Characterization of Chromium Waste Form Based on Biocementation by Microbacterium sp. GM-1.

This paper demonstrated a biocementation technology for chromium slag by strain GM-1, a calcifying ureolytic bacterium identified as Microbacterium, based on microbially induced calcium carbonate. The characterization of Microbacterium sp. GM-1 was assessed to know the growth curve in different concentrations of Cr(VI). Microbacterium sp. GM-1 was tolerant to a concentration of 120 mg/L Cr(VI). Chromium waste forms were prepared using chromium, sand, soil and bacterial culture. There we had three quality ratios (8:2:1; 8:1:1; 8:2:0.5) of material (chromium, sand and soil, respectively). Bacterial and control chromium waste forms were analyzed by thermal gravimetric analyzer. All bacterial forms (8:2:1; 8:1:1; 8:2:0.5 J) showed sharp weight loss near the decomposition temperature of calcium carbonate between 600 and 700 °C. It indicated that the efficient bacterial strain GM-1 had induced calcium carbonate precipitate during bioremediation process. A five step Cr(VI) sequential extraction was performed to evaluate its distribution pattern in chromium waste forms. The percentage of Cr(VI) was found to significantly be decreased in the exchangeable fraction of chromium waste forms and subsequently, that was markedly increased in carbonated fraction after biocementation by GM-1. Further, compressive strength test and leaching test were carried out. The results showed that chromium waste forms after biocementation had higher compressive strength and lower leaching toxicity. Additionally, the samples made of 8:1:1 (m/m/m) chromium + sand + soil were found to develop the highest compressive strength and stand the lowest concentration of Cr(VI) released into the environment.

Green conversion of waste alkaline battery material to zeolitic imidazolate framework-8 and its iodine capture mechanism.

Zeolitic imidazolate framework-8 (ZIF-8) exhibits excellent performance in capturing iodine. However, the solvent-based procedures and raw materials for ZIF-8 synthesis often lead to secondary pollution. We developed a solvent-minimizing method for preparing ZIF-8 via ball milling of raw material obtained from spent alkaline batteries, and studied its iodine-capture performance and structural changes. Exposure of the ZIF-8 to iodine vapor for 60 min demonstrated that it exhibited industrially competitive iodine-capture performance (the adsorbed amount reaches to 1123 mg g-1 within 60 min). Spectroscopic studies showed that ZIF-8 underwent a structural transformation upon iodine loading. Iodine molecules were adsorbed onto the surface of ZIF-8 and also formed C-I bond with the methyl groups on the imidazole rings, reducing iodine release. This work represents a comprehensive revelation of long-range order and short-range order evolution of ZIF-8 during iodine vapor adsorption over time. Moreover, this green synthesis of ZIF-8 is of lower cost and generates fewer harmful by-products than existing methods, and the produced ZIF-8 effectively entraps toxic iodine vapor. Thus, this synthesis enables a sustainable and circular material flow for beneficial utilization of waste materials.

Evaluation of physicochemical characteristics and centerline temperatures of Sr ceramic waste form.

When disposing of spent fuel, nuclides such as Cs-137 and Sr-90, which generate short-term decay heat, must be removed from the spent nuclear fuel for efficient storage facility utilization. The Korea Atomic Energy Research Institute (KAERI) has been developing a nuclide management process that can enhance disposal efficiency by sorting and collecting primary nuclides and a technology for separating Sr nuclides from the spent nuclear fuels using precipitation and distillation. In this study, we prepared Sr ceramic waste form, SrTiO3, using the solid-state reaction method to immobilize the Sr nuclides, and its physicochemical properties were evaluated. Moreover, the radiological and thermal characteristics of the Sr waste form were evaluated by estimating the composition of Sr nuclides considering the spent nuclear fuel history such as burn-up and cooling period. The waste form was found to be stable with good mechanical strength and leaching properties in addition to a low coefficient of thermal expansion, which would be advantageous for intermediate storage. Based on the experimental and radiological results, the centerline temperature of the waste form caused by Sr-90 nuclide was estimated using the steady-state conduction equation. The centerline temperature increased with increasing diameter of the waste form. When generating the SrTiO3 waste form using the Sr nuclide recovered after a cooling period of 10 years, the centerline temperature was estimated to exceed the melting point of SrTiO3 at a diameter of 0.275 m, under all burn-up conditions. These results provide fundamental data for the management and intermediate storage of Sr waste.

