["Load-Unload" Effect of Manganese Oxides on Phosphorus in Surface Water of the Pearl River Estuary].

Phosphorus (P) conveyed by surface runoff plays an essential role in regulating nutrient balance and primary production in estuarine waters. In this study, basic physiochemical properties, total phosphorus (TP, including speciation), particulate iron (PFe), particulate manganese (PMn), and particulate aluminum (PAl) of the surface water in the Pearl River Estuary (PRE) in different seasons were determined to investigate the spatiotemporal distribution characteristics of P and to identify the crucial factor controlling P migration and transformation in the freshwater-saltwater interaction zone. TP concentrations (28.88-233.68 µg·L-1) decreased with increasing salinity gradient owing to deposition and dilution. The proportions of P speciation followed a decreasing order as dissolved inorganic phosphorus (DIP, 37.3%) > particulate inorganic phosphorus (PIP, 22.7%) > dissolved organic phosphorus (DOP, 21.0%) > particulate organic phosphorus (POP, 19.0%). PIP was positively related to PFe, PMn, and PAl (P < 0.05), confirming their concurrent migration behaviors. In addition, the increase in salinity promoted the desorption of phosphate on the suspended particulate matters, which mainly took place near the freshwater-saltwater interface. A significant positive correlation (P < 0.001) between the solid-liquid phase partitioning coefficient (Kd) of phosphate and salinity indicated that PIP was present mainly in more stable forms in the brackish water. Most importantly, a better relationship between Kd and PMn (P < 0.01) supported our scientific hypothesis of the "load-unload" effect of Mn oxides on P:particulate-carrying phosphates transported from the freshwater zone tend to be desorbed and released into the brackish water.

[Sources and Variation Characteristics of Dissolved Lipid Biomarkers in a Typical Karst Underground River].

Water samples in Qingmuguan underground river were collected to determine the concentration of dissolved lipids, and their sources, composition and migration characteristics in underground river were studied. The results were obtained as follows. (1) The average content of various dissolved lipids decreased with increasing distance of migration in Qingmuguan underground river, and the most distinctive was dissolved saturated straight chain fatty acids with its content decreasing by about 81.71%, from the initial 5,704 ng · L⁻¹ to 1,043 ng · L⁻¹. (2) N-alkane could indicate the sources of dissolved organic matter in underground river, but saturated straight chain fatty acid and fatty alcohol had the advantage in indicating algae, bacteria and other microorganisms. (3) With the increasing migration distance of Qingmuguan underground river, the input type of dissolved organic matter in underground river was different, which might be resulted from the heterogeneity of karst surface. (4) In ternary plot of alkane sources, aquatic plants constituted the major contribution of dissolved organic matter in Qingmuguan underground river, followed by higher plant, algae/ bacteria. Unlike higher plants and algae/bacteria, the contribution from aquatic plants decreased with increasing migration distance of underground river. (5) To a certain extent, TAR (alkane) values could reflect the rainfall, and the values of CPI, L/H in saturated straight chain fatty acids might indicate the degradation activities of bacteria.

[Distribution Characteristics and Source Identification of Polycyclic Aromatic Hydrocarbons, Fatty Acids in Water of Karst Underground River].

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.

[Fecal Contamination in Laolongdong Underground River as Measured by the Sterol Biomarkers].

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.

[Impacts of Land Use on the Source of Dissolved Fatty Acids in Epikarst Spring During Rainy Season].

Fatty acids were quantitatively analyzed by gas chromatography-mass spectrometer (GC-MS). Dissolved fatty acids were collected from Nanchuan epikarst spring. The results of BQ, LQ, HQ showed that the average contents of fatty acids were 14870, 12912 and 8801 ng·L-1 from May to July, respectively, and followed the order of SFA> MUFA> BrFA> PUFA. The monomers with highest content were C16:0 and C18:0. From May to July, the fatty acid content increased in BQ , LQ, HQ. The differences in vegetation coverage and bedrock bare rate, as well as the interaction of the dilution effect and soil transfer increase, led to the changes in content and the composition of the fatty acids. Based on the molecular characteristic indices of fatty acids, like H/L, CPIh, TARFA about BQ, LQ, HQ, and contents of fatty acids which were mainly originated from bacteria, phytoplankton or terrigenous higher plant, it was indicated that fatty acids were mainly originated from higher plant in LQ in May, from phytoplankton input in HQ in July, while from bacteria in the other months in LQ, HQ and from May to July in BQ.

