Seasonal Evolution and Influencing Factors of Groundwater Chemistry in the Baiquan Spring Area of Jinan
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摘要: 为探究季节变化对济南白泉泉域地下水文地球化学过程的影响，深化对泉域地下水形成与演化机制的认识，本文以济南白泉泉域枯水期和丰水期的地下水为研究对象，采用 Gibbs 图解法、饱和指数法、离子比值法、离子相关性分析法、因子分析法及自组织映射（SOM）等方法对地下水水化学特征、形成机制及季节分异规律进行了系统分析。结果显示:济南白泉泉域地下水水化学类型以 HCO3-Ca 为主，枯水期地下水TDS值略高，碱性略强。两期地下水化学组成主要受水-岩相互作用控制，其中碳酸盐岩溶解和硅酸盐水解是主要的水文地球化学过程。从枯水期到丰水期，部分方解石和白云石由饱和状态转为不饱和，表明降水补给促进了碳酸盐矿物的持续溶解。离子比值与主成分分析表明，地下水中${\rm{SO}}_4^{2-} $和${\rm{NO}}_3^{-} $主要来源于农业化肥与城市生活污水的混合输入。SOM 聚类结果进一步表明，研究区地下水化学组成具有明显的空间异质性和季节分异特征，枯水期分区更清晰稳定，丰水期则更易反映降水补给增强条件下污染物向浅层地下水迁移的影响。白泉泉域作为济南市重要水源地，其地下水水质已受到一定程度的人类活动干扰，建议加强地下水动态监测与分区保护，以保障区域供水安全。Abstract:
The Baiquan spring area in eastern Jinan, China, is an important karst groundwater system and regional water-supply source. However, compared with the well-studied Baotu Spring catchment, seasonal hydrochemical evolution and its controlling mechanisms in the Baiquan spring area remain insufficiently characterized. To clarify the seasonal response of groundwater chemistry and distinguish the effects of natural processes and human activities, 48 groundwater samples were collected in both the dry and wet seasons, yielding 96 samples in total. The samples were mainly obtained from production and domestic wells with depths of approximately 30−450 m. Major hydrochemical parameters, including pH, K+, Na+, Ca2+, Mg2+, Cl−, ${\rm{SO}}_4^{2-}$, ${\rm{HCO}}_3^{-}$, ${\rm{NO}}_3^{-}$, and total dissolved solids (TDS), were analyzed. Descriptive statistics, Piper and Gibbs diagrams, ionic ratios, correlation analysis, mineral saturation indices calculated using PHREEQC, factor analysis, and a self-organizing map (SOM) combined with K-means clustering were integrated to identify hydrochemical characteristics, dominant geochemical reactions, seasonal differences, and spatial heterogeneity. Groundwater was generally weakly alkaline and dominated by ${\rm{HCO}}_3^{-}$ and Ca2+, with the HCO3-Ca hydrochemical facies prevailing in both seasons. The mean pH and TDS were 7.74 and 558.5 mg/L in the dry season and 7.28 and 524.4 mg/L in the wet season, respectively, indicating slightly stronger alkalinity and mineralization during the dry season and an overall dilution effect during the wet season. Chloride showed particularly strong spatial variability, with coefficients of variation greater than 1 in both seasons, while ${\rm{SO}}_4^{2-}$ and Na+ also displayed marked spatial dispersion. Together with locally elevated ${\rm{SO}}_4^{2-}$ and Cl− concentrations, these patterns indicate spatially heterogeneous groundwater chemistry and external inputs at some locations. The Gibbs diagrams showed that most samples fell within the rock-weathering dominance field, demonstrating that water−rock interaction is the primary control on groundwater chemistry. Ionic relationships further suggested that carbonate dissolution and silicate hydrolysis jointly contribute to the major-ion composition. Mineral saturation calculations revealed clear seasonal changes in carbonate equilibrium. Gypsum and halite remained undersaturated in