Leaching characteristics of paraffin waste forms generated from Korean nuclear power plants

Leaching tests of paraffin waste forms including boric acid, cobalt, strontium and cesium were performed to investigate the leaching characteristics of paraffin waste forms which had been generated in Korean nuclear power plants. The leaching tests were conducted according to ANSI/ANS-16.1 test procedure and the cumulative fractions leached (CFLs) of boric acid, cobalt, strontium and cesium were obtained. The compressive strength before and after the leaching test was measured for various waste forms with different mixing ratios of boric acid to paraffin. It was observed that boric acid and other nuclides immobilized within paraffin waste forms were congruently released and the leaching rates were influenced by reacted layer depth as the dissolution reaction progressed. A shrinking core model based on the diffusion-controlled dissolution kinetics was developed in order to simulate the test results. The CFLs and the leaching rates were well expressed by the shrinking core model and the cross-sectional view of specimen after the test demonstrated the applicability of this model with the shrinking dissolution front to the leaching analysis of paraffin waste forms.     

The leaching behavior of borate waste glass SL-1

Vitrification is an attractive approach for treatment of the borate waste from nuclear power plants. SL-1 glass is a suitable borosilicate glass form to solidify the borate waste containing relatively high quantities of B and Na. The leaching behavior of SL-1 glass in deionized water has been investigated. Compared to the HLW-glass, the network structure of SL-1 glass is weak. It was found that the ion-exchange reactions dominated the glass corrosion process with water in low temperature leaching conditions (⩽70°C). The ion-exchange and network hydrolysis reactions together controlled the glass dissolution in high temperature leaching conditions (>70°C). There was a peak in leach rate at about 70°C and a valley at about 110°C. The surface layer thickness was about 25 μm (MCC-1, 90°C for 28 days in deionized water). Na was almost totally depleted in the surface layer. At low temperature, the glass corrosion increases with leaching time. The glass corrosion remains about constant with leaching time at 90°C. The surface layer formed at 90°C is protective, which is less porous than the surface layer formed at 40 and 70°C.     

Bioleaching of metals from spent lithium ion secondary batteries using Acidithiobacillus ferrooxidans

Bioleaching of spent lithium ion secondary batteries, containing LiCoO2, was attempted in this investigation. The present study was carried out using chemolithotrophic and acidophilic bacteria Acidithiobacillus ferrooxidans, which utilized elemental sulfur and ferrous ion as the energy source to produce metabolites like sulfuric acids and ferric ion in the leaching medium. These metabolites helped dissolve metals from spent batteries. Bio-dissolution of cobalt was found to be faster than lithium. The effect of initial Fe(II) concentration, initial pH and solid/liquid (w/v) ratio during bioleaching of spent battery wastes were studied in detail. Higher Fe(II) concentration showed a decrease in dissolution due co-precipitation of Fe(III) with the metals in the residues. The higher solid/liquid ratio (w/v) also affected the metal dissolution by arresting the cell growth due to increased metal concentration in the waste sample. An EDXA mapping was carried out to compare the solubility of both cobalt and lithium, and the slow dissolution rate was clearly found from the figures.     

Improvement of nuclide leaching resistance of paraffin waste form with low density polyethylene

Low-level liquid borate wastes have been immobilized with paraffin wax using a concentrate waste drying system (CWDS) in Korean nuclear power plants. The possibility for improving chemical durability of paraffin waste form was suggested in this study. A small amount of low density polyethylene (LDPE) was added to increase the leaching resistance of the existing paraffin waste form. The influence of LDPE on the leaching behavior of waste form was investigated by performing leaching test according to ANSI/ANS-16.1 procedure during 325 days. It was observed that the leaching of nuclides immobilized within paraffin waste form made a marked reduction although little content of LDPE was added to waste form. The acceptance criteria of paraffin waste form associated with leachability index (LI) and compressive strength after the leaching test were fully satisfied with the help of LDPE.     

