• Title/Summary/Keyword: Chemical Speciation

Search Result 108, Processing Time 0.034 seconds

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

  • Linak, William P.
    • Proceedings of the Korea Air Pollution Research Association Conference
    • /
    • 2003.11a
    • /
    • pp.195-195
    • /
    • 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.

  • PDF

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 (2007년 6월 수도권 오존모사 I - 광화학측정자료를 이용한 SAPRC99 화학종별 휘발성유기물질 배출량 입력자료 평가)

  • Kim, Soon-Tae
    • Journal of Korean Society for Atmospheric Environment
    • /
    • v.27 no.5
    • /
    • pp.580-602
    • /
    • 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
    • /
    • v.2 no.1
    • /
    • pp.34-46
    • /
    • 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
    • /
    • v.34 no.5
    • /
    • pp.517-531
    • /
    • 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.

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

  • Ko, Il-Won;Kim, Ju-Yong;Kim, Gyeong-Ung;An, Ju-Seong;Davis, A. P.
    • Economic and Environmental Geology
    • /
    • v.38 no.1
    • /
    • pp.23-31
    • /
    • 2005
  • This study was performed to investigate the effect of humic acid on the adsorption of arsenic onto hematite and its binding mechanism through the chemical speciation modeling in the binary system and the adsorption modeling in the ternary system. The complexation modeling of arsenic and humic acid was suitable for the binding model with the basis of the electrostatic repulsion and the effect of bridging metal. In comparison with the experimental adsorption data in the ternary system, the competitive adsorption model from the binary intrinsic equilibrium constants was consistent with the amount of arsenic adsorption. However, the additive rule showed the deviation of model in the opposite way of cationic heavy metals, because the reduced organic complexation of arsenic and the enhanced oxyanionic competition diminished the adsorption of arsenic. In terms of the reaction mechanism, the organic complex of arsenic, neutral As(III) and oxyanionic As(V) species were transported and adsorbed competitively to the hematite surface forming the inner-sphere complex in the presence of humic acid.

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

  • Cho, Hye-Ryun;Kim, Hee Kyung;Jung, Euo Chang;Cha, Wansik
    • Proceedings of the Korean Radioactive Waste Society Conference
    • /
    • 2017.10a
    • /
    • pp.137-138
    • /
    • 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.

  • PDF

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

  • 이상훈;천찬란;심지애
    • Economic and Environmental Geology
    • /
    • v.36 no.5
    • /
    • pp.349-356
    • /
    • 2003
  • As industrial activities are growing, pollutants found in the contaminated land are getting diverse. Some contaminated areas are subject to mixed wastes containing both organic and inorganic wastes such as hydrocarbon and heavy metals. This study concerns with the influence of the degradation of organic pollutants on the coexisting heavy metals, expecially for As. As mainly exists as two different oxidation state; As(III) and As(V) and the conversion between the two chemical forms may be induced by organic degradation in the soil contaminated by mixed wastes. We operated microcosm in an anaerobic chamber for 60 days, using sandy loam. The soils in the microcosm are artificially contaminated both by tetradecane and As, with different combination of As(III) and As(V); As(III):As(V) 1:1, As(III) only and As(V) only. Although not systematic, ratio of As(III)/As(Total) increase slightly at the later stage of experiment. Considering complicated geochemical reactions involving oxidation/reduction of organic materials, Mn/Fe oxides and As, the findings in the study seem to indicate the degradation of the organics is connected with the As speciation. That is to say, the As(V) can be reduced to As(III) either by direct or indirect influence induced by the organic degradation. Although Fe and Mn are good oxidising agent for the oxidation of As(III) to As(V), organic degradation may have suppressed reductive dissolution of the Fe and Mn oxides, causing the organic pollutants to retard the oxidation of As(III) to As(V) until the organic degradation ceases. The possible influence of organic degradation on the As speciation implies that the As in mixed wastes may be have elevated toxicity and mobility by partial conversion from As(V) to As(III).

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
    • /
    • v.34 no.12
    • /
    • pp.3817-3824
    • /
    • 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.

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

  • Yu, Byung-Kyu;Lyu, Mu-Sang;Sun, Yle-Shik;Cho, Ki-Sung
    • Journal of the Korean Society of Food Science and Nutrition
    • /
    • v.41 no.5
    • /
    • pp.674-680
    • /
    • 2012
  • As(III) and As(V) were analyzed in bamboo salts by hydride generation ICP-AES. In order to quantify the total amount of As in bamboo salts, $AsH_3$ was producted by reacting with 6 mol/L hydrochloric acid and $NaBH_4$, which was then analyzed by hydride generation ICP-AES. As(V) was quantified simultaneously after selectively quantifying As(III). As(III) was quantified by determining the total amount of As and then correcting for the amount of As(III). To improve the reliability of the analysis we repeated the experiment several times to check the detection limit, quantification limit, and measurements of our testing methods. According to the result of our quantification analysis of As existing in bamboo salt, the range of total As content was 0.05 mg/kg~0.2 mg/kg and As(V) was over 90% of the total As.

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
    • /
    • v.26 no.3
    • /
    • pp.440-446
    • /
    • 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.