Cementitious Waste Forms Research Articles

Getters for improved technetium containment in cementitious waste forms

A cementitious waste form, Cast Stone, is a possible candidate technology for the immobilization of low activity nuclear waste (LAW) at the Hanford site. This work focuses on the addition of getter materials to Cast Stone that can sequester Tc from the LAW, and in turn, lower Tc release from the Cast Stone. Two getters which produce different products upon sequestering Tc from LAW were tested: Sn(II) apatite (Sn-A) that removes Tc as a Tc(IV)-oxide and potassium metal sulfide (KMS-2) that removes Tc as a Tc(IV)-sulfide species, allowing for a comparison of stability of the form of Tc upon entering the waste form. The Cast Stone with KMS-2 getter had the best performance with addition equivalent to ∼0.08wt% of the total waste form mass. The observed diffusion (Dobs) of Tc decreased from 4.6±0.2×10−12cm2/s for Cast Stone that did not contain a getter to 5.4±0.4×10−13cm2/s for KMS-2 containing Cast Stone. It was found that Tc-sulfide species are more stable against re-oxidation within getter containing Cast Stone compared with Tc-oxide and is the origin of the decrease in Tc Dobs when using the KMS-2.

Mercury in aqueous tank waste at the Savannah River Site: Facts, forms, and impacts

ABSTRACTOver the past two years, there has been an intense effort to understand the chemistry of mercury across the Savannah River Site’s high-level liquid waste system to determine the impacts of various mercury species. This effort began after high concentrations of mercury were measured in the leachates from a toxicity characteristic leaching procedure (TCLP) test on the low-level cementitious waste form produced in the Savannah River Saltstone facility. Speciation showed the dominant form of leached mercury to be the methylmercury cation. Neither the source of the methylmercury nor its concentration in the Saltstone feed was well established at the time of the testing. This assessment of mercury was necessary to inform points in the process operations that may be subject to new separation technologies for the removal of mercury.

Environmental geochemistry of technetium

Technetium-99 (99Tc) is a radioactive isotope with a half-life of 2.13 × 105 year. 99Tc is a major radionuclide contaminant of concern for the world. Therefore, detailed understanding of 99Tc environmental chemistry is important for protecting human and ecological health. Here, we review the aqueous geochemistry of 99Tc, focusing on chemical properties and behavior of 99Tc in the hydrosphere and pedosphere. We describe the general chemistry of Tc including coordination chemistry, isotope chemistry and solid-state chemistry. Then we present anthropogenic and indigenous sources of 99Tc and their environmental distribution. We also discuss the radiotoxicity of 99Tc and the use of 99Tc for medical purpose. Tc biogeochemistry is described through sorption and desorption reactions at the mineral–water interface, thermodynamic of surface complexation, abiotic and biotic redox reaction of Tc(VII). Finally, we summarize the 99Tc remediation technologies including cement waste forms, natural remediation, vitrification, nuclear waste transmutation.

Spatial distribution, chemical state, solubility of rhenium in a reducing cement waste form: Implications for predicting technetium mobility in saltstone

Reducing cementitious materials (RCMs) are presently being developed for the long-term, subsurface disposal of low-level radioactive waste within the United States Department of Energy complex. Slag is included in the formulation of the RCM to facilitate the reductive precipitation of redox-sensitive radionuclides, particularly 99Tc. Using Re(VII)O4− as a chemical surrogate for Tc(VII)O4−, depth sequence Re distribution, solubility, and chemical state were evaluated to provide a spatial measure of the impact of atmospheric O2 migration into field aged (<300 d) RCM monoliths. Total digestion analysis showed that total Re concentration increased with decreasing depth, indicating more Re was concentrated at the surface. A synchrotron based X-ray microprobe energy map also supports this finding. There was no clear depth dependent trend in Re solubility. Overall 30–60% of the total Re was soluble at the depth up to ∼3 cm. Partial reduction of Re(VII) to Re(IV) was also observed at these depths. These results suggest that long-term immobilization of Tc in RCM waste forms may be more complicated than previous thought and may require the consideration of non-uniform distribution of redox sensitive Tc in RCMs.

