[Spatial Variations of CO2 Degassing Across Water-air Interface and Its Impact Factors in Summer in Guijiang River, China].

River is characterized by obvious spatial heterogeneity in catchment, which is exacerbated by special environment features of calcium-rich, alkaline and DIC-rich(dissolved inorganic carbon) in karst river. Thus, it also leads to significant spatial variation in the CO2 degassing across water-air interface. Main ions, physicochemical parameters, δ13CDIC value and two common approaches(floating chamber(FC) and thin boundary layer models(TBL) were used to analyze the CO2 degassing characteristics in Guijiang River, a karst river, China. The results were as follows:1 Hydrochemistry in Guijiang River basin showed a significant spatial change. All of HCO3-, Ca2+, specific conductivity, total dissolved solids(TDS), SIc and pCO2 showed similar distribution characteristics in the following order:tributaries in the middle reaches > middle reaches > Downstream > Upstream of Guijiang River. 2 During the monitoring period, CO2 degassing occurred in all the sampling sites and it was the CO2 source for the atmosphere. The mean CO2 evasion was 237 mg·(m2·h)-1 in Guijiang River, which located in the range of average CO2 evasion of global river. However, significant spatial variations also occurred along Guijiang River. The CO2 degassing flux in tributaries of the middle reaches and middle reaches of the mainstream were obviously larger than those in downstream and upstream of the mainstream. 3 CO2 degassing was mainly affected by carbonate equilibrium system in tributaries in the middle reaches and middle reaches in the mainstream of the Guijiang River basin, which resulted in obviously larger CO2 degassing than those in downstream and upstream of mainstream. However, the CO2 degassing flux in tributaries of the middle reaches was also simultaneously affected by biological photosynthesis, and the minimum CO2 degassing flux[6.38 mg·(m2·h)-1] appeared in tributaries of the middle reaches. In addition, the CO2 degassing flux in mainstream upstream was mainly affected by atmospheric environmental factors, while it was synergetically influenced by many factors in mainstream downstream.

[Variations of Inorganic Carbon and its Impact Factors in Surface-Layer Waters in a Groundwater-Fed Reservoir in Karst Area, SW China].

In order to understand the inorganic carbon cycle of the groundwater-fed reservoir in karst area, Dalongdong Reservoir, which is located at Shanglin County, Guangxi Zhuang Autonomous Region, China, was investigated from 12th to 20th July, 2014. Concentration of dissolved inorganic carbon (DIC), delta13C of DIC (delta13C(DIC)), partial CO2 pressure (pCO2) and CO2 flux across water-air interface were studied by observation in situ and high-resolution diel monitoring. Results show that: (1) DIC concentration and water pCO2 increased from upstream area to downstream area [DIC(average)): from 122.88 to 172.02 mg x L(-1), pCO2(average) : from 637.91 x 10(-6) to 1399.97 x 10(-6)], while delta13C(DIC) decreased from upstream area to downstream area [delta13C(DIC(average): from -4.34% per hundred to -6.97% per hundred] in the reservoir. (2) CO2 efflux across water-air interface varied from 7.11 to 335.54 mg x (m2 x h)(-1) with mean of 125.03 mg x (m2 x h)(-1) in Dalongdong reservoir surface-layer waters, which was the source of atmospheric CO2. CO2 effluxes across water-air interface in upstream area [mean 131.73 mg x (m2 x h)(-1)] and downstream area [mean 170.25 mg x (m2 x h)(-1)] were higher than that in middle area [mean 116.05 mg x (m2 x h))(-1)] in the reservoir. (3) Water pCO2 and CO2 efflux across water-air interface showed similar characteristics of diel variations, which decreased in daylight and increased in night and showed a negative correlation with chlorophyll a (Chla). Possible reasons of research results are found as follows: (1) DIC concentration, water pCO2 and delta13C(DIC) are influenced by biomass of phytoplankton, turbidity, conductivity, the depth of water and transparency, while CO2 efflux across water-air interface is controlled by both of biomass of phytoplankton and wind speed. (2) Photosynthesis, respiration and vertical motion of phytoplankton possibly affect diel variations of DIC cycle in the groundwater-fed reservoir in karst area.

[Hydrochemistry and Dissolved Inorganic Carbon Stable Isotope of Shibing Dolomite Karst Area in Guizhou Province].

