Characteristics of solidified products containing radioactive molten salt waste

The molten salt waste from a pyroprocess to recover uranium and transuranic elements is one of the problematic radioactive wastes to be solidified into a durable wasteform for its final disposal. By using a novel method, named as the GRSS (gel-route stabilization/solidification) method, a molten salt waste was treated to produce a unique wasteform. A borosilicate glass as a chemical binder dissolves the silicate compounds in the gel products to produce one amorphous phase while most of the phosphates are encapsulated by the vitrified phase. Also, Cs in the gel product is preferentially situated in the silicate phase, and it is vitrified into a glassy phase after a heat treatment. The Sr-containing phase is mainly phosphate compounds and encapsulated by the glassy phase. These phenomena could be identified by the static and dynamic leaching test that revealed a high leach resistance of radionuclides. The leach rates were about 10(-3) - 10(-2) g/m2 x day for Cs and 10(-4) - 10(-3) g/m2 x day for Sr, and the leached fractions of them were predicted to be 0.89% and 0.39% at 900 days, respectively. This paper describes the characteristics of a unique wasteform containing a molten salt waste and provides important information on a newly developed immobilization technology for salt wastes, the GRSS method.     

Characteristics of wasteform composing of phosphate and silicate to immobilize radioactive waste salts

In the radioactive waste management, metal chloride wastes from a pyrochemical process is one of problematic wastes not directly applicable to a conventional solidification process. Different from a use of minerals or a specific phosphate glass for immobilizing radioactive waste salts, our research group applied an inorganic composite, SAP (SiO(2)-Al(2)O(3)-P(2)O(5)), to stabilize them by dechlorination. From this method, a unique wasteform composing of phosphate and silicate could be fabricated. This study described the characteristic of the wasteform on the morphology, chemical durability, and some physical properties. The wasteform has a unique "domain-matrix" structure which would be attributed to the incompatibility between silicate and phosphate glass. At higher amounts of chemical binder, "P-rich phase encapsulated by Si-rich phase" was a dominant morphology, but it was changed to be Si-rich phase encapsulated by P-rich phase at a lower amount of binder. The domain and subdomain size in the wasteform was about 0.5-2 μm and hundreds of nm, respectively. The chemical durability of wasteform was confirmed by various leaching test methods (PCT-A, ISO dynamic leaching test, and MCC-1). From the leaching tests, it was found that the P-rich phase had ten times lower leach-resistance than the Si-rich phase. The leach rates of Cs and Sr in the wasteform were about 10(-3)g/m(2)· day, and the leached fractions of them were about 0.04% and 0.06% at 357 days, respectively. Using this method, we could stabilize and solidify the waste salt to form a monolithic wasteform with good leach-resistance. Also, the decrease of waste volume by the dechlorination approach would be beneficial in the final disposal cost, compared with the present immobilization methods for waste salt.     

Fractional factorial design to investigate the influence of heavy metals and anions on acid neutralization behavior of cement-based products

A major concern of cement-based solidification/stabilization of hazardous wastes is the interaction of waste contaminants on cement properties. Literature contains many examples of studies on the interference of individual contaminants on cement properties. Conversely, little information is available on how the interactions between contaminants affectthe properties of cement/waste systems. This paper provides a discussion on the interference mechanisms exerted by seven contaminants, five heavy metals and two anions, on cement hydration. The seven contaminants were selected on the basis of the typical composition of municipal solid waste incineration (MSWI) fly ash. Spiking experiments using pure compounds were performed according to a 2IV(7-3) fractional factorial design to simulate addition of MSWI fly ash to ordinary Portland cement. The acid neutralization behavior of the laboratory cement-contaminant mixtures was studied to detect the presence of solid phases responsible for the buffering capacity of the solid matrix. The results from the experimental work showed that Zn, Cl-, and SO4(2-) were the major factors influencing, occasionally in combination with other contaminants, strength and acid neutralization capacity of the cementitious products. The release of Cd, Cr, Cu, and Pb in the eluates as a function of pH also suggested possible chemical immobilization mechanisms of such metals within the hardened matrix.     

