• Journal of Korean Society of Water and Wastewater
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• v.37 no.6
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• pp.375-382
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• 2023

The binary oxide adsorbent using Fe and Mn (Fe-Mn) has been prepared by precipitation method to enhance the removal of phosphate. Different amounts of chitosan, a natural organic polymer, were used during preparation of Fe-Mn as a stabilizer to protect an aggregation of Fe-Mn particles. The optimal amount of chitosan has been determined considering the separation of the Fe-Mn particles by gravity from solution and highest removal efficiency of phosphate (Fe-Mn10). The application of Fe-Mn10 increased removal efficiency at least 15% compared to bare Fe-Mn. According to the Langmuir isotherm model, the maximum uptake (q_m) and affinity coefficient (b) were calculated to be 184 and 240 mg/g, and 4.28 and 7.30 L/mg for Fe-Mn and Fe-Mn10, respectively, indicating 30% and 70% increase. The effect of pH showed that the removal efficiency of phosphate was decrease with increase of pH regardless of type of adsorbent. The enhanced removal efficiency for Fe-Mn10 was maintained in entire range of pH. In the kinetics, both adsorbents obtained 70% removal efficiency within 5 min and 90% removal efficiency was achieved at 1 h. Pseudo second order (PSO) kinetic model showed higher correlation of determination (R²), suggesting chemisorption was the primary phosphate adsorption for both Fe-Mn and Fe-Mn10.

• Journal of Korean Society of Water and Wastewater
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• v.37 no.4
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• pp.177-186
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• 2023

Perfluorooctanoic acid(PFOA) was one of widely used per- and poly substances(PFAS) in the industrial field and its concentration in the surface and groundwater was found with relatively high concentration compared to other PFAS. Since various processes have been introduced to remove the PFOA, adsorption using GAC is well known as a useful and effective process in water and wastewater treatment. Surface modification for GAC was carried out using Cu and Fe to enhance the adsorption capacity and four different adsorbents, such as GAC-Cu, GAC-Fe, GAC-Cu(OH)₂, GAC-Fe(OH)₃ were prepared and compared with GAC. According to SEM-EDS, the increase of Cu or Fe was confirmed after surface modification and higher weight was observed for Cu and Fe hydroxide(GAC-Cu(OH)₂ and GAC-Fe(OH)₃, respectively). BET analysis showed that the surface modification reduced specific surface area and total pore volumes. The highest removal efficiency(71.4%) was obtained in GAC-Cu which is improved by 17.9% whereas the use of Fe showed lower removal efficiency compared to GAC. PFOA removal was decreased with increase of solution pH indicating electrostatic interaction governs at low pH and its effect was decreased when the point of zero charges(pzc) was negatively increased with an increase of pH. The enhanced removal of PFOA was clearly observed in solution pH 7, confirming the Cu in the surface of GAC plays a role on the PFOA adsorption. The maximum uptake was calculated as 257 and 345 ㎍/g for GAC and GAC-Cu using Langmuir isotherm. 40% and 80% of removal were accomplished within 1 h and 48 h. According to R², only the linear pseudo-second-order(pso) kinetic model showed 0.98 whereas the others obtained less than 0.870.

• Journal of Korean Society of Water and Wastewater
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• v.38 no.4
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• pp.199-208
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• 2024

In this paper, the adsorption removal characteristic for 10 species of perfluoroalkyl and polyfluoroalkyl substances (PFAS) was investigated using GAC and modified GAC (GAC-Cu). After modification with Cu(II), the amount of copper was to 1.93 and 4.73 mg/g for GAC and GAC-Cu, respectively. The total amount of 10 species of PFAS per specific area was obtained to 0.548 and 0.612 ng/m² for GAC and GAC-Cu, respectively. A series of batch test confirmed lower efficiency was observed with a smaller number of carbon chain length and the removal efficiency of PFCA (perfluoroalkyl carboxylic acids) was lower than that of PFSA (perfluoroalkyl sulfonic acids) with the same carbon chain length. Regarding the pH effect, the adsorption capacity was decreased with increase of pH due to the increase of electrostatic repulsion. According to pseudo first and second order (PFO and PSO) kinetic models, while the values of equilibrium uptake and time did not show significant difference, a difference in uptake was observed between 24-48h. Furthermore, based on correlation analysis, Log K_ow and uptake have a high correlation with molecular weight (M.W.) and initial concentration, respectively. These results show that long-chain PFAS have higher removal efficiency due to their increased hydrophobicity.

