Distribution characteristics, ecological risk assessment and source analysis of heavy metals in soil of Beizhen agricultural area, Jinzhou City, Liaoning Province
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摘要:
研究目的 查明辽宁省锦州市北镇农业区重金属分布特征，可以为当地特色农业开发、全域旅游和土壤重金属污染管控提供科学依据。
研究方法 本文通过地质调查查明成土母质，采集表层土壤样品，以元素含量分布特征、富集程度为基础，开展土壤环境质量评价，利用地累积指数法进行重金属污染程度评价， Hakanson生态风险指数法识别研究区潜在生态风险程度，并通过Pearson相关性分析和聚类分析，定量分析不同重金属的主要来源。
研究结果 北镇农业区土壤中Cr和Pb的均值低于辽宁省辽河流域背景值，表层土壤重金属富集程度由大到小排序为Hg>As>Cd>Pb>Zn>Cu>Cr>Ni。研究区土壤质量总体良好，在超标样品中Cd、Cu和Zn含量超过风险筛选值的占比分别为45.56%、29.11%和11.47%，占总超标数的86.12%；As和Cd为轻度污染状态，大部分土壤样品的重金属为无—轻度的污染状态，仅Hg元素个别采样点位为强—极强污染。单指标潜在生态风险由高到低排序为：Hg>Cd>As>Cu>Ni>Pb>Cr>Zn，土壤潜在生态风险综合指数RI分布范围为29.7~2358.16，平均值为141.9，以低度风险为主，其次中度风险。相关性分析和聚类分析结果表明，Ni、Cr、As、Pb主要受母岩自然风化影响，Cu、Zn、Cd、Hg受农业生产、工业生产、交通运输，甚至建筑活动等多种来源影响。
结论 农用物质的不合理施用、大气沉降、工业生产、生活垃圾和煤炭燃烧等产生的物质在土壤中富集可能对研究区生态环境质量造成污染风险，未来需要加强对Hg、Cd、Cu和Zn元素在不同地块中富集趋势监测和研究。
Abstract:This paper is the result of environmental geological survey engineering.
Objective To investigate the distribution characteristics of heavy metals and provide a scientific basis for local characteristic agricultural development, comprehensive tourism, and soil heavy metal pollution control.
Methods Through geological investigation, the soil parent material was identified, and topsoil samples were collected. Soil environmental quality evaluation was carried out based on the distribution characteristics and enrichment degree of element content. The degree of heavy metal pollution was evaluated using the ground accumulation index method. The Hakanson ecological risk index method was used to identify the degree of potential ecological risk in the study area. Furthermore, Pearson correlation analysis and cluster analysis were employed to quantitatively determine the main sources of different heavy metals.
Results The average values of Cr and Pb in the soil of the Beizhen agricultural area were lower than the background values of the Liaohe River Basin in Liaoning Province. The enrichment degree of heavy metals in the topsoil, from high to low, was Hg > As > Cd > Pb > Zn > Cu > Cr > Ni. The soil quality in the study area is generally good. The proportion of Cd, Cu, and Zn contents exceeding the risk screening values in the exceeding standard samples was 45.56%, 29.11%, and 11.47%, respectively, accounting for 86.12% of the total number of exceeding standards. The evaluation results of heavy metal pollution showed that As and Cd were in a mildly polluted state, most heavy metals in soil samples were in no to mild pollution, and only Hg elements had strong to extremely strong pollution at individual sampling points. The order of potential ecological risk of single indices from high to low is Hg > Cd > As > Cu > Ni > Pb > Cr > Zn. The distribution range of the potential ecological risk comprehensive index (RI) of surface soil in the whole region is 29.7 to 2358.16, with an average value of 141.9, primarily indicating low risk, followed by moderate risk. The results of correlation analysis and cluster analysis show that Ni, Cr, As, and Pb are mainly affected by the natural weathering of the parent rock, while Cu, Zn, Cd, and Hg are influenced by agricultural production, industrial production, transportation, and even construction activities.
Conclusions The enrichment of substances produced by the unreasonable application of agricultural substances, atmospheric deposition, industrial production, domestic garbage, and coal combustion in the soil may pose pollution risks to the ecological environment quality of the study area. In the future, it is necessary to strengthen the monitoring and research on the enrichment trend of Hg, Cd, Cu, and Zn elements in different plots.
