The Corrosion of Spent UO2 Fuel in Synthetic Groundwater

1985 ◽  
Vol 50 ◽  
Author(s):  
R. S. Forsyth ◽  
L.O. Werme

AbstractLeaching of high burnup BWR fuel for up to 3 years showed that both U and Pu attain saturation rapidly at pH 8.1, giving values of 1–2 mg/l and 1 μg/l respectively. The leaching rate for Sr-90 decreased from about 10−5/d to 10−7/d but was always higher than the rates for U, Pu, Cm, Ce, Eu and Ru. Congruent dissolution was only attained at pH values of about 4.The hypothesis that alpha radiolytic decomposition of water is a driving force for UO2 corrosion even under reducing conditions has been examined in leaching tests on low burnup (low alpha dose-rate) fuel. No significant effect of alpha radiolysis under the experimental conditions was detected.

Catalysts ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 855
Author(s):  
Ahmed Amine Azzaz ◽  
Salah Jellali ◽  
Nasser Ben Harharah Hamed ◽  
Atef El Jery ◽  
Lotfi Khezami ◽  
...  

In the present study, methylene blue (MB) removal from aqueous solutions via the photocatalytic process using TiO2 as a catalyst in the presence of external ultra-violet light (UV) was investigated. The results of adsorption in the absence of UV radiation showed that adsorption reached an equilibrium state at 60 min. The experimental kinetic data were found to be well fitted by the pseudo-second-order model. Furthermore, the isotherm study suggested that dye uptake by TiO2 is a chemisorption process with a maximum retention capacity of 34.0 mg/g. The photodegradation of MB was then assessed under various experimental conditions. The related data showed that dye mineralization decreased when dye concentrations were increased and was favored at high pH values and low salt concentrations. The simultaneous presence of organic and inorganic pollution (Zinc) was also evaluated. The effect of the molar ratio Zn2+/MB+ in the solution at different pH values and NaCl concentrations was also monitored. The corresponding experimental results showed that at low values of Zn2+ in the solution (30 mg/L), the kinetic of the MB removal became faster until reaching an optimum at Zn2+/MB+ concentrations of 60/60 mg/L; it then slowed down for higher concentrations. The solutions’ carbon contents were measured during the degradation process and showed total mineralization after about 5 h for the optimal Zn2+/MB+ condition.


2021 ◽  
Vol 62 (08) ◽  
pp. 887-903
Author(s):  
D.A. Novikov ◽  
A.V. Chernykh ◽  
L.N. Konstantinova ◽  
F.F. Dultsev ◽  
I.I. Yurchik

Abstract —The Vendian deposits of the Siberian Platform are represented by four regional horizons (from bottom to top): Nepa, Vilyuchan, Tira, and Danilovka. The TDS of brines in the Nepa and Vilyuchan horizons varies from 170.3 to 470.1 g/L, and the TDS in the overlying Tira and Danilovka horizons, from 84.6 to 583.1 g/L. Brines of Cl Na, Cl Na–Ca, Cl Ca–Na, Cl Ca, and Cl Ca–Mg types have been identified. The pH values of the brines vary from 3.0 to 7.0; acidic and weakly acidic brines (pH = 3.0–5.5) prevail. The redox potential Eh varies from –440 mV (highly reducing conditions) to +130 mV (oxidizing conditions), averaging –176 mV. Areal regional hydrogeochemical zoning is controlled by the outer (on the periphery of the Siberian Platform, where infiltration of meteoric waters took place) and inner feeding areas. The outer feeding areas bear infiltrogenic brines of different ages (group I), mostly of Cl Na composition. They are characterized by TDS ≤ 280 g/L, rNa/rCl ≤ 1.55, Cl/Br ≤ 2512, and average Ca/Cl = 0.3. The average values of the integrated brine metamorphization index S (according to S.L. Shvartsev) range from 50 to 200. In the intraplatform feeding areas, there are several phases of brines that underwent gravitational sinking into the Vendian horizons in the periods when Cambrian salt-bearing basins existed on the platform. These brines were metamorphosed during filtration along the fracture and fault zones. The intrusion of traps in the late Permian–early Triassic was accompanied by hydrothermal activity. The waters of the enclosing Cambrian dolomite horizons were heated to 800–1000 °C; their subsequent interaction with carbonate rocks and evaporites (in particular, chlorides) resulted in extrastrong saturated brines. These brines were also subjected to gravitational sinking into the Vendian reservoirs, which was the main cause of the inverse vertical hydrogeochemical zoning in the hydrogeologic subsalt formation. The brine metamorphism processes and temperature changes in the rock horizons during the intrusion of traps and their subsequent cooling led to a significant alteration of the enclosing rocks under interaction with brines and to salinization of the reservoirs, an increase in the total salinity of the brines, and catagenetic changes in their composition. The brines closest to the maximum saturation with halite were found in reservoir zones with the highest salinization and near faults and boundaries of intrusive bodies. During the pre-Vilyuchan, pre-Nepa, pre-Tira, and pre-Danilovka sedimentation breaks, infiltrogenic waters penetrated into the Vendian sediments. Geochemically, the sedimentogenic, infiltrogenic, and metamorphic strong brines (group II) have a predominantly Cl Ca or Cl Ca–Mg composition with TDS > 350 g/L. They are characterized by low rNa/rCl ratios (on average, 0.3), Cl/Br ≤ 100, high Ca/Cl values (on average, 0.4), and S > 250.


