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Karst groundwater plays an irreplaceable role in the formation and development of urban areas, and land-use and land-cover change (LUCC) and the input of pollutants during the urbanization process would pose potential environmental risks to underground rivers. We analysed the relationship between urbanization processes and underground river hydrochemistry over nearly 35 years in Guiyang city, southwest of China, it was found that concentrations of various cations and anions, as well as total dissolved solids (TDS), gradually increased with the urbanization process, with significant fluctuations during the rapid urbanization periods. The Hydrochemical Facies Evolution Diagram (HFED) clearly showed the influence of urbanization on the hydrochemistry of the underground rivers. The ion ratios of γMg2+/γCa2+-γHCO3-, γNa+/γCl-, Ca2+/Mg2+-Ca2+ or Mg2+/Σ cations, HCO3-/SO42--HCO3- or SO42-/Σ anions revealed two distinct phases in the hydrochemical evolution of the underground river system, highly consistent with the urbanization process. Before the rapid urbanization, acid deposition and agricultural activities affected the hydrochemistry, with HCO3-Ca·Mg and HCO3·SO4-Ca·Mg as the dominant types controlled by limestone and dolomite dissolution in water-rock interactions. As acid deposition diminished, the input of SO42- from urban sewage compensated for the reduced impact, but the increased impermeable surfaces reduced the infiltration of atmospheric precipitation, leading to a reduced dissolution of dolomite minerals in water-rock interactions, resulting in a decrease in Mg2+ and a change in the hydrochemical type. The hydrochemical type evolved from a single HCO3·SO4-Ca·Mg type and HCO3-Ca·Mg type to multiple types, such as HCO3·Cl-Ca, HCO3·SO4-Ca, HCO3-Ca, and HCO3·SO4-Ca·Mg, and was highly unstable. With changes in land use, the proportions of various cations and anions in the hydrochemistry changed, especially NH4+, NO3-, SO42-, Na+, and Cl-, which were more sensitive to human activities. This study indicated the impact of urbanization on the hydrochemistry of the underground river system, with the input of SO42- from human activities and the increase in paved surfaces due to urbanization collectively altering the hydrochemical types of the underground river system. The rapid response of karst underground river system hydrochemistry indicates a potential impact on groundwater system by urbanization that should not be ignored.

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Fractured-vuggy reservoirs are mainly composed of three types: underground rivers, vugs, and fractured-vuggy structures. Based on the similarity criterion, a 3D model can truly reflect the characteristics of the multi-scale space of a fractured-vuggy reservoir, and it can reflect fluid flow laws in the formation. Water flooding, gas flooding, and gel foam flooding were carried out in the model sequentially. Based on gas flooding, the enhanced recovery ratio of gel foam flooding in the underground river was approximately 12%. By changing the injection rate, the average recovery ratio of nitrogen flooding was 6.84% higher than that of other injection rates at 5 mL/min, and that of gel foam flooding was 1.88% higher than that of other injection rates at 5 mL/min. The experimental results showed that the gel foam induced four oil displacement mechanisms, which selectively plugged high-permeability channels, controlled the mobility ratio, reduced oil-water interfacial tension, and changed the wettability of rock surfaces. With different injection-production methods, gel foam flooding can spread across two underground river channels. Two cases of nitrogen flooding affected one underground river channel and two underground river channels. By adjusting the injection rate, it was found that after nitrogen flooding, there were mainly four types of residual oil, and gel foam flooding mainly yielded three types of remaining oil. This study verified the influencing factors of extracting residual oil from an underground river and provides theoretical support for the subsequent application of gel foam flooding in underground rivers.

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Underground rivers are an important source of groundwater in karst area. Recently, nitrate pollution of underground rivers has become a serious issue. To identify the sources of nitrate in Guancun typical karst underground river basin, stable isotope techniques (δ15N-NO3-, δ18O-NO3-, and δ18O-H2O) were applied in this study. The contribution rates of different nitrate sources in groundwater were quantitatively identified based on the stable isotope analysis in R (SIAR) model, and the influence of land use type on nitrate distribution and source in watershed water was clarified. The results showed that ① nitrate mainly came from fertilizers, soil organic nitrogen, and manure/sewage based to the isotopic composition of nitrate nitrogen and oxygen isotopes. It was revealed that non-point sources significantly contributed to nitrate in waters of the Guancun underground river basin. ② Nitrification dominated the formation process of nitrate in groundwater, and the initial values of nitrogen and oxygen isotopes were not affected by fractionation. ③ Based on SIAR, the contribution of different sources to nitrate in water in the basin varied seasonally, and the contributions of fertilizer, soil organic nitrogen, and manure/sewage to nitrate were 57.07%, 34.06%, and 8.87% in the wet season and 34.14%, 33.02%, and 32.84% in the dry season, respectively. Overall, the present study quantitatively evaluated the temporal variations of nitrate sources in a typical karst groundwater river basin and provided a theoretical foundation for prevention and control management of non-point source pollution and watershed management in karst areas.

