Hydrochemical characteristics and genetic analysis of the Xianju basin in southern Zhejiang Province
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摘要: 仙居盆地是浙南诸河流域主要盆地和社会经济活动区域。为揭示盆地内地表水和地下水的水化学特征，综合利用数理统计、Piper三线图、主成分分析和离子比等方法对盆地内地表水及浅层地下水进行水化学统计分析及成因判别。结果表明，仙居盆地水化学类型主要为HCO3-Ca·Na型，阳离子以Ca2+、Na+为主，阴离子HCO$_3^{-}$为主。${\rm{NO}}_3^{-}$、Cl−变异系数较大；地下水溶解性总固体为45.50~288.00 mg·L−1，地表水为20.10~95.80 mg·L−1。盆地内水化学特征主要受岩石风化及人类活动影响，Ca2+、Mg2+、HCO$_3^{-}$主要来源于硅酸盐岩溶解，其次为碳酸盐岩；K+、Na+、Cl−主要来源硅酸盐岩溶解，部分来自于人类活动输入；NO$_3^{-}$则主要来源于人类活动，其中地表水质量主要受工矿业的影响，地下水质量受工矿活动及农业、生活污水等多种因素影响。研究成果可为区域水资源合理开发利用及保护提供依据。Abstract:
The Xianju basin is a typical hydrogeological unit and the main basin in the watershed of southern Zhejiang in which socio-economic activities are concentrated. Therefore, studying the hydrochemical characteristics of this basin is important for the development and utilization of groundwater resources and for the water environmental protection in southern Zhejiang. To reveal the hydrochemical characteristics of surface water and groundwater in the basin, we comprehensively analyzed the hydrochemical characteristics and origins of surface water and shallow groundwater in the Xianju basin with mathematical methods, Piper trilinear diagrams, principal component analysis, and ion ratios. The results show that HCO3-Ca·Na dominates the hydrochemical type of the Xianju basin, with Ca2+ and Na+ as the dominant cations, and HCO$_3^{-}$ as the dominant anion. The pH values range from 6.48 to 7.81, indicating an overall hydrochemical characteristic of being slightly alkaline to neutral. The values of Total Dissolved Solids (TDS) of groundwater range from 45.5 mg·L−1 to 288 mg·L−1, while TDS values of surface water range from 20.1 mg·L−1 to 95.8 mg·L−1. The variation coefficients of major ions in groundwater are generally higher than those in surface water, with K+, Na+, Cl−, and NO$_3^{-}$ showing larger variations, especially NO$_3^{-}$ with a maximum coefficient of 36.80 mg·L−1 and a minimum of 0.13 mg·L−1. TDS values range from 45.50 mg·L−1 to 288.00 mg·L−1 in groundwater, and from 20.10 mg·L−1 to 95.80 mg·L−1 water. Principal component analysis indicates that the hydrochemical characteristics in the Xianju basin are mainly influenced by rock weathering and human activities. Rock weathering accounts for 67.89% of the influence, while human activities contribute 12.74%. Silicate weathering plays a predominant role in rock weathering processes, followed by carbonate weathering, with negligible influence from evaporite dissolution. In terms of correlation analysis of hydrochemical parameters, strong correlations are observed among values of TDS, K+, Na+, Ca2+, Mg2+, Cl−, SO$_4^{2-} $, and HCO$_3^{-}$ in surface water, while NO$_3^{-}$ values show weaker correlations with those of other hydrochemical components. In groundwater, values of TDS correlate significantly with those of Na+, Ca2+, Mg2+, Cl−, and HCO$_3^{-}$, whereas values of HCO$_3^{-}$ show strong correlations with those of TDS, Na+ , Ca2+, and Mg2+. Values of NO$_3^{-}$ show weak correlation with those of other chemical components. Ca2+, Mg2+, and HCO$_3^{-}$ primarily originated from silicate rock dissolution, and secondarily from calcite dissolution in carbonate rocks. K+, Na+, Cl− mainly originated from silicate rock