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Comparative Analysis of UN and UO2 Oxidation in Air and Nitrogen Hemioxide UN 和 UO2 在空气和二氧化氮中的氧化对比分析
IF 0.9 Q4 Chemistry Pub Date : 2024-02-19 DOI: 10.1134/s1066362223060024
M. I. Volgin, S. A. Kulyukhin, Yu. M. Nevolin

Abstract

Oxidation of UO2 and UN by atmospheric oxygen and nitrogen hemioxide, which is a hard-to-localize greenhouse gas, was investigated by thermal analysis. For oxidation, mixtures of N2O–N2 and O2–N2 were used with a 20% volume fraction of the oxidizing agent. For UO2 and UN, the phase composition of the final oxidation product in air and in N2O is the same―U3O8. In both cases, N2O behaves as a milder oxidizing agent compared to atmospheric oxygen. Oxidation of UO2 and UN in an N2O flow starts at a temperature 180 and 70°C higher than in air, respectively. The oxidation of UN in an N2O flow proceeds in three stages. At the first stage, the reaction products are UO2 and U2N3; UO2 is the product of the second stage; and at the third stage U3O8 is produced. No pronounced staging is observed in the UO2 oxidation process. The possibility of utilizing nitrogen hemioxide when it is used in the course of voloxidation (oxidation) of spent nuclear fuel is shown.

摘要 通过热分析研究了大气中的氧气和二氧化氮(一种难以定位的温室气体)对二氧化铀和联合国的氧化作用。在氧化过程中,使用了氧化剂体积分数为 20% 的 N2O-N2 和 O2-N2 混合物。对于二氧化铀和联合国,最终氧化产物在空气中和在一氧化二氮中的相组成相同--U3O8。在这两种情况下,与大气中的氧气相比,N2O 是一种较温和的氧化剂。二氧化铀和联合国军在一氧化二氮气流中开始氧化时的温度分别比在空气中高 180°C 和 70°C。UN 在一氧化二氮气流中的氧化过程分为三个阶段。在第一阶段,反应产物是 UO2 和 U2N3;UO2 是第二阶段的产物;第三阶段产生 U3O8。在二氧化铀氧化过程中没有观察到明显的分级。这说明在乏核燃料的伏氧化(氧化)过程中使用二氧化氮的可能性。
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引用次数: 0
Sorption of Sr(II) Ions with Tricalcium Phosphate in the Presence of Humic Acids 腐殖酸存在时硒(II)离子与磷酸三钙的吸附作用
IF 0.9 Q4 Chemistry Pub Date : 2024-02-19 DOI: 10.1134/s1066362223060073
A. A. Ioshin, I. V. Volkov, E. V. Polyakov

Abstract

The sorption behavior of traces Sr(II) toward β-Ca3(PO4)2 (TCP) depending on the concentration of the cation, pH, and concentrations of humic acids (HA) in the solution was studied. Thermodynamic analysis of the solubility of TCP (1) was performed taking into account the formation of Ca(OH)2 (CH, 2), Ca(H2PO4)2 (MCPA, 3), CaHPO4·2H2O (DCPD, 4), Ca5(PO4)3OH (hydroxyapatite, OHAp, 5), and Ca2P2O7 (DCPP, 6). It was shown that, depending on the pH of the solution, the main equilibrium phases with the solution are phases 4 and 5. X-ray diffraction analysis, Raman spectroscopy, and 31P NMR data of the phase (1) samples after contact with a solution of 0.01 M NaNO3 for about 10 days showed the presence of only the phase 1. The solubility of 1 regarding the concentration of Ca2+, PO43– ions and the stoichiometric ratio (Ca/P) in solutions, depending on pH, correspond to the presence of surface phases 4 or 5. The model of surface complexation in the Henry region adequately describes the mechanism of Sr(II) sorption by the surface phase 5 on TCP particles in the form of the SrHPO40 complex. The formation of the HA complex of Sr(II) in solution does not affect distribution coefficient Kd(Sr) in the range of HA concentrations of 0–150 mg/L due to the competitive effect of hydrogen phosphate ions on strontium complexes.

