Concentration and Fractionation of Rare Earth Elements in Soils Surrounding Rare Earth Ore Area
-
摘要: 研究不同类型稀土矿区周边土壤中稀土元素（REE）的含量与形态特征，可为矿区周边污染环境治理提供理论支持与科学建议。本文采用欧盟BCR顺序提取法、电感耦合等离子体质谱测定的方法，对内蒙古白云鄂博稀土尾矿区和江西赣南稀土矿区周边6个土壤样品中15种稀土元素进行了含量及形态分析测定。结果表明：矿区周边土壤中稀土元素总量约为264~15955μg/g，明显高于全国土壤背景值（186μg/g），白云鄂博尾矿区周边土壤富集轻稀土元素，稀土元素主要以残渣态富集，占总含量的64.0%~89.4%，生物有效性较低，对环境影响较小；赣南矿区周边土壤富集重稀土元素，稀土元素的主要存在形式是弱酸提取态和可还原态，占总含量的70%以上，易发生迁移转化及对周边环境造成污染。土壤中稀土元素的形态分布与pH值有显著相关性，随着土壤pH值的降低，稀土元素的弱酸提取态含量不断升高，残渣态含量不断降低。Abstract:
BACKGROUNDThe study on content and fractionation characteristics of rare earth elements (REE) in soils around different types of rare earth mining areas can provide theoretical support and scientific advice for the control of the polluted environment around the rare earth mining areas. OBJECTIVESTo reveal the concentration and fractionation characteristics of REE in the soils around different types of rare earth mining areas. METHODSThe content and fractionation of 15 rare earth elements in 6 soil samples from the Bayan Obo rare earth tailings area in Inner Mongolia and the Gannan rare earth mining area in Jiangxi Province were determined by the method of Community Bureau of Reference (BCR) sequential extraction and Inductively Coupled Plasma-Mass Spectrometry. RESULTS∑REE in the soil around the mining area were 264-15955μg/g, significantly higher than the background value (186μg/g) of soils in China. LREE were enriched in the surrounding soils of the Bayan Obo mining area, and REE mainly existed in residual fraction, accounting for 64.0%-89.4% of the total content. HREE were enriched in the soils of the Gannan mining area, the main forms of REE in this area are acid-soluble fraction and reducible fraction, accounting for more than 70% of the total content. REE in the Gannan area were readily transferable and polluted the surrounding environment. CONCLUSIONSThe fractionation characteristics of rare earth elements in soils are strongly correlated with pH value. With the decrease of soil pH value, the content of acid extraction fraction of rare earth elements is increasing and the content of residual fraction is decreasing. -
Key words:
- soil /
- REE /
- fractionation analysis /
- sequential extraction procedure
-
-
表 1 采样点分布情况
Table 1. Information of soil sampling points in collecting areas
样品编号 采样地点 采样点
概况土壤
类型BTS-1 内蒙古白云鄂博稀土尾矿坝70m处 荒地 栗钙土 BTS-2 内蒙古白云鄂博稀土尾矿坝8km处 农田区 栗钙土 BTS-3 内蒙古白云鄂博稀土尾矿坝16km处 农田区 栗钙土 JXS-1 江西赣南龙南黄沙窑 矿区边 砖红壤 JXS-2 江西赣南龙南黄沙矿区 农田区 砖红壤 JXS-3 江西赣南定南岭北蔡阳 农田区 砖红壤 
下载: 导出CSV
表 2 BCR顺序提取法
Table 2. BCR sequential extraction procedure
步骤 形态 提取方法 1 弱酸提取态 40mL 0.11mol/L乙酸提取，22±5℃，振荡提取16h，离心分离 2 可还原态 40mL 0.5mol/L盐酸羟胺提取，22±5℃，振荡提取16h，离心分离 3 可氧化态 10mL过氧化氢，室温消化1h；82±5℃消化，体积减至约3mL；再加入10mL过氧化氢，82±5℃消化，体积减至约1mL；加入50mL 1.0mol/L乙酸铵，22±5℃，振荡提取16h，离心分离 4 残渣态 封闭酸溶
