Disentangling sources and transformation mechanisms of nitrogen, sulfate, and carbon in water of a Karst Critical Zone.

In the Karst Critical Zone (KCZ), mining and urbanization activities produce multiple pollutants, posing a threat to the vital groundwater and surface water resources essential for drinking and irrigation. Despite their importance, the interactions between these pollutants in the intricate hydrology and land use of the KCZ remain poorly understood. In this study, we unraveled the transformation mechanisms and sources of nitrogen, sulfate, and carbon using multiple isotopes and the MixSIAR model, following hydrology and surface analyses conducted in spatial modelling with ArcGIS. Our results revealed frequent exchange between groundwater and surface water, as evidenced by the analysis of δD-H2O and δ18O-H2O. Nitrification predominantly occurred in surface water, although denitrification also made a minor contribution. Inorganic nitrogen in both groundwater and surface water primarily originated from soil nitrogen (48 % and 49 %, respectively). Sewage and manure were secondary sources of inorganic nitrogen in surface water, accounting for 41 % in urban and 38 % in mining areas. Notably, inorganic sulfur oxidation displayed significant spatial disparities between urban and mining areas, rendering groundwater more susceptible to sulfur pollution compared to surface water. The frequent interchange between groundwater and surface water posed a higher pollution risk to groundwater. Furthermore, the primary sources of CO2 and HCO3- in both groundwater and surface water were water­carbonate reactions and soil respiration. Sulfide oxidation was found to enhance carbonate dissolution, leading to increased CO2 release from carbonate dissolution in the KCZ. These findings enhance our understanding of the transformation mechanisms and interactions of nitrogen, sulfur, and carbon in groundwater and surface water. This knowledge is invaluable for accurately controlling and treating water pollution in the KCZ.

Sources and fates of particulate organic matter in inland waters with complex land use patterns.

Elucidating the sources of particulate organic matter (POM) is the foundation for understanding their fates and the seasonal variation of their movement from the land-to-ocean aquatic continuum (LOAC). The POM from different sources has different reactivity, which determines their fates. However, the key link between the sources and fates of POM, especially in the complex land use watersheds in bays is still unclear. Stable isotopes and contents of organic carbon and nitrogen were applied to reveal them in a complex land use watershed with different gross domestic production (GDP) in a typical Bay, China. Our results showed that the POMs preserved in suspended particulate organic matter (SPM) were weakly controlled by assimilation and decomposition in the main channels. Source apportionments of SPM in the rural area were controlled by soil (46 % ~ 80 %), especially inert soils eroded from land to water due to precipitation. The contribution of phytoplankton resulted from slower water velocity and longer residence time in the rural area. The soil (47 % ~ 78 %) and manure and sewage (10 % ~ 34 %) were the two major contributors to SOMs in the developed and developing urban areas. The manure and sewage were important sources of active POM in the urbanization of different LUI, which showed discrepancies in the three urban areas (10 % ~ 34 %). Due to soil erosion and the most intensive industry supported by GDP, the soil (45 % ~ 47 %) and industrial wastewater (24 % ~ 43 %) were the two major contributors to SOMs in the industrial urban area. This study demonstrated the close relationship between the sources and fates of POM with complex land use patterns, which could reduce uncertainties in future estimates of the LOAC fluxes and secure ecological and environmental barriers in a bay area.

Distribution and source apportionment of phenolic EDCs in rivers in the Pearl River Delta, South China.