摘要 研究了痕量 Sr(II) 对 β-Ca3(PO4)2 (TCP) 的吸附行为,该行为取决于阳离子的浓度、pH 值和溶液中腐植酸 (HA) 的浓度。考虑到 Ca(OH)2 (CH,2)、Ca(H2PO4)2(MCPA,3)、CaHPO4-2H2O(DCPD,4)、Ca5(PO4)3OH(羟基磷灰石,OHAp,5)和 Ca2P2O7(DCPP,6)的形成,对 TCP (1) 的溶解度进行了热力学分析。研究表明,根据溶液的 pH 值,与溶液的主要平衡相为相 4 和相 5。相(1)样品与 0.01 M NaNO3 溶液接触约 10 天后的 X 射线衍射分析、拉曼光谱和 31P NMR 数据显示,只存在相 1。根据溶液中 Ca2+、PO43- 离子的浓度和化学计量比 (Ca/P),1 相的溶解度取决于 pH 值,与表面相 4 或 5 的存在相对应。亨利区域的表面络合模型充分描述了表面相 5 以 SrHPO40 复合物的形式吸附 TCP 颗粒上的 Sr(II)的机理。在 HA 浓度为 0-150 mg/L 的范围内,溶液中 Sr(II) 的 HA 复合物的形成不会影响分布系数 Kd(Sr),这是因为磷酸氢离子对锶复合物有竞争作用。
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引用次数: 0
Influence of Irradiation on the Stability of Extraction Mixtures Based on Methyltri-n-Octylammonium Carbonate 辐照对基于碳酸甲基三辛铵的萃取混合物稳定性的影响
IF 0.9 Q4 Chemistry Pub Date : 2024-02-19 DOI: 10.1134/s1066362223060061
A. S. Obedkov, I. A. Bolshakova, E. V. Belova, G. V. Kostikova, O. A. Raitman, S. I. Stepanov

Abstract

The radiation thermal stability of extraction mixtures based on methyltrioctylammonium (MTOA) carbonate was studied. The volumes and maximum rate of release of gaseous products at atmospheric and elevated pressures were determined. No exothermic processes were shown to occur in the studied mixtures under experimental conditions. Irradiation up to a dose of 1 MGy has little effect on the density, viscosity, and surface tension of mixtures, but significantly reduces the phase separation rate. The distribution coefficients of Am(III) in the system of 50% MTOA carbonate in toluene are practically independent of the absorbed dose; however, irradiation can significantly affect the composition of the extractable americium complexes. The results of the study of extraction systems showed their high radiation thermal stability.

摘要 研究了基于碳酸甲基三辛基铵(MTOA)的萃取混合物的辐射热稳定性。确定了在常压和高压下气态产物的体积和最大释放率。结果表明,在实验条件下,所研究的混合物中没有放热过程。剂量不超过 1 MGy 的辐照对混合物的密度、粘度和表面张力影响不大,但会显著降低相分离率。在甲苯中含有 50% MTOA 碳酸盐的体系中,Am(III) 的分布系数实际上与吸收剂量无关;但辐照会显著影响可萃取镅络合物的组成。对萃取体系的研究结果表明,它们具有很高的辐照热稳定性。
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引用次数: 0
Nanofiltration Purification of Liquid Radioactive Waste 纳滤净化液体放射性废物
IF 0.9 Q4 Chemistry Pub Date : 2023-12-11 DOI: 10.1134/s1066362223050053
V. O. Kaptakov, V. V. Milyutin

Abstract

The paper presents the results of testing the purification of real liquid radioactive waste from radionuclides, bottom residues of the Kola and Beloyarsk nuclear power plants (NPP), as well as low-level wastewater from the radiochemical building of the Institute of Physical Chemistry and Electrochemistry RAS (IPCE RAS) using the method of nanofiltration (NF) using a polymer membrane manufactured by the Russian company “RM Nanotech.” It has been shown that in the case of single-stage NF purification of bottoms of the Kola NPP, the coefficient of purification from 60Co is 2.8, while no purification from 137Cs practically occurs. When cleaning the bottom residues of the Beloyarsk NPP from 60Co using a five-stage scheme, a coefficient of purification from 60Co equal to 388 was obtained. The combination of nanofiltration purification and selective sorption of cesium on the ferrocyanide sorbent Temoksid-35 makes it possible to obtain a dry salt residue that is not related to radioactive waste. When using the method of nanofiltration for the treatment of low-level wastewater of the Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences, the degree of purification was, %: 137Сs ~ 75; 90Sr ~ 91; 241Am ~ 99.5; 152Eu ~ 91; 239Pu ~ 99.5.

