Real time alteration of a nuclear waste glass and remobilization of lanthanide into an interphase

The development of predictive models for the long term evolution of nuclear waste glass requires the complete knowledge of the glass dissolution at the laboratory scale. A new approach was developed to determine the initial reaction during the first steps of experience, a new concept was developed, based on the combination of dynamic leaching test and the characterization of the altered materials. With this experimental set-up it is possible to follow in real time the glass alteration process at a fine temporal scale. The results put in evidence a singular behaviour of the lanthanide, shown by a concentration peak of La, Nd and Ce after 2 h and a quick decrease of their concentration measured on line in the solution during the leaching test. This fact is directly linked to the development of an interphase (altered layer which differs from the initial solid by its texture, structure and chemical composition) at the interface of the glass surface and the leaching solution. This work is an attempt to integrate the formation of the alteration products (here the interphase) during leaching into the dissolution mechanisms of a nuclear waste glass. A model is proposed and discussed.     

Leaching of mecoprop and dichlorprop in calcareous soil. Effect of the exogen organic matter addition in this process

Abstract

Leaching studies of mecorprop (R,S)‐2‐(4‐chloro‐2‐methylphenoxy)propanoic acid, and dichlorprop, (R,S)‐2‐(4‐chloro‐2,4‐dichlorophenoxy) propanoic acid, under saturated conditions were conducted in unamended and amended soil columns. The purpose of the study was to investigate the leaching of these herbicides in three type of soils and the exogen organic matter effect on this process. The leaching patterns could be related to variation in the soil texture and diffusion processes of the herbicides into micropores within the walls of conducting pore. The leaching rate in the amended soil columns decreased with the addition of organic matter. The breakthrough curves (BTC) of these herbicides in the leachates of the amended soil columns were wider and more diffused than the BTC obtained for the corresponding unamended soil. The theoretical BTC overestimated the pore volume required for the displacement of these pesticides from the soil column. This may be due to the differences in the adsorption process between the bacth and soil columns methods     

Reduced Downward Mobility of Metolachlor and Metribuzin from Surfactant-Modified Clays

The study aims to prepare the organoclay complexes of metolachlor and metribuzin so as to reduce their downward mobility in soil profile. The organoclays were preadsorbed with phenyltrimethylammonium (PTMA) (50% of cation exchange capacity [CEC]) and hexadecyltrimethylammonium (HDTMA) (100% of CEC). Four metolachlor formulations, two for each organoclay, were prepared having 1% and 2% load of herbicide and were called PTMA-Metol-1%, PTMA-Metol-2%, HDTMA-Metol-1% and HDTMA-Metol-2%. Two metribuzin formulations were prepared and were called PTMA-Metri-1% and HDTMA-Metri-1%. Soil column leaching experiment showed that compared to their commercially available formulations, organoclay complexes were effective in reducing the downward mobility of both herbicides. Organoclay complexes of metolachlor and metribuzin prepared using PTMA-Montmorillonite performed better than the HDTMA-Montmorillonite complexes.     

Leaching behavior of heavy metals from municipal solid waste incineration bottom ash and its geochemical modeling

With the increase in the number of municipal solid waste incineration (MSWI) plants constructed in China recently, great attention has been paid to the heavy metal leaching toxicity of MSWI residues. In this study, the effects of various parameters, including extractant, leaching time, liquid-to-solid ratio, leachate pH, and heavy metal content, on the release properties of Cd, Cr, Cu, Ni, Pb, and Zn from MSWI bottom ash were investigated. Partial least-squares analysis was employed to highlight the interrelationships between the factors and response variables. Both experimental research and geochemical modeling using Visual MINTEQ software were conducted to study the pH-dependent leaching behavior of these metals in fresh and weathered bottom ash, considering precipitation/dissolution and surface complexation reactions (adsorption by hydrous ferric oxide and amorphous aluminum oxide/hydroxide). The results showed that leachate pH was the predominant factor influencing heavy metal leachability. The leaching of Cu, Pb, and Zn was mainly controlled by precipitation/dissolution reactions, whereas surface complexation had some effect on the leaching of Cr, Cd, and Ni for certain pH ranges. The modeling results aggreed well with the experimental results. Part of this work was presented at the Fourth International Conference on Combustion, Incineration/Pyrolysis and Emission Control (i-CIPEC)     

The use of a sequential leaching procedure for assessing the heavy metal leachability in lime waste from the lime kiln at a caustizicing process of a pulp mill

