Implications of Analcime Hydrothermally Formed from Na-alumino-borosilicate Glasses Containing Cs and Sr for the Stability of High-level Radioactive Waste Form

Abstract. In order to know the behaviors of radioactive elements such as cesium and strontium during a hydrothermal alteration of borosilicate glass of radioactive waste, some alumino-borosilicate glasses belonging to the systems Na₂O-Al₂O₃-B₂O₃-SiO₂-SrO, Na₂O-Al₂O₃-B₂O₃-SiO₂-Cs₂O and Na₂O-Al₂-O₃-B₂O₃-SiO₂-SrO-Cs₂O have been treated hydrothermally at 200C under a vapor pressure of 1.54 MPa. The result shows that all glasses are changed into crystalline phases with running time up to 60 days, and that analcime-type zeolite is formed as a major product. The formed zeolite is shown to contain cesium and/or strontium. Considering the fact that natural zeolite occurs in wide physicochemical conditions including hydrothermal one, the analcime-type zeolite is expected to fix stably the radioactive elements in the disposal site. Since aluminum is necessary for the formation of the analcime-type zeolite, the waste glass should have aluminum as one of major components.     

青藏高原盐湖水化学及其矿物组合特征

青藏高原湖泊的矿化度与其湖泊演化所处的自然环境,特别是与气候条件关系密切,根据取得盐湖数量和卫片解译,本区湖泊矿化度在空间上变化的总趋势是由北、西北向南、东南趋向下降,大体上与现代高原年干燥度(年蒸发量/年降水量)呈同步变化。高原盐湖的pH值既与水化学类型有关,又与湖水矿化度有关,即由碳酸盐型→硫酸钠亚型→硫酸镁亚型→氧化物型,其pH值趋于下降,而湖泊的pH值与矿化度大体呈反相关。根据库尔纳可夫—瓦良什科分类法及作者对碳酸盐型的细分,对青藏高原盐湖水化学进行了全面细致划分,从而取得了清晰的规律性认识:本区盐湖水化学具有南北分带,东西分区的特点。不同的盐湖水化学类型,具有不同的专属性,碳酸盐型代表性成矿组合为硼砂(三方硼砂)或硼砂—扎布耶石,以及碱—芒硝组合;硫酸钠亚型代表性成矿组合为芒硝(无水芒硝)—石盐以及镁硼酸盐(库水硼镁石、柱硼镁石等)—钠硼解石—芒硝;硫酸镁亚型代表性成矿组合为硫酸镁盐(泻利盐、白钠镁矾)—石盐、镁硼酸盐—芒硝、芒硝—软钾镁矾—石盐以及大量石膏;氯化物型代表性成矿组合则为光卤石—水氯镁石—石盐、光卤石—石盐,个别盐湖共生南极石。由此可见,青藏高原各类型盐湖矿物组合基本上具有冷相组合特征,芒硝及与其共生的冷相盐类矿物,可成为研究古气候变化的重要标志物。目前已检出青藏高原盐湖水含有59种元素,其中B与Li、Cs、K、Rb有密切共生关系,其含量随湖水矿化度增长大致呈正相关;B、Li、Cs、K、Rb最高正异常落在羌南碳酸盐型带(Ⅰ2)西段—昂拉陵湖区为中心地区;并与本区中新世火山沉积岩系和地热水B、Li、Cs、Rb等高值区并行不悖。以上有力证明B、Li、Cs等特殊元素物质与深部来源有关。据近期大量地球物理和火山岩岩石地球化学研究,其成因与印度—欧亚陆陆碰撞引起的重熔岩浆作用有密切成因联系。南美科迪勒拉高原硼锂(铯)盐湖即生成于活动大陆边缘,两者均说明全球特定的活动构造带是造成天然水B、Li、Cs(K、Rb)高丰度及其成矿作用的主因。     

西藏搭格架热泉型铯矿床矿物学与矿石组构特征及地质意义

在查明搭格架铯矿床产出的地质背景、成矿阶段及其年龄、地球化学与同位素组成的基础上,本文较为系统地研究了硅华的矿物学与组构特征,加深了对硅华形成演化过程的认识.研究表明成矿早期,矿石中存在大量的石英,晚期全为蛋白石.粒状蛋白石自早到晚均有出现,胶状蛋白石主要出现于晚期.早期矿石出现脱水造成的菜花状、粗粒块状与粗大孔隙状构造及溶蚀结构.晚期出现细粒块状与细小孔隙状构造.在第3阶段存在硅藻Denticula属,体现出低温阶段的特征.由早到晚,矿石的SiO2呈降低趋势,而(Na2O Al2O3 K2O CaO)与Cs2O呈升高趋势,是随着矿石中SiO2有序度的降低而其它成分被保留在晶格中所致.     

Characterisation of Two New Reference Materials: STL-1, the Stewart Lepidolite and ZA-1, the Zapot Amazonite

The analysis of granitic pegmatites still remains a challenge because suitable natural reference materials are scarce or not available. Two new reference materials were prepared at the Smithsonian Institution, to provide an avenue to pursue the geochemical analysis of micas and feldspars in granitic pegmatites: STL-1, the Stewart lepidolite (NMNH 174041) and ZA-1, the Zapot amazonite (NMNH 174042). STL-1 was prepared from lepidolite collected from the lithium-rich Stewart pegmatite, San Diego County, California (33°22'52'N, 117°03'41'W). ZA-1 was prepared from an amazonite from the topaz-bearing Zapot pegmatite, Mineral County, Nevada, (38° 41'N, 118 °33'W). The results of this study indicated that STL-1 and ZA-1 are homogeneous and could be used as reference materials that would allow the expansion of calibration curves in XRF analysis up to 16000 μg g⁻¹ for Rb, 2000 μg g⁻¹ for Cs and 100 μg g⁻¹ for Tl. STL-1 and ZA-1 also contain unusually high concentrations of Ga and Tl, and STL-1 of Nb.     

