• 한국균학회소식:학술대회논문집
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• 한국균학회 2016년도 춘계학술대회 및 임시총회
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• pp.19-20
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• 2016

Sesquiterpenoids are defined as $C_{15}$ compounds derived from farnesyl pyrophosphate (FPP), and their complex structures are found in the tissue of many diverse plants (Degenhardt et al. 2009). FPP's long chain length and additional double bond enables its conversion to a huge range of mono-, di-, and tri-cyclic structures. A number of cyclic sesquiterpenes with alcohol, aldehyde, and ketone derivatives have key biological and medicinal properties (Fraga 1999). Fungi, such as the wood-rotting Polyporus brumalis, are excellent sources of pharmaceutically interesting natural products such as sesquiterpenoids. In this study, we investigated the biosynthesis of P. brumalis sesquiterpenoids on modified medium. Fungal suspensions of 11 white rot species were inoculated in modified medium containing $C_6H_{12}O_6$, $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ for 20 days. Cultivation was stopped by solvent extraction via separation of the mycelium. The metabolites were identified as follows: propionic acid (1), mevalonic acid lactone (2), ${\beta}$-eudesmane (3), and ${\beta}$-eudesmol (4), respectively (Figure 1). The main peaks of ${\beta}$-eudesmane and ${\beta}$-eudesmol, which were indicative of sesquiterpene structures, were consistently detected for 5, 7, 12, and 15 days These results demonstrated the existence of terpene metabolism in the mycelium of P. brumalis. Polyporus spp. are known to generate flavor components such as methyl 2,4-dihydroxy-3,6-dimethyl benzoate; 2-hydroxy-4-methoxy-6-methyl benzoic acid; 3-hydroxy-5-methyl phenol; and 3-methoxy-2,5-dimethyl phenol in submerged cultures (Hoffmann and Esser 1978). Drimanes of sesquiterpenes were reported as metabolites from P. arcularius and shown to exhibit antimicrobial activity against Gram-positive bacteria such as Staphylococcus aureus (Fleck et al. 1996). The main metabolites of P. brumalis, ${\beta}$-Eudesmol and ${\beta}$-eudesmane, were categorized as eudesmane-type sesquiterpene structures. The eudesmane skeleton could be biosynthesized from FPP-derived IPP, and approximately 1,000 structures have been identified in plants as essential oils. The biosynthesis of eudesmol from P. brumalis may thus be an important tool for the production of useful natural compounds as presumed from its identified potent bioactivity in plants. Essential oils comprising eudesmane-type sesquiterpenoids have been previously and extensively researched (Wu et al. 2006). ${\beta}$-Eudesmol is a well-known and important eudesmane alcohol with an anticholinergic effect in the vascular endothelium (Tsuneki et al. 2005). Additionally, recent studies demonstrated that ${\beta}$-eudesmol acts as a channel blocker for nicotinic acetylcholine receptors at the neuromuscular junction, and it can inhibit angiogenesis in vitro and in vivo by blocking the mitogen-activated protein kinase (MAPK) signaling pathway (Seo et al. 2011). Variation of nutrients was conducted to determine an optimum condition for the biosynthesis of sesquiterpenes by P. brumalis. Genes encoding terpene synthases, which are crucial to the terpene synthesis pathway, generally respond to environmental factors such as pH, temperature, and available nutrients (Hoffmeister and Keller 2007, Yu and Keller 2005). Calvo et al. described the effect of major nutrients, carbon and nitrogen, on the synthesis of secondary metabolites (Calvo et al. 2002). P. brumalis did not prefer to synthesize sesquiterpenes under all growth conditions. Results of differences in metabolites observed in P. brumalis grown in PDB and modified medium highlighted the potential effect inorganic sources such as $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ on sesquiterpene synthesis. ${\beta}$-eudesmol was apparent during cultivation except for when P. brumalis was grown on $MgSO_4$-free medium. These results demonstrated that $MgSO_4$ can specifically control the biosynthesis of ${\beta}$-eudesmol. Magnesium has been reported as a cofactor that binds to sesquiterpene synthase (Agger et al. 2008). Specifically, the $Mg^{2+}$ ions bind to two conserved metal-binding motifs. These metal ions complex to the substrate pyrophosphate, thereby promoting the ionization of the leaving groups of FPP and resulting in the generation of a highly reactive allylic cation. Effect of magnesium source on the sesquiterpene biosynthesis was also identified via analysis of the concentration of total carbohydrates. Our current study offered further insight that fungal sesquiterpene biosynthesis can be controlled by nutrients. To profile the metabolites of P. brumalis, the cultures were extracted based on the growth curve. Despite metabolites produced during mycelia growth, there was difficulty in detecting significant changes in metabolite production, especially those at low concentrations. These compounds may be of interest in understanding their synthetic mechanisms in P. brumalis. The synthesis of terpene compounds began during the growth phase at day 9. Sesquiterpene synthesis occurred after growth was complete. At day 9, drimenol, farnesol, and mevalonic lactone (or mevalonic acid lactone) were identified. Mevalonic acid lactone is the precursor of the mevalonic pathway, and particularly, it is a precursor for a number of biologically important lipids, including cholesterol hormones (Buckley et al. 2002). Farnesol is the precursor of sesquiterpenoids. Drimenol compounds, bi-cyclic-sesquiterpene alcohols, can be synthesized from trans-trans farnesol via cyclization and rearrangement (Polovinka et al. 1994). They have also been identified in the basidiomycota Lentinus lepideus as secondary metabolites. After 12 days in the growth phase, ${\beta}$-elemene caryophyllene, ${\delta}$-cadiene, and eudesmane were detected with ${\beta}$-eudesmol. The data showed the synthesis of sesquiterpene hydrocarbons with bi-cyclic structures. These compounds can be synthesized from FPP by cyclization. Cyclic terpenoids are synthesized through the formation of a carbon skeleton from linear precursors by terpene cyclase, which is followed by chemical modification by oxidation, reduction, methylation, etc. Sesquiterpene cyclase is a key branch-point enzyme that catalyzes the complex intermolecular cyclization of the linear prenyl diphosphate into cyclic hydrocarbons (Toyomasu et al. 2007). After 20 days in stationary phase, the oxygenated structures eudesmol, elemol, and caryophyllene oxide were detected. Thus, after growth, sesquiterpenes were identified. Per these results, we showed that terpene metabolism in wood-rotting fungi occurs in the stationary phase. We also showed that such metabolism can be controlled by magnesium supplementation in the growth medium. In conclusion, we identified P. brumalis as a wood-rotting fungus that can produce sesquiterpenes. To mechanistically understand eudesmane-type sesquiterpene biosynthesis in P. brumalis, further research into the genes regulating the dynamics of such biosynthesis is warranted.