both seasons. In the dry season, calcite and dolomite were supersaturated, with mean saturation indices of 0.82 and 1.26, respectively. In the wet season, calcite became undersaturated in approximately 12.5% of the samples and dolomite in approximately 25%. This shift suggests that precipitation recharge, likely accompanied by relatively CO2-rich infiltrating water, enhances carbonate dissolution and changes mineral−water equilibrium. Significant positive correlations of TDS with Ca2+, Mg2+, Na+, Cl−, ${\rm{SO}}_4^{2-}$, and ${\rm{HCO}}_3^{-}$, together with the strong Ca2+−Mg2+ relationship, further support the dominant role of mineral dissolution and carbonate weathering in groundwater mineralization. Anthropogenic inputs were also evident. Variations in ${\rm{SO}}_4^{2-}$/Cl− and ${\rm{NO}}_3^{-}$/Cl− molar ratios, together with ion correlations, indicate that ${\rm{SO}}_4^{2-}$ and ${\rm{NO}}_3^{-}$ are influenced by mixed inputs from agricultural fertilizers and urban sources such as domestic sewage and manure. ${\rm{SO}}_4^{2-}$ appears more closely associated with agricultural inputs, whereas increasing Cl− concentrations correspond to a stronger urban pollution signal. Factor analysis further differentiated the controlling processes. In the dry season, three factors explained 79.3% of the total variance: water−rock interaction, a mixed influence of silicate weathering and nitrogen-related anthropogenic input, and cation exchange. In the wet season, three factors explained 71.73% of the variance. Rock weathering remained dominant, while combined natural−anthropogenic effects and a more complex process involving cation exchange and possible sulfate reduction also contributed to groundwater chemistry. The SOM analysis revealed pronounced spatial heterogeneity and seasonal differentiation. Groundwater in both seasons was classified into four hydrochemical clusters. During the dry season, high-mineralization clusters were concentrated mainly in the northern discharge area and adjacent runoff−discharge transition zone, whereas low-mineralization groundwater occurred mainly in the central and southern recharge and runoff zones. This pattern was relatively clear and stable, indicating stronger control by internal groundwater evolution along the regional flow path. During the wet season, high-mineralization groundwater remained concentrated mainly in the northern discharge area, but its spatial distribution became more dispersed, likely because enhanced recharge and mixing weakened the continuity of hydrochemical zones. Overall, groundwater hydrochemistry in the Baiquan spring area is jointly controlled by hydrogeological setting, water−rock interaction, seasonal recharge, and human activities. Natural mineral dissolution determines the basic hydrochemical composition, whereas seasonal precipitation regulates mineral equilibrium, groundwater mixing, and contaminant transport. The northern discharge area is the principal zone of mineralization and hardness accumulation, while the central and southern recharge areas have lower mineralization and greater sensitivity to external disturbance. -
