The effects of heavy rain on the fate of urban and agricultural pollutants in the riverside area around weirs using multi-isotope, microbial data and numerical simulation.

The increase in extreme heavy rain due to climate change is a critical factor in the fate of urban and agricultural pollutants in aquatic system. Nutrients, including NO3- and PO43-, are transported with surface and seepage waters into rivers, lakes and aquifers and can eventually lead to algal blooms. δ15N-NO3-, δ18O-NO3-, and δ11B combined with hydrogeochemical and microbial data for groundwater and surface water samples were interpreted to evaluate the fate of nutrients in a riverside area around weirs in Daegu, South Korea. Most of the ions showed similar concentrations in the groundwater samples before and after heavy rain while concentrations of major ions in surface water samples were diluted after heavy rain. However, Si, PO43-, Zn, Ce, La, Pb, Cu and a number of waterborne pathogens increased in surface water after heavy rain. The interpretation of δ11B, δ15N-NO3-, and δ18O-NO3- values using a Bayesian mixing model revealed that sewage and synthetic fertilizers were the main sources of contaminants in the groundwater and surface water samples. δ18O and SiO2 interpreted using the Bayesian mixing model indicated that the groundwater component in the surface water increased from 4.4 % to 17.9 % during the wet season. This is consistent with numerical simulation results indicating that the direct surface runoff and the groundwater baseflow contributions to the river system had also increased 6.4 times during the wet season. The increase in proteobacteria and decrease of actinobacteria in the surface water samples after heavy rain were also consistent with an increase of surface runoff and an increased groundwater component in the surface water. This study suggests that source apportionment based on chemical and multi-isotope data combined with numerical modeling approaches can be useful for identifying main hydrological and geochemical processes in riverside areas around weirs and can inform suggestions of effective methods for water quality management.

Spatial investigation of water quality and estimation of groundwater pollution along the main stream in the Geum River Basin, Korea.

This study aims to identify spatially water quality distribution of groundwater and surface water in reservoirs, and comprehensively to address possible influencing factors. The concentration of NO3 in the reservoirs along the main stream of the Geum River was generally lower than that in groundwater. The pollution level of the reservoir, especially the particulate pollutant SS, clearly showed seasonal variations and increased significantly downstream. The H-3 concentration of the groundwater was high in the plains and low in the mountain areas, indicating a difference in residence time between the two regions. The hydrochemical properties and factor loading values of the principal components indicated that the major factors were water‒rock interactions and residence time, but a positive correlation of K-NO3 and Mg-Cl showed the influence of agricultural activities. The main groundwater pollutants were likely to be contributed by agricultural activities at upstream and seawater intrusion at downstream. The sensitive redox species uranium in the groundwater of this region existed as the uranyl ion, and it showed a positive correlation with HCO3, pH, and Ca. The results emphasize the importance of monitoring both tributaries and groundwater together in order to effectively manage the water quality of the Geum River basin.

National-scale investigation of dual nitrate isotopes and chloride ion in South Korea: Nitrate source apportionment for stream water.

Nitrate sources in surface water have been identified using dual-isotope compositions of nitrate with various tools to efficiently manage the water quality at the local scale. Correlation between Cl and NO3 has also been used to identify NO3. In this study, we assess the reliability of the dual-isotope approach and Cl in terms of nitrate source apportionment. To this end, we collected stream water samples throughout South Korea to estimate nitrate sources in streams and determine whether the land-use pattern was closely related to nitrate sources. The δ15N-NO3 ranging from -1.3 to 14.8‰ showed a spatial distribution that was lower in mountain ranges (<7‰) than plain areas (>8‰). The Cl concentration in this national-scale distribution was also assessed. The relationship between the proportion of Cl and δ15N-NO3 classifies nitrate sources into areas characterized by three land-use patterns: (1) agricultural and business areas, (2) forests in highlands, and (3) lowland forests, of which (1) had proportions of Cl >50%, while (2) and (3) were <50%. The samples in (3) showed δ15N-NO3 values > 6‰, similar to those of (1). Deuterium excess of samples was negatively correlated (R2 = 0.53) with δ15N-NO3, accounting for the fact that δ15N-NO3 reflected land-use patterns. Samples were dominantly affected by agriculture-derived sources and domestic sewage showed NO3/Cl of <0.4 and δ15N-NO3 of >6‰. These results suggest that nitrate source apportionment should be comprehensively evaluated considering the dual-isotope approach, land-use patterns, and Cl proportions.