Totally 49 water samples were collected in Shibing Dolomite Karst World Natural Heritage Site in Guizhou Province to analyze the characteristics and controlling factors of both the surface and underground waters, as well as the features and their origins of the dissolved inorganic carbon isotope. It was found that the pH of the study area was neutral to alkaline with low concentrations of total dissolved solids. The cations were dominated by Ca2+, Mg2 and anions by HCO3-, featured by HCO3-Ca x Mg type water. The ratios of Cl-, NO3- and SO4(2-) in the allogenic water from the shale area in the northern catchment were higher than those in autogenic water from the dolomite karst area, so did the concentration of Si. The SIc and SId of the allogenic waters in the shale area were negative. After the waters entered into and flew by the dolomite karst area, both the SIc and SId increased to over 0. It could be told by the water chemistry that the hydrochemistry was little impacted by the rainfall and human activities. The Gibbs plot revealed that the chemical composition of the waters was mainly controlled by rock weathering. The δ(13)C(DIC) of the surface waters ranged from -8.27% to -11.55% per hundred, averaging -9.45% per hundredo, while that of the underground waters ranged from -10.57% per hundred to -15.59% per hundred, averaging -12.04% per hundred, which was lighter than that of surface water. For the distribution features, it was found the δ(13)C(DIC), of the upper reaches of branches of Shangmuhe River was lighter than that of the lower reach, while that of the main river Shangmuhe River was relatively complex. Based on the mass balance of stable isotopes and the δ(13)C(DIC), the ratio of the origin of DIC of the ground water was calculated. It was found that 51.2% was from soil CO2, and 48.8% was from the rock itself.

[Vertical Migration Characteristics of Organochlorine Pesticides in Overlying Soil in Karst Terranes and Its Impact on Groundwater].

Five soil profiles and four typical epikarst springs were selected in Nanchuan District, Chongqing Municipality as objects of the study on vertical migration of organochlorine pesticides (OCPs) in the soils and its impact on groundwater. OCPs in soil and epikarst spring water samples were quantitatively analyzed by gas chromatography. The results showed that HCHs and DDTs were detected in all the 5 soil profiles, varying in the range of 0.77-18.3 and 0.34-226 ng · g(-1), and averaging 5.16 and 16 ng · g(-1) in concentration, respectively. The highest concentrations of HCHs and DDTs were found in the subsoil (10-40 cm) in most sampling sites. The detection ratios of HCHs and DDTs in four springs were 100%. The concentrations of HCHs and DDTs fluctuated greatly in epikarst spring water during the one-year observation, and the concentration ranged from 2.09 to 60.1 and from N. D. to 79.8 ng · L(-1), with a mean value of 12 and 9.16 ng · L(-1), respectively. The concentrations of HCHs and DDTs in Hougou, Baishuwan and Lanhuagou spring in rainy season were all. higher than those in dry season in these three epikarst springs. There were no good corresponding relationship between HCHs and DDTs contents in spring water and those in corresponding spring catchment soil. TOC, soil water content, clay content and pH all inhibited the vertical migration of OCPs in Hougou spring catchment, which led to the lowest content of OCPs in spring water, although the OCPs content in Hougou spring catchment soils was the highest in the four spring catchments. However, the four factors didn't inhibit the vertical migration of OCPs in Shuifang spring catchment, which led to higher OCPs content in spring water, although the OCPs content in spring catchment soils was the lowest in the four spring catchments.

[Altitudinal Gradient Distribution and Source Analysis of PAHs Content of Topsoil in Jinfo Mountain, Chongqing].

The condensation effect has made high mountains the storage vault of durable organic pollutants. This research measured the content and constitutes of polycyclic aromatic hydrocarbons (PAHs) in 10 topsoil samples collected at different altitudes from the south slope of Chongqing Jinfo Mountain by gas chromatograph-mass spectrometer (GC/MC). And the pollution source of PAHs was analyzed by ratio method and principal component regression. The ecological risk of PAHs was evaluated using BaP toxic equivlants (TEQ(BaP)) The results showed that the concentrations of 16 priority PAHs in topsoil ranged from 240-2 121 ng x g(-1). The average value of PAHs was 849 ng x g(-1), and 2 to 3-ring PAHs were the dominant compounds. The concentrations of 7 carcinogenic PAHs accounted for 17.8% of total PAHs averagely. In the research area, various-ring PAHs and gross PAHs increased with the rise of altitude. The increase of low-ring PAHs was most obvious, and the volatility of high-ring PAHs was relatively high. But the ratio of different-ring PAHs in gross PAHs showed no regularity with the rise of altitude. The PAHs of soil in the research area mainly came from the oil sources, oil products, and combustion sources of coal and biomass. In the research area, the soil has been polluted to a certain extent, but the toxicity risk is relatively low.