The sources and distribution characteristics of three phenolic endocrine-disrupting compounds (EDCs), e.g., alkylphenols (APs) (including nonylphenols (NPs) and 4-t-octylphenol (OP)) and Bisphenol A (BPA), were investigated in the rivers of the Pearl River Delta Region (PRDR) with complex land-use types. The mean concentrations of NPs, OP, and BPA in river water including wet and dry seasons were 87, 6, and 74 ng/L in the agricultural regions (n = 10), 135, 7, and 61 ng/L in the transitional regions (n = 8), and 249, 15, and 152 ng/L in the urban regions (n = 28). Contents of NPs and BPA were high in the river sediments (ranged from 7 to 3048 ng/g and 2 to 271 ng/g, respectively). Equilibrium analysis results suggested that sediment release was not the main source of the river EDCs. Principal component analysis (PCA) showed that sewage was the major source of EDCs in the dry season, while the leaching effect of rainfall on the agricultural soils, urban roads, and commercial products was an important source in the wet season. Furthermore, the ratio of APs and total concentration of phenolic EDCs (ΣEDCs) was used to characterize the agricultural regions and urban regions in the PRDR. The ratio was less than 0.6 in the agricultural regions while the ratio was large than 0.6 in the dry season and less than 0.6 in the wet season in urban regions. BPA and NPs in transitional region and urban region had small/medium potential risk to aquatic organisms.

The health halo effect of 'low sugar' and related claims on alcoholic drinks: an online experiment with young women.

AIMS: To investigate whether 'low sugar' and related claims influence consumers' perceptions of the healthiness or other attributes of alcoholic drinks, promote greater consumption or impact diet and activity behaviour intentions. METHOD: N = 501 Australian women aged 18-35 viewed and rated six images of alcoholic drinks in a randomized online experiment with a 2 (claim: low sugar claim, no claim control) × 2 (drink type: cider, ready-to-drink spirits) between-subjects design. RESULTS: Participants who viewed drinks with low sugar claims rated them as healthier, less harmful to health, lower in sugar and kilojoules, and more suitable for weight management and a healthy diet than participants who viewed identical drinks with no claim (P < 0.001-P = 0.002). Drinks with low sugar claims were also perceived as being lower in alcohol (P < 0.001) despite being of equivalent alcohol content. There were no significant differences in anticipated social approval associated with consumption or in hypothetical intended consumption of the drinks, but participants who viewed drinks with low sugar claims were less likely to indicate they would compensate for consumption of the drink by modifying food intake or physical activity (P = 0.01). CONCLUSIONS: Low sugar and related claims on alcoholic drinks can generate a health halo: consumers generalise from a specific favourable attribute (low sugar) to misperceive other favourable health- and nutrition-related attributes, including lower alcohol content. Findings support calls to reconsider the permissibility of low sugar claims on alcoholic drinks as they may mislead consumers.

Contribution of ammonia-oxidizing archaea and bacteria to nitrification under different biogeochemical factors in acidic soils.

Nitrification in soils is an essential process that involves archaeal and bacterial ammonia-oxidizers. Despite its importance, the relative contributions of soil factors to the abundance of ammonia-oxidizing archaea (AOA) and bacteria (AOB) and their nitrification performances are seldom discussed. The aim of this study was to determine the effects of AOA and AOB abundance and different environmental conditions (pH, TC, TN, moisture, and temperature) on nitrification performance. The soils of the long-term fertilized tea orchards and forests were sampled in the field, and nitrification experiments were conducted in the laboratory. The acid soils were collected from the field and used in laboratory incubation experiments to calculate the nitrification rate, including the net nitrification rate (NN rate), nitrification potential (NP), and nitrification kinetics. The basic parameters, different forms of nitrogen content, and AOA and AOB amoA gene copies were also analyzed. Compared with the forest soil, the tea orchard soil had a lower pH and higher nitrogen content (p < 0.05). The AOA and AOB abundance in the soils of the forests and tea orchards were pH-dependent. The NN rate and NP had good relationships with AOA or AOB in the forest soil; however, poor relationships were observed in the tea orchard soil. When pH < 4, the performances of AOA and AOB were restricted by pH and the environment, especially in long-term fertilized farmlands. Long-term fertilization can cause soil acidification, which regulates the abundance of AOA and AOB and their nitrifying ability. The soil environment rather than AOA or AOB could control nitrification in long-term fertilized farmlands with a pH below 4. These findings could improve fertilization efficiency and control nutrient runoff in hilly agricultural ecosystems.

Sources and transformation mechanisms of inorganic nitrogen: Evidence from multi-isotopes in a rural-urban river area.