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表 1 农用地土壤污染风险筛选值
Table 1. Pollution risk screening value of agricultural land soil
序号 项目 风险筛选值/(mg/kg) pH≤5.5 5.5<pH≤6.5 6.5<pH≤7.5 pH>7.5 1 Cd 水田 0.3 0.4 0.6 0.8 其他 0.3 0.3 0.3 0.6 2 Hg 水田 0.5 0.5 0.6 1.0 其他 1.3 1.8 2.4 3.4 3 As 水田 30 30 25 20 其他 40 40 30 25 4 Pb 水田 80 100 140 240 其他 70 90 120 170 5 Cr 水田 250 250 300 350 其他 150 150 200 250 6 Cu 果园 150 150 200 200 其他 50 50 100 100 7 镍 60 70 100 190 8 锌 200 200 250 300 
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表 2 农用地土壤污染风险管制值
Table 2. Pollution risk control value of agricultural land soil
序号 项目 风险管制值/(mg/kg) pH≤5.5 5.5<pH≤6.5 6.5<pH≤7.5 pH>7.5 1 Cd 1.5 2.0 3.0 4.0 2 Hg 2.0 2.5 4.0 6.0 3 As 200 150 120 100 4 Pb 400 500 700 1000 5 Cr 800 850 1000 1300
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表 3 土壤环境地球化学等级划分
Table 3. Geochemical classification of soil environment
等级 一等 二等 三等 四等 五等 土壤环境 Pi≤1 1<Pi≤2 2<Pi≤3 3<Pi≤5 Pi>5 清洁 轻微污染 轻度污染 中度污染 重度污染
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表 4 地质累积指数分级标准
Table 4. Classification standard of geological accumulation index
等级 1级 2级 3级 4级 5级 6级 7级 Igeo <0 0~1 1~2 2~3 3~4 4~5 >5 描述 无污染 无到中度污染 中度污染 中度到强度污染 强度污染 强度到极强污染 极强污染
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表 5 重金属潜在生态风险等级
Table 5. Potential ecological risk levels of heavy metals
生态风险指数 生态风险等级 低度 中度 重度 严重 Eri <40 40~80 80~160 >160 RI <150 150~300 300~600 >600
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表 6 表层土壤重金属元素地球化学参数特征
Table 6. Characteristics of chemical parameters of heavy metal elements in surface soil
元素 最大值 最小值 平均值 中位数 标准差 偏度 峰度 变异系数 剔除3倍离差
后平均值富集
系数辽河流域
背景值As 75.5 0.001 7.23 6.8 2.63 6.27 124.44 0.36 7.03 1.05 6.70 Cd 1.98 0.03 0.17 0.16 0.09 6.37 84.28 0.55 0.16 1.23 0.13 Cr 112.7 17.4 55.3 53.1 13.24 0.64 0.21 0.24 55.04 0.92 60.00 Hg 1.73 0 0.05 0.05 0.06 14.87 321.78 1.15 0.045 1.50 0.03 Pb 134.5 10.1 23.54 23.1 4.04 8.52 207.99 0.17 23.34 0.97 24.00 Ni 95.2 5.7 23.08 21.7 7.38 0.88 2.13 0.32 22.94 1.00 23.00 Cu 313.2 2.4 24.13 20.8 17.56 7.21 78.26 0.73 21.1 1.13 18.70 Zn 712.4 14.8 65.82 56.6 43.52 6.88 69.79 0.66 58.37 1.08 54.00 注：标准差/富集系数/变异系数/偏度/峰度均无量纲；其他指标值的质量分数单位为mg/kg；土壤背景值来自于辽宁省辽河流域农业地质调查数据背景值。
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表 7 农用地土壤污染风险筛选情况统计
Table 7. Statistics of pollution risk screening of agricultural land soil
pH值范围 样品数量/个 重金属风险筛选超标数/个 As Cd Cr Cu Hg Ni Pb Zn ≤5.5 1308 0 32 0 11 1 1 1 2 5.5~6.5 1091 1 54 0 59 0 0 1 34 6.5~7.5 881 0 49 0 15 0 0 0 14 >7.5 753 15 1 0 0 0 0 0 1 合计 4033 16 136 0 85 1 1 2 51 超标率/% — 0.40 3.37 0 2.12 0.025 0.025 0.05 1.27
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表 8 农用地土壤污染风险管制情况统计
Table 8. Statistics of pollution risk control of agricultural land soil
pH值范围 Cd Hg As Pb Cr 管制值 超标数/个 管制值 超标数/个 管制值 超标数/个 管制值 超标数/个 管制值 超标数/个 ≤5.5 1.5 1 2 0 200 0 400 0 800 0 5.5~6.5 2 0 2.5 0 150 0 500 0 850 0 6.5~7.5 3 0 4 0 120 0 700 0 1000 0 >7.5 4 0 6 0 100 0 1000 0 1300 0 合计 1 0 0 0 0 超标率/% 0.025 0 0 0 0
