Removal of mixed contaminants by Fe0-based biobarrier in flow-through columns using recycled waste materials

The present study investigated the reactivity and ability of permeable reactive barriers [zero-valent iron (ZVI)-barrier plus biobarrier) to remove various contaminants (Cd, As, Zn, Cu, Mn, Cr, NO₃ ⁻, NH₄ ⁺, and COD_cr) from synthetic leachate. Two different reactive materials were used in this study, namely ZVI and autoclaved lightweight concrete (ALC). After 90 days of column operation, the contaminant profiles were determined along the length of the columns. The heavy metals were extensively removed in the bio-ALC and sequential barriers (ZVI plus bio-ALC), however the removal efficiencies for the heavy metals Zn and Cr in the ALC and bio-ALC barriers were comparatively low. Nitrate was completely removed (>99.9%) in the ALC, bio-ALC, and sequential barriers. More than 50% of the produced ammonium and organic materials were removed in the biologically reactive zone of the sequential barriers. The results of the present study suggest that sequential barriers are one of the best solutions for in situ remediation and that they can be applied to clean up the leachate released from landfills.     

Estimating bulk optical properties of aerosols over the western North Pacific by using MODIS and CERES measurements

Over the western North Pacific, a large amount of land aerosols from Asian-Pacific countries is transported by the prevailing westerlies. This transport makes the radiative characteristics of these aerosols diverse, particularly when one compares those characteristics over the coastal sea with those over the open sea. In this paper we discuss a method that uses satellite data to obtain the single-scattering albedo (ω) and asymmetry factor (g) of atmospheric aerosols for two large-scale subdivisions—the coastal sea (within 250 km from the coast) and the open sea (the remaining area)—over the western North Pacific (110°E–180°, 20°N–50°N). Our estimation method uses satellite measurements, obtained over a six-year period (2000–2005), of aerosol optical depth (AOD) and shortwave fluxes at both the surface and the top of the atmosphere (TOA); the measurements are obtained using the Moderate Resolution Imaging Spectroradiometer (MODIS) and the Clouds and the Earth's Radiant Energy System (CERES). For the two subdivisions, the estimated annual means of (ω,g) at 630 nm are significantly different: (0.94, 0.65) over the coastal sea and (0.97, 0.70) over the open sea. From a quantitative viewpoint, this result indicates that in comparison with aerosols over the open sea, those over the coastal sea show greater absorption and lesser forward scattering of solar radiation. The estimated optical properties are responsible for the aerosol surface cooling observed by MODIS and CERES, which is approximately 138 and 108 W m⁻² per AOD over the coastal sea and open sea, respectively.     

Monitoring of PBDEs concentration in umbilical cord blood and breast milk from Korean population and estimating the effects of various parameters on accumulation in humans

In this study, we investigated concentration, congener distribution pattern, and effects of potential environmental factors that affect PBDE accumulation. We also estimated correlation between PBDE concentration and health status or thyroid function by analyzing 90 cord blood and 21 breast milk samples obtained from Korean population. Seven from tri- to hepta-BDEs were analyzed by solid phase extraction-high-resolution gas chromatography/high-resolution mass spectrometry (SPE-HRGC/HRMS). The total concentration of 7 PBDEs in cord blood was 2.786-94.64 ng g(-1) lipid and that in breast milk was 1.076-8.664 ng g(-1) lipid. Tetra-BDE (#47) was the predominant type of PBDE and was present at concentrations of over 40% in both sample types. A weak correlation was observed between the concentration of BDE28 and 153 and thyroid hormone concentration only in the breast milk samples. In children, a weak negative correlation was observed between free thyroxine (FT4) concentration and BDE28 concentration (0.302, p<0.05), while in mothers, a weak positive correlation was observed between thyroid hormone concentration and BDE153 concentration (0.403, p<0.05). No significant correlations between PBDE concentration and work and residential environments were found in this study, but a weak correlation between BDE concentration in cord blood and potential PBDE sources was confirmed by investigating the frequency of oil paint usage (0.510, p<0.001). A weak correlation was also found between PBDE concentration in breast milk during pregnancy and dietary habits such as green tea drinking (0.541, p=0.025) and Trichiuridae intake (0.565, p=0.015).     

