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  • 期刊名称:

    Journal of Hazardous Materials

  • 中文名称: 危险材料杂志
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  • ISSN: 0304-3894
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  • 机译 控制河流溢流水浓度的过程
    摘要:The aqueous concentrations of sparingly soluble compounds resulting from oil, fuel, or chemical spills onto rivers predicted by numerical spill models contain an inherent degree of uncertainty due to the inaccuracies, or bias, of the user supplied rate coefficients. Methods for estimating the values of spreading, evaporation, dissolution, volatilization, and longitudinal dispersion coefficients for a small sheltered river are reviewed, and the uncertainties associated with each coefficient are estimated. The uncertainties in the predicted aqueous concentrations are then computed using a concurrently developed riverine spill model for a simulated spill of 10,000 kg of jet fuel. The resulting aqueous concentrations were found to be most sensitive to the saturation concentrations and the dissolution rates, moderately sensitive to the evaporation rates and longitudinal dispersion coefficient, and nearly completely insensitive to the volatilization coefficient.
  • 机译 准自催化分解型固体的自加速分解温度(SADT)
    摘要:Self-heating or thermally explosible chemicals are divided into two large groups, the thermal decomposition or TD type and the autocatalytic decomposition or AC type. The TD type is further divided into liquids, for each of which the critical temperature for thermal explosion or T_c is calculated by applying the Semenov equation, and, solids, for each of which the Tc is calculated by applying the Frank--Kamenetskii or F--K equation. On the other hand, the AC type is further divided into solids of the quasi-AC type, in each of which the exothermic decomposition reaction occurs almost simultaneously with the endothermic melting, and, liquid or solid high explosives of the true AC type, in each of which the self accelerating exothermic decomposition reaction begins after an autocatalyst has appeared and accumulated. Neither of the two critical conditions for thermal explosion, i.e., the Semenov equation or the F--K equation, is applicable to the self heating behaviour of each individual chemical of the AC type for the calculation of the Tc. Instead, the respective self heating behaviour of them is in accord with the concept of the self accelerating decomposition temperature (SADT) in principle. The SADT of each individual solid of the quasi-AC type discussed in this paper as well as the critical temperature for self heating or Tc, of each individual high explosive of the true AC type is determined by the isothermal storage test. In this study, the respective SADTs of five solids of the quasi-AC type were determined using a simple and safe isothermal storage testing device.
  • 机译 在用氯化剂焙烧垃圾焚烧炉粉煤灰的条件下金属的行为
    摘要:A total elemental analysis was performed on a municipal solid waste (MSW) fly ash sample, before and after it was treated at l000deg.C, to reveal the metal distribution between the volatile matter and the ash residue. Metals such as Pb, Zn, Cd, and to a lesser degree, Cr, Mn and Ni, were volatilized. Addition of chlorinating agents generally increased the volatility of certain elements. More acid resistant compounds were formed in the ash residue after the heat treatment using CaCl, as a chlorinating agent. The efficiencies of volatilization of the metals, using Cl_2, as a chlorinating agent, were generally higher compared with using CaCl_2. However, CaCl_2 was found to be a more selective chlorinating agent for volatilizing the heavy metals of concern, i.e., Pb, Cd, Zn and Cu. The efficiencies of volatilization of the recovered metals were approximately proportional to their standard free-energy changes (AG) for the corresponding chlorination reactions.
  • 机译 河流溢流的水浓度模型
    摘要:A numerical model is developed to predict the aqueous concentrations of sparingly soluble compounds resulting from oil, fuel, or chemical spills onto rivers. The model computes the concentration of compounds both in the slick phase and in the aqueous phase by simulating the processes that affect the fate of the spilled compound. Processes simulated by the model include spreading and drifting of the surface slick, evaporation from the slick, dissolution from the slick into the water, volatilization from the water, and longitudinal dispersion in the river. The model is used to simulate a hypothetical spill of jet fuel, demonstrating that the concentration of a compound in the aqueous phase is strongly linked to its concentration in the slick phase. The most soluble and most volatile compounds exhibit the highest aqueous concentrations in the early stages of the spill, but ultimately the less soluble and less volatile compounds reach the highest aqueous concentrations. Streamwise concentration gradients in the slick due to the rapid evaporation of the more volatile compounds are shown to have an effect on the aqueous concentration.
