Chemical characteristics and formation mechanism of shallow groundwater in Shijiazhuang area
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摘要:
研究目的 为了全面了解石家庄地区浅层地下水化学特征及其成因机制，为水环境管理部门提供科学参考。
研究方法 基于2019—2020年石家庄地区浅层地下水水质监测数据，综合运用地理统计学、Piper图、Gibbs模型和离子比等方法，分析了石家庄地区不同水文地质单元浅层地下水化学特征、影响水质的主要化学指标及其形成机制。
研究结果 石家庄地区浅层地下水pH值在7.13~8.48之间，介于中性水和弱碱性水之间；TH（总硬度）和TDS（溶解性总固体）均值分别为391.03 mg/l和590.60 mg/l，沿地下水径流方向呈逐渐降低趋势；全区和各水文地质单元阴、阳离子基本以HCO3−、SO42−、Ca2+和Na+为主，台地、河谷平原区阳离子表现为以Ca2+和Mg2+为主，且Na+、Cl−、SO42−、NO3−等离子空间变异系数相对较大；浅层地下水化学类型以HCO3·SO4−Ca·Mg为主，其次为SO4·HCO3−Ca·Mg型，且从台地区到冲洪积平原区水化学类型逐渐变得复杂；浅层地下水化学组分形成主要受岩石风化作用影响，冲洪积平原和台地区部分地下水化学组分形成受到人类活动影响显著。研究区浅层地下水主要超标指标为TH、SO42−和NO3−，河谷平原区3项指标综合超标率最高，达到62.5%。TH、SO42−和NO3−三项指标超标的地下水样品的化学组分除受碳酸盐矿物溶解影响外，也受到硫酸盐矿物溶解和人类活动（农业活动和市政污水排放）影响。
结论 石家庄地区浅层地下水化学特征呈明显的分带性，从台地区到冲洪积平原区地下水的TH和TDS浓度逐渐降低，水化学类型逐渐复杂化，水质超标率逐渐降低，且水质超标现象是自然因素和人类活动共同作用的结果。本次对石家庄地区浅层不同水文地质单元的水化学特征及其成因机制研究，为水环境管理部门提供了重要科学依据。
Abstract:Objective To gain a comprehensive understanding of the chemical characteristics and formation mechanism of shallow groundwater in the Shijiazhuang area and provide scientific references for water environment management departments.
Methods Based on the shallow groundwater quality monitoring data of the Shijiazhuang area from 2019 to 2020, methods such as geostatistics, Piper diagram, Gibbs model, and ion ratio were comprehensively employed to analyze the chemical characteristics of shallow groundwater in different hydrogeological units of the Shijiazhuang area, the main chemical indicators affecting water quality, and their formation mechanisms.
Results The pH value of shallow groundwater in the Shijiazhuang area ranged from 7.13 to 8.48, falling between neutral water and weak alkaline water; the average values of TH (total hardness) and TDS (total dissolved solids) were 391.03 mg/l and 590.60 mg/l respectively, showing a gradually decreasing trend along the groundwater runoff direction; the anions and cations in the entire area and each hydrogeological unit were mainly HCO3−, SO42−, Ca2+ and Na+, and the cations in the platform and river valley plain area were mainly Ca2+ and Mg2+, and the spatial variation coefficients of ions such as Na+, Cl−, SO42−, NO3− were relatively large; the chemical type of shallow groundwater was mainly HCO3·SO4−Ca·Mg, followed by SO4·HCO3−Ca·Mg type, and the chemical type of water gradually became more complex from the platform area to the alluvial−proluvial plain area; The formation of chemical components in shallow groundwater is primarily controlled by rock weathering. In alluvial−proluvial plains and tableland regions, the formation of certain chemical components in groundwater is significantly influenced by human activities. The main indicators exceeding standards in shallow groundwater within the study area are total hardness (TH), sulfate (SO42−), and nitrate (NO3−). The comprehensive exceedance rate of these three indicators is highest in the valley plain area, reaching 62.5%. The formation of chemical components in groundwater samples with exceeded TH, SO42−, and NO3− standards is not only affected by the dissolution of carbonate minerals but also by the dissolution of sulfate minerals and anthropogenic factors, such as agricultural activities and municipal sewage discharge.
