Temporal and Spatial Variation and Influencing Factors of Heavy Metals in the Water of the Chenjiagou River in a Certain Place
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摘要:
河水重金属污染一直是环境污染防治领域的热点。秦岭某地石煤矿区陈家沟河水中重金属含量严重超标，但重金属来源不明，为污染治理带来困扰。为了查明陈家沟河水中重金属来源和时空变化情况，采集了2期河水、废弃石煤矿硐排水、废渣堆淋溶水等地表水样品，采用污染指数法、主成分分析法和Pearson相关性分析方法，研究河水中重金属污染程度、空间分布，并对河水中重金属来源进行了解析。研究表明，陈家沟源头河水（对照点）重金属含量可以达到地表水的Ⅰ类标准，中游受废弃石煤矿矿硐排水及废渣堆淋溶水的影响，河水中重金属含量显著升高，汇入干流前河水中重金属含量是对照点的3.5～312倍；河水中Cd、Cu、Zn、Ni、Mn等重金属元素同源，均来源于矿硐排水、废渣淋溶水。河水中重金属含量的空间分布与地质体、污染源分布以及河水pH、盐度等因素有关。研究结果可为陈家沟河水重金属污染防治提供科学依据。
Abstract:River water heavy metal pollution has always been a hot spot problem in the field of environmental pollution prevention and control. The heavy metal content in the water of the Chenjiagou river in a stone coal mining area in Qinling exceeded the standard seriously, but the source of heavy metals was unknown, which caused trouble for pollution control. In order to find out the source and temporal and spatial changes of heavy metals in the Chenjiagou river, surface water samples such as Phase II river water, waste stone coal mine drainage and waste residue pile leaching water were collected, and the pollution index method, principal component analysis and Pearson correlation analysis methods were used to study the degree and spatial distribution of heavy metal pollution in river water, and the sources of heavy metals in river water were analyzed. The results show that the heavy metal content of the river water at the source of Chenjiagou (control point) can reach the Class I standard of surface water, and the heavy metal content in the middle reaches is significantly increased by the drainage of waste stone coal mines and the leaching water of waste residue pile in the middle reach, and the heavy metal content in the river water before entering the main stream is 3.5～312 times that of the control point; the heavy metals such as Cd, Cu, Zn, Ni, and Mn in the river water are homologous, all from the mine drainage and waste residue leaching water in the upper reaches of the river. The spatial distribution of heavy metal content in river water is related to geological bodies, pollution source distribution, river pH, salinity and other factors. The research results provide a scientific basis for the prevention and control of heavy metal pollution in Chenjiagou river.
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图 2 陈家沟地表水样品类型及采样点分布图
Figure 2. Chenjiagou surface water sample type and sampling point distribution map
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图 3 陈家沟河水从上游到下游PH值及重金属含量的空间变化及超标情况
Figure 3. Spatial variation and excesses of PH、heavy metal content in Chenjiagou River from upstream to downstream
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图 4 河水中重金属含量的时间变化
8月. 累计降雨量＜50 mm；9月. 降雨量＞100 mm；10月. 降雨量＞180 mm（降雨量计算了采样前15天总降雨量） ；数据来源：2022年8～10月紫阳县天气（中国气象网https://www.cma.gov.cn）
Figure 4. Time variation of heavy metal content in river water
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图 6 河水中重金属离子浓度含量随pH值的变化
Figure 6. The concentration of heavy metal ions in river water varies with pH
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图 7 河水中重金属离子浓度含量随盐度的变化
Figure 7. The concentration of heavy metal ions in river water varies with salinity
表 1 样品分析方法、检出限及检测仪器概况表
Table 1 Sample analysis methods, detection limits and monitoring instruments
分析对象 分析方法 检出限 检测仪器 pH 玻璃电极法现场 / pH计、PHSJ-4F As、Hg、Se 原子荧光光谱法（AFS） 0.1 μg/L、0.05 μg/L、0.1 μg/L 原子荧光光度计AFS-2202E Cd、Al、Cu、
Zn、Ni、Mn电感耦合等离子体质谱（ICP–MS） 0.06 μg/L、0.6 μg/L、0.09 μg/L、
0.8 μg/L、0.07 μg/L、0.06 μg/L电感耦合等离子质谱ICAP-RQ Cr6+ 二苯碳酰二肼分光光度法（COL） 0.004 mg/L 紫外可见分光光度计UV-1800 TFe 电感耦合等离子体光谱法（ICP–AES） 4.5 μg/L 电感耦合等离子光谱ICAP7400 
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表 2 河水环境质量标准表（mg/L）
Table 2 Water environmental quality standard Unit (mg/L)