Mathematical Modeling of Heavy Metals Removal from Bio-film Coated Cylindrical Cement Base Waste Forms

Abstract A mathematical description is presented for the leaching behavior of cobalt and chromium from their solidified/stabilized forms under the attack from biofilms commonly developed by acid forming bacteria such as Thiobacillus thiooxidans or Thiobacillus ferooxidans. The proposed model predicts the metals diffusion and subsequent removal from cylindrical cement waste forms using a Michaelis-Menten-type kinetics, as a special case of the widely accepted Langmuir-Hinshelwood mechanism at the surface of the encapsulating cylinder. The resulting nonlinear model is solved by applying boundary perturbation to reduce the nonlinear problem to an infinite series of linear problems that are solvable by Laplace transform methods. Model predictions compares well with published experimental data and confirms that a Michaelis-Menten-type kinetics is most probably the dominant mechanism for the leaching of heavy metals from cement based waste forms.

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, 99Tc) 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 (<300d) 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 5–30mm 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 ⩽300d of aging time.

Leaching Tests and Modelling of Cementitious Wasteforms Corrosion

Leaching Tests and Modelling of Cementitious Wasteforms Corrosion

Technetium Getters to Improve Cast Stone Performance

ABSTRACTA cementitious waste form known as Cast Stone is the baseline waste form for solidification of aqueous secondary wastes, including Hanford Tank Waste Treatment and Immobilization Plant (WTP) secondary liquid effluents to be treated and solidified at the Hanford Site Effluent Treatment Facility. Cast Stone is also being evaluated as a possible supplemental immobilization technology to provide the necessary low activity waste (LAW) treatment capacity to complete the Hanford tank waste cleanup mission in a timely and cost effective manner. Two radionuclides of particular concern in these waste streams are technetium-99 (99Tc) and iodine-129 (129I). These radioactive tank waste components are predicted to contribute the most risk to groundwater – the most probable pathway for future environmental impacts associated with the cleanup of the Hanford site. A recent environmental assessment of Cast Stone performance, which assumes a diffusion controlled release of contaminants from the waste form, calculates groundwater in excess of the allowable maximum permissible concentrations for both contaminants. There is, therefore, a need and an opportunity to improve the retention of both 99Tc and 129I in Cast Stone. One method to improve the performance of Cast Stone is through the addition of “getters” that selectively sequester Tc and I, therefore reducing their diffusion out of Cast Stone. In this paper, we present results of Tc and I removal from solution with various getters. Batch sorption experiments were conducted with deionized water (DIW) and a highly caustic LAW simulant with a 7.8 M average Na concentration. In general, the data show that the selected getters are effective in DIW but their performance is compromised when experiments are performed with the 7.8 M Na Ave LAW simulant. The diminished performance in the LAW simulant may be due to competition with Cr present in the 7.8 M Na Ave LAW simulant and to a pH effect that may create a negatively charged surface that can repel negatively charged species.

The characterization of cement waste form for final disposal of decommissioning concrete wastes

In Korea, the decontamination and decommissioning of KRR-1, 2 at KAERI have been under way. The decommissioning of the KRR-2 was finished completely by 2011, whereas the decommissioning of KRR-1 is currently underway. A large quantity of slightly contaminated concrete waste has been generated from the decommissioning projects. The concrete wastes, 83ea of 200L drums, and 41ea of 4m3 containers, were generated in the decommissioning projects. The conditioning of concrete waste is needed for final disposal. Concrete waste is conditioned as follows: mortar using coarse and fine aggregates is filled with a void space after concrete rubble pre-placement into 200L drums. Thus, this research developed an optimizing mixing ratio of concrete waste, water, and cement, and evaluated the characteristics of a cement waste form to meet the requirements specified in the disposal site specific waste acceptance criteria. The results obtained from a compressive strength test, leaching test, and thermal cycling test of cement waste forms conclude that the concrete waste, water, and cement have been suggested as an optimized mixing ratio of 75:15:10. In addition, the compressive strength of the cement waste form was satisfied, including a fine powder up to a maximum of 40wt% in concrete debris waste of about 75%. According to the scale-up test, the mixing ratio of concrete waste, water, and cement is 75:10:15, which meets the satisfied compressive strength because of an increase in the particle size in the waste.

