• Title/Summary/Keyword: Speciation

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New Analytical Method to Identify Chromium Species, Cr(III) and Cr(VI), and Characteristic Distribution of Chromium Species in the Han River (한강수계해서의 크롬(III,VI) 종(species) 분포 및 분석방법 정립)

  • Jeong, Gwan-Jo;Kim, Dok-Chan;Park, Hyeon
    • Journal of Korean Society of Environmental Engineers
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    • v.27 no.6
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    • pp.590-598
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    • 2005
  • An adequate method to identify chromium separation, Cr(III) and Cr(VI), in water samples were studied by using High Performance Liquid Chromatography(HPLC) coupled with Inductively Coupled Plasma Mass Spectometer(ICP-MS) equipped with Dynamic Reaction Cell(DRC). The characteristic distribution of Cr(III) and Cr(VI) in the raw water taken at the six water intake stations in Seoul, was analyzed by the method developed by the authors. The chromium species separated by HPLC was isocratically conducted by using tetrabutylammonium phosphate monobasic(1.0 mM TBAP), ethylenediaminetetraacetic acid(0.6 mM EDTA) and 2% v/v methanol as the mobile phase. 5% v/v methanol was used as flushing solvent. A reactive ammonia($NH_3$) gas was used to eliminate the potential interference of $ArC^+$. Several Parameters such as solvent ratio, pH, flow rate and sample injection volume were optimized for the successful separation and reproducibility. Although it has been reported thai the separation sensitivity of Cr(III) is superior to that of Cr(VI), the authors observed Cr(VI) was more sensitive than Cr(III) when ammonia($NH_3$) gas was used as the reaction gas. It took less than 3 minutes to analyze chromium species with this method and the estimated detection limits were $0.061\;{\mu}g/L$ for Cr(III) and $0.052\;{\mu}g/L$, for Cr(VI). According to the results from the analysis on chromium species in the raw water of the six intake stations, the concentrations of Cr(III) ranged from 0.048 to $0.064\;{\mu}g/L$(ave. $0.054\;{\mu}g/L$) while that of Cr(VI) ranged from 0.014 to $0.023\;{\mu}g/L$(ave. $0.019\;{\mu}g/L$). Recovery ratio was very high($90.1{\sim}94.1%$). There were two or three times more Cr(III) than Cr(VI) in the raw water.

The Copper Adsorption onto Hwangto Suspension from Pankok-ri, Kosung-gun (경남 고성군 판곡리 황토 현탁액의 구리 흡착 특성)

  • Cho Hyen Goo;Park Sooja;Choo Chang Oh
    • Journal of the Mineralogical Society of Korea
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    • v.17 no.3
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    • pp.209-220
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    • 2004
  • Adsorption behavior of Cu onto Hwangto, from Pankok-ri, Kosung-gun, suspension was studied using Cu batch adsorftion experiment and computer program MINTEQA2 and FITEQL 3.2. The sorption of copper was investigated as a function of pH, copper concentration and $NaNO_3$ background concentration (0.01 and 0.1 M). The concentration of copper was analyzed using ICP-AES. The sorption of copper onto Hwangto suspension increased with increasing pH and copper concentration. The adsorption percentage of copper drastically increased from pH 5.5 to 6.5, and reached nearly 100% at pH 7.5. Because the amount of copper solution and the ionic strength of background electrolyte may not affect the sorption of copper onto Hwangto, the copper ion may be combined at the surface of Hwangto as an inner-sphere complex. Using the MINTEQA2 program, the speciation of copper was calculated as a function of pH and copper concentration. The concentration of $Cu^{2+}$ decreased and that of $Cu(OH)_2$ increased with increasing pH. The uptake of copper in the Hwangto suspension was simulated by FITEQL3.2 program using two sites-three pKas model, which is composed of silicate reaction site and Fe oxide reaction site. The copper absorption reaction constants were calculated in the case of 2~6 mL of copper solution. The Fe oxide reaction site rapidly adsorbs copper ion between pH 4.5~6.5. Silicate reaction site adsorbs little copper ion at low copper concentration but much at high copper concentration. The removal amount of copper by precipitation was negligible in comparison with that of adsorption. The Fe oxide reaction site may has higher adsorption affinity of copper ion than silicate reaction site.