Sb release characteristics of the solid waste produced in antimony mining smelting process

Sb release characteristics of blast furnace slag, mining waste rock and tailing sand were investigated in static immersion and dynamic leaching test. These three kinds of waste samples were collected from the antimony mine in Lengshuijiang, China, produced in mining smelting process. Effects of solid/liquid ratio, sample size and pH of leaching solution on Sb release characteristics were inspected based on the analysis of scanning electron microscope, pH and EC of leachate. The optimal parameters for Sb leaching of each sample were analyzed. For blast furnace slag and mining waste rock, Sb release contents increased along with the decline of solid/liquid ratio. The maximum accumulative release contents were 42.13, 34.26 mg/kg at the solid/liquid ratio of 1:20. While Sb release content for tailing sand decreased first and then increased with the reduction of solid/liquid ratio. When the solid/liquid ratio was 1:5, the accumulative Sb release content reached the most (24.30 mg/kg). Sb release content of mining waste rock increased with the drop of leaching solution pH, with the highest accumulative release content of 26.01 mg/kg at pH 2.0. Sb release contents of blast furnace slag and tailing sand showed positive correlation with the variation of leaching solution pH. The maximum accumulative release contents of these two samples were 215.91 and 147.83 mg/kg, respectively, when leaching solution pH was 7.0. In summary, Sb release capacity of the three samples in descending order was tailing sand, blast furnace slag and mining waste rock. pH and EC of the leachate in dynamic test varied independently with the initial pH of leaching solution while showing close relationship with mineral hydrolysis in the waste.     

Analysis of high-level waste glass performance by the physical and geochemical simulation code STRAG4

A source term release analysis code for high-level waste glass has been developed for simulation of long-term dissolution behavior under repository conditions. The STRAG4 code consists of models for (a) element diffusion in both the bulk glass and surface layer, (b) glass dissolution kinetics at the interface between glass and water, and (c) geochemical reactions of dissolved elements in underground water. The simulations for various conditions of glass dissolution, including a static and dynamic system, show accordance with the experimental observations even in the relatively complicated case where bentonite is present. Long-term dissolution analyses of a borosilicate waste glass were carried out as preliminary study. The calculations were achieved by considering detrimental effects due to interactions between the glass and surrounded materials which are presumed to be in a repository environment (i.e., compacted bentonite, corrosion products from the iron overpack, and underground water). The environmental conditions such as temperature and geochemical reactions are also taken into account in the calculations. The results suggest the life of the waste glass would be more than 50,000 years even if the glass surface area increased by a factor of 10 due to crack formation.     

SERIAL BATCH TESTS PERFORMED ON MUNICIPAL SOLID WASTE INCINERATION BOTTOM ASH AND ELECTRIC ARC FURNACE SLAG,IN COMBINATION WITH COMPUTER MODELLING

To predict long-term behaviour of wastes, knowledge is needed about the mechanisms controlling the leaching. The serial batch leaching test, developed in this study, is a version of an ordinary column test that allows sampling at different places in the column. In this study the results from the experiment are compared with computer simulations made with the coupled geochemical and transport program CHEM- FRONTS. The experiments showed that some elements, for example potassium, are easily leached, while the leaching of others, for example iron, is slower. The leaching of some elements is solubility controlled whereas others are controlled by dissolution kinetics. The comparison between the experiments and the computer simulations shows good agreement for most elements. A flow through system has been simulated for the steel slag based on the results from the experiments and the computer simulation thereof. The latter simulation gives an idea of the long-term leaching behaviour of the steel slag. The conclusion of the work is that a combination of serial batch leaching test and computer simulation with a geochemical transport program can give good information about the long-term leaching of waste materials.     

