铀在地下水中化学形态及地球化学工程屏障研究
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摘要
本文叙述了含铀极低放废物填埋处置的地球化学工程屏障研究。通过理论计算确定铀在地下水中的化学形式;针对地下水中铀(Ⅵ)的化学形态特点,开展了添加剂实验;利用土壤表面电荷特征,对土壤介质进行了筛选;分别进行了静态吸附实验和柱迁移实验。
利用化学热力学平衡分析模式、地球化学条件及已知的热力学数据,完成了铀在地下水中存在形式和迁移形态的理论计算。结果表明场址地下水中U(Ⅵ)主要以络合物形态存在,主要有:UO_2(CO_3)_2~(2-)、UO_2(CO_3)_3~(4-)、UO_2CO_3~0、UO_2(HPO_4)_2~(2-)等,占绝对优势(>99%);其次为UO_2(OH)_2~0和UO_2(OH)~+、UO_2~(2+)等,但不足1%。
添加剂实验结果表明大部分添加剂没有达到改善基础物料吸附性能的效果,甚至起到反效果;还原性添加剂Na_2S等难于实现铀(Ⅵ)→铀(Ⅳ)的还原沉积;唯有第Ⅲ号土样,即产生于场址的橙黄色砂质亚粘土,对铀的吸附力很强,实验表明,Ⅲ号土空白样的K_d值高达1228.4ml.g~(-1),综合其土粒结构、岩性、来源广泛性等因素,选定为地球化学屏障材料的首选,对其进行了进一步的实验研究。
土样表面电荷测定结果表明:Ⅲ号土样的正电荷值高达9.60mmol/100g,居各样品之首,清楚地表现出K_d值与岩土正电荷值的正向相关性,反映了正电荷胶体对铀酰络合阴离子的强吸附机制。
“Ⅲ号表层土样”与“Ⅲ号深层土样”的对照静态实验结果表明:“Ⅲ号表层土样”各粒径组与“Ⅲ号深层土样”的主要矿物组成及含量相同;表层土样随粒径减小其表面正电荷降低,而深层土样的表面正电荷几乎比前者高一倍;表层土样随粒径减小其对铀的吸附比降低,而深层土样基本没有变化;两类样品均随pH值的升高,吸附比增大;均随铀浓度的增大,吸附比先增大再缓慢下降;均随固液比的增大,吸附比增大;表层样品在常温下吸附比最大;两类样品均在14天左右达到吸附平衡;各个实验条件下,深层样品的吸附比均比表层样品相应的吸附比高数倍至一个数量级。实验结果表明:铀络合物离子在土样中的吸附滞留量正向相关于表面正电荷值,为静电吸附机制。
深层土样加入Ca(OH)_2后大大改善了吸附能力,吸附比高达1.9×10~4ml.g~(-1);加入炭质砂岩后也改善了吸附能力,且吸附比与加入量基本成线性关系。
动态柱迁移实验结果表明:实验条件下得出的吸附比比静态法得出的吸附比普遍小1个量级。主要是由于在实验条件下铀的吸附未达到平衡所至,但该条件类似于地下水流动时其所携带的铀离子被所流经土壤吸附滞留的状态,因此,动态柱迁移实验获得的吸附比具有实际参考价值。
The treatment of radioactive wastewater is one of the important concerns and must be seriously considered in the nuclear industry, whereas the geochemical engineering barrier is one of the basic and key issue for the buried disposal of radioactive waste.In this paper, study on geochemical engineering barrier for the buried disposal of very low-level radioactive waste containing uranium was performed. The chemical species of U in groundwater was analyzed by a theoretical calculation method, and the effect of the additives on the engineering barrier was investigated on the basis of the calculated chemical characteristic of U(Ⅵ)'s species. Then, the appropriate soil medium was selected according to the surface electric charge, and the adsorption of uranium on the soil was investigated in a static way while the migration of U was performed in column experiments.The theoretical calculation for the chemical species and migration behavior of uranium in groundwater were accomplished by combining the thermodynamics balance analysis mode, the geochemical condition and the known thermodynamics data. The results indicated that the overwhelming majority (more than 99%) of U(VI) in the groundwater exit as the complex species, such as UO_2(CO_3)_2~(2-), UO_2(CO_3)_3~(4-), UO_2CO_3~0 and UO_2(HPO_4)_2~(2-), while the other species as UO_2(OH)_2~0, UO_2(OH)~+ or UO_2~(2+), account for less than 1%.It can be shown by the additive experiment that most of the investigated additives can not remarkably improve the adsorption performance of the soil for uranium, whereas some additive have reverse effect. Also, it is very difficult for reductive sediment of U(Ⅵ) to U(Ⅳ)by adding some reduction additives, such as N_2S. Fortunately, the soil sample Ⅲ, a kind of arenaceous clay with orange yellow color from the disposal site, has very strong adsorption ability to uranium with a K_d value of up tol228. 4ml. g~(-1). It can be conclude that this soil should be the best candidate for the geochemical engineering barrier materials, if the granularity, lithology and commercial availability were comprehensively considered. Then the further experiment was performed.Surface electric charge of the soil was measured, and the result that the soil sample Ⅲ has the highest positive charge value of 9. 60mmol/100g among the investigated soil samples was noted. It is thus clear that the K_d value is direct ration to the positive charge of the soil, and the adsorption mechanism of uranium on soil should involve the strong adsorption of uranyl complex anion onto the positive charge colloid.