• 자원환경지질
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• 제19권spc호
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• pp.19-41
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• 1986

Structural, radioactive, petrological, petrochemical, mineralogical and stable isotopic study as well as the review of previous studies of the uranium-bearing slates in the Ogcheon sequence were carried out to examine the lithological and structural controls, and geochemical environment in the uranium deposition in the sequence. And the study was extended to the coal-bearing formation (Jangseong Series-Permian) to compare the geochemical and sedimentologic aspects of uranium chemistry between Ogcheon and Hambaegsan areas. The results obtained are as follows: 1. The uranium mineralization occurs in the carbonaceous black slates of the middle to lower Guryongsan formation and its equivalents in the Ogcheon sequence. In general, two or three uranium-bearing carbonaceous beds are found with about 1 to 1.5km stratigraphic interval and they extend from Chungju to Jinsan for 90km in distance, with intermittent igneous intrusions and structural Jisturbances. Average thickness of the beds ranges from 20 to 1,500m. 2. These carbonaceous slate beds were folded by a strong $F_1$-fold and were refolded by subsequent $F_1$-fold, nearly co-axial with the $F_1$, resulting in a repeated occurrence of similar slate. The carbonaceous beds were swelled in hing zones and were shrinked or thined out in limb by the these foldings. Minor faulting and brecciation of the carbonaceous beds were followed causing metamorphism of these beds and secondary migration and alteration of uranium minerals and their close associations. 3. Uranium-rich zones with high radioactive anomalies are found in Chungju, Deogpyong-Yongyuri, MiwonBoun, Daejeon-Geumsan areas in the range of 500~3,700 cps (corresponds to 0.017~0.087%U). These zones continue along strike of the beds for several tens to a few hundred meters but also discontinue with swelling and pinches at places that should be analogously developed toward underground in their vertical extentions. The drilling surveyings in those area, more than 120 holes, indicate that the depth-frequency to uranium rich bed ranging 40~160 meter is greater. 4. The features that higher radioactive anomalies occur particularly from the carbonaceous beds among the argillaceous lithologic units, are well demonstrated on the cross sections of the lithology and radioactive values of the major uranium deposits in the Ogcheon zone. However, one anomalous radioactive zone is found in a l:ornfels bed in Samgoe, near Daejeon city. This is interpreted as a thermal metamorphic effect by which original uranium contents in the underlying black slate were migrated into the hornfels bed. 5. Principal minerals of the uranium-bearing black slates are quartz, sericite, biotite and chlorite, and as to chemical composition of the black slates, $Al_2O_3$ contents appear to be much lower than the average values by its clarke suggesting that the Changri basin has rather proximal to its source area. 6. The uranium-bearing carbonaceous beds contain minor amounts of phosphorite minerals, pyrite, pyrrhotite and other sulfides but not contain iron oxides. Vanadium. Molybdenum, Barium, Nickel, Zirconium, Lead, Cromium and fixed Carbon, and some other heavy metals appear to be positive by correlative with uranium in their concentrations, suggesting a possibility of their genetic relationships. The estimated pH and Eh of the slate suggests an euxenic marine to organic-rich saline water environment during uranium was deposited in the middle part of Ogcheon zone. 7. The Carboniferous shale of Jangseong Series(Sadong Series) of Permian in Hambaegsan area having low radioactivity and in fluvial to beach deposits is entirely different in geochemical property and depositional environment from the middle part of Ogcheon zone, so-called "Pibanryong-Type Ogcheon Zone". 8. Synthesizing various data obtained by several aspects of research on uranium mineralization in the studied sequence, it is concluded that the processes of uranium deposition were incorporated with rich organic precipitation by which soluble uranyl ions, $U{_2}^{+{+}}$ were organochemically complexed and carried down to the pre-Ogcheon sea bottoms formed in transitional environment, from Red Sea type basin to Black Sea type basin. Decomposition of the organic matter under reducing conditions to hydrogen sulfide, which reduced the $UO{_2}^{+2}$ ions to the insoluble uranium dioxide($UO_2$), on the other side the heavy metals are precipitated as sulfides. 9. The EPMA study on the identification of uraninite and others and the genetic interpretation of uranium bearing slates by isotopic values of this work are given separately by Yun, S. in 1984.

• 공업화학
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• 제21권1호
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• pp.52-57
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• 2010

중금속 이온이나 방사성 양이온을 처리하는 공정으로서 화학약품에 의한 침전법이나 일반 이온교환법을 가장 보편적으로 활용하고 있으나, 이 공정들은 약품의 과다 투여, 유효 금속의 폐기, 고형 폐기물에 의한 2차적인 토양 오염 유발 등과 같은 문제점을 가지고 있다. 이에 따라 최근 들어 선진국을 중심으로 전해환원 전착반응과 이온교환 반응을 결합시킨 전기화학적 이온교환법을 대체 신기술로 개발하고자 많은 관심과 연구가 집중되고 있다. 본 연구에서는 전기화학적 이온교환체 중의 하나인 nickel hexacyanoferrate (NiHCNFe)의 최적 제조조건을 규명하기 위해, 기지금속인 니켈판 표면에 화학적 방법과 전기화학적 방법으로 NiHCNFe 막을 생성하였으며, NiHCNFe의 구조 형태와 조성을 각각 SEM과 EDS 분석을 통하여 조사하였다. 또한 NiHCNFe 막이 생성된 니켈판을 운전전극으로 설치한 단일 평행평판 이온교환 전극반응기에서 산화-환원 전위를 연속적으로 순환시켜 순환전위곡선을 측정하고 피크 전류의 변화 거동을 조사하였다. 본 연구의 실험 결과에 의하면, 화학적으로 제조한 NiHCNFe가 전기화학적으로 제조한 경우보다 우수함을 알 수 있었고, 특히 118 h 화학반응시킨 NiHCNFe 이온교환체의 조밀도, 밀착성, 내구력이 가장 우수하게 나타났다.

