Heavy metal pollution of soil and its ecological risk evaluation in the phosphate mining area in central Guizhou
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摘要: 为评价黔中磷矿区土壤重金属污染风险，采用梅花布点法在磷矿区周边区域和无矿区不同地层天然土壤采集24件表层土壤样品，测定Cu、Pb、Zn、As、Hg、Se、Cd、和Cr含量，并采用内梅罗综合污染指数（NPI）、地累积指数（Igeo）以及Hankanson潜在生态危害指数（RI）对磷矿区土壤重金属的污染程度和潜在生态风险进行评价。结果表明，黔中磷矿区土壤中Hg、Se、Cd、As、Pb、Zn和Cr等元素平均含量分别为贵州土壤背景值的37.58倍、24.40倍、19.26倍、18.09倍、2.67倍、2.17倍和1.78倍，各重金属富集特征明显，Cu元素平均含量未超过贵州省土壤背景值。研究区土壤中Hg、Se、Cd、As、Pb、Zn和Cr等元素NPI平均值介于4.59~69.32之间，处于重度污染水平，而Cr和Cu元素NPI平均值分别为1.89和1.21，处于轻度污染水平。研究区Hg元素Igeo平均值为4.45，处于严重至极重污染；As、Se和Cd元素Igeo平均值介于3.35~3.65之间，处于重度污染；Pb、Zn和Cr元素Igeo平均值0.21~0.44之间，处于未污染至中度污染水平，而Cu元素Igeo平均值为−0.83，显示其未受到污染。潜在生态风险评价结果表明，研究区土壤Hg元素处于极强生态风险水平，Cd处于强生态风险水平，Ad处于中等生态风险水平，而Cu、Pb、Zn和Cr均处于轻微风险水平。黔中磷矿区土壤RI平均值为2 285.50，显示出极强生态风险，Hg是最主要的生态风险元素，应引起高度重视。Abstract:
To investigate the current status of heavy metal pollution of soil in the phosphate mining area in central Guizhou and to comprehensively evaluate the potential pollution risks of eight heavy metal elements, a systematic sampling approach was employed in a plum blossom pattern. A total of 24 topsoil samples were collected from the surrounding areas of the phosphate mining area and from different strata in the non-mining area. The concentrations of Cu, Pb, Zn, As, Hg, Se, Cd, and Cr were determined. Based on the test results, comprehensive evaluations of the degree of heavy metal pollution and potential ecological risks in the topsoil of the mining area were conducted in terms of the Nemerow Pollution Index (NPI), Geo-accumulation Index (Igeo), and Hankanson Potential Ecological Risk Index (RI). The results indicate that the average concentrations of Hg, Se, Cd, As, Pb, Zn, and Cr in the topsoil of the phosphate mining area in central Guizhou were 3.83 mg·kg−1, 8.42 mg·kg−1, 2.29 mg·kg−1, 240.6 mg·kg−1, 65.83 mg·kg−1, 141.4 mg·kg−1, and 145.8 mg·kg−1, respectively. These values were 37.58, 24.40, 19.26, 18.09, 2.67, 2.17, and 1.78 times higher than the corresponding background values of soil in Guizhou, indicating significant enrichment of these heavy metals in the study area. In contrast, the average concentration of Cu did not exceed the background value of the surrounding soil. The evaluation of heavy metal pollution in the topsoil showed that NPI values for Hg, Se, Cd, As, Pb, Zn, and Cr ranged from 4.59 to 69.32, indicating a general level of heavy pollution. Specifically, NPI values for Hg, Se, As, Cd, and Pb were 75.73, 55.21, 35.36, 19.75, and 10.32, respectively, all demonstrating heavy pollution. NPI values of Cr and Zn were 2.17 and 2.11, respectively, suggesting moderate pollution. The lowest NPI values were observed in Cr and Cu, with averages of 1.89 and 1.21, respectively, indicating light pollution. The Igeo analysis revealed that the average Igeo