groundwater from the vapor plume is weak, which corresponds to 285 g of TCE, approximately 4% of the initial mass. To cite this article: H. Benremita, G. Schäfer, C. R. Mecanique 331 (2003).     

Compound-specific stable isotope analysis of organic contaminants in natural environments: a critical review of the state of the art,prospects, and future challenges

Compound-specific stable isotope analysis (CSIA) using gas chromatography-isotope ratio mass spectrometry (GC/IRMS) has developed into a mature analytical method in many application areas over the last decade. This is in particular true for carbon isotope analysis, whereas measurements of the other elements amenable to CSIA (hydrogen, nitrogen, oxygen) are much less routine. In environmental sciences, successful applications to date include (i) the allocation of contaminant sources on a local, regional, and global scale, (ii) the identification and quantification of (bio)transformation reactions on scales ranging from batch experiments to contaminated field sites, and (iii) the characterization of elementary reaction mechanisms that govern product formation. These three application areas are discussed in detail. The investigated spectrum of compounds comprises mainly n-alkanes, monoaromatics such as benzene and toluene, methyl tert-butyl ether (MTBE), polycyclic aromatic hydrocarbons (PAHs), and chlorinated hydrocarbons such as tetrachloromethane, trichloroethylene, and polychlorinated biphenyls (PCBs). Future research directions are primarily set by the state of the art in analytical instrumentation and method development. Approaches to utilize HPLC separation in CSIA, the enhancement of sensitivity of CSIA to allow field investigations in the µg L^–1 range, and the development of methods for CSIA of other elements are reviewed. Furthermore, an alternative scheme to evaluate isotope data is outlined that would enable estimates of position-specific kinetic isotope effects and, thus, allow one to extract mechanistic chemical and biochemical information.Abbreviations BTEX benzene, toluene, ethylbenzene, xylenes - MTBE methyl tert-butyl ether - PAHs polycyclic aromatic hydrocarbons - VOCs volatile compounds - PCBs polychlorinated biphenyls - CSIA compound-specific (stable) isotope (ratio) analysis - GC-IRMS, GC/IRMS or GCIRMS gas chromatography-isotope ratio mass spectrometry - GC-C-IRMS, GC/C/IRMS or GCC-IRMS gas chromatography-combustion-isotope ratio mass spectrometry - irmGC/MS isotope ratio monitoring gas chromatograph-mass spectrometry - GC/P/IRMS gas chromatography-pyrolysis-isotope ratio mass spectrometry (used for D/H) - KIE kinetic isotope effect - PSIA position-specific isotope analysis (for intramolecular isotope distribution) - SNIF-NMR site-specific natural isotopic fractionation by nuclear magnetic resonance spectroscopy     

Chlorinated Organic Compounds Decomposition in a Dielectric Barrier Discharge

The decomposition of chlorinated volatile organic compounds by non-thermal plasma generated in a dielectric barrier discharge was investigated. As model compounds trichloroethylene (TCE) and 1,2-dichloroethane (DCE) were chosen. It was found that TCE removal exceeds 95% for input energy densities above 0.2 eV/molecule, regardless of the initial concentration of TCE, in the range 100–750 ppm. On the other hand, DCE was more difficult to decompose, the removal rate reached a maximum of 60% at the highest input energy used. For both investigated compounds the selectivity towards carbon dioxide was significantly influenced by their initial concentration, increasing when low concentrations were used. The gas flow rate had also an effect on CO₂ selectivity, which is higher at low flow rate, due to the higher residence time of the gas in the plasma. The best values obtained in these experiments were around 80%.     

The fundamental surface science of wurtzite gallium nitride

A review is presented that covers the experimental and theoretical literature relating to the preparation, electronic structure and chemical and physical properties of the surfaces of the wurtzite form of GaN. The discussion includes the adsorption of various chemical elements and of inorganic, organometallic and organic species. The focus is on work that contributes to a microscopic, atomistic understanding of GaN surfaces and interfaces, and the review concludes with an assessment of possible future directions.     

Photocatalytic oxidation of aqueous trichloroethylene using dye sensitized buoyant photocatalyst monitored via micro-headspace solid-phase microextration gas chromatography/electron capture detection and mass spectrometry

Trichloroethylene (TCE), a useful industrial agent which unfortunately exhibits carcinogenic properties, has become an extremely prevalent environmental contaminant. As such, new rapid, sensitive, and cost effective detection methods are needed for the identification of potential point sources of contamination. A new analytic micro-headspace method is described, utilizing solid phase micro-extraction (SPME) fibers and routine gas chromatography/electron capture detection (GC/ECD) for the detection of TCE to the 3.89 ppb level in aqueous samples. The polydimethylsiloxane (PDMS) fiber was shown to have the greatest analytical promise, with excellent sensitivity and minimal carry over. This method was employed in the monitoring of the photo-oxidation of TCE using buoyant TiO₂ coated microspheres, which were sensitized using natural anthocyanin dyes obtained from fruits. Solar mediated photo-oxidation was shown to be a successful method for the removal of aqueous organic contaminants. The dye sensitized system yielded excellent remediation with 93% of the TCE removed from the system within 12 h. As irradiation was executed, overall TCE concentrations were reduced, while the expected mineralization product of hydrochloric acid was produced. The micro-headspace SPME procedure described here, offers considerably improved sensitivity, with orders of magnitude improvement in method detection limits, over previously published micro-headspace methods.     

OH与TCE和PCE加成中间体消除反应的机理

用从头计算法在UHF/6-31G水平研究了羟基自由基与三氯乙烯和四氯乙烯形成的加成中间体的消除反应,通过振动分析确认了过渡态,计算了内禀反应坐标(IRC).研究表明,该反应消除一个氯化氢分子,形成具有平面构型的另一个中间体,反应活化势垒较低,分别为79.84kJ mol-1和62.68kJ mol-1,且二者反应在常温常压下是熵增、放热、吉布斯自由能ΔGΘ<Ο,具有较大自发趋势的过程。