• 한국산학기술학회논문지
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• 제13권11호
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• pp.5601-5609
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• 2012

본 논문은 포항철강공단 및 주변지역의 보건 및 환경영향 인자를 확인하기 위하여 미세먼지($PM_{10}$) 농도와 성분을 측정 및 분석하였다. 또한 지역대기자동측정망 자료를 이용하여 연별, 계절별 $PM_{10}$ 농도분포를 조사하였다. 공단지역 내 $PM_{10}$을 측정한 결과, 동일산업에서 측정된 $PM_{10}$ 평균농도는 $61.3{\pm}12.1{\mu}g/m^3$, 철강공단관리사무소에서 측정된 $PM_{10}$ 평균농도는 $44.3{\pm}8.1{\mu}g/m^3$으로 나타나 대기환경기준을 만족하였다. 공단지역 동일산업과 철강공단관리사무소에서 측정된 $PM_{10}$ 중 이차생성 이온인 ${SO_4}^{2-}$, $NO_3{^-}$, $NH_4{^+}$의 분율을 확인한 결과, ${SO_4}^{2-}$의 분율이 높게 나타났고, 황산염과 관련된 오염원이 철강공단지역에 존재하는 것으로 판단된다. 전체적으로 동일산업 지점에서는 ${SO_4}^{2-}$ > $Cl^-$ > $NO_3{^-}$ > $F^-$ > $NH_4{^+}$ 순으로 나타났고, 철강공단관리사무소 지점에서는 ${SO_4}^{2-}$ > $Cl^-$ > $NO_3{^-}$ > $NH_4{^+}$ > $F^-$ 순으로 나타났다.

• 공업화학
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• 제31권1호
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• pp.97-102
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• 2020

최근 리튬이차전지 양극 소재의 다양한 열화 메커니즘들이 밝혀지면서 이것을 제어하여 새로운 전기화학적 특성을 구현하고 기존 소재의 한계점을 극복하고자 하는 연구결과들이 많이 보고되고 있다. 특히, 리튬과잉산화물은 250 mA h g^-1 이상의 고 용량 차세대 리튬이차전지 양극 물질로 주목받고 있으나, 충방전 과정 중에 소재 특유의 원자 구조 열화로 인해 활용이 제한되고 있다. 본 연구는 0.4Li₂MnO₃_0.6LiNi_1/3Co_1/3Mn_1/3O₂ 리튬과잉소재의 충방전 과정 중에서 겪는 원자 구조 변화 과정을 분석하여 소재의 열화 과정을 밝히고 이를 개선하기 위한 연구 방향을 제시하고자 한다. 이를 위해, 원자 단위의 분해능을 갖는 전자투과현미경을 활용하여 충방전 중 원자 구조의 변화 과정을 분석하고 이러한 구조 변화가 소재의 전기화학적 특성에 어떠한 영향을 미치는지 밝히고자 하였다. 충전 과정 중에 발생한 다량의 리튬 빈자리로 인해 구조 불안정성이 일어났고, 이로 인해 전이 금속이 리튬 빈 자리로 이동하면서 구조 열화가 확인되었다. 결과적으로 이러한 구조 변이는 리튬과잉소재의 가장 큰 문제점인 방전 전압 강하 특성을 야기한다는 것을 알아내었다.

