温度对Np在北山花岗岩上吸附行为的影响

    Effect of Temperature on Sorption of Np(Ⅳ)/ Np(Ⅴ) on Beishan Granite

    • 摘要: 采用批式实验法研究了低氧条件下,温度对Np(Ⅳ)、Np(Ⅴ)在磁分离后的花岗岩和北山花岗岩上吸附行为的影响。测定了30、45、60、80 ℃下Np(Ⅳ)、Np(Ⅴ)在磁分离后的花岗岩和北山花岗岩上吸附的Kd值。研究发现,温度升高有利于Np(Ⅳ)、Np(Ⅴ)在花岗岩上的吸附;在近中性地下水体系中,Np(Ⅴ)较Np(Ⅳ)更易被花岗岩吸附,这可能是因为Np(Ⅳ)、Np(Ⅴ)在水溶液中的存在形式不同;以NpO2+形态存在的Np(Ⅴ)比以Np(OH)4(aq)形态存在的Np(Ⅳ)更容易吸附在花岗岩上。利用解吸研究了吸附机理,发现温度升高不利于Np(Ⅳ)和Np(Ⅴ)进入到矿物晶格内。通过拟合得到了不同温度下Np(Ⅳ)和Np(Ⅴ)吸附在花岗岩上的吉布斯自由能以及熵变和焓变。

       

      Abstract: Sorption and desorption of Np(Ⅳ)/ Np(Ⅴ)on granite and magnetically separated granite were studied by batch experiment under anaerobic ( in glover box with an φ(O2)≤5×10-6) at 30℃, 45℃, 60℃, 80℃. The Kd of Np(Ⅳ)/ Np(Ⅴ) sorption on granite and separated granite increase with rise in temperature. The sorption of Np(Ⅴ) is stronger than Np(Ⅳ)due to the dominate species of Np(Ⅳ)and Np(Ⅴ) are different. The dominant species of Np(Ⅳ)and Np(Ⅴ) are Np(OH)4 (aq)and NpO2+, respectively. Sorption of Np(Ⅳ)/ Np(Ⅴ) on/into the surface and non-crystalline phases of granite is found to be temperature dependent. The ΔS, ΔH, ΔG of Np(Ⅳ)/ Np(Ⅴ)sorption on granite and magnetically separated granite were calculated by least square method linear fitting.

       

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