Characterization of Arsenic Adsorption onto Hematite (적철석(Hematite) 표면의 비소 흡착 특성)

  • Kim, Seong Hee;Lee, Woo Chun;Cho, Hyen Goo;Kim, Soon-Oh
    • Journal of the Mineralogical Society of Korea
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    • v.25 no.4
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    • pp.197-210
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    • 2012
  • Hematite has been known to be the most stable form of various iron (oxyhydr)oxides in the surface environments. In this study, its properties as an adsorbent were examined and also adsorption of arsenic onto hematite was characterized as well. The specific surface area of hematite synthesized in our laboratory appeared to be $31.8g\;m^2/g$ and its point of zero salt effect, (PZSE) determined by potentiometric titration was observed 8.5. These features of hematite may contribute to high capacity of arsenic adsorption. From several adsorption experiments undertaken at the identical solution concentrations over pH 2~12, the adsorption of As(III) (arsenite) was greater than that of As(V) (arsenate). As of pH-dependent adsorption patterns, in addition, arsenite adsorption gradually increased until pH 9.2 and then sharply decreased with pH, whereas adsorption of arsenate was greatest at pH 2.0 and steadily decreased with the increasing pH from 2 to 12. The characteristics of these pH-dependent adsorption patterns might be caused by combined effects of the variation in the chemical speciation of arsenic and the surface charge of hematite. The experimental results on adsorption kinetics show that adsorption of both arsenic species onto hematite approached equilibrium within 20 h. Additionally, the pseudo-second-order model was evaluated to be the best fit for the adsorption kinetics of arsenic onto hematite, regardless of arsenic species, and the rate constant of As(V) adsorption was investigated to be larger than that of As(III).

Difference in Electrophoretic Phenotypes of rice Cultivars Selected to Bensulfuron (Bensulfuron에 대(對)한 내성(耐性) 및 감수성(感受性) 수도품종(水稻品種)의 전기영동(電氣泳動) 표현형(表現型) 차이(差異))

  • Kuk, Y.I.;Guh, J.O.;Kim, Y.J.;Lee, D.J.
    • Korean Journal of Weed Science
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    • v.8 no.3
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    • pp.250-257
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    • 1988
  • The study was intended to know any relations between the rice tolerance to bensulfuron and varietal speciation in seed protein composition or any enzymatical allelies with or without chemical treatment. Rice varieties used were UCP-28, Chinsurah Boro II, Fukunohama, Fadehpur-2, IR 14252-13-2-2-5 as the tolerant group, and HP 93(3) FA, HP94(9) FA, Padilabou Alumbis, KH-17854, and IR 1846-2841-1 as the susceptible, respectively. Electrophoretic methods used were SDS-PAGE for seed protein, 7% PAGE for isozymes (acid phosphatase, peroxidase, malate dehydrogenase, and esterase from rice seedling) and variation in isoenzyme profiles (malate dehydrogenase, peroxidase, and esterase) as affected by different concentrations of bensulfuron(0, $10^{-6}$, $10^{-5}$ and $3{\times}10^{-5}M$) was also studied. The results are summarized as follows. -Among 16 bands separated in seed proteins, two different rice groups selected in terms of tolerance to bensulfuron were clustered in dissimilarity, which was based on relatively larger area in whole peaks and higher activities in N, O, P bands for the tolerant group. -Among isozymes obtained from rice seedlings without chemical treatments, the following specificities were obtained. The tolerant varieties had the relatively higher activity in D band out of 4 peroxidase bands. Malate dehydrogenase was separated into 3 bands and only tolerant varieties had A band and higher activities in Band C bands. Esterase was separated into 3-4 bands with higher activities in A and B bands for tolerant varieties. There were one major band accompanied by 2-3 minor bands for acid phosphatase in which only tolerant varieties had the B band. -The effect of Bensulfuron concentration on the isozyme activities showed that the activity of C band in peroxidase was not present in tolerant varieties which was contrary to the increased activities in susceptible varieties. However, D band was gradually disappeared only in susceptible varieties as the concentration of bensulfuron was increased. For malate dehydrogenase in the susceptible varieties, major bands D, E and F kept consistantly higher activities while minor bands A, B and C disappeared sensitively. Among 5 bands of esterase separated, D band was present only in the tolerant varieties while E band only in the susceptible. The activities in A, C, E bands were sharply decreased in the susceptible varieties as the concentration of bensulfuron was increased.