Multi-isotope tracers were applied to quantitatively reveal the sources and transformation mechanisms of inorganic nitrogen both spatially and seasonally in a complex land use area in China. Based on land use and the level of socioeconomic development, the study area was divided into four zones: the rural area, developed urban area, developing urban area and industrial urban area. The redox condition and isotope analysis results indicated that the nitrification process dominated in the Han and Rong River, which were characterized by ammonium nitrogen (NH4+-N) and oxidizing conditions, while neither nitrification nor denitrification occurred in the Lian River. The inorganic nitrogen sources of the four areas were revealed from the results of a stable isotope analysis in R (SIAR) and a two-component mixing model after determining the transformation mechanisms. In the rural area, nitrate nitrogen (NO3--N) was mainly sourced from the increased fertilization of nitrogen fertilizer (42-56%) to farmland during the wet season, and from soil nitrogen (33-62%) related to increased nitrification during the dry season. In the urban area, the contributions of soil nitrogen, manure and sewage and industrial wastewater to the total inorganic nitrogen exhibited large seasonal and spatial differences, which were distinguished by the environmental management supported by gross domestic production (GDP). In the developed and developing urban areas, soil nitrogen contributed 41% and 47% of the NO3--N, respectively, during the wet season, and 47% and 54%, respectively, during the dry season. The second highest contribution was from manure and sewage (30-41%) with no seasonal differences. In the industrial urban area, the dominant contribution to the NH4+-N was from manure and sewage (81%) during the wet season, but industrial wastewater (84%) in the dry season. Our findings elucidate the multiplex sources and transformation mechanisms of inorganic nitrogen, and promote the management of nitrogen tracing to control nitrogen pollution in complex land use areas.

Primary role of increasing urea-N concentration in a novel Microcystis densa bloom: Evidence from ten years of field investigations and laboratory experiments.

A novel Microcystis bloom caused by Microcystis densa has occurred in a typical subtropical reservoir every spring and summer since 2012, and it has caused several ecological and economic losses. To determine the environmental factors that influence the growth and physiological characteristics of M. densa, we investigated the variations in physicochemical factors and M. densa cell density from 2007 to 2017. The results showed that the urea-N concentration increased significantly (from 0.02 ± 0.00-0.20 ± 0.01 mg N l-1), whereas other factors did not vary significantly. NO3--N and urea-N concentrations were higher than the NH4+-N concentration during the M. densa bloom. The nitrogen composition changed, and urea-N and NO3--N became a major nitrogen sources in the reservoir. Water temperature and increased urea-N concentrations were the primary factors that influenced variations in M. densa cell density (45.5%, p < 0.05). Laboratory experiments demonstrated that M. densa cultured with urea-N exhibited a higher maximum cell density (9.8 ± 0.5 × 108 cells l-1), more cellular pigments for photosynthesis (chlorophyll a and phycocyanin) and photoprotection (carotenoid), and more proteins than those cultured with NH4+-N and NO3--N. These results suggested that M. densa cultured with urea-N exhibited preferable growth and physiological conditions. Moreover, M. densa exhibited an increased maximum specific uptake rate (0.93 pg N cell-1 h-1) and reduced half-saturation constant (0.03 mg N l-1) for urea-N compared with NH4+-N and NO3--N, suggesting that M. densa preferred urea-N as its major nitrogen source. These results collectively indicated that the increasing urea-N concentration was beneficial for the growth and physiological conditions of M. densa. This study provided ten years of field data and detailed physiological information supporting the critical effect of urea-N on the growth of a novel bloom species M. densa. These findings helped to reveal the mechanism of M. densa bloom formation from the perspective of dissolved organic nitrogen.

[Hydrogen and oxygen stable isotope characteristics of water in SPAC system of evergreen broadleaved forest in subtropical region]. / 亚热带地区常绿阔叶林SPACç³»ç»Ÿæ°´åˆ†çš„æ°¢æ°§ç¨³å®šåŒä½ç´ ç‰¹å¾.

