A new N3O2 pentadentate ligand, N,N'-Bis(2-hydroxybenzyl)-ethylenetriamine(H-BHET․3HCl) was synthesized. The hydrochloric acid salts of Br-BHET․3HCl, Cl-BHET․3HCl, CH3O-BHET․3HCl and CH3-BHET․3HCl containing Br-, Cl-, H-, CH3O- and CH3- groups at the para-site of the phenol group of the H-BHEP were synthesized. The structures of the ligands were confirmed by C. H. N. atomic analysis and 1H NMR, 13C NMR, UV-visible and mass spectra. The calculated stepwise protonation constants(logKnH) of the synthesized N3O2 ligands showed six steps of the proton dissociation. The orders of the overall protonation constants(logβp) of the ligands were Br-BHET < Cl-BHET < H-BHET < CH3O-BHET < CH3-BHET. The orders agreed well with that of para Hammett substituent constants(δp). The calculated stability constants(logKML) between the ligands and heavy metal ions (Co(Ⅱ) , Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Cd(Ⅱ) and Pb(Ⅱ)) agreed well with the order of the overall proton dissociation constants of the ligands but they showed a reverse order in para Hammestt substituent constants(δp). The order of the stability constants between the heavy metal ions with the synthesized ligands were Co(Ⅱ) < Ni(Ⅱ) < Cu(Ⅱ) > Zn(Ⅱ) > Cd(Ⅱ) > Pb(Ⅱ).

화장품 중 불순물로서 미량의 중금속이 함유되어 있는 경우 이들의 피부흡착이 알러지를 일으킬 수가 있다. 이에 중금속으로부터 안전한 화장품인지를 신속하고 정확하게 판단하는 것이 중요하여 색소원료와 화장품 중 미량의 중금속들(Pb²+, Fe²+, Cu²+, Ni²+, Zn²+, Co²+, Cd²+ 및 Mn²+)을 동시에 분석할 수 있는 이온크로마토그래피 분석법을 개발하였다. 8종의 중금속들은 이온교환 컬럼(IonPac CS5A)으로 잘 분리되었고, post-column 장치와 UV 분광기로 검출하였다. 0.1 ~ 1000 g/mL 농도범위에서 8종의 중금속들의 검량선은 선형적이었고(r² > 0.999), 검출한계는 제품이 안전한지를 판단할 수 있는 g/L 수준이었다. 피크들의 머무름 시간과 면적의 상대표준편차는 0.21 %과 0.24 %이고, 회수율은 97 ~ 104 %이다. 이 결과들은 개발된 분석방법이 화장품 중의 미량의 중금속들을 신속하고 정확하게 분석할 수 있다는 것을 보여준다. 본 분석방법은 22개 화장품과 11개 색소원료 중의 중금속들의 함량을 분석하는데 활용하였다.

Hydrochloride acid salts of new N2O2 tetradentate ligands containing amine and phenol N,N'-bis(2-hydroxybenzyl)-o-phenylenediamine(H-BHP), N,N'-bis(5-bromo-2-hydroxybenzyl)-o-phenylenediamine(Br-BHP), N,N'-bis (5-chloro-2-hydroxybenzyl)-o-phenylene-diamine(Cl-BHP), N,N'-bis(5-methyl-2-hydroxybenzyl)-o-phenylene-diamine (Me-BHP) and N,N'-bis(5-methoxy-2-hydroxybenzyl)-o-phenylenediamine(MeO-BHP) were synthesized. The ligands were characterized by elemental analysis, mass and NMR spectroscopy. The elemental analysis showed that the ligands were isolated as dihydrochloride salt. The potentiometry study revealed that the proton dissociation constants(logKnH) of ligands and stability constants (logKML) of transition and heavy metals complexes. The order of the stability constants of each metal ions for ligands was Br-BHP < Cl-BHP < H-BHP < MeO-BHP < Me-BHP.

본 연구에서는 석탄 광산배수에 함유된 중금속을 부유선별로 제거하기에 앞서 부유선별 조건에 영향을 미치는 철, 망간, 알루미늄 이온의 침전특성을 알아보았다. Fe(III), Mn(II), Al(III) 이온을 NaOH와 반응시켜 1 h 동안 침전시키면 Fe(III)은 pH 5.0 이상에서, Mn(II)은 pH 10.0 이상에서 그리고 Al(III)은 pH 6.0~9.0의 범위에서 대부분 침전되어 여액에 1.0mgL-1 이하로 잔류되었다. Fe(III), Mn(II), Al(III)의 혼합 용액에 포수제인 올레인산나트륨을 첨가하였을 경우, 각각의 중금속 이온은 올레인산나트륨과 반응하여 불용성 염을 거의 형성하지 않았기 때문에 침전 부선법으로 광산배수에 함유된 중금속을 제거해야 하는 것으로 나타났다.

