• 제목/요약/키워드: chemical speciation

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Combustion Generated Fine Particles, Trace Metal Speciation, and Health Effects

  • Linak, William P.
    • 한국대기환경학회:학술대회논문집
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    • 한국대기환경학회 2003년도 추계학술대회 논문집
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    • pp.195-195
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    • 2003
  • Combustion generated fine particles, defined as those with aerodynamic diameters less than 2.5 m, have come under increased regulatory scrutiny because of suspected links to adverse human health effects. Transition metals are of particular interest due to the results of a number of studies that have shown cardiopulmonary damage associated with exposure to these elements and their presence in coal, residual fuel oils, sewage sludge, and other combusted fuels and wastes. This lecture will review results from multi-di sciplinary studies being conducted at EPA and elsewhere examining the physical, chemical, and toxicological characteristics of combustion generated particles. The research describes how collaborative work between combustion engineers and health scientists can provide insight on how combustion processes affect particle properties and subsequent health effects as measured by a combination of in-vitro and in-vivo studies using a variety of animal models. The focus of this lecture is on the interdisciplinary approach required to address the problem. Difficulties are discussed. Engineering aspects involved in this approach are described in detail. Physical and chemical characterizations are performed using a variety of analytical approaches including new techniques of x-ray absorption fine structure (XAFS) spectroscopy and x-ray absorption near-edge structure (XANES) deconvolution of these spectra to gather metal speciation information.

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2007년 6월 수도권 오존모사 I - 광화학측정자료를 이용한 SAPRC99 화학종별 휘발성유기물질 배출량 입력자료 평가 (Ozone Simulations over the Seoul Metropolitan Area for a 2007 June Episode, Part I: Evaluating Volatile Organic Compounds Emissions Speciated for the SAPRC99 Chemical Mechanism)

  • 김순태
    • 한국대기환경학회지
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    • 제27권5호
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    • pp.580-602
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    • 2011
  • Volatile organic compound (VOC) emissions in the 2007 CAPSS (Clean Air Protection Supporting System) emissions inventory are chemically speciated for the SAPRC99 (Statewide Air Pollution Research Center 99) mechanism, following the Source Classification Code (SCC) matching method to borrow the U.S.EPA's chemical speciation profiles. CMAQ simulations with High-order Direct Decoupled Method (HDDM) are in turn applied to evaluate uncertainty in the method by comparing the simulated model VOC species to the observations in the Seoul Metropolitan Area (SMA) for a 2007 June episode. Simulations under-predicted ALK1 to ALK4 in SAPRC99 by a factor of 2 to 5 and over-predicted ALK5 by a factor of 7.5 while ARO1, ARO2, OLE1, and ethylene (ETH) are comparable to the observations, showing relative difference by 10 to 30%. OLE2 emissions are roughly 4 times overestimated. Emission rates for individual VOC model species are revised referring to the ratio of simulated to observed concentrations. Impact of the VOC emission changes on the overall ozone prediction was insignificant for the days of which 1-hr maximum ozone are lower than 100 ppb. However, simulations showed ozone difference by 5 to 10 ppb when high ozone above 120 ppb was observed in the vicinity of Seoul. This result suggests that evaluations on individual model VOC emissions be necessary to lead ozone control plans to the right direction. Moreover, the simulated ratios of ARO1 and ARO2 to $NO_x$ are roughly 50% lower than the observed ones, which imply that adjustment in $NO_x$ and VOC emission rates may be required to mimic the real VOC/$NO_x$ condition over the area.

