Characterization of binding site heterogeneity for copper within dissolved organic matter fractions using two-dimensional correlation fluorescence spectroscopy

The heterogeneity of copper binding characteristics for dissolved organic matter (DOM) fractions was investigated based on the fluorescence quenching of the synchronous fluorescence spectra upon the addition of copper and two-dimensional correlation spectroscopy (2D-COS). Hydrophobic acid (HoA) and hydrophilic (Hi) fractions of two different DOM (algal and leaf litter DOM) were used for this study. For both DOM, fluorescence quenching occurred at a wider range of wavelengths for the HoA fractions compared to the Hi fractions. The combined information of the synchronous and asynchronous maps derived from 2D-COS provided a clear picture of the heterogeneous distribution of the copper binding sites within each DOM fraction, which was not readily recognized by a simple comparison of the changes in the synchronous fluorescence spectra upon the addition of copper. For the algal DOM, higher stability constants were exhibited for the HoA versus the Hi fractions. The logarithms of the stability constants ranged from 4.8 to 6.1 and from 4.5 to 5.0 for the HoA and the Hi fractions of the algal DOM, respectively, depending on the associated wavelength and the fitted models. In contrast, no distinctive difference in the binding characteristics was found between the two fractions of the leaf litter DOM. This suggests that influences of the structural and chemical properties of DOM on copper binding may differ for DOM from different sources. The relative difference of the calculated stability constants within the DOM fractions were consistent with the sequential orders interpreted from the asynchronous 2D-COS. It is expected that 2D-COS will be widely applied to other DOM studies requiring detailed information on the heterogeneous nature and subsequent effects under a range of environmental conditions.     

Spatial variability in chromophoric dissolved organic matter for an artificial coastal lake (Shiwha) and the upstream catchments at two different seasons

Selected water quality parameters and spectroscopic characteristics of dissolved organic matter (DOM) were examined during two different seasons for an artificial coastal lake (Shiwha Lake in South Korea), which are affected by seawater exchange due to the operation of a tidal power plant and external organic loadings from the upstream catchments. The coastal lake exhibited much lower concentrations of organic matter and nutrients than the upstream sources. The spectroscopic properties of the lake DOM were easily distinguished from those of the catchment sources as revealed by a lower absorption coefficient, lower degree of humification, and higher spectral slopes. The observed DOM properties suggest that the lake DOM may be dominated by smaller molecular size and less condensed structures. For the lake and the upper streams, higher absorption coefficients and fluorescence peak intensities but lower spectral slopes and humification index were found for the premonsoon versus the monsoon season. However, such seasonal differences were less pronounced for the industrial channels in the upper catchments. Three distinctive fluorophore groups including microbial humic-like, tryptophan-like, and terrestrial humic-like fluorescence were decomposed from the fluorescence excitation-emission matrix (EEM) of the DOM samples by parallel factor analysis (PARAFAC) modeling. The microbial humic-like component was the most abundant for the industrial channels, suggesting that the component may be associated with anthropogenic organic pollution. The terrestrial humic-like component was predominant for the upper streams, and its relative abundance was higher for the rainy season. Our principal component analysis (PCA) results demonstrated that exchange of seawater and seasonally variable input of allochthonous DOM plays important roles in determining the characteristics of DOM in the lake.     

Effects of organic ligands and pH on the leaching of copper from brake wear debris in model environmental solutions

Copper leaching from a disc brake wear debris sample was examined in a variety of aqueous solutions to simulate potential leaching processes during rain events and in surface waters. Synthetic rainwater leached 40% of the total copper present in the brake wear debris into solution after 18 h in batch reactors, which was approximately three times more copper than that extracted by the US Environmental Protection Agency's Synthetic Precipitation Leaching Procedure. Formate and acetate were responsible for the enhanced copper leaching, as demonstrated by higher average amounts of leached copper in synthetic rainwater with- versus without the organic acids (40 versus 31% recovery). This observation suggests leaching tests that do not incorporate the appropriate types and concentrations of organic ligands present in rainwater will likely underestimate copper mobilization from brake wear debris during rain events. Leaching of copper from the brake wear debris ranged from 23 to 40% in solutions containing 3 to 15 mg C L(-1) dissolved humic substances, and was higher still in solutions containing relatively high concentrations of the synthetic metal chelating agent ethylenediaminetetraacetic acid. Static pH tests demonstrated that copper leaching from brake wear debris is highly pH dependent, with more leaching occurring at lower solution pH values. Leaching rate studies revealed that equilibrium generally was not attained within 48 h in the model solutions, indicating that additional copper can be expected to be released in environments where brake wear debris is exposed to long-term leaching processes.     

