• Bulletin of the Korean Chemical Society
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• 제34권11호
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• pp.3362-3366
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• 2013

A simple and quick separation technique for selenite in natural water was developed using $TiO_2$@$SiO_2/Fe_3O_4$ nanoparticles. For the synthesis of nanoparticles, a polymer-assisted sol-gel method using hydroxypropyl cellulose (HPC) was developed to control particle dispersion in the synthetic procedure. In addition, titanium butoxide (TBT) precursor, instead of the typical titanium tetra isopropoxide, was used for the formation of the $TiO_2$ shell. The synthesized nanoparticles were used to separate selenite ($Se^{4+}$) in the presence of $Se^{6+}$ or selenium anions for the photocatalytic reduction to $Se^0$ atom on the $TiO_2$ shell, followed by magnetic separation using $Fe_3O_4$ nanoparticles. The reduction efficiency of the photocatalytic reaction was 81.4% at a UV power of 6W for 3 h with a dark adsorption of 17.5% to the nanoparticles, as determined by inductively coupled plasma-mass spectrometry (ICP-MS). The developed separation method can be used for the speciation and preconcentration of selenium cations in environmental and biological analysis.

• 한국지구물리탐사학회:학술대회논문집
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• 한국지구물리탐사학회 2003년도 Proceedings of the international symposium on the fusion technology
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• pp.522-525
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• 2003

Mine waters, surface waters and groundwaters were sampled around seven Au-Ag mine areas (Dongil, Okdong, Dongjung, Songcheon, Ssangjeon, Dogok and Gubong Au-Ag mines). The main contamination sources of As in these abandoned Au-Ag mines can be suggested as mine tailings and waste rocks including the sulfide gangue minerals (arsenopyrite). The relatively high concentration of As in mine waters was shown in the Dongil (524 ${\mu}g/L$) and the Dogok (56 ${\mu}g/L$) mine areas. Arsenic concentrations in stream waters from the Dongil ($0.9\~118{\mu}g/L$), the Songchon ($0.8\~63{\mu}g/L$), the Ssangjeon ($1.6\~109{\mu}g/L$) and the Gubong ($3.6\~63{\mu}g/L$) mine areas exceeded the permissible level for stream water in Korea. Groundwaters collected from the Dongil ($0.9\~64{\mu}g/L$ ), the Okdong ($0.2\~69{\mu}g/L$) and the Gubong ($0.5\~101{\mu}g/L$) mine areas contained high As concentration to cause the arsenicosis in these areas. In As speciation, the concentration ratios of As(III) to As(total) present up to $75\%$ and $100\%$ in stream waters from the Okdong and the Songcheon mines, and $70\%$ in groundwaters from the Okdong and the Dongjung mines. Arsenic concentration decreases downstream from the tailing dump correlatively with pH and Fe concentration. Highly elevated As concentrations are found in the dry season (such as April and March) than in the wet season (September) due to the dilution effect by heavy rain during summer in stream waters from the Dongil and the Songcheon mine areas.

• 한국지하수토양환경학회:학술대회논문집
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• 한국지하수토양환경학회 2002년도 추계학술발표회
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• pp.291-295
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• 2002

We measured the concentrations of heavy metals and VOCs in groundwaters (N=38) in Seoul. The comparison of our data with U.S. Environmental Protection Agency's Maximum Contaminant Levels for Drinking Water and with the Korean Drinking Water Standards shows that most of the metals except for Fe and Mn do not exceed the levels. However, the concentrations of most heavy metals (esp., Zn, Cu, Cr, Ni) tend to increase in residential and industrialized areas. The examination of the metal speciation using Anodic Stripping Voltammetry (ASV) and TOC analyzer Indicates that large amounts of Zn occur as labile metal fraction, whereas Cu occurs as non- labile forms at many sites, possibly due to its tendency to be adsorbed onto inorganic colloidal particles to form electroinactive species in groundwater. The most frequently existed VOCs in Seoul groundwaters are trichloroethylene and tetrachloroethylene, especially in agricultural, industrial, and high traffic areas.

