Antimony Concentration and Distribution in Groundwater of Zi River Estuary and Source Analysis
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摘要: 为查明资水尾闾第四系盆地地下水Sb含量特征，通过采集资水干流及尾闾地表水和不同类型地下水样品，运用水化学和$ {\rm{ \mathsf{ δ} }}^{2}\mathrm{H} $、$ {\rm{ \mathsf{ δ} }}^{18}\mathrm{O} $同位素与Sb含量的相关性分析，对地下水中Sb的含量及来源进行了研究.非汛期时，资水干流属于C类（> 5 μg/L），志溪河为B类（1~5 μg/L），其余地表水系为A类（< 1 μg/L），汛期时地表水系均属B类；A类孔隙潜水主要位于丘陵、岗地区资水两岸和部分平原滨湖地区，B类区域主要位于泉交河附近岗地区和大部分平原地区；部分孔隙承压水及受构造断裂影响的裂隙水为B类.含Sb矿物的溶解是孔隙承压水和裂隙水Sb的来源；地表水补给和灌溉水入渗导致潜水含水层Sb含量升高.Abstract: To find out the characteristics of Sb content in groundwater of Quaternary basin on the Zi River estuary area, in this paper it studies the distribution characteristics of Sb concentration and sources of Sb in groundwater by collecting surface water and groundwater samples from the main stream and estuary area, combined the correlation analysis of $ {\rm{ \mathsf{ δ} }}^{2}\mathrm{H},{\rm{ \mathsf{ δ} }}^{18}\mathrm{O} $ stable isotopes, hydrochemistry and Sb content. In non-flood season, the concentration of Sb in main streams of Zi River belongs to type C (> 5 μg/L), Zhixi River belongs to type B (1-5 μg/L), and other surface water samples belong to type A (< 1 μg/L). During flood period, all the surface water systems belong to type B. Type A areas of phreatic water were mainly distributed on part of plain area, lakeside area and Zi River bank which are at hills or hillock areas. Type B areas were those located at Quanjiao River and most of the plain area. Part of confined water was type A and the rest was type B. Fracture water which was affected by structural faults belongs to type B, otherwise was type A.The dissolution of Sb bearing minerals in the aquifer is the source of Sb in confined water and fracture water. The groundwater recharge from surface water and irrigation water resulted in Sb enrichment in phreatic water.
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图 1 研究区流域内锑矿分布（a）、研究区地貌分带、地表水系及采样点分布（b）
Fig. 1. Antimony mine distribution in Zi River basin (a) and geomorphic types, distribution of river systems and sampling points (b)
图 2 研究区地质简图及地下水流向示意（a）研究区第四系地层剖面（b, A‒A’）
图a中蓝色箭头示意地下水流向，红色箭头示意地表水补给地下水；F1.城步‒桃江断裂；F2.常德‒安仁转换断裂
Fig. 2. Lithological diagram and groundwater flow direction (a) and geological profile of study area (b, A‒A')
图 4 地表水及地下水样品氢氧稳定同位素关系
a.地表水及平原区地下水样品；b.丘陵和岗地区地下水样品
Fig. 4. Plots of $ {\rm{ \mathsf{ δ} }}^{2}\mathrm{H} $ and $ {\rm{ \mathsf{ δ} }}^{18}\mathrm{O} $ in surface water and groundwater samples
图 5 资水和丘陵至平原区孔隙潜水Sb浓度插值图
Fig. 5. Distribution of Sb concentration in Zi River and phreatic water from hills to hillock area
图 6 典型剖面地下水样品Sb浓度示意
a.岗地区B‒B’剖面；b.平原区C‒C’剖面
Fig. 6. Distribution of Sb concentration in representative profiles
图 7 孔隙潜水样品Ca[Sb(OH)6]2和Mg[Sb(OH)6]2·6H2O饱和指数
Fig. 7. Saturation indices (SI) of Ca[Sb(OH)6]2 and Mg[Sb(OH)6]2·6H2O in phreatic water
表 1 样品水化学分析结果描述性统计