Evaluating the sources and fate of nitrate in riparian aquifers under agricultural land using in situ-measured noble gases, stable isotopes, and metabolic genes.

Riparian zones with their buffering ability and abundant water supply are often subjected to intensive agricultural activities. We investigated a riparian aquifer located near a stream in South Korea that recently experienced sharply decreasing groundwater levels and elevated nitrate (NO3-) concentrations, which were attributed to local agricultural activities. Our goal was to identify the predominant nitrogen sources and NO3- removal processes. Multiple approaches including geochemical and isotopic tracers, land-use analysis, metabolic gene quantification, and inert gas tracers were used to elucidate groundwater and nutrient dynamics in stream-side granitic aquifers. The dual isotopic composition of NO3- identified manure and sewage as the major sources of NO3- contamination. Denitrification was the dominant NO3- removal process in the aquifer, as demonstrated by the negative relationship between δ15N and δ18O values in NO3-and NO3-/Cl-. Denitrification and anammox genes were also observed in microbial communities of the aquifer throughout the study site, suggesting that these processes support effective natural NO3- attenuation in groundwater. A mixing model constructed using a catchment-scale dataset including SiO2 concentrations and δ18O-H2O suggested that mixing with paddy soil water was the major driver of denitrification in the aquifer at the study site, where impervious layers provided anaerobic conditions for natural NO3- attenuation. Denitrification reduced the NO3- flux into the nearby stream by up to 114.4 NO3- kg/ha/y (26 kg N/ha/y). The N2 generated by denitrification did not accumulate in the groundwater, but mostly escaped from groundwater to the atmosphere, as demonstrated by the degassed signature of dissolved inert gases below the air saturated water level. This study identified the predominant NO3- sources and conceptualized N cycling in the heavily developed agricultural riparian aquifer using multiple tracers, demonstrating that NO3- is partially removed through denitrification and possibly anammox while N2 mostly escapes into the atmosphere.

Estimation of nutrient sources and fate in groundwater near a large weir-regulated river using multiple isotopes and microbial signatures.

The excessive input of nutrients into groundwater can accelerate eutrophication in associated surface water systems. This study combined hydrogeochemistry, multi isotope tracers, and microbiological data to estimate nutrient sources and the effects of groundwater-surface water interactions on the spatiotemporal variation of nutrients in groundwater connected to a large weir-regulated river in South Korea. δ11B and δ15N-NO3- values, in combination with a Bayesian mixing model, revealed that manure and sewage contributed 40 % and 25 % respectively to groundwater nitrate, and 42 % and 27 % to nitrate in surface water during the wet season. In the dry season, the source apportionment was similar for groundwater while the sewage contribution increased to 52 % of nitrate in river water. River water displayed a high correlation between NO3- concentration and cyanobacteria (Microcystis and Prochlorococcus) in the wet season. The mixing model using multiple isotopes indicated that manure-derived nutrients delivered with increased contributions of groundwater to the river during the wet season governed the occurrence of cyanobacterial blooms in the river. We postulate that the integrated approach using multi-isotopic and microbiological data is highly effective for evaluating nutrient sources and for delineating hydrological interactions between groundwater and surface water, as well as for investigating surface water quality including eutrophication in riverine and other surface water systems.

Analysis of Natural Organic Matter in Water from Cold and Hot Mineral Springs in South Korea Using 15T FT-ICR-MS.

The natural organic matter (NOM) properties in water from cold and hot mineral springs in South Korea are not well documented. We analyzed the characteristics of NOM in water from 25 cold and hot mineral springs located across South Korea. The NOM of each sample was concentrated using solid-phase extraction and analyzed using 15T Fourier-transform ion cyclotron resonance mass spectrometry. The origin of NOM was identified using van Krevelen diagrams. This study suggests that an analytical method to evaluate the characteristics of water in each region of South Korea can be established and used as a baseline for further research.