Cast Stone Formulation for Nuclear Waste Immobilization at Higher Sodium Concentrations

Low activity radioactive waste at U.S. Department of Energy sites can be immobilized for permanent disposal using cementitious waste forms. This study evaluated waste forms produced with simulated wastes at concentrations up to twice that of currently operating processes. The simulated materials were evaluated for their fresh properties, which determine processability, and cured properties, which determine waste form performance. The results show potential for greatly reducing the volume of material. Fresh properties were sufficient to allow for processing via current practices. Cured properties such as compressive strength meet disposal requirements. Leachability indices provide an indication of expected long‐term performance.

Characterisation of Ba(OH)2–Na2SO4–blast furnace slag cement-like composites for the immobilisation of sulfate bearing nuclear wastes

Soluble sulfate ions in nuclear waste can have detrimental effects on cementitious wasteforms and disposal facilities based on Portland cement. As an alternative, Ba(OH)2–Na2SO4–blast furnace slag composites are studied for immobilisation of sulfate-bearing nuclear wastes. Calcium aluminosilicate hydrate (C–A–S–H) with some barium substitution is the main binder phase, with barium also present in the low solubility salts BaSO4 and BaCO3, along with Ba-substituted calcium sulfoaluminate hydrates, and a hydrotalcite-type layered double hydroxide. This reaction product assemblage indicates that Ba(OH)2 and Na2SO4 act as alkaline activators and control the reaction of the slag in addition to forming insoluble BaSO4, and this restricts sulfate availability for further reaction as long as sufficient Ba(OH)2 is added. An increased content of Ba(OH)2 promotes a higher degree of reaction, and the formation of a highly cross-linked C–A–S–H gel. These Ba(OH)2–Na2SO4–blast furnace slag composite binders could be effective in the immobilisation of sulfate-bearing nuclear wastes.

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 5mol/L, was employed to prepare the alkaline activating solution. Fly ash was incorporated at up to 60wt% into the binder materials, whereas metakaolin was kept constant at 26wt%. 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.

Effects of iron oxides on the rheological properties of cementitious slurry

Iron oxide has been considered a promising host for immobilizing and encapsulating radioactive 99Tc (t1/2=2.1×105 year), which significantly enhances the stability of 99Tc within a cementitious waste form. However, the flow behavior of cementitious slurry containing iron oxide has never been investigated to ensure its workability, which directly influences the preparation and performance of the cementitious waste form monolith. Variation in the rheological properties of the cementitious slurry were studied using rheometry and ultrasonic wave reflection to understand the effects of various iron oxides (magnetite, hematite, ferrihydrite, and goethite) during the cement setting and stiffening processes. The rheological behavior significantly varied with the addition of different chemical compounds of iron oxides. Complementary microscopic characteristics such as colloidal vibration currents, morphology, and particle size distributions further suggest that the most adverse alteration of cement setting and stiffening behavior caused by the presence of goethite may be attributed to its acicular shape.

Leaching behaviour of cementitious nuclear wasteforms containing caesium and strontium

The leaching behaviour and physicochemical properties of cementitious nuclear wasteforms containing caesium and strontium waste simulants has been investigated. The cement wasteform consisted of a 9∶1 blend of blast furnace slag and ordinary Portland cement. Both non-loaded samples and samples that were waste loaded with 3 wt-% caesium and strontium added as nitrates have been studied. The cement hydration phases in the samples were identified, and the porosity and microstructure were analysed before leaching. The samples were leached for up to 6 months and the leached elements quantified. In the waste loaded cements, portlandite was not formed, and the monosulphate AFm phase appeared to be altered by the incorporation of the Sr(NO3)2. Incorporation of Cs and Sr also resulted in the increase in the leach rate of Ca2+.

