[Sources and Biogeochemical Processes of Nitrate in the Laolongdong Karst Underground River Basin, Chongqing].

Samples of sewage, well water, and underground river water of the urbanized Laolongdong karst underground river basin in Chongqing, China were collected during July 2019 and October 2020 and measured to determine the nitrate origin and biogeochemical processes based on geochemistry and dual nitrate isotope (δ15N-NO3- and δ18O-NO3-) data. The results showed that:① the isotopic nitrate compositions of sewage ranged from -3.3‰ to 14.6‰ for δ15N-NO3- and from -5.2‰ to 20.6‰ for δ18O-NO3-, which indicated that nitrate originated from manure and sewage, fertilizer, and soil organic nitrogen. The δ15N-NO3- and δ18O-NO3- of well water varied from 3.1‰ to 12.6‰ and 2.9‰ to 8.9‰, respectively, suggesting nitrate was mainly from soil organic nitrogen and manure and sewage. For the underground river water, the δ15N-NO3- and δ18O-NO3- ranged from 5.6‰ to 28.6‰ and from -2.0‰ to 15.7‰, respectively, suggesting that municipal sewage and manure were the dominate nitrate sources. ② Based on the MixSIAR model, manure and sewage were the primary nitrate source of the underground river water, accounting for 89.1% of the total contribution, whereas the contributions of soil organic nitrogen, fertilizer, and atmospheric precipitation were 4.4%, 3.4%, and 3.1%, respectively. ③ In the basin, the concentration ratios of COD:ρ(NO3-) from low to high were as follows:well water (0.14-5.15), underground river water (0.50-9.36), and sewage (4.08-89.50). Only 50% of well water samples with COD:ρ(NO3-) were slightly higher than 0.65, which is the minimum stoichiometric ratio for denitrification occurrence. This indicated that there were insufficient COD concentrations to support that denitrification occurred in the well water. This was further verified by no significant enrichment of nitrogen and oxygen isotopes. As much as 90% of underground river water samples had a COD:ρ(NO3-) higher than 0.65, and the dual nitrate isotopes were simultaneously enriched with a δ15N:δ18O of 1.8, which is within the ratios ranging from 1.3 to 2.1, indicating that denitrification occurred. The COD:ρ(NO3-) for all wastewater samples was much higher than 0.65, of which 25% were higher than the stoichiometric ratio (29.34) for the occurrence of dissimilation reduction nitrate to ammonium (DNRA). The δ15N-NO3- and ρ(NH4+):ρ(NO3-) of sewage increased simultaneously, indicating that DNRA may have occurred in the sewage.

[Comparison of the Geochemical Characteristics of Karst Springs of a Vertically Zoned Climate Region under Human Activity: A Case of Shuifang Spring and Bitan Spring in the Jinfo Mountain Area, Chongqing].

To investigate the hydrochemical variation of karstic groundwaters in a vertically zoned climate region affected by human activity, Shuifang Spring and Bitan Spring in the Jinfo Mountain area of Chongqing were selected as a study site. Based on the differences between the natural state and intensity of human activity of these two springs, their hydrogeochemical characteristics and the controlling factors on karstic groundwaters were analyzed by means of independent sample t tests, the Gibbs graphic method, principle component analysis (PCA), and geochemical susceptivity analysis. The results show that differences in karst development in the vertical climatic zone leads to higher total ion concentrations in Bitan Spring than in Shuifang Spring. The hydrochemical types of Shuifang Spring and Bitan Spring are HCO3-Ca and HCO3-Ca·Mg, respectively, which reflect the lithology of their different elevations. Carbonate rock dissolution is the main source of Ca2+, Mg2+, and HCO3- in karstic groundwaters. Hotel sewage discharge supplies SO42-, NO3-, PO43-, K+, and Na+ in Shuifang Spring, which peaked in winter and summer, while hydrochemical parameters of Bitan Spring changed smoothly throughout the year. The water quality of Bitan Spring is better than Shuifang Spring (Shuifang Spring water is classified as Class Ⅳ). PCA shows that the water-rock interaction was the first controlling factor. Hotel sewage discharge and ions from precipitation had important effects on Shuifang Spring and Bitan Spring, respectively. In addition, the effects of soil erosion and leaching caused by precipitation also impact on the water quality of two springs to some extent. The geochemical susceptibility of Shuifang Spring was greater than that of Bitan Spring; therefore, corresponding measures should be formulated according to the characteristics of these differently elevated karst systems when exploiting groundwater resources. This is especially the case for the treatment of hotel sewage.

