The Content and Distribution Characteristics of Heavy Metals in Root Soils in the Jiajika Lithium Resource Area, Western Sichuan Province
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摘要: 锂能源金属的战略地位不断提高，与锂矿床及锂金属相关的研究也在不断跟进，锂矿区土壤重金属污染近年来持续受到关注，其含量分布情况值得深入研究。本文对亚洲最大的锂矿区——川西甲基卡根系土壤环境进行重金属含量监测，调查和评价锂矿区土壤重金属含量水平及其安全性。2016-2018年于川西甲基卡锂资源富集区采集根系土壤样品68件，采用电感耦合等离子体质谱法（ICP-MS）测定根系土壤Cd、As、Pb、Cr、Cu、Ni、Zn含量。测试结果表明，甲基卡矿区根系土壤Cd、As、Pb、Cr、Cu、Ni、Zn含量平均值分别为0.13、15.31、25.47、60.57、16.12、23.59、66.83mg/kg，与2018年8月最新颁布的农用地土壤标准对比，无一超标，均低于风险筛选值及管制值。常见矿床的尾矿库区土壤一般存在严重的重金属污染，而甲基卡尾矿库土壤重金属含量均低于环境标准限值，且矿业活动停止的三年期间尾矿库区根系土壤中Cd、As、Cr含量明显呈逐年下降趋势。本研究认为，选矿厂房及尾矿库周边根系土壤重金属由于人为源的存在有一定的富集现象，但不构成危害，废弃物对环境污染小。要点
(1) 调查了亚洲最大的锂辉石矿区三年间根系土壤重金属含量水平及时空分布特征。
(2) 矿区根系土壤重金属含量水平均低于最新发布的环境限值，处于安全范围。
(3) 选矿厂房和尾矿库由于人为源的影响存在轻微的重金属富集现象，但远低于环境限值。
HIGHLIGHTS(1) The temporal and spatial distribution characteristics of heavy metal content in root soils in the largest spodumene mine in Asia were investigated.
(2) The level of heavy metal in the root soils of the mining area was lower than the newly released environmental limit and was in a safe range.
(3) The beneficiation area and tailings pond had slight heavy metal enrichment due to the influence of anthropogenic sources, but far below the environmental limit.
Abstract:BACKGROUNDWhen inductively coupled plasma-mass spectrometry (ICP-MS) is used to determine the rare earth elements (REE) in the barite-associated light rare earth ores, Ba and light rare earth elements La, Ce, Pr, Nd, Sm, cause severe mass spectral overlap interference to the medium and heavy rare earths. Therefore, under the condition that complete digestion of oress, if the appropriate pretreatment method can be selected to achieve effective separation of the target elements from the matrix, it will be beneficial to reduce mass spectrum interferences.OBJECTIVES To reduce the mass spectrum interferences by establishing a simple and effective pretreatment method for separation of rare earth elements from barium and other coexisting elements in barite-associated rare earth ores.METHODSThe barite-associated rare earth ores samples were fused with sodium peroxide and sodium carbonate. After dissolution of the fusion cake, the target REE and the undesired barium were precipitated in triethanolamine solution, but some matrix elements like Si, Fe, Mg, and Al in samples, and most fusion agents, were separated by filtration. The target REE were secondly precipitated in ammonium hydroxide after dissolution of the precipitates by acid, so that Ba, Sr and Ca could be separated from REE. The separation exceeds 96%, so the mass spectrum interferences caused by barium polyatomic ions were effectively reduced. In addition, the interference correction coefficients by measuring the interference concentration at m/z 138-175 of the high concentration lighter rare earths standard single element solution were adopted to account for the oxide and hydroxide overlap problem for the determination of middle and heavier rare earth elements.RESULTSThe validity of the method was evaluated by analyses of rare earth ores certified reference materials and the results were in good agreement with certified values (|RE| < 10%). For the actual sample analysis of the barite-associated rare earth ores, the relative standard deviations (n=12) were from 0.5% to 4.6%, which proved that the method can be used to analyze rare earth elements in high-Ba ores.CONCLUSIONSThe results demonstrate that this method is both practical and effective for rare earth elements analysis in barite-associated rare earth ores.