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Sarah B. Duckworth ◽  
Xavier Gaona ◽  
Alexander Baumann ◽  
Kathy Dardenne ◽  
Jörg Rothe ◽  
...  

Abstract The solubility of 99Tc(IV) was investigated from undersaturation conditions in NaCl–Na2SO4 (0.3 M ≤ I ≤ 5.0 M), MgCl2–MgSO4 (I = 13.5 M) and CaCl2–CaSO4 (I = 13.5 M) systems with 0.001 M ≤ [SO4 2−]tot ≤ 1.0 M and 1 ≤ pH m  ≤ 12 (with pH m  = −log[H+], in molal units). Reducing conditions were set by either Sn(II) or Fe(0). Special efforts were dedicated to accurately characterize the correction factors A m required for the determination of pH m from the experimentally measured pH values in the mixed salt systems investigated, with pH m  = pHexp + A m . The combination of (pe + pH m ) measurements with Pourbaix diagrams of Tc suggests that technetium is present in its +IV redox state. This hypothesis is confirmed by XANES, which unambiguously shows the predominance of Tc(IV) both in the aqueous and solid phases of selected solubility samples. XRD and SEM–EDS support the amorphous character of the solid phase controlling the solubility of Tc(IV). EXAFS data confirm the predominance of TcO2(am, hyd) at pH m  > 1.5, whereas the formation of a Tc(IV)–O–Cl solid phase is hinted at lower pHm values in concentrated NaCl–Na2SO4 systems with ≈5 M NaCl. Solubility data collected in sulfate-containing systems are generally in good agreement with previous solubility studies conducted in sulfate-free NaCl, MgCl2 and CaCl2 solutions of analogous ionic strength. Although the complexation of Tc(IV) with sulfate cannot be completely ruled out, these results strongly support that, if occurring, complexation must be weak and has no significant impact on the solubility of Tc(IV) in dilute up to highly saline media. Solubility upper-limits determined in this work can be used for source term estimations including the effect of sulfate in a variety of geochemical conditions relevant in the context of nuclear waste disposal.


1992 ◽  
Vol 20 (6) ◽  
pp. 454-460 ◽  
Author(s):  
M Lazzaroni ◽  
O Sangaletti ◽  
G Bianchi Porro

A comparison was made of the antisecretory activity of orally administered nizatidine and ranitidine by measuring intragastric pH under basal conditions and during and after pentagastrin stimulation. Intragastric pH values were measured with a bipolar glass electrode in 10 patients with healed duodenal ulcers treated with nizatidine or ranitidine according to a randomized single-blind design. The antisecretory activity of the two drugs was similar during the 4 h of monitoring following drug administration. Nizatidine, however, showed a more rapid inhibitory action than ranitidine, producing a significantly greater increase in pH with respect to basal values during pentagastrin infusion. In the period following infusion the pH values observed with ranitidine were higher than with nizatidine, but not significantly so. Under these experimental conditions, therefore, the antisecretory activity of nizatidine was shown to be more rapid than that of ranitidine and equally effective.


