[Quantification of Nitrate Sources to Groundwater in Karst Trough-valley Areas Based on Dual Stable Isotopes of δ15N-NO3- and δ18O-NO3- and the IsoSource Model].

Due to the vulnerability of karst hydrological systems, nitrate pollution in karst groundwater has become a global common and serious environmental problem. In order to ensure drinking water safety, it is very important to accurately identify groundwater nitrate sources. The groundwater hydrochemistry and δ15N-NO3- and δ18O-NO3- isotopes were analyzed in samples taken from a suburb of Chongqing:the Longfeng karst trough-valley, which is mainly affected by agricultural activities, and the Longche karst trough-valley, which is primarily affected by urbanization. The IsoSource model was then used to quantify the groundwater nitrate sources. The results showed that:① The NO3- concentration in groundwater ranged from 19.31 mg·L-1 to 37.01 mg·L-1(mean of 28.21 mg·L-1) in the Longfeng karst trough-valley, and from 2.15 mg·L-1 to 27.69 mg·L-1(mean of 10.31 mg·L-1) in the Longche karst trough-valley. The groundwater NO3- concentration exhibited an obvious seasonal variation in both valleys. ② The δ15N-NO3- and δ18O-NO3- isotopes in groundwater in the Longfeng karst trough-valley ranged from 3.29‰ to 11.03‰ (mean of 6.74‰) and 0.88‰ to 7.51‰ (mean of 3.18‰), respectively. In contrast, groundwater in the Longche karst trough-valley presented higher δ15N-NO3- and δ18O-NO3- values that ranged from 5.25‰ to 11.40‰ (mean of 7.95‰) and 2.90‰ to 19.94‰ (mean of 11.18‰), respectively. The lower values of δ15N-NO3- and δ18O-NO3- in groundwater in the Longfeng karst trough-valley suggest that groundwater NO3- was mainly sourced from agricultural N fertilizer, while the higher values of δ15N-NO3- and δ18O-NO3- in groundwater in the Longche karst trough-valley indicate that groundwater NO3- was primarily sourced from domestic sewage. Moreover, such δ15N-NO3- and δ18O-NO3- values in groundwater indicate that nitrification was the primary process for nitrogen conversion in both valleys. Meanwhile, significant seasonal differences in groundwater δ15N-NO3- and δ18O-NO3- were observed in both valleys; the δ15N-NO3- and δ18O-NO3- values were higher during the dry season (means of 8.83‰ and 2.79‰, respectively) than during the rainy season (means of 4.64‰ and 3.58‰, respectively) in the Longfeng karst trough-valley, whereas the δ15N-NO3- and δ18O-NO3- values were lower during the dry season (means of 9.79‰ and 14.56‰, respectively) than during the rainy season (means of 5.12‰ and 7.8‰, respectively) in the Longche trough-valley. This suggests that there were differences in the seasonal NO3- sources to groundwater in both valleys. During the rainy season, the groundwater NO3- concentration in the Longfeng karst trough-valley was mainly due to the nitrification of NH4+ in precipitation and fertilizer as well as organic nitrogen in soil, whereas during the dry season, the groundwater NO3- concentration primarily originated from domestic sewage. In contrast, the groundwater NO3- concentration in the Longche karst trough-valley primarily originated from domestic sewage in both seasons. ③ The results of the IsoSource model indicated that the nitrification of NH4+ from fertilizer and rainwater was the primary NO3- source to groundwater (44.63% of the total) in the Longfeng trough valley, and was followed by domestic sewage (29.5%), soil organic nitrogen (22.38%), and NO3- from rainwater and fertilizer (<10%). During the rainy season, the groundwater NO3- concentration was mainly due to the nitrification of NH4+ from fertilizer and rainwater (52.25% of the total) in Longfeng trough-valley, while groundwater NO3- concentration primarily originated from domestic sewage during the dry season (41% of the total). In contrast, the groundwater NO3- concentration was mainly from domestic sewage (36.17%) in Longche karst trough-valley, and was followed by the nitrification of NH4+ from fertilizer and rainwater (23.5%), soil organic nitrogen (22.5%), and NO3- from rainwater and fertilizer (<10%). The groundwater NO3- concentration in the Longche karst trough-valley primarily originated from domestic sewage in both seasons, and accounted for 47% and 25% during the rainy season and dry season, respectively.