Korea Emissions Inventory Processing Using the US EPA's SMOKE System

  • Kim, Soon-Tae;Moon, Nan-Kyoung;Byun, Dae-Won W.
    • Asian Journal of Atmospheric Environment
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    • 제2권1호
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    • pp.34-46
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    • 2008
  • Emissions inputs for use in air quality modeling of Korea were generated with the emissions inventory data from the National Institute of Environmental Research (NIER), maintained under the Clean Air Policy Support System (CAPSS) database. Source Classification Codes (SCC) in the Korea emissions inventory were adapted to use with the U.S. EPA's Sparse Matrix Operator Kernel Emissions (SMOKE) by finding the best-matching SMOKE default SCCs for the chemical speciation and temporal allocation. A set of 19 surrogate spatial allocation factors for South Korea were developed utilizing the Multi-scale Integrated Modeling System (MIMS) Spatial Allocator and Korean GIS databases. The mobile and area source emissions data, after temporal allocation, show typical sinusoidal diurnal variations with high peaks during daytime, while point source emissions show weak diurnal variations. The model-ready emissions are speciated for the carbon bond version 4 (CB-4) chemical mechanism. Volatile organic carbon (VOC) emissions from painting related industries in area source category significantly contribute to TOL (Toluene) and XYL (Xylene) emissions. ETH (Ethylene) emissions are largely contributed from point industrial incineration facilities and various mobile sources. On the other hand, a large portion of OLE (Olefin) emissions are speciated from mobile sources in addition to those contributed by the polypropylene industry in point source. It was found that FORM (Formaldehyde) is mostly emitted from petroleum industry and heavy duty diesel vehicles. Chemical speciation of PM2.5 emissions shows that PEC (primary fine elemental carbon) and POA (primary fine organic aerosol) are the most abundant species from diesel and gasoline vehicles. To reduce uncertainties in processing the Korea emission inventory due to the mapping of Korean SCCs to those of U.S., it would be practical to develop and use domestic source profiles for the top 10 SCCs for area and point sources and top 5 SCCs for on-road mobile sources when VOC emissions from the sources are more than 90% of the total.

Speciation and Solubility of Major Actinides Under the Deep Groundwater Conditions of Korea

  • Dong-Kwon Keum;Min-Hoon Baik;Pil-Soo Hahn
    • Nuclear Engineering and Technology
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    • 제34권5호
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    • pp.517-531
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    • 2002
  • The speciation and solubility of Am, Np, Pu and U have been analyzed by means of the geochemical code MUGREM, under the chemical conditions of domestic deep groundwater, in order to support the preliminary safety assessment for a Korean HLW disposal concept. Under the conditions of groundwaters studied, the stable solid phase is AmOHC $O_3$(s) or Am(OH)$_3$(s), soddyite((U $O_2$)$_2$ $SiO_2$.2$H_2O$) or N $a_2$ $U_2$ $O_{7}$ (c), Np(OH)$_4$(am), and Pu(OH)$_4$(am) for Am, U, Np, and Pu, respectively. The dominating aqueous species are as follows: the complexes of Am(III), Am(OH)$_2$$^{+}$ and Am(C $O_3$)$_2$$^{[-10]}$ , the complexes of U(VI), U $O_2$(OH)$_3$$^{[-10]}$ and U $O_2$(C $O_3$)$_3$$^{4-}$, the complexes of Np(IV), Np(OH)$_4$(aq) and Np(OH)$_3$C $O_3$, and the complexes of Pu(IV), Pu(OH)$_4$(aq) and Pu(OH)$_3$C $O_3$$^{[-10]}$ . The calculated solubilities exist between 1.9E-10 and 1.3E-9 mol/L for Am, between 5.6E-6 and 1.2E-4 mol/L for U, between 3.1E-9 and 1.3E-8 mol/L for Np, and between 6.6E-10 and 2.4E-10 mol/L for Pu, depending on groundwater conditions. The present solubilities of each actinide agree well with the results of other studies obtained under similar conditions.s.

비소의 적철석 표면 흡착에 토양유기물이 미치는 영향: 화학종 모델링과 흡착 기작 (Effect of Soil Organic Matter on Arsenic Adsorption in the Hematite-Water Interface: Chemical Speciation Modeling and Adsorption Mechanism)

  • 고일원;김주용;김경웅;안주성
    • 자원환경지질
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    • 제38권1호
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    • pp.23-31
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    • 2005
  • 본 연구는 이성분계의 화학종 모델링과 삼성분계의 흡착 모델링으로부터 As(III)와 As(V)의 적철석 표면 흡착에 휴 믹산의 영향과 그 결합기작을 고찰하였다. 비소와 휴믹산의 유기 결합의 모델링은 음이온 사이의 정전기적인 반발력 과 비소의 유기 결합을 위한 결합금속의 영향을 고려한 결합 모델이 적합하였다. 삼성분계의 흡착 실험 자료와 비교 할 때 이성분계의 고유상수를 사용한 음이온 경쟁 모델이 음이온 경쟁에 따른 비소의 흡착량과 일치하였다. 반면, 비 소의 유기 결합량의 감소와 휴믹산과의 음이온 흡착경쟁이 흡착량을 감소시키기 때문에 단순합모델은 양이온 중금속 과는 반대로 모델의 편차를 보였다. 반응 기작의 관점에서 휴믹산의 공존하에 비소 유기결합 화학종과 중성화학종의 As(III) 및 음이온의 As(V)가 속착물을 형성하며, 경쟁적으로 적철석 표면으로 이동하여 흡착하게 된다.

