Immobilization Of Technetium Research Articles

Modification of Portland cement matrix with diethyldithiocarbamate for technetium immobilization

The paper considers the effect of sodium diethyldithiocarbamate (SDDC) addition on the immobilization of technetium in a Portland cement matrix. The leaching process was evaluated in a model solution that simulated the conditions of the future radioactive waste (RW) storage site at the Yeniseisky site. The results demonstrated that the addition of 1.0 wt % SDDC to the cement composite increased the incorporation of immobilized technetium into the cement matrix by 35% in comparison to the blank sample. Furthermore, the retention of technetium in the cement matrix was observed to be enhanced, with a retention of up to 90% observed on the 200th day of the experiment. Resulting materials fulfill the necessary technical characteristics for use as a matrix and engineered safety barrier in the concept of deep RW disposal. The addition of SDDC into cement results in microbial respiratory activity decreasing. In order to evaluate the mechanisms of technetium immobilization, the structure of the technetium compound with diethyldithiocarbamate (DDC) [Tc(C5H10NS2)4]TcO4 is described for the first time. This compound contains a Tc(V) atom which coordinates four diethyldithiocarbamate C5H10NS2 moieties through eight sulfur atoms to form a complex cation. The addition of SDDC in cement is presumed to result in a cascade of disproportionation reactions and the formation of stable Tc(IV) compounds, as it was evidenced by XANES spectroscopy.

Immobilization of technetium by iron corrosion phases: lessons learned and future perspectives

Abstract. Technetium-99 (99Tc) is a long-lived fission product (2.13×105 years) of uranium-235 (235U) and plutonium-239 (239Pu) and, therefore, of great concern for the long-term safe management of nuclear waste. The migration of Tc in the environment is highly influenced by the redox conditions, since Tc may be present in various oxidation states. Depending on the chemical properties of environmentally relevant systems, Tc is expected to mainly occur as Tc(VII) and as Tc(IV) under oxidizing and reducing conditions, respectively. The anion pertechnetate (Tc(VII)O4-) is known to barely interact with mineral surfaces; this, in turn, enhances its migration in groundwater and favors its entry into the biosphere. On the contrary, the formation of Tc(IV) limits the migration of Tc, since it forms a low soluble solid (TcO2) and/or species, whose interaction with minerals is more favorable. In the last few decades Tc migration has been focused on the reduction of Tc(VII) to Tc(IV) by various reductants, such as Fe(II), Sn(II), or S(-II), which are either present in solution, taking part in mineral structures (Pearce et al., 2019), or metabolically induced by microbial cascades (Newsome et al., 2014). We have studied the immobilization of technetium (Tc) by various Fe(II)-containing phases, including Fe2+ pre-sorbed on alumina nanoparticles (Mayordomo et al., 2020), Fe(II)-Al(III)-layered double hydroxide (Mayordomo et al., 2021), and Fe(II) sulfides (Rodríguez et al., 2020; Rodríguez et al., 2021). We have combined sorption experiments with microscopic and spectroscopic techniques (scanning electron microscopy, Raman microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and X-ray absorption spectroscopy) to elucidate the mechanisms responsible for Tc(VII) reductive immobilization. Those works have been focused on binary systems (i.e., studies of the interaction of Tc with a given reductant). However, the environment is a complex system, where different components often depend on and modify each other. Thus, Tc migration is susceptible and varies, depending on environmental conditions, and should not be studied in an isolated manner. The young investigator group TecRad (HZDR, 2022), funded by the German Federal Ministry of Education and Research, aims at analyzing Tc chemistry from a wider perspective. Our goal is to study the biogeochemical behavior of Tc when it interacts with (i) microorganisms, (ii) metabolites, (iii) Fe(II) minerals, and (iv) Fe(II) minerals in presence of metabolites. An important part of this project deals with implementing new spectro-electrochemical methods to monitor the in situ the behavior of Tc in solution and at interfaces as a function of the redox potential. With these tools, we aspire to characterize the molecular structures of Tc species under a variable range of redox conditions to broaden the understanding of the chemical behavior of the pollutant. We aim at generating valuable thermodynamic data (complex formation constants, solubility constants of minerals, redox potentials, and Tc distribution coefficients) that will be used to implement a geochemical modeling able to explain Tc's environmental fate, even under different redox conditions.