[Nitrate-Nitrogen Pollution Sources of an Underground River in Karst Agricultural Area Using 15N and 18O Isotope Technique].

The objectives of this study were to reveal the sources of nitrate and the ratio of karst in an agricultural basin based on a 15N and 18O isotope technique and quantitative calculation of the IsoSource model. From May to October 2017, six sampling points in the Qingmuguan river basin, Chongqing, were monitored every 24 d. Results showed that there was a great risk of nitrate pollution in the underground river system, because most NO3--N concentrations of the sampling points exceeded the threshold. Spatially, NO3--N concentrations in the underground river increased from upstream to downstream. Temporally, NO3--N concentrations of Fishpond and Yankou Ponor upstream and Jiangjia Spring downstream were impacted by agricultural fertilizer from May to June and fluctuated from June to September due to precipitation. With decreased agricultural activities, NO3--N concentrations gradually decreased after September. NO3--N concentrations were high in midstream soil water. Daluchi, in the middle and lower reaches, maintained relatively low NO3--N concentrations with stable fluctuations. Dual 15N and 18O isotopic compositions suggested that the upstream nitrates were derived from soil organic nitrogen and a mixture of manure and sewage. The midstream nitrates originated from soil organic nitrogen and NH4+ from fertilizer and rain. Nitrates in the middle and lower reaches were derived from the mixing of manure and sewage, soil organic nitrogen, and NH4+ from fertilizer and rain. Jiangjia Spring, the outlet of the underground river, was seriously polluted by nitrates. It is believed that soil organic nitrogen, NH4+ in fertilizer and rain, the mixing of manure and sewage, and NO3- in precipitation were the main nitrate sources in the outlet. Nitrate source contribution of the outlet was calculated with the IsoSource model. The calculation results showed that manure and sewage, soil organic nitrogen, NH4+ in fertilizer and rain, and NO3- in precipitation contributed 46.4%, 32.6%, 18.6%, and 2.4%, respectively.

[Geochemical Characteristics of Lateral Hyporheic Zone Between the River Water and Groundwater, a Case Study of Maanxi in Chongqing].

The hyporheic zone is a place where river water and groundwater mutually exchange and mix. It plays an important role in protecting the ecology and water quality of river water and groundwater. In order to study the geochemical characteristics of lateral hyporheic zone in river and ground water, water temperature, dissolved oxygen, pH, electrical conductivity were measured automatically at the hyporheic zone of Maanxi in Chongqing. The concentrations of ions in water and elements in sediment within the hyporheic zone were also analyzed. The results showed that the hydrochemical species of lateral hyporheic zone in Maanxi was HCO3-Ca·Mg. Affected by the infiltration of river water, the coefficient variations of water temperature, dissolved oxygen, pH and electrical conductivity in the hyporheic zone were lower than those observed in the river under the buffer action. Along with the farther distance from the riverbank, an anoxia redox environment was formed in the hyporheic zone due to a physical, chemical and biological interactions. An acid and alkali environment was also formed with a decreasing pH trend near the riverbank and hyporheic zone. Under its influence, concentrations of K+, NH4+-N, NO3- and SO42- decreased. Mn, electrical conductivity, and the concentrations of Ca2+, Mg2+, Ba2+ and Sr2+ firstly increased and then decreased, while the concentrations of Fe, Al3+ were elevated. Affected by the long-time interaction of river water and groundwater, the elementary concentrations in the sediment were relatively high at the place of about 30 cm away from the riverbank. This consequently formed a hydrogeochemical gradient in the hyporheic zone. The boundary of the hyporheic zone was inferred at 30 to 50 cm away from the riverbank, whereas the boundary of shallow hyporheic zone was located at 10 cm away from the riverbank. In the process of river water recharging groudnwater, hyporheic zone of river and groundwater played an important role in the purification of water quality.