  • 机译 气体污染物在博物馆内部文化和艺术价值表面上沉积的腐蚀作用
    摘要:The objectives of the project were to assess the critical relationships between environmental factors and damage of the artefacts and other cultural property exposed inside museums, by studying: (a) the outdoor/indoor pollutant concentration and their transfer inside the museum, (b) the distribution and circulation of pollutants inside the museum influenced by various factors; (c) chemical interactions between pollutants in the gas phase leading to removal and/or formation of secondary pollutants; (d) the final deposition of the indoor pollutants on surfaces of artistic interest and the damage on them, governed by strictly defined physicochemical parameters. All the above information, together with the main factors influencing each stage, were obtained by applying the methodology developed and described in detail here. Measurements of rate constants of reactions in the gas phase, of physicochemical deposition parameters on artefacts, and the synergistic effects of pollutants on the deposition parameters, were conducted. Seven PC programmes for analysing the experimental data were written and used. The pollutants, the solid materials and the museums chosen in this programme are only examples needed to develop the necessary methodology.
  • 机译 UV / H_2O_2光氧化法估算苯酚和氯化苯酚的'OH自由基反应速率常数
    摘要:A detailed investigation on UV/H_2O_2 photooxidation has been carried out in order to determine the kinetics of the oxidative degradation of phenol and 2- and 4-chlorophenols in dilute aqueous solutions. Effects of different process parameters, such as initial substrate and H_2O_2 concentrations, substrate to H_2O_2 ratio on the degradation kinetics of the phenolic substrates, have been studied. Degradation rates of phenol and chlorophenols are insignificantly small with ultraviolet radiation only and also with hydrogen peroxide (in the absence of UV radiation), but the synergistic effect of UV/H_2O_2 results in a marked enhancement of the rates of degradation. A mechanistic model for UV/H_2O_2 photooxidation has been developed. Room temperature (27deg.C) rate constants for the reaction of 'OH radical (formed by absorption of photons) with the substrates have been estimated by using the model equation.
  • 机译 气体浓度波动产生有效毒物负荷的模型
    摘要:At any receptor position in a dispersing gas plume there will be large fluctuations in concentration for the duration of the exposure. The non-linearity of acute toxicity with exposure concentration means that these fluctuations are important to evaluating the overall effect of a release. In this paper, an effective toxic load model with three receptor response parameters was proposed to provide a realistic model of toxicity when applied to a fluctuating concentration time series. The receptor response factors included were an uptake time constant, a recovery time constant, and a saturation concentration. The effective toxic load model was compared with the standard toxic load model using simulated time series produced by a stochastic model. For a realistic simulated hydrogen sulphide exposure, the effective toxic load was found to provide more realistic estimates of fatalities than the conventional exposure toxic load calculations.
  • 机译 残留油和废油中芳烃化合物的固定床和间歇浸出特性的比较
    摘要:The fixed-bed dissolution characteristics were characterized for five aromatic components in two crude oils residually trapped in glass beads and two refinery residuals containing an oily phase. Good agreement between predicted and experimental results for the fixed-bed dissolution of benzene, toluene, ethylbenzene, p- and m-xylenes, and naphthalene (BTEXN) from the two crude oils was observed over a wide range (three to four orders of magnitude) in aqueous effluent concentrations. The partition coefficients used to describe the experimental leaching curves agreed well with those independently measured from multiple-batch aqueous extractions. For the two refinery residuals, good agreement between predicted and experimental fixed-bed dissolution was also observed for a one- to two-orders of magnitude range in leachate concentrations. These results illustrate a methodology for predicting time-dependent leaching behavior for an oily residual using partition coefficients measured from batch leaching tests. In addition, it was found that when the oil content of the oily residuals was accounted for, the partition coefficients measured for BTEXN for the oily residuals were similar to those for the crude oils. In the absence of batch measurements for a given oily residual, this latter result suggests that the time-dependent leaching behavior, under local equilibrium conditions, can be estimated from measurements of only the contaminant concentrations in the waste and the oil content.
