• Title/Summary/Keyword: Reaction Equilibrium

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Adsorption Characteristics and Thermodynamic Parameters of Acid Fuchsin on Granular Activated Carbon (입상 활성탄에 대한 Acid Fuchsin의 흡착특성과 열역학 파라미터)

  • Lee, Jong-Jib
    • Clean Technology
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    • v.27 no.1
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    • pp.47-54
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    • 2021
  • The adsorption of Acid Fuchsin (AF) on granular activated carbon (GAC) was investigated for isothermal adsorption and kinetics and thermodynamic parameters by experimenting with the initial concentration, contact time, temperature, and pH of the dye as adsorption parameters. In the pH effect experiment, the adsorption of AF on activated carbon showed a bathtub type with increased adsorption at pH 3 and 11. The adsorption equilibrium data of AF fit well with the Freundlich isotherm model, and the calculated separation factor (1/n) value was found in which activated carbon can effectively remove AF. The pseudo-second-order kinetic model fits well within 7.88% of the error percent in the adsorption process. According to Weber and Morris's model plot, it was divided into two straight lines. The intraparticle diffusion rate was slow because the stage 2 (intraparticle diffusion) slope was smaller than that of stage 1 (boundary layer diffusion). Therefore, it was confirmed that the intraparticle diffusion was a rate-controlling step. The activation energy of AF (13.00 kJ mol-1) corresponded to the physical adsorption process (5 - 40 kJ mol-1). The free energy change of the AF adsorption by activated carbon showed negative values at 298-318 K. As the spontaneity increased with increasing temperature. The adsorption of AF was an endothermic reaction (ΔH = 22.65 kJ mol-1).

Stabilization Mechanisms of Powdered and Bead Type Stabilizer Made of Mg-Fe Layered Double Hydroxide (LDH) for the Arsenic Contaminated Soil (Mg-Fe 이중층수산화물로 제조한 분말상과 입상 안정화제의 비소 오염토양 안정화 기작)

  • Kim, Seonhee;Kim, Kyeongtae;Oh, Yuna;Han, Yikyeong;Lee, Minhee
    • Journal of Soil and Groundwater Environment
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    • v.27 no.4
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    • pp.49-62
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    • 2022
  • The magnesium and iron-based layered double hydroxide (Mg-Fe LDH) was synthesized by the co-precipitation process and the bead type LDH (BLDH, 5~6 mm in diameter) was manufactured by using the Mg-Fe LDH and the starch as a binder. To evaluate the feasibility of the BLDH as the As stabilizer in the soil, various experiments were performed and the As stabilization efficiency of the BLDH was compared to that of powdered type LDH (PLDH, <149 ㎛ in diameter). For the As sorption batch experiment, the As sorption efficiency of both of the PLDH and the BLDH showed higher than 99%. For the stabilization experiment with soil, the As extraction reducing efficiency of the PLDH was higher than 87%, and for the BLDH, it was higher than 80%, suggesting that the BLDH has similar the feasibility of As stabilization for the contaminated soil, compared to the PLDH. From the continuous column experiments, when more than 7% BLDH was added into the soil, the As stabilization efficiency of the column maintained at over 91% for 7 pore volume flushing (simulating about 21 months of rainfall) and slowly decreased down to 64% after that time (to 36 months) under the non-equilibrium conditions. Results suggested that more than 7% of BLDH added in As-contaminated soil could be enough to stabilize As in soil for a long time. The main As fixation mechanisms on the LDH were also identified through the X-ray fluorescence (XRF), the X-ray diffraction (XRD), and the Fourier transform infrared (FT-IR) analyses. Results showed that the LDH has enough of an external surface adsorption capacity and an anion exchange capability at the interlayer spaces. Results of SEM/EDS and BET analyses also supported that the Mg-Fe LDH used in this study has sufficient porous structures and outer surfaces to fix the As. The reduction of carbonate (CO32-) and sulfate (SO42-) anions in the LDH after the reaction between As and the LDH was observed through the FT-IR, the XRF, and the XRD analyses, suggesting that the exchange of some of these anions with the arsenate (H2AsO4- or HAsO42-) occurs at the LDH interlayers during the stabilization process in soil.