dissolution, and partially from anthropogenic sources. The reverse exchange of Na+ with Ca2+ or Mg2+ contributes to an increase of Na+ contents in hydrochemical compositions, and groundwater exhibits stronger ion exchange capacity compared to surface water. NO$_3^{-}$ primarily originated from anthropogenic activities. Surface water quality is mainly influenced by industrial and mining activities, possibly related to fluorite mining in Jiaoshan township and central Bulu township in the upstream basin. Groundwater, on the other hand, is affected by a complex array of factors including industrial and mining activities, agriculture, and domestic sewage. Spatially, there is a distinct zonation of major ion contents in groundwater and surface water in the basin. From the upper reaches to the lower reaches of Yong'an Creek, the transition occurs from the phenomenon that major ion contents are influenced by natural dissolution to phenomenon that the contents are jointly influenced by natural dissolution and human activities. From the edge to the center of basin, natural dissolution processes in groundwater gradually intensify. The areas with a dense population and with intensive agricultural activities are more susceptible to human activity. In conclusion, the findings provide a scientific basis for the rational exploitation and protection of regional water resources. Understanding the hydrochemical characteristics and spatial distribution of water bodies in the Xianju basin is crucial for the sustainable utilization of water resources and environmental conservation in southern Zhejiang. -
图 2 仙居盆地水化学Piper图
Figure 2. Piper diagram of hydrochemistry of groundwater and river water of the Xianju basin
图 4 仙居盆地地表水与地下水Gibbs图
Figure 4. Gibbs diagram of groundwater and surface water of the Xianju basin
图 5 水化学主要离子比例关系图
Figure 5. Relationship between the rates of the main ions in terms of hydrochemistry
图 7 水样品中（NO$_3^{-}$/Ca2+）与（SO$_4^{2-} $/Ca2+）比值图
Figure 7. Relationship between the rate of (${\rm{NO}}_3^{-}$/Ca2+) and (${\rm{SO}}_4^{2-}$/Ca2+) of water samples
表 1 水化学参数统计
Table 1. Statistics of hydrochemical parameters of groundwater and river water
单位为 mg·L−1 Unit: mg·L−1 分类 项目 pH TDS K+ Na+ Ca2+ Mg2+ Cl− SO$_4^{2-} $ HCO$_3^{-}$ NO$_3^{-}$ 地下水 最小值 6.48 45.50 1.79 1.74 3.44 0.60 1.45 1.42 20.30 0.25 最大值 7.81 288.00 51.60 37.70 52.00 6.96 27.40 25.90 287.00 36.80 平均值 7.13 155.53 10.58 12.48 23.19 3.54 8.53 12.17 107.65 10.85 标准差 0.34 82.64 12.45 10.14 15.56 2.34 7.15 7.05 80.66 11.45 变异系数 0.05 0.53 1.18 0.81 0.67 0.66 0.84 0.58 0.75 1.06 地表水 最小值 6.33 20.10 0.89 2.52 0.10 0.01 0.67 3.23 15.00 0.13 最大值 7.10 95.80 4.49 10.50 15.30 2.05 6.25 11.20 58.80 7.31 平均值 6.82 54.11 2.36 5.08 7.44 0.94 2.25 6.07 32.47 2.61 标准差 0.19 18.04 0.96 2.01 3.50 0.46 1.41 2.01 10.81 2.03 变异系数 0.03 0.33 0.41 0.39 0.47 0.49 0.63 0.33 0.33 0.78 
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表 2 水样品中主离子成分分析及方差累积量
Table 2. Principal component analysis of major ions and cumulative variance of water samples
变量 pH TDS K+ Na+ Ca2+ Mg2+ Cl− SO$_4^{2-} $ HCO$_3^{-}$ NO$_3^{-}$ 特征值 方差百分比/% 累积百分比/% 第1因子 0.66 0.99 0.61 0.90 0.95 0.97 0.85 0.77 0.92 0.42 6.79 67.89 67.89 第2因子 −0.29 −0.06 0.12 −0.38 −0.12 0.12 0.14 0.50 −0.35 0.78 1.27 12.74 80.63 提取方法：主成分分析法
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