[Comparison on the Hydrogeochemical Characteristics of Typical Karst Groundwater System in Southwest China, a Case of Qingmuguan and Laolongdong in Chongqing].

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.

[Influences of Biological Processes on Geochemical Characteristics: An Example of a Mountain Karst Pool in Spring Season].

Karst hydrologic system is quite sensitive to the surrounding environment, which leads to changes in the quality of karst water within diel, hours even minutes. Many surface water undergoes changes of pH value, dissolved gas, trace elements, nutrition and other hydrochemical parameters in a daily timescale. The Shuifang spring and its draining pool are located in Jinfo Mountain in Chongqing, the middle karst mountain belonging to temperate climate with an elevation of about 2050 m a. s. l. Diel cycles of geochemistry were measured for three days and nights to investigate the influence of biological processes on the geochemistry of the karst pool. Results showed that the geochemistry of Shuifang spring didn't exhibit diel variations, while the pool water appeared diurnal change, even if the variation amplitudes of water temperature, pH value, dissolved oxygen and specific conductance were slight. Under different weather conditions, variation amplitude of the geochemical parameters in the pool appeared discriminatory. pCO2 and concentrations of Ca2+, dissolved inorganic carbon (DIC) decreased during the day time and increased in night, while calcite saturation index (SIc) showed an inverse trend. Those phenomena might be attributed to water temperature change, calcite precipitation or dissolution and the process of metabolism by the aquatic plants in the pool. It was found that the influence of water temperature change on pCO2 accounted for only 0.79% to 10.01% by means of calculation of Henry constants. DIC loss contributed by physical factors, such as temperature and calcite precipitation, accounted for 39%, whereas the metabolism of aquatic plants accounted for 61%.

[Variation Characteristics and Sources of Heavy Metals in an Urban Karst Groundwater System during Rainfall Event].

The groundwater discharge and heavy metal concentrations (Mn, Pb, Cu and As) at the outlet of Nanshan Laolongdong karst subterranean river, located at the urban region in Chongqing, were observed during the rainfall events. Analysis of flow and concentrations curves was employed to study their responses to the rainfall events and explore the internal structure of karst hydrological system. Principal component analysis (PCA) and measurements were used to identify the sources of heavy metals during rainfall. The result showed that the discharge and concentrations of the heavy metals responded promptly to the rainfall event. The variation characteristics of flow indicated that Laolongdong subterranean river system belonged to a karst hydrological system including fractures together with conduits. Urban surface runoff containing large amounts of Mn, Pb and Cu went directly to subterranean river via sinkholes, shafts and karst windows. As a result, the peak concentrations of contaminants (Mn, Pb and Cu) flowed faster than those of discharge. The major sources of water pollution were derived from urban surface runoff, soil and water loss. Cave dripwater and rainwater could also bring a certain amount of Mn, Pb and As into the subterranean river. Urban construction in karst areas needs scientific and rational design, perfect facilities and well-educated population to prevent groundwater pollution from the source.

[Characteristics and Resources of Fly Ash Particles in the Snowpack of Jinfo Mountain, Chongqing].