Studies on Food Preservation by Controlling Water Activity III. Quality Changes of Fish Meat during Drying and Storage (식품보장과 수분활성에 관한 연구 3. 어육의 건조 및 저장중의 품질)

  • HAN Bong-Ho;LEE Jong-Gab;BAE Tae-Jin
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.16 no.3
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    • pp.181-189
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    • 1983
  • A study on the qualify changes of fish meat during drying and storage has been carried out with filefish meat. Filefish meat was dried in a forced air dryer at 40 and $55\%$ for 20 hours with an air velocity of 0.4 m/sec under different conditions of relative air humidities in the range of 10 to $50\%$. The dried fish meat was stored at $30^{\circ}C$ in chambers with constant relative humidities controlled by the use of conditioned air stream passing through the saturated salt solutions. The qualify of filefish meat was evaluated with the brown color densities developed by lipid oxidation and Maillard reaction. Changes of viable cell count during drying and storage were also discussed. The predominant reaction for the brown color developed during the study period was the lipid oxidation. The lipid oxidation rate during drying at constant temperature was appreciably affected by water activities at the drying surfaces of filefish meat during the falling drying rate period. The lipid oxidation rate was the slowest under the condition of the relative air humidity of around $30\%$. In samples stored at water activity of 0.33, the lipid oxidation rate was retarded remarkably in comparison with the samples with lower or higher water activities. The addition of $1\%$ table salt, $1.5\%$ D-sorbitol and $6\%$ sucrose slightly lowered the water activity with the slowest lipid oxidation rate. Such additives resulted the increase of the water soluble brown color densities, which seemed due to the increase of mobility of the water soluble substances by the result of the increase of equilibrium water content. Microflora of the samples immediately after drying consisted of ca. $30\%$ of coccus types, ca. $65\%$ of rod types and ca. $5\%$ of molds and yeasts. During the storage of the samples with a water activity of 0.76, the ratio of the coccus types to the total microflora was increased remarkably while that of the Gram negative non-spore rod types was decreased. The ratios of the Gram positive rod types, molds and yeasts during the storage were nearly constant.

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Synthesis of Artificial Zeolite from Fly Ash for Preparing Nursery Bed Soils and the Effects on the Growth of Chinese Cabbage (석탄회(石炭灰)를 이용한 육묘(育苗) 상토용(床土用) 인공(人工) 제올라이트의 제조와 배추 생육에 미치는 효과(效果))

  • Kim, Yong-Woong;Lee, Hyun-Hee;Yoon, Chung-Han;Shin, Bang-Sup;Kim, Kwang-Sik
    • Korean Journal of Soil Science and Fertilizer
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    • v.31 no.2
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    • pp.95-106
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    • 1998
  • To reduce the environmental contamination and to utilize fly ash massively produced from the coal power plant every year, we synthesized the artificial zeolite using fly ash treated with alkaline, and then analyzed the mineralogical and morphological properties by X-ray, IR, and SEM. The amount of $NH_4{^+}$, $K^+$, and $H_2PO_4{^-}$ adsorbed by the fly ash and the artificial zeolite were determined with reaction time, amount of adsorbate used, ion concentrations. The results obtained from the pot experiments packed with the top soil, amended with granulated artificial zeolite which was made by treatment of 4% polyvinylalcohol, showed that CEC of the artificial zeolite was $257.7cmol^+kg^{-1}$, that was almost 36 times greater than that of fly ash. The ratio of $SiO_2/Al_2O_3$ decreased but the amount of Na increased. The physico-chemical properties analyzed by X-ray, IT, and SEM represented that the artificial zeolite synthesized had a similar morphological structure to that of the natural zeolite. The structures of the artificial zeolite had a significantly enlarged surface having a lot of pores, while the fly ash looked like spherical smooth shape with having not pores on the surface. Thus, the artificial zeolite was successfully synthesized. The results of adsorption isotherms of fly ash and artificial zeolite showed that the amount of $NH_4{^+}$, $K^+$, and $H_2PO_4{^-}$ adsorbed increased as the equilibrium concentration increased, while $NH_4{^+}$ was strongly adsorbed on the surface of fly ash and artificial zeolite than that of $K^+$. The most distinctive growth of Chinese cabbage was found from the top soil(NPK + soils + 20% of granulated artificial zeolite + 5% of compost). Therefore, we concluded that one of the most effective methods to effectively recycle a fly ash was to make the artificial zeolite as we did in this experiment.

