• Analytical Science and Technology
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• v.5 no.1
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• pp.41-49
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• 1992

An attempt was made to prepare two series of tetrakis eight-coordinate tungsten(IV) and cerium(IV) complexes containing the 5,7-dichloro-8-quinolinol(N:${\pi}$-acceptor atom, O:${\pi}$-donor atom) ligand. Tetrakis eight-coordinate tungsten(IV) complex of 2-mercaptopyrimidine(N:${\pi}$-acceptor atom, S:${\pi}$-donor atom) ligand have also been prepared. And the new series of mixed-ligand eight-coordinate tungsten(IV) complexes containing bidentate ligands 5,7-dichloro-8-quinolinol and 2-mercaptopyrimidine have been prepared, isolated by TLC and characterized. $W(dcq)_4$, $W(dcq)_3(mpd)_1$, $W(dcq)_2(mpd)_2$, $W(dcq)_1W(dcq)_3$ and $W(mpd)_4$ complexes of MLCT absorption band appeared to 710nm, 680nm, 625nm, 581nm, and 571nm(${\varepsilon}\;max={\sim}>{\times}10^4$) on low-energy respectively. The specific absorption wave length of $Ce(dcq)_4$ is appeared 520nm(${\varepsilon}\;max={\sim}>{\times}10^4$). The Chemical shift values by proton of coordinated position appeared to $W(dcq)_4$ [$H_2:8.9ppm$]; $W(dcq)_3(mpd)_1$ [$H_2:9.3$,$H_6:9.2ppm$]; $W(dcq)_2(mpd)_2$ [$H_2:9.7$,$H_6:8.95ppm$]; $W(dcq)_1(mpd)_3$ [$H_2:9.8$,$H_6:9.4ppm$]; $W(mpd)_4$ [$H_6:8.8ppm$]; $Ce(dcq)_4$ [$H_2:9.3ppm$] with $^1H$-NMR. The inertness of mixed-ligand eight coordinate tungsten(IV) complexes have been investigated by UV-Vis. spectroscopic method in dimethylsulfoxide at $90^{\circ}C$. The inertness of $W(dcq)_n(mpd)_{4-n}$ complexes showed the following order, $W(dcq)_3(mpd)_1;k_{obs.}=3.8{\times}10^{-6}$ > $W(mpd)_4;k_{obs.}=6.0{\times}10^{-6}$ > $W(dcq)_4;k_{obs.}=6.4{\times}10^{-6}$ > $W(dcq)_2(mpd)_2;k_{obs.}=7.0{\times}10^{-6}$ > $W(dcq)_1(mpd)_3;k_{obs.}=1.7{\times}10^{-5}$, which showed the inertness until 16days, 10days, 9days, 8days, and 4days. The $W(mpd)_4$ is very inert as $k_{obs.}=3.6{\times}10^{-6}$(16days) in xylene at $90^{\circ}C$ and $k_{obs.}=6.0{\times}10^{-6}$(10days) in DMSO at $90^{\circ}C$.

• Korean Journal of Fisheries and Aquatic Sciences
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• v.23 no.3
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• pp.225-237
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• 1990

