Dynamic N transport and N2O emission during rainfall events in the coastal river.

The coastal zone exhibited a high population density with highly impacted by anthropogenic activities, such as river impoundment to prevent saline intrusion, which resulted in weak hydrological conditions. Rainfall events can result in dramatic changes in hydrological and nutrient transportation conditions, especially in rivers with weak hydrological conditions. However, how the nitrogen transport and N2O emissions or biogeochemistry responds to the different types of rainfall events in the weak hydrodynamics rivers is poorly understood. In this study, the hydrological, nitrogenous characteristic, as well as N2O dynamics, were studied by high-frequency water sampling during two distinct rainfall events, high-intensity with short duration (E1) and low-intensity with long duration (E2). The results displayed that the hydrologic condition in E1 with a wider range of d-excess values (from -9.50 to 32.1 ‰), were more dynamic than those observed in E2. The N2O concentrations (0.01-3.33 µmol/L) were higher during E1 compared to E2 (0.03-1.11 µmol/L), which indicated that high-intensity rainfall has a greater potential for N2O emission. On the contrary, the concentrations of nitrogen (e.g., TN and NO3--N) were lower during E1 compared to E2. Additionally, hysteresis was observed in both water and nitrogen components, resulting in a prolonged recovery time for pre-rainfall levels during the long-duration event. Moreover, the results showed that the higher average N2O flux (78.3 µmol/m2/h) in the rainfall event period was much larger than that in the non-rainfall period (1.63 µmol/m2/h). The frequency dam regulation resulted in the water level fluctuation, which could enhance wet-dry alternation and simulated N2O emissions. This study highlighted the characteristic of N dynamic and hydrological responses to diverse rainfall events occurrences in the coastal river. Rainfall could increase the N2O emission, especially during high-intensity rainfall events, which cannot be ignored in the context of annual N2O release.

Organic carbon preservation in wetlands: Iron oxide protection vs. thermodynamic limitation.

The sequestration of organic carbon (OC) in wetland sediments is influenced by the presence of oxygen or lack thereof. The mechanisms of OC sequestration under redox fluctuations, particularly by the co-mediation of reactive iron (Fe) protection and thermodynamic limitation by the energetics of the OC itself, remain unclear. Over the past 26 years, a combination of field surveys and remote sensing images had revealed a strong decline in both natural and constructed wetland areas in Tianjin. This decline could be attributed to anthropogenic landfill practices and agricultural reclamation efforts, which may have significant impacts on the oxidation-reduction conditions for sedimentary OC. The Fe-bound OC (CBD extraction) decreased by 2 to 10-fold (from 8.3 to 10% to 0.7-4.5%) with increasing sediment depth at three sites with varying water depths (WD). The high-resolution spectro-microscopy analysis demonstrated that Fe (oxyhydr)oxides were colocalized with sedimentary OC. Corresponding to lower redox potential, the nominal oxidation state of C (NOSC), which corresponds to the energy content in OC, became more negative (energy content increased) with increasing sediment depth. Taken together, the preservation of sedimentary OC is contingent on the prevailing redox conditions: In environments where oxygen availability is high, reactive Fe provides protection for OC, while in anoxic environments, thermodynamic constraints (i.e., energetic constraints) limit the oxidation of OC.

Linking deeply-sourced volatile emissions to plateau growth dynamics in southeastern Tibetan Plateau.

The episodic growth of high-elevation orogenic plateaux is controlled by a series of geodynamic processes. However, determining the underlying mechanisms that drive plateau growth dynamics over geological history and constraining the depths at which growth originates, remains challenging. Here we present He-CO2-N2 systematics of hydrothermal fluids that reveal the existence of a lithospheric-scale fault system in the southeastern Tibetan Plateau, whereby multi-stage plateau growth occurred in the geological past and continues to the present. He isotopes provide unambiguous evidence for the involvement of mantle-scale dynamics in lateral expansion and localized surface uplift of the Tibetan Plateau. The excellent correlation between 3He/4He values and strain rates, along the strike of Indian indentation into Asia, suggests non-uniform distribution of stresses between the plateau boundary and interior, which modulate southeastward growth of the Tibetan Plateau within the context of India-Asia convergence. Our results demonstrate that deeply-sourced volatile geochemistry can be used to constrain deep dynamic processes involved in orogenic plateau growth.

High abundances of dicarboxylic acids, oxocarboxylic acids, and α-dicarbonyls in fine aerosols (PM2.5) in Chengdu, China during wintertime haze pollution.