Effect of Si/Al molar ratio and curing temperatures on the immobilization of radioactive borate waste in metakaolin-based geopolymer waste form.

Immobilization of radioactive borate waste (RBW) using a geopolymer with a high Si/Al ratio has been challenging because boron-silicon networks lower the compressive strength and delay the setting time. In this study, metakaolin-based geopolymer waste form to immobilize simulant RBW was fabricated using different Si/Al ratios (1.0-1.4) and curing temperatures (26 and 60 â„ƒ). The 7-day compressive strength results revealed that a certain amount of silicon and an elevated curing temperature are required to achieve high compressive strength and waste loading. Following waste acceptance criteria tests, all geopolymers exhibited compressive strengths higher than 3.445 MPa. The leachability index of boron was higher than 6.0, and the leaching mechanism was identified as diffusion. No significant structural changes in the geopolymer were observed after thermal cycling and gamma irradiation tests. The physically bound or unincorporated RBW was leached out of the geopolymer during water immersion and leaching tests; however, boron, which was chemically connected with silicon, was present as an inert phase together with a geopolymer binder. Consequently, immobilizing RBW using a geopolymer with a low Si/Al ratio (1.4) is beneficial in terms of RBW loading and structural durability.

Solidification/Stabilization Technology for Radioactive Wastes Using Cement: An Appraisal.

Across the world, any activity associated with the nuclear fuel cycle such as nuclear facility operation and decommissioning that produces radioactive materials generates ultramodern civilian radioactive waste, which is quite hazardous to human health and the ecosystem. Therefore, the development of effectual and commanding management is the need of the hour to make certain the sustainability of the nuclear industries. During the management process of waste, its immobilization is one of the key activities conducted with a view to producing a durable waste form which can perform with sustainability for longer time frames. The cementation of radioactive waste is a widespread move towards its encapsulation, solidification, and finally disposal. Conventionally, Portland cement (PC) is expansively employed as an encapsulant material for storage, transportation and, more significantly, as a radiation safeguard to vigorous several radioactive waste streams. Cement solidification/stabilization (S/S) is the most widely employed treatment technique for radioactive wastes due to its superb structural strength and shielding effects. On the other hand, the eye-catching pros of cement such as the higher mechanical strength of the resulting solidified waste form, trouble-free operation and cost-effectiveness have attracted researchers to employ it most commonly for the immobilization of radionuclides. In the interest to boost the solidified waste performances, such as their mechanical properties, durability, and reduction in the leaching of radionuclides, vast attempts have been made in the past to enhance the cementation technology. Additionally, special types of cement were developed based on Portland cement to solidify these perilous radioactive wastes. The present paper reviews not only the solidification/stabilization technology of radioactive wastes using cement but also addresses the challenges that stand in the path of the design of durable cementitious waste forms for these problematical functioning wastes. In addition, the manuscript presents a review of modern cement technologies for the S/S of radioactive waste, taking into consideration the engineering attributes and chemistry of pure cement, cement incorporated with SCM, calcium sulpho-aluminate-based cement, magnesium-based cement, along with their applications in the S/S of hazardous radioactive wastes.

Incorporation of lead into pyromorphite: Effect of anion replacement on lead stabilization.