pH Cd Cr Cu Zn Ni Mn Fe Al 《地表水环境质量标准》
（GB 3838–2002）Ⅱ类标准 6～9 0.005 0.05 1 1 Ⅲ类标准 6～9 0.005 0.05 1 1 Ⅳ类标准 6～9 0.005 0.05 2 2 Ⅴ类标准 6～9 0.01 0.1 2 2 《地表水环境质量标准》集中式生活饮用水
地表水源地标准（GB 3838–2002）0.02 0.1 0.3 生活饮用水卫生标准（GB 5749–2006） 0.2
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表 3 河水重金属超标倍数及污染程度分级表
Table 3 The excessive multiple of heavy metals and the degree of pollution in river water
等级划分 单项污染超标倍数 污染程度 综合污染指数 污染程度 Ⅰ Pc≤0 无污染 Pz≤0.7 清洁（安全级） Ⅱ 0＜Pc≤1 轻度污染 0.7＜Pz≤1.0 尚清洁（警戒限） Ⅲ 1＜Pc≤2 中度污染 1.0＜Pz≤2.0 轻度污染 Ⅳ 2＜Pc≤4 重度污染 2.0＜Pz≤3.0 中度污染 Ⅴ Pc＞4 极度污染 Pz＞3.0 重度污染
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表 4 陈家沟河水中不同点位重金属元素含量表（mg/L）
Table 4 Heavy metal content in Chenjiagou river water (mg/L)
编号 位置 pH Cd Cu Zn Ni Mn Fe Al S121 源头（对照点） 7.48 0.0011 0.003 0.046 0.011 0.035 0.02 0.081 S101 沿河道距源头82m 6.46 0.0006 0.001 0.023 0.004 0.001 0.02 0.045 S103 沿河道距源头369m 5.05 0.01 0.052 0.15 0.048 0.3 0.02 1.142 S124 与S103相距1376m 3.75 0.38 1.41 6.12 2.2 11.4 0.41 20.56 S126 与S124相距1143m 4.62 0.28 0.94 5.61 1.92 9.72 0.09 14.36
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表 5 陈家沟矿山污染源中重金属元素含量表（mg/L）
Table 5 Heavy metal content in Chenjiagou pollution source (mg/L)
编号 位置 类型 pH Cd Cu Zn Ni Mn Fe Al S102 距河道51m 矿硐积水 4.04 0.16 1.42 1.06 0.4 0.94 0.08 9.76 S104 与S103相距470m 矿硐排水 5.8 0.096 0.022 6.03 1.8 14.8 0.02 0.39 S122 汇入河道处与S104相距104m 废渣淋溶水 3 0.9 11.2 22.4 12.4 50.6 15.37 185.6 S3 汇入河道处与S122相距243m 矿硐排水 3.47 2.5 4.68 27.8 7.86 54.1 19.57 - S123 距离主河道直线距离65m 矿硐排水 6 0.0037 0.004 2 1.0 2.6 0.04 0.443
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表 6 河水中pH、重金属相关性分析 统计表（n=11）
Table 6 Correlation analysis of pH and heavy metals in river water (n=11)
pH Cd Cr Cu Zn Ni Mn Fe Al pH 1 Cd −0.603* 1 Cr −0.685* 0.550 1 Cu −0.768** 0.824** 0.744** 1 Zn −0.586 0.988** 0.447 0.797** 1 Ni −0.636* 0.980** 0.486 0.842** 0.991** 1 Mn −0.531 0.947** 0.326 0.724* 0.977** 0.969** 1 Fe −0.694* 0.510 0.552 0.632* 0.523 0.556 0.560 1 Al −0.492 0.741** 0.426 0.462 0.759** 0.733* 0.734* 0.568 1 注：* 表示p＜0.05 水平显著；**表示 p＜0.01水平显著。
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表 7 河水中重金属主成分分析结果表
Table 7 Analysis results of heavy metal principal components in river water
元素 主成分 PC1 PC2 PC3 PC4 Cd 0.885 0.326 0.127 0.292 Cr 0.181 0.941 0.214 0.173 Cu 0.701 0.611 0.324 −0.081 Zn 0.915 0.204 0.173 0.298 Ni 0.910 0.250 0.211 0.245 Mn 0.916 0.050 0.268 0.278 Fe 0.268 0.290 0.893 0.213 Al 0.480 0.161 0.247 0.821
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表 8 矿体及岩层中重金属元素平均含量统计表（mg/L）
Table 8 Average content of heavy metal elements in ore bodies and rock formations (mg/L)
指标 Cd Cr Cu Zn Ni Mn 陈家沟石煤矿体 0.9 169 34 86.3 64.6 230 南秦岭斑鸠关组平均值* 1.58 183 21.9 133 60 516 大陆上地壳* 0.098 35 25 71 20 600 注：*表示数据来自中国地质调查局西安地质调查中心（2021）。
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表 9 陈家沟不同地表水中重金属平均含量统计表（mg/L）
Table 9 Average content of heavy metals in different surface waters of Chenjiagou (mg/L)
Cd Cu Zn Ni Mn Fe Al 废渣堆淋溶水（S122） 0.9 11.2 22.4 12.4 50.6 15.37 185.6 矿硐排水（n=4） 0.69 1.53 9.22 2.76 18.11 4.93 3.53 河水（n=5） 0.13 0.48 2.39 0.84 4.29 0.11 7.24 对照值（S121） 0.0011 0.003 0.046 0.011 0.035 0.02 0.081
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表 10 金属氢氧化物沉淀的pH值及其溶度积统计表（25 ℃）
Table 10 pH value and solubility product of metal hydroxide precipitation (25°C)
氢氧化物 pH 溶度积 氢氧化物 pH 溶度积 Fe（OH）3 2.48 4×10−38 Cu（OH）2 5.4 1.6×10−19 Fe（OH）2 5.5 4.8×10−17 Mn（OH）2 9.0 4.1×10−14 Al（OH）3 4.1 1.9×10−33 Zn（OH）2 5.2 4.5×10−17 Cr（OH）3 5.3 7×10−31 Cd（OH）2 6.7 2.3×10−14
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表 11 河水盐度与重金属元素含量的相关性统计表（n=8）
Table 11 Correlation between salinity of river water and heavy metal content (n=8)
Cd Cu Zn Ni Mn Fe 盐度 0.694 0.176 0.820* 0.843** 0.764* −0.287 注：* 表示p＜0.05 水平显著；**表示 p＜0.01水平显著。
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