Distribution, sources and environmental risk assessment on potential toxic elements in soils along coast of Sanmen Bay
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摘要:
土壤中潜在有毒元素(PTEs)易通过食物链的累积对人体健康构成严重威胁，探究其浓度对于生态环境安全具有重要意义。为查明浙江三门湾沿岸土壤中PTEs含量、分布特征及主要来源，在三门湾沿岸4个小流域采集了36个站位土壤样品，进行了土壤黏土矿物、土壤酸碱度、10种PTEs及Si、Al、Fe和TOC含量分析。利用相关性和主成分分析进行了来源分析，并采用《土壤环境质量》（GB 15618—2018）、富集因子（EF）、内梅罗污染指数（PI）及潜在生态风险污染指数（RI）评价模型进行了环境风险评价。结果表明，不同地貌单元土壤黏土矿物组成差异明显，山间平原土壤高岭石和绿泥石占比相对高(平均值>30%)，海积平原伊利石占比相对高（>60%）。山间平原土壤主要为原地母岩风化成壤，而海积平原区土壤主要为历史时期长江来源沉积物改造而成。土壤PTEs整体上呈现流域上游向下游增加的分布趋势。平均富集程度依次为Hg>Cd>Sb>As>Pb>Ni>Cr>Co>Zn> Cu。Hg元素轻微富集、中等富集和中等严重富集站位占比分别为27.8%、2.8%和2.8%。Cd、Sb、As和Pb分别有13.9%、8.3%、8.3%和16.7%的站位为轻微富集。PI值显示，5.6%的站位为严重和重度污染。RI值显示，16.7%的站位处于中生态风险水平，其中Hg和Cd分别贡献了44.8%和25.9%。相关性及主成分分析表明，Cu、Zn、Cr、Ni、Co、As、Sb主要是自然来源，受到成土母质、土壤机械组成、土壤pH等因素的影响。Pb、Cd、Hg主要为工业、农业及交通等人类活动来源。
Abstract:The accumulation of potential toxic elements (PTEs) in soil through the food chain poses a serious threat to human health. Therefore, it is important to investigate the concentration of PTEs in soil for ecological and environmental safety. To identify the content, distribution, and main sources of PTEs in soils along coast of Sanmen Bay, Zhejiang, soil samples were collected in 36 sites in four sub-basins along Sanmen Bay. The analyses of clay minerals, pH, 10 PTEs, Si, Al, Fe, and TOC in the soils were performed. Source analysis of PTEs was performed using correlation and principal component analysis. Assessment on environmental risk of PTEs based on the Soil Environmental Quality (China National Standard GB 15618—2018), Enrichment Factor (EF), Nemerow Pollution Index (PI), and Potential Ecological Risk Pollution Index (RI) was conducted. Results show that the clay mineral composition of soils in different geomorphic units varied significantly. In comparison, the proportions of kaolinite and chlorite in the intermontane plain soils were relatively high (>30% on average), and that of illite in the marine plain was relatively high (>60%). The intermontane plain soils are mainly from local weathered parent rocks, while the marine accumulation plain soils are mainly modified by sediment from the Changjiang (Yangtze) River during the historical period. The concentration of soil PTEs shows an increasing trend from upstream to downstream in all sub-basins. The order in average enrichment of PTEs from high to low was Hg, Cd, Sb, As, Pb, Ni, Cr, Co, Zn, and Cu. In addition, 27.8%, 2.8%, and 2.8% of the sites were in minor enrichment, moderate enrichment, and moderately-severe enrichment in Hg, respectively; 13.9%, 8.3%, 8.3%, and 16.7% of the sites were in minor enrichment in Cd, Sb, As, and Pb, respectively. PI values showed that 86.1%, 2.8%, and 2.8% of the sites were moderately polluted, heavily polluted, and severely polluted, respectively. RI values showed that 16.7% of the sites ranked in ecological grade of moderate risk, whose Hg and Cd were amounted to 44.8% and 25.9%, respectively. The correlation and principal component analysis suggested that Cu, Zn, Cr, Ni, Co, As, and Sb were mainly in natural origination from soil-forming parent rocks, soil mechanical composition, soil pH, etc. On the other hand, Pb, Cd, and Hg were mainly anthropogenic from activities of industry, agriculture, and transportation.