Conclusions The chemical characteristics of shallow groundwater in the Shijiazhuang area exhibit distinct zonation. From the tableland region to the alluvial−proluvial plain, the concentrations of TH and total dissolved solids (TDS) in groundwater gradually decrease, water chemistry types become increasingly complex, and the water quality exceedance rate progressively declines. Furthermore, the phenomenon of water quality exceedance results from the combined effects of natural and anthropogenic factors. This study on the hydrochemical characteristics and their formation mechanisms of shallow groundwater in different hydrogeological units in the Shijiazhuang area provides a critical scientific basis for water environment management departments.
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图 6 TH、SO42−和NO3−三项指标超标的地下水样品中γ(NO3−)/γ(Na+)和γ(Cl−)/N(Na+)（图a）、γ(SO42−)/γ(Ca2+)和γ(NO3−)/γ(Ca2+)(图b)关系图
Figure 6.
表 1 浅层地下水主要离子含量统计
Table 1. Statistical table of main ion content in shallow groundwater
指标 全区 台地 山前冲洪积扇 冲洪积平原 河谷平原区 范围 均值 变异系数/% 均值 变异系数/% 均值 变异系数/% 均值 变异系数/% 均值 变异系数/% pH 7.13~8.48 7.77 5.04 7.85 7.56 7.63 2.99 7.77 3.78 7.72 5.94 TH 68.05~2437 391.03 59.74 461.61 69.03 464.49 36.56 336.07 57.91 438.99 31.44 TDS 115.5~3016 590.6 61.98 635.49 64.40 667.43 40.11 549.01 68.44 586.73 33.86 K+ 0.17~12.24 2.02 69.77 1.77 105.07 1.71 57.91 2.15 56.49 3.21 53.82 Na+ 8.62~521 48.4 115.04 29.25 68.99 42.44 68.16 60.09 115.13 21.78 42.34 Ca2+ 9.1~786.3 103.36 68.96 134.84 78.23 132.43 37.97 79.71 58.46 128.13 39.47 Mg2+ 5.98~178.7 32.28 61.6 30.32 51.98 32.50 38.28 33.27 70.65 28.90 17.80 Cl− 1.75~1105 67.52 131.53 79.59 183.64 78.18 80.91 60.36 99.15 48.23 58.72 SO42− 4.7~1749 138.59 121.49 148.63 65.33 164.24 65.31 125.87 164.01 153.56 59.19 HCO3− 29.59~876.6 257.82 36.47 213.83 45.51 276.55 25.43 273.43 34.55 226.71 25.37 NO3− 0~402.4 48.74 114.1 84.08 86.08 59.68 58.87 28.61 149.02 74.64 53.31 F− 0.2~1.42 0.44 39.23 0.40 51.67 0.34 25.37 0.48 33.23 0.39 29.49 COD 0.45~16.17 1.09 105.69 1.25 63.04 0.87 32.39 1.08 132.48 1.17 54.61 有效个案数/个 234 57 38 8 131 注：离子含量及其平均值单位为mg/L，pH除外 
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表 2 地下水水质超标率统计
Table 2. Statistics of Exceeding Standard Proportion of Groundwater Quality
指标 国标Ⅲ类（除PH
外，mg/L）全区 台地 山前冲
洪积扇河谷平原 冲洪积
平原超标率% PH 6.5~8.5 0 0 0 0 0 TH ≤450 29.91 38.6 55.26 62.5 16.79 TDS ≤1000 8.56 12.28 10.53 0 6.87 K + — — — — — — Na + ≤200 2.10 0 0 0 3.82 Ca2 + — — — — — — Mg2 + ≤50 8.55 3.51 5.26 0 6.43 Cl− ≤250 1.71 1.75 0 0 2.29 SO42− ≤250 13.68 14.04 18.42 12.5 12.21 HCO3− — — — — — — NO3− ≤88.6 12.82 24.56 7.89 0 7.63 F− ≤1.00 0.85 3.51 0 0 0 COD ≤3.29 2.14 5.26 0 0 1.53
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