Distribution Characteristics and Ecological Risk Assessment of Heavy Metals in Soils from Jiulong Li-Be Mining Area, Western Sichuan Province, China
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摘要:
川西九龙地区是近年来中国关键矿产资源勘查的热点地区之一，区内锂铍等稀有金属矿产资源优势突出，有望逐步发展成为国家级大型资源基地。作为长江上游生态保护屏障，该区生态环境脆弱，面对矿业开发的巨大机遇，在当前“环保优先”的现实情况下，急需摸清该区环境家底，支撑国家能源战略发展。本文用ICP-MS方法检测了该区352件土壤样品中7种重金属元素（Cd、As、Pb、Cr、Cu、Ni、Zn）的含量，运用地累积指数法、污染负荷指数法、潜在生态风险指数法和健康风险评价模型，结合GIS空间分析，综合研究了该区土壤中重金属的空间分布特征和生态风险。结果表明：①研究区土壤7种重金属元素浓度的平均值均没有超过国家农用土壤污染风险筛选值。As和Pb平均含量低于四川省土壤背景值，Cd、Cr、Cu、Ni和Zn含量高于背景值，分别是背景值的2.44、1.04、1.15、1.28和1.17倍。②Cd、Pb、Cr、Cu、Ni和Zn六种重金属元素浓度的空间分布特征明显受到区内黑云母花岗岩的影响，Pb的高浓度中心以及Cr、Cu、Ni和Zn的低浓度中心与岩体的空间位置对应关系明显。③地累积指数法评价结果显示，研究区土壤区域整体上不存在重金属异常累积；污染负荷指数法评价结果显示污染负荷指数均小于1，不存在重金属的污染；除Cd存在轻微的潜在生态风险外，其余6种元素均不存在潜在生态风险。④健康风险评价模型分析结果显示，空间上，Cd元素的单元素潜在生态风险指数空间分布规律与岩体存在一定联系，无生态风险区域与黑云母花岗岩岩体位置对应。土壤中的重金属可以通过手口、呼吸和皮肤直接接触三种途径进入人体，其中手口途径是产生健康风险的最主要途径。在全部重金属元素产生的健康风险中，除Cr的手口途径会产生可以接受的正常的自然致癌风险外，其余元素均不存在致癌性和非致癌性。研究表明，当前研究区土壤不存在重金属污染，潜在危害程度较低，且不存在非致癌和致癌性风险。但基于土壤中重金属存在一定的累积效应，在今后矿业开发过程中要密切关注土壤重金属浓度的变化，防止重金属污染带来的风险。
Abstract:BACKGROUND The Jiulong area in western Sichuan is an important rare metal production area in China, which has a large resource potential. As an ecological protection barrier on the upper reaches of the Yangtze River, the ecological environment of this area is fragile. Facing the huge opportunities of mining development and under the current situation of 'environmental protection first', it is urgent to investigate the environmental background of this area to support the development of national energy strategy.
OBJECTIVES To evaluate the ecological risk of heavy metals in soils from the Jiulong Li-Be mining area.
METHODS A total of 352 soil samples were collected. The concentration of 7 heavy metals (Cd, As, Pb, Cr, Cu, Ni, Zn) in soil was analyzed by NexION 300x inductively coupled plasma-mass spectrometer (ICP-MS). The comprehensive assessment methods including geoaccumulation index, pollution load index, potential ecological risk index, and health risk model, combined with GIS spatial analysis were used to study the spatial distribution characteristics and ecological risk of heavy metals in the soil.
RESULTS The average concentration of all 7 heavy metals in the soil in Jiulong did not exceed the Chinese national standard. There was no soil heavy metals pollution in the studied area. Compared with the soil background value of Sichuan Province, the average concentrations of As and Pb were lower than the background; the concentrations of Cd, Cr, Cu, Ni, and Zn were higher than the background, which were 2.44, 1.04, 1.15, 1.28, and 1.17 times the background values, respectively. The spatial distribution characteristics of these elements except As were affected by biotite granite in the study area. The high concentration center of Pb and the low concentration center of Cr, Cu, Ni and Zn had an obvious correspondence with the spatial position of the rock mass. Except for the weak accumulation indicated by Cd Igeo, there was no accumulation of other heavy metals. Similarly, there was no potential ecological risk in the study area, except for the slight potential ecological risk of Cd. Spatially, the distribution of Cd single element potential ecological risk index was related to the rock mass, and the area without potential ecological risk corresponded to the location of the biotite granite rock mass. Heavy metals in the soil can enter the human body through direct contact with hands, mouth, and skin, and through inhalation. The hand-to-mouth approach is the most important way to generate health risks among all 3 approaches. Except hand-to-mouth approach of Cr, which has an acceptable and normal natural carcinogenic risk, there is no carcinogenic risk for other metals.
CONCLUSIONS At present, there is no pollution of heavy metals in the soil in the studied area. The potential risk of heavy metals is low, and there are no non-carcinogenic and carcinogenic risks. However, due to the cumulative effect of heavy metals in the soil, close attention must be paid to changes in the concentration of heavy metals in the soil in the future mining development process, to prevent the risk caused by heavy metals pollution.