Snow can preserve the atmospheric information, which makes it become a good media in studying regional environment. Jinfo Mountain with an elevation of 2251.1 m, located at the transition zone between Sichuan basin and Yunnan-Guizhou Plateau, is deeply affected by human activities, and snowfall is the main form of precipitation during the winter. While the literature focus on single spherical particles in this area is uncommon. Five snow samples were collected, and determined morphology and chemical composition of 132 single spherical particles by the scanning electron microscope couples with energy dispersive X-ray spectrometer (SEM-EDS). Results show that snowfall in Jinfo Mountain includes the massive fly ash particles with 1.64 µm in average diameter and 1.09 in average roundness which contains smooth particles, rough particles and soot particles, accounting for 80. 31% , 14. 39% and 5.30% of statistical particles respectively. Furthermore, on the basis of chemical information obtained from EDS, the fly ash particles counted in this research can be classified into 5 types, namely, Si-dominant particles, C-dominant particles, Fe-dominant particles, Al-dominant particles and Ti-dominant particles, which make up 34.09%, 49.24%, 12.88%, 2.27% and 1.52% respectively. In conclusion, it can be inferred, based on the analysis of meteorological information, the properties of fly ash particles, and backward air mass trajectory and dispersion analysis, that C-dominant fly ash mainly comes from daily life and industry activities, Si-dominant fly ash particles may originate from the plant industry located in west Chingqing, north of Guizhou province, central of Hunan province, Zhejiang province, Jiangxi province and the west of Guangdong province, while the activities of foundry and iron or steel plants in the west of Chongqing, the north of Guizhou province and the central of Hunan province may be the main sources of Fe-dominant fly ash particles in our samples.

[Hydrogeochemical characteristics of a typical karst groundwater system in Chongqing].

The two-year hydrologic process, hydrochemistry, and a portion of deltaD, delta18O of both the surface water at the inlet and the groundwater at the outlet, were investigated to identify the spatial and temporal variations of hydrogeochemistry in the Qingmuguan karst groundwater system. Research results show that there are wet and dry periods in the groundwater system owing to the striking influence of seasonal rainfall. The evolution of the chemical compositions in the groundwater is significantly influenced by the water and rock interaction, anthropogenic activities and rainwater dilution. The variations of the chemical compositions in the groundwater exhibit obvious spatiality and temporality. The deltaD and delta18O of the surface water beneath the local Meteoric Water Line of Chonqing indicate that the surface water is strongly evaporated. Furthermore, the deltaD and delta18O of the surface water are more positive in the dry period than in the wet period, showing a distinct seasonal effect. The deltaD and delta18O of the groundwater are quite stable and much negative compared with those of the surface water, which suggests that the rainwater recharge the groundwater via two pathways, one directly through sinkholes and the other via the vadose zone.

[Investigation of nitrogen, phosphorus and microbial contamination in Laolongdong underground river system of Chongqing].

With urbanization, groundwater in China has been widely polluted. Karst groundwater is important in southwest China, and would be difficult to recover once contaminated. NO3(-), PO4(3), NH4(+), total coliform, total E. coli and fecal coliform were chosen as indexes in the study of groundwater of Laolongdong Underground River System in Nanshan Mountain, Chongqing. After a few years of survey, the results showed that NO3(-), NH4(+) and PO4(3-) concentrations in the water were all above the nature value, especially NH4(+) and PO4(3-). The NO3(-) concentration of Guihuawan spring ranged from 19.78-68.55 mg x L(-1), in some months, above the recommended water quality guideline (50 mg x L(-1)) according to Standards for Drinking Water Quality set by World Health Organization. NH4(+) and PO4(3-) concentrations in Laolongdong underground river varied from 2.71-12.92 mg x L(-1) and 0.16-11.22 mg x L(-1). The NO3(-) concentration in Laolongdong underground river was lower than in karst spring; however, the concentrations of NH4(+) and PO4(3-) were higher than in the spring. It seemed that the NO3(-) concentration tended to decrease from 2008 to 2013 in the underground river caused by urbanization, reduction of farmland and reducing environment. However, waste water with a high PO4(3-) concentration led to an increasing trend in the PO4(3-) concentration in underground river. Microbial contamination was extremely serious, and even far exceeded class V of water quality standards of China. For example, the concentration of fecal coliform in the groundwater ranged from 3.4 x 10(4)-3.68 x 10(4) CFU x mL(-1). Because of the special hydrogeological structure, karst depressions, skylights and sinkholes can lead pollutants easily to the underground water. Agriculture activity, sewage from towns, enterprises and residential areas were the major sources of nitrogen, phosphorus and microbial contamination.