Spectroscopic Studies on Pu(III) Hydrolysis Under Reducing and Elevated Temperatures Conditions

  • Cho, Hye-Ryun;Kim, Hee Kyung;Jung, Euo Chang;Cha, Wansik
    • 한국방사성폐기물학회:학술대회논문집
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    • 한국방사성폐기물학회 2017년도 추계학술논문요약집
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    • pp.137-138
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    • 2017
  • The spectroscopic reference data for plutonium at different temperatures are necessary information for the chemical speciation and evaluation of thermodynamic data at elevated temperature. This work is the initial step to extend research activities for understanding the plutonium chemistry in aquatic solutions at high temperature. The hydrolysis of Pu(III) and the solubility of Pu(III) hydroxide at the elevated temperature will be discussed.

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유기물분해에 따른 유류${\cdot}$중금속 복합오염토양내 비소화학종 변화의 기초연구 (Preliminary Study on Arsenic Speciation Changes Induced by Biodegradation of Organic Pollutants in the Soil Contaminated with Mixed Wastes)

  • 이상훈;천찬란;심지애
    • 자원환경지질
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    • 제36권5호
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    • pp.349-356
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    • 2003
  • 최근 산업활동의 종류가 점차 복잡해지면서 오염물질의 종류도 많아지고 있으며 오염물질의 성상도 점차 복합화하고 있다. 이런 경향은 과거 단일 물질에 의한 오염에서 점차 유기물과 중금속이 동시에 오염되는 것과 같은 혼합 오염형태가 증가하고 있는데서 인지된다. 본 연구는 유류와 중금속이 동시에 오염된 지역에서 유류분해에 따른 혐기성 환경전환이 비소의 농도와 화학종에 어떤 영향을 미치며 그 결과가 위해성과 정화작용에 어떤 영향을 미치는지를 확인하고자 하였다. 충적대수층에서 채취한 사질토양을 tetradecane으로 오염시킨 후 As(III)과 As(V)를 각각 1:1, As(III)로만 그리고 As(V)로만 등으로 혼합비율을 달리하여 오염시킨 후 마이크로코즘을 제작하여 혐기성 반응기안에 방치, 60일간 운전하였다. 매 10일마다 마이크로코즘을 개방하여 유기물, As(III) 및 As(V)의 농도 그리고 Fe, Mn의 농도변화를 측정하였다. 전체 As 농도에 대한 As(III)의 비율, As(III) 자체의 농도 변화 그리고 유기물 분해경향 등을 바탕으로 유기물분해에 따라 As(III)의 증가에 영향을 미치는 것이 확인되었다. Fe, Mn의 환원에 따른 As의 산화와 유기물 분해에 따른 환원이 서로 상충할 수 있으며 실제 분해 단계에 따라 어느 한쪽의 작용이 우세해지는 것으로 판단된다. 즉, Fe, Mn의 환원은 유기물의 분해에 의해 억제되었으며 유기물 분해가 상당히 진행 된 이후 Fe, Mn의 혐기성 용출이 일어나는 것으로 생각된다. 본 연구 결과는 혼합오염지역의 경우 유기물분해는 비소종의 화학형태에 영향을 미칠 것으로 예상되며 만약 As(III)의 비율이 증가할 경우 비소종의 위해성은 증가하게 될 것으로 판단되며 점차 증가하고 있는 혼합오염물 지역에 대한 정량적 위해성 평가가 요구된다.

Quantitative Speciation of Selenium in Human Blood Serum and Urine with AE- RP- and AF-HPLC-ICP/MS

  • Jeong, Ji-Sun;Lee, Jonghae;Pak, Yong-Nam
    • Bulletin of the Korean Chemical Society
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    • 제34권12호
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    • pp.3817-3824
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    • 2013
  • Various separation modes in HPLC, such as anion exchange (AE), reversed-phase (RP), and affinity (AF) chromatography were examined for the separation of selenium species in human blood serum and urine. While RP- and AE-HPLC were mainly used for the separation of small molecular selenium species, double column AF-HPLC achieved the separation of selenoproteins in blood serum efficiently. Further, the effluent of AF-HPLC was enzymatically hydrolyzed and then analyzed with RP HPLC for selenoamino acid study. The versatility of the hybrid technique makes the in-depth study of selenium species possible. For quantification, post column isotope dilution (ID) with $^{78}Se$ spike was performed. ORC ICP/MS (octapole reaction cell inductively coupled plasma/mass spectrometry) was used with 4 mL $min^{-1}$ Hydrogen as reaction gas. In urine sample, inorganic selenium and SeCys were identified. In blood serum, selenoproteins GPx, SelP and SeAlb were detected and quantified. The concentration for GPx, SelP and SeAlb was $22.8{\pm}3.4\;ng\;g^{-1}$, $45.2{\pm}1.7\;ng\;g^{-1}$, and $16.1{\pm}2.2\;ng\;g^{-1}$, respectively when $^{80}Se/^{78}Se$ was used. The sum of these selenoproteins ($84.1{\pm}4.4\;ng\;g^{-1}$) agrees well with the total selenium concentration measured with the ID method of $87.0{\pm}3.0\;ng\;g^{-1}$. Enzymatic hydrolysis of each selenium proteins revealed that SeCys is the major amino acid for all three proteins and SeMet is contained in SeAlb only.