• Journal of Korean Society of Environmental Engineers
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• v.33 no.6
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• pp.396-404
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• 2011

An investigation on the removals of PAH-quinone compounds, which are commonly produced from the biological and/or chemical treatments of PAH-contaminated soils, from the aqueous phase via birnessite (${\delta}-MnO_2$)-mediated oxidative transformation is described. It was demonstrated that acenaphthenequinone (APQ), p-PAH quinone can be removed via birnessite-mediated oxidative-coupling reactions, and anthraquinone (AQ) and 1,4-naphthoquinone (1,4-NPQ), o-PAH quinones were efficiently removed by birnessite-mediated cross-coupling reactions in the presence of catechol (CAT) as a reactive mediator. The removals of PAH-quinone compounds followed pseudo-first-order reactions, and the rate constant (k, $hr^{-1}$) for the removals of 1,4-NPQ under the experiment conditions (1,4-NPQ = 10 mg/L, CAT = 50 mg/L, ${\delta}-MnO_2$ = 1.0 g/L, pH 5, Reaction time = 6~96 hr) was 0.0426, which was about 4 times lower than that of APQ (0.173). With the observed pseudo-first order rate constants with respect to birnessite loadings under the same experimental conditions, the surface-normalized specific rate constant, $K_{surf}$, for 1,4-NPQ was determined to be $8.5{\times}10^{-4}L/m^2{\cdot}hr$. The analysis of the kinetic data with respect to birnessite loading indicated that the cross-coupling reactions of 1,4-NPQ consist of two different reaction steps over time and the results have also been discussed in terms of the reaction mechanisms.

• 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).

• Journal of Korean Society of Environmental Engineers
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• v.33 no.2
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• pp.85-92
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• 2011

Evaluation of the removal efficiencies of Fe(II) by reactive sand media coated with manganese (MCS), iron (ICS) and both of iron and manganese (IMCS) was investigated as functions of solution pH ranging from 2 to 9, reaction time and concentration of Fe(II) in a batch reactor using each reactive medium and additional oxidants such as $KMnO_4$ and NaOCl. When only Fe(II) was present in solution without any reactive medium, removal of Fe(II) was quite low below pH 5 due to a slow oxidation of Fe(II) and/or negligible precipitation but greatly increased above pH 5 due to a rapid oxidation of Fe(II) and subsequent precipitation of oxidized Fe species. ICS showed negligible efficiency on the removal of Fe(II) through adsorption. However, an efficient removal of Fe(II) was observed at low solution pH in the presence of IMCS or MCS through rapid oxidation and subsequent precipitation. Removal efficiency of Fe(II) by IMCS in the presence or absence of NaOCl was quite similar. Removal rate of Fe(II) by IMCS and additional oxidants gradually increased as the solution pH increased. From the kinetic experiments, removal pattern of Fe(II) was better described by pseudo-second-order equation than pseudo-first-order equation. A rapid removal of Fe(II) using IMCS in the presence of $KMnO_4$ was observed in the first 10 min. The initial removal rate of Fe(II) using $KMnO_4$ was 14,286 mg/kg hr. In case of using NaOCl, the removal of Fe(II) occurred rapidly in the first 6 hrs and then reached the near-equilibrium state. Removal of Fe(II) on IMCS was well expressed by Langmuir isotherm and the maximum removal capacity of Fe(II) was calculated as 1,088 mg/kg.

• Applied Biological Chemistry
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• v.47 no.3
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• pp.344-350
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• 2004

This study was conducted to develop and assess the applicability of mixed-bed ion exchange resin capsules for water quality monitoring in small agricultural watershed. Recoveries of resin capsules for inorganic N and P ranged from 96 to 102%. The net activation energies and pseudo-thermodynamic parameters, such as ${\Delta}G^{o\ddag},\;{\Delta}H^{o\ddag},\;and\;{\Delta}S^{o\ddag}$ for ion adsorption by resin capsules, exhibited relatively low values, indicating the process might be governed by chemical reactions such as diffusion. However, those values increased with temperature coinciding with the theory. The reaction reached pseudo-equilibrium within 24 hours for $NH_4-N\;and\;NO_3-N$, and only 8 hours for $PO_4-P$, respectively. The selectivity of resin capsules were in the order of $NO_3\;^-\;>\;NH_4\;^+\;>\;PO_4\;^{3-}$, coinciding with that of encapsulated Amberlite IRN-150 resin. At the initial state of equilibrium, the resin adsorption quantity was linearly proportional to the mass of ions in the streams, but the rate of movement leveled off, following Langmuir-type sorption isotherm. The overall results demonstrated that the resin capsule system was suitable for water quality monitoring in small agricultural watershed, judging from the reaction mechanism(s) of the resin capsule and the significance of model in field calibration.