Modeling uptake kinetics of cadmium by field-grown lettuce

Cadmium uptake by field grown Romaine lettuce treated with P-fertilizers of different Cd levels was investigated over an entire growing season. Results indicated that the rate of Cd uptake at a given time of the season can be satisfactorily described by the Michaelis-Menten kinetics, that is, plant uptake increases as the Cd concentration in soil solution increases, and it gradually approaches a saturation level. However, the rate constant of the Michaelis-Menten kinetics changes over the growing season. Under a given soil Cd level, the cadmium content in plant tissue decreases exponentially with time. To account for the dynamic nature of Cd uptake, a kinetic model integrating the time factor was developed to simulate Cd plant uptake over the growing season: C Plant=C Solution.PUF max.exp[-b.t], where C Plant and C Solution refer to the Cd content in plant tissue and soil solution, respectively, PUF max and b are kinetic constants.     

Aquatic toxicity of cartap and cypermethrin to different life stages of Daphnia magna and Oryzias latipes

Cartap and cypermethrin, which are among the most widely used pesticides in many countries, are considered safe because of their low mammalian toxicity and their low persistence in the environment. However, recent findings of endocrine-disrupting effects and developmental neurotoxicity have raised concerns about the potential ecological impacts of these pesticides. We evaluated the aquatic toxicity of cartap [S,S'-(2-dimethylaminotrimethylene) bis(thiocarbamate), unspecified hydrochloride] and cypermethrin [(RS)-alpha-cyano-3-phenoxybenzyl-(1RS,3RS,1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylate], both individually and combined, on different life stages of the freshwater cladoceran Daphnia magna and a freshwater teleost, Japanese medaka (Oryzias latipes). The 96-hr Daphnia median effective concentrations (EC50s) for cartap and cypermethrin were 91.0 microg/L and 0.00061 microg/L, respectively. Rapid recovery of Daphnia was observed after short-term pulsed exposure to cartap and cypermethrin; there were no adverse effects on reproduction or survival 20 d after a 24 hr exposure to cartap up to 1240 microg/L and cypermethrin up to 1.9 microg/L. Chronic continuous exposure (for 21 d) of 7-d-old Daphnia to cypermethrin significantly reduced the intrinsic population growth rate in a concentration-dependent manner. However, because the intrinsic population growth rates were all above zero, populations did not decrease even at the highest experimental concentration of 200 ng/L. Exposure of Daphnia neonates (< 24 hr old) to cypermethrin for 21 d caused significant, sub-lethal reproduction-related problems, such as increased time to first brood, reduced brood size, and reduced total brood number, at 0.0002, 0.002, and 0.2 ng/L cypermethrin, but the intrinsic population growth rate was not significantly affected. Oryzias latipes was relatively more resistant to both pesticides. In particular, embryos appeared to be more resistant than juveniles or adults, which may be partly due to the protective role of the chorion. The incidence of larval fish deformity was significantly higher after a 96 hr exposure to as low as 250 microg/L of cartap or 40 microg/L of cypermethrin. The mixture of both compounds showed no synergistic toxicity. The extremely high acute-to-chronic ratio suggests that the standard acute lethal toxicity assessment might not reflect the true environmental hazards of these frequently used pesticides. Ecological hazard assessments of long-term low dose or pulsed exposures to cartap and cypermethrin may reveal more realistic consequences of these compounds in surface water.     

Analysis of Extreme Summer Rainfall Using Climate Teleconnections and Typhoon Characteristics in South Korea1

Abstract: It is now widely acknowledged that climate variability modulates the frequency of extreme hydrological events. Traditional methodologies for hydrologic frequency analysis are not devised to account for variation in the exogenous teleconnections. Flood frequency analysis is further plagued by the assumptions of stationary in the causal structure as well as ergodicity. Here, we propose a dynamical hierarchical Bayesian analysis to account for exogenous forcing that govern the summer season rainfall. The precursors for Korean summer rainfall at different frequencies are identified utilizing wavelet and independent component analyses. The sea surface temperatures, the ensemble of rainfall predictions by General Circulation Model, in addition to the typhoon attributes were found to have direct correlation with extreme rainfall events and were used as inputs to the logistic regression model. The model parameters are estimated using Markov Chain Monte Carlo and the resulting posterior distributions associated with individual inputs are analyzed to advance our understanding of the spatiotemporal impact of the teleconnections. Eight rainfall stations throughout Korea are considered in this analysis. We demonstrate that the probability of occurrence of extreme events could be successfully projected at a 90% rate of correct classification of extreme events.     

