Bin Sun

Karst areas are widespread in China and can be divided into southern karst and northern karst based on the geographical boundary of Qinling Mountains and Huaihe River. In northern karst regions, karst springs are the predominant landform. Previous studies on karst springs have predominantly focused on macroscopic perspectives, such as water chemistry characteristics, with less attention given to the microscopic characteristics of springs. Therefore, this study focused on the Jinan Baotu Spring area, representative of a typical northern karst region, and investigated the natural nanoparticles present in different aquifers at various depths from a microscopic point of view. Through the observation of nanoparticle tracking analyzer (NTA), numerous nanoparticles were identified in the groundwater samples. The particle size range of the particles contained in groundwater is mainly concentrated in the range of 150–500 nm, and the particle concentration is mainly concentrated in the range of 1.5–5.0 × 10⁵ Particles/L. The microstructure, chemical composition, and element distribution of these nanoparticles were analyzed using TEM-EDS techniques. The results unveiled the presence of Ti-bearing nanoparticles in various groundwater layers, including both crystalline and amorphous states, as well as nanoparticles exhibiting the coexistence of crystal and amorphous structures. By comparing the measured lattice spacing with PDF cards, the crystalline Ti-bearing nanoparticles were identified as rutile, brookite, anatase, ilmenite, pseudorutile, and ulvospinel. Furthermore, the main components of the amorphous Ti-bearing nanoparticles predominantly consisted of Ti or a mixture of Ti and Fe. EDS analysis further indicated that the Ti-bearing nanoparticles carried additional metal elements, such as Zn, Ca, Mn, Mo, Cr, and Ni, suggesting their potential role as carriers of metal elements during groundwater transportation. This discovery provided new insights into the migration of metal elements in groundwater and underscores the capacity of nanoparticles to enhance the mobility of inorganic substances within the water environment. Notably, brookite was detected in three different areas, including the direct discharge area, indirect recharge area, and discharge area, which may indicate that some special natural nanoparticles could serve as natural mineral tracer particles in the process of groundwater migration.

Karst groundwater is an important water supply, especially in northern China. With the rapid development of China’s economy, anthropogenic activities have had a significant impact on karst groundwater formation, circulation and other processes. In this paper, the Baotu spring basin, which is closely related to anthropogenic activities, was selected as the research object to carry out a study of water chemical characteristics and evolutionary processes. And, mathematical statistics, Piper trilinear diagram, Gibbs diagram, and ion ratio methods were used to analyze the characteristics and evolution processes of groundwater. The results of this study show that the hydrogeochemical components of karst groundwater are mainly controlled by the weathering of rocks, mainly by the dissolution of carbonate rocks and silicates with the dominant cation of Ca²⁺ and the dominant anion of HCO₃⁻. Considering the role of anthropogenic activities, including agricultural and industrial activities, the evolution process of karst groundwater is mainly controlled by hydrogeochemical effects such as mineral dissolution and filtration, the mixing of multiple water bodies, anthropogenic activities (domestic sewage, industrial and agricultural wastes), oxidation–reduction and cation alternating adsorption. Moreover, the influence of anthropogenic activities on the formation and evolution of karst groundwater gradually increases, leading to the rise in nitrate content in karst groundwater and accelerating carbonate rock dissolution. The research results of this paper can provide a favorable reference for environmental protection and research on karst groundwater in areas of intensive anthropogenic activity.

The Yellow River has played an indispensable role in supporting Chinese civilization because it provides water resources and rich soil for agriculture. This study analyzes the major ions and the isotopic ratios of the hydrogen (δD), oxygen (δ¹⁸O), and carbon (¹⁴C) of groundwater samples to identify the sources of recharge and the impact of the Yellow River on the Changqing-Xiaolipu karst aquifer. The major ion/Cl⁻ ratios generally follow the mixing line between the Yellow River and the karst groundwater recharge in the southern mountain areas, indicating the importance of mixing under natural influences in the Yellow River Basin. The dominant hydrochemical type of karst groundwater is Ca·Mg-HCO₃·SO₄, whereas that of Yellow River water is Ca·Na·Mg-SO₄·Cl. Most karst groundwater consists of 10–30% Yellow River water, indicating that the water resources of the Yellow River Basin are generally supplemented by the Yellow River. Therefore, the Yellow River must be considered during the characterization of the chemistry and budget of water resources in the Yellow River Basin.