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Sample records for aerosol chemical speciation

  1. Improving Molecular Level Chemical Speciation of Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Worton, D. R.; Decker, M.; Isaacman, G. A.; Chan, A.; Wilson, K. R.; Goldstein, A. H.

    2013-12-01

    A substantial fraction of fine mode aerosols are organic with the majority formed in the atmosphere through oxidation of gas phase compounds emitted from a variety of natural and man-made sources. As a result, organic aerosols are comprised of thousands of individual organic species whose complexity increases exponentially with carbon number and degree of atmospheric oxidation. Chemical characterization of individual compounds present in this complex mixture provides information on sources and transformation processes that are critical for apportioning organic carbon from an often convoluted mixture of sources and to constrain oxidation mechanisms needed for atmospheric models. These compounds also affect the physical and optical properties of the aerosol but the vast majority remain unidentified and missing from published mass spectral libraries because of difficulties in separating and identifying them. We have developed improved methodologies for chemical identification in order to better understand complex environmental mixtures. Our approach has been to combine two-dimensional gas chromatography with high resolution time of flight mass spectrometry (GC×GC-HRTOFMS) and both traditional electron ionization (EI) and vacuum ultraviolet (VUV) photoionization. GC×GC provides improved separation of individual compounds over traditional one dimensional GC and minimizes co-elution of peaks resulting in mass spectra that are virtually free of interferences. VUV ionization is a ';soft' ionization technique that reduces fragmentation and enhances the abundance of the parent or molecular ion, which when combined with high resolution mass spectrometry can provide molecular formulas for chromatographic peaks. We demonstrate our methodology by applying it to identify more than 500 individual compounds in aerosol filter samples collected at Blodgett Forest, a rural site in the Sierra Nevada Mountains. Using the EI NIST mass spectral library and molecular formulas determined

  2. Intercomparison of an Aerosol Chemical Speciation Monitor (ACSM) with ambient fine aerosol measurements in downtown Atlanta, Georgia

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S. H.; Canagaratna, M. R.; Croteau, P. L.; Baumann, K.; Edgerton, E. S.; Kollman, M. S.; Ng, N. L.; Verma, V.; Shaw, S. L.; Knipping, E. M.; Worsnop, D. R.; Jayne, J. T.; Weber, R. J.; Surratt, J. D.

    2014-07-01

    Currently, there are a limited number of field studies that evaluate the long-term performance of the Aerodyne Aerosol Chemical Speciation Monitor (ACSM) against established monitoring networks. In this study, we present seasonal intercomparisons of the ACSM with collocated fine aerosol (PM2.5) measurements at the Southeastern Aerosol Research and Characterization (SEARCH) Jefferson Street (JST) site near downtown Atlanta, GA, during 2011-2012. Intercomparison of two collocated ACSMs resulted in strong correlations (r2 > 0.8) for all chemical species, except chloride (r2 = 0.21) indicating that ACSM instruments are capable of stable and reproducible operation. In general, speciated ACSM mass concentrations correlate well (r2 > 0.7) with the filter-adjusted continuous measurements from JST, although the correlation for nitrate is weaker (r2 = 0.55) in summer. Correlations of the ACSM NR-PM1 (non-refractory particulate matter with aerodynamic diameter less than or equal to 1 μm) plus elemental carbon (EC) with tapered element oscillating microbalance (TEOM) PM2.5 and Federal Reference Method (FRM) PM1 mass are strong with r2 > 0.7 and r2 > 0.8, respectively. Discrepancies might be attributed to evaporative losses of semi-volatile species from the filter measurements used to adjust the collocated continuous measurements. This suggests that adjusting the ambient aerosol continuous measurements with results from filter analysis introduced additional bias to the measurements. We also recommend to calibrate the ambient aerosol monitoring instruments using aerosol standards rather than gas-phase standards. The fitting approach for ACSM relative ionization for sulfate was shown to improve the comparisons between ACSM and collocated measurements in the absence of calibrated values, suggesting the importance of adding sulfate calibration into the ACSM calibration routine.

  3. Intercomparison of an Aerosol Chemical Speciation Monitor (ACSM) with ambient fine aerosol measurements in Downtown Atlanta, Georgia

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S. H.; Canagaratna, M. R.; Croteau, P. L.; Baumann, K.; Edgerton, E. S.; Kollman, M. S.; Ng, N. L.; Verma, V.; Shaw, S. L.; Knipping, E. M.; Worsnop, D. R.; Jayne, J. T.; Weber, R. J.; Surratt, J. D.

    2013-12-01

    The Aerodyne Aerosol Chemical Speciation Monitor (ACSM) was recently developed to provide long-term real-time continuous measurements of ambient non-refractory (i.e., organic, sulfate, ammonium, nitrate, and chloride) submicron particulate matter (NR-PM1). Currently, there are a limited number of field studies that evaluate the long-term performance of the ACSM against established monitoring networks. In this study, we present seasonal intercomparisons of the ACSM with collocated fine aerosol (PM2.5) measurements at the Southeastern Aerosol Research and Characterization (SEARCH) Jefferson Street (JST) site near downtown Atlanta, GA, during 2011-2012. The collocated measurements included a second ACSM, continuous and integrated sulfate, nitrate, and ammonium measurements, as well as a semi-continuous Sunset organic carbon/elemental carbon (OC/EC) analyzer, continuous tapered element oscillating microbalance (TEOM), 24 h integrated Federal Reference Method (FRM) filters, and continuous scanning electrical mobility system-mixing condensation particle counter (SEMS-MCPC). Intercomparison of the two collocated ACSMs resulted in strong correlations (r2 > 0.8) for all chemical species, except chloride (r2 = 0.21); mass concentration for all chemical species agreed within ±27%, indicating that ACSM instruments are capable of stable and reproducible operation. Chemical constituents measured by the ACSM are also compared with those obtained from the continuous measurements from JST. Since the continuous measurement concentrations are adjusted to match the integrated filter measurements, these comparisons reflect the combined uncertainties of the ACSM, continuous, and filter measurements. In general, speciated ACSM mass concentrations correlate well (r2 > 0.7) with the continuous measurements from JST, although the correlation for nitrate is weaker (r2 = 0.55) in summer. Differences between ACSM mass concentrations and the filter-adjusted JST continuous data are 5-27%, 4

  4. The ToF-ACSM: a portable aerosol chemical speciation monitor with TOFMS detection

    NASA Astrophysics Data System (ADS)

    Fröhlich, R.; Cubison, M. J.; Slowik, J. G.; Bukowiecki, N.; Prévôt, A. S. H.; Baltensperger, U.; Schneider, J.; Kimmel, J. R.; Gonin, M.; Rohner, U.; Worsnop, D. R.; Jayne, J. T.

    2013-11-01

    We present a new instrument for monitoring aerosol composition, the time-of-flight aerosol chemical speciation monitor (ToF-ACSM), combining precision state-of-the-art time-of-flight mass spectrometry with stability, reliability, and easy handling, which are necessities for long-term monitoring operations on the scale of months to years. Based on Aerodyne aerosol mass spectrometer (AMS) technology, the ToF-ACSM provides continuous online measurements of chemical composition and mass of non-refractory submicron aerosol particles. In contrast to the larger AMS, the compact-sized and lower-priced ToF-ACSM does not feature particle sizing, similar to the widely-used quadrupole-ACSM (Q-ACSM). Compared to the Q-ACSM, the ToF-ACSM features a better mass resolution of M/ΔM = 600 and better detection limits on the order of < 30 ng m-3 for a time resolution of 30 min. With simple upgrades these limits can be brought down by another factor of ~ 8. This allows for operation at higher time resolutions and in low concentration environments. The associated software packages (single packages for integrated operation and calibration and analysis) provide a high degree of automation and remote access, minimising the need for trained personnel on site. Intercomparisons with Q-ACSM, C-ToF-AMS, nephelometer and scanning mobility particle sizer (SMPS) measurements, performed during a first long-term deployment (> 10 months) on the Jungfraujoch mountain ridge (3580 m a.s.l.) in the Swiss Alps, agree quantitatively. Additionally, the mass resolution of the ToF-ACSM is sufficient for basic mass defect resolved peak fitting of the recorded spectra, providing a data stream not accessible to the Q-ACSM. This allows for quantification of certain hydrocarbon and oxygenated fragments (e.g. C3H7+ and C2H3O+, both occurring at m/Q = 43 Th), as well as improving inorganic/organic separation.

  5. The ToF-ACSM: a portable aerosol chemical speciation monitor with TOFMS detection

    NASA Astrophysics Data System (ADS)

    Fröhlich, R.; Cubison, M. J.; Slowik, J. G.; Bukowiecki, N.; Prévôt, A. S. H.; Baltensperger, U.; Schneider, J.; Kimmel, J. R.; Gonin, M.; Rohner, U.; Worsnop, D. R.; Jayne, J. T.

    2013-07-01

    We present a new instrument for monitoring aerosol composition, the economy time-of-flight-aerosol chemical speciation monitor (ToF-ACSM), combining precision of state-of-the-art time-of-flight mass spectrometry with stability, reliability, and easy handling, which are necessities for long-term monitoring operations on the scale of months to years. Based on Aerodyne aerosol mass spectrometer (AMS) technology, the ToF-ACSM provides continuous online measurements of chemical composition and mass of non-refractory submicron aerosol particles. In contrast to the larger AMS, the compact-sized and lower-priced ToF-ACSM does not feature particle sizing, similar to the widely-used quadrupole-ACSM (Q-ACSM). Compared to the Q-ACSM, the ToF-ACSM features a better mass resolution of M/ΔM = 600 and better detection limits on the order of <30 ng m-3 for a time resolution of 30 min. With simple upgrades these limits can be brought down by another factor of ~8. This allows for operation at higher time resolutions and in low concentration environments. The associated software packages (single packages for integrated operation & calibration and analysis) provide a high degree of automation and remote access, minimising the need for trained personnel on site. Intercomparisons with Q-ACSM, C-ToF-AMS, nephelometer and scanning mobility particle sizer (SMPS) measurements, performed during a first long-term deployment (>6 months) on the Jungfraujoch mountain ridge (3580 m a.s.l.) in the Swiss Alps agree quantitatively. Additionally, the mass resolution of the ToF-ACSM is sufficient for basic mass defect resolved peak fitting of the recorded spectra, providing a data stream not accessible to the Q-ACSM. This allows for quantification of certain hydrocarbon and oxygenated fragments (e.g. C3H7+ and C2H3O+, both occurring at m/Q = 43 Th), as well as improving inorganic/organic separation.

  6. Chemical speciation of vanadium in particulate matter emitted from diesel vehicles and urban atmospheric aerosols.

    PubMed

    Shafer, Martin M; Toner, Brandy M; Overdier, Joel T; Schauer, James J; Fakra, Sirine C; Hu, Shaohua; Herner, Jorn D; Ayala, Alberto

    2012-01-01

    We report on the development and application of an integrated set of analytical tools that enable accurate measurement of total, extractable, and, importantly, the oxidation state of vanadium in sub-milligram masses of environmental aerosols and solids. Through rigorous control of blanks, application of magnetic-sector-ICPMS, and miniaturization of the extraction/separation methods we have substantially improved upon published quantification limits. The study focused on the application of these methods to particulate matter (PM) emissions from diesel vehicles, both in baseline configuration without after-treatment and also equipped with advanced PM and NO(x) emission controls. Particle size-resolved vanadium speciation data were obtained from dynamometer samples containing total vanadium pools of only 0.2-2 ng and provide some of the first measurements of the oxidation state of vanadium in diesel vehicle PM emissions. The emission rates and the measured fraction of V(V) in PM from diesel engines running without exhaust after-treatment were both low (2-3 ng/mile and 13-16%, respectively). The V(IV) species was measured as the dominant vanadium species in diesel PM emissions. A significantly greater fraction of V(V) (76%) was measured in PM from the engine fitted with a prototype vanadium-based selective catalytic reductors (V-SCR) retrofit. The emission rate of V(V) determined for the V-SCR equipped vehicle (103 ng/mile) was 40-fold greater than that from the baseline vehicle. A clear contrast between the PM size-distributions of V(V) and V(IV) emissions was apparent, with the V(V) distribution characterized by a major single mode in the ultrafine (<0.25 μm) size range and the V(IV) size distribution either flat or with a small maxima in the accumulation mode (0.5-2 μm). The V(V) content of the V-SCR PM (6.6 μg/g) was 400-fold greater than that in PM from baseline (0.016 μg/g) vehicles, and among the highest of all environmental samples examined. Synchrotron

  7. Long-term Measurements of Submicrometer Aerosol Chemistry at the Southern Great Plains (SGP) Using an Aerosol Chemical Speciation Monitor (ACSM)

    SciTech Connect

    Parworth, Caroline; Fast, Jerome D.; Mei, Fan; Shippert, Timothy R.; Sivaraman, Chitra; Tilp, Alison; Watson, Thomas; Zhang, Qi

    2015-04-01

    In this study the long-term trends of non-refractory submicrometer aerosol (NR-PM1) composition and mass concentration measured by an Aerosol Chemical Speciation Monitor (ACSM) at the U.S. Department of Energy’s Southern Great Plains (SGP) site are discussed. Over the period of 19 months (Nov. 20, 2010 – June 2012) highly time resolved (~30 min.) NR-PM1 data was recorded. Using this dataset the value-added product (VAP) of deriving organic aerosol components (OACOMP) is introduced. With this VAP, multivariate analysis of the measured organic mass spectral matrix can be performed on long term data to return organic aerosol (OA) factors that are associated with distinct sources, evolution processes, and physiochemical properties. Three factors were obtained from this VAP including two oxygenated OA (OOA) factors, differing in degrees of oxidation, and a biomass burning OA (BBOA) factor. Back trajectory analyses were performed to investigate possible sources of major NR-PM1 species at the SGP site. Organics dominated NR-PM1 mass concentration for the majority of the study with the exception of winter, when nitrate increased due to transport of precursor species from surrounding urban and agricultural areas and also due to cooler temperatures. Sulfate mass concentrations showed little seasonal variation with mixed regional and local sources. In the spring BBOA emissions increased and were mainly associated with local fires. Isoprene and carbon monoxide emission rates were computed by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) to represent the spatial distribution of biogenic and anthropogenic sources, respectively. From this model there is evidence to support that biogenic emissions from the southeast contribute to SOA formation at the SGP site during the summer.

  8. Long-term measurements of submicrometer aerosol chemistry at the Southern Great Plains (SGP) using an Aerosol Chemical Speciation Monitor (ACSM)

    SciTech Connect

    Parworth, Caroline; Tilp, Alison; Fast, Jerome; Mei, Fan; Shippert, Tim; Sivaraman, Chitra; Watson, Thomas; Zhang, Qi

    2015-04-01

    In this study the long-term trends of non-refractory submicrometer aerosol (NR-PM1) composition and mass concentration measured by an Aerosol Chemical Speciation Monitor (ACSM) at the Atmospheric Radiation Measurement (ARM) program's Southern Great Plains (SGP) site are discussed. NR-PM1 data was recorded at ~30 min intervals over a period of 19 months between November 2010 and June 2012. Positive Matrix Factorization (PMF) was performed on the measured organic mass spectral matrix using a rolling window technique to derive factors associated with distinct sources, evolution processes, and physiochemical properties. The rolling window approach also allows us to capture the dynamic variations of the chemical properties in the organic aerosol (OA) factors over time. Three OA factors were obtained including two oxygenated OA (OOA) factors, differing in degrees of oxidation, and a biomass burning OA (BBOA) factor. Back trajectory analyses were performed to investigate possible sources of major NR-PM1 species at the SGP site. Organics dominated NR-PM1 mass concentration for the majority of the study with the exception of winter, when ammonium nitrate increases due to transport of precursor species from surrounding urban and agricultural areas and also due to cooler temperatures. Sulfate mass concentrations have little seasonal variation with mixed regional and local sources. In the spring BBOA emissions increase and are mainly associated with local fires. Isoprene and carbon monoxide emission rates were obtained by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the 2011 U.S. National Emissions Inventory to represent the spatial distribution of biogenic and anthropogenic sources, respectively. The combined spatial distribution of isoprene emissions and air mass trajectories suggest that biogenic emissions from the southeast contribute to SOA formation at the SGP site during the summer.

  9. Long-term measurements of submicrometer aerosol chemistry at the Southern Great Plains (SGP) using an Aerosol Chemical Speciation Monitor (ACSM)

    DOE PAGESBeta

    Parworth, Caroline; Tilp, Alison; Fast, Jerome; Mei, Fan; Shippert, Tim; Sivaraman, Chitra; Watson, Thomas; Zhang, Qi

    2015-04-01

    In this study the long-term trends of non-refractory submicrometer aerosol (NR-PM1) composition and mass concentration measured by an Aerosol Chemical Speciation Monitor (ACSM) at the Atmospheric Radiation Measurement (ARM) program's Southern Great Plains (SGP) site are discussed. NR-PM1 data was recorded at ~30 min intervals over a period of 19 months between November 2010 and June 2012. Positive Matrix Factorization (PMF) was performed on the measured organic mass spectral matrix using a rolling window technique to derive factors associated with distinct sources, evolution processes, and physiochemical properties. The rolling window approach also allows us to capture the dynamic variations ofmore » the chemical properties in the organic aerosol (OA) factors over time. Three OA factors were obtained including two oxygenated OA (OOA) factors, differing in degrees of oxidation, and a biomass burning OA (BBOA) factor. Back trajectory analyses were performed to investigate possible sources of major NR-PM1 species at the SGP site. Organics dominated NR-PM1 mass concentration for the majority of the study with the exception of winter, when ammonium nitrate increases due to transport of precursor species from surrounding urban and agricultural areas and also due to cooler temperatures. Sulfate mass concentrations have little seasonal variation with mixed regional and local sources. In the spring BBOA emissions increase and are mainly associated with local fires. Isoprene and carbon monoxide emission rates were obtained by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the 2011 U.S. National Emissions Inventory to represent the spatial distribution of biogenic and anthropogenic sources, respectively. The combined spatial distribution of isoprene emissions and air mass trajectories suggest that biogenic emissions from the southeast contribute to SOA formation at the SGP site during the summer.« less

  10. Long-term measurements of submicrometer aerosol chemistry at the Southern Great Plains (SGP) using an Aerosol Chemical Speciation Monitor (ACSM)

    NASA Astrophysics Data System (ADS)

    Parworth, Caroline; Fast, Jerome; Mei, Fan; Shippert, Tim; Sivaraman, Chitra; Tilp, Alison; Watson, Thomas; Zhang, Qi

    2015-04-01

    In this study the long-term trends of non-refractory submicrometer aerosol (NR-PM1) composition and mass concentration measured by an Aerosol Chemical Speciation Monitor (ACSM) at the Atmospheric Radiation Measurement (ARM) program's Southern Great Plains (SGP) site are discussed. NR-PM1 data was recorded at ∼30 min intervals over a period of 19 months between November 2010 and June 2012. Positive Matrix Factorization (PMF) was performed on the measured organic mass spectral matrix using a rolling window technique to derive factors associated with distinct sources, evolution processes, and physiochemical properties. The rolling window approach also allows us to capture the dynamic variations of the chemical properties in the organic aerosol (OA) factors over time. Three OA factors were obtained including two oxygenated OA (OOA) factors, differing in degrees of oxidation, and a biomass burning OA (BBOA) factor. Back trajectory analyses were performed to investigate possible sources of major NR-PM1 species at the SGP site. Organics dominated NR-PM1 mass concentration for the majority of the study with the exception of winter, when ammonium nitrate increases due to transport of precursor species from surrounding urban and agricultural areas and also due to cooler temperatures. Sulfate mass concentrations have little seasonal variation with mixed regional and local sources. In the spring BBOA emissions increase and are mainly associated with local fires. Isoprene and carbon monoxide emission rates were obtained by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the 2011 U.S. National Emissions Inventory to represent the spatial distribution of biogenic and anthropogenic sources, respectively. The combined spatial distribution of isoprene emissions and air mass trajectories suggest that biogenic emissions from the southeast contribute to SOA formation at the SGP site during the summer.

  11. X-RAY POWDER DIFFRACTION SYSTEM FOR CHEMICAL SPECIATION OF PARTICULATE AEROSOL SAMPLES

    EPA Science Inventory

    An x-ray powder diffraction system has been developed for the automated measurement and analysis of particulate aerosol samples. The system is optimized to process samples with particle loadings of about 100 micrograms/sq cm which are acquired with dichotomous air samplers. A pos...

  12. Continuous measurements at the urban roadside in an Asian Megacity by Aerosol Chemical Speciation Monitor (ACSM): particulate matter characteristics during fall and winter seasons in Hong Kong

    NASA Astrophysics Data System (ADS)

    Sun, C.; Lee, B. P.; Huang, D.; Li, Y. J.; Schurman, M. I.; Louie, P. K. K.; Luk, C.; Chan, C. K.

    2015-07-01

    Non-refractory submicron aerosol is characterized using an Aerosol Chemical Speciation Monitor (ACSM) in the fall and winter seasons of 2013 at the roadside in an Asian megacity environment in Hong Kong. Organic aerosol (OA), characterized by application of Positive Matrix Factorization (PMF), and sulfate are found dominant. Traffic-related organic aerosol shows good correlation with other vehicle-related species, and cooking aerosol displays clear meal-time concentration maxima and association with surface winds from restaurant areas. Contributions of individual species and OA factors to high NR-PM1 are analyzed for hourly data and daily data; while cooking emissions in OA contribute to high hourly concentrations, particularly during meal times, secondary organic aerosol components are responsible for episodic events and high day-to-day PM concentrations. Clean periods are either associated with precipitation, which reduces secondary OA with a~lesser impact on primary organics, or clean oceanic air masses with reduced long-range transport and better dilution of local pollution. Haze events are connected with increases in contribution of secondary organic aerosol, from 30 to 50 % among total non-refractory organics, and influence of continental air masses.

  13. Continuous measurements at the urban roadside in an Asian megacity by Aerosol Chemical Speciation Monitor (ACSM): particulate matter characteristics during fall and winter seasons in Hong Kong

    NASA Astrophysics Data System (ADS)

    Sun, C.; Lee, B. P.; Huang, D.; Jie Li, Y.; Schurman, M. I.; Louie, P. K. K.; Luk, C.; Chan, C. K.

    2016-02-01

    Non-refractory submicron aerosol is characterized using an Aerosol Chemical Speciation Monitor (ACSM) in the fall and winter seasons of 2013 on the roadside in an Asian megacity environment in Hong Kong. Organic aerosol (OA), characterized by application of Positive Matrix Factorization (PMF), and sulfate are found to be dominant. Traffic-related organic aerosol shows good correlation with other vehicle-related species, and cooking aerosol displays clear mealtime concentration maxima and association with surface winds from restaurant areas. Contributions of individual species and OA factors to high NR-PM1 are analyzed for hourly data and daily data; while cooking emissions in OA contribute to high hourly concentrations, particularly during mealtimes, secondary organic aerosol components are responsible for episodic events and high day-to-day PM concentrations. Clean periods are either associated with precipitation, which reduces secondary OA with a lesser impact on primary organics, or clean oceanic air masses with reduced long-range transport and better dilution of local pollution. Haze events are connected with increases in contribution of secondary organic aerosol, from 30 to 50 % among total non-refractory organics, and the influence of continental air masses.

  14. Instrumentation for Aerosol and Gas Speciation

    NASA Technical Reports Server (NTRS)

    Coggiola, Michael J.

    1998-01-01

    Using support from NASA Grant No. NAG 2-963, SRI International successfully completed the project, entitled, 'Instrumentation for Aerosol and Gas Speciation.' This effort (SRI Project 7383) covered the design, fabrication, testing, and deployment of a real-time aerosol speciation instrument in NASA's DC-8 aircraft during the Spring 1996 SUbsonic aircraft: Contrail and Cloud Effects Special Study (SUCCESS) mission. This final technical report describes the pertinent details of the instrument design, its abilities, its deployment during SUCCESS and the data acquired from the mission, and the post-mission calibration, data reduction, and analysis.

  15. Non-refractory PM1 in SE Asia: Chemically speciated aerosol fluxes and concentrations above contrasting land-uses in SE Asia.

    NASA Astrophysics Data System (ADS)

    Phillips, Gavin; Farmer, Delphine; di Marco, Chiara; Misztal, Pawel; Sueper, Donna; Kimmel, Joel; Jimenez, Jose; Fowler, David; Nemitz, Eiko

    2010-05-01

    New measurements of VOC emissions (measured with leaf cuvettes, and ecosystem fluxes obtained from eddy covariance measurements) suggest that oil palm (Elaeis guineensis Jacq) is a significantly larger source of isoprene than tropical forest, in Borneo. These larger sources of isoprene measured over oil palm, allied with a larger anthropogenic component of local emissions, contrasts with the composition of the atmosphere in the semi-remote tropical forest environment. The difference in the atmospheric composition above different land-uses has the potential to lead to contrasting chemistry and physics controlling the formation and processing of particulate matter. Thus land use changes, driven by the economics of biofuels, could give rise to rapidly changing chemical and aerosol regimes in the tropics. It is therefore important to understand the current emissions, chemical processing and composition of organic aerosol over both (semi-)natural and anthropogenic land uses in the tropical environment. Ecosystem flux measurements of chemically-speciated non-refractory PM1 were made over two contrasting land uses in the Malaysian state of Sabah, on the island of Borneo during 2008. A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed at the Global Atmospheric Watch (GAW) site at a tropical rain forest location as well as the Sabahmas (PPB OIL) oil palm plantation near Lahad Datu, in Eastern Sabah, as a collaboration between three UK NERC funded projects (OP3, APPRAISE/ACES and DIASPORA). Recent technical developments using ToF detectors allow us to record 10 Hz full mass spectra at both high resolution (HR) and unit-mass resolution (UMR), suitable for the calculation of local eddy-covariance fluxes. The measurements provide information on the deposition rate of anthropogenic aerosol components (e.g. sulphate, nitrate, ammonium and hydrocarbon-like aerosol) to tropical forest and oil palm. At the same time, any biogenic secondary organic

  16. Two years of near real-time chemical composition of submicron aerosols in the region of Paris using an Aerosol Chemical Speciation Monitor (ACSM) and a multi-wavelength Aethalometer

    NASA Astrophysics Data System (ADS)

    Petit, J.-E.; Favez, O.; Sciare, J.; Crenn, V.; Sarda-Estève, R.; Bonnaire, N.; Močnik, G.; Dupont, J.-C.; Haeffelin, M.; Leoz-Garziandia, E.

    2015-03-01

    Aerosol mass spectrometer (AMS) measurements have been successfully used towards a better understanding of non-refractory submicron (PM1) aerosol chemical properties based on short-term campaigns. The recently developed Aerosol Chemical Speciation Monitor (ACSM) has been designed to deliver quite similar artifact-free chemical information but for low cost, and to perform robust monitoring over long-term periods. When deployed in parallel with real-time black carbon (BC) measurements, the combined data set allows for a quasi-comprehensive description of the whole PM1 fraction in near real time. Here we present 2-year long ACSM and BC data sets, between mid-2011 and mid-2013, obtained at the French atmospheric SIRTA supersite that is representative of background PM levels of the region of Paris. This large data set shows intense and time-limited (a few hours) pollution events observed during wintertime in the region of Paris, pointing to local carbonaceous emissions (mainly combustion sources). A non-parametric wind regression analysis was performed on this 2-year data set for the major PM1 constituents (organic matter, nitrate, sulfate and source apportioned BC) and ammonia in order to better refine their geographical origins and assess local/regional/advected contributions whose information is mandatory for efficient mitigation strategies. While ammonium sulfate typically shows a clear advected pattern, ammonium nitrate partially displays a similar feature, but, less expectedly, it also exhibits a significant contribution of regional and local emissions. The contribution of regional background organic aerosols (OA) is significant in spring and summer, while a more pronounced local origin is evidenced during wintertime, whose pattern is also observed for BC originating from domestic wood burning. Using time-resolved ACSM and BC information, seasonally differentiated weekly diurnal profiles of these constituents were investigated and helped to identify the main

  17. Speciation of Fe in ambient aerosol and cloudwater

    SciTech Connect

    Siefert, L.

    1996-08-15

    Atmospheric iron (Fe) is thought to play an important role in cloudwater chemistry (e.g., S(IV) oxidation, oxidant production, etc.), and is also an important source of Fe to certain regions of the worlds oceans where Fe is believed to be a rate-limiting nutrient for primary productivity. This thesis focuses on understanding the chemistry, speciation and abundance of Fe in cloudwater and aerosol in the troposphere, through observations of Fe speciation in the cloudwater and aerosol samples collected over the continental United States and the Arabian Sea. Different chemical species of atmospheric Fe were measured in aerosol and cloudwater samples to help assess the role of Fe in cloudwater chemistry.

  18. Characterization of Speciated Aerosol Direct Radiative Forcing Over California

    SciTech Connect

    Zhao, Chun; Leung, Lai-Yung R.; Easter, Richard C.; Hand, Jenny; Avise, J.

    2013-03-16

    A fully coupled meteorology-chemistry model (WRF-Chem) with added capability of diagnosing the spatial and seasonal distribution of radiative forcings for individual aerosol species over California is used to characterize the radiative forcing of speciated aerosols in California. Model simulations for the year of 2005 are evaluated with various observations including meteorological data from California Irrigation Management Information System (CIMIS), aerosol mass concentrations from US EPA Chemical Speciation Network (CSN) and Interagency Monitoring of Protected Visual Environments (IMPROVE), and aerosol optical depth from AErosol RObotic NETwork (AERONET) and satellites. The model well captures the observed seasonal meteorological conditions over California. Overall, the simulation is able to reproduce the observed spatial and seasonal distribution of mass concentration of total PM2.5 and the relative contribution from individual aerosol species, except the model significantly underestimates the surface concentrations of organic matter (OM) and elemental carbon (EC), potentially due to uncertainty in the anthropogenic emissions of OM and EC and the outdated secondary organic aerosol mechanism used in the model. A sensitivity simulation with anthropogenic EC emission doubled significantly reduces the model low bias of EC. The simulation reveals high anthropogenic aerosol loading over the Central Valley and the Los Angeles metropolitan regions and high natural aerosol (dust) loading over southeastern California. The seasonality of aerosol surface concentration is mainly determined by vertical turbulent mixing, ventilation, and photochemical activity, with distinct characteristics for individual aerosol species and between urban and rural areas. The simulations show that anthropogenic aerosols dominate the aerosol optical depth (AOD). The ratio of AOD to AAOD (aerosol absorption optical depth) shows distinct seasonality with a winter maximum and a summer minimum

  19. Two years of near real-time chemical composition of submicron aerosols in the region of Paris using an Aerosol Chemical Speciation Monitor (ACSm) and a multi-wavelength Aethalometer

    NASA Astrophysics Data System (ADS)

    Petit, J.-E.; Favez, O.; Sciare, J.; Crenn, V.; Sarda-Estève, R.; Bonnaire, N.; Močnik, G.; Dupont, J.-C.; Haeffelin, M.; Leoz-Garziandia, E.

    2014-09-01

    Aerosol Mass Spectrometer (AMS) measurements have been successfully used towards a better understanding of non-refractory submicron (PM1) aerosol chemical properties based on short-term campaign. The recently developed Aerosol Chemical Speciation Monitor (ACSM) has been designed to deliver quite similar artefact-free chemical information but for low-cost, and to perform robust monitoring over long-term period. When deployed in parallel with real-time Black Carbon (BC) measurements, the combined dataset allows for a quasi-comprehensive description of the whole PM1 fraction in near real-time. Here we present a 2 year long ACSM and BC datasets, between mid-2011 and mid-2013, obtained at the French atmospheric SIRTA supersite being representative of background PM levels of the region of Paris. This large dataset shows intense and time limited (few hours) pollution events observed during wintertime in the region of Paris pointing to local carbonaceous emissions (mainly combustion sources). A non-parametric wind regression analysis was performed on this 2 year dataset for the major PM1 constituents (organic matter, nitrate, sulphate and source apportioned BC) and ammonia in order to better refine their geographical origins and assess local/regional/advected contributions which information are mandatory for efficient mitigation strategies. While ammonium sulphate typically shows a clear advected pattern, ammonium nitrate partially displays a similar feature, but less expected, it also exhibits a significant contribution of regional and local emissions. Contribution of regional background OA is significant in spring and summer while a more pronounced local origin is evidenced during wintertime which pattern is also observed for BC originating from domestic wood burning. Using time-resolved ACSM and BC information, seasonally differentiated weekly diurnal profiles of these constituents were investigated and helped to identify the main parameters controlling their temporal

  20. Iodine speciation in rain, snow and aerosols

    NASA Astrophysics Data System (ADS)

    Gilfedder, B. S.; Lai, S. C.; Petri, M.; Biester, H.; Hoffmann, T.

    2008-10-01

    Iodine oxides, such as iodate, should be the only thermodynamically stable sink species for iodine in the troposphere. However, field observations have increasingly found very little iodate and significant amounts of iodide and soluble organically bound iodine (SOI) in precipitation and aerosols. The aim of this study was to investigate iodine speciation, including the organic fraction, in rain, snow, and aerosols in an attempt to further clarify aqueous phase iodine chemistry. Diurnal aerosol samples were taken with a 5 stage cascade impactor and a virtual impactor (PM2.5) from the Mace Head research station, Ireland, during summer 2006. Rain was collected from Australia, New Zealand, Patagonia, Germany, Ireland, and Switzerland and snow was obtained from Greenland, Germany, Switzerland, and New Zealand. Aerosols were extracted from the filters with water and all samples were analysed for total soluble iodine (TSI) by inductively coupled plasma mass spectrometry (ICP-MS) and iodine speciation was determined by coupling an ion chromatography unit to the ICP-MS. The median concentration of TSI in aerosols from Mace Head was 222 pmol m-3 (summed over all impactor stages) of which the majority was associated with the SOI fraction (median day: 90±4%, night: 94±2% of total iodine). Iodide exhibited higher concentrations than iodate (median 6% vs. 1.2% of total iodine), and displayed significant enrichment during the day compared to the night. Interestingly, up to 5 additional, presumably anionic iodo-organic peaks were observed in all IC-ICP-MS chromatograms, composing up to 15% of the TSI. Soluble organically bound iodine was also the dominant fraction in all rain and snow samples, with lesser amounts of iodide and iodate (iodate was particularly low in snow). Two of the same unidentified peaks found in aerosols were also observed in precipitation from both Southern and Northern Hemispheres. This suggests that these species are transferred from the aerosols into

  1. Major 20th century changes of the content and chemical speciation of organic carbon archived in Alpine ice cores: Implications for the long-term change of organic aerosol over Europe

    NASA Astrophysics Data System (ADS)

    Legrand, M.; Preunkert, S.; May, B.; Guilhermet, J.; Hoffman, H.; Wagenbach, D.

    2013-05-01

    Dissolved organic carbon (DOC) and an extended array of organic compounds were investigated in an Alpine ice core covering the 1920-1988 time period. Based on this, a reconstruction was made of the long-term trends of water-soluble organic carbon (WSOC) aerosol in the European atmosphere. It is shown that light mono- and dicarboxylates, humic-like substances, and formaldehyde account together for more than half of the DOC content of ice. This extended chemical speciation of DOC is used to estimate the DOC fraction present in ice that is related to WSOC aerosol and its change over the past. It is suggested that after World War II, the WSOC levels have been enhanced by a factor of 2 and 3 in winter and summer, respectively. In summer, the fossil fuel contribution to the enhancement is estimated to be rather small, suggesting that it arises mainly from an increase in biogenic sources of WSOC.

  2. Chemical Composition of Semivolatile Compounds and Organic Aerosol in a Pine Forest: Bulk and Speciated Measurements by In-situ TAG-AMS and Offline GCxGC/HRTOFMS at BEACHON-RoMBAS 2011

    NASA Astrophysics Data System (ADS)

    Chan, A. W.; Kreisberg, N. M.; Zhao, Y.; Hohaus, T.; Campuzano Jost, P.; Teng, A.; Huang, I.; Jayne, J.; Worsnop, D. R.; Jimenez, J. L.; Hering, S. V.; Goldstein, A. H.

    2012-12-01

    Semivolatile organic compounds (SVOCs) represent an important source of organic aerosol (OA) in remote forested regions. Understanding their composition is essential to identifying their sources and processing, but the chemical complexity often limits such analysis. Here we present concurrent bulk and speciated measurements of semivolatile and particle-phase organic compounds using a novel combined instrument (TAG-AMS) at Manitou Forest, CO during the BEACHON-RoMBAS 2011 campaign. The Thermal desorption Aerosol Gas chromatograph (TAG) provides on-line organic speciation of ambient SVOCs with bihourly time resolution, while the AMS provides bulk mass spectral analysis of the concurrent OA sample. This deployment was a unique and experimental version of the TAG-AMS instrument, with a prototype filter cell designed to quantitatively collect and analyze SVOCs. The combined instrument provides quantitative measurements of organic and inorganic mass loadings, and elemental and PMF analysis of the bulk OA, simultaneously with detailed organic speciation of SVOCs. Additionally, filter samples are analyzed by comprehensive GCxGC/HR-TOF-MS to assist in compound identification by TAG. The system provided around-the-clock measurements for a 2-week period. Online and offline measurements reveal > 100 compounds, a subset of which is observed at a bihourly time resolution, and is used to identify the sources of organic aerosol in the region. Bihourly measurements of sesquiterpenes, which represent a major fraction of observed SVOCs, are used to investigate their emission sources and subsequent processing into OA. These observations are also compared to a previous study conducted at a similar pine forest in California.

  3. ACTRIS ACSM intercomparison - Part 1: Reproducibility of concentration and fragment results from 13 individual Quadrupole Aerosol Chemical Speciation Monitors (Q-ACSM) and consistency with co-located instruments

    NASA Astrophysics Data System (ADS)

    Crenn, V.; Sciare, J.; Croteau, P. L.; Verlhac, S.; Fröhlich, R.; Belis, C. A.; Aas, W.; Äijälä, M.; Alastuey, A.; Artiñano, B.; Baisnée, D.; Bonnaire, N.; Bressi, M.; Canagaratna, M.; Canonaco, F.; Carbone, C.; Cavalli, F.; Coz, E.; Cubison, M. J.; Esser-Gietl, J. K.; Green, D. C.; Gros, V.; Heikkinen, L.; Herrmann, H.; Lunder, C.; Minguillón, M. C.; Močnik, G.; O'Dowd, C. D.; Ovadnevaite, J.; Petit, J.-E.; Petralia, E.; Poulain, L.; Priestman, M.; Riffault, V.; Ripoll, A.; Sarda-Estève, R.; Slowik, J. G.; Setyan, A.; Wiedensohler, A.; Baltensperger, U.; Prévôt, A. S. H.; Jayne, J. T.; Favez, O.

    2015-12-01

    As part of the European ACTRIS project, the first large Quadrupole Aerosol Chemical Speciation Monitor (Q-ACSM) intercomparison study was conducted in the region of Paris for 3 weeks during the late-fall - early-winter period (November-December 2013). The first week was dedicated to the tuning and calibration of each instrument, whereas the second and third were dedicated to side-by-side comparison in ambient conditions with co-located instruments providing independent information on submicron aerosol optical, physical, and chemical properties. Near real-time measurements of the major chemical species (organic matter, sulfate, nitrate, ammonium, and chloride) in the non-refractory submicron aerosols (NR-PM1) were obtained here from 13 Q-ACSM. The results show that these instruments can produce highly comparable and robust measurements of the NR-PM1 total mass and its major components. Taking the median of the 13 Q-ACSM as a reference for this study, strong correlations (r2 > 0.9) were observed systematically for each individual Q-ACSM across all chemical families except for chloride for which three Q-ACSMs showing weak correlations partly due to the very low concentrations during the study. Reproducibility expanded uncertainties of Q-ACSM concentration measurements were determined using appropriate methodologies defined by the International Standard Organization (ISO 17025, 1999) and were found to be 9, 15, 19, 28, and 36 % for NR-PM1, nitrate, organic matter, sulfate, and ammonium, respectively. However, discrepancies were observed in the relative concentrations of the constituent mass fragments for each chemical component. In particular, significant differences were observed for the organic fragment at mass-to-charge ratio 44, which is a key parameter describing the oxidation state of organic aerosol. Following this first major intercomparison exercise of a large number of Q-ACSMs, detailed intercomparison results are presented, along with a discussion of some

  4. ACTRIS ACSM intercomparison - Part I: Reproducibility of concentration and fragment results from 13 individual Quadrupole Aerosol Chemical Speciation Monitors (Q-ACSM) and consistency with Time-of-Flight ACSM (ToF-ACSM), High Resolution ToF Aerosol Mass Spectrometer (HR-ToF-AMS) and other co-located instruments

    NASA Astrophysics Data System (ADS)

    Crenn, V.; Sciare, J.; Croteau, P. L.; Verlhac, S.; Fröhlich, R.; Belis, C. A.; Aas, W.; Äijälä, M.; Alastuey, A.; Artiñano, B.; Baisnée, D.; Bonnaire, N.; Bressi, M.; Canagaratna, M.; Canonaco, F.; Carbone, C.; Cavalli, F.; Coz, E.; Cubison, M. J.; Esser-Gietl, J. K.; Green, D. C.; Gros, V.; Heikkinen, L.; Herrmann, H.; Lunder, C.; Minguillón, M. C.; Močnik, G.; O'Dowd, C. D.; Ovadnevaite, J.; Petit, J.-E.; Petralia, E.; Poulain, L.; Priestman, M.; Riffault, V.; Ripoll, A.; Sarda-Estève, R.; Slowik, J. G.; Setyan, A.; Wiedensohler, A.; Baltensperger, U.; Prévôt, A. S. H.; Jayne, J. T.; Favez, O.

    2015-07-01

    As part of the European ACTRIS project, the first large Quadrupole Aerosol Chemical Speciation Monitor (Q-ACSM) intercomparison study was conducted in the region of Paris for three weeks during the late fall-early winter period (November-December 2013). The first week was dedicated to tuning and calibration of each instrument whereas the second and third were dedicated to side-by-side comparison in ambient conditions with co-located instruments providing independent information on submicron aerosol optical, physical and chemical properties. Near real-time measurements of the major chemical species (organic matter, sulfate, nitrate, ammonium and chloride) in the non-refractory submicron aerosols (NR-PM1) were obtained here from 13 Q-ACSM. The results show that these instruments can produce highly comparable and robust measurements of the NR-PM1 total mass and its major components. Taking the median of the 13 Q-ACSM as a reference for this study, strong correlations (r2 > 0.9) were observed systematically for each individual ACSM across all chemical families except for chloride for which three ACSMs showing weak correlations partly due to the very low concentrations during the study. Reproducibility expanded uncertainties of Q-ACSM concentration measurements were determined using appropriate methodologies defined by the International Standard Organization (ISO 17025) and were found to be of 9, 15, 19, 28 and 36 % for NR-PM1, nitrate, organic matter, sulfate and ammonium respectively. However, discrepancies were observed in the relative concentrations of the constituent mass fragments for each chemical component. In particular, significant differences were observed for the organic fragment at mass-to-charge ratio 44, which is a key parameter describing the oxidation state of organic aerosol. Following this first major intercomparison exercise of a large number of ACSMs, detailed intercomparison results are presented as well as a discussion of some recommendations

  5. Speciation of arsenic in ambient aerosols collected in Los Angeles.

    PubMed

    Rabano, E S; Castillo, N T; Torre, K J; Solomon, P A

    1989-01-01

    First-time measurements of the potentially toxic inorganic species of arsenic (arsenite and arsenate) have been obtained in fine (less than 2.5 microns AD) and coarse (greater than 2.5 microns AD) atmospheric particles in the Los Angeles area. A recently developed method that includes procedures for sample collection, preparation, and analysis was used in this study. Size-fractionated aerosol samples were collected with a high-volume dichotomous virtual impactor that employed polytetrafluoroethylene filters. Results were obtained for the recovery of arsenic standards added to unexposed and collected filters. Data from this study, indicated that the recently developed speciation method can be used to determine concentrations of As(III) and As(V) in atmospheric particulate matter samples. Size-fractionated aerosol samples were collected in the city of Industry during January and February 1987. In most samples, As(III) and As(V) were above the detection limit (approximately 1 ng m-3 of either species) in both aerosol size fractions. A greater portion (about 75 percent) of the two species were observed in the fine particles. The As(III)/As(V) ratio for both particle sizes was close to 1 (i.e., an equal mixture of both species). Comparison of total suspended particulate arsenic measured by the speciation method to that measured by a routine California Air Resources Board-approved procedure showed good agreement (r = 0.94), indicating both methods were approximately equivalent for the collection and analysis of aerosol arsenic. PMID:2709077

  6. Speciation of Organic Aerosols in the Tropical Mid-Pacific and Their Relationship to Light Scattering.

    NASA Astrophysics Data System (ADS)

    Crahan, Kathleen K.; Hegg, Dean A.; Covert, David S.; Jonsson, Haflidi; Reid, Jeffrey S.; Khelif, Djamal; Brooks, Barbara J.

    2004-11-01

    Although the importance of the aerosol contribution to the global radiative budget has been recognized, the forcings of aerosols in general, and specifically the role of the organic component in these forcings, still contain large uncertainties. In an attempt to better understand the relationship between the background forcings of aerosols and their chemical speciation, marine air samples were collected off the windward coast of Oahu, Hawaii, during the Rough Evaporation Duct project (RED) using filters mounted on both the Twin Otter aircraft and the Floating Instrument Platform (FLIP) research platform. Laboratory analysis revealed a total of 17 species, including 4 carboxylic acids and 2 carbohydrates that accounted for 74% ± 20% of the mass gain observed on the shipboard filters, suggesting a possible significant unresolved organic component. The results were correlated with in situ measurements of particle light scattering (σsp) at 550 nm and with aerosol hygroscopicities. Principal component analysis revealed a small but ubiquitous pollution component affecting the σsp and aerosol hygroscopicity of the remote marine air. The Princeton Organic-Electrolyte Model (POEM) was used to predict the growth factor of the aerosols based upon the chemical composition. This output, coupled with measured aerosol size distributions, was used to attempt to reproduce the observed σsp. It was found that while the POEM model was able to reproduce the expected trends when the organic component of the aerosol was varied, due to large uncertainties especially in the aerosol sizing measurements, the σsp predicted by the POEM model was consistently higher than observed.


  7. Chemical speciation of radionuclides migrating in groundwaters

    SciTech Connect

    Robertson, D.; Schilk, A.; Abel, K.; Lepel, E.; Thomas, C.; Pratt, S.; Cooper, E.; Hartwig, P.; Killey, R.

    1994-04-01

    In order to more accurately predict the rates and mechanisms of radionuclide migration from low-level waste disposal facilities via groundwater transport, ongoing studies are being conducted at field sites at Chalk River Laboratories to identify and characterize the chemical speciation of mobile, long-lived radionuclides migrating in groundwaters. Large-volume water sampling techniques are being utilized to separate and concentrate radionuclides into particular, cationic, anionic, and nonionic chemical forms. Most radionuclides are migrating as soluble, anionic species that appear to be predominantly organoradionuclide complexes. Laboratory studies utilizing anion exchange chromatography have separated several anionically complexed radionuclides, e.g., {sup 60}Co and {sup 106}Ru, into a number of specific compounds or groups of compounds. Further identification of the anionic organoradionuclide complexes is planned utilizing high resolution mass spectrometry. Large-volume ultra-filtration experiments are characterizing the particulate forms of radionuclides being transported in these groundwaters.

  8. Electrostatic sampler for semivolatile aerosols: chemical artifacts.

    PubMed

    Volckens, John; Leith, David

    2002-11-01

    Electrostatic precipitators (ESPs) show promise as an alternative sampling method for semivolatile aerosols because they are less susceptible to adsorptive and evaporative artifacts than filter based methods. However, the corona discharge may after the chemical composition of a sampled aerosol. Chemical artifacts associated with electrostatic precipitation of semivolatile aerosols were investigated in the laboratory. ESPs and filters sampled both particles and vapors of alkanes, polycyclic aromatic hydrocarbons, and alkenes across varying concentrations. Gravimetric measurements between the two sampling methods were well correlated. Ozone generated by the ESP corona was the primary cause of alkene reactions in the gas phase. Particles collected within the corona region were vulnerable to irradiation by corona ions overtime. Particles collected outside the corona region did not react. Vapors passing through the corona reacted to a lesser extent. Vapors captured after passing through the ESP reacted with ozone that was not removed by the vapor trap. Chemical speciation of highly reactive compounds (i.e., alkenes or other compounds with relatively short half-lives outdoors) is not appropriate with ESPs. Electrostatic precipitation of these compounds is appropriate, however, when total organic carbon is of interest as the ESP does not alter the amount of mass measured gravimetrically. ESPs can make accurate measurements of more persistent semivolatile compounds, such as alkanes and PAHs. PMID:12433171

  9. Chemical Properties of Combustion Aerosols: An Overview

    EPA Science Inventory

    A wide variety of pyrogenic and anthropogenic sources emit fine aerosols to the atmosphere. The physical and chemical properties of these aerosols are of interest due to their influence on climate, human health, and visibility. Aerosol chemical composition is remarkably complex. ...

  10. Investigating Chemical and Thermodynamic Conditions that Determine the Aerosol Inorganic Nitrate Size Distribution: Insights from Speciated PM2.5 and PM10 Hourly Datasets from an Urban Site

    NASA Astrophysics Data System (ADS)

    Griffith, S. M.; Huang, X. H. H.; Louie, P. K. K.; Yu, J. Z.

    2015-12-01

    Nitric acid (HNO3), the gas-phase precursor to aerosol nitrate is known to rapidly transfer to aerosols where NH4+ is in excess to SO42- present in the aerosol, but the HNO3 is also subject to the slower uptake onto sea salt and dust laden particles. Understanding the competition between these routes is necessary to predict the NO3- distribution and impact on aerosols. In this study, we investigated the conditions leading to predominant fine or coarse mode aerosol nitrate using an hourly MARGA 2S dataset from an urban site in Hong Kong. The hourly dataset of inorganic ions (SO42-, NH4+, NO3-, Na+, Cl-, Ca2+, K+, Mg2+) in 2 size ranges (fine, < 2.5 μm; fine+coarse, < 10 μm) and water-soluble gases (HNO3, HCl, and NH3) spanning more than 1 year provides a rich trove for analyzing aerosol nitrate chemistry and the underlying mechanisms that ultimately determine the fraction of NO3- in the fine mode. The urban site in this study is initially characterized for seasonal environmental conditions and the aerosol chemical composition. The relationship between excess NH4+ and NO3- in the fine mode is detailed and contrasted with the influence on fine mode NO3- from uptake on sea salt and dust, which is typically relegated as a 'coarse-mode' mechanism. The distribution of NO3- in the fine and coarse modes is compared with the distribution of the other inorganic ions, where sea-salt ion (Na+, Mg2+) distributions yield the highest explained variability for the nitrate distributions. As a complement to that finding, the cation equivalency (excluding NH4+) in the coarse mode proves to be a crucial factor in leveraging the distribution away from fine mode nitrate. The uptake potential of the water-soluble gases is used to drive a mass transfer model and compare with thermodynamic equilibrium results. In the modeling, the partitioning cycles of fine and coarse mode aerosol nitrate highlight the dynamic relationship between NO3- and Cl- in both the fine and coarse modes, where the

  11. VARIATION OF ELEMENT SPECIATION IN COAL COMBUSTION AEROSOLS WITH PARTICLE SIZE

    EPA Science Inventory

    The speciation of sulfur, iron and key trace elements (Cr, As, Se, Zn) in combustion ash aerosols has been examined as a function of size from experimental combustion units burning Utah and Illinois bituminous coals. Although predominantly present as sulfate, sulfur was also pre...

  12. Speciation of radiocesium and radioiodine in aerosols from Tsukuba after the Fukushima nuclear accident.

    PubMed

    Xu, Sheng; Zhang, Luyuan; Freeman, Stewart P H T; Hou, Xiaolin; Shibata, Yasuyuki; Sanderson, David; Cresswell, Alan; Doi, Taeko; Tanaka, Atsushi

    2015-01-20

    Aerosol samples were collected from Tsukuba, Japan, soon after the 2011 Fukushima nuclear accident and analyzed for speciation of radiocesium and radioiodine to explore their chemical behavior and isotopic ratios after the release. Most (134)Cs and (137)Cs were bound in organic matter (53–91%) and some in water-soluble fractions (5–15%), whereas a negligible proportion of radiocesium remained in minerals. This pattern suggests that sulfate salts and organic matter may be the main carrier of Cs-bearing particles. The (129)I in aerosol samples is contained in various proportions as soluble inorganic iodine (I(–) and IO3(–)), soluble organic iodine, and unextractable iodine. The measured mean (129)I/(131)I atomic ratio of 16.0 ± 2.2 is in good agreement with that measured from rainwater and consistent with ratios measured in surface soil samples. Together with other aerosols and seawater samples, an initial (129)I/(137)Cs activity ratio of ∼4 × 10(–7) was obtained. In contrast to the effectively constant (134)Cs/(137)Cs activity ratios (1.04 ± 0.04) and (129)I/(131)I atomic ratios (16.0 ± 2.2), the (129)I/(137)Cs activity ratios scattered from 3.5 × 10(–7) to 5 × 10(–6) and showed temporally and spatially different dispersion and deposition patterns between radiocesium and radioiodine. These findings confirm that (129)I, instead of (137)Cs, should be considered as a proxy for (131)I reconstruction. PMID:25522224

  13. Chemical PM2.5 Speciation in Major Cities Worldwide

    NASA Astrophysics Data System (ADS)

    Snider, Graydon; Weagle, Crystal; Brauer, Michael; Cohen, Aaron; Gibson, Mark; Liu, Yang; Martins, Vanderlei; Rudich, Yinon; Martin, Randall

    2016-04-01

    We examined the chemical composition of fine particulate matter (PM2.5) across 13 globally dispersed urban locations (including Atlanta, Buenos Aires, Beijing, Manila, and Dhaka), as part of the Surface PARTiculate mAtter Network (SPARTAN). At each site sampling was conducted over 4 to 24 months for the years 2013 to 2015. Analysis of filter samples revealed that several PM2.5 chemical components varied by more than an order of magnitude between sites. Ammonium sulfate ranged from 2 μg m‑3 (Ilorin) to 17 μg m‑3 (Kanpur). Ammonium nitrate ranged from 0.2 μg m‑3 (Atlanta) to 6.7 μg m‑3 (Kanpur). Effective black carbon ranged from 0.4 μg m‑3 (Atlanta) to 5 μg m‑3 (Dhaka and Kanpur). The all-site mean values of major PM2.5 constituents were ammonium sulfate (20 ± 10 %), crustal material (12 ± 6.5%), effective black carbon (10 ± 7.4 %), ammonium nitrate (3.7 ± 2.5%), sea salt (2.2 ± 1.5%), trace element oxides (0.9 ± 0.7 %), water (7.2 ± 3.0%) and residue materials (44 ± 24%). Based on the evaluation with collocated studies we treated residue material as mostly organic. Major ions generally agreed well with previous studies at the same urban locations (e.g. sulfate fractions agreed within 4% for eight out of 11 collocation comparisons). Enhanced crustal material (CM) concentrations with high Zn:Al ratios at large cities (e.g. Hanoi, Dhaka, Manila) imply significant anthropogenic CM contributions that deserve more attention. Detailed chemical speciation also aided our characterization of site-specific PM2.5 water retention. The expected water contribution to aerosols was calculated via the hygroscopicity parameter for each filter. Hourly PM2.5 at specified relative humidity (35%) was inferred from nephelometer measurements of light scatter at ambient relative humidity and 9-day filter measurements of PM2.5 mass. Our PM2.5 estimates compared favorably with a beta attenuation monitor (BAM) at the nearby US embassy in Beijing, with a coefficient of

  14. Speciated organic composition of atmospheric aerosols: Development and application of a Thermal desorption Aerosol Gas chromatograph (TAG)

    NASA Astrophysics Data System (ADS)

    Williams, Brent James

    This dissertation describes the invention and first applications of an in-situ instrument, Ṯhermal desorption A&barbelow;erosol G&barbelow;as chromatograph (TAG), capable of automated hourly measurements of speciated organic compounds in atmospheric aerosols. Atmospheric particles alter the Earth's radiation balance and hydrological cycle and are detrimental to human health. There are hundreds to thousands of different compounds present in the carbonaceous component of atmospheric particles. These organic marker compounds offer information on atmospheric aerosol sources, formation processes, and transformation processes. TAG is the first instrument to achieve automated in-situ hourly measurements, improving upon traditional 12--24 hour filter-based methods and making it possible to analyze changes in organic aerosol speciation over timescales ranging from hours to seasons. Reported here are results from TAG development and laboratory-based testing, as well as new findings from two separate field campaigns. The first field study took place in Nova Scotia as part of the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT). Hourly TAG measurements were used to define several aerosol sources, including aged anthropogenics from the US, oxidized biogenic aerosol from Maine/Canada, local oxidized biogenics, local anthropogenic contributions to primary organic aerosol (POA), and a potential marine or dairy source. The second field deployment was in southern California during the Study of Organic Aerosol at Riverside (SOAR). Particle sources included several types of oxidized secondary organic aerosol (SOA), vehicle emissions, food cooking, biomass burning, and primary and secondary biogenics. SOA-associated aerosol dominated POA-associated aerosol in both locations, with SOA comprising an approximate 90% (60%) of the total organic aerosol mass in Nova Scotia (Riverside, CA), and in Riverside, summertime afternoon SOA

  15. Chemical Speciation of Chromium in Drilling Muds

    SciTech Connect

    Taguchi, Takeyoshi; Yoshii, Mitsuru; Shinoda, Kohzo

    2007-02-02

    Drilling muds are made of bentonite and other clays, and/or polymers, mixed with water to the desired viscosity. Without the drilling muds, corporations could not drill for oil and gas and we would have hardly any of the fuels and lubricants considered essential for modern industrial civilization. There are hundreds of drilling muds used and some kinds of drilling muds contain chromium. The chemical states of chromium in muds have been studied carefully due to concerns about the environmental influence. However it is difficult to determine the chemical state of chromium in drilling muds directly by conventional analytical methods. We have studied the chemical form of chromium in drilling muds by using a laboratory XAFS system and a synchrotron facility.

  16. Iron Speciation and Mixing in Single Aerosol Particles from the Asian Continental Outflow

    SciTech Connect

    Moffet, Ryan C.; Furutani, Hiroshi; Rodel, Tobias; Henn, Tobias R.; Sprau, Peter; Laskin, Alexander; Uematsu, Mitsuo; Gilles, Marry K.

    2012-04-04

    Bioavailable iron from atmospheric aerosol is an essential nutrient that can control oceanic productivity, thereby impacting the global carbon budget and climate. Particles collected on Okinawa Island during an atmospheric pollution transport event from China were analyzed using complementary single particle techniques to determine the iron source and speciation. Comparing the spatial distribution of iron within ambient particles and standard Asian mineral dust, it was determined that field-collected atmospheric Fe-containing particles have numerous sources, including anthropogenic sources such as coal combustion. Fe-containing particles were found to be internally mixed with secondary species such as sulfate, soot, and organic carbon. The mass weighted average Fe(II) fraction (defined as Fe(II)/[Fe(II)+Fe(III)]) was determined to be 0.33 {+-} 0.08. Within the experimental uncertainty, this value lies close to the range of 0.26-0.30 determined for representative Asian mineral dust. Previous studies have indicated that the solubility of iron from combustion is much higher than that from mineral dust. Therefore, chemical and/or physical differences other than oxidation state may help explain the higher solubility of iron in atmospheric particles.

  17. Elucidating the Chemical Complexity of Organic Aerosol Constituents Measured During the Southeastern Oxidant and Aerosol Study (SOAS)

    NASA Astrophysics Data System (ADS)

    Yee, L.; Isaacman, G. A.; Spielman, S. R.; Worton, D. R.; Zhang, H.; Kreisberg, N. M.; Wilson, K. R.; Hering, S. V.; Goldstein, A. H.

    2013-12-01

    Thousands of volatile organic compounds are uniquely created in the atmosphere, many of which undergo chemical transformations that result in more highly-oxidized and often lower vapor pressure species. These species can contribute to secondary organic aerosol, a complex mixture of organic compounds that is still not chemically well-resolved. Organic aerosol collected on filters taken during the Southeastern Oxidant and Aerosol Study (SOAS) constitute hundreds of unique chemical compounds. Some of these include known anthropogenic and biogenic tracers characterized using standardized analytical techniques (e.g. GC-MS, UPLC, LC-MS), but the majority of the chemical diversity has yet to be explored. By employing analytical techniques involving sample derivatization and comprehensive two-dimensional gas chromatography (GC x GC) with high-resolution-time-of-flight mass spectrometry (HR-ToF-MS), we elucidate the chemical complexity of the organic aerosol matrix along the volatility and polarity grids. Further, by utilizing both electron impact (EI) and novel soft vacuum ultraviolet (VUV) ionization mass spectrometry, a greater fraction of the organic mass is fully speciated. The GC x GC-HR-ToF-MS with EI/VUV technique efficiently provides an unprecedented level of speciation for complex ambient samples. We present an extensive chemical characterization and quantification of organic species that goes beyond typical atmospheric tracers in the SOAS samples. We further demonstrate that complex organic mixtures can be chemically deconvoluted by elucidation of chemical formulae, volatility, functionality, and polarity. These parameters provide insight into the sources (anthropogenic vs. biogenic), chemical processes (oxidation pathways), and environmental factors (temperature, humidity), controlling organic aerosol growth in the Southeastern United States.

  18. Organosulfates and organic acids in Arctic aerosols: speciation, annual variation and concentration levels

    NASA Astrophysics Data System (ADS)

    Hansen, A. M. K.; Kristensen, K.; Nguyen, Q. T.; Zare, A.; Cozzi, F.; Nøjgaard, J. K.; Skov, H.; Brandt, J.; Christensen, J. H.; Ström, J.; Tunved, P.; Krejci, R.; Glasius, M.

    2014-02-01

    Sources, composition and occurrence of secondary organic aerosols (SOA) in the Arctic were investigated at Zeppelin Mountain, Svalbard, and Station Nord, northeast Greenland, during the full annual cycle of 2008 and 2010 respectively. We focused on the speciation of three types of SOA tracers: organic acids, organosulfates and nitrooxy organosulfates from both anthropogenic and biogenic precursors, here presenting organosulfate concentrations and compositions during a full annual cycle and chemical speciation of organosulfates in Arctic aerosols for the first time. Aerosol samples were analysed using High Performance Liquid Chromatography coupled to a quadrupole Time-of-Flight mass spectrometer (HPLC-q-TOF-MS). A total of 11 organic acids (terpenylic acid, benzoic acid, phthalic acid, pinic acid, suberic acid, azelaic acid, adipic acid, pimelic acid, pinonic acid, diaterpenylic acid acetate (DTAA) and 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA)), 12 organosulfates and one nitrooxy organosulfate were identified at the two sites. Six out of the 12 organosulfates are reported for the first time. Concentrations of organosulfates follow a distinct annual pattern at Station Nord, where high concentration were observed in late winter and early spring, with a mean total concentration of 47 (±14) ng m-3, accounting for 7 (±2)% of total organic matter, contrary to a considerably lower organosulfate mean concentration of 2 (±3) ng m-3 (accounting for 1 (±1)% of total organic matter) observed during the rest of the year. The organic acids followed the same temporal trend as the organosulfates at Station Nord; however the variations in organic acid concentrations were less pronounced, with a total mean organic acid concentration of 11.5 (±4) ng m-3 (accounting for 1.7 (±0.6)% of total organic matter) in late winter and early spring, and 2.2 (±1) ng m-3 (accounting for 0.9 (±0.4)% of total organic matter) during the rest of the year. At Zeppelin Mountain

  19. CHEMICAL ANALYSIS METHODS FOR ATMOSPHERIC AEROSOL COMPONENTS

    EPA Science Inventory

    This chapter surveys the analytical techniques used to determine the concentrations of aerosol mass and its chemical components. The techniques surveyed include mass, major ions (sulfate, nitrate, ammonium), organic carbon, elemental carbon, and trace elements. As reported in...

  20. Atmospheric aerosols as prebiotic chemical reactors

    PubMed Central

    Dobson, Christopher M.; Ellison, G. Barney; Tuck, Adrian F.; Vaida, Veronica

    2000-01-01

    Aerosol particles in the atmosphere have recently been found to contain a large number of chemical elements and a high content of organic material. The latter property is explicable by an inverted micelle model. The aerosol sizes with significant atmospheric lifetimes are the same as those of single-celled organisms, and they are predicted by the interplay of aerodynamic drag, surface tension, and gravity. We propose that large populations of such aerosols could have afforded an environment, by means of their ability to concentrate molecules in a wide variety of physical conditions, for key chemical transformations in the prebiotic world. We also suggest that aerosols could have been precursors to life, since it is generally agreed that the common ancestor of terrestrial life was a single-celled organism. The early steps in some of these initial transformations should be accessible to experimental investigation. PMID:11035775

  1. Physical and Chemical Properties of Anthropogenic Aerosols: An Overview

    EPA Science Inventory

    Aerosol chemical composition is complex. Combustion aerosols can comprise tens of thousands of organic compounds, refractory brown and black carbon, heavy metals, cations, anions, salts, and other inorganic phases. Aerosol organic matter normally contains semivolatile material th...

  2. Study of Aerosol Chemical Composition Based on Aerosol Optical Properties

    NASA Astrophysics Data System (ADS)

    Berry, Austin; Aryal, Rudra

    2015-03-01

    We investigated the variation of aerosol absorption optical properties obtained from the CIMEL Sun-Photometer measurements over three years (2012-2014) at three AERONET sites GSFC; MD Science_Center and Tudor Hill, Bermuda. These sites were chosen based on the availability of data and locations that can receive different types of aerosols from land and ocean. These absorption properties, mainly the aerosol absorption angstrom exponent, were analyzed to examine the corresponding aerosol chemical composition. We observed that the retrieved absorption angstrom exponents over the two sites, GSFC and MD Science Center, are near 1 (the theoretical value for black carbon) and with low single scattering albedo values during summer seasons indicating presence of black carbon. Strong variability of aerosol absorption properties were observed over Tudor Hill and will be analyzed based on the air mass embedded from ocean side and land side. We will also present the seasonal variability of these properties based on long-range air mass sources at these three sites. Brent Holben, NASA GSFC, AERONET, Jon Rodriguez.

  3. GEOCHEM-EZ: a chemical speciation program with greater power and flexibility

    Technology Transfer Automated Retrieval System (TEKTRAN)

    GEOCHEM –EZ is a multi-functional chemical speciation program, which was designed to replace the existing GEOCHEM-PC, a program that can only be used on DOS consoles. Chemical speciation programs, such as GEOCHEM (Sposito and Mattigod, 1980) and GEOCHEM-PC (Parker et al., 1995), have been excellent ...

  4. Physical and Chemical Properties of Anthropogenic Aerosols: An overview

    EPA Science Inventory

    A wide variety of anthropogenic sources emit fine aerosols to the atmosphere. The physical and chemical properties of these aerosols are of interest due to their influence on climate, human health, and visibility. Aerosol chemical composition is complex. Combustion aerosols can c...

  5. Chemical aerosol flow synthesis of semiconductor nanoparticles.

    PubMed

    Didenko, Yuri T; Suslick, Kenneth S

    2005-09-01

    Nanometer-sized semiconductor particles (quantum dots) have been the subject of intense research during the past decade owing to their novel electronic, catalytic, and optical properties. Fundamental properties of these nanoparticles (1-20 nm diameter) can be systematically changed simply by controlling the size of the crystals while holding their chemical composition constant. We describe here a new methodology for the continuous production of fluorescent CdS, CdSe, and CdTe nanoparticles using ultrasonically generated aerosols of high boiling point solvents. Each submicron droplet serves as a separate nanoscale chemical reactor, with reactions proceeding as the liquid droplets (which hold both reactants and surface stabilizers) are heated in a gas stream. The method is inexpensive, scalable, and allows for the synthesis of high quality nanocrystals. This chemical aerosol flow synthesis (CAFS) can be extended to the synthesis of nanostructured metals, oxides, and other materials. PMID:16131177

  6. A STUDY OF GAS-PHASE MERCURY SPECIATION USING DETAILED CHEMICAL KINETICS

    EPA Science Inventory

    Mercury (Hg) speciation in combustion-generated flue gas is modeled using a detailed chemical mechanism consisting of 60 reactions and 21 species. This speciation model accounts for chlorination and oxidation of key flue-gas components, including elemental mercury. Results indica...

  7. Aerosol simulation including chemical and nuclear reactions

    SciTech Connect

    Marwil, E.S.; Lemmon, E.C.

    1985-01-01

    The numerical simulation of aerosol transport, including the effects of chemical and nuclear reactions presents a challenging dynamic accounting problem. Particles of different sizes agglomerate and settle out due to various mechanisms, such as diffusion, diffusiophoresis, thermophoresis, gravitational settling, turbulent acceleration, and centrifugal acceleration. Particles also change size, due to the condensation and evaporation of materials on the particle. Heterogeneous chemical reactions occur at the interface between a particle and the suspending medium, or a surface and the gas in the aerosol. Homogeneous chemical reactions occur within the aersol suspending medium, within a particle, and on a surface. These reactions may include a phase change. Nuclear reactions occur in all locations. These spontaneous transmutations from one element form to another occur at greatly varying rates and may result in phase or chemical changes which complicate the accounting process. This paper presents an approach for inclusion of these effects on the transport of aerosols. The accounting system is very complex and results in a large set of stiff ordinary differential equations (ODEs). The techniques for numerical solution of these ODEs require special attention to achieve their solution in an efficient and affordable manner. 4 refs.

  8. Survey of chemical speciation of trace elements using synchrotron radiation

    SciTech Connect

    Gordon, B.M.

    1985-01-01

    Information concerning the chemical state of trace elements in biological systems generally has not been available. Such information for toxic elements and metals in metalloproteins could prove extremely valuable in the elucidation of their metabolism and other biological processes. The shielding of core electrons by binding electrons affect the energy required for creating inner-shell holes. Furthermore, the molecular binding and the symmetry of the local environment of an atom affect the absorption spectrum in the neighborhood of the absorption edge. X-ray absorption near-edge structure (XANES) using synchrotron radiation excitation can be used to provide chemical speciation information for trace elements at concentrations as low as 10 ppM. The structure and position of the absorption curve in the region of an edge can yield vital data about the local structure and oxidation state of the trace element in question. Data are most easily interpreted by comparing the observed edge structure and position with those of model compounds of the element covering the entire range of possible oxidation states. Examples of such analyses are reviewed. 14 refs., 1 fig.

  9. Speciated local aerosol characteristics and radiative forcing at a rural midwestern site

    NASA Astrophysics Data System (ADS)

    Dillner, Ann Marie

    2000-11-01

    In this research, physical and chemical properties of ambient aerosols were measured at a rural perturbed mid- latitude site (Bondville, IL) and used to calculate the aerosol optical properties and the resulting direct radiative forcing. Size-segregated aerosol samples were collected during the summer of 1997 using three parallel MOUDIs operating at ambient relative humidity. Two sample sets were used to obtain sulfate, organic carbon (OC), elemental carbon (EC), carbonate and total aerosol mass. The third sample set was used to obtain the size-specific and wavelength-dependent extinction efficiency of EC. The measured submicrometer mass concentration was 11.4 +/- 4.0 μg m-3. Ammonium sulfate comprised nearly half of the submicrometer aerosol and OC plus EC comprised 25%. Water content for ammonium sulfate and OC was estimated using both Köhler theory and parameterized water uptake curves from the literature. Water content for internally mixed aerosols was determined using a ZSR method. Aerosol optical properties (extinction efficiency, asymmetry parameter, single scatter albedo) were calculated from measured size distributions and wavelength dependent refractive indexes for each species and for internal and external mixtures using Mie theory. A technique, utilizing transmission measurements through extracts of size segregated ambient aerosol samples, was developed to obtain the extinction efficiency of EC. Measured EC extinction efficiencies ranged from 7.3 to 1.7 m2 g-1 at 550 nm, depending on particle diameter. Normalized direct aerosol radiative forcing (W g-1 ) was calculated using the Column Radiation Module (CRM) of the National Center for Atmospheric Research (NCAR) Community Climate Model (CCM3). Aerosol optical properties, used in the model, were assumed to be uniform throughout the lowest one kilometer of the atmosphere. The normalized forcing due to ammonium sulfate was -340 +/- 10 W g-1. OC was 1/3 larger and residue was 1/3 smaller. EC within an

  10. Investigation of aerosol formation and sulfur speciation in subsonic jet aircraft engines

    NASA Astrophysics Data System (ADS)

    Durlak, Susan Kaye

    1997-12-01

    Combustion-related atmospheric pollutants, both gaseous and particulate, can contribute to short-term health risks, as well as long-term climate change. While aircraft engine emissions may present short-term health risks near airports, aircraft are uniquely able to impact long-term climate change due to their insertion of anthropogenic pollutants in the upper troposphere and lower stratosphere. Aircraft emissions can impact the climate either directly, via emissions of light- scattering particulates, or indirectly, via emission of cloud condensation nuclei (CCN) particulates which influence cloud formation, or through heterogeneous reactions in the atmosphere. Carbonaceous aerosol emissions from aircraft engines can directly impact the climate, whereas speciation of sulfur emissions from aircraft engines can indirectly impact the climate by forming submicron, sulfuric acid particles which then form CCN. The number, size and composition of carbonaceous aerosol, and speciation of sulfur in the exhaust, are the main parameters influencing these emissions' fate in the environment and impact on the climate. However, little is understood about the formation of these pollutants within aircraft engines, due in part to the complexity and cost involved in testing these highly engineered machines. This study examines the feasibility of using a miniature working jet aircraft engine (Sophia J450 Model Jet Engine) to perform lab-scale, controlled tests to explore the formation of aircraft engine emissions. The miniature engine was run at a variety of power levels, and emissions were sampled at the exhaust. Two types of jet fuel (JP-5 and Jet A) and one other fuel (White Gas, or Coleman Fuel) were combusted in the engine. Engine performance is characterized and exhaust carbonaceous aerosol size distribution measurements are compared to full-scale turbojet engines. Measurements were made of sulfur speciation in the exhaust of the miniature jet engine burning Jet A and JP-5 with

  11. Speciation and chemical activities in superheated sodium borate solutions

    SciTech Connect

    Weres, O. )

    1993-06-01

    The system H[sub 2]O-B[sub 2]O[sub 3]-Na[sub 2]O has been studied experimentally at 277[degrees] and 317[degrees]C. The activities of water and boric acid have been determined at mole ratios Na/B from 0 to 1.5, and total dissolved solids 3 to 80 weight percent. The activity of boric acid has been fitted to within experimental error using a speciation model with eight complex species. This model is consistent with the model previously published by Mesmer et al. The electrolyte properties of the liquid are modelled using the Pitzer-Simonson Model of very concentrated electrolyte solutions. The calculated values of water activity agree with experiment, and the activity of NaOH and pOH have also been calculated. These data will allow prediction of the composition and chemical behavior of sodium borate liquids that may accumulate in the superheated crevices within a steam generator. A modified form of the model is provided for use with MULTEQ. The potassium borate system also was briefly studied at 317[degrees]C, and is adequately described by a model with five complex species. The potassium borate liquid is more alkaline at K/B = 1 than a sodium borate liquid at the same mole ratio, but pOH in the two systems is the same at lower mole ratios.

  12. Aerosol Chemical and Physical Characterization in Central Amazonia during the 2013 Dry Season

    NASA Astrophysics Data System (ADS)

    Artaxo, P.; Stern, R.; Brito, J.; Carbone, S.

    2015-12-01

    During the dry season, the central Amazon forest is highly influenced by forest fires transported through large distances, changing drastically the atmospheric composition even in remote places. This work focuses on a physical-chemical characterization of the aerosol population over a pristine site in Central Amazonia during the dry season. The submicrometer organic aerosols were measured with the Aerodyne ACSM (Aerosol Chemical Speciation Monitor, Aerodyne Inc). Optical properties, size distribution and other micro-physical characteristics were also analyzed. Other instruments were simultaneously used. The measurements were taken during the dry season of 2013 in the Cuieiras ecological reserve (ZF2), northwest of Manaus. The statistical analysis of the data was done with the PMF (Positive Matrix Factorization) technique, in which the organic aerosol was separated into different factors, and then its sources and forming processes were attributed. Results show that the mean aerosol loading was 5,91 μg m-3, from which 78% are of organic composition, 8.5% are sulfate, 6.5% are equivalent black carbon, 4% are ammonium and 3% are nitrate. The mass spectra variability can be explained by 3 factors only, determined with the PMF technique. They were identified as BBOA (Biomass Burning Organic Aerosol), representing 12% of the total organic mass, OOA (Oxygenated Organic Aerosol), representing 66% of the total organic mass and IEPOX-SOA (Isoprene derived Epoxydiol-Secondary Organic Aerosol), representing 21% of the total organic mass. Even in remote and pristine regions, Central Amazonia is highly impacted by biomass burning. Biogenic secondary organic aerosols are also present during the dry season, and the suppression of its wet deposition processes increases their concentration. The oxidation level and other physical-chemical characteristics indicate that the long range transport is responsible for the regional range of this impact.

  13. Organic aerosols in a Brazilian agro-industrial area: Speciation and impact of biomass burning

    NASA Astrophysics Data System (ADS)

    Urban, R. C.; Alves, C. A.; Allen, A. G.; Cardoso, A. A.; Campos, M. L. A. M.

    2016-03-01

    This work presents the first comprehensive organic characterization of atmospheric aerosols from an agro-industrial region (São Paulo State, Brazil) highly impacted by biomass burning. The organic speciation was performed using different solvents of increasing polarity, enabling the identification and quantification of 172 different organic species by GC-MS. The mass of organic compounds reached 123 μg m- 3 in an aerosol sample collected during the sugar cane harvest period compared with 0.82 μg m- 3 in the non-harvest period. The samples most impacted by biomass burning were those with the highest percentages of non-polar compounds (n-alkanes; up to 96%). However, in absolute terms, the total mass of polar compounds in such samples was greater than for samples less impacted by this activity. Retene (a marker for biomass combustion) was the most abundant of the 19 polycyclic aromatic hydrocarbons quantified, corresponding to 14%-84%. This work shows that biomass burning was responsible for a benzo(a)pyrene equivalent index value that exceeded the recommendation of the World Health Organization. Principal component analysis indicated that agricultural biomass burning and emissions from crop processing facilities explained 42% of the variance of the data, while 37% was explained by urban emissions, 10% by vehicle emissions, and 10% by biogenic sources. This study provides insights into the emissions of a suite of organic compounds that could participate in anthropic alteration of regional cloud formation and precipitation patterns.

