Accumulation and Source Apportionment of Soil Heavy Metals in Molybdenum-Lead-Zinc Polymetallic Ore Concentration Area of Luanchuan
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摘要:
河南栾川钼铅锌多金属矿集区内长期矿产资源开发产生了大量的重金属，目前研究区农田表层土壤重金属累积及不同种类矿业活动对其影响尚不明晰。本文选取研究区内5个典型小流域，采集河流沿岸29条水平土壤剖面上95件农田表层土壤样品，采用极谱法测定Mo，电感耦合等离子体质谱法测定Cd，X射线荧光光谱法测定Cr、Cu、Pb和Zn，原子荧光分光光度法测定Hg和As含量，通过地累积指数法、内梅罗综合污染指数法和潜在生态风险指数法分别评价重金属的累积特征、污染程度和生态风险；采用多元统计分析和PMF模型对表层土壤重金属的来源进行解析。结果表明：研究区农田表层土壤中主要污染物为Mo，局部为Hg；除Cr外，其他重金属均不同程度地受到周边矿业活动的影响；5个流域土壤重金属富集程度依次是：北沟河＞淯河＞石宝沟＞陶湾北沟＞伊河。北沟河土壤总体为重污染，中等生态风险，其他流域土壤总体污染程度为轻度，生态风险等级为轻微；但不同流域均存在重金属污染较重和生态风险较强的点位。典型横向土壤剖面分析表明，近岸部分土壤重金属富集程度明显高于远岸土壤。研究区农田表层土壤重金属来源于自然源（32.9%）、铅锌矿矿业活动（30.6%）、钼矿矿业活动（26.8%）和金矿矿业活动（9.7%）。
Abstract:BACKGROUND The Luanchuan Mo-Pb-Zn polymetallic ore concentration area, located in Henan Province, China, has a long-term history of mining activities. Heavy metals have been liberated during mining, which induces heavy metal pollution of water and soil near the mines. There have been many studies about the pollution of heavy metals by mining activities, but it is still unclear as to the impact of various mine types in a polymetallic ore concentration area on accumulation of heavy metals in soil.
OBJECTIVES To study the impact of various mine types on accumulation of soil heavy metals, pollution level and ecological risk, and to identify the sources of soil heavy metals.
METHODS A total of 95 surface soil samples were collected from 29 soil profiles along the rivers in five typical basins in the Luanchuan Mo-Pb-Zn polymetallic ore concentration area, Henan Province, China. Mo, Hg, As, Cd, Cr, Cu, Pb and Zn in soil were measured by polarography, atomic fluorescence spectrophotometry (AFS) and inductively coupled plasma-mass spectrometry (ICP-MS). The Igeo, Nemerow index and potential ecological risk index were used to study the accumulation, pollution level and source apportionment of heavy metals.
RESULTS The results showed that Mo was the main pollutant, and part of the soil was obviously polluted by Hg. Cd, Pb, Zn, Cu and As in soil were also affected by the mining activities in the study area to some extent. Accumulation extent of heavy metals in soil from various river basins followed Beigou River > Yu River > Shibao River > Taowanbei River > Yi River. Soil samples from the Beigouhe River Basin were heavily polluted and posed a moderate risk level. In addition, soil samples from other river basins contained a low level of pollution and ecological risk. However, some sites which possessed a higher pollution level and ecological risk were found in all of the river basins. It was worth noting that soil samples near a river in a soil profile can accumulate more heavy metals than other soil samples, indicating that accumulation of heavy metals in the soil is affected by the river. The main sources of heavy metals in the surface soil were parent rock weathering (32.9%), lead zinc mining activities of Pb/Zn mines (30.6%), mining activities of Mo mines (26.8%), and mining activities of Au (9.7%), respectively.
CONCLUSIONS Mining activities cause heavy metal accumulation in the soil to some extent, and Mo and Hg pollution more heavily. Pb/Zn mines account for 30.59% of the source of soil heavy metals, which are higher than Mo mines and Au mines, indicating mining activities of Pb/Zn should be paid more attention. More heavy metals from parent rock (32.9%) indicate that it is necessary to measure the speciation of soil heavy metals and concentrations of heavy metals in crops.
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Key words:
- Mo-Pb-Zn molybdenum ore concentration area /
- heavy metals /
- soil /
- accumulation /
- PMF model /
- source apportionment
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表 1 栾川钼铅锌多金属矿集区农田表层土壤重金属含量特征（N=95）
Table 1. Characteristics of heavy metal contents in agricultural surface soils in Luanchuan Mo-Pb-Zn polymetallic ore concentration area (N=95).
重金属
元素最大值
（mg/kg）最小值
（mg/kg）中位数
（mg/kg）算术平均值
（mg/kg）标准差 变异系数
（%）土壤背景值
（mg/kg）Mo 366.85 1.31 32.35 71.77 81.60 113.69 0.98 Cd 6.56 0.12 0.85 1.23 1.17 95.14 0.19 Hg 0.78 0.01 0.05 0.09 0.12 131.35 0.04 As 124.20 2.71 15.00 20.27 18.96 93.56 7.92 Cr 120.00 18.70 67.10 66.31 17.75 26.77 75.80 Cu 438.80 25.70 52.70 74.19 57.88 78.02 29.60 Pb 595.60 16.60 82.70 139.33 130.87 93.93 31.60 Zn 1226.00 86.30 229.70 315.54 240.46 76.21 101.40 
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表 2 栾川钼铅锌多金属矿集区土壤重金属Spearman相关关系矩阵（N=95）
Table 2. Spearman’s correlation matrix for heavy metals in soils of Luanchuan Mo-Pb-Zn polymetallic ore concentration area (N=95).
元素 Mo Cd Hg As Cr Cu Pb Zn Mo 1 Cd 0.552** 1 Hg −0.104 −0.057 1 As 0.142 0.402** −0.063 1 Cr −0.301** −0.073 0.011 0.02 1 Cu 0.359** 0.299** 0.006 −0.105 0.263* 1 Pb 0.381** 0.612** −0.122 0.446** −0.139 0.157 1 Zn 0.537** 0.830** 0.002 0.376** 0.008 0.436** 0.607** 1 注：**表示在0.01的水平上显著相关；*表示在0.05水平上显著相关。
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表 3 主成分分析因子载荷系数
Table 3. Factor loading factor of PCA.
重金属元素 因子1 因子2 因子3 因子4 Mo 0.364 0.587 −0.526 −0.103 Cd 0.780 0.423 −0.151 0.004 Hg −0.049 −0.005 0.010 0.995 As 0.819 −0.320 0.137 −0.032 Cr −0.020 0.165 0.940 −0.011 Cu 0.046 0.885 0.228 0.008 Pb 0.788 0.142 −0.160 −0.107 Zn 0.750 0.532 −0.052 0.068
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