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Carbonate weathering and the CO 2 consumption in karstic area are extensive affected by anthropogenic activities, especially sulfuric and nitric acids usage in the upper-middle reaches of Wujiang River, China. The carbonic acid would be substituted by protons from sulfuric and nitric acids which can be reduce CO 2 absorption. Therefore, The goal of this study was to highlight the impacts of sulfuric and nitric acids on carbonate dissolution and the associated deficit of CO 2 uptaking during carbonate weathering. The hydrochemistries and carbon isotopic signatures of dissolved inorganic carbon from groundwater were measured during the rainy season (July; 41 samples) and post-rainy season (October; 26 samples). Our results show that Ca 2 + and Mg 2 + were the dominant cations (55.87–98.52%), and HCO 3 – was the dominant anion (63.63–92.87%). The combined concentrations of Ca 2 + and Mg 2 + commonly exceeded the equivalent concentration of HCO 3 − , with calculated [Ca 2 + + Mg 2 + ]/[HCO 3 − ] equivalent ratios of 1.09–2.12. The mean measured groundwater δ 13 C DIC value (− 11.38‰) was higher than that expected for carbonate dissolution mediated solely by carbonic acid (− 11.5‰), and the strong positive correlation of these values with [SO 4 2 − + NO 3 − ]/HCO 3 – showed that additional SO 4 2 − and NO 3 − were required to compensate for this cation excess. Nitric and sulfuric acids are, therefore, suggested to have acted as the additional proton-promoted weathering agents of carbonate in the region, alongside carbonic acid. The mean contribution of atmospheric/pedospheric CO 2 to the total aquatic HCO 3 – decreased by 15.67% (rainy season) and 14.17% (post-rainy season) due to the contributions made by these acids. The annual mean deficit of soil CO 2 uptake by carbonate weathering across the study area was 14.92%, which suggests that previous workers may have overestimated the absorption of CO 2 by carbonate weathering in other karstic areas worldwide. [ABSTRACT FROM AUTHOR]

To investigate the environmental quality and human health risks of different types of groundwater at Xiangshui, Chongzuo, several regular water quality indexes and concentrations of metals in 60 groundwater samples were measured and analyzed. The environmental quality of groundwater was analyzed by means of the Nemerow index. The health risks were assessed by using a human health risk assessment model. The regular water quality indexes and concentrations of metals of the well water, spring water, and underground river water exceeded the standards to different degrees. The environmental quality of groundwater was at a poor grade. The comprehensive evaluation score of underground river water ( F =4.26) was the lowest. The well water had the same score as spring water ( F =7.10). The high hardness and salinity were conducive to enrichment of Cr, and the reducing environment was of great advantage for the enrichment of As. The environmental geochemistry of Zn, Pb, Cd, and Cu was similar. The sources of Fe, Al, and Mn were similar. The results of the health risk assessment indicated that the health risks of well water, spring water, and underground river water were relatively high. The health risks decreased in the order of well water > underground river water > spring water. The health risks mainly came from the carcinogenic metallic element Cr. Carcinogenic risks were 4-6 orders of magnitude higher than non-carcinogenic risks. Carcinogenic risks were higher than the maximum allowance levels (5.0×10 -5 a -1 ). Non-carcinogenic risks were lower than the allowance levels (10 -6 a -1 ). Children had greater health risks than adults. The health risks of metals through the drinking pathway were 2-3 orders of magnitude higher than the values caused by the dermal contact pathway. For the sake of drinking water safety, the well water, underground river water, and spring water should be properly treated and the concentration of Cr in groundwater should be controlled before drinking.

