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1.
The sorption of boron from aqueous solution onto Caulerpa racemosa var. cylindracea (CRC), collected from Seferihisar/Izmir region in Turkey, was investigated as a function of pH, temperature, initial boron concentration, adsorbent dosage, contact time and ionic strength. Optimum conditions for the sorption of boron were obtained at pH 7.5, 318 K, 8 mg L−1 initial boron concentration, 0.2 g of CRC, 2.5 h contact time and greater ionic strength (10−1 M NaCl). As the temperature was increased the boron removal took place with higher percentages. In experiments conducted at optimum conditions, maximum boron sorption was determined to be about 63%. The experimental data were analyzed by Freundlich, Langmuir and Dubinin–Radusckevich (DR) equations. Freundlich and DR models provide best conformity with the experimental data. In order to describe kinetics of boron sorption onto CRC, first-order Lagergren equation, pseudo-second-order kinetic model and intraparticle diffusion model were used. It was seen that the first order Lagergren equation was better described than the pseudo-second-order kinetic model. Thermodynamic parameters of sorption process were also calculated. It was obtained that sorption process was not spontaneous. The characterization of CRC was carried out by Fourier transform infrared spectroscopy (FTIR) analysis.  相似文献   

2.
Sorption of radionuclides onto a stable colloidal phase may significantly enhance their transport in groundwater. A key point, to be analysed to assess the relevance of colloids in the safety of a deep geological radioactive waste repository, is the irreversibility of the colloid/radionuclide bond.In this work, sorption and desorption kinetics of cesium and uranium(VI) onto bentonite colloids in a granitic reduced environment was studied by means of batch experiments, carried out in anoxic conditions under N2 atmosphere. Sorption kinetics was followed during 18 weeks, and sorption isotherms were also carried out to get additional information on sorption mechanisms. The water used in all the experiments was an alkaline, low ionic strength (pH=9.5 and I=1×10−3M) granitic groundwater from the NAGRA's Grimsel Test Site (GTS), Switzerland, which also presents reduced Eh (−200 mV). In this water, bentonite colloids were shown to be stable during several months.Both cesium and uranium presented a nonlinear sorption behaviour in the range of concentration investigated. In kinetic experiments, the measured log Kd for Cs ([Cs]=1×10−7 M) was 3.94±0.15, and this value did not show significant variations with time. However, the adsorption of cesium on bentonite colloids involves two reactions, a rapid exchange on planar sites (hours) and a slower component (days) in which cesium diffuses to less available but highly selective sites. This slow process, that can be evidenced only when very low tracer concentrations are used (<1×10−9 M), is most probably responsible for the fixation of a fraction of the sorbed cesium, and for the partial sorption irreversibility shown in desorption tests. Kd values measured after several desorption experiments increased significantly with the age of the sorption complex. For example, for the sample with 1-day contact time, the second desorption Kd was 8600 ml/g whereas the 5 and 8 weeks contact time samples showed second desorption Kd 15 000 and 30 000 ml/g, respectively.The measured log Kd for U ([U(VI)]=4×10−7 M) varied from 2.91 to 3.21 (±0.15) during 18 weeks of the kinetic experiment. The main variation of Kd values took place in the first 4 weeks, and then a very slow increasing trend was observed, which could be probably attributed to a partial reduction of U(VI) to U(IV).In desorption tests with uranium, desorption Kds were independent on the initial contact time. Nevertheless, a certain sorption/desorption hysteresis was observed, which is most probably due to the contribution of surface complexation reactions, at the edge sites of clay colloids, to uranium sorption. Hence, U sorption is not completely reversible.  相似文献   