value for Hg was 4.45, showing severe to extreme pollution. The average Igeo values for As, Se, and Cd ranged from 3.35 to 3.65, indicating heavy pollution. Igeo values of Pb, Zn, and Cr averaged between 0.21 and 0.44, suggesting a range from unpolluted to moderate levels of pollution. The average Igeo value for Cu was -0.83, indicating an unpolluted level. The evalution of potential ecological risk showed that the single-element RI for Hg in the topsoil was 1,533.33, indicating an extremely high ecological risk. The single-element RI value for Cd was 298.91, indicating a high ecological risk, while the value of As is 180.92, indicating a very high ecological risk. The values for Cu, Pb, Zn, and Cr were all below 10, suggesting minor risk levels. Overall, the average RI value for the topsoil in the phosphate mining area was 2,285.50, indicating an extremely high potential ecological risk. Hg was identified as the primary ecological risk element, followed by Cd and As, warranting significant attention and management measures. -
图 1 取样点分布图
1.碳酸盐岩含水岩组 2.碳酸盐岩夹非碳酸盐岩含水岩组 3.碎屑岩含水岩组 4.变质岩 5.第四系 6.磷化企业 7.取样点位置及编号 8.断层 9.地层界线
Figure 1. Distribution of sampling points
1.water-bearing rock formation comprised of carbonate rock; 2.water-bearing rock formation comprised of carbonate rock and non-carbonate rock; 3. water-bearing rock formation comprised of clastic rock; 4.metamorphic rock; 5.Quaternary; 6.phosphating enterprise; 7. locations and numbers of sampling points; 8.fault; 9.stratigraphic boundary
图 2 黔中磷矿区土壤重金属元素标准化图解
Figure 2. Standardized diagram of heavy metal elements in soil of the phosphate mine area in central Guizhou
表 1 研究区土壤样品采集清单
Table 1. List of soil sample collection in the study area
序号
样品编号 备注 1 T1 寒武系中统清虚洞组∈2q 2 T2 寒武系苗岭统至芙蓉统奥陶系下统娄山关组∈3-4O1l 3 T3 寒武系苗岭统石冷水组∈3sh 4 T4 三叠系下统夜郎组第二段T1y2 5 T5 二叠系阳新统栖霞-茅口组P2q-m 6 T6 震旦系上统灯影组Pt33b∈1dy 7 T7 三叠系下统至中统嘉陵江组第三段T1-2j3 8 T8 三叠系下统至中统嘉陵江组第一段T1-2j1 9 T9 三叠系中统关岭组第二段T2g2 10 T10 路发磷石膏堆场下游 11 T11 川东化工下游 12 T12 大水工业园区下游 13 T13 磷矿开采区 14 T14 开阳化工下游 15 T15 西洋肥业下游 16 T16 采石场 17 T17 寒武系苗岭统至芙蓉统奥陶系下统娄山关组∈3-4O1l 18 T18 交椅山磷石膏堆场下游 19 T19 铝土矿开采区 20 T20 三叠系下统至中统嘉陵江组T1-2j 21 T21 三叠系下统夜郎组第二段T1y2 22 T22 三叠系中统关岭组第一段T2g1 23 T23 寒武系第二统清虚洞组∈2q 24 T24 明泥湾磷矿开采区 
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表 2 土壤样品检测方法仪器及其精度表
Table 2. Testing methods, instruments and their precision of testing soil samples
重金属元素 检测方法 仪器型号 精度/mg·kg−1 检出限/mg·kg−1
Cu LY/T 3129-2019 森林土壤铜、锌、铁、锰全量的测定电感耦合等离子体发射光谱法 iCAP6300 2.0 0.7 Pb GB/T 39229-2020 肥料和土壤调理剂 砷、镉、铬、铅、汞含量的测定 iCAP6300 9 3.0 Zn LY/T 3129-2019 森林土壤铜、锌、铁、锰全量的测定电感耦合等离子体发射光谱法 iCAP6300 15 5 As GB/T 39229-2020 肥料和土壤调理剂 砷、镉、铬、铅、汞含量的测定 iCAP6300 6 2 Hg GB/T 39229-2020 肥料和土壤调理剂 砷、镉、铬、铅、汞含量的测定 iCAP6300 6 2 Se GB/T 39356-2020 肥料中总镍、总钴、总硒、总钒、总锑、总铊含量的测定 电感耦合等离子体发射光谱法 iCAP6300 15 5 Cd GB/T 39229-2020 肥料和土壤调理剂 砷、镉、铬、铅、汞含量的测定 iCAP6300 6 2 Cr GB/T 39229-2020 肥料和土壤调理剂 砷、镉、铬、铅、汞含量的测定 iCAP6300 6 2.0