• 한국자기학회지
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• 제20권4호
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• pp.134-142
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• 2010

바륨 페라이트($BaFe_{12}O_{19}$) 분말을 공침법을 이용하여 합성하였다. 출발물질의 조성은 $Fe^{3+}:Ba^{2+}$ 몰 비를 8로 고정하고 $Fe^{3+}$와 $Ba^{2+}$의 상대적인 양을 조절하였다. pH(= 8, 9, 10), 열처리 온도와 시간에 따른 자기적 성질과 결정구조 입자형상의 변화를 XRD, FESEM, VSM을 이용하여 조사하였다. pH, $Fe^{3+}$와 $Ba^{2+}$의 상대적인 양 그리고 열처리 온도와 시간에 따라 보자력과 자화 값이 다양하게 나타났다. pH가 9인 경우에는 $Fe^{3+}$와 $Ba^{2+}$의 비가 14.4 : 1.8인 경우를 제외한 모든 분말에서 바륨 페라이트의 단일 상을 얻을 수 있었다. $Fe^{3+}$와 $Ba^{2+}$의 비가 12.8 : 1.6이며 공기중에서 $900^{\circ}C$로 열처리한 분말이 가장 큰 자화 값(65.7 emu/g)을 얻을 수 있었으며 산소분위기에서 $900^{\circ}C$로 열처리한 분말이 가장 큰 보자력 값(5280 Oe)을 얻을 수 있었다.

• 지질공학
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• 제12권1호
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• pp.95-109
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• 2002

새로이 형성되는 이차광물들이 콘크리트의 조기 성능 저하 (열화)에 미치는 영향은 현재까지 명확히 규명되지 않고 있다. 이들 광물들은 시멘트 페이스트와 골재간의 화학적 반응의 결과로 시멘트 페이스트 내에 형성된다. 조기 성능 저하 현상을 보이는 미국 아이오와주의 콘크리트 포장의 고속도로들로부터 채취된 시료들 내의 골재와 시멘트 페이스트에서의 화학적 광물학적 변화를 규명하기 위하여 암석학적 관찰과 SEM/EDAX 분석을 실시하였다. 이러한 분석에 의거 성능 저하에 연관된 이차광물의 형성과 팽창 메카니즘에 대하여 연구하였다. 브루사이트(Brucite, Mg(OH)2)는 골재의 탈백운석화(dedolomitization) 반응의 결과로 시멘트 페이트스 내에 생성되는 잠재적인 팽창성 광물이다. 시멘트 페이스트의 균열현상은 이들 광물과 공간적인 연관성을 보여주지는 않으나, 대부분이 극 미세입자의 크기로 조기 성능 저하 현상을 나타내는 콘크리트의 시멘트 페이스트 내에 광범위하게 산재되어 나타난다. 무수한 미세공간들에서의 이들 광물 성장에 의한 팽창성 응력은 콘크리트내부의 약한 부분에서 균열로 나타난다. 에트린자이트(3CaO.Al2O3.3CaSO4.32H2O)는 많은 작은 공극들을 완전히 채우고 있으며, 큰 공극들의 가장자리에 테두리와 같은 형태로 나타난다. 미세한 에트린자이트가 많은 콘크리트 시료들의 시멘트 페이스트에 산재해서 나타나기도 한다. 조기 성능 저하의 원인이 되는 시멘트 페이스트의 심한 균열이 에트린자이트와 공간적으로 연관되어 나타나는데, 이러한 사실은 에트린자이트가 콘크리트의 성능 저하에 기여한다는 것을 지시한다. 황철석 (FeS2)이 일반적으로 골재 내에 산재하는데, 이 광물의 산화작용의 산물이 많은 콘크리트 시료들에서 관찰된다. 이런 황철석의 산화작용은 에트린자이트를 형성하기 위한 황산염을 공급하게된다.

• 대기
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• 제29권4호
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• pp.403-416
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• 2019