Daytime and nighttime fine aerosol (PM2.5) samples were collected during a haze episode in January 2013 within the urban area of Chengdu, southwest China. Aerosol samples were analyzed for low-molecular-weight homologous dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls, as well as organic carbon and elemental carbon. Concentration ranges of diacids, oxoacids, and α-dicarbonyls were 1,400-5,250, 272-1,380, and 88-220 ng m(-3), respectively. Molecular distributions of diacids (mean 3,388 ± 943 ng m(-3)) were characterized by a predominance of oxalic acid (C2; 1,373 ± 427 ng m(-3)), followed by succinic (C4), terephthalic (tPh), and phthalic (Ph) acids. Such high levels of tPh and Ph were different from those in other Asian cities where malonic acid (C3) is the second or third highest species, mostly owing to significant emissions from coal combustion and uncontrolled waste incineration. High contents of diacids, oxoacids, and α-dicarbonyls were detected on hazy days, suggesting an enhanced emission and/or formation of these organics during such a weather condition. Concentrations of unsaturated aliphatic diacids (e.g., maleic acid) and phthalic acids were higher in nighttime than in daytime. Good positive correlations of C2 with C3, C4, ketomalonic (kC3), pyruvic (Pyr), and glyoxylic (É·C2) acids in daytime suggest secondary production of C2 via the photooxidation of longer chain diacids and É·C2. This study demonstrated that both primary emissions and secondary production are important sources of dicarboxylic acids and related compounds in atmospheric aerosols in the Sichuan Basin.

Identification of anthropogenic and natural inputs of sulfate and chloride into the karstic ground water of Guiyang, SW China: combined delta37Cl and delta34S approach.

Because of active exchange between surface and groundwater of a karstic hydrological system, the groundwater of Guiyang, the capital city of Guizhou Province, southwest China, has been seriously polluted by anthropogenic inputs of NO3-, SO4(2-), Cl-, and Na+. In this work, delta37Cl of chloride and delta34S variations of sulfate in the karstic surface/groundwater system were studied, with a main focus to identify contaminant sources, including their origins. The surface, ground, rain, and sewage water studied showed variable delta37Cl and delta34S values, in the range of -4.1 to +2.0 per thousand, and -20.4 to +20.9 per thousand for delta37Cl and delta34S (SO4(2-)), respectively. The rainwater samples yielded the lowest delta37Cl values among those observed to date for aerosols and rainwater. Chloride in the Guiyang area rain waters emanated from anthropogenic sources rather than being of marine origin, probably derived from HCl (g) emitted by coal combustion. By plotting 1/SO4(2-) vs delta34S and 1/Cl- vs delta37Cl, respectively, we were able to identify some clusters of data, which were assigned as atmospheric deposition (acid rain component), discharge from municipal sewage, paleo-brine components in clastic sedimentary rocks, dissolution of gypsum mainly in dolomite, oxidation of sulfide minerals in coal-containing clastic rocks, and possibly degradation of chlorine-containing organic matter. We conclude that human activities give a significant input of sulfate and chloride ions, as well as other contaminants, into the studied groundwater system through enhanced atmospheric deposition and municipal sewage, and that multiple isotopic tracers constitute a powerful tool to ascertain geochemical characteristics and origin of complex contaminants in groundwater.

Using delta15N- and delta18O-values to identify nitrate sources in karst ground water, Guiyang, southwest China.

Nitrate pollution of the karstic groundwater is an increasingly serious problem with the development of Guiyang, the capital city of Guizhou Province, southwest China. The higher content of NO3- in groundwater compared to surface water during both summer and winter seasons indicates that the karstic groundwater system cannot easily recover once contaminated with nitrate. In order to assess the sources and conversion of nitrate in the groundwater of Guiyang, we analyzed the major ions, delta(15)N-NH4+, delta(15)N-NO3-, and delta(18)O-NO3- in surface and groundwater samples collected during both summer and winter seasons. The results show that nitrate is the major dominant species of nitrogen in most water samples and there is a big variation of nitrate sources in groundwater between winter and summer season, due to fast response of groundwater to rain or surface water in the karst area. Combined with information on NO3- /Cl-, the variations of the isotope values of nitrate in the groundwater show a mixing process of multiple sources of nitrate, especially in the summer season. Chemical fertilizer and nitrification of nitrogen-containing organic materials contribute nitrate to suburban groundwater, while the sewage effluents and denitrification mainly control the nitrate distribution in urban groundwater.

Carbon biogeochemistry of ground water, Guiyang, southwest China.

Variations in the concentrations and isotopic compositions (delta13C(DIC)) of dissolved inorganic carbon (DIC) reflect contamination and biogeochemical cycling of the carbon in ground water. In order to understand contamination and biogeochemical cycling of DIC, we carried out research on the geochemistry of ground water of Guiyang, the capital city of Guizhou Province, China. Results show that ground water is mainly characterized by SO4.HCO3-Ca.Mg and HCO3-Ca.Mg chemical compositions. The hydrochemical characteristics of these types of water are mainly controlled by lithology of the aquifers. HCO3- is the dominant species of DIC in ground water and has lower concentrations and more negative values of delta13C(DIC) in the high-flow (summer monsoon) season, as compared to the low-flow season. This indicates that DIC is relatively enriched in carbon of biological origin in the high-flow season as compared to the low-flow season and that biological activities are the predominant control on shifts of stable carbon isotope values. The evidence that the delta13C(DIC) values of ground water decrease with increasing concentrations of anthropogenic species shows that the carbon isotopic composition of DIC can be a useful tracer of contamination, in addition to biogeochemical cycling of inorganic carbon in ground water. Results from this study show that ground water is impacted by significant levels of contamination from human activities, especially in the urban areas, as well as the northeast and west suburbs, in Guiyang city, southwest China.