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致谢: 全部样品的测试工作由国家地质实验测试中心完成，样品测试过程中得到了屈文俊研究员、马生凤教授级高级工程师及该单位其他工作人员的悉心指导和大力帮助，在此一并致谢。
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图 2 2016—2018年甲基卡矿区根系土壤重金属含量对比
Figure 2. Yearly comparison of heavy metal content of root soils in Jiajika mining area from 2016 to 2018
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图 3 甲基卡矿区根系土壤样品重金属含量与风险筛选值对比
Figure 3. Comparison of heavy metal content of soils in Jiajika mining area and risk screening values
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图 4 甲基卡矿区根系土壤重金属元素地球化学图
Figure 4. Geochemical maps of heavy metal content in the root soils of Jiajika mining area
表 1 甲基卡矿区2016—2018年根系土壤重金属元素含量测试结果
Table 1 Heavy metal content in root soils in Jiajika mining area from 2016 to 2018
采样时间
(年份)采样点位置 样品编号 重金属元素含量(mg/kg) Cd As Pb Cr Cu Ni Zn 2016 融达厂房海子北侧 16JJKS01 0.18 14.75 25.67 66.97 20.49 27.35 89.29 绝情谷海子东侧 16JJKS02 0.13 11.61 29.42 64.59 20.59 24.74 35.84 绝情谷海子东侧 16JJKS04 0.21 8.74 26.50 66.41 17.49 29.32 55.05 石英采矿址裂隙水旁 16JJKS05 0.07 19.42 29.34 62.24 17.45 17.65 45.70 绝情谷海子东侧 16JJKS07 0.24 8.58 25.34 65.06 17.38 28.79 58.94 508脉北侧干流旁 16JJKS09 0.12 14.83 30.14 75.89 18.98 25.37 49.29 36号点上游支流旁 16JJKS10 0.10 13.54 29.41 76.19 17.51 23.46 60.84 308号脉 16JJKS11 0.06 29.37 31.85 58.07 19.24 25.57 42.89 308脉旁海子边 16JJKS12 0.07 8.59 20.77 43.40 10.78 17.60 58.42 X03脉上游支流旁 16JJKS14 0.12 13.00 24.61 60.57 14.59 21.08 46.76 134脉矿区支流旁 16JJKS16 0.14 11.17 23.36 69.15 19.53 28.70 77.04 仁尼措东侧干流旁 16JJKS22 0.21 28.40 20.90 46.40 21.10 23.00 40.00 仁尼措东侧海子边 16JJKS23 0.09 11.20 30.20 56.10 11.50 17.00 41.90 X03脉 16JJKS26 0.21 12.40 25.00 61.40 15.50 23.70 62.30 X03脉 16JJKS27 0.13 14.30 28.20 71.20 18.50 25.20 75.30 X03脉 16JJKS30 0.15 29.20 26.30 64.50 16.70 22.40 63.50 X03脉 16JJKS31 0.17 12.90 28.10 66.00 19.50 22.20 79.50 308东侧草地 16JJKS32 0.16 14.20 28.70 69.60 19.30 18.90 80.70 X05脉 16JJKS33 0.11 4.18 28.00 63.10 19.10 26.70 43.40 X03脉 16JJKS35 0.08 8.55 24.30 56.10 15.20 23.50 52.80 308号脉 16JJKS36 0.13 5.84 24.90 50.20 13.20 21.00 51.60 矿区支流旁 16JJKS38 0.03 9.91 25.90 62.50 15.60 20.50 63.20 134脉下游 16JJKS39 0.08 7.65 23.70 58.20 14.50 20.20 