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Recycling of Acidic Etching Waste Solution Containing Heavy Metals by Nanofiltration (I): Evaluation of Acid Stability of Commercial Nanofiltration Membranes (나노여과에 의한 중금속 함유 산성 폐에칭액의 재생(I): 상용 나노여과 막의 산 안정성 평가)

  • Youm, Kyung-Ho;Shin, Hwa-Sup;Jin, Cheon-Deok
    • Membrane Journal
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    • v.19 no.4
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    • pp.317-323
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    • 2009
  • In this study the nanofiltration (NF) membrane treatment of a nitric acid waste solutions containing $Pb^{+2}$ heavy metal ion discharging from the etching processes of an electronics and semiconductors industry has been studied for the purpose of recycling of nitric acid etching solutions. Three kinds of NF membranes (General Electric Co. Duraslick NF-4040 membrane, Dow Co. Filmtec LP-4040 membrane and Koch Co. SelRO MPS-34 4040 membrane) were tested for their separation efficiency (total rejection) of $Pb^{+2}$ ion and membrane stability in nitric acid solution. NF experiments were carried out with a dead-end membrane filtration laboratory system. The membrane permeate flux was increased with the increasing storage time in nitric acid solution and lowering pH of acid solution because of the enhancing of NF membrane damage by nitric acid. The membrane stability in nitric acid solution was more superior in the order of Filmtec LP-4040 < Duraslick NF-4040 < SelRO MPS-34 4040 membrane. The total rejection of Pb+2 ion was decreased with the increasing storage time in nitric acid solution and lowering the pH of acid solution. The total rejection of $Pb^{+2}$ ion after 4 months NF treatment was decreased from 95% initial value to 20% in the case of Duraslick NF-4040 membrane, from 85% initial value to 65% in the case of SelRO MPS-34 4040 membrane and from 90% initial value to 10% in the case of Filmtec LP-4040 membrane. These results showed that SelRO MPS-34 4040 NF membrane was more suitable for the treatment of an acidic etching waste solutions containing heavy metal ions.

Physico.chemical Properties of Peatmoss and Coir Dust Currently Used as Root Medium Components for Crop Production in Korean Plant Factories (국내에서 식물공장용 배지 재료로 유통되는 피트모스와 코이어 더스트의 물리.화학적 특성)

  • Shin, Bo Kyoung;Son, Jung Eek;Choi, Jong Myung
    • Journal of Bio-Environment Control
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    • v.21 no.4
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    • pp.362-371
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    • 2012
  • Objective of this research was to secure the information on physical and chemical properties of peatmoss and coir dust. To achieve this, 6 kinds of peatmoss and 10 kinds of coir dust currently used in the country as the root medium components in plant factories were collected and analysed. The mean ${\pm}$ standard deviation (SD) of total porosity and container capacity in peatmoss and coir dust were $79.6{\pm}5.04$ and $83.6{\pm}6.18%$, and $69.9{\pm}10.17$ and $65.9{\pm}3.46%$, respectively. These indicate that peatmoss has higher water holding capacity than coir dust and the characteristics are highly varied among peatmoss. The 4 out of 5 kinds of peatmoss had lower than 10%, but coir dust had 12~26%, of air-filled porosity. The percentage of easily available water and buffering water in peatmoss and coir dust was 18~22 and 11~16% and 9~13 and 5.5~7.5%, respectively. These results indicate that precise irrigation is required when coir dust is used as the root medium. The ranges of pH and electrical conductivity (EC) were 3.46~4.17 and $0.137{\sim}0.253dS{\cdot}m^{-1}$ in peatmoss and 5.31~6.48 and $0.250{\sim}0.1.580dS{\cdot}m^{-1}$ in coir dust. However, $0.563{\pm}0.83dS{\cdot}m^{-1}$ in mean ${\pm}$SD of coir dust EC indicates that it is higher than that of peatmoss, and the coir dust are highly varied in EC. The cation exchange capacity of peatmoss was 3 to 4 times as high as that of coir dust. The coir dust had higher $NO_3$ and $PO_4$ and lower $NH_4$ than peatmoss. The K and Na concentrations in coir dust were extremely high indicating that these ions caused the rising in EC. The percentage of hot water and alkali extracts of peatmoss were 6.67~16.37 and 0~38%, whereas those of coir dust were 30.0~65.1 and 23.1~70.3%. These results mean that possible existence of growth inhibiting materials in coir dust.

