Application of Eichrom Sr Resin to the Separation and Enrichment of Lead and Strontium in Uranium Ore Concentrates
-
摘要: 铀矿浓缩物的溯源研究在核法证学中具有重要地位,通过测量其中的铅、锶同位素丰度比能为溯源提供部分地理指示信息。对铀矿浓缩物中铅、锶同位素的精准测量主要受制于大量铀与微量铅、锶的分离、富集。本文利用Eichrom Sr树脂对铅、锶的特效吸附性,通过正交试验对影响铅、锶回收率的主要因素(淋洗酸度、流速、体积)进行了优化,确定了最佳淋洗条件;进而利用UTEVA树脂对铀的特效吸附性,与Eichrom Sr树脂联用,实现了铀矿浓缩物中大量铀与微量铅、锶的分离,有效降低了因铅、锶洗脱液中铀含量过高而引起的基体效应。实验结果表明:铅、锶回收率均>90%,铅、锶洗脱液中的铀含量低于500ng,优于文献报道值(48.8μg)。利用该方法对实际铀矿浓缩物样品进行测量,分析结果显示铅、锶同位素丰度比可以作为铀矿浓缩物的地理溯源判据,为今后建立铀矿浓缩物中铅、锶同位素数据库提供技术支持。
-
关键词:
- Eichrom Sr树脂 /
- 铀矿浓缩物 /
- 铅 /
- 锶 /
- 基体效应
Abstract:BACKGROUNDThe traceability study of uranium ore concentrates plays an important role in nuclear forensics. By measuring the abundance ratios of lead and stontium isotopes, the results can provide some geographical indication information for traceability. OBJECTIVESTo achieve the separation of large amounts of uranium from trace lead and strontium and to establish a set of methods for separating lead and strontium from uranium ore concentrate, while providing technical support for the establishment of a lead and strontium isotopes database in uranium ore concentrate. METHODSBased on Eichrom Sr resin's adsorption properties for lead and strontium, the main factors (acidity, current velocity and volume) affecting the recovery of lead and strontium were optimized by orthogonal testing. The best washing conditions have been determined. The combination of UTEVA resin and Eichrom Sr resin can effectively reduce uranium content in lead and strontium eluent and thus reduce the matrix effect. RESULTSThe results show that the recovery of lead and strontium is more than 90% and the uranium content in lead and strontium eluent is less than 500ng, an improvement on the reported value of 48.8μg. CONCLUSIONSThe actual uranium ore concentrate samples were measured by this method. The results show that the lead and strontium isotope abundance ratios can be used as the geographical traceability criteria for uranium ore concentrates, providing a technique for the future establishment of lead and strontium isotope databases for uranium ore concentrates. -
Key words:
- Eichrom Sr resin /
- uranium ore concentrates /
- lead /
- strontium /
- matrix effect
-
表 1 Eichrom Sr树脂柱上Pb、Sr分配比
Table 1. Distribution ratio of Pb and Sr on Eichrom Sr resin
实验序号 硝酸酸度(mol/L) Pb/K Sr/K 1 1 1063 83 2 2 1277 96 3 3 1253 96 4 4 889 99 5 5 726 100 6 6 578 100 注:K=树脂相含量/液相含量。 表 2 Pb、Sr正交试验
Table 2. Orthogonal tests of Pb and Sr
水平 因素A 因素B 因素C Sr淋洗酸度
(硝酸,mol/L)Pb淋洗酸度
(盐酸,moL/L)淋洗流速
(mL/min)淋洗体积
(mL)1 0.01 6 1 2 2 0.05 7 0.5 3 3 0.1 8 0.2 4 表 3 不同酸度、流速和体积条件下Sr的正交试验结果