Environmental behaviour of a construction made of a mixture of hydraulic binders and air pollution control residues from municipal solid waste incineration Part 2. Simulation tests and validation of the source term modelling

The reuse of waste materials requires the development of assessment methods for the long-term release of pollutants (source term) from wastes (or materials containing wastes) in contact with water. These methods depend on the scenario conditions: characteristics of the materials (especially physical structure and composition), contact with water… The scenario studied here is a water storage reservoir for fire extinguishing. The reservoir construction is made of a mixture of hydraulic binders and air pollution control (APC) residues from municipal solid waste incinerator (MSWI). The modelling of the source term is performed in five steps ranging from the physico-chemical characterisation of the material to the validation of the proposed model by means of field simulation devices. This paper follows a first publication on source term modelling using laboratory tests which therefore concerns the comparison of the results obtained with the previously established model. The first laboratory scale simulation test aims at taking into account the role of the leachate carbonation in the leaching behaviour of the studied material. The results obtained show that air carbonation of the leachate does not fundamentally change mass transfer mechanisms of easily soluble species (especially for alkaline metals). For these species, the use of the apparent diffusional model (model proposed in the previous paper) is, therefore, at first, a satisfactory solution for the prediction of long term leaching behaviour. The field scale test enables us to validate and calibrate the release model determined on a laboratory scale basis.     

Treatment of copper industry waste and production of sintered glass-ceramic.

Copper waste is iron-rich hazardous waste containing heavy metals such as Cu, Zn, Co, Pb. The results of leaching tests show that the concentration of these elements exceeds the Turkish and EPA regulatory limits. Consequently, this waste cannot be disposed of in its present form and therefore requires treatment to stabilize it or make it inert prior to disposal. Vitrification was selected as the technology for the treatment of the toxic waste under investigation. During the vitrification process significant amounts of the toxic organic and inorganic chemical compounds could be destroyed, and at the same time, the metal species are immobilized as they become an integral part of the glass matrix. The copper flotation waste samples used in this research were obtained from the Black Sea Copper Works of Samsun, Turkey. The samples were vitrified after being mixed with other inorganic waste and materials. The copper flotation waste and their glass-ceramic products were characterized by X-ray analysis (XRD), scanning electron microscopy and by the toxicity characteristic leaching procedure test. The products showed very good chemical durability. The glass-ceramics fabricated at 850 degrees C/2 h have a large application potential especially as construction and building materials.     

Influence of composition variations on the initial alteration rate of vitrified domestic waste incineration fly-ash

Vitrification as a waste stabilization technology has often been considered applicable only to high-level radioactive waste for which, with the use of suitable additives, it yields a vitreous material with excellent chemical durability. It has become apparent in recent years that some waste forms-notably domestic waste incineration fly-ash purification residues--contain most of the ingredients of a vitrified material, although their composition variations are difficult to control. It is thus important to ensure not only that the materials are suitable for vitrification, but also that the resulting product exhibits acceptable long-term behavior under all circumstances. An initial study showed that, allowing for the compensation changes inherent in the melting process builtby EDF**, the residue collected by a single fly-ash dust separation defines a composition range within which the suitability of the vitrified material can be verified. "Vitrified material" refers to a melted material that contains no unmelted inclusions after cooling, but that may contain a variable fraction of crystallized phases. Five composition parameters were identified for the long-term behavior assessment: the concentrations of the three major elements (silicon, aluminum and calcium), the total alkali metal (sodium and potassium) concentration, and the sum of the concentrations of two toxic elements (zinc and lead). The other elements were assumed constant at molar ratios representative of industrial wastes. The experimentation plan methodology applied to the composition range identified fourteen materials suilable for developing and validating first-order models of the material components. The fly-ash composition had a very significant effect on the degree and kinetics and crystallization in the vitrified material within the experimental composition range; the cooling rate was the determining factor for some of the fourteen materials studied. Two crystailine phases predominated: spinels rich in chromium, zinc, aluminum, magnesium and iron formed quickly on cooling, and accounted for about 2 vol% of the final material. Gehelenite (Ca2Al2SiO7) crystallized massively in some vitrified materials, accounting for more than half the final product and giving it a rock-like appearance. The effect of composition alone must therefore be distinguished from the effect of crystallization on the leaching behavior. Soxhlet tests were conducted for 14 days according to a protocol based on that of the French AFNOR draft standard NF-M 60313 to determine the maximum alteration rate in pure water at 100 degrees C. The measured rate ranged from 4 to 40 gm(-2) day(-1), illustrating the crucial role of the silicon concentration: within the test composition range, a low silicon content (< 30 wt%) tended to result in a significantly higher initial rate. However, the initial rate alone is not sufficient to assess the chemical durability of the material. Further tests will be carried out at 25 degrees C under conditions approximating those of a proposed disposal site to highlight the role of the alteration layer and the effect of rising concentrations in solution on the decreasing alteration rate.     