Forest soil-plant-atmosphere continuum (SPAC) is an important continuous process of water cycle. In this study, we analyzed hydrogen and oxygen stable isotope compositions of the precipitation, atmospheric water vapor, soil water, branch water, and leaf water to explain the characteristics of the continuous process and the associated controlling factors in a subtropical evergreen broadleaved forest. The results showed that the regression equations between hydrogen and oxygen stable isotopes were δDP=7.97δ18OP+12.68(R2=0.97) for precipitation, δDS=4.29δ18OS-18.62(R2=0.81) for soil water, δDB=3.31δ18OB-29.73(R2=0.49) for branch water and δDL=1.49δ18OL-10.09(R2=0.81) for leaf water of Podocarpus nagi, δDV=3.89δ18OV-51.29(R2=0.46) for atmospheric water vapor, respectively. In the process of water transport from precipitation to soil water to plant water, hydrogen and oxygen isotopes gradually enrich, while water vapor isotopes evaporated from soil and evaporated from plants were depleted. With the influence of precipitation and evaporation, soil water isotopes depleted with depth, and more enriched in the dry season than that in the rainy season. During the observation period, isotope content of branch water was slightly higher than that of soil water, indicating that water might be enriched by transpiration during the transportation process in plants. In the dry season, water isotope in branches of arbor plants was poorer than that of shrubs, indicating that arbor plants with deeper root distribution tended to use deep soil water. Because of the differences of leaf traits, transpiration rate and the response degree of environmental factors, the variation characteristics of water isotope composition in leaves of diffe-rent plants varied with the increases of leaf age. Environmental conditions in rainy season were more conducive to leaf transpiration, which made leaf water isotope enriched in rainy season than in dry season. The isotopic compositions in leaf water of Podocarpus nagi had a positive relationship with leaf water content (LWC), and a negative one with relative humidity, reflecting the water regulation function of plants in response to environmental changes.

History traces of HCHs and DDTs by groundwater dating and their behaviours and ecological risk in northeast China.

Organochlorine pesticides legacies, such as hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT), remained in sediments or soils due to their difficulty in decomposition, especially in the agricultural areas where pesticides were widely used historically. Different from the little disturbed depositional environment of lake, it was difficult for rivers to explore the timing of DDT and HCH inputs through dating sediment cores as records. Based on groundwater dating, this study ascertained the historic pollution of DDT and HCH in Taizi River basin. HCH and DDT residues in groundwater were consistent with the historical production and usage, which increased from the 1950s to the 1980s and declined from the 1980s to the 1990s. Moreover, the partitioning behaviours of HCHs and DDTs in surface water and suspended particulate matter were discussed. It was revealed that ß-HCH and o,p'-DDT were more likely to attach to suspended particulate matter than other isomers. Furthermore, species sensitivity distribution curves were generated using 54 toxicity data records to assess the risk of HCHs and DDTs in water and suspended particulate matter. These results indicated that p,p'-DDT in surface water posed a high risk to 95% of the aquatic life in the long run.

Changes in dissolved inorganic carbon in river water due to urbanization revealed by hydrochemistry and carbon isotope in the Pearl River Delta, China.

Under natural conditions, the dissolved inorganic carbon (DIC) in river water is dominantly derived from carbonate or silicate dissolution by carbonic acid. However, sulfuric and nitric acids produced by human activities provide additional acidity for chemical weathering, which would affect the DIC flux and change its isotopic composition. To identify the natural and anthropogenic impacts on DIC, the major ion concentrations and stable carbon isotopes of the DIC (δ13C-DIC) of river waters were measured in the Pearl River Delta (PRD) region, which is one of the most developed and populated areas in China. The mass balance calculations for DIC-apportionment showed that carbonate dissolution by carbonic acid was the dominant origin of DIC in the Beijiang (BJ) River (67%) and Xijiang (XJ) River (78%) and silicate dissolution by carbonic acid was the dominant origin of DIC in the Guangzhou (GZ) Channel (37%) and Dongjiang (DJ) River (50%), which was related to the lithology of the catchment. The contribution of carbonate dissolution by sulfuric and nitric acids, which represented the contribution of human activities to the total DIC concentrations in river water, showed high proportions in the GZ Channel and DJ River, with averages of 42% and 34%, respectively, which were associated with a high degree of urbanization. Evidence of hydrochemical parameters and δ13C-DIC signatures indicated that human activities had impacts on the DIC pool. Carbonate dissolution by sulfuric and nitric acids caused by human activities changed DIC apportionments rather than the DIC flux, and this part of DIC would ultimately become a source of CO2 to the atmosphere on the geological timescale and affects the CO2 budget. An increase in nutrient concentration due to increased sewage discharge in the urbanized area could promote phytoplankton photosynthesis, which could change the DIC pool and increase the δ13C-DIC value. This study quantitatively highlights the influence of human activities on DIC apportionment in river water, suggesting that anthropogenic impacts should be seriously considered when evaluating the evolution of DIC.