3.
Argillaceous rocks are considered potential host rocks for radioactive waste repositories. The concrete matrix that could be used as a barrier could react with the groundwater of the geological site, inducing a drastic change in its chemical composition and its pH (10–13). Consequently, the physicochemical properties of the rock in contact with this alkaline solution may be modified and, in turn, may induce modification on the behaviour of radioelements. This study, applied to the argillite of Tournemire, involves characterizing I sorption to an argillaceous rock in alkaline media in batch experiments under N2-controlled conditions. I was added as a 125I radiotracer and measured by γ spectrometry.Preliminary experiments were conducted with different solution/solid ratios (v/m=2.5, 5 and 20 ml g−1) and contact times (1–14 days) in order to determine the optimal experimental conditions. The chosen v/m ratio was 5 ml g−1 as the best compromise between a high Kd value and a low error of the measure. The chosen experiment duration was 1 day because I sorption was highest and to limit the effects of pyrite oxidation. One of the experiments, performed with a radio-sterilized sample to test possible effects from microorganisms, showed that they could enhance iodide retention, particularly during the first 2 contact days.The influence of pH on I sorption was tested using solutions between values of 8.3 and 12.8. The Kd values were independent of pH and very low (0.3 ml g−1).Finally, the influence of the chemical composition of concrete fluids was also tested. Three solution compositions corresponding to different steps in the evolution of fluids in contact with altering concrete were used: fluid in contact with fresh concrete (pH 13.2), with moderately degraded concrete (pH 12.1) and with strongly degraded concrete (pH 11.5). Each solution contained variable amounts of sodium, potassium, calcium, silica and sulphate. I sorption was also very low (Kd0.2 ml g−1). Additional experiments were conducted with alkaline solutions containing different amounts of SO42− ions (10−3–10−2 M) to test sulphate–iodide sorption competition. I retention was independent of the sulphate concentration.  相似文献   

4.
5.
The DI-B experiment is a long-term, natural-scale, in situ diffusion experiment, which is being performed in the Opalinus Clay formation at the Mont Terri Underground Rock Laboratory (URL), in Switzerland, employing nonradioactive tracers. One of the key aspects to be addressed for nuclear waste repository safety assessment purposes is the understanding of the transport mechanisms of the radionuclides contained in the radioactive waste. Consolidated clay formations display very low water hydraulic conductivities, so it is expected that the predominant transport process will be diffusion.The experimental set-up has been designed to withstand the site conditions and for monitoring and recording several physicochemical parameters (pH, conductivity, oxidation–reduction potential), as well as the pressures in the circuit and for the long-distance monitoring of the data acquisition system.The tracer selection has been made based on previous investigations carried out at CIEMAT, including a literature survey, laboratory sorption experiments and hydrogeochemical modeling for determining tracer stability under the physicochemical conditions to be expected in the site. The final selection includes 6Li, 87Rb, D (as D2O) and I (as I). Hydrogeochemical modeling confirmed the stability of all the tracers selected. Batch sorption experiments showed that no sorption in the rock occurred in the case of 6Li, D and I (conservative tracers), whereas 87Rb was 100% sorbed. However, 87Rb was chosen because of its analogy with Cs, a relevant radionuclide commonly present in the nuclear spent fuel.Diffusion experiments have been carried out at laboratory scale with Opalinus Clay samples to provide diffusion parameters for modeling purposes. Effective diffusion coefficients, perpendicular and parallel to the bedding planes of the rock, respectively, were (1.68± 0.42)×10−11 and (4.02± 0.30)×10−11 m2/s for tritium, and (2.70± 0.27)×10−12 and (1.38± 0.49)×10−11 m2/s for iodide. Additional through-diffusion experiments (parallel to the bedding) were performed with the nonsorbing tracer 36Cl, in order to check the results obtained for iodide. The effective diffusion coefficient measured for chloride ions was (1.18± 0.27)×10−11 m2/s, which is practically equal to the value obtained for iodide.Preliminary diffusion calculations have been carried out using two transport codes: GIMRT and CORE2D, with conservative and nonconservative tracers, using effective diffusion coefficients (De) obtained experimentally in the laboratory (through-diffusion experiments) or selected from the literature. The diffusion profiles obtained from the calculations showed slight variations, which were consistent with the different modeling approaches employed. The predictive modeling results have been used to determine the initial tracer concentration that should be added to the circuit to assure well-defined profiles at the end of the experiment.This long-term in situ diffusion experiment will also provide useful data for the interpretation of previous diffusion experiments performed at the Mont Terri URL.  相似文献   