Structural Analysis of the Unusual Sugar-Containing Oligosaccharides Formed by the Selective Cleavage of Weakly Acidic Polysaccharide (약산성 다당의 선택적 분해 과정에서 얻어진 특이당 함유 Oligo당의 구조적 분석)

  • Shin, Kwang-Soon;Lee, Ho
    • Korean Journal of Food Science and Technology
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    • v.29 no.6
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    • pp.1105-1112
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    • 1997
  • By sequential degradation using partial acid hydrolysis of a weakly acidic polysaccharide (GL-4IIb2'), two acidic oligosaccharide fragments, PA-2' and PA-1-III were isolated and their structures were characterized. PA-2' consisted of almost equal proportion of a rhamnose (Rha) and an unusual sugar, 3-deoxy-D-manno-2-octurosonic acid (Kdo). When permethylated oligosaccharide-alditol derived from PA-2' was analyzed by GC-MS, the peak gave the fragment ions at m/z 189 $(bA_1,\;6-deoxyhexose)$ and at m/z 308 $(aJ_2,\;alditol\;from\;Kdo)$. The peak also gave the characteristic ion at m/z 162 but it did not give the fragment ion at m/z 177, suggesting that Kdo is substituted at C5 but not at C4. Methylation analysis also indicated that PA-2' was composed mainly of terminal Rhap and 5-substituted Kdo. When the reduced product from PA-2' was analyzed by $^1H-NMR$, it gave a signal at 5.09 ppm due to an anomeric proton of ${\alpha}-L-Rha$. These results indicated that PA-2' mainly contained ${\alpha}-L-Rhap-(1{\rightarrow}5)-Kdo$. On the other hand, PA-1-III mainly comprised Rha and Kdo in addition to small proportions of arabinose (Ara) and 3-deoxy-D-lyxo-2-heptulosaric acid (Dha). MS analysis of permethylated oligosaccharide-alditols from PA-1-III suggested that the major peak 1P was $Rhap-(1{\rightarrow}5)-Kdo$ whereas the minor peaks 2P and 3P possessed $Araf-(1{\rightarrow}5)-Dha$ unit and these peaks were produced as epimers during reduction of carbonyl groups in Dha.

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Transport of Zn Ion under various pH Conditions in a Sandy Soil (사질토양에서의 pH조건에 따른 Zn의 이동특성)

  • Park, Min-Soo;Kim, Dong-Ju
    • Journal of Korean Society of Environmental Engineers
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    • v.22 no.1
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    • pp.33-42
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    • 2000
  • Adsorption onto the surfaces of solid particles is a well known phenomenon that causes the retardation effect of heavy metals in soils. For adequate remediation of soil and groundwater contamination, it is important to investigate the mobility of heavy metals that largely depends on pH conditions in the soil water since adsorption of heavy metals is pH-dependent. In this study, we investigated the transport of Zn ion under various pH conditions in a sandy soil by conducting batch and column tests. The batch test was performed using the standard procedure of equilibrating fine fractions collected from the soil with eleven different initial $ZnCl_2$ concentrations, and analysis of Zn ion in the equilibrated solutions using ICP-AES. The column test consisted of monitoring the concentrations of soil solutions exiting the soil column with time known as a breakthrough curve (BTC). We injected respectively $ZnCl_2$ and KCl solutions with the concentration of 10 g/L as a tracer in a square pulse type under three different pH conditions (7.7, 5.8, 4.1) and monitored the flux concentration at the exit boundary using an EC meter and ICP-AES. The resident concentration was also monitored at the 10cm-depth by Time Domain Reflectometry (TDR). The results of batch test showed that ion exchange process between Zn and other cations (Ca, Mg) was predominant. The retardation coefficients obtained from adsorption isotherms (Linear, Freundlich, Langmuir) resulted in the various values ranging from 1.2 to 614.1. No retardation effect but ion exchange was found for the BTCs under all pH conditions. This can be explained by the absence of other cations to desorb Zn ion from soil exchange sites under the conditions of ETC experiment imposing blank water as leachate in steady-state flow. As pH decreased, the peak concentration of Zn increased due to the competition of Zn with hydrogen ions ($H^+$) and the concentrations of other cations decreased. The peak concentration of Zn was increased by 12.7 times as pH decreased from 7.7 to 4.1.