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Dissolved organic matter (DOM) in karst water is one of the most important carbon sink components, whose origins, distributions, and transport processes are of significance to carbon sink studies. Chromophoric dissolved organic matter (CDOM) can be utilized to express the composition and structural properties of DOM. In this paper, water samples were collected monthly from Xueyu Cave in a karst underground river from both inside and outside the cave. The changes in hydrochemistry and CDOM spectral characteristics as well as the influencing factors for CDOM changes were studied, with the aim of providing experimental support for carbon sink fluxes in karst processes. The main results were as follows. ① The dominant type of CDOM in Xueyu Cave karst water consisted of small molecular weight organic matter that was autochthonously derived and easily bio-degraded, and the tryptophan-like and tyrosine-like components accounted for more than 60% of the total CDOM. ② The most effective influencing factor inside the cave was microbes, which degraded the small molecular DOM in groundwater and induced slight decreases in the TOC and DOC concentrations; they also increased the humic index (HIX). ③ However, the dominant factor outside the cave was submerged aquatic plant photosynthesis, which induced significant increases in the TOC and DOC concentrations and autochthonous small molecular weight DOM contents.

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The concentration and fluxes of polycyclic aromatic hydrocarbons (PAHs) were investigated in a karst underground river system in southwest China. Groundwater, particles, and sediments from underground river, topsoil, and surface water were monitored, allowing establishment of a conceptual model of PAH transport at the watershed scale. The results showed that PAHs could be transported from the surface to the subsurface through two migration pathways, which were slow-flowing water in the karst fissure and fast-flowing water in conduits. During rainfall events, increasing PAH levels (concentrations and fluxes) at the underground river exit indicated that hydrodynamic force could facilitate PAH transport. The PAHs in water were dominated by dissolved PAHs, accounting for 58.7% of total, especially in the freely dissolved phase, in which SPM-associated PAHs accounted for 41.3% of the total PAHs. Low molecular weight PAHs dominated transport and were mainly transported in dissolved form, whereas high molecular weight PAHs were dominated by SPM-associated transport during the rainfall events. A significantly positive correlation was observed between two-ring and three-ring freely dissolved PAHs and dissolved organic carbon (p < 0.01), respectively. Moreover, PAHs with four to five rings were relatively more abundant in the dissolved organic matter (DOM) associated phase than in the freely dissolved phase, suggesting a major role of DOM in their transport during rainfall events. The trend of PAH fluxes suggested that particle-facilitated transport was another dominant cause of PAH mobilization.

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In this research, the bacterial community compositions of underground water in a tourist and pristine cave were studied. Xueyu Cave and Shuiming Cave are tourist and pristine caves, respectively, in the same karst cave system located in Chongqing, southwest China. To understand the impact of tourism on bacterial community compositions in underground water that flows through the caves, filtered materials from water were collected, and 16S rDNA gene sequences were obtained by high-throughput sequencing. The Shuiming Cave (the pristine cave) had less diversity than Xueyu Cave (the tourist cave) based on the Shannon's diversity index according to Illumina operational taxonomic units (OTUs). Proteobacteria, represented mostly by γ-Proteobacterium and Bacteroidetes, dominated both systems. OTUs from Shuiming Cave were dominated by 38% Proteobacteria, 24% Chlorobi, and 19% Bacteroidetes. In the Xueyu Cave, OTUs from upstream samples were comprised of 62% Proteobacteria but comprised 64% in the downstream samples. In the Xueyu Cave, Bacteroidetes accounted for 11% of the total OTUs in the upstream sample and 16% in the downstream. Among the γ-Proteobacterium and Bacteroidetes, Acinetobacter, Pseudomonas spp., and Flavobacteriaceae, which are related to potentially pathogenic species, were prevalent in the Xueyu Cave, while Methylococcaceae-uncultured, Methylomonas spp., and Methylobacter, all methane-oxidizing bacteria, had high relative abundances in the Shuiming Cave. These results revealed that potentially more pathogenic bacteria are present in the stream waters from the tourist cave, which has important implications for the protection of tourist caves. The RDA analysis of the environmental factor and bacteria community in groundwater showed that the distribution of pathogenic bacteria was positively correlated with the cave air CO2, and the Spearman correlation analysis of the two environmental factors indicated that the influence of the number of tourists on the structure of the bacterial community in the groundwater was more obvious and led to the disappearance of a large number of native bacteria. We proposed that tourist caves control the number of daily tourists and that they enter in batches and increase the import and export of closed devices to avoid the cave air exchange inside and outside. In addition, it was recommended that they increase the import and export of sterilization devices to reduce tourists with bacteria and organic matter, and avoid leaving garbage in the hole to avoid cave microbial exchange inside and outside. A reduction in the fixed lighting inside caves should be required to reduce long exposure, since the tourists can bring individual source lighting.