[Variation characteristics and environmental significant of trace elements under rainfall condition in karst groundwater].

Chemical dynamics of Qingmuguan karst groundwater system were continuously monitored during the rainfall events. A series of high-resolution concentrations data on trace elements, such as barium, strontium, iron, manganese, aluminum, and other major elements were acquired. Correlation analysis and analysis of concentration curve were employed to identify the sources and migration path of the trace elements. And the formation process of trace elements in groundwater was discussed with the geological background of underground river basin. Research shows that barium and strontium derived from carbonate dissolution appeared to be stored in features such as fissures and pores. These two ions were recharged into the underground river by diffusion during precipitation, which resulted in small changes in the their concentration. However total iron, total manganese and aluminum derived from soil erosion varied relatively widely with strong response to rainfall, attributing to the migration of total iron and aluminum with overland flow to recharge the subterranean river directly via sinkholes while total manganese via soil-rock porous media. The results showed that concentrations of all the five trace elements were below 1 mg x L(-1), and the highest concentrations of total iron, total manganese and aluminum exceeded the limit of drinking water. To some extent, the concentrations of total iron and aluminum may be an indicator for soil erosion and water quality.

[Contamination and ecological risk assessment of polycyclic aromatic hydrocarbons in water and in Karst underground river catchment].

Water samples in Laolongdong underground river catchment were collected to determine the concentration, compositional profiles, and evaluate ecological risk of 16 priority polycyclic aromatic hydrocarbons (PAHs). PAHs were measured by GC/MS. The total concentrations of 16 PAH ranged from 81.5-8019 ng · L(-1) in underground river, 288.7-15,200 ng · L(-1) in karst springs, and 128.4-2,442 ng · L(-1) in surface water. Affected by waste water from Huangjueya town, concentrations of PAHs in underground river were higher than those in surface water and waste water from sinkhole. The PAHs profiles were dominated by 3 ring PAHs. There were differences of monthly variations of PAHs contents in the water, due to waste water, season and different characteristics of PAH. Surface water and waste water from sinkhole played an important role on contamination in the river. The levels of ecological risk were generally moderately polluted and heavily polluted according to all detected PAH compounds in the water.

[Research on the sensitivity of geochemical of underground river in Chongqing Xueyu Cave].

Quoted geochemical susceptivity index and isosensitive line on geochemical susceptivity, analyzed the data of underground rivers of Xueyu Cave in Chongqing from September 2010 to August 2011, we found that the chemical composition of the underground river was controlled by the bedrock, due to the composition of high concentration of Ca2+ and low concentration of Mg2+. Owing to the effects of the monsoon, water chemistry was different between drought season and rainy season: the value of [Mg2+]/[Ca2+] was 0.018-0.051 in the rainy season, but in dry season the value was 0.038-0.064. The value of [HCO3(-)]/[SO4(2-)] was 4.86-36.62 in the rainy season, and 6.23-46.67 in the dry season. The seasonal change of Karstification made Ca2+ and HCO3(-) become the most sensitive ion. As a result of the special hydrogeological structure in Karat area, rain, surface water and groundwater transformed rapidly, which caused the underground river was sensitive to agricultural activities, especially for Cl- and NO3(-), and their sensitive indices were 0.286 and 0.022 respectively. The influence of tourism activities on the underground river was less than the management. The management work of ecological system should be strengthen in the recharge area, thus the largest economic and environmental benefits in the Karst area could be achieved.

[Nitrate storage and transport within a typical karst aquifer system in the paralleled ridge-valley of east Sichuan].