Author(s):  
R. F. Sabirov ◽  
A. F. Makhotkin ◽  
Yu. N. Sakharov ◽  
I. A. Makhotkin ◽  
I. Yu. Sakharov

Experimental studies of the kinetics and mechanism of the process, decomposition of apatite by phosphoric acid, in the Apatite-H3PO4-H2O system without the addition of sulfuric acid have been performed. The study of the decomposition process of Kovdorsky apatite with certain particle sizes was carried out in a batch reactor with a volume of 1 dm3 with stirring of the reaction mixture, and an initial concentration of phosphoric acid of 17% by weight, at a temperature of 78–82 °C. Observation of the process was carried out by determining the concentration of phosphoric acid and the concentration of monocalcium phosphate. The acidity of the reaction mixture was determined by the pH meter readings (pH-105 MA with a glass combined-ESC-10603 electrode). It was shown that during the whole process a constant smooth increase in the pH value of the reaction mixture to pH 6 occurs. Comparison of the pH values of the reaction mixture during the actual at the time of determining the concentration of phosphoric acid and pH of phosphoric acid of the corresponding concentration in the aqueous solution shows that the pH value of the reaction mixture is significantly affected by the presence of monocalcium phosphate gel. During the process, during the first thirty minutes, the concentration of phosphoric acid decreases from 17 to 10% by weight, the corresponding quantitative formation of monocalcium phosphate gel and a proportional increase in the pH of the reaction mixture. Then, as the concentration of phosphoric acid decreases, the process slows down and does not proceed to the end under the experimental conditions. The dependence of the concentration of hydrogen ions in the reaction mixture on the time of the process of decomposition of apatite in phosphoric acid, which is presented in logarithmic coordinates, shows that the mechanism of formation of hydrogen ions during the whole process does not change. Thus, it is shown that the process of decomposition of apatite by phosphoric acid in the Apatite-H3PO4-H2O system proceeds with the formation of an intermediate product - monocalcium phosphate gel. When this occurs, a corresponding significant change in the pH values of the reaction mixture occurs. During the whole process there is a constant decrease in the concentration of phosphoric acid.


2021 ◽  
Vol 69 (4) ◽  
pp. 871-904
Author(s):  
Zlate Veličković ◽  
Bogdan Vujičić ◽  
Vladica Stojanović ◽  
Predrag Stojisavljević ◽  
Zoran Bajić ◽  
...  

Introduction/purpose: In this study, we investigated the possibility of removing the organophosphorus pesticide malathion from water using a new adsorbent based on the biowaste of river shell shards from the Anodonta Sinadonta woodiane family, a material that accumulates in large quantities as waste on the banks of large rivers. Two adsorbents were tested - mechanically comminuted river shells (MRM) and mechanosynthetic hydroxyapatite from comminuted river shells (RMHAp). Methods: The obtained adsorbents were characterized and tested for the removal of the organophosphorus pesticide malathion from water. In order to predict the optimal adsorption conditions using the Response Surface Method (RSM), the authors investigated the influence of variable factors (adsorption conditions), pH values, adsorbent doses, contact times, and temperatures on the adsorbent capacity. Results: The best adsorption of malathion was achieved at mean pH values between 6.0 and 7.0. The adsorption data for malathion at 25, 35, and 45 °C were compared using the Langmuir, Freundlich, DubininRadushkevich (DR), and Temkin isothermal models, as well as pseudofirst order, pseudo-second order and Elovic kinetic models for modeling adsorption kinetics. The maximum Langmuir adsorption capacity for MRM and RMHAp at 25 °C was 46,462 mg g-1 and 78,311 mg g-1 , respectively. Conclusion: The results have showed that malathion adsorption on both adsorbents follows the pseudo-second kinetic model and the Freundlich isothermal model. The thermodynamic parameters indicate the endothermic, feasible, and spontaneous nature of the adsorption process.