Previous studies demonstrate that the leaching of heavy metals in unreliable waste forms causes serious environmental pollution and health concerns. Thus, research is focused on identifying an effective, safe strategy for disposing of metal-laden solid waste such as lead (Pb). This study evaluated the effect of anion replacement in the structure of pyromorphite (Pb10(PO4)6Cl2, a common mineral phase for Pb sequestering) on Pb stabilization. Phosphate (PO43-) at the tetrahedral pyromorphite site was simultaneously replaced by silicate (SiO44-) and sulphate (SO42-) in a controlled thermal treatment. The lattice expanded with the incorporation of additional SiO44- and SO42-. Furthermore, the unit cell parameters of the solid solutions evolved linearly with an increase in the substitution degree (x in Pb10(SiO4)x(SO4)x(PO4)(6-2x)Cl2). This research also demonstrated that Pb distributed into amorphous in a PO43--deficient matrix, while asisite (Pb7SiO8Cl2) was formed when the matrix was dominated by SiO44- and SO42-. The leaching results showed the isomorphous substitution in the target system rendered the products less durable towards acidic attack. Moreover, the fully isomorphous-substituted product (x = 3) showed more than two orders of magnitude lower leaching resistance than the PO43--rich phase (x = 0). The lattice expansion, resulting from the isomorphous substitution, suggested that a lower dissolution energy was required in a PO43--deficient matrix. The leaching kinetics pointed to a product with a lower apparent activation energy in the leaching process. The findings of this study provide unique insight into the design and optimization of waste forms for the immobilization of heavy metals.

Leaching and transport of technetium from reducing cementitious waste forms in field lysimeters.

Field lysimeters tests examined leaching of technetium-99 (99Tc) from two types of cementitious waste forms and found that the presence of blast furnace slag reduced the overall leaching of 99Tc from the waste form. The two cementitious waste forms were a slag-grout 45%/45%/10% mixture of fly ash, blast furnace slag, and cement, respectively, referred to as slag-grout or a 55%/45% mixture of cement and fly ash, respectively, referred to here simply as cement. Duplicate sources of each composition were buried in four lysimeters for approximately 10 months to evaluate leaching characteristics under natural meteorological conditions in South Carolina, USA. Effluent samples were collected four times during the experiment, and the distribution of 99Tc in the sediment was determined by destructively segmenting the lysimeters at the end of the experiment. The transport of Tc within the lysimeter was simulated by assuming advection, dispersion, and sorption in partially saturated porous media, and by using a shrinking-core type approximation for the release of Tc from the source. The shrinking-core model predicted that the oxidation front created by the oxygenated infiltrating groundwater moved into the cementitious source at a rate of 14 µm/day. As this front moved through the source, Tc(IV) was oxidized to the highly mobile Tc(VII) (as TcO4-) species, which then was transported through the sediment primarily via advection due to a small partitioning coefficient (Csolid/Caq; Kd = 0.14 mL/g). The simulations predicted a cycle of accumulation of Tc in sediment at the source between rainfall events, followed by downward advection due to infiltration during rainfall events. The anomalous upward movement of Tc peak was predicted to be due to upward flux caused by evaporation after the experiment was terminated by capping the lysimeter. These experiments demonstrate that Tc leaching from cementitious waste forms under simulated vadose zone oxidizing conditions can be reasonably approximated by the shrinking core model, and the migration of Tc through the sediment is profoundly influenced by the presence of slag in the grout formulation and hydraulic conditions due to the low sorption affinity of TcO4-.

Monazite-Type SmPO4 as Potential Nuclear Waste Form: Insights into Radiation Effects from Ion-Beam Irradiation and Atomistic Simulations.

