Pu在花岗岩中的吸附行为

为了解Pu在甘肃北山地区地下深度约为600 m的花岗岩中的吸附行为,研究了各种水质(重蒸水、模拟地下水、BS03井地下水)、pH值(3.0~10.0)、CO32-离子浓度(4.0×10-3~1.0×10-1mol/L)、氧浓度等因素对吸附的影响。通过对吸附后水相物化参数(如pH值、Eh、电导率等)、Pu的价态、固相表面特征参数(比表面、孔径、总孔容等)等数据的比较以及解吸实验结果,推测可能的吸附机理:Pu在花岗岩上以表面配合物的形式吸附,且可用Freundlich吸附等温式描述。     

Pu在地质环境中化学行为的研究进

着重评述了近年来与高放废物深部地质处置有关的地质环境中Pu化学的研究进展,重点讨论了Pu从高放玻璃固化体中的浸出行为、Pu在地下水中的溶解度、配合反应(包括水解反应)、氧化还原反应、胶体的形成等。提出了近期和长期应开展的若干研究课题。     

国际高放废物处置研发工作在花岗岩地区的进展

论述了处置库候选围岩的岩石类型、花岗岩特征,以及一些国家在花岗岩地区开展高放废物处置研发工作的进展情况。经过几十年的工作,国外有些经验值得我们今后工作时参考:1)重视志愿者选址工作。国际上不少国家认为这是地质选址工作的先导,选址工作的成败常与此项工作的进展情况有关;2)近年来,单纯处置高放废物的处置库,已逐渐发展成为多功能处置库,即,它既处置高放废物和乏燃料,同时还处置其他各类核废物;3)由瑞典SKB开发的KBS-3高放废物处置方案和处置工程的设计模式已被不少国家所接受;4)特定场址地下实验室的工程设计完全与处置库的工程设计融为一体,这样既节省工程成本,又提高处置库工程设计的可靠性;5)花岗岩具有良好的岩石力学性能,这对处置库工程结构的长期稳定性和安全处置核废物提供有效的物理保障和良好的物理隔绝性能。但在选址时要特别注意场址的区域地壳稳定性、岩体的处置容量和埋藏深度,以及处置地段的构造发育程度和岩石的含水性;6)处置后废物的回取。     

低氧条件下Tc的吸附、解吸和扩散行为研究

研究了低氧条件下Tc在花岗岩上的吸附、解吸和扩散,内容包括溶液pH、含铁矿物(还原铁粉和Fe_3O_4)、膨润土、阴、阳离子浓度(CO_3~(2-)、Fe~(3 )、Fe~(2 )对Tc在花岗岩(石英、黑云母)上吸附Kd值的影响;在解吸剂中加入H_2O_2,对Tc进行解吸,探讨其吸附机理;将扩散系数代入扩散方程的解析解,预测了10 000年后Tc的扩散距离。实验结果表明:低氧条件下Tc的行为具有如下特点。     

Am在花岗岩中的吸附行为

高放废物中的一些核素（^237Np、^99Tc、^239Pu、^241Am等）毒性大、半衰期长，处置不当将会严重危害人类生存环境。采用深地质处置，随着时间的延长，由于地下水的侵蚀以及不可预见情况的发生，废物库以及废物包装体的完整性将会被破坏，高放废物中的各种放射性核素将随着地下水而迁移到生物圈中，危害到人类的安全。     

90Sr、237Np、238Pu和241Am在水平土柱中迁移的实验场示踪研究

将装有示踪剂和含水层未扰动土的水平土柱,通过竖井壁水平插入含水层,天然地下水通过与含水层介质紧密相连的一端流过土柱,在另一端接取水样;通过测量实验期间采集的水样和实验结束后切割的土壤样品中示踪剂的浓度,得到核素的迁移数据。实验结果表明,所用核素中迁移最快的90Sr的延迟系数>290,说明黄土对实验所用的90Sr、237Np、238Pu和241Am都有较强或很强的吸附能力;有腐殖酸的3号和8号土柱中90Sr的延迟系数大于无腐殖酸的2号土柱的延迟系数,说明腐殖酸延缓了90Sr的迁移;无腐殖酸的2号水平土柱中90Sr的延迟系数与实验室模拟土柱的延迟系数基本相同。     

137Cs和90Sr在北山花岗岩中吸附和扩散探究

关键核素在相关介质中的吸附和扩散参数获取是深地质处置安全评价的重要组成部分。探究了¹³⁷Cs和⁹⁰Sr在北山不同地区花岗岩中的吸附和扩散过程,并通过拟合扩散数据给出有效扩散系数。不同地区花岗岩矿物组成基本类似,但是具体比例有所差异。吸附实验结果表明：算井子地区的花岗岩对¹³⁷Cs和⁹⁰Sr的吸附性能最强,而新场和沙枣园地区的花岗岩的吸附性能相当。¹³⁷Cs在新场、算井子和沙枣园地区的有效扩散系数分别为9.0×10^-14、9.3×10^-14和1.0×10^-13 m²·s^-1,⁹⁰Sr在新场、算井子和沙枣园地区的有效扩散系数分别为1.2×10^-13、5.6×10^-13和3.2×10^-13 m²·s^-1,两种核素在3个地区的花岗岩中的有效扩散系数...     