Spatial distributions of oxygen and hydrogen isotopes in multi-level groundwater across South Korea: A case study of mountainous regions.

This study presents the spatial distributions of stable isotopes for groundwater according to well depth and spring water across South Korea, using an interpolation model to provide baseline information for hydrological studies. In total, 888 groundwater and 108 spring water samples were collected across South Korea; their oxygen and hydrogen isotopic compositions (δ18O and δ2H) were analyzed. δ18O and δ2H values biased toward the summer local meteoric water line and low d-excess values indicate that summer precipitation is important for groundwater recharge. The δ18O and δ2H values for groundwater and spring water decrease progressively from the southwest to the northeast on the Korean Peninsula. Based on eight hydrological regions, the average δ18O values of groundwater and spring water are negatively correlated with latitude, but they are positively correlated with temperature. This result indicates that the spatial distributions of groundwater isotopic values in South Korea are significantly influenced by latitude and altitude effects associated with the movement of the North Pacific air mass in summer. Spring waters showed a negative correlation between δ18O and d-excess, with more depleted 18O values than groundwater, indicating that local recharge and flow within mountainous areas is dominant. Considering that the correlation in multi-level groundwater located in northern regions is similar to that of spring water, the contribution of regional groundwater flow, which is recharged in mountainous areas, is considered to be higher in the northern regions. The spatial distribution of δ18O in groundwater gradually approached the spatial distribution of spring water with increasing well depth, indicating that the contribution of regional groundwater flow may be greater in deep groundwater. Our results provide estimates for data-poor regions, supporting the investigation of links between groundwater and other hydrological factors.

Exposure of Metal Oxide Nanoparticles on the Bioluminescence Process of Pu- and Pm-lux Recombinant P. putida mt-2 Strains.

Comparison of the effects of metal oxide nanoparticles (NPs; CuO, NiO, ZnO, TiO2, and Al2O3) on different bioluminescence processes was evaluated using two recombinant (Pm-lux and Pu-lux) strains of Pseudomonas putida mt-2 with same inducer exposure. Different sensitivities and responses were observed according to the type of NPs and recombinant strains. EC50 values were determined. The negative effects on the bioluminescence activity of the Pm-lux strain was greater than for the Pu-lux strains for all NPs tested. EC50 values for the Pm-lux strain were 1.7- to 6.2-fold lower (corresponding to high inhibition) than for Pu-lux. ZnO NP caused the greatest inhibition among the tested NPs in both strains, showing approximately 11 times less EC50s of CuO, which appeared as the least inhibited. Although NPs showed different sensitivities depending on the bioluminescence process, similar orders of EC50s for both strains were observed as follows: ZnO > NiO, Al2O3 > TiO2 > CuO. More detailed in-depth systematic approaches, including in the field of molecular mechanisms, is needed to evaluate the accurate effect mechanisms involved in both bioluminescence metabolic processes.

Review on Applications of 17O in Hydrological Cycle.

The triple oxygen isotopes (16O, 17O, and 18O) are very useful in hydrological and climatological studies because of their sensitivity to environmental conditions. This review presents an overview of the published literature on the potential applications of 17O in hydrological studies. Dual-inlet isotope ratio mass spectrometry and laser absorption spectroscopy have been used to measure 17O, which provides information on atmospheric conditions at the moisture source and isotopic fractionations during transport and deposition processes. The variations of δ17O from the developed global meteoric water line, with a slope of 0.528, indicate the importance of regional or local effects on the 17O distribution. In polar regions, factors such as the supersaturation effect, intrusion of stratospheric vapor, post-depositional processes (local moisture recycling through sublimation), regional circulation patterns, sea ice concentration and local meteorological conditions determine the distribution of 17O-excess. Numerous studies have used these isotopes to detect the changes in the moisture source, mixing of different water vapor, evaporative loss in dry regions, re-evaporation of rain drops during warm precipitation and convective storms in low and mid-latitude waters. Owing to the large variation of the spatial scale of hydrological processes with their extent (i.e., whether the processes are local or regional), more studies based on isotopic composition of surface and subsurface water, convective precipitation, and water vapor, are required. In particular, in situ measurements are important for accurate simulations of atmospheric hydrological cycles by isotope-enabled general circulation models.

