Pollutants leaching behaviour from solidified wastes: a selection of adapted various models

Leaching tests are essential in the environmental assessment of stabilized wastes. Research programmes were conducted on their interpretation in order to develop tools for the evaluation of long term release of pollutants contained in solidified wastes. Models for the leaching of porous materials are discussed in this paper according to the specificity of the chemical species (i.e. transport model with total dissolution of species-diffusional model; transport model with progressive dissolution of species due to limitation of solubility-shrinking core model; and the model coupling transport and chemical phenomena). The leaching behaviour of pollutants (i.e. lead) solidified in a cement matrix was studied under different chemical conditions. Results have shown that the release of species whose solubilities depend on the physico-chemical conditions, and especially the pH (e.g. amphoteric metals), is governed by the solubility of the species in the pore water at local conditions and by the pH evolution within the matrix. A coupled dissolution/diffusion model was developed to describe the release of chemically complex species contained in a porous medium in contact with water. Leaching tests of cement matrices and artificial porous matrices containing calcium hydroxide and pollutants were conducted in order to validate the coupled dissolution/diffusion model. A good assessment of the retention of some pollutants contained in cement matrices could then be obtained by the association of two tests: solubilization of the pollutants related to the chemical context (pH) under steady state conditions and monolithic long term dynamic leaching tests in order to characterize the evolution of the chemical context (pH) and consequently the release of pollutants. The objective is to integrate this approach in the standardization process (CEN TC 292- WG 6, in progress).     

Dissolution kinetics of cerussite in an alternative leaching reagent for lead

The dissolution kinetics of cerussite was investigated using methanesulphonic acid (MSA) as an alternative leaching reagent. The effects of particle size, stirring speed, acid concentration, and reaction temperature on the lead dissolution rate were determined. The dissolution process followed the kinetic law of the shrinking-core model, and a corresponding mixed control model was found suitable for representing the rate-controlling step. The mixed kinetic model comprised two stages: surface chemical reaction (283 K to 303 K) and diffusion through the product layer (303 K to 323 K). The activation energies of these sequential stages were 43.20 kJ mol^?1 and 17.20 kJ mol^?1, respectively. The corresponding dissolution kinetic equations are also presented to describe the dissolution reaction. The results indicated that methanesulphonic acid could be used as an effective leaching reagent for extracting lead from cerussite minerals.     

Remobilization of pentavalent antimony and vanadium from a granular iron hydroxide material--a comparative study of different leaching systems

The remobilization of antimony and vanadium from previously loaded commercial granular ferric-hydroxide GEH material (intended for water treatment) was examined by using a sequential extraction procedure and three different leaching systems to evaluate their physicochemical mobility and potential availability under different simulated environmental conditions. A classical batch extraction, an extraction cell (EC) and rotating-coiled columns (RCC) were used as extraction systems.For each system it could be shown that the content of ion-exchangeable antimony and vanadium in previously loaded material is negligible (<1.5%). The oxyanions were sorbed strongly and could be predominantly remobilized through reducing agents, which means through dissolution of the iron (hydr)oxide matrix.The major advantages of dynamic systems in comparison to batchwise fractionation technique are the drastically reduced extraction time and the possibility of generating information to the leaching kinetics. It is shown that the efficiency of the three leaching systems is quite different employing Wenzel's sequential fractionation protocol. Only by working with RCC, the iron (hydr)oxide matrix was completely dissolved within four steps resulting in the total mobilization of antimony and vanadium. EC seems to be less suitable for leaching studies of Sb and V sorbed on iron(hydr)oxide. The remobilizable proportion of the several fractions was lower in comparison to batch and RCC and seems to be a result of an agglomeration of the GEH in the EC device.     

Factors affecting the leaching mechanism of Mg bearing oxide impurities in Hydrogen Assisted Magnesiothermic Reduction (HAMR) of TiO2

Titanium production by a direct TiO₂ reduction route which is highly energy-efficient and environment-friendly compared to commercial Kroll's process, known as HAMR (Hydrogen Assisted Magnesiothermic Reduction) process has been developed in recent times to meet the growing global demands of low-cost pure Ti. Removal of the Mg compounds after each reduction and de-oxygenation step in the HAMR process by leaching, is essential to ensure good purity and mechanical properties of the final Ti powder. In this study, we investigate the effects of temperature, particle size, and pH on the dissolution kinetics of Mg from Mg-bearing compounds such as MgO and MgCl₂ that remain after the HAMR Process. We also report the underlying mechanism and rate-controlling steps of Mg removal using HCl in connection with the HAMR process. The dissolution kinetics followed a logarithmic rate kinetic model for diffusion through a porous medium that is commonly used for battery research. Kinetics of leaching were significantly improved using finer particles with 99.96 wt.% Mg removal and corresponding Ti loss of only 1.8 wt. %. The rate of dissolution exhibited a weak dependence with the pH and did not abide by the rate-controlling steps of dissolution of ionic oxides like MgO proposed by previous kinetic models.     