[Summer Greenhouse Gases Exchange Flux Across Water-air Interface in Three Water Reservoirs Located in Different Geologic Setting in Guangxi, China].

Due to special hydrogeochemical characteristics of calcium-rich, alkaline and DIC-rich ( dissolved inorganic carbon) environment controlled by the weathering products from carbonate rock, the exchange characteristics, processes and controlling factors of greenhouse gas (CO2 and CH4) across water-air interface in karst water reservoir show obvious differences from those of non-karst water reservoir. Three water reservoirs (Dalongdong reservoir-karst reservoir, Wulixia reservoir--semi karst reservoir, Si'anjiang reservoir-non-karst reservoir) located in different geologic setting in Guangxi Zhuang Autonomous Region, China were chosen to reveal characteristics and controlling factors of greenhouse gas exchange flux across water-air interface. Two common approaches, floating chamber (FC) and thin boundary layer models (TBL), were employed to research and contrast greenhouse gas exchange flux across water-air interface from three reservoirs. The results showed that: (1) surface-layer water in reservoir area and discharging water under dam in Dalongdong water reservoir were the source of atmospheric CO2 and CH4. Surface-layer water in reservoir area in Wulixia water reservoir was the sink of atmospheric CO2 and the source of atmospheric CH4, while discharging water under dam was the source of atmospheric CO2 and CH4. Surface-layer water in Si'anjiang water reservoir was the sink of atmospheric CO2 and source of atmospheric CH4. (2) CO2 and CH4 effluxes in discharging water under dam were much more than those in surface-layer water in reservoir area regardless of karst reservoir or non karst reservoir. Accordingly, more attention should be paid to the CO2 and CH4 emission from discharging water under dam. (3) In the absence of submerged soil organic matters and plants, the difference of CH4 effluxes between karst groundwater-fed reservoir ( Dalongdong water reservoir) and non-karst area ( Wulixia water reservoir and Si'anjiang water reservoir) was less. However, CO2 efflux in karst groundwater-fed reservoir was much higher than that of reservoir in non-karst area due to groundwater of DIC-rich input from karst aquifer and thermal stratification.

[Distribution and Transportation Characteristics of Heavy Metals in Nanshan Laolongdong Subterranean River System and Its Capacity of Self-Purification in Chongqing].

For figuring out the distribution and transportation characteristics of heavy metals Mn, Pb, Cu and As among overlying water-pore water-surface sediments so as to offer a scientific basis for the development of urban construction and protection of karst groundwater, overlying water, pore water and surface sediment samples were collected in December 2013 ( winter) and June 2014 (summer) respectively. Results show that the detection rates of Mn, Pb, Cu and As are 100% both in overlying water and pore water with the concentration Mn > Pb > Cu > As, summer > winter, pore water > overlying water, respectively, and the groundwater could not be a source of drinking water because of the excessive content of Mn and Pb. In addition, the concentration of heavy metals Mn, Pb, Cu and As in pore water are higher than that in overlying water, indicating that heavy metals could diffuse into overlying water from pore water because of concentration gradient, especially in summertime. Moreover, study also finds that heavy metals are accumulated in surface sediments, the total content of four heavy metals has a decreasing trend between UGR6( sampling site 7) and UGR5 (sampling site 6), but has an increasing trend from UGR5 (sampling site 6) to URG0 (sampling site 1). Mn, in surface sediments, has strong instability and mobility, which can not only cause the pollution of overlying water but also enlarge contaminated area. In a word, Laolongdong subterranean river has strong capacity of self-purification, especially the surface sediments.

[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.

[Source and contamination of polycyclic aromatic hydrocarbons in surface soil in karst underground river basin].

Surface soil (0-20 cm) from various agricultural sites in Laolongdong underground river basin was collected to determine the concentrations, compositional profiles, and sources of 16 priority polycyclic aromatic hydrocarbons (PAHs). PAHs were measured by GC/MC. The total concentrations of PAH16 ranged from 277-3 301 ng x g(-1), with a mean of 752.6 ng x g(-1) +/- 635.5 ng x g(-1), and 57%, 29% and 14% of soil samples were slightly, moderately and heavily polluted by PAHs, respectively. The PAH compositional profiles were dominated by 2,3 ring compounds, which accounted for 28.72% -72.68% (a mean of 48.20%) of the total PAHs, while 4 ring and 5,6 ring PAHs accounted for an average of 7.77% and 34.03%, respectively. Soil organic matter (SOM) was found to be significantly correlated with the 16 PAHs and total PAHs. However, pH value was slightly correlated with the 16 PAHs and total PAHs. Isomer pair ratios and Principal component analysis (PCA) suggested vehicles, coal, petroleum and biomass combustion as the main sources of PAHs, and another major source was petroleum.