• Journal of the Mineralogical Society of Korea
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• v.26 no.4
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• pp.229-244
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• 2013

Arsenic contamination may be brought about by a variety of natural and anthropogenic causes. Among diverse naturally-occurring chemical speciations of arsenic, trivalent (As(III), arsenite) and pentavalent (As(V), arsenate) forms have been reported to be the most predominant ones. It has been well known that the behavior of arsenic is chiefly affected by aluminum, iron, and manganese oxides. For this reason, this study was initiated to evaluate the applicability of manganese slag (Mn-slag) containing high level of Mn, Si, and Ca as an efficient sorbent of arsenic. The main properties of Mn-slag as a sorbent were investigated and the sorption of each arsenic species onto Mn-slag was characterized from the aspects of equilibrium as well as kinetics. The specific surface area and point of zero salt effect (PZSE) of Mn-slag were measured to be $4.04m^2/g$ and 7.73, respectively. The results of equilibrium experiments conducted at pH 4, 7 and 10 suggest that the sorbed amount of As(V) was relatively higher than that of As(III), indicating the higher affinity of As(V) onto Mn-slag. As a result of combined effect of pH-dependent chemical speciations of arsenic as well as charge characteristics of Mn-slag surface, the sorption maxima were observed at pH 4 for As(V) and pH 7 for As(III). The sorption of both arsenic species reached equilibrium within 3 h and fitting of the experimental results to various kinetic models shows that the pseudo-second-order and parabolic models are most appropriate to simulate the system of this study.

• Economic and Environmental Geology
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• v.43 no.6
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• pp.589-601
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• 2010

Recently it has been frequently reported arsenic contamination of geologic origin in groundwater. The iron-impregnated ranular activated carbon (Fe-GAC) was developed for effective removal of arsenic from groundwater n the study. Fe-GACs were prepared by impregnating iron compounds into a supporting medium (GAC) with 0.05 M iron nitrate solution. The materials were used in arsenic adsorption isotherm tests to know the effect of iron impregnation time, batch kinetic tests to understand the influence of pH, and column tests to evaluate for the preliminary operation of water treatment system. The results showed that the minimum twelve hours of impregnation time were required for making the Fe-GAC with sufficient iron content for arsenic removal, confirmed by a high arsenic adsorption capacity evaluated in the isotherm tests. Most of the impregnated iron compounds were iron hydroxynitrate $Fe_4(OH)_{11}NO_3{\cdot}2H_2O$ but a mall quantity of hematite was also identified in X-ray diffraction(XRD) analysis. The batch isotherms of Fe-GAC for arsenic adsorption were well explained by Langmuir than Freundlich model and the iron contents of Fe-GAC have positive linear correlations on logarithmic plots with Freundlich distribution coefficients ($K_F$ and Langmuir maximum adsorption capacities ($Q_m$. The results of kinetic experiments suggested hat Fe-GAC had he excellent arsenic adsorption capacities regardless of all pH conditions except for pH 11 and could be used a promising adsorbents for groundwater arsenic removal considering the general groundwater pH range of 6-8. The pseudo-second order model, based on the assumption that the ate-limiting step might be chemisorption, provided the best correlation of the kinetic experimental data and explained the arsenic adsorption system f Fe-GAC. The column test was conducted to valuate the feasibility of Fe-GAC use and the operation parameters in arsenic groundwater treatment system. The parameters obtained from the column test were the retardation actor of 482.4 and the distribution coefficient of 581.1 L/mg which were similar values of 511.5-592.5 L/mg acquired from Freundlich batch isotherm model. The results of this study suggested that Fe-GAC could be used as promising adsorbent of arsenic removal in a small groundwater supply system with water treatment facility.

• Journal of the Korean Chemical Society
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• v.66 no.2
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• pp.78-85
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• 2022

Natural white clay was treated with 6 M of H₂SO₄ and heated at 80℃ for 6 h under mechanical stirring and the resulting acid active clay was used as an adsorbent for the removal of Cs⁺ in water. The physicochemical changes of natural white clay and acid active clay were observed by X-ray Fluorescence Spectrometry (XRF), BET Surface Area Analyser and Energy Dispersive X-line Spectrometer (EDX). While activating natural white clay with acid, the part of Al₂O₃, CaO, MgO, SO₃ and Fe₂O₃ was dissolved firstly from the crystal lattice, which bring about the increase in the specific surface area and the pore volume as well as active sites. The specific surface area and the pore volume of acid active clay were roughly twice as high compared with natural white clay. The adsorption of Cs⁺ on acid active clay was increased rapidly within 1 min and reached equilibrium at 60 min. At 25 mg L^- of Cs⁺ concentration, 96.88% of adsorption capacity was accomplished by acid active clay. The adsorption data of Cs⁺ were fitted to the adsorption isotherm and kinetic models. It was found that Langmuir isotherm was described well to the adsorption behavior of Cs⁺ on acid active clay rather than Freundlich isotherm. For adsorption Cs⁺ on acid active clay, the Langmuir isotherm coefficients, Q, was found to be 10.52 mg g^-1. In acid active clay/water system, the pseudo-second-order kinetic model was more suitable for adsorption of Cs⁺ than the pseudo-first-order kinetic model owing to the higher correlation coefficient R² and the more proximity value of the experimental value q_e,exp and the calculated value q_e,cal. The overall results of study showed that acid active clay could be used as an efficient adsorbent for the removal of Cs⁺ from water.