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表 3 内梅罗综合污染指数法评价分级标准
Table 3. Grading criteria of Nemero comprehensive pollution index
等级 Pi分级标准 NPI分级标准 污染等级 污染评价 Ⅰ Pi≤0.7 NPI≤0.7 清洁 无污染 Ⅱ 0.7<Pi≤1.0 0.7<E≤1.0 轻微 基本无污染 Ⅲ 1.0<Pi≤2.0 1.0<RI≤2.0 轻度 轻度污染 Ⅳ 2.0<Pi≤3.0 2.0<RI≤3.0 中度 污染较严重 Ⅴ Pi>3.0 E>3.0 重度 污染非常严重
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表 4 潜在生态风险指数法评价分级标准
Table 4. Grading criteria of potential ecological risk index
分级标准 等级 潜在生态风险 E≤40; RI≤150 Ⅰ 轻微 40<E≤80; 150<RI≤300 Ⅱ 中等 80<E≤160; 300<RI≤600 Ⅲ 较强 160<E≤320; 600<RI≤ 1200 Ⅳ 很强 E>320; RI> 1200 Ⅴ 极强
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表 5 黔中磷矿区土壤重金属含量统计表
Table 5. Statistics of heavy metal contents in soil of the phosphate mine area in central Guizhou
重金属元素 样本数N 最小值/mg·kg−1 最大值/mg·kg−1 均值/mg·kg−1 变异系数 土壤背景值/mg·kg−1 Cu 24 11.00 45.00 25.33 0.36 35.97 Pb 24 30.00 484.00 65.83 1.37 33.47 Zn 24 58.00 420.00 141.40 0.61 148.67 As 24 54.00 620.00 240.60 0.58 13.30* Hg 24 0.00 10.00 3.83 0.61 0.10* Se 24 0.00 26.00 8.42 1.03 0.35* Cd 24 1.00 6.00 2.29 0.51 0.23 Cr 24 80.00 204.00 145.80 0.23 81.80* 注：*代表贵州省土壤背景值，来源于夏曾禄著《土壤元素背景值及其研究方法》[25]，其余背景值来源于文献[11]。
Note: * represents soil background in Guizhou Province and it is derived from Xia Zenglu's "Background values of soil element and its research methods". Other background values are derived from an abstract [11].
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表 6 黔中磷矿区土壤重金属内梅罗综合污染指数法计算评价结果
Table 6. Calculation and evaluation results of Nemerow comprehensive pollution index for heavy metals in soil of the phosphate mine area in central Guizhou
重金属元素
内梅罗综合污染指数NPI 重金属污染评价结果 Cu 1.02 轻度污染 Pb 10.32 重污染 Zn 2.11 中度污染 As 35.36 重污染 Hg 75.73 重污染 Se 55.21 重污染 Cd 19.75 重污染 Cr 2.17 中度污染
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表 7 黔中磷矿区土壤重金属地累积指数Igeo计算评价结果表
Table 7. Calculation and evaluation results of soil heavy metal geo-accumulation index Igeo in the phosphate mine area of central Guizhou
检测编号 地累积指数Igeo Cu Pb Zn As Hg Se Cd Cr 2019G-857 −0.62 3.27 0.80 3.85 3.74 3.54 4.12 0.54 2019G-858 −1.36 −0.13 −1.22 3.08 2.74 − 2.54 −0.03 2019G-859 −0.90 −0.36 −1.03 4.30 4.32 0.95 1.54 0.30 2019G-860 −0.51 0.48 −0.57 3.15 3.74 4.95 3.12 0.45 2019G-861 −2.29 −0.56 −1.06 2.34 4.32 3.27 3.12 0.73 2019G-862 −0.95 0.69 0.91 4.68 6.06 − 3.54 0.41 2019G-863 −1.51 −0.74 −0.76 3.95 3.74 − 2.54 −0.03 2019G-864 −1.00 −0.10 −0.42 3.44 − 1.95 3.12 0.27 2019G-865 −0.75 −0.29 −0.48 4.96 2.74 2.54 0.37 2019G-866 −0.51 0.26 −0.82 4.19 4.32 1.95 2.54 0.17 2019G-867 −1.36 0.64 −0.98 4.07 2.74 0.95 1.54 0.13 2019G-868 −0.67 −0.56 −1.13 3.24 3.74 1.54 −0.28 2019G-869 −1.43 0.33 −0.92 2.46 5.06 1.95 1.54 −0.53 2019G-870 −1.36 0.16 −0.76 3.41 5.32 4.54 1.54 0.32 2019G-881 −0.58 −0.26 −0.52 2.53 5.06 4.65 3.12 0.65 