水资源中氯代烃污染物的去除方法

随着工业化的发展。氯代有机溶剂使用越来越广泛。并且难于去除。在20世纪90年代初期，人们就已认识到用Fe^0恢复污染的地下水的潜力。国外正在研究帮使用扔几种还原挥发性氯代烃的还原反应介质，尤其要提高的是双金属反应系统，反应速度快，而且脱Cl中国难解产物少，目前国也只停留在实验室研究阶段，个别做了地上反应器的验证实验，它的脱Cl机理、介质钝化和完全脱Cl问题还有待于进一步研究。     

某城市工业区浅层地下水CAHs污染特征

2000—2002年采用气相色谱法对某市工业区浅层地下水中氯代脂肪烃(CAHs)含量进行了分析,在综合分析CAH污染的原因和途径的基础上,着重探讨了CAH在地下水系统中的迁移转化规律。结果表明,地下水中CAH检出率48 15%~85 19%,检出值质量浓度为0 1~71 89μg/L,与美国“EPA”标准5μg/L 相比,三氯乙烯、四氯乙烯超标率分别为59 26%和25 93%,超标倍数分别可达14 38 和9 128;三氯乙烯(TCE)和四氯乙烯(PCE)是主要污染物,重现性好;CAH对地下水的污染与其本身的物理性质、包气带的结构和地下水动力条件等因素有关,防污性能差的工业区CAH容易污染地下水;CAH在砂土中的迟后因子R值很小,很容易在地下环境中迁移;地下水流场是决定CAH分布的一个重要因素,沿着地下水流向,CAH浓度呈逐渐降低的趋势;地下水动态变化是引起CAH呈现季节性变化的主要原因。     

Identifying sources of chlorinated aliphatic hydrocarbons in a residential area in Italy using the integral pumping test method

The results of integral pumping tests (IPTs) performed in the city of Fabriano, Italy, are presented. The IPT methodology was developed by the European Union project INCORE, as a tool for groundwater investigation and source localization in contaminated areas. This methodology consists of a multiple-well pumping test in which the wells are positioned along a control plane downstream of suspected contaminant source zones and perpendicular to the mean groundwater flow direction. During the pumping, concentration time series of target contaminants are measured. In Fabriano, two control planes were realized to identify a chlorinated aliphatic hydrocarbon plume, to estimate the mass fluxes and draw up a ranked list of the main contamination sources. A numerical flow model was implemented to support the IPT design and to interpret the results. This study revealed low-level trichloroethylene contamination (concentration below 8 μg/l), tetrachloroethylene contamination (mean concentration up to 500 μg/l) and a mass flow rate of about 300 g/day. Through the application of the IPT method, the mean contaminant concentrations, the spatial distribution of concentration values along the control planes, and the total contaminant mass flow rates were evaluated, and the investigation area was reduced for further and deeper investigation activities.     

Biosorption of hexavalent chromium from aqueous solution onto pomegranate seeds: kinetic modeling studies

Hexavalent chromium has been proved to be the reason of several health hazards. This study aimed at evaluating the application of pomegranate seeds powder for chromium adsorption (VI) from aqueous solution. Chromium adsorption percentage (VI) increased with increasing the adsorbent dosage. Chromium adsorption capacity (VI), at pH = 2 and 10 mg/L initial metal concentration, decreased from 3.313 to 1.6 mg/g through increasing dosage of adsorbent from 0.2 to 0.6 g/100 ml. The adsorption rate increased through increase in chromium initial concentration (VI). However, there was a removal percentage reduction of chromium (VI). Chromium adsorption kinetics by different models (pseudo-first-order, modified pseudo-first-order, pseudo-second-order, Elovich, intraparticle diffusion, Boyd kinetic) was investigated as well. Studies on adsorption kinetic indicated that the experimental data were matched by pseudo-second-order model (R ² = 0.999) better. Obtained results demonstrated the pomegranate seeds can be used as an effective biomaterial and biosorbent for hexavalent chromium adsorption from aqueous solutions.     