The thiophene or furan-containing hexadentate ligands 1,12-bis (2-theophene)-2,5,8,11-tetraazadodecane(Thiotrien ․4HCl) and 1,12-bis (2-furan)-2,5,8,11-tetraazadodecane(Furatrien․4HCl) were synthesized as their tetrahydrochloride salt and characterized by EA, IR, NMR, and Mass spectrum. Their protonation constants (logKnH) and stability constants (logKML) for Cd2+, Pb2+, Zn2+ and Cu2+ ions were determined in aqueous solution by potentiometry and compared with 1,12-bis(2-pyridyl)-2,5,8,11-tetra-azadodecane(Pytrien) of pyridyl-containing ligand. The effect stability constants of ligands and metal ion for removal of heavy metals in aqueous solution were described.

The new tridentate ligands of nitrogen doner atoms N,N-Bis(2-amino-ethyl)-benzyl-amine·2HCl(BABEA·2HCl) and 2,6-Bis(amino-methyl)-pyridien·2HCl(BAMP·2HCl) were synthesized as their dihydrochloride salts and characterized by EA, IR, Mass and NMR spectroscopy. The protonation constants of the ligands and stability constants for Cd2+, Pb2+, Zn2+and Cu2+ ions were determined by potentiometric titration in aqueous solutions and compared with those of analogous ligands. The effect stability constants of ligands and metal ions for removal of heavy metals in aqueous solution were described.

Waste paper cup was sulfonated to be used as ion exchanger. Removal characteristic of copper and lead ion by prepared ion exchanger was investigated. The sulfonation was conformed by the high intensity band of SO3H group around 1100～1160cm-1. The synthesized ion exchanger had greater removal ability for copper and lead ion than the original waste paper cup. Ion exchange system reached the final equilibrium plateau within 30min. The maximum removal capacities (qmax) were calculated as 9.79mg/g for copper and 15.95mg/g for lead, respectively. The affinity of lead based on a weight was higher than that of copper. The ion exchange phenomena appeared to follow a typical Freundlich isotherm.

이 논문은 온산공업단지 내 화강암의 풍화 및 토양화 과정, 그리고 토양 내 중금속 오염과 토양 광물간의 관계에 관한 연구이다. 프로화일 연구를 위해 각 깊이별로 토양시료를 채취하여 각 샘플에 대한 실험분석을 실시하였다. X선 회절분석 결과 주 구성 점토광물은 캐올린 광물과 버미큘라이트, 그리고 미량의 일라이트이다. 포름아마이드 처리를 통해 프로화일 내 토양 중의 캐올린 광물의 종류에 대해 분석한 결과 프로화일 하부에 존재하는 캐올린 광물은 대부분 할로이사이트 임이 밝혀졌으며, 지표면으로 갈수록 상대적으로 캐올리나이트에 대한 할로이사이트의 양이 감소하는 경향을 보이는데, 이는 상부로 갈수록 할로이사이트에서 캐올리나이트로의 전환이 이루어지고 있음을 의미한다. 110℃, 300℃, 550℃ 열처리를 한 결과 X선회절분석 그래프 상의 10 a에서 14 a 사이의 피크가 분화된 형태를 보여주는 것이 관찰된다. 이는 시료상에 수산화알루미늄 혼합층 버미큘라이트가 존재함을 지시한다. 이것은 구연산나트륨 처리실험을 통해 버미큘라이트 층간 불순 알루미늄 이온을 추출하여 원형상으로 전환시킴으로써 열처리시 14 a피크가 다시 10 a으로 변화하는 것을 관찰함으로써 재확인하였다. 토양의 수소이온농도 분포 양상이 하부에서 3.9, 상부에서 3.6으로 상부로 갈수록 산성화경향이 심해지는 경향을 보여주는데, 이는 산성화된 토양에서 안정적으로 나타나는 수산화알루미늄 혼합층 버미큘라이트의 존재를 뒷받침하고 있다. 토양 내 중금속 이온의 존재양상에 대한 연구를 위해 연속추출실험을 실시하였다. 그 결과 상대적으로 많은 양의 중금속 이온이 프로화일의 상부의 철/망간 산화물과 유기물에 흡착되어 있으며 점토광물에는 적은 양만이 흡착되어 있는 것으로 밝혀졌다. 이러한 결과는 대부분의 중금속 오염물들이 상부 토양에 농집되어 있고 점토광물에는 낮은 중금속 함량을 보여주는 것은 산성화된 토양을 이루고 있는 주 점토광물인 캐올린광물과 수산화알루미늄 혼합층 버미큘라이트가 낮은 흡착능력을 가지고 있기 때문인 것으로 판단한다.