Comparisons of the Effect of Different Metal Oxide Nanoparticles on the Root and Shoot Growth under Shaking and Non-Shaking Incubation, Different Plants, and Binary Mixture Conditions.

We evaluated the toxicity of five metal oxide nanoparticles (NPs) in single or binary mixtures based on root and shoot growth of two plant species under non-shaking and shaking conditions. The effects of NPs on root and shoot growth differed depending on the NP type, incubation condition, and plant type. The half maximal effective concentration (EC50) of NPs based on root growth were significantly lower, by 2.6-9.8 times, under shaking than non-shaking conditions (p = 0.0138). The magnitude of the effects of NPs followed the order CuO > ZnO > NiO >> Al2O3, TiO2. In addition, Lactuca sativa L. was more sensitive to the tested NPs than Raphanus sativus L., with an EC50 0.2-0.7 times lower (p = 0.0267). The observed effects of 12 combinations of binary NP mixtures were slightly, albeit non-significantly, lower than expected, indicative of an additive effect of the individual NPs in the mixtures. The results emphasize the importance of careful plant model selection, appropriate application of incubation conditions, and consideration of chemical mixtures rather than single compounds when evaluating the effects of metal oxide NPs.

Evaluation of the Effects of Particle Sizes of Silver Nanoparticles on Various Biological Systems.

Seven biological methods were adopted (three bacterial activities of bioluminescence, enzyme, enzyme biosynthetic, algal growth, seed germination, and root and shoot growth) to compare the toxic effects of two different sizes of silver nanoparticles (AgNPs). AgNPs showed a different sensitivity in each bioassay. Overall, the order of inhibitory effects was roughly observed as follows; bacterial bioluminescence activity ≈ root growth > biosynthetic activity of enzymes ≈ algal growth > seed germination ≈ enzymatic activity > shoot growth. For all bacterial activities (bioluminescence, enzyme, and enzyme biosynthesis), the small AgNPs showed statistically significantly higher toxicity than the large ones (p < 0.0036), while no significant differences were observed among other biological activities. The overall effects on the biological activities (except shoot growth) of the small AgNPs were shown to have about 4.3 times lower EC50 (high toxicity) value than the large AgNPs. These results also indicated that the bacterial bioluminescence activity appeared to be an appropriate method among the tested ones in terms of both sensitivity and the discernment of particle sizes of AgNPs.

Comparative Effects of Particle Sizes of Cobalt Nanoparticles to Nine Biological Activities.

The differences in the toxicity of cobalt oxide nanoparticles (Co-NPs) of two different sizes were evaluated in the contexts of the activities of bacterial bioluminescence, xyl-lux gene, enzyme function and biosynthesis of ß-galactosidase, bacterial gene mutation, algal growth, and plant seed germination and root/shoot growth. Each size of Co-NP exhibited a different level of toxicity (sensitivity) in each biological activity. No revertant mutagenic ratio (greater than 2.0) of Salmonella typhimurium TA 98 was observed under the test conditions in the case of gene-mutation experiments. Overall, the inhibitory effects on all five bacterial bioassays were greater than those on algal growth, seed germination, and root growth. However, in all cases, the small Co-NPs showed statistically greater (total average about two times) toxicity than the large Co-NPs, except in shoot growth, which showed no observable inhibition. These findings demonstrate that particle size may be an important physical factor determining the fate of Co-NPs in the environment. Moreover, combinations of results based on various biological activities and physicochemical properties, rather than only a single activity and property, would better facilitate accurate assessment of NPs' toxicity in ecosystems.

Oxidation and reduction of redox-sensitive elements in the presence of humic substances in subsurface environments: A review.