[Impact of Urbanization on the Sources of Dissolved n-alkane in Underground River].

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.

[Comparison Study of the Alkanes in Different Aquifer Medium Under Qingmuguan Underground System].

Dissolved alkanes were collected from Dalv spring and Jiangjia spring from July to November, 2013, and were quantitatively analyzed by the gas chromatography-mass spectrometer (GC-MS). The results show that the total content of dissolved alkanes in Dalv spring is 175-3279 ng x L(-1), with a mean value of 1011 ng x L(-1). In Jiangjia spring, the total content of dissolved alkanes is 282-775 ng x L(-1), with a mean value of 527 ng x L(-1). Ratios of the content of alkanes with high carbon number( C25-C32) to the total alkanes vary from 27.89% to 52.92% in Dalv spring, and 23.66% to 49.73% in Jangjia spring. Combined with CPI and OEP the relative contribution to the dissolved alkanes of higher plants are increasing in Dalv spring, however, it is different in Jiangjia spring. In addition, the values of L/H couldn't reflect different organic contributions to the dissolved alkanes, and the values of TAR may relate with rainfall.

[Difference of Karst Carbon Sink Under Different Land Use and Land Cover Areas in Dry Season].

In order to identify the distinction of soil CO2 consumed by carbonate rock dissolution, Baishuwan spring, Lanhuagou spring and Hougou spring were selected as objects to monitor the hydrochemistry from November 2013 to May 2014. The results showed that the highest HCO3- concentration was observed in Baishuwan spring which is covered by pine forest, while the lowest HCO3- concentration was observed in Hougou spring which is mainly covered by cultivated land. In Baishuwan spring, HCO3- was mainly derived from carbonic acid dissolving carbonate rock and the molar ratio between Ca(2+) + Mg2+ and HCO3- was close to 0. 5; while the molar ratio between Ca(2+) + Mg2+ and HCO3- exceeded 0.5 because the carbonate rock in Lanhuagou spring and Hougou spring was mainly dissolved by nitric acid and sulfuric acid. Because of the input of litter and the fact that gas-permeability of soil was limited in Baishuwan spring catchment, most of soil CO2 was dissolved in infiltrated water and reacted with bedrock. However, in Lanhuagou spring catchment and Hougou spring catchment, porous soil made soil CO2 easier to return to the atmosphere in the form of soil respiration. Therefore, in order to accurately estimate karst carbon sink, it was required to clarify the distinction of CO2 consumption by carbonate rock dissolution under different land use and land cover areas.

[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.

[Contamination and ecological risk assessment of polycyclic aromatic hydrocarbons in surface sediment in karst underground river].

In order to understand pollution characteristics and ecological risk of polycyclic aromatic hydrocarbons (PAHs) in surface sediment from Laolongdong underground river, the concentration and composition of 16 priority PAHs were analyzed. The results showed that the total concentrations of PAHs ranged from 58.2 to 3 598 ng x g(-1), and most of the values were between 100 and 5 000 ng x g(-1). It means that sediments in the river were moderately and heavily polluted by PAHs. The PAH composition were dominated by 2-4 rings (accounted for 75.1%) compounds in Laolongdong, while 4-6 rings PAHs accounted for 56.6% in Xiannvdong. Sediments in Laolongdong mainly came from the transportation of the upstream water and surface soil. 2 - 3 rings PAHs had higher transport capability with farther migration distance, while 4-6 rings PAHs had lower transport capability and shorter migration distance in the conduit, because 4-6 rings PAHs could be easily absorbed by sediments. The result of ecological assessment of PAHs showed that the ecological risk level in Laolongdong was low, leading to little negative ecological impact. However, the level in Xiannvdong was high. Once PAHs migrated from upstream to downstream, it would result in ecological threat for the downstream area.

[Sources, Migration and Conversion of Dissolved Alkanes, Dissolved Fatty Acids in a Karst Underground River Water, in Chongqing Area].