6.
Gel beads of calcium alginate, pectate and polygalacturonate salts have been tested as sorbent materials for mercury(II) removal from aqueous solutions. Physico-chemical properties of gel beads, defined by SEM–EDX, TGA and texture and density analysis, were correlated with gel beads sorption capacity towards Hg2+ ion. A speciation study in aqueous solution was carried out to define the strength of interaction of mercury ion with the polymers investigated and to assess the more suitable experimental conditions to achieve the best effectiveness of Hg2+ sorption by gel beads. On the basis of the speciation study, pH values in the 3–5.5 pH range were considered appropriated for mercury(II) sorption by gel beads. Kinetics of mercury(II) sorption and calcium(II) release from the sorbent materials were studied at pH 3, 3.6 and 5.2. The highest sorption rate (K) and amount of mercury(II) adsorbed were obtained at pH 3 and 3.6; therefore, pH 3.3 was chosen for the equilibrium study of Hg2+ sorption at 25 °C. The results obtained by using Langmuir and Freundlich isotherm equations show the following sorption capacity trend: Ca–Pect > Ca–PGA > Ca–AA.  相似文献   

7.
A cyclic voltammetric study of the behaviour of Br and Br 3 at Pt electrodes, in the potential range between hydrogen and oxygen evolution, is described. Different experiments were carried out, in the presence of Br and Br 3, in which the ratio between the species has been kept constant and equal to 1. The halide concentration was varied between 4 × 10–6 and 1 × 10–3 and mol dm–3, at constant ionic strength, in 1 M HclO4 as well as in 1 M NaClO4 adjusted to a pH of 2. Underpotential deposition of Br is observed at potentials as low as –0.125 V vs SCE. The adsorption parameters of Br species were determined from the adsorption/desorption peak pair in the hydrogen adsorption/desorption region, and from the oxide reduction peak data. In the absence of oxygen adsorption, a relatively high coverage of the electrode surface is attained. A Langmuir-type adsorption is observed under the different experimental conditions.  相似文献   

8.
An earlier study of phosphate sorption by some savanna soils from Nigeria suggested that increased P sorption when pH was raised might be due to precipitation of exchangeable Al as amorphous polymeric Al species with increased sorption sites. But these savanna soils have Ca as the dominant cation in their exchange sites, and low exchangeable Al. The objective of this study was to determine the role played by Ca in pH-induced P sorption of three savanna soils under continuous cultivation. Phosphorus sorption increased when pH was raised from 4.5 to 7.0. Similarly, Ca retention increased with increasing pH. Regression of P sorption on Ca retention indicated a significant linear relationship in the three soils. Three possible mechanisms were proposed to explain the increasing P sorption with increasing pH: precipitation of Ca-phosphates, Ca-induced P sorption or co-adsorption of Ca and H2PO 4 or HPO 4 2– as ion pairs or complexes. Available evidence suggests that all three mechanisms can operate together to enhance P retention as pH increases. The paper proposes that increased P sorption by savanna soils when pH is raised is likely to be related to the chemistry and retention of Ca rather than to hydrolytic reactions of Al.  相似文献   

9.
Co3O4 layers were prepared by thermal decomposition of Co(NO3)2 at various temperatures in the range 200–500° C on a Ti support with and without an interlayer of RuO2. Kinetic studies were carried out with and without dissolved Cl2 at various partial pressures in NaCl solutions of concentration in the range 0.5–5 mol dm–3. The effect of the solution pH was especially investigated. Kinetic measurements were carried out both close to and far from equilibrium. The following parameters were determined: transfer coefficient, Tafel slope, stoichiometric number, reaction orders with respect to Cl, H+ and surface sites, activation energy. The most intriguing feature observed was the retarding effect of acidity on the anodic Cl2 reaction. This has been ascribed to the complex surface behaviour of oxides in solution. A detailed mechanistic scheme has been proposed and discussed. The stability of the oxide surface was monitored by measuring the voltammetric charge in alkaline solution after sets of experiments.Paper presented at the 34th Meeting of the International Society of Electrochemistry, Erlangen, 19–23 September, 1983.  相似文献   