Mortality rates of pathogen indicator microorganisms discharged from point and non-point sources in an urban area

This research measured the mortality rates of pathogen indicator microorganisms discharged from various point and non-point sources in an urban area.Water samples were collected from a domestic sewer,a combined sewer overflow,the effluent of a wastewater treatment plant,and an urban river.Mortality rates of indicator microorganisms in sediment of an urban river were also measured.Mortality rates of indicator microorganisms in domestic sewage,estimated by assuming first order kinetics at 20°C were 0.197 day -1 ,0.234 day -1 ,0.258 day -1 and 0.276 day -1 for total coliform,fecal coliform,Escherichia coli,and fecal streptococci,respectively.Effects of temperature,sunlight irradiation and settlement on the mortality rate were measured.Results of this research can be used as input data for water quality modeling or can be used as design factors for treatment facilities.     

Salinity intrusion characteristics analysis using EFDC model in the downstream of Geum River

As social interest in the environmental conservation and ecological restoration has recently increased, more research works have been done to resolve problems concerning environmental management of estuaries. In this study, a three-dimensional numerical model, Environmental Fluid Dynamics Code (EFDC) was used in the analysis of the salinity intrusion characteristics in the downstream of Geum River. The numerical simulation was performed to investigate the influence range for salinity intrusion when the gates were fully opened. The conditions used for simulation were the four flow regimes in Geum River Basin, Korea. Results indicated that the ranges of salinity intrusion from the barrage were 50.72 km (drought flow), 48.87 km (low flow), 46.56 km (normal flow) and 42.10 km (flood flow). These results indicated that the EFDC model used for numerical simulation has high accuracy. The result concluded in this study can be used as a basis in understanding the extent of salinity intrusion e ects at di erent flow rates.     

Influence of soil conditions on dissolved organic matter leached from forest and wetland soils: a controlled growth chamber study

This study investigated the effects of various soil conditions, including drying-rewetting, nitrogen deposition, and temperature rise, on the quantities and the composition of dissolved organic matter leached from forest and wetland soils. A set of forest and wetland soils with and without the nitrogen deposition were incubated in the growth chambers under three different temperatures. The moisture contents were kept constant, except for two-week drying intervals. Comparisons between the original and the treated samples revealed that drying-rewetting was a crucial environmental factor driving changes in the amount of dissolved organic carbon (DOC). The DOC was also notably increased by the nitrogen deposition to the dry forest soil and was affected by the temperature of the dry wetland soil. A parallel factor (PARAFAC) analysis identified three sub-fractions of the fluorescent dissolved organic matter (FDOM) from the fluorescence excitation–emission matrices (EEMs), and their compositions depended on drying-rewetting. The data as a whole, including the DOC and PARAFAC components and other optical indices, were possibly explained by the two main variables, which were closely related with the PARAFAC components and DOC based on principal component analysis (PCA). Our results suggested that the DOC and PARAFAC component information could provide a comprehensive interpretation of the changes in the soil-leached DOM in response to the different environmental conditions.     

From manager's emotional intelligence to objective store performance: Through store cohesiveness and sales‐directed employee behavior

The relationships among manager's emotional intelligence, store cohesiveness, sales‐directed employee behavior, and objective store performance were investigated. Non‐managerial sales employees of a large retail electronics chain in South Korea (N = 1611) rated the emotional intelligence of their own store managers as well as the group cohesiveness within their stores. Store managers (N = 253) separately rated the sales‐directed behavior of their employees. Objective sales data were collected one month later for each store. No direct relationship between manager emotional intelligence and objective store performance was found. Instead, the results supported the hypothesized four‐variable, three‐path mediation model: store manager's emotional intelligence was related to store cohesiveness, which in turn was related to the sales‐directed behavior of the frontline employees, which ultimately predicted the objective performance of the stores. Manager emotional intelligence and store cohesiveness are seen as intangible organizing resources or socio‐psychological capital for non‐managerial store employees. Implications for future research and more effective management of retail firms are discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