43.10 尾矿库 16JJKS40 0.13 37.80 25.20 72.60 18.70 24.90 81.10 尾矿库下游 16JJKS42 0.18 29.80 23.70 67.90 26.30 32.80 105.00 尾矿库下游 16JJKS43 0.08 16.60 27.20 81.80 25.30 36.20 89.60 308脉北侧干流旁 16JJKS46 0.10 8.74 23.40 61.20 17.70 24.60 52.00 308脉北侧支流旁 16JJKS48 0.10 4.17 23.40 56.50 14.10 16.00 42.50 308脉北侧支流旁 16JJKS49 0.21 6.47 20.80 52.20 11.40 18.30 48.70 308脉北侧支流旁 16JJKS52 0.12 10.30 23.10 61.70 24.10 27.30 74.40 矿区支流旁 16JJKS53 0.14 11.00 28.10 72.50 23.00 34.40 60.70 2017 绝情谷海子边 17JJKS01 0.08 7.07 24.90 52.30 10.00 17.90 35.70 出拉海子东侧支流旁 17JJKS02 0.19 10.60 23.60 56.40 18.00 25.90 48.40 308脉上游支流旁 17JJKS04 0.29 9.82 20.20 47.50 14.70 18.20 116.00 308脉西北侧干流旁 17JJKS05 0.17 16.60 24.10 53.10 11.90 21.80 65.40 308脉干流旁 17JJKS06 0.19 29.10 26.20 56.60 17.90 27.60 60.70 308脉海子边 17JJKS07 0.12 19.30 31.60 60.20 17.10 21.30 54.20 X03脉上游 17JJKS08 0.13 12.20 23.10 62.50 11.20 26.00 57.00 134脉西侧干流旁 17JJKS09 0.09 8.08 26.50 62.20 14.60 22.20 36.30 134脉矿区支流旁 17JJKS10 0.11 12.40 25.20 73.40 16.10 25.60 43.40 134脉下游 17JJKS11 0.15 7.55 24.60 59.40 12.40 20.50 73.10 融达北西海子边 17JJKS12 0.11 9.46 24.20 68.10 15.90 28.60 65.30 融达北海子边 17JJKS13 0.15 11.70 24.20 45.00 16.00 15.80 32.80 尾矿库 17JJKS14 0.11 32.80 26.90 67.80 18.80 27.30 99.40 融达北海子边 17JJKS21 0.12 11.00 29.90 72.40 16.70 24.60 94.60 融达东北坡 17JJKS22 0.25 25.30 23.00 43.50 20.90 21.40 124.00 融达东北坡 17JJKS23 0.12 21.70 26.50 72.80 17.00 23.40 75.50 融达东北坡 17JJKS24 0.15 11.30 25.70 68.40 17.80 24.40 88.00 融达东北坡 17JJKS25 0.12 20.50 28.40 74.00 20.50 26.80 85.80 融达东北坡 17JJKS26 0.16 9.22 27.80 70.60 16.60 25.20 101.00 融达东北坡 17JJKS28 0.23 7.49 22.20 33.60 11.90 13.60 56.00 烧炭沟河边片岩旁 17STGS01 0.26 25.50 21.40 66.20 12.50 22.20 87.10 烧炭沟含锂辉石伟晶岩旁 17STGS02 0.23 16.10 28.60 68.60 19.00 23.20 103.00 烧炭沟伟晶岩转石旁 17STGS03 0.28 10.60 32.70 71.40 16.60 25.80 82.60 烧炭沟海子边 17STGS04 0.18 13.80 32.70 78.40 15.20 27.60 80.90 2018 308脉 18JJKS01 0.08 18.40 28.90 66.30 16.70 31.30 80.00 134脉矿区支流旁 18JJKS02 0.11 10.30 27.90 32.70 10.50 15.30 62.30 134脉下游 18JJKS03 0.07 12.20 24.20 60.60 18.10 26.60 71.70 融达北西方向支流 18JJKS04 0.08 7.10 21.70 65.70 14.10 38.70 65.60 融达海子北侧 18JJKS05 0.03 21.80 21.70 60.10 14.80 26.40 97.40 尾矿库 18JJKS06 0.03 