The oxidation and reduction (redox) processes of redox-sensitive elements (RSE) in the presence of humic substances (HS) have become a significantly important issue in the terms of biogeochemical cycles. Redox processes are crucial for determining the speciation, mobility, toxicity, and bioavailability of RSE in natural environments. It is known that HS act as an effective redox mediator for accepting and donating electrons, and thereby transfers them to RSE. We review the recent progress in the field of the redox processes of RSE including As, Cr, Cu, Fe, Hg, and Se in the presence of HS. The extent and rate of the redox processes of these RSE are significantly affected by the concentration of functional groups and the chemical composition of HS. In subsurface environments, pH, ionic strength, and the presence of competitive components, microorganisms, and oxygen need to be considered to elucidate the redox processes of RSE in the presence of HS. In addition, improved analytical techniques for the characterization of HS has the potential to advance the study on the redox processes of RSE in the presence of HS. It may contribute to understanding the mechanism for the redox processes between RSE and HS in the biogeochemical cycles.

Toxicity Evaluation of Individual and Mixtures of Nanoparticles Based on Algal Chlorophyll Content and Cell Count.

The toxic effects of individual and binary mixtures of five metal oxide nanoparticles (NPs) were evaluated based on changes in two endpoints of algal growth: the cell count and chlorophyll content. Various effects were observed according to the concentration tested and type of NPs, and there were no significant differences in findings for the two endpoints. In general, ZnO NPs caused the greatest inhibition of algal growth, and Fe2O3 NPs the least. The EC50 for ZnO was 2.0 mg/L for the cell count and 2.6 mg/L for the chlorophyll content, and it was 76 and 90 mg/L, respectively, for Fe2O3. The EC50 values were in the order ZnO > NiO > CuO > TiO2 > Fe2O3. Subsequently, the effects of 30 binary mixture combinations on the chlorophyll content were evaluated. Comparisons were made between the observed and the expected toxicities calculated based on the individual NP toxicities. Overall, additive action (67%) was mainly observed, followed by antagonistic (16.5%) and synergistic (16.5%) actions. These results suggest that environmental exposure to NP mixtures may cause toxicity levels similar to the sum of those of the constituent NPs.

Evaluation of the Effects of Nanoparticle Mixtures on Brassica Seed Germination and Bacterial Bioluminescence Activity Based on the Theory of Probability.

Effects of binary mixtures of six metal oxide nanoparticles (NPs; 54 combinations) on the activities of seed germination and bacterial bioluminescence were investigated using the theory of probability. The observed toxicities of various NPs combinations were compared with the theoretically expected toxicities, calculated based on individual NPs toxicities. Different sensitivities were observed depending on the concentrations and the types of NPs. The synergistic mode (67%; observed toxicity greater than expected toxicity) was predominantly observed in the bioluminescence test, whereas both synergistic (47%) and additive (50%) modes were prevalent in the activity of seed germination. With regard to overall analysis, a slightly high percentage (56%) of the synergistic mode of action was (30 out of 54 binary mixture combinations; p < 0.0392) observed. These results suggest that the exposure of an NPs mixture in the environment may lead to a similar or higher toxicity level than the sum of its constituent NPs would suggest. In addition, one organism for assessment did not always show same results as those from a different assessment. Therefore, combining results of different organisms exposed to a wide range of concentrations of binary mixture will more properly predict and evaluate the expected ecotoxicity of pollutants on environments.

Hydrologic Controls on Nitrogen Cycling Processes and Functional Gene Abundance in Sediments of a Groundwater Flow-Through Lake.

The fate and transport of inorganic nitrogen (N) is a critically important issue for human and aquatic ecosystem health because discharging N-contaminated groundwater can foul drinking water and cause algal blooms. Factors controlling N-processing were examined in sediments at three sites with contrasting hydrologic regimes at a lake on Cape Cod, MA. These factors included water chemistry, seepage rates and direction of groundwater flow, and the abundance and potential rates of activity of N-cycling microbial communities. Genes coding for denitrification, anaerobic ammonium oxidation (anammox), and nitrification were identified at all sites regardless of flow direction or groundwater dissolved oxygen concentrations. Flow direction was, however, a controlling factor in the potential for N-attenuation via denitrification in the sediments. Potential rates of denitrification varied from 6 to 4500 pmol N/g/h from the inflow to the outflow side of the lake, owing to fundamental differences in the supply of labile organic matter. The results of laboratory incubations suggested that when anoxia and limiting labile organic matter prevailed, the potential existed for concomitant anammox and denitrification. Where oxic lake water was downwelling, potential rates of nitrification at shallow depths were substantial (1640 pmol N/g/h). Rates of anammox, denitrification, and nitrification may be linked to rates of organic N-mineralization, serving to increase N-mobility and transport downgradient.