Clay and carbon materials-based engineered barriers for technetium immobilization

Immobilization of long-lived 99Tc is one of the most complicated tasks faced during disposal of radioactive waste. Bentonite clays, which are common components used for construction of engineered barriers are not capable of preventing migration of highly soluble oxidized technetium forms. Modification of bentonite clay materials with natural and industrial coals of various genesis, added in amount of 5 mass %, was carried out as part of this research. The anthracite from Omsukchan coal cluster, coke of Kuznetsk basin and activated carbons of AG-3 and CAU marks have demonstrated high ability to immobilize technetium under oxidizing conditions with values of partition coefficient exceeding 103 ml/g. The resulting composite materials are characterized by low water permeability (Kp < 1–5·10−11 m/s at a dry density of 1.1–1.2 g/cm3), which is mandatory for engineered barriers. Dispersed materials are easy-flowing (ff > 4), which allows the construction of clay barriers by dry, cavity-free backfilling. Quantitative immobilization of technetium occurs during the first day of interaction, with strongly-bonded forms accounting for over 90% of all technetium in the barrier material.

Ceramics Based on the NaRe2(PO4)3 Phosphate with the Kosnarite Structure as Waste Forms for Technetium Immobilization

NaRe$_2$(PO$_4$)$_3$ phosphate-based ceramic with the structure of kosnarite mineral was obtained by spark plasma sintering. Rhenium (Re) served as a chemical and structural analog of technetium. The ceramic relative density was 85%. The mechanism of Re static leaching from NaRe$_2$(PO$_4$)$_3$ ceramic at room temperature was investigated. The leaching rate of rhenium was $1.3\times10^{-5}$ g/(cm$^2$*day).

Immobilization of Technetium into a Sodium-Aluminum-Iron Phosphate Glass: Degree of Oxidation of Technetium and Iron, Hydrothermal Stability of the Glass

Immobilization of Technetium into a Sodium-Aluminum-Iron Phosphate Glass: Degree of Oxidation of Technetium and Iron, Hydrothermal Stability of the Glass

Hypolimnion behavior of technetium in freshwater at various stages of eutrophication

The article presents a study of various mechanisms of hypolimnion technetium behavior which occur at different stages of waterbodies eutrophication. Eutrophication stage was found to be positively correlated with the rate of 99Tc removal from water phase. The study identified a complex biogeochemical mechanism of technetium behavior. Planktonic phototrophic community plays a pivotal role in such a mechanism by ensuring fast oxygen consumption in hypolimnion. This creates favorable conditions for the active development of anaerobic bottom bacteria of sulfur and iron cycles given nutrients inflow. Sulfates and nitrates were discovered to have inhibitory effect on 99Tc biosorption by bottom sediments due to oxidizing conditions. Apart from the shift of redox potential of the medium to reducing values, the 99Tc removal and partial immobilization are also promoted by the presence of inorganic mineral phases of reduced sulfur and iron. These phases form a reducing barrier in the silt, thus preventing the oxidation and migration of technetium. We suggest the ways of stimulating in situ waterbody remediation by means of various additives, which will allow irreversible immobilization of technetium in silt once several growth periods have passed.