Table 1. Descriptive statistical analysis of sample hydrochemistry data
pH Eh（mV） TDS (mg/L) K+ (mg/L) Na+ (mg/L) Ca2+ (mg/L) Mg2+ (mg/L) Cl‒ (mg/L) NO3‒ (mg/L) SO42‒ (mg/L) HCO3‒ (mg/L) 非汛期地表水（n=8） 最小值 6.90 126.00 158.02 1.86 3.17 19.07 2.20 3.08 1.99 6.00 85.40 最大值 8.67 201.00 245.02 3.59 8.30 67.06 8.82 7.38 8.26 23.08 128.90 平均值 7.86 165.00 194.23 2.52 5.44 34.71 5.91 4.89 4.09 14.18 108.86 C.V.(%) 7.19 13.90 15.38 27.02 31.26 43.66 40.36 32.38 52.22 42.51 13.27 汛期地表水（n=7） 最小值 6.78 64.60 119.67 1.93 3.75 22.61 3.00 5.40 4.29 12.68 54.90 最大值 7.44 146.90 178.34 3.74 5.63 35.85 5.31 6.29 10.34 20.36 99.13 平均值 7.18 104.59 152.76 2.47 4.53 29.71 4.17 5.90 7.64 16.73 81.59 C.V.(%) 3.63 30.35 15.42 23.98 15.93 16.20 19.87 5.25 31.25 13.77 22.69 孔隙潜水（n=71） 最小值 5.10 ‒181.00 59.38 0.18 0.96 3.20 0.91 0.00 0.00 0.00 10.68 最大值 8.65 251.00 864.04 6.75 34.77 137.88 40.52 55.65 250.07 167.93 318.73 平均值 6.30 79.80 229.68 1.80 10.70 31.60 8.65 10.94 10.86 14.39 121.46 C.V.(%) 9.03 174.75 57.86 73.95 69.22 82.57 83.33 84.19 306.68 170.80 59.27 孔隙承压水（n=5） 最小值 5.70 22.00 86.61 3.39 3.65 8.58 2.00 3.44 1.36 2.43 51.85 最大值 7.04 183.00 184.53 7.99 13.90 21.23 5.34 7.44 2.14 19.85 105.99 平均值 6.31 92.80 135.56 5.01 8.62 14.40 3.65 5.57 1.63 7.93 80.37 C.V.(%) 8.82 69.87 27.62 38.14 44.55 38.74 40.73 30.35 18.62 86.08 28.08 裂隙水（n=6） 最小值 5.88 79.00 50.70 0.36 1.22 3.04 1.60 1.86 0.79 0.92 18.30 最大值 7.86 195.00 710.15 3.73 11.08 80.44 17.47 18.22 10.62 71.83 410.36 平均值 6.75 153.33 193.11 1.54 4.59 20.27 4.69 6.36 5.69 14.66 98.01 C.V.(%) 11.96 29.22 131.62 104.11 84.39 146.34 133.66 98.83 76.75 191.81 156.71 
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表 2 样品Sb含量描述性统计
Table 2. Descriptive statistical analysis of Sb concentration
非汛期地表水（n=9） 汛期地表水（n=7） 孔隙潜水（n=71） 孔隙承压水（n=5） 裂隙水（n=3） 最小值 0.29 1.10 0.00 0.00 0.00 最大值 7.70 5.08 10.10 3.68 2.12 平均值 3.10 3.21 1.40 1.77 0.84 C.V.(%) 89.42 50.22 107.99 89.61 113.65
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表 3 裂隙水水样点数据
Table 3. Data of fracture water samples
ID 类型 井深（m） 取水岩层 TDS（mg/L） 水化学类型 Sb含量（μg/L） GW30 裂隙泉水 \\ Ptln 50.70 HCO3-CaMg 0 GW36 裂隙泉水 \\ Ptln 93.07 HCO3-Ca 0 ZX11 裂隙泉水 \\ D3 710.15 HCO3-Ca 2.12 GW31 基岩裂隙水 120 Ptbn 111.91 HCO3-CaMg 1.34 GW40 基岩裂隙水 50 γδ3 102.51 HCO3-Ca 0 ZX01 基岩裂隙水 60 Ptbn 90.31 HCO3-CaMg 1.57
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表 4 孔隙水Sb含量与水化学指标及微量元素的皮尔逊相关关系
Table 4. Pearson correlation coefficient of Sb concentration and hydrochemistry and trace elements in pore water
水岩作用来源（孔隙承压水） pH Eh TDS K+ Na+ Ca2+ Mg2+ Cl- Sb ‒0.10 ‒0.34 0.77* 0.49 0.52 0.58 0.56 0.80 NO3‒ SO42‒ HCO3‒ Fe Mn Zn Rb Sr Sb 0.48 0.76 0.70 ‒0.20 ‒0.38 0.87 0.67 0.64 随地表水‒地下水交互来源（孔隙潜水） pH Eh TDS K+ Na+ Ca2+ Mg2+ Cl‒ Sb ‒0.05 0.11 ‒0.13 ‒0.14 ‒0.05 ‒0.06 ‒0.09 ‒0.08 NO3‒ SO42‒ HCO3‒ Fe Mn Zn Rb Sr Sb 0.47** ‒0.15 ‒0.09 ‒0.10 0.02 ‒0.26 ‒0.17 ‒0.10 注：*在0.05级别（双尾），相关性显著；**在0.01级别（双尾），相关性显著.
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