A multiple isotope (H, O, N, C and S) approach to elucidate the hydrochemical evolution of shallow groundwater in a rapidly urbanized area of the Pearl River Delta, China.

A comprehensive understanding of the impacts of natural and human activities on groundwater evolution is critical for sustainable groundwater resource management, as groundwater quality degradation from urbanization has raised widespread concerns. However, conclusions based only on basic hydrochemical data would be fragmentary because complex processes occur with high concentrations of pollutants in rapidly urbanized areas. Thus, the hydrogeochemical and multi-isotope approaches were combined to elucidate the groundwater hydrogeochemical evolution in such an area. The results demonstrated that the major hydrochemical types of groundwater were ClNa and HCO3-Ca in 2018 and that the hydrochemical patterns had changed since 1980. The predominant controlling factors for groundwater hydrochemistry were rock weathering due to carbonic, sulfuric and nitric acids, while the cation exchange and evaporation processes acted as natural factors; redox reactions, including denitrification, sulfate reduction, and methanogenesis, also affected groundwater hydrochemistry. The impacts of anthropogenic activities on groundwater hydrochemistry consisted of direct impacts that referred to the infiltration of manure and septic waste responsible for the occurrence of high NO3- content and part of the SO42- content in groundwater and indirect impacts that included the following issues: (1) acid rain accelerated water-rock interactions and resulted in the accumulation of SO42-; (2) sulfate reduction and methanogenesis increased the HCO3- content and expanded the distribution of HCO3-type water; (3) organic matter associated with manure and septic waste accelerated the development of a reducing environment in groundwater; and (4) the occurrence of a strong reducing environment promoted the release of Mn, aggravated heavy metal pollution and imposed adverse effects on the ecological system.

Accumulation and associated phytotoxicity of novel chlorinated polyfluorinated ether sulfonate in wheat seedlings.

Novel alternatives of perfluorooctane sulfonate (PFOS), chlorinated polyfluorinated ether sulfonates (Cl-PFAESs) are increasingly being detected in the aquatic and terrestrial environment. Previous studies mainly focused on aquatic biota; however, the knowledge about the ecotoxicological risk they pose to terrestrial plants was still lacking. In this study, the accumulation of two Cl-PFAES (6:2 and 8:2 Cl-PFAES) and PFOS in wheat seedlings at environmentally relevant levels (50 and 100 µg L-1) was investigated. Concentrations of Cl-PFAESs in the roots were an order of magnitude higher than those in shoots, indicating that they were primarily accumulated in the roots. The values of root and shoot bioconcentration factor was comparable between 6:2 Cl-PFAES and PFOS. However, these indexes of 8:2 Cl-PFAES were 42-91% higher and 70-76% lower than PFOS, respectively. As a result, 6:2 Cl-PFAES had a similar accumulation pattern as PFOS, whereas 8:2 Cl-PFAES was predominantly restricted to the roots, which might be attributed to their hydrophobicity and carbon chain length. In addition, at 250 mg L-1 of Cl-PFAESs, plant biomass and pigment content were 24-30% and 0.4-18%, respectively, which were lower than those of PFOS. As compared with PFOS, Cl-PFAESs induced higher levels of root membrane permeability, reactive oxygen species and malondialdehyde content, as well as reduced the activities of antioxidant enzymes and glutathione content. These suggested the occurrence of a severer oxidative damage and the breakdown of the antioxidant defence system in wheat cells. Therefore, we conclude that Cl-PFAESs might pose a higher potential threat to the environment than PFOS.