Table 3. Orthogonal test results of Sr in various acidity, current velocity and volume
实验序号 影响因素 Sr回收率(%) A
(mol/L)B
(mL/min)C
(mL)组1 组2 组3 平均值 1 0.01 1 2 68.1 72.4 72.2 70.9 2 0.01 0.5 3 79.9 78.5 82.1 80.2 3 0.01 0.2 4 92.9 94.7 92.1 93.2 4 0.05 1 3 75.1 78.8 76.2 76.7 5 0.05 0.5 4 86.5 88.8 86.2 87.2 6 0.05 0.2 2 69.5 70.8 69.5 69.9 7 0.1 1 4 83.2 82.3 79.8 81.8 8 0.1 0.5 2 65.7 67.6 63.8 65.7 9 0.1 0.2 3 89.8 86.9 88.5 88.4 T1 732.9 688.1 619.6 T2 701.4 699.1 735.8 T3 707.6 754.7 786.5 x1 81.4 76.5 68.8 x2 77.9 77.7 81.8 x3 78.6 83.9 87.4 R 3.5 7.4 18.5 注:Ti代表各因素相同水平实验结果之和,同一因素下,T值越大表明该水平对结果影响的贡献越大;R代表极差,即各水平最大与最小平均值之差,其大小反映了各个因素对结果的影响,R值越大,表明该因素对结果的影响越大;xi代表实验结果的平均值。 表 4 不同酸度、流速和体积条件下Pb的正交试验结果
Table 4. Orthogonal test results of Pb in various acidity, current velocity and volume
实验序号 影响因素 Pb回收率(%) A
(mol/L)B
(mL/min)C
(mL)组1 组2 组3 平均值 1 6 1 2 58.2 61.5 58.9 59.5 2 6 0.5 3 63.6 66.1 64.5 64.7 3 6 0.2 4 71.7 69.1 72.9 71.2 4 7 1 3 75.3 76 74.5 75.3 5 7 0.5 4 80.3 81.4 79.3 80.3 6 7 0.2 2 76.6 78.1 77.7 77.5 7 8 1 4 80.1 82.8 81.6 81.5 8 8 0.5 2 81.4 82.6 82.7 82.2 9 8 0.2 3 93.5 92.8 92.4 92.9 T1 586.5 648.9 657.7 T2 699.2 681.9 698.7 T3 769.9 724.8 699.2 x1 65.2 72.1 73.1 x2 77.7 75.8 77.6 x3 85.5 80.5 77.7 R 20.4 8.4 4.6 表 5 实际铀矿浓缩物样品中Pb、Sr同位素丰度比
Table 5. Isotope abundance ratio of Pb and Sr in actual uranium ore concentrate sample
样品编号 208Pb/204Pb 207Pb/204Pb 206Pb/204Pb 87Sr/86Sr X1 39.16 17.09 46.53 0.71683 X2 39.18 17.02 46.84 0.71685 X3 39.09 16.92 46.34 0.71683 X4 39.92 17.06 46.87 0.71693 平均值 39.34 17.02 46.64 0.71686 RSD(%) 0.3 0.4 0.6 0.007 Y1 38.207 15.596 18.019 0.71892 Y2 38.219 15.613 17.968 0.71903 Y3 38.181 15.628 18.022 0.71888 Y4 38.247 15.624 18.011 0.71890 平均值 38.214 15.615 18.005 0.71893 RSD(%) 0.07 0.09 0.14 0.010 -
[1] 郭晓兵.奥巴马政府核安全外交的特点及未来走势[J].现代国际关系, 2016(3):9-13. http://d.old.wanfangdata.com.cn/Periodical/xdgjgx201603003
Guo X B.Characteristics and prospective tendency of Obama administration's nuclear security diplomacy[J].Modern International Relations, 2016(3):9-13. http://d.old.wanfangdata.com.cn/Periodical/xdgjgx201603003
[2] Keegan E, Kristo M J, Colella M, et al.Nuclear forensic analysis of an unknown uranium ore concentrate sample seized in a criminal investigation in Australia[J].Forensic Science International, 2014, 240(3):111-121. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=7dfe7ae715a520bae8659d9348e5a98f
[3] 孙境蔚, 于瑞莲, 胡恭任, 等.应用铅锶同位素示踪研究泉州某林地垂直剖面土壤中重金属污染及来源解析[J].环境科学, 2017, 38(4):1566-1575. http://d.old.wanfangdata.com.cn/Periodical/hjkx201704034