Hydrothermal solidification of municipal solid waste incineration bottom ash with slag addition

Hydrothermal solidification of municipal solid waste incineration (MSWI) bottom ash has been carried out under saturated steam pressure (1.56 MPa) at 200 °C for up to 24 h by mixing quartz, slaked lime and water-cooled blast furnace slag (WBFS). The strength enhancement for the WBFS addition was best. The strength development was shown to be due mainly to tobermorite formation, and the tobermorite formation densified matrix, thus promoting the strength development. WBFS seemed to have a higher reactivity than the quartz during the initial hydrothermal process, which provided more silica available to harden the solidified specimens. However, a longer curing time (24 h) was favorable to the quartz dissolution for tobermorite formation, which in turn, enhanced the strength for quartz addition. Curing time affected the crystal morphology evolution, and the stubby plate of tobermorite seemed to result in a high strength enhancement in this study. Laboratory leaching tests were conducted to determine the amount of heavy metals dissolved from the final solidified specimens, and the leaching results showed that after hydrothermal processing the heavy metals dissolved from the solidified specimens were reduced effectively. As such, the hydrothermal processing may have a high potential for recycling/reusing MSWI ash on a large scale.     

Crystal-chemistry of alteration products of vitrified wastes: implications on the retention of polluting elements

Alteration products of vitrified wastes coming from the incineration of household refuse (MSW) are described. Two vitrified wastes containing 50% and 70% of fly ash and a synthetic stained-glass with a composition close to that of an ancient glass (medieval stained-glass) were altered under different pH conditions (1, 5.5 corresponding to demineralized water and 10) during 181 days. Under acidic condition, the alteration layer is made of an amorphous hydrated silica gel impoverished in most of the initial elements. A minor phase MPO(4)*nH(2)O, where M represents Fe, Ti, Al, Ca and K cations, also constitutes the altered layer of the synthetic stained-glass. Under neutral and basic conditions, the altered layer is made of an amorphous hydrated silica gel and a crystallized calcium phosphate phase. The silica gel is depleted in alkalis and alkali-earth elements but contains significant amounts of aluminium, magnesium and transition elements, whereas the calcium phosphate is a hydroxylapatite-like phase with P-Si substitutions and a Ca/P ratio depending on the pH of the solution. This study shows: (i) the strong influence of pH conditions on the crystal-chemistry of alteration products and thus on the mechanisms of weathering resulting in different trapping of polluting elements, and (ii) that glass alteration does not necessary produce thermodynamically stable phases which has to be taken into account for the prediction of the long-term behavior.     

Predicting the mobility of Zn, Fe, Cu, Pb, Cd from roasted sulfide (pyrite) residues—A case study of wastes from the sulfuric acid industry in Sweden

Leachates from roasted sulfide residues, which are the wastes from the production of sulfuric acid at Falun, Sweden, have low pH and high concentrations of Zn, Fe, and SO₄. The minerals are mainly hematite and maghemite and, because the various sulfides in the feed behave differently during the roasting process, the residual sulfides minerals are pyrrhotite and sphalerite. Oxidation of the residual sulfides contributes acidity, Zn, Fe, Cu, Cd, and sulfate to the effluents from the waste deposits. The dissolution of sphalerite is most likely accelerated in acid solution rich in Fe (III). The formation of Pb-sulfate coatings on galena may provides an armoring effect which slows the oxidation of the galena. Residual sulfides are source phases controlling long-term contaminant release. Other source minerals for Zn, Fe, Pb, Cu, Cd and SO₄ in the effluents are iron oxides which retained percentage quantities of SO₄, roast-derived alteration rims of Zn oxides on sphalerite, alterated silicates formed during the roasting process, and secondary minerals (e.g. Zn, Fe, Cu sulfates, iron hydroxides) that were precipitated by in-site oxidation in the waste dumps. The Zn, Fe, and Cu sulfates most likely control short-term changes in the chemistry of the leachate, while Pb concentration in the leachates may be controlled predominantly by Pb-release from the altered silicates. The mineralogical and geochemical data provide fundamental information essential for the remedial management of this type of industial waste.     