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Potassium and Clay Minerals in Upland Soils (밭 토양(土壤)의 점토(粘土) 광물(鑛物)과 가리(加里))

  • Kim, Tai-Soon
    • Korean Journal of Soil Science and Fertilizer
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    • v.10 no.3
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    • pp.135-151
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    • 1977
  • The present paper summerizes the studies on clay mineralogical characteristics of Korean soil, relationship between potassium and clay minerals, potassium release pattern of clay minerals and utilization of clay minerals for soil conditioner and fertilizers, which have been carried out in this laboratory. 1. The red yellow podzolic soil is mostly abundant in the upland of Korea and mainly consists of halloysite and weathered intermediates of mica such as illite and vermiculite. 2. With regard to soil parent material, kaolin mineral occurs abundant in soils derived from granite and granite gneiss. Mica is dominant in basaltic soil. The main clay mineral of the soil, originated from the Tertiary, is found montmorillonite and the volcanic soil of Jeju Island has plenty of allophane as its main clay mineral. 3. It is confirmed that the soil fertility depends on the composition of clay minerals. The red yellow podzolic soil, containing lot of kaolin, shows low productivity while the montmorillonite soil has higher productivity. 4. The release rate of solid phase potassium (micas and fixed potassium) follows the 1st order reaction equation in the equilibrium solution of $IN-NH_4OAc$. The potassium release constant is positively correlated with the mica content of the clay but negatively correlated with the content of $14.5{\AA}$ minerals. On the other hand, the potassium release constant has very high correlation with the ratio(Kex/Kt) of exchangeable potassium(Kex) to total potassium(Kt). 5. It is also found that Kex/Kt has rather high correlation with the content of mica and $14.5{\AA}$ minerals existed in the clay as well as the mica content of the soil.

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Genetic Environments of Hydrothermal Vein Deposits in the Pacitan District, East Java, Indonesia (인도네시아 동부자바 빠찌딴(Pacitan) 광화대 열수 맥상 광상의 성인 연구)

  • Choi, Seon-Gyu;So, Chil-Sup;Choi, Sang-Hoon;Han, Jin-Kyun
    • Economic and Environmental Geology
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    • v.28 no.2
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    • pp.109-121
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    • 1995
  • The hydrothermal vein type deposits which comprise the Kasihan, Jompong and Gempol mineralized areas are primarily copper and zinc deposits, but they are also associated with lead and/or gold mineralization. The deposits occur within the Tertiary sedimentary and volcanic rocks in the Southern Mountain zone of the eastern Java island, Indonesia. Mineralization can be separated into two or three distinct stages (pre-and/or post- ore mineralization stages and main ore mineralization stage) which took place mainly along pre-existing fault breccia zones. The main phase of mineralization (the main ore stage) can be usually classified into three substages (early, middle and late) according to ore mineral assemblages, paragenesis, textures and their chemical compositions. Ore mineralogy and paragenesis of the three areas in the district are different from each other. Pyrite, pyrrhotite (/arsenopyrite), iron-rich (up to 20.5 mole % FeS) sphalerite and (Cu-)Pb-Bi sulfosalts are characteristic of the deposits in the Kasihan (/Jompong) area. On the other hand, pyrite + hematite + magnetite + iron-poor (2.7 to 3.6 mole % FeS) sphalerite assemblage is restricted to the Gempol area. Fluid inclusion data suggest that fluids of the main ore stage evolved from initial high temperatures (near $350^{\circ}C$) to later lower temperatures (near $200^{\circ}C$) with salinities ranging from 0.8 to 10.1 equiv. wt. percent NaCl. Each area represents a separate hydrothermal system: the mineralization at Kasihan and Jompong were largely due to early fluid boiling coupled with later cooling and dilution, whereas the mineralization at Gempol was mainly resulted from cooling and dilution by an influx of cooler meteoric waters. Fluid inclusion evidence of boiling indicates that pressures of ${\geq}95$ to 255 bars (${\geq}95$ bars for the Gempol area: $\approx$ 120 to 170 bars for the Jompong area: $\approx$ 140 to 255 bars for the Kasihan area) during portions of main ore stage mineralization. Equilibrium thermodynamic interpretation indicates that the evolution trends of the temperature versus fS2 variation of ore stage fluids in the Pacitan district follow two fashions: ore fluids at Kasihan and Jompong changed from the pyrite-pyrrhotite sulfidation stage towards pyritehematite- magnetite state, whereas those at Gempol evolved nearly along pyrite-hematite-magnetite reaction curve with decreasing temperature. The sulfur isotope compositions of sulfide minerals are consistent with an igneous source of sulfur with a ${\delta}^{34}S_{{\Sigma}s}$ value of about 3.3 per mil. The oxygen and hydrogen isotopic compositions of the fluids in each area indicate a progressive shift from the dominance of highly exchanged meteoric water at early hydrothermal systems towards an un- or less-exchanged meteoric water at later hydrothermal systems.