10.
Triangular potential sweep voltammetry, potentiokinetic generation of polarization curves, and coupon corrosion tests have been carried out to determine the influence of 2-mercaptobenzothiazole (MBT) on the dissolution of silver in cyanide solutions at pH 11. MBT has been shown to be an effective inhibitor for silver dissolution at concentrations similar to those used when MBT is applied as a flotation collector. The inhibition efficiency (i.e., [1 – the ratio of the corrosion rates in the presence and absence of MBT], expressed as a percentage) in 10–2 and 10–3 mol dm–3 CN was found to increase with increase in MBT concentration in the range 10–6 to 10–4 mol dm–3, and with increase in time of exposure of the silver to the MBT solution. The inhibition efficiency found for 10–4 mol dm–3 MBT in quiescent 10–2 mol dm–3 CN solution at 23 °C was 98.9%, 99.4% and 99.99% for exposure times of 10 min, 2 h and 5 days, respectively. Surface enhanced Raman spectroscopy showed that inhibition was associated with adsorption of MBT displacing cyanide from the silver surface.  相似文献   

11.
Surface complexation model of uranyl sorption on Georgia kaolinite   总被引:2,自引:0,他引:2  
The adsorption of uranyl on standard Georgia kaolinites (KGa-1 and KGa-1B) was studied as a function of pH (3–10), total U (1 and 10 μmol/l), and mass loading of clay (4 and 40 g/l). The uptake of uranyl in air-equilibrated systems increased with pH and reached a maximum in the near-neutral pH range. At higher pH values, the sorption decreased due to the presence of aqueous uranyl carbonate complexes. One kaolinite sample was examined after the uranyl uptake experiments by transmission electron microscopy (TEM), using energy dispersive X-ray spectroscopy (EDS) to determine the U content. It was found that uranium was preferentially adsorbed by Ti-rich impurity phases (predominantly anatase), which are present in the kaolinite samples. Uranyl sorption on the Georgia kaolinites was simulated with U sorption reactions on both titanol and aluminol sites, using a simple non-electrostatic surface complexation model (SCM). The relative amounts of U-binding >TiOH and >AlOH sites were estimated from the TEM/EDS results. A ternary uranyl carbonate complex on the titanol site improved the fit to the experimental data in the higher pH range. The final model contained only three optimised log K values, and was able to simulate adsorption data across a wide range of experimental conditions. The >TiOH (anatase) sites appear to play an important role in retaining U at low uranyl concentrations. As kaolinite often contains trace TiO2, its presence may need to be taken into account when modelling the results of sorption experiments with radionuclides or trace metals on kaolinite.  相似文献   

12.
Polarization studies have been carried out to determine the influence of diisobutyldithiophosphinate (DIBDTPI) on the dissolution of silver in cyanide solutions at pH 11. DIBDTPI was found to inhibit dissolution at concentrations similar to those used when this compound is applied as a flotation collector. The inhibition efficiency in 10–2 mol dm–3 CN was found to increase with increase in DIBDTPI concentration in the range 10–6–10–4 mol dm–3, and with increase in time of exposure of the silver to the DIBDTPI solution. The inhibition efficiency found for 10–4 mol dm–3 DIBDTPI in quiescent 10–2 mol dm–3 CN solution at 23 °C was 64.6% and 95.0% for exposure times of 10 min and 2 h, respectively. These values are significantly less than those found previously for 2-mercaptobenzothiazole under the same conditions. Surface enhanced Raman spectroscopy showed that inhibition was associated with adsorption of DIBDTPI displacing cyanide from the silver surface. Voltammetry at 0.5 mV s–1 indicated that adsorption of DIBDTPI involves charge transfer.  相似文献   

13.
Removal/preconcentration of thallium(I) ions from aqueous solution by sawdust; a waste material derived from the commercial processing of Cedrus Deodar wood for furniture production was investigated. A simple and low-cost modification results in increasing the sorption capacity of raw sawdust from 2.71 to 13.18 mg g−1. Sorption was found to be rapid (98% within 8 min). The binding of metal ions was found to be pH dependent, optimal sorption accruing at around pH 6–9. Potentiometeric titrations of sawdust revealed two distinct pKa values, the first having the value similar to carboxylic groups (3.3–4.8) and second comparable with that of amines (8.53–10.2) with the surface site densities of 1.99 × 10−4 and 7.94 × 10−5 mol g−1, respectively. Retained Tl(I) ions were eluted with 5 ml 0.1 mol l−1 HCl. Detection limit of 0.0125 μg ml−1 was achieved with an enrichment factor of 160. Recovery was quantitative using sample volume of 800 ml. The Langmuir, Freundlich and D–R isotherm equations were used to describe partitioning behavior for the system at different temperatures. Kinetic and thermodynamic behavior of sawdust for Tl(I) ions removal was also studied.  相似文献   