Single-phase monazite-type ceramics are considered as potential host matrices for the conditioning of separated plutonium and minor actinides. Sm-orthophosphates were synthesised and their behaviour under irradiation was investigated with respect to their long-term performance in the repository environment. Sintered SmPO4 pellets and thin lamellae were irradiated with 1, 3.5, and 7 MeV Au ions, up to fluences of 5.1 × 1014 ions cm-2 to simulate ballistic effects of recoiling nuclei resulting from α-decay of incorporated actinides. Threshold displacement energies for monazite-type SmPO4 subsequently used in SRIM/TRIM simulations were derived from atomistic simulations. Raman spectra obtained from irradiated lamellae revealed vast amorphisation at the highest fluence used, although local annealing effects were observed. The broadened, but still discernible, band of the symmetrical stretching vibration in SmPO4 and the negligible increase in P-O bond lengths suggest that amorphisation of monazite is mainly due to a breaking of Ln-O bonds. PO4 groups show structural disorder in the local environment but seem to behave as tight units. Annealing effects observed during the irradiation experiment and the distinctively lower dose rates incurred in actinide bearing waste forms and potential α-radiation-induced annealing effects indicate that SmPO4-based waste forms have a high potential for withstanding amorphisation.

Immobilization of cesium and iodine into Cs3Bi2I9 perovskite-silica composites and core-shell waste forms with high waste loadings and chemical durability.

Cs3Bi2I9, a defect perovskite derivative, is a potential host phase to immobilize iodine and cesium with high waste loadings. In this work, two strategies were explored to form Cs3Bi2I9-silica composites and a core-shell structure in order to improve chemical durability of waste form materials meanwhile maintaining high waste loadings. Cs3Bi2I9 loadings as high as 70 wt.% were incorporated into a silica matrix to form silica-ceramic composites, and 20 wt.% Cs3Bi2I9 was encapsulated into silica to form a core-shell structure by low temperature spark plasma sintering. Chemical durability of the composite and core-shell waste forms was evaluated by semi-dynamic leaching experiments, and Cs and I were incongruently released from waste form matrices. A BiOI alteration layer formed, acting as a passivation layer to reduce the release of radionuclides. The long-term iodine release rate was low (30 mg m-2 day-1) for the 70 wt.% Cs3Bi2I9-silica composite leached in deionized water at 90 °C, which can be further reduced to 5 × 10-3 mg m-2 day-1 for the 20 wt.% core-shell structure. This work highlights a robust way to immobilize the highly mobile radionuclides with high waste loadings through encapsulation into durable matrices and a surface passivating mechanism that can greatly reduce the elemental transport from waste form materials and significantly enhance their chemical durability.

Insight Into Disorder, Stress and Strain of Radiation Damaged Pyrochlores: A Possible Mechanism for the Appearance of Defect Fluorite.

We have examined the irradiation response of a titanate and zirconate pyrochlore-both of which are well studied in the literature individually-in an attempt to define the appearance of defect fluorite in zirconate pyrochlores. To our knowledge this study is unique in that it attempts to discover the mechanism of formation by a comparison of the different systems exposed to the same conditions and then examined via a range of techniques that cover a wide length scale. The conditions of approximately 1 displacement per atom via He2+ ions were used to simulate long term waste storage conditions as outlined by previous results from Ewing in a large enough sample volume to allow for neutron diffraction, as not attempted previously. The titanate sample, used as a baseline comparison since it readily becomes amorphous under these conditions behaved as expected. In contrast, the zirconate sample accumulates tensile stress in the absence of detectable strain. We propose this is analogous to the lanthanide zirconate pyrochlores examined by Simeone et al. where they reported the appearance of defect fluorite diffraction patterns due to a reduction in grain size. Radiation damage and stress results in the grains breaking into even smaller crystallites, thus creating even smaller coherent diffraction domains. An (ErNd)2(ZrTi)2O7 pyrochlore was synthesized to examine which mechanism might dominate, amorphization or stress/strain build up. Although strain was detected in the pristine sample via Synchrotron X-ray diffraction it was not of sufficient quality to perform a full analysis on.

Evaluation of Getter Metals in Na-Al-Si-O Aerogels and Xerogels for the Capture of Iodine Gas.