The adsorption behavior of uranium onto the topsoil and deep soil from the soil sample III was evaluated. The topsoil with different granularity has same principle mineral components and contents as the deep soil. The surface positive charge of the topsoil declined with decrease of the granularity, and almost one time less than the topsoil sample. Also, the adsorption rate of the topsoil for uranium dropped along with decrease of the granularity, while no significant change was observed with the deep soil sample. However, the adsorption rate of the topsoil and deep soil both rose with the increasing of pH or ratio of solid to liquid, and increased first, then declined gradually with the increasing of uranium concentration. The adsorption equilibrium with the two samples was achieved within 14 days, while the maximal adsorption rate with the topsoil was observed at normal temperature. Moreover, it could be seen that the absorption rates of the deep soil sample were always several to ten times higher than that of the topsoil sample in each experimental conditions. Absorbed and retarded capacity of Uranyl complex ion direct ratio surface positive charge in soil, and the mechanism is static absorption.The absorption ability of the deep soil sample for uranium could been greatly improved by adding Ca(0H)2, leading to the adsorption rate up to 1. 9X 104ml. g"1. The similar result could be obtained by adding charry gritstone, and the adsorption rate and the quantity of the added charry gritstone was usually in keeping with linear correlation.It should also be paid much attention to that the adsorption rate resulted from dynamic column migration experiments was ten times less than that from static experiments. The main reason is that column migration experiments don' t attain equilibrium. Yet, this condition is similar to the groundwater flow and the Uranyl ion is retarded by the soil with the groundwater flow, so the results of column migration experiments have actual value.In summary, several factors related to the geochemical engineering barrier for the buried disposal of very low-level radioactive waste containing uranium, such as the chemical species and migration behavior of uranium in groundwater, the effect of the additives on the engineering barrier, and the adsorption behavior of uranium on the soil had been investigated in this paper, and enormous expeimrntal data summarized. It is indubitable that all these will be useful to disposition and safety assessment of radioactive waste containing uranium.
利用化学热力学平衡分析模式、地球化学条件及已知的热力学数据,完成了铀在地下水中存在形式和迁移形态的理论计算。结果表明场址地下水中U(Ⅵ)主要以络合物形态存在,主要有:UO_2(CO_3)_2~(2-)、UO_2(CO_3)_3~(4-)、UO_2CO_3~0、UO_2(HPO_4)_2~(2-)等,占绝对优势(>99%);其次为UO_2(OH)_2~0和UO_2(OH)~+、UO_2~(2+)等,但不足1%。
添加剂实验结果表明大部分添加剂没有达到改善基础物料吸附性能的效果,甚至起到反效果;还原性添加剂Na_2S等难于实现铀(Ⅵ)→铀(Ⅳ)的还原沉积;唯有第Ⅲ号土样,即产生于场址的橙黄色砂质亚粘土,对铀的吸附力很强,实验表明,Ⅲ号土空白样的K_d值高达1228.4ml.g~(-1),综合其土粒结构、岩性、来源广泛性等因素,选定为地球化学屏障材料的首选,对其进行了进一步的实验研究。
土样表面电荷测定结果表明:Ⅲ号土样的正电荷值高达9.60mmol/100g,居各样品之首,清楚地表现出K_d值与岩土正电荷值的正向相关性,反映了正电荷胶体对铀酰络合阴离子的强吸附机制。
“Ⅲ号表层土样”与“Ⅲ号深层土样”的对照静态实验结果表明:“Ⅲ号表层土样”各粒径组与“Ⅲ号深层土样”的主要矿物组成及含量相同;表层土样随粒径减小其表面正电荷降低,而深层土样的表面正电荷几乎比前者高一倍;表层土样随粒径减小其对铀的吸附比降低,而深层土样基本没有变化;两类样品均随pH值的升高,吸附比增大;均随铀浓度的增大,吸附比先增大再缓慢下降;均随固液比的增大,吸附比增大;表层样品在常温下吸附比最大;两类样品均在14天左右达到吸附平衡;各个实验条件下,深层样品的吸附比均比表层样品相应的吸附比高数倍至一个数量级。实验结果表明:铀络合物离子在土样中的吸附滞留量正向相关于表面正电荷值,为静电吸附机制。
深层土样加入Ca(OH)_2后大大改善了吸附能力,吸附比高达1.9×10~4ml.g~(-1);加入炭质砂岩后也改善了吸附能力,且吸附比与加入量基本成线性关系。
动态柱迁移实验结果表明:实验条件下得出的吸附比比静态法得出的吸附比普遍小1个量级。主要是由于在实验条件下铀的吸附未达到平衡所至,但该条件类似于地下水流动时其所携带的铀离子被所流经土壤吸附滞留的状态,因此,动态柱迁移实验获得的吸附比具有实际参考价值。
The treatment of radioactive wastewater is one of the important concerns and must be seriously considered in the nuclear industry, whereas the geochemical engineering barrier is one of the basic and key issue for the buried disposal of radioactive waste.In this paper, study on geochemical engineering barrier for the buried disposal of very low-level radioactive waste containing uranium was performed. The chemical species of U in groundwater was analyzed by a theoretical calculation method, and the effect of the additives on the engineering barrier was investigated on the basis of the calculated chemical characteristic of U(Ⅵ)'s species. Then, the appropriate soil medium was selected according to the surface electric charge, and the adsorption of uranium on the soil was investigated in a static way while the migration