Behavior of TiO2 nanoparticles during incineration of solid paint waste: A lab-scale test

In order to assess the potential impacts posed by products containing engineered nanoparticles, it is essential to generate more data about the release of these particles from products’ life cycle. Although first studies were performed to investigate the release of nanoparticles from use phase, very few data are available on the potential release from recycling or disposal of nano-enhanced products.In this work, we investigated the behavior of TiO₂ nanoparticles from incineration of solid paint waste containing these particles. Solid paint debris with and without TiO₂ nanoparticles were treated in a lab scale incineration plant at 950 °C (combustion temperature) and in oxidizing atmosphere. The obtained ashes were also vitrified with additives and the release of Ti was finally evaluated by leaching test. From our incineration lab-scale experiment, we did not observe a release of TiO₂ nanoparticles into the atmosphere, and Ti was attached to the surface of obtained solid residues (i.e. ashes). The characterization of ashes showed that TiO₂ nanoparticles reacted during the incineration to give calcium titanate. Finally, a very low release of Ti was measured, less 1 mg/kg, during the leaching test of ashes vitrified with glass cullet and feldspathic inert. Our work suggests that TiO₂ nanoparticles added in paints may undergo to physicochemical transformation during the incineration, and that Ti found in ashes may be strongly immobilized in glass matrix. Since this conclusion is based on lab-scale experiment, further research is required to identify which nanoparticles will be emitted to the environment from a real-word-incineration system of household hazardous waste.     

Recycling of cathode ray tube panel glasses as aggregates of concrete blocks and clay bricks

While the cathode ray tube (CRT) funnel containing lead could be transported to a smelting facility to recover lead, which could be an available option in domestic, a proper technology to recycle a CRT panel must be developed. Thus, it was suggested that CRT panel glass be used as aggregates of concrete blocks and clay bricks. Samples of blocks and bricks were fabricated with CRT powders and tested to measure their strength and absorption rate to determine their qualities, and environmental soundness was determined by measuring the leaching rate of hazardous metals. For concrete blocks, CRT panel glass powders incorporated as aggregates up to 40 % replacing stone powder was proposed as the proper condition for manufacturing blocks. Around 2 % of CRT panel incorporated into clay brick to substitute Kaoline was suggested to fabricate the best quality of clay brick. Results of leaching test met the criteria with much less concentration of hazardous metals, even lead compound containing in the CRT funnel. To conclude, the use of CRT panel powder after crushing it to the proper size as an aggregate of concrete blocks or clay bricks could be one of the appropriate alternatives to recycle for CRT glass waste being generated drastically in a short term.     

煤矸石中铅、铬、镉的溶出性能

以滕南煤田某煤矿风化煤矸石为研究对象,应用主成分分析法分析了煤矸石粒径对Pb,Cr,Cd溶出浓度的影响,应用回归分析法分析了浸溶时间与Pb,Cr,Cd溶出浓度的关系特征。实验结果表明：模拟湿地浸溶条件下,煤矸石中Pb,Cd,Cr溶出浓度均超出或接近Ⅲ类水体水质标准,对水环境存在污染风险;煤矸石粒径对Pb,Cd,Cr溶出浓度存在影响,粒径越小则Pb、Cr、Cd溶出浓度越大,粒径小于8.0 cm的煤矸石浸溶贡献较大。建立了表征Pb,Cr,Cd溶出浓度与浸溶时间对数（以10为底）关系的一元三次多项式回归方程,经检验均具有显著性。     