14.
The kinetics and equilibria of sorption of the divalent metal ions cobalt and nickel onto anaerobic granular sludge are described. Single component and binary equimolar systems were studied at different pH values (pH 6, 7 and 8). The kinetic modelling of metal sorption by anaerobic granular sludge has been carried out using Lagergren equations. On fitting the experimental kinetic data both in first‐ and pseudo‐second‐order equations, the regression analysis of a pseudo‐second‐order equation gave a higher r2 value, indicating that both external mass transfer and intra‐particle diffusion are involved in the sorption process. The experimental isotherm data were analysed using the Langmuir, Freundlich and Redlich–Peterson equations. The Redlich isotherm, a combination of the Langmuir and Freundlich equations, was found to have the highest regression correlation coefficients at pH 7. At pH 8, the Langmuir mechanism dominated for cobalt and nickel adsorption. In contrast, at pH 6, the Freundlich equation gave a better correlation coefficient which suggests a more heterogeneous adsorption at that pH. The maximal adsorption capacity of the granular sludge, as determined by the Langmuir equation, for cobalt or nickel in single systems (8.92 mg g?1 Co TSS; 9.41 mg g?1 Ni TSS, pH 7) compared with binary systems (8.06 mg g?1 Co TSS; 8.43 mg g?1 Ni TSS, pH 7) showed no great difference in the accumulation of these metals onto granular sludge. Copyright © 2004 Society of Chemical Industry  相似文献   

15.
Five field experiments involving P application rates from 0 to 66 kg P ha–1 were conducted on irrigated wheat at Tandojam, Pakistan. The soils belonged to two great soil groups, Torrifluvent and Camborthid. All soils were calcareous. Olsen-P contents ranged from 3.5 to 6.3 mg P kg–1. Phosphate sorption curves were developed for soils from control (no P) plots at each site. Concentrations of P in solution established by fertilization in the field as estimated from the sorption curves ranged from 0.008 to 0.16mg P L–1. Actual grain yields were converted to relative grain yields and plotted against corresponding concentrations of P in solution. Yield response to P application was obtained in each experiment. Control plot yields ranged from 57 to 89% of maximum yield of respective experiments. Phosphorus requirements of wheat were 0.032 mg L–1 for 95% yield as determined from a composite yield response curve. Predicted quantities of P required to attain 0.032 mg P L–1 ranged from 18 to 29 kg P ha–1. The results of the study suggest that the P sorption approach can be used as a rational basis for making P fertilizer recommendations for various soil-crop combinations.  相似文献   

16.
Separation of Cs+ from acidic solution was investigated using ammonium molybdo- phosphate (AMP) based sorbents. Four sorbents including two AMP powders and two composites prepared by coating of AMP powder on polymethylmethacrylate (PMMA) beads were used in this study. Equilibrium sorption isotherms for Cs+ on AMP sorbents were determined. The effect of H+ concentration on Cs+ uptake by AMP–PMMA beads was examined. Two column runs were carried out to establish the Cs+ separation performance of AMP–PMMA beads from 1.0 M nitric acid having Cs+ concentration equivalent to 10 Ci of 137Cs per litre. Recovery of Cs+ from loaded AMP–PMMA column was carried out by dissolution of AMP using NaOH solution. The feasibility of ion exchange purification of the recovered Cs+ solution was examined using resorcinol formaldehyde polycondensate resin (RFPR). The Cs+ sorption isotherm on RFPR from Cs-bearing dissolved AMP solution was determined. Purification of Cs+ from dissolved AMP solution was studied in two column runs using RFPR in loading-elution cycles. The results of these studies are useful in formulating a scheme for the recovery of purified 137Cs product from high level waste for large-scale utilization as a radiation source in industrial irradiators.  相似文献   