• 동의생리병리학회지
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• 제16권2호
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• pp.365-372
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• 2002

The mineral medicines mean a sort of mineral or rock for medical treatment and natural material using their chemical components and physical properties. In this study, it was apprehended the mineralogical characteristics of As-bearing group mineral medicines. The extraction test is an vitro test system for predicting the bioavailability of the major and minor elements from mineral medicines and incorporates gastrointestinal tract parameters representative of a human(including stomach and small intestinal pH, stomach mixing time and velocity). The results of the extraction test are used for reaction path modeling in human body. Reaction path modeling in human body can predict digestion with gastric juice as well as bioavailability, speciation. Also, it can predict accumulation of arsenic as pH condition. As the results of the extraction test for digestion, the amounts of Fe extraction was the highest, followed by As, Ca, Ni. In addition, as the results of the reaction path modeling between arsenic compounds and gastric juice using thermodynamic data, when absorbed, major species are followed by H₃As₃S/sub 6/(aq), As₃S/sub 6/ (aq), AsO/sup +/, H₂As₃S/sup 6-/, H₂AsO/sup 3-/, HAs₃S6/sup 2-/, HAsO/sub 3//sup 2-/ and AsO/sub 3//sup 3-/. Specifically the concentration of H₃As₃S/sub 6/(aq) is the highest. As pH increases, the concentration of H₂AsO/sup 3-/, HAsO/sub 3//sup 2-/, HAsO/sub 3//sup 3-/, HAs₃S/sub 6//sup 2-/, H₂As₃S/sup 6-/, and H₃As₃S/sub 6/ increases, whereas the concentration of H₃As₃S/sub 6/ and AsO/sup +/ decreases. On the results of this study, it is able to find out effective and toxic components of poisonous arsenic group of mineral medicines and expected to be widely used for the development of new medicines.

• Environmental Engineering Research
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• 제13권3호
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• pp.131-135
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• 2008

In this study, Fe(VI) was employed as a multi-functional agent to treat the simulated industrial wastewater contaminated with Cu(II)-EDTA through oxidation of EDTA, decomplexation of Cu(II)-EDTA and subsequent removal of free copper through precipitation. The decomplexation of $10^{-4}\;M$ Cu(II)-EDTA species was performed as a function of pH at excess concentration of Fe(VI). It was noted that the acidic conditions favor the decomplexation of Cu(II)-EDTA as the decomplxation was almost 100% up to pH 6.5, while it was only 35% at pH 9.9. The enhanced degradation of Cu(II)-EDTA with decreasing the pH could be explained by the different speciation of Fe(VI). $HFeO_4^-$ and $H_2FeO_4$, which are relatively more reactive than the unprotonated species $FeO_4^{2-}$, are predominant species below neutral pH. It was noted that the decomplexation reaction is extremely fast and within 5 to10 min of contact, 100% of Cu(II)-EDTA was decomplexed at pH 4.0. However, at higher pH (i.e., pH 10.0) the decomplexation process was relatively slow and it was observed that even after 180 min of contact, maximum ca 37% of Cu(II)-EDTA was decomplexed. In order to discuss the kinetics of the decomplexation of Cu(II)-EDTA, the data was slightly fitted better for the second order rate reaction than the first order rate reaction in the excess of Fe(VI) concentration. On the other hand, the removal efficiency of free Cu(II) ions was also obtained at pH 4.0 and 10.0. It was probably removed through adsorption/coagulation with the reduced iron i.e., Fe(III). The removal of total Cu(II) was rapid at pH 4.0 whereas, it was slow at pH 10.0. Although the decomplexation was 100% at lower pH, the removal of free Cu(II) was relatively slow. This result may be explicable due to the reason that at lower pH values the adsorption/coagulation capacity of Fe(III) is greatly retarded. On the other hand, at higher pH values the decomplexation of Cu(II)-EDTA was partial, hence, slower Cu(II) removal was occurred.

• 한국해양학회지:바다
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• 제20권4호
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• pp.159-168
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• 2015

