• Applied Biological Chemistry
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• 제41권4호
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• pp.241-245
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• 1998

Two oxidation states of chromium commonly occur in natural soil/water systems, Cr(III) and Cr(VI). The oxidized form, Cr(VI), exists as the chromate ion and is more mobile and toxic than Cr(III). Therefore oxidation of Cr(III) by various Mn-oxides in natural systems is a very important environmental concern. Organic substances can inhibit the Cr(III) oxidation by binding, Cr(III) strongly and also by dissolving Mn-oxides. Most of Cr(III) oxidation studies were carried out using in vitro systems without organic substances which exist in natural soil/water systems. In this study effect of organic acids - oxalate and pyruvate - on Cr(III) oxidation by $birnessite({\delta}-MnO_2)$ was examined. The two organic acids significantly inhibited Cr(III) oxidation by birnessite. Oxalate showed more significant inhibition than pyruvate. As solution pH was lowered in the range of 3.0 to 5.0, the Cr(III) oxidation was more strongly depressed. Addition of more organic acids reduced the Cr(III) oxidation mare extensively. Different inhibition effects by the organic acids could be due to their ability of reductive dissolution of Mn-oxides and/or Cr(III) binding. Organic acids dissolved Mn-oxide during the Cr(III) oxidation by the oxide, Dissolution by oxalic acid was much greater than that by pyruvate, and the dissolution was more extensive at lower pH. Inhibition of Cr(III) oxidation was parallel to the dissolution of Mn-oxide by organic acids. Although the effect of Cr(III) binding by organic acids on Cr(III) oxidation is not known yet, Mn-oxide dissolution by organic acids could be a main reason for the inhibition of Cr(III) oxidation by Mn-oxide in presence of organic acids. Thus oxidation of Cr(III) to Cr(VI) by various Mn-oxides in natural systems could be much less than the oxidation estimated by in vitro studies with only Cr(III) and Mn-oxides.

• 대한화학회지
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• 제25권4호
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• pp.270-274
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• 1981

Al(III)과 Cr(III)을 여러 양이온과 음이온의 공존하에서 가리움제를 사용하지 않고 Bismark Brown R{4,4'[(4-methyl-1,3-phenylene)bis(azo)]-bis(6-methyl-1,3-benzenediamine)dihydrochloride)을 사용하여 정량하였다. 그러나 타르타르산과 시트르산이 공존하면 방해하였다. Al(III)과 Cr(III)은 같은 파장에서 최대흡광도를 나타내므로 Cr(III)을 Cr(VI)으로 산화시키면 Al(III)과 Cr(III)을 선택적으로 정량할 수 있었다.

• 한국산업보건학회지
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• 제4권2호
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• pp.189-197
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• 1994

Analytic methods for Cr(VI) level in industrial hygienic field were suggested by the National Institute for Occupational Safety and Health(NIOSH method 7600, 7604). There were growing needs for measurement of Cr(III) and Cr(VI) levels simultaneously. Two analytical methods were suggested to determine Cr(III) and Cr(VI) levels simultaneously. The one is method by using reversed phase high peformance liquid chromatography(HPLC) and the other is by using ion exchange HPLC. The purpose of this work was to evaluate the usefulness of these two analytic methods. For the difference of ionic charges of Cr(III)-ethylendiamine tetraacetic acid(EDTA) chelate and $CrO_4{^-2}$, we could detect them simultaneously by ion exchange HPLC. Also, we attempted to determine the levels of Cr(III) and Cr(VI) chelated with sodium diethyldithiocarbamate(NaDDTC) by using reversed phase HPLC. The confirmation of Cr(III) and Cr(VI) were checked by fraction collector and nameless atomic absorption spectrometer. The optimal conditions for the formation of Cr(III)-EDTA chelate were two hours incubation period with pH 5. Cr(III)-EDTA and Cr(VI) in EDTA solution were successfully separated by anion exchange column using $Na_2CO_3/NaOH$ mixture as mobile phase. Peaks of Cr(III)-EDTA and Cr(VI) in EDTA were identified at 5 minutes and 7 minutes of retention time respectively by the ion exchange HPLC. The formation of Cr(III)-NaDDTC and Cr(VI)-NaDDTC chelates were twelve hours incubation period. Cr(III)-NaDDTC and Cr(VI)-NaDDTC chelates were separated by reversed phase column using methanol and water mixture as mobile phase. Peaks of Cr(VI)NaDDTC and Cr(III)-NaDDTC chelates were identified at 13 minutes and 26 minutes of retention time respectively by the reversed phase HPLC. Due to reduction of Cr(VI) to Cr(III), it seems to be not suitable for simultaneous determination of Cr(III)-NaDDTC and Cr(VI)-NaDDTC chelates by reversed phase HPLS. Simultaneos determination of Cr(III) and Cr(VI) by ion exchange HPLC was more accurate and simple method.