  • 机译 用于连续催化湿式氧化苯酚的双金属催化剂
    摘要:Catalytic wet oxidation has proved to be effective at eliminating hazardous organic com- pounds, such as phenol, from waste waters. However, the lack of active long-life oxidation catalysts which can perform in aqueous phase is its main drawback. This study explores the ability of bimetallic supported catalysts to oxidize aqueous phenol solutions using air as oxidant. Combinations of 2/100 of CoO, Fe_2O_3, MnO or ZnO with l0/100 CuO were supported on γ-alumina by pore fllling, calcined and later tested. The oxidation was carried out in a packed bed reactor operating in trickle flow regime at l40deg.C and 900 kPa of oxygen partial pressure. Lifetime tests were conducted for 8 days. The pH of the feed solution was also varied. The results show that all the catalysts tested undergo severe deactivation during the first 2 days of operation. Later, the catalysts present steady activity until the end of the test. The highest residual phenol conversion was obtained for the ZnO--CuO, which was significantly higher than that obtained with the l0/100 CuO catalyst used as reference. The catalyst deactivation is related to the dissolution of the metal oxides from the catalyst surface due to the acidic reaction conditions. Generally, the performance of the catalysts was better when the pH of the feed solution was increased.
  • 机译 北极阿拉斯加固相氧的氧气释放动力学
    摘要:Child's Pad is a gravel construction surface that was contaminated with petroleum during oil-field service operations in Deadhorse, Alaska. As part of a remedial action plan, a buffer strip of uncontaminated sandy gravel was placed along sections of the pad boundary. A magnesium peroxide formulation manufactured by Regenesis, and sold as Oxygen Release Compound (ORC), was placed in the buffer strips. The ORC was intended to supply oxygen to aerobic microorganisms capable of degrading petroleum. Studies were conducted in the laboratory to determine initial oxygen release kinetics from ORC in contact with barrier soil. Studies quantified the biotic and abiotic catalytic mechanisms for converting hydrogen peroxide (a possible MgO_2 intermediate) and ORC to oxygen and water, the effects of temperature on oxygen release from ORC, and the effect of field exposure on ORC viability. Barrier soil exhibited sufficient catalytic activity to convert hydrogen peroxide to oxygen faster than the expected biological demand. The oxygen evolution rate (OER) from ORC was lower at 7deg.C than 2ldeg.C by more than two times. The ORC recovered from Child's Pad after less than l year retained nearly all of the original available oxygen, although physical bridging was evident.
  • 机译 修复木材防腐废物污染的土壤:逆流和逆流溶剂洗涤
    摘要:Solvent washing was evaluated as a method to remove pentachlorophenol (PCP) from aged field soils contaminated with wood treating wastes. Several soil:solvent contact ratios were considered. Solvent washing processes were evaluated based on the removal of PCP from the soil throughout the process. Mixtures with at least 50/100 (mass) ethanol extracted statistically equivalent amounts of PCP, removing as much as 730 mg/kg for one soil. Kinetic experiments demonstrated that soil-solvent contact times of approximately l h were adequate to remove a majority of the PCP. A crosscurrent soil washing procedure was developed to determine the solvent volume required to remove PCP from field soils. Consecutive wash stages with the 50/100 ethanol solvent were followed by water rinse stages. The crosscurrent washes were performed in three- and two-stage processes where soils were washed with the 50/100 ethanol solvent in three- and two-successive stages followed by water rinse stages. Ethanol recoveries were greater than 90/100 for both the three- and the two-stage wash trains. In addition to PCP, hydrocarbons were removed from the field soils by the 50/100 ethanol solvent. Effective removal of PCP bV the 50/100 ethanol solvent was not impeded by the presence of hydrocarbons in the soils. Three-stage countercurrent soil washing with 50/100 ethanol was successful in reducing PCP contamination on the soil from 785 to less than 40 mg/kg.