  14. One year online chemical speciation of submicron particulate matter (PM1) sampled at a French industrial and coastal site

    NASA Astrophysics Data System (ADS)

    Zhang, Shouwen; Riffault, Véronique; Dusanter, Sébastien; Augustin, Patrick; Fourmentin, Marc; Delbarre, Hervé

    2015-04-01

    The harbor of Dunkirk (Northern France) is surrounded by different industrial plants (metallurgy, petrochemistry, food processing, power plant, etc.), which emit gaseous and particulate pollutants such as Volatile Organic Compounds (VOCs), oxides of nitrogen (NOx) and sulfur (SO2), and submicron particles (PM1). These emissions are poorly characterized and their impact on neighboring urban areas has yet to be assessed. Studies are particularly needed in this type of complex environments to get a better understanding of PM1sources, especially from the industrial sector, their temporal variability, and their transformation. Several instruments, capable of real-time measurements (temporal resolution ≤ 30 min), were deployed at a site located downwind from the industrial area of Dunkirk for a one-year duration (July 2013-September 2014). An Aerosol Chemical Speciation Monitor (ACSM) and an Aethalometer monitored the main chemical species in the non-refractory submicron particles and black carbon, respectively. Concomitant measurements of trace gases and wind speed and direction were also performed. This dataset was analyzed considering four wind sectors, characteristics of marine, industrial, industrial-urban, and urban influences, and the different seasons. We will present a descriptive analysis of PM1, showing strong variations of ambient concentrations, as well as evidences of SO2 to SO4 gas-particle conversion when industrial plumes reached the monitoring site. The organic fraction measured by ACSM (37% of the total mass on average) was analyzed using a source-receptor model based on Positive Matrix Factorization (PMF) to identify chemical signatures of main emission sources and to quantify the contribution of each source to the PM1 budget given the wind sector. Four main factors were identified: hydrocarbon organic aerosol (HOA), oxygenated organic aerosol (OOA), biomass burning organic aerosol (BBOA) and cooking-like organic aerosol (COA). Overall, the total PM

  15. Mercury Speciation by X-ray Absorption Fine Structure Spectroscopy and Sequential Chemical Extractions: A Comparison of Speciation Methods

    USGS Publications Warehouse

    Kim, C.S.; Bloom, N.S.; Rytuba, J.J.; Brown, Gordon E., Jr.

    2003-01-01

    Determining the chemical speciation of mercury in contaminated mining and industrial environments is essential for predicting its solubility, transport behavior, and potential bioavailability as well as for designing effective remediation strategies. In this study, two techniques for determining Hg speciation-X-ray absorption fine structure (XAFS) spectroscopy and sequential chemical extractions (SCE)-are independently applied to a set of samples with Hg concentrations ranging from 132 to 7539 mg/kg to determine if the two techniques provide comparable Hg speciation results. Generally, the proportions of insoluble HgS (cinnabar, metacinnabar) and HgSe identified by XAFS correlate well with the proportion of Hg removed in the aqua regia extraction demonstrated to remove HgS and HgSe. Statistically significant (> 10%) differences are observed however in samples containing more soluble Hg-containing phases (HgCl2, HgO, Hg3S2O 4). Such differences may be related to matrix, particle size, or crystallinity effects, which could affect the apparent solubility of Hg phases present. In more highly concentrated samples, microscopy techniques can help characterize the Hg-bearing species in complex multiphase natural samples.

  16. CCN frequency distributions and aerosol chemical composition from long-term observations at European ACTRIS supersites

    NASA Astrophysics Data System (ADS)

    Decesari, Stefano; Rinaldi, Matteo; Schmale, Julia Yvonne; Gysel, Martin; Fröhlich, Roman; Poulain, Laurent; Henning, Silvia; Stratmann, Frank; Facchini, Maria Cristina

    2016-04-01

    Cloud droplet number concentration is regulated by the availability of aerosol acting as cloud condensation nuclei (CCN). Predicting the air concentrations of CCN involves knowledge of all physical and chemical processes that contribute to shape the particle size distribution and determine aerosol hygroscopicity. The relevance of specific atmospheric processes (e.g., nucleation, coagulation, condensation of secondary organic and inorganic aerosol, etc.) is time- and site-dependent, therefore the availability of long-term, time-resolved aerosol observations at locations representative of diverse environments is strategic for the validation of state-of-the-art chemical transport models suited to predict CCN concentrations. We focused on long-term (year-long) datasets of CCN and of aerosol composition data including black carbon, and inorganic as well as organic compounds from the Aerosol Chemical Speciation Monitor (ACSM) at selected ACTRIS supersites (http://www.actris.eu/). We discuss here the joint frequency distribution of CCN levels and of aerosol chemical components concentrations for two stations: an alpine site (Jungfraujoch, CH) and a central European rural site (Melpitz, DE). The CCN frequency distributions at Jungfraujoch are broad and generally correlated with the distributions of the concentrations of aerosol chemical components (e.g., high CCN concentrations are most frequently found for high organic matter or black carbon concentrations, and vice versa), which can be explained as an effect of the strong seasonality in the aerosol characteristics at the mountain site. The CCN frequency distributions in Melpitz show a much weaker overlap with the distributions of BC concentrations or other chemical compounds. However, especially at high CCN concentration levels, a statistical correlation with organic matter (OM) concentration can be observed. For instance, the number of CCN (with particle diameter between 20 and 250 nm) at a supersaturation of 0.7% is

  17. Apparatus for rapid measurement of aerosol bulk chemical composition

    DOEpatents

    Lee, Yin-Nan E.; Weber, Rodney J.; Orsini, Douglas

    2006-04-18

    An apparatus for continuous on-line measurement of chemical composition of aerosol particles with a fast time resolution is provided. The apparatus includes an enhanced particle size magnifier for producing activated aerosol particles and an enhanced collection device which collects the activated aerosol particles into a liquid stream for quantitative analysis by analytical means. Methods for on-line measurement of chemical composition of aerosol particles are also provided, the method including exposing aerosol carrying sample air to hot saturated steam thereby forming activated aerosol particles; collecting the activated aerosol particles by a collection device for delivery as a jet stream onto an impaction surface; and flushing off the activated aerosol particles from the impaction surface into a liquid stream for delivery of the collected liquid stream to an analytical instrument for quantitative measurement.

  18. Apparatus for rapid measurement of aerosol bulk chemical composition

    DOEpatents

    Lee, Yin-Nan E.; Weber, Rodney J.

    2003-01-01

    An apparatus and method for continuous on-line measurement of chemical composition of aerosol particles with a fast time resolution are provided. The apparatus includes a modified particle size magnifier for producing activated aerosol particles and a collection device which collects the activated aerosol particles into a liquid stream for quantitative analysis by analytical methods. The method provided for on-line measurement of chemical composition of aerosol particles includes exposing aerosol carrying sample air to hot saturated steam thereby forming activated aerosol particles; collecting the activated aerosol particles by a collection device for delivery as a jet stream onto an impaction surface; flushing off the activated aerosol particles from the impaction surface into a liquid stream for delivery of the collected liquid stream to an analytical instrument for quantitative measurement.

  19. METHODS INTERCOMPARISON OF SAMPLERS FOR EPA'S NATIONAL PM 2.5 CHEMICAL SPECIATION NETWORK

    EPA Science Inventory

    The objective of this sampler intercomparison field study is to determine the performance characteristics for the collection of the chemical components of PM2.5 by the chemical speciation monitors developed for the national PM2.5 network relative to each other, to the Federal R...

  20. PM 2.5 CHEMICAL SPECIATION SAMPLER EVALUATION FIELD PROGRAM: RESULTS FROM THE FOUR CITY STUDY

    EPA Science Inventory

    The objective of this sampler intercomparison field study is to determine the performance characteristics for the collection of the chemical components of PM2.5 by the chemical speciation monitors developed for the national network relative to each other, to the Federal Referen...

  1. A PERSONAL PARTICLE SPECIATION SAMPLER

    EPA Science Inventory

    Dr. Susanne Hering of Aerosol Dynamics Inc and her colleagues expect to design and validate a personal monitoring sampler for particles smaller than 2.5 µm (PM2.5) that is suitable for subsequent chemical speciation work. The investigators believe the result will be a...

  2. Relating Aerosol Absorption due to Soot, Organic Carbon, and Dust to Emission Sources Determined from In-situ Chemical Measurements

    SciTech Connect

    Cazorla, Alberto; Bahadur, R.; Suski, Kaitlyn; Cahill, John F.; Chand, Duli; Schmid, Beat; Ramanathan, V.; Prather, Kimberly

    2013-09-17

    Estimating the aerosol contribution to the global or regional radiative forcing can take advantage of the relationship between the spectral aerosol optical properties and the size and chemical composition of aerosol. Long term global optical measurements from observational networks or satellites can be used in such studies, and using in-situ chemical mixing state measurements can help us to constrain the limitations of such an estimation. In this study, the Absorption Ångström Exponent (AAE) and the Scattering Ångström Exponent (SAE) are used to develop a new methodology for deducing chemical speciation based on wavelength dependence of the optical properties. In addition, in-situ optical properties and single particle chemical composition measured during three aircraft field campaigns are combined in order to validate the methodology for the estimation of aerosol composition using spectral optical properties. Results indicate a dominance of mixed types in the classification leading to an underestimation of the primary sources, however secondary sources are better classified. The distinction between carbonaceous aerosols from fossil fuel and biomass burning origins is not clear. On the other hand, the knowledge of the aerosol sources in California from chemical studies help to identify other misclassification such as the dust contribution.

  3. Physico-chemical properties of aerosols in Sao Paulo, Brazil and mechanisms of secondary organic aerosol formation.

    NASA Astrophysics Data System (ADS)

    Artaxo, Paulo; Ferreira de Brito, Joel; Varanda Rizzo, Luciana; Luiza Godoy, Maria; Godoy, Jose Marcus

    2013-04-01

    Megacities emissions are increasingly becoming a global issue, where emissions from the transportation sector play an increasingly important role. Sao Paulo is a megacity with a population of about 18 million people, 7 million cars and large-scale industrial emissions. As a result of the vehicular and industrial emissions, the air quality in Sao Paulo is bellow WMO standards for aerosol particles and ozone. Many uncertainties are found on gas- and particulate matter vehicular emission factors and their following atmospheric processes, e.g. secondary organic aerosol formation. Due to the uniqueness of the vehicular fuel in Brazil, largely based on ethanol use, such characterization currently holds further uncertainties. To improve the understanding of the role of this unique emission characteristics, we are running a source apportionment study in Sao Paulo focused on the mechanisms of organic aerosol formation. One of the goals of this study is a quantitative aerosol source apportionment focused on vehicular emissions, including ethanol and gasohol (both fuels used by light-duty vehicles). This study comprises four sampling sites with continuous measurements for one year, where trace elements and organic aerosol are being measured for PM2.5 and PM10 along with real-time NOx, O3, PM10 and CO measurements. Aerosol optical properties and size distribution are being measured on a rotation basis between sampling stations. Furthermore, a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS) and an Aerosol Chemical Speciation Monitor (ACSM) are used to measure in real time VOCs and aerosol composition, respectively. Trace elements were measured using XRF and OC/EC analysis was determined with a Sunset OC/EC instrument. A TSI Nephelometer with 3 wavelengths measure light scattering and a MAAP measure black carbon. Results show aerosol number concentrations ranging between 10,000 and 35,000 cm-3, mostly concentrated in the nucleation and Aitken modes, with a peak in size at 80

  4. Speciation and sources of atmospheric aerosols in a highly industrialised emerging mega-city in central China.

    PubMed

    Querol, Xavier; Zhuang, Xinguo; Alastuey, Andrés; Viana, Mar; Lv, Weiwei; Wang, Yanxin; López, Angel; Zhu, Zhichao; Wei, Hongmin; Xu, Shuangqin

    2006-10-01

    Monitoring air quality in large urban agglomerations is the key to the prevention of air pollution-related problems in emerging mega-cities. The city of Wuhan is a highly industrialised city with >9 million inhabitants in Central China. Simultaneous PM10 sampling was performed during 1 year at one urban and one industrial site. Mean PM10 daily levels (156 microg m(-3) at the urban site and 197 microg m(-3) at the industrial hotspot) exceed the US-EPA or EU annual limit values by 3-4 times. A detailed study of daily speciation showed that the mean chemical composition of PM10 presents minimal differences between peak and low PM episodes. This implies that PM10 aerosols in the study area result from local emissions, and air quality management and abatement strategies in Wuhan should thus focus on local anthropogenic sources. The levels of some elements of environmental concern are relatively high (409-615 ngPb m(-3), 66-70 ngAs m(-3), 116-227 ngMn m(-3), 10-12 ngCd m(-3)) due to industrial, but also urban emissions. Principal component analysis identified a mineral source (probably cement and steel manufacture) and smelting as the main contributors to PM10 levels at the industrial site (34%), followed by a coal fired power plant (20%) and the anthropogenic regional background (16%). At the urban site the major PM10 source is a mixed coal combustion source (31%), followed by the anthropogenic regional background (28%) and traffic (16%). PMID:17240911

  5. Plasma mass spectrometry as a detector for chemical speciation studies.

    PubMed

    Tomlinson, M J; Lin, L; Caruso, J A

    1995-03-01

    Inductively coupled plasma mass spectrometry (ICP-MS), when coupled with the unique separating power of various chromatographic techniques, allows the detection of various elements at ultra-trace levels. The investigation of various toxic elements of environmental concern coupling relatively recent techniques, such as supercritical fluid chromatography (SFC) and capillary zone electrophoresis (CZE), to ICP-MS, is discussed. Comparisons have been made with detection limits obtained by using the flame ionization detector. The conventional technique of liquid chromatography for the speciation of vanadium, chromium and nickel is also discussed. PMID:7741220

  6. Demonstration of a VUV lamp photoionization source for improvedorganic speciation in an aerosol mass spectrometer

    SciTech Connect

    Northway, M.J.; Jayne, J.T.; Toohey, D.W.; Canagaratna, M.R.; Trimborn, A.; Akiyama, K-I.; Shimono, A.; Jimenez, J.L.; DeCarlo, P.F.; Wilson, K.R.; Worsnop, D.R.

    2007-10-03

    In recent years, the Aerodyne AerosolMass Spectrometer(AMS) has become a widely used tool for determining aerosol sizedistributions and chemical composition for non-refractory inorganic andorganic aerosol. The current version of the AMS uses a combination offlash thermal vaporization and 70 eV electron impact (EI) ionization.However, EI causes extensive fragmentation and mass spectra of organicaerosols are difficult to deconvolute because they are composites of theoverlapping fragmentation patterns of all species present. Previous AMSstudies have been limited to classifying organics in broad categoriessuch as oxidized and hydrocarbon-like." In this manuscript we present newefforts to gain more information about organic aerosol composition byemploying the softer technique of vacuum ultraviolet (VUV) ionization ina Time-of-Flight AMS (ToF-AMS). In our novel design a VUV lamp is placedin direct proximity of the ionization region of the AMS, with only awindow separating the lamp and the ionizer. This design allows foralternation of photoionization and electron impact ionization within thesame instrument on the timescale of minutes. Thus, the EI-basedquantification capability of the AMS is retained while improved spectralinterpretation is made possible by combined analysis of the complementaryVUV and EI ionization spectra. Photoionization and electron impactionization spectra are compared for a number of compounds including oleicacid, long chain hydrocarbons, and cigarette smoke. In general, the VUVspectra contain much less fragmentation than the EI spectra and for manycompounds the parent ion is the dominant ion in the VUV spectrum. As anexample of the usefulness of the integration of PI within the fullcapability of the ToF-AMS, size distributions and size-segregated massspectra are examined for the cigarette smoke analysis. As a finalevaluation of the new VUV module, spectra for oleic acid are compared tosimilar experiments conducted using the tunable VUV radiation

  7. Speciation of the major inorganic salts in atmospheric aerosols of Beijing, China: Measurements and comparison with model

    NASA Astrophysics Data System (ADS)

    Tang, Xiong; Zhang, Xiaoshan; Ci, Zhijia; Guo, Jia; Wang, Jiaqi

    2016-05-01

    In the winter and summer of 2013-2014, we used a sampling system, which consists of annular denuder, back-up filter and thermal desorption set-up, to measure the speciation of major inorganic salts in aerosols and the associated trace gases in Beijing. This sampling system can separate volatile ammonium salts (NH4NO3 and NH4Cl) from non-volatile ammonium salts ((NH4)2SO4), as well as the non-volatile nitrate and chloride. The measurement data was used as input of a thermodynamic equilibrium model (ISORROPIA II) to investigate the gas-aerosol equilibrium characteristics. Results show that (NH4)2SO4, NH4NO3 and NH4Cl were the major inorganic salts in aerosols and mainly existed in the fine particles. The sulfate, nitrate and chloride associated with crustal ions were also important in Beijing where mineral dust concentrations were high. About 19% of sulfate in winter and 11% of sulfate in summer were associated with crustal ions and originated from heterogeneous reactions or direct emissions. The non-volatile nitrate contributed about 33% and 15% of nitrate in winter and summer, respectively. Theoretical thermodynamic equilibrium calculations for NH4NO3 and NH4Cl suggest that the gaseous precursors were sufficient to form stable volatile ammonium salts in winter, whereas the internal mixing with sulfate and crustal species were important for the formation of volatile ammonium salts in summer. The results of the thermodynamic equilibrium model reasonably agreed with the measurements of aerosols and gases, but large discrepancy existed in predicting the speciation of inorganic ammonium salts. This indicates that the assumption on crustal species in the model was important for obtaining better understanding on gas-aerosol partitioning and improving the model prediction.

  8. An advanced technique for speciation of organic nitrogen in atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Samy, S.; Robinson, J.; Hays, M. D.

    2011-12-01

    The chemical composition of organic nitrogen (ON) in the environment is a research topic of broad significance. The topic intersects the branches of atmospheric, aquatic, and ecological science; thus, a variety of instrumentation, analytical methods, and data interpretation tools have evolved for determination of ON. Recent studies that focus on atmospheric particulate nitrogen (N) suggest a significant fraction (20-80%) of total N is bound in organic compounds. The sources, bioavailability and transport mechanisms of these N-containing compounds can differ, producing a variety of environmental consequences. Amino acids (AA) are a key class of atmospheric ON compounds that can contribute to secondary organic aerosol (SOA) formation and potentially influence water cycles, air pollutant scavenging, and the radiation balance. AA are water-soluble organic compounds (WSOC) that can significantly alter the acid-base chemistry of aerosols, and may explain the buffering capacity that impacts heterogeneous atmospheric chemistry. The chemical transformations that N-containing organic compounds (including AA) undergo can increase the light-absorbing capacity of atmospheric carbon via formation of 'brown carbon'. Suggested sources of atmospheric AA include: marine surface layer transport from bursting sea bubbles, the suspension of bacteria, fungi, algae, pollen, spores, or biomass burning. Methodology for detection of native (underivatized) amino acids (AA) in atmospheric aerosols has been developed and validated (Samy et al., 2011). This presentation describes the use of LC-MS (Q-TOF) and microwave-assisted gas phase hydrolysis for detection of free and combined amino acids in aerosols collected in a Southeastern U.S. forest environment. Accurate mass detection and the addition of isotopically labeled surrogates prior to sample preparation allows for sensitive quantitation of target AA in a complex aerosol matrix. A total of 16 native AA were detected above the reporting

  9. Parameterization of Aerosol Sinks in Chemical Transport Models

    NASA Technical Reports Server (NTRS)

    Colarco, Peter

    2012-01-01

    The modelers point of view is that the aerosol problem is one of sources, evolution, and sinks. Relative to evolution and sink processes, enormous attention is given to the problem of aerosols sources, whether inventory based (e.g., fossil fuel emissions) or dynamic (e.g., dust, sea salt, biomass burning). On the other hand, aerosol losses in models are a major factor in controlling the aerosol distribution and lifetime. Here we shine some light on how aerosol sinks are treated in modern chemical transport models. We discuss the mechanisms of dry and wet loss processes and the parameterizations for those processes in a single model (GEOS-5). We survey the literature of other modeling studies. We additionally compare the budgets of aerosol losses in several of the ICAP models.

  10. Chemical characterization of secondary organic aerosol constituents from isoprene ozonolysis in the presence of acidic aerosol

    NASA Astrophysics Data System (ADS)

    Riva, Matthieu; Budisulistiorini, Sri Hapsari; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.

    2016-04-01

    Isoprene is the most abundant non-methane hydrocarbon emitted into Earth's atmosphere and is predominantly derived from terrestrial vegetation. Prior studies have focused largely on the hydroxyl (OH) radical-initiated oxidation of isoprene and have demonstrated that highly oxidized compounds, such as isoprene-derived epoxides, enhance the formation of secondary organic aerosol (SOA) through heterogeneous (multiphase) reactions on acidified sulfate aerosol. However, studies on the impact of acidified sulfate aerosol on SOA formation from isoprene ozonolysis are lacking and the current work systematically examines this reaction. SOA was generated in an indoor smog chamber from isoprene ozonolysis under dark conditions in the presence of non-acidified or acidified sulfate seed aerosol. The effect of OH radicals on SOA chemical composition was investigated using diethyl ether as an OH radical scavenger. Aerosols were collected and chemically characterized by ultra performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) and gas chromatography/electron impact ionization-mass spectrometry (GC/EI-MS). Analysis revealed the formation of highly oxidized compounds, including organosulfates (OSs) and 2-methylterols, which were significantly enhanced in the presence of acidified sulfate seed aerosol. OSs identified in the chamber experiments were also observed and quantified in summertime fine aerosol collected from two rural locations in the southeastern United States during the 2013 Southern Oxidant and Aerosol Study (SOAS).

  11. Measurements of aerosol chemical composition in boreal forest summer conditions

    NASA Astrophysics Data System (ADS)

    ńijälä, M.; Junninen, H.; Ehn, M.; Petäjä, T.; Vogel, A.; Hoffmann, T.; Corrigan, A.; Russell, L.; Makkonen, U.; Virkkula, A.; Mäntykenttä, J.; Kulmala, M.; Worsnop, D.

    2012-04-01

    Boreal forests are an important biome, covering vast areas of the northern hemisphere and affecting the global climate change via various feedbacks [1]. Despite having relatively few anthropogenic primary aerosol sources, they always contain a non-negligible aerosol population [2]. This study describes aerosol chemical composition measurements using Aerodyne Aerosol Mass Spectrometer (C-ToF AMS, [3]), carried out at a boreal forest area in Hyytiälä, Southern Finland. The site, Helsinki University SMEAR II measurement station [4], is situated at a homogeneous Scots pine (Pinus sylvestris) forest stand. In addition to the station's permanent aerosol, gas phase and meteorological instruments, during the HUMPPA (Hyytiälä United Measurements of Photochemistry and Particles in Air) campaign in July 2010, a very comprehensive set of atmospheric chemistry measurement instrumentation was provided by the Max Planck Institute for chemistry, Johannes Gutenberg-University, University of California and the Finnish Meteorological institute. In this study aerosol chemical composition measurements from the campaign are presented. The dominant aerosol chemical species during the campaign were the organics, although periods with elevated amounts of particulate sulfates were also seen. The overall AMS measured particle mass concentrations varied from near zero to 27 μg/m observed during a forest fire smoke episode. The AMS measured aerosol mass loadings were found to agree well with DMPS derived mass concentrations (r2=0.998). The AMS data was also compared with three other aerosol instruments. The Marga instrument [5] was used to provide a quantitative semi-online measurement of inorganic chemical compounds in particle phase. Fourier Transform Infrared Spectroscopy (FTIR) analysis was performed on daily filter samples, enabling the identification and quantification of organic aerosol subspecies. Finally an Atmospheric Pressure Chemical Ionization Ion Trap Mass Spectrometer (APCI

  12. Carbon speciation in ash, residual waste and contaminated soil by thermal and chemical analyses.

    PubMed

    Kumpiene, Jurate; Robinson, Ryan; Brännvall, Evelina; Nordmark, Désirée; Bjurström, Henrik; Andreas, Lale; Lagerkvist, Anders; Ecke, Holger

    2011-01-01

    Carbon in waste can occur as inorganic (IC), organic (OC) and elemental carbon (EC) each having distinct chemical properties and possible environmental effects. In this study, carbon speciation was performed using thermogravimetric analysis (TGA), chemical degradation tests and the standard total organic carbon (TOC) measurement procedures in three types of waste materials (bottom ash, residual waste and contaminated soil). Over 50% of the total carbon (TC) in all studied materials (72% in ash and residual waste, and 59% in soil) was biologically non-reactive or EC as determined by thermogravimetric analyses. The speciation of TOC by chemical degradation also showed a presence of a non-degradable C fraction in all materials (60% of TOC in ash, 30% in residual waste and 13% in soil), though in smaller amounts than those determined by TGA. In principle, chemical degradation method can give an indication of the presence of potentially inert C in various waste materials, while TGA is a more precise technique for C speciation, given that waste-specific method adjustments are made. The standard TOC measurement yields exaggerated estimates of organic carbon and may therefore overestimate the potential environmental impacts (e.g. landfill gas generation) of waste materials in a landfill environment. PMID:20630737

  13. CHEMICAL SPECIATION OF FLUE GAS DESULFURIZATION SLUDGE CONSTITUENTS

    EPA Science Inventory

    This project addresses the problem of flue gas desulfurization (FGD) sludge disposal to land. Specifically, the chemical species of FGD sludge constituents are thermodynamically modeled using the equilibrium constant approach, in an attempt to predict the constituent concentratio...

  14. Analysis of the chemical and physical properties of combustion aerosols: Properties overview

    EPA Science Inventory

    Aerosol chemical composition is remarkably complex. Combustion aerosols can comprise tens of thousands of organic compounds and fragments, refractory carbon, metals, cations, anions, salts, and other inorganic phases and substituents [Hays et al., 2004]. Aerosol organic matter no...

  15. [Determination the chemical speciation of Cu, Zn, Fe and Mn in Radix Scutellariae by AAS].

    PubMed

    Miao, Shan; Sun, Ji-yuan; Xie, Yan-hua; Wang, Jian-bo; Shi, Xiao-peng; Ding, Yuan-yuan; Bi, Lin-lin; Gao, Shuang-bin; Wang, Si-wang

    2009-05-01

    An analysis method was developed to determine the chemical speciation of Cu, Zn, Fe and Mn in radix scutellariae decoction using atomic absorption spectroscopy(AAS). The decoction can be divided into suspension and soluble species by 0.45 microm filter membrane and the soluble species can be separated into organism and inorganic species by LSA-10 macroporous resin. These elements in water-soluble test samples can be divided into alcohol-soluble and water-soluble by adopting n-octyl alcohol-water allocation system in man-made gastric acidity. Then, the concentration of these elements was determined by AAS, which provided more chemical speciation information about these elements instead of the total amount of them only in radix scutellariae. Deteotion limit of Cu, Zn and Mn by using the method was all 0.01 microg x mL(-1) and was 0.02 microg x mL(-1) for Fe. The RSD was in the range of 1.5%-3.6% (n=11) and the recovery rate of soluble species and inorganic species were in range of 96.7%-105.0%. The method has been successfully applied to determine the chemical speciation of Cu, Zn, Fe and Mn in radix scutellariae, which was very important for overall study of radix scutellariae. PMID:19650506

  16. Physical and Chemical Characterization of Carbonaceous Aerosols in Korea

    NASA Astrophysics Data System (ADS)

    Choung, S.; Jin, J. S.; Hwang, G. S.; Jang, K. S.; Han, W. S.; OH, J.; Kwon, Y.

    2014-12-01

    Atmospheric aerosols have been recently paid attention more in environmental research due to their negative effects on air quality, public health, and climate change. The aerosols contain approximately >20-50% carbonaceous components such as organic carbon (OC) and black carbon (BC) (or elemental carbon [EC]) derived from organic compounds, biomass burning, and incomplete combustion of fossil fuels. The physical, chemical, and biological properties of atmospheric aerosols are strongly dependent on the carbonaceous components. In particular, the BC could significantly affect the regional air quality in the northeastern Asia, because China is one of the foremost BC emission country in the world. Previous studies have mainly focused on the quantification and source identification for carbonaceous aerosols. However, understanding of physical and chemical properties for the carbonaceous aerosols related to environmental contamination and toxicity was still incomplete due to analytical difficulties. This study is addressed to evaluate the contribution of carbonaceous aerosols to air pollution through the surface, mass spectroscopic, and electron microscopic analyses, and determination of chemical composition and structure using the air particulate matter (PM2.5 and >PM2.5) samples.

  17. CHEMICAL SPECIATION OF INORGANIC COMPOUNDS UNDER HYDROTHERMAL CONDITIONS

    EPA Science Inventory

    This research will utilize the high-intensity x-rays available at the Advance Photon Source (APS) to study the inorganic chemistry occurring during the hydrothermal oxidation of tank waste and the chemistry associated with tank waste vitrification. Although the chemical conversio...

  18. Partitioning of silver and chemical speciation of free Ag in soils amended with nanoparticles

    PubMed Central

    2013-01-01

    Background Knowledge about silver nanoparticles in soils is limited even if soils are a critical pathway for their environmental fate. In this paper, speciation results have been acquired using a silver ion selective electrode in three different soils. Results Soil organic matter and pH were the most important soil properties controlling the occurrence of silver ions in soils. In acidic soils, more free silver ions are available while in the presence of organic matter, ions were tightly bound in complexes. The evolution of the chemical speciation of the silver nanoparticles in soils was followed over six months. Conclusion During the first few hours, there appeared to be a strong sorption of the silver with soil ligands, whereas over time, silver ions were released, the final concentration being approximately 10 times higher than at the beginning. Ag release was associated with either the oxidation of the nanoparticles or a dissociation of adsorbed silver from the soil surfaces. PMID:23617903

  19. Chemical Speciation of Neptunium in Spent Fuel. 1st Progress Report

    SciTech Connect

    Czerwinski, Ken; Sherman, Christi; Reed, Don

    2000-03-02

    This project will examine the chemical speciation of neptunium in spent nuclear fuel. The R&D fields covered by the project include waste host materials and actinide chemistry. Examination of neptunium is chosen since it was identified as a radionuclide of concern by the NERI workshop. Additionally, information on the chemical form of neptunium in spent fuel is lacking. The identification of the neptunium species in spent fuel would allow a greater scientific based understanding of its long-term fate and behavior in waste forms. Research to establish the application and development of X-ray synchrotrons radiation (XSR) techniques to determine the structure of aqueous, adsorbed, and solid actinide species of importance to nuclear considerations is being conducted at Argonne. These studies extend current efforts within the Chemical Technology Division at Argonne National Laboratory to investigate actinide speciation with more conventional spectroscopic and solids characterization (e.g. SEM, TEM, and XRD) methods. Our project will utilize all these techniques for determining neptunium speciation in spent fuel. We intend to determine the chemical species and oxidation state of neptunium in spent fuel and alteration phases. Different types of spent fuel will be examined. Once characterized, the chemical behavior of the identified neptunium species will be evaluated if it is not present in the literature. Special attention will be given to the behavior of the neptunium species under typical repository near-field conditions (elevated temperature, high pH, varying Eh). This will permit a timely inclusion of project results into near-field geochemical models. Additionally, project results and methodologies have applications to neptunium in the environment, or treatment of neptunium containing waste.

  20. Long-term Chemical Characterization of Submicron Aerosol Particles in the Amazon Forest - ATTO Station

    NASA Astrophysics Data System (ADS)

    Carbone, S.; Brito, J.; Rizzo, L. V.; Holanda, B. A.; Cirino, G. G.; Saturno, J.; Krüger, M. L.; Pöhlker, C.; Ng, N. L.; Xu, L.; Andreae, M. O.; Artaxo, P.

    2015-12-01

    The study of the chemical composition of aerosol particles in the Amazon forest represents a step forward to understand the strong coupling between the atmosphere and the forest. For this reason submicron aerosol particles were investigated in the Amazon forest, where biogenic and anthropogenic aerosol particles coexist at the different seasons (wet/dry). The measurements were performed at the ATTO station, which is located about 150 km northeast of Manaus. At ATTO station the Aerosol chemical speciation monitor (ACSM, Aerodyne) and the Multiangle absorption photometer (MAAP, Thermo 5012) have been operated continuously from March 2014 to July 2015. In this study, long-term measurements (near-real-time, ~30 minutes) of PM1 chemical composition were investigated for the first time in this environment.The wet season presented lower concentrations than the dry season (~5 times). In terms of chemical composition, both seasons were dominated by organics (75 and 63%) followed by sulfate (11 and 13%). Nitrate presented different ratio values between the mass-to-charges 30 to 46 (main nitrate fragments) suggesting the presence of nitrate as inorganic and organic nitrate during both seasons. The results indicated that about 75% of the nitrate signal was from organic nitrate during the dry season. In addition, several episodes with elevated amount of chloride, likely in the form of sea-salt from the Atlantic Ocean, were observed during the wet season. During those episodes, chloride comprised up to 7% of the PM1. During the dry season, chloride was also observed; however, with different volatility, which suggested that Chloride was present in different form and source. Moreover, the constant presence of sulfate and BC during the wet season might be related to biomass burning emissions from Africa. BC concentration was 2.5 times higher during the dry season. Further characterization of the organic fraction was accomplished with the positive matrix factorization (PMF), which

  1. Aerosol chemical mass closure during the EUROTRAC-2 AEROSOL Intercomparison 2000

    NASA Astrophysics Data System (ADS)

    Maenhaut, Willy; Schwarz, Jaroslav; Cafmeyer, Jan; Chi, Xuguang

    2002-04-01

    The field work for the AEROSOL Intercomparison 2000 took place from 4 to 14 April 2000 at Melpitz, Germany. One objective was to assess to which extent aerosol chemical mass closure could be obtained for the site. For this purpose, we operated four filter samplers in parallel (mostly using 12-h collections): two Gent PM10 stacked filter unit (SFU) samplers (one with coarse and fine Nuclepore polycarbonate filters, the other with a Gelman Teflo filter as fine filter) and two single filter holders (one with PM2.5 inlet, the other with PM10 inlet) with Whatman QM-A quartz fibre filters. All samples were analysed for the particulate mass (PM) by weighing; the samples from the first SFU were analysed for 42 elements by a combination of particle-induced X-ray emission spectroscopy and instrumental neutron activation analysis, those from the other SFU for major anions and cations by ion chromatography. All quartz filters were analysed for organic carbon and elemental carbon by a thermal-optical transmission technique. Aerosol chemical mass closure calculations were done for the separate fine (PM2) and coarse (2-10 μm) size fractions. As gravimetric PM data we used the averages from the parallel SFU collections. For reconstituting this PM, nine aerosol types (or components) were considered. Crustal matter, organic aerosol and nitrate were the major aerosol types in the coarse size fraction; the dominant aerosol types in the fine fraction were organic aerosol, nitrate and sulphate. The included components explained 116% and 86% of the gravimetric PM in the coarse and fine size fractions, respectively.

  2. Nitrogen speciation in various types of aerosol in spring over the northwestern Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Luo, L.; Yao, X. H.; Gao, H. W.; Hsu, S. C.; Li, J. W.; Kao, S.-J.

    2015-09-01

    The cumulative atmospheric nitrogen deposition has been found to profoundly impact the nutrient stoichiometry of the East China seas (ECSs) and the northwestern Pacific Ocean (NWPO). In spite of the potential significance of dry deposition in those regions, ship-board observations of atmospheric aerosols remain insufficient, particularly, for compositions of water-soluble nitrogen species (nitrate, ammonium and water-soluble organic nitrogen - WSON). We conducted a cruise covering the ECSs and the NWPO during the spring of 2014 and observed three types of atmospheric aerosols. Al content, air mass backward trajectory, weather condition, and ion stoichiometry allowed us to discern dust aerosol patches and sea fog modified aerosols (widespread on the ECSs) from background aerosols (open ocean). Among the three types, sea fog modified aerosols contained the highest concentrations of nitrate (536 ± 300 nmol N m-3), ammonium (442 ± 194 nmol N m-3) and WSON (147 ± 171 nmol N m-3); moreover, ammonium and nitrate together occupied ~ 65 % molar fraction of total ions. The dust aerosols also contained significant amounts of nitrate (100 ± 23 nmol N m-3) and ammonium (138 ± 24 nmol N m-3) which were obviously larger than those in background aerosols (26 ± 32 and 54 ± 45 nmol N m-3, respectively, for nitrate and ammonium), yet this was not the case for WSON. It appeared that dust aerosols had less of a chance to contact WSON during its transport. In the open ocean, we found that sea salt (e.g. Na+, Cl-, Mg2+), as well as WSON, correlates positively with wind speed. Apparently, marine WSON was emitted during breaking waves. Regardless of the variable wind speeds from 0.8 to as high as 18 m s-1 nitrate and ammonium, by contrast, remained in narrow ranges implying that some supply and consumption processes of nitrate and ammonium were required to maintain such a quasi-static condition. Mean dry deposition of total dissolved nitrogen (TDN) for sea fog modified aerosols

  3. Nitrogen speciation in various types of aerosols in spring over the northwestern Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Luo, L.; Yao, X. H.; Gao, H. W.; Hsu, S. C.; Li, J. W.; Kao, S. J.

    2016-01-01

    The cumulative atmospheric nitrogen deposition has been found to profoundly impact the nutrient stoichiometry of the eastern China seas (ECSs: the Yellow Sea and East China Sea) and the northwestern Pacific Ocean (NWPO). In spite of the potential significance of dry deposition in those regions, shipboard observations of atmospheric aerosols remain insufficient, particularly regarding the compositions of water-soluble nitrogen species (nitrate, ammonium and water-soluble organic nitrogen - WSON). We conducted a cruise covering the ECSs and the NWPO during the spring of 2014 and observed three types of atmospheric aerosols. Aluminum content, air mass backward trajectories, weather conditions, and ion stoichiometry allowed us to discern dust aerosol patches and sea-fog-modified aerosols (widespread over the ECSs) from background aerosols (open ocean). Among the three types, sea-fog-modified aerosols contained the highest concentrations of nitrate (536 ± 300 nmol N m-3), ammonium (442 ± 194 nmol N m-3) and WSON (147 ± 171 nmol N m-3); furthermore, ammonium and nitrate together occupied ˜ 65 % of the molar fraction of total ions. The dust aerosols also contained significant amounts of nitrate (100 ± 23 nmol N m-3) and ammonium (138 ± 24 nmol N m-3) which were obviously larger than those in the background aerosols (26 ± 32 for nitrate and 54 ± 45 nmol N m-3 for ammonium), yet this was not the case for WSON. It appeared that dust aerosols had less of a chance to come in contact with WSON during their transport. In the open ocean, we found that sea salt (e.g., Na+, Cl-, Mg2+), as well as WSON, correlated positively with wind speed. Apparently, marine dissolved organic nitrogen (DON) was emitted from breaking waves. Regardless of the variable wind speeds from 0.8 to as high as 18 m s-1, nitrate and ammonium, by contrast, remained in narrow ranges, implying that some supply and consumption processes of nitrate and ammonium were required to maintain such a quasi

  4. Influence of Aerosol Acidity on the Chemical Composition of Secondary Organic Aerosol from β-caryophyllene

    NASA Astrophysics Data System (ADS)

    Chan, M.; Surratt, J. D.; Chan, A. W.; Schlling, K.; Offenberg, J. H.; Lewandowski, M.; Edney, E.; Kleindienst, T. E.; Jaoui, M.; Edgerton, E. S.; Tanner, R. L.; Shaw, S. L.; Zheng, M.; Knipping, E. M.; Seinfeld, J.

    2011-12-01

    The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI- TOFMS). A number of first- , second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increased acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are suggested as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS).

  5. Influence of aerosol acidity on the chemical composition of secondary organic aerosol from β-caryophyllene

    NASA Astrophysics Data System (ADS)

    Chan, M. N.; Surratt, J. D.; Chan, A. W. H.; Schilling, K.; Offenberg, J. H.; Lewandowski, M.; Edney, E. O.; Kleindienst, T. E.; Jaoui, M.; Edgerton, E. S.; Tanner, R. L.; Shaw, S. L.; Zheng, M.; Knipping, E. M.; Seinfeld, J. H.

    2011-02-01

    The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI-TOFMS). A number of first-, second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increased acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. To our knowledge, this is the first detection of organosulfates and nitrated organosulfates derived from a sesquiterpene. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are suggested as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS).

  6. Influence of aerosol acidity on the chemical composition of Secondary Organic Aerosol from β-caryophyllene

    NASA Astrophysics Data System (ADS)

    Chan, M. N.; Surratt, J. D.; Chan, A. W. H.; Schilling, K.; Offenberg, J. H.; Lewandowski, M.; Edney, E. O.; Kleindienst, T. E.; Jaoui, M.; Edgerton, E. S.; Tanner, R. L.; Shaw, S. L.; Zheng, M.; Knipping, E. M.; Seinfeld, J. H.

    2010-11-01

    The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI-TOFMS). A number of first-, second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increase of acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. To our knowledge, this is the first detection of organosulfates and nitrated organosulfates derived from a sesquiterpene. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are identified as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS).

  7. Chemical speciation of lead dust associated with primary lead smelting.

    PubMed Central

    Spear, T M; Svee, W; Vincent, J H; Stanisich, N

    1998-01-01

    The research presented in this article assessed geochemical factors relating to dust produced during primary lead smelting. Bulk dust samples and size-selective airborne dust samples were collected from four areas of a primary lead smelter and analyzed by X-ray diffraction and sequential chemical extraction. X-ray diffraction showed that the smelter dusts were composed primarily of sulfides, oxides, sulfates, and silicates of metal ores, with galena being the primary dust component. Sequential extraction revealed the solubility of lead compounds at less than 7% in the exchangeable and mildly acidic steps for the bulk dusts collected from four smelter areas. The later steps of the extraction procedure were more effective in dissolving the lead compounds associated with the bulk dust samples, with 43%, 26%, and 8% of the total lead, in the ore storage, sinter, and blast/dross smelter areas, respectively, being extracted in the residual step. Sequential extraction of coarse airborne dust samples from the ore storage and sinter plant showed that 1.2% and 4.1% of the total lead, respectively, was exchangeable. The finer particle size fractions from these areas of the smelter showed higher percentages of exchangeable lead. Of the course airborne dust from the blast/dross furnace processes, 65% of the total lead was exchangeable. However, the largest percentage of lead from these areas was associated with the finer particle-size fractions. If lead bioavailability is related to its solubility as determined through sequential extraction, the health hazards associated with lead exposure may be appreciably enhanced in the blast and dross furnace processes. Images Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 PMID:9721256

  8. Raman spectroscopic studies of chemical speciation in calcium chloride melts

    SciTech Connect

    Windisch, Charles F.; Lavender, Curt A.

    2005-02-01

    Raman spectroscopy was applied to CaCl2 melts at 900 degrees C under both non-electrolyzed and electrolyzed conditions. The later used titania cathodes supplied by TIMET, Inc. and graphite anodes. Use of pulse-gating to collect the Raman spectra successfully eliminated any interference from black-body radiation and other stray light. The spectrum of molten CaCl2 exhibited no distinct, resolvable bands that could be correlated with a calcium chloride complex similar to MgCl42- in MgCl2 melts. Rather, the low frequency region of the spectrum was dominated by a broad “tail” arising from collective oscillations of both charge and mass in the molten salt “network.” Additions of both CaO and Ca at concentrations of a percent or two resulted in no new features in the spectra. Addition of CO2, both chemically and via electrolysis at concentrations dictated by stability and solubility at 900 degrees C and 1 bar pressure, also produced no new bands that could be correlated with either dissolved CO2 or the carbonate ion. These results indicated that Raman spectroscopy, at least under the conditions evaluated in the research, was not well suited for following the reactions and coordination chemistry of calcium ions, nor species such as dissolved metallic Ca and CO2 that are suspected to impact current efficiency in titanium electrolysis cells using molten CaCl2. Raman spectra of TIMET titania electrodes were successfully obtained as a function of temperature up to 900 degrees C, both in air and in-situ in CaCl2 melts. However, spectra of these electrodes could only be obtained when the material was in the unreduced state. When reduced, either with hydrogen or within an electrolysis cell, the resulting electrodes exhibited no measurable Raman bands under the conditions used in this work.

  9. Indian emissions of technology-linked NMVOCs with chemical speciation: An evaluation of the SAPRC99 mechanism with WRF-CAMx simulations

    NASA Astrophysics Data System (ADS)

    Sarkar, M.; Venkataraman, C.; Guttikunda, S.; Sadavarte, P.

    2016-06-01

    Non-methane volatile organic compounds (NMVOCs) are important precursors to reactions producing tropospheric ozone and secondary organic aerosols. The present work uses a detailed technology-linked NMVOC emission database for India, along with a standard mapping method to measured NMVOC profiles, to develop speciated NMVOC emissions, which are aggregated into multiple chemical mechanisms used in chemical transport models. The fully speciated NMVOC emissions inventory with 423 constituent species, was regrouped into model-ready reactivity classes of the RADM2, SAPRC99 and CB-IV chemical mechanisms, and spatially distributed at 25 × 25 km2 resolution, using source-specific spatial proxies. Emissions were considered from four major sectors, i.e. industry, transport, agriculture and residential and from non-combustion activities (use of solvents and paints). It was found that residential cooking with biomass fuels, followed by agricultural residue burning in fields and on-road transport, were largest contributors to the highest reactivity group of NMVOC emissions from India. The emissions were evaluated using WRF-CAMx simulations, using the SAPRC99 photochemical mechanism, over India for contrasting months of April, July and October 2010. Modelled columnar abundance of NO2, CO and O3 agreed well with satellite observations both in magnitude and spatial distribution, in the three contrasting months. Evaluation of monthly and spatial differences between model predictions and observations indicates the need for further refinement of the spatial distribution of NOX emissions, spatio-temporal distribution of agricultural residue burning emissions.

  10. Characterization of Chemical Speciation in Ultra Thin Uranium Oxide Films by Neutron Reflectometry

    SciTech Connect

    Wang, Peng

    2012-06-20

    Motivation for this project is due to more than 17 kg of HEU and 400 g of Pu have been interdicted through an international effort to control nuclear smuggling. Nuclear forensics - Detection and analysis of nuclear materials recovered from either the capture of unused materials or from the radioactive debris following a nuclear explosion or activities, which can contribute significantly for national security. Develop new nuclear forensic methods can be applied to: (a) Environmental swipes, (b) Small particulates, and (c) Thin films. Conclusions of the project are: (1) A unique approach: Neutron Reflectometry + Surface Enhanced Raman Spectroscopy; and (2) Detection of chemical speciation with {angstrom}-level resolution.

  11. [Application of ICP-AES to the chemical speciation of heavy metals in flyash].

    PubMed

    Guo, Yu-Wen; Pu, Li-Mei; Qiao, Wei; Wang, Wei; Wan, Xiao; Zhang, Xin-Rong

    2006-08-01

    Chemical speciation of seven heavy metals of flyashes in incinerator was quantitatively tested using ICP-AES. Results showed that ICP-AES procedure could carry out quick, exact and high precision experiments. RSD ratio for most detected metals was lower than 3% while few metals present a comparatively high RSD when whose content was near the detection limits. The recovery ratio was 85.7%-100.63% flyashes were found to have high content of Zn, Pb. Cd, Cu, Mn, Pb and Zn existed mostly as carbonates and were leachable, while Cr and Ni were combined to metal oxides substrates and present immobilization characteristics. PMID:17058967

  12. Chemical speciation of trace metals emitted from Indonesian peat fires for health risk assessment

    NASA Astrophysics Data System (ADS)

    Betha, Raghu; Pradani, Maharani; Lestari, Puji; Joshi, Umid Man; Reid, Jeffrey S.; Balasubramanian, Rajasekhar

    2013-03-01

    Regional smoke-induced haze in Southeast Asia, caused by uncontrolled forest and peat fires in Indonesia, is of major environmental and health concern. In this study, we estimated carcinogenic and non-carcinogenic health risk due to exposure to fine particles (PM2.5) as emitted from peat fires at Kalimantan, Indonesia. For the health risk analysis, chemical speciation (exchangeable, reducible, oxidizable, and residual fractions) of 12 trace metals (Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn) in PM2.5 was studied. Results indicate that Al, Fe and Ti together accounted for a major fraction of total metal concentrations (~ 83%) in PM2.5 emissions in the immediate vicinity of peat fires. Chemical speciation reveals that a major proportion of most of the metals, with the exception of Cr, Mn, Fe, Ni and Cd, was present in the residual fraction. The exchangeable fraction of metals, which represents their bioavailability, could play a major role in inducing human health effects of PM2.5. This fraction contained carcinogenic metals such as Cd (39.2 ng m- 3) and Ni (249.3 ng m- 3) that exceeded their WHO guideline values by several factors. Health risk estimates suggest that exposure to PM2.5 emissions in the vicinity of peat fires poses serious health threats.

  13. Chemical composition of aerosol particles and light extinction apportionment before and during the heating season in Beijing, China

    NASA Astrophysics Data System (ADS)

    Wang, Qingqing; Sun, Yele; Jiang, Qi; Du, Wei; Sun, Chengzhu; Fu, Pingqing; Wang, Zifa

    2015-12-01

    Despite extensive efforts into characterization of the sources and formation mechanisms of severe haze pollution in the megacity of Beijing, the response of aerosol composition and optical properties to coal combustion emissions in the heating season remain poorly understood. Here we conducted a 3 month real-time measurement of submicron aerosol (PM1) composition by an Aerosol Chemical Speciation Monitor and particle light extinction by a Cavity Attenuated Phase Shift extinction monitor in Beijing, China, from 1 October to 31 December 2012. The average (±σ) PM1 concentration was 82.4 (±73.1) µg/m3 during the heating period (HP, 15 November to 31 December), which was nearly 50% higher than that before HP (1 October to 14 November). While nitrate and secondary organic aerosol (SOA) showed relatively small changes, organics, sulfate, and chloride were observed to have significant increases during HP, indicating the dominant impacts of coal combustion sources on these three species. The relative humidity-dependent composition further illustrated an important role of aqueous-phase processing for the sulfate enhancement during HP. We also observed great increases of hydrocarbon-like OA (HOA) and coal combustion OA (CCOA) during HP, which was attributed to higher emissions at lower temperatures and coal combustion emissions, respectively. The relationship between light extinction and chemical composition was investigated using a multiple linear regression model. Our results showed that the largest contributors to particle extinction were ammonium nitrate (32%) and ammonium sulfate (28%) before and during HP, respectively. In addition, the contributions of SOA and primary OA to particle light extinction were quantified. The results showed that the OA extinction was mainly caused by SOA before HP and by SOA and CCOA during HP, yet with small contributions from HOA and cooking aerosol for the entire study period. Our results elucidate substantial changes of aerosol

  14. Linking the chemical speciation of cerium to its bioavailability in water for a freshwater alga.

    PubMed

    El-Akl, Philippe; Smith, Scott; Wilkinson, Kevin J

    2015-08-01

    Over the past decade, researchers have begun to use metals of the lanthanide family for numerous applications, including liquid crystal display (LCD) screens, optical fibers, and laser technology. Unfortunately, little is presently known about their bioavailability or the mechanisms by which they might cause toxicity. The present study focuses on cerium (Ce), one of the most widely used lanthanides, and on validating the biotic ligand model as a means to predict Ce bioaccumulation. Short-term exposures to Ce were performed using the unicellular alga Chlamydomonas reinhardtii, to better relate Ce bioavailability to its chemical speciation in solution. Maximum uptake fluxes (Jmax ) and affinity constants for the binding of Ce to the biological uptake sites (KS ) were established at pH 5.0 and pH 7.0. An apparent affinity constant of 1.8 × 10(7) M(-1) was observed at pH 5.0, with a larger value obtained at pH 7.0 (6 × 10(7) M(-1) ), albeit under conditions where equilibrium could not be confirmed. By evaluating Ce speciation using centrifugal ultrafiltration and single-particle inductively coupled plasma spectrometry, it could be concluded that very little (∼30%) Ce was truly dissolved at pH 7.0, with the majority of the metal being present in colloidal species. Speciation was also monitored by fluorescence to evaluate Ce complexation by natural organic matter (NOM). The presence of NOM decreased Ce bioaccumulation in line with free Ce concentrations. Finally, competition with calcium for the metal uptake sites was shown to result in a decrease in Ce uptake by C. reinhardtii. PMID:25772589

  15. Organic speciation of aerosols from wildfires in central Portugal during summer 2009

    NASA Astrophysics Data System (ADS)

    Vicente, Ana; Alves, Célia; Monteiro, Cristina; Nunes, Teresa; Mirante, Fátima; Cerqueira, Mário; Calvo, Ana; Pio, Casimiro

    2012-09-01

    The aim of this study was the detailed organic speciation of fine (PM2.5) and coarse (PM2.5-10) particles and gaseous carbonyl compounds from plumes emitted by wildfires during the summer of 2009 in Portugal. Complementary characterisation of the smoke particulate inorganic fraction, along with emission factors of major trace gases, have already been published in Atmospheric Environment. The detailed speciation of organic compounds in particle samples was carried out by gas chromatography-mass spectrometry after multi-solvent extraction, flash chromatography on silica gel and appropriate derivatisation techniques. PM2.5 constitutes an important fraction of PM10 (PM2.5/PM10 > 80%). Gaseous carbonyls were sampled from the Tedlar bags containing the smoke samples in DNHP cartridges and analysed by high-performance liquid chromatography. A clear predominance of carbonaceous constituents was observed, with OC concentrations always much higher than EC in both particle size fractions (OC/EC >> 7). The chromatographically resolved organics were dominated by diterpenoids, acids, sugars, phenols and aliphatic compounds in both size fractions. Retene, a biomarker of softwood smoke, was the dominant aromatic hydrocarbon in samples. The major anhydrosugar detected was levoglucosan, followed by mannosan and galactosan. Among the measured oxygenated volatile organic compounds, the most abundant was acetaldehyde with EFs (dry basis) between 1.03 and 1.87 g kg-1, followed by formaldehyde with values in the range of 0.09-0.96 g kg-1. Propionaldehyde was the less abundant carbonyl, with values in the range of 0.03-0.17 g kg-1.

  16. Chemical and physicochemial properties of submicron aerosol agglomerates

    SciTech Connect

    Scripsick, R.C.; Ehrman, S.; Friedlander, S.K.

    1998-12-31

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory. The formation of nanometer-sized aerosol particles in a premixed methane flame from both solid-phase aerosol precursors and gas-phase precursors was investigated. Techniques were developed to determine the distribution of the individual chemical species as a function of agglomerate size by using inductively coupled plasma atomic emission spectroscopy (ICP-AES). To determine the distribution of chemical species both from particle to particle and within the particles on a nanometer scale, we used the analytical electron microscopy techniques of energy dispersive x-ray spectrometry (EDS) and electron energy loss spectrometry (EELS) coupled with transmission electron microscopy (TEM). The observed distribution of individual chemical species as a function of agglomerate size was linked to the material properties of the solid-phase precursors. For aerosol formed from gas-phase precursors by gas-to-particle conversion, the distribution of species on a manometer scale was found to correspond to the equilibrium phase distribution expected from equilibrium for the system at the flame temperatures.

  17. Chemical evolution of multicomponent aerosol particles during evaporation

    NASA Astrophysics Data System (ADS)

    Zardini, Alessandro; Riipinen, Ilona; Pagels, Joakim; Eriksson, Axel; Worsnop, Douglas; Switieckli, Erik; Kulmala, Markku; Bilde, Merete

    2010-05-01

    Atmospheric aerosol particles have an important but not well quantified effect on climate and human health. Despite the efforts made in the last decades, the formation and evolution of aerosol particles in the atmosphere is still not fully understood. The uncertainty is partly due to the complex chemical composition of the particles which comprise inorganic and organic compounds. Many organics (like dicarboxylic acids) can be present both in the gas and in the condensed phase due to their low vapor pressure. Clearly, an understanding of this partition is crucial to address any other issue in atmospheric physics and chemistry. Moreover, many organics are water soluble, and their influence on the properties of aqueous solution droplets is still poorly characterized. The solid and sub-cooled liquid state vapor pressures of some organic compounds have been previously determined by measuring the evaporation rate of single-compound crystals [1-3] or binary aqueous droplets [4-6]. In this work, we deploy the HTDMA technique (Hygroscopicity Tandem Differential Mobility Analyzer) coupled with a 3.5m laminar flow-tube and an Aerosol Mass Spectrometer (AMS) for determining the chemical evolution during evaporation of ternary droplets made of one dicarboxylic acid (succinic acid, commonly found in atmospheric samples) and one inorganic compound (sodium chloride or ammonium sulfate) in different mixing ratios, in equilibrium with water vapor at a fixed relative humidity. In addition, we investigate the evaporation of multicomponent droplets and crystals made of three organic species (dicarboxylic acids and sugars), of which one or two are semi-volatile. 1. Bilde M. and Pandis, S.N.: Evaporation Rates and Vapor Pressures of Individual Aerosol Species Formed in the Atmospheric Oxidation of alpha- and beta-Pinene. Environmental Science and Technology, 35, 2001. 2. Bilde M., et al.: Even-Odd Alternation of Evaporation Rates and Vapor Pressures of C3-C9 Dicarboxylic Acid Aerosols

  18. In Situ Chemical Characterization of Organic Aerosol Surfaces using Direct Analysis in Real Time

    NASA Astrophysics Data System (ADS)

    Chan, M.; Nah, T.; Wilson, K. R.

    2012-12-01

    Obtaining in situ information on the molecular composition of atmospheric aerosol is important for understanding the sources, formation mechanisms, aging and physiochemical properties of atmospheric aerosol. Most recently, we have used Direct Analysis in Real Time (DART), which is a "soft" atmospheric pressure ionization technique, for in situ chemical characterization of a variety of laboratory generated organic aerosol and heterogeneous processing oleic acid aerosol. A stream of aerosol particles is crossed with a thermal flow of metastable He atoms (produced by the DART source) in front of an inlet of a mass spectrometer. The thermally desorbed analytes are subsequently ionized with minimal fragmentation by reactive species in the DART ionization source (e.g., metastable He atoms). The ion signal scales with the aerosol surface area rather than aerosol volume, suggesting that aerosol particles are not completely vaporized in the ionization region. The DART can thus measure the chemical composition as a function of aerosol depth. Probing aerosol depth is determined by the thermal desorption rates of aerosol particles. Here, we investigate how the experimental parameters (e.g., DART gas temperature and residence time) and the physiochemical properties of aerosol particles (e.g., enthalpy of vaporization) affect the probing aerosol depth and the desorption-ionization mechanism of aerosol particles in the DART using a series of model organic compounds. We also demonstrate the potential application of DART for in situ chemically analyzing wet aerosol particles undergoing oxidation reactions.

  19. Secondary organic aerosol in the global aerosol - chemical transport model Oslo CTM2

    NASA Astrophysics Data System (ADS)

    Hoyle, C. R.; Berntsen, T.; Myhre, G.; Isaksen, I. S. A.

    2007-11-01

    The global chemical transport model Oslo CTM2 has been extended to include the formation, transport and deposition of secondary organic aerosol (SOA). Precursor hydrocarbons which are oxidised to form condensible species include both biogenic species such as terpenes and isoprene, as well as species emitted predominantly by anthropogenic activities (toluene, m-xylene, methylbenzene and other aromatics). A model simulation for 2004 gives an annual global SOA production of approximately 55 Tg. Of this total, 2.5 Tg is found to consist of the oxidation products of anthropogenically emitted hydrocarbons, and about 15 Tg is formed by the oxidation products of isoprene. The global production of SOA is increased to about 69 Tg yr-1 by allowing semi-volatile species to partition to ammonium sulphate aerosol. This brings modelled organic aerosol values closer to those observed, however observations in Europe remain significantly underestimated. Allowing SOA to partition into ammonium sulphate aerosol increases the contribution of anthropogenic SOA from about 4.5% to 9.4% of the total production. Total modelled organic aerosol (OA) values are found to represent a lower fraction of the measured values in winter (when primary organic aerosol (POA) is the dominant OA component) than in summer, which may be an indication that estimates of POA emissions are too low. Additionally, for measurement stations where the summer OA values are higher than in winter, the model generally underestimates the increase in summertime OA. In order to correctly model the observed increase in OA in summer, additional SOA sources or formation mechanisms may be necessary. The importance of NO3 as an oxidant of SOA precursors is found to vary regionally, causing up to 50%-60% of the total amount of SOA near the surface in polluted regions and less than 25% in more remote areas, if the yield of condensible oxidation products for β-pinene is used for NO3 oxidation of all terpenes. Reducing the yield

  20. Ground based chemical characterization of submicron aerosol during the South American Biomass Burning Analysis (SAMBBA) field experiment

    NASA Astrophysics Data System (ADS)

    Brito, Joel; Artaxo, Paulo; Varanda Rizzo, Luciana; Johnson, Ben; Haywood, Jim; Longo, Karla; Freitas, Saulo; Coe, Hugh

    2013-04-01

    This work presents the results of an Aerosol Chemical Speciation Monitor (ACSM) which was successfully operated at a ground station in Porto Velho, Brazil, during the South American Biomass Burning Analysis (SAMBBA). SAMBBA is an international research project based on experimental and modeling activities designed to investigate the impacts of biomass burning emissions on climate, air quality and numerical weather prediction over South America. The measurement program was headed by the deployment of UK's Facility for Airborne Atmospheric Measurements (FAAM) BAe-146 research aircraft over Brazil during the dry season of 2012. The aircraft operation was coordinated with ground-based measurements at Porto Velho, operated by the University of Sao Paulo. Besides the aerosol chemical speciation, continuous measurements of aerosol size distribution and optical properties were carried out at the ground station, together with CO, CO2 and O3. Filters for trace elements measured by XRF and for OC/EC determined using a Sunset instrument were also collected at the ground based component of SAMBBA. The ACSM collected data for three weeks during September 2012. This period included a strong biomass burning event which showed a marked peak in f60, linked with Levoglucosan, a well-known biomass burning marker. During the biomass burning event, organics concentrations rose up to 80 μg/m3, black carbon close to 6 μg/m3 and CO mixing ratio above 2 ppmv. Fast biomass burning aerosol processing in the atmosphere could be observed through the relative contributions of C2H3O+ vs. CO2+ relative to total organic mass (f44 vs. f43). A clear diurnal variation throughout the sampling period has been observed for organic aerosols with a median peak of 9 μg/m3 at 04:00 LT and a minima of 5 μg/m3 at 18:00 LT. Preliminary results indicate that organics are responsible for 85% of PM1 non-refractory aerosols. The data set will allow the study of interactions between biomass burning and biogenic

  1. Chemical speciation and source apportionment of Non-Methane Volatile Organic Compounds (NMVOCs) in a Middle Eastern country

    NASA Astrophysics Data System (ADS)

    Salameh, Therese; Sauvage, Stéphane; Afif, Charbel; Borbon, Agnès; Locoge, Nadine

    2014-05-01

    NMVOCs, emitted from various sources, are of particular interest since they contribute to the formation of tropospheric ozone, PAN and secondary organic aerosols resulting in negative impacts on human health, climate and on the environment. To identify abatement measures, a profound knowledge of emission sources and their composition is a prerequisite. Air pollution in the Middle East region remains difficult to assess and understand because of a lack of ground-based measurements and the limited information on NMVOC chemical speciation and source apportionment. Based on a large database of NMVOC observations obtained in Beirut, the capital of Lebanon (a developing country in the Middle East region, located in Western Asia on the eastern shore of the Mediterranean Sea), the overall objective of this work is to apportion the sources of NMVOCs encountered in Lebanon. First, source profiles were determined with field measurements close to the main potential emitters namely the road transport, gasoline vapour, power generation and solvent uses. The results obtained are compared to other studies held in other regions and are used to assess the emission inventory developed for Lebanon. Secondly, two intensive field campaigns were held in a receptor site in Beirut during summer 2011 and winter 2012 in order to obtain a large time resolved dataset. The PMF analysis of this dataset was applied to apportion anthropogenic sources in this area. In both seasons, combustion (road transport and power generation) and gasoline evaporation, especially in winter, were the main sources contributing to the NMVOCs in Beirut. The results will support model implementation especially by completing the emission inventory established for the year 2010 by Waked et al. 2012 according to the EEA/EMEP guidelines because of the lack of Lebanon-specific emission factor.

  2. Speciation of organic compounds in aerosols from urban background sites in the winter season

    NASA Astrophysics Data System (ADS)

    Alves, Célia; Nunes, Teresa; Vicente, Ana; Gonçalves, Cátia; Evtyugina, Margarita; Marques, Telma; Pio, Casimiro; Bate-Epey, Frieda

    2014-12-01

    Winter aerosol samples were daily collected during one-month long campaign in Oporto and Coimbra. The high-volume PM2.5 samples were solvent extracted and their organic content separated into several functional groups, which were then analysed by gas chromatography-mass spectrometry. The organic compounds identified and quantified revealed some differences between samples from the two urban areas. In general, the levels of total hydrocarbons in the urban background station of Oporto were higher than those of Coimbra. Concentration ratios between specific compounds and the presence of molecular markers derived from petroleum, such as hopanes, pristane and phytane, point out vehicles as the main source of pollutants. The contribution of biogenic compounds, mainly hydrocarbons associated with the waxy cuticle of vegetation, is also observable in both cities. The benzo[a]pyrene equivalent daily values were frequently higher than 1 ng m- 3 in Oporto suggesting an additional cancer risk for the population. The PM2.5 mass attributable to vehicle emissions is higher in the background atmosphere of Oporto than in Coimbra. On weekends, biomass burning emissions could represent up to 74% of the organic carbon content of the urban aerosols.

  3. Optical and Chemical Characterization of Aerosols Produced from Cooked Meats

    NASA Astrophysics Data System (ADS)

    Niedziela, R. F.; Foreman, E.; Blanc, L. E.

    2011-12-01

    Cooking processes can release a variety compounds into the air immediately above a cooking surface. The distribution of compounds will largely depend on the type of food that is being processed and the temperatures at which the food is prepared. High temperatures release compounds from foods like meats and carry them away from the preparation surface into cooler regions where condensation into particles can occur. Aerosols formed in this manner can impact air quality, particularly in urban areas where the amount of food preparation is high. Reported here are the results of laboratory experiments designed to optically and chemically characterize aerosols derived from cooking several types of meats including ground beef, salmon, chicken, and pork both in an inert atmosphere and in synthetic air. The laboratory-generated aerosols are studied using a laminar flow cell that is configured to accommodate simultaneous optical characterization in the mid-infrared and collection of particles for subsequent chemical analysis by gas chromatography. Preliminary optical results in the visible and ultra-violet will also be presented.

  4. U.S. National PM2.5 Chemical Speciation Monitoring Networks – CSN and IMPROVE: Description of Networks

    EPA Science Inventory

    The U.S. Environmental Protection Agency (EPA) initiated the national PM2.5 Chemical Speciation Monitoring Network (CSN) in 2000 to support evaluation of long-term trends and to better quantify the impact of sources on particulate matter (PM) concentrations in the size range belo...

  5. Chemical composition, sources and evolution processes of aerosol at an urban site in Yangtze River Delta, China during wintertime

    NASA Astrophysics Data System (ADS)

    Zhang, Yunjiang; Tang, Lili; Yu, Hongxia; Wang, Zhuang; Sun, Yele; Qin, Wei; Chen, Wentai; Chen, Changhong; Ding, Aijun; Wu, Jing; Ge, Shun; Chen, Cheng; Zhou, Hong-cang

    2015-12-01

    To investigate the composition, sources and evolution processes of submicron aerosol during wintertime, a field experiment was conducted during December 1-31, 2013 in urban Nanjing, a megacity in Yangtze River Delta of China. Non-refractory submicron aerosol (NR-PM1) species were measured with an Aerodyne Aerosol Chemical Speciation Monitor. NR-PM1 is dominated by secondary inorganic aerosol (55%) and organic aerosol (OA, 42%) during haze periods. Six OA components were identified by positive matrix factorization of the OA mass spectra. The hydrocarbon-like OA and cooking-related OA represent the local traffic and cooking sources, respectively. A highly oxidized factor related to biomass burning OA accounted for 15% of the total OA mass during haze periods. Three types of oxygenated OA (OOA), i.e., a less-oxidized OOA (LO-OOA), a more-oxidized OOA (MO-OOA), and a low-volatility OOA (LV-OOA), were identified. LO-OOA is likely associated with fresh urban secondary OA. MO-OOA likely represents photochemical products showing a similar diurnal cycle to nitrate with a pronounced noon peak. LV-OOA appears to be a more oxidized factor with a pronounced noon peak. The OA composition is dominated by secondary species, especially during haze events. LO-OOA, MO-OOA and LV-OOA on average account for 11%, (18%), 24% (21%) and 23% (18%) of the total OA mass for the haze (clean) periods respectively. Analysis of meteorological influence suggested that regional transport from the northern and southeastern areas of the city is responsible for large secondary and low-volatility aerosol formation.

  6. Analysis of the Effects of Chemical Composition and Humidity on Visibility using Highly Time Resolved Aerosol Data

    NASA Astrophysics Data System (ADS)

    Lunden, M. M.; Brown, N. J.; Liu, D.; Tonse, S.

    2005-12-01

    Transported aerosols from populated and industrial areas result in regional haze that causes visibility degradation in areas valued for their scenic beauty, such as the National Parks. These areas are designated as Class I Areas in the United States, and there are specific visibility goals put forth to ultimately return these areas to natural conditions. To both understand current conditions and chart progress towards meeting these goals requires measurement of important aerosol species and an understanding of how these different aerosol species affect light attenuation to allow for predictive modeling capabilities. The current investigation seeks to understand if more highly time resolved measurements of chemically speciated particle mass, relative humidity, scattering, and absorption would enable a better estimation of extinction as the relationship between these variables is non-linear. Our particular objective is to explore the contributions of the aerosol species mentioned above to visibility degradation, and the role played by relative humidity. We performed analyses on a data set collected in Central California from the intensive ambient aerosol sampling campaign conducted from 2000 summer-2001 winter1. The data include PM-2.5 mass concentrations of nitrate, sulfate, organic carbon and black carbon aerosol, as well as simultaneous measurements on light scattering, ambient temperature and relative humidity. The dataset is highly time-resolved, allowing the affect of temporal variations of particle chemical composition and meteorological features to be considered. The final results provide response curves that allow calculation of light scattering given aerosol concentrations and relative humidity. Our results are compared with those obtained using formulae suggested for analysis of IMPROVE (a regional haze monitoring network2) data collected under lower temporal resolution to understand the effects of temporal resolution on the characteristics of the

  7. Complete chemical analysis of aerosol particles in real-time

    SciTech Connect

    Yang, Mo; Reilly, P.T.A.; Gieray, R.A.; Whitten, W.B.; Ramsey, J.M.

    1996-12-31

    Real-time mass spectrometry of individual aerosol particles using an ion trap mass spectrometer is described. The microparticles are sampled directly from the air by a particle inlet system into the vacuum chamber. An incoming particle is detected as it passes through two CW laser beams and a pulsed laser is triggered to intercept the particle for laser ablation ionization at the center of the ion trap. The produced ions are analyzed by the ion trap mass spectrometer. Ions of interest are selected and dissociated through collision with buffer gas atoms for further fragmentation analysis. Real-time chemical analyses of inorganic, organic, and bacterial aerosol articles have been demonstrated. It has been confirmed that the velocity and the size of the incoming particles highly correlate to each other. The performance of the inlet system, particle detection, and preliminary results are discussed.

  8. Multi- year Arctic and Antarctic aerosol chemical characterization

    NASA Astrophysics Data System (ADS)

    Udisti, Roberto; Becagli, Silvia; Caiazzo, Laura; Calzolai, Giulia; Cappelletti, David; Giardi, Fabio; Grotti, Marco; Malandrino, Mery; Nava, Silvia; Severi, Mirko; Traversi, Rita

    2016-04-01

    Long term measurements of aerosol chemical composition in polar region are particularly relevant to investigate potential climatic effects of atmospheric components arising from both natural and anthropogenic emissions. In order to improve our knowledge on the atmospheric load and chemical composition of polar aerosol, several measurements and sampling campaigns were carried out both in Antarctica and in the Arctic since 2005.The main results are here reported. As regard as Antarctica, a continuous all-year-round sampling of size-segregated aerosol was carried from 2005 to 2013 at Dome C (East Antarctica; 75° 60' S, 123° 200' E, 3220 m a.s.l. and 1100 km away from the nearest coast). Aerosol was collected by PM10 and PM2.5 samplers and by multi-stage impactors (Dekati 4-stage impactor). Chemical analysis was carried out by Ion Chromatography (ions composition) and ICP-MS (trace metals). Sea spray showed a sharp seasonal pattern, with winter (Apr-Nov) concentrations about ten times larger than summer (Dec-Mar). Besides, in winter, sea spray particles are mainly sub micrometric, while the summer size-mode is around 1-2 um. Meteorological analysis and air mass back trajectory reconstructions allowed the identification of two major air mass pathways: micrometric fractions for transport from the closer Indian-Pacific sector, and sub-micrometric particles for longer trajectories over the Antarctic Plateau. The markers of oceanic biogenic emission (methanesulfonic acid - MSA, and non-sea-salt sulphate) exhibit a seasonal cycle with summer maxima (Nov-Mar). Their size distributions show two modes (0.4- 0.7 um and 1.1-2.1 um) in early summer and just one sub-micrometric mode in full summer. The two modes are related to different transport pathways. In early summer, air masses came primarily from the Indian Ocean and spent a long time over the continent. The transport of sulphur compounds is related to sea spray aerosols and the resulting condensation of H2SO4 and MSA over

  9. Chemical characterization of aerosol particles by laser Raman spectroscopy. Revision

    SciTech Connect

    Fung, K.H.

    1999-12-01

    The importance of aerosol particles in many branches of science, such as atmospheric chemistry, combustion, interfacial science, and material processing, has been steadily growing during the past decades. One of the unique properties of these particles is the very high surface-to-volume ratios, thus making them readily serve as centers for gas-phase condensation and heterogeneous reactions. These particles must be characterized by size, shape, physical state, and chemical composition. Traditionally, optical elastic scattering has been applied to obtain the physical properties of these particle (e.g., particle size, size distribution, and particle density). These physical properties are particularly important in atmospheric science as they govern the distribution and transport of atmospheric aerosols.

  10. Chemical Speciation of PM-2.5 Collected During Prescribed Burns of the Coconino National Forest

    NASA Astrophysics Data System (ADS)

    Robinson, M.; Chavez, J.; Valazquez, S.

    2001-12-01

    In 1997, the EPA promulgated regulations for fine particulate matter (PM-2.5) due to concerns that PM-2.5 can contribute to pulmonary disease. A major source of PM-2.5 is smoke from forest fires (natural or prescribed). The use of prescribed fire is expected to increase in the next decade as a method for restoring wildland ecosystems. The fire-suppression policy of the past century has left forests overgrown with heavy fuel loads, increasing the likelihood of catastrophic fire. Prescribed fire, combined with mechanical thinning, is a method-of-choice to reduce this fuel load. The apparent conflict between the intentional use of fire and air quality can be addressed by increasing our understanding of PM-2.5 and its toxicity. To this end, we will monitor the chemical composition of PM-2.5 generated during three prescribed fires of the Coconino National Forest in October 2001. PM-2.5 will be collected using a battery-operated chemical speciation sampler (MetOne SuperSASS) positioned to collect smoke during the fire. Samples will be taken during the ignition and combustion phases, as well as the day after the burn. Each sampling period will collect 3 filters (PTFE, nylon + MgO denuder, and quartz), which will be analyzed (Research Triangle International) respectively for mass and elements, ions, and total, organic, and elemental carbon. In addition, a fourth PTFE filter will be collected and analyzed at NAU for lead isotope ratios using inductively-coupled plasma mass spectrometry. Results will be correlated to meteorological factors collected during the burns (relative humidity, wind speed, air stability, and surface temperature, etc.) and to characteristics of the burn itself (fuel load, fuel type, fire type, combustion phase, etc.). Results will be compared to the national database collected in EPA's PM-2.5 speciation trends monitoring network (STN).

  11. Chemical behavior of Cu, Zn, Cd, and Pb in a eutrophic reservoir: speciation and complexation capacity.

    PubMed

    Tonietto, Alessandra Emanuele; Lombardi, Ana Teresa; Choueri, Rodrigo Brasil; Vieira, Armando Augusto Henriques

    2015-10-01

    This research aimed at evaluating cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn) speciation in water samples as well as determining water quality parameters (alkalinity, chlorophyll a, chloride, conductivity, dissolved organic carbon, dissolved oxygen, inorganic carbon, nitrate, pH, total suspended solids, and water temperature) in a eutrophic reservoir. This was performed through calculation of free metal ions using the chemical equilibrium software MINEQL+ 4.61, determination of labile, dissolved, and total metal concentrations via differential pulse anodic stripping voltammetry, and determination of complexed metal by the difference between the total concentration of dissolved and labile metal. Additionally, ligand complexation capacities (CC), such as the strength of the association of metals-ligands (logK'ML) and ligand concentrations (C L) were calculated via Ruzic's linearization method. Water samples were taken in winter and summer, and the results showed that for total and dissolved metals, Zn > Cu > Pb > Cd concentration. In general, higher concentrations of Cu and Zn remained complexed with the dissolved fraction, while Pb was mostly complexed with particulate materials. Chemical equilibrium modeling (MINEQL+) showed that Zn(2+) and Cd(2+) dominated the labile species, while Cu and Pb were complexed with carbonates. Zinc was a unique metal for which a direct relation between dissolved species with labile and complexed forms was obtained. The CC for ligands indicated a higher C L for Cu, followed by Pb, Zn, and Cd in decreasing amounts. Nevertheless, the strength of the association of all metals and their respective ligands was similar. Factor analysis with principal component analysis as the extraction procedure confirmed seasonal effects on water quality parameters and metal speciation. Total, dissolved, and complexed Cu and total, dissolved, complexed, and labile Pb species were all higher in winter, whereas in summer, Zn was mostly present in the

  12. Heavy metals and its chemical speciation in sewage sludge at different stages of processing.

    PubMed

    Tytła, Malwina; Widziewicz, Kamila; Zielewicz, Ewa

    2016-04-01

    The analysis of heavy metal concentrations and forms in sewage sludge constitutes an important issue in terms of both health and environmental hazards the metals pose. The total heavy metals concentration enables only the assessment of its contamination. Hence the knowledge of chemical forms is required to determine their environmental mobility and sludge final disposal. Heavy metals speciation was studied by using four-stage sequential extraction BCR (Community Bureau of Reference). This study was aimed at determining the total concentration of selected heavy metals (Zn, Cu, Ni, Pb, Cd, Cr and Hg) and their chemical forms (except for Hg) in sludge collected at different stages of its processing at two municipal Wastewater Treatment Plants in southern Poland. Metals contents in sludge samples were determined by using flame atomic absorption spectrometry (FAAS) and electrothermal atomic absorption spectrometry (ETAAS). This study shows that Zn and Cu appeared to be the most abundant in sludge, while Cd and Hg were in the lowest concentrations. The sewage sludge revealed the domination of immobile fractions over the mobile ones. The oxidizable and residual forms were dominant for all the heavy metals. There was also a significant difference in metals speciation between sludges of different origin which was probably due to differences in wastewater composition and processes occurring in biological stage of wastewater treatment. The results indicate a negligible capability of metals to migrate from sludge into the environment. Our research revealed a significant impact of thickening, stabilization and hygienization on the distribution of heavy metals in sludge and their mobility. PMID:26419833

  13. Uncertainties of simulated aerosol optical properties induced by assumptions on aerosol physical and chemical properties: an AQMEII-2 perspective

    EPA Science Inventory

    The calculation of aerosol optical properties from aerosol mass is a process subject to uncertainty related to necessary assumptions on the treatment of the chemical species mixing state, density, refractive index, and hygroscopic growth. In the framework of the AQMEII-2 model in...

