• Journal of the Korean Chemical Society
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• v.54 no.5
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• pp.541-550
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• 2010

A new $N_4O_3$ heptadentate ligand, N,N'-Bis(2-hydroxybenzyl)-1,3-bis[(2-aminoethyl)amino]-2-propanol(H-BAP 4HCl)was synthesized. The hydrochloric acid salts of Br-BAP 4HCl, Cl-BAP 4HCl, $CH_3O$-BAP 4HCl and $CH_3$-BAP 4HCl containing Br-, Cl-, H-, $CH_3O-$ and $CH_{3^-}$ groups at the para-site of the phenol group of the H-BAP were synthesized. The structures of the ligands were confirmed by C. H. N. atomic analysis and $^1H$ NMR, $^{13}C$ NMR, UV-visible and mass spectra. The elemental stepwise protonation constants(${logK_n}^H$) of the synthesized $N_4O_3$ ligands showed six steps of the proton dissociation. The orders of the overall dissociation constants($log{\beta}_p$) of the ligands were Br-BAP < Cl-BAP < H-BAP < $CH_3O$-BAP < $CH_3$-BAP. The orders agreed well with that of Hammett substituent constants($\sigma_p$). The calculated stability constants($logK_{ML}$) between the ligands and transition metal ions agreed well with the order of the overall proton dissociation constants of the ligands but they showed a reverse order in Hammestt substituent constants($\sigma_p$). The order of the stability constants between the transition metal ions with the ligands were Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II).

• Korean Journal of Environmental Agriculture
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• v.23 no.2
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• pp.92-98
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• 2004

The adsorption and desorption of Pb, Cd, Co, Zn, Cr, Co, Ni, and Mo on the waste Undaria sp. were studied. Except for Pb. the mono adsorption rate for all heavy metals were lower than that of the heavy metals mixed. However, the adsorption capacity of the heavy metals by 1g of biosorption, in mixed heavy metals increased According to FT-IR analysis of the biosorbent after heavy metal biosorption, the replacement of the functional group by the heavy metals ions could be confirmed and the inverted peaks became larger after heavy metals adsorption. The adsorption equilibrium of heavy metals was reached in about 1 hour. The equilibrium parameters were determined based on Langmuir and Freundlich isotherms. The affinity of metals on the biosorbent decreased in the following order: Pb>Cu>Cr>Cd>Co. The desorption rate decreased in the following sequence: NTA>$H_2SO_4$>HCl>EDTA. The desorption rate of heavy metals by NTA increased with increase in the concentration from 0.1 to 0.3% but the desorption rate became constant beyond 0.3%. Therefore, it represented that desorption rate of heavy metals was suitable under optimized condition ($30^{\circ}C$, pH 2 and 0.3% NTA solution) and was fast with 80% or more the uptake occurring within 10 min of contact time.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.6 no.1
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• pp.13-26
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• 2001

Six ferromanganese crusts from the Lomilik and Litatfooki seamounts in the Marshall Islands were analyzed for texture, geochemistry and stratigraphy to delineate the paleoceanographic conditions. The crusts can be divided into three layers; 1) outermost massive layer (Layer 1), 2) middle porous Fe-oxides rich layer infllled with biointemal clasts (Layer 2), and 3) innermost massive layer cemented and/or replaced by carbonate fluoapatite (CFA) (Layer 3). The Layer 1 contains higher Mn, Co, Ni, and Mg than other two layers, and the Layer 2 was relatively more enriched in Fe, Al, Ti, Ba, Cu, and Zn. However, the Layer 3 shows higher Ca and P and lower Mn, Fe, Co, and Ni contents than overlying two layers. Based on the Co-chronometry, the crusts are postulated to have begun to grow from 56-31 Ma (early Eocene to Oligocene). The boundaries between layers 1 and 2, and layers 2 and 3 are dated to be 7-3 Ma and 26-14 Ma, respectively. High contents of Ca and P in Layer 3 clearly indicate that the layer had been phosphatized prior to the formation of Layer 2. Considering the well-preserved mjcrostructures in Layer 3, it is unlike that the crusts themselves were recrystallized in suboxic condition. Also, the lower Co concentrations in Layer 3 may imply that the Co supply was not constant during the formation of Layer 3. Layer 2, characterized by the porous texture, grew over Layer 3 during 26-9 Ma. Internal biogenic sediments including foraminifera within the original cavities and the enrichment of organophillic elements such as Ba, Cu, and Zn, suggest that Layer 2 have below high production regions. Also, high content of allumino silicate components may indicate increased terrigeneous input during the formation of Layer 2. The Layer 2. The Layer 1 has been subjected to little diagenetic influence since the Pliocene.