  • 机译 在有害有机液体存在下高密度聚乙烯土工膜的吸附/解吸,扩散,渗透和溶胀
    摘要:The laboratory findings on sorption and desorption of l4 organic liquids into high density polyethylene (HDPE) geomembranes are presented at 25, 50 and 70deg.C. The values of diffusion and permeation coefficients have been calculated using these data. Swelling of the HDPE geomembrane was studied by monitoring its increase in thickness and diameter and thereby calculating the increase in volume. From a temperature dependence of sorption, diffusion and permeation coefficients, the Arrhenius parameters have been calculated. From the sorption data, the concentration profiles of liquids inside the HDPE by solving Fick's diffusion equation under the appropriate initial and boundary conditions. Results of this research may have relevance in the application of HDPE geomembrane in the hazardous waste environment containing the solvents used in this research.
  • 机译 氧化物催化剂对4-氯酚的光催化分解
    摘要:4-Chlorophenol in the presence of catalysts was decomposed in aqueous solution by a l25 W medium pressure mercury lamp in a thermostated quartz batch photoreactor, and the organic bound chlorine was catalytically converted into the environmentally less harmful inorganic chloride. Differences in the concentration of 4-chlorophenol and of the intermediates, such as hydroquinone and quinone, are followed by HPLC. The best catalyst among a homolog series for the photo-decomposition of 4-chlorophenol was selected as finely dispersed platinum oxide on a TiO_2 semiconductor support, and kinetic parameters of the Langmuir-Hinshelwood type decomposition reaction were reported for the selected catalyst. A simple mechanism of substrate degradation in accord with the chosen kinetic model was postulated. The developed process may serve photooxidative removal of chlorophenols in wastewater without using costly oxidants.
  • 机译 城市固体废物焚烧炉底灰的表征
    摘要:The particles with diameter > l mm present in the bottom ash of Municipal solid waste incinerator (MSWI) were characterized by identifying the main constituent materials. This characterization may be used to evaluate the potential applications of bottom ash and its environmental hazards, and to evaluate the possibilities of recycling its main components. The effectiveness of the voluntary recycling programs of bottom ash can also be assessed. The main components of the bottom ash are glass, magnetic metals, minerals, synthetic ceramics, paramagnetic metals and unburned organic matter. The 4-25 mm size fraction accounts for approximately 50/100 of the bottom ash weight and comprises mainly glass (> 50/100 of this fraction), synthetic ceramics (> 26/100) and minerals (> 8/100), and thus appears to be suitable for reuse as secondary building materials or for glass recycling. Magnetic metals accumulate in the l-6 mm particle size fraction (6/100 of this fraction). Heavy metals accumulate in the fraction under l mm, unlikely the acid-soluble fraction, which diminishes as particle size diminishes.
  • 机译 在恒定pH下土壤电动处理过程中温度对离子迁移的影响
    摘要:Laboratory experiments and theoretical modelling generally proposed for electrokinetic soil processing consider isothermal conditions at room temperature. Important increases of the soil temperature, due to the Joule effect, have been observed during pilot or field-scale tests. The temperature effect on the transport of ionic species present in the pore solution is investigated when an electric field is applied through the soil mass. Laboratory experiments are run at 20 and 40deg.C using kaolinite as soil model and one anion and one cation as model pollutants. An adapted methodology (pH control, steady state conditions) allows the measurement and the comparison of the ionic electrokinetic velocities at the two temperatures. Under the conditions developed, the temperature mainly influences the ionic velocities, which increase, for the two ions of interest, when the temperature rises.
  • 机译 拉格朗日粉扑扩散模型中动态流动效应的表示
    摘要:A technique for incorporating buoyancy-driven dynamics in a Lagrangian puff model is described. The dynamic effects are non-linear and therefore proper treatment requires interaction integrals for overlapping puffs. Conservation laws for the volume integral of momentum and buoyancy over an individual puff are based on the fundamental equations of motion. A simplified representation of the field of motion associated with the buoyancy-driven dynamics is then used to move and distort the puffs. The effects associated with dense gas 'slumping' on the ground are represented by lateral divergence of the velocity field, with a magnitude based on conservation of the moment of vorticity. The model predictions are compared with a number of experimental results on buoyant plume rise and dense gas dispersion.