Solid waste management of a chemical-looping combustion plant using Cu-based oxygen carriers

Waste management generated from a Chemical-Looping Combustion (CLC) plant using copper-based materials is analyzed by two ways: the recovery and recycling of the used material and the disposal of the waste. A copper recovery process coupled to the CLC plant is proposed to avoid the loss of active material generated by elutriation from the system. Solid residues obtained from a 10 kWth CLC prototype operated during 100 h with a CuO-Al2O3 oxygen carrier prepared by impregnation were used as raw material in the recovery process. Recovering efficiencies of approximately 80% were obtained in the process, where the final products were an eluate of Cu(NO3)2 and a solid. The eluate was used for preparation of new oxygen carriers by impregnation, which exhibited high reactivity for reduction and oxidation reactions as well as adequate physical and chemical properties to be used in a CLC plant. The proposed recovery process largely decreases the amount of natural resources (Cu and Al203) employed in a CLC power plant as well as the waste generated in the process. To determine the stability of the different solid streams during deposition in a landfill, these were characterized with respect to their leaching behavior according to the European Union normative. The solid residue finally obtained in the CLC plant coupled to the recovery process (composed by Al2O3 and CuAl2O4) can be classified as a stable nonreactive hazardous waste acceptable at landfills for nonhazardous wastes.     

Ecotoxicity assessment of stabilized/solidified foundry sludge

The aim of this study is to evaluate the toxicity of the leachates from a foundry sludge and the derived products based on the stabilization/solidification (S/S) processes. Foundry sludge is an industrial hazardous waste containing inorganic and organic pollutants. The immobilization of the foundry waste has been performed using different S/S procedures based on cement or lime as binder agents and foundry sand fines, calcium-magnesium lignosulfonate, silica fume, activated carbon and black carbon as additives. The waste and stabilized/solidified derived products have been evaluated according to environmental considerations. The relation between the chemical composition and the ecotoxicity of the leachates has been studied in this paper. The ecotoxicity of the leachates has been related to the heavy metals and the organic pollutants by an empirical logarithmic linear expression. Different parameters of the logarithmic fitting have been obtained for the studied binder agents and additives allowing the establishment of a relationship between the S/S process and the ecotoxicity of the derived products. Results of this study have wide-ranging implications for immediate management strategies of waste with organic and inorganic pollutants in addition to application in long-term remediation efforts.     

Separating and stabilizing phosphate from high-level radioactive waste: process development and spectroscopic monitoring

Removing phosphate from alkaline high-level waste sludges at the Department of Energy's Hanford Site in Washington State is necessary to increase the waste loading in the borosilicate glass waste form that will be used to immobilize the highly radioactive fraction of these wastes. We are developing a process which first leaches phosphate from the high-level waste solids with aqueous sodium hydroxide, and then isolates the phosphate by precipitation with calcium oxide. Tests with actual tank waste confirmed that this process is an effective method of phosphate removal from the sludge and offers an additional option for managing the phosphorus in the Hanford tank waste solids. The presence of vibrationally active species, such as nitrate and phosphate ions, in the tank waste processing streams makes the phosphate removal process an ideal candidate for monitoring by Raman or infrared spectroscopic means. As a proof-of-principle demonstration, Raman and Fourier transform infrared (FTIR) spectra were acquired for all phases during a test of the process with actual tank waste. Quantitative determination of phosphate, nitrate, and sulfate in the liquid phases was achieved by Raman spectroscopy, demonstrating the applicability of Raman spectroscopy for the monitoring of these species in the tank waste process streams.     