[Sources of Nitrate in Groundwater and Its Environmental Effects in Karst Trough Valleys: A Case Study of an Underground River System in the Longfeng Trough Valley, Chongqing].

Water samples from the two underground rivers (Fenghuang River and Longju River) and samples of the dry and wet deposition of atmospheric dissolved inorganic nitrogen were taken from the Longfeng karst trough valley located in the Zhongliang mountain in the suburbs of Chongqing from May 2017 to April 2018. Anions, cations, δ15 N(NO3-), δ18 O(NO3-), δ18 O(H2O), and δ13C(DIC) isotope data were used to investigate the NO3- source and its environmental effects. The results showed:① The hydrochemistry of the two underground rivers is of the type HCO3-Ca. The NO3- concentration varied from 17.58 to 32.58 mg·L-1, with an average of 24.02 mg·L-1, and was slightly higher in rainy season than the dry season, revealing that the underground rivers were polluted. ② The δ15 N(NO3-) value ranged from -3.14‰ to 12.67‰, with an average value of 7.45‰. The δ18 O(NO3-) value ranged from -0.77‰ to 12.05‰ with an average value of 2.90‰, and was higher in the dry season than the rainy season, indicating that animal excreta and domestic sewage were main NO3- sources throughout the year. In addition, rainfall, fertilizer, and soil nitrogen were the NO3- sources during the rainy season. There are no significant differences between the NO3- sources of the two underground rivers, and nitrification is the main nitrogen conversion process. ③ The molar ratio of (Ca2++Mg2+)/HCO3- varied from 0.65 to 0.82. That of the Fenghuang River was 0.75 and that of the Longju River was 0.70. The δ13C(DIC) value ranged from -12.46‰ to -9.20‰, with a mean of -11.10‰ in the Longju River and -10.72‰ in the Fenghuang River. These values indicated that the HNO3 derived from the nitrification of NH4+ was involved in the weathering of carbonate rocks. ④ HNO3 dissolved carbonate rocks and aggravated the chemical weathering of carbonate rock in the basin, contributing 8% of the DIC in groundwater, and 9% and 7% in Fenghuang River and Longju River, respectively.

[Characteristics and Sources of Atmospheric Inorganic Nitrogen Wet Deposition in Xueyu Cave Watershed, Outer Suburbs of Chongqing City].

Xueyu Cave watershed is located in Fengdu County in the outskirts of Chongqing, where rainfall events were monitored continuously from July 2015 to December 2017. We explored the variation of mass concentration of atmospheric dissolved inorganic nitrogen (NH4+-N and NO3--N), and quantitatively calculated its wet deposition fluxes, then the sources of NH4+-N and NO3--N were tracked using the Xueyu cave air mass backward trajectory model. The results showed that:①During the monitoring period, the average annual dissolved inorganic nitrogen (DIN) deposition in the watershed was 14.25 kg·(hm2·a)-1, of which NH4+-N and NO3--N were 7.72 kg·(hm2·a)-1 and 6.53 kg·(hm2·a)-1, accounting for 54% and 46% of DIN wet precipitation, respectively, and indicating that NH4+-N is the dominant species, followed by NO3--N; ②DIN wet deposition flux and concentration showed marked seasonal changes. The DIN wet deposition flux in spring and summer was 50% higher than that in autumn and winter, while the DIN concentration of wet deposition in autumn and winter was 30% higher than those in spring and summer. ③NH4+-N/NO3--N was between 0.29 and 2.27, and NH4+-N/NO3--N > 1 during the rainy season (April to October) and NH4+-N/NO3--N < 1 during the dry season (November to March), indicating that the main sources of DIN wet deposition results from agricultural activities in the rainy season, and urban contributions in the dry season. ④In the study area, the southeastern winds are dominant in the rainy season but southwestern winds are dominant in the dry season. These determine the sources of DIN wet deposition (agricultural or urban).