Precipitation samples were collected at the GAW Stations in Anmyeon-do and Gosan for 10 years (2008-2017) to analyze pH, electrical conductivity and NH₄⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, SO₄^2-, NO₃^-, Cl^-, and F^- ions. From the analysis, the correlation between pH and rainfall, the composition of precipitation and comparison with other regions, and the results of neutralization characteristics by seasonal and pH were determined. In the comparison of ion balance and conductivity for the validation of analytical data, the correlation coefficients were within the range of 0.996~0.999, implying good linear relationship. The volume-weighted pH of the Anmyeon-do and Gosan areas were 4.7 and 4.9, respectively. The pH of the rainfall was affected by washout and rainout in both areas. The ionic strength of precipitation at Anmyeondo and Gosan were 0.42 ± 0.63 mM and 0.37 ± 0.75 mM, indicating about 27.6% and 35.3% of the total precipitation as per a pure precipitation criterion (10^-4 M), respectively. The composition ratio of ionic species were 44.7% and 57.5% for marine sources (Na⁺, Mg²⁺, Cl^-), 40.6% and 22.2% for the secondary inorganic components (NH₄⁺, nss-SO₄^2-, NO₃^-), and 5.6% and 4.0% for the soil source (nss-Ca²⁺), respectively. The neutralization factor of Anmyeon-do and Gosan were 0.43~0.65 and 0.34~0.48, and the neutralization factors of calcium carbonate were 0.15~0.34 and 0.25~0.30, respectively. Thus, both regions have the highest rate of neutralization caused by ammonia. As pH increased in Anmyeon-do and Gosan, change in calcium carbonate became greater than that in ammonia.

• 한국대기환경학회지
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• 제34권3호
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• pp.393-405
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• 2018

Volatile organic compounds (VOCs) are representative air pollutants due to their detrimental effects on human health and their role in formation of secondary organic aerosols. Assessments and monitoring programs of VOCs using periodic grab sampling like Tedlar bags, canisters, and sorbent traps provide limited information, often with delay times of days or weeks. Selected ion flow tube mass spectrometry (SIFT-MS) is an emerging analytical technique for the real-time quantification of VOCs in air. It relies on chemical ionization of the VOCs molecules in air introduced into helium carrier gas using $H_3O^+$, $NO^+$, and $O_2{^+}$ precursor ions. Real-time monitoring method of 60 VOCs in the ambient air was developed using TO-15 standard gas mixture. Calibration curves, method detection limit, and quantitation reproducibility of the target compounds were tested. Dynamic dilution system was used to dilute standard gas from 0.174 ppbv to 100 ppbv, where calibration curves showed good linearity with $r^2$> 0.95 in all target analytes. Limit of detection (LOD) all compounds were sub ppbv, and some halogenated compounds showed pptv levels. Seven consecutive analyses of target compounds showed good repeatability with relative standard deviation of less than 10%. One day monitoring of VOCs in ambient air was conducted in Geoje. Average concentration of target VOCs in Geoje were relatively lower than other regions, among which formaldehyde showed the highest concentration ($15.4{\pm}5.78ppbv$). SIFT-MS provided good temporal resolution data (1 data per 3.2 minute), which can be used for identifying ephemeral short-term event. It is expected that SIFT-MS will be a versatile monitoring platform for VOCs in ambient air.

• 한국대기환경학회지
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• 제29권1호
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• pp.74-85
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• 2013

Since the underground transportation system is a closed environment, indoor air quality problems may seriously affect many passengers' health. The purpose of this study was to understand $PM_{10}$ characteristics in the underground air environment and further to quantitatively estimate $PM_{10}$ source contributions in a Seoul Metropolitan subway station. The $PM_{10}$ was intensively collected on various filters with $PM_{10}$ aerosol samplers to obtain sufficient samples for its chemical analysis. Sampling was carried out in the M station on the Line-4 from April 21 to 28, July 13 to 21, and October 11 to 19 in the year of 2010 and January 11 to 17 in the year of 2011. The aerosol filter samples were then analyzed for metals, water soluble ions, and carbon components. The 29 chemical species (OC1, OC2, OC3, OC4, CC, PC, EC, Ag, Al, Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Si, Ti, V, Zn, $Cl^-$, $NO_3{^-}$, $SO_4{^{2-}}$, $Na^+$, $NH_4{^+}$, $K^+$, $Mg^{2+}$, $Ca^{2+}$) were analyzed by using ICP-AES, IC, and TOR after proper pretreatments of each sample filter. Based on the chemical information, positive matrix factorization (PMF) model was applied to identify the $PM_{10}$ sources and then six sources such as biomass burning, outdoor, vehicle, soil and road dust, secondary aerosol, ferrous, and brakewear related source were classified. The contributions rate of their sources in tunnel are 4.0%, 5.8%, 1.6%, 17.9%, 13.8% and 56.9% in order.