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表 9 研究区土壤环境元素等级统计
Table 9. Statistics of soil environmental element levels in the study area
元素 一级 二级 三级 四级 五级 Cu 面积/km2 1114.199 5.449 0.774 0.673 0.056 比例/% 99.38 0.486 0.069 0.06 0.005 Ni 面积/km2 1121.15 比例/% 100.00 Cd 面积/km2 1105.017 15.337 0.482 0.280 0.022 比例/% 98.561 1.368 0.043 0.025 0.002 Pb 面积/km2 1120.99 0.16 比例/% 99.99 0.01 As 面积/km2 1118.88 2.27 比例/% 99.80 0.20 Hg 面积/km2 1119.832 1.313 比例/% 99.88 0.12 Zn 面积/km2 1117.986 2.218 0.912 0.029 比例/% 99.72 0.198 0.081 0.003 Cr 面积/km2 1121.15 比例/% 100.00 综合 面积/km2 1095.168 23.461 1.406 0.982 0.078 比例/% 97.683 2.093 0.125 0.093 0.007
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表 10 研究区单元素地累积指数分级统计
Table 10. Classification statistics of single element ground accumulation index in the study area
等级 1级 2级 3级 4级 5级 6级 7级 Igeo
均值受污染点位占比% 描述 无污染 无—中度污染 中度污染 中度—强度污染 强度污染 强—极强污染 极强污染 As 1940 2037 51 4 1 0 0 0.04 51.90 Hg 2041 1706 213 53 13 4 3 0.03 49.39 Cr 3989 44 0 0 0 0 0 −0.74 1.09 Pb 4018 13 2 0 0 0 0 −0.63 0.37 Cd 3001 961 59 10 2 0 0 −0.33 25.59 Cu 3233 684 88 22 6 0 0 −0.38 19.84 Zn 3399 540 71 20 3 0 0 −0.44 15.72 Ni 3699 333 1 0 0 0 0 −0.65 8.28
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表 11 研究区重金属元素潜在生态风险指数分级统计
Table 11. Classification statistics of potential ecological risk index of heavy metal elements in the study area
风险等级 潜在生态风险指数 各风险等级样本数/个 最小值 最大值 平均值 低度 中度 重度 严重 $ {E}_{r}^{i} $ As 0.0015 112.61 10.79 4028 4 1 0 Cd 7.25 455.85 39.21 2516 1408 93 16 Cr 0.58 3.76 1.84 4033 0 0 0 Hg 0.0013 2311.42 72.48 592 2596 689 156 Pb 2.1 28.03 4.9 4033 0 0 0 Ni 1.23 20.69 5.02 4033 0 0 0 Cu 0.65 83.76 6.45 4017 15 1 0 Zn 0.27 13.19 1.22 4033 0 0 0 RI 29.7 2358.16 141.9 2842 1091 80 20
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表 12 研究区表层土壤重金属元素含量相关性
Table 12. Correlation of heavy metal elements in surface soil of study area
重金属 As Cd Cr Hg Pb Ni Cu Zn As 1 Cd 0.3039 1 Cr 0.6444** 0.2807 1 Hg 0.0639 0.1725 0.092 1 Pb 0.4505* 0.2987 0.4201* 0.0612 1 Ni 0.7019** 0.2457 0.935** 0.0528 0.3924 1 Cu 0.2485 0.4099* 0.2797 0.2482 0.1237 0.2776 1 Zn 0.2729 0.3801 0.2913 0.2729 0.1284 0.2975 0.9304** 1 注：**表示P<0.01，为极显著相关；*表示P<0.05，为显著相关。
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表 13 表层土壤重金属元素含量主成分
Table 13. Principal component of heavy metal elements content in surface soil
成分 初始特征值 提取平方和荷载 旋转成分矩阵 特征值 贡献率/% 累积贡献率/% 特征值 贡献率/% 累积贡献率/% 重金属 F1 F2 1 3.49 43.58 43.58 3.49 43.58 43.58 As 0.828 0.145 2 1.69 21.1 64.68 1.69 21.1 64.68 Cd 0.311 0.531 3 0.89 11.09 75.77 Cr 0.902 0.153 4 0.83 10.4 86.17 Hg −0.031 0.490 5 0.59 7.34 93.52 Pb 0.636 0.050 6 0.39 4.91 98.43 Ni 0.914 0.136 7 0.07 0.86 99.28 Cu 0.147 0.925 8 0.06 0.72 100 Zn 0.16 0.921
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