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Key words:
- Sanmen Bay /
- soil /
- clay minerals /
- potential toxic elements /
- pollution assessment
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表 1 农用地土壤污染风险管控标准
Table 1. Standard of risk control on soil contamination in agricultural land
污染元素 风险筛选值/（μg/g） 风险管控值/（μg/g） pH≤5.5 5.5<pH≤6.5 6.5<pH≤7.5 pH>7.5 pH≤5.5 5.5<pH≤6.5 6.5<pH≤7.5 pH>7.5 Cd 0.3 0.3 0.3 0.6 1.5 2 3 4 Hg 1.3 1.8 2.4 3.4 2 2.5 4 6 As 40 40 30 25 200 150 120 100 Pb 70 90 120 170 400 500 700 1000 Cr 150 150 200 250 800 850 1000 1300 Cu 50 50 100 100 - - - - Ni 60 70 100 190 - - - - Zn 200 200 250 300 - - - - 
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表 2 三门湾沿岸土壤潜在有毒元素含量
Table 2. Concentration of potential toxic elements in soils along coast of Sanmen Bay
μg/g 范围 Cu Pb Zn Cr Ni Co Cd As Hg Sb 最小值 全部 5.2 21.7 45.8 11.9 6.3 3.5 0.046 2.0 0.036 0.26 最大值 全部 38.4 50.8 111.0 108.0 53.4 23.3 0.220 15.7 0.200 1.07 平均值 全部 23.6 31.6 84.7 71.9 32.3 14.0 0.111 9.5 0.069 0.63 流域A 24.3 32.2 84.8 74.8 33.6 14.9 0.089 10.1 0.057 0.65 流域B 22.4 31.7 87.0 65.9 30.3 13.7 0.120 8.3 0.064 0.55 流域C 24.3 34.4 84.9 68.8 30.4 12.7 0.129 9.2 0.088 0.67 流域D 23.2 27.6 83.3 79.0 35.3 15.0 0.103 10.5 0.060 0.67
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表 3 三门湾沿岸土壤黏土矿物含量
Table 3. Content of clay minerals in the soils along coast of Sanmen Bay
蒙脱石/% 伊利石/% 高岭石/% 绿泥石/% 数据来源 上游山间平原土壤 范围 - 14.5～42.8 26.6～39.7 30.2～45.8 本研究 平均值 - 34.1 31.4 34.5 下游海积平原土壤 范围 2.8～5.9 61.6～65.8 12.3～16.5 16.8～19.2 本研究 平均值 4.2 63.8 13.7 18.3 三门湾海域表层沉积物 范围 2.4～5.8 61.3～65.9 14.3～15.5 16.2～18.9 本研究 平均值 63.3 15.0 18.1 象山外海表层沉积物 4.0 61.5 15.6 18.8 周晓静 [44] 椒江口外表层沉积物 2.3 62.6 16.5 18.6 周晓静 [44] 椒江河流沉积物 3.7 52.7 27.3 16.3 薛成凤等[45] 长江河流沉积物 10 65 14 11 杨作升 [46] 长江河流沉积物 5 67 9 19 XU等 [47]
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表 4 潜在有毒元素毒性系数及背景值
Table 4. Toxicity coefficients and background concentration of potential toxic elements
元素 Cu Pb Zn Cr Ni Co Cd As Sb Hg 文献来源 毒性系数 5a 4a 1a 2a 5b 5b 30a 10a 7c 40a aHAKANSON [40]
b徐争启等 [42]
cWANG [43]Hakanson背景值/（μg/g） 50 70 175 90 1 15 0.25 HAKANSON [40] 浙江近岸表层沉积物/（μg/g） 20 27 75 75 0.102 9.1 0.034 张志忠等 [53] 浙东近海沉积物背景值/（μg/g） 36.1 35.3 116.7 96.8 45.9 18.3 0.089 9.8 0.59 0.050 未发表数据 浙江中酸性火山岩/（μg/g） 12.1 30.1 72.2 34.9 11.3 9.2 0.133 6.6 0.52 0.044 汪庆华等 [50]
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表 5 土壤环境质量指数（基于风险筛选值）