• Journal of the Korean Chemical Society
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• v.44 no.5
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• pp.403-409
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• 2000

The formation and dissociation rates of $Zn^{2+}$ Complexes with l,4,7,10-tetraaza-13,16-diox-acyclooctadecane-N,N',N",N'"-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetramethylacetic acid (2), and 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetrapropionic acid(3) have been measured by stopped-flow and conventional spectrophotometry. Observations were made at 25.0$\pm$0.1 $^{\circ}C$ and at an ionic strength of 0.10 M NaClO$_4$. The formation reactions of $Zn^{2+}$ ion with 1 and 2 took place by the rapid formation of an intermediate complex (ZnH$_3L^+$) in which the $Zn^{2+}$ ion is incompletely coor-dinated. This might then lead to be a final product in the rate-determining step.ln the pH range 4.76-5.76, the diprotonated (H2L2-) form is the kinetically active species despite of its low concentration. The stability con-stants (log$K_{(ZnH$_3$3$L^+$)}$) and specific water-assisted rate constants (koH) of intermediate complexes have been deter-mined from the kinetic data. The dissociation reactions of $Zn^{2+}$ complexes of 1,2, and 3 were investigated with $Cu^{2+}$ ions as a scavenger in acetate buffer. All complexes exhibit acid-independent and acid-catalyzed con-tributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on t dissociation rate of $Zn^{2+}$ complexes is discussed in terms of the side-pendant armsand the chelate ring sizes of the ligands.

• Korean Journal of Soil Science and Fertilizer
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• v.38 no.5
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• pp.259-268
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• 2005

Most of the tailings have been left without any management in their mines and have become the main source of serious environmental problems in nearby groundwater, stream and cultivated lands. To compare fractionation and potential mobility of heavy metals in tailings and paddy soils near abandoned 10-metalliferous mines in Korea, the distribution and chemical fractions of heavy metal and their mobility in relation to chemical compositions were investigated. The pollution index of heavy metal in mine tailing calculated with the permissible levels were in the order Cheongyang>Dogok>Beutdeun>Baegwoul mine, which were considered sufficient to raise environmental problems. The rates of 0.1M-HCl extractable Cd, Cu, Pb, Zn, and Ni to total content in paddy soils were 49.1, 50.7, 26.8, 18.4 and 2.9%, respectively, and their rates of heavy metals in paddy soils were higher than that of mine tailing. Dominant chemical forms of heavy metals in tailings were sulfide and residual form (63-91%), specially, the exchangeable portion of Cd (21%) was relatively higher than that of other metals in paddy soils. The mobility factor of heavy metals in tailings and paddy soils was in the order Cd>Zn>Cu>Pb, and the mobility factor in tailing varied considerably among the mines. The potential mobility of heavy metals in tailings showed significant positive correlation with water-soluble $Al^{3+}$ and $Fe^{3+}$ contents, while in paddy soils, it correlated negatively with soil pH values.

• Journal of Korean Society of Forest Science
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• v.84 no.4
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• pp.465-478
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• 1995

The objective of this study was to investigate the impacts of large-scale timber harvesting on the environment of a mature hardwood forest. To achieve the objective, the effects of harvesting on forest environmental factors were analyzed quantitatively using the field data measured in the study sites of Seoul National University Research Forests [(Mt.) Paekunsan] for two years(1993-1994) following timber harvesting. The field data include information on vegetation, soil mesofauna, physicochemical characteristics of soil, surface water runoff, water quality in the stream, and hillslope erosion. For comparison, field data for each environmental factor were collected in forest areas disturbed by logging and undisturbed, separately. The results of this study were as follows : The diversity of vegetational species increased in the harvested sites. However, the similarity index value of species between harvested and non-harvested sites was close to each other. Soil bulk density and soil hardness were increased after timber harvesting, respectively. The level of organic matter, total-N, avail $P_2O_5$, CEC($K^+$, $Na^+$, $Ca^{{+}{+}}$, $Mg^{{+}{+}}$) in the harvested area were found decreased. While the population of Colembola spp., and Acari spp. among soil mesofauna in harvested sites increased by two to seven times compared to those of non-harvested sites during the first year, the rates of increment decreased in the second year. However, those members of soil mesofauna in harvested sites were still higher than those of non-harvested sites in the second year. The results of statistical analysis using the stepwise regression method indicated that the diversity of soil mesofauna were significantly affected by soil moisture, soil bulk density, $Mg^{{+}{+}}$, CEC, and soil temperature at soil depth of 5(0~10)cm in the order of importance. The amount of surface water runoff on harvested sites was larger than that of non-harvested sites by 28% in the first year and 24.5% in the second year after timber harvesting. The level of BOD, COD, and pH in the stream water on the harvested sites reached at the level of the domestic use for drinking in the first and second year after timber harvesting. Such heavy metals as Cd, Pb, Cu, and organic P were not found. Moreover, the level of eight factors of domestic use for drinking water designated by the Ministry of Health and Welfare of Korea were within the level of the first class in the quality of drinking water standard. The study also showed that the amount of hillslope erosion in harvested sites was 4.77 ton/ha/yr in the first year after timber harvesting. In the second year, the amount decreased rapidly to 1.0 ton/ha/yr. The impact of logging on hillslope erosion in the harvested sites was larger than that in non-harvested sites by seven times in the first year and two times in the second year. The above results indicate that the large-scale timber harvesting cause significant changes in the environmental factors. However, the results are based on only two-year field observation. We should take more field observation and analyses to increase understandings on the impacts of timber harvesting on environmental changes. With the understandings, we might be able to improve the technology of timber harvesting operations to reduce the environmental impacts of large-scale timber harvesting.

