EEMs characteristics of dissolved organic matter in water environment and its implications for antimony contamination in antimony mine of Xikuangshan, Hunan Province
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摘要:
溶解性有机质(dissolved organic matter, 简称DOM)是影响锑迁移转化的重要因素之一。湖南锡矿山锑矿是世界最大的锑矿, 水环境中锑污染情况严重。为查明锡矿山矿区水环境中DOM特征及其影响, 对锡矿山水环境样品进行三维荧光分析, 利用平行因子法提取水环境中天然有机组分, 分析荧光特征, 探究各组分之间与锑的相关关系。分析表明, 矿区水体环境中DOM以低腐殖化、陆源与微生物源混合来源为特点, 多数水样以陆源有机物为主。锡矿山锑矿区水体中包括了3种不同的组分: C1组分为陆源类腐殖质, C2组分为醌类腐殖质, C3组分为类蛋白质(酪氨酸); 水环境中C1组分相对含量最高, 地表水中C3组分相对含量高于地下水。研究认为, 存在以下途径影响地下水环境中锑的释放: ①类蛋白质组分与锑的络合促进锑的溶解释放; ②腐殖质组分与锑的直接络合。低锑地表水中天然有机组分相对含量受稀释作用的影响, 高锑地表水中天然有机组分相对含量对锑的来源有一定的指示作用。
Abstract:Dissolved organic matter (DOM) is an important factor affecting the migration and transformation of antimony(Sb). The Hunan Xikuangshan Sb mine is the largest Sb mine in the world and antimony pollution in the aquatic environment is serious. To determine the characteristics of DOM in the water environment of the Xikuangshan mining area and its influences, three-dimensional fluorescence analysis was performed on the water environment samples of the Xikuangshan mining area. PARAFAC was used to extract the natural organic components in the water environment and the relationship between each component and Sb was explored. The analysis shows that the DOM in the water environment of the mining area is characterized by low humification and mixed sources of terrestrial and microbial sources, and most water samples are mainly terrestrial organic matter. There are three different components in the water body of the Sb mining area of Xikuangshan: the C1 component is terrestrial humus; the C2 component is quinone humus; the C3 component is protein-like (tyrosine). The relative content of the C1 component in the water environment is the highest and the relative content of the C3 component in surface water is higher than that in groundwater. Studies have shown that there are the following ways to affect the release of Sb in the groundwater environment: (1) the complexation of protein-like components with Sb promotes the dissolution and release of Sb; (2) the direct complexation of humus components with Sb. The relative content of natural organic components in surface water with low Sb is affected by dilution. The relative content of natural organic components in surface water with high Sb has a certain indication for the source of Sb.
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图 1 研究区采样点分布图
Figure 1. Sampling sites for surface water and groundwater in the study area
图 2 研究区地下水与地表水水化学Piper三线图
Figure 2. Piper diagram of groundwater and surface water in the study area
图 4 研究区地下水、地表水中BIX与HIX(a)，SUVA254与SUVA260(b)的关系
Figure 4. Relationship between the BIX and HIX value (a), SUVA254 and SUVA260 value (b) of surface water and groundwater in the study area
图 5 平行因子法鉴别出的3个荧光组分及其荧光特征
Figure 5. Spectral characteristics of the 3 components model identified by EEM-PARAFAC in the water environment
图 6 研究区地下水与地表水中DOM各组分相对含量
Figure 6. Relative content of each component of DOM in groundwater and surface water of the study area
图 7 锡矿山水环境中FI、SUVA254、天然有机组分的相对含量与ρ(Sb)的关系
Figure 7. Relationships between Sb concentration and FI, SUVA254, and relative content of natural organic components in the water environment of the study area
图 8 研究区地表水中天然有机组分相对含量及ρ(Sb)沿程分布
Figure 8. Relative content of natural organic components and the distribution of Sb concentration along the flow direction in the surface water of the study area
表 1 研究区地下水、地表水指标统计
Table 1. Statistics of indexes of groundwater and surface water in the study area
指标 锡矿山组 佘田桥组 地表水 最大值 最小值 平均值 最大值 最小值 平均值 最大值 最小值 平均值 pH 7.44 6.16 7.06 7.03 6.42 6.82 9.19 4.31 7.85 EC/(μS·cm-1) 1 237.0 231.0 593.0 1 119.0 189.4 570.0 1 018.0 297.0 588.7 Sb 2.70 0.015 0.49 7.45 0.51 2.51 5.39 0.028 1.60 HCO3- 492.3 45.4 251.1 257.5 36.4 153.3 181.8 104.5 146.0 SO42- 228.90 26.36 77.48 381.51 65.83 138.90 997.60 34.57 246.66 Cl- 27.42 4.41 8.09 8.85 3.10 5.27 293.66 3.60 25.67 Na+ 54.60 1.16 14.38 67.97 0.97 16.60 310.35 1.78 44.73 Ca2+ ρB/(mg·L-1) 128.72 27.64 78.51 124.85 22.61 72.86 160.16 36.66 73.15 K+ 9.72 0.78 3.62 5.57 1.22 3.73 9.40 1.63 4.25 Mg2+ 17.57 3.04 7.21 14.80 2.92 7.92 26.67 2.53 9.03 DOC 2.276 0.565 1.120 1.663 0.567 1.134 2.294 0.880 1.374 HIX 6.44 0.58 3.06 7.91 1.75 5.08 6.09 0.64 2.48 BIX 1.16 0.71 0.87 0.97 0.74 0.85 0.98 0.70 0.78 FI 1.90 1.52 1.65 1.75 1.57 1.66 1.67 1.51 1.57 SUVA254 2.00 -0.49 0.54 1.66 0 0.77 3.28 1.26 2.13 注: HIX.腐殖化指数; BIX.生物指数; FI.荧光指数; SUVA254.254 nm处UV的吸光系数与DOC浓度的比值 
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表 2 锡矿山水体中3个荧光组分特征及与前人研究确定组分的对比
Table 2. Characteristics of three components in the water environment of study area and their comparison with previously identified components
组分 (Ex/Em)/nm 本研究中DOM组分 前人研究中DOM组分描述 C1 235(295)/414 陆源类腐殖质 C2： < 240/416，类腐殖酸[7];
C1： < 236~260/400~500，陆源腐殖质[32];
C2：225(330)/410，陆地来源[36]C2 260/464 腐殖质类，醌类 C2： < 240~275/434~520，腐殖质类[32];
C3： < 250，366/468，醌类[25];
SQ2：270(375)/462，还原醌类[33]C3 220(270)/306 类蛋白质(酪氨酸) 220(270)/(300~305)，类酪氨酸[37];
B峰：(225~237)/(309~321)和275/310，类酪氨酸[35];
C4：275/313，类酪氨酸[38]注：括号中数据为次级峰波长
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