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To investigate the influence of urbanization on the component features of dissolved n-alkanes (D-ALK) in the underground river in the dry season, water samples were collected respectively at the outlet of the two underground rivers. Components of D-ALK in these samples were quantitatively analyzed by gas chromatography-mass spectrometry (GC-MS). The results showed that the distribution of D-ALK carbon number at the two sites ranged from nC14 to nC35 in dry season. The total concentration of D-ALK (DT-ALK) in Jiangjia spring ranged from 102 to 356 ng·L-1, with an average of 230 ng·L-1. The low-number carbons were predominant in December 2014, January and April 2015. The ratios of LMH/HMH (nC21-/nC22+) ranged from 2.0 to 10. The carbon preference index (CPI) between nC14 and nC25 ranged from 0.19 to 0.57, with a maximum of C16 (Cmax16). However, in November 2014, February and March 2015, these samples had a bimodal distribution in n-alkane. All of the CPI14-25 and the ratios of LMH/HMH were less than 1. The CPI24-35 ranged from 1.2 to 23 with the Cmax 31 or Cmax33. During the three months, the values of Paq were 0.2, 0.7 and 0.1, respectively. The alkane indexes (AI) in November 2014 and March 2015 were 0.95 and 0.98, respectively. The values of DT-ALK in Laolongdong ranged from 110 to 697 ng·L-1 with an average of 310 ng·L-1. The carbon number distribution of each month had a low predominance, and the CPI14-25 was less than 1. In the dry season, under the influence of different human activities, the content and component of D-AKL in Laolongdong which originated mainly from microorganisms was more stable than that in Jiangjia spring, which was mainly derived from microorganisms and a mixture of microorganisms and plants.

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In order to explore the contents, composition, distribution characteristics, sources and pollution level of polycyclic aromatic hydrocarbons(PAHs) and fatty acids in water of Qingmuguan karst underground river in Chongqing, water samples were respectively collected from underground river in rainy season and dry season, 2013 and polycyclic aromatic hydrocarbons, fatty acids of the water samples were quantitatively analyzed by Gas Chromatography-Mass Spectrometer(GC-MS). The results showed that the contents of PAHs and fatty acids in water of Qingmuguan karst underground river ranged from 77.3 to 702ng·L-1 and 3302 to 45254 ng·L-1, respectively. In terms of composition, the PAHs profiles were dominated by (2-3) rings PAHs in water samples, which accounted for more than 90% of the total PAHs contents, while the carbon numbers of fatty acids ranged from C10 to C28, and fatty acids profiles were dominated by saturated straight chain fatty acids, followed by mono-unsaturated fatty acids. In terms of the distribution characteristics, the contents of PAHs had minor difference at each sample point in water of underground river in rainy season. At the entrance, exposed and exits, the contents of fatty acids reduced in turn, moreover the contents of fatty acids were close at the exposed and exits. dry season:at the entrance, exposed and exits, the contents of PAHs in water of underground river decreased firstly and then increased. The contents of fatty acids were close at each sample point in water of underground river. As a whole, the contents of PAHs and fatty acids in water of underground river in rainy season were significantly higher than those in dry season. Source analysis indicated that the PAHs in water of Qingmuguan underground river were mainly originated from the combustion of coal and biomass (wood, crop straw, etc) at the underground river catchment. The fatty acids were mainly originated from aquatic algae (diatoms and green alga, etc), and bacteria, with the contribution of aquatic algae dominated. The water of underground river was suffered the middle to mild pollution by PAHs, and compared with the dry season, the rainy season was more severely polluted.