  14. Levels and Speciation of Platinum in Size-Fractionated Atmospheric Aerosol in Urban and Rural Sites across Europe

    NASA Astrophysics Data System (ADS)

    Shafer, Martin; Antkiewicz, Dagmara; Overdier, Joel; Schauer, James

    2016-04-01

    In this study we characterized the levels and speciation of platinum in a unique set of size-resolved atmospheric aerosol (PM) samples obtained from urban environments across Europe. From April-July 2012 we collected PM from roadside canyon, roadside motorway, and background urban sites in each of six European cities (Amsterdam, Frankfurt, London, Milan, Stockholm, and Thessaloniki). A Hi-Vol sampler was used to collect PM in three size classes (>PM7, PM7-PM3, PM3) and characterized for total platinum, soluble platinum (in a suite of physiologically relevant fluids - lung fluid (ALF), Gambles saline, 0.07M HCl, and MQ) and speciated forms (colloidal and anionic) within the soluble fractions. In addition we measured 50 other elements by SF-ICPMS, soluble ions by IC, and soluble organic carbon in the PM. Order-of-magnitude differences in air concentrations of total platinum were observed between urban sites, ranging from 4 to over 45 pg/m3; with a median level of 6 pg/m3. When platinum concentrations are normalized to PM mass the cross Europe and site-to-site variability was substantially reduced - a 3-fold variation from 200 to 600 ng/g was observed. Roadside canyon sites in London, Stockholm and Thessaloniki exhibited the highest concentrations; however levels at urban background sites were remarkably similar across the cities. Relatively consistent and low concentrations (1 to 2 pg/m3) of total platinum were observed at rural background sites across Europe. The contribution of coarse particles (>7 micron and 7-3 micron) to air concentrations of total platinum was very significant (>35% at nearly all sites). Soluble platinum fractions ranged from 2 to 6% (MQ to HCl) in rural background sites to 5 to 20% (MQ to HCl) in roadway canyon sites in London and Thessaloniki; with the extractable platinum fractions a strong function of pH. With the exception of urban canyon sites in London and Thessaloniki, soluble platinum concentrations in the fine aerosol (PM3) were all

  15. Expert judgment and occupational hygiene: application to aerosol speciation in the nickel primary production industry.

    PubMed

    Ramachandran, Gurumurthy; Banerjee, Sudipto; Vincent, James H

    2003-08-01

    In many situations characterized by sparse data, occupational hygienists have used subjective judgments that are claimed to be derived from their experience and knowledge. While this practice is widespread, there has been no systematic study of 'expert judgment' or the 'art' of occupational hygiene. Indeed, there is a need to address the question of whether there is such a thing as 'expert opinion' in occupational hygiene that is broadly shared by practicing professionals. This research, employing 11 experts who estimate an exposure parameter (the percentages of four nickel species) in 12 workplaces in a nickel primary production industry, provides a large dataset from which useful inferences can be drawn about the quality of expert judgments and the variability among the experts. A well-designed questionnaire that provided succinct information about the processes and baseline data served to calibrate the experts. The Bayesian framework has been used in this work to develop posterior means and standard deviations of the percentages of the four nickel species in the 12 workplaces of interest in the company. These estimates of the nickel speciation are at least as precise as--and most of the time more precise than--those provided by the sparse measurement data. There was a very high degree of agreement among the experts. A majority of the experts agreed among themselves 92% of the time, while almost two-thirds agreed 73% of the time. This, coupled with the fact that the experts came from varied backgrounds, seems to suggest that there is indeed some broad body of specialized knowledge that the experts are drawing on to reach similar judgments. It also seems that one type of expert is not necessarily any better than any other kind, and expertise does not necessarily require intimate familiarity with the workplace. In this example, the expert judgment exercise has indeed enhanced the quality of our knowledge of the exposure 'fingerprints' for the nickel industry

  16. Impact of Environmentally Based Chemical Hardness on Uranium Speciation and Toxicity in Six Aquatic Species

    PubMed Central

    Goulet, Richard R; Thompson, Patsy A; Serben, Kerrie C; Eickhoff, Curtis V

    2015-01-01

    Treated effluent discharge from uranium (U) mines and mills elevates the concentrations of U, calcium (Ca), magnesium (Mg), and sulfate (SO42–) above natural levels in receiving waters. Many investigations on the effect of hardness on U toxicity have been experiments on the combined effects of changes in hardness, pH, and alkalinity, which do not represent water chemistry downstream of U mines and mills. Therefore, more toxicity studies with water chemistry encountered downstream of U mines and mills are necessary to support predictive assessments of impacts of U discharge to the environment. Acute and chronic U toxicity laboratory bioassays were realized with 6 freshwater species in waters of low alkalinity, circumneutral pH, and a range of chemical hardness as found in field samples collected downstream of U mines and mills. In laboratory-tested waters, speciation calculations suggested that free uranyl ion concentrations remained constant despite increasing chemical hardness. When hardness increased while pH remained circumneutral and alkalinity low, U toxicity decreased only to Hyalella azteca and Pseudokirchneriella subcapitata. Also, Ca and Mg did not compete with U for the same uptake sites. The present study confirms that the majority of studies concluding that hardness affected U toxicity were in fact studies in which alkalinity and pH were the stronger influence. The results thus confirm that studies predicting impacts of U downstream of mines and mills should not consider chemical hardness. PMID:25475484

  17. Direct Measurement and Chemical Speciation of Top Ring Zone Liquid During Engine Operation

    SciTech Connect

    Splitter, Derek A; Burrows, Barry Clay; Lewis Sr, Samuel Arthur

    2015-01-01

    The present manuscript consists of proof of concept experiments involving direct measurements and detailed chemical speciation from the top ring zone of a running engine. The work uses a naturally aspirated single cylinder utility engine that has been modified to allow direct liquid sample acquisition from behind the top ring. Samples were analyzed and spectated using gas chromatographic techniques. Results show that the liquid mixture in the top ring zone is neither neat lubricant nor fuel but a combination of the two with unique chemical properties. At the tested steady state no-load operating condition, the chemical species of the top ring zone liquid were found to be highly dependent on boiling point, where both low reactivity higher boiling point fuel species and lubricant are observed to be the dominant constituents. The results show that at least for the tested condition, approximately 25% of the top ring zone is comprised of gasoline fuel like molecules, which are dominated by high octane number aromatic species, while the remainder of the liquid is comprised of lubricant like species.

  18. Chemical Characterization of Submicron Aerosol Particles in São Paulo, Brazil

    NASA Astrophysics Data System (ADS)

    Ferreira De Brito, J.; Rizzo, L. V.; Godoy, J.; Godoy, M. L.; de Assunção, J. V.; Alves, N. D.; Artaxo, P.

    2013-12-01

    Megacities, large urban conglomerates with a population of 10 million or more inhabitants, are increasingly receiving attention as strong pollution hotspots with significant global impact. The emissions from such large centers in both the developed and developing parts of the world are strongly impacted by the transportation sector. The São Paulo Metropolitan Area (SPMA), located in the Southeast of Brazil, is a megacity with a population of 18 million people and 7 million vehicles, many of which fuelled by a considerably amount of anhydrous ethanol. Such fleet is considered a unique case of large scale biofuel usage worldwide. Despite the large impact on human health and atmospheric chemistry/dynamics, many uncertainties are found in terms of gas and particulate matter emissions from vehicles and their atmospheric reactivity, e.g. secondary organic aerosol formation. In order to better understand aerosol life cycle on such environment, a suite of instruments for gas and particulate matter characterization has been deployed in two sampling sites within the SPMA, including an Aerosol Chemical Speciation Monitor (ACSM). The instrumentation was deployed at the rooftop of a 45m high building in the University of São Paulo during winter/spring 2012. The site is located roughly 6km downwind of the city center with little influence from local sources. The second site is located in a downtown area, sampling at the top floor of the Public Health Faculty, approximately 10m above ground. The instrumentation was deployed at the Downtown site during summer/fall 2013. The average non-refractory submicron aerosol concentration at the University site was 6.7 μg m-3, being organics the most abundant specie (70%), followed by NO3 (12%), NH4 (8%), SO4 (8%) and Chl (2%). At the Downtown site, average aerosol concentration was 15.1 μg m-3, with Organics composing 65% of the mass, followed by NH4 (12%), NO3 (11%), SO4 (11%) and Chl (1%). The analysis of specific fragmentation

  19. Chemical characterization of Brown Carbon from biomass burning aerosols

    NASA Astrophysics Data System (ADS)

    Mayol-Bracero, O. L.; Andreae, M. O.; Andreae, T. W.; Artaxo, P.; Gelencser, A.; Graham, B.; Guyon, P.; Maenhaut, W.

    2003-04-01

    The term "elemental carbon" (EC) is used to describe the most polymerized and refractory fraction of combustion-produced atmospheric carbonaceous aerosols, having chemical properties similar to graphitic carbon (disordered graphite lattice, mostly with carbon, but also with some oxygen and hydrogen atoms, and highly resistant to thermal degradation and oxidation). This species is insoluble either in water or organic solvents. In evolved gas analysis (EGA), it is usually represented by the peak evolving above ca. 400 ^oC in the thermograms. EGA analyses before and after water extraction have shown that in samples from biomass burning aerosols ca. 50% of the material evolving above 400 ^oC was removed by extraction with water and therefore was not true EC. These results suggest that this apparent EC (EC_a) is high-molecular weight organic material with thermal and oxidative properties similar to EC. This EC_a material also absorbs light, therefore, we have adopted the term of "brown carbon" (Cbrown) to refer to it. Here we will present a detailed chemical characterization of EC_a and Cbrown using EGA, optical transmission, thermo-optical analysis and pyrolysis GC/MS. This last technique will provide, for the first time, molecular characterization of Cbrown. The results of these analytical techniques will improve our understanding of the chemical, thermal and oxidative properties of true EC, EC_a and Cbrown from biomass burning aerosols. Brown carbon can be formed both during thermal decomposition of organic matter (charring) and through low-temperature microbial and abiotic reactions (humic/fulvic acids).

  20. Aerosol chemical vapor deposition of metal oxide films

    DOEpatents

    Ott, Kevin C.; Kodas, Toivo T.

    1994-01-01

    A process of preparing a film of a multicomponent metal oxide including: forming an aerosol from a solution comprised of a suitable solvent and at least two precursor compounds capable of volatilizing at temperatures lower than the decomposition temperature of said precursor compounds; passing said aerosol in combination with a suitable oxygen-containing carrier gas into a heated zone, said heated zone having a temperature sufficient to evaporate the solvent and volatilize said precursor compounds; and passing said volatilized precursor compounds against the surface of a substrate, said substrate having a sufficient temperature to decompose said volatilized precursor compounds whereby metal atoms contained within said volatilized precursor compounds are deposited as a metal oxide film upon the substrate is disclosed. In addition, a coated article comprising a multicomponent metal oxide film conforming to the surface of a substrate selected from the group consisting of silicon, magnesium oxide, yttrium-stabilized zirconium oxide, sapphire, or lanthanum gallate, said multicomponent metal oxide film characterized as having a substantially uniform thickness upon said FIELD OF THE INVENTION The present invention relates to the field of film coating deposition techniques, and more particularly to the deposition of multicomponent metal oxide films by aerosol chemical vapor deposition. This invention is the result of a contract with the Department of Energy (Contract No. W-7405-ENG-36).

  1. Quantification of aerosol chemical composition using continuous single particle measurements

    NASA Astrophysics Data System (ADS)

    Jeong, C.-H.; McGuire, M. L.; Godri, K. J.; Slowik, J. G.; Rehbein, P. J. G.; Evans, G. J.

    2011-07-01

    Mass concentrations of sulphate, nitrate, ammonium, organic carbon (OC), elemental carbon (EC) were determined from real time single particle data in the size range 0.1-3.0 μm measured by an Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) at urban and rural sites in Canada. To quantify chemical species within individual particles measured by an ATOFMS, ion peak intensity of m/z -97 for sulphate, -62 for nitrate, +18 for ammonium, +43 for OC, and +36 for EC were scaled using the number and size distribution data by an Aerodynamic Particle Sizer (APS) and a Fast Mobility Particle Sizer (FMPS). Hourly quantified chemical species from ATOFMS single-particle analysis were compared with collocated fine particulate matter (aerodynamic diameter < 2.5 μm, PM2.5) chemical composition measurements by an Aerosol Mass Spectrometer (AMS) at a rural site, a Gas-Particle Ion Chromatograph (GPIC) at an urban site, and a Sunset Lab field OCEC analyzer at both sites. The highest correlation was found for nitrate, with correlation coefficients (Pearson r) of 0.89 (ATOFMS vs. GPIC) and 0.85 (ATOFMS vs. AMS). ATOFMS mass calibration factors, determined for the urban site, were used to calculate mass concentrations of the major PM2.5 chemical components at the rural site near the US border in southern Ontario. Mass reconstruction using the ATOFMS mass calibration factors agreed very well with the PM2.5 mass concentrations measured by a Tapered Element Oscillating Microbalance (TEOM, r = 0.86) at the urban site and a light scattering monitor (DustTrak, r = 0.87) at the rural site. In the urban area nitrate was the largest contributor to PM2.5 mass in the winter, while organics and sulphate contributed ~64 % of the summer PM2.5 in the rural area, suggesting a strong influence of regional/trans-boundary pollution. The mass concentrations of five major species in ten size-resolved particle-types and aerosol acidity of each particle-type were determined for the rural site. On a mass basis

  2. Aerosol chemical components in Alaska air masses: 1. Aged pollution

    NASA Astrophysics Data System (ADS)

    Shaw, Glenn E.

    1991-12-01

    A 4-year Alaska chemical data set of aerosols or "dust" in the air clearly reveals a mixture of distinct aerosol components with different and interesting chemical composition, one or two being ascribed to pollution imported to Alaska by winds all the way from other continents. Of particular note is a strong chemical contrast between what we imagine to be highly scavenged, orographically lifted, northern Pacific air (Pacific marine air mass) and stagnant Arctic air (polar air mass), the latter containing seasonal average concentrations of between 2-4 times the concentration of the former, at least for pollution markers noncrustal vanadium, noncrustal manganese, arsenic, selenium, bromine, and antimony. The findings concur our old discovery that Arctic air is persistently polluted (Arctic haze), but Pacific air is relatively clean, in spite of the fact that Alaska is downwind of major pollution sources in the Orient. This is remarkable. In this the first of a two-part paper, we concentrate on the pollution component found primarily during incursion of Arctic polar air. Two major occurrences of visual haze with optical depths of approximately 0.2 and elevated aerosol concentration lasting about a month (spring 1985 and 1986) were affiliated with strong incoming transport of polar air, temperatures ranging from 10° to 20°C below normal (polar air) and air trajectory hindcasts leading back to industrial pollution sources in Eurasia. These long-range transport pollution events brought metal-rich aerosol of removal-resistant submicron particles. The size, chemistry, and meteorology all strongly suggest the presence of a well-aged (10-100 day) polluted air mass. An important implication is that in spring a large fraction of the Arctic polar air mass becomes charged with by-products of industrial pollution. In this multiyear chemical data set one finds a notable summer-winter contrast, changing by factors of 2 to 4 for pollution markers As, Se, Sb, and noncrustal

  3. Polycyclic Aromatic Aerosol Components: Chemical Analysis and Reactivity

    NASA Astrophysics Data System (ADS)

    Schauer, C.; Niessner, R.; Pöschl, U.

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants in the atmosphere and originate primarily from incomplete combustion of organic matter and fossil fuels. Their main sources are anthropogenic (e.g. vehicle emissions, domes- tic heating or tobacco smoke), and PAHs consisting of more than four fused aromatic rings reside mostly on combustion aerosol particles, where they can react with atmo- spheric trace gases like O3, NOx or OH radicals leading to a wide variety of partially oxidized and nitrated derivatives. Such chemical transformations can strongly affect the activity of the aerosol particles as condensation nuclei, their atmospheric residence times, and consequently their direct and indirect climatic effects. Moreover some poly- cyclic aromatic compounds (PACs = PAHs + derivatives) are known to have a high carcinogenic, mutagenic and allergenic potential, and are thus of major importance in air pollution control. Furthermore PACs can be used as well defined soot model sub- stances, since the basic structure of soot can be regarded as an agglomerate of highly polymerized PAC-layers. For the chemical analysis of polycyclic aromatic aerosol components a new analyti- cal method based on LC-APCI-MS has been developed, and a data base comprising PAHs, Oxy-PAHs and Nitro-PAHs has been established. Together with a GC-HRMS method it will be applied to identify and quantify PAHs and Nitro-PAHs in atmo- spheric aerosol samples, diesel exhaust particle samples and model soot samples from laboratory reaction kinetics and product studies. As reported before, the adsorption and surface reaction rate of ozone on soot and PAH-like particle surfaces is reduced by competitive adsorption of water vapor at low relative humidity (< 25 %). Recent results at higher relative humidities (ca. 50 %), however, indicate re-enhanced gas phase ozone loss, which may be due to absorbtion of ozone into an aqueous surface layer. The interaction of ozone and nitrogen

  4. Hygroscopic, Morphological, and Chemical Properties of Agricultural Aerosols

    NASA Astrophysics Data System (ADS)

    Hiranuma, N.; Brooks, S. D.; Cheek, L.; Thornton, D. C.; Auvermann, B. W.; Littleton, R.

    2007-12-01

    Agricultural fugitive dust is a significant source of localized air pollution in the semi-arid southern Great Plains. In the Texas Panhandle, daily episodes of ground-level fugitive dust emissions from the cattle feedlots are routinely observed in conjunction with increased cattle activity in the late afternoons and early evenings. We conducted a field study to characterize size-selected agricultural aerosols with respect to hygroscopic, morphological, and chemical properties and to attempt to identify any correlations between these properties. To explore the hygroscopic nature of agricultural particles, we have collected size-resolved aerosol samples using a cascade impactor system at a cattle feedlot in the Texas Panhandle and have used the Environmental Scanning Electron Microscope (ESEM) to determine the water uptake by individual particles in those samples as a function of relative humidity. To characterize the size distribution of agricultural aerosols as a function of time, A GRIMM aerosol spectrometer and Sequential Mobility Particle Sizer and Counter (SMPS) measurements were simultaneously performed in an overall size range of 11 nm to 20 µm diameters at a cattle feedlot. Complementary determination of the elemental composition of individual particles was performed using Energy Dispersive X-ray Spectroscopy (EDS). In addition to the EDS analysis, an ammonia scrubber was used to collect ammonia and ammonium in the gas and particulate phases, respectively. The concentration of these species was quantified offline via UV spectrophotometry at 640 nanometers. The results of this study will provide important particulate emission data from a feedyard, needed to improve our understanding of the role of agricultural particulates in local and regional air quality.

  5. Modeling regional secondary organic aerosol using the Master Chemical Mechanism

    NASA Astrophysics Data System (ADS)

    Li, Jingyi; Cleveland, Meredith; Ziemba, Luke D.; Griffin, Robert J.; Barsanti, Kelley C.; Pankow, James F.; Ying, Qi

    2015-02-01

    A modified near-explicit Master Chemical Mechanism (MCM, version 3.2) with 5727 species and 16,930 reactions and an equilibrium partitioning module was incorporated into the Community Air Quality Model (CMAQ) to predict the regional concentrations of secondary organic aerosol (SOA) from volatile organic compounds (VOCs) in the eastern United States (US). In addition to the semi-volatile SOA from equilibrium partitioning, reactive surface uptake processes were used to simulate SOA formation due to isoprene epoxydiol, glyoxal and methylglyoxal. The CMAQ-MCM-SOA model was applied to simulate SOA formation during a two-week episode from August 28 to September 7, 2006. The southeastern US has the highest SOA, with a maximum episode-averaged concentration of ∼12 μg m-3. Primary organic aerosol (POA) and SOA concentrations predicted by CMAQ-MCM-SOA agree well with AMS-derived hydrocarbon-like organic aerosol (HOA) and oxygenated organic aerosol (OOA) urban concentrations at the Moody Tower at the University of Houston. Predicted molecular properties of SOA (O/C, H/C, N/C and OM/OC ratios) at the site are similar to those reported in other urban areas, and O/C values agree with measured O/C at the same site. Isoprene epoxydiol is predicted to be the largest contributor to total SOA concentration in the southeast US, followed by methylglyoxal and glyoxal. The semi-volatile SOA components are dominated by products from β-caryophyllene oxidation, but the major species and their concentrations are sensitive to errors in saturation vapor pressure estimation. A uniform decrease of saturation vapor pressure by a factor of 100 for all condensable compounds can lead to a 150% increase in total SOA. A sensitivity simulation with UNIFAC-calculated activity coefficients (ignoring phase separation and water molecule partitioning into the organic phase) led to a 10% change in the predicted semi-volatile SOA concentrations.

  6. Chemical Speciation of Strontium, Americium, and Curium in High Level Waste: Predictive Modeling of Phase Partitioning During Tank Processing

    SciTech Connect

    Felmy, Andrew R.; Choppin, Gregory; Dixon, David A.; Campbell, James A.

    1999-06-01

    In this research program, Pacific Northwest National Laboratory (PNNL) and Florida State University (FSU) are investigating the speciation of strontium and americium/curium in the presence of selected organic chelating agents (ethylenediaminetetraacetic acid (EDTA), N-(2-hydroxyethyl) aethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), and iminodiacetic acid (IDA)) over ranges of hydroxide, carbonate, ionic strength, and competing metal ion concentrations present in high-level waste tanks. The project is composed of integrated research tasks that approach the problem of chemical speciation using macroscopic thermodynamic measurements of metal-ligand competition reactions, molecular modeling studies to identify structures or complexes of unusual stability, and mass spectrometry measurements of complex charge/mass ratio that can be applied to mixed metal-chelate systems. This fundamental information is then used to develop thermodynamic models, which allow the prediction of changes in chemical speciation and solubility that can occur in response to changes in tank processing conditions. In this way, we can develop new approaches that address fundamental problems in aqueous speciation and at the same time provide useful and practical information needed for tank processing.

  7. Properties and sources of individual particles and some chemical species in the aerosol of a metropolitan underground railway station

    NASA Astrophysics Data System (ADS)

    Salma, Imre; Pósfai, Mihály; Kovács, Kristóf; Kuzmann, Ernő; Homonnay, Zoltán; Posta, József

    Aerosol samples in PM 10-2.0 and PM 2.0 size fractions were collected on the platform of a metropolitan underground railway station in central Budapest. Individual aerosol particles were studied using atomic force microscopy, scanning electron microscopy and transmission electron microscopy with energy-dispersive X-ray spectrometry and electron diffraction. The bulk aerosol samples were investigated by 57Fe Mössbauer spectroscopy, and they were subjected to chemical speciation analysis for Cr. The particles were classified into groups of iron oxides and iron, carbonates, silicates, quartz and carbonaceous debris. Electron micrographs showed that the Fe-rich particles in the PM 2.0 size fraction typically consisted of aggregates of nano-sized hematite crystals that were randomly oriented, had round shapes and diameters of 5-15 nm. In addition to hematite, a minor fraction of the iron oxide particles also contained magnetite. In addition, the PM 2.0-fraction particles typically had a rugged surface with layered or granular morphologies. Mössbauer spectroscopy suggested that hematite was a major Fe-bearing species in the PM 10-2.0 size fraction; its mass contribution to the Fe was 36%. Further constituents (ferrite, carbides and FeOOH) were also identified. The water soluble amounts of Cr for the underground railway station and city center were similar. In the PM 10-2.0 size fraction, practically all dissolved Cr had an oxidation state of three, which corresponds to ambient conditions. In the PM 2.0 size fraction, however, approximately 7% of the dissolved Cr was present as Cr(VI), which was different from that for the urban aerosol. It is suggested that the increased adverse health effects of aerosol particles in metros with respect to ambient outdoor particles is linked to the differences in the oxidation states, surface properties or morphologies.

  8. Seasonal characterization of submicron aerosol chemical composition and organic aerosol sources in the southeastern United States: Atlanta, Georgia,and Look Rock, Tennessee

    NASA Astrophysics Data System (ADS)

    Hapsari Budisulistiorini, Sri; Baumann, Karsten; Edgerton, Eric S.; Bairai, Solomon T.; Mueller, Stephen; Shaw, Stephanie L.; Knipping, Eladio M.; Gold, Avram; Surratt, Jason D.

    2016-04-01

    A year-long near-real-time characterization of non-refractory submicron aerosol (NR-PM1) was conducted at an urban (Atlanta, Georgia, in 2012) and rural (Look Rock, Tennessee, in 2013) site in the southeastern US using the Aerodyne Aerosol Chemical Speciation Monitor (ACSM) collocated with established air-monitoring network measurements. Seasonal variations in organic aerosol (OA) and inorganic aerosol species are attributed to meteorological conditions as well as anthropogenic and biogenic emissions in this region. The highest concentrations of NR-PM1 were observed during winter and fall seasons at the urban site and during spring and summer at the rural site. Across all seasons and at both sites, NR-PM1 was composed largely of OA (up to 76 %) and sulfate (up to 31 %). Six distinct OA sources were resolved by positive matrix factorization applied to the ACSM organic mass spectral data collected from the two sites over the 1 year of near-continuous measurements at each site: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), semi-volatile oxygenated OA (SV-OOA), low-volatility oxygenated OA (LV-OOA), isoprene-derived epoxydiols (IEPOX) OA (IEPOX-OA) and 91Fac (a factor dominated by a distinct ion at m/z 91 fragment ion previously observed in biogenic influenced areas). LV-OOA was observed throughout the year at both sites and contributed up to 66 % of total OA mass. HOA was observed during the entire year only at the urban site (on average 21 % of OA mass). BBOA (15-33 % of OA mass) was observed during winter and fall, likely dominated by local residential wood burning emission. Although SV-OOA contributes quite significantly ( ˜ 27 %), it was observed only at the urban site during colder seasons. IEPOX-OA was a major component (27-41 %) of OA at both sites, particularly in spring and summer. An ion fragment at m/z 75 is well correlated with the m/z 82 ion associated with the aerosol mass spectrum of IEPOX-derived secondary organic aerosol (SOA). The

  9. Influence of clinoptilolite rock on chemical speciation of selected heavy metals in sewage sludge.

    PubMed

    Sprynskyy, M; Kosobucki, P; Kowalkowski, T; Buszewski, B

    2007-10-22

    The chemical speciation of Cd, Cu, Pb, Cr and Ni in Torun municipal sewage sludge is investigated with addition of a natural sorbent (clinoptilolite rock). The total contents of the heavy metals in the sludge are substantially lower than the corresponding limits established by European or Polish legislation excepting nickel only. But the metals concentrations excepting lead exceed significantly the natural background (average contents in soils and in the Earth's crust) in dozens. Application of the sequential chemical extraction indicated that the metals in the sewage sludge are bound mainly (over 50%) in the residual fraction. The metals form the following order by parts of the mobile form: Ni> Cd> Cr> Cu> Pb. Addition of the clinoptilolite to the sludge leads to the metals contents fall in all four fractions of the sequential procedure. Concentrations of mobile forms of cadmium, chromium, copper and nickel decrease by 87, 64, 35 and 24%, respectively, as a result of addition of 9.09% of the clinoptilolite. The total decreases of the metals amount after 9.09% clinoptilolite addition to the sludge are around 11, 15, 25, 41 and 51% for copper, nickel, chromium, cadmium and lead, respectively. PMID:17513045

  10. Gas uptake and chemical aging of semisolid organic aerosol particles

    PubMed Central

    Shiraiwa, Manabu; Ammann, Markus; Koop, Thomas; Pöschl, Ulrich

    2011-01-01

    Organic substances can adopt an amorphous solid or semisolid state, influencing the rate of heterogeneous reactions and multiphase processes in atmospheric aerosols. Here we demonstrate how molecular diffusion in the condensed phase affects the gas uptake and chemical transformation of semisolid organic particles. Flow tube experiments show that the ozone uptake and oxidative aging of amorphous protein is kinetically limited by bulk diffusion. The reactive gas uptake exhibits a pronounced increase with relative humidity, which can be explained by a decrease of viscosity and increase of diffusivity due to hygroscopic water uptake transforming the amorphous organic matrix from a glassy to a semisolid state (moisture-induced phase transition). The reaction rate depends on the condensed phase diffusion coefficients of both the oxidant and the organic reactant molecules, which can be described by a kinetic multilayer flux model but not by the traditional resistor model approach of multiphase chemistry. The chemical lifetime of reactive compounds in atmospheric particles can increase from seconds to days as the rate of diffusion in semisolid phases can decrease by multiple orders of magnitude in response to low temperature or low relative humidity. The findings demonstrate that the occurrence and properties of amorphous semisolid phases challenge traditional views and require advanced formalisms for the description of organic particle formation and transformation in atmospheric models of aerosol effects on air quality, public health, and climate. PMID:21690350

  11. Chemical Speciation of Sulfur in Marine Cloud Droplets and Particles: Analysis of Individual Particles from Marine Boundary Layer over the California Current

    SciTech Connect

    William R. Wiley Environmental Sciences Laboratory, Pacific Northwest National Laboratory; Gilles, Mary K; Hopkins, Rebecca J.; Desyaterik, Yury; Tivanski, Alexei V.; Zaveri, Rahul A.; Berkowitz, Carl M.; Tyliszczak, Tolek; Gilles, Mary K.; Laskin, Alexander

    2008-03-12

    Detailed chemical speciation of the dry residue particles from individual cloud droplets and interstitial aerosol collected during the Marine Stratus Experiment (MASE) was performed using a combination of complementary microanalysis techniques. Techniques include computer controlled scanning electron microscopy with energy dispersed analysis of X-rays (CCSEM/EDX), time-of-flight secondary ionization mass spectrometry (TOF-SIMS), and scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Samples were collected at the ground site located in Point Reyes National Seashore, approximately 1 km from the coast. This manuscript focuses on the analysis of individual particles sampled from air masses that originated over the open ocean and then passed through the area of the California current located along the northern California coast. Based on composition, morphology, and chemical bonding information, two externally mixed, distinct classes of sulfur containing particles were identified: chemically modified (aged) sea salt particles and secondary formed sulfate particles. The results indicate substantial heterogeneous replacement of chloride by methanesulfonate (CH3SO3-) and non-sea salt sulfate (nss-SO42-) in sea-salt particles with characteristic ratios of nss-S/Na>0.10 and CH3SO3-/nss-SO42->0.6.

  12. Relationship between redox activity and chemical speciation of size-fractionated particulate matter

    PubMed Central

    Ntziachristos, Leonidas; Froines, John R; Cho, Arthur K; Sioutas, Constantinos

    2007-01-01

    Background Although the mechanisms of airborne particulate matter (PM) related health effects remain incompletely understood, one emerging hypothesis is that these adverse effects derive from oxidative stress, initiated by the formation of reactive oxygen species (ROS) within affected cells. Typically, ROS are formed in cells through the reduction of oxygen by biological reducing agents, with the catalytic assistance of electron transfer enzymes and redox active chemical species such as redox active organic chemicals and metals. The purpose of this study was to relate the electron transfer ability, or redox activity, of the PM samples to their content in polycyclic aromatic hydrocarbons and various inorganic species. The redox activity of the samples has been shown to correlate with the induction of the stress protein, hemeoxygenase-1. Results Size-fractionated (i.e. < 0.15; < 2.5 and 2.5 – 10 μm in diameter) ambient PM samples were collected from four different locations in the period from June 2003 to July 2005, and were chemically analyzed for elemental and organic carbon, ions, elements and trace metals and polycyclic aromatic hydrocarbons. The redox activity of the samples was evaluated by means of the dithiothreitol activity assay and was related to their chemical speciation by means of correlation analysis. Our analysis indicated a higher redox activity on a per PM mass basis for ultrafine (< 0.15 μm) particles compared to those of larger sizes. The PM redox activity was highly correlated with the organic carbon (OC) content of PM as well as the mass fractions of species such as polycyclic aromatic hydrocarbons (PAH), and selected metals. Conclusion The results of this work demonstrate the utility of the dithiothreitol assay for quantitatively assessing the redox potential of airborne particulate matter from a wide range of sources. Studies to characterize the redox activity of PM from various sources throughout the Los Angeles basin are currently

  13. Chemical characterization of springtime submicrometer aerosol in Po Valley, Italy

    NASA Astrophysics Data System (ADS)

    Saarikoski, S.; Carbone, S.; Decesari, S.; Giulianelli, L.; Angelini, F.; Canagaratna, M.; Ng, N. L.; Trimborn, A.; Facchini, M. C.; Fuzzi, S.; Hillamo, R.; Worsnop, D.

    2012-09-01

    The chemistry of submicron particles was investigated at San Pietro Capofiume (SPC) measurement station in the Po Valley, Italy, in spring 2008. The measurements were performed by using both off-line and on-line instruments. Organic carbon (OC) and elemental carbon, organic acids and biomass burning tracers were measured off-line by using a 24-h PM1 filter sampling. More detailed particle chemistry was achieved by using a Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and analyzing the data by positive matrix factorization (PMF). Oxalic acid had the highest concentrations of organic acids (campaign-average 97.4 ng m-3) followed by methane sulfonic, formic, malonic, and malic acids. Samples were also analyzed for glyoxylic, succinic, azelaic and maleic acids. In total, the nine acids composed 1.9 and 3.8% of OC and water-soluble OC, respectively (average), in terms of carbon atoms. Levoglucosan concentration varied from 17.7 to 495 ng m-3 with the concentration decreasing in the course of the campaign most likely due to the reduced use of domestic heating with wood. Six factors were found for organic aerosol (OA) at SPC by PMF: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), nitrogen-containing OA (N-OA) and three different oxygenated OAs (OOA-a, OOA-b and OOA-c). Most of the OA mass was composed of OOA-a, HOA and OOA-c (26, 24 and 22%, respectively) followed by OOA-b (13%), BBOA (8%) and N-OA (7%). As expected, OOAs were the most oxygenated factors with organic matter:organic carbon (OM : OC) ratios ranging from 1.9 to 2.2. The diurnal variability of the aerosol chemical composition was greatly affected by the boundary layer meteorology. Specifically, the effect of the nocturnal layer break-up in morning hours was most evident for nitrate and N-OA indicating that these compounds originated mainly from the local sources in the Po Valley. For sulfate and OOA-a the concentration did not change during the break-up suggesting their

  14. Chemical characterization of springtime submicrometer aerosol in Po Valley, Italy

    NASA Astrophysics Data System (ADS)

    Saarikoski, S.; Carbone, S.; Decesari, S.; Giulianelli, L.; Angelini, F.; Teinilä, K.; Canagaratna, M.; Ng, N. L.; Trimborn, A.; Facchini, M. C.; Fuzzi, S.; Hillamo, R.; Worsnop, D.

    2012-03-01

    The chemistry of submicron particles was investigated at San Pietro Capofiume (SPC) measurement station in the Po Valley, Italy, in spring 2008. The measurements were performed by using both off-line and on-line instruments. Organic carbon (OC) and elemental carbon, organic acids and biomass burning tracers were measured off-line by using a 24-h PM1 filter sampling. More detailed particle chemistry was achieved by using an Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and analyzing the data by positive matrix factorization (PMF). Oxalic acid had the highest concentrations of organic acids (campaign-average 97.4 ng m-3) followed by methane sulfonic, formic, malonic, and malic acids. Samples were also analyzed for glyoxylic, succinic, azelaic and maleic acids. In total, the nine acids composed 1.9 and 3.8% of OC and water-soluble OC, respectively (average), in terms of carbon atoms. Levoglucosan concentration varied from 17.7 to 495 ng m-3 with the concentration decreasing in the course of the campaign most likely due to the reduced use of domestic heating with wood. Six factors were found for organic aerosol (OA) at SPC by PMF: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), nitrogen-containing OA (N-OA) and three different oxygenated OAs (OOA-a, OOA-b and OOA-c). Most of the OA mass was composed of OOA-a, HOA and OOA-c (26, 24 and 22%, respectively) followed by OOA-b (13%), BBOA (8%) and N-OA (7%). As expected, OOAs were the most oxygenated factors with organic matter:organic carbon (OM:OC) ratios ranging from 1.9 to 2.2. The diurnal variability of the aerosol chemical composition was greatly affected by the boundary layer meteorology. Specifically, the effect of the nocturnal layer break-up in morning hours was most evident for nitrate and N-OA indicating that these compounds originated mainly from the local sources in the Po Valley. For sulfate and OOA-a the concentration did not change during the break-up suggesting their

  15. Preliminary Results of Aerosol Chemical Composition Measurements in the Gulf of Maine with an Aerosol Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Middlebrook, A. M.; Canagaratna, M. R.; Worsnop, D. R.

    2002-12-01

    The New England Air Quality Study is a multi-institutional research project to improve understanding of the atmospheric processes that control the production and distribution of air pollutants in the New England region. During July-August, 2002 a large, collaborative, intensive period of atmospheric measurement and model comparisons took place. As part of this study, an Aerosol Mass Spectrometer (AMS) was deployed aboard the NOAA ship RONALD H. BROWN in the Gulf of Maine. The AMS measures semi-volatile components of aerosol particles with aerodynamic diameters between roughly 40 and 1500 nm. During this study, the AMS collected 2-minute averaged particle mass spectra as well as speciated organic, sulfate, and nitrate size distributions. Sodium chloride, sodium sulfate, and sodium nitrate components of the aerosol, which are relatively non-volatile at the AMS heater temperature, were not detected with the AMS. A wide variety of air masses were sampled during the intensive period, including clean marine, clean continental, and polluted continental air masses. In general, the volatile particle composition was mostly organic and sulfate with lesser amounts of nitrate. Furthermore, particle mass loadings typically peaked around 400-600 nm in aerodynamic diameter. Several events with high aerosol organic, sulfate, and/or nitrate mass loadings were observed and the atmospheric processes that cause them will be discussed.

  16. Size-Resolved Volatility and Chemical Composition of Aged European Aerosol Measured During FAME-2008

    NASA Astrophysics Data System (ADS)

    Hildebrandt, L.; Mohr, C.; Lee, B.; Engelhart, G. J.; Decarlo, P. F.; Prevot, A. S.; Baltensperger, U.; Donahue, N. M.; Pandis, S. N.

    2008-12-01

    We present first results on the volatility and chemical composition of aged organic aerosol measured during the Finokalia Aerosol Measurement Experiment - 2008 (FAME-2008). Finokalia is located in the Southeast of Crete, Greece, and this remote site allows for the measurement of aged European aerosol as it is transported from Central to Southeastern Europe. We measured the volatility of the aerosol at Finokalia as a function of its size by combining several instruments. We used an Aerodyne quadrupole aerosol mass spectrometer (Q-AMS) to measure the size-resolved chemical composition of the particles, a scanning mobility particle sizer (SMPS) to measure the volume distribution of particles, and a thermodenuder system to induce changes in size and composition via moderate heating of the particles. The largest fraction of the non-refractory material in the aerosol sampled was ammonium sulfate and ammonium bisulfate, followed by organic material and a small contribution from nitrate. Most of the organic aerosol was highly oxidized, even after only a few days of transport over continental Europe. These highly oxidized organics had lower volatility than fresh primary or secondary aerosol measured in the laboratory. Significant changes in air-parcel trajectories and wind direction led to changes in the chemical composition of the sampled aerosol and corresponding changes of the volatility. These results allow the quantification of the effect of atmospheric processing on organic aerosol volatility and can be used as constraints for atmospheric Chemical Transport Models that predict the aerosol volatility.

  17. Runoff rates, chemical speciation and bioavailability of copper released from naturally patinated copper.

    PubMed

    Karlén, C; Wallinder, I Odnevall; Heijerick, D; Leygraf, C

    2002-01-01

    The release of copper, induced by atmospheric corrosion, from naturally patinated copper of varying age (0 and 30 years) has been investigated together with its potential ecotoxic effect. Results were generated in an interdisciplinary research effort in which corrosion science and ecotoxicology aspects were combined. The aim of the investigation was to elucidate the situation when copper-containing rainwater leaves a roof in terms of runoff rate, chemical speciation, bioavailability and ecotoxicity effects. Data have been collected during a three-year field exposure conducted in the urban environment of Stockholm, Sweden. The potential environmental effects have been evaluated using a combination of a copper specific biosensor test with the bacterium Alcaligenes eutrophus and the conventional 72-h growth inhibition test with the green alga Raphidocelis subcapitata. The results show annual runoff rates between 1.0 and 1.5 g/m2 year for naturally patinated copper of varying age. The runoff rate increased slightly with patina age, which mainly is attributed to the enhanced first flush effect observed on thicker patina layers. The total copper concentration in investigated runoff samplings ranged from 0.9 to 9.7 mg/l. Both computer modeling and experimental studies revealed that the majority (60-100%) of released copper was present as the free hydrated cupric ion, Cu(H2O)6(2+), the most bioavailable copper species. However, other copper species in the runoff water, such as, e.g. Cu(OH)+ and Cu2(OH)2(2+), were also bioavailable. The copper-containing runoff water, sampled directly after release from the roof, caused significant reduction in growth rate of the green alga. It should be emphasized that the results describe the runoff situation immediately after release from the copper roof and not the real environmental ecotoxicity. Therefore the data should only be used as an initial assessment of the potential environmental effect of copper runoff from building

  18. Impact of environmentally based chemical hardness on uranium speciation and toxicity in six aquatic species.

    PubMed

    Goulet, Richard R; Thompson, Patsy A; Serben, Kerrie C; Eickhoff, Curtis V

    2015-03-01

    Treated effluent discharge from uranium (U) mines and mills elevates the concentrations of U, calcium (Ca), magnesium (Mg), and sulfate (SO4 (2-) ) above natural levels in receiving waters. Many investigations on the effect of hardness on U toxicity have been experiments on the combined effects of changes in hardness, pH, and alkalinity, which do not represent water chemistry downstream of U mines and mills. Therefore, more toxicity studies with water chemistry encountered downstream of U mines and mills are necessary to support predictive assessments of impacts of U discharge to the environment. Acute and chronic U toxicity laboratory bioassays were realized with 6 freshwater species in waters of low alkalinity, circumneutral pH, and a range of chemical hardness as found in field samples collected downstream of U mines and mills. In laboratory-tested waters, speciation calculations suggested that free uranyl ion concentrations remained constant despite increasing chemical hardness. When hardness increased while pH remained circumneutral and alkalinity low, U toxicity decreased only to Hyalella azteca and Pseudokirchneriella subcapitata. Also, Ca and Mg did not compete with U for the same uptake sites. The present study confirms that the majority of studies concluding that hardness affected U toxicity were in fact studies in which alkalinity and pH were the stronger influence. The results thus confirm that studies predicting impacts of U downstream of mines and mills should not consider chemical hardness. Environ Toxicol Chem 2015;34:562-574. © 2014 The Authors. Published by Wiley Periodicals, Inc. on behalf of SETAC. PMID:25475484

  19. Chemical Speciation and Quantitative Evaluation of Heavy Metal Pollution Hazards in Two Army Shooting Range Backstop Soils.

    PubMed

    Islam, Mohammad Nazrul; Nguyen, Xuan Phuc; Jung, Ho-Young; Park, Jeong-Hun

    2016-02-01

    The chemical speciation and ecological risk assessment of heavy metals in two shooting range backstop soils in Korea were studied. Both soils were highly contaminated with Cd, Cu, Pb, and Sb. The chemical speciation of heavy metals reflected the present status of contamination, which could help in promoting management practices. We-rye soil had a higher proportion of exchangeable and carbonate bound metals and water-extractable Cd and Sb than the Cho-do soil. Bioavailable Pb represented 42 % of the total Pb content in both soils. A significant amount of Sb was found in the two most bioavailable fractions, amounting to ~32 % in the soil samples, in good agreement with the batch leaching test using water. Based on the values of ecological risk indices, both soils showed extremely high potential risk and may represent serious environmental problems. PMID:26546228

  20. Simulation of aerosol chemical compositions in the Western Mediterranean Sea

    NASA Astrophysics Data System (ADS)

    Chrit, Mounir; Kata Sartelet, Karine; Sciare, Jean; Marchand, Nicolas; Pey, Jorge; Sellegri, Karine

    2016-04-01

    This work aims at evaluating the chemical transport model (CTM) Polair3d of the air-quality modelling platform Polyphemus during the ChArMex summer campaigns of 2013, using ground-based measurements performed at ERSA (Cape Corsica, France), and at determining the processes controlling organic aerosol concentrations at ERSA. Simulations are compared to measurements for concentrations of both organic and inorganic species, as well as the ratio of biogenic versus anthropogenic particles, and organic aerosol properties (oxidation state). For inorganics, the concentrations of sulphate, sodium, chloride, ammonium and nitrate are compared to measurements. Non-sea-salt sulphate and ammonium concentrations are well reproduced by the model. However, because of the geographic location of the measurement station at Cape Corsica which undergoes strong wind velocities and sea effects, sea-salt sulphate, sodium, chloride and nitrate concentrations are strongly influenced by the parameterizations used for sea-salt emissions. Different parameterizations are compared and a parameterization is chosen after comparison to sodium measurements. For organics, the concentrations are well modelled when compared to experimental values. Anthropogenic particles are influenced by emission of semi-volatile organic compounds (SVOC). Measurements allow us to refine the estimation of those emissions, which are currently missing in emission inventories. Although concentrations of biogenic particles are well simulated, the organic chemical compounds are not enough oxidised in the model. The observed oxidation state of organics shows that the oligomerisation of pinonaldehyde was over-estimated in Polyphemus. To improve the oxidation property of organics, the formation of extremely low volatile organic compounds from autoxidation of monoterpenes is added to Polyphemus, using recently published data from chamber experiments. These chemical compounds are highly oxygenated and are formed rapidly, as first

  1. Spatio-temporal Distribution and Chemical Speciation of Iron and Manganese in Sediments from Lake Aha, China

    NASA Astrophysics Data System (ADS)

    Liu, Feng; Hu, Jiwei; Qin, Fanxin; Jiang, Cuihong; Huang, Xianfei; Deng, Jiajun; Li, Cunxiong

    2010-11-01

    This paper reports an investigation on pollution and potential risk on elements of iron (Fe) and manganese (Mn) in sediments from Lake Aha, which is a drinking-water source for Guiyang City, the capital of Guizhou Province in southwestern China. In the present research, chemical speciation of Fe and Mn in sediments from the lake was studied based on the sequential extraction procedure developed by Tessier et al.. The results obtained from the study are as follows. The average values of total Fe were 47617 mg/kg and 70325 mg/kg in sediments from the lake in summer and winter respectively, and its speciation consisted mainly of residual and Fe-Mn oxides fractions. The amounts of total Fe and the distribution of its speciation in the sediments should be affected by effluents from a large quantity of deserted coal mines in the lake basin in summer and winter. The average values of total Mn were 7996 mg/kg and 1753 mg/kg in summer and winter respectively, and its speciation is primarily comprised of carbonate and Fe-Mn oxides fractions. The amounts of total Mn and its distribution in different fractions in the sediments were believed to be primarily influenced by effluents from those deserted coal mines in summer and by the condition of redox interface in winter.

  2. Biological availability of lead in a paint aerosol. 1. Physical and chemical characterization of a lead paint aerosol.

    PubMed

    Kalman, D; Schumacher, R; Covert, D; Eaton, D L

    1984-09-01

    This study was conducted to determine the physical and chemical characteristics of an aerosol of lead-based paint, generated in an industrial spray operation, that might influence the biological availability of lead present in inhaled aerosols. Paint aerosols were collected, and mass-size distribution was determined using a portable cascade impactor under actual occupational conditions. Approx. 2% of the particulate mass collected was in the respirable range (less than 10 micron mean aerodynamic diameter), although the maximum airborne concentration of lead was found to be 2-3 mg/m3. The lead concentration in a dried aerosol was very resistant to chemical digestion. Analysis by X-ray diffraction, atomic absorption spectroscopy and inductively coupled plasma emission spectroscopy showed approx. 11% lead by dry weight, although the wet weight concentration of lead reported by the manufacturer was 12.8%. PMID:6485003

  3. Chemical-thermal quantitative methodology for carbon speciation in damage layers on building surfaces.

    PubMed

    Ghedini, Nadia; Sabbioni, Cristina; Bonazza, Alessandra; Gobbi, Giancarlo

    2006-02-01

    The issue of environment protection, including the conservation of the monumental heritage worldwide, is related to atmospheric pollution, and its future therefore depends on air pollutant reduction. Carbonaceous particles emitted by combustion processes are the main factors responsible for the blackening of buildings. The identification and evaluation of the carbon species constituting the noncarbonate fraction of total carbon in damage layers, particularly in urban areas, are required in orderto investigate atmospheric deposition on building surfaces. Since noncarbonate carbon contains organic and elemental carbon originating from various human activities, its measurement and speciation are crucial to the protection and conservation of monuments and ancient masonry, playing an important role both in the proposal of mitigation strategies and in the definition of conservation treatments. The availability of a correct, accurate, and reproducible analytical method for a complete carbon balance is essential in studying the effects of atmospheric pollutants on the environment, including those affecting cultural heritage. A chemical-thermal methodology was set up, and its sensitivity, accuracy, repeatability, and reproducibility were tested on appropriate standard samples of composition similar to the black crusts on stones and mortars. The results indicate thatthe technique satisfactorily distinguishes among carbon species, particularly those of anthropogenic origin, allowing a reliable evaluation of their quantities in damage layers. In view of the difficulties encountered in applying the thermo-optical methods adopted for the measurement of carbon filters, the proposed methodology contributes to filling the current gap in suitable and reliable analytical procedures in the field of cultural heritage protection. PMID:16509340

  4. Retention and chemical speciation of uranium in an oxidized wetland sediment from the Savannah River Site

    SciTech Connect

    Li, Dien; Seaman, John C.; Chang, Hyun-Shik; Jaffe, Peter R.; Koster van Groos, Paul; Jiang, De-Tong; Chen, Ning; Lin, Jinru; Arthur, Zachary; Pan, Yuanming; Scheckel, Kirk G.; Newville, Matthew; Lanzirotti, Antonio; Kaplan, Daniel I.

    2014-05-01

    Uranium speciation and retention mechanism onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction desorption tests and U L{sub 3}-edge X-ray absorption near-edge structure (XANES) spectroscopy of contaminated wetland sediments. U was highly retained by the SRS wetland sediments. In contrast to other similar but much lower natural organic matter (NOM) sediments, significant sorption of U onto the SRS sediments was observed at pH <4 and pH >8. Sequential extraction tests indicated that the U(VI) species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and NOM fraction (Na-pyrophosphate extractable). Uranium L3- edge XANES spectra of the U-retained sediments were nearly identical to that of uranyl acetate. The primary oxidation state of U in these sediments was as U(VI), and there was little evidence that the high sorptive capacity of the sediments could be ascribed to abiotic or biotic reduction to the less soluble U(IV) species. The molecular mechanism responsible for the high U retention in the SRS wetland sediments is likely related to the chemical bonding of U to organic carbon.

  5. Speciation and chemical activities in superheated sodium borate solutions. Final report

    SciTech Connect

    Weres, O.

    1993-06-01

    The system H{sub 2}O-B{sub 2}O{sub 3}-Na{sub 2}O has been studied experimentally at 277{degrees} and 317{degrees}C. The activities of water and boric acid have been determined at mole ratios Na/B from 0 to 1.5, and total dissolved solids 3 to 80 weight percent. The activity of boric acid has been fitted to within experimental error using a speciation model with eight complex species. This model is consistent with the model previously published by Mesmer et al. The electrolyte properties of the liquid are modelled using the Pitzer-Simonson Model of very concentrated electrolyte solutions. The calculated values of water activity agree with experiment, and the activity of NaOH and pOH have also been calculated. These data will allow prediction of the composition and chemical behavior of sodium borate liquids that may accumulate in the superheated crevices within a steam generator. A modified form of the model is provided for use with MULTEQ. The potassium borate system also was briefly studied at 317{degrees}C, and is adequately described by a model with five complex species. The potassium borate liquid is more alkaline at K/B = 1 than a sodium borate liquid at the same mole ratio, but pOH in the two systems is the same at lower mole ratios.

  6. Chemical Speciation of Americium, Curium and Selected Tetravalent Actinides in High Level Waste

    SciTech Connect

    Felmy, Andrew R.

    2004-06-01

    Large volumes of high-level waste (HLW) currently stored in tanks at DOE sites contain both sludges and supernatants. The sludges are composed of insoluble precipitates of actinides, radioactive fission products, and nonradioactive components. The supernatants are alkaline carbonate solutions, which can contain soluble actinides, fission products, metal ions, and high concentrations of major electrolytes including sodium hydroxide, nitrate, nitrite, phosphate, carbonate, aluminate, sulfate, and organic complexants. The organic complexants include several compounds that can form strong aqueous complexes with actinide species and fission products including ethylenediaminetetraacetic acid (EDTA), N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), citrate, glycolate, gluconate, and degradation products, formate and oxalate. The goal of this project is to determine the effects of hydrolysis, carbonate complexation, and metal ion displacement on trivalent and selected tetravalent actinide speciation in the presence of organic chelates present in tank waste and to use these data to develop accurate predictive thermodynamic models for use in chemical engineering applications at Hanford and other DOE sites.

  7. Chemical Speciation and Potential Mobility of Heavy Metals in the Soil of Former Tin Mining Catchment

    PubMed Central

    Ashraf, M. A.; Maah, M. J.; Yusoff, I.

    2012-01-01

    This study describes the chemical speciation of Pb, Zn, Cu, Cr, As, and Sn in soil of former tin mining catchment. Total five sites were selected for sampling and subsequent subsamples were collected from each site in order to create a composite sample for analysis. Samples were analysed by the sequential extraction procedure using optical emission spectrometry (ICP OES). Small amounts of Cu, Cr, and As retrieved from the exchangeable phase, the ready available for biogeochemical cycles in the ecosystem. Low quantities of Cu and As could be taken up by plants in these kind of acidic soils. Zn not detected in the bioavailable forms while Pb is only present in negligible amounts in very few samples. The absence of mobile forms of Pb eliminates the toxic risk both in the trophic chain and its migration downwards the soil profile. The results also indicate that most of the metals have high abundance in residual fraction indicating lithogenic origin and low bioavailability of the metals in the studied soil. The average potential mobility for the metals giving the following order: Sn > Cu > Zn > Pb > Cr > As. PMID:22566758

  8. Chemical-thermal quantitative methodology for carbon speciation in damage layers on building surfaces

    SciTech Connect

    Nadia Ghedini; Cristina Sabbioni; Alessandra Bonazza; Giancarlo Gobbi

    2006-02-01

    Carbonaceous particles emitted by combustion processes are the main factors responsible for the blackening of buildings. The identification and evaluation of the carbon species constituting the noncarbonate fraction of total carbon in damage layers, particularly in urban areas, are required in order to investigate atmospheric deposition on building surfaces. Since noncarbonate carbon contains organic and elemental carbon originating from various human activities, its measurement and speciation are crucial to the protection and conservation of monuments and ancient masonry, playing an important role both in the proposal of mitigation strategies and in the definition of conservation treatments. The availability of a correct, accurate, and reproducible analytical method for a complete carbon balance is essential in studying the effects of atmospheric pollutants on the environment, including those affecting cultural heritage. A chemical-thermal methodology was set up, and its sensitivity, accuracy, repeatability, and reproducibility were tested on appropriate standard samples of composition similar to the black crusts on stones and mortars. The results indicate that the technique satisfactorily distinguishes among carbon species, particularly those of anthropogenic origin, allowing a reliable evaluation of their quantities in damage layers. In view of the difficulties encountered in applying the thermo-optical methods adopted for the measurement of carbon filters, the proposed methodology contributes to filling the current gap in suitable and reliable analytical procedures in the field of cultural heritage protection. 24 refs., 1 fig., 4 tabs.

  9. Chemical speciation of arsenic in the livers of higher trophic marine animals.

    PubMed

    Kubota, Reiji; Kunito, Takashi; Tanabe, Shinsuke

    2002-01-01

    Concentrations of total arsenic and individual arsenic compounds were determined in livers of cetaceans (Dall's porpoise and short-finned pilot whale), pinnipeds (harp and ringed seals), sirenian (dugong), and sea turtles (green and loggerhead turtles) to characterize arsenic accumulation profiles in higher trophic marine animals. Hepatic arsenic concentrations in sea turtles were highest among the species examined. Chemical speciation of arsenic revealed that arsenobetaine was the major arsenic compound in almost all the species. In contrast, arsenobetaine was a minor constituent in dugong. Dimethylarsinic acid, methylarsonic acid, arsenocholine, tetramethylarsonium ion, arsenite, and an unidentified arsenic compound were also detected as minor constituents. However, the composition of arsenic compounds was different among these species. These results might reflect the differences in the metabolism of arsenic and/or the compositions of arsenic compounds in their preys. To our knowledge, this is the first report on the large variation in the composition of arsenic species in liver of marine mammals and sea turtles. PMID:12398388

  10. Organic speciation of fine aerosol to assess sources in Mumbai city.

    PubMed

    Joseph, Abba Elizabeth; Unnikrishnan, Seema; Kumar, Rakesh

    2013-01-01

    Increasing ambient levels of fine particles due to anthropogenic activities are leading to adverse effects on human health and climate change. The present study on PM2.5 carbonaceous characterization for different land use patterns attempts to improve spatial understanding of sources in Mumbai city. The average of PM2.5 mass concentrations at Control (C), Kerb (K), Residential (R) and Industrial (I) site were 69±20, 84±31, 89±33, and 95±36.01 μg/m3 respectively. The average OC contributions at C, K, R and I sites were 30, 34, 35 and 31%, respectively and EC contributions were 7, 11,9 and 8%, respectively. Organic marker contains useful information of the sources especially of combustion origin. About 40 PAHs, 24 alkanes, 18 hopanes, 12 sterane, 2 methyl alkanes, 3 branched alkanes, 5 cycloalkanes and 1 alkene were identified and quantified from each category. The Carbon Preference Index for alkanes between C25 and C33 was greater than one and less than three, indicating anthropogenic sources like petroleum hydrocarbons. The H+S/EC ratio at C, K, R and I were 0.0022, 0.0011, 0.0083 and 0.0027 respectively, suggesting contribution from diesel exhaust emission. Levoglucosan . at all the sites indicates presence of biomass burning as an important source to fine particles. In the present study, detailed chemical analysis of particulate matter samples provides data useful in pinpointing sources of pollution as also in predicting potential health effects. PMID:25464705

  11. Organic speciation of fine aerosol to assess sources in Mumbai city.

    PubMed

    Joseph, Abba Elizabeth; Unnikrishnan, Seema; Kumar, Rakesh

    2013-01-01

    Increasing ambient levels of fine particles due to anthropogenic activities are leading to adverse effects on human health and climate change. The present study on PM2.5 carbonaceous characterization for different land use patterns attempts to improve spatial understanding of sources in Mumbai city. The average of PM2.5 mass concentrations at Control (C), Kerb (K), Residential (R) and Industrial (I) site were 69±20, 84±31, 89±33, and 95±36.01 μg/m3 respectively. The average OC contributions at C, K, R and I sites were 30, 34, 35 and 31%, respectively and EC contributions were 7, 11,9 and 8%, respectively. Organic marker contains useful information of the sources especially of combustion origin. About 40 PAHs, 24 alkanes, 18 hopanes, 12 sterane, 2 methyl alkanes, 3 branched alkanes, 5 cycloalkanes and 1 alkene were identified and quantified from each category. The Carbon Preference Index for alkanes between C25 and C33 was greater than one and less than three, indicating anthropogenic sources like petroleum hydrocarbons. The H+S/EC ratio at C, K, R and I were 0.0022, 0.0011, 0.0083 and 0.0027 respectively, suggesting contribution from diesel exhaust emission. Levoglucosan . at all the sites indicates presence of biomass burning as an important source to fine particles. In the present study, detailed chemical analysis of particulate matter samples provides data useful in pinpointing sources of pollution as also in predicting potential health effects. PMID:25508336

  12. Microphysical, chemical and optical aerosol properties in the Baltic Sea region

    NASA Astrophysics Data System (ADS)

    Kikas, Ülle; Reinart, Aivo; Pugatshova, Anna; Tamm, Eduard; Ulevicius, Vidmantas

    2008-11-01

    The microphysical structure, chemical composition and prehistory of aerosol are related to the aerosol optical properties and radiative effect in the UV spectral range. The aim of this work is the statistical mapping of typical aerosol scenarios and adjustment of regional aerosol parameters. The investigation is based on the in situ measurements in Preila (55.55° N, 21.00° E), Lithuania, and the AERONET data from the Gustav Dalen Tower (58 N, 17 E), Sweden. Clustering of multiple characteristics enabled to distinguish three aerosol types for clear-sky periods: 1) clean maritime-continental aerosol; 2) moderately polluted maritime-continental aerosol; 3) polluted continental aerosol. Differences between these types are due to significant differences in aerosol number and volume concentration, effective radius of volume distribution, content of SO 4- ions and Black Carbon, as well as different vertical profiles of atmospheric relative humidity. The UV extinction, aerosol optical depth (AOD) and the Ångstrom coefficient α increased with the increasing pollution. The value α = 1.96 was observed in the polluted continental aerosol that has passed over central and eastern Europe and southern Russia. Reduction of the clear-sky UV index against the aerosol-free atmosphere was of 4.5%, 27% and 41% for the aerosol types 1, 2 and 3, respectively.

  13. Speciation of 127I and 129I in atmospheric aerosols at Risø, Denmark: insight into sources of iodine isotopes and their species transformations

    NASA Astrophysics Data System (ADS)

    Zhang, L. Y.; Hou, X. L.; Xu, S.

    2015-09-01

    Speciation analysis of iodine in aerosols is a very useful approach for understanding geochemical cycling of iodine in the atmosphere. In this study, overall iodine species, including water-soluble iodine species (iodide, iodate and water-soluble organic iodine), NaOH-soluble iodine and insoluble iodine have been determined for 129I and 127I in the aerosols collected at Risø, Denmark, between March and May 2011 (shortly after the Fukushima nuclear accident) and in December 2014. The measured concentrations of total iodine are in the range of 1.04-2.48 ng m-3 for 127I and (11.3-97.0) × 105 atoms m-3 for 129I, and 129I / 127I atomic ratios of (17.8-86.8) × 10-8. The contribution of Fukushima-derived 129I (peak value of 6.3 × 104 atoms m-3) is estimated to be negligible (less than 6 %) compared to the total 129I concentration in northern Europe. The concentrations and species of 129I and 127I in the aerosols are found to be strongly related to their sources and atmospheric pathways. Aerosols that were transported over the contaminated ocean, contained higher amounts of 129I than aerosols transported over the European continent. The high 129I concentrations of the marine aerosols are attributed to secondary emission from heavily 129I-contaminated seawater rather than primary gaseous release from nuclear reprocessing plants. Water-soluble iodine was found to be a minor fraction to total iodine for both 127I (7.8-13.7 %) and 129I (6.5-14.1 %) in ocean-derived aerosols, but accounted for 20.2-30.3 % for 127I and 25.6-29.5 % for 129I in land-derived aerosols. Iodide was the predominant form of water-soluble iodine, accounting for more than 97 % of the water-soluble iodine. NaOH-soluble iodine seems to be independent of the sources of aerosols. The significant proportion of 129I and 127I found in NaOH-soluble fractions is likely bound with organic substances. In contrast to water-soluble iodine however, the sources of air masses exerted distinct influences on insoluble

  14. Speciation of 127I and 129I in atmospheric aerosols at Risø, Denmark: insight into sources of iodine isotopes and their species transformations

    NASA Astrophysics Data System (ADS)

    Zhang, Luyuan; Hou, Xiaolin; Xu, Sheng

    2016-02-01

    Speciation analysis of iodine in aerosols is a very useful approach for understanding geochemical cycling of iodine in the atmosphere. In this study, overall iodine species, including water-soluble iodine species (iodide, iodate and water-soluble organic iodine), NaOH-soluble iodine, and insoluble iodine have been determined for 129I and 127I in the aerosols collected at Risø, Denmark, during March and May 2011 (shortly after the Fukushima nuclear accident) and in December 2014. The measured concentrations of total iodine are in the range of 1.04-2.48 ng m-3 for 127I and (11.3-97.0) × 105 atoms m-3 for 129I, corresponding to 129I / 127I atomic ratios of (17.8-86.8) × 10-8. The contribution of Fukushima-derived 129I (peak value of 6.3 × 104 atoms m-3) is estimated to be negligible (less than 6 %) compared to the total 129I concentration in northern Europe. The concentrations and species of 129I and 127I in the aerosols are found to be strongly related to their sources and atmospheric pathways. Aerosols that were transported over the contaminated seas contained higher concentrations of 129I than aerosols transported over the European continent. The high 129I concentrations of the marine aerosols are attributed to secondary emission of marine discharged 129I in the contaminated seawater in the North Sea, North Atlantic Ocean, English Channel, Kattegat, etc., rather than direct gaseous release from the European nuclear reprocessing plants (NRPs). Water-soluble iodine was found to be a minor fraction to the total iodine for both 127I (7.8-13.7 %) and 129I (6.5-14.1 %) in ocean-derived aerosols, but accounted for 20.2-30.3 % for 127I and 25.6-29.5 % for 129I in land-derived aerosols. Iodide was the predominant form of water-soluble iodine, accounting for more than 97 % of the water-soluble iodine. NaOH-soluble iodine seems to be independent of the sources of aerosols. The significant proportion of 129I and 127I found in NaOH-soluble fractions is likely bound with

  15. Chemical Speciation of Trace Metals in Superficial Sediment from Lake Hongfeng, China

    NASA Astrophysics Data System (ADS)

    Hu, Jiwei; Huang, Xianfei; Zhang, Yuxia; Li, Cunxiong; Qin, Fanxin

    2010-11-01

    Heavy metals have been well known to cause numerous adverse effects to humans and ecological systems, and pollution of aquatic systems with heavy metals has aroused a huge public concern. The work reported in this paper deals with the distribution characteristics of trace metals (Pb, Cu, Zn and Ni) in ten surface sediments from Lake Hongfeng, situated in Guizhou Province of southwestern China. Apart from total concentration, the distribution of these metals in four fractions (exchangeable and weak acid soluble fraction (F1), reducible fraction (F2), oxidizable fraction (F3) and residual fraction (F4)) was also studied by means of an analytical procedure involving sequential chemical extraction that was proposed by the Commission of the European Communities Bureau of Reference (BCR). Analysis of total concentration suggested that the mean concentrations of heavy metals under study decreased in the order of Zn>Cu>Pb>Ni, and pollution of all these heavy metals in the North Lake was more serious than that in the South Lake. Study of heavy metals chemical speciation revealed that Pb and Cu were mainly distributed in reducible and residual fractions, and Zn and Ni mainly existed in residual fraction. Therefore, special attention should be paid to Pb and Cu since they presented a large fraction distributed in the exchangeable and weak acid soluble fraction and reducible fraction that were associated with high potential bioavailability. The Pearson correlation analysis between these heavy metals distributed in different fractions and some major elements were also carried out, and the results proved that sulfur (H2S) played an important role in distribution and transformation of heavy metals, especially for Pb, Cu and Zn.

  16. Arsenic Speciation in Groundwater: Role of Thioanions

    EPA Science Inventory

    The behavior of arsenic in groundwater environments is fundamentally linked to its speciation. Understanding arsenic speciation is important because chemical speciation impacts reactivity, bioavailability, toxicity, and transport and fate processes. In aerobic environments arsen...

  17. Chemical characterization of submicron aerosol and particle growth events at a national background site (3295 m a.s.l.) on the Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Du, W.; Sun, Y. L.; Xu, Y. S.; Jiang, Q.; Wang, Q. Q.; Yang, W.; Wang, F.; Bai, Z. P.; Zhao, X. D.; Yang, Y. C.

    2015-09-01

    Atmospheric aerosols exert highly uncertain impacts on radiative forcing and also have detrimental effects on human health. While aerosol particles are widely characterized in megacities in China, aerosol composition, sources and particle growth in rural areas in the Tibetan Plateau remain less understood. Here we present the results from an autumn study that was conducted from 5 September to 15 October 2013 at a national background monitoring station (3295 m a.s.l.) in the Tibetan Plateau. The submicron aerosol composition and particle number size distributions were measured in situ with an Aerodyne Aerosol Chemical Speciation Monitor (ACSM) and a Scanning Mobility Particle Sizer (SMPS). The average mass concentration of submicron aerosol (PM1) is 11.4 μg m-3 (range: 1.0-78.4 μg m-3) for the entire study, which is much lower than observed at urban and rural sites in eastern China. Organics dominated PM1, accounting for 43 % on average, followed by sulfate (28 %) and ammonium (11 %). Positive Matrix Factorization analysis of ACSM organic aerosol (OA) mass spectra identified an oxygenated OA (OOA) and a biomass burning OA (BBOA). The OOA dominated OA composition, accounting for 85 % on average, 17 % of which was inferred from aged BBOA. The BBOA contributed a considerable fraction of OA (15 %) due to the burning of cow dung and straw in September. New particle formation and growth events were frequently observed (80 % of time) throughout the study. The average particle growth rate is 2.0 nm h-1 (range: 0.8-3.2 nm h-1). By linking the evolution of particle number size distribution to aerosol composition, we found an elevated contribution of organics during particle growth periods and also a positive relationship between the growth rate and the fraction of OOA in OA, which potentially indicates an important role of organics in particle growth in the Tibetan Plateau.

  18. Chemical, physical, and optical evolution of biomass burning aerosols: a case study

    NASA Astrophysics Data System (ADS)

    Adler, G.; Flores, J. M.; Abo Riziq, A.; Borrmann, S.; Rudich, Y.

    2010-10-01

    In-situ chemical composition measurements of ambient aerosols have been used for characterizing the evolution of submicron aerosols from a large anthropogenic biomass burning (BB) event in Israel. A high resolution Time of Flight Aerosol Mass Spectrometer (Hi-RES-TOF-AMS) was used to follow the chemical evolution of BB aerosols during a night-long, extensive nationwide wood burning event and during the following day. While extensive BB is not common in this region, burning of agricultural waste is a common practice. The aging process of the BB aerosols was followed through their chemical, physical and optical properties. Mass spectrometric analysis of the aerosol organic component showed that aerosol aging is characterized by shifting from less oxidized fresh BB aerosols to more oxidized aerosols. Evidence for aerosol aging during the day following the BB event was indicated by an increase in the organic mass, its oxidation state, the total aerosol concentration, and a shift in the modal particle diameter. The effective broadband refractive index (EBRI) was derived using a white light optical particle counter (WELAS). The average EBRI for a mixed population of aerosols dominated by open fires was m=1.53(±0.03)+0.07i(±0.03), during the smoldering phase of the fires we found the EBRI to be m=1.54(±0.01)+0.04i(±0.01) compared to m=1.49(±0.01)+0.02i(±0.01) of the aged aerosols during the following day. This change indicates a decrease in the overall aerosol absorption and scattering. Elevated levels of particulate Polycyclic Aromatic Hydrocarbons (PAHs) were detected during the entire event, which suggest possible implications for human health during such extensive event.

  19. Chemical, physical, and optical evolution of biomass burning aerosols: a case study

    NASA Astrophysics Data System (ADS)

    Adler, G.; Flores, J. M.; Abo Riziq, A.; Borrmann, S.; Rudich, Y.

    2011-02-01

    In-situ chemical composition measurements of ambient aerosols have been used for characterizing the evolution of submicron aerosols from a large anthropogenic biomass burning (BB) event in Israel. A high resolution Time of Flight Aerosol Mass Spectrometer (HR-RES-TOF-AMS) was used to follow the chemical evolution of BB aerosols during a night-long, extensive nationwide wood burning event and during the following day. While these types of extensive BB events are not common in this region, burning of agricultural waste is a common practice. The aging process of the BB aerosols was followed through their chemical, physical and optical properties. Mass spectrometric analysis of the aerosol organic component showed that aerosol aging is characterized by shifting from less oxidized fresh BB aerosols to more oxidized aerosols. Evidence for aerosol aging during the day following the BB event was indicated by an increase in the organic mass, its oxidation state, the total aerosol concentration, and a shift in the modal particle diameter. The effective broadband refractive index (EBRI) was derived using a white light optical particle counter (WELAS). The average EBRI for a mixed population of aerosols dominated by open fires was m = 1.53(±0.03) + 0.07i(±0.03), during the smoldering phase of the fires we found the EBRI to be m = 1.54(±0.01) + 0.04i(±0.01) compared to m = 1.49(±0.01) + 0.02i(±0.01) of the aged aerosols during the following day. This change indicates a decrease in the overall aerosol absorption and scattering. Elevated levels of particulate Polycyclic Aromatic Hydrocarbons (PAHs) were detected during the entire event, which suggest possible implications for human health during such extensive event.

  20. Single Particle Chemical Speciation of Ambient Ultrafine Particulate Matter in Atlanta, GA

    NASA Astrophysics Data System (ADS)

    Sipin, M. F.; Su, Y.; Prather, K. A.

    2002-12-01

    Ultrafine particles, particles with aerodynamic diameters lower than 100 nm, have recently gained increasing attention because of their hypothesized adverse heath effects and potential as cloud condensation nuclei. Chemical characterization of the ultrafine particles at the single particle level is important for assessing their impact on human health and understanding their formation and behavior. This is beneficial for modeling studies and regulations on pollution control. In August 2002, continuous ambient monitoring was performed in an industrial area in Atlanta, GA. Characterization of the urban particulate matter with aerodynamic diameters 30A›ƒ,ªƒ_o300 nm was carried out using a dual polarity aerosol time-of-flight mass spectrometer (ATOFMS) interfaced with an aerodynamic lens system. This configuration allows on-line real time simultaneous acquisition of size and chemical information for individual particles down to 30 nm. The ultrafine particles observed consisted of elemental carbon (EC), organic carbon (OC), and a mixture of OC and EC as a result of vehicular, industrial, and biogenic emissions. These major particle types, their associations with inorganics (i.e. ammonium, sulfate, nitrate, potassium, calcium, and metal oxides), and their temporal and size variations will be presented.

  1. Chemical, physical, and optical evolution of biomass burning aerosols: A case study

    NASA Astrophysics Data System (ADS)

    Adler, G.; Flores, M.; Borrmann, S.; Rudich, Y.

    2010-12-01

    In-situ chemical composition measurements of ambient aerosols have been used for characterizing the evolution of submicron aerosols of a large anthropogenic biomass burning (BB) event in Israel. A high resolution Time of Flight Aerosol Mass Spectrometer (Hi-RES-TOF-AMS) was used to follow the chemical evolution of BB aerosols during a night-long, extensive nationwide wood burning event and during the following day. While extensive BB is not common in this region, burning of agricultural waste is a common practice. The aging process of the BB aerosols was followed through their chemical, physical and optical properties. Mass spectrometric analysis of the aerosol organic component showed that aerosol aging is characterized by shifting from less oxidized fresh BB aerosols to more oxidized aerosols. Evidence for aerosol aging during the day following the BB event was indicated by an increase in the organic mass, its oxidation state, the total aerosol concentration, and a shift in the modal particle diameter. The effective broadband refractive index (EBRI) was derived using a white light optical particle counter (WELAS). EBRI during the smoldering phase of the fires was m=1.54(±0.01)+0.04i(±0.01) compared to m=1.49(±0.01)+0.02i(±0.01) of the aged aerosols during the following day. This change indicates a decrease in the overall aerosol absorption and scattering. Elevated levels of particulate Polycyclic Aromatic Hydrocarbons (PAHs) were detected during the entire event, which suggest possible implications for human health during such extensive event.

  2. Biokinetics and dosimetry of inhaled Cm aerosols in beagles: effect of aerosol chemical form.

    PubMed

    Guilmette, R A; Kanapilly, G M

    1988-12-01

    This study was designed to provide tissue distribution data of 244Cm that was inhaled by beagle dogs. Two chemical forms that were presumed to bracket the solubility of pure Cm compounds in vivo were used: 244Cm2O3 (oxide) and 244Cm(NO3)3 (nitrate). Adult dogs of both sexes received a single brief pernasal exposure to either a monodisperse aerosol of 244Cm2O3 (1.4 micron activity median aerodynamic diameter, AMAD, and 1.16 geometric standard deviation, sigma g) or a polydisperse aerosol of 244Cm(NO3)3 (1.1 micron AMAD, 1.74 sigma g). The resulting initial pulmonary burdens (IPB) were 1.5 and 1.7 kBq kg-1 body mass for the oxide and nitrate groups, respectively. The tissue distribution data obtained from the dogs that were serially sacrificed from 4 h to 2 y after exposure showed that both chemical forms were very soluble in vivo. For the oxide group, 78% IPB was cleared from the lung with a T 1/2 of 7.6 d, whereas for the nitrate group, 42% IPB cleared with a T 1/2 of 0.6 d. The lung retention for each group was described by three-component exponential functions. Most of the Cm that cleared the lung was redeposited in the liver (37% IPB) and skeleton (27% IPB), with lesser amounts in the muscle, fat and connective tissue (3.5% IPB) and kidney (approximately 2% IPB). The only significant difference noted in the biokinetics of Cm for the two exposure groups was a more rapid translocation of Cm from the lung to liver and bone during the first 10-20 d after exposure to the nitrate compared to the oxide chemical form. Extrapolation of these data to obtain estimates of committed dose equivalents for man indicate substantial agreement with the limits for occupational exposure specified by ICRP 30 (1979). PMID:3198400

  3. Chemical characterization and physico-chemical properties of aerosols at Villum Research Station, Greenland during spring 2015

    NASA Astrophysics Data System (ADS)

    Glasius, M.; Iversen, L. S.; Svendsen, S. B.; Hansen, A. M. K.; Nielsen, I. E.; Nøjgaard, J. K.; Zhang, H.; Goldstein, A. H.; Skov, H.; Massling, A.; Bilde, M.

    2015-12-01

    The effects of aerosols on the radiation balance and climate are of special concern in Arctic areas, which have experienced warming at twice the rate of the global average. As future scenarios include increased emissions of air pollution, including sulfate aerosols, from ship traffic and oil exploration in the Arctic, there is an urgent need to obtain the fundamental scientific knowledge to accurately assess the consequences of pollutants to environment and climate. In this work, we studied the chemistry of aerosols at the new Villum Research Station (81°36' N, 16°40' W) in north-east Greenland during the "inauguration campaign" in spring 2015. The chemical composition of sub-micrometer Arctic aerosols was investigated using a Soot Particle Time-of-Flight Aerosol Mass Spectrometer (SP-ToF-AMS). Aerosol samples were also collected on filters using both a high-volume sampler and a low-volume sampler equipped with a denuder for organic gases. Chemical analyses of filter samples include determination of inorganic anions and cations using ion-chromatography, and analysis of carboxylic acids and organosulfates of anthropogenic and biogenic origin using ultrahigh-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS). Previous studies found that organosulfates constitute a surprisingly high fraction of organic aerosols during the Arctic Haze period in winter and spring. Investigation of organic molecular tracers provides useful information on aerosol sources and atmospheric processes. The physico-chemical properties of Arctic aerosols are also under investigation. These measurements include particle number size distribution, water activity and surface tension of aerosol samples in order to deduct information on their hygroscopicity and cloud-forming potential. The results of this study are relevant to understanding aerosol sources and processes as well as climate effects in the Arctic, especially during the Arctic haze

  4. Chemical composition of atmospheric aerosols between Moscow and Vladivostok

    NASA Astrophysics Data System (ADS)

    Kuokka, S.; Teinilä, K.; Saarnio, K.; Aurela, M.; Sillanpää, M.; Hillamo, R.; Kerminen, V.-M.; Vartiainen, E.; Kulmala, M.; Skorokhod, A. I.; Elansky, N. F.; Belikov, I. B.