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Determination of Adsorption Isotherms of Hydrogen at an Ir Electrode Interface Using the Phase-Shift Method and Correlation Constants (Ir 전극 계면에서 위상이동 방법 및 상관계수를 이용한 수소의 흡착동온식 결정)

  • Jeon, Sang-K.
    • Journal of the Korean Electrochemical Society
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    • v.10 no.2
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    • pp.132-140
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    • 2007
  • The phase-shift method and correlation constants for studying a linear relationship between the behavior ($-{\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and that (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}\theta{\geq}0$) have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) at noble metal/aqueous electrolyte interfaces. At an Ir/0.1 M KOH aqueous electrolyte interface, the Langmuir and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=3.3{\times}10^{-4}\;mol^{-1}$ for the Langmuir and $K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}$ for the Temkin adsorption isotherm), interaction parameter (g = 4.6 for the Temkin adsorption isotherm), and standard free energies (${\Delta}G_{ads}^0=19.9kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-4}\;mol^{-1}$ and $16.5<{\Delta}G_{\theta}^0<23.3\;kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}\;and\;0.2<\theta<0.8$) of H for the cathodic $H_2$ evolution reaction are determined using the phase-shift method and correlation constants. The inhomogeneous and lateral interaction effects on the adsorption of H are negligible. At the intermediate values of ${\theta},\;i.e,\;0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms (${\theta}\;vs.\;E$) and related electrode kinetic and thermodynamic parameters(K, g, ${\Delta}G_{ads}^0, {\Delta}G_{\theta}^0$).

Removal of Soluble Fe(II) using Reactive Media Coated with both Fe and Mn (철과 망간이 동시에 코팅된 반응성 매질을 이용한 용존 Fe(II) 제거)

  • Min, Sang-Yoon;Chang, Yoon-Young;Yang, Jae-Kyu
    • 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.

Study on Synthesis of Pyrochlore in Gd-Ti-O and Gd-Zr-O Systems (Gd-Ti-O계 및 Gd-Zr-O 계에서의 파이로클로어 합성연구)

  • ;;;S.V. Yudintsev
    • Economic and Environmental Geology
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    • v.37 no.3
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    • pp.303-309
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    • 2004
  • Pyrochlores were known as promising materials for the immobilization of radioactive actinide. Accordingly, we synthesized pyrochlores with Gd$_2$Ti$_2$$O_7$ and Gd$_2$Zr$_2$$O_7$compositions by sintering method, and studied its properties and phase relations in Gd-Ti-O and Gd-Zr-O system. The mixed powders were pressed into pellets under 200-400 kgf/cm$^2$ at room temperature. and then sintered at 1000-1$600^{\circ}C$ for 0.5-40 hours. The synthesized samples were analyzed and were identified with XRD and SEM/EDS analyses. The optimal synthetic conditions of pyrochlores with Gd$_2$Ti$_2$$O_7$composition were at 140$0^{\circ}C$/0.5hrs, 130$0^{\circ}C$/3hrs and 120$0^{\circ}C$/20hrs. Its chemical composition was $Gd_{2.0-2.1}$$Ti_{1.9-2.0}$$O_7$ and similar to the stoichiometric composition without any relationship in temperature and atmosphere. The optimal synthetic conditions of pyrochlores with $Gd_{2}$$Zr_{2}$$O_7$composition were at 155$0^{\circ}C$/40hrs and 1$600^{\circ}C$/30hrs. The compositions of pyrochlore synthesized from these optimal conditions were irregular with $Gd_{1.5-2.4}$$Zr_{1.7-2.4}$$O_7$. Such heterogeneity indicates that the reaction rate of pyrochlore with Gd$_2$Zr$_2$$O_7$composition is very low, and then its equilibrium state could not be attained even for 40 hours which was the longest sintering time in this research.

