Mixtures of dense non-aqueous phase liquids (DNAPLs) trapped in the subsurface can act as long-term sources of contamination by dissolving into flowing groundwater. In general, the components of higher solubility are removed more quickly, thus altering the composition of the remaining DNAPL, and possibly leading to changes in its physical properties. Through the development of a simple compositional model, Roy et al. [J. Contam. Hydrol. 2002 (59) 163] showed that preferential dissolution of a mixed DNAPL could potentially result in changes in density and interfacial tension that could subsequently lead to remobilization of an initially static DNAPL pool. The laboratory experiments presented in this next paper provide a proof-of-concept for the previously presented theory, demonstrating and quantifying this process of remobilization. In addition, the experiments provide a data set for evaluation of the model presented by Roy et al. [J. Contam. Hydrol. 2002 (59) 163]. In the four experiments, a DNAPL pool comprised of tetrachloroethene and benzene was created as an open pool overlying glass beads within a water-saturated 2-D flow box. Experiments included rectangular and triangular pools. In each of the experiments, remobilization (as breakthrough) was observed more than 2 weeks after formation of the initial pool. During each experiment, the pool height declined as mass was lost by dissolution, while sampling indicated a decrease in the mole fraction of benzene, the more soluble component. Small protuberances formed along the bottom of the pool as its composition changed with time and the displacement pressure was achieved for various pore throats. Eventually one of the protuberances extended further, forming a finger (breakthrough). In general, the pool emptied as the finger proceeded further into the beads. It was also shown theoretically and experimentally that remobilization will occur sooner for pools with a triangular (pointing down), rather than rectangular, shape. The experimental results were simulated using the model developed by Roy et al. [J. Contam. Hydrol. 2002 (59) 163]. The model matched the observations well, suggesting that it accurately represents the primary mechanisms involved with natural remobilization under the conditions of the study. 相似文献
Dibenzofuran (DF) is formed from phenol and benzene in combustion gas exhaust streams prior to particle collection equipment. Subsequent chlorination at lower temperatures on particle surfaces is a potential source of chlorinated dibenzofuran (CDF). Gas streams containing 8% O2 and approximately 0.1% DF vapor were passed through particle beds containing copper (II) chloride (0.5% Cu, mass) at temperatures ranging from 200 to 400 °C to investigate the potential for CDF formation during particle collection. Experiment duration was sufficient to provide an excess amount of DF (DF/Cu=3). The efficiency of DF chlorination by CuCl2 and the distribution of CDF products were measured, with effects of temperature, gas velocity, and experiment duration assessed. Results of a more limited investigation of dibenzo-p-dioxin (DD) chlorination by CuCl2 to form chlorinated DD (CDD) products are also presented.
The efficiency of DF/DD chlorination by CuCl2 was high, both in terms of CuCl2 utilization and DF/DD conversion. Total yields of Cl on CDF/CDD products of up to 0.5 mole Cl per mole CuCl2 were observed between 200 and 300 °C; this suggests that nearly 100% CuCl2 was utilized, assuming a conversion of two moles of CuCl2 to CuCl per mole Cl added to DD/DF. In a short duration experiment (DF/Cu=0.3), nearly 100% DF adsorption and conversion to CDF was achieved. The degree of CDF chlorination was strongly dependent on gas velocity. At high gas velocity, corresponding to a gas–particle contact time of 0.3 s, mono-CDF (MCDF) yield was largest, with yields decreasing with increasing CDF chlorination. At low gas velocity, corresponding to a gas–particle contact time of 5 s, octa-CDF yield was largest. DF/DD chlorination was strongly favored at lateral sites, with the predominant CDF/CDD isomers within each homologue group those containing Cl substituents at only the 2,3,7,8 positions. At the higher temperatures and lower gas velocities studied, however, broader isomer distributions, particularly of the less CDD/CDF products, were observed, likely due to preferential destruction of the 2,3,7,8 congeners. 相似文献
BACKGROUND, AIMS AND SCOPE: In the first part of this paper the main principles which control the dehalogenation of polychlorinated aromatic compounds on municipal waste incineration fly ash (MWI-FA) have been discussed and the model fly ash of similar dehalogenation activity has been proposed. Even if both systems show comparable dehalogenation properties, the main question concerning the postulated identical reaction mechanism in both cases is left unanswered. The other very important point is to what extent is this dechlorination mechanism thermodynamically controlled. The same problem is often discussed in the literature also for the de novo synthetic reactions. From the data it is clear that metallic copper plays a decisive role in the mechanism of the dehalogenation reaction. Although the results reported in the first part strongly support the idea that copper acts in this dechlorination as the reaction component, in contrast to its generally accepted catalytic behaviour, we believed that additional support for this conclusion can be obtained with the help of a thermodynamic interpretation of the mechanism of the reaction. RESULTS AND DISCUSSION: The pathways of hexachlorobenzene dechlorination on MWI-FA and model fly ash were studied in a closed system at 260-300 degrees C under nitrogen atmosphere. These pathways were the same for both systems, with the following prevailing sequences: hexachlorobenzene --> pentachlorobenzene --> 1,2,3,5-tetrachlorobenzene --> 1,3,5-trichlorobenzene --> 1,3-dichlorobenzene. Thermodynamic calculations were carried out by using the method of minimization total Gibbs energy of the whole system. In the calculations, the following reaction components were taken into account: all gaseous chlorinated benzenes, benzene, hydrogen chloride, a gaseous trimer Cu3Cl3, and also Cu2O and CuCl2 as solid components. The effect of the reaction temperature and the amount of copper and water vapour were considered as well. The effect of reaction temperature was determined from the data calculated for the 500 to 750 K temperature region. The effect of the initial composition was determined for the molar amounts of copper = 0.01-3 moles and water vapour = 0.2 to 3 moles per mole of chlorobenzene isomer CONCLUSIONS: The results of hexachlorobenzene dechlorination by MWI-FA and model fly ash under comparable reaction conditions allow us to conclude that both dechlorinations proceed via the same dechlorination pathways, which can be taken as an evidence of the identical dehalogenation mechanism for both systems. The relative percentual distribution of the dehalogenated products depends on the temperature, but not on the initial amount of water vapour or copper metal. On the other hand, the initial amount of copper substantially affects the conversion of the dehalogenation as well as the molar ratio of Cu3Cl3 to HCl in the equilibrium mixture. Comparison of the experimental with thermodynamic results supports the idea that dehalogenation reactions are thermodynamically controlled. RECOMMENDATIONS AND OUTLOOK: Thermodynamic analysis of the dehalogenation reactions may prove useful for a wide range of pollutants. The calculations concerning polychlorinated biphenyls and phenols are under study. 相似文献
The mill waste water holds a large amount of polyphenols, preventing the biodegradation processes because of their inhibitory action on microbial growth. Thus, its disposal represents an environmental problem for the great olive oil producing countries in the Mediterranean area. In this work, we present the preliminary results from the application of a photo-oxidative process on mill waste water to evaluate the organic matter degradation potential and the biodegradability of the treated residue. The total organic carbon is reduced up to 35% after 6 hours but the cost-effectiveness is unfavourable. In contrast, the aim of toxicity reduction is less expensive and shows good applicable chances; after 2 h, the polyphenols concentration drops by 60%. 相似文献