In order to investigate the nitrate storage and transport in the karst aquifer system, the hydrochemical dynamics of Qingmuguan underground river system was monitored online by achieving high-resolution data during storm events and monthly data in normal weather. The principal component analysis was employed to analyze the karst water geochemistry. Results showed that nitrate in Jiangjia spring did not share the same source with soluble iron, manganese and aluminum, and exhibited different geochemical behaviors. Nitrate was derived from land surface and infiltrated together with soil water, which was mainly stored in fissure, pore and solution crack of karst unsaturated zone, whereas soluble iron, manganese and aluminum were derived from soil erosion and directly recharged the underground river through sinkholes and shafts. Nitrate transport in the karst aquifer system could be ideally divided into three phases, including input storage, fast output and re-inputting storage. Under similar external conditions, the karstification intensity of vadose zone was the key factor to determine the dynamics of nitrate concentrations in the groundwater during storm events. Nitrate stored in the karst vadose zone was easily released, which would impair the aquatic ecosystem and pose seriously threats to the local health. Thus, to strengthen the management of ecological system, changing the land-use patterns and scientifically applying fertilizer could effectively make a contribution to controlling mass nutrient input from the surface.

[Transportation and sources of the suspended particle in a karst spring during a storm event].

Storm periods are the crucial stage to reveal input and outlet of material and energy in groundwater system. Jiangjia spring, the outlet of Qingmuguan groundwater system, was taken as an example. Distribution of suspended particle in the Jiangjia spring was continuously monitored. Supported by hydrochemical data, characteristics and sources of the suspended particle in the karst groundwater system were investigated. Results show that the number of suspended particle in size of 0-11 microm abruptly increased in the channel of Jiangjia spring at the beginning of rainfall occurred. It indicates the suspended particle was derived from allochthonous material. While the groundwater was recharged by karst fissure, the number of suspended particle in size of 0-11 microm sharply raised, which shows that the suspended particle was autochthonous. Finally, the number of suspended particle in size of 0-4 microm elevated due to the entire groundwater watershed recharged by rainfall and dilution effect occurring again, suggesting the suspended particle was derived from allochthonous material. Owing to the intrinsic hydrogeological settings and rainfall intensity, the threshold of size for the suspended particle was 4 pm in Qingmuguan groundwater system. It probably was a high practical significance to indicate the groundwater was whether polluted by microbe or not.

[High-resolution research on the NO3- changes of karst groundwater and its responses to the outside environmental variations].

In order to thoroughly reveal the karst groundwater system in response to the external environment, multi-index high-resolution auto-monitoring instruments were used to research the hydrogeochemistry variations of Qingmuguan subterranean stream. The monitoring indicators were pH value, electrical conductivity (EC), water level, rainfall and NO3-. In the observed 6 times rainfall events, the pH value was mainly controlled by acid rain and EC was impacted by the rain chemistry, physical dilution effect of rainfall and agricultural wastewater. NO3- derived from agricultural activities was less impacted by rain chemistry; and its variations were mainly affected by physical dilution effect of rainfall and agricultural wastewater. Under the influences of the R1 rainfall, the rapid changes of EC and NO3- were contrary in generally, but pH value decreased due to the acid rain. In the R2, R3, R4 and R6 rain events, the water level was positively response to the rainfall and the pH value decreased due to the acid rain; however both of the EC and NO3- decreased due to the dilution effect. With the afflux of agricultural wastewater, both of the EC and NO3- were rapidly changed in synchronization within the shortest of 5 h of and the longest of only 27 h and the pH value showed accelerated decline. During the R5 torrential rain events, water level abruptly increased and all of the pH value, EC and NO3- sharply decreased as a result of dilution effect. The groundwater quality was changed because the afflux of agricultural wastewaters in the entire rainfall periods. According to the National Groundwater Quality Standard, P. R. China (GB/T 14848-9), the groundwater quality of the QSS showed the following order in the entire rainfall events: Grade III --> Grade IV --> Grade V --> Grade 1V --> Grade V --> Grade LV --> Grade V --> Grade IV --> Grade III. As a important drinking water source around local inhabitants, the groundwater quality of Qingmuguan subterranean stream was deteriorated to Grade V in rain-fertilize periods. However, the sampling methods in field did show a simple variation curve. Consequently,the results from the research illustrate the need to redesign hydrochemical sampling methods for karat hydrology system, especially under the impact of human activities.