^99Tc在膨润土材料中扩散行为研究

对放射性核素的迁移行为和规律的研究是高放废物处置的一个极其关键问题。长寿裂变产物。^99Tc是高放废物的主要成分之一，因其毒性大，半衰期长，一直是研究的重点，在高放废物地质处置安全及环境评价中是一重要核素。     

衰变和吸附对放射性核素在花岗岩

为了获取关键核素在北山花岗岩中的有效扩散系数,依据125I-在甘肃北山深部花岗岩中的一维扩散曲线,用参数拟合方法得到了125I-在北山花岗岩中的有效扩散系数,并依据扩散方程讨论了衰变和吸附对扩散曲线的影响.研究结果表明,衰变常量和吸附速率常数对一维扩散曲线的影响各不相同,衰变常量的大小影响扩散曲线的形状,吸附速率常数的大小则影响扩散曲线的走势,不同核素的扩散曲线可有很大的差别.     

Consideration on Effective Diffusivity of Strontium in Granite

Abstract

Diffusive behavior of strontium and certain kinds of divalent cations in Inada granite were studied by a through-diffusion method. In order to examine the effect of sorption onto overall diffusive behavior, two kinds of solutions were used: 0.1M KCl solution and deionized water. The effective diffusion coefficient (D_e ) and rock capacity factor (a) were (2.0–3.6) xl0–¹³ m²/s and less than 0.022 in 0.1M KCl solution and (0.32–1.7) x 10 ^?13m²/s and 1.5–2.4 in deionized water respectively. The D_e , and α in deionized water were much larger than those in 0.1M KCl solution. These results are well explained by taking into account the diffusion of sorbed ion or the surface diffusion. In support of this mechanism, most D_e , values of Sr reported for various rocks are found proportional to the sorptivity ( _ρR_d )-In the case that the sorptivity is low, D_e of Sr depends on porosity like that of nonsorbed iodide. The effective diffusion coefficient of Sr in rocks was well explained by taking into account pore and surface diffusion and was expressed as D_e=2.1 xl0^?10 _? ^1.3+3.5xl0″^?12 _ρR_d . The effective diffusion coefficient of divalent cations in the granite was found proportional to their diffusion coefficients in bulk solution.     

Np，Pu在地下水和工程屏障平衡水中的形态计算研究

采用EQ3／6地球化学模式和计算方法研究了放射性废物处置中Np和Pu在地下水和工程屏障平衡水中的化学形态,计算分析了温度、浓度、pH值、Eh值、CO2等对上述2个元素形态的影响。结果表明,地下水中Np的形态主要有4种：NpO2^ ,NpO2CO3^-,NpO2OH和Np(OH)5^-,当CO3^2-质量浓度高时,Np主要以NpO2(CO3)2^3-存在。pH值以Np形态的影响主要表面在上述4种形态分布的相对比例及OH^-与CO3^2-的竞争配合作用。Eh值低于0．2V时,Np主要为四价;0．2－0．7V时,五价为主;大于0．7V时,出现六价。Pu的形态主要为Pu(OH)5^-。CO3^2-的质量浓度对四价钚的形态分布不产生影响,但CO3^2-却与Pu（Ⅵ）有很强的配合能力。Eh值低于－0．5V时,Pu主要为三价;－0．4－0．6V,五价为主;大于0．7V时,六价为主。     

脉冲柱法研究碘在北山花岗岩中的迁移

¹²⁹I是一重要的裂变产物,其在环境中的行为受到人们的重视。本工作利用脉冲柱法研究了¹²⁹I（作为¹²⁹I的替代物）在北山花岗岩中的迁移情况。实验结果表明,对流水力学弥散是碘迁移的主要机制。碘的弥散系数D随流速的增加而增加,随淋洗液pH的增加而减小。D随pH的变化趋势与岩粉表面的电荷变化吻合。当流速为0.07 mL·min^-1、pH=8.0时,D=3.29×10^-5m²·min^-1,和已有的实验结果相符,验证了弥散度只与介质有关这一结论。     