Technetium immobilization by chukanovite and its oxidative transformation products: Neural network analysis of EXAFS spectra

The uptake of the fission product technetium (Tc) by chukanovite, an FeII hydroxy carbonate mineral formed as a carbon steel corrosion product in anoxic and carbonate-rich environments, was studied under anoxic, alkaline to hyperalkaline conditions representative for nuclear waste repositories in deep geological formations with cement-based inner linings. The retention potential of chukanovite towards TcVII is high in the pH range 7.8 to 12.6, evidenced by high solid-water distribution coefficients, log Rd ~ 6, and independent of ionic strength (0.1 or 1 M NaCl). Using Tc K-edge X-ray absorption spectroscopy (XAS) two series of samples were investigated, Tc chukanovite sorption samples and coprecipitates, prepared with varying Tc loadings, pH values and contact times. From the resulting 37 XAS spectra, spectral endmembers and their dependence on chemical parameters were derived by self-organizing (Kohonen) maps (SOM), a neural network-based approach of machine learning. X-ray absorption near-edge structure (XANES) data confirmed the complete reduction of TcVII to TcIV by chukanovite under all experimental conditions. Consistent with mineralogical phases identified by X-ray diffraction (XRD), SOM analysis of the extended X-ray absorption fine-structure (EXAFS) spectra revealed the presence of three species in the sorption samples, the speciation predominately controlled by pH: Between pH 7.8 and 11.8, TcO2-dimers form inner-sphere sorption complexes at the surface of the initial chukanovite as well as on the surface of secondary magnetite formed due to redox reaction. At pH ≥ 11.9, TcIV is incorporated in a mixed, chukanovite-like, Fe/Tc hydroxy carbonate precipitate. The same species formed when using the coprecipitation approach. Reoxidation of sorption samples resulted in a small remobilization of Tc, demonstrating that both the original chukanovite mineral and its oxidative transformation products, magnetite and goethite, contribute to the immobilization of Tc in the long term, thus strongly attenuating its environmental transport.

Analysis of technetium immobilization and its molecular retention mechanisms by Fe(II)-Al(III)-Cl layered double hydroxide

Layered double hydroxides (LDH) play a decisive role in regulating the mobility of contaminants in natural and engineered environments. In this work, the retention of an Fe(II)-Al(III)-Cl LDH towards pertechnetate (TcO4–), which is the most stable and highly mobile form of Tc under aerobic conditions, is investigated comprehensively as a function of pH, Tc concentration and ionic strength. For a technetium initial concentration of 5 µM, its retention yield is higher than 80% from pH 3.5 to pH 10.5, especially at NaCl concentration below 0.1 M. A combination of vibrational and X-ray absorption spectroscopy provides structural information on the retention mechanism on a molecular scale. X-ray absorption near edge spectroscopy (XANES) confirms that most of the Tc uptake is due to an initial Tc(VII) reduction to Tc(IV), and consecutive Tc(IV) interaction with the solid. The analysis of the extended X-ray absorption fine structure (EXAFS) reveals two different mechanisms of Tc(IV) interaction with hematite (sub-product of the LDH oxidation and confirmed by Raman microscopy). At low pH, sorption of Tc(IV) dimers via inner-sphere monodentate complexation on hematite dominates. In contrast, under alkaline conditions, Tc(IV) is incorporated into the structure of hematite. Additionally, in situ attenuated total reflection Fourier-transform infrared spectroscopy (ATR FT-IR) evidences a small contribution of the total uptake corresponding to Tc(VII) anion exchange.The derived molecular structures increase confidence in predictive modelling of Tc migration patterns in subsurface environments, e.g. in the vicinity of a radioactive waste repository and treatment sites or in polluted areas due to other anthropogenic Tc sources.