The biosorption abilities of different parts of waste brown seaweeds and their derivatives to remove heavy metals(Cd, Zn, Pb, Cu, Fe, Ni, Mn) from waste water were evaluated. The two parts of waste brown seaweeds (Undaria pinnatifida) were stems and sporophyls, and the brown seaweed derivatives were alginic fibers, active carbon added alginate(AC-alginate) and dealginate. The abilities of the sporophyls to adsorb the heavy metal ions were higher than those of stems, and those of alginates were slightly higher than those of dealginate in single ion solution. With decreasing the size of biosorbents, the velocity and the amount of adsorption increased. The abilities of alginate to remove the heavy metal ions increased in multi-ion solutions by adding active carbon to alginate. The selectivity of these biosorbents(alginate, AC-alginate) to lead ion was highest and to manganese ion was lowest.

Removal of Cu(Ⅱ), Cr(Ⅱ) and Pb(Ⅲ) ions from aqueous solutions using the adsorption process on the loesses has been investigated. Variations of contact time, pH, adsorption isotherms and selectivity of coexisting ions were experimental parameters. pH of KJ and YIK samples diluted to 1% solution, was rearly the same with each value of pH 5.58 and 5.49, and both samples showed weak acidic properties. From chemical analysis, both samples contain remarkably different amounts of SiO2, Al2O3 and Fe2O3. From XRD measurement, quartz was mainly observed in both samples. Kaolinite was also observed, also in both samples, but Feldspar was only observed in KJ sample. Adsorption of metal ions on the loesses were reached at equilibrium by shaking for about 30min. The adsorption of Cr(Ⅲ) ion was higher than that of Cu(Ⅱ) and Pb(Ⅱ) ions. The order of amount adsorbed among the investigated ions was Cr(Ⅲ)>Pb(Ⅱ)>Cu(Ⅱ). In acidic solution, the adsorptivity of loesses was increased as pH increased. The adsorption of Cr(Ⅲ) ion on the loesses were fitted to the Freundlich isotherms. Freundlich constants(l/n) of KJ and YIK loesses were 0.54 and 0.55, respectively.

The three domestic natural zeolites(Yong dong-ri (Y), Daesin-ri (D), Seogdong-ri (S)) harvested in Kyeongju-shi and Pohang-shi, Kyungsangbug-Do, were pretreated with each of the NaOH, Ca(OH)2, and NaOH following HCl solutions, and the removal performances of divalent heavy metals(Cu, Mn, Pb, and Sr) for natural and pretreated zeolites were investigated and compared in the single and mixed solutions. The natural zeolite-heavy metal system attained the final equilibrium plateau within 20 min, irrespective of initial heavy metal concentration. The heavy metal uptakes increased with increasing initial heavy metal concentration and pH. The heavy metal uptakes for natural zeolites decreased in the following sequences : D>Y>S among the natural zeolites; Pb>Cu>Sr>Mn among the heavy metals. The pretreated zeolites showed higher heavy metal removal performances than natural zeolites and decreased in the order of NaOH, NaOH following HCl, Ca(OH)2 treatment among the pretreatment methods. The heavy metal ion exchange capacity by natural and pretreated zeolites was described either by Freundlich equation or Langmuir equation, but it followed the former better than the latter. The heavy metal uptakes for natural zeolites decreased in the mixed solution, in comparing with those in the single solution and especially, the manganese uptake decreased greatly in the mixed solution. The pretreated zeolites showed the improved removal performances of heavy metals in the mixed solution than in the single solution and the heavy metal uptakes by those in the mixed solution showed the same trends in the single solution among the chemical treatment methods and heavy metals.

Surface complexation models(SCMs) have been performed to predict metal ion adsorption behavior onto the mineral surface. Application of SCMs, however, requires a self-consistent approach to determine model parameter values. In this paper, in order to determine the metal ion adsorption parameters for the triple layer model(TLM) version of the SCM, we used the zeta potential data for Zeolite and Kaolinite, and the metal ion adsorption data for Pb(Ⅱ) and Cd(Ⅱ). Fitting parameters determined for the modeling were as follows ; total site concentration, site density, specific surface area, surface acidity constants, etc. Zeta potential as a new approach other than the acidic-alkalimetric titration method was adopted for simulation of adsorption phenomena. Some fitting parameters were determined by the trial and error method. Modeling approach was successful in quantitatively simulating adsorption behavior under various geochemical conditions.