Mengnan Zhang

Groundwater in the Qingshui River Plain of southern Ningxia is one of the main water sources for local domestic and agricultural use. However, due to the geological background of the area, 33.94% of the groundwater samples had fluoride concentrations that exceeded the WHO drinking water standards. To examine the spatial patterns and formation processes of fluoride in groundwater, researchers gathered 79 rock samples, 2618 soil samples, 21 sediment samples, 138 groundwater samples, and 82 surface water samples across the southern Qingshui River Plain. The collected data were analyzed using statistical approaches and hydrogeochemical diagrams. The findings reveal that fluoride levels in groundwater exhibit a gradual increase from the eastern, western, and southern peripheral sloping plains toward the central valley plain. Vertically, higher fluoride concentrations are found within 100 m of depth. Over a ten-year period, fluoride concentrations have shown minimal variation. Fluoride-rich rocks, unconsolidated sediments, and soils are the primary sources of fluoride in groundwater. The primary mechanisms governing high-fluoride groundwater formation are rock weathering and evaporative concentration, whereas cation exchange adsorption promotes fluoride (F⁻) mobilization into the aquifer. Additional sources of fluoride ions include leaching of fluoride-rich sediments during atmospheric precipitation infiltration and recharge from fluoride-rich surface water.

Groundwater plays an irreplaceable role in all aspects of the Loess Plateau. In this study, the loess phreatic water (LPW) and bedrock phreatic water (BPW) in the Ning County area (NCA) were sampled and analyzed, and the characteristics and controlling factors of groundwater were determined by using statistical analysis, hydrochemical methods, and hydrogeochemical simulation. The results indicated that the groundwater in the NCA was alkaline as a whole, and the average pH values of LPW and BPW were 8.1 and 7.8, respectively. The mean values of TDS concentrations of LPW and BPW were 314.9 mg/L and 675.3 mg/L, and the mean values of TH contents were 194.6 mg/L and 286.6 mg/L, respectively, which were mainly divided into hard fresh water. The Piper diagram illustrated that the hydrochemical type of groundwater in the NCA was mainly the HCO₃·Ca type. The main recharge source of groundwater was atmospheric precipitation, and it was affected by evaporation to a certain extent. The linear relationships of δ¹⁸O and δ²H of LPW and BPW were δ²H = 6.998δ¹⁸O − 3.802 (R² = 0.98) and δ²H = 6.283δ¹⁸O − 10.536 (R² = 0.96), respectively. Hydrochemical analysis indicated that the groundwater in the NCA was mainly controlled by rock weathering and cation exchange. BPW was affected by the dissolution of gypsum. The possible mineral phases were identified on the basis of the main soluble minerals in the aquifer, and hydrogeochemical reverse simulations were performed. The dissolution of calcite, illite, and hornblende, and the precipitation of dolomite, plagioclase, and microcline occurred on both the LPW and BPW pathways.

Perchlorate (ClO₄⁻) is an emerging persistent pollutant that is ubiquitous in the environment at trace concentrations. Perchlorate ingestion poses a risk to human health because it interferes with thyroidal hormone production. The identification of perchlorate sources in groundwater is a primary concern. Chlorine and multi-oxygen isotopic tracing of perchlorate (δ³⁷Cl, ³⁶Cl/Cl, δ¹⁸O, and Δ¹⁷O) can provide a unique tool for identifying the origin and transport of perchlorate in groundwater. Along with the kinetic fractionation of chlorine and oxygen isotopes, the Δ¹⁷O value, ³⁶Cl/Cl ratio, and ε¹⁸O/ε³⁷Cl (the fractionation coefficient of oxygen and chlorine isotopes) are constant, potentially indicating the biodegradation of perchlorate, without disguising its source information. Therefore, comprehensive characterization of stable chlorine and poly-oxygen isotopes is expected to provide direct evidence for identifying the source of perchlorate in groundwater. However, further studies are needed to increase the amount of isotopic data of different perchlorate sources, to make the end-member model available to broader regions. It is critically important to understand the range of values and differences of isotopes among natural perchlorate sources and the perchlorate formation mechanisms.