图 5 地下水${\rm{HCO}}_3^{-}$/ Na+与Ca2+/ Na+、Mg2+/ Na+与Ca2+/ Na+关系及矿物饱和指数与TDS关系图
Figure 5. Relationship between ${\rm{HCO}}_3^{-}$/ Na+and Ca2+/ Na+, Mg2+/ Na+and Ca2+/ Na+ in groundwater, and relationship between mineral saturation index and TDS
图 6 地下水${\rm{SO}}_4^{2-}$/ Cl−、${\rm{NO}}_3^{-}$/ Cl−与Cl−关系图
Figure 6. Relationship between groundwater ${\rm{SO}}_4^{2-}$/ Cl−,${\rm{NO}}_3^{-}$/ Cl− and Cl−
图 7 地下水化学指标SOM聚类结果及空间分布：（a）枯水期，（b）丰水期
Figure 7. SOM clustering results and spatial distribution of groundwater hydrochemical indicators: (a) dry season, (b) wet season
表 1 研究区地下水水化学组分统计
Table 1. Statistics of chemical components of groundwater in the study area
枯水期 丰水期 最大值 最小值 平均值 标准差 变异系数 最大值 最小值 平均值 标准差 变异系数 K+ 1.86 0.05 0.74 0.45 0.60 3 0.4 0.97 0.47 0.49 Na+ 97.54 4.09 23.32 20.04 0.86 107 5.9 22.32 19.93 0.89 Ca2+ 317.6 63.53 132.6 47.93 0.36 250 71 122.6 36.86 0.30 Mg2+ 59.55 9.6 24.61 9.86 0.40 51.1 13.1 24.45 8.05 0.33 Cl− 359.6 6.82 48.15 57.26 1.19 327.7 13.6 50.97 53.31 1.05 ${\rm{SO}}_4^{2-}$ 617.0 54.69 134.2 93.83 0.70 542 49.5 107.5 73.93 0.69 ${\rm{HCO}}_3^{-}$ 483.3 178.2 293.5 57.54 0.20 434 156 291.6 55.62 0.19 F− 0.85 0.1 0.23 0.16 0.70 0.83 0.06 0.35 0.13 0.36 ${\rm{NO}}_3^{-}$ 89 6.18 36.98 16.24 0.44 110 8.9 38.60 19.17 0.50 TDS 1292 282 558.5 205.3 0.37 822 296 524.4 140.8 0.27 pH 8.3 7.3 7.74 0.23 0.03 8.07 6.9 7.28 0.30 0.04 
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表 2 地下水成分相关性分析
Table 2. Correlation analysis of groundwater components
枯水期 K+ Na+ Ca2+ Mg2+ Cl− ${\mathrm{SO}}_4^{2-} $ $ {\mathrm{HCO}}_3^-$ F− NO3− TDS K+ − Na+ 0.160 − Ca2+ −0.058 0.383** − Mg2+ 0.070 0.328* 0.726** − Cl− 0.073 0.510** 0.769** 0.686** − SO42− 0.177 0.296* 0.781** 0.558** 0.364* − HCO3− −0.251 0.591** 0.444** 0.573** 0.387** 0.135 − F− 0.523** 0.163 0.030 0.027 −0.099 0.400** −0.146 − NO3− −0.562** 0.015 0.255 −0.067 0.183 −0.158 0.278 −0.542** − TDS 0.031 0.571** 0.966** 0.778** 0.783** 0.806** 0.528** 0.120 0.157 − 丰水期 K+ Na+ Ca2+ Mg2+ Cl− ${\mathrm{SO}}_4^{2-} $ ${\mathrm{HCO}}_3^- $ F− ${\mathrm{NO}}_3^- $ TDS K+ − Na+ 0.437** − Ca2+ 0.005 0.115 − Mg2+ −0.032 0.041 0.667** − Cl− 0.124 0.469** 0.610** 0.549** − SO42− 0.218 0.148 0.708** 0.358* 0.095 − HCO3− −0.029 0.366* 0.340* 0.536** 0.222 0.097 − F− 0.304* 0.276 0.291* 0.199 0.100 0.576** −0.028 − NO3− −0.391** −0.174 0.022 −0.019 −0.001 −0.174 −0.065 −0.114 − TDS 0.113 0.533** 0.862** 0.700** 0.780** 0.570** 0.540** 0.311* −0.055 − **. 在 0.01 级别（双尾），相关性显著。*. 在 0.05 级别（双尾），相关性显著。
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表 3 地下水成分因子分析
枯水期 F1 F2 F3 丰水期 F1 F2 F3 K+ 0.04 0.80 0.19 K+ 0.24 0.78 0.19 Na+ 0.63 0.07 0.66 Na+ 0.51 0.43 0.57 Ca2+ 0.93 −0.07 −0.31 Ca2+ 0.86 −0.24 −0.31 Mg2+ 0.84 0.04 −0.04 Mg2+ 0.75 −0.38 −0.06 Cl− 0.82 −0.11 0.03 Cl− 0.72 −0.17 0.35 ${\rm{SO}}_4^{2-}$ 0.73 0.39 −0.42 ${\rm{SO}}_4^{2-}$ 0.65 0.26 −0.61 ${\rm{HCO}}_3^{-}$ 0.62 −0.37 0.52 ${\rm{HCO}}_3^{-}$ 0.54 −0.26 0.42 F− 0.10 0.83 0.05 F− 0.45 0.49 −0.46 ${\rm{NO}}_3^{-}$ 0.14 −0.83 −0.12 ${\rm{NO}}_3^{-}$ −0.14 −0.59 −0.14 TDS 0.99 0.02 −0.13 TDS 0.97 −0.13 0.09
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