Integrated sustainable process design framework for cassava biobased packaging materials: Critical review of current challenges,emerging trends and prospects

BackgroundCassava represents a reasonable share in biobased material development globally. The production of its biopolymer derivatives using conventional techniques/methods is accompanied by significant wastes with potential negative environmental impact. Among the biopolymer derivatives, starch dominates as lone additive in cast matrices with packaging limitations, requiring other biopolymer derivatives, and/or external-source modifiers for matrix improvement. Exploiting integrated sustainable engineering process design of all biopolymer derivatives, is a novel approach in designing efficient system of cassava biobased materials for food and non-food applications.Scope and approachA critical review on the current and emerging techniques and methodologies to address cassava wastes and challenges of cassava research for application on biobased packaging are provided. The potential of integrated sustainable engineering process design framework for packaging system is discussed, and prospects for improvement suggested.Key findings and conclusionsChallenges of significant waste generated during conventional processing and on the application process aiming at tailoring materials to industrial needs are reported. These materials should be improved using a holistic approach reflecting the target products, variable environment, minimising production costs and energy. Use of novel material resources, eliminating waste, and employing a standardised methodology via desirability optimisation, present a promising process integration tool for development of sustainable cassava biobased systems.     

Recent development of anaerobic digestion processes for energy recovery from wastes

Anaerobic digestion leads to the overall gasification of organic wastewaters and wastes, and produces methane and carbon dioxide; this gasification contributes to reducing organic matter and recovering energy from organic carbons. Here, we propose three new processes and demonstrate the effectiveness of each process. By using complete anaerobic organic matter removal process (CARP), in which diluted wastewaters such as sewage and effluent from a methane fermentation digester were treated under anaerobic condition for post-treatment, the chemical oxygen demand (COD) in wastewater was decreased to less than 20 ppm. The dry ammonia-methane two-stage fermentation process (Am-Met process) is useful for the anaerobic treatment of nitrogen-rich wastes such as waste excess sludge, cow feces, chicken feces, and food waste without the dilution of the ammonia produced by water or carbon-rich wastes. The hydrogen-methane two-stage fermentation (Hy-Met process), in which the hydrogen produced in the first stage is used for a fuel cell system to generate electricity and the methane produced in the second stage is used to generate heat energy to heat the two reactors and satisfy heat requirements, is useful for the treatment of sugar-rich wastewaters, bread wastes, and biodiesel wastewaters.     

基于生物工程的废次烟叶资源化技术研究

烟叶生产过程中废弃烟叶约占33%。本研究通过生物技术措施从废弃烟草中提取烟碱等植物次生代谢物质形成化工原料,为医药、生物农药产品开发以及食用菌栽培和生物有机肥生产提供优质原料。研究表明,通过提取纯化烟碱等重要化工原料物质,可以作为特定医药品的前体和具有有效抑制微生物生长和具杀虫抑菌作用的生物农药物质;脱毒后的废弃烟叶是食用菌的良好栽培原料。同时,废弃烟草通过微生物发酵生产的生物有机肥,可作为优质高效的绿色肥料。     

Ferrate treatment for removing chromium from high-level radioactive tank waste

A method has been developed for removing chromium from alkaline high-level radioactive tank waste. Removing chromium from these wastes is critical in reducing the volume of waste requiring expensive immobilization and deep geologic disposition. The method developed is based on the oxidation of insoluble chromium(III) compounds to soluble chromate using ferrate. This method could be generally applicable to removing chromium from chromium-contaminated solids, when coupled with a subsequent reduction of the separated chromate back to chromium(III). The tests conducted with a simulated Hanford tank sludge indicate that the chromium removal with ferrate is more efficient at 5 M NaOH than at 3 M NaOH. Chromium removal increases with increasing Fe(VI)/Cr(II) molar ratio, but the chromium removal tends to level out for Fe(VI)/ Cr(III) greaterthan 10. Increasingtemperature leadsto better chromium removal, but higher temperatures also led to more rapid ferrate decomposition. Tests with radioactive Hanford tank waste generally confirmed the simulant results. In all cases examined, ferrate enhanced the chromium removal, with a typical removal of around 60-70% of the total chromium present in the washed sludge solids. The ferrate leachate solutions did not contain significant concentrations of transuranic elements, so these solutions could be disposed as low-activity waste.     