• 대한화학회지
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• 제55권3호
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• pp.454-462
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• 2011

C-Metylcalix[4]resorcinarene(CMCR)에서 Pb(II)와 Cr(III)의 흡착 특징에 대한 연구는 수행되어왔다. CMCR은 resorcinol, acetaldehyde 그리고 HCl로 부터 1단계 합성으로 만들어졌다. 일괄처리시스템에서 대부분의 변수는 CMCR이 Pb(II)와 Cr(III)에 대해 좋은 흡착제라는 것을 확인했다. Cr(III)은 Pb(II)보다 더 크게 흡착되지만 Cr(III)의 흡착속도는 Pb(II) 보다 더 느리다. Pb(II)와 Cr(III) 흡착의 흡착운동에너지는 batch안에서 유사 2차 운동 모델을 따른다. 그러나 고정상 컬럼 시스템에서 Pb(II)의 운동에너지는 일차 모델을 따른다. 흡착된 Pb(II)을 되찾기 위한 탈착 연구는 증류수와 HCl을 가지고 순차적으로 수행되었다. 그리고 그 결과는 흡착은 화학흡착에 의해 지배된다는 것을 보여주었다.

• 한국토양환경학회지
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• 제4권2호
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• pp.11-31
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• 1999

회분식 및 연속류 주상 실험을 통해 인공 조제 지하수로부터 입상활성탄에 의한 6가크롬 (Cr(VI)) 제거에 대한 연구를 수행하였다. 실험에 적용된 변수로는 용액의 pH, 용존산소의 존재여부를 사용하였고 2가철(Fe(II))로 활성탄을 전처리한 것을 처리하지 않은 활성탄과 그 결과를 비교하였다. 용액의 pH를 4.0에서 7.5로 증가 시킴에 따라 무처리 및 Fe(II)로 전처리한 활성탄 모두에 흡착된 Cr(VI)의 양이 현저히 감소하였다. 용존산소가 배제 (무산소조건) 되었을 경우 Cr(VI) 제기량이 증가하였는데, 이는 Cr(VI)의 Cr(III)로의 환원 때문으로 추측된다. 그러나, Fe(II)에 의한 활성탄의 전처기는 Cr(Vl)제거에 거의 영향을 미치지 않았다 흡착된 Cr(VI)를 추출하기위해 0.01M $K_2$$HPO_4$와 침전 또는 흡착된 Cr(III)를 제거하기위해 0.02N $K_2$$HPO_4$로 세척하였는데, 이는 Cr(VI)로 흡착능이 고갈된 활성탄 재생의 한 방법으로 고려될 수 있으리라 사료된다. 재생된 활성탄은 본래의 활성탄보다 큰 흡착능을 보였는데, 그 이유는 Cr(VI)가 낮은 pH에서 흡착이 잘되며 또 Cr(III)로 환원되기 때문으로 사료된다. 산세척수중의 Cr(III)의 존재는 비교적 산성 조건하에서 Cr(VI)의 Cr(III)로의 환원을 보여주는 증거로 사료된다. 5회의 재생 및 재사용 실험에서 이 재생방법이 흡착능을 악화시키는 것 없이 지속적으로 사용될 수 있음을 알 수 있었다.

• 대한환경공학회지
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• 제27권6호
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• pp.590-598
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• 2005

본 연구에서는 HPLC와 DRC ICP-MS를 연결하여 수중의 Cr(III)와 Cr(VI) 측정을 위한 최적의 분석조건을 설정하고, 서울시 6개 취수장 원수에서의 Cr(III)와 Cr(VI)의 분포 특성을 조사하였다. 크롬 종(species) 분리를 위한 HPLC 이동상으로는 tetrabutylammonium phosphate monobasic(1.0 mM TBAP), ethylenediaminetetraacetic acid(0.6 mM EDTA) 그리고 2% v/v 메탄올을 사용하였으며, flushing solvent로는 5% v/v 메탄올을 사용하였다. 또한 크롬 종 분리 시 방해물질인 $ArC^+$의 제거를 위한 반응가스로 암모니아($NH_3$) 가스를 사용하였으며, Cr(III)와 Cr(VI)의 최적의 분리를 위해 이동상의 solvent ratio, pH 유속 및 시료 주입량의 변화에 따른 시험을 실시하였다. 외국의 경우 Cr(III)가 Cr(VI)보다 분석 감도가 우수한 것으로 보고되고 있으나 본 연구 결과 반응가스($NH_3$)를 사용할 경우, Cr(III)에 비해 Cr(VI)의 분석 감도가 더 우수한 것으로 나타났으며, 검출한계는 Cr(III)와 Cr(VI)에 대해 각각 $0.061\;{\mu}g/L$, $0.052\;{\mu}g/L$로 분석시간은 3분 이내로 나타났다. 서울시 6개 취수장 원수에서의 Cr(III)는 $0.048{\sim}0.064\;{\mu}g/L$(평균 $0.054\;{\mu}g/L$), Cr(VI)는 $0.014{\sim}0.023\;{\mu}g/L$(평균 $0.019\;{\mu}g/L$)의 농도 범위로 검출되었다. 회수율은 $90.1{\sim}94.1%$ 범위로 우수하게 나타났으며, Cr(III)가 Cr(VI)에 비해 $2{\sim}3$배 정도 높은 농도로 나타났다.

