Discussion

Environmental and Ecological Statistics -     

Effect of temperature on single and competitive adsorptions of Cu(II) and Zn(II) onto natural clays

This study conducted a combined adsorption-sequential extractionanalysis (CASA), by which five phases (i.e., exchangeable, carbonate, Mn-Oxide, organic, and Fe-Oxide phases) of adsorbed heavy metals were analyzed, to investigate temperature effects on single and competitive adsorptions of Zn(II) and Cu(II) ontonatural clays. In the case of single adsorption of Zn, the exchangeable phase adsorption decreased from 65 to 40%, but thecarbonate phase adsorption increased from 30 to 40%, with an increase in temperature from 15 to 55 °C. However, in itscompetitive adsorption with Cu, Zn was mostly present in the exchangeable phase (over 90%), and with an increase in temperature, the exchangeable phase adsorption decreased only 10%. In the case of Cu, over 50% among the total amount of adsorption was present in the carbonate phase in both cases ofsingle and competitive adsorptions. The carbonate phaseadsorption of Cu increased from 56 to 61% and from 60 to 66% in single and competitive adsorptions, respectively, with atemperature increase. These results show that in the case of Zn,the major mechanism of retention in natural clay soils might beexchangeable phase adsorption, especially in the case of competitive adsorption with Cu. However, in the case of Cu, the major mechanism might be carbonate phase adsorption, which is known to be a more immobile phase than exchangeable phase adsorption. It seems that the adsorption of Zn and Cu onto natural clays is an endothermic reaction, which represents thatthe adsorption equilibrium constants and capacities increase with a temperature increase, with the exception of exchangeablephase adsorption.     

Characterization and optimization of long-term controlled release system for groundwater remediation: a generalized modeling approach

A well-based reactive barrier system using controlled-release KMnO4 has been recently developed as a long-term in situ treatment option for plumes of dense and non-aqueous phase liquids in groundwater. In order to take advantage of the merits of controlled release systems (CRS) in environmental remediation, the release behavior needs to be optimized for the hydrologic and environmental conditions of target treatment zone. Where release systems are expected to be operated over long times, like for the reactive barriers, it may only be practical to describe the long-term behavior numerically. We developed a numerical model capable of describing release characteristics associated with variable forms and structures of long-term CRS. Sensitivity analyses and illustrative simulations showed that the release kinetics and durations would be constrained by changes in agent solubility, bulk diffusion coefficients, or structures of the release devices. The generality of the numerical model was demonstrated through simulations for CRS with monolithic and double-layered matrices. The generalized model was then used for actual design and analyses of an encapsulated-matrix CRS, which can yield constant release kinetics for several years. A well-based reactive barrier system (4.05 x 10(3)m3) using the encapsulated-matrix CRS can release approximately 1.65 kg of active agent (here MnO4(-)) daily over the next 6.6 yr, creating prolonged reaction zone in the subsurface. The generalized model-based, target-specific approach using the long-term CRS could provide practical tool for improving the efficacy of advanced in situ remediation schemes such as in situ chemical oxidation, bioremediation, or in situ redox manipulation. Development of techniques for adjusting the bulk diffusion coefficients of the release matrices and facilitating the lateral spreading of the released agent is warranted.     

Comparison of organic compositions in dust storm and normal aerosol samples collected at Gosan,Jeju Island,during spring 2005