To investigate the major ionic characteristics, seasonal variation, and controlling factors of karst groundwater at Xiangshui, Chongzuo, 210 groundwater samples were collected and measured in wet season, dry season, and flat season in 2016. The controlling factors of karst groundwater were analyzed by using multivariate statistical analysis method. The results showed that the groundwater samples were weakly alkaline fresh water and rich in Ca 2+ and HCO 3 - , which accounted for more than 75% and 70% of total ion concentration. The average concentrations of K + , Na + , Cl - , and NO 3 - decreased in the order of wet season > flat season > dry season. None of the concentrations of Ca 2+ , Mg 2+ , HCO 3 - , SO 4 2- , pH, TDS, TZ + , and TZ - showed significant seasonal variation. The hydrochemical characteristics were found to be of HCO 3 -Ca type and mainly determined by carbonate rock dissolution. Only a small proportion of them were of HCO 3 ·Cl-Ca and HCO 3 ·SO 4 -Ca type in wet season and flat season, Cl·NO 3 -Ca type appeared in flat season, and HCO 3 -Ca·Mg type appeared in dry season, reflecting the influence of dolomite and ferric mudstone dissolution in the stratum, and of NO 3 - and Cl - input from anthropogenic activities. Groundwater Ca 2+ and HCO 3 - mainly came from limestone dissolution; Na + , Cl - , K + , and NO 3 - came from atmospheric precipitation and human activities; while Mg 2+ and SO 4 2- came from dolomite and ferric mudstone dissolution. The chemical composition of groundwater was controlled by water-rock interaction, the groundwater in the carbonate aquifer was controlled by carbonate rocks dissolution, and the groundwater in villages and densely populated areas was affected by atmospheric precipitation and human activity.

Fluorescent substances are used as good tracers in dissolved organic matter (DOM) to identify the source of DOM and its geochemical behavior in a hydrological system. However, there are few studies on the karst aquifer system. Many parameters in karst systems affect the DOM spectral information. A typical karst watershed in Northern China was selected in this research. Excitation-emission matrices (EEMs), parallel factor analysis (PARAFAC), and hydrochemical data were applied to reveal the relationship between the composition and transformation of DOM fluorescent substances in different karst water-bearing spaces. The source of DOM and the effect of water chemistry on DOM transfer were also discussed. The results showed that DOM in exogenous surface water and karst surface water in the Yufu River watershed were mainly composed of tryptophan-like substances, while the DOM in shallow karst water and deep karst water consisted of tryptophan-like and tyrosine-like substances. A comprehensive analysis by fluorescence index (FI), biological index (BIX), and humification index (HIX) displayed that the DOM in shallow and deep karst water resulted from microbial decomposition. In contrast, the DOM in karst surface water and exogenous surface water resulted from land-based input and endogenous microbial decomposition, in which endogenous contributions occupy a large proportion. Due to the chemical parameters of karst water, these three kinds of fluorescent substances extracted by PARAFAC had obviously different characteristics, i.e., ① the tyrosine-like substances had a strong adaptability to Ca 2+ and HCO 3 - , and the proportion of the tyrosine in karst water was relatively large; ② the tryptophan substance followed an opposite trend; and ③ there was a significant positive correlation between fulvic acid and TDS, turbidity, Cl - , and SO 4 2- . Observations of the watershed runoff revealed that the DOM in shallow karst water in the upper reaches came mainly from the soil and microbial degradation. The organic matter underwent a large amount of microbial decomposition and exogenous input when the water was rejuvenated with springs. After infiltration to the deep karst water in the lower reaches, the DOM gradually were converted to low aromatic hydrocarbon organic compounds and decreased macromolecules of DOM. Subsequently, the fluorescence intensity was weakened. The principal component analysis (PCA) extracted three principal components. They were the water mineralization index, soil leaching index, and hydrochemical/biochemical process index. The water mineralization index consists of hydrochemical parameters reflecting the water infiltration, transformation, and flow conditions in the karst system. The soil leaching index contains TOC, NO 3 - , and protein-like indicators relating to the relationship between protein-like substances and soil and natural leaching. The hydrochemical/biochemical process index is composed of Ca 2+ , HCO 3 - , FI, and fulvic acid indicators that illustrate the water chemistry and biochemical processes in the karst water system. In addition, the study also showed that total fluorescence intensity, fulvate-like substances, and protein-like substances can be used as a tracer for rapid seepage, transformation, and aquifer fragility for karst water, respectively. The results of the study are important in understanding the biogeochemical cycle of DOM in the karst water system and also helpful for controlling organic pollution. It also provides a new tool for characterizing the geochemical processes of organic matter in karst system.