• 한국생물공학회:학술대회논문집
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• 한국생물공학회 2000년도 춘계학술발표대회
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• pp.113-116
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• 2000

Hexavalent chromium was removed by means of biosorption onto the protonated brown seaweed biomass. During the biosorption Cr(VI) was reduced to Cr(III), which resulted in accumulation of Cr(III) in the solution. The Cr(VI) reduction rate increased with increases of initial Cr(VI) and biosorbent concentrations and decrease of solution pH. Based upon the experimental results at various conditions, we suggested the mechanism for the chromium removal as following serial reactions: (1) sorption of anionic Cr(VI) onto the positively charged site of biomass, (2) reduction of Cr(VI) to Cr(III) on the positively charged site, (3) desorption of Cr(III) from the positively charged site, and (4) sorption of cationic Cr(III) onto the negatively charged site of biomass.

• 한국지하수토양환경학회:학술대회논문집
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• 한국지하수토양환경학회 1999년도 추계학술발표회
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• pp.81-84
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• 1999

The aqueous geochemical characteristics of Cr(III) and Cr(Ⅵ) in environmental systems are very different from one another: Cr(Ⅵ) is highly soluble, mobile and toxic relative to Cr(III) Reduction of Cr(Ⅵ) to Cr(III) are beneficial in aquatic systems because of the transformation of a highly mobile and toxic species to one having a low solubility in water, thus simultaneously decreasing chromium mobility and toxicity. Fe(II) species are excellent reductants for transforming Cr(Ⅵ) to Cr(III), and in addition, keeping Cr(III) concentrations below the drinking water standard of 52 ppb at pH values between 5 and 11. Investigations of the effects of NOM on Cr(Ⅵ) reduction are for examining the feasibility of using ferrous iron to reduce hexavalent chromium in subsurface environments. Experiments in the presence of soils, however, showed that the solid phase consumes some of the reducing capacity of Fe(II) and makes the overall reduction kinetics slower. The soil components bring about consumption of the ferrous iron reductant. Particular attention is devoted to the complexation of Fe(II) by NOM and the subsequent effect on Cr(Ⅵ) reduction. Cr(Ⅵ) reduction rate by Fe(II) was affected by the presence of NOM (humic acid), The effects of humic acid was different from the solution pH values and the concentration of humic acid. It was probably due to the reactions between humic acid and Cr(Ⅵ), humic acid and Fe(II), and between Cr(Ⅵ) and Fe(II), at each pH.

• Advances in environmental research
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• 제1권2호
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• pp.167-179
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• 2012

Pistachio shell (Pistacia vera) (PS), a low-cost material, has been utilized for the removal of the Cr(VI) ions after treatment with citric acid. Batch experimental steps were applied to obtain Cr(VI) ion adsorption details for the equilibrium between Cr(VI) and modified pistachio shell (MPS). The influences of contact time, pH, adsorbent dose and initial chromium concentration on the adsorption performance of MPS was investigated in detail. The results displayed that adsorption of Cr(VI) by MPS reached to equilibrium after 2 h and after that a little change of Cr(VI) removal efficiency was observed. The sorption percent is higher at lower pH and lower chromium concentration. Two possible mechanisms for reduction of Cr(VI) to Cr(III) can be suggested in Cr(VI) removal. In the first mechanism, Cr(VI) is reduced to Cr(III) by surface electron-donor groups of the adsorbent and the reduced Cr(III) forms complexes with adsorbent or remains in the solution. This Cr(III) is not adsorbed by adsorbent at pH 1.8. But in second mechanism, the adsorption-coupled reduction of Cr(VI) to Cr(III) occurred on the adsorbent sites. The equilibrium sorption capacity of Cr(VI) ion after 2 h was 64.35 mg/g for MPS.

• Bulletin of the Korean Chemical Society
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• 제27권5호
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• pp.694-698
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• 2006

A method has been described for the chemical speciation, preconcentration and determination of Cr(III) and Cr(VI) species in filtered tannery waste waters by flame atomic absorption spectrometry using ion-exchange resins. Amberlite IR-120($H^+$) strongly acidic cation exchanger and Amberlite IRA-410($CI ^-$) strongly basic anion exchanger resins were used for the separation and preconcentration of Cr(III) and Cr(VI) species, respectively. Optimum condition for preconcentration and speciation was obtained by testing pH of sample and eluent, flow rates of sample and eluent, amount of resins, volume of sample and eluents, and effect of foreign ions. The recommended method has been successfully applied for the preconcentration and determination of chromium species in the dissolved phase of waste water samples collected from a tannery waste water treatment plant in Kayseri, Turkey. The detection limits achieved were 0.73 $\mu$g/L for Cr(III) and 0.81 $\mu$g/L for Cr(VI). Recovery studies showed 99% for Cr(III) and 98% for Cr(VI), for samples spiked with single species.