Analysis of chemical substance sources in the groundwater of karst-fissure groundwater system in the Qinglian River, Guangdong Province, China
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摘要: 作为国家“两屏三带”生态安全格局中典型流域的基本单元，掌握青莲水流域地下水水质状况，对筑牢南方丘陵山地带生态安全屏障、维护粤港澳大湾区生态安全具有重要意义。结合水文地质调查和地下水化学指标特征分析，采用正矩阵因子分解模型（PMF）分析方法，追踪地下水化学物质来源并定量分析影响地下水质量的因子贡献率。研究结果表明，流域内地下水化学物质主要来源于含镁碳酸盐和硅酸盐矿物的风化溶解（F1）、生活废水、农用肥料等人类活动（F2）、碳酸盐矿物的水−岩作用（F3）、含硫化肥的使用（F4）以及硅酸盐矿物和岩盐的风化溶解（F5）。各类矿物的风化和含水层水−岩作用等自然因素的贡献率为64%，是流域内地下水化学物质的主要来源，人类活动影响的来源仅占36%。水化学指标高含量分布区域和来源因子贡献率的空间分布区域有显著相关性，表明水化学对岩性和土地利用空间分布有响应关系。整体而言，岩溶水化学成分来源主要是碳酸盐、硅酸盐和岩盐矿物等风化溶解，局部地区还受生活废水和农用化肥的使用等人为活动的影响；火成岩裂隙水来源主要为硅酸盐矿物的风化溶解。地下水离子来源贡献率的定量分析有助于加深对研究区裂隙和岩溶含水层的认识，为地下水的科学管理提供依据。Abstract:
The Qinglian River Basin is a typical basin unit within the ecological security pattern. Therefore, clarifying its groundwater quality is crucial for strengthening the ecological security barrier of the hilly and mountainous areas in South China and for maintaining the ecological security of the Guangdong−Hong Kong−Macao Greater Bay Area. The chemical composition of water is significantly related to water potability, availability for agriculture and tourism, and interaction with biological systems. However, the lack of understanding regarding the nature of groundwater has presented some challenges for the scientific management of groundwater in the Qinglian Basin, particularly concerning irrational spatial exploitation of groundwater. To address these challenges, methods such as hydrochemical parameters and multivariate statistical techniques-including Durov diagram, Gibbs plot, Schoeller diagram and Positive Matrix Factorization (PMF) model-were employed to trace the sources of chemical substances in groundwater and quantify the contribution rates of various factors affecting groundwater quality. The main land use types in the study area include forest land, cultivated land, construction land, and water bodies, which account for 87.30%, 11.31%, 1.14%, and 0.27%, respectively. Based on the deposit conditions of groundwater and the characteristics of water-bearing media, the types of groundwater are mainly classified as karst water, igneous-fissure water, clastic-fissure water, and pore water. According to the extended Durov diagram, the pore water in Quaternary sediments predominantly exhibits HCO3·SO4−Ca characteristics, while the igneous-fissure water is classified as HCO3−Ca·Na (Na). The groundwater in areas with dolomitic limestone and clastic rocks is primarily of HCO3−Ca·Mg types, whereas the other karst water is mainly classified as HCO3−Ca type. In the PMF model, a total of 53 groundwater samples were used for the identification and apportionment of groundwater chemical sources. Five major factors of groundwater chemical sources within the basin were identified. Factor 1 (F1) is characterized by Mg2+, ${\rm{HCO}}_3^{-}$, and total dissolved solids (TDS), originating from weathering and dissolution of dolomitic limestone and Mg-containing silicate minerals, with a contribution rate of 18%. Factor 2 (F2) is characterized by ${\rm{NO}}_3^{-}$, Cl−, and Na+, which are derived from anthropogenic activities such as domestic and agriculture practices, with a contribution rate of 20%. In addition, agricultural activities on sloping farmland can cause substances such as ${\rm{NO}}_3^{-}$ to be discharged into the karst basin through underground runoff, further increasing the concentrations of chemical substances in the groundwater of the karst basin. Factor 3 (F3), is characterized by ${\rm{HCO}}_3^{-}$, Ca2+, and TDS, resulting from the weathering and dissolution of carbonate minerals, and it is the factor with the highest contribution rate (27%). The dominance of F3 among the five factors corresponds to the largest proportion of karst area in the basin (55%), making it the primary source of chemical substances in the groundwater of the Qinglian River Basin. The most relevant parameter of Factor 4 (F4) is mainly ${\rm{SO}}_4^{2-}$, and its apportioned contribution rate is 16%. The