• Applied Biological Chemistry
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• v.41 no.4
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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.

• Journal of the Korean Chemical Society
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• v.25 no.4
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• pp.270-274
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• 1981

Al(III) and Cr(III) were determined selectively by colorimetry of Bismark Brown R {4,4'[(4-methyl-1,3-phenylene)bis(azo)]-bis(6-methyl-1,3-benzenediamine) dihydrochloride} in the presence of the various cations and anions without the using of any masking agents, but tartrate and citrate ions were interfered. The ligand of Bismark Brown R and complexes of Al(III) and Cr(III) were shown the maximum absorbance at the same wavelength together and both metallic ion were interfered to determine each other, but Al(III) were able to determine after oxidation of Cr(III) to Cr(VI).

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.4 no.2
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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.

• Journal of the Korean Chemical Society
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• v.55 no.3
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• pp.454-462
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• 2011

A study on the adsorption characteristics of Pb(II) and Cr(III) cations onto C-methylcalix[4]resorcinarene (CMCR) has been conducted. CMCR was produced by one step synthesis from resorcinol, acetaldehyde, and HCl. Most parameters in batch system confirm that CMCR is a good adsorbent for Pb(II) and Cr(III). Cr(III) uptake was bigger than that of Pb(II), but Cr(III) adsorption rate was slower than Pb(II). The adsorption kinetic of Pb(II) and Cr(III) adsorptions in batch followed pseudo $2^{nd}$ order kinetics model, but the kinetic of Pb(II) adsorption in fixed bed column system followed first order model. Desorption studies to recover the adsorbed Pb(II) was performed sequentially with distilled water and HCl, and the results showed that the adsorption was dominated by chemisorption.

• Journal of Korea Soil Environment Society
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• v.4 no.2
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• pp.11-31
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• 1999

Removal of hexavalent chromium from artificial groundwater (AGW) by granular activated carbon (GAC) was investigated in batch and continuous-flow column studies. Experimental parameters that were examined included solution pH, presence of dissolved oxygen (DO), and GAC pretreatment with Fe(II). As the solution pH increased from 4 to 7.5, the amount of Cr(VI) removed by both GACs decreased significantly. Exclusion of DO from the experimental systems resulted in greater removal of Cr(VI) from solution, possibly as a result of reduction to Cr(III). However, pretreatment of the GAC with a reductant (Fe(II)) did not improve Cr(VI) removal. Equilibration With 0.01 M $K_2$$HPO_4$[to extract adsorbed Cr(VI)] followed by a wash with 0.02 N $K_2$$HPO_4$[to remove precipitated/sorbed Cr(III)] proved to be a viable approach for the regeneration of carbons whose Cr(VI) removal capacities had been exhausted. The performance of the regenerated carbons exceeded that of the virgin carbons, primarily because of the favorable adsorption of Cr(VI) at lower pH values and the reduction of Cr(VI) to Cr(III), The presence of Cr(III) in acid wash solutions provides direct evidence that Cr(VI) is reduced to Cr(III) in GAC systems under relatively acidic conditions. GAC performance over five complete cycles was consistently high, which suggests that such a system will be able to function over many operation cycles without deleterious effects.

• 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.

• 한국생물공학회:학술대회논문집
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• 2000.04a
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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.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 1999.10a
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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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• v.1 no.2
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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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• v.27 no.5
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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.