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Treatment of N, P of Auto-Thermal Thermophilic Aerobic Digestion Filtrate with Struvite Crystallization (Struvite 결정화 반응을 이용한 고온 소화 여과액의 N, P 처리 특성)

  • Choo, Yeon-Duk;Kim, Keum-Yong;Ryu, Hong-Duck;Lee, Sang-Ill
    • Journal of Korean Society of Environmental Engineers
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    • v.33 no.11
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    • pp.783-789
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    • 2011
  • Recently, auto-thermal thermophilic aerobic digestion (ATAD) has a great attention for destruction of wasted sludge biomass in wastewater treatment plant. Reduction of sludge concentration has been successfully achieved with pilot scale ATAD and ceramic filtration process in field condition. However, high concentration of COD, total nitrogen (TN) and total phosphorus (TP) was observed in filtrate, which should be treated before recirculation of filtrate to biological wastewater treatment plant. This study was focused on removal of nitrogen and phosphorus contained in the filtrate of ATAD, using struvite crystallization method. The effect of operational and environmental parameters (such as, N, P and Mg ion concentration and molar ratio, pH, reaction time, agitation strength, seed dosage, and reaction temperature) on the treatment of TN and TP with struvite crystallization were evaluated. Magnesium (as $MgCl_26H_2O$) and phosphorus (as $K_2HPO_4$) ions were, if necessary, added to increase nitrogen removal efficiency by the crystal formation. Average concentration of $NH_4^+-N$ and $PO_4^{3-}-P$ of the filtrate were 1716.5 mg/L and 325.5 mg/L, respectively. Relationship between removal efficiencies of nitrogen and phosphorus and molar ratios of $Mg^{2+}$ and $PO_4^{3-}-P$ to $NH_4^+-N$ was examined. Crystal formation and nitrogen removal efficiencies were significantly increased as increasing molar ratios of magnesium and phosphorus to nitrogen. As molar ratio of $Mg^{2+}:PO_4^{3-}-P:NH_4^+-N$ were maintained to 2 : 1 : 1 and 2 : 2 : 1, removal efficiencies of nitrogen and phosphorus were 71.6% and 99.9%, and 93.8% and 98.6%, respectively. However, the effect of reaction time, mixing intensity, seed dose and temperature on the struvite crystallization reaction was not significant, comparing to those of molar ratios. Settled sludge volume after struvite crystallization was observed to be reduced with increase of seed dose and to be increased at high temperature.

Application of Reused Powdered Waste Containing Aluminum Oxide on the Treatment of Cr(VI) (6가 크롬 처리를 위한 알루미늄 산화물을 함유한 재생 분말 폐기물의 적용)

  • Lim, Jae-Woo;Kim, Tae-Hwan;Kang, Hyung-Sik;Kim, Do-Son;Kim, Han-Seon;Cho, Seok-Hee;Yang, Jae-Kyu;Chang, Yoon-Young
    • Journal of Korean Society of Environmental Engineers
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    • v.31 no.3
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    • pp.179-185
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    • 2009
  • In this research, the removal capacity of Cr(VI) by the reused powdered wastes (RPW) containing aluminium oxides was studied. As a pre-treatment process for the preparation of calcined wastes, calcination was conducted at $550^{\circ}C$ to remove organic fraction in the raw wastes. In order to study the adsorption trend of Cr(VI) ions from aqueous solutions, the pH-edge adsorption, adsorption kinetic and adsorption isotherm were investigated using a batch reactor in the presence of four different background electrolytes($NO_3\;^-,\;CO_3\;^{2-},\;SO_4\;^{2-},\;PO_4\;^{3-}$). Cr(VI) adsorption was greatly reduced in the presence of $SO_4\;^{2-}$ and $PO_4\;^{3-}$ over the entire pH range. Meanwhile the inhibition effect by $NO_3\;^-$ and $CO_3\;^{2-}$ was relatively lower than that by $SO_4\;^{2-}$ and $PO_4\;^{3-}$. Cr(VI) adsorption was maximum around pH 4.5 in the presence of $NO_3\;^-$ and $CO_3\;^{2-}$. As the concentration of background electrolytes increased, Cr(VI) adsorption decreased. This result mightly suggests that adsorption between the surface of RPW and Cr(VI) occurs through outer-sphere complex. Cr(VI) adsorption onto the RPW was well described by second-order kinetics. From the Langmuir isotherm at initial pH 3, the maximum adsorbed amount of Cr(VI) onto the RPW was 11.1, 10, 3.3, 5 mg/g in the presence of $NO_3\;^-,\;CO_3\;^{2-},\;SO_4\;^{2-}$, and $PO_4\;^{3-}$, respectively.