摘要 本文介绍了使用俄罗斯 "RM Nanotech "公司生产的聚合物膜,采用纳滤(NF)方法对实际液体放射性废物、科拉和别洛雅尔斯克核电站(NPP)底部残留物以及俄罗斯科学院物理化学和电化学研究所(IPCE RAS)放射化学大楼低浓度废水进行放射性核素净化的测试结果。研究表明,在对科拉核电站底部进行单级纳滤净化时,60Co 的净化系数为 2.8,而 137Cs 几乎没有净化。在采用五级方案净化贝洛亚尔斯克核电厂底部残留物中的 60Co 时,60Co 的净化系数为 388。纳滤净化和铁氰化物吸附剂 Temoksid-35 对铯的选择性吸附相结合,可以获得与放射性废物无关的干盐残留物。俄罗斯科学院物理化学和电化学研究所使用纳滤方法处理低浓度废水时,净化程度为:137Сs ~ 75;90Sr ~ 91;241Am ~ 99.5;152Eu ~ 91;239Pu ~ 99.5。
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引用次数: 0
Influence of the Nature of Diluent on the Extractability of N,N,N',N'-Tetrabutyldiglycolamide for Eu(III), Am(III), and Cm(III) 稀释剂的性质对 N,N,N',N'-四丁基二乙二醇酰胺提取 Eu(III)、Am(III) 和 Cm(III) 的能力的影响
IF 0.9 Q4 Chemistry Pub Date : 2023-12-11 DOI: 10.1134/s106636222305003x
V. E. Sharov, G. V. Kostikova

Abstract

The effect of HNO3 concentration on the extraction of Eu(III), Am(III), and Cm(III) with N,N,N',N'-tetrabutyldiglycolamide was studied in 5 different diluents: nitrobenzene, toluene, chloroform, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane. The distribution coefficients of these metals as a function of the nature of the diluent in the following series of compounds was established: nitrobenzene > m-trifluoromethylnitrobenzene > mixture of n-dodecane with decanol-1 (volume ratio 90 : 10) > carbon tetrachloride > 1,2-dichloroethane > benzene > 1,1,2,2-tetrachloroethane > toluene > chloroform. The conditions for the partioning Eu(III)/Am(III) and Am(III)/Cm(III) pairs were found. An explanation was proposed for the observed increase in the separation factors of the Am(III)/Cm(III) pair with increasing concentration of nitric acid in the equilibrium aqueous phase.

摘要 研究了硝基苯、甲苯、氯仿、1,2-二氯乙烷和1,1,2,2-四氯乙烷等5种不同稀释剂中HNO3浓度对N,N,N',N'-四丁基二乙二醇酰胺萃取Eu(III)、Am(III)和Cm(III)的影响。确定了这些金属在以下系列化合物中的分布系数与稀释剂性质的函数关系:硝基苯;间三氟甲基硝基苯;正十二烷与癸醇-1 的混合物(体积比为 90:10);四氯化碳;1,2-二氯乙烷;苯;1,1,2,2-四氯乙烷;甲苯;氯仿。找到了使 Eu(III)/Am(III) 和 Am(III)/Cm(III) 成对的条件。对所观察到的 Am(III)/Cm(III) 对的分离因子随平衡水相中硝酸浓度的增加而增加的现象提出了解释。
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引用次数: 0
Modern Radioecological Situation at the Site of the Peaceful Underground Nuclear Explosion “Crystal” and Radionuclides in the Surface Waters of the Adjacent Territory (Western Yakutia) 水晶 "和平地下核爆炸现场的现代放射生态状况及邻近地区(西雅库特)地表水中的放射性核素
IF 0.9 Q4 Chemistry Pub Date : 2023-12-11 DOI: 10.1134/s1066362223050119
S. Yu. Artamonova, L. G. Bondareva, M. S. Melgunov, G. V. Simonova

Abstract

The radioecological situation at the site of the peaceful underground nuclear explosion “Crystal” after removal land cover and installation of the artificial cover of rock from nearby quarry above the epicenter is considered. In 2012 the ambient dose equivalent rate of gamma radiation varied from 0.04 to 0.066 µSv/h, in 2019 the content of radionuclides in soils was (Bq/kg): 90Sr 2.5–5.3, 239,240Pu 0.03–25.4, 137Cs <2.0. In 2018–2020 the activity of radionuclides in surface water was (Bq/dm3): in drains from under the artificial cover 3H 4–12, 90Sr 0.004–0.4, 239,240Pu < 10–6, in local river water 3H 4–10.2, 90Sr 0.004–0.3. At present, the impact of surface drains from the “Crystal” site on the river network is assessed as insignificant. No more than 1/3 of 3H in the local river water comes with precipitation, and the rest of 3H comes from the “Crystal” explosion zone, mainly by an underground route. At least 91–96% of 90Sr in the local river water is due to the “Crystal” explosion: part of it comes from the explosion zone by an underground route, part is washed off from the surface of landscapes.