[Distinguishing the Compositions and Sources of the Chromophoric Dissolved Organic Matter in a Typical Karst River During the Dry Season: A Case Study in Bitan River, Jinfo Mountain].

Since resistant dissolved organic matter (RDOM) plays a critically important role in a karst carbon sink, one of the most important continental carbon sinks, research focusing on the origination, transportation, and translation of RDOM in a karst water system is important. Currently, 3D-fluorescence EEMs are used to detect the composition and origination of chromophoric dissolved organic matter (CDOM), an important part of RDOM. This is a very fast and efficient method for CDOM analysis. In this study, 3D-fluorencence EEMs combined with UV-visible absorption spectrum were used to analyze the composition and origination of CDOM in the Bitan River at Jinfo Mountain. Samples were collected from nine sampling sites from January to March 2017 and analyzed with CDOM EEMs and UV-visible absorption spectrums. In addition hydrochemical characteristics were determined and then samples were stimulated with PARAFAC to detect the chromophoric fluorescent groups and indexes. The PARAFAC stimulation revealed three chromophoric fluorescent groups in which fulvic acid was the largest component, accounting for about 44%, with a humic acid content of about 32% and tyrosine-like acid content of about 24%. Four indexes: FI, BIX, HIX, and ß∶α, were calculated, and the mean values were 2.06, 0.87, 4.35 and 0.69, which showed relatively high FI, BIX, and ß∶α values and a low HIX value, implying that the CDOM was autochthonous and originated from microbes and aquatic plants in the dry season. The spatial dynamic of the index revealed an increased BIX and decreased HIX from the upstream area to the downstream area, implying the impact of land-use and human activities. The forest soil input more humic acid and agriculture input more N and P resulting in flourishing aquatic plants and microbes. Moreover, the correlation coefficients of DIC and humic acid, tyrosine-like acid were 0.515 (P<0.05) and 0.644 (P<0.01), from which it could be inferred that DIC contributed to CDOM formation. The conclusions of this study revealed that DIC would be fixed by karst water aquatic plants and microbes and then sink as autochthonous CDOM and become part of karst water carbon sink.

[Temporal and Spatial Distribution of the Soil Water δD and δ18O in a Typical Karst Valley: A Case Study of the Zhongliang Mountain, Chongqing City].

In this study, we analyzed the stable hydrogen and oxygen isotopes of precipitation and three different land use patterns (cultivated land, grass land, and forest land) at 0-15 cm and 15-45 cm in a karst ridge-trough area (Zhongliang Mountain, Beibei District, Chongqing) in May 2017 and September 2017 to investigate the spatial and temporal variation of stable isotopes in different soil profiles using the isotope tracer technique. The results show that:① The average values of the soil water δD and δ18O are -50.0‰±33.6‰ and -7.9‰±4.3‰, respectively, and all plot around the local meteoric water line (LMWL), indicating that precipitation is the main source of the soil water supply in this area. ② The seasonal variations of δD and δ18O of the soil water are significant in different months of the rainy season, May (-19.4‰±6.8‰ and -4.1‰±1.0‰)>September (-82.2 ‰±14.0‰ and -11.9‰±2.2‰). ③ However, there is no significant difference in the soil water δD and δ18O under different land use patterns. ④ The soil water δD and δ18O change with soil depth gradients, which decrease along the depth in vertical direction for all types of soil land use in May but mainly increase/decrease in the cultivated land and woodland/grassland in September, respectively.