    2007-05-01

    The TROICA-9 expedition (Trans-Siberian Observations Into the Chemistry of the Atmosphere) was carried out at the Trans-Siberian railway between Moscow and Vladivostok in October 2005. Measurements of aerosol physical and chemical properties were made from an observatory carriage connected to a passenger train. Black carbon (BC) concentrations in fine particles (PM2.5, aerodynamic diameter <2.5 μm) were measured with an aethalometer using a five-minute time resolution. Concentrations of inorganic ions and some organic compounds (Cl-, NO3-, SO42-, Na+, NH4+, K+, Ca2+, Mg2+, oxalate and methane sulphonate) were measured continuously by using an on-line system with a 15-min time resolution. In addition, particle volume size distributions were determined for particles in the diameter range 3-850 nm using a 10-min. time resolution. The continuous measurements were completed with 24-h. PM2.5 filter samples which were stored in a refrigerator and later analyzed in chemical laboratory. The analyses included mass concentrations of PM2.5, ions, monosaccharide anhydrides (levoglucosan, galactosan and mannosan) and trace elements (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sb, V and Zn). The mass concentrations of PM2.5 varied in the range of 4.3-34.8 μg m-3 with an average of 21.6 μg m-3. Fine particle mass consisted mainly of BC (average 27.6%), SO42- (13.0%), NH4+ (4.1%), and NO3- (1.4%). One of the major constituents was obviously also organic carbon which was not determined. The contribution of BC was high compared with other studies made in Europe and Asia. High concentrations of ions, BC and particle volume were observed between Moscow and roughly 4000 km east of it, as well as close to Vladivostok, primarily due to local anthropogenic sources. In the natural background area between 4000 and 7200 km distance from Moscow, observed concentrations were low, even though there were local particle sources, such as forest fires, that increased occasionally concentrations. The

  5. Questions concerning environmental mobility of arsenic: needs for a chemical data base and means for speciation of trace organoarsenicals.

    PubMed

    Brinckman, F E; Parris, G E; Blair, W R; Jewett, K L; Iverson, W P; Bellama, J M

    1977-08-01

    Biomethylation of metals, including arsenic, apparently occurs as a global process. Health control strategies therefore depend on accurate analysis of arsenic's environmental mobility. Determining to what extent biotransformations occur and how resultant organometal(loids) are sequestered in food chains requires sophistication beyond present-day total element determinations. Rather, active molecular forms of arsenic must be speciated for each environmental compartment, and it is necessary to quantify the dynamics of arsenic's mobility. Thus, new chemical facts are needed yielding rates of methylation or demethylation of arsenic; partition coefficients of organoarsenicals between air, water, and organic phases; and arsenic redox chemistry in polar media. NBS research in this context is reviewed with examples of recent results emphasizing speciation methodology. Topic areas discussed are: the nature of aquated methylarsenic species (NMR and laser-Raman spectroscopy); transport of methylarsenicals from aqueous media (gas chromatography-graphic furnace AA detection applied to metabolic Me3As formation); and speciation of involatile organoarsenicals in aqueous media (demonstration of HPLC utilizing element-specific AA detection and appraisal of electrochemical detectors). PMID:908286

  6. Mercury speciation modeling using site specific chemical and redox data from the TNXOD OU

    SciTech Connect

    Kaplan, D.I.

    2000-03-22

    The objective of this study was to evaluate mercury speciation under reducing conditions expected in sediments at the TNX Outfall Delta Operable Unit. These changes in speciation would then be used to infer whether mercury toxicity and mobility would be expected to be significantly altered under reducing conditions. The results from this work suggest that mercury would likely become more strongly retained by the solid phase under reducing conditions than under oxidizing conditions at the TNX Outfall Delta Site. Considering that experimental results indicate that mercury is extremely tightly bound to the solid phase under oxidizing conditions, little mercury mobility would therefore be expected under reducing conditions.

  7. Canadian National Air Pollution Surveillance (NAPS) PM 2.5 speciation program: Methodology and PM 2.5 chemical composition for the years 2003-2008

    NASA Astrophysics Data System (ADS)

    Dabek-Zlotorzynska, Ewa; Dann, Tom F.; Kalyani Martinelango, P.; Celo, Valbona; Brook, Jeffrey R.; Mathieu, David; Ding, Luyi; Austin, Claire C.

    2011-01-01

    The Canadian National Air Pollution Surveillance (NAPS) network, monitoring criteria gases (CO, O 3, NO x, and SO 2), PM 2.5, PM 10, volatile organic compounds (VOCs), semi-volatile organic compounds (SVOCs) and particle chemical mass and composition, has been in operation for over 40 years. Since 1984 both fine (<2.5 μm - PM 2.5) and coarse (2.5-10 μm - PM 10-2.5) particle mass measurements have been made at NAPS network sites using dichotomous samplers. In January 2003, the NAPS PM 2.5 speciation program was initiated with the purpose of measuring all major components of PM 2.5, including ammonium nitrate, ammonium sulphate, metals, and organic and elemental carbon. The present paper describes the improved sampling (e.g. Teflon/Nylon filter packs for nitrate loss, and an active blank for each and every sample in the determination of positive organic carbon artifacts), and analytical methods used in the Canadian NAPS PM 2.5 speciation program. A detailed dataset was then analyzed for seasonal and geographical variations in the major components of 24-h time integrated PM 2.5 samples collected at eight urban and three rural measurement sites across Canada (2003-2008). Chemical mass reconstruction was used for assessment of the adequacy of selected sampling and chemical parameters as well as for the determination of the relative contributions of different compound classes to PM 2.5 mass. The highest frequency of PM 2.5 episodes exceeding 30 μg m -3 were observed in Ontario and southern Quebec. In general, the most important contributions to PM 2.5 mass were secondary aerosol sulphate and nitrate (38-63% for western sites and 3-44% for eastern sites), depending on the season. Organic matter (OM) was found to be the second most important component (21-45%), while particle-bound water (PBW) accounted for 6-12% of the PM 2.5 mass. Golden B.C. was an exception, exhibiting high levels of OM (60-70%) and low levels of PBW (˜3%).

  8. The Speciation and Solubility of Aerosol Iron and Aluminum in the Northwest Pacific Ocean: Results From the 2002 NSF/IOC Cruise

    NASA Astrophysics Data System (ADS)

    Buck, C. S.; Landing, W. M.; Resing, J.; Lebon, G. T.

    2002-12-01

    As part of the 2002 NSF/IOC cruise in the northwest Pacific, we collected separate 10-hour aerosol samples during both the day and night aboard the R/V Melville leaving Osaka, Japan on May 1, 2002 and arriving in Honolulu, HI on June 5, 2002. The goal of this research was to measure the solubility and speciation of Fe and Al in Asian continental dust. Four replicate samples were collected using an automatic sector-controlled aerosol sampling system that collected only when the wind was \\pm90o off the bow of the ship and exceeded 0.5 m/sec. The aerosols were collected on 47 mm PCTE and polypropylene filters for roughly 10-hour periods, filtering as much as 35 m3 of air through each filter. The filters were changed twice each day for a total of 60 samples. The filters were quickly leached with 100 mL of either freshly collected 0.2μm filtered surface seawater at natural pH or 100 mL of unacidified ultrapure water. Seawater filtrates were analyzed for soluble Fe(II) using the FeLume chemiluminescent system. These samples were also analyzed for total soluble Fe using the ICP-MS isotope dilution method upon returning to FSU. The ultrapure water filtrate samples were frozen until they could be analyzed at FSU for major anions using ion chromotography. A replicate PCTE filter was analyzed for total Fe (and other elements) using energy-dispersive X-ray fluorescence at the NOAA/PMEL laboratory. Soluble total aerosol Fe concentrations ranged from 8-130 pmol/m3 of filtered air. The concentrations of soluble Fe(II) ranged from 0.35-95 pmol/m3 and total soluble Al ranged from 20-600 pmol/m3. We will also compare total Fe and Al solubilities in seawater and ultrapure water.

  9. Chemical and hygroscopic properties of aerosol organics at Storm Peak Laboratory

    NASA Astrophysics Data System (ADS)

    Hallar, A. Gannet; Lowenthal, Douglas H.; Clegg, Simon L.; Samburova, Vera; Taylor, Nathan; Mazzoleni, Lynn R.; Zielinska, Barbara K.; Kristensen, Thomas B.; Chirokova, Galina; McCubbin, Ian B.; Dodson, Craig; Collins, Don

    2013-05-01

    A combined field and laboratory study was conducted to improve our understanding of the chemical and hygroscopic properties of organic compounds in aerosols sampled in the background continental atmosphere. PM2.5 (particles with aerodynamic diameters smaller than 2.5 µm) aerosols were collected from 24 June to 28 July 2010 at Storm Peak Laboratory (SPL) in the Park Range of northwestern Colorado. New particle formation (NPF) was frequent at SPL during this campaign, and the samples were not influenced by regional dust storms. Filter samples were analyzed for organic carbon (OC) and elemental carbon (EC), water soluble OC (WSOC), major inorganic ions, and detailed organic speciation. WSOC was isolated from inorganic ions using solid phase absorbents. Hygroscopic growth factors (GFs) and cloud condensation nucleus (CCN) activity of the WSOC were measured in the laboratory. Organic compounds compose the majority (average of 64% with a standard deviation (SD) of 9%) of the mass of measured species and WSOC accounted for an average of 89% (with a SD of 21%) of OC mass. Daily samples were composited according to back trajectories. On average, organic acids, sugars, and sugar alcohols accounted for 12.5 ± 6.2% (average ± SD) of WSOC. Based on the composition of these compounds and that of high molecular weight compounds identified using ultra high resolution mass spectrometry, the organic mass to OC ratio of the WSOC is estimated to be 2.04. The average hygroscopic GFs at RH = 80% (GF80) were 1.10 ± 0.03 for particles derived from isolated WSOC and 1.27 ± 0.03 for particles derived from the total water-soluble material (WSM). CCN activity followed a similar pattern. The critical diameters at a super-saturation of 0.35% were 0.072 ± 0.009 and 0.094 ± 0.006 µm for particles derived from WSM and isolated WSOC, respectively. These GF results compare favorably with estimates from thermodynamic models, which explicitly relate the water activity (RH) to concentration for

  10. Cadmium chemical speciation and absorption in plant in a polluted soil

    NASA Astrophysics Data System (ADS)

    Gigliotti, Giovanni; Massaccesi, Luisa

    2013-04-01

    speciation results showed that a significant amount of Cd (45%), before plant seeding, was associated with the metal oxide fraction (typically Fe-Mn oxides and hydroxides) followed to Cd bound to soil organic matter (39%), despite the content of organic matter in the soil was very low. Instead the amount of Cd bound to carbonates (13%), exchangeable phase (1%) and residue fraction (2.5%) were negligible. After six weeks of plant seeding the Cd fractionation was slightly different, with a decrease of metal bound to oxide and hydroxide from 45% to 29% and an increase of fraction bound to carbonate from 13% to 19% and exchangeable fraction from 1% to 8%. The roots system of Festuca had colonized all pot and the fractionation of metal was disturbed by plants growth. Roots may induce changes in the biochemical, chemical and physical properties of the rhizosphere increasing potentially toxic elements diffusion through the production of roots exudates. The soil environment immediately adjacent to the root can be strongly influenced by root exudates, so that chemical process of dissolution, chelation and precipitation outside the root also occur. Cd was absorbed by plant root in a great concentration, but not translocation to leafs was noticed.

  11. Real-time chemical analysis of aerosol particles

    SciTech Connect

    Yang, M.; Whitten, W.B.; Ramsey, J.M.

    1995-04-01

    An important aspect of environmental atmospheric monitoring requires the characterization of airborne microparticles and aerosols. Unfortunately, traditional sample collection and handling techniques are prone to contamination and interference effects that can render an analysis invalid. These problems can be avoided by using real-time atmospheric sampling techniques followed by immediate mass spectrometric analysis. The former is achieved in these experiments via a two state differential pumping scheme that is attached directly to a commercially available quadruple ion trap mass spectrometer. Particles produced by an external particle generator enter the apparatus and immediately pass through two cw laser/fiberoptic based detectors positioned two centimeters apart. Timing electronics measure the time between detection events, estimate the particles arrival in the center of the ion trap and control the firing of a YAG laser. Ions produced when the UV laser light ablates the particle`s surface are stored by the ion trap for mass analysis. Ion trap mass spectrometers have several advantages over conventional time-of-flight instruments. First, they are capable of MS/MS analysis by the collisional dissociation of a stored species, This permits complete chemical characterization of airborne samples. Second, ion traps are small and lend themselves to portable, field oriented applications.

  12. Chemical speciation and source apportionment of fine particulate matter in Santiago, Chile, 2013.

    PubMed

    Villalobos, Ana M; Barraza, Francisco; Jorquera, Héctor; Schauer, James J

    2015-04-15

    Santiago is one of the largest cities in South America and has experienced high fine particulate matter (PM2.5) concentrations in fall and winter months for decades. To better understand the sources of fall and wintertime pollution in Santiago, PM2.5 samples were collected for 24 h every weekday from March to October 2013 for chemical analysis. Samples were analyzed for mass, elemental carbon (EC), organic carbon (OC), water soluble organic carbon (WSOC), water soluble nitrogen (WSTN), secondary inorganic ions, and particle-phase organic tracers for source apportionment. Selected samples were analyzed as monthly composites for organic tracers. PM2.5 concentrations were considerably higher in the coldest months (June-July), averaging (mean ± standard deviation) 62±15 μg/m(3) in these two months. Average fine particle mass concentration during the study period was 40±20 μg/m(3). Organic matter during the peak winter months was the major component of fine particles comprising around 70% of the particle mass. Source contributions to OC were calculated using organic molecular markers and a chemical mass balance (CMB) receptor model. The four combustion sources identified were wood smoke, diesel engine emission, gasoline vehicles, and natural gas. Wood smoke was the predominant source of OC, accounting for 58±42% of OC in fall and winter. Wood smoke and nitrate were the major contributors to PM2.5. In fall and winter, wood smoke accounted for 9.8±7.1 μg/m(3) (21±15%) and nitrate accounted for 9.1±4.8 μg/m(3) (20±10%) of fine PM. The sum of secondary inorganic ions (sulfate, nitrate, and ammonium) represented about 30% of PM2.5 mass. Secondary organic aerosols contributed only in warm months, accounting for about 30% of fine PM during this time. PMID:25617780

  13. Chemical Speciation of Sulfur in Marine Cloud Droplets and Particles: Analysis of Individual Particles from the Marine Boundary Layer Over the California Current

    SciTech Connect

    Hopkins, Rebecca J; Desyaterik, Yury; Tivanski, Alexei V; Zaveri, Rahul A; Berkowitz, Carl M; Tyliszczak, T; Gilles, Marry K; Laskin, Alexander

    2008-02-27

    Detailed chemical speciation of the dry residue particles from individual cloud droplets and interstitial aerosol collected during the Marine Stratus Experiment (MASE) was performed using a complementary combination of microanalysis techniques. Techniques include computer controlled scanning electron microscopy with energy dispersed analysis of X-rays (CCSEM/EDX), time-of-flight secondary ionization mass spectrometry (TOFSIMS), and scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Samples were collected at the ground site located in Point Reyes National Seashore, approximately 1 km from the coast. This manuscript focuses on the analysis of individual particles sampled from an air mass that originated over the open ocean and then passed through the area of the California current located along the northern California coast. Based on composition, morphology, and chemical bonding information, two externally mixed, distinct classes of sulfur containing particles were identified: chemically modified (aged) sea salt particles and secondary formed sulfate particles. The results indicate substantial heterogeneous replacement of chloride by methanesulfonate (CH3SO3-) and non-sea salt sulfate (nss-SO42-) in sea-salt particles with the characteristic ratios of CH3SO3-/nss-SO42-> 0.6. Although this value seems too high for a mid-latitude site, our model calculations suggest that high CH3SO3-/nss-SO42- ratios are expected during the early stages of dimethyl sulfide (DMS) oxidation when CH3SO3H forms more rapidly than H2SO4.

  14. Effects of aerosol sources and chemical compositions on cloud drop sizes and glaciation temperatures

    NASA Astrophysics Data System (ADS)

    Zipori, Assaf; Rosenfeld, Daniel; Tirosh, Ofir; Teutsch, Nadya; Erel, Yigal

    2015-09-01

    The effect of aerosols on cloud properties, such as its droplet sizes and its glaciation temperatures, depends on their compositions and concentrations. In order to examine these effects, we collected rain samples in northern Israel during five winters (2008-2011 and 2013) and determined their chemical composition, which was later used to identify the aerosols' sources. By combining the chemical data with satellite-retrieved cloud properties, we linked the aerosol types, sources, and concentrations with the cloud glaciation temperatures (Tg). The presence of dust increased Tg from -26°C to -12°C already at relatively low dust concentrations. This result is in agreement with the conventional wisdom that desert dust serves as good ice nuclei (INs). With higher dust concentrations, Tg saturated at -12°C, even though cloud droplet sizes decreased as a result of the cloud condensation nucleating (CCN) activity of the dust. Marine air masses also encouraged freezing, but in this case, freezing was enhanced by the larger cloud droplet sizes in the air masses (caused by low CCN concentrations) and not by IN concentrations or by aerosol type. An increased fraction of anthropogenic aerosols in marine air masses caused a decrease in Tg, indicating that these aerosols served as poor IN. Anthropogenic aerosols reduced cloud droplet sizes, which further decreased Tg. Our results could be useful in climate models for aerosol-cloud interactions, as we investigated the effects of aerosols of different sources on cloud properties. Such parameterization can simplify these models substantially.

  15. Prediction of chemical speciation in stabilized/solidified wastes using a general chemical equilibrium model. 2: Doped waste contaminants in cement porewaters

    SciTech Connect

    Park, J.Y.; Batchelor, B.

    1999-01-01

    In the previous paper, SOLTEQ demonstrated its ability to represent chemical speciation in the pure s/s binder systems. The objective of this paper is to provide a method for representing doped waste contaminants in SOLTEQ so that their speciation can be determined. To evaluate this method, model predictions were compared with measured concentrations in the porewaters expressed from cement pastes doped with various metal salts. Among doped metals, only mercury showed concentrations that indicated primary control by precipitation. The other metals, such as Cr(VI), Cd, Pb, and Na, showed behaviors that imply sorption as a major immobilization mechanism. The Langmuir isotherm was found to be well suited to describe the sorption of Na{sup +} ions onto the effective surface of CSH. To support the sorption of metal anions onto presumably negatively charged silica surface in cement porewater, a hypothesis of super-equivalent adsorption is proposed.

  16. Combined measurements of organic aerosol isotopic and chemical composition to investigate day-night differences in carbonaceous aerosol

    NASA Astrophysics Data System (ADS)

    Dusek, Ulrike; Holzinger, Rupert; Meijer, Harro A. J.; Röckmann, Thomas

    2014-05-01

    PM2.5 filter samples have been collected during the Pegasos (Mai, 2012) and Actris (June/July 2012) campaigns at the CESAR site near Cabauw, the Netherlands. This site lies in a rural location surrounded by major urban centers and highways and is a good location for measuring the regional aerosol contamination in the Netherlands. High volume filter samples were taken over several days, but the aerosol was collected on separate filters during day and night time periods. We analyzed these filters for carbon isotopes (14C and 13C) and detailed chemical composition of the organic fraction, which can be a powerful tool, for investigating sources and processing of the organic aerosol. Measurement of the radioactive carbon isotope 14C in aerosols can provide a direct estimate of the contribution of fossil fuel sources to aerosol carbon. The stable carbon isotopes 12C and 13C can be used to get information about sources and processing of organic aerosol. We use a method to measure d13C values of OC desorbed from the filter samples in He at different temperature steps. The chemical composition of the organic fraction at the same temperature steps can be determined using a Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS). The PTR-MS method is applied to the filter samples as well to aerosol collected in situ by a impaction using a Collection-Thermal-Desorption Cell. First results show that the mass concentration of the carbonaceous aerosol is higher during night time than during day time, dominated by a strong increase of biogenic organic aerosol. This is at least partially caused by a shallow night time boundary layer combined with decreased traffic sources and increased condensation of semi-volatile biogenic gases during night-time. Evidence for the role of semi-volatile compounds in enhancing organic carbon (OC) night time concentrations comes from several observations: (1) semi-volatile OC with desorption temperatures lower than 250 °C increases

  17. Methodology for the passive detection and discrimination of chemical and biological aerosols

    NASA Astrophysics Data System (ADS)

    Marinelli, William J.; Shokhirev, Kirill N.; Konno, Daisei; Rossi, David C.; Richardson, Martin

    2013-05-01

    The standoff detection and discrimination of aerosolized biological and chemical agents has traditionally been addressed through LIDAR approaches, but sensor systems using these methods have yet to be deployed. We discuss the development and testing of an approach to detect these aerosols using the deployed base of passive infrared hyperspectral sensors used for chemical vapor detection. The detection of aerosols requires the inclusion of down welling sky and up welling ground radiation in the description of the radiative transfer process. The wavelength and size dependent ratio of absorption to scattering provides much of the discrimination capability. The approach to the detection of aerosols utilizes much of the same phenomenology employed in vapor detection; however, the sensor system must acquire information on non-line-of-sight sources of radiation contributing to the scattering process. We describe the general methodology developed to detect chemical or biological aerosols, including justifications for the simplifying assumptions that enable the development of a real-time sensor system. Mie scattering calculations, aerosol size distribution dependence, and the angular dependence of the scattering on the aerosol signature will be discussed. This methodology will then be applied to two test cases: the ground level release of a biological aerosol (BG) and a nonbiological confuser (kaolin clay) as well as the debris field resulting from the intercept of a cruise missile carrying a thickened VX warhead. A field measurement, conducted at the Utah Test and Training Range will be used to illustrate the issues associated with the use of the method.

  18. Chemical and size effects of hygroscopic aerosols on light scattering coefficients

    NASA Astrophysics Data System (ADS)

    Tang, Ignatius N.

    1996-08-01

    The extensive thermodynamic and optical properties recently reported [Tang and Munkelwitz, 1994a] for sulfate and nitrate solution droplets are incorporated into a visibility model for computing light scattering by hygroscopic aerosols. The following aerosol systems are considered: NH4HSO4, (NH4)2SO4, (NH4)3H(SO4), NaHSO4, Na2SO4, NH4NO3, and NaNO3. In addition, H2SO4 and NaCl are included to represent freshly formed sulfate and background sea-salt aerosols, respectively. Scattering coefficients, based on 1 μg dry salt per cubic meter of air, are calculated as a function of relative humidity for aerosols of various chemical compositions and lognormal size distributions. For a given size distribution the light scattered by aerosol particles per unit dry-salt mass concentration is only weakly dependent on chemical constituents of the hygroscopic sulfate and nitrate aerosols. Sulfuric acid and sodium chloride aerosols, however, are exceptions and scatter light more efficiently than all other inorganic salt aerosols considered in this study. Both internal and external mixtures exhibit similar light-scattering properties. Thus for common sulfate and nitrate aerosols, since the chemical effect is outweighed by the size effect, it follows that observed light scattering by the ambient aerosol can be approximated, within practical measurement uncertainties, by assuming the aerosol being an external mixture. This has a definite advantage for either visibility degradation or climatic impact modeling calculations, because relevant data are now available for external mixtures but only very scarce for internal mixtures.

  19. Direct aerosol chemical composition measurements to evaluate the physicochemical differences between controlled sea spray aerosol generation schemes

    NASA Astrophysics Data System (ADS)

    Collins, D. B.; Zhao, D. F.; Ruppel, M. J.; Laskina, O.; Grandquist, J. R.; Modini, R. L.; Stokes, M. D.; Russell, L. M.; Bertram, T. H.; Grassian, V. H.; Deane, G. B.; Prather, K. A.

    2014-11-01

    Controlled laboratory studies of the physical and chemical properties of sea spray aerosol (SSA) must be under-pinned by a physically and chemically accurate representation of the bubble-mediated production of nascent SSA particles. Bubble bursting is sensitive to the physico-chemical properties of seawater. For a sample of seawater, any important differences in the SSA production mechanism are projected into the composition of the aerosol particles produced. Using direct chemical measurements of SSA at the single-particle level, this study presents an intercomparison of three laboratory-based, bubble-mediated SSA production schemes: gas forced through submerged sintered glass filters ("frits"), a pulsed plunging-waterfall apparatus, and breaking waves in a wave channel filled with natural seawater. The size-resolved chemical composition of SSA particles produced by breaking waves is more similar to particles produced by the plunging waterfall than those produced by sintered glass filters. Aerosol generated by disintegrating foam produced by sintered glass filters contained a larger fraction of organic-enriched particles and a different size-resolved elemental composition, especially in the 0.8-2 μm dry diameter range. Interestingly, chemical differences between the methods only emerged when the particles were chemically analyzed at the single-particle level as a function of size; averaging the elemental composition of all particles across all sizes masked the differences between the SSA samples. When dried, SSA generated by the sintered glass filters had the highest fraction of particles with spherical morphology compared to the more cubic structure expected for pure NaCl particles produced when the particle contains relatively little organic carbon. In addition to an intercomparison of three SSA production methods, the role of the episodic or "pulsed" nature of the waterfall method on SSA composition was under-taken. In organic-enriched seawater, the continuous

  20. Application of EPA unmix and nonparametric wind regression on high time resolution trace elements and speciated mercury in Tampa, Florida aerosol.

    PubMed

    Pancras, Joseph Patrick; Vedantham, Ram; Landis, Matthew S; Norris, Gary A; Ondov, John M

    2011-04-15

    Intensive ambient air sampling was conducted in Tampa, FL, during October and November of 2002. Fine particulate matter (PM(2.5)) was collected at 30 min resolution using the Semicontinuous Elements in Aerosol Sampler II (SEAS-II) and analyzed off-line for up to 45 trace elements by high-resolution ICPMS (HR-ICPMS). Divalent reactive gaseous mercury and particulate bound mercury were also measured semicontinuously (2 h). Application of the United States Environmental Protection Agency's (EPA) Unmix receptor model on the 30 min resolution trace metals data set identified eight possible sources: residual oil combustion, lead recycling, coal combustion, a Cd-rich source, biomass burning, marine aerosol, general industrial, and coarse dust contamination. The source contribution estimates from EPA Unmix were then run in a nonparametric wind regression (NWR) model, which convincingly identified plausible source origins. When the 30 min ambient concentrations of trace elements were time integrated (2 h) and combined with speciated mercury concentrations, the model identified only four sources, some of which appeared to be merged source profiles that were identified as separate sources by using the 30 min resolution data. This work demonstrates that source signatures that can be captured at 30 min resolution may be lost when sampling for longer durations. PMID:21401082

  1. Effects of Particle Size on Chemical Speciation and Bioavailability of Copper to Earthworms ( Eisenia fetida ) Exposed to Copper Nanoparticles

    SciTech Connect

    J Unrine; O Tsyusko; S Hunyadi; J Judy; P Bertsch

    2011-12-31

    To investigate the role of particle size on the oxidation, bioavailability, and adverse effects of manufactured Cu nanoparticles (NPs) in soils, we exposed the earthworm Eisenia fetida to a series of concentrations of commercially produced NPs labeled as 20- to 40-nm or <100-nm Cu in artificial soil media. Effects on growth, mortality, reproduction, and expression of a variety of genes associated with metal homeostasis, general stress, and oxidative stress were measured. We also used X-ray absorption spectroscopy and scanning X-ray fluorescence microscopy to characterize changes in chemical speciation and spatial distribution of the NPs in soil media and earthworm tissues. Exposure concentrations of Cu NPs up to 65 mg kg{sup -1} caused no adverse effects on ecologically relevant endpoints. Increases in metallothionein expression occurred at concentrations exceeding 20 mg kg-1 of Cu NPs and concentrations exceeding 10 mg kg{sup -1} of CuSO{sub 4} Based on the relationship of Cu tissue concentration to metallothionein expression level and the spatial distribution and chemical speciation of Cu in the tissues, we conclude that Cu ions and oxidized Cu NPs were taken up by the earthworms. This study suggests that oxidized Cu NPs may enter food chains from soil but that adverse effects in earthworms are likely to occur only at relatively high concentrations (>65 mg Cu kg{sup -1} soil).

  2. Seasonal characterization of submicron aerosol chemical composition and organic aerosol sources in the southeastern United States: Atlanta, Georgia and Look Rock, Tennessee

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S. H.; Baumann, K.; Edgerton, E. S.; Bairai, S. T.; Mueller, S.; Shaw, S. L.; Knipping, E. M.; Gold, A.; Surratt, J. D.

    2015-08-01

    A yearlong near-real-time characterization of non-refractory submicron aerosol (NR-PM1) was conducted at an urban (Atlanta, Georgia) and rural (Look Rock, Tennessee) site in the southeastern US using the Aerodyne aerosol chemical speciation monitor (ACSM) collocated with established air-monitoring network measurements. Seasonal variations in organic aerosol (OA) and inorganic aerosol species are attributed to meteorological conditions as well as anthropogenic and biogenic emissions in this region. The highest concentrations of NR-PM1 were observed during winter and fall seasons at the urban site and during spring and summer at the rural site. Across all seasons and at both sites, NR-PM1 was composed largely of OA (50-76 %) and inorganic sulfate (12-31 %). Six distinct OA sources were resolved by positive matrix factorization applied to the ACSM organic mass spectral data collected from the two sites over the one year of near-continuous measurements at each site: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), semi-volatile oxygenated OA (SV-OOA), low-volatility oxygenated OA (OOA), isoprene-derived epoxydiol (IEPOX) OA (IEPOX-OA), and 91Fac OA (a factor dominated by a distinct ion at m/z 91 fragment ion previously observed in biogenic influenced areas). LV-OOA was observed throughout the year at both sites and contributed 30-66 % of total OA mass. HOA was also observed during the entire year only at the urban site (15-24 % of OA mass). BBOA (15-33 % of OA mass) was observed during winter and fall, likely dominated by local residential wood burning emission. Although SV-OOA contributes quite significantly (∼ 27 %), it was observed only at the urban site during colder seasons. IEPOX-OA was a major component (27-41 %) of OA at both sites, particularly in spring and summer. An ion fragment at m/z 75 is proposed as an additional marker for IEPOX-OA, as it is shown to correlate well with the m/z 82 ion shown to be associated with the aerosol mass spectrum of

  3. Chemical speciation and enzymatic impact of silver in antimicrobial fabric buried in soil.

    PubMed

    Takeuchi, Satoshi; Hashimoto, Yohey; Yamaguchi, Noriko; Toyota, Koki

    2016-11-01

    This study investigated the impact of Ag in antibacterial fabric on soil enzymes in relation to solubility and speciation of Ag. Sections of Ag-containing sock fabric (1.0-1.5cm(2)) were incubated in soils with aerobic and anaerobic conditions and periodically determined activity of arylsulfatase, dehydrogenase and urease. Microscale distribution and speciation of Ag at the interface between socks and soil particles were investigated using micro-focused X-ray fluorescence (μ-XRF), and Ag speciation was determined using micro-focused X-ray absorption near edge structure (μ-XANES) spectroscopy. Results showed that the sock fabric consisted of elemental Ag and Ag2S. After 60-day exposure to soil, majority (50-90%) of Ag in sock did not undergo phase transformation and present as elemental Ag and Ag2S in aerobic and anaerobic conditions. A part of Ag in sock fabric was bound with soil colloids (<15%), depending on the distance from the edge of sock fabric. Soil enzyme activities were overall unaffected by Ag in sock textile after 60days of incubation, although a significant decrease in arylsulfatase activity was found only in the initial stage of soil incubation. Silver in the sock fabric is relatively stable and has little detrimental impacts on enzyme activity in ordinary soil conditions. PMID:27351904

  4. REPRESENTING AEROSOL DYNAMICS AND PROPERTIES IN CHEMICAL TRANSPORT MODELS BY THE METHOD OF MOMENTS.

    SciTech Connect

    SCHWARTZ, S.E.; MCGRAW, R.; BENKOVITZ, C.M.; WRIGHT, D.L.

    2001-04-01

    Atmospheric aerosols, suspensions of solid or liquid particles, are an important multi-phase system. Aerosols scatter and absorb shortwave (solar) radiation, affecting climate (Charlson et al., 1992; Schwartz, 1996) and visibility; nucleate cloud droplet formation, modifying the reflectivity of clouds (Twomey et al., 1984; Schwartz and Slingo, 1996) as well as contributing to composition of cloudwater and to wet deposition (Seinfeld and Pandis, 1998); and affect human health through inhalation (NRC, 1998). Existing and prospective air quality regulations impose standards on concentrations of atmospheric aerosols to protect human health and welfare (EPA, 1998). Chemical transport and transformation models representing the loading and geographical distribution of aerosols and precursor gases are needed to permit development of effective and efficient strategies for meeting air quality standards, and for examining aerosol effects on climate retrospectively and prospectively for different emissions scenarios. Important aerosol properties and processes depend on their size distribution: light scattering, cloud nucleating properties, dry deposition, and penetration into airways of lungs. The evolution of the mass loading itself depends on particle size because of the size dependence of growth and removal processes. For these reasons it is increasingly recognized that chemical transport and transformation models must represent not just the mass loading of atmospheric particulate matter but also the aerosol microphysical properties and the evolution of these properties if aerosols are to be accurately represented in these models. If the size distribution of the aerosol is known, a given property can be evaluated as the integral of the appropriate kernel function over the size distribution. This has motivated the approach of determining aerosol size distribution, and of explicitly representing this distribution and its evolution in chemical transport models.

  5. Chemical speciation of neptunium in spent fuel. Annual report for period 15 August 1999 to 15 August 2000

    SciTech Connect

    Ken Czerwinski; Don Reed

    2000-09-01

    (B204) This project will examine the chemical speciation of neptunium in spent nuclear fuel. The R&D fields covered by the project include waste host materials and actinide chemistry. Examination of neptunium is chosen since it was identified as a radionuclide of concern by the NERI workshop. Additionally, information on the chemical form of neptunium in spent fuel is lacking. The identification of the neptunium species in spent fuel would allow a greater scientific based understanding of its long-term fate and behavior in waste forms. Research to establish the application and development of X-ray synchrotrons radiation (XSR) techniques to determine the structure of aqueous, adsorbed, and solid actinide species of importance to nuclear considerations is being conducted at Argonne. These studies extend current efforts within the Chemical Technology Division at Argonne National Laboratory to investigate actinide speciation with more conventional spectroscopic and solids characterization (e.g. SEM, TEM, and XRD) methods. Our project will utilize all these techniques for determining neptunium speciation in spent fuel. We intend to determine the chemical species and oxidation state of neptunium in spent fuel and alteration phases. Different types of spent fuel will be examined. Once characterized, the chemical behavior of the identified neptunium species will be evaluated if it is not present in the literature. Special attention will be given to the behavior of the neptunium species under typical repository near-field conditions (elevated temperature, high pH, varying Eh). This will permit a timely inclusion of project results into near-field geochemical models. Additionally, project results and methodologies have applications to neptunium in the environment, or treatment of neptunium containing waste. Another important aspect of this project is the close cooperation between a university and a national laboratory. The PI has a transuranic laboratory at MIT where

  6. Chemical composition of aerosols over Bay of Bengal during pre-monsoon: Dominance of anthropogenic sources

    NASA Astrophysics Data System (ADS)

    Nair, Prabha R.; George, Susan K.; Aryasree, S.; Jacob, Salu

    2014-03-01

    Total suspended particulates were collected from the marine boundary layer of Bay of Bengal (BoB) as part of the Integrated Campaign for Aerosols gases & Radiation Budget (ICARB) conducted under the Geosphere Biosphere Programme of Indian Space Research Organisation during pre-monsoon period. These samples were analyzed to quantify various chemical species and to bring out a comprehensive and quantitative picture of the chemical composition of aerosols in the marine environment of Bay of Bengal. Almost all the species showed highest mass concentration over north/head BoB. On the other hand, their mass fractions were high over mid/south BoB which has implications on the radiative forcing in this region. The source characteristics of various species were identified using specific chemical components as tracers. Presence of significant amount of non-sea-salt aerosols (~7-8 times of sea-salt) and several trace species like Ni, Pb, Zn, etc were observed in this marine environment indicating significant continental/anthropogenic influence. An approximate estimate of the contributions of anthropogenic and natural aerosols to the total aerosol mass loading showed prominence of anthropogenic component over mid and south BoB also. Based on this study first-cut aerosol chemical models were evolved for BoB region.

  7. Aerosol Optical Properties Measured Onboard the Ronald H. Brown During ACE Asia as a Function of Aerosol Chemical Composition and Source Region

    NASA Technical Reports Server (NTRS)

    Quinn, P. K.; Coffman, D. J.; Bates, T. S.; Welton, E. J.; Covert, D. S.; Miller, T. L.; Johnson, J. E.; Maria, S.; Russell, L.; Arimoto, R.

    2004-01-01

    During the ACE Asia intensive field campaign conducted in the spring of 2001 aerosol properties were measured onboard the R/V Ronald H. Brown to study the effects of the Asian aerosol on atmospheric chemistry and climate in downwind regions. Aerosol properties measured in the marine boundary layer included chemical composition; number size distribution; and light scattering, hemispheric backscattering, and absorption coefficients. In addition, optical depth and vertical profiles of aerosol 180 deg backscatter were measured. Aerosol within the ACE Asia study region was found to be a complex mixture resulting from marine, pollution, volcanic, and dust sources. Presented here as a function of air mass source region are the mass fractions of the dominant aerosol chemical components, the fraction of the scattering measured at the surface due to each component, mass scattering efficiencies of the individual components, aerosol scattering and absorption coefficients, single scattering albedo, Angstrom exponents, optical depth, and vertical profiles of aerosol extinction. All results except aerosol optical depth and the vertical profiles of aerosol extinction are reported at a relative humidity of 55 +/- 5%. An over-determined data set was collected so that measured and calculated aerosol properties could be compared, internal consistency in the data set could be assessed, and sources of uncertainty could be identified. By taking into account non-sphericity of the dust aerosol, calculated and measured aerosol mass and scattering coefficients agreed within overall experimental uncertainties. Differences between measured and calculated aerosol absorption coefficients were not within reasonable uncertainty limits, however, and may indicate the inability of Mie theory and the assumption of internally mixed homogeneous spheres to predict absorption by the ACE Asia aerosol. Mass scattering efficiencies of non-sea salt sulfate aerosol, sea salt, submicron particulate organic

  8. Quantum Chemical Calculations Resolved Identification of Methylnitrocatechols in Atmospheric Aerosols.

    PubMed

    Frka, Sanja; Šala, Martin; Kroflič, Ana; Huš, Matej; Čusak, Alen; Grgić, Irena

    2016-06-01

    Methylnitrocatechols (MNCs) are secondary organic aerosol (SOA) tracers and major contributors to atmospheric brown carbon; however, their formation and aging processes in atmospheric waters are unknown. To investigate the importance of aqueous-phase electrophilic substitution of 3-methylcatechol with nitronium ion (NO2(+)), we performed quantum calculations of their favorable pathways. The calculations predicted the formation of 3-methyl-5-nitrocatechol (3M5NC), 3-methyl-4-nitrocatechol (3M4NC), and a negligible amount of 3-methyl-6-nitrocatechol (3M6NC). MNCs in atmospheric PM2 samples were further inspected by LC/(-)ESI-MS/MS using commercial as well as de novo synthesized authentic standards. We detected 3M5NC and, for the first time, 3M4NC. In contrast to previous reports, 3M6NC was not observed. Agreement between calculated and observed 3M5NC/3M4NC ratios cannot unambiguously confirm the electrophilic mechanism as the exclusive formation pathway of MNCs in aerosol water. However, the examined nitration by NO2(+) is supported by (1) the absence of 3M6NC in the ambient aerosols analyzed and (2) the constant 3M5NC/3M4NC ratio in field aerosol samples, which indicates their common formation pathway. The magnitude of error one could make by incorrectly identifying 3M4NC as 3M6NC in ambient aerosols was also assessed, suggesting the importance of evaluating the literature regarding MNCs with special care. PMID:27136117

  9. MOLECULAR SPECIATION OF SECONDARY ORGANIC AEROSOL FROM PHOTOOXIDATION OF THE HIGHER ALKENES: 1-OCTENE AND 1-DECENE. (R824970)

    EPA Science Inventory

    Outdoor smog chamber photooxidations to determine the molecular composition of secondary organic aerosol (SOA) from 1-octene and 1-decene in sunlight-irradiated hydrocarbon-NOx mixtures are reported. The observed products are consistent with the current under...

  10. Chemical fractionation and speciation modelling for optimization of ion-exchange processes to recover palladium from industrial wastewater.

    PubMed

    Folens, K; Van Hulle, S; Vanhaecke, F; Du Laing, G

    2016-01-01

    Palladium is used in several industrial applications and, given its high intrinsic value, intense efforts are made to recover the element. In this hydrometallurgic perspective, ion-exchange (IEX) technologies are principal means. Yet, without incorporating the chemical and physical properties of the Pd present in real, plant-specific conditions, the recovery cannot reach its technical nor economic optimum. This study characterized a relevant Pd-containing waste stream of a mirror manufacturer to provide input for a speciation model, predicting the Pd speciation as a function of pH and chloride concentration. Besides the administered neutral PdCl2 form, both positively and negatively charged [PdCln](2-n) species occur depending on the chloride concentration in solution. Purolite C100 and Relite 2AS IEX resins were selected and applied in combination with other treatment steps to optimize the Pd recovery. A combination of the cation and anion exchange resins was found successful to quantitatively recover Pd. Given the fact that Pd was also primarily associated with particles, laboratory-scale experiments focused on physical removal of the Pd-containing flow were conducted, which showed that particle-bound Pd can already be removed by physical pre-treatment prior to IEX, while the ionic fraction remains fully susceptible to the IEX mechanism. PMID:27054747

  11. The concentration and chemical speciation of arsenic in the Nanpan River, the upstream of the Pearl River, China.

    PubMed

    Yang, Silin; Zhao, Ning; Zhou, Dequn; Wei, Rong; Yang, Bin; Pan, Bo

    2016-04-01

    The concentration and chemical speciation of arsenic (As) in different environmental matrixes (water, sediment, agricultural soils, and non-agricultural soils) were investigated in the Nanpan River area, the upstream of Pearl River, China. The results did not show any obvious transport of As along the flow direction of the river (from upstream to downstream). Total As concentrations in sediment were significantly different from those in agricultural soil. According to the comparison to quality standards, the As in sediments of the studied area have potential ecological risks and a minority of the sampling sites of agricultural soils in the studied area were polluted with As. As speciations were analyzed using sequential extraction and the percentage of non-residual fraction in sediment predominated over residual fraction. We thus believe that As in the studied area was with low mobility and bioavailability in sediment, agricultural soils, and non-agricultural soils. However, the bioavailability and mobility of As in sediment were higher than in both agricultural and non-agricultural soils, and thus, special attention should be paid for the risk assessment of As in the river in future studies. PMID:26627697

  12. Measurement and chemical speciation of PM10 in Mumbai City, India.

    PubMed

    Salunkhe, Abhaysinh; Gupta, Indrani; Shetye, Sugandha; Kumar, Rakesh

    2013-10-01

    Mass concentrations of PM10 were high at all locations of Mumbai city in all seasons. From the enrichment analysis, it was observed that high enrichment of metals existed at all sites, the reason for which could be the effects of meteorology and trans-boundary movement of pollutants. Multivariate statistical analysis tools were used to identify common sources, viz. road dust, biomass burning, secondary aerosol, brake wear, residual oil combustion, smelting, natural soil, vehicles tyre wear, and marine aerosol. Findings indicate that most of the sites were dominated by local sources based on activities in the vicinity of the sampling locations. PMID:25906590

  13. Influence of continental outflow on aerosol chemical characteristics over the Arabian Sea during winter

    NASA Astrophysics Data System (ADS)

    Kumar, Ashwini; Sudheer, A. K.; Goswami, Vineet; Bhushan, Ravi

    2012-04-01

    The chemical composition of aerosol over the Arabian Sea was investigated during December 2007. Elemental Carbon (EC), Organic Carbon (OC), water soluble organic and inorganic constituents and crustal elements (Al, Fe, Ca, and Mg) were measured in total suspended particulate samples (TSP) collected from marine boundary layer of the Arabian Sea when the oceanic region is influenced by continental outflow. Anthropogenic and natural mineral aerosol originating from continental regions dominates the aerosol composition contributing ∼88% of total aerosol mass. The sea-salt aerosol comprises only ∼12% of TSP. The carbonaceous aerosol exhibits spatial trend similar to that of K+ suggesting major source could be biomass burning. Secondary organic aerosol (SOA) contribution estimated by EC-tracer method suggests that up to 67% of OC can be of secondary origin. Average water soluble organic carbon to OC ratio is ∼0.9, indicates significant formation of SOA during transport of continental air masses. These results demonstrate the dominance of continental aerosol over the Arabian Sea during wintertime where deposition may have major impact on surface ocean biogeochemistry.

  14. Chemical Speciation and Oxidation Kinetics of Iron and Sulfur in Subseafloor Basement Fluids on the Juan de Fuca Ridge Flanks

    NASA Astrophysics Data System (ADS)

    Glazer, B. T.; Matzinger, M.; Cowen, J. P.

    2011-12-01

    Redox reactive chemical species circulate throughout the upper oceanic crust, and are involved in a variety of abiotic and microbially-mediated reactions. Through exchange with bottom seawater, fluids circulating in the upper basement have the potential to influence scales ranging from global-scale biogeochemical cycling to micro-scale microbe-mineral interactions. Understanding fundamental chemical speciation, distribution, bioavailability, and rates of transformations for key chemical redox species is crucial to understanding processes in the subsurface. In-situ electrochemical analyses were conducted in real-time at CORK (Circulation Obviation Retrofit Kit) observatories affixed to Integrated Ocean Drilling Program (IODP) boreholes in Cascadia Basin on the Juan de Fuca Ridge Flanks. Voltammetric electrodes were mounted into a flow cell to allow for simultaneous detection of redox species (O2, H_{2}O2, HS^{-}, S(0), Sx^{2-}, S2O_{3}2-, S_{4}O6^{2-}, Fe(II), Fe(III), FeS$_{(aq)}) concurrent to sample filtering or fluid collection. During real-time voltammetric scanning, qualitative assessment of the integrity of fluids delivered through the Fluid Delivery Lines could be made, allowing for comparisons between CORK sites and various sampling strategies. Newly installed CORKs at IODP sites 1362A and 1362B are producing the highest-integrity basement fluids collected to date, deplete in oxygen (<3uM) and enriched in iron (>1uM). Here, we report results of in situ electrochemical measurements at multiple borehole observatories, including the newly installed 1362A & 1362B sites, and present results of speciation analyses and kinetics of oxidation for iron and sulfur in discrete samples.

  15. Aerosol chemical and optical properties over the Paris area within ESQUIF project

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Vautard, R.; Chazette, P.; Menut, L.; Bessagnet, B.

    2006-01-01

    Aerosol chemical and optical properties are extensively investigated for the first time over the Paris Basin in July 2000 within the ESQUIF project. The measurement campaign offers an exceptional framework to evaluate the performances of the chemistry-transport model CHIMERE in simulating concentrations of gaseous and aerosol pollutants, as well as the aerosol-size distribution and composition in polluted urban environment against ground-based and airborne measurements. A detailed comparison of measured and simulated variables during the second half of July with particular focus on 19 and 31 pollution episodes reveals an overall good agreement for gas-species and aerosol components both at the ground level and along flight trajectories, and the absence of systematic biases in simulated meteorological variables such as wind speed, relative humidity and boundary layer height as computed by the MM5 model. A good consistency in ozone and NO concentrations demonstrates the ability of the model to reproduce fairly well the plume structure and location both on 19 and 31 July, despite an underestimation of the amplitude of ozone concentrations on 31 July. The spatial and vertical aerosol distributions are also examined by comparing simulated and observed lidar vertical profiles along flight trajectories on 31 July and confirmed the model capacity to simulate the plume characteristics. The comparison of observed and modeled aerosol components in the southwest suburb of Paris during the second half of July indicated that the aerosol composition is rather correctly reproduced, although the total aerosol mass is underestimated of about 20%. The simulated Parisian aerosol is dominated by primary particulate matter that accounts for anthropogenic and biogenic primary particles (40%) and inorganic aerosol fraction (40%) including nitrate (8%), sulfate (22%) and ammonium (10%). The secondary organic aerosols (SOA) represent 12% of the total aerosol mass, while the mineral dust

  16. Aerosol chemical and optical properties over the Paris area within ESQUIF project

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Vautard, R.; Chazette, P.; Menut, L.; Bessagnet, B.

    2006-08-01

    Aerosol chemical and optical properties are extensively investigated for the first time over the Paris Basin in July 2000 within the ESQUIF project. The measurement campaign offers an exceptional framework to evaluate the performances of the chemistry-transport model CHIMERE in simulating concentrations of gaseous and aerosol pollutants, as well as the aerosol-size distribution and composition in polluted urban environments against ground-based and airborne measurements. A detailed comparison of measured and simulated variables during the second half of July with particular focus on 19 and 31 pollution episodes reveals an overall good agreement for gas-species and aerosol components both at the ground level and along flight trajectories, and the absence of systematic biases in simulated meteorological variables such as wind speed, relative humidity and boundary layer height as computed by the MM5 model. A good consistency in ozone and NO concentrations demonstrates the ability of the model to reproduce the plume structure and location fairly well both on 19 and 31 July, despite an underestimation of the amplitude of ozone concentrations on 31 July. The spatial and vertical aerosol distributions are also examined by comparing simulated and observed lidar vertical profiles along flight trajectories on 31 July and confirm the model capacity to simulate the plume characteristics. The comparison of observed and modeled aerosol components in the southwest suburb of Paris during the second half of July indicates that the aerosol composition is rather correctly reproduced, although the total aerosol mass is underestimated by about 20%. The simulated Parisian aerosol is dominated by primary particulate matter that accounts for anthropogenic and biogenic primary particles (40%), and inorganic aerosol fraction (40%) including nitrate (8%), sulfate (22%) and ammonium (10%). The secondary organic aerosols (SOA) represent 12% of the total aerosol mass, while the mineral dust

  17. Aerosols and clouds in chemical transport models and climate models.

    SciTech Connect

    Lohmann,U.; Schwartz, S. E.

    2008-03-02

    Clouds exert major influences on both shortwave and longwave radiation as well as on the hydrological cycle. Accurate representation of clouds in climate models is a major unsolved problem because of high sensitivity of radiation and hydrology to cloud properties and processes, incomplete understanding of these processes, and the wide range of length scales over which these processes occur. Small changes in the amount, altitude, physical thickness, and/or microphysical properties of clouds due to human influences can exert changes in Earth's radiation budget that are comparable to the radiative forcing by anthropogenic greenhouse gases, thus either partly offsetting or enhancing the warming due to these gases. Because clouds form on aerosol particles, changes in the amount and/or composition of aerosols affect clouds in a variety of ways. The forcing of the radiation balance due to aerosol-cloud interactions (indirect aerosol effect) has large uncertainties because a variety of important processes are not well understood precluding their accurate representation in models.

  18. Effects of Transport and Processing on Aerosol Chemical and Optical Properties Across the Gulf of Maine

    NASA Astrophysics Data System (ADS)

    Quinn, P.; Bates, T.; Baynard, T.; Onasch, T.; Coffman, D.; Covert, D.; Worsnop, D.; Goldan, P.; Kuster, B.; Degouw, J.; Stohl, A.

    2005-12-01

    NEAQS-ITCT 2004 took place in July and August to study natural and anthropogenic emissions from North America including the processing of gas and particle phase species during transport over the North Atlantic and the resulting impact on air quality and climate. During the experiment, measurements were made onboard the NOAA RV Ronald H. Brown with a ship track that extended from the coast along Cape Cod, MA, Boston, MA and Portland, ME, east into the Gulf of Maine and out to Chebogue Point, Nova Scotia. Although measurements on the ship were not made in a true Lagrangian sense, they reveal information about the effects of transport and processing on aerosol chemical and optical properties. Photochemical age based on measured toluene to benzene ratios can be used in this region to indicate 'younger' versus 'older' aerosol. This approach, coupled with FLEXPART estimates of source contributions and age, reveals that continental aerosol becomes more acidic as it ages with transport over the Gulf of Maine. The increasing acidity is due to the conversion of SO2 to SO4= with no further significant input of NH3 in the well-capped marine boundary layer to neutralize the aerosol. In addition, as the aerosol ages, the organic mass fraction decreases while the organics that are present become more oxidized. These same chemical features were observed in aerosol transported from the Ohio River Valley and beyond. In contrast, recently formed aerosol from urban centers along the Eastern Seaboard are neutralized, have a higher organic content, and the organics are less oxidized. The impact of the observed range of aerosol acidity, organic mass fraction, and degree of oxidation of the organic matter on the f(RH) of the aerosol will be described. Here, f(RH) refers to the dependence of light extinction on relative humidity.

  19. Programmable thermal dissociation of reactive gaseous mercury - a potential approach to chemical speciation: results from a field study

    NASA Astrophysics Data System (ADS)

    Tatum Ernest, C.; Donohoue, D.; Bauer, D.; Ter Schure, A.; Hynes, A. J.

    2012-12-01

    The use of programmable thermal dissociation (PTD) as an approach to investigating the chemical speciation of reactive gaseous mercury (RGM, Hg2+) has been explored in a field study. In this approach RGM is collected on a denuder and analyzed using PTD. The denuder is placed in an oven and the dissociation of the RGM is measured, as a function of temperature, by monitoring the evolution of elemental mercury (GEM, Hg0) in real time using laser-induced fluorescence (LIF). The technique was tested in a field campaign at a coal-fired power plant in Pensacola, Florida. Uncoated tubular denuders were used to obtain samples from the plant's stack exhaust gases and from the stack plume, downwind of the stack using an airship. The PTD profiles from these samples were compared with PTD profiles of HgCl2.

  20. Observation operator for the assimilation of aerosol type resolving satellite measurements into a chemical transport model

    NASA Astrophysics Data System (ADS)

    Schroedter-Homscheidt, M.; Elbern, H.; Holzer-Popp, T.

    2010-11-01

    Modelling of aerosol particles with chemical transport models is still based mainly on static emission databases while episodic emissions cannot be treated sufficiently. To overcome this situation, a coupling of chemical mass concentration modelling with satellite-based measurements relying on physical and optical principles has been developed. This study deals with the observation operator for a component-wise assimilation of satellite measurements. It treats aerosol particles classified into water soluble, water insoluble, soot, sea salt and mineral dust containing aerosol particles in the atmospheric boundary layer as separately assimilated aerosol components. It builds on a mapping of aerosol classes used both in observation and model space taking their optical and chemical properties into account. Refractive indices for primary organic carbon particles, anthropogenic particles, and secondary organic species have been defined based on a literature review. Together with a treatment of different size distributions in observations and model state, this allows transforming the background from mass concentrations into aerosol optical depths. A two-dimensional, variational assimilation is applied for component-wise aerosol optical depths. Error covariance matrices are defined based on a validation against AERONET sun photometer measurements. Analysis fields are assessed threefold: (1) through validation against AERONET especially in Saharan dust outbreak situations, (2) through comparison with the British Black Smoke and Sulphur Dioxide Network for soot-containing particles, and (3) through comparison with measurements of the water soluble components SO4, NH4, and NO3 conducted by the EMEP (European Monitoring and Evaluation Programme) network. Separately, for the water soluble, the soot and the mineral dust aerosol components a bias reduction and subsequent a root mean square error reduction is observed in the analysis for a test period from July to November 2003

  1. Observation operator for the assimilation of aerosol type resolving satellite measurements into a chemical transport model

    NASA Astrophysics Data System (ADS)

    Schroedter-Homscheidt, M.; Elbern, H.; Holzer-Popp, T.

    2010-06-01

    Modelling of aerosol particles with chemical transport models is still based mainly on static emission databases while episodic emissions can not be treated sufficiently. To overcome this situation, a coupling of chemical mass concentration modelling with satellite-based measurements relying on physical and optical principles has been developed. This study deals with the observation operator for a component-wise assimilation of satellite measurements. It treats aerosol particles classified into water soluble, water insoluble, soot, sea salt and mineral dust containing aerosol particles in the atmospheric boundary layer as separately assimilated aerosol components. It builds on a mapping of aerosol classes used both in observation and model space taking their optical and chemical properties into account. Refractive indices for primary organic carbon particles, anthropogenic particles, and secondary organic species have been defined based on a literature review. Together with a treatment of different size distributions in observations and model state, this allows transforming the background from mass concentrations into aerosol optical depths. A two-dimensional, variational assimilation is applied for component-wise aerosol optical depths. Error covariance matrices are defined based on a validation against AERONET sun photometer measurements. Analysis fields are assessed threefold: (1) through validation against AERONET especially in Saharan dust outbreak situations, (2) through comparison with the British Black Smoke and Sulphur Dioxide Network for soot-containing particles, and (3) through comparison with measurements of the water soluble components SO4, NH4, and NO3 conducted by the EMEP (European Monitoring and Evaluation Programme) network. Separately, for the water soluble, the soot and the mineral dust aerosol components a bias reduction and subsequent a root mean square error reduction is observed in the analysis for a test period from July to November 2003

  2. Aerosol chemical characterization and role of carbonaceous aerosol on radiative effect over Varanasi in central Indo-Gangetic Plain

    NASA Astrophysics Data System (ADS)

    Tiwari, S.; Dumka, U. C.; Kaskaoutis, D. G.; Ram, Kirpa; Panicker, A. S.; Srivastava, M. K.; Tiwari, Shani; Attri, S. D.; Soni, V. K.; Pandey, A. K.

    2016-01-01

    This study investigates the chemical composition of PM10 aerosols at Varanasi, in the central Indo-Gangetic Plain (IGP) during April to July 2011, with emphasis on examining the contribution of elemental carbon (EC) to the estimates of direct aerosol radiative effect (DARE). PM10 samples are analysed for carbonaceous aerosols (Organic Carbon, OC and EC) and water-soluble ionic species (WSIS: Cl-, SO42-, NO3-, PO42- NH4+, Na+, K+, Mg2+ and Ca2+) and several diagnostic ratios (OC/EC, K+/EC, etc) have been also used for studying the aerosol sources at Varanasi. PM10 mass concentration varies between 53 and 310 μg m-3 (mean of 168 ± 73 μg m-3), which is much higher than the National and International air quality standards. The OC mass concentration varies from 6 μg m-3 to 24 μg m-3 (mean of 12 ± 5 μg m-3; 7% of PM10 mass), whereas EC ranges between 1.0 and 14.3 μg m-3 (4.4 ± 3.9 μg m-3; ˜3% of PM10 mass). The relative low OC/EC of 3.9 ± 2.0 and strong correlation (R2 = 0.82) between them suggest the dominance of primary carbonaceous aerosols. The contribution of WSIS to PM10 is found to be ˜12%, out of which ˜57% and 43% are anions and cations, respectively. The composite DARE estimates via SBDART model reveal significant radiative effect and atmospheric heating rates (0.9-2.3 K day-1). Although the EC contributes only ˜3% to the PM10 mass, its contribution to the surface and atmospheric forcing is significantly high (37-63% and 54-77%, respectively), thus playing a major role in climate implications over Varanasi.

  3. The Effect of Aerosol Hygroscopicity and Volatility on Aerosol Optical Properties During Southern Oxidant and Aerosol Study

    NASA Astrophysics Data System (ADS)

    Khlystov, A.; Grieshop, A. P.; Saha, P.; Subramanian, R.

    2014-12-01

    Secondary organic aerosol (SOA) from biogenic sources can influence optical properties of ambient aerosol by altering its hygroscopicity and contributing to light absorption directly via formation of brown carbon and indirectly by enhancing light absorption by black carbon ("lensing effect"). The magnitude of these effects remains highly uncertain. A set of state-of-the-art instruments was deployed at the SEARCH site near Centerville, AL during the Southern Oxidant and Aerosol Study (SOAS) campaign in summer 2013 to measure the effect of relative humidity and temperature on aerosol size distribution, composition and optical properties. Light scattering and absorption by temperature- and humidity-conditioned aerosols was measured using three photo-acoustic extinctiometers (PAX) at three wavelengths (405 nm, 532 nm, and 870 nm). The sample-conditioning system provided measurements at ambient RH, 10%RH ("dry"), 85%RH ("wet"), and 200 C ("TD"). In parallel to these measurements, a long residence time temperature-stepping thermodenuder (TD) and a variable residence time constant temperature TD in combination with three SMPS systems and an Aerosol Chemical Speciation Monitor (ACSM) were used to assess aerosol volatility and kinetics of aerosol evaporation. We will present results of the on-going analysis of the collected data set. We will show that both temperature and relative humidity have a strong effect on aerosol optical properties. SOA appears to increase aerosol light absorption by about 10%. TD measurements suggest that aerosol equilibrated fairly quickly, within 2 s. Evaporation varied substantially with ambient aerosol loading and composition and meteorology.

  4. Mass spectrometric approaches for chemical characterisation of atmospheric aerosols: critical review of the most recent advances

    SciTech Connect

    Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A.

    2012-06-29

    This manuscript presents an overview of the most recent instrument developments for the field and laboratory applications of mass spectrometry (MS) to investigate the chemistry and physics of atmospheric aerosols. A range of MS instruments, employing different sample introduction methods, ionisation and mass detection techniques are used both for ‘online’ and ‘offline’ characterisation of aerosols. Online MS techniques enable detection of individual particles with simultaneous measurement of particle size distributions and aerodynamic characteristics and are ideally suited for field studies that require high temporal resolution. Offline MS techniques provide a means for detailed molecular-level analysis of aerosol samples, which is essential to gain fundamental knowledge regarding aerosol chemistry, mechanisms of particle formation and atmospheric aging. Combined, complementary MS techniques provide comprehensive information on the chemical composition, size, morphology and phase of aerosols – data of key importance for evaluating hygroscopic and optical properties of particles, their health effects, understanding their origins and atmospheric evolution. Over the last few years, developments and applications of MS techniques in aerosol research have expanded remarkably as evident by skyrocketing publication statistics. Finally, the goal of this review is to present the most recent developments in the field of aerosol mass spectrometry for the time period of late 2010 to early 2012, which have not been conveyed in previous reviews.

  5. A Comparison of Aerosol Optical, Microphysical, and Chemical Measurements between LAX and Long Beach Harbor

    NASA Astrophysics Data System (ADS)

    Thornhill, K. L.; Anderson, B. E.; Chen, G.; Winstead, E.; Ziemba, L. D.; Beyersdorf, A. J.; Diskin, G. S.; Nenes, A.; Lathem, T. L.; Arctas Science Team

    2010-12-01

    In the summer of 2008, measurements of aerosols were made on-board the NASA DC-8 over the state of California, as part of the second phase of the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) on behalf of the California Air resources Board (CARB). The DC-8 made four flights, between 18 June and 26 June, totaling 33 hours, to examine California’s atmosphere to better understand the chemical dynamics of smog and greenhouse gases over the state. The NASA DC-8 had a suite of aerosol instruments, capable of measuring the number concentrations, optical properties, and size distributions of aerosols between 0.003 and 1500 um. In this presentation, we will compare aerosol observations made at two areas within the Los Angeles Basin, Los Angeles International airport (LAX) and Long Beach Harbor. LAX is in the middle of the second most populated metropolitan area in the United States and is the fifth busiest airport in the world, while Long Beach Harbor (20 miles south of LAX) is the world’s 2nd busiest container port. Initial results suggest a greater aerosol loading and additional presence of ultrafine aerosols during the week due to vehicular emissions. We will also present analysis of aerosol observations as a function of time of day from the four missed approaches at LAX and four over flights of Long Beach Harbor.

  6. Aerosol chemical elemental mass concentration at lower free troposphere

    NASA Astrophysics Data System (ADS)

    do Carmo Freitas, Maria; Dionísio, Isabel; Fialho, Paulo; Barata, Filipe

    2007-08-01

    This paper shows the use of Instrumental neutron activation analysis (INAA) technique to determine elemental masses collected by a seven-wavelength Aethalometer instrument at the summit of Pico mountain in the Azorean archipelago, situated in the Central North Atlantic Ocean. Each sample corresponds to air particulate matter measured continuously for periods of approximately 24 h taken from 14th July 2001 through 14th July 2002. The statistical analysis of the coefficients of correlation between all the elements identified, permitted to establish six groups that could potentially be associated with the type of source responsible for the aerosol sampled in the lower free troposphere at the Azorean archipelago. Calculation of the synoptic back trajectories helped to corroborate the use of the iron/cesium relation as a tracer for the Saharan dust aerosol. It was demonstrated that INAA constituted an important tool to identify these events.

  7. Chemical characterization of challenge aerosols for HEPA filter penetration testing

    SciTech Connect

    Strandberg, S.W.

    1985-04-01

    Quality assurance penetration testing of high efficiency particulate air (HEPA) filters use oil mists as challenge aerosols. Concern over the carcinogenic risk associated with the use of di-(2-ethylhexyl)phthalate (DEHP) has led to the investigation of alternative materials and generation methods for these aerosols. Since several commonly used generation methods for quality assurance testing of HEPA filters utilize heating of the starting material, it was determined essential to evaluate the starting material and the resultant aerosol which might contain thermal degradation by-products. A penetrometer utilizing flash vaporization has been developed by A.D. Little, Inc., for the US Government as a possible alternative generation method to the Q-127 thermally generated DEHP penetrometer. Tetraethylene glycol, oleic acid, and DEHP aerosols were generated in this unit, and particulate and vapor samples were collected and identified using gas chromatography/mass spectrometry techniques. Thermally generated DEHP by-products were also sampled and identified using a Q-107 penetrometer used in the testing of large HEPA filters. Determination of the toxicological hazards of starting materials and all of the identified compounds was made by reviewing available literature obtained on the Toxline system of the National Library of Medicine. No major degradation products were found in the flash vaporization penetrometer although a number of thermally generated by-products were found in the Q-107 penetrometer. Toxicologically, no hazards were found to preclude the use of either tetraethylene glycol or oleic acid as tested in the A.D. Little penetrometer. 133 refs., 5 figs., 9 tabs.

  8. Chemical characteristics of aerosol mists in phosphate fertilizer manufacturing facilities.

    PubMed

    Hsu, Yu-Mei; Wu, Chang-Yu; Lundgren, Dale A; Nall, J Wesley; Birky, Brian K

    2007-01-01

    Of the carcinogens listed by the National Toxicology Program (NTP), strong inorganic mists containing sulfuric acid were identified as a known human carcinogen. In this study, aerosol sampling was conducted at 24 locations in eight Florida phosphoric acid and concentrated fertilizer manufacturing plants and two locations as background in Winter Haven and Gainesville, Florida, using dichotomous samplers. The locations were selected where sulfuric acid mist may potentially exist, including sulfuric acid pump tank areas, belt or rotating table phosphoric acid filter floors, sulfuric acid truck loading/unloading stations, phosphoric acid production reactors (attack tanks), and a concentrated fertilizer granulator during scrubbing with a weak sulfuric acid mixture. An ion chromatography system was used to analyze sulfate and other water soluble ion species. In general, sulfate, fluoride, ammonium, and phosphate were the major species in the fertilizer facilities. For the rotating table/belt phosphoric acid filter floor, phosphate and fluoride were the dominant species for PM10, and the maximum concentrations were 170 and 106 microg/m3, respectively. For the attack tank, fluoride was the dominant species for PM10, and the maximum concentration was 462 microg/m3. At the sulfuric acid pump tank, sulfate was the dominant species, and the maximum PM10 sulfate concentration was 181 microg/m3. The concentration of PM10 sulfate including ammonium sulfate, calcium sulfate, and sulfuric acid were lower than 0.2 mg/m3 at all locations. The aerosols at the filter floor and the attack tank were acidic. The coarse mode aerosol at the sulfuric acid pump tank (an outdoor location) was acidic, whereas the fine mode aerosol was neutral to basic. PMID:17162477

  9. Chemical Composition and Cloud Condensation Nuclei Properties of Marine Aerosols during the 2005 Marine Stratus Experiment

    NASA Astrophysics Data System (ADS)

    Lee, Y.; Hudson, J.; Daum, P.; Springston, S.; Wang, J.; Senum, G.; Alexander, L.; Jayne, J.; Hubbe, J.

    2006-12-01

    Marine aerosol chemical composition and cloud condensation nuclei (CCN) spectrum were determined on board the DOE G1 aircraft during the Marine Stratus Experiment conducted over the coastal waters between Point Reyes National Seashore and Monterey Bay, California, in July 2005. Aerosol components, including sea-salt- (sodium, chloride, magnesium, methansulfonate) and terrestrial/pollution-derived (ammonium, sulfate, nitrate, organics, potassium, and calcium) were measured using the particle-into-liquid sampler-ion chromatography technique and an Aerodyne AMS at a time resolution of 4 min and 30 s, respectively, both covering the size range of ~0.08 to 1.5 micrometers. The CCN spectrum was determined at a 1-s time resolution covering a supersaturation range between 0.02% and 1%. The accumulation mode particle size- number distribution was measured using a passive cavity aerosol spectrometer probe; the cloud droplet size- number distribution was determined using a Cloud Aerosol Probe. During the campaign sulfate/organic aerosols were always present, sea-salt aerosols were observed on half of the flights, and no dust or biomass burning contribution was noted as calcium and potassium were always below their limits-of-detection. Based on CCN spectra and cloud droplet number concentrations, the typical supersaturation of the marine stratus clouds was ~0.06%, corresponding to a CCN critical diameter between 0.1 and 0.2 micrometer. This large critical diameter makes the aerosol chemical composition measured appropriate for investigating the CCN properties and marine stratus clouds. We note that while sea-salt aerosols and sulfate aerosols were most likely externally mixed, the ensemble exhibits similar CCN properties irrespective of the relative mass concentrations of these two types of aerosols, owing partly to the similar activation properties of NaCl and (NH4)2SO4 aerosols, and that sea-salt particles were larger but fewer, accounting for a small fraction of cloud

  10. Direct aerosol chemical composition measurements to evaluate the physicochemical differences between controlled sea spray aerosol generation schemes

    NASA Astrophysics Data System (ADS)

    Collins, D. B.; Zhao, D. F.; Ruppel, M. J.; Laskina, O.; Grandquist, J. R.; Modini, R. L.; Stokes, M. D.; Russell, L. M.; Bertram, T. H.; Grassian, V. H.; Deane, G. B.; Prather, K. A.

    2014-07-01

    Controlled laboratory studies of the physical and chemical properties of sea spray aerosol (SSA) must be underpinned by a physically and chemically accurate representation of the bubble mediated production of nascent SSA particles. Since bubble bursting is sensitive to the physicochemical properties of seawater, any important differences in the SSA production mechanism are projected into SSA composition. Using direct chemical measurements of SSA at the single-particle level, this study presents an inter-comparison of three laboratory-based, bubble-mediated SSA production schemes: gas forced through submerged sintered glass filters ("frits"), a pulsed plunging waterfall apparatus, and breaking waves in a wave channel filled with natural seawater. The size-resolved chemical composition of SSA particles produced by breaking waves is more similar to particles produced by the plunging waterfall than sintered glass filters. Aerosol generated by disintegrating foam produced by sintered glass filters contained a larger fraction of organic enriched particles and a different size-resolved elemental composition, especially in the 0.8-2 μm size range. These particles, when dried, had more spherical morphologies compared to the more cubic structure expected for pure NaCl particles, which can be attributed to the presence of additional organic carbon. In addition to an inter-comparison of three SSA production methods, the role of the episodic or "pulsed" nature of the waterfall method utilized in this study on SSA composition was undertaken. In organic-enriched seawater, the continuous operation of the plunging waterfall mechanism resulted in the accumulation of surface foam and an over-expression of organic matter in SSA particles compared to pulsed plunging waterfall. Throughout this set of experiments, comparative differences in the SSA number size distribution were coincident with differences in aerosol composition, indicating that the production mechanism of SSA exerts

  11. Influence of aqueous chemistry on the chemical composition of fog water and interstitial aerosol in Fresno

    NASA Astrophysics Data System (ADS)

    Kim, Hwajin; Ge, Xinlei; Collier, Sonya; Xu, Jianzhong; Sun, Yele; Wang, Youliang; Herckes, Pierre; Zhang, Qi

    2015-04-01

    A measurement study was conducted in the Central Valley (Fresno) of California in January 2010, during which radiation fog events were frequently observed. Fog plays important roles in atmospheric chemistry by scavenging aerosol particles and trace gases and serving as a medium for various aqueous-phase reactions. Understanding the effects of fog on the microphysical and chemical processing of aerosol particles requires detailed information on their chemical composition. In this study, we characterized the chemical composition of fog water and interstitial aerosol particles to study the effects of fog processing on aerosol properties. Fog water samples were collected during the 2010 Fresno campaigns with a Caltech Active Strand Cloud water Collector (CASCC) while interstitial submicron aerosols were characterized in real time with an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and a scanning Mobility Particle Sizer (SMPS). The fog water samples were later analyzed using the HR-ToF-AMS, ion chromatography, and a total carbon analyzer. The chemical composition and characteristics of interstitial particles during the fog events were compared to those of dissolved inorganic and organic matter in fog waters. Compared to interstitial aerosols, fog water is composed of a higher fraction of ammonium nitrate and oxygenated organics, due to aqueous formation of secondary aerosol species as well as enhanced gas-to-particle partitioning of water soluble species under water rich conditions. Sulfate is formed most efficiently in fog water although its contribution to total dissolved mass is relatively low. The HR-ToF-AMS mass spectra of organic matter in fog water (FOM) are very similar to that of oxygenated organic aerosols (OOA) derived from positive matrix factorization (PMF) of the HR-ToF-AMS spectra of ambient aerosol (r2 = 0.96), but FOM appears to contain a large fraction of acidic functional groups than OOA. FOM is also enriched of

  12. Chemical and Optical Properties of Titan Aerosol Analogs Produced from Aromatic Precursors

    NASA Astrophysics Data System (ADS)

    Trainer, M. G.; Sebree, J. A.; Anderson, C. M.; Loeffler, M. J.; Stern, J. C.

    2012-04-01

    Since Cassini’s arrival at Titan, ppm levels of benzene (C6H6) as well as large positive ions, which may be polycyclic aromatic hydrocarbons (PAHs), have been detected in the atmosphere. Aromatic molecules, photolytically active in the ultraviolet, may be important in the formation of the organic aerosol comprising the Titan haze layer even when present at low mixing ratios. Yet there have not been laboratory simulations exploring the impact of these molecules as precursors to Titan’s organic aerosol. We will discuss laboratory studies forming aerosol analogs via FUV irradiation of several aromatic precursors - with and without nitrogen heteroatoms - to understand how the unique chemical architecture of the products will influence the observable aerosol characteristics. Optical analyses are focused on the far- and mid-IR spectra of the aromatic aerosol for comparison to the observations of Titan by the Cassini Composite Infrared Spectrometer (CIRS). In particular, observations of Titan by the Cassini Composite Infrared Spectrometer (CIRS) between 560 and 20 cm-1 (~18 to 500 µm) have revealed a broad emission feature centered approximately at 140 cm-1 (71 µm), which cannot be reproduced using currently available optical constants (Anderson et al., 2011; Khare et al., 1984). Chemical analysis is focused on the isotopic fractionation observed in the aerosol relative to molecular precursors, showing that the aerosol may serve as a sink for the lighter carbon and nitrogen atoms. References: Anderson, C.M., et al.: "Titan’s aerosol and stratospheric ice opacities between 18 and 500 µm: Vertical and spectral characteristics from Cassini CIRS”. Icarus, Vol. 212, pp. 762-778, 2011. Khare, B. N., et al.: “Optical constants of organic Tholins produced in a simulated Titanian Atmosphere: From soft X-ray to Microwave Frequencies”. Icarus, Vol. 60, pp. 127-137, 1984.

  13. The Effects of Soil Type and Chemical Treatment on Nickel Speciation in Refinery Enriched Soils: A Multi-Technique Investigation

    SciTech Connect

    McNear, Jr.,D.; Chaney, R.; Sparks, D.

    2007-01-01

    Aerial deposition of Ni from a refinery in Port Colborne, Ontario, Canada has resulted in the enrichment of 29 km{sup 2} of land with Ni concentrations exceeding the Canadian Ministry of the Environment's remedial action level of 200 mg kg{sup -1}. Several studies on these soils have shown that making the soils calcareous was effective at reducing chemically extractable Ni, as well as alleviating Ni phytotoxicity symptoms in vegetable crops grown in the vicinity of the refinery. Conversely, dolomitic limestone additions resulted in increased uptake of Ni in the Ni hyperaccumulator Alyssum murale 'Kotodesh', a plant whose use was proposed as a remediation strategy for this area. In this paper we use multiple techniques to directly assess the role soil type and lime treatments play in altering the speciation of Ni in the Welland loam and Quarry muck soils around the refinery and relate these findings to Ni mobility and bioavailability. Stirred-flow dissolution experiments using pH 4 HNO{sub 3} showed that Ni release from the limed Quarry muck and Welland loam soils was reduced ({approx}0.10%) relative to the unlimed soils ({approx}2.0%). Electron microprobe analysis (EMPA) identified approximately spherical NiO and Ni metal particles, which are associated with no other metals, and range from 5 to 50 {mu}m in diameter. Synchrotron micro-X-ray absorption fine structure and X-ray fluorescence spectroscopies showed that Ni and Al layered double hydroxide (Ni-Al LDH) phases were present in both the limed and unlimed mineral soils, with a tendency towards more stable (e.g., aged-LDH and phyllosilicate) Ni species in the limed soil, possibly aided by the solubilization of Si with increasing pH. In the muck soils, Ni-organic complexes (namely fulvic acid) dominated the speciation in both limed and unlimed soils. The results reported herein show that both soil type and treatment have a pronounced effect on the speciation of Ni in the soils surrounding the Port Colborne

  14. Tying Biological Activity to Changes in Sea Spray Aerosol Chemical Composition via Single Particle Analyses

    NASA Astrophysics Data System (ADS)

    Sultana, C. M.; Lee, C.; Collins, D. B.; Axson, J. L.; Laskina, O.; Grandquist, J. R.; Grassian, V. H.; Prather, K. A.