Activated carbon additives for technetium immobilization in bentonite-based engineered barriers for radioactive waste repositories

Safe disposal of nuclear waste in a geologic repository will rely on natural geologic features and engineered barriers to greatly retard the movement of radionuclides from the repository. Clay minerals including bentonite are effective in retarding the migration of many radionuclides, but are ineffective for anionic radionuclides, of which pertechnetate is of particular concern owing to its relatively long half-life and the lack of natural isotopes that dilute it. Activated carbon is proposed as an additive material for reducing pertechnetate mobility in the nearfield. Activated carbon materials of different origins quantitatively sorb pertechnetate from aqueous solution under oxidizing conditions during the first day of contact, and sequential extraction showed that 73 % of this technetium is in the strongly bound fraction. X-ray photoelectron spectra (XPS) and extended X-ray absorption fine structure (EXAFS) spectra both demonstrated that no reduction of technetium occurred in the studied systems. The interaction of technetium with a composite material consisting of bentonite and activated carbon was studied at the first time. Effective technetium sorption was shown, with distribution coefficients (Kd) up to 740 cm3. g−1.

Technetium immobilization by materials through sorption and redox-driven processes: A literature review.

The objective of this review is to evaluate materials for use as a barrier or other deployed technology to treat technetium-99 (Tc) in the subsurface. To achieve this, Tc interactions with different materials are considered within the context of remediation strategies. Several naturally occurring materials are considered for Tc immobilization, including iron oxides and low solubility sulfide phases. Synthetic materials are also considered, and include tin-based materials, sorbents (resins, activated carbon, modified clays), layered double hydroxides, metal organic frameworks, cationic polymeric networks and aerogels. All of the materials were evaluated for their potential in-situ and ex-situ performance with respect to long-term Tc uptake and immobilization, environmental impacts and deployability. Other factors such as the technology maturity, cost and availability were also considered. Given the difficulty of evaluating materials under different experimental conditions (e.g., solution chemistry, redox conditions, solution to solid ratio, Tc concentration etc.), a subset of these materials will be selected, on the basis of this review, for subsequent standardized batch loading tests.

Evaluation of materials for iodine and technetium immobilization through sorption and redox-driven processes.

Radioactive iodine-129 (129I) and technetium-99 (99Tc) pose a risk to groundwater due to their long half-lives, toxicity, and high environmental mobility. Based on literature reviewed in Moore et al. (2019) and Pearce et al. (2019), natural and engineered materials, including iron oxides, low-solubility sulfides, tin-based materials, bismuth-based materials, organoclays, and metal organic frameworks, were tested for potential use as a deployed technology for the treatment of 129I and 99Tc to reduce environmental mobility. Materials were evaluated with metrics including capacity for IO3- and TcO4- uptake, selectivity and long-term immobilization potential. Batch testing was used to determine IO3- and TcO4- sorption under aerobic conditions for each material in synthetic groundwater at different solution to solid ratios. Material association with IO3- and TcO4- was spatially resolved using scanning electron microscopy and X-ray microprobe mapping. The potential for redox reactions was assessed using X-ray absorption near edge structure spectroscopy. Of the materials tested, bismuth oxy(hydroxide) and ferrihydrite performed the best for IO3-. The commercial Purolite A530E anion-exchange resin outperformed all materials in its sorption capacity for TcO4-. Tin-based materials had high capacity for TcO4-, but immobilized TcO4- via reductive precipitation. Bismuth-based materials had high capacity for TcO4-, though slightly lower than the tin-based materials, but did not immobilize TcO4- by a redox-drive process, mitigating potential negative re-oxidation effects over longer time periods under oxic conditions. Cationic metal organic frameworks and polymer networks had high Tc removal capacity, with TcO4- trapped within the framework of the sorbent material. Although organoclays did not have the highest capacity for IO3- and TcO4- removal in batch experiments, they are available commercially in large quantities, are relatively low cost and have low environmental impact, so were investigated in column experiments, demonstrating scale-up and removal of IO3- and TcO4- via sorption, and reductive immobilization with iron- and sulfur-based species.

Long-Term Immobilization of Technetium via Bioremediation with Slow-Release Substrates.