17.50 20.60 57.10 15.20 22.70 89.60 尾矿库支流旁 18JJKS07 0.03 38.50 18.20 33.50 9.11 12.80 59.00 甲基措海子北侧 18JJKS08 0.08 7.61 25.50 45.30 9.79 19.20 51.00 308脉上游支流旁 18JJKS09 0.03 6.88 21.20 55.20 8.87 22.10 53.60 308脉上游支流旁 18JJKS10 0.09 26.70 28.50 75.70 15.60 27.10 70.20 308脉干流旁 18JJKS11 0.10 33.50 30.20 52.90 11.70 24.30 47.00 融达南西侧 18JJKS13 0.03 7.34 10.30 11.20 5.06 9.93 58.50 融达南西侧 18JJKS14 0.09 37.20 23.10 57.70 13.00 22.50 101.00 
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表 2 甲基卡矿区不同区域根系土壤重金属元素含量统计结果
Table 2 Statistical results of heavy metal content of root soils in different areas of Jiajika mining area
重金属
元素参数 尾矿库区 选矿
厂房已开采
矿区未开采资
源富集区无矿业活动区 甲基卡根系
土壤均值全国A层
土壤背景值Cd 最小值(mg/kg) 0.03 0.03 0.03 0.10 0.03 0.13 0.10 最大值(mg/kg) 0.18 0.25 0.29 0.28 0.24 平均值(mg/kg) 0.09 0.13 0.11 0.17 0.13 As 最小值(mg/kg) 16.60 7.10 5.84 4.18 4.17 15.32 11.20 最大值(mg/kg) 38.50 37.20 33.50 29.20 28.40 平均值(mg/kg) 28.83 15.42 15.37 14.41 11.28 Pb 最小值(mg/kg) 18.20 10.30 20.20 23.10 20.77 25.47 26.00 最大值(mg/kg) 27.20 29.90 31.85 32.70 30.20 平均值(mg/kg) 23.63 23.88 26.59 26.84 25.27 Cr 最小值(mg/kg) 33.50 11.20 32.70 60.57 43.40 60.57 61.00 最大值(mg/kg) 81.80 74.00 76.19 78.40 72.50 平均值(mg/kg) 63.45 57.86 60.58 66.26 57.91 Cu 最小值(mg/kg) 9.11 5.06 8.87 11.20 9.79 16.12 22.60 最大值(mg/kg) 26.30 20.90 19.53 19.50 24.10 平均值(mg/kg) 18.90 15.77 15.40 16.34 16.04 Ni 最小值(mg/kg) 12.80 9.93 15.30 21.08 16.00 23.59 26.90 最大值(mg/kg) 36.20 38.70 31.30 27.60 34.40 平均值(mg/kg) 26.12 23.48 23.69 24.22 22.32 Zn 最小值(mg/kg) 59.00 32.80 36.30 43.40 35.70 66.83 74.2 最大值(mg/kg) 105.00 124.00 116.00 103.00 80.70 平均值(mg/kg) 87.28 81.06 60.74 69.45 53.30
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表 3 农用地(非水田)土壤污染风险筛选值、管制值及矿区土壤重金属含量对比(基本项目)
Table 3 Risk screening values and control values for soil contamination of agricultural land and heavy metal content in root soils in Jiajika mining area (non-paddy field)
污染物
项目风险筛选值
(mg/kg)
pH≤5.5风险管制值
(mg/kg)pH≤5.5甲基卡根系土壤重金属
元素含量(mg/kg)Cd 0.3 1.5 0.03~0.29 Hg 1.3 2.0 - As 40 200 4.17~38.5 Pb 79 400 10.3~32.7 Cr 150 800 11.2~81.8 Cu 50 - 5.06~26.3 Ni 60 - 9.3~38.7 Zn 200 - 32.8~124
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