Hydrogen and ethanol production from glycerol-containing wastes discharged after biodiesel manufacturing process

H2 and ethanol production from glycerol-containing wastes discharged after a manufacturing process for biodiesel fuel (biodiesel wastes) using Enterobacter aerogenes HU-101 was evaluated. The biodiesel wastes should be diluted with a synthetic medium to increase the rate of glycerol utilization and the addition of yeast extract and tryptone to the synthetic medium accelerated the production of H2 and ethanol. The yields of H2 and ethanol decreased with an increase in the concentrations of biodiesel wastes and commercially available glycerol (pure glycerol). Furthermore, the rates of H2 and ethanol production from biodiesel wastes were much lower than those at the same concentration of pure glycerol, partially due to a high salt content in the wastes. In continuous culture with a packed-bed reactor using self-immobilized cells, the maximum rate of H2 production from pure glycerol was 80 mmol/l/h yielding ethanol at 0.8 mol/mol-glycerol, while that from biodiesel wastes was only 30 mmol/l/h. However, using porous ceramics as a support material to fix cells in the reactor, the maximum H2 production rate from biodiesel wastes reached 63 mmol/l/h obtaining an ethanol yield of 0.85 mol/mol-glycerol.     

Increased significance of food wastes: Selective recovery of added-value compounds

A single-step selective separation of two food additives was investigated using alcohol-salt aqueous two-phase systems (ATPS). The selective partitioning of two of the most used additives from a processed food waste material, vanillin and l-ascorbic acid, was successfully accomplished. The results obtained prove that alcohol-salt ATPS can be easily applied as cheaper processes for the selective recovery of valuable chemical products from food wastes and other sources.     

Retention of trace metals by solidified/stabilized wastes: assessment of long-term metal release

Toxic elements found in wastes may have a negative impact on the environment, especially through the contamination of groundwater and plants. To reduce their mobility and availability, French regulations mandate the solidification and stabilization of toxic wastes. Many methods to stabilize and solidify wastes exist, among them the Ecofix process which employs low cost materials and consists of mixing wastes with lime, aluminum hydroxide, and silica. To evaluate the long-term behavior of solidified/stabilized (S/S) samples, their alteration under saturated conditions was studied in a water extractor, a Soxhlet-like device, used to follow the weathering of rocks. Kinetic measurements have shown that the release of Fe, Pb, Cd, Cr, and Cu was very slow, indicating a strong retention of these elements by the S/S materials prepared by the Ecofix process. To elucidate the mechanisms of retention of the trace metals, the mineral phases that existed in the S/S samples throughout and at the end of the extraction runs were studied by X-ray diffraction and by infrared and nuclear magnetic resonance spectroscopies. Scanning electron microscopic (SEM) examinations and electron microprobe analyses of the S/S samples were also performed at different stages of weathering. These observations revealed that assorted calcium silicate hydrates (C-S-H) were the predominant phases in the S/S preparations and that gradual alterations occurred in the structure of the investigated materials. The overall Ca/Si ratio of the C-S-H phases decreased as the enhanced alteration progressed. Although trace metals in oxide, hydroxide, and carbonate forms were found in the S/S materials, the bulk of the trace metals was incorporated in the matrix of the C-S-H phases.     

Co speciation in hardened cement paste: a macro- and micro-spectroscopic investigation