Dissolved alkanes and dissolved fatty acids were collected from Qingmuguan underground river in July, October 2013. By gas chromatography-mass spectrometer (GC-MS), alkanes and fatty acids were quantitatively analyzed. The results showed that average contents of alkanes and fatty acids were 1 354 ng.L-1, 24203 ng.L-1 in July, and 667 ng.L-1, 2526 ng.L-1 in October respectively. With the increasing migration distance of dissolved alkanes and dissolved fatty acids in underground river, their contents decreased. Based on the molecular characteristic indices of alkanes, like CPI, OEP, Paq and R, dissolved alkanes were mainly originated from microorganisms in July, and aquatic plants in October. Saturated straight-chain fatty acid had the highest contents in all samples with the dominant peak in C16:0, combined with the characteristics of carbon peak, algae or bacteria might be the dominant source of dissolved fatty acids.

[Sources, Migration and Conversion of Dissolved Sterols in Qingmuguan Underground River].

Water samples were collected from the Qinmuguan underground river from July to November in 2013. By gas chromatography-mass spectrometer (GC-MS), dissolved sterols were quantitatively analyzed. The results show that the average variation content of dissolved sterols ranges from 415 to 629 ng x L(-1), with the increasing migration distance of dissolved sterols in underground river, its contents are decreased. Between the inlet and outlet of Qingmuguan underground river, the average variation contents of dissolved sterol are between 724 and 374 ng x L(-1), and the average variation ratios of the content of stigmasterol with cholesterol range from 0.29 to 0.12. In short, their values are decreased accompanied by the increasing migration distance of underground river. The composing component in dissolved sterols varied differently between July to December, and the main component of dissolved sterols is cholesterin, the ratios of the content of dissolved sterols with cholesterin to the total dissolved sterols range from 37.30% to 94.85%. In addition, the ratios of the content of dissolved sterols with coprostanol to cholesterin, coprostanol to cholesterin are below 0.2 respectively, indicating the water quality of underground river is not contaminated by domestic sewage, but with the passage of time water quality tends to deterioration.

[Variation Characteristics and Sources of Polycyclic Aromatic Hydrocarbons in Karst Subterranean River During Rainfall Events].

The water samples were continuously collected at the outlet of Nanshan Laolongdong subterranean river basin, which is located in Chongqing, during the rainfall event in June 2014. Sixteen priority polycyclic aromatic hydrocarbons (PAHs) in water were quantitatively analyzed by gas chromatography-mass spectrometry (GC-MS). The objectives of this study were to reveal the variation characteristics and sources of PAH16 in karst subterranean river during the rainfall event. The results showed that the subterranean river responded promptly to the rainfall, and there were four peaks of the total concentrations of PAH16, two peaks occurred during the flow rise stage, the others were in the maximum flow and flow decline stages. The total concentrations of PAH16 ranged 101-3 624 ng x L(-1), with a mean of 578 ng x L(-1), the total concentrations of 7 carcinogenic PAHs ranged ND-336 ng x L(-1), with a mean of 31.1 ng x L(-1). The PAH compositional profiles were dominated by 2,3-ring compounds, which accounted for 86.17% of the total concentrations of PAH16. The total concentrations of PAH16 were most influenced by the rainfall, through the cleaning of atmospheric pollutants by the rain and the scouring of the surface contaminants by the rainfall runoff. The PAHs in water mainly originated from the incomplete combustion of petroleum products and fossil fuels such as coal, as well as natural digenetic process. Compared to other areas in the world, the concentrations of PAH16 were generally at moderately polluted and heavily polluted levels.

[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.

[Formation of geochemistry in underground river under rainfall conditions: an examule for underground river at Xueyu Cave, Chongqing].

Through the monitoring of geochemical indexes in underground river of Xueyu Cave in Chongqing under rainfall conditions, we found that all indexes responded quickly to rainfall, and there was a correlation among them. Each index was analyzed with the principal component analysis, three main components were extracted which can represent 82.761% of the information to reflect the formation of geochemistry in underground river under rainfall conditions. The results showed that the contribution rates of soil leaching represented as increased concentration of total Fe, total Mn, and Al3+, and dilution effect represented as reduced concentration of K+, Na+ and Sr2+ to the change of geochemical characteristics were 41.718%, which should be paid more attentions for its great damage to karst soil and safety of drinking water. Karst water dissolution of dolomite and recharge area of agricultural activities, caverns were 29.958%, as for karst water on limestone dissolution represented, as increased concentration of Ca2+ the contribution rate was 11.084%.