Table 5. Indices of soil environmental quality (based on risk filter value)
元素 Cu Pb Zn Cr Ni Cd As Hg 最小值 0.10 0.13 0.23 0.08 0.10 0.22 0.05 0.01 最大值 0.71 0.73 0.56 0.67 0.76 0.90 0.63 0.15 平均值 0.29 0.29 0.33 0.32 0.23 0.44 0.35 0.03
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表 6 土壤潜在有害元素富集因子
Table 6. Enrichment factors of potential toxic elements in the soil samples
Cu Pb Zn Cr Ni Co Cd As Hg Sb EF 最小值 0.56 0.71 0.72 0.38 0.61 0.48 0.29 0.34 0.70 0.55 最大值 1.38 2.02 1.21 1.13 1.19 1.43 2.80 1.87 5.24 1.72 平均值 0.86 1.04 0.88 0.92 0.94 0.89 1.20 1.09 1.61 1.19 EF区间比例/% <1.5 100 83.3 100 100 100 100 86.1 91.7 66.6 91.7 1.5～3 0 16.7 0 0 0 0 13.9 8.3 27.8 8.3 3～5 0 0 0 0 0 0 0 0 2.8 0 5～10 0 0 0 0 0 0 0 0 2.8 0
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表 7 三门湾沿岸土壤潜在有毒元素Pearson相关性矩阵
Table 7. The Pearson correlation matrix of potential toxic elements in soils along coast of Sanmen Bay
Cu Pb Zn Cr Ni Co Cd As Hg Sb Si Al Fe TOC pH Cu 1 Pb −0.47** 1 Zn 0.91** −0.30 1 Cr 0.93** −0.59** 0.85** 1 Ni 0.94** −0.57** 0.87** 0.99** 1 Co 0.92** −0.58** 0.87** 0.98** 0.99** 1 Cd 0.17 0.31 0.19 −0.02 −0.02 −0.04 1 As 0.89** −0.54** 0.77** 0.91** 0.91** 0.91** −0.02 1 Hg −0.33* 0.66** −0.32 −0.43** −0.45** −0.49** 0.47** −0.43** 1 Sb 0.71** −0.19 0.55** 0.66** 0.64** 0.62** 0.24 0.79** 0.01 1 Si −0.92** 0.59** −0.90** −0.95** −0.96** −0.95** 0.02 −0.89** 0.46** −0.63** 1 Al 0.82** −0.41** 0.91** 0.83** 0.86** 0.87** −0.05 0.75** −0.42* 0.50** −0.92** 1 Fe 0.92** −0.59** 0.89** 0.97** 0.98** 0.99** −0.03 0.93** −0.50** 0.63** −0.97** 0.89** 1 TOC −0.51** 0.46** −0.49** −0.55** −0.57** −0.61** 0.50** −0.66** 0.62** −0.36* 0.56** −0.49** −0.62** 1 pH 0.79** −0.71** 0.65** 0.87** 0.85** 0.82** −0.16 0.85** −0.49** 0.57** −0.84** 0.63** 0.83** −0.64** 1 注：**在p<0.01水平显著（双尾）；*在 p<0.05水平显著（双尾）。
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表 8 三门湾沿岸土壤潜在有毒元素旋转成分矩阵
Table 8. Rotation component matrix of potential toxic elements in the soils along coast of Sanmen Bay
变量 因子载荷（旋转） PC1 PC2 Cu 0.966 −0.103 Pb −0.403 0.687 Zn 0.919 −0.055 Cr 0.937 −0.279 Ni 0.942 −0.282 Co 0.926 −0.319 Cd 0.249 0.826 As 0.904 −0.276 Hg −0.239 0.835 Sb 0.775 0.162 Si −0.934 0.288 Al 0.848 −0.234 Fe 0.933 −0.324 TOC −0.450 0.686 pH 0.769 −0.453 特征值 9.356 3.146 方差贡献率/% 62.375 20.973 累积方差贡献率/% 62.375 83.349 注：旋转方法为凯撒正态化最大方差法；旋转在3次迭代后已收敛。
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