Competitive adsorption of strontium and fulvic acid at the muscovite-solution interface observed with resonant anomalous X-ray reflectivity

Molecular-scale distributions of Sr²⁺ and fulvic acid (FA) adsorbed on the muscovite (0 0 1) surface were investigated using in situ specular X-ray reflectivity (XR) and resonant anomalous X-ray reflectivity (RAXR). The total amount of Sr²⁺ adsorbed from a 1 × 10⁻² mol/kg SrCl₂ and 100 mg/kg Elliott Soil Fulvic Acid II (ESFA II) solution at pH 5.5 compensated 81 ± 5% of the muscovite surface charge, less than previously measured (118 ± 5%) in an ESFA II-free solution with the same Sr concentration and pH. Inner-sphere (IS) and outer-sphere (OS) Sr²⁺ constituted 87% of the total adsorbed species in IS:OS proportions of 19:81 compared to 42:58 in the solution without FA, suggesting that adsorbed FA competes with the IS Sr²⁺ for surface sites. The coverage of both IS and OS Sr²⁺ decreased even more in a pH 3.5 solution containing the same concentration of FA and 0.5 × 10⁻² mol/kg Sr(NO₃)₂, whereas a significant amount of Sr²⁺ accumulated farther from the surface in the FA layer. The amount of Sr²⁺ incorporated in the ∼10 Å thick FA layer decreased by 79% with decreasing FA concentration (100 → 1 mg/kg) and increasing Sr²⁺ concentration (0.5 × 10⁻² → 1 × 10⁻² mol/kg) and pH (3.5 → 3.6). These results indicate not only that adsorbed FA molecules (and perhaps also H₃O⁺) displace Sr²⁺ near the muscovite surface, but also that the sorbed FA film provides binding sites for additional Sr²⁺ away from the surface. When a muscovite crystal pre-coated with FA after reaction in a 100 mg/kg ESFA II solution for 50 h was subsequently reacted with a 0.5 × 10⁻² mol/kg Sr(NO₃)₂ and 100 mg/kg ESFA II solution at pH 3.7, a significant fraction of Sr²⁺ was distributed in the outer part of the FA film similar to that observed on fresh muscovite reacted at pH 3.5 with a pre-mixed Sr-FA solution at the same concentrations. However, this Sr²⁺ sorbed in the pre-adsorbed organic film was more widely distributed and had a lower coverage, suggesting that pre-sorbed FA may undergo fractionation and/or conformational changes that diminish its capacity, and that of the muscovite (0 0 1) surface, for adsorbing the aqueous Sr cation.     

Effects of BPA and DES on longchin goby (Chasmichthys dolichognathus) in vitro during the oocyte maturation

This study was performed in order to assess whether bisphenol (BPA) and diethylstilbestrol (DES) had agonistic or antagonistic effects on oocyte maturation using marine fish. We tested the effects of these chemicals on in vitro maturation, germinal vesicle breakdown (GVBD), assay using oocytes from the longchin goby, Chasmichthys dolichognathus. During the maturation process, low concentrations of BPA and DES triggered GVBD depending on the stage of oocyte development; BPA at 0.044 nM and DES at 0.037, 0.37, and 3.73 nM induced GVBD in 0.82-0.88 mm diameter oocytes (germinal vesicle located near the center of oocytes). In 0.76-0.80 mm diameter oocytes (fully vitellogenic oocytes), BPA induced GVBD at relatively higher concentrations (4.38, 43.8, and 438 nM). In 0.86-0.90 mm diameter oocytes, BPA and DES had no observable effect on GVBD at the concentrations tested. Oocytes with diameters between 0.82 and 0.88 mm appeared to be more sensitive to these chemicals. Moreover, our results showed that BPA and DES did not inhibit GVBD.     

Impact of urbanization on recent temperature and precipitation trends in the Korean peninsula

Urbanization has a significant impact on climate in urban areas. In this study, we investigate urbanization impacts on temperature and precipitation trends in Korean peninsula based on statistical relationship between these trends and local population growth. We found that there is a significant positive correlation between temperature rise and local population growth, indicating that urbanization has a significant contribution to temperature increase in city climate. As for temperature, the population growth in Korean cities is positively correlated with precipitation trend. The positive correlation is higher during summer time when small-scale convective activity is dominant. Furthermore, it is demonstrated that the correlation is significantly increased when stations in rural areas and small cities are excluded. Such nonlinear relation between precipitation and urbanization is also discussed.     