    2014-12-01

    In remote marine environments, sea spray aerosols (SSA) often represent the greatest aerosol burden, thus having significant impacts on direct radiative interactions and cloud processes. Previous studies have shown that SSA is a complex mixture of inorganic salts and an array of dissolved and particulate organic components. Enrichment of SSA organic content is often correlated to seawater chlorophyll concentrations, a measure of oceanic biological activity. As the physical and chemical properties of aerosols control their radiative effects, recent studies conducted by the Center for Aerosol Impacts on Climate and the Environment have endeavored to further elucidate the ties between marine biological activity and primary SSA chemical composition using highly time resolved single particle analyses. A series of experiments performed in the recently developed Marine Aerosol Reference Tank evaluated the effect of changing marine microbial populations on SSA chemical composition, which was monitored via an aerosol time-of-flight mass spectrometer and a variety of offline spectroscopic and microscopic techniques. Each experiment was initiated using unfiltered and untreated seawater, thus maintaining a high level of biogeochemical complexity. This study is the first of its kind to capture daily changes in the primary SSA mixing state over the growth and death of a natural phytoplankton bloom. Increases in organic aerosol types (0.4-3 μm), internally and externally mixed with sea salt, could not be correlated to chlorophyll concentrations. Maximum production of these populations occurred two to four days after the in vivo chlorophyll fluorescence peaked in intensity. This work is in contrast to the current paradigm of correlating SSA organic content to seawater chlorophyll concentration.

  15. Effects of Chemical Aging on the Heterogeneous Freezing of Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Collier, K.; Brooks, S. D.

    2014-12-01

    Organic aerosols are emitted into the atmosphere from a variety of sources and display a wide range of effectiveness in promoting the nucleation of ice in clouds. Soot and polycyclic aromatic hydrocarbons (PAHS) arise from incomplete combustion and other pollutant sources. Hydrocarbon compounds in diesel motor oil and other fuel blends include compounds such as octacosane (a straight saturated alkane), squalane (a branched saturated alkane) and squalene (an unsaturated branched alkene). At temperatures above -36°C, the formation of ice crystals in the atmosphere is facilitated by heterogeneous freezing processes in which atmospheric aerosols act as ice nuclei (IN). The variability in ability of organic particles to facilitate heterogeneous ice nucleation causes major uncertainties in predictions of aerosol effects on climate. Further, atmospheric aerosol composition and ice nucleation ability can be altered via chemical aging and reactions with atmospheric oxidants such as ozone. In this study, we take a closer look at the role of chemical oxidation on the efficiency of specific IN during contact freezing laboratory experiments. The freezing temperatures of droplets in contact with representative organic aerosols are determined through the use of an optical microscope apparatus equipped with a cooling stage and a digital camera. Chemical changes at the surface of aerosols due to ozone exposure are characterized using Raman Microspectroscopy and Fourier Transform Infrared Spectroscopy with Horizontal Attenuated Total Reflectance. Our results indicate that oxidation of certain atmospheric organics (soot and PAHS) enhances their ice nucleation ability. In this presentation, results of heterogeneous nucleation on various types of organic aerosols will be presented, and the role of structure in promoting freezing will be discussed.

  16. Assessment of microphysical and chemical factors of aerosols over seas of the Russian Artic Eastern Section

    NASA Astrophysics Data System (ADS)

    Golobokova, Liudmila; Polkin, Victor

    2014-05-01

    The newly observed kickoff of the Northern Route development drew serious attention to state of the Arctic Resource environment. Occurring climatic and environmental changes are more sensitively seen in polar areas in particular. Air environment control allows for making prognostic assessments which are required for planning hazardous environmental impacts preventive actions. In August - September 2013, RV «Professor Khlustin» Northern Sea Route expeditionary voyage took place. En-route aerosol sampling was done over the surface of the Beringov, Chukotka and Eastern-Siberia seas (till the town of Pevek). The purpose of sampling was to assess spatio-temporal variability of optic, microphysical and chemical characteristics of aerosol particles of the surface layer within different areas adjacent to the Northern Sea Route. Aerosol test made use of automated mobile unit consisting of photoelectric particles counter AZ-10, aetalometr MDA-02, aspirator on NBM-1.2 pump chassis, and the impactor. This set of equipment allows for doing measurements of number concentration, dispersed composition of aerosols within sizes d=0.3-10 mkm, mass concentration of submicron sized aerosol, and filter-conveyed aerosols sampling. Filter-conveyed aerosols sampling was done using method accepted by EMEP and EANET monitoring networks. The impactor channel was upgraded to separate particles bigger than 1 mkm in size, and the fine grain fraction settled down on it. Reverse 5-day and 10-day trajectories of air mass transfer executed at heights of 10, 1500 and 3500 m were analyzed. The heights were selected by considerations that 3000 m is the height which characterizes air mass trend in the lower troposphere. 1500 m is the upper border of the atmospheric boundary layer, and the sampling was done in the Earth's surface layer at less than 10 m. Minimum values of the bespoken microphysical characteristics are better characteristic of higher latitudes where there are no man induced sources of

  17. Modelling the optical properties of aerosols in a chemical transport model

    NASA Astrophysics Data System (ADS)

    Andersson, E.; Kahnert, M.

    2015-12-01

    According to the IPCC fifth assessment report (2013), clouds and aerosols still contribute to the largest uncertainty when estimating and interpreting changes to the Earth's energy budget. Therefore, understanding the interaction between radiation and aerosols is both crucial for remote sensing observations and modelling the climate forcing arising from aerosols. Carbon particles are the largest contributor to the aerosol absorption of solar radiation, thereby enhancing the warming of the planet. Modelling the radiative properties of carbon particles is a hard task and involves many uncertainties arising from the difficulties of accounting for the morphologies and heterogeneous chemical composition of the particles. This study aims to compare two ways of modelling the optical properties of aerosols simulated by a chemical transport model. The first method models particle optical properties as homogeneous spheres and are externally mixed. This is a simple model that is particularly easy to use in data assimilation methods, since the optics model is linear. The second method involves a core-shell internal mixture of soot, where sulphate, nitrate, ammonia, organic carbon, sea salt, and water are contained in the shell. However, by contrast to previously used core-shell models, only part of the carbon is concentrated in the core, while the remaining part is homogeneously mixed with the shell. The chemical transport model (CTM) simulations are done regionally over Europe with the Multiple-scale Atmospheric Transport and CHemistry (MATCH) model, developed by the Swedish Meteorological and Hydrological Institute (SMHI). The MATCH model was run with both an aerosol dynamics module, called SALSA, and with a regular "bulk" approach, i.e., a mass transport model without aerosol dynamics. Two events from 2007 are used in the analysis, one with high (22/12-2007) and one with low (22/6-2007) levels of elemental carbon (EC) over Europe. The results of the study help to assess the

  18. Aerosolization, Chemical Characterization, Hygroscopicity and Ice Formation of Marine Biogenic Particles

    NASA Astrophysics Data System (ADS)

    Alpert, P. A.; Radway, J.; Kilthau, W.; Bothe, D.; Knopf, D. A.; Aller, J. Y.

    2013-12-01

    The oceans cover the majority of the earth's surface, host nearly half the total global primary productivity and are a major source of atmospheric aerosol particles. However, effects of biological activity on sea spray generation and composition, and subsequent cloud formation are not well understood. Our goal is to elucidate these effects which will be particularly important over nutrient rich seas, where microorganisms can reach concentrations of 10^9 per mL and along with transparent exopolymer particles (TEP) can become aerosolized. Here we report the results of mesocosm experiments in which bubbles were generated by two methods, either recirculating impinging water jets or glass frits, in natural or artificial seawater containing bacteria and unialgal cultures of three representative phytoplankton species, Thalassiosira pseudonana, Emiliania huxleyi, and Nannochloris atomus. Over time we followed the size distribution of aerosolized particles as well as their hygroscopicity, heterogeneous ice nucleation potential, and individual physical-chemical characteristics. Numbers of cells and the mass of dissolved and particulate organic carbon (DOC, POC), TEP (which includes polysaccharide-containing microgels and nanogels >0.4 μm in diameter) were determined in the bulk water, the surface microlayer, and aerosolized material. Aerosolized particles were also impacted onto substrates for ice nucleation and water uptake experiments, elemental analysis using computer controlled scanning electron microscopy and energy dispersive analysis of X-rays (CCSEM/EDX), and determination of carbon bonding with scanning transmission X-ray microscopy and near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Regardless of bubble generation method, the overall concentration of aerosol particles, TEP, POC and DOC increased as concentrations of bacterial and phytoplankton cells increased, stabilized, and subsequently declined. Particles <100 nm generated by means of jets

  19. Systematic Relationships among Background SE U.S. Aerosol Optical, Micro-physical, and Chemical Properties-Development of an Optically-based Aerosol Characterization

    NASA Astrophysics Data System (ADS)

    Sherman, J. P.; Link, M. F.; Zhou, Y.

    2014-12-01

    Remote sensing-based retrievals of aerosol composition require known or assumed relationships between aerosol optical properties and types. Most optically-based aerosol classification schemes apply some combination of the spectral dependence of aerosol light scattering and absorption-using the absorption and either scattering or extinction Angstrom exponents (AAE, SAE and EAE), along with single-scattering albedo (SSA). These schemes can differentiate between such aerosol types as dust, biomass burning, and urban/industrial but no such studies have been conducted in the SE U.S., where a large fraction of the background aerosol is a variable mixture of biogenic SOA, sulfates, and black carbon. In addition, AERONET retrievals of SSA are often highly uncertain due to low AOD in the region during most months. The high-elevation, semi-rural AppalAIR facility at Appalachian State University in Boone, NC (1090m ASL, 36.210N, 81.690W) is home to the only co-located NOAA-ESRL and AERONET monitoring sites in the eastern U.S. Aerosol chemistry measured at AppalAIR is representative of the background SE U.S (Link et al. 2014) Dried aerosol light absorption and dried and humidified aerosol light scattering and hemispheric backscattering at 3 visible wavelengths and 2 particle size cuts (sub-1μm and sub-10μm) are measured continuously. Measurements of size-resolved, non-refractory sub-1μm aerosol composition were made by a co-located AMS during the 2012-2013 summers and 2013 winter. Systematic relationships among aerosol optical, microphysical, and chemical properties were developed to better understand aerosol sources and processes and for use in higher-dimension aerosol classification schemes. The hygroscopic dependence of visible light scattering is sensitive to the ratio of sulfate to organic aerosol(OA), as are SSA and AAE. SAE is a less sensitive indicator of fine-mode aerosol size than hemispheric backscatter fraction (b) and is more sensitive to fine-mode aerosol

  20. Chemical speciation and bioavailability of selenium in the rhizosphere of Symphyotrichum eatonii from reclaimed mine soils.

    PubMed

    Oram, Libbie L; Strawn, Daniel G; Möller, Gregory

    2011-02-01

    Knowledge of rhizosphere influences on Se speciation and bioavailability is required to predict Se bioavailability to plants. In the present study, plant-availability of Se to aster (Symphyotrichum eatonii (A. Gray) G.L. Nesom) was compared in rhizosphere soils and nonrhizosphere (bulk) soils collected from a reclaimed mine site in southeastern Idaho, U.S. X-ray spectroscopy was used to characterize the oxidation state and elemental distribution of Se in aster roots, rhizosphere soils, and bulk soils. Percent extractable Se in aster rhizosphere soil was greater than extractable Se in corresponding bulk soils in all samples (n = 4, p = 0.042, 0.051, and 0.052 for three extractions). Selenium oxidation state mapping of 28 regions within the samples and X-ray absorption near edge structure (XANES) spectra from 26 points within the samples indicated that the rhizosphere and bulk soil Se species was predominantly reduced Se(-II,0), while in the aster roots, high concentrations of Se(VI) were present. Results show that within the rhizosphere, enhanced Se bioavailability is occurring via oxidation of reduced soil Se to more soluble Se(VI) species. PMID:21166454

  1. Comparison of the spectroscopic speciation and chemical fractionation of chromium in contaminated paddy soils.

    PubMed

    Hsu, Liang-Ching; Liu, Yu-Ting; Tzou, Yu-Min

    2015-10-15

    Sequential extraction has been widely used to classify metal species in soils and sediments; however, the lack of selectivity in extraction reagents may lead to the misinterpretation of metal speciation. In this study, we used X-ray absorption near edge structure (XANES) spectroscopy to classify Cr species based on its molecular form. These results complement the conventional Cr fractionation derived from the Tessier extraction method. The linear combination fitting (LCF) for the Cr-XANES spectra indicated that the Cr species in the soils could generally be described as Cr(III) sorbed on ferrihydrite (Cr-FH), Cr(III) complexed with humic acid (Cr-HA), and precipitated Cr. While the sum of the adsorbed Cr(III) and Cr(III)/Fe coprecipitates showed a nearly 1:1 relationship with reducible Cr, the total of Cr precipitates and organic Cr also followed the same trend with oxidizable Cr. This result indicated that there might be a underestimation in the reducible fraction as pure Cr(III) precipitates associated with surfaces of Fe minerals would not be extracted in the reducible process. Instead, such pure Cr(III) precipitates were dissolved during the oxidizable process, resulting in a overestimation in the fractionation of organic-related Cr. PMID:25935296

  2. Retention and chemical speciation of uranium in an oxidized wetland sediment from the Savannah River Site.

    PubMed

    Li, Dien; Seaman, John C; Chang, Hyun-Shik; Jaffe, Peter R; Koster van Groos, Paul; Jiang, De-Tong; Chen, Ning; Lin, Jinru; Arthur, Zachary; Pan, Yuanming; Scheckel, Kirk G; Newville, Matthew; Lanzirotti, Antonio; Kaplan, Daniel I

    2014-05-01

    Uranium speciation and retention mechanisms onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction, U L3-edge X-ray absorption near-edge structure (XANES) spectroscopy, fluorescence mapping and μ-XANES. Under oxidized conditions, U was highly retained by the SRS wetland sediments. In contrast to other similar but much lower natural organic matter (NOM) sediments, significant sorption of U onto the SRS sediments was observed at pH < 4 and pH > 8. Sequential extraction indicated that the U species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and organic fraction (Na-pyrophosphate extractable). Uranium L3-edge XANES spectra of the U-bound sediments were nearly identical to that of uranyl acetate. Based on fluorescence mapping, U and Fe distributions in the sediment were poorly correlated, U was distributed throughout the sample and did not appear as isolated U mineral phases. The primary oxidation state of U in these oxidized sediments was U(VI), and there was little evidence that the high sorptive capacity of the sediments could be ascribed to abiotic or biotic reduction to the less soluble U(IV) species or to secondary mineral formation. Collectively, this study suggests that U may be strongly bound to wetland sediments, not only under reducing conditions by reductive precipitation, but also under oxidizing conditions through NOM-uranium bonding. PMID:24238918

  3. Internal iron biomineralization in Imperata cylindrica, a perennial grass: chemical composition, speciation and plant localization.

    PubMed

    Rodríguez, N; Menéndez, N; Tornero, J; Amils, R; de la Fuente, V

    2005-03-01

    * The analysis of metal distribution in Imperata cylindrica, a perennial grass isolated from the banks of Tinto River (Iberian Pyritic Belt), an extreme acidic environment with high content in metals, has shown a remarkable accumulation of iron. This property has been used to study iron speciation and its distribution among different tissues and structures of the plant. * Mossbauer (MS) and X-ray diffraction (XRD) were used to determine the iron species, scanning electron microscopy (SEM) to locate iron biominerals among plant tissue structures, and energy-dispersive X-ray microanalysis (EDAX), X-ray fluorescence (TXRF) and inductively coupled plasma emission spectroscopy (ICP-MS) to confirm their elemental composition. * The MS spectral analysis indicated that iron accumulated in this plant mainly as jarosite and ferritin. The presence of jarosite was confirmed by XRD and the distribution of both minerals in structures of different tissues was ascertained by SEM-EDAX analysis. * The convergent results obtained by complementary techniques suggest a complex iron management system in I. cylindrica, probably as a consequence of the environmental conditions of its habitat. PMID:15720689

  4. XPS analysis of combustion aerosols for chemical composition, surface chemistry, and carbon chemical state.

    PubMed

    Vander Wal, Randy L; Bryg, Vicky M; Hays, Michael D

    2011-03-15

    Carbonaceous aerosols can vary in elemental content, surface chemistry, and carbon nano-structure. Each of these properties is related to the details of soot formation. Fuel source, combustion process (affecting formation and growth conditions), and postcombustion exhaust where oxidation occurs all contribute to the physical structure and surface chemistry of soot. Traditionally such physical and chemical parameters have been measured separately by various techniques. Presented here is the unified measurement of these characteristics using X-ray photoelectron spectroscopy (XPS). In the present study, XPS is applied to combustion soot collected from a diesel engine (running biodiesel and pump-grade fuels); jet engine; and institutional, plant, and residential oil-fired boilers. Elemental composition is mapped by a survey scan over a broad energy range. Surface chemistry and carbon nanostructure are quantified by deconvolution of high-resolution scans over the C1s region. This combination of parameters forms a distinct matrix of identifiers for the soots from these sources. PMID:21322576

  5. Production Mechanism, Number Concentration, Size Distribution, Chemical Composition, and Optical Properties of Sea Spray Aerosols Workshop, Summer 2012

    SciTech Connect

    Meskhidze, Nicholas

    2013-10-21

    The objective of this workshop was to address the most urgent open science questions for improved quantification of sea spray aerosol-radiation-climate interactions. Sea spray emission and its influence on global climate remains one of the most uncertain components of the aerosol-radiation-climate problem, but has received less attention than other aerosol processes (e.g. production of terrestrial secondary organic aerosols). Thus, the special emphasis was placed on the production flux of sea spray aerosol particles, their number concentration and chemical composition and properties.

  6. Development of Fundamental Data on Chemical Speciation and Solubility for Strontium and Americium in High Level Waste: Predictive Modeling of Phase Partitioning During Tank Processing

    SciTech Connect

    Felmy, Andrew R.; Choppin, Gregory; Dixon, David A.; Campbell, James A.

    2000-06-01

    In this research program, Pacific Northwest National Laboratory (PNNL) and Florida State University (FSU) are investigating the speciation of Sr and Am/Cm in the presence of selected organic chelating agents (ethylenediaminetetraacetic acid (EDTA), N-(2- hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), and iminodiacetic acid (IDA)) over ranges of hydroxide, carbonate, ionic strength, and competing metal ion concentrations present in high level waste tanks. The project is comprised of integrated research tasks that approach the problem of chemical speciation using macroscopic thermodynamic measurements of metal-ligand competition reactions, molecular modeling studies to identify structures or complexes of unusual stability, and mass spectrometry measurements of complex charge/mass ratio that can be applied to mixed metal-chelate systems. This fundamental information is then used to develop thermodynamic models which allows the prediction of changes in chemical speciation and solubility which can occur in response to changes in tank processing conditions. In this way we can both develop new approaches that address fundamental problems in aqueous speciation and at the same time provide useful and practical information needed for tank processing.

  7. Development of Fundamental Data on Chemical Speciation and Solubility for Strontium and Americium in High- Level Waste: Predictive Modeling of Phase Partitioning During Tank Processing

    SciTech Connect

    Felmy, Andrew R.; Choppin, Gregory; Dixon, David A.

    2001-06-01

    In this research program, Pacific Northwest National Laboratory and Florida State University are investigating the speciation of Sr and Am/Cm in the presence of selected organic chelating agents (ethylenediaminetetraacetic acid [EDTA], N-(2-hydroxyethyl)ethylenediaminetriacetic acid [HEDTA], nitrilotriacetic acid [NTA], iminodiacetic acid [IDA], citrate, and oxalate) over ranges of hydroxide, carbonate, ionic strength, and competing metal ion concentrations present in high-level waste stored in tanks at Hanford and other U.S. Department of Energy (DOE) sites. The project comprises integrated research tasks that approach the problem of chemical speciation using macroscopic thermodynamic measurements of metal-ligand competition reactions, molecular modeling studies to identify structures or complexes of unusual stability, and mass spectrometry measurements of complex charge/mass ratio that can be applied to mixed metalchelate systems. This fundamental information then is used to develop thermodynamic models designed to predict changes in chemical speciation and solubility resulting from various tank processing conditions. In this way we can develop new approaches that address fundamental problems in aqueous speciation and, at the same time, provide useful and practical information needed for tank waste processing.

  8. Speciation and pulmonary effects of acidic SO x formed on the surface of ultrafine zinc oxide aerosols

    NASA Astrophysics Data System (ADS)

    Amdur, Mary O.; Chen, Lung Chi; Guty, John; Lam, Hua Fuan; Miller, Patricia D.

    Ultrafine metal oxides and SO 2 react during coal combustion or smelting operations to form primary emissions coated with an acidic SO x layer. A ZnO-SO 2-H 2O (mixed 500°C) system generates such particles to provide greatly needed information on both quantitative composition of the surface layer and its effects on the lung. Total S on the particles is related to ZnO concentration and is predominantly S VI. As a surface layer, 20 μg m -3 H 2SO 4 decreases pulmonary diffusing capacity in guinea pigs after four daily 3-h exposures and produces bronchial hypersensitivity following a single 1-h exposure. That 200 μg m -3 H 2SO 4 aerosols of equivalent particle size are needed to produce the same degree of bronchial hypersensitivity emphasizes the importance of the surface layer.

  9. Chemical composition of Eastern Black Sea aerosol--preliminary results.

    PubMed

    Balcılar, Ilker; Zararsız, Abdullah; Kalaycı, Yakup; Doğan, Güray; Tuncel, Gürdal

    2014-08-01

    Trace element composition of atmospheric particles collected at a high altitude site on the Eastern Black Sea coast of Turkey was investigated to understand atmospheric transport of pollutants to this semi-closed basin. Aerosol samples were collected at a timber-storage area, which is operated by the General Directorate of Forestry. The site is situated at a rural area and is approximately 50 km to the Black Sea coast and 200 km to the Georgia border of Turkey. Coarse (PM2.5-10) and fine (PM2.5) aerosol samples were collected between 2011 and 2013 using a "stacked filter unit". Collected samples were shipped to the Middle East Technical University in Ankara, where Na, Mg, Al, Si, S, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Ba, Pb were measured by Energy dispersive x-ray fluorescence technique (EDXRF). Comparison of measured concentrations of elements with corresponding data generated at other parts of Turkey demonstrated that concentrations of pollution derived elements are higher at Eastern Black Sea than their corresponding concentrations measured at other parts of Turkey, which is attributed to frequent transport of pollutants from north wind sector. Positive matric factorization revealed four factors including three anthropogenic and a crustal factor. Southeastern parts of Turkey, Georgia and Black Sea coast of Ukraine were identified as source regions affecting composition of particles at our site, using trajectory statistics, namely "potential source contribution function" (PSCF). PMID:24373640

  10. Aerosol chemical vapor deposition of metal oxide films

    DOEpatents

    Ott, K.C.; Kodas, T.T.

    1994-01-11

    A process of preparing a film of a multicomponent metal oxide including: forming an aerosol from a solution comprised of a suitable solvent and at least two precursor compounds capable of volatilizing at temperatures lower than the decomposition temperature of said precursor compounds; passing said aerosol in combination with a suitable oxygen-containing carrier gas into a heated zone, said heated zone having a temperature sufficient to evaporate the solvent and volatilize said precursor compounds; and passing said volatilized precursor compounds against the surface of a substrate, said substrate having a sufficient temperature to decompose said volatilized precursor compounds whereby metal atoms contained within said volatilized precursor compounds are deposited as a metal oxide film upon the substrate is disclosed. In addition, a coated article comprising a multicomponent metal oxide film conforming to the surface of a substrate selected from the group consisting of silicon, magnesium oxide, yttrium-stabilized zirconium oxide, sapphire, or lanthanum gallate, said multicomponent metal oxide film characterized as having a substantially uniform thickness upon said substrate.

  11. Aerosol physical, chemical and optical properties observed in the ambient atmosphere during haze pollution conditions

    NASA Astrophysics Data System (ADS)

    Li, Zhengqiang; Xie, Yisong; Li, Donghui; Li, Kaitao; Zhang, Ying; Li, Li; Lv, Yang; Qie, Lili; Xu, Hua

    Aerosol’s properties in the ambient atmosphere may differ significantly from sampling results due to containing of abundant water content. We performed sun-sky radiometer measurements in Beijing during 2011 and 2012 winter to obtain distribution of spectral and angular sky radiance. The measurements are then used to retrieve aerosol physical, chemical and optical properties, including single scattering albedo, size distribution, complex refractive indices and aerosol component fractions identified as black carbon, brown carbon, mineral dust, ammonium sulfate-like components and water content inside particle matters. We found that during winter haze condition aerosol is dominated by fine particles with center radius of about 0.2 micron. Fine particles contribute about 93% to total aerosol extinction of solar light, and result in serious decrease of atmospheric visibility during haze condition. The percentage of light absorption of haze aerosol can up to about 10% among its total extinction, much higher than that of unpolluted conditions, that causes significant radiative cooling effects suppressing atmospheric convection and dispersion of pollutants. Moreover, the average water content occupies about one third of the ambient aerosol in volume which suggests the important effect of ambient humidity in the formation of haze pollution.

  12. A model for studying the composition and chemical effects of stratospheric aerosols

    SciTech Connect

    Tabazadeh, A.; Turco, R.P.; Jacobson, M.Z.

    1994-06-01

    We developed polynomial expressions for the temperature dependence of the mean binary and water activity coefficients for H2SO4 and HNO3 solutions. These activities were used in an equilibrium model to predict the composition of stratospheric aerosols under a wide range of environmental conditions. For typical concentrations of H2O, H2SO4, HNO3, HCl, HBr, HF, and HOCl in the lower stratosphere, the aerosol composition is estimated as a function of the local temperature and the ambient relative humidity. For temperatures below 200 K, our results indicate that (1) HNO3 contributes a significant mass fraction to stratospheric aerosols, and (2) HCl solubility is considerably affected by HNO3 dissolution into sulfate aerosols. We also show that, in volcanically disturbed periods, changes in stratospheric aerosol composition can significantly alter the microphysics that leads to the formation of polar stratospheric clouds. The effects caused by HNO3 dissolution on the physical and chemical properties of stratospheric aerosols are discussed.

  13. A model for studying the composition and chemical effects of stratospheric aerosols

    NASA Technical Reports Server (NTRS)

    Tabazadeh, Azadeh; Turco, Richard P.; Jacobson, Mark Z.

    1994-01-01

    We developed polynomial expressions for the temperature dependence of the mean binary and water activity coefficients for H2SO4 and HNO3 solutions. These activities were used in an equilibrium model to predict the composition of stratospheric aerosols under a wide range of environmental conditions. For typical concentrations of H2O, H2SO4, HNO3, HCl, HBr, HF, and HOCl in the lower stratosphere, the aerosol composition is estimated as a function of the local temperature and the ambient relative humidity. For temperatures below 200 K, our results indicate that (1) HNO3 contributes a significant mass fraction to stratospheric aerosols, and (2) HCl solubility is considerably affected by HNO3 dissolution into sulfate aerosols. We also show that, in volcanically disturbed periods, changes in stratospheric aerosol composition can significantly alter the microphysics that leads to the formation of polar stratospheric clouds. The effects caused by HNO3 dissolution on the physical and chemical properties of stratospheric aerosols are discussed.

  14. Atmospheric aerosols: A literature summary of their physical characteristics and chemical composition

    NASA Technical Reports Server (NTRS)

    Harris, F. S., Jr.

    1976-01-01

    This report contains a summary of 199 recent references on the characterization of atmospheric aerosols with respect to their composition, sources, size distribution, and time changes, and with particular reference to the chemical elements measured by modern techniques, especially activation analysis.

  15. Winter time chemical characteristics of aerosols over the Bay of Bengal: continental influence.

    PubMed

    Aryasree, S; Nair, Prabha R; Girach, I A; Jacob, Salu

    2015-10-01

    As part of the Integrated Campaign for Aerosols, gases and Radiation Budget (ICARB) conducted under the Geosphere Biosphere Programme of Indian Space Research Organisation, ship-based aerosol sampling was carried out over the marine environment of Bay of Bengal (BoB) during the northern winter months of December 2008 to January 2009. About 101 aerosol samples were collected, covering the region from 3.4° to 21° N latitude and 76° to 98° E longitude-the largest area covered-including the south east (SE) BoB for the first time. These samples were subjected to gravimetric and chemical analysis and the total aerosol loading as well the mass concentration of the ionic species namely F(-), Cl(-), Br(-), NO2 (-), NO3 (-), PO4 (2-), SO4 (2-), NH4 (+), etc. and the metallic species, Na, Mg, Ca, K, Al, Fe, Mn, Zn, and Pb were estimated for each sample. Based on the spatial distribution of individual chemical species, the air flow pattern, and airmass back trajectory analysis, the source characteristics of aerosols for different regions of BoB were identified. Significant level of continental pollution was noticed over BoB during winter. While transport of pollution from Indo-Gangetic Plain (IGP) contributed to aerosols over north BoB, those over SE BoB were influenced by SE Asia. A quantitative study on the wind-induced production of sea salt aerosols and a case study on the species dependent effect of rainfall are also presented in this paper. PMID:25994269

  16. Sensitivity of Scattering and Backscattering Coefficients to Microphysical and Chemical Properties: Weakly Absorbing Aerosol

    NASA Astrophysics Data System (ADS)

    Kassianov, E.; Barnard, J.; Pekour, M. S.; Berg, L. K.; Shilling, J.; Flynn, C. J.; Mei, F.; Jefferson, A.

    2014-12-01

    Scattering and backscattering coefficients of atmospheric aerosol are crucial parameters for numerous climate-relevant applications, including studies related to the Earth's radiation budget. Due to their strong connection to aerosol chemical and microphysical characteristics, in situ measurements have been commonly used for evaluating optical properties routines in global and regional scale models. However, these in situ measurements, including size distribution and chemical composition data, can be subject to uncertainties. Techniques for obtaining these data depend on particle size (submicron versus supermicron) and relative humidity range (dry versus wet conditions). In this study, we examine how the data uncertainties can impact the level of agreement between the calculated and measured optical properties (commonly known as optical closure). Moreover, we put forth a novel technique for inferring in parallel the effective density and real refractive index of weakly absorbing aerosols from simultaneously measured size distributions (with mobility and aerodynamic sizes), and two optical properties, namely the scattering coefficient and hemispheric backscatter fraction, measured by integrating nephelometer. We demonstrate the performance of our technique, which permits discrimination between the retrieved aerosol characteristics of sub-micron and sub-10-micron particles, using both a sensitivity study with synthetically generated inputs with random noise and a six-week case study with real measurements. These measurements cover a wide range of coastal summertime conditions observed during the recent Two-Column Aerosol Project (TCAP, http://campaign.arm.gov/tcap/) and include periods with a wide range of aerosol loading and relative humidity. Finally, we discuss how in situ data and retrievals of aerosol characteristics can be applied for model evaluation.

  17. The application of thermal methods for determining chemical composition of carbonaceous aerosols: a review.

    PubMed

    Chow, Judith C; Yu, Jian Zhen; Watson, John G; Ho, Steven Sai Hang; Bohannan, Theresa L; Hays, Michael D; Fung, Kochy K

    2007-09-01

    Thermal methods of various forms have been used to quantify carbonaceous materials. Thermal/optical carbon analysis provides measurements of organic and elemental carbon concentrations as well as fractions evolving at specific temperatures in ambient and source aerosols. Detection of thermally desorbed organic compounds with thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) identifies and quantifies over 100 individual organic compounds in particulate matter (PM) samples. The resulting mass spectra contain information that is consistent among, but different between, source emissions even in the absence of association with specific organic compounds. TD-GC/MS is a demonstrated alternative to solvent extraction for many organic compounds and can be applied to samples from existing networks. It is amenable to field-deployable instruments capable of measuring organic aerosol composition in near real-time. In this review, thermal stability of organic compounds is related to chemical structures, providing a basis for understanding thermochemical properties of carbonaceous aerosols. Recent advances in thermal methods applied to determine aerosol chemical compositions are summarized and their potential for uncovering aerosol chemistry are evaluated. Current limitations and future research needs of the thermal methods are included. PMID:17849294

  18. Modelling Aerosol Influences on Temperature and Visibility as a Module for Chemical Weather Forecasts

    NASA Astrophysics Data System (ADS)

    Riemer, N.; Vogel, B.; Vogel, H.; Kottmeier, Ch.

    2003-04-01

    Aerosol particles modify the radiative transfer in the atmosphere pronouncedly. Their impact on the global radiation and on the heating or cooling rates within the atmosphere is not very well quantified. Moreover, the presence of aerosol particles in the atmosphere determines the visual range which is an important parameter for aviation and other traffic systems and for tourism. While the optical properties of the aerosol particles depend on their chemical composition and size distribution, present day’s operational forecast models, however, use a highly simplified scheme using the relative humidity in combination with statistical models to forecast the visual range. We used the mesoscale-gamma model KAMM/DRAIS to determine the influence of aerosol particles on the global radiation, the vertical profiles of the heating rates and the visual range. Applications are run for south-western Germany, but the methods can be also used for weather forecast models. The aerosol model MADEsoot is used to calculate the size dependent aerosol dynamics. It takes into account secondary inorganic and organic particles and soot in internal and external mixture. With the exception of the radiative transfer calculations, the model system is run in a fully coupled mode. To determine the spatial distribution of the extinction coefficient, the single scattering albedo, and the phase-function Mie calculations are carried out based on the simulated aerosol distributions. Using this data radiative transfer calculations with libRadtran are performed to determine the impact of the aerosols on the global radiation and the vertical profiles of the heating rates for a clear summer day. Based on the extinction coefficients the visual range is calculated. Diurnal cycles of the visual range are compared to observed ones.

  19. Studies of the chemical mixing state of sea spray aerosol and associated climate relevant properties (Invited)

    NASA Astrophysics Data System (ADS)

    Prather, K. A.; Bertram, T. H.; Grassian, V. H.; Collins, D. B.; Ault, A. P.; Ruppel, M. J.; Axson, J. L.; Ryder, O. S.; Schill, S.

    2013-12-01

    The ocean plays a large but highly uncertain role in affecting clouds and climate, generating sea spray aerosols that can directly impact climate by scattering solar radiation and indirectly through nucleating clouds. A tremendous amount has been learned about these interactions over decades of marine studies, however the goal of establishing robust relationships between seawater composition and sea spray climate properties has remained elusive. Much of the impediment stems from difficulties associated with unraveling the impacts of nascent sea spray and background marine aerosols which have been shown to dominate field measurements. In an effort to advance our understanding of nascent sea spray properties, we have developed a new approach for studying this issue in a newly developed ocean-atmosphere facility equipped with breaking waves. After establishing extremely low background aerosol concentrations (< 1 per cc), studies have probed the size distribution and chemical mixing state of sea spray aerosols produced by breaking waves in natural seawater. The critical importance of using bubble size distributions representative of real breaking waves to generate sea spray aerosol (SSA) is discussed. Using a combination of techniques probing individual particle composition and morphology including aerosol time-of-flight mass spectrometry (ATOFMS), scanning tunnel x-ray microscopy (STXM), and electron microscopy, four major sea spray particle types are prevalent in all studies, consisting of sea salt, mixed sea salt and biogenic organic species, biogenic organic species, and primary biological aerosol particles (PBAP). Results from studies aimed at probing how changes in seawater composition due to biological activity impact sea spray aerosol composition and climate properties will be discussed.

  20. Modelling of primary aerosols in the chemical transport model MOCAGE: development and evaluation of aerosol physical parameterizations

    NASA Astrophysics Data System (ADS)

    Sič, B.; El Amraoui, L.; Marécal, V.; Josse, B.; Arteta, J.; Guth, J.; Joly, M.; Hamer, P. D.

    2015-02-01

    This paper deals with recent improvements to the global chemical transport model of Météo-France MOCAGE (Modèle de Chimie Atmosphérique à Grande Echelle) that consists of updates to different aerosol parameterizations. MOCAGE only contains primary aerosol species: desert dust, sea salt, black carbon, organic carbon, and also volcanic ash in the case of large volcanic eruptions. We introduced important changes to the aerosol parameterization concerning emissions, wet deposition and sedimentation. For the emissions, size distribution and wind calculations are modified for desert dust aerosols, and a surface sea temperature dependant source function is introduced for sea salt aerosols. Wet deposition is modified toward a more physically realistic representation by introducing re-evaporation of falling rain and snowfall scavenging and by changing the in-cloud scavenging scheme along with calculations of precipitation cloud cover and rain properties. The sedimentation scheme update includes changes regarding the stability and viscosity calculations. Independent data from satellites (MODIS, SEVIRI), the ground (AERONET, EMEP), and a model inter-comparison project (AeroCom) are compared with MOCAGE simulations and show that the introduced changes brought a significant improvement on aerosol representation, properties and global distribution. Emitted quantities of desert dust and sea salt, as well their lifetimes, moved closer towards values of AeroCom estimates and the multi-model average. When comparing the model simulations with MODIS aerosol optical depth (AOD) observations over the oceans, the updated model configuration shows a decrease in the modified normalized mean bias (MNMB; from 0.42 to 0.10) and a better correlation (from 0.06 to 0.32) in terms of the geographical distribution and the temporal variability. The updates corrected a strong positive MNMB in the sea salt representation at high latitudes (from 0.65 to 0.16), and a negative MNMB in the desert

  1. Coupling aerosol optics to the chemical transport model MATCH (v5.5.0) and aerosol dynamics module SALSA (v1)

    NASA Astrophysics Data System (ADS)

    Andersson, E.; Kahnert, M.

    2015-12-01

    Modelling aerosol optical properties is a notoriously difficult task due to the particles' complex morphologies and compositions. Yet aerosols and their optical properties are important for Earth system modelling and remote sensing applications. Operational optics models often make drastic and non realistic approximations regarding morphological properties, which can introduce errors. In this study a new aerosol optics model is implemented, in which more realistic morphologies and mixing states are assumed, especially for black carbon aerosols. The model includes both external and internal mixing of all chemical species, it treats externally mixed black carbon as fractal aggregates, and it accounts for inhomogeneous internal mixing of black carbon by use of a novel "core-grey shell" model. Simulated results of radiative fluxes, backscattering coefficients and the Ångström exponent from the new optics model are compared with results from another model simulating particles as externally mixed homogeneous spheres. To gauge the impact on the optical properties from the new optics model, the known and important effects from using aerosol dynamics serves as a reference. The results show that using a more detailed description of particle morphology and mixing states influences the optical properties to the same degree as aerosol dynamics. This is an important finding suggesting that over-simplified optics models coupled to a chemical transport model can introduce considerable errors; this can strongly effect simulations of radiative fluxes in Earth-system models, and it can compromise the use of remote sensing observations of aerosols in model evaluations and chemical data assimilation.

  2. Chemical Composition and Size Distributions of Coastal Aerosols Observed on the U.S. East Coast

    NASA Astrophysics Data System (ADS)

    Xia, L.; Song, F.; Jusino-Atresino, R.; Thuman, C.; Gao, Y.

    2008-12-01

    Aerosol input is an important source of certain limiting nutrients, such as iron, for phytoplankton growth in several large oceanic regions. As the efficiency of biological uptake of nutrients may depend on the aerosol properties, a better knowledge of aerosol properties is critically important. Characterizing aerosols over the coastal ocean needs special attention, because the properties of aerosols could be altered by many anthropogenic processes in this land-ocean transition zone before they are transported over the remote ocean. The goal of this experiment was to examine aerosol properties, in particular chemical composition, particle-size distributions and iron solubility, over the US Eastern Seaboard, an important boundary for the transport of continental substances from North America to the North Atlantic Ocean. Our field sampling site was located at Tuckerton (39°N, 74°W) on the southern New Jersey coast. Fourteen sets of High-Volume aerosol samples and three sets of size segregated aerosol samples by a 10-stage MOUDI impactor were collected during 2007 and 2008. The ICP-MS methodology was used to analyze aerosol samples for the concentrations of thirteen trace elements: Al, Fe, Mn, Sc, Cd, Pb, Sb, Ni, Co, Cr, Cu, Zn and V. The IC procedures were applied to determine five cations (sodium, ammonium, potassium, magnesium and calcium) and eleven anions (fluoride, acetate, propionate, formate, MSA, chloride, nitrate, succinate, malonate, sulfate and oxalate). The UV spectrometry was employed for the determination of iron solubility. Preliminary results suggest three major sources of aerosols: anthropogenic, crustal and marine. At this location, the concentrations of iron (II) ranged from 2.8 to 29ng m-3, accounting for ~20% of the total iron. The iron concentrations at this coastal site were substantially lower than those observed in Newark, an urban site in northern NJ. High concentrations of iron (II) were associated with both fine and coarse aerosol

  3. High-Resolution Desorption Electrospray Ionization Mass Spectrometry for Chemical Characterization of Organic Aerosols

    SciTech Connect

    Laskin, Julia; Laskin, Alexander; Roach, Patrick J.; Slysz, Gordon W.; Anderson, Gordon A.; Nizkorodov, Serguei; Bones, David L.; Nguyen, Lucas

    2010-03-01

    Characterization of the chemical composition and chemical transformations of secondary organic aerosol (SOA) is both a major challenge and the area of greatest uncertainty in current aerosol research. This study presents the first application of desorption electrospray ionization combined with high-resolution mass spectrometry (DESI-MS) for detailed chemical characterization and studies of chemical aging of OA collected on Teflon substrates. DESI-MS offers unique advantages both for detailed characterization of chemically labile components in OA that cannot be detected using more traditional electrospray ionization mass spectrometry (ESI-MS) and for studying chemical aging of OA. DESI-MS enables rapid characterization of OA samples collected on substrates by eliminating the sample preparation stage. In addition, it enables detection and structural characterization of chemically labile molecules in OA samples by minimizing the residence time of analyte in the solvent. SOA produced by the ozonolysis of limonene (LSOA) was allowed to react with gaseous ammonia. Chemical aging resulted in measurable changes in the optical properties of LSOA observed using UV- visible spectroscopy. DESI-MS combined with tandem mass spectrometry experiments (MS/MS) enabled identification of species in aged LSOA responsible for absorption of the visible light. Detailed analysis of the experimental data allowed us to identify chemical changes induced by reactions of LSOA constituents with ammonia and distinguish between different mechanisms of chemical aging.

  4. Assessment of primary and secondary ambient particle trends using satellite aerosol optical depth and ground speciation data in the New England region, United States

    PubMed Central

    Lee, Hyung Joo; Kang, Choong-Min; Coull, Brent A.; Bell, Michelle L.; Koutrakis, Petros

    2014-01-01

    The effectiveness of air pollution emission control policies can be evaluated by examining ambient pollutant concentration trends that are observed at a large number of ground monitoring sites over time. In this paper, we used ground monitoring measurements in conjunction with satellite aerosol optical depth (AOD) data to investigate fine particulate matter (PM2.5; particulate matter with aerodynamic diameter ≤2.5 μm) trends and their spatial patterns over a large U.S. region, New England, during 2000–2008. We examined the trends in rural and urban areas to get a better insight about the trends of regional and local source emissions. Decreases in PM2.5 concentrations (μg/m3) were more pronounced in urban areas than in rural ones. In addition, the highest and lowest PM2.5 decreases (μg/m3) were observed for winter and summer, respectively. Together, these findings suggest that primary particle concentrations decreased more relative to secondary ones. This is also supported by the analysis of the speciation data which showed that downward trends of primary pollutants including black carbon were stronger than those of secondary pollutants including sulfate. Furthermore, this study found that ambient primary pollutants decreased at the same rate as their respective source emissions. This was not the case for secondary pollutants which decreased at a slower rate than that of their precursor emissions. This indicates that concentrations of secondary pollutants depend not only on the primary emissions but also on the availability of atmospheric oxidants which might not change during the study period. This novel approach of investigating spatially varying concentration trends, in combination with ground PM2.5 species trends, can be of substantial regulatory importance. PMID:24906074

  5. Chemical speciation of heavy metals by surface-enhanced Raman scattering spectroscopy: identification and quantification of inorganic- and methyl-mercury in water.

    PubMed

    Guerrini, Luca; Rodriguez-Loureiro, Ignacio; Correa-Duarte, Miguel A; Lee, Yih Hong; Ling, Xing Yi; García de Abajo, F Javier; Alvarez-Puebla, Ramon A

    2014-07-21

    Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels. Specifically, the inorganic Hg(2+) and the more toxicologically relevant methylmercury (CH₃Hg(+)) are selected as analytical targets. The sensing platform consists of a self-assembled monolayer of 4-mercaptopyridine (MPY) on highly SERS-active and robust hybrid plasmonic materials formed by a dense layer of interacting gold nanoparticles anchored onto polystyrene microbeads. The co-ordination of Hg(2+) and CH₃Hg(+) to the nitrogen atom of the MPY ring yields characteristic changes in the vibrational SERS spectra of the organic chemoreceptor that can be qualitatively and quantitatively correlated to the presence of the two different mercury forms. PMID:24938410

  6. a Study on the Physical and Chemical Properties of Stratospheric Aerosols.

    NASA Astrophysics Data System (ADS)

    Tabazadeh, Azadeh

    The physical and chemical properties of stratospheric aerosols under background and perturbed conditions are discussed. First, a multi-component aerosol physical chemistry model was developed to study the composition and reactivity of stratospheric aerosols. The compositions are predicted from an equilibrium assumption between the condensed-and gas-phases, and they are calculated as a function of ambient temperature, relative humidity, and the total mass of nitric acid and sulfuric acid present per unit volume of air. The water and solute activity parameters in the aerosol model are derived from various laboratory sources, and the set of equilibrium equations are solved using a unique numerical scheme. The aerosol model is applied to study the formation of nitric acid-containing aerosols in the stratosphere. Also, the equilibrium compositions are used to estimate the extent of aqueous phase processing of chlorine species in the aerosol solutions. This processing can contribute to the depletion of the stratospheric ozone layer, especially after major volcanic eruptions where sulfate aerosols are more abundant. Second, a surface chemistry model was constructed that includes Langmuir trace-gas adsorption and desorption, Brunauer, Emmett and Teller adsorption of water vapor, surface poisoning, solvation and diffusion of molecules on the surface, chemical activation and reaction of adsorbates, and product desorption or reaction. This model is used to study the effects of relative humidity and other physical parameters on the efficiency of heterogeneous chemical processes which occur on the surfaces of solid polar stratospheric clouds. These heterogeneous chemical processes are responsible for the formation of the "ozone hole", can contribute to global ozone depletion, and may have tropospheric significance. Finally, a fluid dynamics and thermodynamics model of volcanic eruption columns was used to develop a scheme for predicting the extent of HCl removal from volcanic

  7. Bringing the ocean into the laboratory to probe the chemical complexity of sea spray aerosol.

    PubMed

    Prather, Kimberly A; Bertram, Timothy H; Grassian, Vicki H; Deane, Grant B; Stokes, M Dale; Demott, Paul J; Aluwihare, Lihini I; Palenik, Brian P; Azam, Farooq; Seinfeld, John H; Moffet, Ryan C; Molina, Mario J; Cappa, Christopher D; Geiger, Franz M; Roberts, Gregory C; Russell, Lynn M; Ault, Andrew P; Baltrusaitis, Jonas; Collins, Douglas B; Corrigan, Craig E; Cuadra-Rodriguez, Luis A; Ebben, Carlena J; Forestieri, Sara D; Guasco, Timothy L; Hersey, Scott P; Kim, Michelle J; Lambert, William F; Modini, Robin L; Mui, Wilton; Pedler, Byron E; Ruppel, Matthew J; Ryder, Olivia S; Schoepp, Nathan G; Sullivan, Ryan C; Zhao, Defeng

    2013-05-01

    The production, size, and chemical composition of sea spray aerosol (SSA) particles strongly depend on seawater chemistry, which is controlled by physical, chemical, and biological processes. Despite decades of studies in marine environments, a direct relationship has yet to be established between ocean biology and the physicochemical properties of SSA. The ability to establish such relationships is hindered by the fact that SSA measurements are typically dominated by overwhelming background aerosol concentrations even in remote marine environments. Herein, we describe a newly developed approach for reproducing the chemical complexity of SSA in a laboratory setting, comprising a unique ocean-atmosphere facility equipped with actual breaking waves. A mesocosm experiment was performed in natural seawater, using controlled phytoplankton and heterotrophic bacteria concentrations, which showed SSA size and chemical mixing state are acutely sensitive to the aerosol production mechanism, as well as to the type of biological species present. The largest reduction in the hygroscopicity of SSA occurred as heterotrophic bacteria concentrations increased, whereas phytoplankton and chlorophyll-a concentrations decreased, directly corresponding to a change in mixing state in the smallest (60-180 nm) size range. Using this newly developed approach to generate realistic SSA, systematic studies can now be performed to advance our fundamental understanding of the impact of ocean biology on SSA chemical mixing state, heterogeneous reactivity, and the resulting climate-relevant properties. PMID:23620519

  8. Bringing the ocean into the laboratory to probe the chemical complexity of sea spray aerosol

    PubMed Central

    Prather, Kimberly A.; Bertram, Timothy H.; Grassian, Vicki H.; Deane, Grant B.; Stokes, M. Dale; DeMott, Paul J.; Aluwihare, Lihini I.; Palenik, Brian P.; Azam, Farooq; Seinfeld, John H.; Moffet, Ryan C.; Molina, Mario J.; Cappa, Christopher D.; Geiger, Franz M.; Roberts, Gregory C.; Russell, Lynn M.; Ault, Andrew P.; Baltrusaitis, Jonas; Collins, Douglas B.; Corrigan, Craig E.; Cuadra-Rodriguez, Luis A.; Ebben, Carlena J.; Forestieri, Sara D.; Guasco, Timothy L.; Hersey, Scott P.; Kim, Michelle J.; Lambert, William F.; Modini, Robin L.; Mui, Wilton; Pedler, Byron E.; Ruppel, Matthew J.; Ryder, Olivia S.; Schoepp, Nathan G.; Sullivan, Ryan C.; Zhao, Defeng

    2013-01-01

    The production, size, and chemical composition of sea spray aerosol (SSA) particles strongly depend on seawater chemistry, which is controlled by physical, chemical, and biological processes. Despite decades of studies in marine environments, a direct relationship has yet to be established between ocean biology and the physicochemical properties of SSA. The ability to establish such relationships is hindered by the fact that SSA measurements are typically dominated by overwhelming background aerosol concentrations even in remote marine environments. Herein, we describe a newly developed approach for reproducing the chemical complexity of SSA in a laboratory setting, comprising a unique ocean-atmosphere facility equipped with actual breaking waves. A mesocosm experiment was performed in natural seawater, using controlled phytoplankton and heterotrophic bacteria concentrations, which showed SSA size and chemical mixing state are acutely sensitive to the aerosol production mechanism, as well as to the type of biological species present. The largest reduction in the hygroscopicity of SSA occurred as heterotrophic bacteria concentrations increased, whereas phytoplankton and chlorophyll-a concentrations decreased, directly corresponding to a change in mixing state in the smallest (60–180 nm) size range. Using this newly developed approach to generate realistic SSA, systematic studies can now be performed to advance our fundamental understanding of the impact of ocean biology on SSA chemical mixing state, heterogeneous reactivity, and the resulting climate-relevant properties. PMID:23620519

  9. Development of Fundamental Data on Chemical Speciation and Solubility for Strontium and Americium in High-Level Waste: Predictive Modeling of Phase Partitioning During Tank Processing

    SciTech Connect

    Felmy, Andrew R.; Choppin, Gregory; Dixon, David A.

    2002-06-01

    In this project, Pacific Northwest National Laboratory (PNNL) and Florida State University (FSU) are investigating the speciation of Sr and Am/Cm in the presence of selected organic chelating agents over ranges of hydroxide, carbonate, ionic strength, and competing metal ion concentrations present in high-level waste (HLW) stored in tanks at Hanford and other U.S. Department of Energy (DOE) sites. The chelating agents that are being studied are EDTA (ethylenediaminetetraacetic acid), HEDTA (N-(2-hydroxyethyl)ethylenediaminetriacetic acid), NTA (nitrilotriacetic acid), IDA (iminodiacetic acid), citrate, and oxalate. The project comprises integrated research tasks that approach the problem of chemical speciation using macroscopic thermodynamic measurements of metal-ligand competition reactions, molecular modeling studies to identify structures or complexes of unusual stability, and mass spectrometry measurements of complex charge/mass ratio that can be applied to mixed metalchelate systems. This fundamental information then is used to develop thermodynamic models designed to predict changes in chemical speciation and solubility resulting from various tank processing conditions. In this way we can develop new approaches that address fundamental problems in aqueous speciation and, at the same time, provide useful and practical information needed for tank waste processing. Current strategies for reducing the total volume of radioactive tank waste requiring disposal at Hanford and other DOE sites call for the development of methods that can be used to selectively dissolve and remove non-radioactive elements, such as Al, P, and Cr, while retaining or precipitating the radioactive elements, including Sr and the actinide elements, in the tank sludge. This partitioning between solids and precipitates is fundamentally dependent on the chemical speciation of the elements present in the tank processing solutions. Of particular importance is separation of the radioactive and

  10. Coupling aerosol optics to the MATCH (v5.5.0) chemical transport model and the SALSA (v1) aerosol microphysics module

    NASA Astrophysics Data System (ADS)

    Andersson, Emma; Kahnert, Michael

    2016-05-01

    A new aerosol-optics model is implemented in which realistic morphologies and mixing states are assumed, especially for black carbon particles. The model includes both external and internal mixing of all chemical species, it treats externally mixed black carbon as fractal aggregates, and it accounts for inhomogeneous internal mixing of black carbon by use of a novel "core-grey-shell" model. Simulated results of aerosol optical properties, such as aerosol optical depth, backscattering coefficients and the Ångström exponent, as well as radiative fluxes are computed with the new optics model and compared with results from an older optics-model version that treats all particles as externally mixed homogeneous spheres. The results show that using a more detailed description of particle morphology and mixing state impacts the aerosol optical properties to a degree of the same order of magnitude as the effects of aerosol-microphysical processes. For instance, the aerosol optical depth computed for two cases in 2007 shows a relative difference between the two optics models that varies over the European region between -28 and 18 %, while the differences caused by the inclusion or omission of the aerosol-microphysical processes range from -50 to 37 %. This is an important finding, suggesting that a simple optics model coupled to a chemical transport model can introduce considerable errors affecting radiative fluxes in chemistry-climate models, compromising comparisons of model results with remote sensing observations of aerosols, and impeding the assimilation of satellite products for aerosols into chemical-transport models.

  11. Chemical and Aerosol Signatures of Biomass Burning via Long Range Transport observed at Storm Peak Laboratory

    NASA Astrophysics Data System (ADS)

    Hallar, A. G.; Obrist, D.; McCubbin, I. B.; Fain, X.; Rahn, T.

    2008-12-01

    The Desert Research Institute operates a high elevation facility, Storm Peak Laboratory (SPL), located on the Steamboat Springs Ski Resort in Colorado at an elevation 3.2 km. During the spring of 2008, two field projects were conducted at SPL; Storm Peak Cloud and Aerosol Characterization (SPACC) and a State of Colorado Mercury Monitoring project. Measurements of gaseous elemental mercury (GEM), along with CO, ozone and aerosol concentrations and aerosol size distributions will be presented from April 28 to July 1st 2008. This work focuses on specific case studies pertaining to long range transport events. Specifically, high levels of GEM and CO will be presented from May 15, 2008. This data will be coupled with HYSPLIT backtrajectories, chemical modeling via MOZART, and satellite imagery (MODIS) to present evidence that Siberian wildfires impacted the air quality at Storm Peak Laboratory.

  12. Experimental Determination of Chemical Diffusion within Secondary Organic Aerosol Particles

    SciTech Connect

    Abramson, Evan H.; Imre, D.; Beranek, Josef; Wilson, Jacqueline; Zelenyuk, Alla

    2013-02-28

    Formation, properties, transformations, and temporal evolution of secondary organic aerosols (SOA) particles strongly depend on particle phase. Recent experimental evidence from a number of groups indicates that SOA is in a semi-solid phase, the viscosity of which remained unknown. We find that when SOA is made in the presence of vapors of volatile hydrophobic molecules the SOA particles absorb and trap them. Here, we illustrate that it is possible to measure the evaporation rate of these molecules that is determined by their diffusion in SOA, which is then used to calculate a reasonably accurate value for the SOA viscosity. We use pyrene as a tracer molecule and a-pinene SOA as an illustrative case. It takes ~24 hours for half the pyrene to evaporate to yield a viscosity of 10^8 Pa s for a-pinene. This viscosity is consistent with measurements of particle bounce and evaporation rates. We show that viscosity of 10^8 Pa s implies coalescence times of minutes, consistent with the findings that SOA particles are spherical. Similar measurements on aged SOA particles doped with pyrene yield a viscosity of 10^9 Pa s, indicating that hardening occurs with time, which is consistent with observed decrease in water uptake and evaporation rate with aging.

  13. Aerosol-induced chemical perturbations of stratospheric ozone: Three-dimensional simulations and analysis of mechanisms

    NASA Astrophysics Data System (ADS)

    Zhao, Xuepeng; Turco, Richard P.; Kao, C.-Y. Jim; Elliott, Scott

    1997-02-01

    An atmospheric general circulation model is coupled with a stratospheric photochemical model to simulate the chemical/dynamical perturbations associated with background and volcanically perturbed aerosols in the lower stratosphere. The present work focuses on short-term anomalies at middle and high latitudes in the northern hemisphere, where large ozone depletions have been observed in late winter and early spring, particularly following the eruption of Mount Pinatubo. Five fully coupled simulations are analyzed, corresponding to a control case with only gas phase chemistry, and cases including heterogeneous chemistry on background aerosols, on El Chichón-type, and on Pinatubo-type aerosols. It is found that heterogeneous reactions occurring on sulfate aerosols (background or postvolcanic) can strongly perturb the chemical partitioning in the lower stratosphere, leading to significant ozone depletion through enhanced chlorine, bromine, and odd-hydrogen catalytic cycles. In the Arctic lower stratosphere, the maximum zonal and March monthly mean local ozone reductions (with respect to the control case) can exceed 15% for the background aerosol case, 40% for the El Chichón case, and 50% for the Pinatubo case. The corresponding zonal mean total column ozone decreases are roughly 5% and 15% for the background and volcanic aerosol cases, respectively. In the most extreme case tested (post-Pinatubo), a large ozone depletion below 30 mbar is offset to some extent by an ozone increase above that level. The results of a sensitivity study (in which the aerosols are distributed closer to the tropics, as might occur early after an eruption at low latitude) lead to relatively small total ozone depletions at northern high latitudes, and small ozone increases in the tropical lower stratosphere. The reduced impact on total ozone at high latitudes is associated both with local ozone increases above 30 mbar and with poleward transport of enhanced ozone from the tropical lower

  14. Laboratory Study of Chemical Speciation of Mercury in Lake Sediment and Water under Aerobic and Anaerobic Conditions

    PubMed Central

    Regnell, Olof; Tunlid, Anders

    1991-01-01

    Chemical speciation and partitioning of radiolabeled HgCl2 were studied in model aquatic systems consisting of undisturbed eutrophic lake sediment and water in plastic cylinders. The cylinders were either gradually made anaerobic by a gentle flow of N2-CO2 or kept aerobic by air flow. The proportion of methylated 203Hg was significantly higher, in both water and sediment, in the anaerobic systems than in the aerobic systems. The composition and total concentration of fatty acids originating from bacterial phospholipids, as well as the concentration of vitamin B12, including related cobalamins, were similar in sediments from the anaerobic and aerobic systems. Bacterial cell numbers were, on average, 3.6 times higher in the anaerobic water columns than in the aerobic ones. Volatilization of 203Hg occurred in all systems except in an autoclaved control and was of similar magnitudes in the anaerobic and aerobic systems. Incorporation of 203Hg into the sediment was significantly faster in the aerobic systems than in the anaerobic systems. These results suggest that episodes of anoxia in bottom waters and sediment cause an increase in net mercury methylation and, hence, an increase in bioavailable mercury. PMID:16348444

  15. [Physical-chemical characteristics and phosphorus speciation of the sediments in the upper and middle reaches of the Yellow River].

    PubMed

    Wang, Xiao-Li; Bao, Hua-Ying; Guo, Bo-Shu

    2009-03-15

    The physical and chemical characteristics, various phosphorus forms from 10 sites in Yellow River's sediments were analyzed, and their relations were discussed. The results showed that, the values of total phosphorus, organic matter and active Fe, Al are 97.86-129.33 mg x kg(-1), 0.11%-1.96%, 2.02-7.40 mg x g(-1), 0.29-0.90 mg x g(-1), respectively. The main mineral compositions of the sediments are quartz and albite; the main clay minerals are montmorillonate, illite, chlorite and kaolinite. Inorganic-P is the main form of phosphorus speciation. Ca-P is 37.61-64.04 mg x kg(-1) and is the main form of IP. The cation exchange capacity was linearly correlated with the sum of clay and silt (R2 = 0.76). Also, the organic matter was linearly correlated with inorganic sedimentary phosphorus (R2 = 0.66). Moreover, the linear relationship between the sum of NaOH-P and BD-P and the sum of active Fe and active Al content was observed within the ten sediments investigated (R2 = 0.80). PMID:19432318

  16. Fine particulate matter source apportionment for the chemical speciation trends network site at Birmingham, Alabama, using positive matrix factorization

    SciTech Connect

    Baumann, K.; Jayanty, R.K.; Flanagan, J.B.

    2008-01-15

    The Positive Matrix Factorization (PMF) receptor model version 1.1 was used with data from the fine particulate matter (PM2.5) Chemical Speciation Trends Network (STN) to estimate source contributions to ambient PM2.5 in a highly industrialized urban setting in the southeastern United States. Model results consistently resolved 10 factors that are interpreted as two secondary, five industrial, one motor vehicle, one road dust, and one biomass burning sources. It was found that most PMF factors did not cleanly represent single source types and instead are 'contaminated' by other sources. Secondary particulate matter formed by atmospheric processes, such as sulfate and secondary OC, contribute the majority of ambient PM2.5 and exhibit strong seasonality 37 {+-} 10% winter vs. 55 {+-} 16% summer average. Motor vehicle emissions constitute the biggest primary PM2.5 mass contribution. In summary, this study demonstrates the utility of the EC tracer method to effectively blank-correct the OC concentrations in the STN dataset. In addition, examination of the effect of input uncertainty estimates on model results indicates that the estimated uncertainties currently being provided with the STN data may be somewhat lower than the levels needed for optimum modeling results. An appendix , available to members on the website www.awma lists stationary sources of PM2.5 within 10 km of the NHBM site and PM2.5 emissions greater than 1 ton per year. 71 refs., 7 figs., 9 tabs.

  17. Analysis of Chemical Composition of Atmospheric Aerosols Above a South East Asian Rainforest

    NASA Astrophysics Data System (ADS)

    Robinson, N. H.; Allan, J. D.; Williams, P. I.; Hamilton, J. F.; Chen, Q.; Martin, S. T.; Coe, H.; McFiggans, G. B.

    2008-12-01

    The tropics emit a huge amount of volatile organic compounds (VOCs) into the Earth's atmosphere. The processes by which these gases are oxidised to form secondary organic aerosol (SOA) are not well understood or quantified. Insight into the origins and properties of these particles can be gained by analysis of their composition. Intensive field measurements were carried out as part of the Oxidant and Particle Photochemical Processes (OP3) and the Aerosol Coupling in the Earth System (ACES) projects in the rainforest in Malaysian Borneo. This is the first campaign of its type in a South East Asian rainforest. We present detailed organic aerosol composition measurements made using an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) at Bukit Atur, a Global Atmosphere Watch site located in the Danum Valley Conservation Area. This is a state-of-the-art field deployable instrument that can provide real time composition, mass loading and aerodynamic particle sizing information. In addition, the mass spectral resolution is sufficient to perform an analysis of the elemental composition of the organic species present. Other tools such as positive matrix factorisation (PMF) have been used to help assess the relative source contributions to the organic aerosol. The aerosol's chemical origins have been further investigated by comparing these spectra to chamber experiments, mass spectral libraries and data from comparable locations in other locations. These data are also being analysed in conjunction with high complexity offline techniques applied to samples collected using filters and a Particle-Into-Liquid Sampler (PILS). Methods used include liquid chromatography and comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry. These techniques provide a more detailed chemical characterisation of the SOA and water soluble organic carbon, allowing direct links back to gas phase precursors.

  18. Global and regional impacts of HONO on the chemical composition of clouds and aerosols

    NASA Astrophysics Data System (ADS)

    Elshorban, Y. F.; Crutzen, P. J.; Steil, B.; Pozzer, A.; Tost, H.; Lelieveld, J.

    2013-09-01

    Nitrous acid (HONO) photolysis can significantly increase HOx (OH+HO2) radical formation, enhancing organic and inorganic oxidation products in polluted regions, especially during winter. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that HONO can significantly enhance aerosol sulphate (S(VI)), mainly due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model-measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and the central role of cloud chemical processing in aerosol formation.

  19. Measurements of Semi-volatile Aerosol and Its Effect on Aerosol Optical Properties During Southern Oxidant and Aerosol Study

    NASA Astrophysics Data System (ADS)

    Khlystov, A.; Grieshop, A. P.; Saha, P.; Subramanian, R.

    2013-12-01

    Semi-volatile compounds, including particle-bound water, comprise a large part of aerosol mass and have a significant influence on aerosol lifecycle and its optical properties. Understanding the properties of semi-volatile compounds, especially those pertaining to gas/aerosol partitioning, is of critical importance for our ability to predict concentrations and properties of ambient aerosol. A set of state-of-the-art instruments was deployed at the SEARCH site near Centerville, AL during the Southern Oxidant and Aerosol Study (SOAS) campaign in summer 2013 to measure the effect of temperature and relative humidity on aerosol size distribution, composition and optical properties. Light scattering and absorption by temperature- and humidity-conditioned aerosols was measured using three photo-acoustic extinctiometers (PAX) at three wavelengths (405 nm, 532 nm, and 870 nm). In parallel to these measurements, a long residence time temperature-stepping thermodenuder and a variable residence time constant temperature thermodenuder in combination with three SMPS systems and an Aerosol Chemical Speciation Monitor (ACSM) were used to assess aerosol volatility and kinetics of aerosol evaporation. It was found that both temperature and relative humidity have a strong effect on aerosol optical properties. The variable residence time thermodenuder data suggest that aerosol equilibrated fairly quickly, within 2 s, in contrast to other ambient observations. Preliminary analysis show that approximately 50% and 90% of total aerosol mass evaporated at temperatures of 100 C and 180C, respectively. Evaporation varied substantially with ambient aerosol loading and composition and meteorology. During course of this study, T50 (temperatures at which 50% aerosol mass evaporates) varied from 60 C to more than 120 C.

  20. Chemical speciation and leaching properties of elements in municipal incinerator ashes

    SciTech Connect

    Kida, Akiko; Noma, Yukio; Imada, Teruji

    1996-12-31

    Different chemical properties of bottom ash and fly ash from municipal solid waste incinerators were compared based on the results of the five measuring techniques: (1) total contents and leaching amounts by regulatory leaching test in Japan; (2) leaching properties by pH-dependent leaching test; (3) modeling of pH-dependent leaching test using model compounds; (4) enriched chemical composition compared with bulk composition by an X-ray photoelectron spectrometer (XPS); (5) estimation of chemical states of elements by XPS analysis. The difference between bottom ash and EP ash was clearly found in element content, leaching behavior and release rate. The release rates of many elements in bottom ash were lower than in electrostatic precipitation (EP) ash even in an acidic condition of pH 3 as well as at the inherent pH of 12. Corresponding to the relatively complicated components in bottom ash, leaching patterns depending on pH were not simple. Comparison between the pH-dependent pattern of Ca in a sample and in model compounds resulted in the estimation of some Ca compounds in ash. The surface analysis by XPS showed results that Na, Cl, Zn, Pb and S were enriched in EP ash and Fe and Ti were rarely found in the surface of ash. Possible chemical states of Na, Ca, K, Cl and S were estimated by a new method of comparing binding energies of standard compounds and their mixtures.

  1. Measurements of the aerosol chemical composition and mixing state in the Po Valley using multiple spectroscopic techniques

    NASA Astrophysics Data System (ADS)

    Decesari, S.; Allan, J.; Plass-Duelmer, C.; Williams, B. J.; Paglione, M.; Facchini, M. C.; O'Dowd, C.; Harrison, R. M.; Gietl, J. K.; Coe, H.; Giulianelli, L.; Gobbi, G. P.; Lanconelli, C.; Carbone, C.; Worsnop, D.; Lambe, A. T.; Ahern, A. T.; Moretti, F.; Tagliavini, E.; Elste, T.; Gilge, S.; Zhang, Y.; Dall'Osto, M.

    2014-11-01

    The use of co-located multiple spectroscopic techniques can provide detailed information on the atmospheric processes regulating aerosol chemical composition and mixing state. So far, field campaigns heavily equipped with aerosol mass spectrometers have been carried out mainly in large conurbations and in areas directly affected by their outflow, whereas lesser efforts have been dedicated to continental areas characterised by a less dense urbanisation. We present here the results obtained at a background site in the Po Valley, Italy, in summer 2009. For the first time in Europe, six state-of-the-art spectrometric techniques were used in parallel: aerosol time-of-flight mass spectrometer (ATOFMS), two aerosol mass spectrometers (high-resolution time-of-flight aerosol mass spectrometer - HR-ToF-AMS and soot particle aerosol mass spectrometer - SP-AMS), thermal desorption aerosol gas chromatography (TAG), chemical ionisation mass spectrometry (CIMS) and (offline) proton nuclear magnetic resonance (1H-NMR) spectroscopy. The results indicate that, under high-pressure conditions, atmospheric stratification at night and early morning hours led to the accumulation of aerosols produced by anthropogenic sources distributed over the Po Valley plain. Such aerosols include primary components such as black carbon (BC), secondary semivolatile compounds such as ammonium nitrate and amines and a class of monocarboxylic acids which correspond to the AMS cooking organic aerosol (COA) already identified in urban areas. In daytime, the entrainment of aged air masses in the mixing layer is responsible for the accumulation of low-volatility oxygenated organic aerosol (LV-OOA) and also for the recycling of non-volatile primary species such as black carbon. According to organic aerosol source apportionment, anthropogenic aerosols accumulating in the lower layers overnight accounted for 38% of organic aerosol mass on average, another 21% was accounted for by aerosols recirculated in

  2. Chemical speciation of polyurethane polymers by soft-x-ray spectromicroscopy

    SciTech Connect

    Rightor, E.G.; Hitchcock, A.P.; Urquhart, S.G.

    1997-04-01

    Polyurethane polymers are a versatile class of materials which have numerous applications in modern life, from automotive body panels, to insulation, to household furnishings. Phase segregation helps to determine the physical properties of several types of polyurethanes. Polymer scientists believe that understanding the connections between formulation chemistry, the chemical nature of the segregated phases, and the physical properties of the resulting polymer, would greatly advance development of improved polyurethane materials. However, the sub-micron size of segregated features precludes their chemical analysis by existing methods, leaving only indirect means of characterizing these features. For the past several years the authors have been developing near edge X-ray absorption spectromicroscopy to study the chemical nature of individual segregated phases. Part of this work has involved studies of molecular analogues and model polymers, in conjunction with quantum calculations, in order to identify the characteristic near edge spectral transitions of important chemical groups. This spectroscopic base is allowing the authors to study phase segregation in polyurethanes by taking advantage of several unique capabilities of scanning transmission x-ray microscopy (STXM) - high spatial resolution ({approximately} 0.1 {mu}m), high spectral resolution ({approximately}0.1 eV at the C 1s edge), and the ability to record images and spectra with relatively low radiation damage. The beamline 7.0 STXM at ALS is being used to study microtomed sections or cast films of polyurethanes. Based on the pioneering work of Ade, Kirz and collaborators at the NSLS X-1A STXM, it is clear that scanning X-ray transmission microscopy using soft X-rays can provide information about the chemical origin of phase segregation in radiation-sensitive materials on a sub-micron scale. This information is difficult or impossible to obtain by other means.

  3. Long-term real-time chemical characterization of submicron aerosols at Montsec (Southern Pyrenees, 1570 m a.s.l.)

    NASA Astrophysics Data System (ADS)

    Ripoll, A.; Minguillón, M. C.; Pey, J.; Jimenez, J. L.; Day, D. A.; Querol, X.; Alastuey, A.

    2014-11-01

    Real-time measurements of inorganic (sulfate, nitrate, ammonium, chloride and black carbon (BC)) and organic submicron aerosols from a continental background site (Montsec, MSC, 1570 m a.s.l.) in the Western Mediterranean Basin (WMB) were conducted for 10 months (July 2011-April 2012). An Aerosol Chemical Speciation Monitor (ACSM) was co-located with other on-line and off-line PM1 measurements. Analyses of the hourly, diurnal, and seasonal variations are presented here, for the first time for this region. Seasonal trends in PM1 components are attributed to variations in: evolution of the planetary boundary layer (PBL) height, air mass origin, and meteorological conditions. In summer, the higher temperature and solar radiation increases convection, enhancing the growth of the PBL and the transport of anthropogenic pollutants towards high altitude sites. Furthermore, the regional recirculation of air masses over the WMB creates a continuous increase in the background concentrations of PM1 components and causes the formation of reserve strata at relatively high altitudes. Sporadically, MSC is affected by air masses from North Africa. The combination of all these atmospheric processes at local, regional and continental scales results in a high variability of PM1 components, with poorly defined daily patterns, except for the organic aerosols (OA). OA was mostly oxygenated organic aerosol (OOA), with two different types: semi-volatile (SV-OOA) and low-volatile (LV-OOA), and both showed marked diurnal cycles regardless of the air mass origin, especially SV-OOA. This different diurnal variation compared to inorganic aerosols suggested that OA components at MSC are not only associated with anthropogenic and long-range-transported secondary OA (SOA), but also with recently-produced biogenic SOA. Very different conditions drive the aerosol phenomenology in winter at MSC. The thermal inversions and the lower vertical development of the PBL leave MSC in the free troposphere

  4. Aerosol Physical, Optical and Chemical Properties during African Dust Events at Cape San Juan (CPR)

    NASA Astrophysics Data System (ADS)

    Reyes de Jongh, C.; Mayol Bracero, O. L.; Rivera Vazquez, H.; Sheridan, P.; Ogren, J. A.

    2008-12-01

    Large amounts of atmospheric dust are lifted from the North African deserts and are transported by the trade winds over the Caribbean region, especially during the summer months. How African dust particles influence the earth's radiative budget is not well understood because these particles are highly variable and their physical, optical, and chemical properties are poorly characterized, especially when they are atmospherically processed as are those that travel from Africa to the Caribbean region. Here we present results of aerosol measurements performed at Cape San Juan (CPR), a ground-based station located at the northeastern tip of the Caribbean island of Puerto Rico. We used a condensation particle counter to determine the particle number concentration, a sunphotometer (part of the AErosol RObotical NETwork, AERONET, aeronet.gsfc.nasa.gov) to determine volume size distributions and aerosol optical thickness, and a 3-wavelength nephelometer and particle/soot absorption photometer to determine the scattering and absorption coefficients. Filter samples for chemical analyses were collected with stacked-filter units. Preliminary results show that African dust air masses have higher average particle number concentrations (N=720 cm -3 ), aerosol optical depth (AOD = 0.27), and scattering and absorption coefficients (σ s = 30 Mm -1 , σ a = 0.46 Mm -1 ) than clean air masses (N = 460 cm -3 , AOD= 0.08, σ s = 11 Mm -1 , σ a = 0.37 Mm -1 . Results presented will also show how changes in aerosol optical properties in the presence and absence of African dust relate to the physical and chemical composition of the particles.

  5. Hygroscopic properties of the Paris urban aerosol in relation to its chemical composition

    NASA Astrophysics Data System (ADS)

    Kamilli, K. A.; Poulain, L.; Held, A.; Nowak, A.; Birmili, W.; Wiedensohler, A.

    2014-01-01

    Aerosol hygroscopic growth factors and chemical properties were measured as part of the MEGAPOLI "Megacities Plume Case Study" at the urban site Laboratoire d'Hygiène de la Ville de Paris (LHVP) in the city center of Paris from June to August 2009, and from January to February 2010. Descriptive hygroscopic growth factors (DGF) were derived in the diameter range from 25 to 350 nm at relative humidities of 30, 55, 75, and 90% by applying the summation method on humidified and dry aerosol size distributions measured simultaneously with a humidified differential mobility particle sizer (HDMPS) and a twin differential mobility particle sizer (TDMPS). For 90% relative humidity, the DGF varied from 1.06 to 1.46 in summer, and from 1.06 to 1.66 in winter. Temporal variations in the observed mean DGF could be well explained with a simple growth model based on the aerosol chemical composition measured by aerosol mass spectrometry (AMS) and black carbon photometry (MAAP). In particular, good agreement was observed when sulfate was the predominant inorganic factor. A clear overestimation of the predicted growth factor was found when the nitrate mass concentration exceeded values of 10 μg m-3, e.g., during winter.

  6. Hygroscopic properties of the Paris urban aerosol in relation to its chemical composition

    NASA Astrophysics Data System (ADS)

    Kamilli, K. A.; Poulain, L.; Held, A.; Nowak, A.; Birmili, W.; Wiedensohler, A.

    2013-05-01

    Aerosol hygroscopic growth factors and chemical properties were measured as part of the MEGAPOLI "Megacities Plume Case Study" at the urban site LHVP in the city center of Paris from June to August 2009, and from January to February 2010. Descriptive hygroscopic growth factors (DGF) were derived in the diameter range from 25 to 350 nm at relative humidities of 30, 55, 75, and 90% by applying the summation method on humidified and dry aerosol size distributions measured simultaneously with a humidified differential mobility particle sizer (HDMPS) and a twin differential mobility particle sizer (TDMPS). For 90% relative humidity, the DGF varied from 1.06 to 1.46 in summer, and from 1.06 to 1.66 in winter. Temporal variations in the observed mean DGF could be well explained with a simple growth model based on the aerosol chemical composition measured by aerosol mass spectrometry (AMS) and black carbon photometry (MAAP). In particular, good agreement was observed when sulfate was the predominant inorganic factor. A clear overestimation of the predicted growth factor was found when the nitrate mass concentration exceeded values of 10 μg m3, e.g. during winter.

  7. Chemical composition, sources, and processes of urban aerosols during summertime in Northwest China: insights from High Resolution Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Xu, J.; Zhang, Q.; Chen, M.; Ge, X.; Ren, J.; Qin, D.