Understanding the inorganic carbon transport and carbon dioxide evasion in groundwater with multiple sulfate sources during different seasons using isotope records.

The geochemical cycle of carbon under anthropogenic activities controls the transport of carbon between surface sediments, hydrosphere and atmosphere, especially for atmospheric and marine carbon dioxide. Currently, the anthropogenically-induced carbon cycle in groundwater is an important part of the cycle in inland waters and cannot be underestimated as a geochemical process affecting the global carbon cycle. Therefore, there is a need to conduct deep research using isotopes in which the isotopic mixing and fractionation response to the carbon cycle can be assessed. The results showed that the δ34S-SO42- and δ18O-SO42- values in groundwater inherited the isotopic characteristics of four sulfate sources and shifted from acid mine drainage (AMD) derived from pyrite oxidation to atmospheric sulfates and agricultural fertilizers as well as domestic sewage along the groundwater flow path. In particular, the evolution of sulfate sources was accompanied by changes in the δ13C-DIC values in different seasons. During the dry season, the Rayleigh function described a possibility of enriched δ13C-DIC values in an AMD-affected aquifer, where a dropping water table or decreasing water content in unsaturated zones provided favorable acid buffering conditions. Bicarbonate neutralized protons to CO2 that was in turn spilled over the water surface. During the wet season, the depleted δ13C-DIC values in the AMD-affected aquifer reflected another possibility of the carbon cycle in which a rising water table caused a similar closed system to some extent and slowed down the replenishment of bicarbonate so that δ13C-DIC almost recorded the δ13C of soil CO2. In spite of the same AMD source, their influences on the carbon cycle in the dry and wet seasons were CO2 evasion and deficient CO2 uptake, respectively. By contrast, regardless of the season, the carbon cycle gradually shifted towards a net consumption of CO2 in the aquifer with atmospheric and agricultural sulfates as well as domestic sewage, and δ13C-DIC inherited the characteristic of HCO3-, indicating that these sources in anthropogenically-induced carbon processes hardly involved in isotopic fractionation of δ13C-DIC.

Evidence for the Primary Role of Phytoplankton on Nitrogen Cycle in a Subtropical Reservoir: Reflected by the Stable Isotope Ratios of Particulate Nitrogen and Total Dissolved Nitrogen.

Knowledge about the primary factor controlling stable isotope ratios of particulate nitrogen (δ15NPN) and total dissolved nitrogen (δ15NTDN) in a subtropical reservoir can improve the understanding of regional and global nitrogen cycles. Taking Lianhe Reservoir as a representative subtropical reservoir, we studied the spatial and temporal distributions of δ15NPN andδ15NTDN and their relationships with the surrounding physicochemical factors and phytoplankton. The results showed that variations in δ15NPN and δ15NTDN followed seasonal thermal cycles. The values of δ15NTDN were inversely proportional to those of δ15NPN. PCA showed that phytoplankton cell density and pH were the primary drivers of the variation of δ15NPN (45.2%). The primary factors influencing δ15NTDN were Chl a and phytoplankton cell density, which both indicated phytoplankton biomass. We also determined that the dominant species was Microcystis densa during the thermal stratification period and Staurodesmus aristiferus during the mixing period. Laboratory experiments showed that δ15NPN values in both M. densa (from 19.5 to 14.6‰) and S. aristiferus (from 19.4 to 16.0 ‰) media decreased significantly as the algal cells grew. Furthermore, the δ15NTDN values increased from 4.9 to 7.9‰ and from 4.7 to 6.9‰ in M. densa and S. aristiferus media, respectively, when the δ15NPN values decreased. These experimental results were consistent with field investigation results and indicated that variations in δ15NPN and δ15NTDN were mainly controlled by phytoplankton cell density, especially the cell density of the dominant species, in both the thermal stratification and mixing periods. The results also suggested that cell density, not phytoplankton species, was the key factor regulating the distribution of nitrogen stable isotopes. These results together indicated that phytoplankton cell density is the primary factor in the regulation of nitrogen stable isotope composition and that its influence is greater than that of other physical and chemical factors. This study provided detailed information supporting the primary role of phytoplankton in the nitrogen geochemical cycle and improved the understanding of biochemical processes in natural subtropical reservoirs.