한국 남서해 연안의 도암만에서 44개 표층퇴적물을 채취하여 총유기탄소(TOC), 총질소(TN) 및 중금속(Al, Fe, Mn, Cr, Cu, Ni, Pb, Zn)을 분석하였으며, 11개 시료에 대해서는 화학적 존재형태별 분석을 병행하였다. TOC(0.32~3.10%), TN(0.03~0.26%)은 주변 해역의 평균 수준이었고, C/N 비(7.9~11.9)에 근거할 때 육상기원 유기물의 영향이 반영된 일부 지역이 구분되었다. 중금속 함량은 대부분의 정점에서 해양퇴적물 주의기준(TEL) 이하였고, 화학적 존재형태별 함량은 광물격자부분에서 Cr, Cu, Ni 등이, 비광물격자부분에서 Mn, Pb가 총량의 절반을 상회하였다. 연구지역의 중금속 배경농도를 누적빈도곡선과 선형회귀분석에 의해 추정한 결과 Cu=11.8, Ni=23.1, Pb=26.8, Zn=76.6, Cr=56.7, Mn=585 mg/kg으로 계산되었으며, 이를 바탕으로 한 농축지수($I_{geo}$)에 근거해 국지적인 Mn 농축의 징후를 확인하였다. 그러나 농축지수와 존재형태비를 고려할 때 Zn, Pb도 환경변화에 따른 용출 가능성이 추정되었다.

• 한국광물학회지
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• 제11권1호
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• pp.20-31
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• 1998

Adsorption of metal elements onto illite and halloysite was investigated at $25^{\circ}C$ using pollutant water collected from the gold-bearing metal mine. Incipient solution of pH 3.19 was reacted with clay minerals as a function of time: 10 minute, 30 minute, 1 hour, 12 hour, 24 hour, 1 day, 2 day, 1 week, and 2 week. Twenty-seven cations and six anions from solutions were analyzed by AAs (atomic absorption spectrometer), ICP(induced-coupled plasma), and IC (ion chromatography). Speciation and saturation index of solutions were calculated by WATEQ4F and MINTEQA2 codes, indicating that most of metal ions exist as free ions and that there is little difference in chemical species and relative abundances between initial solution and reacted solutions. The adsorption results showed that the adsorption extent of elements varies depending on mineral types and reaction time. As for illite, adsorption after 1 hour-reaction occurs in the order of As>Pb>Ge>Li>Co, Pb, Cr, Ba>Cs for trace elements and Fe>K>Na>Mn>Al>Ca>Si for major elements, respectively. As for halloysite, adsorption after 1 hour-reaction occurs in the order of Cu>Pb>Li>Ge>Cr>Zn>As>Ba>Ti>Cd>Co for trace elements and Fe>K>Mn>Ca>Al>Na>Si for major elements, respectively. After 2 week-reaction, the adsorption occurs in the order of Cu>As>Zn>Li>Ge>Co>Ti>Ba>Ni>Pb>Cr>Cd>Se for trace elements and Fe>K>Mn>Al, Mg>Ca>Na, Si for major elements, respectively. No significant adsorption as well as selectivity was found for anions. Although halloysite has a 1:1 layer structure, its capacity of adsorption is greater than that of illite with 2:1 structure, probably due to its peculiar mineralogical characteristics. According to FTIR (Fourier transform infrared spectroscopy) results, there was no shift in the OH-stretching bond for illite, but the ν1 bond at 3695 cm-1 for halloysite was found to be stronger. In the viewpoint of adsorption, illite is characterized by an inner-sphere complex, whereas halloysite by an outer-sphere complex, respectively. Initial ion activity and dissociation constant of metal elements are regarded as the main factors that control the adsorption behaviors in a natural system containing multicomponents at the acidic condition.

• 한국광물학회지
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• 제26권2호
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• pp.129-138
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• 2013

최근 들어 안정된 수자원 확보를 위해 하천수를 강변의 충적층을 통과시켜 취수하는 강변 여과수 개발이 각광을 받고 있다. 지표수 및 지하수와 반응하는 주변 충적층 퇴적물에 존재하는 철은 강변 여과 후 양수정을 통해 얻어지는 지하수의 수질을 결정하는 데 매우 중요한 요소이다. 본 연구에서는 퇴적물-지하수-지표수의 상호 작용에 의한 철 화학종의 존재 변화를 알아보기 위해 창원시 대산면 낙동강변의 강변여과 부지에서 채취한 대수층 퇴적물 내에 존재하는 철 함유량을 퇴적물 심도 및 입자 크기에 따라 다양한 화학적 철 추출법을 통해 비교하였다. 실험 결과는 전체적으로 지표로부터 20 m 부근까지는 2가철 및 총 철 함량이 전체적으로 감소하다 20 m 깊이 이하에서는 증가하는 경향을 나타내었다. 이러한 결과는 육안으로 관찰되는 퇴적물 색깔이 지시하는 산화/환원 환경 특성과도 일치하였다. 한편, 퇴적물의 모래 부분보다 미사/점토 부분에서 추출법에 따라 2~10배의 철이 추출되었다. 그리고, 다양한 추출법 중 DCB 용액에 의해 가장 많은 철이 추출되었다. 이와 같은 다양한 철 분석법으로 추출되는 철 함량 특성은 퇴적물 내에서 철의 용해 및 침전을 결정짓는 심도에 따른 산화/환원 조건의 좋은 지시자로 활용될 수 있을 것으로 판단된다.