Molecular analysis of spatial variation of iron-reducing bacteria in riverine alluvial aquifers of the Mankyeong River.

Alluvial aquifers are one of the mainwater resources in many countries. Iron reduction in alluvial aquifers is often a major anaerobic process involved in bioremediation or causing problems, including the release of As trapped in Fe(III) oxide. We investigated the distribution of potential iron-reducing bacteria (IRB) in riverine alluvial aquifers (B1, B3, and B6 sites) at the Mankyeong River, Republic of Korea. Inactive iron reduction zones, the diversity and abundance of IRB can be examined using a clone library and quantitative PCR analysis of 16S rRNA genes. Geobacter spp. are potential IRB in the iron-reducing zone at the B6 (9 m) site, where high Fe(II) and arsenic (As) concentrations were observed. At the B3 (16 m) site, where low iron reduction activity was predicted, a dominant clone (10.6%) was 99% identical in 16S rRNA gene sequence with Rhodoferax ferrireducens. Although a major clone belonging to Clostridium spp. was found, possible IRB candidates could not be unambiguously determined at the B1 (18 m) site. Acanonical correspondence analysis demonstrated that, among potential IRB, only the Geobacteraceae were well correlated with Fe(II) and As concentrations. Our results indicate high environmental heterogeneity, and thus high spatial variability, in thedistribution of potential IRB in the riverine alluvial aquifersnear the Mankyeong River.

Land-use controls on sources and fate of nitrate in shallow groundwater of an agricultural area revealed by multiple environmental tracers.

Sources and transformation processes of nitrate in groundwater from shallow aquifers were investigated in an agricultural area in the mid-western part of South Korea using a multi-tracer approach including δ²H and δ¹8O values of water, δ¹5N and δ¹8O values of nitrate, Cl/Br ratios and chlorofluorocarbons (CFCs). The study area was comprised of four land-use types with natural areas at higher altitudes, upland areas with fruit orchards, paddy fields and residential areas at lower elevations. The isotopic composition of water was suitable for distinguishing groundwater that had infiltrated in the higher elevation natural areas with lower δ²H and δ¹8O values from groundwater underneath paddy fields that was characterized by elevated δ²H and δ¹8O values due to evaporation. δ¹8O-H2O values and Cl⁻ concentrations indicated that groundwater and contaminant sources were derived from three land-use types: natural areas, residential areas and paddy fields. Groundwater age determination based on CFCs showed that nitrate contamination of groundwater is primarily controlled by historic nitrogen loadings at least in areas with higher nitrate contamination. Nitrate sources were identified using the stable isotope composition of nitrate and Cl/Br ratios. Higher δ¹5N-NO3⁻ values and Cl/Br ratios of 300 to 800 in residential areas indicated that waste water and septic effluents were major nitrate sources whereas lower δ¹5N-NO3⁻ values and Cl/Br ratios of 100 to 700 in upland areas suggested that synthetic fertilizers constituted a major source of nitrate contamination of aquifers. With only few exceptions in the natural area, contributions of atmospheric nitrate were insignificant due to the resetting of δ¹8O-NO3⁻ values via immobilization and re-mineralization of nitrate in the soil zone. In groundwater underneath paddy fields, 30% of samples had δ¹8O-NO3⁻ values at least 2‰ higher than expected for nitrate formed by chemolithoautotrophic nitrification; these samples were also characterized by low DO and NO3-N concentrations and elevated Cl and Mn concentrations indicating anthropogenic contamination and denitrification in the aquifer. These conditions were observed primarily in aquifers on floodplains. Statistical comparison between land-use groups revealed that Cl/Br ratios were more diagnostic for the impact of different land-use types on groundwater quality than stable isotope compositions of nitrate. This indicates that the former is an additional efficient tracer for the effect of land use on groundwater quality in agricultural areas. We conclude that the combination of groundwater age dating together with the use of chemical and isotopic parameters is a highly effective but yet underutilized approach for elucidating the sources and the fate of nitrate in aquifers in Asia.