下载: 导出CSV
表 3 ICP-MS工作参数
Table 3. Working parameters of ICP-MS
工作参数 设定条件 ICP功率 1300W 冷却气流量 13.0L/min 辅助气流量 0.75L/min 雾化气流量 1.0L/min 采样锥孔径 1.0mm 截取锥孔径 0.7mm 测量方式 跳峰 扫描次数 50 停留时间/通道 10ms 每个质量通道数 3 总采集时间 48s
下载: 导出CSV
表 4 土壤中稀土元素含量及特征参数
Table 4. Concentrations and characteristic parameters of REE in soils
元素 含量(μg/g) 全国土壤
背景值
(μg/g)BTS-1 BTS-2 BTS-3 JXS-1 JXS-2 JXS-3 Y 89.1 26.2 27.9 413 314 167 22.9 La 3931 447 49.7 94.6 93.7 262 39.7 Ce 7696 884 105 142 143 315 68.4 Pr 836 96.8 11.4 25.9 27.4 57.8 7.17 Nd 2968 339 42.2 106 112 217 26.4 Sm 240 29.6 7.33 36.6 40.9 40.6 5.22 Eu 42.5 5.32 1.32 2.53 2.61 3.12 1.03 Gd 69.4 9.05 5.55 48.3 47.6 32.0 4.60 Tb 7.42 1.19 0.87 9.43 8.83 4.90 0.63 Dy 44.2 7.83 5.31 61.3 53.8 29.3 4.13 Ho 3.95 1.05 1.04 12.1 10.3 5.27 0.87 Er 22.2 4.23 3.07 35.3 28.5 15.1 2.54 Tm 0.72 0.35 0.41 5.14 3.85 1.94 0.37 Yb 4.21 2.27 2.76 33.6 23.7 12.2 2.44 Lu 0.55 0.35 0.43 5.02 3.41 1.78 0.36 ∑REE 15955 1854 264 1030 914 1165 186 LREE 15713 1801 216 407 420 895 147 HREE 241 52.5 47.3 623 494 269 38.8 $\frac{{{\rm{LREE}}}}{{{\rm{HREE}}}} $ 65.0 34.3 4.58 0.65 0.85 3.32 3.81 δEu 0.77 0.77 0.61 0.18 0.18 0.26 0.63 δCe 0.98 0.98 1.02 0.68 0.67 0.59 0.91 注：REE为不含Pm、Sc的15个稀土元素的总含量, LREE为轻稀土元素La~Eu，HREE为重稀土元素Gd~Lu+Y。全国土壤背景值参考《中国土壤元素背景值》[26]。
下载: 导出CSV
表 5 土壤理化性质和形态测定结果
Table 5. Results of soil physicochemical properties and REE fractions
样品编号 pH 黏土矿物
含量(%)弱酸提取态稀土
含量百分比(%)可还原态稀土
含量百分比(%)可氧化态稀土
含量百分比(%)残渣态稀土
含量百分比(%)稀土总量
(μg/g)BTS-1 8.32 18.7 1.11 7.20 2.34 89.4 15437 BTS-2 8.28 7.5 0.95 11.8 16.0 71.3 1580 BTS-3 8.25 15.2 0.63 23.5 11.9 64.0 267 JXS-1 5.18 32.8 16.6 62.4 8.93 12.0 988 JXS-2 5.72 39.6 9.12 70.1 12.0 8.78 842 JXS-3 4.51 24.2 21.0 62.4 9.67 6.90 1087 注：稀土元素各相态百分比为该相态稀土含量/稀土总量×100%。
下载: 导出CSV
-
[1] 樊连杰, 裴建国, 赵良杰, 等.利用ICP-MS研究桂林寨底地下河系统中碳酸盐岩稀土元素特征及其形成环境[J].岩矿测试, 2016, 35(3):251-258. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2016.03.006
Fan L J, Pei J G, Zhao L J, et.al.Rare earth element composition of carbonate rocks afforded by ICP-MS and formation environment of the Zhaidi underground river in Guilin[J].Rock and Mineral Analysis, 2016, 35(3):251-258. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2016.03.006
[2] 刘菁钧, 赖子娟, 刘颖.黄河甘宁蒙段表层沉积物中稀土元素形态和分馏作用研究[J].光谱学与光谱分析, 2013, 33(3):798-803. doi: 10.3964/j.issn.1000-0593(2013)03-0798-06
Liu J J, Lai Z J, Liu Y.Study on speciation and fractionation of rare earth elements in surface sediments in Gansu, Ningxia and Inner Mongolia Sections of Yellow River[J].Spectroscopy and Spectral Anaylsis, 2013, 33(3):798-803. doi: 10.3964/j.issn.1000-0593(2013)03-0798-06