해체 콘크리트 폐기물 최종처분을 위한 시멘트 고화체 특성 평가

원자력 발전소와 연구시설의 해체 시 다량의 오염된 방사성 콘크리트 폐기물이 발생한다. 현재 국내에는 연구로 1, 2호기의 해체와 제염사업이 진행 중이며, 약 800여 드럼 (200 L)의 콘크리트 폐기물이 발생하였다. 이들 방사성 콘크리트 폐기물은 최종처분을 위해 200 L 드럼에 덩어리 크기의 콘크리트를 채우고, 시멘트 모르타르 형태로 제조한 입자상 폐기물로 빈 공간을 채우며 혼용 고정화 및 안정화하는 일련의 과정이 필요하다. 이에 본 연구에서는 콘크리트 폐기물, 물, 시멘트의 최적의 혼합비율을 찾고, 처분장 폐기물 인수기준에 준하기 위한 고화체의 특성을 평가하였다. 모르타르 유동도, 고화체 압축강도, 침출에 대한 안정성, 열 저항성 등의 인자에 따라 평가한 결과, 콘크리트 폐기물, 물, 시멘트의 배합비 75:15:10wt%에서평가인자 기준에 도달하였으며, 콘크리트 폐기물 75%에 미분말 콘크리트 폐기물을 최대 40wt%까지 포함시켜 시멘트 고화체를 제조한 경우에도 압축강도를 만족하였다. 입자의 충진 밀도의 증가로 scale-up실험에서는 75:10:15wt%의 배합비에서작업도 및 압축강도 범위를 만족하였다.

Docking 90Sr radionuclide in cement: An atomistic modeling study

Cementitious materials are considered to be a waste form for the ultimate disposal of radioactive materials in geological repositories. We investigated by means of atomistic simulations the encapsulation of strontium-90, an important radionuclide, in calcium–silicate–hydrate (C–S–H) and its crystalline analog, the 9Å-tobermorite. C–S–H is the major binding phase of cement. Strontium was shown to energetically favor substituting calcium in the interlayer sites in C–S–H and 9Å-tobermorite with the trend more pronounced in the latter. The integrity of the silicate chains in both cementitious waste forms were not affected by strontium substitution within the time span of molecular dynamics simulation. Finally, we observed a limited degradation of the mechanical properties in the strontium-containing cementitious waste form with the increasing strontium concentration. These results suggest the cement hydrate as a good candidate for immobilizing radioactive strontium.

Stability of cemented dried water hyacinth used for biosorption of radionuclides under various circumstances

This paper investigates the influence of frost attack and flooding conditions during disposal on the compressive strength, porosity and durability of cemented waste form contained dried and grinded water hyacinth. This plant was used as a phytoremediating agent to treat liquid waste simulate contaminated with radionuclides. The obtained results showed that an increase in the incorporated dry plants decreases the compressive strength and increases the porosity of the solidified waste form. Raising the number of freeze–thaw cycles was accompanied with noticeable increase in the mass-loss of tested specimens and unsteady trend of compressive strength and consequently the mechanical integrity. The presence and increase of immersion duration per turned positively the mass change and affect in different ways on the solidified waste form. Spectroscopic analyses such as infrared and X-ray as well as microscopic investigation were performed to evaluate the solidified waste form exposed to different undesirable climatic conditions during extending disposal durations. The use of Portland cement as a stabilizer for water hyacinth, following the phytoremediation process, achieves the requirements for durability and strength against the freeze–thaw cycles or flooding in different types of water during prolonged disposal.