In this paper, sodium aluminosilicate aerogels and xerogels were evaluated as scaffolds for a variety of different getters including Ag+, Cs+, Cu2+, Fe3+, K+, Li+, Rb+, Sb3+, Sn2+, and Sn4+ for the capture of gaseous iodine coming from nuclear facilities. The exchange capacities varied widely from a near complete exchange in the case of Ag+ to much lower exchange levels for some of the Sn compounds [i.e., colloidal SnO2, Sn(II) acetate, and Sn(IV) acetate]. Several of the additives showed great promise at allowing for high iodine loadings in the base materials including the following: AgNO3, colloidal SnO2, Sn(II) acetate, Sn(IV) acetate, Cu(NO3)2, and CuSO4. From the standpoint of iodine uptake as a function of getter loading, Sn4+ was the most promising with a getter utilization (mass of iodine divided by mass of Sn, in atomic %) of 8.4, a chemical uptake of 60.7 mass % (oxygen excluded), and an mI ms-1 (mass of iodine per mass of sorbent) value of 0.881; these are some of the highest values reported to date for inorganic iodine sorbents.

Investigating the Durability of Iodine Waste Forms in Dilute Conditions.

To prevent the release of radioiodine during the reprocessing of used nuclear fuel or in the management of other wastes, many technologies have been developed for iodine capture. The capture is only part of the challenge as a durable waste form is required to ensure safe disposal of the radioiodine. This work presents the first durability studies in dilute conditions of two AgI-containing waste forms: hot-isostatically pressed silver mordenite (AgZ) and spark plasma sintered silver-functionalized silica aerogel (SFA) iodine waste forms (IWF). Using the single-pass flow-through (SPFT) test method, the dissolution rates respective to Si, Al, Ag and I were measured for variants of the IWFs. By combining solution and solid analysis information on the corrosion mechanism neutral-to-alkaline conditions was elucidated. The AgZ samples were observed to have corrosion preferentially occur at secondary phases with higher Al and alkali content. These phases contained a lower proportion of I compared with the matrix. The SFA samples experienced a higher extent of corrosion at Si-rich particles, but an increased addition of Si to the waste led to an improvement in corrosion resistance. The dissolution rates for the IWF types are of similar magnitude to other Si-based waste form materials measured using SPFT.

Synthesis and crystal structure of a neodymium borosilicate, Nd3BSi2O10.

A lanthanide borosilicate, trineodymium borosilicate or Nd3BSi2O10, was synthesized using a flux method with LiCl, and its structure was determined from X-ray powder diffraction (XRD) and electron probe microanalysis (EPMA). The structure is composed of layers with [SiO4]4- and [BSiO6]5- anions alternating along the c axis linked by Nd3+ cations between them.

A new route to the stable capture and final immobilization of radioactive cesium.

Radioactive Cs released from damaged fuel materials in the event of nuclear accidents must be controlled to prevent the spreading of hazardous Cs into the environment. This study describes a simple and novel process to safely manage Cs gas by capturing it within ceramic filters and converting it into monolithic waste forms. The results of Cs trapping tests showed that CsAlSiO4 was a reaction product of gas-solid reactions between Cs gas and our ceramic filters. Monolithic waste forms were readily prepared from the Cs-trapping filters by the addition of a glass frit followed by thermal treatment at 1000°C for 3h. Major findings revealed that the Cs-trapping filters could be added up to 50wt% to form durable monoliths. In 30-50wt% of waste fraction, CsAlSiO4 was completely converted to pollucite (CsAlSi2O6), which is a potential phase for radioactive Cs due to its excellent thermal and chemical stability. A static leaching test for 28 d confirmed the excellent chemical resistance of the pollucite structure, with a Cs leaching rate as low as 7.21×10-5gm-2/d. This simple scheme of waste processing promises a new route for radioactive Cs immobilization by synthesizing pollucite-based monoliths.

Chemical stabilization of chromate in blast furnace slag mixed cementitious materials.

