Stimulation of pyrene mineralization in freshwater sediments by bacterial and plant bioaugmentation

As a means to study the fate of polycyclic aromatic hydrocarbons (PAHs) in freshwater sediments, pyrene mineralization was examined in microcosms spiked with [14C]pyrene. Some microcosms were planted with reeds (Phragmites australis) and/or inoculated with a pyrene-degrading strain, Mycobacterium sp. 6PY1. Mineralization rates recorded over a 61 d period showed that reeds promoted a significant enhancement of pyrene degradation, which possibly resulted from a root-mediated increase of oxygen diffusion into the sediment layer, as indicated by in situ redox measurements. In inoculated microcosms, mineralization reached a higher level in the absence (8.8%) than in the presence of plants (4.4%). Mineralization activity was accompanied by the release of water-soluble pyrene oxidation products, the most abundant of which was identified as 4,5-diphenanthroic acid. Pyrene was recovered from plant tissues, including stems and leaves, at concentrations ranging between 40 and 240 microg/g of dry mass. Plants also accumulated labeled oxidation products likely derived from microbial degradation. Pyrene-degrading strains were 35-70-fold more abundant in inoculated than in noninoculated microcosms. Most of the pyrene-degrading isolates selected from the indigenous microflora were identified as Mycobacterium austroafricanum strains. Taken together, the results of this study show that plants or PAH-degrading bacteria enhance pollutant removal, but their effects are not necessarily cumulative.     

Elemental, isotopic, and spectroscopic assessment of chemical fractionation of dissolved organic matter sampled with a portable reverse osmosis system

Portable reverse osmosis (RO) systems are increasingly being used for isolating dissolved organic matter (DOM) from freshwater aquatic systems because of their high volume processing capacity and high absolute DOM recoveries. However, obtaining complete recoveries implies the rinsing of the reverse osmosis system with a solution of dilute NaOH and combining the rinse solution and the DOM concentrate. Because of the potential chemical alterations that can affect the integrity of the organic pool leached from the RO system at high pHs, this approach is not compatible with studies based on the molecular-level analysis of DOM.The potential for elemental, isotopic, and chemical fractionation was thus evaluated on a series of freshwater DOM samples concentrated in the field with a portable RO system when the concentrate and the rinse solution are not combined. DOC recoveries in the concentrate varied between 81.6 and 88.8%, and total balance calculations showed total recoveries of dissolved and particulate organic carbon ranging between 96.4 and 106.9%. Despite similar delta13C signatures, differences in N content and FTIR-based chemical composition between the concentrate and the rinse DOM solutions suggest some degree of chemical fractionation.     

Long-term cycling behavior of asymmetric activated carbon/MnO2 aqueous electrochemical supercapacitor

Activated carbon–MnO₂ hybrid electrochemical supercapacitor cells have been assembled and characterized in K₂SO₄ aqueous media. A laboratory cell achieved 195,000 cycles with stable performance. The maximal cell voltage was 2 V associated with 21 ± 2 F g⁻¹ of total composite electrode materials (including activated carbon and MnO₂, binder and conductive additive) and an equivalent serie resistance (ESR) below 1.3 Ω cm². Long-life cycling was achieved by removing dissolved oxygen from the electrolyte, which limits the corrosion of current collectors. Scaling up has been realized by assembling several electrodes in parallel to build a prismatic cell. A stable capacity of 380 F and a cell voltage of 2 V were maintained over 600 cycles. These encouraging results show the interest of developing such devices, including non-toxic and safer components as compared to the current organic-based devices.     

Poly(di(ω-alkylphenyl)stannane)s

Poly(di(ω-alkylphenyl)stannane)s, [Sn(C _n H_2n Ph)₂] _m with n = 2–4, and a copolymer of di(3-propylphenyl)stannane and dibutylstannane of weight-average molar masses of 2–8 · 10⁴ g/mol were synthesized by dehydropolymerization of stannanes of the composition H₂SnR₂ using Wilkinson’s catalyst [RhCl(PPh₃)₃]. At least two methylene groups were required as spacers between the phenyl group and the tin atom for polymerization to occur. The polystannanes were characterized by, among other techniques, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy, thermal analysis and X-ray diffraction. The polymers featured properties different from those of the corresponding poly(dialkylstannane)s. Specifically, the [Sn(C _n H_2n Ph)₂] _m family displayed glass transitions at remarkably low temperatures, down to ca. −50 °C, and a lower value for a copolymer (−68 °C). Polymers [Sn(C_nH_2nPh)₂]_m with n = 2 and 3 and a copolymer at room temperature were of a gel-like concistence, which enabled facile orientation with shear forces. Finally, the temperature-dependent electrical conductivity was determined for poly(di(3-propylphenyl)stannane), which followed the law of typical semiconductors, with an activation energy for conduction of 0.12 eV.     