To better understand the current physical and chemical properties of East Asian aerosols, an intensive observation of atmospheric particles was conducted at Gosan site, Jeju Island, South Korea during 2005 spring. Total suspended particle (TSP) samples were collected using pre-combusted quartz filters and a high-volume air sampler with the time intervals ranging from 3 h to 48 h. The kinds and amount of various organic compounds were measured in the samples using gas chromatography–mass spectrometry. Among the 99 target compounds detected, saccharides (average, 130 ± 14 ng m^?3), fatty acids (73 ± 7 ng m^?3), alcohols (41 ± 4 ng m^?3), n-alkanes (32 ± 3 ng m^?3), and phthalates (21 ± 2 ng m^?3) were found to be major compound classes with polyols/polyacids, lignin and resin products, PAHs, sterols and aromatic acids being minor. Compared to the previous results reported for 2001 late spring samples, no significant changes were found in the levels of their concentrations and compositions for 4 years, although the economy in East Asia, especially in China, has sharply expanded from 2001 to 2005. During the campaign at Gosan site, we encountered two distinct dust storm episodes with high TSP concentrations. The first dust event occurred on March 28, which was characterized by a predominance of secondary organic aerosols. The second event that occurred on the next day (March 29) was found to be characterized by primary organic aerosols associated with forest fires in Siberia/northeastern China. A significant variation in the molecular compositions, which was found within a day, suggests that the compositions of East Asian aerosols are heterogeneous due to multi-contributions from different source regions together with different pathways of long-range atmospheric transport of particles.     

Fate of polycyclic aromatic hydrocarbons during vitrification of incinerator ash in a coke bed furnace

Fate of polycyclic aromatic hydrocarbons (PAHs) during the vitrification of fly ash and bottom ash from the municipal waste incinerator in a coke bed furnace was investigated. In this system, both coke and lime were added to enhance the melting reaction. The major PAH sources in this system were ash and coke, which respectively contributed 97% and 3% of PAHs in the input-mass. During vitrification process, low molecular PAHs (LM-PAH, 2-3-ring), median molecular PAHs (MM-PAH, 4-ring) and high molecular PAHs (HM-PAH, 5-7-ring) mass respectively accounted for >99%, >99% and 84% of the output-mass emitted as the stack flue gas; while those discharged from the slag were <1%, <1% and 16%, respectively. The O/I (output-mass/input-mass) ratio of LM-, MM- and HM-PAHs were 0.063, 0.002 and <0.001, respectively. The high distribution in flue gas and O/I ratio of LM-PAHs is reasonable since they are more easily evaporated, hence difficult to be removed by air pollution control devices. On the contrary, the HM-PAHs, having lower vapor pressure, primarily stays mainly in slag. Based on the 21 total PAH content in feeding ash and slag, the reduction efficiency of the coke bed furnace was >99.9%. To minimize the risk of secondary pollution, the efficiency of coke bed furnace should be improved to reduce the PAH emission into ambient air.     

Distribution of polycyclic aromatic hydrocarbons in agricultural soils in South Korea

The content and type of polycyclic aromatic hydrocarbons (PAH) in soils from paddy fields and upland areas in South Korea were determined using gas chromatography linked to mass spectrometry (GC–MS). The distribution map of total PAH content was obtained as a contour plot using a geographical information system. The overall distribution of PAH was found to be closely related to the pollution sources, the size of city and the type of industry. The average content of total PAH in all samples was 236 μg kg⁻¹, and the range was from 23.3 to 2834 μg kg⁻¹. The highest concentrations were found in soils sampled near iron processing plants. The concentration of PAH decreased in the order fluoroanthene>benzo(b)fluoroanthene>pyrene. Special PAH compound ratios, such as phenanthrene/anthracene and fluoroanthene/pyrene, were calculated to evaluate the origin. The collected data suggested that the pyrogenic origins such as motor vehicle exhaust and heavy industry emission were the dominant source of PAH in Korean soils.     

Metal contamination and solid phase partitioning of metals in urban roadside sediments

This study was undertaken to assess the anthropogenic impact on metal concentrations of urban roadside sediments (N = 633) in Seoul city, Korea and to estimate the potential mobility of selected metals (Zn, Cu, Pb, Cr, Ni, and Cd) using sequential extraction. Comparison of metal concentrations in roadside sediments with mean background values in sediments collected from first- or second-order streams in Korea shows that Zn, Cu and Pb are most affected by anthropogenic inputs. The 206Pb/207Pb ratios of roadside sediments (range = 1.1419-1.1681; mean 1.1576 +/- 0.0068) suggest that Pb is mainly derived from industrial sources rather than from leaded gasoline. A five-step sequential extraction of roadside sediments showed that Zn, Cd and to a lesser degree Ni occur predominantly in the carbonate bound fraction, while Pb is highest in the reducible fraction, Cu in the organic fraction, and Cr in the residual fraction. It was found that the concentrations in the readily available exchangeable fraction were generally low for most metals examined, except for Ni whose exchangeable fraction was appreciable (average 15.2%). Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreases in the order of Zn > Ni > Cd > Pb > Cu > Cr. As potential changes of redox state and pH may remobilize the metals bound to carbonates, reducible, and/or organic matter, and may release and flush them through drain networks into streams, careful monitoring of environmental conditions appears to be very important. With respect to ecotoxicity, it is apparent the Zn and Cu pollution is of particular concern in Seoul city.     