Radionuclides are present in groundwater at contaminated nuclear facilities with technetium-99, one of the most mobile radionuclides encountered. In situ bioremediation via the generation of microbially reducing conditions has the potential to remove aqueous and mobile Tc(VII) from groundwater as insoluble Tc(IV). However, questions remain regarding the optimal methods of biostimulation and the stability of reduced Tc(IV) phases under oxic conditions. Here, we selected a range of slow-release electron donor/chemical reduction based substrates available for contaminated land treatment, and assessed their potential to stimulate the formation of recalcitrant Tc(IV) biominerals under conditions relevant to radioactively contaminated land. These included a slow-release polylactate substrate (HRC), a similar substrate with an additional organosulfur ester (MRC) and a substrate containing zerovalent iron and plant matter (EHC). Results showed that Tc was removed from solution in the form of poorly soluble hydrous Tc(IV)-oxides or Tc(IV)-sulfides during the development of reducing conditions. Reoxidation experiments showed that these phases were largely resistant to oxidative remobilization and were more resistant than Tc(IV) produced via biostimulation with an acetate/lactate electron donor mix in the sediments tested. The implications of the targeted formation of recalcitrant Tc(IV) phases using these proprietorial substrates in situ is discussed in the context of the long-term management of technetium at legacy nuclear sites.

Rhenium volatilization in waste glasses

We investigated volatilization of rhenium (Re), sulfur, cesium, and iodine during the course of conversion of high-level waste melter feed to glass and compared the results for Re volatilization with those in low-activity waste borosilicate glasses. Whereas Re did not volatilize from high-level waste feed heated at 5Kmin−1 until 1000°C, it began to volatilize from low-activity waste borosilicate glass feeds at ∼600°C, a temperature ∼200°C below the onset temperature of evaporation from pure KReO4. Below 800°C, perrhenate evaporation in low-activity waste melter feeds was enhanced by vigorous foaming and generation of gases from molten salts as they reacted with the glass-forming constituents. At high temperatures, when the glass-forming phase was consolidated, perrhenates were transported to the top surface of glass melt in bubbles, typically together with sulfates and halides. Based on the results of this study (to be considered preliminary at this stage), the high-level waste glass with less foaming and salts appears a promising medium for technetium immobilization.

Technetium Incorporation into C14 and C15 Laves Intermetallic Phases

ABSTRACTLaves-type intermetallic phases have been observed to be the dominant phases in a series of alloy compositions being designed for the immobilization of technetium in a metallic waste form. The dominant metals in the alloy compositions were Fe-Mo and Fe-Mo-Zr. The alloy composition, Fe-Mo-Zr, also contained Pd, Zr, Cr, and Ni. Both non-radioactive rhenium-containing and radioactive technetium-bearing alloy compositions were investigated. In the Fe-Mo series, the phases observed were Fe2Mo (C14 Laves phase) and ferrite in agreement with predictions. Both Tc and Re resided predominantly in the Laves phases. In the Fe-Mo-Zr system, the phases included hexagonal C14 with the composition (Fe,Cr)2Mo, cubic C15 phase with a (Fe,Ni)2Zr composition, and the hcp phase Pd2Zr. The observation of these phases was in agreement with predictions. Re was found in the C14 intermetallic, (Fe,Cr)2Mo. Technetium was also observed to be partitioned preferentially into the (Fe,Cr)2Mo phase; however, this phase exhibited a cubic structure consistent with the C15 structural type. The composition of Laves phases is influenced by both the atomic size and electro-negativity of the constituent elements. The long-term release behavior of technetium under nuclear waste disposal conditions may be more dependent on the corrosion characteristics of these individual Laves phases containing Tc than the other metallic phases.