    2014-06-01

    An aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed along with a Scanning Mobility Particle Sizer (SMPS) and a Multi Angle Absorption Photometers (MAAP) to measure the temporal variations of the mass loading, chemical composition, and size distribution of sub-micrometer particulate matter (PM1) in Lanzhou, northwest China, during 12 July-7 August 2012. The average PM1 mass concentration including non-refractory PM1 (NR-PM1) measured by HR-ToF-AMS and black carbon (BC) measured by MAAP during this study was 24.5 μg m-3 (ranging from 0.86 to 105μg m-3), with a mean composition consisting of 47% organics, 16% sulfate, 12% BC, 11% ammonium, 10% nitrate, and 4% chloride. The organics was consisted of 70% carbon, 21% oxygen, 8% hydrogen, and 1% nitrogen, with the average oxygen-to-carbon ratio (O / C) of 0.33 and organic mass-to-carbon ratio (OM / OC) of 1.58. Positive matrix factorization (PMF) of the high-resolution mass spectra of organic aerosols (OA) identified four distinct factors which represent, respectively, two primary OA (POA) emission sources (traffic and food cooking) and two secondary OA (SOA) types - a fresher, semi-volatile oxygenated OA (SV-OOA) and a more aged, low-volatility oxygenated OA (LV-OOA). Traffic-related hydrocarbon-like OA (HOA) and BC displayed distinct diurnal patterns both with peak at ~07:00-11:00 (BJT: UTC +8) corresponding to the morning rush hours, while cooking OA (COA) peaked during three meal periods. The diurnal profiles of sulfate and LV-OOA displayed a broad peak between ∼07:00-15:00, while those of nitrate, ammonium, and SV-OOA showed a narrower peak at ~08:00-13:00. The later morning and early afternoon peak in the diurnal profiles of secondary aerosol species was likely caused by mixing down of pollutants aloft, which were likely produced in the residual layer decoupled from the boundary layer during night time. The mass spectrum of SV-OOA also showed similarity with that of

  8. PHYSICAL AND CHEMICAL CHARACTERIZATION OF INDOOR AEROSOLS RESULTING FROM THE USE OF TAP WATER IN PORTABLE HOME HUMIDIFIERS

    EPA Science Inventory

    An indoor air quality study was conducted in Boise, ID, residences to evaluate the range of aerosol concentrations that result from using tap water in portable home humidifiers and to characterize the physical and chemical properties of the humidifier aerosol. M10 concentrations ...

  9. Two years of near real-time observations of the chemical composition of submicron aerosols in Cape Corsica obtained by Q-ACSM

    NASA Astrophysics Data System (ADS)

    Sciare, Jean; Dulac, François; Crenn, Vincent; Hamonou, Eric; Baisnée, Dominique; Nicolas, José B.; Pont, Véronique; Lambert, Dominique; Gheusi, François; Mallet, Marc; Tison, Emmanuel; Sauvage, Stéphane; Bourrianne, Thierry; Roberts, Gregory; Colomb, Aurélie; Pichon, Jean-Marc; Sellegri, Karine; Savelli, Jean-Luc

    2015-04-01

    As part of the MISTRALS/ChArMEx (Mediterranean Integrated Studies aT Regional And Local Scales/the Chemistry-Aerosol Mediterranean Experiment; http://www.mistrals-home.org; http://charmex.lsce.ipsl.fr) and the CORSiCA (http://www.obs-mip.fr/corsica) programs, 2-year continuous observations of near real-time chemical composition of submicron aerosols were performed between June 2012 & July 2014 at the Cape Corsica atmospheric supersite (http://gaw.empa.ch/gawsis/reports.asp?StationID=2076203042), a remote marine site in the Western Mediterranean. Submicron organic aerosols (OA) and the major inorganic salts (sulfate, ammonium, nitrate) were monitored every 30 min using a Quadripole Aerosol Chemical Speciation Monitor (Q-ACSM; Aerodyne Res. Inc. MA, USA). Quality control of this large dataset (24-month continuous observations) was performed through closure studies (using co-located SMPS and TEOM-FDMS measurements), direct comparisons with other on-line / off-line instruments running in parallel (filter sampling, OPC, nephelometer …), and large intercomparison of 13 Q-ACSM performed within the EU-FP7 ACTRIS program (http://www.actris.net/). Source apportionment of OA was then performed on a monthly basis using the SourceFinder software (SoFi, http://www.psi.ch/acsm-stations/me-2) allowing the distinction between hydrogen- and oxygen-like organic aerosols (HOA and OOA, respectively). This monthly resolved source apportionment was first compared with co-located real-time tracer measurements (NOx, BC, CO, VOC …) available at the Cape Corsica station. Seasonal patterns of the various properties of (secondary) OOA (OSc, O/C ratio …) were then investigated from monthly resolved source apportionment results (monthly OOA mass spectra) obtained over the period June 2012 - July 2014. Acknowledgements: Atmospheric measurements performed at Cape Corsica Station were funded by CNRS-INSU, ADEME, CEA, and METEO-FRANCE. This work was carried out in the framework of the CORSi

  10. Numerical Simulation of the Transport and Speciation of Nonconservative Chemical Reactants in Rivers

    NASA Astrophysics Data System (ADS)

    Chapman, Bernard M.

    1982-02-01

    A computer model, previously used to simulate the transport of conservative chemical components in streams, has been used as a basis for a more complex model which includes the effects due to processes such as precipitation and sedimentation and adsorption onto stationary reactive surfaces which render the reactants nonconservative with respect to the flowing waters. The model uses, as before, the program MINEQL as a basis for the chemical equilibrium submodel. The physical transport submodel employs a convolution integral procedure, with an approximate form of the impulse function to solve a one-dimensional convective-diffusion equation. Although the model essentially assumes chemical equilibrium, a pseudokinetic treatment is necessary to deal with redissolution of precipitates and dissociation of surface species. Simple hypothetical examples are given to illustrate the operation of the model. The model is then applied to an experiment in which the base NaOH is injected into a creek draining an abandoned base metal mine. Concentrations of the metals Zn, Al, Cu, Fe, and Na in the flowing waters, expressed in terms of total metals and as suspended solids, are followed as a function of time and distance downstream. Significant sedimentation of the precipitates formed is evident, and the existence of substantial quantities of protons and/or metal ions, adsorbed on the streambed, is implied from the model calculations. The model was able to simulate successfully the major features observed. This simulation involved the simultaneous formation of five distinct precipitates and one surface species.

  11. Efficient chemical equilibrium calculations for geochemical speciation and reactive transport modelling

    NASA Astrophysics Data System (ADS)

    Leal, Allan M. M.; Blunt, Martin J.; LaForce, Tara C.

    2014-04-01

    Chemical equilibrium calculations are essential for many environmental problems. It is also a fundamental tool for chemical kinetics and reactive transport modelling, since these applications may require hundreds to billions equilibrium calculations in a single simulation. Therefore, an equilibrium method for such critical applications must be very efficient, robust and accurate. In this work we demonstrate the potential effectiveness of a novel Gibbs energy minimisation algorithm for reactive transport simulations. The algorithm includes strategies to converge from poor initial guesses; capabilities to specify non-linear equilibrium constraints such as pH of an aqueous solution and activity or fugacity of a species; a rigorous phase stability test to determine the unstable phases; and a strategy to boost the convergence speed of the calculations to quadratic rates, requiring only few iterations to converge. We use this equilibrium method to solve geochemical problems relevant to carbon storage in saline aquifers, where aqueous, gaseous and minerals phases are present. The problems are formulated to mimic the ones found in kinetics and transport simulations, where a sequence of equilibrium calculations are performed, each one using the previous solution as the initial guess. The efficiency and convergence rates of the calculations are presented, which require an average of 1-2 iterations. These results indicate that critical applications such as chemical kinetics and reactive transport modelling can potentially benefit by using this multiphase equilibrium algorithm.

  12. Chemical Composition of Atmospheric Aerosols Above a Pristine South East Asian Rainforest

    NASA Astrophysics Data System (ADS)

    Robinson, N. H.; Allan, J. D.; Williams, P. I.; Coe, H.; Hamilton, J.; Chen, Q.; Martin, S.; Trembath, J.

    2009-04-01

    conjunction with a constant pressure inlet. The aerosols' chemical origins have been further investigated by comparing these spectra to chamber experiments, mass spectral libraries and data from comparable experiments in other locations. These data are also being analysed in conjunction with offline techniques applied to samples collected using filters and a Particle-Into-Liquid Sampler (PILS). Methods used include liquid chromatography and comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry. These techniques provide a more detailed chemical characterisation of the SOA and water soluble organic carbon, allowing direct links back to gas phase precursors. In conjunction with the field measurements, a programme of chamber experiments is being carried out at Manchester as part of the ACES project. This will generate comparable SOA under controlled conditions and subjecting them to similar analysis.

  13. Chemical Analysis of Fractionated Halogens in Atmospheric Aerosols Collected in Okinawa, Japan

    NASA Astrophysics Data System (ADS)

    Tsuhako, A.; Miyagi, Y.; Somada, Y.; Azechi, S.; Handa, D.; Oshiro, Y.; Murayama, H.; Arakaki, T.

    2013-12-01

    Halogens (Cl, Br and I) play important roles in the atmosphere, e.g. ozone depletion by Br during spring in Polar Regions. Sources of halogens in atmospheric aerosols are mainly from ocean. But, for example, when we analyzed Br- with ion chromatography, its concentrations were almost always below the detection limit, which is also much lower than the estimated concentrations from sodium ion concentrations. We hypothesized that portions of halogens are escaped to the atmosphere, similar to chlorine loss, changed their chemical forms to such as BrO3- and IO3-, and/or even formed precipitates. There was few reported data so far about fractionated halogen concentrations in atmospheric aerosols. Thus, purpose of this study was to determine halogen concentrations in different fractions; free ion, water-soluble chemically transformed ions and precipitates using the authentic aerosols. Moreover, we analyzed seasonal variation for each fraction. Atmospheric aerosol samples were collected at Cape Hedo Atmosphere and Aerosol Monitoring Station (CHAAMS) of Okinawa, Japan during January 2010 and August 2013. A high volume air sampler was used for collecting total particulate matters on quartz filters on a weekly basis. Ultrapure water was used to extract water-soluble factions of halogens. The extracted solutions were filtered with the membrane filter and used for chemical analysis with ion chromatography and ICP-MS. Moreover, the total halogens in aerosols were obtained after digesting aerosols with tetramethylammonium hydroxide (TMAH) using the microwave and analysis with ICP-MS. For Cl, water-soluble Cl- accounted for about 70% of the estimates with Na content. No other forms of water-soluble Cl were found. About 30% of Cl was assumed volatilized to the gas-phase. For Br, water-soluble Br accounted for about 43% of the estimates with Na content, and within the 43%, about 10% of Br was not in the form of Br-. About 46% of Br was assumed volatilized to the gas-phase. For I

  14. Biomass burning aerosol over the Amazon during SAMBBA: impact of chemical composition on radiative properties

    NASA Astrophysics Data System (ADS)

    Morgan, William; Allan, James; Flynn, Michael; Darbyshire, Eoghan; Hodgson, Amy; Liu, Dantong; O'shea, Sebastian; Bauguitte, Stephane; Szpek, Kate; Langridge, Justin; Johnson, Ben; Haywood, Jim; Longo, Karla; Artaxo, Paulo; Coe, Hugh

    2014-05-01

    Biomass burning represents one of the largest sources of particulate matter to the atmosphere, resulting in a significant perturbation to the Earth's radiative balance coupled with serious impacts on public health. Globally, biomass burning aerosols are thought to exert a small warming effect but with the uncertainty being 4 times greater than the central estimate. On regional scales, the impact is substantially greater, particularly in areas such as the Amazon Basin where large, intense and frequent burning occurs on an annual basis for several months. Absorption by atmospheric aerosols is underestimated by models over South America, which points to significant uncertainties relating to Black Carbon (BC) aerosol properties. Initial results from the South American Biomass Burning Analysis (SAMBBA) field experiment, which took place during September and October 2012 over Brazil on-board the UK Facility for Airborne Atmospheric Measurement (FAAM) BAe-146 research aircraft, are presented here. Aerosol chemical composition was measured by an Aerodyne Aerosol Mass Spectrometer (AMS) and a DMT Single Particle Soot Photometer (SP2). The physical, chemical and optical properties of the aerosols across the region will be characterized in order to establish the impact of biomass burning on regional air quality, weather and climate. The aircraft sampled a range of conditions including sampling of pristine Rainforest, fresh biomass burning plumes, regional haze and elevated biomass burning layers within the free troposphere. The aircraft sampled biomass burning aerosol across the southern Amazon in the states of Rondonia and Mato Grosso, as well as in a Cerrado (Savannah-like) region in Tocantins state. This presented a range of fire conditions, both in terms of their number, intensity, vegetation-type and their combustion efficiencies. Near-source sampling of fires in Rainforest environments suggested that smouldering combustion dominated, while flaming combustion dominated

  15. Chemical and physical properties of single aerosol particles using a quadrupole trap

    SciTech Connect

    Carleton, K.L.; Sonnenfroh, D.M.; Kang, S.

    1995-12-31

    The importance of aerosols in controlling the chemical balance of the stratosphere has been demonstrated through studies of the polar ozone hole and polar stratospheric clouds. Our laboratory program is designed to explore the physical and chemical properties of aerosol particles under stratospheric conditions for single particles suspended in the electrodynamic field of a quadrupole trap. The goal of this work is to provide data on important stratospheric processes, with particular attention to processes resulting from increased aircraft emissions from the current subsonic fleet or a proposed fleet of supersonic aircraft. Optical methods including Mie scattering and Raman spectroscopy are used to probe the phase and composition of individual particles. Results will be presented on the freezing behavior of sulfuric acid particles.

  16. Optical, physical, and chemical properties of springtime aerosol over Barrow Alaska in 2008

    SciTech Connect

    Shantz, Nicole C.; Gultepe, Ismail; Andrews, Elisabeth; Earle, Michael; MacDonald, A. M.; Liu, Peter S.K.; Leaitch, W. R.

    2014-03-06

    Airborne observations from four flights during the 2008 Indirect and Semi-Direct Aerosol Campaign (ISDAC) are used to examine some cloud-free optical, physical, and chemical properties of aerosol particles in the springtime Arctic troposphere. The number concentrations of particles larger than 0.12 μm (Na>120), important for light extinction and cloud droplet formation, ranged from 15 to 2260 cm-3, with the higher Na>120 cases dominated by measurements from two flights of long-range transported biomass burning (BB) aerosols. The two other flights examined here document a relatively clean aerosol and an Arctic Haze aerosol impacted by larger particles largely composed of dust. For observations from the cleaner case and the BB cases, the particle light scattering coefficients at low relative humidity (RH<20%) increased nonlinearly with increasing Na>120, driven mostly by an increase in mean sizes of particles with increasing Na>120 (BB cases). For those three cases, particle light absorption coefficients also increased nonlinearly with increasing Na>120 and linearly with increasing submicron particle volume concentration. In addition to black carbon, brown carbon was estimated to have increased light absorption coefficients by 27% (450 nm wavelength) and 14% (550 nm) in the BB cases. For the case with strong dust influence, the absorption relative to submicron particle volume was small compared with the other cases. There was a slight gradient of Passive Cavity Aerosol Spectrometer Probe (PCASP) mean volume diameter (MVD) towards smaller sizes with increasing height, which suggests more scavenging of the more elevated particles, consistent with a typically longer lifetime of particles higher in the atmosphere. However, in approximately 10% of the cases, the MVD increased (>0.4 μm) with increasing altitude, suggesting transport of larger fine particle mass (possibly coarse particle mass) at high levels over the Arctic. This may be because of transport of

  17. Chemical speciation of strontium, americium, and curium in high level waste: Predictive modeling of phase partitioning during tank processing. 1998 annual progress report

    SciTech Connect

    Felmy, A.R.

    1998-06-01

    'In this research program, Pacific Northwest National Laboratory (PNNL) and Florida State University (FSU) are investigating the speciation of Sr and Am/Cm in the presence of selected organic chelating agents (ethylenediaminetetraacetic acid (EDTA), N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), and iminodiacetic acid (IDA)) over ranges of hydroxide, carbonate, ionic strength, and competing metal ion concentrations present in high level waste tanks. The fundamental understanding of chemical speciation reactions gained from these studies is also used to propose methodologies for removal of Sr and Am/Cm from organic chelates present in high level tank waste, via competition, displacement or other reactions, without the need for the development of costly and potentially hazardous organic destruction technologies.'

  18. Chemical speciation of strontium, americium, and curium in high-level waste: Predictive modeling of phase partitioning during tank processing. 1997 annual progress report

    SciTech Connect

    Felmy, A.R.; Choppin, G.R.

    1997-06-01

    'In this research program, Pacific Northwest National Laboratory (PNNL) and Florida State University (FSU) are investigating the speciation of Sr and Am/Cm in the presence of selected organic chelating agents (ethylenediaminetetraacetic acid (EDTA), N-(2-hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), and iminodiacetic acid (IDA)) over ranges of hydroxide, carbonate, and ionic strength conditions present in high-level waste tanks. This fundamental understanding of chemical speciation reactions is essential to develop methodologies for removal of Sr and Am/Cm from the chelates, via competition, displacement or other reactions, without the need for the development of costly and potentially hazardous organic destruction technologies. These studies specifically focus on the effects of hydrolysis, carbonate concentration, ionic strength, and selected cation competition on the removal of Sr and Am/Cm from the organic chelates.'

  19. Development of aerosol assisted chemical vapor deposition for thin film fabrication

    NASA Astrophysics Data System (ADS)

    Maulana, Dwindra Wilham; Marthatika, Dian; Panatarani, Camellia; Mindara, Jajat Yuda; Joni, I. Made

    2016-02-01

    Chemical vapor deposition (CVD) is widely used to grow a thin film applied in many industrial applications. This paper report the development of an aerosol assisted chemical vapor deposition (AACVD) which is one of the CVD methods. Newly developed AACVD system consists of a chamber of pyrex glass, two wire-heating elements placed to cover pyrex glass, a substrate holder, and an aerosol generator using an air brush sprayer. The temperature control system was developed to prevent condensation on the chamber walls. The control performances such as the overshoot and settling time were obtained from of the developed temperature controller. Wire-heating elements were controlled at certain setting value to heat the injected aerosol to form a thin film in the substrate. The performance of as-developed AACVD system tested to form a thin film where aerosol was sprayed into the chamber with a flow rate of 7 liters/minutes, and vary in temperatures and concentrations of precursor. The temperature control system have an overshoot around 25 °C from the desired set point temperature, very small temperature ripple 2 °C and a settling time of 20 minutes. As-developed AACVD successfully fabricated a ZnO thin film with thickness of below 1 µm. The performances of system on formation of thin films influenced by the generally controlled process such as values of setting temperature and concentration where the aerosol flow rate was fixed. Higher temperature was applied, the more uniform ZnO thin films were produced. In addition, temperature of the substrate also affected on surface roughness of the obtained films, while concentration of ZnO precursor determined the thickness of produce films. It is concluded that newly simple AACVD can be applied to produce a thin film.

  20. Soft ionization chemical analysis of secondary organic aerosol from green leaf volatiles emitted by turf grass.

    PubMed

    Jain, Shashank; Zahardis, James; Petrucci, Giuseppe A

    2014-05-01

    Globally, biogenic volatile organic compound (BVOC) emissions contribute 90% of the overall VOC emissions. Green leaf volatiles (GLVs) are an important component of plant-derived BVOCs, including cis-3-hexenylacetate (CHA) and cis-3-hexen-1-ol (HXL), which are emitted by cut grass. In this study we describe secondary organic aerosol (SOA) formation from the ozonolysis of dominant GLVs, their mixtures and grass clippings. Near-infrared laser desorption/ionization aerosol mass spectrometry (NIR-LDI-AMS) was used for chemical analysis of the aerosol. The chemical profile of SOA generated from grass clippings was correlated with that from chemical standards of CHA and HXL. We found that SOA derived from HXL most closely approximated SOA from turf grass, in spite of the approximately 5× lower emission rate of HXL as compared to CHA. Ozonolysis of HXL results in formation of low volatility, higher molecular weight compounds, such as oligomers, and formation of ester-type linkages. This is in contrast to CHA, where the hydroperoxide channel is the dominant oxidation pathway, as oligomer formation is inhibited by the acetate functionality. PMID:24666343

  1. Effects of Chemical Aging on Global Secondary Organic Aerosol using the Volatility Basis Set Approach

    NASA Astrophysics Data System (ADS)

    Park, R.; Jo, D.; Kim, M.; Spracklen, D. V.; Hodzic, A.

    2014-12-01

    Organic aerosol (OA) constitutes significant mass fractions (20-90%) of total dry fine aerosols in the atmosphere. However, global models of OA have shown large discrepancies when compared to the observations because of the limited capability to simulate secondary OA (SOA). For reducing the discrepancies between observations and models, recent studies have shown that chemical aging reactions in the atmosphere are important because they can lead to decreases in organic volatility, resulting in increase of SOA mass yields. To efficiently simulate chemical aging of SOA in the atmosphere, we implemented the volatility basis set approach in a global 3-D chemical transport model (GEOS-Chem). We present full-year simulations and their comparisons with multiple observations - global aerosol mass spectrometer dataset, the Interagency Monitoring of Protected Visual Environments from the United States, the European Monitoring and Evaluation Programme dataset and water-soluble organic carbon observation data collected over East Asia. Using different input parameters in the model, we also explore the uncertainty of the SOA simulation for which we use an observational constraint to find the optimized values with which the model reduces the discrepancy from the observations. Finally, we estimate the effect of OA on climate using our best simulation results.

  2. Chemical speciation and source apportionment of gaseous precursors observed at a remote site in the Mediterranean basin

    NASA Astrophysics Data System (ADS)

    Michoud, Vincent; Sauvage, Stéphane; Dusanter, Sébastien; Leonardis, Thierry; Locoge, Nadine

    2014-05-01

    Models of atmospheric chemistry suggest that aged anthropogenic air masses still contain significant levels of reactive trace gases such as mono- and multi-functional oxygenated volatile organic compounds, even after several days of oxidation. These air masses can significantly impact the oxidative capacity and the formation rate of secondary pollutants (ozone, SOA…) at remote locations. However, large uncertainties still remain about chemical processes occurring during long range transport that leads to the oxidation of anthropogenic pollutants. Long term measurements of volatile organic compounds and inorganic species are being conducted since July 2012 at a remote site in Cape Corsica, a receptor site experiencing events of long range transport of air masses from different urbanized areas (south of France, Spain, Italia, North of Africa). In addition to the long term monitoring, an extended suite of trace gases and aerosols was acquired as part of the 2013 ChArMEx field campaign at Cape Corsica. One of the objectives was to better understand chemical and physical processes occurring during long range transport of anthropogenic plumes. In this presentation, we will first apportion primary and secondary sources of VOCs observed at this remote site using an analysis of spatial and temporal variations of their concentrations, ratios of chemical tracers, and air mass trajectory clustering. We will then present the results from a concentration field approach. This statistical method, based on a large set of data, consists in redistributing the concentrations of selected VOCs to the trajectories in order to identify potential source areas influencing the receptor site. The results of these two approaches will provide relevant information to study chemical processes occurring in different types of plumes transported over the Mediterranean basin.

  3. Aerosol-halogen interaction: Change of physico-chemical properties of SOA by naturally released halogen species

    NASA Astrophysics Data System (ADS)

    Ofner, J.; Balzer, N.; Buxmann, J.; Grothe, H.; Krüger, H.; Platt, U.; Schmitt-Kopplin, P.; Zetzsch, C.

    2011-12-01

    Reactive halogen species are released by various sources like photo-activated sea-salt aerosol or salt pans and salt lakes. These heterogeneous release mechanisms have been overlooked so far, although their potential of interaction with organic aerosols like Secondary Organic Aerosol (SOA), Biomass Burning Organic Aerosol (BBOA) or Atmospheric Humic LIke Substances (HULIS) is completely unknown. Such reactions can constitute sources of gaseous organo-halogen compounds or halogenated organic particles in the atmospheric boundary layer. To study the interaction of organic aerosols with reactive halogen species (RHS), SOA was produced from α-pinene, catechol and guaiacol using an aerosol smog-chamber. The model SOAs were characterized in detail using a variety of physico-chemical methods (Ofner et al., 2011). Those aerosols were exposed to molecular halogens in the presence of UV/VIS irradiation and to halogens, released from simulated natural halogen sources like salt pans, in order to study the complex aerosol-halogen interaction. The heterogeneous reaction of RHS with those model aerosols leads to different gaseous species like CO2, CO and small reactive/toxic molecules like phosgene (COCl2). Hydrogen containing groups on the aerosol particles are destroyed to form HCl or HBr, and a significant formation of C-Br bonds could be verified in the particle phase. Carbonyl containing functional groups of the aerosol are strongly affected by the halogenation process. While changes of functional groups and gaseous species were visible using FTIR spectroscopy, optical properties were studied using Diffuse Reflectance UV/VIS spectroscopy. Overall, the optical properties of the processed organic aerosols are significantly changed. While chlorine causes a "bleaching" of the aerosol particles, bromine shifts the maximum of UV/VIS absorption to the red end of the UV/VIS spectrum. Further physico-chemical changes were recognized according to the aerosol size-distributions or the

  4. Improving aerosol interaction with clouds and precipitation in a regional chemical weather modeling system

    NASA Astrophysics Data System (ADS)

    Zhou, C.; Zhang, X.; Gong, S.

    2015-12-01

    A comprehensive aerosol-cloud-precipitation interaction (ACI) scheme has been developed under CMA chemical weather modeling system GRAPES/CUACE. Calculated by a sectional aerosol activation scheme based on the information of size and mass from CUACE and the thermal-dynamic and humid states from the weather model GRAPES at each time step, the cloud condensation nuclei (CCN) is fed online interactively into a two-moment cloud scheme (WDM6) and a convective parameterization to drive the cloud physics and precipitation formation processes. The modeling system has been applied to study the ACI for January 2013 when several persistent haze-fog events and eight precipitation events occurred. The results show that interactive aerosols with the WDM6 in GRAPES/CUACE obviously increase the total cloud water, liquid water content and cloud droplet number concentrations while decrease the mean diameter of cloud droplets with varying magnitudes of the changes in each case and region. These interactive micro-physical properties of clouds improve the calculation of their collection growth rates in some regions and hence the precipitation rate and distributions in the model, showing 24% to 48% enhancements of TS scoring for 6-h precipitation in almost all regions. The interactive aerosols with the WDM6 also reduce the regional mean bias of temperature by 3 °C during certain precipitation events, but the monthly means bias is only reduced by about 0.3°C.

  5. Investigating the Chemical Pathways to PAH- and PANH-Based Aerosols in Titan's Atmospheric chemistry

    NASA Technical Reports Server (NTRS)

    Sciamma-O'Brien, Ella Marion; Contreras, Cesar; Ricketts, Claire Louise; Salama, Farid

    2011-01-01

    A complex organic chemistry between Titan's two main constituents, N2 and CH4, leads to the production of more complex molecules and subsequently to solid organic aerosols. These aerosols are at the origin of the haze layers giving Titan its characteristic orange color. In situ measurements by the Ion Neutral Mass Spectrometer (INMS) and Cassini Plasma Spectrometer (CAPS) instruments onboard Cassini have revealed the presence of large amounts of neutral, positively and negatively charged heavy molecules in the ionosphere of Titan. In particular, benzene (C6H6) and toluene (C6H5CH3), which are critical precursors of polycyclic aromatic hydrocarbon (PAH) compounds, have been detected, suggesting that PAHs might play a role in the production of Titan s aerosols. Moreover, results from numerical models as well as laboratory simulations of Titan s atmospheric chemistry are also suggesting chemical pathways that link the simple precursor molecules resulting from the first steps of the N2-CH4 chemistry (C2H2, C2H4, HCN ...) to benzene, and to PAHs and nitrogen-containing PAHs (or PANHs) as precursors to the production of solid aerosols.

  6. Improving aerosol interaction with clouds and precipitation in a regional chemical weather modeling system

    NASA Astrophysics Data System (ADS)

    Zhou, C.; Zhang, X.; Gong, S.; Wang, Y.; Xue, M.

    2015-06-01

    A comprehensive aerosol-cloud-precipitation interaction (ACI) scheme has been developed under CMA chemical weather modeling system GRAPES/CUACE. Calculated by a sectional aerosol activation scheme based on the information of size and mass from CUACE and the thermal-dynamic and humid states from the weather model GRAPES at each time step, the cloud condensation nuclei (CCN) is fed online interactively into a two-moment cloud scheme (WDM6) and a convective parameterization to drive the cloud physics and precipitation formation processes. The modeling system has been applied to study the ACI for January 2013 when several persistent haze-fog events and eight precipitation events occurred. The results show that interactive aerosols with the WDM6 in GRAPES/CUACE obviously increase the total cloud water, liquid water content and cloud droplet number concentrations while decrease the mean diameter of cloud droplets with varying magnitudes of the changes in each case and region. These interactive micro-physical properties of clouds improve the calculation of their collection growth rates in some regions and hence the precipitation rate and distributions in the model, showing 24 to 48% enhancements of TS scoring for 6 h precipitation in almost all regions. The interactive aerosols with the WDM6 also reduce the regional mean bias of temperature by 3 °C during certain precipitation events, but the monthly means bias is only reduced by about 0.3 °C.

  7. Chemical Characterization of Biomass Burning Aerosols and an Examination of Their Impact on Clouds

    NASA Astrophysics Data System (ADS)

    Pratt, K. A.; Murphy, S. M.; Twohy, C. H.; Subramanian, R.; Seinfeld, J.; Prather, K. A.

    2009-12-01

    Biomass burning is a considerable global source of carbon dioxide, methane, and carbonaceous aerosols. In addition to exerting a significant, but uncertain, direct radiative forcing, biomass burning aerosols impact cloud formation and properties by serving as cloud condensation nuclei and impacting cloud droplet and ice crystal size. During the 2007 Ice in Clouds Experiment - Layer Clouds (ICE-L), detailed size-resolved chemical composition measurements of biomass burning particles were completed using an aircraft aerosol time-of-flight mass spectrometer (A-ATOFMS), compact time-of-flight aerosol mass spectrometer (C-TOF-AMS), single-particle soot photometer (SP2), and electron microscopy. Aboard the NCAR/NSF C-130, real-time sampling of the smoke plumes of two prescribed fires allowed characterization of fresh biomass burning particles having aged less than one hour. Knowledge of fuel characteristics and burn conditions on the ground allowed a detailed comparison with emphasis on smoldering versus flaming combustion. In addition, using a counterflow virtual impactor (CVI) in series with the above techniques, aged biomass burning particles were found as residues of homogeneously-nucleated cloud ice crystals within orographic wave clouds. A comparison between A-ATOFMS, C-TOF-AMS, SP2, and electron microscopy results will be presented, as well as a discussion of the impacts of fresh and aged biomass burning particles on clouds.

  8. Measurements of the aerosol chemical composition and mixing state in the Po Valley using multiple spectroscopic techniques

    NASA Astrophysics Data System (ADS)

    Decesari, S.; Allan, J.; Plass-Duelmer, C.; Williams, B. J.; Paglione, M.; Facchini, M. C.; O'Dowd, C.; Harrison, R. M.; Gietl, J. K.; Coe, H.; Giulianelli, L.; Gobbi, G. P.; Lanconelli, C.; Carbone, C.; Worsnop, D.; Lambe, A. T.; Ahern, A. T.; Moretti, F.; Tagliavini, E.; Elste, T.; Gilde, S.; Zhang, Y.; Dall'Osto, M.

    2014-04-01

    The use of co-located multiple spectroscopic techniques can provide detailed information on the atmospheric processes regulating aerosol chemical composition and mixing state. So far, field campaigns heavily equipped with aerosol mass spectrometers have been carried out mainly in large conurbations and in areas directly affected by their outflow, whereas lesser efforts have been dedicated to continental areas characterized by a less dense urbanization. We present here the results obtained in San Pietro Capofiume, which is located in a sparsely inhabited sector of the Po Valley, Italy. The experiment was carried out in summer 2009 in the framework of the EUCAARI project ("European Integrated Project on Aerosol, Cloud Climate Aerosol Interaction"). For the first time in Europe, six state-of-the-art techniques were used in parallel: (1) on-line TSI aerosol time-of-flight mass spectrometer (ATOFMS), (2) on-line Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS), (3) soot particle aerosol mass spectrometer (SP-AMS), (4) on-line high resolution time-of-flight mass spectrometer-thermal desorption aerosol gas chromatograph (HR-ToFMS-TAG), (5) off-line twelve-hour resolution proton nuclear magnetic resonance (H-NMR) spectroscopy, and (6) chemical ionization mass spectrometry (CIMS) for the analysis of gas-phase precursors of secondary aerosol. Data from each aerosol spectroscopic method were analysed individually following ad-hoc tools (i.e. PMF for AMS, Art-2a for ATOFMS). The results obtained from each techniques are herein presented and compared. This allows us to clearly link the modifications in aerosol chemical composition to transitions in air mass origin and meteorological regimes. Under stagnant conditions, atmospheric stratification at night and early morning hours led to the accumulation of aerosols produced by anthropogenic sources distributed over the Po Valley plain. Such aerosols include primary components such as black carbon (BC

  9. Chemical Speciation and Bioaccessibility of Arsenic and Chromiumin Chromated Copper Arsenate-Treated Wood and Soils

    SciTech Connect

    Nico, Peter S.; Ruby, Michael V.; Lowney, Yvette W.; Holm,Stewart E.

    2005-10-12

    This research compares the As and Cr chemistry ofdislodgeable residues from Chromated Copper Arsenate (CCA)-treated woodcollected by two different techniques (directly from the board surfaceeither by rubbing with a soft bristle brush or from human hands aftercontact with CCA-treated wood), and demonstrates that these materials areequivalent in terms of the chemical form and bonding of As and Cr and interms of the As leaching behavior. This finding links the extensivechemical characterization and bioavailability testing that has been donepreviously on the brush-removed residue to a material that is derivedfrom human skin contact with CCA-treated wood. Additionally, thisresearch characterizes the arsenic present in biological fluids (sweatand simulated gastric fluid) following contact with these residues. Thedata demonstrate that in biological fluids, the arsenic is presentprimarily as free arsenate ions.Arsenic-containing soils were alsoextracted into human sweat to evaluate the potential for arsenicdissolution from soils at the skin surface. For soils from field sites,only a small fraction of the total arsenic is soluble in sweat. Based oncomparisons to reference materials that have been used in in vivo dermalabsorption studies, these findings suggest that the actual relativebioavailability via dermal absorption of As from CCA-residues and soilmay be well below the current default value of 3 percent used by U.S.EPA.

  10. Distribution and chemical speciation of arsenic in ancient human hair using synchrotron radiation.

    PubMed

    Kakoulli, Ioanna; Prikhodko, Sergey V; Fischer, Christian; Cilluffo, Marianne; Uribe, Mauricio; Bechtel, Hans A; Fakra, Sirine C; Marcus, Matthew A

    2014-01-01

    Pre-Columbian populations that inhabited the Tarapacá mid river valley in the Atacama Desert in Chile during the Middle Horizon and Late Intermediate Period (AD 500-1450) show patterns of chronic poisoning due to exposure to geogenic arsenic. Exposure of these people to arsenic was assessed using synchrotron-based elemental X-ray fluorescence mapping, X-ray absorption spectroscopy, X-ray diffraction and Fourier transform infrared spectromicroscopy measurements on ancient human hair. These combined techniques of high sensitivity and specificity enabled the discrimination between endogenous and exogenous processes that has been an analytical challenge for archeological studies and criminal investigations in which hair is used as a proxy of premortem metabolism. The high concentration of arsenic mainly in the form of inorganic As(III) and As(V) detected in the hair suggests chronic arsenicism through ingestion of As-polluted water rather than external contamination by the deposition of heavy metals due to metallophilic soil microbes or diffusion of arsenic from the soil. A decrease in arsenic concentration from the proximal to the distal end of the hair shaft analyzed may indicate a change in the diet due to mobility, though chemical or microbiologically induced processes during burial cannot be entirely ruled out. PMID:24320096

  11. Real-time characterization of the size and chemical composition of individual particles in ambient aerosol systems in Riverside, California

    SciTech Connect

    Noble, C.A.; Prather, K.A.

    1995-12-31

    Atmospheric aerosols, although ubiquitous, are highly diverse and continually fluctuating systems. A typical aerosol system may consist of particles with diameters between {approximately}0.002 {mu}m and {approximately}200 {mu}m. Even in rural or pristine areas, atmospheric particle concentration is significant, with concentrations up to 10{sup 8} particles/cm{sup 3} not being uncommon. Chemical composition of atmospheric particles vary from simple water droplets or acidic ices to soot particles and cigarette smoke. Due to changes in atmospheric conditions, processes such as nucleation, coagulation or heterogeneous chemistry may effect both physical and chemical properties of individual particles over relatively short time intervals. Recently, aerosol measurement techniques are focusing on determining the size and/or chemical composition of individual aerosol particles. This research group has recently developed aerosol time-of-flight mass spectrometry (ATOFMS), a technique which allows for real-time determination of the size and chemical composition of individual aerosol particles. Single particle measurements are performed in one instrument using dual laser aerodynamic particle sizing and time-of-flight mass spectrometry. Aerosol-time-of-flight mass spectrometry is briefly described in several other abstracts in this publication.

  12. Long-term measurement of aerosol chemical composition in Athens, Greece.

    NASA Astrophysics Data System (ADS)

    Paraskevopoulou, Despina; Liakakou, Eleni; Theodosi, Christina; Gerasopoulos, Evangelos; Mihalopoulos, Nikolaos

    2014-05-01

    The collection of our samples was conducted for a period of five years (2008 - 2013) in Athens, Greece. The site is situated at the premises of the National Observatory of Athens on Penteli Hill, northeast Athens suburbs, and is considered an urban background station. The aim of our study was a first long-term estimation of the chemical mass closure of aerosol. For the purposes of the study, we applied three filter samplers during the sampling period: two Partisol FRM Model 2000 air samplers (one of them collecting PM10 and the other PM2.5 fractions of aerosol) and one Dichotomous Partisol auto-sampler (with PM2.5 and PM2.5-10 inlet). Aerosols were collected on Whatman QM-A quartz fiber filters and the mass of the collected samples was estimated by weighing the pre-combusted filters before and after sampling, under controlled conditions, using a microbalance. All quartz filters were analysed for organic (OC) and elemental carbon (EC) by a thermal - optical transmission technique. The concentration of water soluble organic carbon (WSOC) was defined for each filter using a total organic carbon analyzer, while the content in main water soluble ions (Cl-, Br-, NO-3, SO4-2, PO4-3, C2O4-2, NH4+, K+, Na+, Mg+2, Ca+2) was determined by ion chromatography. Additionally the filters were analyzed for trace metals by inductively coupled plasma optical emission spectrometry (ICP-OES). Aerosol chemical mass closure calculations were conducted for the PM2.5 fraction. The area of Athens is characterized by aged aerosol that can originate from the marine boundary layer, the European mainland and occasionally from North African desert areas. The contribution of dust and particulate organic matter on PM levels was estimated taking into consideration the location of the sampling site, while identification and evaluation of sources was performed. Additionally, non-sea salt concentrations of the main ions were estimated to complete the chemical closure in the extended area. According to

  13. Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing

    NASA Astrophysics Data System (ADS)

    Pacold, J. I.; Lukens, W. W.; Booth, C. H.; Shuh, D. K.; Knight, K. B.; Eppich, G. R.; Holliday, K. S.

    2016-05-01

    Nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. We find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. The resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.

  14. Chemical speciation of redox sensitive elements during hydrocarbon leaching in the Junggar Basin, Northwest China

    NASA Astrophysics Data System (ADS)

    Zheng, Guodong; Fu, Bihong; Takahashi, Yoshio; Kuno, Akihito; Matsuo, Motoyuki; Zhang, Jindong

    2010-11-01

    Bleaching related to seepage of petroleum fluids and subsurface migration of crude oil and natural gas can alter the chemical and mineralogical properties of rocks, while concurrently depleting hydrocarbon reservoirs. Mud volcanoes constitute one type of petroleum seepage present in several areas on the southern margin of the Junggar Basin in the Xinjiang Uygur Autonomous Region, NW China. The results of XRD, XRF, XANES, and Mössbauer spectroscopy on rock samples collected from areas affected by these mud volcanoes revealed an enrichment of certain minerals and elements, as well changes in mineralogical, molecular, or ionic carrier ("species"). After bleaching, reddish sedimentary rocks showed depletion in silica and enrichment of calcium, magnesium, manganese, and iron. Other elements, including aluminum, potassium, sodium, and titanium, were largely unchanged. Reduced iron and sulfur compounds predominated in the bleached rocks, producing changes in color from the original reddish into green, deep gray, and black. Iron and calcium were associated with carbonates, indicating carbonation of these elements during the bleaching processes. Manganese also appeared to be associated with carbonate, though not with sulfate even though sulfate was present in the bleached rocks. Alkaline conditions were apparently the dominant because reduced manganese would have been absent under acidic condition. The alteration of certain minerals, clay minerals in particular, was also observed in bleached rocks, the alteration of smectite-group minerals to chlorite and muscovite, for example. Mineralogical and geochemical changes in rocks bleached by hydrocarbon fluids could provide a better overall understanding of bleaching processes, and may have applications in surface geochemical exploitation and remote imaging.

  15. Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing

    DOE PAGESBeta

    Pacold, J. I.; Lukens, W. W.; Booth, C. H.; Shuh, D. K.; Knight, K. B.; Eppich, G. R.; Holliday, K. S.

    2016-05-18

    We report that nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. Wemore » find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. Lastly, the resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.« less

  16. Chemical speciation in laser-desorption and impact-induced vapor in minerals

    NASA Astrophysics Data System (ADS)

    Shen, A. H.; Dundas, C. M.; Ahrens, T. J.; Beauchamp, J. L.

    2002-12-01

    Knowledge of the chemical species in vapors produced by hypervelocity impact on spacecraft impact detectors as well as planetary surfaces have applications ranging from determination of the composition of cosmic dust to the effects on atmospheres and climates of large impactors. Direct study of resulting atomic, molecular and ionic species is best accomplished via mass spectrometry. Pulsed laser desorption can be used to approximate small impacts on solid surfaces. We conducted pulsed laser desorption-ionization experiments using two different instruments: (1) a Caltech-built Time-of-Flight Mass Spectrometer (TOFMS) similar to that on board the Cassini spacecraft and (2) a commercial Matrix Assisted Laser Desorption Ionization TOFMS made by Applied Biosystems (Model, Voyager-DE Pro). Minerals included in this study were calcite, dolomite, gypsum, anhydrite, olivine, kamacite, brucite, serpentine, and pyrrhotite. We collected only positive ions. A nitrogen laser (337 nm wavelength, 4 μsec pulse width, and 300 mJ) with power density ranging from 1.0x107 to 1.3x109 W/cm2 induced vaporization and ionization. The results can be summarized as: (1) from kamacite and pyrrhotite, only 54Fe+, 56Fe+, 57Fe+ (both kamacite and pyrrhotite) and 58Ni+, 60Ni+ (kamacite only) as well as contamination ions such as 23Na+ and 39K+, 41K+were observed; (2) Ca-containing minerals (calcite, dolomite, gypsum and anhydrite) produced vapors containing 40Ca+ ions, and, at higher laser power, both 40Ca+ as well as CaO+ ions; (3) Mg-containing minerals (dolomite, olivine, brucite and serpentine) produced vapors containing MgO+ ion; (4) for all hydrous minerals, neither H+ nor H3O+ were observed in the vapor; (5) in the vapors of silicate minerals (olivine and serpentine), SiO+ was observed only from serpentine but not from olivine.

  17. Chemical speciation of heavy metals by surface-enhanced Raman scattering spectroscopy: identification and quantification of inorganic- and methyl-mercury in water

    NASA Astrophysics Data System (ADS)

    Guerrini, Luca; Rodriguez-Loureiro, Ignacio; Correa-Duarte, Miguel A.; Lee, Yih Hong; Ling, Xing Yi; García de Abajo, F. Javier; Alvarez-Puebla, Ramon A.

    2014-06-01

    Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels. Specifically, the inorganic Hg2+ and the more toxicologically relevant methylmercury (CH3Hg+) are selected as analytical targets. The sensing platform consists of a self-assembled monolayer of 4-mercaptopyridine (MPY) on highly SERS-active and robust hybrid plasmonic materials formed by a dense layer of interacting gold nanoparticles anchored onto polystyrene microbeads. The co-ordination of Hg2+ and CH3Hg+ to the nitrogen atom of the MPY ring yields characteristic changes in the vibrational SERS spectra of the organic chemoreceptor that can be qualitatively and quantitatively correlated to the presence of the two different mercury forms.Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels

  18. Multisensor analyzer detector (MSAD) for low cost chemical and aerosol detection and pattern fusion

    NASA Astrophysics Data System (ADS)

    Swanson, David C.; Merdes, Daniel W.; Lysak, Daniel B., Jr.; Curtis, Richard C.; Lang, Derek C.; Mazzara, Andrew F.; Nicholas, Nicholas C.

    2002-08-01

    MSAD is being developed as a low-cost point detection chemical and biological sensor system designed around an information fusion inference engine that also allows additional sensors to be included in the detection process. The MSAD concept is based on probable cause detection of hazardous chemical vapors and aerosols of either chemical or biological composition using a small portable unit containing an embedded computer system and several integrated sensors with complementary capabilities. The configuration currently envisioned includes a Surface-Enhanced Raman Spectroscopy (SERS) sensor of chemical vapors and a detector of respirable aerosols based on Fraunhofer diffraction. Additional sensors employing Ion Mobility Spectrometry (IMS), Surface Acoustic Wave (SAW) detection, Flame Photometric Detection (FPD), and other principles are candidates for integration into the device; also, available commercial detectors implementing IMS, SAW, and FPD will be made accessible to the unit through RS232 ports. Both feature and decision level information fusion is supported using a Continuous Inference Network (CINET) of fuzzy logic. Each class of agents has a unique CINET with information inputs from a number of available sensors. Missing or low confidence sensor information is gracefully blended out of the output confidence for the particular agent. This approach constitutes a plug and play arrangement between the sensors and the information pattern recognition algorithms. We are currently doing simulant testing and developing out CINETs for actual agent testing at Edgewood Chemical and Biological Center (ECBC) later this year.

  19. Long-term real-time chemical characterization of submicron aerosols at Montsec (southern Pyrenees, 1570 m a.s.l.)

    NASA Astrophysics Data System (ADS)

    Ripoll, A.; Minguillón, M. C.; Pey, J.; Jimenez, J. L.; Day, D. A.; Sosedova, Y.; Canonaco, F.; Prévôt, A. S. H.; Querol, X.; Alastuey, A.

    2015-03-01

    Real-time measurements of inorganic (sulfate, nitrate, ammonium, chloride and black carbon (BC)) and organic submicron aerosols (particles with an aerodynamic diameter of less than 1 μm) from a continental background site (Montsec, MSC, 1570 m a.s.l.) in the western Mediterranean Basin (WMB) were conducted for 10 months (July 2011-April 2012). An aerosol chemical speciation monitor (ACSM) was co-located with other online and offline PM1 measurements. Analyses of the hourly, diurnal, and seasonal variations are presented here, for the first time, for this region. Seasonal trends in PM1 components are attributed to variations in evolution of the planetary boundary layer (PBL) height, air mass origin, and meteorological conditions. In summer, the higher temperature and solar radiation increases convection, enhancing the growth of the PBL and the transport of anthropogenic pollutants towards high altitude sites. Furthermore, the regional recirculation of air masses over the WMB creates a continuous increase in the background concentrations of PM1 components and causes the formation of reservoir layers at relatively high altitudes. The combination of all these atmospheric processes results in a high variability of PM1 components, with poorly defined daily patterns, except for the organic aerosols (OA). OA was mostly composed (up to 90%) of oxygenated organic aerosol (OOA), split in two types: semivolatile (SV-OOA) and low-volatility (LV-OOA), the rest being hydrocarbon-like OA (HOA). The marked diurnal cycles of OA components regardless of the air mass origin indicates that they are not only associated with anthropogenic and long-range-transported secondary OA (SOA) but also with recently produced biogenic SOA. Very different conditions drive the aerosol phenomenology in winter at MSC. The thermal inversions and the lower vertical development of the PBL leave MSC in the free troposphere most of the day, being affected by PBL air masses only after midday, when the

  20. Chemical speciation of size-segregated floor dusts and airborne magnetic particles collected at underground subway stations in Seoul, Korea.

    PubMed

    Jung, Hae-Jin; Kim, BoWha; Malek, Md Abdul; Koo, Yong Sung; Jung, Jong Hoon; Son, Youn-Suk; Kim, Jo-Chun; Kim, HyeKyoung; Ro, Chul-Un

    2012-04-30

    Previous studies have reported the major chemical species of underground subway particles to be Fe-containing species that are generated from wear and friction processes at rail-wheel-brake and catenaries-pantographs interfaces. To examine chemical composition of Fe-containing particles in more details, floor dusts were collected at five sampling locations of an underground subway station. Size-segregated floor dusts were separated into magnetic and non-magnetic fractions using a permanent magnet. Using X-ray diffraction (XRD) and scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDX), iron metal, which is relatively harmless, was found to be the dominating chemical species in the floor dusts of the <25 μm size fractions with minor fractions of Mg, Al, Si, Ca, S, and C. From SEM analysis, the floor dusts of the <25 μm size fractions collected on railroad ties appeared to be smaller than 10 μm, indicating that their characteristics should somewhat reflect the characteristics of airborne particles in the tunnel and the platform. As most floor dusts are magnetic, PM levels at underground subway stations can be controlled by removing magnetic indoor particles using magnets. In addition, airborne subway particles, most of which were smaller than 10 μm, were collected using permanent magnets at two underground subway stations, namely Jegi and Yangjae stations, in Seoul, Korea. XRD and SEM/EDX analyses showed that most of the magnetic aerosol particles collected at Jegi station was iron metal, whereas those at Yangjae station contained a small amount of Fe mixed with Na, Mg, Al, Si, S, Ca, and C. The difference in composition of the Fe-containing particles between the two subway stations was attributed to the different ballast tracks used. PMID:22381374

  1. Development of a Global Tropospheric Aerosol Chemical Transport Model MASINGAR and its Application to the Dust Storm Forecasting

    NASA Astrophysics Data System (ADS)

    Tanaka, T. Y.

    2002-12-01

    We are developing a new three-dimensional aerosol chemical transport model coupled with the MRI/JMA98 GCM, named Model of Aerosol Species IN the Global AtmospheRe (MASINGAR), for the study of atmospheric aerosols and related trace species. MASINGAR treats four major aerosol species that include nss-sulfate, carbonaceous, mineral dust, and sea-salt aerosols. The model accounts for large-scale advective transport, subgrid-scale eddy diffusive and convective transport, surface emission and deposition, wet deposition, as well as chemical reactions. The advective transport is calculated using the semi-Lagrangian transport scheme. Parameterization of convective transport is based on the convective mass flux by Arakawa-Schubert scheme. The space and time resolution of the model are variable, with a standard resolution of T42 (2.8ox2.8o) and 30 levels (up to 0.8hPa). In addition, the model has a built-in four-dimensional data assimilation with assimilated meteorological field, which enables the model to perform a realistic simulation on a specific period and short-period forecast of aerosols. The model was applied to the numerical forecasting of dust storm in spring, 2002, when the first intensive observational period of Aeolian Dust Experiment on the Climatic impact (ADEC) project was conducted. The model simulation of mineral dust aerosol suggests that the synoptic scale aerosol events can be simulated by MASINGAR.

  2. Chemical and Physical Properties of Bulk Aerosols within Four Sectors Observed during TRACE-P

    NASA Technical Reports Server (NTRS)

    Jordan, C. E.; Anderson, B. E.; Talbot, R. W.; Dibb, J. E.; Fuelberg, E.; Hudgins, C. H.; Kiley, C. M.; Russo, R.; Scheuer, E.; Seid, G.

    2003-01-01

    Chemical and physical aerosol data collected on the DC-8 during TRACE-P were grouped into four sectors based on back trajectories. The four sectors represent long-range transport from the west (WSW), regional circulation over the western Pacific and Southeast Asia (SE Asia), polluted transport from Northern Asia with substantial sea salt at low altitudes (NNW) and a substantial amount of dust (Channel). WSW has generally low mixing ratios at both middle and high altitudes, with the bulk of the aerosol mass due to non-sea-salt water-soluble inorganic species. Low altitude SE Asia also has low mean mixing ratios in general, with the majority of the aerosol mass comprised of non-sea-salts, however, soot is also relatively important m this region. "w had the highest mean sea salt mixing ratios, with the aerosol mass at low altitudes (a km) evenly divided between sea salts, mm-sea-salts, and dust. The highest mean mixing ratios of water-soluble ions and soot were observed at the lowest altitudes (a km) in the Channel sector. The bulk of the aerosol mass exported from Asia emanates h m Channel at both low and midaltitudes, due to the prevalence of dust compared to other sectors. Number densities show enhanced fine particles for Channel and NNW, while their volume distributions are enhanced due to sea salt and dust Low-altitude Channel exhibits the highest condensation nuclei ((34) number densities along with enhanced scattering coefficients, compared to the other sectors. At midaltitudes (2-7 km), low mean CN number densities coupled with a high proportion of nonvolatile particles (265%) observed in polluted sectors (Channel and NNW) are attributed to wet scavenging which removes hygroscopic CN particles. Low single scatter albedo m SE Asia reflects enhanced soot

  3. Chemical and physical properties of bulk aerosols within four sectors observed during TRACE-P

    NASA Astrophysics Data System (ADS)

    Jordan, C. E.; Anderson, B. E.; Talbot, R. W.; Dibb, J. E.; Fuelberg, H. E.; Hudgins, C. H.; Kiley, C. M.; Russo, R.; Scheuer, E.; Seid, G.; Thornhill, K. L.; Winstead, E.

    2003-11-01

    Chemical and physical aerosol data collected on the DC-8 during TRACE-P were grouped into four sectors based on back trajectories. The four sectors represent long-range transport from the west (WSW), regional circulation over the western Pacific and Southeast Asia (SE Asia), polluted transport from northern Asia with substantial sea salt at low altitudes (NNW) and a substantial amount of dust (Channel). WSW has generally low mixing ratios at both middle and high altitudes, with the bulk of the aerosol mass due to non-sea-salt water-soluble inorganic species. Low altitude SE Asia also has low mean mixing ratios in general, with the majority of the aerosol mass comprised of non-sea-salts, however, soot is also relatively important in this region. NNW had the highest mean sea salt mixing ratios, with the aerosol mass at low altitudes (<2 km) evenly divided between sea salts, non-sea-salts, and dust. The highest mean mixing ratios of water-soluble ions and soot were observed at the lowest altitudes (<2 km) in the Channel sector. The bulk of the aerosol mass exported from Asia emanates from Channel at both low and midaltitudes, due to the prevalence of dust compared to other sectors. Number densities show enhanced fine particles for Channel and NNW, while their volume distributions are enhanced due to sea salt and dust. Low-altitude Channel exhibits the highest condensation nuclei (CN) number densities along with enhanced scattering coefficients, compared to the other sectors. At midaltitudes (2-7 km), low mean CN number densities coupled with a high proportion of nonvolatile particles (≥65%) observed in polluted sectors (Channel and NNW) are attributed to wet scavenging which removes hygroscopic CN particles. Low single scatter albedo in SE Asia reflects enhanced soot.

  4. Investigation of the detailed chemical composition of organic aerosol in a South East Asian Rainforest

    NASA Astrophysics Data System (ADS)

    Hamilton, Jacqueline; Ward, Martyn; Rami Alfarra, M.; Lewis, Alastair; McFiggans, Gordon; Robinson, Niall

    2010-05-01

    The formation of secondary organic aerosol (SOA) in tropical regions is a key uncertainty in quantifying the effect of man made emissions on the climate. Large quantities of volatile organic compounds are emitted from natural biogenic sources in the tropics, including isoprene, monoterpenes and sequiterpenes. There are very few studies of the detailed chemical composition of organic aerosols in tropical rainforest regions, but these would provide information on the importance of primary versus secondary organic aerosols, the key VOC precursors, oxidation state and volatility. Particle samples were collected in a tropical rainforest at Danum Valley in Borneo as part of the OP3 field campaign in 2008. Twenty four hour filter samples were collected at the Global Atmospheric Watch station at a height of around 10 m and shipped back to the laboratory (below -4 °C) for offline analysis. The OA composition was studied using multiple high resolution chromatographic techniques including comprehensive two dimensional gas chromatography coupled to time of flight mass spectrometry (GCXGC-TOFMS) and liquid chromatography coupled to ion trap mass spectrometry (LC-MSn). The composition was directly compared to chamber generated SOA (as part of the Aerosol Coupling in the Earths System , ACES, experiment) to determine SOA tracers. A biogenic SOA tracer MS fragmentation library was constructed and a number of SOA components from limonene, linalool and -pinene were identified in the rainforest OA. Very high resolution mass spectrometry (Fourier Transform Ion Cyclotron Resonance FTICR-MS) allowed the O:C and H:C ratios to be determined and these will be compared to those obtained by aerosol mass spectrometry (AMS). In addition, the OA composition from the rainforest will be compared to other locations.

  5. Chemical characteristics of ambient aerosols contributed by cooking process at Noorpur village near New Delhi

    NASA Astrophysics Data System (ADS)

    Singh, Sudha

    Generally, industrial and transport sectors are considered as major contributors of air pollution but recently, biomass burning is also reported as a major source of atmospheric aerosols (1, 2) especially in the developing world where solid fuels such as dung cake, wood and crop residues are used in traditional cooking which are responsible for poor air quality, respiratory problems and radiative forcing etc .In India, most of the research has been focused on emission estimates from biomass burning and cooking. No effort has been made to understand the chemistry and sources of fine aerosols in rural areas during cooking hours. This study fills this knowledge gap and strengthens our understanding about abundance of various chemical constituents of atmospheric aerosols emitted during cooking hours.Aerosol samples were collected from village called Noorpur (28.470 N, 77.030 E) which lies near Delhi city. Sampling was carried out during August 2011-May 2012 by using handy sampler (Envirotech model APM 821) installed at the terrace of a building (~6m). The aerosol samples were collected on 8 hourly basis at a flow rate of 1 LPM. Water extracts of these filters were analyzed for major anions (F-, Cl-, NO3-, SO42-) and major cations (Na+, NH4+, K+, Ca2+ Mg2+) by ion chromatography (Metrohm 883 Basic IC Plus). During cooking period, the concentration of the major ions followed the order of Ca2+> SO42-> NO3-> Cl-> K+> NH4+> Mg2+> Na2+> F-. Among anion SO42 (5 µg/m3) showed highest value and in case of cations Ca2+ (7.32µg/m3) has highest value.

  6. Implications of the chemical transformation of Asian outflow aerosols for the long-range transport of inorganic nitrogen species

    NASA Astrophysics Data System (ADS)

    Chou, Charles C.-K.; Lee, C. T.; Yuan, C. S.; Hsu, W. C.; Lin, C.-Y.; Hsu, S.-C.; Liu, S. C.

    To improve our understanding of the chemical characteristics of aerosols transported from the Asian continent to the western North Pacific, an aerosol observation network has been established in Taiwan. From the measurements made during 2003-2005, it was found that the aerosol concentrations in the continental outflows were much higher than those of remote areas, evidently due to the long-range transport of air pollutants and dust from the Asian continent. Analysis on the chemical compositions of aerosols revealed that the Asian outflow aerosols underwent chemical transformation and, consequently, became more abundant in ammonium and nitrate when they mixed with air pollutants originating from Taiwan. The NH 4+/SO 42- ratio in fine aerosols (PM2.5) increased from 1.55 at the Cape Fuguei, the northern tip of Taiwan, to 2.30 at Penghu, in the middle of the Taiwan Strait. The increased NH 4+/SO 42- ratio implied that the acidity of the sulfate aerosols in Asian outflows was totally neutralized by ammonia as the aerosols traveled through the North Taiwan and its vicinity. In addition, the analysis indicated that the chlorine deficiency of sea salt aerosols was higher at the southern stations than at the Cape Fuguei. The chlorine deficiency was attributed to the heterogeneous reaction of NaCl and HNO 3(g), which means that the oxidation of SO 2 in sea spray droplets was inhibited. Moreover, uptake of secondary acids by the dust particles was observed. The results of this study suggested that the Asian outflow aerosols are important carriers of gaseous inorganic nitrogen species, particularly nitric acid and ammonia, in this region. Hence the atmospheric deposition of soluble inorganic nitrogen could become enhanced in the northern South China Sea, which is downwind of Taiwan during the periods of Asian winter monsoons.

  7. Halogen-induced organic aerosol (XOA): a study on ultra-fine particle formation and time-resolved chemical characterization.

    PubMed

    Ofner, Johannes; Kamilli, Katharina A; Held, Andreas; Lendl, Bernhard; Zetzsch, Cornelius

    2013-01-01

    The concurrent presence of high values of organic SOA precursors and reactive halogen species (RHS) at very low ozone concentrations allows the formation of halogen-induced organic aerosol, so-called XOA, in maritime areas where high concentrations of RHS are present, especially at sunrise. The present study combines aerosol smog-chamber and aerosol flow-reactor experiments for the characterization of XOA. XOA formation yields from alpha-pinene at low and high concentrations of chlorine as reactive halogen species (RHS) were determined using a 700 L aerosol smog-chamber with a solar simulator. The chemical transformation of the organic precursor during the aerosol formation process and chemical aging was studied using an aerosol flow-reactor coupled to an FTIR spectrometer. The FTIR dataset was analysed using 2D correlation spectroscopy. Chlorine induced homogeneous XOA formation takes place at even 2.5 ppb of molecular chlorine, which was photolysed by the solar simulator. The chemical pathway of XOA formation is characterized by the addition of chlorine and abstraction of hydrogen atoms, causing simultaneous carbon-chlorine bond formation. During further steps of the formation process, carboxylic acids are formed, which cause a SOA-like appearance of XOA. During the ozone-free formation of secondary organic aerosol with RHS a special kind of particulate matter (XOA) is formed, which is afterwards transformed to SOA by atmospheric aging or degradation pathways. PMID:24601001

  8. Fourteen months of on-line measurements of the non-refractory submicron aerosol at the Jungfraujoch (3580 m a.s.l.) - chemical composition, origins and organic aerosol sources

    NASA Astrophysics Data System (ADS)

    Fröhlich, R.; Cubison, M. J.; Slowik, J. G.; Bukowiecki, N.; Canonaco, F.; Henne, S.; Herrmann, E.; Gysel, M.; Steinbacher, M.; Baltensperger, U.; Prévôt, A. S. H.

    2015-07-01

    Chemically resolved (organic, nitrate, sulphate, ammonium) data of non-refractory submicron (NR-PM1) aerosol from the first long-term deployment (27 July 2012 to 02 October 2013) of a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) at the Swiss high altitude site Jungfraujoch (3580 m a.s.l.) are presented. Besides total mass loadings, diurnal variations and relative species contributions during the different meteorological seasons, geographical origin and sources of organic aerosol (OA) are discussed. Backward transport simulations shows that the highest (especially sulphate) concentrations of NR-PM1 were measured in air masses advected to the station from regions south of the JFJ while lowest concentrations were seen from western regions. OA source apportionment for each season was performed using the Source Finder (SoFi) interface for the multilinear engine (ME-2). OA was dominated in all seasons by oxygenated OA (OOA, 71-88 %), with lesser contributions from local tourism-related activities (7-12 %) and hydrocarbon-like OA related to regional vertical transport (3-9 %). In summer the OOA can be separated into a background low-volatility OA (LV-OOA I, possibly associated with long range transport) and a slightly less oxidised low-volatility OA (LV-OOA II) associated with regional vertical transport. Wood burning-related OA associated with regional transport was detected during the whole winter 2012/2013 and during rare events in summer 2013, in the latter case attributed to small scale transport for the surrounding valleys. Additionally, the data were divided into periods with free tropospheric (FT) conditions and periods with planetary boundary layer (PBL) influence enabling the assessment of the composition for each. Most nitrate and part of the OA is injected from the regional PBL while sulphate is mainly produced in the FT. The south/north gradient of sulphate is also pronounced in FT air masses (sulphate mass fraction from the south: 45 %, from

  9. Fourteen months of on-line measurements of the non-refractory submicron aerosol at the Jungfraujoch (3580 m a.s.l.) - chemical composition, origins and organic aerosol sources

    NASA Astrophysics Data System (ADS)

    Fröhlich, R.; Cubison, M. J.; Slowik, J. G.; Bukowiecki, N.; Canonaco, F.; Croteau, P. L.; Gysel, M.; Henne, S.; Herrmann, E.; Jayne, J. T.; Steinbacher, M.; Worsnop, D. R.; Baltensperger, U.; Prévôt, A. S. H.

    2015-10-01

    Chemically resolved (organic, nitrate, sulfate, ammonium) data of non-refractory submicron (NR-PM1) aerosol from the first long-term deployment (27 July 2012 to 02 October 2013) of a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) at the Swiss high-altitude site Jungfraujoch (JFJ; 3580 m a.s.l.) are presented. Besides total mass loadings, diurnal variations and relative species contributions during the different meteorological seasons, geographical origin and sources of organic aerosol (OA) are discussed. Backward transport simulations show that the highest (especially sulfate) concentrations of NR-PM1 were measured in air masses advected to the station from regions south of the JFJ, while lowest concentrations were seen from western regions. OA source apportionment for each season was performed using the Source Finder (SoFi) interface for the multilinear engine (ME-2). OA was dominated in all seasons by oxygenated OA (OOA, 71-88 %), with lesser contributions from local tourism-related activities (7-12 %) and hydrocarbon-like OA related to regional vertical transport (3-9 %). In summer the OOA can be separated into a background low-volatility OA (LV-OOA I, possibly associated with long-range transport) and a slightly less oxidised low-volatility OA (LV-OOA II) associated with regional vertical transport. Wood burning-related OA associated with regional transport was detected during the whole winter 2012/2013 and during rare events in summer 2013, in the latter case attributed to small-scale transport for the surrounding valleys. Additionally, the data were divided into periods with free tropospheric (FT) conditions and periods with planetary boundary layer (PBL) influence, enabling the assessment of the composition for each. Most nitrate and part of the OA are injected from the regional PBL, while sulfate is mainly produced in the FT. The south/north gradient of sulfate is also pronounced in FT air masses (sulfate mass fraction from the south: 45

  10. Measurement of organic and elemental carbon in downtown Rome and background area: physical behavior and chemical speciation.

    PubMed

    Avino, Pasquale; Manigrasso, Maurizio; Rosada, Alberto; Dodaro, Alessandro

    2015-02-01

    A significant portion of the particulate matter is the total carbonaceous fraction (or total carbon, TC), composed of two main fractions, elemental carbon (EC) and organic carbon (OC), which shows a large variety of organic compounds, e.g. aliphatic, aromatic compounds, alcohols, acids, etc. In this paper, TC, EC and OC concentrations determined in a downtown Rome urban area are discussed considering the influence of meteorological conditions on the temporal-spatial aerosol distribution. Similar measurements were performed at ENEA Casaccia, an area outside Rome, which is considered as the ome background. Since 2000, TC, EC and OC measurements have been performed by means of an Ambient Carbon Particulate Monitor equipped with a NDIR detector. The EC and OC concentrations trends are compared with benzene and CO trends, which are specific indicators of autovehicular traffic, for identifying the primary EC and OC contributions and the secondary OC fraction origin. Further, a chemical investigation is reported for investigating how the main organic (i.e., n-alkanes, n-alkanoic acids, polyaromatic hydrocarbons and nitro-polyaromatic hydrocarbons) and inorganic (i.e., metals, ions) fractions vary their levels during the investigated period in relationship to new regulations and/or technological innovations. PMID:25341186

  11. Measurement of aerosol chemical, physical and radiative properties in the Yangtze delta region of China

    NASA Astrophysics Data System (ADS)

    Xu, Jin; Bergin, M. H.; Yu, X.; Liu, G.; Zhao, J.; Carrico, C. M.; Baumann, K.

    In order to understand the possible influence of aerosols on the environment in the agricultural Yangtze delta region of China, a one-month field sampling campaign was carried out during November 1999 in Linan, China. Measurements included the aerosol light scattering coefficient at 530 nm, σsp, measured at both dry relative humidity (RH<40%) and under ambient conditions (sample RH=63±19%), and the absorption coefficient at 565 nm, σap, for aerosol particles having diameters <2.5 μm (PM 2.5). At the same time, daily filter samples of PM 2.5 as well as aerosol particles having diameters <10 μm (PM 10) were collected and analyzed for mass, major ion, organic compound (OC), and elemental carbon (EC) concentrations in order to determine which anthropogenic chemical species were primarily responsible for aerosol light extinction. The aerosol loading in the rural Yangtze delta region was comparable to highly polluted urban areas, with mean and standard deviation (S.D.) values for σsp, σap and PM 2.5 of 353 Mm -1 (202 Mm -1), 23 Mm -1 (14 Mm -1) and 90 μg m -3 (47 μg m -3), respectively. A clear diurnal pattern was observed in σsp and σap with minimum values occurring in the middle of the day, most likely associated with the maximum midday mixing height. The ratio of the change in light scattering coefficient at ambient RH to that at controlled RH (RH<40%), Fσsp (RH), indicates that condensed water typically contributed ˜40% to the light scattering budget in this region. The mass scattering efficiency of the dry aerosol, E scat_2.5, and mass absorption efficiency of EC, E abs_2.5, have mean and S.D. values of 4.0 m 2 g -1 (0.4 m 2 g -1) and 8.6 m 2 g -1 (7.0 m 2 g -1), respectively. PM 2.5 concentrations in Linan and two other locations in the Yangtze delta, Sheshan and Changshu (which have monthly mean values ranging from ˜80 to 110 μg m -3), are all significantly higher than the proposed 24-h average US PM 2.5 NAAQS of 65 μg m -3. Organic compounds are

  12. Summertime aerosol chemical components in the marine boundary layer of the Arctic Ocean

    NASA Astrophysics Data System (ADS)

    Xie, Zhouqing; Sun, Liguang; Blum, Joel D.; Huang, Yuying; He, Wei

    2006-05-01

    Samples of aerosols from the marine boundary layer of the Arctic Ocean were collected aboard the R/V Xuelong during summer on the Second Chinese Arctic Research Expedition (July-September 2003). Synchrotron radiation X-ray fluorescence (SR-XRF) was used to determine chemical compositions of aerosol particles. Multivariate analysis of the SR-XRF data resolved a number of components (factors), which, on the basis of their chemical compositions and from their affiliation with specific meteorological flow patterns, were assigned physical meanings. Five factors explaining 94.7% of the total variance were identified. Ship emissions accounted for 35.3% of the variance (factor 1 (F1)) and are loaded significantly with S, Fe, V, and Ni. The total Fe emitted from ships globally was estimated at 8.60 × 106 kg yr-1. Heavy-metal-rich factors included 34.0% of the variance (F2 and F3) and were interpreted to be pollution carried into the Arctic Ocean by long-range transport. Anthropogenic contributions from industrial regions to the Arctic Ocean during the summer vary and depend on the source locations. Air mass backward trajectories indicate that the metals including Hg, Pb, Cu, and Zn come mainly from northern Russia. The third source controlling the chemical compositions of aerosols was sea salt (F4, 12.8%). The role of sea salt decreased from the open sea to areas near pack ice. On the basis of the factor scores of aerosol samples, we infer that chlorine volatilization from sea salt may occur, enhanced by nitrogen and sulfur contamination emitted from ships. Because the global inventories of nitrogen and sulfur for ship exhausts are large, and halogens could have important consequences in possible tropospheric ozone destruction, the role of ships in influencing halogen depression in sea salt should be further investigated. Finally, we also identified a crustal factor (F5, 12.6%) and suggest that crustal elements (e.g., Ca) contaminating sea ice may become reinjected into

  13. WRF-Chem model sensitivity to chemical mechanisms choice in reconstructing aerosol optical properties

    NASA Astrophysics Data System (ADS)

    Balzarini, A.; Pirovano, G.; Honzak, L.; Žabkar, R.; Curci, G.; Forkel, R.; Hirtl, M.; San José, R.; Tuccella, P.; Grell, G. A.

    2015-08-01

    In the framework of the AQMEII initiative WRF-Chem has been applied over Europe adopting two chemical configurations for the calendar year 2010. The first one employed the RADM2 gas-phase chemistry and MADE/SORGAM aerosol module, while the second one implemented the CBM-Z gaseous parameterization and MOSAIC aerosol chemistry. Configurations shared the same domain, meteorological setups and input data. The Comparison demonstrated that CBM-Z has a more efficient ozone-NO titration than RADM2 in regions with sufficiently high levels of NOx and VOCs. At the same time, CBM-Z is found to have a more effective NO2 + OH reaction. The parameterization of the relative humidity of deliquescence point has a strong impact on HNO3 and NO3 concentrations over Europe, particularly over the sea. The MADE approach showed to be more efficient than MOSAIC. Differently, particulate sulfate and SO2 ground concentrations proved to be more influenced by the heterogeneous SO2 cloud oxidation. PM10 and PM2.5 have shown similar results for MOSAIC and MADE/SORGAM, even though some differences were found in the dust and sea salt size partitioning between modes and bins. Indeed, in MADE the sea salt was distributed only in the coarse fraction, while the dust emissions were distributed mainly in the fine fraction. Finally, different chemical mechanisms give different Aerosol Optical Depths (AOD). WRF-Chem is found to under predict the AODs in both configurations because of the misrepresentation of the dust coarse particle, as shown by the analysis of the relationship between the Angström exponent and the AOD bias. Differently, when the AOD is dominated by fine particles, the differences in model performance are more evident, with MADE/SORGAM generally performing better than MOSAIC. Indeed the higher availability of both sulfate and nitrate has a significant influence on reconstruction of the AOD estimations. This paper shows the great importance of chemical mechanisms in both gaseous and

  14. Evaluation of the performance of four chemical transport models in predicting the aerosol chemical composition in Europe in 2005

    NASA Astrophysics Data System (ADS)

    Prank, Marje; Sofiev, Mikhail; Tsyro, Svetlana; Hendriks, Carlijn; Semeena, Valiyaveetil; Vazhappilly Francis, Xavier; Butler, Tim; Denier van der Gon, Hugo; Friedrich, Rainer; Hendricks, Johannes; Kong, Xin; Lawrence, Mark; Righi, Mattia; Samaras, Zissis; Sausen, Robert; Kukkonen, Jaakko; Sokhi, Ranjeet

    2016-05-01

    Four regional chemistry transport models were applied to simulate the concentration and composition of particulate matter (PM) in Europe for 2005 with horizontal resolution ~ 20 km. The modelled concentrations were compared with the measurements of PM chemical composition by the European Monitoring and Evaluation Programme (EMEP) monitoring network. All models systematically underestimated PM10 and PM2.5 by 10-60 %, depending on the model and the season of the year, when the calculated dry PM mass was compared with the measurements. The average water content at laboratory conditions was estimated between 5 and 20 % for PM2.5 and between 10 and 25 % for PM10. For majority of the PM chemical components, the relative underestimation was smaller than it was for total PM, exceptions being the carbonaceous particles and mineral dust. Some species, such as sea salt and NO3-, were overpredicted by the models. There were notable differences between the models' predictions of the seasonal variations of PM, mainly attributable to different treatments or omission of some source categories and aerosol processes. Benzo(a)pyrene concentrations were overestimated by all the models over the whole year. The study stresses the importance of improving the models' skill in simulating mineral dust and carbonaceous compounds, necessity for high-quality emissions from wildland fires, as well as the need for an explicit consideration of aerosol water content in model-measurement comparison.

  15. Effect of phytoplankton biomass in seawater on chemical properties of sea spray aerosols.

    PubMed

    Park, Jiyeon; Kim, Dohyung; Lee, Kwangyul; Han, Seunghee; Kim, Hyunji; Williams, Leah R; Joo, Hung Soo; Park, Kihong

    2016-09-15

    This study is to investigate the effect of biological seawater properties on sea spray aerosols (SSA). Concentrations of chlorophyll-a and bacteria were measured at coastal site in Korea in fall and summer seasons. Also, aerosol mass spectrometer (AMS) was used to determine chemical constituents (organics, sulfate, nitrate, ammonium, and chloride) of non-refractory submicrometer aerosols sprayed from seawaters using a bubble bursting system. The average concentration of chlorophyll-a in seawater in fall was 1.75±0.78μg/l, whereas it significantly increased to 5.11±2.16μg/l in summer. It was found that the fraction of organics in the submicrometer SSA was higher in summer (68%) than fall (49%), and that the organic fraction in the SSA increased as the concentration of chlorophyll-a increased in seawater, suggesting that the high phytoplankton biomass in seawater could lead to the enhancement of organic species in the SSA. PMID:27345708

  16. Formation and aging of secondary organic aerosol from toluene: changes in chemical composition, volatility, and hygroscopicity

    DOE PAGESBeta

    Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.; Nenes, A.; Donahue, N. M.; Pandis, S. N.

    2015-07-24

    Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NOx under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OSc), and mass yield. The OA oxidation state generally increased duringmore » photo-oxidation, and the final OA OSc ranged from -0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

  17. Ion Current Rectification in Nano/Micro-Fluidic Interfaces and Pulsed Glow Discharge Time-of-Flight Mass Spectrometric Chemical Speciation

    NASA Astrophysics Data System (ADS)

    Wang, Han

    Microfluidics continues to be of interest for analyzing chemical and biological samples because of the disposability, portability, low sample consumption, fast analysis time, and parallel analysis potential for multiple samples in a single device. To improve microfluidic device functionality, integrated systems-nanofluidic/microfluidic interfaces (NMIs) have been fabricated for concentrating samples and performing as molecular gates. Ion current rectification has been confirmed in NMI with an asymmetric system. In chapter 2, the asymmetry of the NMI is systematically altered by varying the inner diameter of the nanocapillary membrane (NCM) reservoir, and the current rectification factor is observed to increase as the inner diameter of NCM reservoir increases. The data provide a new approach to tune the ion current rectification of NMIs and strengthen the fundamental knowledge of how these devices function. Glow discharge mass spectrometry (GDMS) is a well-established technique for the direct analysis of elements in solid samples. The introduction of pulsed glow discharge makes the internal energy of GD plasma tunable so that the specific desired ion signal profiles can be obtained and used for chemical speciation. For example, the elemental, structural, and molecular information of organic molecules have been obtained nearly simultaneously using glow discharge time-of-flight mass spectrometry (GDToFMS) coupled with gas chromatography. With careful control of operating parameters of GDToFMS, specific cluster ions or ion abundance ratios can be used for speciation of chromium oxides, manganese oxides, and iron oxides. Chapters 3 and 4 focus on extending the application of pulsed glow discharge time-of-flight mass spectrometry for chemical speciation. Chapter 3 is the analysis of cysteine using pulsed glow discharge time-of-flight mass spectrometry. The characteristic fragment ion at m/z 76 is used for the quantitative analysis for cysteine. The calibration curve for

  18. Chemical composition and sources of coastal marine aerosol particles during the 2008 VOCALS-REx campaign

    SciTech Connect

    Lee, Y. -N.; Springston, S.; Jayne, J.; Wang, J.; Hubbe, J.; Senum, G.; Kleinman, L.; Daum, P. H.