[3] 刘丽君, 赵芝, 付小方, 等.四川稀土矿尾砂的稀土元素和微量元素地球化学特征及开发利用意义[J].岩矿测试, 2013, 32(5):817-824. doi: 10.3969/j.issn.0254-5357.2013.05.023 http://www.cnki.com.cn/Article/CJFDTotal-YKCS201305025.htm
Liu L J, Zhao Z, Fu X F, et al.Geochemistry of rare earth and trace element in rare earth tailings from Sichuan Province and the significance of the exploitation and utilization[J].Rock and Mineral Analysis, 2013, 32(5):817-824. doi: 10.3969/j.issn.0254-5357.2013.05.023 http://www.cnki.com.cn/Article/CJFDTotal-YKCS201305025.htm
[4] Zhang Y, Gao X L, Arthur C, et al.Rare earth elements in intertidal sediments of Bohai Bay, China:Concentration, fractionation and the influence of sediment texture[J].Ecotoxicology and Environmental Safety, 2014, 105:72-79. doi: 10.1016/j.ecoenv.2014.04.006
[5] 程建忠, 车丽萍.中国稀土资源开采现状及发展趋势[J].稀土, 2010, 31(2):65-69. doi: 10.3969/j.issn.1004-0277.2010.02.015
Cheng J Z, Che L P.Current mining situation and potential development of rare earth in China[J].Chinese Rare Earths, 2010, 31(2):65-69. doi: 10.3969/j.issn.1004-0277.2010.02.015
[6] Mittermüller M, Saatz J, Daus B.A sequential extraction procedure to evaluate the mobilization behavior of rare earth elements in soils and tailings materials[J].Chemosphere, 2016, 147:155-162. doi: 10.1016/j.chemosphere.2015.12.101
[7] Gabarrón M, Faz A, Martínez-Martínez S, et al.Assess-ment of metals behaviour in industrial soil using sequential extraction, multivariable analysis and a geostatistical approach[J].Journal of Geochemical Exploration, 2017, 172:174-183. doi: 10.1016/j.gexplo.2016.10.015
[8] Nemati K, Bakar N K A, Abas M R, et al.Speciation of heavy metals by modified BCR sequential extraction procedure in different depths of sediments from Sungai Buloh, Selangor, Malaysia[J].Journal of Hazardous Materials, 2011, 192:402-410. http://cn.bing.com/academic/profile?id=832b507091fcd23b6c9eff3e942fd905&encoded=0&v=paper_preview&mkt=zh-cn
[9] Rao C R M, Sahuquillo A, Lopez-Sanchez J F.Compari-son of single and sequential extraction procedures for the study of rare earth elements remobilisation in different types of soils[J].Analytica Chimica Acta, 2010, 662(2):128-136. doi: 10.1016/j.aca.2010.01.006
[10] 王亚平, 黄毅, 王苏明, 等.土壤和沉积物中元素的化学形态及其顺序提取法[J].地质通报, 2005, 24(8):728-734. doi: 10.3969/j.issn.1671-2552.2005.08.009
Wang Y P, Huang Y, Wang S M, et al.Chemical speciation of elements in sediments and soils and their sequential extraction process[J].Geological Bulletin of China, 2005, 24(8):728-734. doi: 10.3969/j.issn.1671-2552.2005.08.009
[11] Gleyzes C, Tellier S, Astruc M.Fractionation studies of trace elements in contaminated soils and sediments: A review of sequential extraction procedures[J].2002, 21(6): 451-467.