Tetraphenylpyridinium pertechnetate: a promising salt for the immobilization of technetium

AbstractIn the context of the immobilization of technetium, as pertechnetate, from spent nuclear fuel from reprocessing activies, or potentially a scavenger for pertechnetate in repository conditions, the compound tetraphenylpyridinium pertechnetate (TPPy-TcO4) has been synthesized, structurally characterized and its solubility investigated. The compound TPPy-TcO4has been prepared by metathesis from ammonium pertechnetate and 1,2,4,6-tetraphenylpyridinium tetrafluoroborate from a water/acetone media. Diffraction measurements show that the compound crystallizes in the orthorhombic space group (Pbca) witha= 16.1242(10)Å,b= 16.7923(10)Å, andc= 17.6229(11)Å. The solubility of the salt has been investigated at room temperature in aqueous media at pH 2.22, 6.91, and 9.81 where solubility products were determined as 6.16 × 10−12, 4.13 × 10−12, and 1.16 × 10−11, respectively. The compound TPPy-TcO4is not the most insoluble pertechnetate salt reported so far, but comparatively has a lower solubility than that of most other pertechnetate salts.

Isolation of long-lived technetium-99 in confinement matrices

Amongst fission products formed in atomic reactors, 99Tc is the most hazardous for the environment because of its long half-life (213000 yr), high content in spent nuclear fuel (SNF) (0.8–1.0 kg per ton of SNF), low sorption ability, and high mobility under aerobic conditions. The bulk of 99Tc (∼200 t) is incorporated into SNF. In the course of SNF reprocessing, this radioisotope is released as a separate fraction or along with actinides. More than 60 t of highly concentrated 99Tc have been accumulated to date. It is evident that isolation of 99Tc from the environment is a matter of great urgency. The immobilization of technetium in a highly stable and poorly soluble matrix is a necessary element in settling this problem. Ceramics composed of titanates with pyrochlore, perovskite, and rutile structures are proposed as matrices able to retain technetium along with actinides. The high chemical stability of these compounds has been corroborated by experiments. The difficulties in production of such matrices are related to the fugacity of Tc and the necessity of converting it into Tc(IV). To overcome this obstacle, self-propagating high-temperature synthesis (SHS), characterized by reductive conditions and a high reaction rate, is proposed. The charge for matrix synthesis consists of reducing agents (metallic powders with a strong affinity to oxygen, e.g., Ti and Zr), oxidants (MoO3, Fe2O3, CuO), and additives (TiO2, ZrO2, Y2O3, CaO, etc.), which taken together with other elements form target phases. Instead of Tc, Mo, close in chemical properties, is used in matrix synthesis as a simulator. Samples of Mo-bearing matrices have been synthesized with SHS; their phase compositions and Mo distribution therein are characterized. It has been shown that up to 40 wt % Mo can be incorporated into the synthesized matrices in the form of metal or structural admixtures in titanates. The titanate-zirconate pyrochlore-based matrices are the most appropriate for the joint immobilization of actinides, REEs, and 99Tc.

Probing the Biogeochemical Behavior of Technetium Using a Novel Nuclear Imaging Approach

Dynamic gamma-camera imaging of radiotracer technetium ((99m)Tc) was used to assess the impact of biostimulation of metal-reducing bacteria on technetium mobility at 10(-12) mol L(-1) concentrations in sediments. Addition of the electron donor acetate was used to stimulate a redox profile in sediment columns, from oxic to Fe(III)-reducing conditions. When (99m)Tc was pumped through the columns, real-time gamma-camera imaging combined with geochemical analyses showed technetium was localized in regions containing biogenic Fe(II). In parallel experiments, electron microscopy with energy-dispersive X-ray (EDX) mapping confirmed sediment-bound Tc was associated with iron, while X-ray absorption spectroscopy (XAS) confirmed reduction of Tc(VII) to poorly soluble Tc(IV). Molecular analyses of microbial communities in these experiments supported a direct link between biogenic Fe(II) accumulation and Tc(VII) reductive precipitation, with Fe(III)-reducing bacteria more abundant in technetium immobilization zones. This offers a novel approach to assessing radionuclide mobility at ultratrace concentrations in real-time biogeochemical experiments, and confirms the effectiveness of biostimulation of Fe(III)-reducing bacteria in immobilizing technetium.