• Korean Journal of Environmental Agriculture
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• v.23 no.3
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• pp.170-177
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• 2004

Agroenvironmental characteristics in paddy fields irrigated with the water of Nagdong river were analyzed along the river watershed for two years from 1999. The sites monitored from upper reaches of the river were Andong, Sangju, Gumi, Goryeong, Changnyeong, Milyang and Pusan. In paddy soils, the contents of heavy metals such as Cd, Cr, Cu, Pb, Ni, Zn and As were around natural values showing the highest values in Pusan followed by Goryeong. In brown rice, the contents of heavy metals were lower than natural values. Soil chemical properties appeared higher values in the lower reaches including Goryeong than the upper ones. The highest parameters in Goryeong were pH ($5.9{\sim}6.1$), EC ($0.8{\sim}0.9\;dS/m$), $Av.P_2O_5$ ($155{\sim}201\;mg/kg$), exchangeable Ca ($6.7{\sim}7.4\;cmol^+/kg$), Mg ($1.92{\sim}2.50\;cmol^+/kg$), K ($0.18{\sim}0.21\;cmol^+/kg$) and those in Pusan were organic matter ($23.0{\sim}29.1\;g/kg$) and T-N ($1.6{\sim}1.8\;mg/kg$). In conclusion, the recommended rates of N fertilizer for rice cropping were 21.4%, 11.8% and 8.8% high for Andong, Sangju and Gumi, respectively and 14.9%, 4.6%, 4.5% and 11.5% low for Goryeong, Changnyeong, Milyang and Pusan, respectively reflecting the chemical properties of soils and the quality of irrigation water on the basis of 110 kgN/ha. In the case of phosphorous, the rates were 18.9% and 33.3% low for Changnyeong and others, respectively on the basis of $45\;kgP_2O_5/ha$. The populations of bacteria, fungi, actinomycetes, Bacillus, fluorescent Pseudomonas and Biomass C were high at the lower reaches including Goryeong, which showed relatively much nutrient contents of organic matter, total N and phosphorous etc.

• Journal of the Korean Chemical Society
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• v.35 no.2
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• pp.119-127
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• 1991

The protonation and the metal ion complexation of 15 to 18 membered diaza crown ether such as 1,12-diaza-3, 4 : 9, 10-dibenzo-5, 8-dioxacyclopentadecane(NtnOenH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-hydroxy-5,9-dioxacyclohexadecane(NtnOtnH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-15-hydroxy-5,9-dioxacyclohexadecane(Ntn(OH)OtnH$_4$), 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdienH$_4$) and 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane(NtnOdienH$_4$) were studlied by potentiometry and NMR spectroscopy. The protonation constants were used to predict basicity of crown ethers. The sequence of the basicity was NenOdienH$_4$ < Ntn(OH)OtnH$_4$ < NtnOenH$_4$ < NtnOtnH$_4$ < NtnOdienH$_4$. Changes on the basicity were explained in terms of the effects of substituents and the degree of twistness of the macrocyclic ring. The sequence of the complex stabilities were Co(II) < Ni(II) < Cu(II) < Zn(II) for the transition metal complexes and Cd(II) < pb(II) < Hg(II) for the post-transition metal complexes. These changes on the stabilities were dependent on the basicity of the ligand and cavity size of the ring. For the heavy post-transiton metal complexes and Zn(Ⅱ) complex, the former factor was predominent and for the other transition metal complexes, the latter was affected on the stabilities. $^1$H and $^{13}$C-NMR studies for heavy post-transition metal complexes indicated that the nitrogen atom has greater affinity on metal ions than oxygen atom and the planarity of the rings was losed by the complexation with metal ions.