17.
NO x sorption capacities and efficiencies were measured on a new type of sorbent formed by 12-tungstophosphoric acid (HPW) supported on carbon nanotubes. On such a system, the sorption of both NO and NO2 was observed but compared with HPW alone, a complementary sorption of NO x is possible leading to a capacity of 25 mg/gHPW at 300 °C with an efficiency of 50%. The sorption results from the formation of a [H+(NO2 ,NO+)] complex on HPW and an additional mode of adsorption by a free-nitrate which was identified by the bands at 2261, 1384 and 1295 cm–1 using infrared spectroscopy.  相似文献   

18.
The underground disposal of radioactive waste is based upon a multibarrier concept. For long-term performance assessment of radioactive repositories, knowledge concerning the sorption of radionuclides in backfill materials is required. As a part of the multibarrier system for effective isolation of radioactive waste in a repository, Zeolite NaA–X blend was prepared from fly ash, characterized, and evaluated to be used as a backfill material. In this concern, the sorption behavior of Cs+ on the prepared material as a function of pH, initial ion concentration and temperature was studied by batch technique. The sorption isotherm data was interpreted by Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherm models. The application of the Langmuir isotherm yielded monolayer capacity of 1546 mmol/kg at 298 K while the maximum sorption capacity predicted by D–R isotherm was of 2446 mmol/kg. Thermodynamic parameters for the sorption system were determined at three different temperatures. The enthalpy (ΔH°), entropy (ΔS°) and free energy (ΔG°) of sorption at 298 K were found to be 25.43 kJ/mol, 93 J/mol K and −2.316 kJ/mol, respectively. The positive value of ΔH° corresponds to the endothermic nature of the sorption process. The numerical value of ΔG° decreases with an increase in temperature indicating that the sorption was spontaneous and more favorable at higher temperatures.  相似文献   

19.
The effects of boric acid additions on the pH close to the electrode surface, on the hydrogen evolution reaction and on the internal stress in the plated films were studied for the high speed electroplating of nickel from a nickel sulfamate bath at a current density close to the nickel ion limiting current density. The study was carried out at 50 °C and pH 4.0 using a 1.55 M nickel sulfamate plating bath containing boric acid at concentrations ranging from 0 to 0.81 mol L–1. The variation of the internal strain in the plated nickel films was determined in situ using a resistance wire-type strain gauge fitted to the reverse side of the copper electrode substrate. The solution pH at a distance of 0.1 mm from the depositing nickel film was measured in situ using a miniature pH sensor assembly consisting of a thin wire-type antimony electrode and a Ag/AgCl/sat. KCl electrode housed in a thin Luggin capillary. The addition of boric acid was shown to effectively suppress the hydrogen evolution reaction at nickel electrodeposition rates (18.0 A dm–2) close to the limiting current density (~20 A dm–2). Consequently, the solution pH adjacent to the plating metal surface was maintained at a value close to that in the bulk solution and the development of high internal stresses in the deposited nickel films was avoided.  相似文献   

20.
《分离科学与技术》2012,47(14):2123-2141
ABSTRACT

An alizarin red S (ARS)-modified anion-exchange resin was prepared by a simple reaction of ARS with the anion exchanger Doulite A101 and used for the efficient sorption of uranium from aqueous media. The effect of various parameters on the sorption of U(VI) (pH effect, sorption kinetics, resin capacity and breakthrough curves) was investigated. The modified resin sorbs U(VI) over a wide range of pH (2·8–5) with a maximum sorption capacity of 0·68 mmol.g?1 at pH 3·2 to 4·0. Iron (III), Zr(IV), Ti(IV), Cu(II), and Th(IV) ions are also sorbed to different extents, but Be(II), Bi(III), Ca(II), Mg(II), Pb(II), Hg(II), Zn(II), Cd(II), AI(III), Mn(II), Co(II) and Ni(II) are not sorbed; thus, conditions for separating U(VI) from these metal ions have been identified. For eluting U(VI) from the resin, 0·2 mol.L?1 HCl was used and the recovery recorded was as high as 99.9%. The use of ARS is extended to float uranium quantitatively and selectively from aqueous media at pH = 4 by using oleic acid as a surfactant. The different parameters affecting the flotation process have also been investigated. Uranium(VI) has been effectively separated from natural water samples and certified uranium ores using both procedures.  相似文献   

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