Sun J W, Yu R L, Hu G R, et al. Assessment of heavy metal pollution and tracing sources by Pb & Sr isotope in the soil profile of woodland in Quanzhou[J].Environmental Science, 2017, 38(4):1566-1575. http://d.old.wanfangdata.com.cn/Periodical/hjkx201704034
[4] 王华, 石振家, 刘萱, 等.大连典型滩涂养殖区菲律宾蛤仔体内Pb含量及溯源[J].海洋环境科学, 2014, 33(1):78-82. http://d.old.wanfangdata.com.cn/Periodical/hyhjkx201401014
Wang H, Shi Z J, Liu X, et al.Concentration and pollution sources of lead in Ruditapes Philippinarum in Dalian typical coastculture areas[J].Marine Environmental Science, 2014, 33(1):78-82. http://d.old.wanfangdata.com.cn/Periodical/hyhjkx201401014
[5] 孙慧, 毕如田, 郭颖, 等.广东省土壤重金属溯源及污染源解析[J].环境科学学报, 2018, 38(2):704-714. http://d.old.wanfangdata.com.cn/Periodical/hjkxxb201802031
Sun H, Bi R T, Guo Y, et al.Source apportionment analysis of trace metal contamination in soils of Guangdong Province, China[J].Acta Scientiae Circumstantia, 2018, 38(2):704-714. http://d.old.wanfangdata.com.cn/Periodical/hjkxxb201802031
[6] 张棕巍, 胡恭任, 于瑞莲, 等.泉州市大气降尘中金属元素污染特征及来源解析[J].环境科学, 2016, 37(8):2881-2888. http://d.old.wanfangdata.com.cn/Periodical/hjkx201608008
Zhang Z W, Hu G R, Yu R L, et al.Characteristics and source apportionment of metals in the dustfall of Quanzhou city[J].Environmental Science, 2016, 37(8):2881-2888. http://d.old.wanfangdata.com.cn/Periodical/hjkx201608008
[7] 胡恭任, 于瑞莲, 郑志敏.铅稳定同位素在沉积物重金属污染溯源中的应用[J].环境科学学报, 2013, 33(5):1326-1331. http://d.old.wanfangdata.com.cn/Periodical/hjkxxb201305017
Hu G R, Yu R L, Zheng Z M.Application of stable lead isotopes in tracing heavy-metal pollution sources in the sediments[J].Acta Scientiae Circumstantia, 2013, 33(5):1326-1331. http://d.old.wanfangdata.com.cn/Periodical/hjkxxb201305017
[8] 李雪泓, 赵强, 王茜, 等.210Pb分析方法在成都大气气溶胶中的应用[J].四川环境, 2017, 36(4):142-146. http://d.old.wanfangdata.com.cn/Periodical/schj201704026
Li X H, Zhao Q, Wang Q, et al.Application of 210Pb analysis method in aerosol determination of Chengdu[J].Sichuan Environment, 2017, 36(4):142-146. http://d.old.wanfangdata.com.cn/Periodical/schj201704026
[9] 王朝辉, 张亚婷, 闵伟红, 等.水稻品种对大米产地溯源判别正确性的影响[J].吉林农业大学学报, 2017, 39(1):113-119. http://d.old.wanfangdata.com.cn/Periodical/jlnydxxb201701019
Wang C H, Zhang Y T, Min W H, et al.Effects of rice varieties on accuracy of rice origin discrimination[J].Journal of Jilin Agricultural University, 2017, 39(1):113-119. http://d.old.wanfangdata.com.cn/Periodical/jlnydxxb201701019
[10] 李向辉, 陈云堂, 吕晓华, 等.利用土壤Sr-Pb同位素差异性判别山药原产地研究[J].核农学报, 2018, 32(3):515-522. http://d.old.wanfangdata.com.cn/Periodical/hnxb201803012