Various chemical constituents were measured from April to August 1988 at the down-ward 20 stations of Keum River, which is located in the Midwest of Korea, to understand the characteristics of water quality with respect to spatio-temporal variations of each constituent. The 24-hrs continuous measurements with 2-hrs interval were made simultaneously at station 2 near the estuary weir and station 9(Ganggyeong) of 35 km upstream from the weir in April. By the results observed for one day in April at station 2, salinity has a range of $7.88\~22.14\%_{\circ}$ and its temporal variability is identical to the pattern of tidal cycle in the neigh-bouring Kunsan Harbor. However, turbidity shows relatively high values only at an interval of 4~5 hours after the lowest salinity time, though hourly fluctuation of pH is very small. Silicate and dissolved inorganic nitrogen have inversively linear correlationships with salinity, implying the concentration of the two nutrients strongly regulated by estuarine mixing of sea and river waters. In contrast, phosphate sustains roughly a constant level over a wide salinity range and distinctly lower values than those corresponding to nitrate in the oceans. Such distributions of phosphate have been observed in some estuaries, and interpreted as driven by removal of dissolved phosphate into bottom sediments and the bufforing of phosphate by particulate matter. COD values at station 2 are relatively high in day-time(particularly afternoon) and in high-salinity periods. At station 9, saltwater intrusion was never found but water level changed to the extent of 2.5 m for one day. Although each parameter at this station exhibits very slight variations in their abundance for 24 hours compared with station 2, the contents of COD, silicate and ammonia are significantly higher than at station 2. Concentration of suspended matter is relatively high in the brackish water region up to $\~20$ km above the river mouth, probably due to strong tidal stirring of the bottom de-posits. Also, relatively high pH, COD and $O_2$ saturation at the upward stations of $40\~50$ km from the weir are presumably attributable to active photosynthesis of plants in the region. In general, COD and nutrients except phosphate are higher values at the upper stations than in the estuary zone, and show the highest abundances in July nearly at all stations. Finally, in the estuarine region tidal mixing of sea-river waters seems to be an important factor controlling the distributions of turbidity, COD, silicate and nitrate as well as salinity. However, water quality in the upward fresh-water zone is remarkably variable according to months or seasons.

• Economic and Environmental Geology
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• v.56 no.5
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• pp.603-618
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• 2023

This study focused on evaluating the suitability of the WRK (waste repository Korea) bentonite as a buffer material in the SNF (spent nuclear fuel) repository. The U (uranium) adsorption/desorption characteristics and the adsorption mechanisms of the WRK bentonite were presented through various analyses, adsorption/desorption experiments, and kinetic adsorption modeling at various pH conditions. Mineralogical and structural analyses supported that the major mineral of the WRK bentonite is the Ca-montmorillonite having the great possibility for the U adsorption. From results of the U adsorption/desorption experiments (intial U concentration: 1 mg/L) for the WRK bentonite, despite the low ratio of the WRK bentonite/U (2 g/L), high U adsorption efficiency (>74%) and low U desorption rate (<14%) were acquired at pH 5, 6, 10, and 11 in solution, supporting that the WRK bentonite can be used as the buffer material preventing the U migration in the SNF repository. Relatively low U adsorption efficiency (<45%) for the WRK bentonite was acquired at pH 3 and 7 because the U exists as various species in solution depending on pH and thus its U adsorption mechanisms are different due to the U speciation. Based on experimental results and previous studies, the main U adsorption mechanisms of the WRK bentonite were understood in viewpoint of the chemical adsorption. At the acid conditions (＜pH 3), the U is apt to adsorb as forms of UO₂²⁺, mainly due to the ionic bond with Si-O or Al-O(OH) present on the WRK bentonite rather than the ion exchange with Ca²⁺ among layers of the WRK bentonite, showing the relatively low U adsorption efficiency. At the alkaline conditions (>pH 7), the U could be adsorbed in the form of anionic U-hydroxy complexes (UO₂(OH)₃^-, UO₂(OH)₄^2-, (UO₂)₃(OH)₇^-, etc.), mainly by bonding with oxygen (O^-) from Si-O or Al-O(OH) on the WRK bentonite or by co-precipitation in the form of hydroxide, showing the high U adsorption. At pH 7, the relatively low U adsorption efficiency (42%) was acquired in this study and it was due to the existence of the U-carbonates in solution, having relatively high solubility than other U species. The U adsorption efficiency of the WRK bentonite can be increased by maintaining a neutral or highly alkaline condition because of the formation of U-hydroxyl complexes rather than the uranyl ion (UO₂²⁺) in solution,and by restraining the formation of U-carbonate complexes in solution.