수소화물 발생-유도결합 플라즈마 원자 방출 분광법을 이용한 죽염중의 비소 종분리 분석 (Arsenic Speciation Aanalysis in Bamboo Salts by Hydride Generation-ICP-AES)

  • 유병규;유무상;선일식;조기성
    • 한국식품영양과학회지
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    • 제41권5호
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    • pp.674-680
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    • 2012
  • 이 연구에서는 비소의 종분리 분석을 위하여 수소화물발생-ICP-AES를 이용하여 무기비소의 As(III)와 As(V)의 신호세기에 대한 citric acid와 HCl 농도의 영향을 조사하였다. 1.5% $NaBH_4$의 농도에서 HCl 농도 1.0 mol/L, citric acid의 농도 2.0%를 사용하였을 때 As(III)만을 선택 분리할 수 있었고, 정도관리 절차에 따라 분석방법을 수행했을 때 방법 검출한계는 0.003 mg/kg, 정량한계는 0.01 mg/kg으로 산출되었으며, 시료의 매질간섭을 확인하기 위한 매질첨가시료 분석과 정도관리시료 분석의 회수율은 80%~110%, 표준편차는 6.2%로 정밀도와 정확도에서도 만족할 만한 수준을 나타내었다. 이에 따라 정도관리시료로 분석한 결과값과 반복성에 의한 측정불확도를 산출하여 인증표준물질의 인증값과 불확도를 비교 통계 처리함으로써 분석방법에 대한 유의성이 없음을 확인하였다. 또한 이 연구에서 제안된 분석방법에 따라 죽염 중에 존재하는 총 무기비소 분석과 비소 종분리 분석을 실시한 결과 총 무기비소의 함량은 0.05 mg/kg에서 0.21 mg/kg 정도로 나타났으며, 분석방법에 따른 여러 불확도 요인들의 표준불확도를 산출하여 죽염 중에 존재하는 As의 불확도를 구한 결과, As의 함량이 0.14 mg/kg에 대하여 확장불확도가 0.03 mg/kg(95% 신뢰수준, $k$=1.96)으로 최종 결과값의 21%를 나타내었다. 위의 결과로 보아 대부분 As(V)의 형태로 존재하며 일부 시료에 대해 As(III)의 함량이 각각 0.02 mg/kg으로 총 무기비소함량의 14.3%와 9.5%를 차지하는 것으로 나타났다.

Determination of Dibutyltin in Sediments Using Isotope Dilution Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry

  • Yim, Yong-Hyeon;Park, Ji-Youn;Han, Myung-Sub;Park, Mi-Kyung;Kim, Byung-Joo;Lim, Young-Ran;Hwang, Eui-Jin;So, Hun-Young
    • Bulletin of the Korean Chemical Society
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    • 제26권3호
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    • pp.440-446
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    • 2005
  • A method is described for the determination of dibutyltin (DBT) in sediment by isotope dilution using liquid chromatography inductively-coupled plasma/mass spectrometry (LC-ICP/MS). To achieve the highest accuracy and precision, special attentions are paid in optimization and evaluation of overall processes of the analysis including extraction of analytes, characterization of the standards used for calibration and LC-ICP/MS conditions. An approach for characterization of natural abundance DBT standard has been developed by combining inductively-coupled plasma/optical emission spectrometry (ICP/OES) and LC-ICP/MS for the total Sn assay and the analysis of Sn species present as impurities, respectively. An excellent LC condition for separation of organotin species was found, which is suitable for simultaneous DBT and tributyltin (TBT) analysis as well as impurity analysis of DBT standards. Microwave extraction condition was also optimized for high efficiency while preventing species transformation. The present method determines the amount contents of DBT in sediments with expanded uncertainty of less than 5% and its result shows high degree of equivalence with reference values of an international inter-comparison and a certified reference material (CRM) within stated uncertainties.