1986 ◽  
Vol 251 (3) ◽  
pp. G421-G429
Author(s):  
C. Niederau ◽  
J. H. Grendell ◽  
S. S. Rothman

Zymogen granules isolated from tissue homogenates by differential centrifugation in isotonic sucrose solutions show substantial release of digestive enzyme when suspended in isotonic NaCl and in sucrose solutions at pH values above neutrality. A recent study reported a new method for isolating granules, involving the use of a complex homogenization medium and a Percoll gradient that was claimed to produce "stable" granules, i.e., granules that do not release their content in salt solutions and at pH values at or above neutrality. In the present study, we compare granules prepared in both ways, particularly in terms of their tendency to release amylase in isotonic ionic solutions and as a function of pH. The relative absence of amylase release from granules isolated by the new technique was found to be attributable to simple differences in the details of the experimental procedures that were used and not to actual differences in the characteristics of the two granule preparations. For example, previous studies with granules prepared in sucrose solutions reported substantial salt-induced release at 37 degrees C, whereas the recent study reporting the absence of salt-induced release from granules obtained from a Percoll gradient was done at 24 degrees C. Under the identical experimental conditions as used in the present study, little amylase release was seen at 24 degrees C for granules isolated by either technique, but substantial release was seen for both at 37 degrees C.(ABSTRACT TRUNCATED AT 250 WORDS)


1993 ◽  
Vol 333 ◽  
Author(s):  
S. Stroes-Gascoyne ◽  
J.C. Tait ◽  
R.J. Porth ◽  
J.L. McConnell ◽  
A.M. Duclos

ABSTRACTThe separate effects of alpha- and gamma-radiolysis on UO2dissolution can be studied with unirradiated UO2, whereas studies vith used nuclear fuel necessarily always include both alpha- and gamma-radiolysis effects. This paper attempts to separate these effects by comparing the leaching behaviour in saline solution of a number of UO2samples (each vith a particular radiation characteristic or chemical property inherent to used fuel) vith the leaching behaviour of used fuel. Data from leaching experiments vith lov- and high-burnup CANDU (CANada Deuterium Uranium) fuels are also compared. The results indicate that the presence of an alpha field at 100°C under reducing conditions does not increase UO2dissolution but suggest that the combined effects of the beta and gamma fields in used CANDU fuel may enhance UO2dissolution.


1998 ◽  
Vol 330 (3) ◽  
pp. 1423-1431 ◽  
Author(s):  
Hai-Yan ZHOU ◽  
Erdjan SALIH ◽  
J. Melvin GLIMCHER

An 80 kDa protein was purified from calf bone by HCl-demineralization followed by 0.5 M EDTA/1.0 M NaCl extraction and sequential chromatography on DE-52, hydroxyapatite, and TSK-gel G3000SW HPLC columns. From the DE-52 column the protein was eluted at three different fractions, of which one further separated into two fractions on the hydroxyapatite column, indicating that the protein is present in four different molecular forms designated as 80 k-I-1, k-I-2, k-II, k-III. The N-terminal sequence analysis of all four forms gave the same sequence, SEQYNQEPNNV. Several tryptic internal peptides were also generated, purified and sequenced, leading to the identification of several repeat sequences, IFLGXXEI. Homology searching of the N-terminal and internal sequences indicates that this is a novel protein. Both 80 k-I-2 and k-III had similar amino acid composition with high contents of Asx, Glx and Leu and contained 7 and 16 phosphoserines per 1000 total amino acids, respectively. The 80 k-I-1 and 80 k-II forms were stained with Rhodamine B specific for phosphoproteins. The four forms contained different contents of neutral sugars ranging from 5.5 to 26% (w/w protein) and ~ 1.7% sialic acid. These data indicated that the 80 kDa protein exists in four isomeric forms, at least based on the different post-translational modifications. The evaluation of the 80 kDa glycosylated phosphoprotein under alkylating, reducing and non-reducing conditions indicated that this protein undergoes polymerization through intermolecular disulphide bonds. Furthermore, the 80 kDa protein and osteonectin (ON), both of which are cysteine-rich proteins, can cross-link with each other via disulphide bonds, and this process can be induced to take place in vitro under experimental conditions. The occurrence of such a phenomenon in vivo was confirmed from the presence of similar high Mr components containing both 80 kDa and ON in the same SDS/PAGE bands, detected by the respective antibody reactions in crude bone extracts which were extracted in the presence of alkylating agent.


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