• 한국지반신소재학회논문집
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• 제11권4호
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• pp.9-16
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• 2012

비소는 음이온적인 거동을 가지고 Eh-pH의 조건에 따라 특성이 변화하여 비소로 오염된 토양을 정화하기 위한 방법이 확립되어있지 못한 실정이다. 최근 입경분리 식 토양세척을 통하여 비소를 미세토 내로 농축시켜 반출, 처리하는 방법이 많이 이용되고 있으나, 이 때 발생된 미세토는 지정폐기물로 간주, 처리되어야 한다, 따라서 본 연구에서는 토양세척 후 발생되는 탈수미세토 내 비소를 불용화하고, 이를 매립지 차수재로 재이용하는 방안을 연구하고자 한다. 비소를 불용화하기 위한 최적의 조건으로 50% 이상의 함수율과 탈수미세토의 건조중량을 기준으로 8%에 해당하는 FeS가 요구되었고 건조된 탈수미세토 10g 당 0.2ml의 $H_2O_2$가 적절한 것으로 평가되었으며, 안정적인 반응을 위하여 24시간 이상의 반응시간이 요구되었다. 또한 매립지 차수재로서의 재활용을 위한 실험에서 100% 탈수미세토 기준, 시멘트 3%와 벤토나이트 13%의 배합비로 혼합하여 28일 동안 재령한 공시체가 강도와 투수계수 값이 매립지 차수층의 법적기준을 만족하는 것으로 나타났다.

• 한국지하수토양환경학회:학술대회논문집
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• 한국지하수토양환경학회 2004년도 총회 및 춘계학술발표회
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• pp.100-101
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• 2004

Many researches in Korea have been performed to understand the pollution of stream waters by acid mine drainage. However, few studies have been conducted regarding the effect of particulate and colloidal fractions on the transport of trace metals. To estimate harmful effects of trace metals, it is important to evaluate the particulate and colloidal metals as well as dissolved metals, because particulate and colloidal fractions of trace metals play an important role in transport of trace metals and may adversely affect habitats and organisms in riverine system. Colloids are solids with effective diameters in size range from 0.001 $\mu$m to 1 $\mu$m. According to Jone et al. (1974), metals in surface water, like Al, Fe, and Mn, require filtration with pore-size membranes smaller than 0.45 $\mu$m to define dissolved concentrations. The main objective of this study is to understand the effects of particulate, colloidal, and truly dissolved fractions on the transport and fate of trace metals in acid mine drainage. This study was conducted for the Onjeong creek in the Uljin mine area. Sampling was carried out in 13 sites, spatially covering the area from mine dumps to the downstream Onjeong reservoir. To examine the metal partitioning between particulate, colloidal, and truly dissolved fraction, we used successive filtration techniques consisting of conventional method (using 0.45 $\mu$m membranes) and tangential-flow ultrafiltration (using 0.001 $\mu$mm membranes). Ultrafiltration may seperate much smaller particles from aqueous phase (Josephson, 1984; Hernandez and Stallard, 1988). The analysis of metals were performed by inductively coupled plasma - atomic emission spectrometer (ICP-AES: model Perkin Elmer OPTIMA3000XL). Anions such as SO$_4$, Cl and NO$_3$ were measured with ion chromatograph (IC: model Dionex 120). Sample analysis is still in progress. The preliminary data show that the studied creek is severely polluted by Al, Fe, Mn, Pb and Zn. Toward upstream sites with relatively lower pH, less than 50% of Al and Fe occur in the sorbed form on particles or colloids, whereas more than 80% of Al and Fe occur in the sorbed form in downstream sites or tributaries with relatively higher pH. Less than 30% of Zn is present in particle or colloidal forms in the whole range of creek. Truly dissolved fraction of trace metals is negatively correlated with pH. The Kd values for Al, Fe and Zn consistently increase with increasing pH and decrease with increasing particle concentration.