Cement-based materials play an important role in multi-barrier concepts developed worldwide for the safe disposal of hazardous and radioactive wastes. Cement is used to condition and stabilize the waste materials and to construct the engineered barrier systems (container, backfill and liner materials) of repositories for radioactive waste. In this study, Co uptake by hardened cement paste (HCP) has been investigated with the aim of improving our understanding of the immobilization process of heavy metals in cement on the molecular level. X-ray-absorption spectroscopy (XAS) on powder material (bulk-XAS) was used to determine the local environment of Co in cement systems. Bulk-XAS investigations were complemented with micro-beam investigations to probe the inherent microscale heterogeneity of cement by using micro-X-ray-fluorescence (micro-XRF) and micro-XAS. Micro-XRF was used to gain information on the spatial heterogeneity of the Co distribution, whereas micro-XAS was employed to determine the speciation of Co on the microscale. The Co-doped HCP samples hydrated for time-scales from 1 hour up to 1 year were prepared under normal atmosphere, to simulate similar conditions as for waste packages. To investigate the role of oxygen, further samples were prepared in the absence of oxygen. The study showed that, for the samples prepared in air, Co(II) is oxidized to Co(III) after 1 hour of hydration time. Moreover, the relative amount of Co(III) increases with increasing hydration time. The study further revealed that Co(II) is predominately present as a Co-hydroxide-like phase and/or Co-phyllosilicates, whereas Co(III) tends to be incorporated into a CoOOH-like phase and/or Co-phyllomanganates. In contrast to samples prepared in air, XAS experiments with samples prepared in the absence of oxygen revealed solely the presence of Co(II). This finding indicates that oxygen plays an important role for Co oxidation in cement. Furthermore, the study suggests that Co(III) species or Co(III)-containing phases should be taken into account for an overall assessment of the Co release from Co-containing cement-stabilized waste under oxidizing conditions.     

Supercritical water oxidation of the PCB congener 2-chlorobiphenyl in methanol solutions: a kinetic analysis

Incineration is commonly used to destroy polychlorinated biphenyl (PCB) wastes, but this method of treatment is not ideal for all mixed liquid wastes, especially those containing radioactive materials. Therefore, other remediation technologies are needed to efficiently treat these waste forms. This study examined the supercritical water oxidation (SCWO) of 2-chlorobiphenyl (2-PCB), using hydrogen peroxide as the oxidant and methanol as a cosolvent at 2 vol %. Kinetic studies were carried out in a plug flow reactor at temperatures from 686 to 789 K and a pressure of 250 bar, with reactor residence times ranging from 1.1 to 5.8 s. Least-squares regression of the collective reaction rate data revealed that 2-PCB exhibited second-order kinetics, with an Arrhenius frequency factor, A, equal to 10(18.2+/-2.3) L x mol(-1) x s(-1) and activation energy, Ea, of 181.7 +/- 33.2 kJ/mol. The primary organic reaction products from the SCWO of 2-PCB were biphenyl at low temperatures (<700 K) and CO2 at elevated temperatures. No dioxins or chlorinated dibenzofurans were ever detected in any of the effluent samples. Additional experiments with higher organic feed concentrations (4 vol %) illustrated how the exothermic nature of the organic oxidation reactions can be used to render the process self-sustaining. Finally, SCWO destruction rates greater than 99.98% were achieved for a simulated PCB-contaminated job control waste similar to that encountered at many U.S. Department of Energy sites.     

含铬废弃物在皮革化工材料中的应用

本文就含铬下脚料回用于制革的研究进行综述。铬提取回收，可重新制成鞣剂；下脚料水解，分离出多肽，用于复鞣剂、涂饰剂和加脂剂等的合成；水解混合物中的铬与多肽也可不分离，适当改性，直接用作鞣剂。     

Spectroscopic investigation of Ni speciation in hardened cement paste

Cement-based materials play an important role in multi-barrier concepts developed worldwide for the safe disposal of hazardous and radioactive wastes. Cement is used to condition and stabilize the waste materials and to construct the engineered barrier systems (container, backfill, and liner materials) of repositories for radioactive waste. In this study, Ni uptake by hardened cement paste has been investigated with the aim of improving our understanding of the immobilization process of heavy metals in cement on the molecular level. X-ray absorption spectroscopy (XAS) coupled with diffuse reflectance spectroscopy (DRS) techniques were used to determine the local environment of Ni in cement systems. The Ni-doped samples were prepared at two different water/cement ratios (0.4, 1.3) and different hydration times (1 hour to 1 year) using a sulfate-resisting Portland cement. The metal loadings and the metal salts added to the system were varied (50 up to 5000 mg/kg; NO3(-), SO4(2-), Cl-). The XAS study showed that for all investigated systems Ni(ll) is predominantly immobilized in a layered double hydroxide (LDH) phase, which was corroborated by DRS measurements. Only a minor extent of Ni(ll) precipitates as Ni-hydroxides (alpha-Ni(OH)2 and beta-Ni(OH)2). This finding suggests that Ni-Al LDH, rather than Ni-hydroxides, is the solubility-limiting phase in the Ni-doped cement system.     