北山新场BS34钻孔岩样在不同温度下的水岩作用北大核心CSCD

高放废物深地质处置过程中,放射性核素衰变可能产生大量的热量,释放到处置硐室周围环境中将影响深部地质环境局部的水岩作用。为探究温度对新场场址深部地下水化学环境的影响,使用新场场址原状地下水与BS34钻孔深部花岗岩岩样,开展了不同温度下室内水岩作用研究。结果表明:BS34钻孔岩样与原状地下水反应后,水相的pH为6.4~8.5,总溶解固体(TDS)为1653.9~1759.6 mg/L。随着温度的升高,水溶液Na^(+)、K^(+)浓度增大,其中Na^(+)可能来源于钠长石溶解、阳离子交换作用,K^(+)可能来源于钾长石溶解;Ca^(2+)、Mg^(2+)、HCO_(3)^(-)浓度减少,主要以方解石和白云石的形式沉淀析出,反应温度越高,沉淀析出越多。     

环境样品中~(90)Sr和~(239+240)Pu的联合分析

针对气溶胶、沉降灰、土壤、生物及淡水等环境样品中90Sr、239+240Pu的联合分析进行了流程设计,并通过实际样品的测量对流程进行了验证。结果表明:90 Sr分析流程的化学回收率为44.3%~90.2%,平均值为73.8%;239+240Pu分析流程的放化回收率为40.2%~104.3%,平均值为79.3%。在可给出单个样品化学(放化)回收率的前提下,该联合分析流程可以满足日常环境监测的要求。     

Integrated sorption and diffusion model for bentonite. Part 2: porewater chemistry,sorption and diffusion modeling in compacted systems

It is important to understand the coupled processes of sorption and diffusion of radionuclides (RNs) in compacted bentonite, and to develop mechanistic models that can aid in the prediction of the long-term performance of geological disposal systems of radioactive waste. The integrated sorption and diffusion (ISD) model was developed based on the consistent combination of clay–water interaction, sorption and diffusion models. The diffusion model based on the electrical double layer theory describing relative ionic concentrations and viscoelectric effects at the negatively charged clay surface was coupled with porewater chemistry and sorption models. This ISD model was successfully tested for various actinides with a complex chemistry (Np(V), Am(III), U(VI) under conditions where variably charged carbonate complexes are formed) considered in Part 1, by using published diffusion and sorption data (D_a, D_e, K_d) as a function of partial montmorillonite density. Quantitative agreements were observed by considering uncertainty in porewater chemistry and dominant aqueous species. It can therefore be concluded that the ISD model developed here is able to adequately explain the sorption and diffusion behavior of various RNs with a complex chemistry in compacted bentonites. The performed modeling indicates that uncertainties are mainly related to porewater chemistry and RN speciation and that these parameters need to be carefully evaluated.     

Computer Simulation Study of Transient Diffusion of Cesium through Granite with Unsteady-State Diffusion Model

A steady-state diffusion model has been used widely to determine the diffusivities of radionuclides in rocks. Buffer container at the source solution side is used to keep the concentration constant. It is suitable for non-sorptive species, but not for sorptive species. Some researchers proposed a unsteady-state diffusion model recently. It is possible to use simple experimental apparatus without buffer container to measure the diffusivity with this model. To obtain the diffusional information more easily according to the sorption properties of radionuclides, through- diffusion experiments were performed in granites. Methods of determining of diffusivities are discussed according to sorption properties of species. For the non-sorptive species, the steady- state diffusion model was effective to determine the diffusivity. For the sorptive species, the analytical solution of the unsteady-state diffusion model found to be more appropriate to determine the diffusivity. Surface diffusion of sorbed species on rock did important role in diffusive transport.     

Accelerated Leach Tests of SRL-165 High-Level Waste Glass in Deionized Water

Accelerated short-term leach tests in a laboratory are neccessary in order to estimate, with reasonable accuracy, the long-term leaching behavior of high-level waste glass. In the present study, static leach tests of an SRL-165 high-level waste glass were carried out in deionized water at two different glass-surface-area to solution-volume ratios (SA/V-ratio), namely 0.85 and 0.079 cm^?1 at 90°C, and 0.85 cm^?1 at 40°C.

First, an equation was examined which related Si-concentrations with time, temperature and SA/V-ratio under the present static conditions. The parameter determined at 90°C, 0.85 cm^?1 can be used to calculate the Si-concentration at 40°C, 0.85 cm^?1. Second, at the low SA/V- ratio of 0.079 cm^?1, the concentrations of Ca and Mg in the leachates peaked and then decreased a little. The equation used above does not explain the variation of the concentrations of Ca and Mg at a low SA/V-ratio. The precipitation of Ca and Mg onto the glass surface is probably caused by the adsorption efficiency of the surface layer or the formation of crystalline materials at the low SA/V-ratio of 0.079 cm^?1. Third, the in-depth profiles of some elements obtained by secondary ion mass spectroscopy (SIMS) were qualitatively in agreement with the results of solution analyses. This indicates the particular usefulness of SIMS for analyzing leaching behavior of the glass in in-situ burial studies where solution analyses are often impractical.