  • 机译 对六氯苯,4-氯联苯,萘或正癸烷污染的土壤进行热净化的热重研究
    摘要:To determine decontamination behavior as affected by temperature, shallow beds of a clay-rich, a calcerous, and a sedimentary soil, artificially polluted with hexachlorobenzene, 4-chlorobiphenyl, naphthalene, or n-decane, were separately heated at 5deg.C min~-l in a thermo- gravimetric analyzer. Temperatures for deep cleaning of the calcerous and the sedimentary soil increased with increasing boiling point (bp) of the aromatic contaminants, but removal effciencies still approached l00/100 well below the bp. Decontamination rates were therefore modelled according to a pollutant evaporation-diffusion transport model. For the calcerous and sedimentary soils, this model reasonably correlated removal of roughly the first 2/3 of the naphthalene, but gave only fair predictions for hexachlorobenzene and 4-chlorobiphenyl. It was necessary to heat the clay soil above the aromatics bp to achieve high decontamination efficiencies. Weight loss data imply that for temperatures from near ambient to as much as l50deg.C, interactions of each aromatic with the clay soil, or its decomposition products, result in lower net volatilization of the contaminated vs. neat clay. A similar effect was observed in heating calcerous soil polluted with hexachlorobenzene from near ambient to about l40deg.C.
  • 机译 乐果的热分解
    摘要:The thermal decomposition of dimethoate, an organophosphorus pesticide, has been studied with the aim at assessing the reaction kinetics, the energy released during the process and the decomposition products. Dimethoate shows a marked tendency to undergo thermal decomposition at temperature higher than 369 K. A moderate pressure increase has been recorded at the end of all runs. Many thiophosphoric compounds have been identified among the decomposition products.
  • 机译 挥发性有机化合物从土壤中的缓慢解吸:解吸步骤限制的证据
    摘要:Transient adsorption and desorption of l,2 dichloroethane and toluene on dry Yolo silt loam soil were studied by continuously measuring the composition of the effluent from a soil-packed chromatography column with a mass spectrometer. After obtaining complete breakthrough at approximately 30/100 relative saturation of one chemical in nitrogen, pure nitrogen feed was initiated and maintained for several hours. Of the material adsorbed at breakthrough, 9.7/100 of the l,2 dichloroethane and l4.2/100 of the toluene were highly resistant to desorption and remained sorbed on the soil even after 5 h of nitrogen flow. When a second chemical with a higher adsorption affinity was introduced into the soil column (water following toluene or toluene following l,2 dichloroethane), the majority of the first chemical was quickly desorbed and began leaving the soil column before breakthrough of the second chemical. Conversely, when a second chemical with a smaller adsorption affnity was introduced into the soil column, only a small amount of the first chemical was displaced and began leaving the soil column after breakthrough of the second chemical. The results of this study indicate that the desorption step itself may be the rate-limiting step for sorbate which remains after prolonged exposure to sorbate-free gas.
  • 机译 甲烷/空气混合物自燃温度的压力依赖性
    摘要:The results of experiments conducted to determine the auto-ignition temperature (AIT) and the cool flame temperature (CFT) of methane/air mixtures at elevated pressures (200-4700 kPa) and for concentrations from 30 up to 83 vol./100 are reported. The experiments were performed in a closed spherical vessel with a volume of 8 dm~3. It is shown that methane/air mixtures can react spontaneously for methane concentrations far outside the flammability limits. Cool flames are observed for methane concentrations higher than 40 vol./100. The AIT and CFT are strongly pressure-dependent and decrease with increasing pressures. A Semenov correlation is developed for the CFT as a function of the pressure. The upper explosion limit (UEL) of methane/air mixtures at elevated pressure and temperature is linked with the CFT. It is shown that for certain conditions of pressure and temperature, the flammability range increases considerably even for a small temperature rise.
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