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表 1 暴露健康评价模型参数值
Table 1. Parameter values of exposure assessment models
参数 中文含义(单位) 成人 儿童 IngR 摄入土壤的频率(mg/d) 100 200 InhR 呼吸频率(m3/d) 20 5 EF 暴露频率(d/a) 180 180 ED 暴露年限(a) 24 6 BW 平均体质量(kg) 62.4 15 AT 平均暴露时间(d) 365×ED(非致癌) 365×ED(非致癌) 365×70(致癌) 365×70(致癌) PEF 灰尘排放因子(m3/kg) 1.36×109 1.36×109 CF 转换系数(kg/mg) 1.0×10-6 1.0×10-6 SL 皮肤黏着度[mg/(d·cm2)] 0.07 0.2 ABS 皮肤吸收因子(无量纲) 0.001 0.001 SA 暴露皮肤表面积(cm2) 2011 1078 
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表 2 土壤重金属不同暴露途径的RfD和SF值
Table 2. RfD and SF values of heavy metals in the soil of different exposure pathways
非致癌暴露参考剂量和致癌风险斜率 Cd As Pb Cr3+ Cu Zn RfDing(mg/kg·d) 1.00×10-3 3.00×10-4 3.50×10-3 3.00×10-3 4.00×10-2 0.3 RfDinh(mg/kg·d) 1.00×10-3 3.01×10-4 3.52×10-3 2.86×10-5 4.00×10-2 - RfDderm(mg/kg·d) 1.00×10-5 1.23×10-4 5.25×10-4 6.00×10-5 1.20×10-2 0.3 SFing(kg·d/mg) 6.30 15.1 - 1.5 - - SFinh(kg·d/mg) 6.40 15.1 - - - - SFderm(kg·d/mg) 6.30 7.5 - 1.95×10-2 - - 注：“-”表示无相关数据。
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表 3 研究区土壤重金属浓度描述性统计
Table 3. Concentrations of heavy metals in soils of the research area
重金属元素 浓度范围
(mg/kg)平均值
(mg/kg)标准差
(mg/kg)变异系数
(%)偏度 峰度 筛选值
(mg/kg)四川省土壤背景值
(mg/kg)Cd 0.05~0.49 0.19 0.07 0.39 0.88 1.52 0.3 0.079 As 0.34~12.21 2.50 1.74 0.70 1.92 5.33 40 10.4 Pb 6.05~47.28 30.36 4.60 0.15 0.27 2.25 90 30.9 Cr 8.11~133.79 81.98 28.21 0.34 -1.56 1.20 150 79 Cu 4.86~109.89 35.86 15.77 0.44 0.47 1.90 50 31.1 Ni 3.99~75.49 41.65 15.85 0.38 -1.04 0.35 70 32.6 Zn 33.94~157.02 101.35 18.81 0.19 -0.84 0.89 200 86.5 Be 0.98~18.86 3.79 2.09 0.55 3.09 14.81 - 1.80
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表 4 研究区土壤重金属Igeo分级统计
Table 4. Statistical classification of heavy metals Igeo in soils of the research area
重金属元素 Igeo平均值 各分级中样品数占总样品数比例(%) 第0级 第1级 第2级 第3级 第4级 第5级 第6级 Cd 0.59 13.92 62.50 23.30 0.28 0 0 0 As -2.95 100 0 0 0 0 0 0 Pb -0.63 99.72 0.28 0 0 0 0 0 Cr -0.72 99.43 0.57 0 0 0 0 0 Cu -0.57 79.55 19.89 0.57 0 0 0 0 Ni -0.44 62.50 37.50 0 0 0 0 0 Zn -0.39 96.88 3.13 0 0 0 0 0
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表 5 研究区土壤重金属单元素潜在生态风险等级统计
Table 5. Statistics of Eri in soils of the research area
等级 各分级中样品数占总样品数比例(%) Cd As Pb Cr Cu Ni Zn 无 9.94 100 100 100 100 100 100 轻微 56.53 0 0 0 0 0 0 中等 32.39 0 0 0 0 0 0 强烈 1.14 0 0 0 0 0 0 极强 0 0 0 0 0 0 0
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表 6 研究区不同途径土壤重金属日均暴露量、非致癌风险指数和致癌风险指数
Table 6. Daily exposure doses, non-carcinogenic risk index and carcinogenic risk index of heavy metals in soils of the research area
参数 Cd As Pb Cr Cu Ni Zn 合计 LADDing
(mg·kg-1·d-1)1.61×10-7 2.09×10-6 2.24×10-4 6.84×10-5 2.64×10-4 3.07×10-4 7.46×10-4 1.61×10-3 LADDinh
(mg·kg-1·d-1)9.66×10-12 1.25×10-10 2.63×10-6 4.12×10-9 3.10×10-6 3.60×10-6 8.77×10-6 1.81×10-5 LADDderm
(mg·kg-1·d-1)1.90×10-10 2.47×10-9 2.49×10-7 8.11×10-8 2.94×10-7 3.42×10-7 8.31×10-7 1.80×10-6 ΣLADD
(mg·kg-1·d-1)1.61×10-7 2.09×10-6 2.27×10-4 6.85×10-5 2.68×10-4 3.11×10-4 7.56×10-4 1.63×10-3 HQing 1.61×10-4 6.95×10-3 6.39×10-2 2.28×10-2 6.60×10-3 - 2.49×10-3 1.03×10-1 HQinh 9.66×10-9 4.17×10-7 7.46×10-4 1.44×10-4 7.76×10-5 - - 9.68×10-4 HQderm 1.90×10-5 2.01×10-5 4.74×10-4 1.35×10-3 2.45×10-5 - 2.77×10-6 1.89×10-3 HI 1.80×10-4 6.97×10-3 6.51×10-2 2.43×10-2 6.71×10-3 - 2.49×10-3 1.06×10-1 Risking 1.01×10-6 3.15×10-5 - 1.0×10-4 - - - 1.35×10-4 Riskinh 6.19×10-11 1.89×10-9 - - - - - 1.96×10-9 Riskderm 1.20×10-9 1.85×10-8 - 1.58×10-9 - - - 2.13×10-8 CR 1.01×10-6 3.15×10-5 - 1.0×10-4 - - - 1.35×10-4 注：“-”表示无相关数据。
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