Vitrification of electric arc furnace dusts

Electric arc furnace baghouse dust (EAFD), a waste by-product of the steelmaking process, contains the elements that are volatilized from the charge during the melting (Cr, Pb, Zn, Cu and Cd). The results of leaching tests show that the concentration of these elements exceeds the regulatory limits. Consequently, EAFD cannot be disposed of in ordinary landfill sites without stabilization of the heavy metals. In this work, the vitrification of EAFD, from both carbon and stainless steel productions, were studied. The vitrification process was selected as the inertizing process because it permits the immobilization of the hazardous elements in the glass network and represents an environmentally acceptable method for the stabilization of this waste. Classes of various compositions were obtained by mixing EAFD with glass cullet and sand. The EAFD and the glass products were characterized by DTA, TG, X-ray analysis and by the TCLP test. The results show that the stability of the product is influenced by the glass structure, which mainly depends on the Si/O ratio. Secondary crystallization heat-treatment were carried out on some samples. The results highlighted the formation of spinel phases, which reduced the chemical durability in acid media. The possibility to recover Zn from carbon steel production EAFD was investigated and about 60-70% of metal recovery was obtained. The resulting glass show higher chemical stability than glasses obtained without metal recovery.     

Inertization of hazardous dredging spoils

Vitrification and production of ceramics materials starting from sediment excavated from Venice lagoon is described. This sediment is classified as toxic waste because contains several heavy metal ions and organic pollutants and was successfully vitrified at 1200-1350 degrees C. Twenty weight percentage of glass cullet, coming from a community glass recycling program, was added to the raw materials, previously calcined at 900 degrees C, as a way of adjusting the variations of composition of the individual sediment batches. Chemical durability (leaching) tests showed that the optimized glass compositions are inert, and thus not only volume reduction but also inertization of the waste was obtained by this process. Moreover, the economics of the entire process was analysed. The valorization of the waste was accomplished by the subsequent processing of the glass derived from the inertization. Glass ceramic materials were produced by viscous phase sintering of pressed glass powders which crystallized during the densification process. Sintered glass ceramic products had good mechanical characteristics (HV = 7.5 GPa, bending strength 150 +/- 8 MPa), making them suitable for applications in the building industry.     

Mineralogy and pore water chemistry of a boiler ash from a MSW fluidized-bed incinerator

This paper presents an investigation of the mineralogy and pore water chemistry of a boiler ash sampled from a municipal solid waste fluidized-bed incinerator, subject to 18 months of dynamic leaching in a large percolation column experiment. A particular focus is on the redox behaviour of Cr(VI) in relation to metal aluminium Al⁰, as chromium may represent an environmental or health hazard. The leaching behaviour and interaction between Cr(VI) and Al⁰ are interpreted on the basis of mineralogical evolutions observed over the 18-month period and of saturation indices calculated with the geochemical code PhreeqC and reviewed thermodynamic data. Results of mineralogical analyses show in particular the alteration of mineral phases during leaching (e.g. quartz and metal aluminium grains), while geochemical calculations suggest equilibria of percolating fluids with respect to specific mineral phases (e.g. monohydrocalcite and aluminium hydroxide). The combination of leaching data on a large scale and mineralogical analyses document the coupled leaching behaviour of aluminium and chromium, with chromium appearing in the pore fluids in its hexavalent and mobile state once metal aluminium is no longer available for chromium reduction.     

Environmental impact of fly ash utilization in roadway embankments

The leaching potential of heavy metals from a roadway embankment constructed of fly ash and soil mixture was studied. Leaching of eight environmentally concerned metals Ag, As, Ba, Cd, Cr, Hg, Pb, and Se from the fly ash–soil mixtures was examined through batch leaching test and column leaching test. The batch leaching test results showed that the fly ash meets the local regulatory standards for beneficial use of nonhazardous wastes. The column leach test revealed that only Ba, Cr, and Se were detectable in the effluents. The peak concentration of Ba in the effluents was much lower than the US EPA Primary Drinking Water Regulations’ maximum contaminant level (MCL). The peak concentrations of Cr and Se exceeded the MCLs only in the initial flush stage and quickly decreased to below the MCLs. Results of this study suggest a great potential for fly ash to be used in roadway embankments to enhance their mechanical properties, reduce the use of soil, and avoid the disposal of fly ash as waste.