• Environmental Engineering Research
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• 제12권1호
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• pp.16-20
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• 2007

Toxicity of metal plating wastewater was evaluated by using acute toxicity tests on Daphnia magna. To identify toxicants of metal plating wastewater, several manipulations such as solid phase extraction (SPE), ion exchange and graduated pH adjustment were used. The SPE test had no significant effect on baseline toxicity, suggesting absence of toxic non-polar organics in metal plating wastewater. However, anion exchange largely decreased the baseline toxicity by 88%, indicating the causative toxicants were inorganic anions. Considering high concentration of chromium in metal plating wastewater, it is thought the anion is Cr(VI) species. Graduated pH test showing independence of the toxicity on pH change strongly supports this assumption. However, as revealed by toxicity confirmation experiment, the initial toxicity of metal plating wastewater (24-h TU=435) was not explained only by Cr(VI) (24-h TU = 725 at $280\;mg\;L^{-1}$). Addition of nickel($29.5\;mg\;L^{-1}$) and copper ($26.5\;mg\;L^{-1}$) largely decreased the chromium toxicity up to 417 TU, indicating antagonistic interaction between heavy metals. This heavy metal interaction was successfully predicted by an equation of 24-h $TU\;=\;3.67\;{\times}\;\ln([Cu]\;+\;[Ni])\;+\;79.44$ at a fixed concentration of chromium.

• 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.

• Environmental Engineering Research
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• 제25권3호
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• pp.418-425
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• 2020

In this study soft computing techniques including, Artificial Neural Network (ANN) and Adaptive Neuro-Fuzzy Inference System (ANFIS) were investigated for the prediction of Cr(VI) transport efficiency by novel Polymer Inclusion Membranes (PIMs). Transport experiments carried out by varying parameters such as time, film thickness, carrier type, carier rate, plasticizer type, and plasticizer rate. The predictive performance of ANN and ANFIS model was evaluated by using statistical performance criteria such as Root Mean Standard Error (RMSE), Mean Absolute Error (MAE), and Coefficient of Determination (R²). Moreover, Sensitivity Analysis (SA) was carried out to investigate the effect of each input on PIMs Cr(VI) removal efficiency. The proposed ANN model presented reliable and valid results, followed by ANFIS model results. RMSE and MAE values were 0.00556, 0.00163 for ANN and 0.00924, 0.00493 for ANFIS model in the prediction of Cr(VI) removal efficiency on testing data sets. The R² values were 0.973 and 0.867 on testing data sets by ANN and ANFIS, respectively. Results show that the ANN-based prediction model performed better than ANFIS. SA demonstrated that time; film thickness; carrier type and plasticizer type are major operating parameters having 33.61%, 26.85%, 21.07% and 8.917% contribution, respectively.

• Carbon letters
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• 제9권1호
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• pp.23-27
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• 2008

The adsorption and reduction of Cr (VI) to Cr (III) by surface modified activated carbon (AC) in an aqueous solution was studied. The effects of surface modifications on the properties of the carbons were investigated by the analysis of specific surface area, carbon surface pH, acid/base surface values and functional groups. In order to understand the Cr(VI) adsorption and reduction ratio from Cr(VI) to Cr(III), the Cr adsorption capacity of AC was also measured and discussed by using inductively coupled plasma and UV spectrophotometer. The modifications bring about substantial variation in the chemical properties whereas the physical properties such as specific surface area, pore volume and pore size distribution nearly were not changed. Total Cr adsorption efficiency of as-received activated carbon (R-AC) and nitric acid treated activated carbon (N1-AC and N2-AC) were recorded on 98.2, 99.7 and 100%. Cr(III) reduction efficiency of R-AC increased largely from 0.4% to 28.3% compared to N1-AC and N2-AC.