Cement waste form (CWF) technology is among the leading approaches to disposing of metals and liquid low-level nuclear waste in the United States. One such material, saltstone, includes slag, fly ash and Portland cement to enhance the immobilization of contaminants (e.g., Cr, (99)Tc) in alkaline liquid wastes. To evaluate the stability of such redox sensitive contaminants in saltstone, the effects of slag as a source of reductant on Cr immobilization was evaluated in aged (<300 d) saltstone monoliths. Specifically, we investigated the effects of artificial cement pore waters on the Cr release and the spatially resolved Cr chemical state analysis using synchrotron based microfocused X-ray microprobe analysis. The microprobe analysis indicated the heterogeneous distribution of insoluble Cr(III)-species in saltstone. Although at most of 20% Crtotal was leached at the top few (2-3) millimeter depth, the release of Cr(VI) was small (<5%) at 5-30 mm with slight changes, indirectly suggesting that Cr is likely present as insoluble Cr(III) species throughout the depths. The study suggests that this saltstone formulation can effectively retain/immobilize Cr under the oxic field condition after ⩽300 d of aging time.

Performance of the Fluidized Bed Steam Reforming product under hydraulically unsaturated conditions.

Several candidates for supplemental low-activity waste (LAW) immobilization at the Hanford site in Washington State, USA are being considered. One waste sequestering technology considered is Fluidized Bed Steam Reforming (FBSR). The granular product resulting from the FBSR process is composed primarily of an insoluble sodium aluminosilicate matrix with the dominant phases being feldspathoid minerals with a 1:1:1 molar ratio of Na, Al and Si. To demonstrate the durability of the product, which can be disposed of at the unsaturated Integrated Disposal Facility (IDF) at Hanford, a series of tests has been performed using the Pressurized Unsaturated Flow (PUF) system, which allows for the accelerated weathering of the solid materials. The system maintains hydraulically unsaturated conditions, thus mimicking the open-flow and transport properties that will be present at the IDF. Two materials were tested using the system: 1) the FBSR granular product and 2) the FBSR granular product encapsulated in a geopolymer to form a monolith. Results of the experiments show a trend of relatively constant effluent concentration of Na, Si, Al, and Cs as a function of time from both materials. The elements I and Re show a steady release throughout the yearlong test from the granular material but their concentrations seem to be increasing at one year from the monolith material. This result suggests that these two elements may be present in the sodalite cage structure rather than in the predominant nepheline phase because their release occurs at a different rate compared to nepheline phase. Also, these elements to not seem to reprecipitate when released from the starting material. Calculated one-year release rates for Si are on the order of 10(-6) g/(m(2) d) for the granular material and 10(-5) g/(m(2) d) for the monolith material while Re release is seen to be two orders of magnitude higher than Si release rates. SEM imaging and XRD analysis show how the alteration of the two materials is dependent on their depth in the column. This phenomenom is a result of depth-dependent solution concentrations giving rise chemical environments that may be supersaturated with respect to a number of mineral phases.

DuraLith geopolymer waste form for Hanford secondary waste: correlating setting behavior to hydration heat evolution.

The binary furnace slag-metakaolin DuraLith geopolymer waste form, which has been considered as one of the candidate waste forms for immobilization of certain Hanford secondary wastes (HSW) from the vitrification of nuclear wastes at the Hanford Site, Washington, was extended to a ternary fly ash-furnace slag-metakaolin system to improve workability, reduce hydration heat, and evaluate high HSW waste loading. A concentrated HSW simulant, consisting of more than 20 chemicals with a sodium concentration of 5 mol/L, was employed to prepare the alkaline activating solution. Fly ash was incorporated at up to 60 wt% into the binder materials, whereas metakaolin was kept constant at 26 wt%. The fresh waste form pastes were subjected to isothermal calorimetry and setting time measurement, and the cured samples were further characterized by compressive strength and TCLP leach tests. This study has firstly established quantitative linear relationships between both initial and final setting times and hydration heat, which were never discovered in scientific literature for any cementitious waste form or geopolymeric material. The successful establishment of the correlations between setting times and hydration heat may make it possible to efficiently design and optimize cementitious waste forms and industrial wastes based geopolymers using limited testing results.