Solubility control of technetium release from Saltstone by TcO2·xH2O

Saltstone leaching experiments were conducted using a modified single-pass flow-through method under anoxic conditions. The analytical results of leachates collected from these experiments were evaluated using thermodynamic modeling to determine if the data were consistent with potential solubility controlling phases. The results demonstrate that technetium release from Saltstone under anoxic conditions is controlled by the solubility of TcO2·xH2O (likely TcO2·1.6H2O). In our system the solubility of TcO2·1.6H2O appears to have been reached equilibrium within 2weeks, with a Tc concentration of approximately 1.5×10−6M. Because Saltstone is a cementitious material, it is a continuously reacting solid with component phases that continue to change over very long time periods (up to hundreds of years). As a result of this process, the concentrations of technetium in equilibrium with TcO2·1.6H2O are likely to vary as the composition of Saltstone pore fluid evolves over time. In a disposal scenario where the initially high pH values (∼12.5–13) decrease (due to carbonation over very long time periods), the solubility of TcO2·xH2O would decrease significantly. The thermodynamic data used to determine the solubility of TcO2·1.6H2O were taken from the tabulation of critically selected thermodynamic data determined by the Nuclear Energy Agency.Solid phase characterization to demonstrate the presence of TcO2·xH2O was not possible due to the low concentrations of technetium in our samples. Previous solid phase characterization studies with cementitious waste forms that were very similar to our Saltstone samples as well as reaction products derived from reductive immobilization of TcO4- by amorphous FeS clearly indicate the presence of TcO2 with varying degrees of hydration. Although, the presence of TcSx or other reduced technetium sulfide phases are likely present in our samples, release of technetium from Saltstone will be controlled by TcO2·1.6H2O because of its higher solubility.Our results clearly demonstrate that the release mechanism of technetium from Saltstone under reducing conditions controlled by the solubility of TcO2·xH2O (likely TcO2·1.6H2O); however, empirical distribution coefficients (Kds), that describe sorption and not solubility, were calculated for comparison with past literature values. After 84days of reaction under anoxic conditions, the average Kd value for technetium was determined to be 610mL/g. This value is similar to a value determined previously for a similar Saltstone sample under reducing conditions at 56days (712±81mL/g).

The effect of concentration on the structure and crystallinity of a cementitious waste form for caustic wastes

Cement-based waste forms have long been considered economical technologies for disposal of various types of waste. A solidified cementitious waste form, Cast Stone, has been identified to immobilize the radioactive secondary waste from vitrification processes. In this work, Cast Stone was considered for a Na-based caustic liquid waste, and its physical properties were analyzed as a function of liquid waste loading up to 2M Na. Differences in crystallinity (phase composition), microstructure, mesostructure (pore size distribution and surface area), and macrostructure (density and compressive strength) were investigated using various analytical techniques, in order to assess the suitability of Cast Stone as a chemically durable waste. It was found that the concentration of secondary waste simulant (caustic waste) had little effect on the relevant engineering properties of Cast Stone, showing that Cast Stone could be an effective and tolerant waste form for a wide range of concentrations of high sodium waste.

Setting and stiffening of cementitious components in Cast Stone waste form for disposal of secondary wastes from the Hanford waste treatment and immobilization plant

Cast Stone is a cementitious waste form, a viable option to immobilize secondary nuclear liquid wastes generated from the Hanford Waste Treatment and Immobilization Plant. However, no study has been performed to understand the flow and stiffening behavior, which is essential to ensure proper workability and is important to safety in a nuclear waste field-scale application. X-ray diffraction, rheology, and ultrasonic wave reflection methods were used to understand the specific phase formation and stiffening of Cast Stone. Our results showed a good correlation between rheological properties of the fresh mixture and phase formation in Cast Stone. Secondary gypsum formation was observed with low concentration simulants, and the formation of gypsum was suppressed in high concentration simulants. A threshold concentration for the drastic change in stiffening was found at 1.56M Na concentration. It was found that the stiffening of Cast Stone was strongly dependent on the concentration of simulant.