http://cn.bing.com/academic/profile?id=e8857058b6da1459db6129d0176f956d&encoded=0&v=paper_preview&mkt=zh-cn [12] 王立军, 王玉琦, 章申, 等.中国不同类型土壤中稀土元素的形态分布特征[J].中国稀土学报, 1997, 15(1):65-71. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=zgxtxb199701014
Wang L J, Wang Y Q, Zhang S, et al.Speciation of rare earth elements in different types of soils in China[J].Journal of the Chinese Rare Earth Society, 1997, 15(1):65-71. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=zgxtxb199701014
[13] Šmuc N R, Dolenec T, Serafimovski T, et al.Geochemi-cal characteristics of rare earth elements (REEs) in the paddy soil and rice (Oryza sativa L.) system of Koc ǎni Field, Republic of Macedonia[J].Geoderma, 2012, 183-184:1-11. doi: 10.1016/j.geoderma.2012.03.009
[14] 郭鹏然, 贾晓宇, 段太成, 等.土壤中稀土元素的形态分析[J].分析化学, 2008, 36(11):1483-1487. doi: 10.3321/j.issn:0253-3820.2008.11.006
Guo P R, Jia X Y, Duan T C, et al.Speciation analysis of rare earth elements in soil[J].Chinese Journal of Analytical Chemistry, 2008, 36(11):1483-1487. doi: 10.3321/j.issn:0253-3820.2008.11.006
[15] 翟海, 杨永岗, 胡霭堂.对我国二十种土壤中稀土元素形态分组的研究[J].稀土, 2001, 22(3):1-5. doi: 10.3969/j.issn.1004-0277.2001.03.001
Zhai H, Yang Y G, Hu A T.Study of rare earths fractionation in 20 types of soils of China[J].Chinese Rare Earths, 2001, 22(3):1-5. doi: 10.3969/j.issn.1004-0277.2001.03.001
[16] 郭伟, 付瑞英, 赵仁鑫, 等.内蒙古包头白云鄂博矿区及尾矿区周围土壤稀土污染现状和分布特征[J].环境科学, 2013, 34(5):1895-1900. http://d.old.wanfangdata.com.cn/Periodical/hjkx201305034
Guo W, Fu R Y, Zhao R X, et al.Distribution characteristics and current situation of soil rare earth contamination in the Bayan Obo Mining Area and Baotou tailing reservoir in Inner Mongolia[J].Environmental Science, 2013, 34(5):1895-1900. http://d.old.wanfangdata.com.cn/Periodical/hjkx201305034
[17] 金姝兰, 黄益宗, 胡莹, 等.江西典型稀土矿区土壤和农作物中稀土元素含量及其健康风险评价[J].环境科学学报, 2014, 34(12):3084-3093. http://d.old.wanfangdata.com.cn/Periodical/hjkxxb201412018
Jin S L, Huang Y Z, Hu Y, et al.Rare earth elements content and health risk assessment of soil and crops in typical rare earth mine area in Jiangxi Province[J].Acta Scientiae Circumstantiae, 2014, 34(12):3084-3093. http://d.old.wanfangdata.com.cn/Periodical/hjkxxb201412018
[18] 刘斯文, 黄园英, 韩子金, 等.离子型稀土矿山土壤生态修复研究与实践[J].环境工程, 2015, 33(11):160-165. http://d.old.wanfangdata.com.cn/Periodical/hjgc201511034
Liu S W, Huang Y Y, Han Z J, et al.Practices of the soil ecological remediation in ion-absorbed rare earth mine[J].Environmental Engineering, 2015, 33(11):160-165. http://d.old.wanfangdata.com.cn/Periodical/hjgc201511034
[19] 吴石头, 王亚平, 孙德忠, 等.电感耦合等离子体发射光谱法测定稀土矿石中15种稀土元素——四种前处理方法的比较[J].岩矿测试, 2014, 33(1):12-19. doi: 10.3969/j.issn.0254-5357.2014.01.003 http://www.ykcs.ac.cn/article/id/2c32f0ea-719c-486f-aa0d-027493aec6da