Enhancing the total organic carbon measurement efficiency for water samples containing suspended solids using alkaline and ultrasonic pretreatment methods

In this study,we investigated the effect of sample pretreatments(ultrasonication and alkaline extraction) on total organic carbon(TOC) measurements for water samples containing suspended solids(SS) of four different origins(algae,soil,sewage sludge,and leaf litter) to more clearly assess the impact of particulate organic carbon(POC) in water.The effects each of ultrasonication(power,pulse,etc.) and alkaline extraction condition(concentration,time,etc.) on the TOC recovery and precision were inve...     

Copper leaching from brake wear debris in standard extraction solutions

Quantification of the copper content of and copper leaching from a disc brake wear debris sample was performed using microwave-assisted acid digestion, the Federal Toxicity Characteristic Leaching Procedure (TCLP), and the State of California Waste Extraction Test (WET). The brake wear debris tested was a composite sample obtained from a brake dynamometer test of one brake pad source material. Comparative digestion studies demonstrated that a modified aqua regia matrix (HNO3:HCl:H2O2 = 1:3:0.5) optimized the digestion effectiveness for determining the total copper content in the brake wear debris. No significant sample heterogeneity within the brake wear debris was observed, based on statistically indistinguishable total copper content results for subsamples with a wide range of sample masses. Upon pooling all subsample results, an overall total copper content for the composite brake wear debris sample was determined to be 10.8% (g/g), with a 95% confidence limit of +/- 0.5% (g/g). Copper leaching increased with decreasing solid-to-liquid ratios in TCLP tests, but was unaffected by the solid-to-liquid ratio in the WET. For a 1:10(4) (g/g) solid-to-liquid ratio, 85% and 99% of the total mass of copper present in the composite brake wear debris sample was leached into solution during the TCLP and WET, respectively. Rate studies also demonstrated that the WET resulted in a faster rate and higher extent of copper leaching relative to the TCLP. Compared to reference copper-containing materials, the composite brake wear debris sample exhibited relatively higher TCLP and WET copper leaching characteristics. The higher copper leaching exhibited by the brake wear debris sample may have resulted from its higher specific surface area and/or from changes in the chemical form of copper that occurred during the braking process.     

The effects of soil properties on the turbidity of catchment soils from the Yongdam dam basin in Korea

Environmental concerns have been raised that suspended solids in turbid water adversely affect human health, and that their removal increases in the cost of water treatment. The Yongdam dam reservoir, located in the southwestern region of Korea, is severely affected by inflowing turbid water after storms. In this study, soil samples were collected from 37 sites in the Yongdam upstream basin to investigate mineralogical and environmental factors associated with the turbidity potential of soils in water environments. Turbidity potential was estimated by measuring the turbidity of soil-suspension solutions after settling for 24 h. The mineralogy of the soils was dominated by four minerals—quartz, microcline, albite, and muscovite—with lesser amounts of hornblende, chlorite, kaolinite, illite, and mixed layer illite. The quartz content was the most variable of the soil mineralogy among the collected samples. Principal-components analysis (PCA) was used to examine relationships between turbidity potential and other soil properties. The variables considered in the PCA included turbidity potential, quartz content, albite content, mean size of soil particles, clay content, clay mineral content, zeta potential, conductivity, and pH of the soil-suspension solution. The first two components of the PCA explained 52% of the overall variation of the selected variables. The first component was possibly explained by physical properties such as the size of the soil particles; the second was correlated with chemical properties of the soils, for example dissolution and extent of weathering. Closer examination of the PCA results revealed that the quartz content of the soils was negatively correlated with their turbidity potential. A linear correlation (r = 0.63) was obtained between measured turbidity potential and that predicted using multiple regression analysis based on the content of clay-sized particles, clay minerals, and quartz, and the conductivity of the soil-suspension solution.