Geochemical Equilibria and Kinetics of the Formation of Brown-Colored Suspended/Precipitated Matter in Groundwater: Suggestion to Proper Pumping and Turbidity Treatment Methods (지하수내 갈색 부유/침전 물질의 생성 반응에 관한 평형 및 반응속도론적 연구: 적정 양수 기법 및 탁도 제거 방안에 대한 제안)

  • 채기탁;윤성택;염승준;김남진;민중혁
    • Journal of the Korean Society of Groundwater Environment
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    • v.7 no.3
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    • pp.103-115
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    • 2000
  • The formation of brown-colored precipitates is one of the serious problems frequently encountered in the development and supply of groundwater in Korea, because by it the water exceeds the drinking water standard in terms of color. taste. turbidity and dissolved iron concentration and of often results in scaling problem within the water supplying system. In groundwaters from the Pajoo area, brown precipitates are typically formed in a few hours after pumping-out. In this paper we examine the process of the brown precipitates' formation using the equilibrium thermodynamic and kinetic approaches, in order to understand the origin and geochemical pathway of the generation of turbidity in groundwater. The results of this study are used to suggest not only the proper pumping technique to minimize the formation of precipitates but also the optimal design of water treatment methods to improve the water quality. The bed-rock groundwater in the Pajoo area belongs to the Ca-$HCO_3$type that was evolved through water/rock (gneiss) interaction. Based on SEM-EDS and XRD analyses, the precipitates are identified as an amorphous, Fe-bearing oxides or hydroxides. By the use of multi-step filtration with pore sizes of 6, 4, 1, 0.45 and 0.2 $\mu\textrm{m}$, the precipitates mostly fall in the colloidal size (1 to 0.45 $\mu\textrm{m}$) but are concentrated (about 81%) in the range of 1 to 6 $\mu\textrm{m}$in teams of mass (weight) distribution. Large amounts of dissolved iron were possibly originated from dissolution of clinochlore in cataclasite which contains high amounts of Fe (up to 3 wt.%). The calculation of saturation index (using a computer code PHREEQC), as well as the examination of pH-Eh stability relations, also indicate that the final precipitates are Fe-oxy-hydroxide that is formed by the change of water chemistry (mainly, oxidation) due to the exposure to oxygen during the pumping-out of Fe(II)-bearing, reduced groundwater. After pumping-out, the groundwater shows the progressive decreases of pH, DO and alkalinity with elapsed time. However, turbidity increases and then decreases with time. The decrease of dissolved Fe concentration as a function of elapsed time after pumping-out is expressed as a regression equation Fe(II)=10.l exp(-0.0009t). The oxidation reaction due to the influx of free oxygen during the pumping and storage of groundwater results in the formation of brown precipitates, which is dependent on time, $Po_2$and pH. In order to obtain drinkable water quality, therefore, the precipitates should be removed by filtering after the stepwise storage and aeration in tanks with sufficient volume for sufficient time. Particle size distribution data also suggest that step-wise filtration would be cost-effective. To minimize the scaling within wells, the continued (if possible) pumping within the optimum pumping rate is recommended because this technique will be most effective for minimizing the mixing between deep Fe(II)-rich water and shallow $O_2$-rich water. The simultaneous pumping of shallow $O_2$-rich water in different wells is also recommended.

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