• Environmental Engineering Research
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• 제19권2호
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• pp.157-163
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• 2014

The adsorption of Cr(VI) from aqueous solutions to activated carbon fiber (ACF) was investigated using both batch and flow-through column experiments. The batch experiments (adsorbent dose, 10 g/L; initial Cr(VI) concentration, 5-500 mg/L) showed that the maximum adsorption capacity of Cr(VI) to ACF was determined to 20.54 mg/g. The adsorption of Cr(VI) to ACF was sensitive to solution pH, decreasing from 9.09 to 0.66 mg/g with increasing pH from 2.6 to 9.9; the adsorption capacity was the highest at the highly acidic solution pHs. Kinetic model analysis showed that the Elovich model was the most suitable for describing the kinetic data among three (pseudo-first-order, pseudo-second-order, and Elovich) models. From the nonlinear regression analysis, the Elovich model parameter values were determined to be ${\alpha}$ = 162.65 mg/g/h and ${\beta}$ = 2.10 g/mg. Equilibrium isotherm model analysis demonstrated that among three (Langmuir, Freundlich, Redlich-Peterson) models, both Freundlich and Redlich-Peterson models were suitable for describing the equilibrium data. In the model analysis, the Redlich-Peterson model fit was superimposed on the Freundlich fit. The Freundlich model parameter values were determined to be $K_F$ = 0.52 L/g and 1/n = 0.56. The flow-through column experiments showed that the adsorption capacities of ACF in the given experimental conditions (column length, 10 cm; inner diameter, 1.5 cm; flow rate, 0.5 and 1.0 mL/min; influent Cr(VI) concentration, 10 mg/L) were in the range of 2.35-4.20 mg/g. This study demonstrated that activated carbon fiber was effective for the removal of Cr(VI) from aqueous solutions.

• 자원환경지질
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• 제41권6호
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• pp.645-655
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• 2008

국가 지하수 관측망인 대전(문평)관측소 및 주변 보조관측정 지하수 수질을 6개월간 관측한 결과, 관측소 충적관정(MPH-0-1)에서 6가 크롬이 0.5-3.1 mg/L의 범위로 검출되어 수질기준의 10-62배를 초과하는 오염이 지속되고 있었다. 또한 하천 방향에 위치한 두 관정(MPH-1과 MPH-6)에서 6가 크롬이 0.1 mg/L 이하로 검출되어 미세한 오염 확산의 징후가 나타났다. 동일기간 지하수 수위 및 강우 관측자료의 시계열분석 결과 6개 관측정에서의 지하수위는 강우에 대하여 평균 5.65일 후에 최대값을 보였다. 시기별 강우/수위 변화와 6가 크롬 농도의 변화를 통하여 강우 반응에 의한 수위상승이 관측소 충적관정의 6가 크롬 농도 감소와 밀접한 관련이 있는 것으로 파악되었다. 이와 더불어 지하수 내 미생물의 종류 및 다양성을 분석하였으며, 6가 크롬으로 오염된 대전문평지역 지하수(MPH-0-1과 MPH-1 관정)에서 크롬환원 미생물인 Enterobacter aerogenes을 분리 배양하였다. 따라서 유기물, 광물 등의 토양 및 대수층 매질에 의한 6가 크롬 저감뿐만 아니라 이 토착미생물에 의한 크롬 오염 지하수의 자연저감이 실제 진행되고 있음을 확인할 수 있었다. 향후 이 미생물의 활성에 대한 심도 있는 연구를 통하여, 크롬오염 지하수의 저감 및 정화 기술의 개발과 적용에 활용할 수 있을 것으로 기대한다.

• 한국토양비료학회지
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• 제44권5호
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• pp.727-733
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• 2011

A new Korean standard for the determination of Cr(VI) in soils has been officially published as ES 07408.1 in 2009. This analytical method is based on the hot alkaline digestion and colorimetric detection prescribed by U.S. EPA method 3060A and 7196A. The hot alkaline digestion accomplished using 0.28 M $Na_2CO_3$ and 0.5 M NaOH solution (pH 13.4) at $90{\sim}95^{\circ}C$ determines total Cr(VI) in soils extracting all forms of Cr(VI), including water-soluble, adsorbed, precipitated, and mineral-bound chromates. This aggressive alkaline digestion, however, proved to be problematic for certain soils which contain large amounts of soluble humic substances or active manganese oxides. Cr(III) could be oxidized to Cr(VI) by manganese oxides during the strong alkaline extraction, resulting in overestimation (positive error) of Cr(VI). In contrast, Cr(VI) reduction by dissolved humic matter or Fe(II) could occur during the neutralization and acidic colorimetric detection procedure, resulting in underestimation (negative error) of Cr(VI). Futhermore, dissolved humic matter hampered the colorimetric detection of Cr(VI) using UV/Vis spectrophotometer due to the strong coloration of the filtrate, resulting in overestimation (positive error) of Cr(VI). Without understanding the mechanisms of Cr(VI) and Cr(III) transformation during the analysis it could be difficult to operate the experiment in laboratory and to evaluate the Cr(VI) results. For this reason, in this paper we described the theoretical principles and limitations of Cr(VI) analysis and provided useful guidelines for laboratory work and Cr(VI) data analysis.