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To investigate whether the underground river was polluted or not, and trace the source of fecal sterols, the particulate water samples were collected from typical karst underground river named Laolongdong in Nan'an District, Chongqing Municipality in October, 2014, January, March and May, 2015. Ten prior steroids in the underground river were quantitatively analyzed by the gas chromatography-mass spectrometer (GC-MS). The results showed ten steroids including 9 sterols and 1 ketone were detected. During the sampling period, the mass concentrations of particulate steroids (ranging between 1573 and 5007 ng·L-1) in March and May were higher than those in October and January. The 3 principal steroids-cholesterol, ß-sitosterol and coprosterol-in the river accounted for 50.8%-80.4% of the total steroids. The ratios of (epicoprostanol+coprostanol) to (coprostanol+epicoprostanol+cholestanol) of three samples were greater than 0.7, which indicated the river was contaminated in sampling months. The ratio of epicoprostanol to coprostanol was less than 0.2 in October, which indicated the wastewater came from the upstream sewage treatment plant. The ratios of coprostanol to ΣSteroids and coprostanol to 24-ethylcoprostanol in January, March and May were respectively 0.109-0.254 and 6.3-10.3, which indicated that Laolongdong underground river was mainly polluted by human feces. The ratio of 24-ethylcoprostanol to 24-ethylcholestanol in March (0.86) was less than those in January (5.4) and May (2.3), which showed the river was polluted more severely in March than in January and May by poultry dung.

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Chongqing Laolongdong and Qingmuguan karst underground rivers were selected as the research objects, and 21 kinds of OCPs in those two underground rivers were analyzed by gas chromatography (GC-µECD). The results showed that, o,p'-DDE,p,p'-DDE, o,p'-DDD were not detected in Nanshan and Qingmuguan underground rivers; o,p'-DDT and dieldrin were not detected in Qingmugang; but the detection rate of the rest of the OCPs in those two underground rivers was as high as 100%. HCHs and ALDs were the most dominant compounds in Laolongdong underground river, whereas HCHs and methoxychlor were the most dominant compounds in Qingmuguan. The concentration range of total OCPs in Qingmuguan was 145-278 ng·L-1 with a mean value of 213 ng·L-1. The concentration range of total OCPs in Laolongdong was 17.7-40.8 ng·L-1 with a mean value of 32.7 ng·L-1. The OCPs component showed an increasing trend from the entrance to the exit of those two underground rivers. By analyzing the source of OCPs pollution, DDTs in the two underground river basin came from the historical industrial DDTs input; chlordane mainly came from atmospheric deposition. HCHs was the main source of Lin Dan's input, Nanshan underground river was historical pollution, whereas there was a new HCHs input from Ganjiachao in Qingmuguan upstream. Compared with the water bodies at home and abroad, the concentrations of HCHs and DDTs in Nanshan underground river water were at low level, whereas those in Qingmuguan were at medium to high level. Comparing with the hygienic standard of foreign water, it could be observed that Nanshan underground river and Qingmuguan underground river were not able to meet the standard of drinking water safety standard. For the sake of protecting the ecological environment of the underground river, land application of organic chlorine pesticide should be banned in Qingmuguan.

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To study the hydrogeochemical characteristics of southwestern typical karst underground river influenced by different land-use types and human activities, underground rivers of Qingmuguan and Laolongdong, which have similar geological background in Chongqing, were contrastively analyzed from the scale of monthly and rainfall event variation. By the means of independent t-test and principal component analysis(PCA), the results showed that ions of Ca2+, HCO3-, Mg2+, K+, NO3-, Na+, SO42-, Cl- and conductivity were distinctly different at the outlet of the two observed underground rivers, Jiangjia spring and Laolongdong. Compared with Laolongdong, Jiangjia spring showed larger monthly variation range and mean concentrations of K+, NO3-, but ions of Na+, SO42-, Cl- showed an opposite trend. Water-rock interaction played an important role in the hydrogeochemical characteristics and variations of two observed karst underground rivers. Qingmuguan underground river was mainly affected by agricultural activities, while Laolongdong underground river was dominantly influenced by urban and industrial activities. Owing to the difference in manner and intensity of human activities, the two observed karst underground river systems responded differently during a single rainfall event. The variation of water chemical indicators that highly corresponded to discharge at Jiangjia spring were relatively disordered at Laolongdong. It was shown that the hydrogeochemical characteristic of Qingmuguan was primarily influenced by soil erosion and agricultural activities, followed by water-rock interaction, while the hydrochemical characteristic of Laolongdong was dominantly influenced by water-rock interaction, followed by urban activities, industrial activities and soil erosion.