Influence of ozone stress on growth processes, yields and grain quality characteristics among soybean cultivars

Field studies were conducted at USDA Beltsville Agricultural Research Center, Beltsville, Maryland, in 1984 and 1985 using open-top chambers to acquire information on the responses of 12 soybean (Glycine max L. Merr.) cultivars to O3 stress and to examine the interactions between maturity groups and O3 stress. Cultivars representing Groups III, IV, and V were exposed for approximately 3 months to charcoal-filtered air (CF) and nonfiltered air plus 40 nl litre(-1) O3 (NF + O3). Ozone was added 6 h d(-1), 5 d week(-1) for 13 weeks. The CF effectively reduced the accumulative oxidant exposure (AOX) to less than 1.0 microl litre(-1) h and the NF + O3 treatment approximately doubled the ambient AOX (16.7 microl litre(-1) h) to about 30 microl litre(-1) h. The AOX estimates the total O3 exposure above 30 nl litre(-1) during an entire growing season. Plant growth rates and relative growth rates were reduced by 17.0 and 14.4%, respectively, when averaged over cultivars. Based on growth rates, the Group III cultivars were the most affected by O3 stress. Averaged over cultivars, leaf expansion rates, leaf conductance, and transpiration rates were lower in the NF + O3 treatment compared to the CF control; however, wide variation was found with the stomatal results from field observations. Combined over years and cultivars, grain yield was reduced by an average of 12.5% by O3 stress with 3 of 12 cultivars showing significant reductions. Grain protein content was increased by 0.7% by O3 stress, but cultivar differences were equal to the differences caused by the O3 treatments. Grain oil content was unchanged by the O3 treatments. Group IV cultivars showed the greatest decrease in grain yield due to O3 stress. Multiple regression analyses were calculated using the difference between the CF and NF + O3 treatment as a measure of O3 stress. Significant positive relationships were found among net assimilation rates, plant growth rates, relative growth rates, and leaf expansion rates, which suggest that growth analysis characteristics would be useful in addition to yield in air pollution tolerance improvement studies with soybeans.     

The adsorption characteristics of heavy metals by various particle sizes of MSWI bottom ash

The incineration rate of municipal solid waste (MSW) has been increased because of difficulty in securing a proper disposal site for MSW in Korea. The advantage of incineration is reduction of the volume of waste; however, significant amounts of bottom ash and fly ash were generated in the incineration process. Their treatment has attracted growing interest because of the potential toxicity of hazardous heavy metals. Generally, heavy metals are less released from bottom ash than from fly ash. In this study the adsorption characteristics of heavy metals were investigated using various particle sizes of MSWI bottom ash. Since bottom ash has a broad particle size distribution, it was sieved to size classes of +20, -20, -48, -80, -100 mesh. Cation exchange capacity (CEC) was analyzed by the ammonium acetate method to evaluate the potential as an adsorbent. The CEC values and surface areas increase as the range of particle size becomes finer. The adsorption experiment was conducted using synthetic (Cu and Ni) and plating rinse water as a function of reaction time (10-180 min), liquid/solid ratio (2-100) and particle size (+20 to -100 mesh), respectively. The adsorption rate increased with decreasing particle size and with increasing liquid/solid ratio; however, the removal efficiency of Cu was higher than that of Ni. In the case of plating rinse water, the adsorption rate decreased sharply at high liquid/solid ratio, and it showed over 80% of adsorption rates for Cu and Ni at an initial pH of 3.