• Korean Journal of Mineralogy and Petrology
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• v.35 no.2
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• pp.125-140
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• 2022

The Xiquegou Pb-Zn deposit is located at the Qingchengzi orefield which is one of the largest Pb-Zn mineralized zone in the northeast of China. The geology of this deposit consists of Archean granulite, Paleoproterozoinc migmatitic granite, Paleo-Mesoproterozoic sodic granite, Paleoproterozoic Liaohe group, Mesozoic diorite and Mesozoic monzoritic granite. The Xiquegou deposit which is a Triassic magma-hydrothermal type deposit occurs as vein ore filled fractures along fault zone in unit 3 (dolomitic marble and schist) of Dashiqiao formation of the Paleoproterozoic Liaohe group. Xiquegou Pb-Zn deposit consists of quartz, apatite, calcite, pyrite, arsenopyrite, pyrrhotite, marcasite, sphalerite, chalcopyrite, stannite, galena, tetrahedrite, electrum, argentite, native silver and pyrargyrite. Wallrock alteration of this deposit contains silicification, pyritization, dolomitization, chloritization and sericitization. Based on mineral petrography and paragenesis, dolomites from this deposit are classified two type (1. dolomite (D₀) as wallrock, 2. dolomite (D₁) as wallrock alteration in Pb-Zn mineralization quartz vein ore). The structural formulars of dolomites are determined to be Ca_1.03-1.01Mg_0.95-0.83Fe_0.12-0.02Mn_0.02-0.00(CO₃)₂(D₀) and Ca_1.16-1.00Mg_0.79-0.44Fe_0.53-0.13Mn_0.03-0.00As_0.01-0.00(CO₃)₂(D₁), respectively. It means that dolomites from the Xiquegou deposit have higher content of trace elements compared to the theoretical composition of dolomite. The dolomite (D₁) from quartz vein ore has higher content of these trace elements (FeO, PbO, Sb₂O₅ and As₂O₅) than dolomite (D₀) from wallrock. Dolomites correspond to Ferroan dolomite (D₀), and ankerite and Ferroan dolomite (D₁), respectively. The structural formular of chlorite from quartz vein ore is (Mg_1.65-1.08Fe_2.94-2.50Mn_0.01-0.00Zn_0.01-0.00Ni_0.01-0.00Cr_0.02-0.00V_0.01-0.00Hf_0.01-0.00Pb_0.01-0.00Cu_0.01-0.00As_0.03-0.00Ca_0.02-0.01Al_1.68-1.61)_5.77-5.73(Si_2.84-2.76Al_1.24-1.16)_4.00O₁₀(OH)₈. It indicated that chlorite of quartz vein ore is similar with theoretical chlorite and corresponds to Fe-rich chlorite. Compositional variations in chlorite from quartz vein ore are caused by mainly octahedral Fe²⁺ <-> Mg²⁺ (Mn²⁺) substitution and partly phengitic or Tschermark substitution (Al^3+,VI+Al^3+,IV <-> (Fe²⁺ 또는 Mg²⁺)^VI+(Si⁴⁺)^IV).

• Korean Journal of Soil Science and Fertilizer
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• v.43 no.3
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• pp.268-274
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• 2010

The properties of upland soils are much more dependent upon topography than those of paddy soils, and they give us very useful information to manage the upland fields. Therefore, we investigated the selected physical and chemical properties of upland soils at 84 and 150 topographic sampling sites, respectively. The topographic sites included 34.7% of local valley and fans, 18.7% of hilly and mountains, 20.0% of mountain foot slopes, 14.0% of alluvial plains, 8.0% of diluvium, and 4.6% of fluvio-marine deposits. Based on the investigation, soil textures in Jeonbuk upland fields were mostly sandy loam, sandy clay loam, clay loam, and clay soils, especially sandy clay loam soils were evenly distributed in all of the topographic sites. Soil slopes in the sites ranged from 0 to 15%, which showed an optimal condition for farm land. Soil bulk density and compaction values were from 1.19 to 1.24 g $cm^{-3}$ and from 12.1 to 13.9 mm, respectively. As comparing with the optimal conditions of soil chemical properties for upland soils proposed by National Institute of Agricultural Science and Technology, Korea, 37%, 42.7%, 93.0% of the sites were within optimum levels with soil pH, content of soil organic matter, and electrical conductivity, respectively. However, 64.0%, 47.3%, 48.7%, and 42.7% of the upland soils contained excess levels of exchangeable K, Ca, and Mg, and available phosphorus, respectively. In addition, the contents of heavy metals, As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn, in the Jeonbuk upland soils were much less than threshold levels.