Acetylthiocholine (ATC)--cleaving cholinesterase (ChE) activity as a potential biomarker of pesticide exposure in the Manila clam, Ruditapes philippinarum, of Korea

The acetylthiocholine (ATC) - cleaving cholinesterase (ChE) activity in Manila clam, which is widely distributed throughout the coastal environment of Korea, was assayed as a potentially useful biomarker of organophosphorous pesticides (OPs). A clear dose-response relationship was determined between inhibited ChE in adductor muscle of clams and four OPs (methidathion, chlorpyrifos, diazinon, IBP) which are heavily used OPs in Korea. The measured EC(50)-24?h values of methidathion, chlorpyrifos, diazinon, and IBP for Ruditapes philippinarum were 7.16?μg?l(-1), 0.34?mg?l(-1), 3.01?mg?l(-1), and 3.41?mg?l(-1), respectively. In field studies, ChE activity in Manila clams collected from 23 stations in the mid-western coastal region demonstrated spatial variation with statistical differences. These results suggest that ChE activity in R. philippinarum is a potential biomarker for assessing organophosphorous pesticide contamination in coastal environments.     

Natural frequency and damping ratio of a vertically vibrated surface foundation

It is possible and common to obtain equivalent natural frequency and damping for a soil-foundation system from results of experimental or numerical analysis assuming the system has a single degree of freedom. Three approaches to extract natural frequency and damping were applied to the vertically vibrated soil-foundation system. The sensitivity of the computed natural frequency and damping to the soil properties was evaluated through parametric studies. About 10–20% of discrepancy in values of natural frequency was observed due to different approaches. The results help to assess the reliability of equivalent soil properties determined from the reported natural frequency of the system. Finally the results obtained using theoretical predictions with linear soil properties measured in situ were compared to those calculated from experimental data. The prediction and experimental results showed good agreements if the embedment of the foundation is neglected with stepped sine test but considered with impulse test.     

Doppler Shifts of the Hα Line and the Ca ii 854.2 nm Line in a Quiet Region of the Sun Observed with the FISS/NST

The characteristics of Doppler shifts in a quiet region of the Sun are compared between the Hα line and the Ca?ii infrared line at 854.2 nm. A small area of 16″×40″ was observed for about half an hour with the Fast Imaging Solar Spectrograph (FISS) of the 1.6 meter New Solar Telescope (NST) at Big Bear Solar Observatory. The observed area contains a network region and an internetwork region, and identified in the network region are fibrils and bright points. We infer Doppler velocity v _m from each line profile at each individual point with the lambdameter method as a function of half wavelength separation Δλ. It is confirmed that the bisector of the spatially averaged Ca?ii line profile has an inverse C-shape with a significant peak redshift of +?1.8 km?s^?1. In contrast, the bisector of the spatially averaged Hα line profile has a C-shape with a small peak blueshift of ??0.5 km?s^?1. In both lines, the bisectors of bright network points are significantly redshifted not only at the line centers, but also at the wings. The Ca?ii Doppler shifts are found to be correlated with the Hα ones with the strongest correlation occurring in the internetwork region. Moreover, we find that here the Doppler shifts in the two lines are essentially in phase. We discuss the physical implications of our results in view of the formation of the Hα line and Ca?ii 854.2 nm line in the quiet region chromosphere.     

Evaluation of cloud and precipitation parameterization using a single-column model: A TWP-ICE case study