碳棒涂膜式PVC膜铯离子选择电极的研制和应用

本文作者研制成功以四苯硼铯为活性物质的碳棒涂膜式PVC膜铯离子选择性电极。电极最佳膜组成:四苯硼铯5mg,邻苯二甲酸二丁酯0.4ml,硝基苯0.2ml,PVC粉0.2g。电极性能优良,制作简单,操作方便。结合大粒度磷钼酸铵和结晶形锑酸分离K~+,Na~+,巳将此电极用于卤水样中铯的测定,结果令人满意。     

Distribution of local Cs anomalies on the seafloor near the Fukushima Dai-ichi Nuclear Power Plant

An estimated 3.5 ± 0.7 × 10¹⁵ Bq of ¹³⁷Cs is thought to have been discharged into the ocean following the melt down at Fukushima Dai-ichi Nuclear Power Plant (F1NPP). While efforts have been made to monitor seafloor radiation levels, the sampling techniques used cannot capture the continuous distribution of radionuclides. In this work, we apply in situ measurement techniques using a towed gamma ray spectrometer to map the continuous distribution of ¹³⁷Cs on the seafloor within 20 km of the F1NPP. The results reveal the existence of local ¹³⁷Cs anomalies, with levels of ¹³⁷Cs an order of magnitude higher than the surrounding seafloors. The sizes of the anomalies mapped in this work range from a few meters to a few hundreds of meters in length, and it is demonstrated that the distribution of these anomalies is strongly influenced by meter scale features of the terrain.     

西藏盐湖沉积物：一种潜在的铷、铯资源

铷、铯是我国战略性关键矿产资源。西藏盐湖卤水中赋存着丰富的铷、铯资源,但是品位普遍低于10 mg/L。根据热泉与盐湖锂、铷、铯等元素的补给关系和含量差异特征及铷、铯极易被黏土矿物吸附等特点,推测盐湖沉积物中赋存一定规模的铷、铯资源。为验证该推测,本文选取西藏拉果错、聂尔错、依布茶卡、当穹错、扎布耶茶卡等5个典型盐湖,采集卤水和沉积物样品各5件,开展水体中铷、铯含量和沉积物矿物成分分析,结合沉积物分相淋滤实验,得出如下结论：西藏拉果错、当穹错、聂尔错盐湖卤水铷、铯含量和资源量与其补给量差异显著,大量的铷、铯资源消耗于盐湖沉积物中;盐湖沉积物中的铷、铯含量远高于卤水。铷、铯在沉积物水溶相、碳酸盐相中含量较低,主要以吸附形式赋存于黏土矿物(主要为伊利石),吸附点位包括基面位置、难解吸的磨损边缘及层间位置。盐湖沉积物铷、铯资源量远超大型矿床规模,黏土矿物中铷、铯含量高达100 n×10-6,超过固体盐类矿产综合评价指标,相较于现有盐湖钾产品中的铷资源、含铯硅华中的铯资源开发,具有较好的开发利用性,是一种潜在的铷、铯资源。本研究成果有助于完善盐湖铷、铯富集成矿机制,并为高效开发盐湖中的铷、铯资源提供理论支撑。     

四硼酸铯溶液的Raman光谱和物化性质研究

由摩尔比为1∶2的Cs2CO3和H3BO3反应得到四硼酸铯样品,用FT-IR和Raman等方法对其溶液结构进行表征并分析其中的阴离子类型。同时测定了四硼酸铯溶液在298.15 K和333.15 K下的密度、电导及p H,通过298.15 K下的pH测量值和相关硼酸盐平衡常数,计算298.15 K下四硼酸铯溶液的化学物种分布,并对其相互转换反应进行推测。研究表明,298.15 K下四硼酸铯溶液中存在的主要物种有B(OH)4-、B(OH)3、B3O3(OH)4-、B3O3(OH)52-和B4O5(OH)42-,与Raman光谱所得结果基本一致。     

Geotechnical sealing material for coastal disposal facility for soils and wastes contaminated by radioactive cesium

Safe disposal of wastes produced due to the process of decontamination in and around Fukushima No. 1 nuclear power plant is an urgent requirement. The purpose of this study was to develop a sealing material which can be used as an engineered barrier for a final disposal facility for the soils and wastes contaminated by radioactive cesium. The analyses conducted based on 4-m-thick sealing layer revealed that the hydraulic conductivity of the sealing material needs to be kept below 5.0?×?10^?10?m/s to avoid the seepage of contaminants below the environmentally safe limits. Sealing material was developed using marine clay–bentonite mixture and the engineering characteristics were examined. The results of laboratory experiments showed that, with the addition of bentonite, the hydraulic conductivity equal to or less than 5.0?×?10^?10?m/s was achieved when the effective consolidation stress is equal to or more than 27?kPa. From the tests for adsorption properties for cesium, it was found that the sealing material showed the significant capacity of adsorption for cesium in seawater. It was concluded that the construction of waste disposal facility on the sandy seafloor is feasible using the sealing layer proposed in this study.     

火焰发射光谱法测定卤水中铷和铯

选择LaCl3 作电离缓冲剂,用火焰发射光谱法测定卤水中的Rb和Cs,有效地降低了基体干扰,提高了方法的灵敏度。方法的测定下限为: 18μg/LRb, 1. 8μg/LCs;加标回收率在92. 4% ~105. 0%。方法用于实际样品分析,结果与KCl电离缓冲剂原子吸收光谱法相吻合,且减少了预先测定K 的操作。对卤水样品中Rb和Cs11次平行测定,计算方法的RSD分别为5. 78%和8. 11%。