Reduction and long-term immobilization of technetium by Fe(II) associated with clay mineral nontronite

99Tc is formed mostly during nuclear reactions and is released into the environment during weapons testing and inadvertent waste disposal. The long half-life, high environmental mobility (as Tc(VII)O 4 −) and its possible uptake into the food chain cause 99Tc to be a significant environmental contaminant. In this study, we evaluated the role of Fe(II) in biologically reduced clay mineral, nontronite (NAu-2), in reducing Tc(VII)O 4 − to poorly soluble Tc(IV) species as a function of pH and Fe(II) concentration. The rate of Tc(VII) reduction by Fe(II) in NAu-2 was higher at neutral pH (pH 7.0) than at acidic and basic pHs when Fe(II) concentration was low (< 1 mmol/g). The effect of pH, however, was insignificant at higher Fe(II) concentrations. The reduction of Tc(VII) by Fe(II) associated with NAu-2 was also studied in the presence of common subsurface oxidants including iron and manganese oxides, nitrate, and oxygen, to evaluate the effect of these oxidants on the enhancement and inhibition of Tc(VII) reduction, and reoxidation of Tc(IV). Addition of iron oxides (goethite and hematite) to the Tc(VII)-NAu-2 system, where Tc(VII) reduction was ongoing, enhanced reduction of Tc(VII), apparently as a result of re-distribution of reactive Fe(II) from NAu-2 to more reactive goethite/hematite surfaces. Addition of manganese oxides stopped further Tc(VII) reduction, and in case of K +-birnessite, it reoxidized previously reduced Tc(IV). Nitrate neither enhanced reduction of Tc(VII) nor promoted reoxidation of Tc(IV). Approximately 11% of Tc(IV) was oxidized by oxygen. The rate and extent of Tc(IV) reoxidation was found to strongly depend on the nature of the oxidants and concentration of Fe(II). When the same oxidants were added to aged Tc reduction products (mainly NAu-2 and TcO 2•nH 2O), the extent of Tc(IV) reoxidation decreased significantly relative to fresh Tc(IV) products. Increasing NAu-2 concentration also resulted in the decreased extent of Tc(IV) reoxidation. The results were attributed to the effect of NAu-2 aggregation that effectively retained Tc(IV) in the solid and decreased its vulnerability to reoxidation. Overall, our results implied that bioreduced clay minerals could play an important role in reducing Tc(VII) and in maintaining the long-term stability of reduced Tc(IV).

Studies on the Immobilization of Technetium under Near Field Geochemical Conditions

Studies on the Immobilization of Technetium under Near Field Geochemical Conditions

Microbial role in immobilization of technetium in soil under waterlogged conditions

Technetium behaviour in soil depends upon its chemical forms. The nuclide is expected to be in a soluble form of pertechnetate (TcO 4 −) under an aerobic condition, however, this changes through a combination of factors such as a redox condition and microbial activity. In this study, a radiotracer experiment was carried out to clarify the influence of microbial activity on plant available Tc under waterlogged condition. Air-dried soil with 0, 0.05, 0.5% glucose contents and sterile soil were used to compare the effect of microbial activity. The soils were waterlogged with 95mTc or 95mTc solution and kept at room temperature. Relative activities of the bottom solutions which had collected 1 hour after waterlogging indicated high correlations with the amounts of total-C, total-N, active-Al. Relative activities of Tc in the surface solutions of the air-dried soils decreased with increasing glucose concentration, however, those of sterile soils were almost constant during the experiment. Our results showed Tc adsorption onto the soil is influenced by the activity of microorganisms, that is, the redox potential of the soil is lowered by their activity. Most of the Tc in the surface solution is sorbed on the surface soil strongly and this can be a cause of reduced Tc availability to rice plants during the waterlogged period.