of U was performed in column experiments.The theoretical calculation for the chemical species and migration behavior of uranium in groundwater were accomplished by combining the thermodynamics balance analysis mode, the geochemical condition and the known thermodynamics data. The results indicated that the overwhelming majority (more than 99%) of U(VI) in the groundwater exit as the complex species, such as UO_2(CO_3)_2~(2-), UO_2(CO_3)_3~(4-), UO_2CO_3~0 and UO_2(HPO_4)_2~(2-), while the other species as UO_2(OH)_2~0, UO_2(OH)~+ or UO_2~(2+), account for less than 1%.It can be shown by the additive experiment that most of the investigated additives can not remarkably improve the adsorption performance of the soil for uranium, whereas some additive have reverse effect. Also, it is very difficult for reductive sediment of U(Ⅵ) to U(Ⅳ)by adding some reduction additives, such as N_2S. Fortunately, the soil sample Ⅲ, a kind of arenaceous clay with orange yellow color from the disposal site, has very strong adsorption ability to uranium with a K_d value of up tol228. 4ml. g~(-1). It can be conclude that this soil should be the best candidate for the geochemical engineering barrier materials, if the granularity, lithology and commercial availability were comprehensively considered. Then the further experiment was performed.Surface electric charge of the soil was measured, and the result that the soil sample Ⅲ has the highest positive charge value of 9. 60mmol/100g among the investigated soil samples was noted. It is thus clear that the K_d value is direct ration to the positive charge of the soil, and the adsorption mechanism of uranium on soil should involve the strong adsorption of uranyl complex anion onto the positive charge colloid.
The adsorption behavior of uranium onto the topsoil and deep soil from the soil sample III was evaluated. The topsoil with different granularity has same principle mineral components and contents as the deep soil. The surface positive charge of the topsoil declined with decrease of the granularity, and almost one time less than the topsoil sample. Also, the adsorption rate of the topsoil for uranium dropped along with decrease of the granularity, while no significant change was observed with the deep soil sample. However, the adsorption rate of the topsoil and deep soil both rose with the increasing of pH or ratio of solid to liquid, and increased first, then declined gradually with the increasing of uranium concentration. The adsorption equilibrium with the two samples was achieved within 14 days, while the maximal adsorption rate with the topsoil was observed at normal temperature. Moreover, it could be seen that the absorption rates of the deep soil sample were always several to ten times higher than that of the topsoil sample in each experimental conditions. Absorbed and retarded capacity of Uranyl complex ion direct ratio surface positive charge in soil, and the mechanism is static absorption.The absorption ability of the deep soil sample for uranium could been greatly improved by adding Ca(0H)2, leading to the adsorption rate up to 1. 9X 104ml. g"1. The similar result could be obtained by adding charry gritstone, and the adsorption rate and the quantity of the added charry gritstone was usually in keeping with linear correlation.It should also be paid much attention to that the adsorption rate resulted from dynamic column migration experiments was ten times less than that from static experiments. The main reason is that column migration experiments don' t attain equilibrium. Yet, this condition is similar to the groundwater flow and the Uranyl ion is retarded by the soil with the groundwater flow, so the results of column migration experiments have actual value.In summary, several factors related to the geochemical engineering barrier for the buried disposal of very low-level radioactive waste containing uranium, such as the chemical species and migration behavior of uranium in groundwater, the effect of the additives on the engineering barrier, and the adsorption behavior of uranium on the soil had been investigated in this paper, and enormous expeimrntal data summarized. It is indubitable that all these will be useful to disposition and safety assessment of radioactive waste containing uranium.
引文
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