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Adsorption of Arsenic on Goethite (침철석(goethite)과 비소의 흡착반응)

  • Kim, Soon-Oh;Lee, Woo-Chun;Jeong, Hyeon-Su;Cho, Hyen-Goo
    • Journal of the Mineralogical Society of Korea
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    • v.22 no.3
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    • pp.177-189
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    • 2009
  • Iron (oxyhydr)oxides commonly form as secondary minerals of high reactivity and large surface area resulting from alteration and weathering of primary minerals, and they are efficient sorbents for inorganic and organic contaminants. Accordingly, they have a great potential in industrial applications and are also of substantial interest in environmental sciences. Goethite (${\alpha}$-FeOOH) is one of the most ubiquitous and stable forms of iron (oxyhydr)oxides in terrestrial soils, sediments, and ore deposits, as well as a common weathering product in rocks of all types. This study focused on adsorption reaction as a main mechanism in scavenging arsenic using goethite. Goethite was synthesized in the laboratory to get high purity, and a variety of mineralogical and physicochemical features of goethite were measured and related to adsorption characteristics of arsenic. To compare differences in adsorption reactions between arsenic species, in addition, a variety of experiments to acquire adsorption isotherm, adsorption edges, and adsorption kinetics were accomplished. The point of zero charge (PZC) of the laboratory-synthesized goethite was measured to be 7.6, which value seems to be relatively higher, compared to those of other iron (oxyhydr)oxides. Its specific surface area appeared to be $29.2\;m^2/g$ and it is relatively smaller than those of other (oxyhydr)oxides. As a result, it was speculated that goethite shows a smaller adsorption capacity. It is likely that the affinity of goethite is much more larger for As(III) (arsenite) than for As(V) (arsenate), because As(III) was observed to be much more adsorbed on goethite than As(V) in equivalent pH conditions. When the adsorption of each arsenic species onto goethite was characterized in various of pH, the adsorption of As(III) was largest in neutral pH range (7.0~9.0) and decreased in both acidic and alkaline pH conditions. In the case of As(V), the adsorption appeared to be highest in the lowest pH condition, and then decreased with an increase of pH. This peculiarity of arsenic adsorption onto goethite might be caused by macroscopic electrostatic interactions due to variation in chemical speciation of arsenic and surface charge of goethite, and also it is significantly affected by change in pH. Parabolic diffusion model was adequate to effectively evaluate arsenic adsorption on goethite, and the regression results show that the kinetic constant of As(V) is larger than that of As(III).

Arsenic Speciation and Risk Assessment of Miscellaneous Cereals by HPLC-ICP-MS (HPLC-ICP-MS를 활용한 잡곡의 비소 화학종 및 위해 분석)

  • An, Jae-Min;Hong, Kyong-Suk;Kim, Sung-Youn;Kim, Dae-Jung;Lee, Ho-Jin;Shin, Hee-Chang
    • Korean Journal of Environmental Agriculture
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    • v.36 no.2
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    • pp.119-128
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    • 2017
  • BACKGROUND: Miscellaneous cereal have been largely consumed in Korea as due to their physiological functions beneficial to human health. The cereals are currently a social concern because they have been found to contain heavy metals. Thus, monitoring heavy metals in the cereals is an important requirement for food safety analysis. In this study, we determined arsenic concentration in the cereals randomly harvested from different markets. METHODS AND RESULTS: Inorganic arsenic was determined by ICP-MS coupled with HPLC system. The HPLC-ICP-MS analysis was optimized based on the limit of detection and recover test to reach $0.13-1.24{\mu}g/kg$ and 94.3-102.1%, respectively. The concentrations of inorganic arsenic equivalent to daily exposure were levels of $19.91{\mu}g/day$ in mixed grain, $1.07{\mu}g/day$ in glutinous rice, $0.77{\mu}g/day$ in black brown rice, $0.13{\mu}g/day$ in barley and $0.11{\mu}g/day$ in soybeans. CONCLUSION: The levels of arsenic in miscellaneous cereals were found lower than the recommended The Joint FAO/WHO Expert Committee on Food Additives (JECFA) levels, suggesting that the cereals marketed in Korea are not potential concern in risk assessment.