    2014-01-01

    The chemical composition of aerosol particles (Dp ≤ 1.5 μm) was measured over the southeast Pacific Ocean during the VAMOS (Variability of the American Monsoon Systems) Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-Rex) between 16 October and 15 November 2008 using the US Department of Energy (DOE) G-1 aircraft. The objective of these flights was to gain an understanding of the sources and evolution of these aerosols, and of how they interact with the marine stratus cloud layer that prevails in this region of the globe. Our measurements showed that the marine boundary layer (MBL) aerosol mass was dominated by non-sea-salt SO42−, followed by Na+, Cl, Org (total organics), NH4+, and NO3, in decreasing order of importance; CH3SO3 (MSA), Ca2+, and K+ rarely exceeded their limits of detection. Aerosols were strongly acidic with a NH4+ to SO42− equivalents ratio typically < 0.3. Sea-salt aerosol (SSA) particles, represented by NaCl, exhibited Cl deficits caused by both HNO3 and H2SO4, but for the most part were externally mixed with particles, mainly SO42−. SSA contributed only a small fraction of the total accumulation mode particle number concentration. It was inferred that all aerosol species (except SSA) were of predominantly continental origin because of their strong land-to-sea concentration gradient. Comparison of relative changes in median values suggests that (1) an oceanic source of NH3 is present between 72° W and 76° W, (2) additional organic aerosols from biomass burns or biogenic precursors were emitted from coastal regions south of 31° S, with possible cloud processing, and (3) free tropospheric (FT) contributions to MBL gas and aerosol

  19. PM 2.5 ORGANIC SPECIATION INTERCOMPARISON RESULTS

    EPA Science Inventory

    This abstract describes a poster on results to a laboratory intercomparison of organic aerosol speciation analysis to be presented at the 2006 International Aerosol Conference sponsored by the American Association for Aerosol Research in St. Paul, Minnesota on September 10-15. T...

  20. Improving aerosol interaction with clouds and precipitation in a regional chemical weather modeling system

    NASA Astrophysics Data System (ADS)

    Zhou, C.; Zhang, X.; Gong, S.; Wang, Y.; Xue, M.

    2016-01-01

    A comprehensive aerosol-cloud-precipitation interaction (ACI) scheme has been developed under a China Meteorological Administration (CMA) chemical weather modeling system, GRAPES/CUACE (Global/Regional Assimilation and PrEdiction System, CMA Unified Atmospheric Chemistry Environment). Calculated by a sectional aerosol activation scheme based on the information of size and mass from CUACE and the thermal-dynamic and humid states from the weather model GRAPES at each time step, the cloud condensation nuclei (CCN) are interactively fed online into a two-moment cloud scheme (WRF Double-Moment 6-class scheme - WDM6) and a convective parameterization to drive cloud physics and precipitation formation processes. The modeling system has been applied to study the ACI for January 2013 when several persistent haze-fog events and eight precipitation events occurred.

    The results show that aerosols that interact with the WDM6 in GRAPES/CUACE obviously increase the total cloud water, liquid water content, and cloud droplet number concentrations, while decreasing the mean diameters of cloud droplets with varying magnitudes of the changes in each case and region. These interactive microphysical properties of clouds improve the calculation of their collection growth rates in some regions and hence the precipitation rate and distributions in the model, showing 24 to 48 % enhancements of threat score for 6 h precipitation in almost all regions. The aerosols that interact with the WDM6 also reduce the regional mean bias of temperature by 3 °C during certain precipitation events, but the monthly means bias is only reduced by about 0.3 °C.

  1. Chemical Nature Of Titan’s Organic Aerosols Constrained from Spectroscopic and Mass Spectrometric Observations

    NASA Astrophysics Data System (ADS)

    Imanaka, Hiroshi; Cruikshank, D. P.

    2012-10-01

    The Cassini-Huygens observations greately extend our knowledge about Titan’s organic aerosols. The Cassini INMS and CAPS observations clearly demonstrate the formation of large organic molecules in the ionosphere [1, 2]. The VIMS and CIRS instruments have revealed spectral features of the haze covering the mid-IR and far-IR wavelengths [3, 4, 5, 6]. This study attempts to speculate the possible chemical nature of Titan’s aerosols by comparing the currently available observations with our laboratory study. We have conducted a series of cold plasma experiment to investigate the mass spectrometric and spectroscopic properties of laboratory aerosol analogs [7, 8]. Titan tholins and C2H2 plasma polymer are generated with cold plasma irradiations of N2/CH4 and C2H2, respectively. Laser desorption mass spectrum of the C2H2 plasma polymer shows a reasonable match with the CAPS positive ion mass spectrum. Furthermore, spectroscopic features of the the C2H2 plasma polymer in mid-IR and far-IR wavelegths qualitatively show reasonable match with the VIMS and CIRS observations. These results support that the C2H2 plasma polymer is a good candidate material for Titan’s aerosol particles at the altitudes sampled by the observations. We acknowledge funding supports from the NASA Cassini Data Analysis Program, NNX10AF08G, and from the NASA Exobiology Program, NNX09AM95G, and the Cassini Project. [1] Waite et al. (2007) Science 316, 870-875. [2] Crary et al. (2009) Planet. Space Sci. 57, 1847-1856. [3] Bellucci et al. (2009) Icarus 201, 198-216. [4] Anderson and Samuelson (2011) Icarus 212, 762-778. [5] Vinatier et al. (2010) Icarus 210, 852-866. [6] Vinatier et al. (2012) Icarus 219, 5-12. [7] Imanaka et al. (2004) Icarus 168, 344-366. [8] Imanaka et al. (2012) Icarus 218, 247-261.

  2. Global and Regional Impacts of HONO on the Chemical Composition of Clouds and Aerosols

    NASA Technical Reports Server (NTRS)

    Elshorbany, Y. F.; Crutzen, P. J.; Steil, B.; Pozzer, A.; Tost, H.; Lelieveld, J.

    2014-01-01

    Recently, realistic simulation of nitrous acid (HONO) based on the HONO/NO(sub x) ratio of 0.02 was found to have a significant impact on the global budgets of HO(sub x) (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and corroborate the central role of cloud chemical processing in S(IV) formation.

  3. Global and Regional Impacts of HONO on the Chemical Composition of Clouds and Aerosols

    NASA Technical Reports Server (NTRS)

    Elshorbany, Y. F.; Crutzen, P. J.; Steil, B.; Pozzer, A.; Tost, H.; Lelieveld, J.

    2014-01-01

    Recently, realistic simulation of nitrous acid (HONO) based on the HONO / NOx ratio of 0.02 was found to have a significant impact on the global budgets of HOx (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and corroborate the central role of cloud chemical processing in S(IV) formation

  4. Chemical composition of post-harvest biomass burning aerosols in Gwangju, Korea.

    PubMed

    Ryu, Seong Y; Kim, Jeong E; Zhuanshi, H; Kim, Young J; Kang, Gong U

    2004-09-01

    The main objective of this study was to investigate the chemical characteristics of post-harvest biomass burning aerosols from field burning of barley straw in late spring and rice straw in late fall in rural areas of Korea. A 12-hr integrated intensive sampling of particulate matter (PM) with an aerodynamic diameter less than or equal to 10 microm (PM10) and PM with an aerodynamic diameter less than or equal to 2.5 microm (PM2.5) biomass burning aerosols had been conducted continuously in Gwangju, Korea, during two biomass burning periods: June 4--15, 2001, and October 8--November 14, 2002. The fine and coarse particles of biomass burning aerosols were analyzed for mass and ionic, elemental, and carbonaceous species. The average fine and coarse mass concentrations of biomass burning aerosols were, respectively, 129.6 and 24.2 microg/m3 in June 2001 and 47.1 and 33.2 microg/m3 in October--November 2002. An exceptionally high PM2.5 concentration of 157.8 microg/m3 was observed during biomass burning events under stagnant atmospheric conditions. In the fine mode, chlorine and potassium were unusually rich because of the high content of semi-arid vegetation. Both organic carbon (OC) and elemental carbon increased during the biomass burning periods, with the former exhibiting a higher abundance. PM from the open field burning of agricultural waste has an adverse impact on local air quality and regional climate. PMID:15468665

  5. Global and regional impacts of HONO on the chemical composition of clouds and aerosols

    NASA Astrophysics Data System (ADS)

    Elshorbany, Y. F.; Crutzen, P. J.; Steil, B.; Pozzer, A.; Tost, H.; Lelieveld, J.

    2014-02-01

    Recently, realistic simulation of nitrous acid (HONO) based on the HONO / NOx ratio of 0.02 was found to have a significant impact on the global budgets of HOx (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model-measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and corroborate the central role of cloud chemical processing in S(IV) formation.

  6. Measurements of the chemical, physical, and optical properties of single aerosol particles

    NASA Astrophysics Data System (ADS)

    Moffet, Ryan Christopher

    Knowledge of aerosol physical, chemical, optical properties is essential for judging the effect that particulates have on human health, climate and visibility. The aerosol time-of-flight mass spectrometer (ATOFMS) is capable of measuring, in real-time, the size and chemical composition of atmospheric aerosols. This was exemplified by the recent deployments of the ATOFMS to Mexico City and Riverside. The ATOFMS provided rapid information about the major particle types present in the atmosphere. Industrial sources of particles, such as fine mode particles containing lead, zinc and chloride were detected in Mexico City. The rapid time response of the ATOFMS was also exploited to characterize a coarse particle concentrator used in human health effects studies. The ATOFMS showed the ability to detect changes in particle composition with a time resolution of 15 min during short 2 hour human exposure studies. As a major component of this work, an optical measurement has been added to the ATOFMS. The scattered light intensity was acquired for each sized and chemically analyzed particle. This scattering information together with the particle aerodynamic diameter, enabled the refractive index and density of the aerosol to be retrieved. This method was validated in the laboratory using different test particles such as oils, aqueous salt solutions and black carbon particles. It was found that the nozzle-type inlet does not evaporate aqueous salt particles as has been observed for aerodynamic lens inlets. These new optical and microphysical measurements were integrated into the ATOFMS for field deployment in Riverside and Mexico City. For both cities, the different mixing states were found to have unique refractive indexes and densities. A fraction of the strongly absorbing elemental carbon particles were observed to have a spherical morphology due to heavy mixing with secondary species. In addition to the quantitative refractive index and effective density measurements

  7. Chemical properties and morphology of Marine Aerosol in the Mediterranean atmosphere: a mesocosm study

    NASA Astrophysics Data System (ADS)

    D'Anna, Barbara; Sellegri, Karine; Charrière, Bruno; Sempéré, Richard; Mas, Sébastien; Marchand, Nicolas; George, Christian; Même, Aurèlie; R'mili, Badr; Delmont, Anne; Schwier, Allison; Rose, Clémence; Colomb, Aurèlie; Pey, Jorge; Langley Dewitt, Helen

    2014-05-01

    The Mediterranean Sea is a special marine environment characterized by low biological activity and high anthropogenic pressure. It is often difficult to discriminate the contribution of Primary Sea Salt Aerosol formed at the sea surface from background level of the aerosol. An alternative tool to study the sea-air exchanges in a controlled environment is provided by the mesocosms, which represent an important link between field studies and laboratory experiments. The sea-air transfer of particles and gases was investigated in relation to water chemical composition and biological activity during a mesocosm experiment within the SAM project (Sources of marine Aerosol in the Mediterranean) at the Oceanographic and Marine Station STARESO in Western Corsica (May 2013). Three 2 m mesocosms were filled with screened (<1000 µm) 2260 L of subsurface (1 m) seawater and covered with a transparent Teflon film dome to minimize atmospheric contamination. The mesocosms were equipped with a pack of optical and physicochemical sensors and received different treatments: one was left unchanged as control and two were enriched by addition of nitrates and phosphates respecting Redfield ratio (N:P = 16). The evolution of the three systems was followed for 20 days. The set of sensors in each mesocosm was allowed to monitor, at high frequency (every 10 min), the water temperature, conductivity, pH, incident light, fluorescence of chlorophyll a and dissolved oxygen concentration. The mesocosm seawaters were daily sampled for chemical (colored dissolved organic matter, particulate matter and related polar compounds, transparent polysaccharides and nutrients concentration) and biological (chlorophyll a, virus, phytoplankton and zooplankton) analyses. Both dissolved and gaseous VOCs were also analyzed. In addition, few liters of seawater from each mesocosm were daily and immediately collected and transferred to a bubble-bursting apparatus to simulate nascent sea spray aerosol. On

  8. Modal structure of chemical mass size distribution in the high Arctic aerosol

    NASA Astrophysics Data System (ADS)

    Hillamo, Risto; Kerminen, Veli-Matti; Aurela, Minna; MäKelä, Timo; Maenhaut, Willy; Leek, Caroline

    2001-11-01

    Chemical mass size distributions of aerosol particles were measured in the remote marine boundary layer over the central Arctic Ocean as part of the Atmospheric Research Program on the Arctic Ocean Expedition 1996 (AOE-96). An inertial impaction method was used to classify aerosol particles into different size classes for subsequent chemical analysis. The particle chemical composition was determined by ion chromatography and by the particle-induced X-ray emission technique. Continuous particle size spectra were extracted from the raw data using a data inversion method. Clear and varying modal structures for aerosols consisting of primary sea-salt particles or of secondary particles related to dimethyl sulfide emissions were found. Concentration levels of all modes decreased rapidly when the distance from open sea increased. In the submicrometer size range the major ions found by ion chromatography were sulfate, methane sulfonate, and ammonium. They had most of the time a clear Aitken mode and one or two accumulation modes, with aerodynamic mass median diameters around 0.1 μm, 0.3 μm, and between 0.5-1.0 μm, respectively. The overall submicron size distributions of these three ions were quite similar, suggesting that they were internally mixed over most of this size range. The corresponding modal structure was consistent with the mass size distributions derived from the particle number size distributions measured with a differential mobility particle sizer. The Aitken to accumulation mode mass ratio for nss-sulfate and MSA was substantially higher during clear skies than during cloudy periods. Primary sea-salt particles formed a mode with an aerodynamic mass median diameter around 2 μm. In general, the resulting continuous mass size distributions displayed a clear modal structure consistent with our understanding of the two known major source mechanisms. One is the sea-salt aerosol emerging from seawater by bubble bursting. The other is related to

  9. Optical, physical and chemical properties of transported African mineral dust aerosols in the Mediterranean region

    NASA Astrophysics Data System (ADS)

    Denjean, Cyrielle; Di Biagio, Claudia; Chevaillier, Servanne; Gaimoz, Cécile; Grand, Noel; Loisil, Rodrigue; Triquet, Sylvain; Zapf, Pascal; Roberts, Greg; Bourrianne, Thierry; Torres, Benjamin; Blarel, Luc; Sellegri, Karine; Freney, Evelyn; Schwarzenbock, Alfons; Ravetta, François; Laurent, Benoit; Mallet, Marc; Formenti, Paola

    2014-05-01

    The transport of mineral dust aerosols is a global phenomenon with strong climate implications. Depending on the travel distance over source regions, the atmospheric conditions and the residence time in the atmosphere, various transformation processes (size-selective sedimentation, mixing, condensation of gaseous species, and weathering) can modify the physical and chemical properties of mineral dust, which, in turn, can change the dust's optical properties. The model predictions of the radiative effect by mineral dust still suffer of the lack of certainty of these properties, and their temporal evolution with transport time. Within the frame of the ChArMex project (Chemistry-Aerosol Mediterranean experiment, http://charmex.lsce.ipsl.fr/), two intensive airborne campaigns (TRAQA, TRansport and Air QuAlity, 18 June - 11 July 2012, and ADRIMED, Aerosol Direct Radiative Impact in the regional climate in the MEDiterranean region, 06 June - 08 July 2013) have been performed over the Central and Western Mediterranean, one of the two major transport pathways of African mineral dust. In this study we have set up a systematic strategy to determine the optical, physical and optical properties of mineral dust to be compared to an equivalent dataset for dust close to source regions in Africa. This study is based on airborne observations onboard the SAFIRE ATR-42 aircraft, equipped with state of the art in situ instrumentation to measure the particle scattering and backscattering coefficients (nephelometer at 450, 550, and 700 nm), the absorption coefficient (PSAP at 467, 530, and 660 nm), the extinction coefficient (CAPS at 530 nm), the aerosol optical depth (PLASMA at 340 to 1640 nm), the size distribution in the extended range 40 nm - 30 µm by the combination of different particle counters (SMPS, USHAS, FSSP, GRIMM) and the chemical composition obtained by filter sampling. The chemistry and transport model CHIMERE-Dust have been used to classify the air masses according to

  10. Characterization of aerosol optical properties, chemical composition and mixing states in the winter season in Shanghai, China.

    PubMed

    Tang, Yong; Huang, Yuanlong; Li, Ling; Chen, Hong; Chen, Jianmin; Yang, Xin; Gao, Song; Gross, Deborah S

    2014-12-01

    Physical and chemical properties of ambient aerosols at the single particle level were studied in Shanghai from December 22 to 28, 2009. A Cavity-Ring-Down Aerosol Extinction Spectrometer (CRD-AES) and a nephelometer were deployed to measure aerosol light extinction and scattering properties, respectively. An Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) was used to detect single particle sizes and chemical composition. Seven particle types were detected. Air parcels arrived at the sampling site from the vicinity of Shanghai until mid-day of December 25, when they started to originate from North China. The aerosol extinction, scattering, and absorption coefficients all dropped sharply when this cold, clean air arrived. Aerosol particles changed from a highly aged type before this meteorological shift to a relatively fresh type afterwards. The aerosol optical properties were dependent on the wind direction. Aerosols with high extinction coefficient and scattering Ångström exponent (SAE) were observed when the wind blew from the west and northwest, indicating that they were predominantly fine particles. Nitrate and ammonium correlated most strongly with the change in aerosol optical properties. In the elemental carbon/organic carbon (ECOC) particle type, the diurnal trends of single scattering albedo (SSA) and elemental carbon (EC) signal intensity had a negative correlation. We also found a negative correlation (r=-0.87) between high mass-OC particle number fraction and the SSA in a relatively clean period, suggesting that particulate aromatic components might play an important role in light absorption in urban areas. PMID:25499489

  11. Molecular corridors and parameterizations of volatility in the chemical evolution of organic aerosols

    NASA Astrophysics Data System (ADS)

    Li, Ying; Pöschl, Ulrich; Shiraiwa, Manabu

    2016-03-01

    The formation and aging of organic aerosols (OA) proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is challenging for the interpretation of field measurements and laboratory experiments as well as accurate representation of OA evolution in atmospheric aerosol models. Based on data from over 30 000 compounds, we show that organic compounds with a wide variety of functional groups fall into molecular corridors, characterized by a tight inverse correlation between molar mass and volatility. We developed parameterizations to predict the saturation mass concentration of organic compounds containing oxygen, nitrogen, and sulfur from the elemental composition that can be measured by soft-ionization high-resolution mass spectrometry. Field measurement data from new particle formation events, biomass burning, cloud/fog processing, and indoor environments were mapped into molecular corridors to characterize the chemical nature of the observed OA components. We found that less-oxidized indoor OA are constrained to a corridor of low molar mass and high volatility, whereas highly oxygenated compounds in atmospheric water extend to high molar mass and low volatility. Among the nitrogen- and sulfur-containing compounds identified in atmospheric aerosols, amines tend to exhibit low molar mass and high volatility, whereas organonitrates and organosulfates follow high O : C corridors extending to high molar mass and low volatility. We suggest that the consideration of molar mass and molecular corridors can help to constrain volatility and particle-phase state in the modeling of OA particularly for nitrogen- and sulfur-containing compounds.

  12. Sources and chemical characterization of organic aerosol during the summer in the eastern Mediterranean

    NASA Astrophysics Data System (ADS)

    Kostenidou, E.; Florou, K.; Kaltsonoudis, C.; Tsiflikiotou, M.; Vratolis, S.; Eleftheriadis, K.; Pandis, S. N.

    2015-10-01

    The concentration and chemical composition of non-refractory fine particulate matter (NR-PM1) and black carbon (BC) levels were measured during the summer of 2012 in the suburbs of two Greek cities, Patras and Athens, in an effort to better understand the chemical processing of particles in the high photochemical activity environment of the eastern Mediterranean. The composition of PM1 was surprisingly similar in both areas, demonstrating the importance of regional sources for the corresponding pollution levels. The PM1 average mass concentration was 9-14 μg m-3. The contribution of sulfate was around 38 %, while organic aerosol (OA) contributed approximately 45 % in both cases. PM1 nitrate levels were low (2 %). The oxygen to carbon (O : C) atomic ratio was 0.50 ± 0.08 in Patras and 0.47 ± 0.11 in Athens. In both cases PM1 was acidic. Positive matrix factorization (PMF) was applied to the high-resolution organic aerosol mass spectra obtained by an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). For Patras, five OA sources could be identified: 19 % very oxygenated OA (V-OOA), 38 % moderately oxygenated OA (M-OOA), 21 % biogenic oxygenated OA (b-OOA), 7 % hydrocarbon-like OA (HOA-1) associated with traffic sources and 15 % hydrocarbon-like OA (HOA-2) related to other primary emissions (including cooking OA). For Athens, the corresponding source contributions were: V-OOA (35 %), M-OOA (30 %), HOA-1 (18 %) and HOA-2 (17 %). In both cities the major component was OOA, suggesting that under high photochemical conditions most of the OA in the eastern Mediterranean is quite aged. The contribution of the primary sources (HOA-1 and HOA-2) was important (22 % in Patras and 35 % in Athens) but not dominant.

  13. Sources and chemical characterization of organic aerosol during the summer in the eastern Mediterranean

    NASA Astrophysics Data System (ADS)

    Kostenidou, E.; Florou, K.; Kaltsonoudis, C.; Tsiflikiotou, M.; Vratolis, S.; Eleftheriadis, K.; Pandis, S. N.

    2015-02-01

    The concentration and chemical composition of the non-refractory fine particulate matter (NR-PM1) and black carbon (BC) levels were measured during the summer of 2012 in the suburbs of two Greek cities, Patras and Athens, in an effort to better understand the chemical processing of particles in the high photochemical activity environment of the Eastern Mediterranean. The composition of PM1 was surprisingly similar in both areas demonstrating the importance of regional sources for the corresponding pollution levels. The PM1 average mass concentration was 9-14 μg m-3. The contribution of sulphate was around 38%, while organic aerosol (OA) contributed approximately 45% in both cases. PM1 nitrate levels were low (2%). The oxygen to carbon (O : C) atomic ratio was 0.50 ± 0.08 in Patras and 0.47 ± 0.11 in Athens. In both cases the PM1 was acidic. Positive matrix factorization (PMF) was applied to the high resolution organic aerosol mass spectra obtained by an Aerodyne High Resolution Aerosol Mass Spectrometer (HR-AMS). For Patras five OA sources could be identified: 19% very oxygenated OA (V-OOA), 38% moderately oxygenated OA (M-OOA), 21% biogenic oxygenated OA (b-OOA), 7% hydrocarbon-like OA (HOA-1) associated with traffic sources and 15% hydrocarbon-like OA (HOA-2) related to other primary emissions (including cooking OA). For Athens the corresponding source contributions were: V-OOA (35%), M-OOA (30%), HOA-1 (18%) and HOA-2 (17%). In both cities the major component was OOA, suggesting that under high photochemical conditions most of the OA in the Eastern Mediterranean is quite aged. The contribution of the primary sources (HOA-1 and HOA-2) was important (22% in Patras and 33% in Athens) but not dominant.

  14. Flight-based chemical characterization of biomass burning aerosols within two prescribed burn smoke plumes

    NASA Astrophysics Data System (ADS)

    Pratt, K. A.; Murphy, S. M.; Subramanian, R.; Demott, P. J.; Kok, G. L.; Campos, T.; Rogers, D. C.; Prenni, A. J.; Heymsfield, A. J.; Seinfeld, J. H.; Prather, K. A.

    2011-06-01

    Biomass burning represents a major global source of aerosols impacting direct radiative forcing and cloud properties. Thus, the goal of a number of current studies involves developing a better understanding of how the chemical composition and mixing state of biomass burning aerosols evolve during atmospheric aging processes. During the Ice in Cloud Experiment - Layer Clouds (ICE-L) in fall of 2007, smoke plumes from two small Wyoming Bureau of Land Management prescribed burns were measured by on-line aerosol instrumentation aboard a C-130 aircraft, providing a detailed chemical characterization of the particles. After ~2-4 min of aging, submicron smoke particles, produced primarily from sagebrush combustion, consisted predominantly of organics by mass, but were comprised primarily of internal mixtures of organic carbon, elemental carbon, potassium chloride, and potassium sulfate. Significantly, 100 % of the fresh biomass burning particles contained minor mass fractions of nitrate and sulfate, suggesting that hygroscopic material is incorporated very near or at the point of emission. The mass fractions of ammonium, sulfate, and nitrate increased with aging up to ~81-88 min and resulted in acidic particles, with both nitric acid and sulfuric acid present. Decreasing black carbon mass concentrations occurred due to dilution of the plume. Increases in the fraction of oxygenated organic carbon and the presence of dicarboxylic acids, in particular, were observed with aging. Cloud condensation nuclei measurements suggested all particles >100 nm were active at 0.5 % water supersaturation in the smoke plumes, confirming the relatively high hygroscopicity of the freshly emitted particles. For immersion/condensation freezing, ice nuclei measurements at -32 °C suggested activation of ~0.03-0.07 % of the particles with diameters greater than 500 nm.

  15. Flight-based chemical characterization of biomass burning aerosols within two prescribed burn smoke plumes

    NASA Astrophysics Data System (ADS)

    Pratt, K. A.; Murphy, S. M.; Subramanian, R.; Demott, P. J.; Kok, G. L.; Campos, T.; Rogers, D. C.; Prenni, A. J.; Heymsfield, A. J.; Seinfeld, J. H.; Prather, K. A.

    2011-12-01

    Biomass burning represents a major global source of aerosols impacting direct radiative forcing and cloud properties. Thus, the goal of a number of current studies involves developing a better understanding of how the chemical composition and mixing state of biomass burning aerosols evolve during atmospheric aging processes. During the Ice in Clouds Experiment-Layer Clouds (ICE-L) in the fall of 2007, smoke plumes from two small Wyoming Bureau of Land Management prescribed burns were measured by on-line aerosol instrumentation aboard a C-130 aircraft, providing a detailed chemical characterization of the particles. After ~2-4 min of aging, submicron smoke particles, produced primarily from sagebrush combustion, consisted predominantly of organics by mass, but were comprised primarily of internal mixtures of organic carbon, elemental carbon, potassium chloride, and potassium sulfate. Significantly, the fresh biomass burning particles contained minor mass fractions of nitrate and sulfate, suggesting that hygroscopic material is incorporated very near or at the point of emission. The mass fractions of ammonium, sulfate, and nitrate increased with aging up to ~81-88 min and resulted in acidic particles. Decreasing black carbon mass concentrations occurred due to dilution of the plume. Increases in the fraction of oxygenated organic carbon and the presence of dicarboxylic acids, in particular, were observed with aging. Cloud condensation nuclei measurements suggested all particles >100 nm were active at 0.5% water supersaturation in the smoke plumes, confirming the relatively high hygroscopicity of the freshly emitted particles. For immersion/condensation freezing, ice nuclei measurements at -32 °C suggested activation of ~0.03-0.07% of the particles with diameters greater than 500 nm.

  16. Variation of the NMVOC speciation in the solvent sector and the sensitivity of modelled tropospheric ozone

    NASA Astrophysics Data System (ADS)

    von Schneidemesser, E.; Coates, J.; Denier van der Gon, H. A. C.; Visschedijk, A. J. H.; Butler, T. M.

    2016-06-01

    Non-methane volatile organic compounds (NMVOCs) are detrimental to human health owing to the toxicity of many of the NMVOC species, as well as their role in the formation of secondary air pollutants such as tropospheric ozone (O3) and secondary organic aerosol. The speciation and amount of NMVOCs emitted into the troposphere are represented in emission inventories (EIs) for input to chemical transport models that predict air pollutant levels. Much of the information in EIs pertaining to speciation of NMVOCs is likely outdated, but before taking on the task of providing an up-to-date and highly speciated EI, a better understanding of the sensitivity of models to the change in NMVOC input would be highly beneficial. According to the EIs, the solvent sector is the most important sector for NMVOC emissions. Here, the sensitivity of modelled tropospheric O3 to NMVOC emission inventory speciation was investigated by comparing the maximum potential difference in O3 produced using a variety of reported solvent sector EI speciations in an idealized study using a box model. The sensitivity was tested using three chemical mechanisms that describe O3 production chemistry, typically employed for different types of modelling scales - point (MCM v3.2), regional (RADM2), and global (MOZART-4). In the box model simulations, a maximum difference of 15 ppbv (ca. 22% of the mean O3 mixing ratio of 69 ppbv) between the different EI speciations of the solvent sector was calculated. In comparison, for the same EI speciation, but comparing the three different mechanisms, a maximum difference of 6.7 ppbv was observed. Relationships were found between the relative contribution of NMVOC compound classes (alkanes and oxygenated species) in the speciations to the amount of Ox produced in the box model. These results indicate that modelled tropospheric O3 is sensitive to the speciation of NMVOCs as specified by emission inventories, suggesting that detailed updates to the EI speciation

  17. Aerosol-Assisted Chemical Vapor Deposited Thin Films for Space Photovoltaics

    NASA Technical Reports Server (NTRS)

    Hepp, Aloysius F.; McNatt, Jeremiah; Dickman, John E.; Jin, Michael H.-C.; Banger, Kulbinder K.; Kelly, Christopher V.; AquinoGonzalez, Angel R.; Rockett, Angus A.

    2006-01-01

    Copper indium disulfide thin films were deposited via aerosol-assisted chemical vapor deposition using single source precursors. Processing and post-processing parameters were varied in order to modify morphology, stoichiometry, crystallography, electrical properties, and optical properties in order to optimize device-quality material. Growth at atmospheric pressure in a horizontal hot-wall reactor at 395 C yielded best device films. Placing the susceptor closer to the evaporation zone and flowing a more precursor-rich carrier gas through the reactor yielded shinier, smoother, denser-looking films. Growth of (112)-oriented films yielded more Cu-rich films with fewer secondary phases than growth of (204)/(220)-oriented films. Post-deposition sulfur-vapor annealing enhanced stoichiometry and crystallinity of the films. Photoluminescence studies revealed four major emission bands (1.45, 1.43, 1.37, and 1.32 eV) and a broad band associated with deep defects. The highest device efficiency for an aerosol-assisted chemical vapor deposited cell was 1.03 percent.

  18. Aerosols near by a coal fired thermal power plant: chemical composition and toxic evaluation.

    PubMed

    Jayasekher, T

    2009-06-01

    Industrial processes discharge fine particulates containing organic as well as inorganic compounds into the atmosphere which are known to induce damage to cell and DNA, both in vitro and in vivo. Source and area specific studies with respect to the chemical composition, size and shape of the particles, and toxicity evaluations are very much limited. This study aims to investigate the trace elements associated with the aerosol particles distributed near to a coal burning thermal power plant and to evaluate their toxicity through Comet assay. PM(10) (particles determined by mass passing an inlet with a 50% cut-off efficiency having a 10-microm aerodynamic diameter) samples were collected using respirable dust samplers. Twelve elements (Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, Se, Hg, and As) were analyzed using ICP-AES. Comet assay was done with the extracts of aerosols in phosphate buffered saline (PBS). Results show that Fe and Zn were found to be the predominant elements along with traces of other analyzed elements. Spherical shaped ultrafine particles of <1 microm aerodynamic diameter were detected through scanning electron microscope. PM(10) particles near to the coal burning power plant produced comets indicating their potential to induce DNA damage. DNA damage property is found to be depending upon the chemical characteristics of the components associated with the particles besides the physical properties such as size and shape. PMID:19264341

  19. Aerosol Observability and Predictability: From Research to Operations for Chemical Weather Forecasting. Lagrangian Displacement Ensembles for Aerosol Data Assimilation

    NASA Technical Reports Server (NTRS)

    da Silva, Arlindo

    2010-01-01

    A challenge common to many constituent data assimilation applications is the fact that one observes a much smaller fraction of the phase space that one wishes to estimate. For example, remotely sensed estimates of the column average concentrations are available, while one is faced with the problem of estimating 3D concentrations for initializing a prognostic model. This problem is exacerbated in the case of aerosols because the observable Aerosol Optical Depth (AOD) is not only a column integrated quantity, but it also sums over a large number of species (dust, sea-salt, carbonaceous and sulfate aerosols. An aerosol transport model when driven by high-resolution, state-of-the-art analysis of meteorological fields and realistic emissions can produce skillful forecasts even when no aerosol data is assimilated. The main task of aerosol data assimilation is to address the bias arising from inaccurate emissions, and Lagrangian misplacement of plumes induced by errors in the driving meteorological fields. As long as one decouples the meteorological and aerosol assimilation as we do here, the classic baroclinic growth of error is no longer the main order of business. We will describe an aerosol data assimilation scheme in which the analysis update step is conducted in observation space, using an adaptive maximum-likelihood scheme for estimating background errors in AOD space. This scheme includes e explicit sequential bias estimation as in Dee and da Silva. Unlikely existing aerosol data assimilation schemes we do not obtain analysis increments of the 3D concentrations by scaling the background profiles. Instead we explore the Lagrangian characteristics of the problem for generating local displacement ensembles. These high-resolution state-dependent ensembles are then used to parameterize the background errors and generate 3D aerosol increments. The algorithm has computational complexity running at a resolution of 1/4 degree, globally. We will present the result of

  20. Morphological and chemical changes of aerosolized E. coli treated with a dielectric barrier discharge.

    PubMed

    Romero-Mangado, Jaione; Nordlund, Dennis; Soberon, Felipe; Deane, Graham; Maughan, Kevin; Sainio, Sami; Singh, Gurusharan; Daniels, Stephen; Saunders, Ian T; Loftus, David; Meyyappan, M; Koehne, Jessica; Gandhiraman, Ram P

    2016-06-01

    This study presents the morphological and chemical modification of the cell structure of aerosolized Escherichia coli treated with a dielectric barrier discharge (DBD). Exposure to DBD results in severe oxidation of the bacteria, leading to the formation of hydroxyl groups and carbonyl groups and a significant reduction in amine functionalities and phosphate groups. Near edge x-ray absorption fine structure (NEXAFS) measurements confirm the presence of additional oxide bonds upon DBD treatment, suggesting oxidation of the outer layer of the cell wall. Electron microscopy images show that the bacteria undergo physical distortion to varying degrees, resulting in deformation of the bacterial structure. The electromagnetic field around the DBD coil causes severe damage to the cell structure, possibly resulting in leakage of vital cellular materials. The oxidation and chemical modification of the bacterial components are evident from the Fourier transform infrared spectroscopy and NEXAFS results. The bacterial reculture experiments confirm inactivation of airborne E. coli upon treating with DBD. PMID:26872580

  1. Characterization of aerosol-containing chemical simulant clouds using a sensitive, thermal infrared imaging spectrometer

    NASA Astrophysics Data System (ADS)

    Hall, Jeffrey L.; D'Amico, Francis M.; Kolodzey, Steven J.; Qian, Jun; Polak, Mark L.; Westerberg, Karl; Chang, Clement S.

    2011-05-01

    A sensitive, ground-based thermal imaging spectrometer was deployed at the Army's Dugway Proving Ground to remotely monitor explosively released chemical-warfare-agent-simulant clouds from stand-off ranges of a few kilometers. The sensor has 128 spectral bands covering the 7.6 to 13.5 micron region. The measured cloud spectra clearly showed scattering of high-elevation-angle sky radiance by liquid aerosols or dust in the clouds: we present arguments that show why the scattering is most likely due to dust. This observation has significant implications for early detection of dust-laden chemical clouds. On one hand, detection algorithms must properly account for the scattered radiation component, which would include out-of-scene radiation components as well as a dust signature; on the other hand, this scattering gives rise to an enhanced "delta-T" for detection by a ground-based sensor.

  2. Chemical composition and characteristics of ambient aerosols and rainwater residues during Indian summer monsoon: Insight from aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Chakraborty, Abhishek; Gupta, Tarun; Tripathi, Sachchida N.

    2016-07-01

    Real time composition of non-refractory submicron aerosol (NR-PM1) is measured via Aerosol mass spectrometer (AMS) for the first time during Indian summer monsoon at Kanpur, a polluted urban location located at the heart of Indo Gangetic Plain (IGP). Submicron aerosols are found to be dominated by organics followed by nitrate. Source apportionment of organic aerosols (OA) via positive matrix factorization (PMF) revealed several types of secondary/oxidized and primary organic aerosols. On average, OA are completely dominated by oxidized OA with a very little contribution from biomass burning OA. During rain events, PM1 concentration is decreased almost by 60%, but its composition remains nearly the same. Oxidized OA showed slightly more decrease than primary OAs, probably due to their higher hygroscopicity. The presence of organo nitrates (ON) is also detected in ambient aerosols. Apart from real-time sampling, collected fog and rainwater samples were also analyzed via AMS in offline mode and in the ICP-OES (Inductively coupled plasma - Optical emission spectrometry) for elements. The presence of sea salt, organo nitrates and sulfates has been observed. Rainwater residues are also dominated by organics but their O/C ratios are 15-20% lower than the observed values for ambient OA. Alkali metals such as Ca, Na, K are found to be most abundant in the rainwater followed by Zn. Rainwater residues are also found to be much less oxidized than the aerosols present inside the fog water, indicating presence of less oxidized organics. These findings indicate that rain can act as an effective scavenger of different types of pollutants even for submicron particle range. Rainwater residues also contain organo sulfates which indicate that some portion of the dissolved aerosols has undergone aqueous processing, possibly inside the cloud. Highly oxidized and possibly hygroscopic OA during monsoon period compared to other seasons (winter, post monsoon), indicates that they can act

  3. [Chemical Composition of the Single Particle Aerosol in Winter in Nanning Using SPAMS].

    PubMed

    Liu, Hui-lin; Song, Hong-jun; Chen, Zhi-ming; Huang, Jiong-li; Yang, Jun-chao; Mao, Jing-ying; Li, Hong; Liang, Gui-yun; Mo, Zhao-yu

    2016-02-15

    Single Particle Aerosol Mass Spectrometry (SPAMS) was performed to characterize the PM2.5 in Nanning from 15 to 24 February 2015. The correlation (R2) between the PM2.5 number concentration and the mass concentration of PM2.5 obtained using SPAMS was 0.76. The particle number concentration could reflect the atmospheric pollution situation to some degree. The Art-2a classification method was used to classify the chemical composition of PM2.5. The results showed that the principal chemical constituents were elemental carbon, organic elements carbon hybrid particles, organic carbon, rich potassium particles, mineral substance, rich sodium particles, second inorganic particles, levoglucosan and other heavy metals. Among them, the composition of elemental carbon was the highest, followed by organic carbon and rich potassium particles. The particle size of 80% of PM2.5 was mainly concentrated in the range of 0.2 microm to 1.0 microm with a peak value occurring at 0. 62 microm. The particle size distribution characteristics of different chemical components were similar. The number concentration of the chemical components in PM2.5 had the same variation tread with the mass concentration of PM2.5 over time. To a certain extent, the change in chemical composition could reflect the instantaneous pollution source. PMID:27363128

  4. Temporal assessment of copper speciation, bioavailability and toxicity in UK freshwaters using chemical equilibrium and biotic ligand models: Implications for compliance with copper environmental quality standards.

    PubMed

    Lathouri, Maria; Korre, Anna

    2015-12-15

    Although significant progress has been made in understanding how environmental factors modify the speciation, bioavailability and toxicity of metals such as copper in aquatic environments, the current methods used to establish water quality standards do not necessarily consider the different geological and geochemical characteristics of a given site and the factors that affect copper fate, bioavailability potential and toxicity. In addition, the temporal variation in the concentration and bioavailable metal fraction is also important in freshwater systems. The work presented in this paper illustrates the temporal and seasonal variability of a range of water quality parameters, and Cu speciation, bioavailability and toxicity at four freshwaters sites in the UK. Rivers Coquet, Cree, Lower Clyde and Eden (Kent) were selected to cover a broad range of different geochemical environments and site characteristics. The monitoring data used covered a period of around six years at almost monthly intervals. Chemical equilibrium modelling was used to study temporal variations in Cu speciation and was combined with acute toxicity modelling to assess Cu bioavailability for two aquatic species, Daphnia magna and Daphnia pulex. The estimated copper bioavailability, toxicity levels and the corresponding ecosystem risks were analysed in relation to key water quality parameters (alkalinity, pH and DOC). Although copper concentrations did not vary much during the sampling period or between the seasons at the different sites; copper bioavailability varied markedly. In addition, through the chronic-Cu BLM-based on the voluntary risk assessment approach, the potential environmental risk in terms of the chronic toxicity was assessed. A much higher likelihood of toxicity effects was found during the cold period at all sites. It is suggested that besides the metal (copper) concentration in the surface water environment, the variability and seasonality of other important water quality

  5. Distribution of Cd, Pb, Zn and Cu and their chemical speciations in soils from a peri-smelter area in northeast China

    NASA Astrophysics Data System (ADS)

    Du, Ping; Xue, Nandong; Liu, Li; Li, Fasheng

    2008-07-01

    An exploratory study on soil contamination of heavy metals was carried out surrounding Huludao zinc smelter in Liaoning province, China. The distribution of total heavy metals and their chemical speciations were investigated. The correlations between heavy metal speciations and soil pH values in corresponding sites were also analyzed. In general, Cd, Zn, Pb, Cu and As presented a significant contamination in the area near the smelter, comparied with Environmental Quality Standards for Soils in China. The geoaccumulation index showed the degree of contamination: Cd > Zn > Pb > Cu > As. There was no obvious pollution of Cr and Ni in the studied area. The speciation analysis showed that the dominant fraction of Cd and Zn was the acid soluble fraction, and the second was the residual fraction. Pb was mostly associated with the residual fraction, which constituted more than 50% of total concentration in all samples. Cu in residual fraction accounted for a high percentage (40-80%) of total concentration, and the proportion of Cu in the oxidizable fraction is higher than that of other metals. The distribution pattern of Pb and Zn was obviously affected by soil pH. It seemed that Pb and Zn content in acid solution fraction increased with increasing soil pH values, while Cd content in acid soluble fraction accounted for more proportion in neutral and alkaline groups than acidic one. The fraction distribution patterns of Cu in three pH groups were very similar and independent of soil pH values. And the residual fraction of Cu took a predominant part (50%) of the total content.

  6. Evolution of biomass burning aerosol over the Amazon: airborne measurements of aerosol chemical composition, microphysical properties, mixing state and optical properties during SAMBBA

    NASA Astrophysics Data System (ADS)

    Morgan, W.; Allan, J. D.; Flynn, M.; Darbyshire, E.; Hodgson, A.; Liu, D.; O'Shea, S.; Bauguitte, S.; Szpek, K.; Johnson, B.; Haywood, J.; Longo, K.; Artaxo, P.; Coe, H.

    2013-12-01

    Biomass burning represents one of the largest sources of particulate matter to the atmosphere, resulting in a significant perturbation to the Earth's radiative balance coupled with serious impacts on public health. On regional scales, the impacts are substantial, particularly in areas such as the Amazon Basin where large, intense and frequent burning occurs on an annual basis for several months. Absorption by atmospheric aerosols is underestimated by models over South America, which points to significant uncertainties relating to Black Carbon (BC) aerosol properties. Initial results from the South American Biomass Burning Analysis (SAMBBA) field experiment, which took place during September and October 2012 over Brazil on-board the UK Facility for Airborne Atmospheric Measurement (FAAM) BAe-146 research aircraft, are presented here. Aerosol chemical composition was measured by an Aerodyne Aerosol Mass Spectrometer (AMS) and a DMT Single Particle Soot Photometer (SP2). The physical, chemical and optical properties of the aerosols across the region will be characterized in order to establish the impact of biomass burning on regional air quality, weather and climate. The aircraft sampled a range of conditions including sampling of pristine Rainforest, fresh biomass burning plumes, regional haze and elevated biomass burning layers within the free troposphere. The aircraft sampled biomass burning aerosol across the southern Amazon in the states of Rondonia and Mato Grosso, as well as in a Cerrado (Savannah-like) region in Tocantins state. This presented a range of fire conditions, in terms of their number, intensity, vegetation-type and their combustion efficiencies. Near-source sampling of fires in Rainforest environments suggested that smouldering combustion dominated, while flaming combustion dominated in the Cerrado. This led to significant differences in aerosol chemical composition, particularly in terms of the BC content, with BC being enhanced in the Cerrado

  7. Semi-Continuous Measurements of Aerosol Chemical Composition During the Summer 2002 Yosemite National Park Special Study

    SciTech Connect

    Collette, J; Lee, T; Heath, J; Carrico, C; Herckes, P; Engling, G; McMeeking, G; Kreidenweis, S; Day, D; Malm, W; Cahill, T

    2003-02-16

    Semi-continuous measurements of fine particle composition were made over a period of several weeks in summer 2002 in Yosemite National Park, California. These included measurement of aerosol ionic composition (by PILS- Particle-Into-Liquid System) and aerosol carbon (by dual wavelength aethalometer and an R&P particulate carbon monitor). The data reveal that aerosol composition at the site is highly :variable in time, with a strong diurnal cycle. Interestingly, however, different diurnal cycles were sometimes observed for different chemical constituents of the particles. Organic carbon was observed to dominate fine particle mass, with some periods apparently associated with influx of smoke from wildfires in the western U.S. Measurements of fine particle carbon isotopes revealed the fraction of carbon from biogenic sources to range from approximately 73 to 95%. The ionic fraction of the aerosol was usually dominated by ammoniated sulfate. During most periods, PM{sub 2.5} nitrate was found primarily in sea salt particles from which chloride had been displaced. Strong variations in the extent of ammonia neutralization of sulfate were also observed. The ability to observe rapid changes in aerosol composition using these semi-continuous aerosol composition measurements is helpful for understanding the dynamic chemical composition of fine particles responsible for regional haze.

  8. Secondary organic aerosol (trans)formation through aqueous phase guaiacol photonitration: chemical characterization of the products

    NASA Astrophysics Data System (ADS)

    Grgić, Irena; Kitanovski, Zoran; Kroflič, Ana; Čusak, Alen

    2014-05-01

    One of the largest primary sources of organic aerosol in the atmosphere is biomass burning (BB) (Laskin et al. 2009); in Europe its contribution to annual mean of PM10 is between 3 and 14 % (Maenhaut et al. 2012). During the process of wood burning many different products are formed via thermal degradation of wood lignin. Hardwood burning produces mainly syringol (2,6-dimetoxyphenol) derivatives, while softwood burning exclusively guaiacol (2-methoxyphenol) and its derivatives. Taking into account physical properties of methoxyphenols only, their concentrations in atmospheric waters might be underestimated. So, their aqueous phase reactions can be an additional source of SOA, especially in regions under significant influence of wood combustion. An important class of compounds formed during physical and chemical aging of the primary BBA in the atmosphere is nitrocatechols, known as strong absorbers of UV and Vis light (Claeys et al. 2012). Very recently, methyl-nitrocatechols were proposed as suitable markers for highly oxidized secondary BBA (Iinuma et al. 2010, Kitanovski et al. 2012). In the present work, the formation of SOA through aqueous phase photooxidation and nitration of guaiacol was examined. The key objective was to chemically characterize the main low-volatility products and further to check their possible presence in the urban atmospheric aerosols. The aqueous phase reactions were performed in a thermostated reactor under simulated sunlight in the presence of H2O2 and nitrite. Guaiacol reaction products were first concentrated by solid-phase extraction (SPE) and then subjected to semi-preparative liquid chromatography.The main product compounds were fractionated and isolated as pure solids and their structure was further elucidated by using nuclear magnetic resonance spectroscopy (1H, 13C and 2D NMR) and direct infusion negative ion electro-spray ionization tandem mass spectrometry (( )ESI-MS/MS). The main photonitration products of guaiacol (4

  9. Importance of Physico-Chemical Properties of Aerosols in the Formation of Arctic Ice Clouds

    NASA Astrophysics Data System (ADS)

    Keita, S. A.; Girard, E.

    2014-12-01

    Ice clouds play an important role in the Arctic weather and climate system but interactions between aerosols, clouds and radiation are poorly understood. Consequently, it is essential to fully understand their properties and especially their formation process. Extensive measurements from ground-based sites and satellite remote sensing reveal the existence of two Types of Ice Clouds (TICs) in the Arctic during the polar night and early spring. TIC-1 are composed by non-precipitating very small (radar-unseen) ice crystals whereas TIC-2 are detected by both sensors and are characterized by a low concentration of large precipitating ice crystals. It is hypothesized that TIC-2 formation is linked to the acidification of aerosols, which inhibit the ice nucleating properties of ice nuclei (IN). As a result, the IN concentration is reduced in these regions, resulting to a smaller concentration of larger ice crystals. Over the past 10 years, several parameterizations of homogeneous and heterogeneous ice nucleation have been developed to reflect the various physical and chemical properties of aerosols. These parameterizations are derived from laboratory studies on aerosols of different chemical compositions. The parameterizations are also developed according to two main approaches: stochastic (that nucleation is a probabilistic process, which is time dependent) and singular (that nucleation occurs at fixed conditions of temperature and humidity and time-independent). This research aims to better understand the formation process of TICs using a newly-developed ice nucleation parameterizations. For this purpose, we implement some parameterizations (2 approaches) into the Limited Area version of the Global Multiscale Environmental Model (GEM-LAM) and use them to simulate ice clouds observed during the Indirect and Semi-Direct Arctic Cloud (ISDAC) in Alaska. We use both approaches but special attention is focused on the new parameterizations of the singular approach. Simulation

  10. Physico-chemical characterization of African urban aerosols (Bamako in Mali and Dakar in Senegal) and their toxic effects in human bronchial epithelial cells: description of a worrying situation

    PubMed Central

    2013-01-01

    Background The involvement of particulate matter (PM) in cardiorespiratory diseases is now established in developed countries whereas in developing areas such as Africa with a high level of specific pollution, PM pollution and its effects are poorly studied. Our objective was to characterize the biological reactivity of urban African aerosols on human bronchial epithelial cells in relation to PM physico-chemical properties to identify toxic sources. Methods Size-speciated aerosol chemical composition was analyzed in Bamako (BK, Mali, 2 samples with one having desert dust event BK1) and Dakar (DK; Senegal) for Ultrafine UF, Fine F and Coarse C PM. PM reactivity was studied in human bronchial epithelial cells investigating six biomarkers (oxidative stress responsive genes and pro-inflammatory cytokines). Results PM mass concentrations were mainly distributed in coarse mode (60%) and were impressive in BK1 due to the desert dust event. BK2 and DK samples showed a high content of total carbon characteristic of urban areas. The DK sample had huge PAH quantities in bulk aerosol compared with BK that had more water soluble organic carbon and metals. Whatever the site, UF and F PM triggered the mRNA expression of the different biomarkers whereas coarse PM had little or no effect. The GM-CSF biomarker was the most discriminating and showed the strongest pro-inflammatory effect of BK2 PM. The analysis of gene expression signature and of their correlation with main PM compounds revealed that PM-induced responses are mainly related to organic compounds. The toxicity of African aerosols is carried by the finest PM as with Parisian aerosols, but when considering PM mass concentrations, the African population is more highly exposed to toxic particulate pollution than French population. Regarding the prevailing sources in each site, aerosol biological impacts are higher for incomplete combustion sources resulting from two-wheel vehicles and domestic fires than from diesel

  11. The optical, physical and chemical properties of the products of glyoxal uptake on ammonium sulfate seed aerosols

    NASA Astrophysics Data System (ADS)

    Trainic, M.; Riziq, A. A.; Lavi, A.; Flores, J. M.; Rudich, Y.

    2011-07-01

    The heterogeneous reaction between gas phase glyoxal and ammonium sulfate (AS) aerosols, a proxy for inorganic atmospheric aerosol, was studied in terms of the dependence of the optical, physical and chemical properties of the product aerosols on initial particle size and ambient RH. The reactions were studied under different relative humidity (RH) conditions, varying from dry conditions (~20 % RH) and up to 90 % RH, covering conditions prevalent in many atmospheric environments. At λ = 355 nm, the reacted aerosols demonstrate a substantial growth in optical extinction cross section, as well as in mobility diameter under a broad range of RH values (35-90 %). The ratio of the product aerosol to seed aerosol geometric cross section reached up to ~3.5, and the optical extinction cross-section up to ~250. The reactions show a trend of increasing physical and optical growth with decreasing seed aerosol size, from 100nm to 300 nm, as well as with decreasing RH values from 90 % to ~40 %. Optically inactive aerosols, at the limit of the Mie range (100 nm diameter) become optically active as they grow due to the reaction. AMS analyses of the reaction of 300 nm AS at RH values of 50 %, 75 % and 90 % show that the main products of the reaction are glyoxal oligomers, formed by acetal formation in the presence of AS. In addition, imidazole formation, which is a minor channel, is observed for all reactions, yielding a product which absorbs at λ = 290 nm, with possible implications on the radiative properties of the product aerosols. The ratio of absorbing substances (C-N compounds, including imidazoles) increases with increasing RH value. A core/shell model used for the investigation of the optical properties of the reaction products of AS 300nm with gas phase glyoxal, shows that the refractive index (RI) of the reaction products are in the range between 1.57-1.71 for the real part and between 0-0.02 for the imaginary part of the RI at 355 nm. The observed increase in the

  12. Marine Primary Aerosol in the Mediterranean atmosphere: physical and chemical properties from a mesocosm study

    NASA Astrophysics Data System (ADS)

    D'anna, B.; Sellegri, K.; Charriere, B.; Sempere, R.; Mas, S.; George, C.; Meme, A.; R'Mili, B.; Schwier, A. N.; Rose, C.

    2013-12-01

    The Mediterranean Sea is a special marine environment characterized by low biological activity and high anthropogenic pressure. It is often difficult to discriminated the contribution of Primary Sea Salt Aerosol (SSA) formed at the sea-air interface from background level of the aerosol. An alternative tool to study the sea-air exchanges in a controlled environment is provided by the mesocosms, which represent an important link between field studies and laboratory experiments. A mesocosms experiment was performed in May 2013 at the Oceanographic and Marine Station STARESO in Western Corsica. Three mesocosms were simultaneously filled with pooled and screened (<1000 μm) subsurface (1 m) seawater from the Bay. Each mesocosm had a maximum water column depth of 2 m and contained 2260 L of Bay water and covered with transparent (teflon film) dome to prevent atmospheric contamination. The three mesocosms were equipped with a pack of optical and physicochemical sensors and received different treatements: one was left unchanged as control and two were enriched by addition of nitrates and phosphates respecting Redfield ration (N:P = 16). The evolution of the three systems was followed for 20 days. A set of sensors in each mesocosm were established at 0.5 m and allowed to monitor at high frequency (every 2 min): water temperature, conductivity, pH, incident light, fluorescence of chlorophyll a and dissolved oxygen concentration. The mesocosms waters were daily sampled for chemical (dissolved oxygen, colored dissolved organic matter, nitrates, phosphates, silicates, transparent polyssacharides, dicarboxylic acids and related polar compounds) and biological (chlorophyll a, virus, phytoplankton and zooplankton concentration) analyses. Finally, few liters of sea-water from each mesocosms were sampled daily and immediately transferred to a bubble-bursting apparatus to simulate SSA. Size distribution and particle number were followed by SMPS and APS in the range of 10nm to 10

  13. Pampre : a new laboratory experiment to better understand the physico-chemical processes of Titan aerosols formation and growth

    NASA Astrophysics Data System (ADS)

    Szopa, C.; Cernogora, G.; Boufendi, L.; Correia, J. J.; Coll, P.

    2003-04-01

    Titan s atmosphere contains aerosols issued from the organic chemistry induced by the photochemistry of N2 and CH4, the major gaseous atmospheric compounds. These organic aerosols are important as they : i) have a significant influence on the properties of the atmosphere, linked to their optical properties; ii) represent the best known example of transition from the gaseous to the solid phase by chemistry; iii) represent the most complex organics produced in Titan s atmosphere, making them particularly interesting from an exo/astrobiological point of view. However, few direct information are available about them, and their processes of formation and growth are not well understood. In order to bring answers to these questions, we developed a new type of laboratory simulation which is dedicated to better understand the physico-chemical processes involved in the formation and growth of the aerosols. The main originality of this experiment (named PAMPRE) comes from its ability to produce aerosols in volume, as they are maintained in levitation thanks to an electric force compensating gravity, whereas the other similar experiments produce tholins on the reactors walls. Thus, one should produce analogs of Titan s aerosols within representative conditions. Moreover, beyond the ex-situ analyses generally led to characterize the aerosols properties with conventional techniques (MEB, GC-MS), the experimental set-up allows to operate in situ studies of the reactive plasma by UV-vis spectroscopy, in order to deduce the electron energy distribution function which have to be compared with the sun spectrum. Beyond the characterization of the aerosols properties and formation, this experiment will also provide information and materials that will be used to operate the calibrations of the Aerosol and Collector Pyrolyser and Gas Chromatograph-Mass Spectrometer experiments of the Cassini-Huygens mission, and to develop the ICAPS-IMPF facility which should be present in the ISS within

  14. Special Speciation

    ERIC Educational Resources Information Center

    Countryman, Lyn L.; Maroo, Jill D.

    2015-01-01

    Considerable anecdotal evidence indicates that some of the most difficult concepts that both high school and undergraduate elementary-education students struggle with are those surrounding evolutionary principles, especially speciation. It's no wonder that entry-level biology students are confused, when biologists have multiple definitions of…

  15. Cloud Formation Potential of Biomass Burning Aerosol Surrogate-Particles Chemically Aged by OH

    NASA Astrophysics Data System (ADS)

    Slade, J. H.; Thalman, R. M.; Wang, J.; Li, Z. Q.; Knopf, D. A.

    2014-12-01

    Heterogeneous or multiphase reactions between trace gases such as OH and atmospheric aerosol can influence physicochemical properties of the particles including composition, morphology and lifetime. In this work, the cloud condensation nuclei (CCN) activity of laboratory-generated biomass burning aerosol (BBA) exposed to OH radicals is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type and OH exposure ([OH]×time) using a CCN counter coupled to a custom-built aerosol flow reactor (AFR). The composition of particles collected by a micro-orifice uniform deposit impactor (MOUDI) first subjected to different OH exposures is analyzed by Raman and scanning transmission X-ray microscopy coupled with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative compounds found in BBA that have different hygroscopicity, chemical functionalities, and reactivity with OH radicals. BBA surrogate-particles are generated following atomization of aqueous solutions with mass ratios LEV:MNC:KS of 1:0:0, 0:1:0, 0:0:1, 1:1:0, 0:1:1, 1:0:1, 1:1:1, and 1:0.03:0.3. OH radicals are generated in the AFR following photolysis of O3 in the presence of H2O using a variable intensity ultra-violet (UV) lamp, which allows equivalent atmospheric OH exposures from days to weeks. In addition, we investigate how κ changes i) in response to varying [O3] with and without OH, and ii) at a fixed OH exposure while varying RH. The impact of OH exposure on the CCN activity of BBA will be presented and its atmospheric implications will be discussed.

  16. Wintertime aerosol chemical composition, volatility, and spatial variability in the greater London area

    NASA Astrophysics Data System (ADS)

    Xu, L.; Ng, N. L.; Williams, L. R.; Young, D. E.; Allan, J. D.; Coe, H.; Massoli, P.; Fortner, E.; Chhabra, P. S.; Herndon, S. C.; Brooks, B.; Jayne, J. T.; Worsnop, D. R.; Aiken, A. C.; Liu, S.; Gorkowski, K.; Dubey, M. K.; Fleming, Z.; Visser, S.; Prevot, A. S.

    2015-12-01

    In this study, we investigate the spatial distribution of PM1 in the greater London area during the Clean Air for London (ClearfLo) project in winter 2012 by applying two High-Resolution Time-of-Flight Aerosol Mass Spectrometers (HR-ToF-AMS) at a rural site (Detling, Kent) and an urban site (North Kensington, London). While the concentration of organic aerosol (OA) is comparable between the rural and urban sites, the OA sources are distinctly different. Due to elevated domestic heating in the urban area, the concentration of solid fuel OA at the urban site is about twice as high as at the rural site. In contrast, the OOA concentration at the rural site is almost twice that of the urban site. This is likely caused by a steep concentration gradient of OOA when air masses are advected from polluted mainland Europe. Taking advantage of low biogenic emissions in winter, the sources of OOA, which are highly uncertain, are investigated. Combing Positive Matrix Factorization (PMF) analysis and radiocarbon analysis, the majority of OOA is estimated to arise from aged biomass burning. We deploy a suite of instruments to investigate the organic volatility at the rural Detling site. After heating at 250°C in a thermal-denuder (TD), the mass fraction remaining of organics is 16%, which indicates the presence of non-volatile organics. By comparing the OA associated with refractory black carbon (measured by a soot-particle aerosol mass spectrometer) and total OA (measured by a HR-ToF-AMS), we proposed that the non-volatile organics have similar sources or have undergone similar chemical processing as refractory black carbon in the atmosphere. Finally, we will discuss the relationship between the volatility and the degree of oxidation of organics.

  17. Chemical Characterization of Secondary Organic Aerosol Formed from Atmospheric Aqueous-phase Reactions of Phenolic Compounds

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Anastasio, C.; Zhang, Q.

    2012-12-01

    Phenolic compounds, which are released in significant amounts from biomass burning, may undergo fast aqueous-phase reactions to form secondary organic aerosol (SOA) in the atmosphere. Understanding the aqueous-phase reaction mechanisms of these compounds and the composition of their reaction products is thus important for constraining SOA sources and predicting organic aerosol properties in models. In this study, we investigate the aqueous-phase reactions of three phenols (phenol, guaiacol and syringol) with two oxidants - excited triplet states (3C*) of non-phenolic aromatic carbonyls and hydroxyl radical (OH). By employing four analytical methods including high-resolution aerosol mass spectrometry, total organic carbon analysis, ion chromatography, and liquid chromatography-mass spectrometry, we thoroughly characterize the chemical compositions of the low volatility reaction products of phenols and propose formation mechanisms based on this information. Our results indicate that phenolic SOA is highly oxygenated, with O/C ratios in the range of 0.83-1.03, and that the SOA of phenol is usually more oxidized than those of guaiacol and syringol. Among the three precursors, syringol generates the largest fraction of higher molecular weight (MW) products. For the same precursor, the SOA formed via reaction with 3C* is less oxidized than that formed via reaction with OH. In addition, oxidation by 3C* enhances the formation of higher MW species, including phenolic dimers, higher oligomers and hydroxylated products, compared to reactions initiated by OH, which appear to favor the formation of organic acids. However, our results indicate that the yields of small organic acids (e.g., formate, acetate, oxalate, and malate) are low for both reaction pathways, together accounting for less than 5% of total SOA mass.

  18. Identification of the chemical form of sulfur compounds in the Japanese pink coral (Corallium elatius) skeleton using μ-XRF/XAS speciation mapping.

    PubMed

    Tamenori, Yusuke; Yoshimura, Toshihiro; Luan, Nguyen Trong; Hasegawa, Hiroshi; Suzuki, Atsushi; Kawahata, Hodaka; Iwasaki, Nozomu

    2014-05-01

    The distributions and chemical forms of sulfur compounds in the skeleton of Japanese pink coral (Corallium elatius) were investigated using X-ray spectroscopic techniques combined with micro-focused soft X-ray radiation. Microscopic X-ray fluorescence/soft X-ray photoabsorption (μ-XRF/XAS) speciation mapping clarified that sulfate is the primary species in the coral skeleton, with minor amounts of organic sulfur, whereas both sulfate and organic sulfur coexist in coenenchyme. Analysis of the post-edge region of the XAS spectra confirmed that sulfate ions in the coral skeleton are mainly in the form of gypsum-like inorganic sulfate substituting for the carbonate ions in the calcite skeleton. The sulfate concentration was negatively correlated with the magnesium concentration and positively correlated with that of phosphorus. Speciation mapping of sulfate in the coral skeleton showed clear fluctuations with sulfate concentrations being higher at dark bands, whereas the small amount of organic sulfur had unclear dark/bright bands. These results suggest that the little organic sulfur that is present is contained in the organic matter embedded in the biocrystal of coral skeleton. PMID:24727132

  19. Laboratory analogues simulating Titan's atmospheric aerosols: Compared chemical compositions of grains and thin films

    NASA Astrophysics Data System (ADS)

    Carrasco, Nathalie; Jomard, François; Vigneron, Jackie; Etcheberry, Arnaud; Cernogora, Guy

    2016-09-01

    Two sorts of solid organic samples can be produced in laboratory experiments simulating Titan's atmospheric reactivity: grains in the volume and thin films on the reactor walls. We expect that grains are more representative of Titan's atmospheric aerosols, but films are used to provide optical indices for radiative models of Titan's atmosphere. The aim of the present study is to address if these two sorts of analogues are chemically equivalent or not, when produced in the same N2-CH4 plasma discharge. The chemical compositions of both these materials are measured by using elemental analysis, XPS analysis and Secondary Ion Mass Spectrometry. The main parameter probed is the CH4/N2 ratio to explore various possible chemical regimes. We find that films are homogeneous but significantly less rich in nitrogen and hydrogen than grains produced in the same experimental conditions. This surprising difference in their chemical compositions could be explained by the efficient etching occurring on the films, which stay in the discharge during the whole plasma duration, whereas the grains are ejected after a few minutes. The higher nitrogen content in the grains possibly involves a higher optical absorption than the one measured on the films, with a possible impact on Titan's radiative models.

  20. Chemical closure study on hygroscopic properties of urban aerosol particles in Sapporo, Japan.

    PubMed

    Aggarwal, Shankar Gopala; Mochida, Michihiro; Kitamori, Yasuyuki; Kawamura, Kimitaka

    2007-10-15

    To assess the link between hygroscopicity of atmospheric particles and the chemical composition, we performed a chemical closure study on the hygroscopicity of organic-inorganic mixed particles nebulized from water extracts of ambient aerosols collected in Sapporo, Japan during summer 2005. The hygroscopicity of 100 nm particles was measured using a hygroscopicity tandem differential mobility analyzer (HTDMA) at 5-95% relative humidity. The chemical analyses of the extracts showed that inorganic salts accounted for 32-84% of the water-soluble fraction and that the remaining was water-soluble organic matter (WSOM). The liquid water content (LWC) of particles was primarily governed by the relative abundance of inorganic salts in particles. The chemical closure with a thermodynamic model did not indicate a significant perturbation of LWC by WSOM at 85% RH with the consideration of the uncertainties estimated. However, a positive perturbation by WSOM was suggested at 50% RH. Individual oxygenated compounds identified using gas chromatography were not abundant enough to substantially increase the LWC at 85% RH. PMID:17993129

  1. Microbiology and atmospheric processes: biological, physical and chemical characterization of aerosol particles

    NASA Astrophysics Data System (ADS)

    Georgakopoulos, D. G.; Després, V.; Fröhlich-Nowoisky, J.; Psenner, R.; Ariya, P. A.; Pósfai, M.; Ahern, H. E.; Moffett, B. F.; Hill, T. C. J.

    2008-04-01

    The interest in bioaerosols has traditionally been linked to health hazards for humans, animals and plants. However, several components of bioaerosols exhibit physical properties of great significance for cloud processes, such as ice nucleation and cloud condensation. To gain a better understanding of their influence on climate, it is therefore important to determine the composition, concentration, seasonal fluctuation, regional diversity and evolution of bioaerosols. In this paper, we will review briefly the existing techniques for detection, quantification, physical and chemical analysis of biological particles, attempting to bridge physical, chemical and biological methods for analysis of biological particles and integrate them with aerosol sampling techniques. We will also explore some emerging spectroscopy techniques for bulk and single-particle analysis that have potential for in-situ physical and chemical analysis. Lastly, we will outline open questions and further desired capabilities (e.g., in-situ, sensitive, both broad and selective, on-line, time-resolved, rapid, versatile, cost-effective techniques) required prior to comprehensive understanding of chemical and physical characterization of bioaerosols.

  2. Microbiology and atmospheric processes: biological, physical and chemical characterization of aerosol particles

    NASA Astrophysics Data System (ADS)

    Georgakopoulos, D. G.; Després, V.; Fröhlich-Nowoisky, J.; Psenner, R.; Ariya, P. A.; Pósfai, M.; Ahern, H. E.; Moffett, B. F.; Hill, T. C. J.

    2009-04-01

    The interest in bioaerosols has traditionally been linked to health hazards for humans, animals and plants. However, several components of bioaerosols exhibit physical properties of great significance for cloud processes, such as ice nucleation and cloud condensation. To gain a better understanding of their influence on climate, it is therefore important to determine the composition, concentration, seasonal fluctuation, regional diversity and evolution of bioaerosols. In this paper, we will review briefly the existing techniques for detection, quantification, physical and chemical analysis of biological particles, attempting to bridge physical, chemical and biological methods for analysis of biological particles and integrate them with aerosol sampling techniques. We will also explore some emerging spectroscopy techniques for bulk and single-particle analysis that have potential for in-situ physical and chemical analysis. Lastly, we will outline open questions and further desired capabilities (e.g., in-situ, sensitive, both broad and selective, on-line, time-resolved, rapid, versatile, cost-effective techniques) required prior to comprehensive understanding of chemical and physical characterization of bioaerosols.

  3. Technical Note: Evaluation of the WRF-Chem "Aerosol Chemical to Aerosol Optical Properties" Module using data from the MILAGRO campaign

    SciTech Connect

    Barnard, James C.; Fast, Jerome D.; Paredes-Miranda, Guadalupe L.; Arnott, W. P.; Laskin, Alexander

    2010-08-09

    A comparison between observed aerosol optical properties from the MILAGRO field campaign, which took place in the Mexico City Metropolitan Area (MCMA) during March 2006, and values simulated by the Weather Research and Forecasting model (WRF-Chem) model, reveals large differences. To help identify the source of the discrepancies, data from the MILAGRO campaign are used to evaluate the "aerosol chemical to aerosol optical properties" module implemented in the full chemistry version of the WRF-Chem model. The evaluation uses measurements of aerosol size distributions and chemical properties obtained at the MILAGRO T1 site. These observations are fed to the module, which makes predictions of various aerosol optical properties, including the scattering coefficient, Bscat; the absorption coefficient, Babs; and the single-scattering albedo, v0; all as a function of time. This simulation is compared with independent measurements obtained from a photoacoustic spectrometer (PAS) at a wavelength of 870 nm. Because of line losses and other factors, only "fine mode" aerosols with aerodynamic diameters less than 2.5 mm are considered here. Over a 10-day period, the simulations of hour-by-hour variations of Bscat are not satisfactory, but simulations of Babs and v0 are considerably better. When averaged over the 10-day period, the computed and observed optical properties agree within the uncertainty limits of the measurements and simulations. Specifically, the observed and calculated values are, respectively: (1) Bscat, 34.1 ± 5.1 Mm-1 versus 30.4 ± 4.3 Mm-1; (2) Babs, 9.7 ± 1.0 Mm-1 versus 11.7 ± 1.5 Mm-1; and (3) v0, 0.78 ± 0.04 and 0.74 ± 0.03. The discrepancies in values of v0 simulated by the full WRF-Chem model thus cannot be attributed to the "aerosol chemistry to optics" module. The discrepancy is more likely due, in part, to poor characterization of emissions near the T1 site, particularly black carbon emissions.

  4. Seasonal Differences in Aerosol Chemical Properties at a Site Along the Eastern Seaboard: Observations from the Two-Column Aerosol Project (TCAP)

    NASA Astrophysics Data System (ADS)

    Berg, L. K.; Fast, J. D.; Comstock, J. M.; Chand, D.; Hubbe, J. M.; Jefferson, A.; Kassianov, E.; Mei, F.; Sedlacek, A. J., III; Schmid, B.; Shilling, J.; Springston, S. R.; Tomlinson, J. M.; Watson, T. B.; Wilson, J. M.; Zelenyuk, A.

    2015-12-01

    There have been relatively few studies that have quantified the seasonal variability of aerosol chemical and optical properties, as well as cloud-aerosol interactions, over a large portion of the atmospheric column. The Two Column Aerosol Project (TCAP), a U.S. Department of Energy (DOE) supported study, was designed to address this shortcoming with a combination of both ground-based and airborne measurements. The TCAP measurement strategy focused on the aerosol and cloud properties in two columns, one over Cape Cod, Massachusetts and one several hundred kilometers to the east. TCAP included the year-long deployment of the DOE Atmospheric Measurement Program (ARM) Mobile Facility and two individual month-long deployments of the ARM Aerial Facility, in July 2012 and in February 2013. Our work highlights a number of important differences between the summer and winter study periods, including differences in atmospheric flow patterns, the mass loading and chemical composition of the aerosol. The median mass loading of organic aerosol measured at the surface was much larger during July (2.3 μg m-3) than February (0.88 μg m-3). These differences are likely the result of the small amount of biogenic emissions during the winter as well as the reduction in the amount of sunlight available for photochemistry. The amount of sulfate loading was approximately a factor of two larger during February, with a median value of 0.66 μg m-3 compared to only 0.30 μg m-3 measured during July. The median mass loading of nitrate and ammonium did not vary with season, but these two components make up a much larger fraction of the total aerosol mass loading in the winter. Interestingly, the difference in median refractory black carbon (rBC) measured at the surface did not change much between winter and summer (63 ng m-3 during February compared to 70 ng m-3 in July), but the 75th percentile of rBC mass loading is much larger, 127 ng m-3, during July compared to only 95 ng m-3 during

  5. Chemical characteristics of ambient aerosols contributed by cooking process at Noorpur village near Delhi (India)

    NASA Astrophysics Data System (ADS)

    Singh, Sudha; Kumar, Bablu; Gupta, Gyan Prakash; Kulshrestha, U. C.

    2013-05-01

    Combustion of fuels such as wood, crop residue and dung cakes etc. is one of the major sources of air pollution in developing countries. These fuels are still used commonly for cooking purpose in rural India. This study investigates the chemical composition of the ambient aerosols during cooking hours at a village called Noorpur (28.470 N, 77.030 E) which lies near Delhi city. Aerosol sampling was carried out during August 2011-May 2012 by using handy sampler (Envirotech model APM 821) installed at the terrace of a building (˜6m). The samples were collected on 8 hourly basis using Teflon filters. The water extract of these filters was analyzed for major anions (F-, Cl-, NO3-, SO42-) and major cations (Na+, NH4+, K+, Ca2+ Mg2+) by ion chromatography (Metrohm 883 Basic IC Plus). Results highlighted that cooking process contributed significant amount of SO42- and K+ṡ. Biomass burning is considered as a potential source of K+ in air. The high concentration of SO42- might be due to oxidation of SO2 contributed by the combustion of dung cakes. Further, the detailed results will be discussed during the conference.

  6. Amorphous Carbon Deposited by a Novel Aerosol-Assisted Chemical Vapor Deposition for Photovoltaic Solar Cells

    NASA Astrophysics Data System (ADS)

    Ahmad, Nurfadzilah; Kamaruzzaman, Dayana; Rusop, Mohamad

    2012-06-01

    Amorphous carbon (a-C) solar cells were successfully prepared using a novel and self-designed aerosol-assisted chemical vapor deposition (AACVD) method using camphor oil as a precursor. The fabricated solar cell with the configuration of Au/p-C/n-Si/Au achieved an efficiency of 0.008% with a fill factor of 0.15 for the device deposited at 0.5 h. The current-voltage (I-V) graph emphasized on the linear graph (ohmic) for the a-C thin films, whereas for the p-n device structure, a rectifying curve was obtained. The rectifying curves signify the heterojunction between the p-type a-C film and the n-Si substrate and designate the generation of electron-hole pair of the samples under illumination. Photoresponse characteristics of the deposited a-C was highlighted when being illuminated (AM 1.5 illumination: 100 mW/cm2, 25 °C). Transmittance spectrum exhibit a large transmittance value (>85%) and absorption coefficient value of 103-104 cm-1 at the visible range of 390 to 790 nm. The atomization of a liquid precursor solution into fine sub-micrometre-sized aerosol droplets in AACVD induced the smooth surface of a-C films. To the best of our knowledge, fabrication of a-C solar cell using this AACVD method has not yet been reported.

  7. Recent work in Canada for the proposed Chemical and Aerosol Sounding Satellite (CASS) mission

    NASA Astrophysics Data System (ADS)

    Walker, K. A.; Melo, S. M.; Moreau, L. M.; Perron, G. P.; Bourdeau, J.; Michels, J.

    2010-12-01

    The Chemical and Aerosol Sounding Satellite (CASS) mission is a proposed CSA-NASA collaboration to address the Committee on Earth Observation Satellites (CEOS) recommendation for continuity in climate-quality profile measurements of stratospheric and upper tropospheric composition. The mission would include two instruments: an infrared Fourier transform spectrometer (ACE-FTS-II) and a UV/VIS spectrometer (SAGE III). The two CASS sensors would focus primarily on trace gas and aerosol measurements using the solar occultation technique. These global measurements are aimed at understanding the changes that are occurring in our atmosphere including recovery of the stratospheric ozone layer, changes in climate due to increasing greenhouse gases and increasing pollution in the troposphere. Over the past year, two studies have been funded by the Canadian Space Agency (CSA) to examine the development of the ACE-FTS-II instrument and to investigate the accommodation of the CASS instruments on different platforms. In parallel, a small Canadian mission definition team has been established to work on the science objectives and mission requirements within the Canadian context. This presentation will describe the results of these two CSA-funded studies and the progress that has been made by the Canadian definition team.

