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金属元素具有毒性大、持久性强、富集性高和难降解等特点,通过进入土壤、空气和水中而对人体健康产生直接或间接危害[1-4]. 饮水和皮肤接触等途径是地表水体中金属元素对人体造成危害的主要方式[5-6]. 因此,研究地表水中金属元素分布特征,评价其对人体健康风险具有重要意义. 目前,国内外学者多采用美国环境保护署(US EPA)提出的人体健康风险评估方法评价金属元素对人体健康的危害,Egbueri等[7]研究了尼日利亚某地区浅层地下水重金属、Achary等[8]研究了孟加拉湾西南海岸地表水重金属、师环环等[9]研究了雷州半岛地下水重金属、赵玉[10]研究了渭河干流浅层地下水与地表水中Cd污染等评价金属元素对人体健康的危害等.
汾河是山西省的母亲河,每年从汾河取各类水资源24.3×108 m3,占山西省水资源利用总量的46%[11]. 流域内工农业生产排放的废水是其水体污染严重的主要原因,严重威胁着人民身体健康安全,破坏流域生态环境[12-14]. 目前对于汾河流域研究主要集中于水质污染[15]、土壤重金属[16]及沉积物重金属污染[17-18]等研究,但对汾河流域地表水中金属元素对人体健康风险评价研究较少.
本文选取汾河流域地表水金属元素为研究对象,分析对人体有潜在危害的As、Cu、Pb、Zn、Hg、Ni、Mn、Fe和Co共9种金属元素空间分布特征,利用多元统计分析方法分析金属元素之间的相关性和来源,采用US EPA水环境健康风险评价方法评价流域内地表水金属浓度对成人和儿童人体健康产生的危害,以期为汾河流域地表水金属元素监测、水资源保护和开发利用提供依据.
汾河流域地表水金属元素分布特征与健康风险评价
Distribution characteristics and health risk assessment of metal elements in surface water of Fenhe River Basin
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摘要: 为研究汾河流域地表水中金属污染特征及其健康危害程度,本文采集汾河流域主要支流入河口及干流断面水样39组,检测As、Cu、Pb、Zn、Hg、Ni、Mn、Fe和Co共9种金属元素含量,利用多元统计分析法、水环境健康风险评价模型分析了流域地表水中金属元素分布特征及对成人与儿童产生的健康危害. 结果表明,研究区主要超标元素为Hg、Fe和Mn,污染区主要分布于汾河干流中下游和支流. 汾河干流上游Fe、Mn、Zn和Co变化幅度较大,中游、下游次之;各支流金属元素含量差异较大. 多元统计分析显示,Hg和As主要来源于工业污染及农业污染等;Cu、Pb、Zn、Ni、Co、Fe和Mn来源于工农业生产和交通运输. 健康风险评价表明,汾河流域各河段健康总风险为汾河支流>汾河下游>汾河中游>汾河上游,汾河中下游和支流健康风险危害较大,健康风险均为中等;经饮用水途径造成的健康风险儿童是成人的1.15倍,儿童更易受到金属元素的危害;As为支流浍河和昌源河的主要致癌因子;各河段优先控制金属元素为As、Co、Pb、Fe和Hg.Abstract: In order to study the characteristics of metal pollution and health hazards in surface water of Fenhe River Basin, this paper took collected 39 water samples from the main branches of Fenhe River basin flowing into the estuary and main stream sections, and detected the content of nine metal elements, including As, Cu, Pb, Zn, Hg, Ni, Mn, Fe and Co. Multivariate statistical analysis and water environmental health risk assessment model were used to evaluate the distribution characteristics of metal elements in surface water and their health hazards to adults and children. The results showed that Hg, Fe and Mn were the main elements exceeding the standard in the study area, and the polluted areas were mainly distributed in the middle and lower reaches and tributaries of the main stream of Fenhe River. The changes of Fe, Mn, Zn and Co in the upper reaches of Fenhe River are large, followed by the middle and lower reache. The content of metal elements in tributaries varies greatly. Multivariate statistical analysis showed that Hg and As mainly came from industrial pollution and agricultural pollution. Pb, Cu, Zn, Ni, Co, Fe and Mn come from industrial and agricultural production and transportation. The health risk evaluation showed that the total health risk of each section of the Fenhe River basin was tributary>lower reaches> middle reaches> upper reaches. The health risk of children through drinking water was 1.15 times that of adults, and children were more vulnerable to metal elements; As was the main carcinogen of Huihe River and Changyuan River; The priority control metal elements in each river reach were As, Co, Pb, Fe and Hg.