The Effects of pH Control on the Leaching Behavior of Heavy Metals within Tailings and Contaminated Soils : Seobo and Cheongyang Tungsten Mine Areas (광미와 오염토양 내 중금속 용출특성에 미치는 pH영향 : 청양과 서보중석광산)

  • 이평구;강민주;박성원;염승준
    • Economic and Environmental Geology
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    • v.36 no.6
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    • pp.469-480
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    • 2003
  • Laboratory leaching experiment study carried out to estimate a extent of heavy metals that could be leached out when acid rain(pH 5.0-3.0) and strong acidic solution(pH 2.5-1.0) reacted with tailings and contaminated soils from abandoned metal mines. In slightly to moderately acid conditions(pH 5.0-3.0), As, Pb and Zn dissolutions became significantly increased with decreased pH in tailing, while dissolution of these elements was very limited in contaminated soil. These results suggested that moderately acid rainwater leaches Pb, As and Zn from the tailings, while these elements would remain fixed in contaminated soil. In the pH range of 2.5-1.0(strongly acid condition), Zn, Cd and Cu concentrations of leachate rapidly increased with decreased pH in contaminated soil, while Pb, As and Co dissolutions became importantly increased in tailings. The experimental solubility of Zn. Cd and Cu was very low even at very low pH values(up to pH 1), except for CY4(Cheongyang mine). These can result from an incomplete dissolution or the presence of less soluble mineral phases. So, the solubility of heavy metals depends not only on the pH values of leachate but also on the speciation of metals associated with contaminated soils and tailings. The relative mobility of each element within failings at the pH 5.0-3.0 of the reaction solution was in the order of Pb>Zn>Cd>Co=Cu>As. In case of pH 2.5-1.0 of the reaction solution, the relative mobility of each element within contaminated soils and tailings were in the order of Zn>Cd>Cu>Co>Pb=As for contaminated soils, and Pb>Zn>Cd>hs>Co>Cu for tailings. The obtained results could be useful for assessing the environmental effects and setting up the restoration plan in the areas.

Au-Ag-Te Mineralization by Boiling and Dilution of Meteoric Ground-water in the Tongyeong Epithermal sold System, Korea: Implications from Reaction Path Modeling (광화유체의 비등과 희석에 의한 통영 천열수계 Au-Ag-Te 장화작용에 대한 반응경로 모델링)

  • Maeng-Eon Park;Kyu-Youl Sung
    • Economic and Environmental Geology
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    • v.34 no.6
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    • pp.507-522
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    • 2001
  • At the Tongyeong mine, quartz, rhodochrosite (kutnahorite), muscovite, illite, pyrite, galena, chalcopyrite. sphalerite, acanthite, and hessite are the principal vein minerals. They were deposited under epithermal conditions in two stages. Ore mineral assemblages and associated gangue phases in stage can be clearly divided into two general associations: an early cycle (band) that appeared with introduction of most of the sulfides and electrum, and a later cycle in which base metal and carbonate-bearing assemblages (mostly rhodochrosite) became dominant. Tellurides and some electrum occur as small rounded grains within subhedral-to euhedral pyrite or anhedral galena in stageII. Sulfide mineralization is zoned from pyrite to galena and sphalerite. We have used computer modeling to simulate formation of four stages of vein genesis. The reaction of a single fluid with andesite host rock at 28$0^{\circ}C$, isobaric cooling of a single fluid from 26$0^{\circ}C$ to 12$0^{\circ}C$, and boiling and mixing of a fluid with both decreasing pressure and temperature were studied using the CHILLER program. Calculations show that the precipitation of alteration minerals is due to fluid-andesite interaction as temperature drops. Speciation calculations confirm that the hydrothermal fluids with moderately high salinities and pH 5.7 (acid), were capable of transporting significant quantities of base metals. The abundance of gold in fluid depends critically on the ratio of total base metals and iron to sulfide in the aqueous phase because gold is transported as an Au(HS)$_2$- complex, which is sensitive to sulfide activity. Modeling results for Tongyeong mineralization show strong influence of shallow hydrogenic processes such as boiling and fluid mixing. The variable handing in stageII mineralization is best explained by maltiple boilings of hydrothermal fluid followed by lateral mixing of the fluid with overlying diluted, steam-heated ground water. The degree of similarity of calculated mineral assemblages and observed electrum composition and field relationships shows the utility of the numerical simulation method in identifying chemical processes that accompany boiling and mixing in Te-bearing Au-Ag system. This has been applied in models to narrow the search area for epithermal ores.