Wu S T, Wang Y P, Sun D Z, et al.Determination of 15 rare earth elements in rare earth ores by inductively coupled plasma-atomic emission spectrometry:A comparison of four different pretreatment[J].Rock and Mineral Analysis, 2014, 33(1):12-19. doi: 10.3969/j.issn.0254-5357.2014.01.003 http://www.ykcs.ac.cn/article/id/2c32f0ea-719c-486f-aa0d-027493aec6da
[20] 贾双琳, 赵平, 杨刚, 等.混合酸敞开或高压密闭溶样-ICPMS测定地质样品中稀土元素[J].岩矿测试, 2014, 33(2):186-191. doi: 10.3969/j.issn.0254-5357.2014.02.005 http://www.cnki.com.cn/Article/CJFDTotal-YKCS201402006.htm
Jia S L, Zhao P, Yang G, et al.Quick Determination of rare earth elements in geological samples with open acid digestion or high-pressure closed digestion by inductively coupled plasma-mass spectrometry[J].Rock and Mineral Analysis, 2014, 33(2):186-191. doi: 10.3969/j.issn.0254-5357.2014.02.005 http://www.cnki.com.cn/Article/CJFDTotal-YKCS201402006.htm
[21] 孙德忠, 何红蓼.封闭酸溶-等离子体质谱法分析超细粒度地质样品中42个元素[J].岩矿测试, 2007, 26(1):21-25. doi: 10.3969/j.issn.0254-5357.2007.01.006 http://www.ykcs.ac.cn/article/id/ykcs_20070112
Sun D Z, He H L. Determination of 42 elements in ultra-fine geological samples by inductively coupled plasma-mass spectrometry with pressurized acid digestion[J].Rock and Mineral Analysis, 2007, 26(1):21-25. doi: 10.3969/j.issn.0254-5357.2007.01.006 http://www.ykcs.ac.cn/article/id/ykcs_20070112
[22] 吴磊, 刘义博, 王家松, 等.高压密闭消解-电感耦合等离子体质谱法测定锰矿石中的稀土元素前处理方法研究[J].岩矿测试, 2018, 37(6):637-643. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.201712060189
Wu L, Liu Y B, Wang J S, et al.Sample treatment methods for determination of rare earth elements in manganese ore by high-pressure closed digestion-inductively coupled plasma-mass spectrometry[J].Rock and Mineral Analysis, 2018, 37(6):637-643. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.201712060189
[23] 刘晔, 第五春荣, 柳小明, 等.密闭高温高压溶样ICP-MS测定56种国家地质标准物质中的36种痕量元素——对部分元素参考值修正和定值的探讨[J].岩矿测试, 2013, 32(2):221-228. doi: 10.3969/j.issn.0254-5357.2013.02.006 http://www.ykcs.ac.cn/article/id/749f22d1-0b51-470a-b562-8c13659615b9
Liu Y, DiWu C R, Liu X M, et al.Determination of 36 trace elements in 56 chinese national standard reference materials by ICP-MS with pressurized acid-digestion[J].Rock and Mineral Analysis, 2013, 32(2):221-228. doi: 10.3969/j.issn.0254-5357.2013.02.006 http://www.ykcs.ac.cn/article/id/749f22d1-0b51-470a-b562-8c13659615b9
[24] Matong J M, Nyaba L, Nomngongo P N.Fractionation of trace elements in agricultural soils using ultrasound assisted sequential extraction prior to inductively coupled plasma mass spectrometric determination[J].Chemosphere, 2016, 154:249-257. doi: 10.1016/j.chemosphere.2016.03.123
[25] Sutherland R A.BCR®-701:A review of 10-years of sequential extraction analyses[J].Analytica Chimica Acta, 2010, 680(1-2):10-20. doi: 10.1016/j.aca.2010.09.016
[26] 中国环境监测总站.中国土壤元素背景值[M].北京:中国环境科学出版社, 1990.