A five-stage sequential leaching procedure was used to fractionate 13 heavy metals (Cd, Cu, Pb, Cr, Zn, Fe, Mn, Al, Ni, Co, As, V, Ba) and sulphur (S) in lime waste from the lime kiln at the causticizing plant of Stora Enso Oyj Veitsiluoto Pulp Mills at Kemi, Northern Finland, into the following fractions: (1) water-soluble fraction (H₂O), (2) exchangeable fraction (CH₃COOH), (3) easily reduced fraction (HONH₃Cl), (4) oxidizable fraction (H₂O₂ + CH₃COONH₄), and (5) residual fraction (HF + HNO₃ + HCl). Although metals were leachable in all fractions, the highest concentrations for most of the metals were observed in the residual fraction (stage 5). It was also notable that the total heavy metal concentrations in lime waste did not exceed the maximal allowable heavy metal concentrations for soil conditioner agents set by the ministry of the Agricultural and Forestry in Finland. The heavy metals concentrations in lime waste were also lower than the maximal allowable heavy metals concentrations of the European Union Directive 86/278/EEC on the protection of environment, and in particular of the soil, when sewage sludge is used in agriculture. The Ca concentration (420 g kg⁻¹; d.w.) was about 262 times higher than the typical value of 1.6 g kg⁻¹ (d.w.) in arable land in Central Finland. However, the concentration Mg (0.2 g kg⁻¹; d.w.) in lime waste was equal to the Mg concentration in arable land in the Central Finland. The lime waste has strongly alkaline pH (12.8) and a neutralizing value (i.e. liming effect) of 47.9% expressed as Ca equivalents (d.w.). This indicates lime waste to be a potential soil conditioner and improvement as well as a pH buffer.     

Laboratory investigation of Waelz slag stabilization

Electric Arc Furnace dusts are considered hazardous waste due to their high heavy metals content (zinc, lead, etc.). The Waelz process is one of the most efficient technologies, in terms of capacity and quality, able to recover nearly the 90% of zinc contained in such EAF dusts. Unfortunately, the resulting slag still has eco-compatibility problems, although its mechanical and chemical properties are suitable for civil engineering applications. Stabilization tests, by quartz addition, were performed on EAF dusts in a laboratory furnace. Temperature, treatment time and cooling rate were varied in order to define the best conditions for regulating the formation of a stable microstructure able to hinder the release of substances. Microstructural characterization was carried-out using SEM and XRD analysis. Leaching tests were performed according to EN 12457-2 standards and water analyses were performed using ICP-OES. The best chemical stability was achieved when dust powders were mixed with 20% of silica and water-cooled.     

预处理垃圾焚烧飞灰作为碱胶凝材料混合材的研究

试验分析了垃圾焚烧飞灰的主要化学成分及矿物组成,探讨了预处理垃圾焚烧飞灰作为碱胶凝材料混合材的可能性.研究表明,垃圾焚烧飞灰主要由黏土类矿物组成,飞灰直接作为混合材参与水化过程会产生明显膨胀现象,加入30%(质量分数)飞灰制成的矿渣/飞灰试块在成型1 d脱膜时膨胀率达到15.7%,标准养护28 d后无侧压抗压强度只有12.4 MPa.对飞灰进行热活化预处理,900℃条件下活化效果最佳,同样的飞灰掺量下,试块在标准养护28 d后无侧压抗压强度达到46.0 MPa,膨胀现象消失,且碱胶凝材料中重金属稳定性良好.     

柱淋洗法修复铬污染土壤的效果研究

以铬渣污染土壤为供试土壤,采用土柱淋洗法研究柠檬酸、草酸和盐酸单一淋洗以及复合淋洗对铬去除动态和修复效果的影响,并对淋洗前后土壤中铬形态进行分析,探讨修复机理。结果表明,各淋洗方案中,以10体积0.5 mol/L草酸溶液为淋洗剂时的修复效果最好,总Cr累计淋出量为2 304 mg/kg,上层、中层和下层土壤总Cr去除率分别为79.6%、78.1%和69.6%,Cr(VI)去除率为87.8%、86.2%和75%,且土壤Cr(VI)和总Cr随着土壤深度的增加而升高,有在底部积累的可能;淋洗后土壤明显酸化,p H值从10.5降至3左右;以酸作为淋洗剂能有效降低土壤可氧化态铬含量,将其转化为移动性较强的酸可提取态,这有助于达到预期修复效果。     

Immobilization and transformation of co-existing arsenic and antimony in highly contaminated sediment by nano zero-valent iron

Arsenic(As) and antimony(Sb) are usually coexistent in mine wastes and pose a great threat to human health. The As immobilization by nano zero-valent iron(n ZVI) is promising, however, the stabilization for co-occurring As and Sb is not known. Herein, the immobilization and transformation of As and Sb in n ZVI-treated sediments were evaluated using complementary leaching experiments and characterization techniques. Raw sediment samples from a gold-antimony deposit revealed the co-existence of ul...     

Quantification of uncertainty of experimental measurement in leaching test on cement-based materials

When mineral wastes are reused in construction materials, a current practice is to evaluate their environmental impact using standard leaching test. However, due to the uncertainty of the measurement, it is usually quite difficult to estimate the pollutant potential compared to other materials or threshold limits. The aim of this paper is to give a quantitative evaluation of the uncertainty of leachate concentrations of cement-based materials, as a function of the number of test performed. The relative standard deviations and relative confidence intervals are determined using experimental data in order to give a global evaluation of the uncertainty of leachate concentrations (determination of total relative standard deviation). Various combinations were realized in order to point out the origin of large dispersion of the results (determination of relative standard deviation linked to analytical measured and to leaching procedure), generalisation was suggested and the results were compared to literature. An actual example was given about the introduction of residue (meat and bone meal bottom ash--MBM-BA) in mortar, leaching tests were carried out on various samples with and without residue MBM-BA. In conclusion large dispersion were observed and mainly due to heterogeneity of materials. So heightened attention needed to analyse leaching result on cement-based materials and further more other tests (e.g. ecotoxicology) should be performed to evaluate the environmental effect of these materials.