2019G-882 −1.75 −0.19 −1.34 1.44 4.74 3.76 2.54 0.17 2019G-883 −1.00 0.08 −0.94 2.84 5.54 5.65 3.12 0.59 2019G-884 −0.95 0.05 −1.37 2.51 5.06 5.27 2.54 0.42 2019G-885 −2.17 −0.65 −1.94 3.59 4.74 4.86 2.54 0.04 2019G-886 −1.36 −0.19 −0.65 3.83 5.32 5.41 3.12 0.45 2019G-887 −0.26 −0.13 −0.64 1.75 4.32 0.95 3.12 0.65 2019G-888 −1.43 −0.65 −1.59 3.02 5.32 5.54 2.54 0.08 2019G-889 −2.17 −0.74 −1.33 4.07 5.06 5.04 2.54 −0.62 2019G-890 −1.67 −0.26 −0.89 3.74 5.32 4.27 1.54 −0.30 avg. −1.19 0.01 −0.82 3.35 4.48 3.65 2.56 0.21 评价结果 无污染 未污染至中等
程度污染无污染 重污染 严重至极
重污染重污染 中度至
重污染未污染至中等
程度污染
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表 8 内梅罗综合污染指数法和地累积指数污染评价结果表
Table 8. Pollution evaluation results of Nemero comprehensive pollution index and geo-accumulation index
重金属元素 内梅罗综合污染指数NPI评价结果 地累积指数评价结果 Cu 轻度污染 无污染 Pb 重污染 未污染至中等程度污染 Zn 中度污染 无污染 As 重污染 重污染 Hg 重污染 严重至极重污染 Se 重污染 重污染 Cd 重污染 中度至重污染 Cr 中度污染 未污染至中等程度污染
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表 9 土壤重金属潜在生态风险评价结果表
Table 9. Evaluation results of potential ecological risk of soil heavy metal
样品编号 单项潜在生态风险指数$ {\mathit{E}}_{\mathit{j}}^{\mathit{i}} $ 综合潜在生态风险指数
Cu Pb Zn As Hg Cd Cr RIj 2019G-857 4.87 72.30 2.62 216.54 800.00 782.61 4.38 1 883.31 2019G-858 2.92 6.87 0.65 127.07 400.00 260.87 2.93 801.31 2019G-859 4.03 5.83 0.73 295.49 1 200.00 130.43 3.69 1 640.21 2019G-860 5.28 10.46 1.01 133.08 800.00 391.30 4.11 1 345.24 2019G-861 1.53 5.08 0.72 75.94 1 200.00 391.30 4.99 1 679.56 2019G-862 3.89 12.10 2.83 385.71 4 000.00 521.74 3.99 4 930.26 2019G-863 2.64 4.48 0.89 231.58 800.00 260.87 2.93 1 303.39 2019G-864 3.75 7.02 1.12 162.41 0.00 391.30 3.62 569.23 2019G-865 4.45 6.12 1.08 466.17 400.00 260.87 3.89 1 142.57 2019G-866 5.28 8.96 0.85 272.93 1 200.00 260.87 3.37 1 752.27 2019G-867 2.92 11.65 0.76 252.63 400.00 130.43 3.28 801.67 2019G-868 4.73 5.08 0.69 141.35 800.00 130.43 2.47 1 084.75 2019G-869 2.78 9.41 0.79 82.71 2 000.00 130.43 2.08 2 228.21 2019G-870 2.92 8.37 0.89 159.40 2 400.00 130.43 3.74 2 705.75 2019G-881 5.00 6.27 1.05 86.47 2 000.00 391.30 4.69 2 494.79 2019G-882 2.22 6.57 0.59 40.60 1 600.00 260.87 3.37 1 914.23 2019G-883 3.75 7.92 0.78 107.52 2 800.00 391.30 4.52 3 315.80 2019G-884 3.89 7.77 0.58 85.71 2 000.00 260.87 4.01 2 362.83 2019G-885 1.67 4.78 0.39 180.45 1 600.00 260.87 3.08 2 051.24 2019G-886 2.92 6.57 0.96 213.53 2 400.00 391.30 4.11 3 019.39 2019G-887 6.26 6.87 0.96 50.38 1 200.00 391.30 4.69 1 660.46 2019G-888 2.78 4.78 0.50 121.80 2 400.00 260.87 3.18 2 793.91 2019G-889 1.67 4.48 0.60 251.88 2 000.00 260.87 1.96 2 521.45 2019G-890 2.36 6.27 0.81 200.75 2 400.00 130.43 2.44 2 743.08 AVG. $ {\mathit{E}}_{\mathit{j}}^{\mathit{i}} $ 3.52 9.83 0.95 180.92 1 533.33 298.91 3.56 2 031.04 生态风
险评价轻微生
态风险轻微生
态风险轻微生
态风险很强生
态风险极强生
态风险很强生
态风险轻微生
态风险极强生
态风险
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