Residual waste from Hanford tanks 241-C-203 and 241-C-204. 1. Solids characterization

Bulk X-ray diffraction (XRD), synchrotron X-ray microdiffraction (microXRD), and scanning electron microscopy/ energy-dispersive X-ray spectroscopy (SEM/EDS) were used to characterize solids in residual sludge from single-shell underground waste tanks C-203 and C-204 at the U.S. Department of Energy's Hanford Site in southeastern Washington state. Cejkaite [Na4(UO2)(CO3)3] was the dominant crystalline phase in the C-203 and C-204 sludges. This is one of the few occurrences of cejkaite reported in the literature and may be the first documented occurrence of this phase in radioactive wastes from DOE sites. Characterization of residual solids from water leach and selective extraction tests indicates that cejkaite has a high solubility and a rapid rate of dissolution in water at ambient temperature and that these sludges may also contain poorly crystalline Na2U207 [or clarkeite Na[(UO2)O(OH)](H2O)0-1] as well as nitratine (soda niter, NaNO3), goethite [alpha-FeO(OH)], and maghemite (gamma-Fe2O3). Results of the SEM/EDS analyses indicate that the C-204 sludge also contains a solid that lacks crystalline form and is composed of Na, Al, P, O, and possibly C. Other identified solids include Fe oxides that often also contain Cr and Ni and occur as individual particles, coatings on particles, and botryoidal aggregates; a porous-looking material (or an aggregate of submicrometer particles) that typically contain Al, Cr, Fe, Na, Ni, Si, U, P, O, and C; Si oxide (probably quartz); and Na-Al silicate(s). The latter two solids probably represent minerals from the Hanford sediment, which were introduced into the tank during prior sampling campaigns or other tank operation activities. The surfaces of some Fe-oxide particles in residual solids from the water leach and selective extraction tests appear to have preferential dissolution cavities. If these Fe oxides contain contaminants of concern, then the release of these contaminants into infiltrating water would be limited by the dissolution rates of these Fe oxides, which in general have lowto very low solubilities and slow dissolution rates at near neutral to basic pH values under oxic conditions.     

鹿茸废弃物的化学成分及抗氧化、促创面愈合活性研究

为了更好的发挥鹿茸口服液生产过程中所产生废弃物的再利用价值,本研究对废弃物的化学成分及药理活性进行了研究.采用鹿茸口服液生产工艺(卫生部标准:WS3-B-2232-96),对鹿茸药材进行处理.然后对鹿茸口服液生产过程中产生的两种废弃物,采用水提醇沉的方法进行再提取.运用超高效液相色谱-四极杆-静电场轨道阱高分辨质谱(U...     

Nondestructive decontamination of mortar and concrete by electro-kinetic methods: application to the extraction of radioactive heavy metals

Because the service lives of nuclear power plants are limited to a certain number of years, the need for the management of quite a large volume of radioactive contaminated concrete arises, which, in most cases, was not taken into account when the capacities of the low and medium activity repositories were designed. Therefore, the decontamination of these structures would be of great interest in order to declassify the wastes as radioactive and manage them as conventional ones. This research studies the reliability of the application of electrical fields to decontaminate radioactive contaminated concrete. Three series of decontamination experiments have been carried out, using Cs+, Sr2-, Co2+, and Fe3+ ions added during casting and that have penetrated from the outside, testing carbonated and uncarbonated matrixes, and using laboratory devices as well as the homemade device for in situ application named "honeycomb device". As a result, the application of electrical fields to concrete-contaminated structures has been developed as a new technique to extract radioactive ionic species from concrete. This method of decontamination has been patented by ENRESA (Spanish Company for the Management of Radioactive Wastes) in association with the IETcc.