Removal of heavy metal ions from aqueous solutions with multi-walled carbon nanotubes: Kinetic and thermodynamic studies

Multi-walled carbon nanotubes were used successfully for the removal of Copper(II), Lead(II), Cadmium(II), and Zinc(II) from aqueous solution. The results showed that the % adsorption increased by raising the solution temperature due to the endothermic nature of the adsorption process. The kinetics of Cadmium(II), Lead(II), Copper(II), and Zinc(II) adsorption on Multi-walled carbon nanotubes were analyzed using the fraction power function model, Lagergren pseudo-first-order, pseudo-second-order, and Elovich models, and the results showed that the adsorption of heavy metal ions was a pseudo-second-order process, and the adsorption capacity increased with increasing solution temperature. The binding of the metal ions by the carbon nanotubes was evaluated from the adsorption capacities and was found to follow the following order: Copper(II) > Lead(II) > Zinc(II) > Cadmium(II). The thermodynamics parameters were calculated, and the results showed that the values of the free energies were negative for all metals ions, which indicated the spontaneity of the adsorption process, and this spontaneity increased by raising the solution temperature. The change in entropy values were positives, indicating the increase in randomness due to the physical adsorption of heavy metal ions from the aqueous solution to the carbon nanotubes’ surface. Although the enthalpy values were positive for all metal ions, the free energies were negative, and the adsorption was spontaneous, which indicates that the heavy metal adsorption of Multi-walled carbon nanotubes was an entropy-driving process.     

Role of electrochemical reactions in pressure solution

Using a Surface Forces Apparatus we have measured changes in the electrical potential difference between quartz and mica surfaces that correlate with the changing quartz dissolution rate when surfaces are pressed together at relatively low pressures (2-3 atm) in aqueous electrolyte solutions of 30 mM CaCl₂ at 25 °C. No detectable dissolution or voltage potential difference is measured in symmetrical systems (e.g. mica-mica or quartz-quartz) or between dry surfaces subjected to similar pressures, indicating that the dissolution can not be attributed to a simple pressure effect, slow aging (creep), or plastic deformation of the quartz surface. In quartz-mica systems brought together under pressure or to close proximity in electrolyte solution, the onset of quartz dissolution is marked by a sudden, rapid decrease in the quartz thickness at initial rates in the range from 1 to 4 nm/min, which after several hours settles into a constant rate of approximately 0.01 nm/min (∼5 μm/yr). Concomitantly, the potential drops to a constant value once the dissolution rate has stabilized. The decrease in the decay rate is interpreted as being due to saturation of the confined aqueous film and/or to the buildup of a Stern layer on the quartz surface, and the constant rate as being due to the steady-state chemical dissolution and diffusion of the dissolving silica into the surrounding reservoir. The dissolution is ‘non-uniform’: the surfaces become rough as dissolution proceeds, with the appearance of pits in a manner analogous to corrosion. On occasions, the process of rapid dissolution followed by a gradual transition to steady dissolution repeats itself, suggesting that the pit structure and Stern layer are fragile and subject to collapse and/or expulsion from the gap. Preliminary experiments on the dissolution of multi-faceted milled quartz particles (∼1.0 μm diameter) compressed between two muscovite surfaces suggest an asymmetry in the dissolution rates at different crystallographic planes. The origin of the electrical potential is interpreted as arising from the overlapping of the electric double-layers of two dissimilar surfaces when they are forced into close proximity. This electrical potential difference, for as yet unknown reasons, appears to be the driving force for the dissolution, rather than pressure.     

Retention studies of chromium (VI) from aqueous solution on the surface of a novel carbonaceous material

In the present study, the retention capacity of carbonaceous material obtained from the diesel engine exhaust mufflers for Cr(VI) removal has been investigated. The physicochemical properties such as density, pH of aqueous slurry, pH at point of zero charge, ash content, moisture content, volatile matter, surface area, scanning electron microscopy and electron dispersive spectroscopy of the carbonaceous material were determined. The capacity of adsorbent for removal of Cr(VI) from aqueous solution was observed under different experimental condition like contact time, initial concentration of metal ions, pH and temperatures on the adsorption capacity of the adsorbent. Maximum adsorption of Cr(VI) ions was found at low pH. The adsorption process was found to follow second-order kinetics. The rate constant was evaluated at different temperatures along with other thermodynamic parameters like activation energy, Gibbs free energy change, enthalpy change and entropy change. Both Langmuir and Freundlich isotherms were used to describe the adsorption equilibrium of carbonaceous material at different temperatures. Langmuir isotherm shows better fit than Freundlich isotherm at given conditions. The result shows that low-cost carbonaceous material from diesel engine exhaust mufflers can be efficiently used for wastewater treatment containing Cr(VI) ions.     