Characteristic Assessment of Heavy Metals in Dusts Collected by the Air Filtration System at Subway Stations in Daegu, Korea (대구지역 지하철역사 공기여과필터 포집먼지에 함유된 중금속성분의 특성평가)

  • Do, Hwa-Seok;Song, Hee-Bong;Shin, Dong-Chan;Kwak, Jin-Hee;Lee, Myoung-Sook;Yoon, Ho-Suk;Kang, Hye-Jung;Phee, Young-Gyu
    • Journal of Korean Society of Environmental Engineers
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    • v.31 no.1
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    • pp.42-50
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    • 2009
  • Samples of subway dust were collected by the air filter system of 30 subway stations on Daegu subway line 1 in January 2008. Samples were sieved below 100 ${\mu}m$, and 14 elements were analyzed using ICP after acid extraction. Results obtained from the source assessment of trace elements using enrichment factor showed that Ca, Fe, K, Mg, Mn, Na, V were influenced by natural sources such as weathered rock and resuspended soil, while Cd, Cr, Cu, Ni, Pb and Zn were influenced by anthropogenic sources such as fuel combustion and waste incineration. Concentrations were remarkably higher in components from natural sources than in components from anthropogenic sources. Anthropogenic sources were significantly affected by indoor dusts than outdoor dusts. Results of pollution indices of heavy metals indicated that indoor dusts were more contaminated with heavy metal ions than outdoor dusts. The correlation analysis among trace elements indicated that components were much correlated in the order of natural sources-anthropogenic sources, anthropogenic sources-anthropogenic sources, natural sources-natural sources in both indoor and outdoor dusts. Trace element components of outdoor dusts were largely correlated than those of indoor dusts. In addition, indoor dusts were significantly affected by outdoor dusts rather than depth from the surface or the average daily number of subway passengers.

Geochemistry of Geothermal Waters in Korea: Environmental Isotope and Hydrochemical Characteristics II. Jungwon and Munkyeong Areas (한반도 지열수의 지화학적 연구: 환경동위원소 및 수문화학적 특성 II. 중원 및 문경 지역)

  • Yun, Seong-Taek;Koh, Yong-Kwon;Choi, Hyen-Su;Youm, Seung-Jun;So, Chil-Sup
    • Economic and Environmental Geology
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    • v.31 no.3
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    • pp.201-213
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    • 1998
  • From the Jungwon and Munkyeong areas which are among the famous producers of the carbonate-type groundwaters in Korea, various kinds of natural waters (deep groundwater, shallow groundwater and surface water) were collected between 1996 and 1997 and were studied for hydrogeochemical and environmental isotope (${\delta}^{34}S_{so4}$, ${\delta}^{18}O$, ${\delta}D$)systematics. Two types of deep groundwaters (carbonate type and alkali type) occur together in the two areas, and each shows distinct hydrogeochemical and environmental isotope characteristics. The carbonate type waters show the hydrochemical feature of the 'calcium(-sodium)-bicarbonate(-sulfate) type', whereas the alkali type water of the 'sodium-bicarbonate type'. The former type waters are characterized by lower pH, higher Eh, and higher amounts of dissolved ions (especialJy, $Ca^{2+}$, $Na^{+}$, $Mg^{2+}$, $HCO_3{^-}$ and $SO_4{^{2-}}$). Two types of deep groundwaters are all saturated or supersaturated with respect to calcite. Two types of deep groundwaters were both derived from pre-thermonuclear (about more than 40 years old) meteoric waters (with lighter 0 and H isotope data than younger waters, i.e., shallow cold groundwaters and surface waters) which evolved through prolonged water-rock interaction. Based on the geologic setting, water chemistry, and environmental isotope data, however, each of these two different types of deep groundwaters represents distinct hydrologic and hydrogeochemical evolution at depths. The carbonate type groundwaters were formed through mixing with acidic waters that were derived from dissolution of pyrites in hydrothermal vein ores (for the Jungwon area water) or in anthracite coal beds (for the Munkyeong area water). If the deeply percolating meteoric waters did not meet pyrites during the circulation, only the alkali type groundwaters would form. This hydrologic and hydrogeochemical model may be successfully applied to the other carbonate type groundwaters in Korea.