[Diel variations of hydrochemistry and influencing factors in a surface stream in subtropical karst area, SW China].

In order to understand the diel variation and influencing factors of hydrochemistry in a surface creek fed by karst subterranean river in a subtropical area, where is located at Guancun Village, Daliang Township, Rong'an County of Guangxi Zhuang Autonomous Region, China, two monitoring sites were set simultaneously to launch Guancun subterranean river outlet (G1) and surface creek mouth (G2), respectively. Physical and hydrochemical parameters including pH, dissolved oxygen (DO), water temperature (T) and specific conductivity (Spc) were measured at 15-minute intervals and water samples for analyzing major ions such as Ca2+, HCO3- and NO3- as well as delta3C(DIC) were collected at 2-hour intervals. The results showed that: (1) G1 and G2 sites were both HCO3- Ca type water, however the two monitoring sites showed different diel variations of hydrogeochemical process; (2) The physical and hydrochemical parameters (T, DO, pH, Spc) and major ions (Ca2+, Mg2+, Na+, K+, HCO3-, SO4(2-), NO3-, Cl- in G1 site were basically stable, while the physical and hydrochemical parameters (T, DO, pH, Spc) and major ions (Ca2+, HCO3- and NO3-) in G2 site displayed regular diel variation during monitoring; (3) The dissolved inorganic carbon (DIC) and delta13C values in G2 monitoring site showed reverse characteristics in diurnal fluctuations, where DIC decreased in daylight and increased at night while the delta13C value increased in daylight and decreased at night, DIC also showed a negative correlation with the delta13C value (correlation coefficient is -0. 87, P < 0.01) in G2 site. These results indicated that photosynthesis and respiration of aquatic plants, water temperature and degassing jointly affected diurnal variation of hydrochemistry and controlled the cycling process of internal matter in this surface creek fed by karst subterranean river.

[Preliminary research on the feature of dissolved inorganic carbon in Wulixia Reservoir in summer, Guangxi, China].

To gain more knowledge on the transformation process of dissolved inorganic carbon in a karst reservoir, in situ monitoring, sampling and lab experiments of water columns were carried out at various sampling sites along the flow line in Wulixia Reservoir, Guangxi, China during early July, 2013. Results showed that: (1) The hydrochemical characteristics of study areas were controlled by the carbonate equilibrium system and the hydrochemical type of all water samples was HCO3-Ca + Mg. (2) The DIC concentration decreased gradually (DIC(Average) : from 1.03 to 0.78 mmol x L(-1)) and the delta13C(DIC) increased gradually (delta13C(DIC(Average) : from -10.21per thousand to -6.62 per thousand) from the reservoir end area to dam area. Meanwhile, with the depth increase in water column, the DIC concentration increased gradually (DIC(Average) : from 0.86 to 1.05 mmol x L(-1)) and the delta13C(DIC) decreased gradually (delta13C(DIC(Average) : from -7.88 per thousand to -13.39 per thousand) from the surface to the bottom of the reservoir. Possible reasons for these research results were found as follows: (1) Dissolution-precipitation process of carbonate substance could be inhibited by other processes such as biogeochemical processes, which played little role in delta13C(DIC) variations. (2) Thermal stratification existed in the study areas which could influence the distribution of DIC and delta13C(DIC) by affecting the distribution of plankton and its orientation and strength of metabolism process, and the extent of organic matter decomposition, and so on.

[Contamination and source of polycyclic aromatic hydrocarbons in epikarst spring water].

