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铀矿冶理虽经过数十年的发展,对铀尾矿等中低放固废的处置方法仍以近地表处置为主[1-3]。长期露天堆放的铀尾矿,经过雨水淋滤后能析出铀等具有一定生物毒性和放射性的核素[4-6],他们进入土壤后对环境产生了极大的污染[7]。学者们对土壤剖面中铀的分布规律进行了大量研究,目前已知土壤pH、有机质、针铁矿、碳酸盐、磷酸盐、石英等众多因素均能影响铀在土壤剖面中的吸附和空间分布[5, 8-13]。近年来,针对土壤吸附铀的机理研究虽逐渐增加,但相关成果大多聚焦于单一组分对铀的影响[14-16]。
与许多研究结果不同,自然环境中土壤剖面各土层受地表生物活动、风化等因素的影响,土壤形成和发育过程中分化为多个土层,各土层间的理化性质存在较大区别,使得它们对铀吸附能力差异明显。目前,针对铀尾矿库中各土层对铀吸附研究,大多集中在土壤表层(腐殖质层)[17]。绝大部分铀尾矿库,由于年代久远,加上建设之初未设置防渗措施[18],铀等放射性核素不仅污染与其直接接触的腐殖质-淋溶层,也可能同有机胶体、无机胶体络合迁移至土壤剖面中更深的淀积层、母质层甚至地下水中,但目前针对这一情况的研究较少。
本研究采用静态吸附法考察了南方某铀尾矿库附近棕红壤剖面中的淋溶层、淀积层和母质层等土层对U(Ⅵ)吸附差异,从热力学和动力学方面分析吸附过程;并使用XRF、XRD、SEM、FT-IR等表征手段对吸附规律进行了分析。研究了土壤剖面中各土层对外源铀的吸附,有利于探讨铀尾矿库等核设施污染土壤中铀的空间分布及各土层对铀的吸附规律,本研究可为铀尾矿库土壤剖面中的外源铀污染综合治理及地下水防治等工作提供参考。
某尾矿库附近各土壤层对U(VI)的吸附特性
Adsorption characteristics of uranium in soil horizons near tailings impoundment area
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摘要: 针对南方某铀尾矿库附近棕红壤剖面中的淋溶层、淀积层和母质层等土层对铀的吸附机理和空间分布规律进行了探讨。采用比表面测定、X射线荧光、扫描电镜、傅里叶变换和X射线衍射等方法对各土层样的理化性质、结构和形貌进行了表征分析;采用静态吸附法考查了时间、U(Ⅵ)初始浓度、pH、温度、粒径等因素对各土层吸附U(Ⅵ)的影响;并使用热力学和动力学方程对吸附过程进行了模拟分析。结果表明,25 ℃下淋溶层和淀积层pH均为6.2、母质层pH为4.1时,其对U(Ⅵ)最大吸附量分别可达23.60、22.82和13.05 mg·g−1。热力学和动力学拟合结果分别表明,各土层对U(Ⅵ)更符合Langmuir方程(R2>0.999)和准二级动力学模型(R2>0.98)。风化程度,Fe、Mn、Al、Ca等元素及有机质含量,pH和土壤粒径等因素是各土层对U(Ⅵ)吸附能力不同的主要原因;同时,外源铀进入土壤剖面后,大部分聚集在土壤表层,随着深度的下降的铀含量也逐渐降低。研究结果可为土壤剖面中的铀和其他重金属的污染防治提供参考。Abstract: In this study, the adsorption mechanism and spatial distribution of U(Ⅵ) in the eluvial, illuvial and parent material horizon of a brown-red soil profile near a Uranium tailing impoundment in South China were discussed. The physical and chemical properties of the soil horizons were characterized by using surface area measurement, X-ray fluorescence, scanning electron microscope, fourier transform infrared spectroscopy and X-ray diffraction. The effects of time, U(Ⅵ) initial concentration, pH, temperature, and particle sizes on U(Ⅵ) adsorption were investigated by static adsorption experiments. Thermodynamic and kinetic equations were used to simulate the adsorption process. The results showed that the maximum U(Ⅵ) adsorption capacities were 23.60, 22.82 and 13.05 mg·g−1 in the eluvial, illuvial and parent material horizon, respectively, at pH 6.2 for the former two horizons, pH 4.1 for the later one and 25 ℃. The isothermal adsorption models of the soil horizons were more consistent with the Langmuir equation (R2>0.999), and the kinetic adsorption process fitted better with the pseudo-second order kinetic model (R2>0.98). The different adsorption capacities towards U(Ⅵ) on each layer could be caused by the differences of their physico-chemical properties, such as weathering degree, Fe, Mn, Al, Ca, organic matter contents, pH and soil particle sizes. As the external uranium entered the soil profiles, it could accumulate in the surface layer of soil, and the content of uranium decreased with the decrease of depth. The results of this study can provide references for the prevention and control of external uranium or other heavy metal pollution in the soil profile.
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Key words:
- U(Ⅵ) /
- near-surface disposal /
- uranium tailing impoundment /
- soil profile /
- static adsorption
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表 1 各土样粒径分级
Table 1. Particle size classification of soil horizons
土层类型 ≥8目 8~40目 40~60目 60~200目 ≤200目 淋溶层 2.83 50.96 9.29 17.04 19.88 淀积层 10.64 51.22 8.42 13.36 16.36 母质层 32.22 55.62 3.84 4.50 3.82 表 2 各土层理化性质
Table 2. Physico-chemical properties of soil horizons
土层类型 自然密度/(g·cm−3) 干密度/(g·cm−3) 含水率/% pH BET/(g·m−2) 有机质/(g·kg−1) 淋溶层 1.56 1.25 19.87 4.1 40.33 36.51 淀积层 1.66 1.35 18.67 4.6 33.99 25.74 母质层 1.71 1.50 12.28 7.2 17.56 2.10 表 3 各土层主要组成元素
Table 3. Main elements of soil horizons
土层类型 Fe Ca Mn K S Ti P 淋溶层 69.46 1.20 0.21 27.60 3.30 7.56 2.49 淀积层 65.35 1.26 0.15 27.71 4.56 5.68 3.31 母质层 48.51 4.81 1.01 32.74 2.86 4.04 1.85 注:各土层中U含量均低于XRF仪检测下限(十亿分之一)。 -
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