摘要 考察了 "水晶 "和平地下核爆炸现场在清除土地覆盖物并在震中上方附近采石场的岩石上安装人工覆盖物后的放射生态状况。2012 年,环境伽马辐射剂量当量率为 0.04 至 0.066 µSv/h,2019 年,土壤中放射性核素的含量为(Bq/kg):90Sr 2.5-5.3,239,240Pu 0.03-25.4,137Cs <2.0。2018-2020 年地表水放射性核素活度为(Bq/dm3):人工覆盖下排水沟中 3H4-12,90Sr 0.004-0.4,239,240Pu <10-6,当地河水中 3H4-10.2,90Sr 0.004-0.3。目前,"水晶 "地块的地表排水对河网的影响被评估为微不足道。当地河水中不超过 1/3 的 3H 来自降水,其余的 3H 来自 "水晶 "爆炸区,主要通过地下途径。当地河水中至少有 91-96% 的 90Sr 是由 "水晶 "爆炸产生的:一部分通过地下途径来自爆炸区,一部分从地表冲刷下来。
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引用次数: 0
Simulation of Thermal Decomposition of Acetohydroxamic Acid Nitrate Solution upon SNF Reprocessing 模拟 SNF 后处理时乙酰羟肟酸硝酸盐溶液的热分解
IF 0.9 Q4 Chemistry Pub Date : 2023-12-11 DOI: 10.1134/s1066362223050016
V. V. Kalistratova, A. V. Smirnov, E. V. Belova

Abstract

A thermal analysis of an acetohydroxamic acid solution in 12 M HNO3 was carried out. The activation energy, specific thermal effect, time and rate of the exothermic reaction, pre-exponential factor, starting temperature and self-heating value of the sample, pressure change and specific volume of released gases were determined. Under experimental conditions this reaction was found to occur in an autocatalytic mode. Based on experimental data, a kinetic equation for the reaction was derived, which was used to create a model of the reaction under various conditions. The reliability of the modeling results was verified by differential scanning calorimetry.

摘要 对 12 M HNO3 中的乙酰羟肟酸溶液进行了热分析。测定了活化能、比热效应、放热反应的时间和速率、预指数、样品的起始温度和自热值、压力变化和释放气体的比容。在实验条件下,发现该反应以自催化方式发生。根据实验数据,推导出了该反应的动力学方程,并利用该方程建立了不同条件下的反应模型。差示扫描量热法验证了建模结果的可靠性。
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引用次数: 0
Analysis of Operating Modes of a Countercurrent Column for the Chemical Isotope Exchange between Hydrogen and Water with Independent Flows of Water and Hydrogen 分析逆流色谱柱在水和氢独立流动的情况下进行氢与水化学同位素交换的运行模式
IF 0.9 Q4 Chemistry Pub Date : 2023-12-11 DOI: 10.1134/s1066362223050065
M. B. Rozenkevich

Abstract

According results of a theoretical analysis of the countercurrent column operation for the liquid phase catalytic exchange (LPCE) between hydrogen and water in a mode with independent flows of hydrogen and water, it is shown that there are temperature-dependent maximum values of the molar ratio of hydrogen and water flows, at which the separation performance of the column towards isotope mixtures of protium–tritium and protium–deuterium diminishes. Options for the operation of a chemical treatment column were experimentally studied provided that water vapor condensate is returned to the column from the output steam–gas flow or without it. The experimental results are consistent with the theoretical analysis performed.

摘要根据对氢气和水之间液相催化交换(LPCE)的逆流塔操作进行理论分析的结果表明,氢气和水的摩尔比存在与温度相关的最大值,在该值上,塔对氕氚和氕氘同位素混合物的分离性能降低。通过实验研究了化学处理柱的运行方案,即从输出蒸汽气流中返回或不返回水蒸气冷凝液。实验结果与理论分析一致。
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引用次数: 0
Speciation of Plutonium and Some Chemical Elements in the Bottom Sediments of the Laptev Sea and the Kara Sea 拉普捷夫海和喀拉海海底沉积物中钚和一些化学元素的标样
IF 0.9 Q4 Chemistry Pub Date : 2023-12-11 DOI: 10.1134/s1066362223050107
T. A. Goryachenkova, I. E. Kazinskaya, A. V. Travkina, D. P. Starodymova, A. P. Novikov

Abstract

The comparison of the speciations of 239Pu and chemical elements, including rare earth elements (REE), in the bottom sediments of the Kara Sea and the Laptev Sea is given. The speciations were investigated by three different methods of selective leaching. Data were obtained on the content of chemical elements and 239Pu in the composition of complexes with different lability: easily soluble, bound to organic matter, including groups of humic acids (HA) and fulvic acids (FA), as well as to amorphous oxides of Fe and Mn. It is shown that humic and low molecular weight organic acids and their compounds with chemical elements can influence the behavior of plutonium in the seawater–bottom sediments system in the waters of the Arctic seas. The possibility of using a number of REE as a marker for predicting the migration behavior of plutonium is evaluated.