The Wujing River, the largest river in Guizhou Province, is one of the most important water resources for social and economical development. Recently, with the fast population proliferation and rapid economic growth, the drainage basin is intensively interfered by anthropogenic activities. The hydrochemistry of surface water was analyzed from the upper-middle reaches of Wujiang River for investigating the hydrochemical characteristics and their main influencing factors. The results showed that the major cations of the four rivers were Ca²⁺ and Mg²⁺, accounting for more than 70%, and the main anions were HCO₃⁻ and SO₄²⁻, occupying more than 85%. The hydrochemical characteristics in the four rivers were found to be of HCO₃-Ca type, and mainly determined by the carbonate rock dissolution, while only a small proportion of them were of HCO₃ · SO₄-Ca type, reflecting the influence of SO₄²⁻ from anthropogenic activities. Compared to hydrochemical data in 1999, there was an obvious increase in cations and anions concentrations, majorly in NO₃⁻, SO2- ion concentrations, which were significantly affected by human activities. The Na⁺, K⁺ , Cl⁻ in the river mainly came from atmospheric precipitation, and Ca²⁺, HCO₃⁻, Mg²⁺, mainly came from carbonate rocks dissolution, while NO₃⁻ and SO₄²⁻ mainly came from human activities. According to principal component analysis and correlation analysis, hydrochemical composition of Liuchong River was affected by human activity, and that in the upstream of Sancha River was controlled by atmospheric precipitation and the dissolution of carbonate rocks, that to the downstream was enhanced by human activities. The main ion of Maotiao River was controlled by atmospheric precipitation and carbonate rocks dissolution, and also affected by human activity. The Nanming River, the Qingshui river's tributary, was mainly affected by human activity, while the middle and lower reaches of Qingshui River were affected by both the atmospheric precipitation and human activity.

Groundwater and surface water from the Upper and Middle Reaches of the Wujiang River were sampled and analyzed for the hydrochemistry and Carbon isotope in DIC. Then hydrochemical characteristics and the main influencing factors were investigated, and the contributions of carbonate dissolution by sulphuric acid to total(Ca2+ + Mg2+) and HCO3 were calculated using the stoichiometry method. The results showed that the advantage cations of groundwater and surface water is Ca2+, which accounted for more than 50% and the advantage anions is HCO3- and SO(4)2-, which accounted for more than 85%. The hydrochemical characteristics of most samples were of Ca-HCO3 type, and a small part of HCO3.SO4-Ca, reflecting a few samples affected by SO(4)2- from human source. The δ13CDIC of groundwater and surface water, varying from -12. 98%o to -6. 36%o with a changeable molar ratio between (Ca2+ + Mg2+) and HCO3- of 1. 11 to 1. 90, indicated that sulfuric acid has an important influence on hydrochemistry and δ3CDIC. The contributions of carbonate dissolution by sulphuric acid to total (Ca2+ + Mg2+) and HCO3 in groundwater ranged from 20. 59% to 92. 87% (average 51. 50%), and from 11. 47% to 86. 69% (average 36. 90%). While the contributions of carbonate dissolution by sulphuric acid to total (Ca2+ + Mg2+) and HCO3- in surface water ranged from 56. 14% to 94. 55% (with an average of 76. 89%), and 39. 02% to 89. 66% (with an average of 64.24%), respectively, demonstrated that sulphuric acid is an important agent of carbon rock weathering. The results of this study have a great significance for the protection and development and utilization of water resources in the Wujiang River basin and for karst carbon cycle research.