Cloud and precipitation parameterization schemes are evaluated, and their sensitivity to the method and/or parameters used to determine cloud physical processes is examined using a singlecolumn version of the Unified Model (SCUM). In the experiment for TWP-ICE, cloud fraction is overestimated (underestimated) in the upper (lower) troposphere due to the wet (dry) bias. The precipitation rate is well simulated during the active monsoon period, but overestimated during the suppressed monsoon and clear skies periods. In the moist convection scheme, trigger condition and entrainment process affect the lower tropospheric humidity through the impact on convective occurrence frequency and intensity, respectively. Strengthening the trigger condition and using the adaptive entrainment method alleviate the low-level dry bias. In the microphysics scheme, more large-scale precipitation is produced with prognostic rain, due to rain sedimentation considering vertical velocity of rain drop, than with diagnostic rain. Less ice/snow deposition with the prognostic two-ice category results in lower ice water content and upper-level cloud fraction than with the diagnostic splitting method for the twoice category. In the cloud macrophysics scheme, the prognostic cloud fraction and cloud/ice water content scheme produces a larger cloud fraction and more cloud/ice water content than the diagnostic scheme, mainly due to detrainment from moist convection (cloud source) that surpasses the effect of convective heating and drying (cloud sink). This affects temperature by influencing the radiative, convective, and microphysical processes. The experiment with combined modifications in cloud and precipitation schemes shows that interaction between modified moist convection and cloud macrophysics schemes results in more alleviation of the cold bias not only at the lower levels but also at the upper levels.     

Machine learning approaches to coastal water quality monitoring using GOCI satellite data

Since coastal waters are one of the most vulnerable marine systems to environmental pollution, it is very important to operationally monitor coastal water quality. This study attempts to estimate two major water quality indicators, chlorophyll-a (chl-a) and suspended particulate matter (SPM) concentrations, in coastal environments on the west coast of South Korea using Geostationary Ocean Color Imager (GOCI) satellite data. Three machine learning approaches including random forest, Cubist, and support vector regression (SVR) were evaluated for coastal water quality estimation. In situ measurements (63 samples) collected during four days in 2011 and 2012 were used as reference data. Due to the limited number of samples, leave-one-out cross validation (CV) was used to assess the performance of the water quality estimation models. Results show that SVR outperformed the other two machine learning approaches, yielding calibration R² of 0.91 and CV root-mean-squared-error (RMSE) of 1.74 mg/m³ (40.7%) for chl-a, and calibration R² of 0.98 and CV RMSE of 11.42 g/m³ (63.1%) for SPM when using GOCI-derived radiance data. Relative importance of the predictor variables was examined. When GOCI-derived radiance data were used, the ratio of band 2 to band 4 and bands 6 and 5 were the most influential input variables in predicting chl-a and SPM concentrations, respectively. Hourly available GOCI images were useful to discuss spatiotemporal distributions of the water quality parameters with tidal phases in the west coast of Korea.     

Effects of Lime‐Based Waste Materials on Immobilization and Phytoavailability of Cadmium and Lead in Contaminated Soil

Low cost lime‐based waste materials have recently been used to immobilize metals in contaminated soils. This study was conducted to evaluate the effects of oyster shells and eggshells as lime‐based waste materials on immobilization of cadmium (Cd) and lead (Pb) in contaminated soil, as well as their effects on metal availability to maize plants (Zea mays L.). Oyster shells and eggshells were applied to soils at 1 and 5% w/w, after which they were subject to 420 days of incubation. The toxicity characteristic leaching procedure (TCLP) test was employed to determine the mobility of Cd and Pb in soils. The results showed that the addition of waste materials effectively reduced the metal mobility as indicated by the decrease in the concentration of TCLP‐extractable Cd and Pb, and this was mainly due to significant increases in soil pH (from 6.74 in untreated soil to 7.85–8.13 in treated soil). A sequential extraction indicated that the addition of such alkaline wastes induced a significant decline in the concentration of Cd in the exchangeable fraction (from 23.64% in untreated soil to 1.90–3.81% in treated soil), but it increased the concentration of Cd in the carbonate fraction (from 19.59% in untreated soil to 36.66–46.36% in treated soil). In the case of Pb, the exchangeable fraction was also reduced (from 0.67% in untreated soil to 0.00–0.01% in treated soil), and the fraction of Pb bound to carbonate was slightly increased (from 16.61% in untreated soil to 16.41–18.25% in treated soil). Phytoavailability tests indicated that the metal concentrations in the shoots of maize plant were reduced by 63.39–77.29% for Cd and by 47.34–75.95% for Pb in the amended soils, with no significant differences being observed for the amendment types and the application rates. Overall, these results indicate that oyster shells and eggshells can be used as low cost lime‐based amendments for immobilizing Cd and Pb in contaminated soils.