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表 1 金属元素毒理学参数(kg·d·mg−1)
Table 1. Toxicological parameters of the metals
元素
Element致癌强度系数
SF毒性参考剂量
RfDAs 15 — Cu — 0.005 Pb — 0.0014 Zn — 0.3 Hg — 0.0003 Ni — 0.02 Mn — 0.14 Fe — 0.7 Co — 0.0003 注:“—”表示无数据. Note: "-" indicates no data. 表 2 汾河流域主要水化学组分统计结果(μg·L−1)
Table 2. Statistics of major ions in Fenhe River basin
水体
Water数据统计
Data statisticsAs Hg Cu Pb Zn Mn Ni Co Fe 汾河上游
Upper reaches最大值 2.73 0.55 3.87 2.01 10.2 110 4.87 1.66 2270 最小值 0.23 0.26 0.51 2.01 0.91 0.78 1.21 0.16 16 平均值 1.6 0.41 1.41 2.01 2.91 23.23 2.22 0.44 426.45 标准差 0.86 0.09 0.92 0 3.62 29.95 0.99 0.42 631.73 变异系数 0.54 0.22 0.65 0 1.24 1.29 0.45 0.95 1.48 检出率/% 100 100 100 9.1 54.5 100 100 100 100 汾河中游
Middle reaches最大值 4.51 0.59 9.21 6.05 49.8 372 12.1 3.9 4600 最小值 1.54 0.36 1.12 0.14 11.2 19.4 2.53 0.35 140 平均值 3.13 0.5 5 3.34 31.52 194.35 7.8 2.07 2139.09 标准差 1.2 0.07 3.06 2.44 14.14 142.12 3.43 1.39 1590.64 汾河中游
Middle reaches变异系数 0.38 0.14 0.61 0.73 0.45 0.73 0.44 0.67 0.74 检出率/% 100 100 100 90.9 90.9 100 100 100 100 汾河下游
Lower reaches最大值 4.73 0.88 8.45 8.07 37.2 360 12.3 4.43 3920 最小值 2.35 0.09 1.7 1.25 2.09 152 4.77 0.99 150 平均值 3.85 0.62 4.93 4.48 21.65 262 8.38 2.53 2088.89 标准差 0.85 0.24 2.35 2.44 12.9 75.7 2.46 1.12 1227.89 变异系数 0.22 0.39 0.48 0.54 0.6 0.29 0.29 0.44 0.59 检出率/% 100 100 100 100 100 100 100 100 100 汾河支流
Tributaries最大值 21.8 1.21 3.52 1.08 13.2 155 7.31 1.28 1070 最小值 1.09 0.29 0.55 0.56 2.46 4.2 1.44 0.18 110 平均值 5.28 0.54 1.93 0.84 6.29 80.08 3.62 0.74 556.25 标准差 6.91 0.3 0.99 0.22 4.35 59.63 2.28 0.43 321.6 变异系数 1.31 0.55 0.51 0.26 0.69 0.74 0.63 0.58 0.58 检出率/% 100 100 100 50 100 100 100 100 100 地表水Ⅲ类水标准或标准限值
Class III standard or standard limit of surface water50 0.1 1000 50 1000 100 20 1000 300 表 3 国内外不同河流金属元素浓度(μg·L−1)
Table 3. Concentrations of heavy metals in different basins at home and abroad (μg·L−1)
河流
RiverAs Hg Cu Pb Zn Mn Ni Co Fe 汾河(本研究) 2.80 0.50 3.71 3.75 21.10 153.27 5.99 1.63 1516.81 渭河[30] 1.48 0.98 2.09 2.93 7.30 0.86 0.78 — 382.41 黄河[31] 7.30 0.14 36.27 19.51 52.46 597 25.11 — — 长江[32] 13.20 — 10.70 55.10 9.40 5.40 13.40 — 239.80 珠江[33] — — 8.24 — — 5.84 — — — Subarnarekha河(印度)[34] 2.13 — 3.35 — — 1.48 2.39 0.24 98.80 底格里斯河( 土耳其)[35] 2.354 — 165 0.342 37 467 72 111 388 哈拉兹河( 伊朗)[36] 55.35 — 13.25 4.4 52.75 116 22.4 — — 注:“—”表示无数据 表 4 重金属的相关关系矩阵
Table 4. Correlation matrix of the heavy metals
Hg As Cu Pb Zn Mn Ni Co Fe Hg 1 0.676** 0.222 0.043 0.075 0.358* 0.386* 0.287 0.167 As 1 0.267 −0.021 0.099 0.330* 0.372* 0.283 0.206 Cu 1 0.939** 0.954** 0.911** 0.958** 0.968** 0.970** Pb 1 0.849** 0.941** 0.900** 0.964** 0.928** Zn 1 0.826** 0.910** 0.892** 0.917** Mn 1 0.942** 0.950** 0.884** Ni 1 0.966** 0.927** Co 1 0.965** Fe 1 注:**表示在0.01水平上显著相关;*表示在0.05水平上显著相关. 表 5 重金属的主成分因子载荷