Reaction kinetics of malachite in ammonium carbamate solution

The dissolution of malachite particles in ammonium carbamate (AC) solutions was investigated in a batch reactor, using the parameters of temperature, AC concentration, particle size, and stirring speed. The shrinking core model was evaluated for the dissolution rate increased by decreasing particle size and increasing the temperature and AC concentration. No important effect was observed for variations in stirring speed. Dissolution curves were evaluated in order to test shrinking core models for fluid-solid systems. The dissolution rate was determined as being controlled by surface chemical reaction. The activation energy of the leaching process was determined as 46.04 kJ mol^?1.     

黄金矿的催化浸取

基于对金自溶解电化学过程的分析，提出此过程受阴极还原反应所控制，加入阴极反应催化剂，能加快金自溶速度，实验结果充分表明，我们找到的催化剂Ａ能提高金的浸出速度和浸出效率。     

Bioleaching of low grade uranium ore containing pyrite using A. ferrooxidans and A. thiooxidans

A process of uranium extraction from ore containing 3.1 % pyrite by bacterial leaching was investigated in shaken flasks during 90 days. The highest uranium recovery amounting to 85.1 % was obtained using binary mixture of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans that was exceeding results obtained by traditional acid leaching technique up to 27 %. High uranium recovery was founded to be due to the high degree of pyrite dissolution that can be readily achieved by bacterial leaching (up to 98.0 %).     

The leaching kinetics of brannerite ore in sulfate solutions with iron(III)

A kinetic study of the leaching of powdered brannerite ore by sulfuric acid has been investigated. The effects of stirring speed ranging from 100 to 1,000?min^?1, particle size ranging from 20 to 120???m, concentration of Fe(III) ranging from 0.0025 to 0.20?M, acid concentration ranging from 0.1 to 2.0?M and temperature ranging from 15 to 90?°C on uranium dissolution are reported. The dissolution rate was founded to be significantly influenced by the temperature and concentration of the acid in solution. The experimental data for the dissolution rates of uranium have been analyzed with the shrinking-core model for reaction control. The apparent activation energy for the dissolution of uranium has been evaluated using the Arrhenius expression.     

Utilizing Recyclable Task-Specific Ionic Liquid for Selective Leaching and Refining of Scandium from Bauxite Residue

Ionic liquids (ILs) have attracted great interest in the field of extractive metallurgy mainly because they can be utilized in low temperature leaching processes where they exhibit selectivity and recyclability. A major drawback in mixed aqueous-IL systems, is IL dissolution in the aqueous phase, which leads to IL losses, increasing the overall processing cost. This study advances the method for recovering scandium (Sc) from bauxite residue (BR) using as leaching agent the IL betainium bistriflimide, [Hbet][Tf₂N] mixed with water, which has been reported in previous publications. Ionic liquid leachate (IL-PLS) was prepared by leaching BR with a mixture of [Hbet][Tf₂N]-H₂O and subjected to different stripping experiments using hydrochloric acid. The advancement, presented in this work, is related with the optimization of the metal extraction (stripping) from the IL-PLS, where an aqueous solution with high Sc concentration and minimum metal impurities and minimum IL co-extraction is produced. It is further proven that the metal cation extraction is defined by the stoichiometry of the acidic solution and the dissolution (losses) of the IL in the aqueous phase can be minimized by adjusting the volume ratio and the acid concentration. A two-step stripping process described, achieves the selective increase of Sc concentration by 8 times in the aqueous solution, while maintaining cumulative IL losses to similar levels as the optimum 1 step non-Sc selective stripping process.     

Electrochemistry of marmatite-carbon paste electrode in the presence of bacterial strains

The electrochemical behaviors of a marmatite-carbon paste electrode with the chemical leaching of Fe3+ ions, or the microbial leaching using Acidithiobacillus ferrooxidans, were compared. The cyclic voltammograms of the electrode in the presence and absence of bacterial strains showed that the leaching process of marmatite was carried out by the different reactions occurring in the interface of the marmatite electrode-leach liquid. The polarization currents of the electrode under the differently applied potentials suggested that the microbial leaching of marmatite could be accelerated by the applied potential. The SEM observations indicated that the corrosion pits formed in the electrode surface were similar to the attached bacterial cells in shape and size, other than that by the chemical leaching of Fe3+ ions. The contact leaching of the attached cells on the mineral substrate played an important role on the dissolution of marmatite in addition to the chemical leaching of Fe3+ ions.     