Li X H, Chen Y T, Lü X H, et al.Application of Sr-Pb isotopic difference of soils in Yam origin identification[J].Journal of Nuclear Agricultural Sciences, 2018, 32(3):515-522. http://d.old.wanfangdata.com.cn/Periodical/hnxb201803012
[11] 王利超, 胡文瑄, 王小林, 等.白云岩化过程中锶含量变化及锶同位素分馏特征与意义[J].石油与天然气地质, 2016, 37(4):464-472. http://d.old.wanfangdata.com.cn/Periodical/syytrqdz201604002
Wang L C, Hu W X, Wang X L, et al.Variation of Sr content and 87Sr/86Sr isotope fraction ation during dolomitization and their implications[J].Oil & Gas Geology, 2016, 37(4):464-472. http://d.old.wanfangdata.com.cn/Periodical/syytrqdz201604002
[12] 尚海军, 陈维民, 张耀选, 等.新疆阿尔泰克因布拉克铜锌矿区闪长岩锆石U-Pb年龄及地质意义[J].西北地质, 2017, 50(4):59-69. doi: 10.3969/j.issn.1009-6248.2017.04.009
Shang H J, Chen W M, Zhang Y X, et al.Zircon U-Pb dating of diorite from the Keyinbulake Cu-Zn deposit in Altay, Xinjiang and its geological implications[J].Northwest Geology, 2017, 50(4):59-69. doi: 10.3969/j.issn.1009-6248.2017.04.009
[13] 曹亮, 段其发, 张权绪, 等.扬子陆块北缘冰洞山铅锌矿床闪锌矿Rb-Sr定年及其地质意义[J].矿物岩石地球化学通报, 2016, 35(6):1280-1289. doi: 10.3969/j.issn.1007-2802.2016.06.018
Cao L, Duan Q F, Zhang Q X, et al.Rb-Sr dating of sphalerites from the Bingdongshan Pb-Zn deposit in the northern margin of the Yangtze Block and its geological significance[J].Bulletin of Mineralogy, Petrology and Geochemistry, 2016, 35(6):1280-1289. doi: 10.3969/j.issn.1007-2802.2016.06.018
[14] Balboni E, Jones N, Spano T, et al.Chemical and Sr iso-topic characterization of North America uranium ores:Nuclear forensic applications[J].Applied Geochemistry, 2016, 74:24-32. doi: 10.1016/j.apgeochem.2016.08.016
[15] Varga Z, Wallenius M, Mayer K, et al.Application of lea d and strontium isotope ratio measurements for the origin assessment of uranium ore concentrates[J].Analytical Chemistry, 2009, 81(20):8327-8334. doi: 10.1021/ac901100e
[16] Švedkauskaite-LeGore J, Mayer K, Millet S, et al.Investi-gation of the isotopic composition of lead and of trace elements concentrations in natural uranium materials as a signature in nuclear forensics[J].Radiochimica Acta, 2007, 95(10):601-605. https://core.ac.uk/display/38610586
[17] Deniel C, Pin C.Single-stage method for the simultane-ous isolation of lead and strontium from silicate samples for isotopic measurements[J].Analytica Chimica Acta, 2001, 426(1):95-103. doi: 10.1016/S0003-2670(00)01185-5
[18] 王强, 薛晓锋, 赵静.质谱检测技术在蜂蜜溯源分析中的应用[J].中国农业科技导报, 2013, 15(4):42-47. doi: 10.3969/j.issn.1008-0864.2013.04.08
Wang Q, Xue X F, Zhao J.Application of mass spectrometry detection technology in Honey traceability analysis[J].Journal of Agricultural Science and Technology, 2013, 15(4):42-47. doi: 10.3969/j.issn.1008-0864.2013.04.08