Mesomorphism of dialkylterthiophene homologues

New dialkylterthiophene liquid crystalline compounds were synthesised and characterised using differential scanning calorimetry (DSC), X-ray diffraction (XRD) and polarized optical microscopy (POM). Upon cooling from the isotropic state to the crystalline phase, these dialkylterthiophenes present different types of smectic mesophases. For the highest ordered smectic phase, XRD analyses have revealed a molecular organisation within the smectic layers and the key structural parameters are determined by molecular modelling simulations. The structural properties of these smectic phases are discussed in relation to the alkyl chain length.     

New methods for the fast simulations of the extrusion process of hot metals

Being able to find alternatives to the costly and time-consuming trial and error current practice in die design based on know-how acquired by practitioners throughout years is of primary importance in the aluminum extrusion industry. In this paper, two programs aimed at helping extruders in estimating the performance and feasibility of processes and simulating in details the flow of material in the press, are presented. Although they have been used so far for aluminum alloys, they could also be applied to other extrusion applications like that of other metals and polymers for instance. Together with a process simulator, which enables one to obtain a fast estimate of the extrusion process performances and computer-aided production of aluminum extrudates, a three-dimensional software dedicated to the design of dies with complicated shapes is also described.     

In situ mid-IR and UV-visible spectroscopies applied to the determination of kinetic parameters in the anionic copolymerization of styrene and isoprene

In situ MIR and UV-visible spectroscopies have been combined in a set-up that has been used to monitor anionic (co)polymerizations of styrene and isoprene. This experimental set-up gives access to the simultaneous and real time concentrations of monomers and actives species during the polymerization, through optical fibers probes immersed in the reaction medium. This method allows fast, accurate and reproducible measurements of the rate constants of the (co)polymerizations investigated even if it does not resort to high vacuum. The influence of some experimental factors has been examined using this method. Among the kinetic parameters governing the (co)polymerization of styrene and isoprene initiated by sec-butyllithium, the influence of the nature of solvent was investigated. It appears that the only reaction to depend on the nature of the aromatic solvent (k_ss,toluene > k_{ss,ethylbenzene}) is the propagation step of styrene.     

Kinetics and Mechanism of the Water–Gas Shift Reaction Over Platinum Supported Catalysts

A dual-site reaction mechanism is proposed for Pt based water–gas shift catalysts. The sorption equilibrium parameters are evaluated in detail to validate their physical significance. The values of the van ‘t Hoff parameters for CO and H₂ correspond to those for chemisorption on platinum. The sorption parameters of H₂O and CO₂ on the supports have been quantitatively determined from temperature-programmed desorption experiments and have been compared to the values obtained from the kinetic study. Finally the proposed model is able to explain the different activities between the two catalysts.     

Synthesis of Silicon Carbide–Silicon Nitride Composite Ultrafine Particles Using a Carbon Dioxide Laser

The synthesis and the structure of silicon carbide-silicon nitride (SiC─Si₃N₄) composite ultrafine particles have been studied. SiC─Si₃N₄ composite ultrafine particles were prepared by irradiating a SiH₄, C₂H₄, and NH₃ gas mixture with a CO₂ laser at atmospheric pressure. The composition of composite powders changed with the reactant gas flow rate. The carbon and nitrogen content of the powder could be controlled in a wide range from 0 to 30 wt%. The composite powder, which contained 25.3 wt%. carbon and 5.8 wt% nitrogen, had a (β-SiC structure. As the nitrogen con- tent increased, SiC decreased and amorphous phase, Si₃N₄, Si appeared. The results of XPS and lattice constant measurements suggested that Si, C, and N atoms were intimately mixed in the composite particles.     

Functionalized polysulfone membranes by heterogeneous lithiation

Polysulfone membranes were modified heterogeneously by lithiation, using n-butyllithium and low concentrations of tetrahydrofuran (THF). The effects of various conditions of reactant concentration, temperature, and time were determined quantitatively. The degree of substitution was measured by XPS and FTIR, using the carbonyl absorption band of lithium-activated membranes that had been converted to ones containing acyl fluoride substituents. The optimum conditions for membrane functionalization were 0.2M n-butyllithium in hexane at room temperature. The reaction rate increased substantially in the presence of 2% THF. The surface-lithiated membranes can be derivatized, potentially with a wide variety of functional groups. © 1993 John Wiley & Sons, Inc.