The effect of unsaturation on the reaction of aqueous alkyl bromides with brass foil

Brass (a zinc/copper alloy) foil reacts with mixtures of water and alkyl bromides to give dissolution of zinc and copper. The relative rates of leaching depend on the bromide used: saturated bromides favor dissolution of zinc, whereas unsaturated bromides favor dissolution of copper. This difference is attributed to the formation of π-complexes between the unsaturated linkages and the copper atoms.     

Reactivity of NASICON with water and interpretation of the detection limit of a NASICON based Na(+) ion selective electrode

The leaching of Na(+) ions from NASICON of composition Na(3)Zr(2)Si(2)PO(12) to the aqueous solution was evidenced. The origin of the Na(+) leaching was studied using Na(+) concentration and pH measurements as well as solution and X-ray analyses. The Na(+) released was mainly attributed to the dissolution of a second phase, predominantly amorphous. The rate of Na(+) release was found to be dependent on the inverse of the square of the particle size. It is proposed that it is controlled by diffusion within the particle. An effective diffusion coefficient was deduced to be of the order of 5x10(-10) cm(2) s(-1). The nature of the detection limit of the NASICON based Na(+) ion selective electrodes is discussed.     

A fast method for apatite selective leaching from granitic rocks followed through rare earth elements and phosphorus determination by inductively coupled plasma optical emission spectrometry

Rare earth elements (REE) and phosphorus (P) in apatite were determined using inductively coupled plasma optical emission spectrometry (ICP-OES) after partial dissolution of the granitic rocks and pure apatite. The dissolution was performed with nitric acid in an open system and the matrix elements were separated by a cation exchange procedure. Samples of pure apatite from granitic rocks were dissolved with, 0.14 mol L⁻¹ nitric acid. The results showed that the release of REE is due to apatite leaching because it could be assessed by comparing the chondrite-normalised pattern corresponding to the rocks and the pure apatite. Similar results were found for absolute REE abundance from the partial dissolution of the rocks and pure apatite.This simple and rapid method can be applied for the determination of REE in apatite as an indicator for mineral exploration, although its use in petrology could be possible.     

Rapid dissolution of large environmental samples for the determination of fission products

The dissolution of large environmental samples was investigated using a microwave autoclave, capable of digestion conditions of 300 °C and 200 bar, for the application of rapid determination of radionuclides. Six samples of up to 5 g plant material were digested, also eliminating predigestion steps such as ashing and grinding. Batches of forty 1 g samples of plant leaves were also completely digested in 75 minutes. Quantitative recovery of ⁹⁰Sr from 5 g soil samples by leaching with 8M HNO₃ at 200 °C was achieved, whereas ¹³⁷Cs was not completely recovered from the large soil samples using total digestion or leaching (HCl:HNO₃) techniques, but quantitative recovery was achieved using fusion and sinter procedures.     

Radioanalytical determination of actinoids in refractory matrices by alkali fusion

In this work a method used conventionally for ICP-MS measurements have been modified and readapted for the determination of actinides (U and Th isotopes) in refractory samples by alpha-spectrometry. The method is based in a total dissolution of the sample by alkali fusion. In the first stages of our studies, we try to digest refractory samples by leaching with aqua regia followed by the application of a liquid–liquid solvent extraction process for the sequential isolation of the uranium and thorium isotopes from the dissolved fraction. These actinides were finally electroplated in stainless steel discs and measured in an alpha-spectrometer using PIPS detectors. On the other hand, gamma measurements were carried out in aliquots of the same samples in order to check the results produced by alpha spectrometry. Clear disagreements were found between the results obtained by both techniques. This problem was solved by the application of an alkali fusion technique where a total dissolution of the sample is performed. It was found in addition that the alkali fusion is easily applicable, less time-consuming, needs less reagents than leaching and it does not require sophisticated apparatus to be executed. In this paper the whole procedure for U and Th determination in refractory samples by alpha-spectrometry with alkali fusion is presented and validated.     