Dynamics of dissolved greenhouse gas response to seasonal water mixing in subtropical reservoirs.

Although indispensable, significant uncertainty still exists in the underlying processes of the formation, dynamics, and emission of greenhouse gases (GHGs), the critical elements needed for the accurate estimation of greenhouse gas fluxes in inland lakes and reservoirs. Seasonal changes in water thermal stratification and turbulence strongly influence the concentration and emission of dissolved GHGs in water columns. Here, we studied the stratification and overturn processes of water column in the subtropical Lianhe Reservoir during different seasons and determined the dynamics of dissolved CO2, CH4, and N2O in the reservoir. Observation of temperature and analysis of chlorofluorocarbons (CFCs) clearly suggested that stratification of water column occurred in summer, but not in winter. The results showed that while dissolved oxygen (DO) was high in the top 5-m layer (the upper epilimnion layer), it dropped considerably especially below 10 m, resulting in an increase in concentration of CO2 and CH4. The high concentrations of dissolved N2O and CH4 were related to the decomposition of organic matter in the hypolimnion layer under anaerobic conditions after stratification. In winter overturn period, vertical circulants of water not only homogenized the concentration of DO in the water column, but also potentially moved CO2, CH4, and N2O from the bottom to the surface of the reservoir. The estimated GHG flux from the reservoir was - 7.13 mmol m-2 day-1 in summer and 2.14 mmol m-2 day-1 in winter. There was the potential that CO2 fluxes from subtropical lakes and reservoirs are overestimated by traditional geochemical models.

Assessment of trace metals in an aquifer with river-groundwater interaction: The influence of colloidal redistribution and porous matrix change on the migration of metals.

An aquifer where receives steady lateral recharge from an AMD-polluted river, was chosen to understand the profound influence of the "solid-liquid phase" evolution on the mobility of trace metals. The results showed that the accumulation of trace metals in groundwater was observed near the riparian zone. Zn and Cd almost remained in the "truly dissolved" phase (<3 kDa), whereas Cu and Pb were mainly in the coarse colloid (0.22 µm-30 kDa) and shifted from the coarse colloid to the "truly dissolved" phase along the flow path. The evolution of relatively high dispersive colloids to low dispersive colloids indicated that the Al-rich mineral colloids as the dominance migrated with the groundwater flow path, and flocculated gradually so that the porous matrix was coated by gibbsite. The coating of gibbsite dissociates OH- in acidic environment, resulting in the decreasing negative charge in porous matrix. Thus, the mobility of Cu and Pb was shifted from the colloid-facilitated transport to the co-precipitation with colloids, whereas the mobility of Zn and Cd was changed from the high electrostatic binding to the low electrostatic binding. Numerical simulation also confirmed the varying retardation factor and the total penetration time followed an order of Pb > Cu > Zn > Cd. Therefore, the changes in "two phases" in the aquifer-not only in water phase but also in colloid phase and porous matrix-have a profound influence on metal migration that take place in shallow groundwater where there are close hydraulic connection between river and groundwater.

Reconstructing the historical pollution levels and ecological risks over the past sixty years in sediments of the Beijiang River, South China.