[Substances transport in an underground river of typical karst watershed during storm events].

Hydrologic process, turbidity, suspended particles matters (SPM), major cations and TOC concentrations during two storm events in late April 2008 were monitored at Jiangjia Spring which is the outlet of Qingmu Guan underground river system. Scanning electron microscopy (SEM) and energy disperse spectroscopy (EDS) analyses of SPM were also performed in order to investigate the transport characteristics of substances, such as SPM, turbidity and major cations in the underground river of typical karst watershed. The results show that at a single and well-developed karst conduit of Jiangjia Spring, discharge, turbidity, and concentrations of SPM, major cations and TOC respond promptly to the rainfall. The carbonate-derived cations including Ca2+, Mg2+ and Sr2+ are subject to dilution effect during the rising limb of discharge. The elevation in turbidity and SPM concentration is a result of the gradual increase of allochthonous substances (soil) flux input from the surface. Al3+, Fe, Mn, Ba2+ and TOC are concomitant substances of SPM. And their concentrations are ascending with turbid rise. The flux of SPM in diameter > 0.45 microm in the underground river is about 9.7 tons during the events. The bad water quality suggests us that the spring water is unfit to drink without purification during the period of rising and recession time of discharge at Jiangjia Spring. Thus, soil erosion and nutrient losing not only strongly destroy the fragile karst ecological environment, but also lead to non-point source pollution, and seriously threaten the drinking water safety of locals.

[Temporal and spatial variations of the nitrate-nitrogen sources in an underground river using 15N isotope technique].

Groundwater in Qingmuguan underground river was monitored using hydro-chemical and 15N isotope techniques to investigate temporal and spatial variations of nitrate-nitrogen and its possible sources from October, 2007 to October, 2008. The results show that nitrate concentrations are 3.20 mg/L of the inlet (D1) and 20.35 mg/L of the outlet (S2) of the underground river. Affected by the fertilizers in agricultural field and the rainfall flush and dilution,nitrate concentrations of groundwater are higher but less stable from April to July, 2008 than that from October, 2007 to March, 2008. They are elevated during August and September, 2008 due to the residual fertilizers and decreased rainfall events. According to the NO3- -delta 15N values of -0.857% per hundred +/- 2.01% per hundred (n=9), the sources of nitrate-nitrogen of D1 are dominated by residual fertilizers from the paddy fields from October, 2007 to March, 2008 and from July to October, 2008, while the NO3- -delta 15N values of 2.50% per hundred +/- 0.29% per hundred (n=3) demonstrate that the mixture of soil organic nitrogen and fertilizers are the sources from April to middle and late June, 2008. And the NO3- -delta 15N values of -3.74% per hundred in late May and 0.52% per hundred in early June indicate that the nitrate-nitrogen comes from fertilizers applied in the paddy fields in 2008. The nitrate-nitrogen of S2 is partly from fertilizers in the upper basin, and also from fertilizers and soil organic nitrogen carried by lateral fissure and soil permeation water of forest and farm land in the middle and lower basin. The NO3- -delta 15N values of 4.77% per hundred (n=9) show nitrate-nitrogen of S2 mainly originates from fertilizers from October, 2007 to March, 2008 and from July to October, 2008, while NO3- -delta 15N values of 3.16% per hundred +/- 0.39% per hundred (n=5) explain that the nitrate-nitrogen derives from the mixture of soil organic nitrogen and fertilizers from April to June, 2008.