The water samples were collected from four typical epikarst springs in Nanchuan District, Chongqing Municipality between October 2010 and October 2011. Sixteen priority polycyclic aromatic hydrocarbons in epikarst spring waters were quantitatively analyzed by the gas chromatography-mass spectrometer (GC-MS). The objectives of this study were to investigate the seasonal variations of polycyclic aromatic hydrocarbons' concentration, composition, source and contamination characterization in epikarst springs water. The results showed that the detection ratios of 16 PAHs in four springs were 100%. The total concentrations of 16 PAHs fluctuated greatly in epikarst spring water during one year observation, and the concentration ranged from 341 to 4 968 ng x L(-1), with a mean value of 1772 ng x L(-1). The total concentrations of 7 carcinogenic PAHs in rain season were all higher than those in dry season in four epikarst springs. The PAHs profiles were dominated by (2-3) rings PAHs in spring water, which accounted for more than 50% of 16 PAHs. The PAHs in spring water mainly originated from the combustion of coal, biomass and petroleum, and during June to October 2011, PAHs originated from the combustion of coal and biomass had a larger contribution. The ratios of Ant/( Ant + Phe) and Fla/( Fla + Pyr) changing with seasons showed that Ant, Phe, Fla and Pyr were easy to migrate in epikarst soils. In 4 isomeric ratios, the ratios of Fla/(Fla + Pyr) were more sensitive to reflect the information of sources. Compared to other areas in the world, the concentration of 16 PAHs in epikarst spring water is at a higher level, which shows the epikarst spring water has been suffered the PAHs pollution.

[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.

[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.

[Distribution character of organochlorinated pesticides in the karst cavity atmosphere from Guilin City, south China].

The investigation was performed on organochlorinated pesticides (OCPs) pollution in karst cavity atmosphere in Guilin City, South China. The total concentrations of OCPs outside the cave atmosphere ranged from 1.82 to 2.01 ng x m(-1), were far more than those of inside cave (range of 0.27-0.83 ng x m(-3)). OCPs concentrations fell gradually from cave gate to inside, especially to HCH, which reflected outside atmospheric transportation contributed most of pollutants inside cave. OCPs concentrations inside cave equaled to those in South and North poles therefore could be considered as background for OCPs research. The concentrations distribution sequence of HCH isomers corresponded to degradation rates themselves and that might provide critical information on the exhibiting their inherent character differences of HCH pesticides well under peculiarly original surrounding. In addition, a possibly fresh introduction of discofol-type and a historical usage potential for HCH pesticides in studied area were identified by isomer percentage combined isomer ratios.

[Distribution character of polycyclic aromatic hydrocarbons in soils from the karst cavity, Guilin City, South China].

We investigated the distribution characteristic of polycyclic aromatic hydrocarbons (PAHs) of soils from Dayan cave, a karst cavity in Guilin City, South China. The total PAHs concentrations from the inner cave ranged from 7.22 to 117.29 ng x g(-1) were much lower than those of outside cave (range of 51.35-235.73 ng x g(-1)). PAHs in studied area polluted slightly compared with other area. PAHs contents outside the cave and near cave gate were much higher than those within the cave with a little concentration change. In outside cave soils, the heavy molecular weight PAH (HMW) concentrations were higher than those of the light molecular weight PAH (LMW) (mean value 69.25 ng x g(-1) > 38.81 ngx g(-1)) while it was reverse inside cave (mean value 3.93 ng x g(-1) < 7.41 ng x g(-1)),which indicated the inner PAHs might came from atmosphere introduction and rainwater filtering from the top of the cave too. PAHs concentration distribution in the soils presented "trap effect" near the cave gate and a concentration superposition from the slope in the north cave wicket. HMW concentration near the cave gate was even larger by three times than that outside cave gate and a positive relation was found between PAH molecular weight and its falling tendence (R2 = 0.49). Deducing from the analysed data, PAHs concentration contributed by the cave gate was about 17 times of that of the slope. Temperature and molecular weight diversity were important factors influencing PAH concentration distribution.

[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.

Enhancement of Ca2+ release from limestone by microbial extracellular carbonic anhydrase.

Three experimental systems were set up to investigate whether carbonic anhydrase (CA) from microorganisms actually plays the driving role in limestone dissolution. In one, redistilled water served as negative control. In a second, microbial origin CA enzyme solution supplemented with CA special inhibitor acetazolamide (AZ) served as positive control. A third contained a crude enzyme solution of microbial CA. The results showed that the amount of released Ca2+ from limestone in a CA non-inhibited system increased by 2.4 times compared to a CA inhibited system, and increased by 11.7 times compared to the redistilled water control. These experiments demonstrated that microbial origin CA significantly enhanced Ca2+ release from limestone (P < 0.01), and therefore, proved the significant driving effect of microbial CA on limestone dissolution. The results also suggested that microbially derived CA might exert an important influence on biokarst process.