Techniques for High-Quality Ambient Coarse Particle Mass Measurements

ABSTRACT

Several recent studies have shown associations between ambient concentrations of particle mass (PM) and rates of morbidity and mortality in the general population. These studies have raised the issue of quality of coarse mass (CM, PM between 2.5 and 10 µm) data used for these purposes. CM data may have precision three or more times worse than the associated PM _2.5 or PM₁₀ data, depending on the measurement method, PM _2.5 to PM ₁₀ ratios, and CM concentrations. CM is measured either as the difference between collocated _PM10 and _PM2.5 samplers or more directly with a dichotomous (virtual impactor) sampler. CM precision for the difference method is degraded due to the increased errors inherent with using the difference between two independent measurements, as well as the high PM_2.5 to PM₁₀ ratios (and low CM concentrations) typical of the eastern United States. The dichotomous sampler (dichot) makes a more direct measurement of CM, but there is a potential for significant postexposure loss of particles from unoiled CM dichot filters, as well as uncertainties in the dichot’s CM channel enrichment factor. Compared to the dichot, low-volume inertial impactor samplers such as the Harvard Impactor (HI) or PM2.5 Federal Reference Method (FRM) are simpler to operate and maintain, provide sharper cut points, and do not require oiled filters to prevent loss of CM from the filter during transport. With the recent interest in CM spatial and temporal variability with respect to PM health effects, we have developed modifications to the HI PM method to provide measurements of 24-hour PM with estimated CM precision of better than 5% CV and r² higher than 0.95, primarily by lowering field blank variability and increasing gravimetric analytical precision. These high-precision PM techniques are not limited to the HI sampler; they can also be applied to the _PM2.5 FRM sampler. The measurement methods described here can be applied to future PM studies to avoid the potential problems with exposure assessment caused by CM measurements that have poor precision.     

Concentrations and Source Characteristics of Airborne Carbonyl Compounds Measured Outside Urban Residences

Abstract

This paper presents the analysis of ambient air concentrations of 10 carbonyl compounds (aldehydes and ketones) measured in the yards of 87 residences in the city of Elizabeth, NJ, throughout 1999–2001. Most of these residences were measured twice in different seasons; the sampling duration was 48 hr each time. The authors observed higher concentrations for most of the measured carbonyl compounds on warmer days, reflecting larger contributions of photochemical reactions on warmer days. The estimated contributions of photochemical production varied substantially across the measured carbonyl compounds and could be as high as 60%. Photochemical activity, however, resulted in a net loss for formaldehyde. The authors used stepwise multiple linear regression models to evaluate the impact of traffic sources and meteorological conditions on carbonyl concentrations using the data collected on colder days (with lower photochemical activities). They found that the concentrations of formal-dehyde, acetaldehyde, acrolein, propionaldehyde, crotonaldehyde, benzaldehyde, glyoxal, and methylglyoxal significantly decreased with increasing distance between a measured residence and one or more major roadways. They also found significant negative associations between concentrations for most of the measured carbonyl compounds and each of the following meteorological parameters: mixing height, wind speed, and precipitation.     

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.     

Effect of the Mn oxidation state and lattice oxygen in Mn-based TiO2 catalysts on the low-temperature selective catalytic reduction of NO by NH3

TiO₂-supported manganese oxide catalysts formed using different calcination temperatures were prepared by using the wet-impregnation method and were investigated for their activity in the low-temperature selective catalytic reduction (SCR) of NO by NH₃ with respect to the Mn valence and lattice oxygen behavior. The surface and bulk properties of these catalysts were examined using Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and temperature-programmed desorption (TPD). Catalysts prepared using lower calcination temperatures, which contained Mn⁴⁺, displayed high SCR activity at low temperatures and possessed several acid sites and active oxygen. The TPD analysis determined that the Brönsted and Lewis acid sites in the Mn/TiO₂ catalysts were important for the low-temperature SCR at 80～160 and 200～350 °C, respectively. In addition, the available lattice oxygen was important for attaining high NO to NO₂ oxidation at low temperatures.

Implications: Recently, various Mn catalysts have been evaluated as SCR catalysts. However, there have been no studies on the relationship of adsorption and desorption properties and behavior of lattice oxygen according to the valence state for manganese oxides (MnO_x). Therefore, in this study, the catalysts were prepared by the wet-impregnation method at different calcination temperatures in order to show the difference of manganese oxidation state. These catalysts were then characterized using various physicochemical techniques, including BET, XRD, TPR, and TPD, to understand the structure, oxidation state, redox properties, and adsorption and desorption properties of the Mn/TiO₂ catalysts.