Table 5. Factors matrix of the heavy metals in the principal component analysis
元素
ElementPC1 PC2 Hg 0.062 0.929 As 0.045 0.927 Cu 0.990 −0.034 Pb 0.964 −0.042 Zn 0.921 −0.142 Mn 0.966 0.057 Ni 0.968 0.146 Co 0.981 0.015 Fe 0.971 −0.109 特征值 6.540 1.782 方差/% 72.668 19.796 累积方差/% 72.688 92.464 表 6 地表水重金属平均个人年健康风险(×10−11a−1)
Table 6. Average personal annual health risks caused by the heavy metals via drinking pathways in surface water
人群
Crowd水体
Water数据统计
Data statisticsAs Cu Pb Zn Hg Ni Mn Fe Co 成人
Adult汾河上游 最大值 1.90×106 35.85 66.49 1.57 84.91 11.28 36.39 150.18 256.26 最小值 1.60×105 4.72 66.49 0.14 40.14 2.80 0.26 1.06 24.70 平均值 1.11×106 13.09 66.49 0.45 63.57 5.13 7.69 28.21 68.35 汾河中游 最大值 3.13×106 85.31 200.14 7.69 91.08 28.02 123.06 304.34 602.06 最小值 1.07×106 10.37 4.63 1.73 55.58 5.86 6.42 9.26 54.03 平均值 2.17×106 46.32 110.52 4.87 77.33 18.06 64.29 141.52 319.70 汾河下游 最大值 3.28×106 78.27 266.96 5.74 135.85 28.48 119.09 259.35 683.88 最小值 1.63×106 15.75 41.35 0.32 13.89 11.05 50.28 9.92 152.83 平均值 2.67×106 45.67 148.28 3.34 96.23 19.41 86.67 138.20 390.40 汾河支流 最大值 1.51×107 32.60 35.73 2.04 186.79 16.93 51.27 70.79 197.60 最小值 7.57×105 5.09 18.53 0.38 44.77 3.33 1.39 7.28 27.79 平均值 3.65×106 17.90 27.87 0.97 83.56 8.39 26.49 36.80 114.04 儿童
Children汾河上游 最大值 2.18×106 41.28 76.57 1.81 97.78 12.99 41.90 172.95 295.11 最小值 1.84×105 5.44 76.57 0.16 46.22 3.23 0.30 1.22 28.44 平均值 1.28×106 15.07 76.57 0.52 73.21 5.91 8.85 32.49 78.71 汾河中游 最大值 3.60×106 98.24 230.48 8.85 104.89 32.27 141.71 350.48 693.33 最小值 1.23×106 11.95 5.33 1.99 64.00 6.75 7.39 10.67 62.22 平均值 2.50×106 53.34 127.28 5.60 89.05 20.80 74.04 162.98 368.16 汾河下游 最大值 3.78×106 90.13 307.43 6.61 156.44 32.80 137.14 298.67 787.56 最小值 1.88×106 18.13 47.62 0.37 16.00 12.72 57.90 11.43 176.00 平均值 3.08×106 52.60 170.76 3.85 110.81 22.36 99.81 159.15 449.58 汾河支流 最大值 1.73×107 37.55 41.14 2.35 215.11 19.49 59.05 81.52 227.56 最小值 8.72×105 5.87 21.33 0.44 51.56 3.84 1.60 8.38 32.00 平均值 4.21×106 20.61 32.10 1.12 96.22 9.66 30.51 42.38 131.33 表 7 年均总健康风险值(a−1)
Table 7. Average total personal annual health risks
人群
Crowd健康风险
Health risks汾河上游
Upper reaches汾河中游
Middle reaches汾河下游
Lower reaches汾河支流
Tributaries成人
AdultRc 1.11×10−5 2.17×10−5 2.67×10−5 3.65×10−5 Rn 2.21×10−9 9.14×10−9 1.05×10−8 3.39×10−9 RT 1.11×10−5 2.17×10−5 2.67×10−5 3.65×10−5 风险等级 中等 中等 中等 中等 儿童
ChildrenRc 1.28×10−5 2.50×10−5 3.08×10−5 4.21×10−5 Rn 2.21×10−9 8.89×10−9 1.05×10−8 3.48×10−9 RT 1.28×10−5 2.50×10−5 3.08×10−5 4.21×10−5 风险等级 中等 中等 中等 中等 -
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