majority of ratios of ${\rm{SO}}_4^{2-}$ to ${\rm{NO}}_3^{-}$− in groundwater fall between one and four, indicating that the primary source is the use of sulfur-containing fertilizers in agricultural activities. Notably, the pore water in loose rock formations within the karst basin has a relatively high concentration of ${\rm{SO}}_4^{2-}$, with a maximum value of 81.30 mg·L−1, showing a significant impact from human activities. However, the underlying karst water has a lower concentration of ${\rm{SO}}_4^{2-}$ (6.90 mg·L−1), indicating less influence from human activities. F5 is characterized by Na+, K+, Cl−, and TDS, which are derived from the weathering of silicate minerals and the dissolution of a small amount of halite, with a contribution rate of 19%. The distribution areas with high concentrations of chemical parameters are significantly correlated with the spatial distribution of contribution rates of source factors, which indicates that water chemistry responds to the spatial distribution of lithology and land use. F1, F3 and F5, belonging to natural factors such as rock weathering and water−rock interaction, contribute 64% and have a significant correlation with lithology. F2 and F4 are significantly correlated with the distribution of cultivated land and construction land, and are considered to be influenced by human activities, with a contribution rate of 36%. In general, the main sources of the chemical substances in karst water are the weathering and dissolution of carbonate, and silicate and halite minerals. In some areas, human activities such as domestic wastewater and the use of fertilizers areas also have an impact. The main source of igneous-fissure water is the weathering and dissolution of silicate minerals. The quantitative analysis of the contribution rates of groundwater ion sources helps to deepen the understanding of fissures and karst aquifers in the study area, and provide a basis for the scientific management of groundwater. -
图 2 青莲水流域位置图（a）、水文地质图和采样点分布（b）和土地利用分布图（c）
Figure 2. Location (a), hydrogeology and sampling sites (b), and land use (c) of the study area in Qinglian River Basin
图 3 青莲水地质（a）和岩性分布图（b）
Figure 3. Geological map (a) and lithologic distribution (b) of Qinglian River
图 4 地下水化学指标空间分布图（a−j）和Schoeller图(k)
Figure 4. Spatial distribution of chemical parameters (a−j) and the Schoeller diagram of groundwater (k)
图 5 青莲水流域地下水水化学Durov图（a）和水化学类型分布图（b）
Figure 5. Durov diagram (a) and distribution map (b) of groundwater chemistry in the Qinglian River Basin
图 6 地下水物质来源因子贡献率的空间分布图（a−e），饼图（f）和柱状图（g）
Figure 6. Spatial distribution (a−e), pie chart (f), and bar chart (g) of contribution rates of factors of groundwater substance sources
图 8 (Ca2+ + Mg2+)−(${\rm{HCO}}_3^{-}$ + ${\rm{SO}}_4^{2-}$)（a）、Ca2+−${\rm{HCO}}_3^{-}$（b）、${\rm{SO}}_4^{2-}$−${\rm{NO}}_3^{-}$（c）、Na+−Cl−（d）关系图
Figure 8. Relationship plot of (Ca2+ + Mg2+) − (${\rm{HCO}}_3^{-}$ + ${\rm{SO}}_4^{2-}$) (a),Ca2+−${\rm{HCO}}_3^{-}$ (b),${\rm{SO}}_4^{2-}$−${\rm{NO}}_3^{-}$ (c),and Na+−Cl− (d)
图 9 来源因子影响区域的分布图
Figure 9. Distribution of the main areas affected by the source factors
表 1 青莲水流域地下水样品的化学参数统计汇总表
Table 1. Statistical summary of chemical parameters of the groundwater samples in Qinglian River Basin
化学指标 pH K+ Na+ Ca2+ Mg2+ ${\rm{HCO}}_3^{-}$ Cl− ${\rm{SO}}_4^{2-}$ ${\rm{NO}}_3^{-}$ TDS 无量纲 mg·L−1 mg·L−1 mg·L−1 mg·L−1 mg·L−1 mg·L−1 mg·L−1 mg·L−1 mg·L−1 地下水质量标准a 6.50~8.50 − 100.00 − − − 250.00 250.00 20.00 1000.00 岩溶水 最大值 8.09 28.60 13.40 122.00 20.10 360.00 21.00 81.30 49.80 415.00 最小值 6.87 0.10 0.27 16.50 1.10 67.00 1.00 0.80 0.10 95.00 平均值 7.40 1.62 1.91 79.55 5.40 242.46 4.39 10.73 8.31 249.88 标准偏差 0.27 4.31 2.73 20.45 4.70 55.38 4.37 13.81 9.97 63.33 火成岩裂隙水 最大值 7.57 2.64 15.60 12.60 0.78 56.00 8.00 6.80 14.10 110.00 最小值 5.86 0.88 2.32 1.06 0.05 11.00 0.50 0.05 0.10 25.00 平均值 6.76 1.83 4.72 3.66 0.26 22.40 1.95 0.87 2.72 48.80 标准偏差 0.59 0.58 3.96 4.33 0.24 13.32 2.28 2.10 4.17 24.85 注： a，GB/T 14848 −2017《地下水质量标准》[28]，“−”表示不是评价指标，无限值。
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