Dissolved heavy metals (HMs), derived from natural and anthropogenic sources, are an important part of aquatic environment research and gain more international concern due to their acute toxicity. In this study, the geochemistry of dissolved HMs was analyzed in the upper Three Gorges Reservoir (TGR) of the Yangtze River (YZR) watershed to explore their distribution, status, and sources and further evaluate the water quality and HM-related risks. In total, 57 water samples were collected from the main channel and tributaries of the upper TGR. The concentrations of eight HMs, namely V, Ni, Cu, Zn, As, Mo, Cd, and Pb, were measured by ICP-MS. The mean concentrations (in μg/L) of eight HMs decreased in the order: As (1.46), V (1.44), Ni (1.40), Mo (0.94), Cu (0.86), Zn (0.63), Pb (0.03), and Cd (0.01). The concentrations of most HMs were 1.4~8.1 times higher than that in the source area of the YZR, indicating a potential anthropogenic intervention in the upper TGR. Spatially, the concentrations of V, Cu, As, and Pb along the main channel gradually decreased, while the others were relatively stable (except for Cd). The different degrees of variations in HM concentrations were also found in tributaries. According to the correlation analysis and principal component (PC) analysis, three PCs were identified and explained 75.1% of the total variances. combined with the concentrations of each metal, PC1 with high loadings of V, Ni, As, and Mo was considered as the main contribution of human inputs, PC2 (Cu and Pb) was primarily attributed to the contribution of mixed sources of human emissions and natural processes, and Zn and Cd in PC3 were controlled by natural sources. Water quality assessment suggested the good water quality (meeting the requirements for drinking purposes) with WQI values of 14.1 ± 3.4 and 11.6 ± 3.6 in the main channel and tributaries, respectively. Exposure risk assessment denoted that the health effects of selected HMs on the human body were limited (hazard index, HI < 1), but the potential risks of V and As with HI > 0.1 were non-negligible, especially for children. These findings provide scientific support for the environmental management of the upper TGR region and the metal cycle in aquatic systems.

Rivers transport terrestrial matter into the ocean, constituting a fundamental channel between inland and oceanic ecosystem and affect global climate change. To reveal chemical weathering processes and environmental health risks during flood periods, water samples were collected in the upper reaches of Three Gorges Reservoir (TGR) in 2020. HCO₃⁻ and Ca²⁺ were the most abundant anions and cations of the river water, respectively. The range of HCO₃⁻ concentration was between 1.81 and 3.02 mmol/L, while the mean content of Ca²⁺ was 1.03 mmol/L. The results of the Piper diagram and element ratios revealed that the river solutes were mainly contributed by carbonate weathering and gypsum-rich evaporite dissolution. A mass balance model indicated that the contribution order of sources to cations in the main channel (Yibin-Luzhou) was evaporites > carbonates > atmospheric input > silicates. The order in the Chongqing—Three Gorges Dam was carbonates > atmospheric input > evaporites > silicates. These results showed a lithologic control on hydrochemical characteristics. Most sampling sites were suitable for agricultural irrigation according to the water quality assessment. However, indexes sodium adsorption ratio (SAR) and soluble sodium percentage (Na%) were higher than 1.0 in Yibin-Luzhou and 30% in Yibin–Chongqing, respectively, suggesting a potential sodium hazard. In addition, except Tuojiang River and Shennong River, the risk of sodium hazard in tributaries was relatively low. High Na⁺ concentration in irrigation water can damage soil structure and function and ultimately affect agricultural production. Water quality in the upstream of a Piper diagram should attract enough attention.

River water chemistry offers information on watershed weathering and responds to the global carbon cycle. Watershed weathering processes and water chemistry in stratified water are still unclear in Xiaojiang River, as a major tributary of the Three Gorges Reservoir (TGR) which is the largest reservoir in the world. Major ions of river water at different depths were measured to reveal the ionic composition and chemical weathering properties by principal component analysis and stoichiometry in Xiaojiang River. Ca²⁺−HCO₃⁻ dominated the hydrochemical facies of river. Surface river water had the lowest total dissolved solid (146 mg/L) compared to other layers of water. According to principal component analysis, the major ions were divided into two principal components. PC1 was the weathering end-member of rocks, including the main ions except K⁺ and NO₃–N, and PC2 may be the mixed end-member of atmospheric input and anthropogenic input. From stoichiometry, carbonate weathering dominated the cationic composition, with a contribution ratio of 56.7%, whereas atmospheric input (15.2%) and silicates weathering (13.9%) had similar extent of contribution. Compared with other major tributaries of TGR, Xiaojiang had more intense chemical weathering processes. The weathering rates of carbonates and silicates were 19.33 ± 0.68 ton/km²/year and 3.56 ± 0.58 ton/km²/year, respectively. Sulfuric acid as a proton may have participated less in the weathering processes of Xiaojiang River. The CO₂ consumption budgets for silicates and carbonates weathering were 0.8 ± 0.2 × 10⁹ mol/year and 2.8 ± 0.2 × 10⁹ mol/year, respectively. These results enrich the watershed weathering information of TGR tributaries and provide data support for understanding the global carbon cycle.