Fan Qiaohui, Yamaguchi Noriko, Tanaka Masato, Tsukada Hirofumi, Takahashi Yoshio
Department of Earth and Planetary Systems Science, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526, Japan.
National Institute for Agro-Environmental Sciences, 3-1-3, Kannondai, Tsukuba, Ibaraki, 305-8604, Japan.
J Environ Radioact. 2014 Dec;138:92-100. doi: 10.1016/j.jenvrad.2014.08.009. Epub 2014 Sep 7.
This study examined the radiocesium (RCs) interception potential (RIP), cation exchange capacity (CEC), total organic carbon (TOC) content, and adsorption species in soils and minerals by using extended X-ray absorption fine structure (EXAFS) spectroscopy. The RIP related to Cs(+) adsorption by frayed-edge site (FES) has often been used to measure the mobility and bioavailability of RCs in the environment. This study found that the presence of organic matter (OM) can reduce RIP to a certain extent. The adsorption amount (=Q(T)) in soil was obviously correlated to RIP at a small [Cs(+)] region, whereas a linear relationship between Q(T) and CEC was observed at a large [Cs(+)] region. Both the inner-sphere (IS) and outer-sphere (OS) complexes of Cs(+) were observed through EXAFS at a molecular scale. The linear correlation between log (RIP/CEC) and the ratio of the coordination number (CN) of IS (=CNIS) and OS (=CNOS) complexes noted as CNIS/(CNIS + CNOS) suggested that the ratio of CN is very sensitive to Cs(+) adsorption species with variable RIP and CEC. The adsorption species of Cs(+) in soil was mainly dependent on the clay mineral content of soil. RIP was affected not only by FES but also by other strong adsorption sites, such as the interlayers and cavities identified as the IS complex in EXAFS analysis. Findings indicated that the EXAFS approach is a powerful and efficient tool to explore the behavior of Cs(+) in a given environment.
本研究通过使用扩展X射线吸收精细结构(EXAFS)光谱,研究了土壤和矿物中放射性铯(RCs)的截留潜力(RIP)、阳离子交换容量(CEC)、总有机碳(TOC)含量以及吸附物种。与磨损边缘位点(FES)对Cs(+)的吸附相关的RIP常被用于衡量环境中RCs的迁移性和生物有效性。本研究发现,有机质(OM)的存在能在一定程度上降低RIP。在低[Cs(+)]区域,土壤中的吸附量(=Q(T))与RIP明显相关,而在高[Cs(+)]区域,观察到Q(T)与CEC呈线性关系。通过EXAFS在分子尺度上观察到了Cs(+)的内球(IS)和外球(OS)配合物。log(RIP/CEC)与IS(=CNIS)和OS(=CNOS)配合物的配位数(CN)之比(记为CNIS/(CNIS + CNOS))之间的线性相关性表明,CN之比对具有可变RIP和CEC的Cs(+)吸附物种非常敏感。土壤中Cs(+)的吸附物种主要取决于土壤的粘土矿物含量。RIP不仅受FES影响,还受其他强吸附位点影响,如在EXAFS分析中被确定为IS配合物的层间和孔洞。研究结果表明,EXAFS方法是探索给定环境中Cs(+)行为的有力且高效的工具。