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Risk Analysis of Inorganic Arsenic in Foods (식품 중 무기비소의 위해 분석)

  • Yang, Seung-Hyun;Park, Ji-Su;Cho, Min-Ja;Choi, Hoon
    • Journal of Food Hygiene and Safety
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    • v.31 no.4
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    • pp.227-249
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    • 2016
  • Arsenic and its compounds vary in their toxicity according to the chemical forms. Inorganic arsenic is more toxic and known as carcinogen. The provisional tolerable weekly intake (PTWI) of $15{\mu}g/kg$ b.w./week established by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) has been withdrawn, while the EFSA panel suggested $BMDL_{0.1}$ $0.3{\sim}8{\mu}g/kg\;b.w./day$ for cancers of the lung, skin and bladder, as well as skin lesions. Rice, seaweed and beverages are known as food being rich in inorganic arsenic. As(III) is the major form of inorganic arsenic in rice and anaerobic paddy soils, while most of inorganic arsenic in seaweed is present as As(V). The inorganic arsenic in food was extracted with solvent such as distilled water, methanol, nitric acid and so on in heat-assisted condition or at room temperature. Arsenic speciation analysis was based on ion-exchange chromatography and high-performance liquid chromatography equipped with atomic absorption spectrometry and inductively coupled plasma mass spectrometry. However, there has been no harmonized and standardized method for inorganic arsenic analysis internationally. The inorganic arsenic exposure from food has been estimated to range of $0.13{\sim}0.7{\mu}g/kg$ bw/day for European, American and Australian, and $0.22{\sim}5{\mu}g/kg$ bw/day for Asian. The maximum level (ML) for inorganic arsenic in food has established by EU, China, Australia and New Zealand, but are under review in Korea. Until now, several studies have conducted for reduction of inorganic arsenic in food. Inorganic arsenic levels in rice and seaweed were reduced by more polishing and washing, boiling and washing, respectively. Further research for international harmonization of analytical method, monitoring and risk assessment will be needed to strengthen safety management of inorganic arsenic of foods in Korea.

Analyzing the Effectiveness of Argumentation Program to Conceptualize the Concept of Natural Selection for Elementary Science-Gifted Students (초등과학영재들의 자연선택 개념 형성을 위한 논변활동 효과 분석)

  • Park, Chuljin;Cha, Heeyoung
    • Journal of The Korean Association For Science Education
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    • v.36 no.4
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    • pp.591-606
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    • 2016
  • The purpose of this study is to develop the argumentation program to build scientific concepts on natural selection for science-gifted elementary students and to know how to implement this program. For this study, nine key concepts about natural selection such as the overproduction of offspring, limited resources, population stability, competition, variation, heredity of variation, differential survival, change of the population and speciation were selected through the literature study. The programs were developed by learning cycle instructional model. Argument writings and discourses have been collected, analyzed and compared before and after the program. Two questionnaires to compare pre and post concept change consist of multiple choice questionnaire and open-ended response question were developed and applied to 19 science-gifted elementary students. Sufficiency of the explanation and conceptual quality of the explanation were used to assess the quality of their arguments before and after the program. Discourse and visual models collected from the highest and lowest group about score improvement were compared. The scores of the gifted statistically improved significantly in multiple choice questionnaire. Students' alternative conceptions about natural selection at the beginning of the program decreased and changed scientifically after the program. Visual models drawn by the students supported the results as well. This study asserts that elementary science-gifted students are able to explain evolutionary perspectives about organism change and use the key concepts of natural selection. The study means that evolutionary perspective is possible to be reflected in elementary science curriculum for the gifted.