Three sediment cores were collected from the Beijiang River to investigate the effects of human activities on the geochemical fractions of trace metals (Ni, Cr, Cu, Zn, Cd, Pb and Fe) and to reconstruct the ecological risks for the period 1951-2015. Cd had the highest concentration in exchangeable and carbonate fractions and was probably contributed by smelting wastewater. High Cu, Zn and Pb contents were observed in the iron oxide fraction (mean values of 32.2%, 38.2% and 43.9%, respectively), reflecting the influence of mining activities. Flood events led to coarser sediment grain sizes and higher trace metal residual fractions at upstream sites (S1 and S2). Similar to the mining history of the basin, the excess metal fluxes of Cu, Zn, Pb, and Fe in the 210Pb-dating core (S3) increased slowly from 1951 to 1987, increased rapidly from 1988 to 1998 and decreased gradually after 1999 because of government intervention. However, the excess Cd flux decreased continuously from 1951 to 1961, increased from 1961 to 2005, and declined by approximately 78.2% from 2005 to 2014. The excess Ni and Cr fluxes increased noticeably after 1996 because of the increasing sedimentation rate after the construction of the Feilai Gorge Dam. The enrichment factor (EF) and ratio of secondary and primary phases (RSP) indicated that sediments (S3) were moderately to strongly polluted by Cu, Zn and Pb from 1961 to 2007 and extremely polluted by Cd from 1951 to 2011. Human activities increased the bioavailable metal concentrations and resulted in a high risk of toxicity to benthic organisms, especially during intense mining activity (1990s) and Cd pollution incidents (2005). Cd and Pb were primarily responsible for the sediment toxicity in the Beijiang River. The integrated pollution and risk assessment methods provided a clearer understanding of the aquatic environmental quality.

The distribution and partitioning of trace metals (Pb, Cd, Cu, and Zn) and metalloid (As) in the Beijiang River.

The concentrations of Cu, Zn, Pb, Cd, and As varied quite differently in the water, suspended particulate matter (SPM), and sediment along the middle reach of the Beijiang River in southern China. The total concentrations of trace metals and As in the water column were significantly affected by the concentration of SPM, while the metals and As in the sediment were mainly influenced by fine particle component, OM and Fe/Mn/Al. The partitioning coefficient of trace metals and As in the water column generally appeared in the following order: Pb > Cd > Cu > Zn > As. Accordingly, approximately 67.9% of Pb migrated with SPM in the river because of its higher particle reactivity, while the SPM-bound Cu, Zn, and As were approximately 43.4, 37.3, and 26.7%, respectively. The fractions of Cd in the dissolved and particulate phases were almost the same. Sediment resuspension and deposition in the Beijiang River were considered as important factors controlling the concentrations of dissolved Cu, Zn, Pb, Cd, and As in the bottom of the water column.

Groundwater nitrate remediation using plant-chip bioreactors under phosphorus-limited environment.

Groundwater denitrification bioreactors under limited phosphorus conditions were studied in column experiments using four types of plant-chips. When the phosphate-P concentration in the influent increased from 0.04mg/L to 0.4mg/L, the nitrate removal ratio increased from 61.6% to 86.1% in reed, from 7.2% to 12.6% in Japanese cedar, from 37.0% to 73.6% in Moso bamboo, and from 19.2% to 50.5% in Lithocarpus edulis. The carbon source of the denitrifiers' growth was indicated by the content of acid detergent soluble organic matter in the chips. Furthermore, according to the modified Michaelis-Menten-type equation proposed in the study, the denitrification rate was largely limited by the phosphate-P concentration in reed and L. eduilis, and by the dissolved organic carbon (DOC) in Japanese cedar. Denitrification in Moso bamboo was affected by both phosphate-P and DOC. Besides the DOC, phosphorus emerged as an important limiting element of denitrification in some bioreactor plant-chips.

Influence of Seasonal Pumping on Groundwater Sources and Flow System, Nagaoka Plain, Japan.

Intensive groundwater development in the urban area of the Nagaoka Plain, Japan, has induced changes in the pH and saturation index of calcite in groundwater. To account for these chemical changes, it is important to determine seasonal variations of recharge and the groundwater flow system in the aquifer. This study identified the sources and flow system of groundwater in this urban area by a comprehensive method using stable isotope data and a numerical groundwater model of the Nagaoka Plain. Stable isotope evidence shows that the groundwater is recharged by meteoric water originating from low-elevation areas rather than the mountains surrounding the plain. The water table in the study area is drawn down during the winter and recovers in the other seasons. Numerical modeling shows that discharge occurs primarily along the Shinano River during the recovery period, whereas discharge is centered in urbanized areas during the drawdown period, when a conical depression of the water table stimulates recharge from the immediate area. These results are indications of a local groundwater flow system, with its recharge area between the Shinano River and the urban areas, which is governed by intensive seasonal groundwater extraction.