Kinetic research on the sorption of aqueous cadmium on carbonate hydroxyapatite

The sorption of aqueous cadmium on carbonate-hydroxyapatite （CHap） is a complicated non-homogeneous solid/water reaction, From kinetic point of view, it can be described by two stages： at the earlier stage, reaction rate is so fast that its kinetic course is intricate, and at the later stage, the rate of reaction becomes slow and the process of reaction accords with one order reaction kinetic equation. Experimental results show that the relationship between reaction rate constant kl and temperature T accords to Arrhenius Equation, and the activation energy of sorption （Ea） is 6.075 J/mol and frequency factor （A） is 220 s^-1. At the same time, reaction rate constant kl increases with decreasing Cd^2＋ initial concentration, on the contrary, with increasing pH and CHap dosage.     

Adsorption of reactive dyes from aqueous solutions by tannery sludge developed activated carbon: Kinetic and equilibrium studies

Adsorption kinetic and equilibrium studies of two reactive dyes, namely, Reactive Red 31 and Reactive Red 2 were conducted. The equilibrium studies were conducted for various operational parameters such as initial dye concentration, pH, agitation speed, adsorbent dosage and temperature. The initial dye concentration was varied from 10 - 60 mg/L, pH from 2–11, agitation speed from 100–140 rpm, adsorbent dosage from 0.5 g to 2.5 g and temperature from 30 °C -50 °C respectively. The activated carbon of particle size 600 μm was developed from preliminary tannery sludge. The dye removal capacity of the two reactive red dyes decreased with increasing pH. The zero point charge for the sludge carbon was 9.0 and 7.0 for the two dyes, respectively. Batch kinetic data investigations on the removal of reactive dyes using tannery sludge activated carbon have been well described by the lagergren plots. It was suggested that the Pseudo second order adsorption mechanism was predominant for the sorption of the reactive dyes onto the tannery sludge based carbon. Thus, the adsorption phenomenon was suggested as a chemical process. The adsorption data fitted well with Langmuir model than the Freundlich model. The maximum adsorption capacity(q⁰) from Langmuir isotherm were found to have increased in the range of 23.15–39.37 mg/g and 47.62–55.87 mg/g for reactive dyes reactive red 31 and reactive red 2, respectively.     

水溶液中溶质的扩散同位素分馏研究

稳定同位素分析是判定水溶液中溶质的组成、来源、迁移和转化过程与规律的重要工具,在自由扩散等物理化学作用下,对溶质的同位素分馏研究是稳定同位素技术应用的重要基础.本研究介绍了溶质的扩散过程与其同位素分馏效应之间的联系,论述了研究溶质扩散过程中引入的稳定同位素分馏现象的意义,描述了水溶液中溶质扩散的不同模拟实验方法及相关研...     

羟基磷灰石对水溶液中Fe3+的吸附动力学及热力学研究

研究了羟基磷灰石(HAP)对水溶液中Fe3+的吸附动力学及热力学。研究表明,HAP对水溶液中Fe3+的吸附符合Langmiur等温吸附,ct/q=0.006 4 ct+0.018 3;该吸附反应符合一级反应动力学方程,ln CR=-0.043 5 t+4.324 4;吸附反应活化能为Ea=36.26 k J/mol;标准摩尔反应焓为正值表明反应过程吸热;当温度大于285.7 K时,吉布斯自由能小于0,反应可自发进行。     

Molecular dynamics simulation of the titration of polyoxocations in aqueous solution

The aqueous complex ion Al₃₀O₈(OH)₅₆(H₂O)₂₆¹⁸⁺ (Al₃₀) has a variety of bridging and terminal amphoteric surface functional groups which deprotonate over a pH range of 4-7. Their relative degree of protonation is calculated here from a series of molecular dynamics simulations in what appear to be the first molecular dynamics simulations of an acidometric titration. In these simulations, a model M₃₀O₈(OH)₅₆(H₂O)₂₆¹⁸⁺ ion is embedded in aqueous solution and titrated with hydroxide ions in the presence of a charge-compensating background of perchlorate ions. Comparison with titration of a model M₁₃O₄(OH)₂₄(H₂O)₁₂⁷⁺ reveals that the M₃₀ ion is more acidic than the M₁₃ ion due to the presence of acidic ηH₂O functional groups. The higher acidities of the functional groups on the M₃₀ ion appear to result from enhanced hydration. Metal-oxygen bond lengths are calculated for the ion in solution, an isolated ion in the gas phase, and in its crystalline hydrate sulfate salt. Gas-phase and crystalline bond lengths do not correlate well with those calculated in solution. The acidities do not relate in any simple way to the number of metals coordinating the surface functional group or the M-O bond length. Moreover, the calculated acidity in solution does not correlate with proton affinities calculated for the isolated ion in the absence of solvent. It is concluded that the search for simple indicators of structure-reactivity relationships at the level of individual reactive sites faces major limitations, unless specific information on the hydration states of the functional groups is available.     