• Advances in environmental research
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• 제6권2호
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• pp.95-111
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• 2017

The valorization of swine manure samples, i.e., de-watered cake (SMc) and solid digestate (SMd), in products with beneficial value, i.e., low cost activated carbons (ACs), is studied. For this purpose slow pyrolysis and steam activation at three different duration times are applied. Additionally, the obtained ACs are characterized and tested towards removal of Cr(VI) from aqueous solutions. It is revealed that BET surface area varies in the range of $236-267m^2/g$ for ACs prepared from SMc sample and in the range of $411-432m^2/g$ for ACs prepared from SMd sample. Despite the low determined surface area of prepared ACs, a high total Cr removal capacity is observed occurring through a "coupled adsorption-reduction" mechanism. Higher Cr(VI) removal capacity is demonstrated for ACs having higher surface area ($q_m$ is 140.9 mg/g according Langmuir modelling). Cr(VI) removal is found to be pH dependent with a maximum at pH 1. However at that pH significant amounts of Cr remain in the solution as Cr(III). At pH 2 lower amount of Cr(VI) is removed compensated by a higher removal of Cr(III) resulting in a higher amount of adsorbed $Cr_{tot}$. Therefore adsorption at pH 2 is found to be appropriate. The removal capacity of the studied ACs towards Cr(VI) is almost independent of activation time.

• 한국산학기술학회논문지
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• 제14권11호
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• pp.6000-6007
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• 2013

유기합성 과정에서 응용범위가 넓고 안정한 알코올류의 산화제에 대해 많은 연구가 진행 되고 있으며, 그중에서도 Cr(VI)-계열의 시약들이 산화제로 널리 이용되어 왔다. 그러므로 유기 용매에 잘 용해되고, 일차 알코올을 알데히드까지만 산화시키는 산화제의 합성과 그에 따르는 메카니즘 규명이 필요하게 되었다. Cr(VI)-헤테로고리 착물인 Cr(VI)-isoquinoline를 합성하여, 적외선 분광광도법(IR), 유도결합 플라즈마(ICP) 등으로 구조를 확인하였다. 또한 여러가지 용매 하에서 Cr(VI)-isoquinoline를 이용하여 벤질 알코올의 산화반응을 측정한 결과 유전상수(${\varepsilon}$) 값이 큰 용매 순서인 시클로헥센<클로로포름<아세톤$CH_3$, m-Br, m-$NO_2$)을 효과적으로 산화시켰다. 여기서 전자받개 그룹들은 반응 속도가 감소한 반면에 전자주개 치환체들은 반응속도를 증가시켰고, Hammett 반응상수(${\rho}$) 값은 -0.69(308K) 이였다. 그러므로 본 실험에서 알코올의 산화반응 과정은 먼저 크로메이트 에스테르 형성과정을 거친 후, 속도결정단계에서 수소화 전이가 일어나는 메카니즘임을 알 수 있었다.

• Carbon letters
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• 제20권
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• pp.10-18
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• 2016

Nanoporous carbon structures were synthesized by pyrolysis of grass as carbon precursor. The synthesized carbon has high surface area and pore volume. The carbon products were acid functionalized and characterized by Fourier transform infrared spectroscopy, X-ray diffraction, Brunauer–Emmett–Teller, transmission electron microscopy, and Energy Dispersive X-ray microanalysis. Acid functionalized nanoporous carbon was explored for use in removal of toxic Cr(VI) ions from aqueous media. An adsorption study was done as a function of initial concentration, pH, contact time, temperature, and interfering ions. The experimental equilibrium data fits well to Langmuir isotherm model with maximum monolayer adsorption capacity of 35.335 mg/g. The results indicated that removal obeys a pseudo-second-order kinetic model, and that equilibrium was reached in 10 min. A desorption study was done using NaOH. The results of the present study imply that acid functionalized nanoporous carbon synthesized from grass is an efficient, renewable, cost-effective adsorbent material for removal of hexavalent chromium due to its faster removal rate and reusability.