摘要 比较了卡拉海和拉普捷夫海海底沉积物中 239Pu 和包括稀土元素在内的化学元素的规格。通过三种不同的选择性沥滤方法对规格进行了调查。获得了关于化学元素含量和 239Pu 在不同易溶性复合物成分中的含量的数据:易溶性、与有机物结合(包括腐殖酸 (HA) 和富勒酸 (FA) 组)以及与铁和锰的无定形氧化物结合。研究表明,腐殖酸和低分子量有机酸及其与化学元素的化合物会影响北极海域海水-海底沉积物系统中钚的行为。评估了使用一些稀土元素作为预测钚迁移行为的标记的可能性。
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引用次数: 0
137Cs Migration and Profile in Bottom Sediments of Deep Drainage Lakes, North-Western Russia 俄罗斯西北部深流域湖泊底层沉积物中的 137Cs 迁移和剖面图
IF 0.9 Q4 Chemistry Pub Date : 2023-12-11 DOI: 10.1134/s1066362223050090
N. A. Bakunov, D. Yu. Bolshiyanov, A. O. Aksenov

Abstract

Modern contamination of lake–river systems bottom sediments with global and “Chernobyl” 137Cs is estimated. Drainage lakes of North-Western Russia were investigated. Lake Kopanskoe, located south of the Gulf of Finland, is on the “Chernobyl” 137Cs fallout plume, whereas Ladoga, Sukhodolskoe, Vuoksa, Imandra lakes are located at its periphery, in Karelia and Kola Peninsula. Following parameters are distinguished: lakes bottom 137Cs contamination density (kBq/m2), distribution of 137Cs in the profile of bottom sediments, 137Cs diffusion coefficients (D) in bottom sediments and content of the exchange chemical form of the radionuclide. 137Cs contamination of the lakes was formed due to suspended matter sedimentation with 137Cs, 137Cs sorption and diffusion in bottom sediments. With sedimentation ≥3 mm/year, the concentration of 137Cs increased from the top to the bottom of the core (lakes Vuoksa, Ekostrovskaya Imandra), reflecting the gradual process of 137Cs migration into the sediments. The opposite trend of 137Cs concentration was observed in the bottom sediments of lakes Ladoga and Sukhodolskoe with sedimentation ≤0.5 mm/year. Here 137Cs diffusion with D = (0.5–6.2) × 10–8 cm2/s caused slow radionuclide transfer in the bottom sediments. The main inventory of 137Cs was contained in the top layer 0–5 cm. In Lake Sukhodolskoye bottom sediments an absorbed 137Cs in an exchange chemical form, extracted into 1 М NH4Aс solution, amount only 14.4–20%.

摘要 对全球和 "切尔诺贝利 "137Cs 污染湖泊-河流系统底层沉积物的现代污染情况进行了估计。对俄罗斯西北部的排水湖泊进行了调查。位于芬兰湾南部的 Kopanskoe 湖位于 "切尔诺贝利 "137Cs 烟尘羽流上,而 Ladoga 湖、Sukhodolskoe 湖、Vuoksa 湖、Imandra 湖则位于其外围,即卡累利阿和科拉半岛。以下参数可用于区分:湖底 137Cs 污染密度(kBq/m2)、137Cs 在底层沉积物剖面中的分布、137Cs 在底层沉积物中的扩散系数 (D) 以及放射性核素交换化学形式的含量。湖泊的 137Cs 污染是由于湖底沉积物中的 137Cs 悬浮物沉降、137Cs 吸附和扩散造成的。在沉积量≥3 毫米/年的情况下,137Cs 的浓度从湖芯顶部到底部(沃克萨湖、叶科斯特洛夫斯卡娅-伊曼德拉湖)都在增加,这反映了 137Cs 向沉积物迁移的渐进过程。在沉积量≤0.5 毫米/年的拉多加湖和苏霍姆林斯基湖的湖底沉积物中,137Cs 的浓度呈相反趋势。在这里,137Cs 以 D = (0.5-6.2) × 10-8 cm2/s 的速度扩散,导致放射性核素在底层沉积物中缓慢转移。137Cs 的主要存量位于 0-5 厘米的顶层。在苏霍姆林斯基耶湖底沉积物中,以交换化学形式吸收的 137Cs 被提取到 1 М NH4Aс 溶液中,含量仅为 14.4-20%。
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引用次数: 0
期刊
Radiochemistry
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