China National Environmental Monitoring Centre.Background Value of Soil Elements in China[M].Beijing:China Enviromental Science Press, 1990.
[27] 郑春丽, 张志彬, 刘启容, 等.稀土尾矿库区土壤中稀土形态分布规律研究[J].稀土, 2016, 37(2):73-80. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=xitu201602012
Zheng C L, Zhang Z B, Liu Q R, et al.Rare earth distribution in the soil around rare earth tailings[J].Chinese Rare Earths, 2016, 37(2):73-80. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=xitu201602012
[28] 丁友超, 刘国庆, 王晓蓉.稀土元素在土壤中的环境化学行为及其生物效应[J].农业环境科学学报, 2002, 21(6):567-569. doi: 10.3321/j.issn:1672-2043.2002.06.027
Ding Y C, Liu G Q, Wang X R.Environmental chemical behaviors of rare earth elements in soil and their biological effects[J].Agro-Environmental Protection, 2002, 21(6):567-569. doi: 10.3321/j.issn:1672-2043.2002.06.027
[29] 吴澄宇, 黄典豪, 郭中勋.江西龙南地区花岗岩风化壳中稀土元素的地球化学研究[J].地质学报, 1989, 63(4):349-362. http://www.cnki.com.cn/Article/CJFDTOTAL-DZXE198904005.htm
Wu C Y, Huang D H, Guo Z X.REE geochemistry in the weathering process of granites in Longnan county, Jiangxi Province[J].Acta Geologica Sinica, 1989, 63(4):349-362. http://www.cnki.com.cn/Article/CJFDTOTAL-DZXE198904005.htm
[30] 高效江, 王玉琦, 章申, 等.赣南亚热带地球化学景观中稀土元素的分布和分异特征[J].应用基础与工程科学学报, 1997, 5(1):30-38. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=QK199700633303
Gao X J, Wang Y Q, Zhang S, et al.The distribution and differentiation of rare earth elements in the geochemical landscape in a sub-tropical zone, Southern Jiangxi[J].Journal of Basic Science and Engineering, 1997, 5(1):30-38. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=QK199700633303
[31] 曹心德, 陈莹, 王晓蓉.环境条件变化对土壤中稀土元素溶解释放的影响[J].中国环境科学, 2000, 20(6):486-490. doi: 10.3321/j.issn:1000-6923.2000.06.002
Cao X D, Chen Y, Wang X R.The effects of change of environmental conditions on the release ond species transformation of rare earth elements (REEs) in soil[J].China Environmental Science, 2000, 20(6):486-490. doi: 10.3321/j.issn:1000-6923.2000.06.002
[32] 罗才贵, 罗仙平, 苏佳, 等.离子型稀土矿山环境问题及其治理方法[J].金属矿山, 2014, 43(6):91-96. http://d.old.wanfangdata.com.cn/Periodical/jsks201406018
Luo C G, Luo X P, Su J, et al.Environmental problems and treatment measures in ionic-type rare earth mine[J].Metal Mine, 2014, 43(6):91-96. http://d.old.wanfangdata.com.cn/Periodical/jsks201406018
-
图(2)
表(5)
计量
- 文章访问数: 2210
- PDF下载数: 144
- 施引文献: 0