Studies on the kinetics of UO2 dissolution in carbonate-bicarbonate medium using sodium hypochlorite as oxidant

The dissolution of UO₂ in carbonate-bicarbonate solutions containing sodium hypochlorite as an oxidant has been investigated. The effect of temperature, sodium hypochlorite concentration and stirring speed was examined. In the temperature range of 303 to 318 K, the leaching reaction displayed linear kinetics. Apparent activation energy obtained from the differential approach was found to be 57 kJ mol^?1. This relatively high activation energy value indicates a chemically controlled behavior of UO₂ dissolution. The order of reaction with respect to sodium hypochlorite concentration was found to be unity.     

A methodological study of mercury speciation using dogfish liver CRM (DOLT-2)

The purpose of the study was to optimise analytical methods for determination of the chemical speciation of mercury in studies of protective mechanisms of selenium. Optimisation of the methods was performed using CRM DOLT-2 (Dogfish liver), both in its original form and after separation of various fractions. The sample was homogenised with 10 mM Tris-HCl buffer (pH 7.6) and ultracentrifuged. The soluble phase obtained was applied to a size exclusion chromatography column (Sephadex G-75 column) for separation of various protein fractions. Total mercury (total Hg), monomethyl mercury (MeHg) and selenium (Se) were determined in whole dogfish liver tissue and its soluble and insoluble phases (pellet). Different approaches for determination of total Hg and MeHg were compared. Simultaneous determination of MeHg and inorganic mercury (Hg2+) was based on alkaline dissolution and/or acid leaching, followed by ethylation, room temperature precollection, isothermal gas chromatography (GC), pyrolysis and detection with cold vapour atomic fluorescence spectrometry (CVAFS). The sum of MeHg and Hg2+ was compared to total Hg results obtained by acid digestion and CVAAS detection. The accuracy of MeHg determination was checked by its determination using acid leaching at room temperature, solvent extraction, back extraction into Milli-Q water, ethylation, GC and CVAFS detection. For the insoluble phase it is recommended to use solvent extraction for MeHg and acid digestion CVAAS for total Hg. For determination of MeHg and Hg2+ in the lyophilised sample and water soluble fractions containing low concentrations of mercury species, the simultaneous measurement of MeHg and Hg2+ after alkaline dissolution is the most appropriate method.     

Leaching of El-Missikat low-grade fluoritized uranium ore by sulfuric acid: mechanism and kinetic

A well-characterized low-grade fluoritized uranium samples from new occurrence in Gabal El-Missikat prospect, Eastern Desert, Egypt was subjected to sulfuric acid leaching. The effects of leaching parameters on uranium dissolution mechanism were investigated. The shrinking core model was used to model leaching reactions. The kinetics equations indicates that the reactions appear to be controlled by layer diffusion process. The activation energy for uranium dissolution was evaluated. Low activation energy value (2.54 kJ mol⁻¹) confirm the diffusion layer mechanism. The presence of fluoride ions in the solution increases the dissolution of uranium. The optimum process operating parameters were: sulfuric acid concentration: 1.5 M, solid–liquid ratio: 1:3, contact time 8 h; agitation speed rate 200 rpm; and ore particle size − 75 µm at temperature 60 °C, in the absence of an external oxidant. Under these experimental conditions, the extraction efficiency of uranium was about 91%.

     

Assessment of three digestion procedures for Zn contents in Pakistani soil by flame atomic absorption spectrometry

Evaluation of three different digestion procedures for accurate determination of elemental concentration in soils was undertaken. The digestion procedures, two leaching and a total dissolution processes were compared for twenty-one soil samples. The soil standard reference materials (SRMs), IAEA Soil-5 and IAEA Soil-7 were analysed for quality control purposes. Zinc (Zn) was analysed using flame atomic absorption spectrometry (FAAS). Precise analysis was accomplished in the SRM and soil samples, which was better than 4.7% for leaching and total dissolution procedure. Compared with the elemental concentration in soil samples, HF–HClO₄ procedure achieved greater accuracy, where as HNO₃–H₂O₂ and HNO₃–H₂SO₄–HCl procedures were comparable with slight variation in a few samples.     

Studies on the kinetics of UO2 dissolution in carbonate-bicarbonate medium using sodium hypochlorite as oxidant

The dissolution of UO₂ in carbonate-bicarbonate solutions containing sodium hypochlorite as an oxidant has been investigated. The effect of temperature, sodium hypochlorite concentration and stirring speed was examined. In the temperature range of 303 to 318 K, the leaching reaction displayed linear kinetics. Apparent activation energy obtained from the differential approach was found to be 57 kJ mol^–1. This relatively high activation energy value indicates a chemically controlled behavior of UO₂ dissolution. The order of reaction with respect to sodium hypochlorite concentration was found to be unity.