  8. Chemical apportionment of aerosol optical properties during the Asia-Pacific Economic Cooperation summit in Beijing, China

    NASA Astrophysics Data System (ADS)

    Han, Tingting; Xu, Weiqi; Chen, Chen; Liu, Xingang; Wang, Qingqing; Li, Jie; Zhao, Xiujuan; Du, Wei; Wang, Zifa; Sun, Yele

    2015-12-01

    We have investigated the chemical and optical properties of aerosol particles during the 2014 Asia-Pacific Economic Cooperation (APEC) summit in Beijing, China, using the highly time-resolved measurements by a high-resolution aerosol mass spectrometer and a cavity attenuated phase shift extinction monitor. The average (±σ) extinction coefficient (bext) and absorption coefficient (bap) were 186.5 (±184.5) M m-1 and 23.3 (±21.9) M m-1 during APEC, which were decreased by 63% and 56%, respectively, compared to those before APEC primarily due to strict emission controls. The aerosol composition and size distributions showed substantial changes during APEC; as a response, the mass scattering efficiency (MSE) of PM1 was decreased from 4.7 m2 g-1 to 3.5 m2 g-1. Comparatively, the average single-scattering albedo (SSA) remained relatively unchanged, illustrating the synchronous reductions of bext and bap during APEC. MSE and SSA were found to increase as function of the oxidation degree of organic aerosol (OA), indicating a change of aerosol optical properties during the aging processes. The empirical relationships between chemical composition and particle extinction were established using a multiple linear regression model. Our results showed the largest contribution of ammonium nitrate to particle extinction, accounting for 35.1% and 29.3% before and during APEC, respectively. This result highlights the important role of ammonium nitrate in the formation of severe haze pollution during this study period. We also observed very different optical properties of primary and secondary aerosol. Owing to emission controls in Beijing and surrounding regions and also partly the influences of meteorological changes, the average bext of secondary aerosol during APEC was decreased by 71% from 372.3 M m-1 to 108.5 M m-1, whereas that of primary aerosol mainly from cooking, traffic, and biomass burning emissions showed a smaller reduction from 136.7 M m-1 to 71.3 M m-1. As a result

  9. The real part of the refractive indices and effective densities for chemically segregated ambient aerosols in Guangzhou measured by a single-particle aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Zhang, Guohua; Bi, Xinhui; Qiu, Ning; Han, Bingxue; Lin, Qinhao; Peng, Long; Chen, Duohong; Wang, Xinming; Peng, Ping'an; Sheng, Guoying; Zhou, Zhen

    2016-03-01

    Knowledge on the microphysical properties of atmospheric aerosols is essential to better evaluate their radiative forcing. This paper presents an estimate of the real part of the refractive indices (n) and effective densities (ρeff) of chemically segregated atmospheric aerosols in Guangzhou, China. Vacuum aerodynamic diameter, chemical compositions, and light-scattering intensities of individual particles were simultaneously measured by a single-particle aerosol mass spectrometer (SPAMS) during the fall of 2012. On the basis of Mie theory, n at a wavelength of 532 nm and ρeff were estimated for 17 particle types in four categories: organics (OC), elemental carbon (EC), internally mixed EC and OC (ECOC), and Metal-rich. The results indicate the presence of spherical or nearly spherical shapes for the majority of particle types, whose partial scattering cross-section versus sizes were well fitted to Mie theoretical modeling results. While sharing n in a narrow range (1.47-1.53), majority of particle types exhibited a wide range of ρeff (0.87-1.51 g cm-3). The OC group is associated with the lowest ρeff (0.87-1.07 g cm-3), and the Metal-rich group with the highest ones (1.29-1.51 g cm-3). It is noteworthy that a specific EC type exhibits a complex scattering curve versus size due to the presence of both compact and irregularly shaped particles. Overall, the results on the detailed relationship between physical and chemical properties benefits future research on the impact of aerosols on visibility and climate.

  10. Wintertime aerosol chemical composition, volatility, and spatial variability in the greater London area

    NASA Astrophysics Data System (ADS)

    Xu, L.; Williams, L. R.; Young, D. E.; Allan, J. D.; Coe, H.; Massoli, P.; Fortner, E.; Chhabra, P.; Herndon, S.; Brooks, W. A.; Jayne, J. T.; Worsnop, D. R.; Aiken, A. C.; Liu, S.; Gorkowski, K.; Dubey, M. K.; Fleming, Z. L.; Visser, S.; Prevot, A. S. H.; Ng, N. L.

    2015-08-01

    The composition of PM1 (particulate matter with diameter less than 1 μm) in the greater London area was characterized during the Clean Air for London (ClearfLo) project in winter 2012. Two High-Resolution Time-of-Flight Aerosol Mass Spectrometers (HR-ToF-AMS) were deployed at a rural site (Detling, Kent) and an urban site (North Kensington, London). The simultaneous and high-temporal resolution measurements at the two sites provide a unique opportunity to investigate the spatial distribution of PM1. We find that the organic aerosol (OA) concentration is comparable between the rural and urban sites, but the sources of OA are distinctly different. The concentration of solid fuel OA at the urban site is about twice as high as at the rural site, due to elevated domestic heating in the urban area. While the concentrations of oxygenated OA (OOA) are well-correlated between the two sites, the OOA concentration at the rural site is almost twice that of the urban site. At the rural site, more than 70 % of the carbon in OOA is estimated to be non-fossil, which suggests that OOA is likely related to aged biomass burning considering the small amount of biogenic SOA in winter. Thus, it is possible that the biomass burning OA contributes a larger fraction of ambient OA in wintertime than what previous field studies have suggested. A suite of instruments was deployed downstream of a thermal denuder (TD) to investigate the volatility of PM1 species at the rural Detling site. After heating at 250 °C in the TD, 40 % of the residual mass is OA, indicating the presence of non-volatile organics in the aerosol. Although the OA associated with refractory black carbon (rBC, measured by a soot-particle aerosol mass spectrometer) only accounts for < 10 % of the total OA (measured by a HR-ToF-AMS) at 250 °C, the two measurements are well-correlated, suggesting that the non-volatile organics have similar sources or have undergone similar chemical processing as rBC in the atmosphere

  11. Pattern of aerosol mass loading and chemical composition over the atmospheric environment of an urban coastal station

    NASA Astrophysics Data System (ADS)

    Bindu, G.; Nair, Prabha R.; Aryasree, S.; Hegde, Prashant; Jacob, Salu

    2016-02-01

    Aerosol sampling was carried out at four locations in and around Cochin (9°58‧ N, 76°17‧ E), an urban area, located on the southwest coast of India. The gravimetric estimates of aerosol mass loading showed wide range from 78 μg m-3 to >450 μg m-3, occasionally reaching values >500 μg m-3, associated with regional source characteristics. Most of the values were above the air quality standard. Both boundary layer and synoptic scale airflow pattern play role in the temporal features in aerosol mass loading and chemical composition. Chemical analysis of the aerosol samples were done for anionic species viz; F-, Cl-, Br-, NO2-,   NO3-,   PO43-,   SO42- and metallic/cationic species viz; Na, Ca, K, Mg, NH4+, Fe, Al, Cu, Mg, Pb, etc using Ion Chromatography, Atomic Absorption Spectroscopy (AAS) and Inductively Coupled Plasma- Atomic Emission Spectroscopy (ICP-AES). At all the locations, extremely high mass concentration of SO42- was observed with the mean value of 13±6.4 μg m-3 indicating the strong anthropogenic influence. Statistical analysis of the chemical composition data was carried out and the principal factors presented. Seasonal variation of these chemical species along with their percentage contributions and regional variations were also examined. Increase in level of Na in aerosol samples indicated the influence of monsoonal activity. Most of the species showed mass concentrations well above those measured over another coastal site Thiruvananthapuram (8°29‧ N, 76°57‧ E) situated ~220 km south of Cochin revealing the highly localized aerosol features.

  12. Single-particle aerosol mass spectrometry for the detection and identification of chemical warfare agent simulants.

    PubMed

    Martin, Audrey N; Farquar, George R; Frank, Matthias; Gard, Eric E; Fergenson, David P

    2007-08-15

    Single-particle aerosol mass spectrometry (SPAMS) was used for the real-time detection of liquid nerve agent simulants. A total of 1000 dual-polarity time-of-flight mass spectra were obtained for micrometer-sized single particles each of dimethyl methyl phosphonate, diethyl ethyl phosphonate, diethyl phosphoramidate, and diethyl phthalate using laser fluences between 0.58 and 7.83 nJ/microm2, and mass spectral variation with laser fluence was studied. The mass spectra obtained allowed identification of single particles of the chemical warfare agent (CWA) simulants at each laser fluence used although lower laser fluences allowed more facile identification. SPAMS is presented as a promising real-time detection system for the presence of CWAs. PMID:17630721

  13. Formation and chemical composition of atmospheric aerosols in an equatorial forest area

    NASA Astrophysics Data System (ADS)

    Clairac, B.; Delmas, R.; Cros, B.; Cachier, H.; Buat-Menard, P.

    1988-05-01

    The physical properties and the chemical composition of atmospheric aerosols have been studied in an equatorial region in the southern Congo (Africa). Field experiments were conducted between 1978 and 1983 in the equatorial forest of the Mayombe during periods where the influence of biomass burning was minimum. The results indicate that the forest is a net source of both fine particles resulting primarily from gas-to-particle conversion and coarse particles produced by mechanical processes. Carbonaceous matter is the major component of these biogenic particles but the forest is also a significant source of sulfate, nitrate, ammonium and potassium. Half of this carbon is attached to submicron particles and likely derives from organic gaseous precursors naturally emitted by the local biosphere.

  14. Chemical composition, sources, and aging process of submicron aerosols in Beijing: Contrast between summer and winter

    NASA Astrophysics Data System (ADS)

    Hu, Weiwei; Hu, Min; Hu, Wei; Jimenez, Jose L.; Yuan, Bin; Chen, Wentai; Wang, Ming; Wu, Yusheng; Chen, Chen; Wang, Zhibin; Peng, Jianfei; Zeng, Limin; Shao, Min

    2016-02-01

    To investigate the seasonal characteristics of submicron aerosol (PM1) in Beijing urban areas, a high-resolution time-of-flight aerosol-mass-spectrometer (HR-ToF-AMS) was utilized at an urban site in summer (August to September 2011) and winter (November to December 2010), coupled with multiple state of the art online instruments. The average mass concentrations of PM1 (60-84 µg m-3) and its chemical compositions in different campaigns of Beijing were relatively consistent in recent years. In summer, the daily variations of PM1 mass concentrations were stable and repeatable. Eighty-two percent of the PM1 mass concentration on average was composed of secondary species, where 62% is secondary inorganic aerosol and 20% secondary organic aerosol (SOA). In winter, PM1 mass concentrations changed dramatically because of the different meteorological conditions. The high average fraction (58%) of primary species in PM1 including primary organic aerosol (POA), black carbon, and chloride indicates primary emissions usually played a more important role in the winter. However, aqueous chemistry resulting in efficient secondary formation during occasional periods with high relative humidity may also contribute substantially to haze in winter. Results of past OA source apportionment studies in Beijing show 45-67% of OA in summer and 22-50% of OA in winter can be composed of SOA. Based on the source apportionment results, we found 45% POA in winter and 61% POA in summer are from nonfossil sources, contributed by cooking OA in both seasons and biomass burning OA (BBOA) in winter. Cooking OA, accounting for 13-24% of OA, is an important nonfossil carbon source in all years of Beijing and should not be neglected. The fossil sources of POA include hydrocarbon-like OA from vehicle emissions in both seasons and coal combustion OA (CCOA) in winter. The CCOA and BBOA were the two main contributors (57% of OA) for the highest OA concentrations (>100 µg m-3) in winter. The POA

  15. Aqueous-phase photooxidation of levoglucosan - a mechanistic study using aerosol time-of-flight chemical ionization mass spectrometry (Aerosol ToF-CIMS)

    NASA Astrophysics Data System (ADS)

    Zhao, R.; Mungall, E. L.; Lee, A. K. Y.; Aljawhary, D.; Abbatt, J. P. D.

    2014-09-01

    Levoglucosan (LG) is a widely employed tracer for biomass burning (BB). Recent studies have shown that LG can react rapidly with hydroxyl (OH) radicals in the aqueous phase despite many mass balance receptor models assuming it to be inert during atmospheric transport. In the current study, aqueous-phase photooxidation of LG by OH radicals was performed in the laboratory. The reaction kinetics and products were monitored by aerosol time-of-flight chemical ionization mass spectrometry (Aerosol ToF-CIMS). Approximately 50 reaction products were detected by the Aerosol ToF-CIMS during the photooxidation experiments, representing one of the most detailed product studies yet performed. By following the evolution of mass defects of product peaks, unique trends of adding oxygen (+O) and removing hydrogen (-2H) were observed among the products detected, providing useful information for determining potential reaction mechanisms and sequences. Additionally, bond-scission reactions take place, leading to reaction intermediates with lower carbon numbers. We introduce a data analysis framework where the average oxidation state (OSc) is plotted against a novel molecular property: double-bond-equivalence-to-carbon ratio (DBE/#C). The trajectory of LG photooxidation on this plot suggests formation of polycarbonyl intermediates and their subsequent conversion to carboxylic acids as a general reaction trend. We also determined the rate constant of LG with OH radicals at room temperature to be 1.08 ± 0.16 × 109 M-1 s-1. By coupling an aerosol mass spectrometer (AMS) to the system, we observed a rapid decay of the mass fraction of organic signals at mass-to-charge ratio 60 (f60), corresponding closely to the LG decay monitored by the Aerosol ToF-CIMS. The trajectory of LG photooxidation on a f44-f60 correlation plot matched closely to literature field measurement data. This implies that aqueous-phase photooxidation might be partially contributing to aging of BB particles in the

  16. Aqueous-phase photooxidation of levoglucosan - a mechanistic study using Aerosol Time of Flight Chemical Ionization Mass Spectrometry (Aerosol-ToF-CIMS)

    NASA Astrophysics Data System (ADS)

    Zhao, R.; Mungall, E. L.; Lee, A. K. Y.; Aljawhary, D.; Abbatt, J. P. D.

    2014-04-01

    Levoglucosan (LG) is a widely employed tracer for biomass burning (BB). Recent studies have shown that LG can react rapidly with hydroxyl (OH) radicals in the aqueous phase, despite many mass balance receptor models assuming it to be inert during atmospheric transport. In the current study, aqueous-phase photooxidation of LG by OH radicals was performed in the laboratory. The reaction kinetics and products were monitored by Aerosol Time of Flight Chemical Ionization Mass Spectrometry (Aerosol-ToF-CIMS). Approximately 50 reaction products were detected by the Aerosol-ToF-CIMS during the photooxidation experiments, representing one of the most detailed product studies yet performed. By following the evolution of mass defects of product peaks, unique trends of adding oxygen (+O) and removing hydrogen (-2H) were observed among the products detected, providing useful information to determine potential reaction mechanisms and sequences. As well, bond scission reactions take place, leading to reaction intermediates with lower carbon numbers. We introduce a data analysis framework where the average oxidation state (OSc) is plotted against a novel molecular property: double bond equivalence to carbon ratio (DBE / #C). The trajectory of LG photooxidation on this plot suggests formation of poly-carbonyl intermediates and their subsequent conversion to carboxylic acids as a general reaction trend. We also determined the rate constant of LG with OH radicals at room temperature to be 1.08 ± 0.16 × 109 M-1 s-1. By coupling an Aerosol Mass Spectrometer (AMS) to the system, we observed a rapid decay of the mass fraction of organic signals at mass-to-charge ratio 60 (f60), corresponding closely to the LG decay monitored by the Aerosol-ToF-CIMS. The trajectory of LG photooxidation on a f44-f60 correlation plot matched closely to literature field measurement data. This implies that aqueous-phase photooxidation might be partially contributing to aging of BB particles in the ambient

  17. Handheld hyperspectral imager for standoff detection of chemical and biological aerosols

    NASA Astrophysics Data System (ADS)

    Hinnrichs, Michele; Jensen, James O.; McAnally, Gerard

    2004-02-01

    Pacific Advanced Technology has developed a small hand held imaging spectrometer, Sherlock, for gas leak and aerosol detection and imaging. The system is based on a patent technique that uses diffractive optics and image processing algorithms to detect spectral information about objects in the scene of the camera (IMSS Image Multi-spectral Sensing). This camera has been tested at Dugway Proving Ground and Dstl Porton Down facility looking at Chemical and Biological agent simulants. The camera has been used to investigate surfaces contaminated with chemical agent simulants. In addition to Chemical and Biological detection the camera has been used for environmental monitoring of green house gases and is currently undergoing extensive laboratory and field testing by the Gas Technology Institute, British Petroleum and Shell Oil for applications for gas leak detection and repair. The camera contains an embedded Power PC and a real time image processor for performing image processing algorithms to assist in the detection and identification of gas phase species in real time. In this paper we will present an over view of the technology and show how it has performed for different applications, such as gas leak detection, surface contamination, remote sensing and surveillance applications. In addition a sampling of the results form TRE field testing at Dugway in July of 2002 and Dstl at Porton Down in September of 2002 will be given.

  18. Identification and quantification of individual chemical compounds in biogenic secondary organic aerosols using GCxGC-VUV/EI-HRTOFMS

    NASA Astrophysics Data System (ADS)

    Decker, M.; Worton, D. R.; Isaacman, G. A.; Chan, A. W.; Ruehl, C.; Zhao, Y.; Wilson, K. R.; Goldstein, A. H.

    2012-12-01

    Atmospheric aerosols have adverse effects on human health and air quality and affect radiative forcing and thus climate. While the organic fraction of aerosols is substantial, the sources and chemistry leading to the formation of secondary organic aerosols are very poorly understood. Characterizing individual compounds present in organic aerosol provides insights into the sources, formation mechanisms and oxidative transformations that have taken place. Fifteen aerosol samples collected over a 5 day period at the Blodgett Forest Research Station in the Sierra Nevada Mountains, part of the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) in July 2009, were analyzed using comprehensive two dimensional gas chromatography with high resolution time of flight mass spectrometry (GCxGC-HRTOFMS). Approximately 600 compounds were observed in each sample as significant peaks in the chromatogram. Of these, around a third were identified by matching the unique electron ionization (EI) mass spectrum of each compound to the NIST library of characteristic fragmentation patterns. One filter sample was also analyzed using vacuum ultraviolet ionization (VUV) instead of EI. This 'soft' ionization technique results in much less fragmentation yielding the molecular ion of each compound, from which the exact mass was determined. If the formula of the EI library matched compound equaled the high mass resolution VUV molecular weight within a certain tolerance (< 30 ppm), then the library match was considered confirmed; 226 compounds were identified in this way. Using the VUV technique 234 additional compounds that were not in the EI mass spectral database were assigned chemical formulas based on the observed molecular weights. The chemical formulas in conjunction with the location of the compound in the GCxGC chromatogram were used to provide further classification of these compounds based on their likely functionalization. The broad array of observed oxygenated

  19. Sources of atmospheric aerosol from long-term measurements (5 years) of chemical composition in Athens, Greece.

    PubMed

    Paraskevopoulou, D; Liakakou, E; Gerasopoulos, E; Mihalopoulos, N

    2015-09-15

    To identify the sources of aerosols in Greater Athens Area (GAA), a total of 1510 daily samples of fine (PM 2.5) and coarse (PM 10-2,5) aerosols were collected at a suburban site (Penteli), during a five year period (May 2008-April 2013) corresponding to the period before and during the financial crisis. In addition, aerosol sampling was also conducted in parallel at an urban site (Thissio), during specific, short-term campaigns during all seasons. In all these samples mass and chemical composition measurements were performed, the latest only at the fine fraction. Particulate organic matter (POM) and ionic masses (IM) are the main contributors of aerosol mass, equally contributing by accounting for about 24% of the fine aerosol mass. In the IM, nss-SO4(-2) is the prevailing specie followed by NO3(-) and NH4(+) and shows a decreasing trend during the 2008-2013 period similar to that observed for PM masses. The contribution of water in fine aerosol is equally significant (21 ± 2%), while during dust transport, the contribution of dust increases from 7 ± 2% to 31 ± 9%. Source apportionment (PCA and PMF) and mass closure exercises identified the presence of six sources of fine aerosols: secondary photochemistry, primary combustion, soil, biomass burning, sea salt and traffic. Finally, from winter 2012 to winter 2013 the contribution of POM to the urban aerosol mass is increased by almost 30%, reflecting the impact of wood combustion (dominant fuel for domestic heating) to air quality in Athens, which massively started in winter 2013. PMID:25958364

  20. Storm water runoff measurements of copper from a naturally patinated roof and from a parking space. Aspects on environmental fate and chemical speciation.

    PubMed

    Odnevall Wallinder, I; Hedberg, Y; Dromberg, P

    2009-12-01

    Release of copper from a naturally aged copper roof on a shopping centre building in a suburban site of Stockholm has been measured during different rain events after its interaction with the internal drainage system and storm drains made of cast iron and concrete. Concentrations of copper removed by means of urban storm water from a nearby parking space have been determined for comparison. Predictions and measurements of the chemical speciation of released copper are discussed compared to the total concentration, and to threshold values for freshwater and drinking water. The results clearly illustrate that the major part of the released copper from the roof is readily retained already during transport through the internal drainage system of the building, a pathway that also changes the chemical speciation of released copper and its bioavailable fraction. Most copper, not retained by cast iron and concrete surfaces, was strongly complexed to organic matter. The median concentration of free cupric ions and weak copper complexes was less than, or within the range of reported no effect concentrations, NOECs, of copper in surface waters. The parking space contributed with significantly higher and time-dependent concentrations of total copper compared to measured concentrations of copper from the roof after the interaction with the drainage system. Most copper in the surface runoff water was strongly complexed with organic matter, hence reducing the bioavailable fraction significantly to concentrations within the NOEC range. Dilution with other sources of urban storm water will reduce the released concentration of copper even further. The results illustrate that already the internal drainage system and the storm drains made of cast iron and concrete act as efficient sinks for released copper which means that any installation of additional infiltration devices is redundant. PMID:19762062

  1. Photochemistry of limonene secondary organic aerosol studied with chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pan, Xiang

    Limonene is one of the most abundant monoterpenes in the atmosphere. Limonene easily reacts with gas-phase oxidants in air such as NO3, ozone and OH. Secondary organic aerosol (SOA) is formed when low vapor pressure products condense into particles. Chemicals in SOA particles can undergo further reactions with oxidants and with solar radiation that significantly change SOA composition over the course of several days. The goal of this work was to characterize radiation induced reaction in SOA. To perform experiments, we have designed and constructed an Atmospheric Pressure Chemical Ionization Mass Spectrometer (APCIMS) coupled to a photochemical cell containing SOA samples. In APCIMS, (H2O)nH 3O+ clusters are generated in a 63Ni source and react with gaseous organic analytes. Most organic chemicals are not fragmented by the ionization process. We have focused our attention on limonene SOA prepared in two different ways. The first type of SOA is produced by oxidation of limonene by ozone; and the second type of SOA is formed by the NO3-induced oxidation of limonene. They model the SOA formed under daytime and nighttime conditions, respectively. Ozone initiated oxidation is the most important chemical sink for limonene both indoors, where it is used for cleaning purposes, and outdoors. Terpenes are primarily oxidized by reactions with NO3 at night time. We generated limonene SOA under different ozone and limonene concentrations. The resulting SOA samples were exposed to wavelength-tunable radiation in the UV-Visible range between 270 nm and 630 nm. The results show that the photodegradation rates strongly depend on radiation wavelengths. Gas phase photodegradation products such as acetone, formaldehyde, acetaldehyde, and acetic acid were shown to have different production rates for SOA formed in different concentration conditions. Even for SOA prepared under the lowest concentrations, the SOA photodegradation was efficient. The conclusion is that exposure of SOA to

  2. The chemical processing of gas-phase carbonyl compounds by sulfuric acid aerosols: 2,4-pentanedione

    NASA Astrophysics Data System (ADS)

    Nozière, Barbara; Riemer, Daniel D.

    This work investigates the interactions between gas-phase carbonyl compounds and sulfuric acid aerosols. It focuses on understanding the chemical processes, giving a first estimate of their importance in the atmosphere, and suggesting directions for further investigations. The solubility and reactivity of a compound with a large enolization constant, 2,4-pentanedione, in water/sulfuric acid solutions 0-96 wt% have been investigated at room temperature using the bubble column/GC-FID technique. 2,4-pentanedione was found to undergo aldol condensation at acidities as low as 20 wt% H 2SO 4, that is, well in the tropospheric range of aerosol composition. In agreement with well-established organic chemical knowledge, this reaction resulted in changes of color of the solutions of potential importance for the optical properties of the aerosols. 2,4-pentanedione was also found to undergo retroaldol reaction, specific to dicarbonyl compounds, producing acetone and acetaldehyde. The Henry's law coefficient for 2,4-pentanedione was found to be a factor 5 larger than the one of acetone over the whole range of acidity, with a value in water of H (297 K)=(155±27) M atm -1. A chemical system is proposed to describe the transformations of carbonyl compounds in sulfuric acid aerosols. Aldol condensation is likely to be the most common reaction for these compounds, probably involving a large number of the ones present in the atmosphere and a wide range of aerosol compositions. The enolization constant contributes as a proportional factor to the rate constant for aldol condensation, and is shown in this work to contribute as an additive constant to the Henry's law coefficient. In addition to the many important aspects of these reactions illustrated in this work, the rate of aldol condensation was estimated to be potentially fast enough for the losses of some compounds in acidic aerosols to compete with their gas-phase chemistry in the atmosphere.

  3. Chemical speciation of Fe and Ni in residual oil fly ash fine particulate matter using X-ray absorption spectroscopy.

    PubMed

    Pattanaik, Sidhartha; Huggins, Frank E; Huffman, Gerald P

    2012-12-01

    Epidemiological studies have linked residual oil fly ash fine particulate matter with aerodynamic diameter <2.5 μm (ROFA PM(2.5)) to morbidity and mortality from cardiovascular and respiratory illnesses. Bioavailable transition metals within PM have been cited as one of the components that induce such illnesses. By combining synchrotron-based X-ray absorption spectroscopy with leaching experiment, we studied the effect of residual oil compositions and combustion conditions on the speciation of Fe and Ni in ROFA PM(2.5) and the implication of these species for human health and environment. PM(2.5) samples were obtained from two types of combustors, a fire tube boiler (FTB) and a refractory line combustor (RLC). The study reveals that only Fe(2)(SO(4))(3)·nH(2)O is present in RLC PM(2.5) while Fe(2)(SO(4))(3)·nH(2)O predominates in FTB PM(2.5) with inclusion of varying amounts of nickel ferrite. The finding that RLC PM(2.5) is more bioavailable and hence more toxic than FTB PM(2.5) is significant. The reduction of toxicity of FTB PM(2.5) is due to the immobilization of a portion of Fe and Ni in the formation of an insoluble NiFe(2)O(4). This may explain the variation of toxicity from exposure to different ROFA PM(2.5). Additionally, the speciation data are sought for developing emission inventories for source apportionment study and understanding the mechanism of PM formation. PMID:23126560

  4. Aerosol Types using Passive Remote Sensing: Global Distribution, Consistency Check, Total-Column Investigation and Translation into Composition Derived from Climate and Chemical Transport Model

    NASA Astrophysics Data System (ADS)

    Kacenelenbogen, M. S.; Dawson, K. W.; Johnson, M. S.; Burton, S. P.; Redemann, J.; Hasekamp, O. P.; Hair, J. W.; Ferrare, R. A.; Butler, C. F.; Holben, B. N.; Beyersdorf, A. J.; Ziemba, L. D.; Froyd, K. D.; Dibb, J. E.; Shingler, T.; Sorooshian, A.; Jimenez, J. L.; Campuzano Jost, P.; Jacob, D. J.

    2015-12-01

    To improve the predictions of aerosol composition in chemical transport models (CTMs) and global climate models (GCMs), we have developed an aerosol classification algorithm (called Specified Clustering and Mahalanobis Classification, SCMC) that assigns an aerosol type to multi-parameter retrievals by spaceborne, airborne or ground based passive remote sensing instruments [Russell et al., 2014]. The aerosol types identified by our scheme are pure dust, polluted dust, urban-industrial/developed economy, urban-industrial/developing economy, dark biomass smoke, light biomass smoke and pure marine. We apply the SCMC method to two different total-column datasets of aerosol optical properties: inversions from the ground-based AErosol RObotic NETwork (AERONET) and retrievals from the space-borne POLDER (Polarization and Directionality of Earth's Reflectances) instrument. The POLDER retrievals that we use differ from the standard POLDER retrievals [Deuzé et al., 2001] as they make full use of multi-angle, multispectral polarimetric data [Hasekamp et al., 2011]. We analyze agreement in the aerosol types inferred from both AERONET and POLDER globally. Then, we investigate how our total-column "effective" SCMC aerosol types relate to different aerosol types within the column (i.e. either a mixture of different types within one layer in the vertical or the stacking of different aerosol types within the vertical column). For that, we compare AERONET-SCMC aerosol types to collocated NASA LaRC HSRL vertically resolved aerosol types [Burton et al., 2012] during the SEAC4RS and DISCOVER-AQ airborne field experiments, mostly over Texas in Aug-Sept 2013. Finally, in order to evaluate the GEOS-Chem CTM aerosol types, we translate each of our SCMC aerosol type into a unique distribution of GEOS-Chem aerosol composition (e.g. biomass burning, dust, sulfate, sea salt). We bridge the gap between remote sensing and model-inferred aerosol types by using multiple years of collocated AERONET

  5. Deriving simple empirical relationships between aerodynamic and optical aerosol measurements and their application

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Different measurement techniques for aerosol characterization and quantification either directly or indirectly measure different aerosol properties (i.e. count, mass, speciation, etc.). Comparisons and combinations of multiple measurement techniques sampling the same aerosol can provide insight into...

  6. The chemical composition of organic nitrogen in marine rainwater and aerosols

    NASA Astrophysics Data System (ADS)

    Altieri, K. E.; Hastings, M. G.; Peters, A.; Sigman, D. M.

    2010-12-01

    The current state of knowledge on organic nitrogen in the atmosphere is very limited. Atmospheric water soluble organic nitrogen (WSON) is a subset of the complex water soluble organic matter measured in atmospheric aerosols and rainwater; as such, it impacts cloud condensation processes and aerosol chemical and optical properties. In marine and continental atmospheric deposition, the organic N fraction can be 20-80% of total N potentially influencing receiving ecosystems. Therefore, atmospheric WSON plays an important role in both atmospheric chemistry and the global biogeochemical N cycle. However, the sources (i.e., anthropogenic vs. terrestrial vs. marine), composition (e.g., reduced or oxidized N), potential connections to inorganic N (NO3- and NH4+), and spatio-temporal variability of atmospheric WSON are largely unknown. Samples were collected on or near the island of Bermuda (32.27°N, 64.87°W), which is located in the western North Atlantic and experiences seasonal changes in transport that allow for study of both anthropogenically and primarily marine influenced air masses. Rainwater samples (n=7) and aqueous extracted aerosol samples (n=4) were analyzed by positive ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) to characterize the chemical composition of the water soluble organic N on a per compound level. We found ~ 800 N containing compounds in 8 compound classes. The CHON+ compound class contained the largest number of N compounds (~ 460). Compared to continental rainwater [Altieri et al., ES&T, 2009], the CHON+ compounds in the marine samples are as dominant in number, yet have less regular patterns and lower O:C ratios for comparable N:C ratios. In fact, average O:C ratios of all N containing compound classes were lower in the marine samples than in continental rainwater samples. No organosulfates or nitrooxy-organosulfates were detected in the marine samples, both of

  7. Chromism of Model Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Rincon, Angela; Guzman, Marcelo; Hoffmann, Michael; Colussi, Agustin

    2008-03-01

    The optical properties of the atmospheric aerosol play a fundamental role in the Earth's radiative balance. Since more than half of the aerosol mass consists of complex organic matter that absorbs in the ultraviolet and visible regions of the spectrum, it is important to establish the identity of the organic chromophores. Here we report studies on the chromism vs. chemical composition of photolyzed (lambda longer than 305 nm) solutions of pyruvic acid, a widespread aerosol component, under a variety of experimental conditions that include substrate concentration, temperature and the presence of relevant spectator solutes, such ammonium sulfate. We use high resolution mass- and 13C NMR-spectrometries to track chemical speciation in photolyzed solutions as they undergo thermochromic and photobleaching cycles. Since the chemical identity of the components of these mixtures does not change in these cycles, in which photobleached solutions gradually recover their yellow color in the dark with non-conventional kinetics typical of aggregation processes, we infer that visible absorptions likely involve the intermolecular coupling of carbonyl chromophores in supramolecular assemblies made possible by the polyfunctional nature of the products of pyruvic acid photolysis.

  8. The chemical composition of fine ambient aerosol particles in the Beijing area

    NASA Astrophysics Data System (ADS)

    Nekat, Bettina; van Pinxteren, Dominik; Iinuma, Yoshiteru; Gnauk, Thomas; Müller, Konrad; Herrmann, Hartmut

    2010-05-01

    The strong economical growth in China during the last few decades led to heavy air pollution caused by significantly increased particle emissions. The aerosol particles affect not only the regional air quality and visibility, but can also influence cloud formation processes and the radiative balance of the atmosphere by their optical and microphysical properties. The ability to act as Cloud Condensation Nuclei (CCN) is related to microphysical properties like the hygroscopic growth or the cloud droplet activation. The chemical composition of CCN plays an important role on these properties and varies strongly with the particle size and the time of day. Hygroscopic or surface active substances can increase the hygroscopicity and lower the surface tension of the particle liquid phase, respectively. The presence of such compounds may result in faster cloud droplet activation by faster water uptake. The DFG project HaChi (Haze in China) aimed at studying physical and chemical parameters of urban aerosol particles in the Beijing area in order to associate the chemical composition of aerosol particles with their ability to act as CCN. To this end, two measurement campaigns were performed at the Wuqing National Ordinary Meteorological Observing Station, which is a background site near Beijing. The winter campaign was realized in March 2009 and the summer campaign took place from mid July 2009 to mid August 2009. Fine particles with an aerodynamic diameter smaller than or equal 1 μm were continuously sampled for 24h over the two campaigns using a DIGITEL high volume sampler (DHA-80). The present contribution presents and discusses the results of the chemical characterization of the DIGITEL filters samples. The filters were analyzed for the mass concentration, inorganic ions and carbon sum parameters like elemental (EC), organic (OC) and water soluble organic carbon (WSOC). The WSOC fraction was further characterized for hygroscopic substances like low molecular

  9. OH-Radical initiated ageing of biogenic secondary organic aerosols - A detailed chemical analysis

    NASA Astrophysics Data System (ADS)

    Müller, L.; Reinnig, M.-C.; Mentel, Th. F.; Tillmann, R.; Schlosser, E.; Wahner, A.; Saathoff, H.; Donahue, N. M.; Hoffmann, T.

    2009-04-01

    The chemical ageing[1] of secondary organic aerosol (SOA) was investigated in two series of experiments using on-line mass spectrometry and off-line high performance liquid chromatography mass spectrometry (HPLC-MS). In a set of photochemical experiments, performed in the large outdoor reaction chamber SAPHIR (Jülich, Germany), SOA was generated from a boreal mixture including mono- and sesquiterpenes (α-pinene, β-pinene, Δ3-carene, limonene, caryophyllene). During a long time experiment (30h) the generated SOA was exposed to OH-radicals and the chemical composition was analyzed on-line using atmospheric pressure ionization mass spectrometry (API-MS). The on-line method provides highly time resolved chemical information and therefore a direct insight into the temporal changes of SOA-composition. In parallel, filter samples analysed by HPLC-MS allow the enrichment of trace compounds and finally an unambiguous identification of individual substances. In addition, filter samples allow a direct comparison to samples from field studies. The ageing experiments showed a clear change in SOA composition. The compounds observed can be divided into two groups: A group of first generation SOA-compounds, generated by the OH oxidation of the terpenes and a group of second generation compounds, generated by the reaction of OH with SOA compounds. Among the second generation products, especially a tricarboxylic acid (3-methyl-1,2,3-butanetricarboxylic acid, m/z 203)[2] was observed to be a good marker compound for BSOA ageing. A further set of experiments was carried out in another large aerosol chamber facility, the AIDA chamber of the Research Centre Karlsruhe. In this dark chamber, the experiments focused on the OH-induced ageing of α-pinene SOA and the influence of temperature. The results clearly show that the tricarboxylic acid is a distinctive marker for OH radical induced BSOA ageing and identify cis-pinonic acid as its precursor. To connect the results of the

  10. Chemical composition and sources of organic aerosols over London from the ClearfLo 2012 campaigns

    NASA Astrophysics Data System (ADS)

    Finessi, Emanuela; Holmes, Rachel; Hopkins, James; Lee, James; Harrison, Roy; Hamilton, Jacqueline

    2014-05-01

    Air quality in urban areas represents a major public health issue with around one third of the European population concentrated in cities and numbers expected to increase at global scale, particularly in developing countries. Particulate matter (PM) represents a primary threat for human health as numerous studies have confirmed the association between increased levels of cardiovascular and respiratory diseases with the exposure to PM. Despite considerable efforts made in improving air quality and progressively stricter emissions regulations, the PM concentrations have not changed much over the past decades for reasons that remain unclear, and highlight that studies on PM source apportionment are required for the formulation of effective policy. We investigated the chemical composition of organic aerosol (OA) collected during two intensive field campaigns held in winter and summer 2012 in the frame of the project Clean air for London (http://www.clearflo.ac.uk/). PM samples were collected both at a city background site (North Kensington) and at a rural site 50 km southeast of London (Detling) with 8 to 24 hours sampling schedule and analysed using off-line methods. Thermal-optical analysis was used to quantify OC-EC components while a suite of soft ionization mass spectrometric techniques was deployed for detailed chemical characterization. Liquid chromatography mass Spectrometry (LC-MSn) was mostly used for the simultaneous detection and quantification of various tracers for both primary and secondary OA sources. Well-established markers for wood burning primary OA like levoglucosan and azelaic acid were quantified together with various classes of nitroaromatics including methyl-nitrocatechols that are potential tracers for wood burning secondary OA. In addition, oxidation products of biogenic VOCs such as isoprene and monoterpenes were also quantified for both seasons and sites. A non-negligible contribution from biogenic SOA to urban OA was found in summertime

  11. Aerosols Collected at a Tropical Marine Environment: Size-Resolved Chemical Composition Using IC, TOC, and Thermal-Optical Analyses

    NASA Astrophysics Data System (ADS)

    Morales-García, F.; Mayol-Bracero, O. L.; Repollet-Pedrosa, M.; Kasper-Giebl, A.; Ramírez-Santa Cruz, C.; Puxbaum, H.

    2009-05-01

    Size-resolved chemical characterization was performed on aerosol samples collected at two different marine sites in the tropics: Dian Point (DP), Antigua and Cape San Juan (CSJ), Puerto Rico. A 13-stage Dekati low- pressure impactor (Dp 0.1 to 10 μm), a 10-stage micro-orifice uniform deposit impactor (Dp 0.054 to 18 μm), and stacked-filter units (Dp < 1.7 μm) were used to collect the samples. Na+, NH4+, K+, Mg2+, Ca2+, Cl-, NO2-, NO3-, SO42-, acetate, formate, malonate, and oxalate were determined using ion chromatography (IC). Thermal-optical analysis (TOA) was used to determine the concentrations of aerosol total carbon (TC), organic carbon (OC), and elemental carbon (EC). Five-day back trajectories calculated using NOAA's HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectory) model identified air masses coming from the North Atlantic (maritime air), Northwest Africa (desert dust), and North America (anthropogenic pollution). Size-resolved chemical characterization of aerosol samples using IC and TOA confirmed that aerosols become aged as they are transported to the Caribbean and their composition depends on the air mass origin. Gravimetric analyses showed that average fine mass concentrations for CSJ station were higher than for DP station (CSJ: 1.9 μg m-3; DP: 1.2 μg m-3). The aerosol chemical composition changed with air masses of different origin and with different pollution levels. In both locations the predominant water-soluble ions in the fine aerosol fraction were Cl-, Na+, and SO42-. Sulphate was observed in higher concentrations during the polluted case and particulate organic matter concentrations were higher for the maritime case. During desert dust events an increase in Ca2+ and Mg2+ of 4 and 2 times, respectively, was observed mainly in the coarse mode. Results for the size-resolved chemical composition and complete aerosol chemical apportionment including the residual mass will be presented.

  12. Correlations between Optical, Chemical and Physical Properties ofBiomass Burn Aerosols

    SciTech Connect

    Hopkins, Rebecca J.; Lewis, K.; Desyaterik, Yury; Wang, Z.; Tivanski, Alexei V.; Arnott, W.P.; Laskin, Alexander; Gilles, M.K.

    2008-01-29

    Aerosols generated from burning different plant fuels were characterized to determine relationships between chemical, optical and physical properties. Single scattering albedo ({omega}) and Angstrom absorption coefficients ({alpha}{sub ap}) were measured using a photoacoustic technique combined with a reciprocal nephelometer. Carbon-to-oxygen atomic ratios, sp{sup 2} hybridization, elemental composition and morphology of individual particles were measured using scanning transmission X-ray microscopy coupled with near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) and scanning electron microscopy with energy dispersion of X-rays (SEM/EDX). Particles were grouped into three categories based on sp2 hybridization and chemical composition. Measured {omega} (0.4-1.0 at 405 nm) and {alpha}{sub ap} (1.0-3.5) values displayed a fuel dependence. The category with sp{sup 2} hybridization >80% had values of {omega} (<0.5) and {alpha}{sub ap} ({approx}1.25) characteristic of light absorbing soot. Other categories with lower sp2 hybridization (20 to 60%) exhibited higher {omega} (>0.8) and {alpha}{sub ap} (1.0 to 3.5) values, indicating increased absorption spectral selectivity.

  13. Morphological and chemical changes of aerosolized E. coli treated with a dielectric barrier discharge

    DOE PAGESBeta

    Romero-Mangado, Jaione; Nordlund, Dennis; Soberon, Felipe; Deane, Graham; Maughan, Kevin; Sainio, Sami; Singh, Gurusharan; Daniels, Stephen; Saunders, Ian T.; Loftus, David; et al

    2016-02-12

    This paper presents the morphological and chemical modification of the cell structure of aerosolized Escherichia coli treated with a dielectric barrier discharge (DBD). Exposure to DBD results in severe oxidation of the bacteria, leading to the formation of hydroxyl groups and carbonyl groups and a significant reduction in amine functionalities and phosphate groups. Near edge x-ray absorption fine structure(NEXAFS) measurements confirm the presence of additional oxide bonds upon DBD treatment, suggesting oxidation of the outer layer of the cell wall. Electron microscopy images show that the bacteria undergo physical distortion to varying degrees, resulting in deformation of the bacterial structure.more » The electromagnetic field around the DBD coil causes severe damage to the cell structure, possibly resulting in leakage of vital cellular materials. The oxidation and chemical modification of the bacterial components are evident from the Fourier transform infrared spectroscopy and NEXAFS results. The bacterial reculture experiments confirm inactivation of airborne E. coli upon treating with DBD.« less

  14. Handheld hyperspectral imager for standoff detection of chemical and biological aerosols

    NASA Astrophysics Data System (ADS)

    Hinnrichs, Michele; Jensen, James O.; McAnally, Gerard

    2004-08-01

    Pacific Advanced Technology has developed a small hand held imaging spectrometer, Sherlock, for gas leak and aerosol detection and imaging. The system is based on a patented technique, (IMSS Image Multi-spectral Sensing), that uses diffractive optics and image processing algorithms to detect spectral information about objects in the scene of the camera. This cameras technology has been tested at Dugway Proving Ground and Dstl Porton Down facilities looking at Chemical and Biological agent simulants. In addition to Chemical and Biological detection, the camera has been used for environmental monitoring of green house gases and is currently undergoing extensive laboratory and field testing by the Gas Technology Institute, British Petroleum and Shell Oil for applications for gas leak detection and repair. In this paper we will present some of the results from the data collection at the TRE test at Dugway Proving Ground during the summer of 2002 and laboratory testing at the Dstl facility at Porton Down in the UK in the fall of 2002.

  15. Uptake of Organic Vapors by Sulfate Aerosols: Physical and Chemical Processes

    NASA Technical Reports Server (NTRS)

    Michelsen, R. R.; Ashbourn, S. F. M.; Iraci, L.T.; Staton, S. J. R.

    2003-01-01

    While it is known that upper tropospheric sulfate particles contain a significant amount of organic matter, both the source of the organic fraction and its form in solution are unknown. These studies explore how the chemical characteristics of the molecules and surfaces in question affect heterogeneous interactions. The solubilities of acetaldehyde [CH3CHO] and ethanol [CH3CH20H] in cold, aqueous sulfuric acid solutions have been measured by Knudsen cell studies. Henry's law solubility coefficients range from 10(exp 2) to 10(exp 5) M/atm for acetaldehyde, and from 10(exp 4) to 10(exp 9) M/atm for ethanol under upper tropospheric conditions (210-240 K, 40-80 wt. % H2S04). The multiple solvation pathways (protonation, enolization, etc.) available to these compounds in acidic aqueous environments will be discussed. Preliminary results from the interaction of acetaldehyde with solutions of formaldehyde in sulfuric acid will be presented as well. The physical and chemical processes that affect organic uptake by aqueous aerosols will be explored, with the aim of evaluating organic species not yet studied in low temperature aqueous sulfuric acid.

  16. Correlations between optical, chemical and physical properties of biomass burn aerosols

    NASA Astrophysics Data System (ADS)

    Hopkins, R. J.; Lewis, K.; Desyaterik, Y.; Wang, Z.; Tivanski, A. V.; Arnott, W. P.; Laskin, A.; Gilles, M. K.

    2007-09-01

    Aerosols generated from burning different plant fuels were characterized to determine relationships between chemical, optical and physical properties. Single scattering albedo (ω) and Angstrom absorption coefficients (α ap) were measured using a photoacoustic technique combined with a reciprocal nephelometer. Carbon-to-oxygen atomic ratios, sp2 hybridization, elemental composition and morphology of individual particles were measured using scanning transmission X-ray microscopy coupled with near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) and scanning electron microscopy with energy dispersion of X-rays (SEM/EDX). Particles were grouped into three categories based on sp2 hybridization and chemical composition. Measured ω (0.4 - 1.0 at 405 nm) and α ap (1.0 - 3.5) values displayed a fuel dependence. The category with sp2 hybridization >80% had values of ω (<0.5) and α ap (~1.25) characteristic of light absorbing soot. Other categories with lower sp2 hybridization (20 to 60%) exhibited higher ω (>0.8) and α ap (1.0 to 3.5) values, indicating increased absorption spectral selectivity.

  17. Chemically-resolved volatility measurements of organic aerosol fom different sources.

    PubMed

    Huffman, J A; Docherty, K S; Mohr, C; Cubison, M J; Ulbrich, I M; Ziemann, P J; Onasch, T B; Jimenez, J L

    2009-07-15

    A newly modified fast temperature-stepping thermodenuder (TD) was coupled to a High Resolution Time-of-Flight Aerosol Mass Spectrometer for rapid determination of chemically resolved volatility of organic aerosols (OA) emitted from individual sources. The TD-AMS system was used to characterize primary OA (POA) from biomass burning, trash burning surrogates (paper and plastic), and meat cooking as well as chamber-generated secondary OA (SOA) from alpha-pinene and gasoline vapor. Almost all atmospheric models represent POA as nonvolatile, with no allowance for evaporation upon heating or dilution, or condensation upon cooling. Our results indicate that all OAs observed show semivolatile behavior and that most POAs characterized here were at least as volatile as SOA measured in urban environments. Biomass-burning OA (BBOA) exhibited a wide range of volatilities, but more often showed volatility similar to urban OA. Paper-burning resembles some types of BBOA because of its relatively high volatility and intermediate atomic oxygen-to-carbon (O/C) ratio, while meat-cooking OAs (MCOA) have consistently lower volatility than ambient OA. Chamber-generated SOA under the relatively high concentrations used intraditional experiments was significantly more volatile than urban SOA, challenging extrapolation of traditional laboratory volatility measurements to the atmosphere. Most OAs sampled show increasing O/C ratio and decreasing H/C (hydrogen-to-carbon) ratio with temperature, further indicating that more oxygenated OA components are typically less volatile. Future experiments should systematically explore a wider range of mass concentrations to more fully characterize the volatility distributions of these OAs. PMID:19708365

  18. Microstructural, chemical and textural characterization of ZnO nanorods synthesized by aerosol assisted chemical vapor deposition

    SciTech Connect

    Sáenz-Trevizo, A.; Amézaga-Madrid, P.; Fuentes-Cobas, L.; Pizá-Ruiz, P.; Antúnez-Flores, W.; Ornelas-Gutiérrez, C.; Pérez-García, S.A.; Miki-Yoshida, M.

    2014-12-15

    ZnO nanorods were synthesized by aerosol assisted chemical vapor deposition onto TiO{sub 2} covered borosilicate glass substrates. Deposition parameters were optimized and kept constant. Solely the effect of different nozzle velocities on the growth of ZnO nanorods was evaluated in order to develop a dense and uniform structure. The crystalline structure was characterized by conventional X-ray diffraction in grazing incidence and Bragg–Brentano configurations. In addition, two-dimensional grazing incidence synchrotron radiation diffraction was employed to determine the preferred growth direction of the nanorods. Morphology and growth characteristics analyzed by electron microscopy were correlated with diffraction outcomes. Chemical composition was established by X-ray photoelectron spectroscopy. X-ray diffraction results and X-ray photoelectron spectroscopy showed the presence of wurtzite ZnO and anatase TiO{sub 2} phases. Morphological changes noticed when the deposition velocity was lowered to the minimum, indicated the formation of relatively vertically oriented nanorods evenly distributed onto the TiO{sub 2} buffer film. By coupling two-dimensional X-ray diffraction and computational modeling with ANAELU it was proved that a successful texture determination was achieved and confirmed by scanning electron microscopy analysis. Texture analysis led to the conclusion of a preferred growth direction in [001] having a distribution width Ω = 20° ± 2°. - Highlights: • Uniform and pure single-crystal ZnO nanorods were obtained by AACVD technique. • Longitudinal and transversal axis parallel to the [001] and [110] directions, respectively. • Texture was determined by 2D synchrotron diffraction and electron microscopy analysis. • Nanorods have its [001] direction distributed close to the normal of the substrate. • Angular spread about the preferred orientation is 20° ± 2°.

  19. Physical and Chemical Characterization of Particles in the Upper Troposphere and Lower Stratosphere: Microanalysis of Aerosol Impactor Samples

    NASA Technical Reports Server (NTRS)

    Sheridan, Patrick J.

    1999-01-01

    Herein is reported activities to support the characterization of the aerosol in the upper troposphere (UT) and lower stratosphere (LS) collected during the Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft (ASHOE/MAESA) missions in 1994. Through a companion proposal, another group was to measure the size distribution of aerosols in the 0.008 to 2 micrometer diameter range and to collect for us impactor samples of particles larger than about 0.02 gm. In the first year, we conducted laboratory studies related to particulate deposition patterns on our collection substrates, and have performed the analysis of many ASHOE/MAESA aerosol samples from 1994 using analytical electron microscopy (AEM). We have been building an "aerosol climatology" with these data that documents the types and relative abundances of particles observed at different latitudes and altitudes. The second year (and non-funded extension periods) saw continued analyses of impactor aerosol samples, including more ASHOE/MAESA samples, some northern hemisphere samples from the NASA Stratospheric Photochemistry Aerosols and Dynamics Expedition (SPADE) program for comparison, and a few aerosol samples from the NASA Stratospheric TRacers of Atmospheric Transport (STRAT) program. A high-resolution field emission microscope was used for the analysis and re-analysis of a number of samples to determine if this instrument was superior in performance to our conventional electron microscope. In addition, some basic laboratory studies were conducted to determine the minimum detectable and analyzable particle size for different types of aerosols. In all, 61 aerosol samples were analyzed, with a total of over 30,000 individual particle analyses. In all analyzed samples, sulfate particles comprised the major aerosol number fraction. It must be stressed that particles composed of more than one species, for example sulfate and organic carbon, were classified

  20. Chemical speciation of dissolved Cu, Ni, and Co in a contaminated estuary in southwest Spain and its influence on plankton communities.

    PubMed

    Braungardt, Charlotte B; Achterberg, Eric P; Gledhill, Martha; Nimmo, Malcolm; Elbaz-Poulichet, Francoise; Cruzado, Antonio; Velasquez, Zoila

    2007-06-15

    Four surveys of the Huelva Estuary in southwest Spain and its sources, the Tinto and the Odiel Rivers, were carried out between 1996 and 1998. The surveys investigated the impact of metalliferous mining of sulfide-rich ores in the catchment area on metal speciation, metal concentrations in a macrophyte, and phytoplankton diversity and abundance. Chemical speciation measurements in the lower Tinto Estuary showed that metals were predominantly electrochemically labile (> 99% of total dissolved Cu, Co, and Ni at 10 microM Cu, 424 nM Co, and 500 nM Ni, S = 28). Concentrations of Cu complexing ligands and free cupric ions [Cu2+] in the Gulf of Cádiz ranged between 5.3 and 38 nM and 0.2-7.9 pM, respectively, with conditional stability constants of the ligands of log K'(CuL) = 11.7-12.6. At enhanced dissolved Cu concentrations in the lower Huelva Estuary, Cu complexing ligands were saturated with Cu, resulting in nanomolar [Cu2+], which increased upstream. Metal tissue concentrations of the macrophyte Blindingia marginata were high, and a clear relationship between dissolved labile Cu and macrophyte tissue Cu concentrations was observed. A low biodiversity was observed in the Huelva system (Shannon-Wiener indices (H) typically < 0.2). Nevertheless, the maximum biomass was observed in the lower Tinto Estuary, which showed high labile metal and nutrient concentrations and a low biodiversity (H < 0.02), thereby suggesting adaptation through evolutionary processes of the phytoplankton community to the harsh conditions. PMID:17626415

  1. Automated Measurements of Ambient Aerosol Chemical Composition and its Dry and Wet Size Distributions at Pittsburgh Supersite

    NASA Astrophysics Data System (ADS)

    Khlystov, A. Y.; Stanier, C.; Chun, W.; Vayenas, D.; Mandiro, M.; Pandis, S. N.

    2001-12-01

    Ambient aerosol particles change size with changes in ambient relative humidity. The magnitude of the size change depends on the hygroscopic properties of the particles, which is determined by their chemical composition. Hygroscopic properties of particles influence many environmentally important aerosol qualities, such as light scattering and partitioning between the gas and particle phases of semivolitile compounds. Studying the hygroscopic growth of ambient particles is thus of paramount importance. The highroscopic growth of ambient particles and their chemical composition are measured continuously within the Pittsburgh Air Quality Study (EPA supersite program). The hygroscopic size changes are measured using an automated system built for this study. The system consists of two Scanning Mobility Particle Sizers (SMPS, TSI Inc.) and an Aerodynamic Particle Sizer (APS, TSI Inc.). The three instruments measure aerosol size distribution between 5 nanometers and 10 micrometers in diameter. The inlets of the instruments and the sheath air lines of the SMPS systems are equipped with computer controlled valves that direct air through Nafion dryers (PermaPure Inc.) or bypass them. The Nafion dryers are drying the air stream below 40% RH at which point ambient particles are expected to lose most or all water and thus be virtually dry. To avoid changes in relative humidity and evaporation of volatile particles due to temperature differences the system is kept at ambient temperature. The system measures alternatively dry (below 40% RH) and wet (actual ambient RH) aerosol size distributions every 6 minutes. The hygroscopic growth observed with the size-spectrometer system is compared with theoretic predictions based on the chemical composition of aerosol particles. A modified semi-continuous Steam-Jet Aerosol Collector provides the total available budget (particles and gas) of water-soluble species, which is used as an input to the thermodynamic model. The model calculates

  2. Atmospheric mercury concentration and chemical speciation at a rural site in Beijing, China: implication of mercury emission sources

    NASA Astrophysics Data System (ADS)

    Zhang, L.; Wang, S. X.; Wang, L.; Hao, J. M.

    2013-05-01

    Continuous measurements of atmospheric mercury concentration and speciation play a key role in identifying mercury sources and its behavior in the atmosphere. In this study, speciated atmospheric mercury including gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particle-bound mercury (PBM) were continuously measured at Miyun, a rural site in Beijing, China from December 2008 to November 2009. The average GEM, RGM and PBM concentrations were found to be 3.22 ± 1.74 ng m-3, 10.1 ± 18.8 pg m-3 and 98.2 ± 112.7 pg m-3, respectively, about 2-20 times of the background concentration of Northern Hemisphere. The results indicated that atmospheric mercury concentrations in North China were highly affected by anthropogenic emissions. The atmospheric mercury showed obvious seasonal variations with the highest seasonal average GEM concentration in summer (3.48 ng m-3) and the lowest value in winter (2.66 ng m-3). In autumn and winter a diurnal variation of GEM was observed with peak levels in late afternoon till midnight. Most of the high RGM concentration values occurred in the afternoon of all seasons due to the higher oxidation. The PBM concentration was higher in early morning of all seasons because of the atmospheric stratification during nighttime against laminar fluxes during daytime. The ratio of GEM to CO indicates that residential boilers play an important role in the elevation of GEM in winter. The ratio of RGM to O3 could be an indicator of the contribution of local primary sources. The ratio of PBM to PM2.5 reveals that the air mass from east and southwest to the site in spring and summer carries more atmospheric mercury. The HYSPLIT back-trajectory analysis indicated that the monitoring site is affected by local, regional and interregional sources simultaneously during heavy pollution episodes. The results from the potential source contribution function (PSCF) model indicate that the atmospheric transport predominantly from the northwest

  3. Atmospheric mercury concentration and chemical speciation at a rural site in Beijing, China: implications of mercury emission sources

    NASA Astrophysics Data System (ADS)

    Zhang, L.; Wang, S. X.; Wang, L.; Hao, J. M.

    2013-10-01

    Continuous measurements of atmospheric mercury concentration and speciation play a key role in identifying mercury sources and its behavior in the atmosphere. In this study, speciated atmospheric mercury including gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particle-bound mercury (PBM) were continuously measured at Miyun, a rural site in Beijing, China, from December 2008 to November 2009. The average GEM, RGM and PBM concentrations were found to be 3.22 ± 1.74, 10.1 ± 18.8 and 98.2 ± 112.7 pg m-3, respectively, about 2-20 times higher than the background concentration of the Northern Hemisphere. The results indicated that atmospheric mercury concentrations in northern China were highly affected by anthropogenic emissions. The atmospheric mercury showed obvious seasonal variations, with the highest seasonal average GEM concentration in summer (3.48 ng m-3) and the lowest value in winter (2.66 ng m-3). In autumn and winter a diurnal variation of GEM was observed, with peak levels in the late afternoon till midnight. Most of the high RGM concentration values occurred in the afternoon of all seasons due to the higher oxidation. The PBM concentration was higher in early morning of all seasons because of the the temperature inversion that increases in depth as the night proceeds. The ratio of GEM to CO indicates that residential boilers play an important role in the elevation of GEM in winter. The ratio of RGM to O3 could be an indicator of the contribution of local primary sources. The ratio of PBM to PM2.5 reveals that the air mass from the east and southwest of the site in spring and summer carries more atmospheric mercury. The HYSPLIT back-trajectory analysis indicated that the monitoring site is affected by local, regional and interregional sources simultaneously during heavy pollution episodes. The results from the potential source contribution function (PSCF) model indicate that the atmospheric transport predominantly from the northwest

  4. Urban aerosol in Oporto, Portugal: Chemical characterization of PM10 and PM2.5

    NASA Astrophysics Data System (ADS)

    Custódio, Danilo; Ferreira, Catarina; Alves, Célia; Duarte, Mácio; Nunes, Teresa; Cerqueira, Mário; Pio, Casimiro; Frosini, Daniele; Colombi, Cristina; Gianelle, Vorne; Karanasiou, Angeliki; Querol, Xavier

    2014-05-01

    Several urban and industrial areas in Southern Europe are not capable of meeting the implemented EU standards for particulate matter. Efficient air quality management is required in order to ensure that the legal limits are not exceeded and that the consequences of poor air quality are controlled and minimized. Many aspects of the direct and indirect effects of suspended particulate matter on climate and public health are not well understood. The temporal variation of the chemical composition is still demanded, since it enables to adopt off-set strategies and to better estimate the magnitude of anthropogenic forcing on climate. This study aims to provide detailed information on concentrations and chemical composition of aerosol from Oporto city, an urban center in Southern Europe. This city is located near the coast line in the North of Portugal, being the country's second largest urban area. Moreover, Oporto city economic prospects depend heavily on a diversified industrial park, which contribute to air quality degradation. Another strong source of air pollution is traffic. The main objectives of this study are: 1) to characterize the chemical composition of PM10 and PM2.5 by setting up an orchestra of aerosol sampling devices in a strategic place in Oporto; 2) to identify the sources of particles exploring parameters such as organic and inorganic markers (e.g. sugars as tracers for biomass burning; metals and elemental carbon for industrial and vehicular emissions); 3) to evaluate long range transport of pollutants using back trajectory analysis. Here we present data obtained between January 2013 and January 2014 in a heavy traffic roadside sampling site located in the city center. Different PM10 and PM2.5 samplers were operated simultaneously in order to collect enough mass on different filter matrixes and to fulfill the requirements of analytical methodologies. More than 100 aerosol samples were collected and then analysed for their mass concentration and

  5. Optical and chemical properties of marine boundary-layer aerosol around Japan determined from shipboard measurements in 2002

    NASA Astrophysics Data System (ADS)

    Shiobara, Masataka; Hara, Keiichiro; Yabuki, Masanori; Kobayashi, Hiroshi

    Shipboard measurements of the optical and chemical properties of marine boundary-layer aerosol were made around Japan over the period from 28 August to 25 September 2002. Measurements were conducted aboard the Research Vessel (R/V) Shirase along cruise tracks beginning from Yokosuka, and proceeding on to Hakodate, Sakata, Sasebo, Naha, Kure, and Yokkaichi. This paper describes the results of optical measurements using an Optical Particle Counter (OPC), an Integrating Nephelometer (IN), and a Particle Soot/Absorption Photometer (PSAP), as well as chemical analyses of water-soluble aerosol particles collected by impactor and filter systems. Coulter Multisizer measurements were used for water-insoluble aerosol particles. The complex refractive index (CRI), scattering and absorption coefficients, and size distribution of aerosols were estimated from combined measurements made using OPC, IN, and PSAP. Contrasting aerosol characteristics were observed during different stages of the cruise. Discussion on these differences focuses mainly on two legs: Leg-1 from Yokosuka to Hakodate and Leg-4 from Sasebo to Naha. Backward trajectory analyses indicate that the air sampled during Leg-1 originated from the Pacific Ocean, whereas the air sampled during Leg-4 originated from the Chinese Continent via the Korean Peninsula. For the first half of Leg-1, the number concentration was low and larger particles were relatively predominant. The real and imaginary parts of the CRI were estimated to be 1.38-1.40 and close to zero, respectively. This estimation is consistent with the results of chemical analyses, which show that the sea salt is rich in aerosols sourced from remote ocean areas. In contrast, small particles were predominant during Leg-4, and the real and imaginary parts of the CRI were estimated to be 1.52-1.59 and approximately -0.002, respectively. These findings are also consistent with chemical analyses that reveal a mixture of mineral dust and sulfate aerosol likely

  6. Vapor pressure, speciation, and chemical activities in highly concentrated sodium borate solutions at 277 and 317{degrees}C

    SciTech Connect

    Weres, O.

    1995-05-01

    The system H{sub 2}O - B{sub 2}O{sub 3} - Na{sub 2}O has been studied experimentally at 277 and 317{degrees}C. The activities of water and boric acid have been determined at mole ratios Na/B from 0 to 1.5, and total dissolved solids 3 to 8 weight percent. The activity of boric acid has been fitted to within experimental error using a speciation model with eight complex species. This model is consistent with the model previously published by Mesmer et al. The electrolyte properties of the liquid are modeled using the Pitzer-Simonson model of very concentrated electrolyte solutions. The calculated values of water activity agree with experiment, and the activity of NaOH and pOH have also been calculated. The potassium borate system also was briefly studied at 317{degrees}C, and is adequately described by a model with five complex species. The potassium borate liquid is more alkaline at K/B = 1 than a sodium borate liquid at the same mole ratio, but pOH in the two systems is the same at lower mole ratios.

  7. The optical, physical and chemical properties of the products of glyoxal uptake on ammonium sulfate seed aerosols

    NASA Astrophysics Data System (ADS)

    Trainic, M.; Abo Riziq, A.; Lavi, A.; Flores, J. M.; Rudich, Y.

    2011-09-01

    The heterogeneous reaction between gas phase glyoxal and ammonium sulfate (AS) aerosols, a proxy for inorganic atmospheric aerosol, was studied in terms of the dependence of the optical, physical and chemical properties of the product aerosols on initial particle size and ambient relative humidity (RH). Our experiments imitate an atmospheric scenario of a dry particle hydration at ambient RH conditions in the presence of glyoxal gas followed by efflorescence due to decrease of the ambient RH. The reactions were studied under different RH conditions, starting from dry conditions (~20% RH) and up to 90% RH, covering conditions prevalent in many atmospheric environments, and followed by consequent drying of the reacted particles before their analysis by the aerosol mass spectrometer (AMS), cavity ring down (CRD) and scanning mobility particle sizer (SMPS) systems. At λ = 355 nm, the reacted aerosols demonstrate a substantial growth in optical extinction cross section, as well as in mobility diameter under a broad range of RH values (35-90%). The ratio of the product aerosol to seed aerosol geometric cross section reached up to ~3.5, and the optical extinction cross-section up to ~250. The reactions show a trend of increasing physical and optical growth with decreasing seed aerosol size, from 100 nm to 300 nm, as well as with decreasing RH values from 90% to ~40%. Optically inactive aerosols, at the limit of the Mie range (100 nm diameter) become optically active as they grow due to the reaction. AMS analyses of the reaction of 300 nm AS at RH values of 50%, 75% and 90% show that the main products of the reaction are glyoxal oligomers, formed by acetal formation in the presence of AS. In addition, imidazole formation, which is a minor channel, is observed for all reactions, yielding a product which absorbs at λ = 290 nm, with possible implications on the radiative properties of the product aerosols. The ratio of absorbing substances (C-N compounds, including

  8. AEROSOL CHEMICAL CHARACTERISTION ON BOARD THE DOE G1 AIRCRAFT USING A PARTICLE INTO LIQUID SAMPLER DURING THE TEXAQS 2000 EXPERIMENT.

    SciTech Connect

    LEE,Y.N.; SONG,Z.; LIU,Y.; DAUM,P.; WEBER,R.; ORSINI,D.; LAULAINEN,N.; HUBBE,J.; MORRIS,V.

    2001-01-13

    Knowledge of aerosol chemical composition is key to understanding a number of properties of ambient aerosol particles including sources, size/number distribution, chemical evolution, optical properties and human health effects. Although filter based techniques have been widely used to determine aerosol chemical constituents, they generally cannot provide sufficiently fast time resolution needed to investigate sources and chemical evolution that effect aerosol chemical, size and number changes. In order to gain an ability to describe and predict the life cycles of ambient aerosols as a basis for ambient air quality control, fast and sensitive determination of the aerosol chemical composition must be made available. To help to achieve this goal, we deployed a newly developed technique, referred to as PILS (particle-into-liquid-sampler), on the DOE G1 aircraft during the 2000 Texas Air Quality Study (TexAQS 2000) to characterize the major ionic species of aerosol particles with aerodynamic size smaller than 2.5 {micro}m (PM 2.5). The results obtained are examined in the context of other simultaneously collected data for insights into the measurement capability of the PILS system.

  9. Characterisation of chemical species in PM 2.5 and PM 10 aerosols in Brisbane, Australia

    NASA Astrophysics Data System (ADS)

    Chan, Y. C.; Simpson, R. W.; McTainsh, G. H.; Vowles, P. D.; Cohen, D. D.; Bailey, G. M.

    Aerosol samples for PM 10 (particulate matter with aerodynamic diameters less than 10 um) were collected from September 1993 to August 1994 at five sites representing the major land use patterns in Brisbane, a subtropical coastal city in Australia. The samples collected were analysed by techniques such as ion beam analysis and the integrating plate laser absorption method, and the chemical composition of the samples was reconstructed from the observed elemental composition. For these PM 10 samples, the major components, on average, were crustal matter (25% by mass), organics (17%), sea salt (12%), elemental carbon (10%) and ammonium sulphate (7%). Aerosol samples of PM 2.5 (particulate matter with aerodynamic diameter less than 2.5 μm) were collected by a dichotomous sampler at one of the sites (GU), a site on university buildings located in a suburban area of Brisbane but surrounded by a buffer zone provided by a forest conservation area. A high average fine Br/Pb ratio of 0.36 in the GU samples, which is close to that in vehicle exhausts, indicates that this site probably has low background levels of lead even though there has been significant traffic in the area for 20 years, so the forest area is an effective buffer to road dust from the surrounding suburbia. Temporal trends at this site suggest that road side dust and industry-sourced crustal matter could contribute to more than half of the mass of crustal matter. Seasonal meteorological conditions which determine the dispersion of pollutants out of Brisbane and the continuous input of rural dust into Brisbane are potentially important factors influencing the level of crustal matter in Brisbane. However, major rural dust events do not considerably increase the seasonal average level of crustal matter. Also, apart from significant local influences at some sites (such as heavy road traffic network or a cement factory), the results from the GU site show a similar level of elemental and chemical components from

  10. Wintertime aerosol chemical composition, volatility, and spatial variability in the greater London area

    NASA Astrophysics Data System (ADS)

    Xu, L.; Williams, L. R.; Young, D. E.; Allan, J. D.; Coe, H.; Massoli, P.; Fortner, E.; Chhabra, P.; Herndon, S.; Brooks, W. A.; Jayne, J. T.; Worsnop, D. R.; Aiken, A. C.; Liu, S.; Gorkowski, K.; Dubey, M. K.; Fleming, Z. L.; Visser, S.; Prévôt, A. S. H.; Ng, N. L.

    2016-02-01

    The composition of PM1 (particulate matter with diameter less than 1 µm) in the greater London area was characterized during the Clean Air for London (ClearfLo) project in winter 2012. Two high-resolution time-of-flight aerosol mass spectrometers (HR-ToF-AMS) were deployed at a rural site (Detling, Kent) and an urban site (North Kensington, London). The simultaneous and high-temporal resolution measurements at the two sites provide a unique opportunity to investigate the spatial distribution of PM1. We find that the organic aerosol (OA) concentration is comparable between the rural and urban sites, but the contribution from different sources is distinctly different between the two sites. The concentration of solid fuel OA at the urban site is about twice as high as at the rural site, due to elevated domestic heating in the urban area. While the concentrations of oxygenated OA (OOA) are well-correlated between the two sites, the OOA concentration at the rural site is almost twice that of the urban site. At the rural site, more than 70 % of the carbon in OOA is estimated to be non-fossil, which suggests that OOA is likely related to aged biomass burning considering the small amount of biogenic SOA in winter. Thus, it is possible that the biomass burning OA contributes a larger fraction of ambient OA in wintertime than what previous field studies have suggested. A suite of instruments was deployed downstream of a thermal denuder (TD) to investigate the volatility of PM1 species at the rural Detling site. After heating at 250 °C in the TD, 40 % of the residual mass is OA, indicating the presence of non-volatile organics in the aerosol. Although the OA associated with refractory black carbon (rBC; measured by a soot-particle aerosol mass spectrometer) only accounts for < 10 % of the total OA (measured by a HR-ToF-AMS) at 250 °C, the two measurements are well-correlated, suggesting that the non-volatile organics have similar sources or have undergone similar chemical

  11. Wintertime aerosol chemical composition, volatility, and spatial variability in the greater London area

    DOE PAGESBeta

    Xu, L.; Williams, L. R.; Young, D. E.; Allan, J. D.; Coe, H.; Massoli, P.; Fortner, E.; Chhabra, P.; Herndon, S.; Brooks, W. A.; et al

    2016-02-02

    The composition of PM1 (particulate matter with diameter less than 1 µm) in the greater London area was characterized during the Clean Air for London (ClearfLo) project in winter 2012. Two high-resolution time-of-flight aerosol mass spectrometers (HR-ToF-AMS) were deployed at a rural site (Detling, Kent) and an urban site (North Kensington, London). The simultaneous and high-temporal resolution measurements at the two sites provide a unique opportunity to investigate the spatial distribution of PM1. We find that the organic aerosol (OA) concentration is comparable between the rural and urban sites, but the contribution from different sources is distinctly different between the two sites.more » The concentration of solid fuel OA at the urban site is about twice as high as at the rural site, due to elevated domestic heating in the urban area. While the concentrations of oxygenated OA (OOA) are well-correlated between the two sites, the OOA concentration at the rural site is almost twice that of the urban site. At the rural site, more than 70 % of the carbon in OOA is estimated to be non-fossil, which suggests that OOA is likely related to aged biomass burning considering the small amount of biogenic SOA in winter. Thus, it is possible that the biomass burning OA contributes a larger fraction of ambient OA in wintertime than what previous field studies have suggested. A suite of instruments was deployed downstream of a thermal denuder (TD) to investigate the volatility of PM1 species at the rural Detling site. After heating at 250 °C in the TD, 40 % of the residual mass is OA, indicating the presence of non-volatile organics in the aerosol. Although the OA associated with refractory black carbon (rBC; measured by a soot-particle aerosol mass spectrometer) only accounts for < 10 % of the total OA (measured by a HR-ToF-AMS) at 250 °C, the two measurements are well-correlated, suggesting that the non-volatile organics have similar sources or have

  12. Chemical composition of size-segregated aerosols in Lhasa city, Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Wan, Xin; Kang, Shichang; Xin, Jinyuan; Liu, Bin; Wen, Tianxue; Wang, Pengling; Wang, Yuesi; Cong, Zhiyuan

    2016-06-01

    To reveal the chemical characteristics of size-segregated aerosols in the high-altitude city of Tibetan Plateau, eight-size aerosol samples were collected in Lhasa from March 2013 to February 2014. The annual mean of online PM2.5 was 25.0 ± 16.0 μg m- 3, which was much lower than Asian cities but similar with some European cities. The annual mean concentrations of organic carbon (OC, 7.92 μg m- 3 in PM2.1 and 12.66 μg m- 3 in PM9.0) and elemental carbon (EC, 1.00 μg m- 3 in PM2.1 and 1.21 μg m- 3 in PM9.0) in Lhasa aerosols were considerably lower than those heavily polluted cities such as Beijing and Xi'an, China and Kathmandu, Nepal. Sulfate, NO3-, NH4+ and Ca2 + were 0.75 ± 0.31, 0.82 ± 0.35, 0.38 ± 0.34 and 0.57 ± 0.29 μg m- 3 in fine particles while in coarse particles they were 0.57 ± 0.37, 0.73 ± 0.23, 0.07 ± 0.03 and 2.52 ± 1.37 μg m- 3, respectively. Secondary water-soluble ions composed 35.8% of the total ionic components in fine particles according to the established electroneutrality, while in coarse particles they took up only 9.3%. Ca2 + (40.6%) was the major component of the coarse particles. For seasonality, the concentrations of OC, EC, SO42 -, NH4+, K+, Ca2 +, Mg2 +, Cl- and Na+ presented higher values during late autumn and winter but were relatively lower in spring and summer. Nevertheless, NO3- was considerably higher in summer and autumn, presumably due to increased tourist-vehicle emissions. During winter and spring, [Ca2 +]/[NO3-+ SO42 -] ratios in coarse particles showed higher values of 7.31 and 6.17, respectively, emphasizing the dust influence. [NO3-]/[SO42 -] ratios in fine particles during spring, summer and autumn exceeding 1 indicated that the currently predominant vehicle exhaust makes a greater contribution to the aerosols. While more stationary sources such as coal and biomass burning existed in winter since the [NO3-]/[SO42 -] ratio was less than 1. Different sources and formation processes lead to a bimodal size

  13. Temporal variability in Chemical and Stable isotopic characteristics of ambient bulk aerosols over a coastal environment of India

    NASA Astrophysics Data System (ADS)

    Agnihotri, R.; Karapurkar, S. G.; Sarma, V. V.; Praveen, P.; Kumar, M. D.

    2012-12-01

    Atmospheric carbonaceous aerosols are known to influence regional biogeochemical cycles of carbon (C) and nitrogen (N) in addition to regional radiation budgets. Owing to multiplicity of primary sources of natural and anthropogenic origin, their detailed chemical and isotopic characterization can greatly help in source apportionment and identifying secondary processes. From the roof of NIO-Goa (India) [15.46οN, 73.8oE; at ~55.8 MASL], atmospheric bulk aerosols (n=22) were collected on Quartz filters, from 2009 December to January 2011 covering entire 2010 (except monsoon period) to investigate temporal variability in their chemical and isotopic characteristics of the carbonaceous fraction i.e. TC, TOC and TN mass concentrations and their stable isotopic ratios (δ13CTC, δ13CTOC and δ15NTN). Both δ13CTC and δ13CTOC varied in narrow ranges (-24.9±1.1‰, -25.7±0.9‰ respectively), but significant differences were observed between the two during pre-monsoon months (as high as 2.3‰), possibly due to mixing of inorganic mineral dust. δ15NTN values showed a wide range of variability (average = 13.6±7.2‰), with significantly lower values (~2-5‰; as reported earlier by Agnihotri et al. 2011) during pre-monsoon period compared to those during winter (as high as ~26‰). Using δ13CTC values and two end-member mixing model (assuming δ13C of marine and continental carbon as -21 and -27‰ respectively), the average marine carbon fraction for Goa aerosols was estimated as 36±18.5%, significantly higher than reported for Chennai aerosols (~19%) (Pavuluri et al., 2011), but close to the reported average for marine aerosols at Bermuda (38%) (Turekian et al., 2003). Chemical and isotopic characteristics of ambient aerosols over Goa along with contemporaneous meteorological data indicate that winter aerosols contain significant proportion of carbonaceous fraction originated from biomass burning and other anthropogenic activities carried out in northern parts of

  14. Spatial distribution and temporal variation of chemical species in the bulk atmospheric aerosols collected at the Okinawa archipelago, Japan

    NASA Astrophysics Data System (ADS)

    Handa, D.; Somada, Y.; Ijyu, M.; Azechi, S.; Nakaema, F.; Arakaki, T.; Tanahara, A.

    2009-12-01

    The economic development and population growth in recent Asia have been increasing air pollution. A computer simulation study showed that air pollutants emitted from Asian continent could spread quickly within northern hemisphere. We initiated a study to elucidate the special distribution and chemical characterization of atmospheric aerosols around Okinawa archipelago, Japan. Okinawa Island is situated approximately 1500 km south of Tokyo, Japan, 2000 km southeast of Beijing, China, and 1000 km south of South Korea. Its location in Asia is well suited for studying long-range transport of air pollutants in East Asia because maritime air mass prevails during summer, while continental air mass dominates during fall, winter, and spring. The maritime air mass data can be seen as background and can be compared with continental air masses which have been affected by anthropogenic activities. We simultaneously collected bulk aerosol samples by using the same types of high volume air samplers at Cape Hedo Atmosphere and Aerosol Monitoring Station (CHAAMS, Okinawa Island), Kume Island (ca. 160 km south-west of CHAAMS) and Minami-daitou Island (ca. 320 km south-east of CHAAMS). We determined the concentrations of water-soluble anions, cations and dissolved organic carbon (DOC) using ion chromatography, atomic absorption spectrometry, and total organic carbon analyzer, respectively. We report and discuss spatial distribution and temporal variation of chemical species concentrations in bulk atmospheric aerosols collected during July, 2008 to July, 2009. We determine “background” concentration of chemical components in Okinawa archipelago. We then compare each chemical component among CHAAMS, Kume Island and Minami-daito Island to elucidate the influence of the long-range transport of chemical species from Asian continent.

  15. Chemical speciation studies on DU contaminated soils using flow field flow fractionation linked to inductively coupled plasma mass spectrometry (FlFFF-ICP-MS).

    PubMed

    Brittain, S R; Cox, A G; Tomos, A D; Paterson, E; Siripinyanond, A; McLeod, C W

    2012-03-01

    Flow field flow fractionation (FlFFF) in combination with inductively coupled plasma mass spectrometry (ICP-MS) was used to study the chemical speciation of U and trace metals in depleted uranium (DU) contaminated soils. A chemical extraction procedure using sodium pyrophosphate, followed by isolation of humic and fulvic substances was applied to two dissimilar DU contaminated sample types (a sandy soil and a clay-rich soil), in addition to a control soil. The sodium pyrophosphate fractions of the firing range soils (Eskmeals and Kirkcudbright) were found to contain over 50% of the total U (measured aft