Experimental study of the aragonite to calcite transition in aqueous solution

The experimental replacement of aragonite by calcite was studied under hydrothermal conditions at temperatures between 160 and 200 °C using single inorganic aragonite crystals as a starting material. The initial saturation state and the total [Ca²⁺]:[CO₃²⁻] ratio of the experimental solutions was found to have a determining effect on the amount and abundance of calcite overgrowths as well as the extent of replacement observed within the crystals. The replacement process was accompanied by progressive formation of cracks and pores within the calcite, which led to extended fracturing of the initial aragonite. The overall shape and morphology of the parent aragonite crystal were preserved. The replaced regions were identified with scanning electron microscopy and Raman spectroscopy.Experiments using carbonate solutions prepared with water enriched in ¹⁸O (97%) were also performed in order to trace the course of this replacement process. The incorporation of the heavier oxygen isotope in the carbonate molecule within the calcite replacements was monitored with Raman spectroscopy. The heterogeneous distribution of ¹⁸O in the reaction products required a separate study of the kinetics of isotopic equilibration within the fluid to obtain a better understanding of the ¹⁸O distribution in the calcite replacement. An activation energy of 109 kJ/mol was calculated for the exchange of oxygen isotopes between [C¹⁶O₃²⁻]_aq and [H₂¹⁸O] and the time for oxygen isotope exchange in the fluid at 200 °C was estimated at ∼0.9 s. Given the exchange rate, analyses of the run products imply that the oxygen isotope composition in the calcite product is partly inherited from the oxygen isotope composition of the aragonite parent during the replacement process and is dependent on access of the fluid to the reaction interface rather than equilibration time. The aragonite to calcite fluid-mediated transformation is described by a coupled dissolution-reprecipitation mechanism, where aragonite dissolution is coupled to the precipitation of calcite at an inwardly moving reaction interface.     

Complexation of copper with polymeric silica in aqueous solution

A series of experiments was conducted to study the uptake of Cu by colloidal SiO₂ in aqueous solution. Solutions consisting of 2400 mg l⁻¹ monomeric SiO₂ were allowed to polymerize for 24 h at pH values from 4 to 9, producing coexisting populations of monomer and polymer in each solution. These solutions were combined with aqueous CuCl₂ solutions in final Cu concentrations of 5–30 mg l⁻¹. After the solutions had equilibrated for 24 h, they were filtered through 0.1 μm Millipore filters and analyzed by ICP-AES and gel filtration chromatography (GFC).Experiments conducted at pH 7 with varying Cu concentrations yielded a critical coagulation concentration of 15±1 mg l⁻¹ Cu. GFC analyses of solutions in which coagulation occurred revealed no SiO₂ polymer in the filtrates, suggesting that coagulation is due to the coalescence of SiO₂ polymers by Cu. Experiments conducted with 20 mg l⁻¹ Cu exhibited a gradual increase in Cu uptake from pH 5 to 7, followed by a sharp decrease in Cu uptake from pH 7.25 to 7.50. The gradual increase in Cu uptake up to pH 7 may reflect the increasingly negative surface charge of SiO₂ polymer with increasing pH. The abrupt decrease in the adsorption of Cu to SiO₂ polymer at pH values > 7.25 may be attributed to the decrease in dissociated Cu²⁺ relative to Cu(OH)₂° at higher pH. Although it is traditionally held that the formation of Cu silicates, such as chrysocolla, occurs under acid conditions in supergene Cu deposits, this investigation suggests that Cu silicate formation may be favored in near-neutral solutions in nature.     

The diffusion of dissolved silica in dilute aqueous solution

The diffusion coefficient of dissolved silica at 25.5 ± .5°C was determined as a function of concentration using a non-steady-state method whereby agar-gelled solutions containing dissolved silica from 0.09 to 1.50 mM (pH = 5.5) were placed in contact with distilled water in glass cells. Diffusion coefficients were obtained by measuring the dissolved silica content of the distilled water after a given length of time. The measured diffusion coefficients decreased as a function of increasing dissolved silica concentration, which is thought to reflect an increase in dimeric silica according to the equilibrium: 2Si(OH)₄ = Si₂O(OH)₆ + H₂O. The tracer diffusion coefficients for Si(OH)₄ and Si₂O(OH)₆ and an association constant for the above reaction were determined by fitting the following equation to the experimental data: D_obs = αD_monomer + (1 − α)D_dimer where α is the fraction of total dissolved silica which is Si(OH)₄. The best fit yielded tracer D's for Si(OH)₄ and Si₂O(OH)₆ of 2.2 and 1.0 (in units of 10⁻⁵ cm² sec⁻¹), respectively, and an association constant of 330.     