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Silica and Iron Oxide Recovery and Mineral Carbonation from Serpentine Minerals Using Acid Dissolution and pH Swing Processes (산 처리와 pH 조절을 이용한 사문석군 광물로부터 규소와 철산화물 회수 및 광물 탄산화 연구)

  • Baek, Jiyeon;Jo, Yeonu;Lee, Jeongheon;Kwon, Nayoon;Kim, Yeram;Choi, Suk;Kim, Sunghee;Roh, Yul
    • Economic and Environmental Geology
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    • v.49 no.1
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    • pp.13-22
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    • 2016
  • The objectives of this study were to recover silica and iron oxides and $CO_2$ sequestration using serpentine via various acid dissolution and pH swing processes. Serpentine collected from Guhang-myeon in S. Korea were mainly composed of antigorite and magnetite consisting of $SiO_2$ (45.3 wt.%), MgO (41.3 wt.%), $Fe_2O_3$ (12.2 wt.%). Serpentine pulverized ($${\leq_-}75{\mu}m$$) and then dissolved in 3 different acids, HCl, $H_2SO_4$, $HNO_3$. Residues treated with acidic solution were recovered from the solution (step 1). And then the residual solution containing dissolved serpentine was titrated using $NH_4OH$. And pH of the solution increased up to pH=8.6 to obtain reddish precipitates (step 2). After recovery of the precipitates, the residual solution reacted with $CO_2$ and then pH increased up to pH=9.5 to precipitate white materials (step 3). The mineralogical characteristics of the original sample and harvested precipitates were examined by XRD, and TEM-EDS analyses. ICP-AES analysis was also used to investigate solution chemistry. The dissolved ions were Mg, Si, and Fe. The antigorite became noncrystralline silica after acid treatment (step 1). The precipitate at pH=8.6 was mainly amorphous iron oxide, of which size ranged from 2 to 10 nm and mainly consisting of Fe, O, and Si (step 2). At pH=9.5, nesquehonite [$Mg(HCO_3)(OH){\cdot}2(H_2O)$] and lasfordite [$MgCO_3{\cdot}H_2O$] were formed after reaction with $CO_2$ (step 3). The size of carbonated minerals was ranged from 1 to $6{\mu}m$. These results indicated that the acid treatment of serpentine and pH swing processes for the serpentine can be used for synthesis of other materials such as silica, iron oxides and magnesium carbonate. Also, This process may be useful for the precursor synthesis and $CO_2$ sequestration via mineral carbonation.

Remediation of Heavy Metal Contaminated Groundwater by Using the Biocarrier with Dead Bacillus sp. B1 and Polysulfone (Bacillus sp. B1 사균과 Polysulfone으로 이루어진 미생물 담체를 이용한 중금속 오염 지하수 정화)

  • Lee, Min-Hee;Lee, Ji-Young;Wang, Soo-Kyun
    • Economic and Environmental Geology
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    • v.43 no.6
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    • pp.555-564
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    • 2010
  • Remediation process by using the bio-carrier (beads) with dead Bacillus sp. B1 and polysulfone was investigated for heavy metal contaminated groundwater. Sorption batch experiments using the bio-carrier were performed to quantify the heavy metal removal efficiencies from the contaminated solution. The analyses using SEM/EDS and TEM for the structure and the characteristic of precipitates on/inside the beads were also conducted to understand the sorption mechanism by the bio-carrier. Various amounts of freeze-dried dead Bacillus sp. B1 were mixed with polysulfone + DMF(N,N-dimethylformamide) solution to produce the bio-carrier (beads; less than 2mm in diameter) and 5% of Bacillus sp. B1 in the bio-carrier was optimal for Pb removal in the solution. The removal efficiency ratings of the bio-carrier for Pb, Cu and Cd were greater than 80% after adding 2g of bio-carrier in 50ml of aqueous solution (<10mg/L of each heavy metal concentration). Reaction time of the bio-carrier was very fast and most of the sorption reaction for heavy metals were completed within few hours. Batch experiments were duplicated at various pH conditions of aqueous solutions and Cu and Pb removal efficiencies highly maintained at wide pH ranges (pH 2-12), suggesting that the bio-carrier can be useful to clean up the acidic waste water such as AMD. From SEM/EDS and TEM analyses, it was observed that the bio-carrier was spherical shape and was overlapped by many porous layers. During the sorption experiment, Pb was crystallized on the surface of porous layers and also was mainly concentrated at the boundary of Bacillus sp. B1 stroma and polysulfone substrate, showing that the main mechanism of the bio-carrier to remove heavy metals is the sorption on/inside of the bio-carriers and the bio-carriers are excellent biosorbents for the removal of heavy metal ions from groundwater.