Characteristics of Natural Ti-Bearing Nanoparticles in Groundwater within Karst Areas of Northern China

Abstract

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.