Molecular simulation of the diffusion of uranyl carbonate species in aqueous solution

Potential-based molecular dynamics simulations of aqueous uranyl carbonate species (M_xUO₂(CO₃)_y^2+2x−2y with M = Mg, Ca, or Sr) were carried out to gain molecular-level insight into the hydration properties of these species. The simulation results were used to estimate the self-diffusion coefficients of these uranyl carbonate species, which often dominate uranyl speciation in groundwater systems. The diffusion coefficients obtained for the monoatomic alkaline-earth cations and polyatomic ions (uranyl, carbonate, and uranyl tri-carbonate) were compared with those calculated from the Stokes-Einstein (SE) equation and its variant formulation by Impey et al. (1983). Our results show that the equation of Impey et al. (1983), originally formulated for monovalent monoatomic ions, can be extended to divalent monoatomic ions, with some success in reproducing the absolute values and the overall trend determined from the molecular dynamics simulations, but not to polyatomic ions, for which the hydration shell is not spherically symmetrical. Despite the quantitative failure of both SE formulations, a plot of the diffusion coefficients of the uranyl carbonate complexes as a function of the inverse of the equivalent spherical radius showed that a general linear dependence is observed for these complexes as expected from the SE equation. The nature of the alkaline-earth cation in the uranyl carbonate complexes was not found to have a significant effect on the ion’s diffusion coefficient, which suggests that the use of a single diffusion coefficient for different alkaline-earth uranyl carbonate complexes in microscopic diffusion models is appropriate.The potential model reproduced well published quantum mechanical and experimental data of and of the individual constituent ions, and therefore is expected to offer reliable predictions of the structure of magnesium and strontium uranyl carbonate aqueous species, for which there is no structural data available to date. In addition, the interatomic distances reported for could help with the refinement of the interpretation of EXAFS data of these species, which is made difficult by the similar uranium-distant carbonate oxygen and uranium-calcium distances.An analysis of the dynamics of water exchange around the alkaline-earth cations revealed that the presence of the uranyl tri-carbonate molecule has a strong influence on the geometry of the cation’s first hydration shell, which, in turn, can considerably affect the water exchange kinetics depending on whether the imposed geometry matches that around the isolated alkaline-earth cation. This result shows that the alkaline-earth uranyl carbonate complexes have distinct water exchange dynamics, which may lead to different reactivities. Finally, significant changes in water residence time were also predicted when replacing carbonate for water ligands in the uranyl coordination shell.     

Spectral studies of several galaxies in the vicinity of the cluster A0569

The results of spectroscopic studies of several faint galaxies projected onto the cluster A0569 are presented. The observations were carried out at Cananea (Mexico) on the 2.12-m telescope of the Guillermo Haro Observatory equipped with a Boller and Chivens spectrograph. The redshifts of these galaxies have been determined based on their absorption and emission lines.     

Removal of ibuprofen from aqueous solution by functionalized strong nano-clay composite adsorbent: kinetic and equilibrium isotherm studies

The functionalized nano-clay composite adsorbent was prepared, and its properties were characterized using FT-IR, XRD and SEM techniques. The synthesized nano-clay composite was studied with regard to its capacity to remove ibuprofen under different adsorption conditions such as varying pH levels (5–9), initial ibuprofen concentrations (3, 5 and 10 mg L^?1), contact time, and the amount of adsorbent (0.125, 0.25, 0.5 and 1 g). In order to evaluate the nanocomposite adsorption capacity, the adsorption results were assessed using nine isotherm models. The results showed that the optimum adsorption pH was 6 and that an increase or decrease in the pH reduced the adsorption capacity. The adsorption process was fast and reached equilibrium after 120 min. The maximum efficacy of ibuprofen removal was approximately 95.2%, with 1 g of adsorbent, 10 mg L^?1 initial concentration of ibuprofen, 120 min contact time and pH = 6. The optimal adsorption isotherm models were the Freundlich, Fritz–Schlunder, Redlich–Peterson, Radke–Prausnitz, Sip, Toth and Khan models. In addition, four adsorption kinetic models were employed for adsorption system evaluation under a variety of experimental conditions. The kinetic data illustrated that the process is very fast, and the reaction followed the Elovich kinetic model. Therefore, this nano-clay composite can be used as an effective adsorbent for the removal of ibuprofen from aqueous solutions, such as water and wastewater.