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Sample records for aerosol oxidative activity

  1. Microfluidic Electrochemical Sensor for On-line Monitoring of Aerosol Oxidative Activity

    PubMed Central

    Sameenoi, Yupaporn; Koehler, Kirsten; Shapiro, Jeff; Boonsong, Kanokporn; Sun, Yele; Collett, Jeffrey; Volckens, John; Henry, Charles S.

    2012-01-01

    Particulate matter (PM) air pollution has a significant impact on human morbidity and mortality; however, the mechanisms of PM-induced toxicity are poorly defined. A leading hypothesis states that airborne PM induces harm by generating reactive oxygen species (ROS) in and around human tissues, leading to oxidative stress. We report here, a system employing a microfluidic electrochemical sensor coupled directly to a Particle-into-Liquid-Sampler (PILS) system to measure aerosol oxidative activity in an on-line format. The oxidative activity measurement is based on the dithiothreitol assay (DTT assay) where after oxidized by PM, the remaining reduced DTT was analyzed by the microfluidic sensor. The sensor consists of an array of working, reference, and auxiliary electrodes fabricated in a poly(dimethylsiloxane) (PDMS)-based microfluidic device. Cobalt (II) phthalocyanine (CoPC)-modified carbon paste was used as the working electrode material allowing selective detection of reduced DTT. The electrochemical sensor was validated off-line against the traditional DTT assay using filter samples taken from urban environments and biomass burning events. After off-line characterization, the sensor was coupled to a PILS to enable on-line sampling/analysis of aerosol oxidative activity. Urban dust and industrial incinerator ash samples were aerosolized in an aerosol chamber and analyzed for their oxidative activity. The on-line sensor reported DTT consumption rates (oxidative activity) in good correlation with aerosol concentration (R2 from 0.86–.97) with a time-resolution of approximately 3 minutes. PMID:22651886

  2. Photochemical Activation of Chlorine by Iron and Iron Oxide Aerosol

    NASA Astrophysics Data System (ADS)

    Wittmer, J.; Zetzsch, C.

    2015-12-01

    The photochemical activation of chlorine by dissolved iron in sea-salt aerosol droplets and by highly dispersed Fe2O3 aerosol particles (mainly hematite, specific surface > 100 m2/g), exposed to gaseous HCl, was investigated in humidified air in a Teflon simulation chamber. Employing the radical-clock technique, we quantified the production of gaseous atomic Cl. When the artificial sea salt aerosols contained suspended Fe2O3 alone at pH 6, no significant Cl production could be observed, even if the dissolution of iron was forced by "weathering" (repeatedly freezing and thawing for five times). Adjusting the pH in the stock suspension to 2.6, 2.2, and 1.9 and equilibrating for one week resulted in a quantifiable amount of dissolved iron (0.03, 0.2, and 0.6 mmol/L, respectively) and in gaseous Cl production rates of ~1.6, 6, and 8 × 1021 atoms cm-2 h-1, respectively. Exposing the pure Fe2O3 aerosol in the absence of salt to various gaseous HCl concentrations resulted in rates ranging from 8 × 1020 Cl atoms cm-2 h-1 (at ~4 ppb HCl) to 5 × 1022 Cl atoms cm-2 h-1 (at ~350 ppb HCl) and confirmed the uptake and conversion of HCl to atomic Cl (at HCl to Cl conversion yields of 2-5 % mol/mol, depending on the relative humidity). The relevance for environmental processes in the atmosphere will be discussed.

  3. A Microfluidic Paper-Based Analytical Device (μPAD) for Aerosol Oxidative Activity

    PubMed Central

    Sameenoi, Yupaporn; Panymeesamer, Pantila; Supalakorn, Natcha; Koehler, Kirsten; Chailapakul, Orawon; Henry, Charles S.; Volckens, John

    2013-01-01

    Human exposure to particulate matter (PM) air pollution has been linked with respiratory, cardiovascular, and neurodegenerative diseases, in addition to various cancers. Consistent among all of these associations is the hypothesis that PM induces inflammation and oxidative stress in the affected tissue. Consequently, a variety of assays have been developed to quantify the oxidative activity of PM as a means to characterize its ability to induced oxidative stress. The vast majority of these assays rely on high-volume, fixed-location sampling methods due to limitations in assay sensitivity and detection limit. As a result, our understanding of how personal exposure contributes to the intake of oxidative air pollution is limited. To further this understanding, we present a microfluidic paper-based analytical device (μPAD) for measuring PM oxidative activity on filters collected by personal sampling. The μPAD is inexpensive to fabricate and provides fast and sensitive analysis of aerosol oxidative activity. The oxidative activity measurement is based on the dithiothreitol assay (DTT assay), uses colorimetric detection, and can be completed in the field within 30 min following sample collection. The μPAD assay was validated against the traditional DTT assay using 13 extracted aerosol samples including urban aerosols, biomass burning PM, cigarette smoke and incense smoke. The results showed no significant differences in DTT consumption rate measured by the two methods. To demonstrate the utility of the approach, personal samples were collected to estimate human exposures to PM from indoor air, outdoor air on a clean day, and outdoor air on a wildfire-impacted day in Fort Collins, CO. Filter samples collected on the wildfire day gave the highest oxidative activity on a mass normalized basis, whereas typical ambient background air showed the lowest oxidative activity. PMID:23227907

  4. The influence of nitrogen oxides on the activation of bromide and chloride in salt aerosol

    NASA Astrophysics Data System (ADS)

    Bleicher, S.; Buxmann, J. C.; Sander, R.; Riedel, T. P.; Thornton, J. A.; Platt, U.; Zetzsch, C.

    2014-04-01

    Experiments on salt aerosol with different salt contents were performed in a Teflon chamber under tropospheric light conditions with various initial contents of nitrogen oxides (NOx = NO + NO2). A strong activation of halogens was found at high NOx mixing ratios, even in samples with lower bromide contents such as road salts. The ozone depletion by reactive halogen species released from the aerosol, was found to be a function of the initial NOx mixing ratio. Besides bromine, large amounts of chlorine have been released in our smog chamber. Time profiles of the halogen species Cl2, Br2, ClNO2, BrNO2 and BrO, ClO, OClO and Cl atoms were simultaneously measured by various techniques (chemical ionization mass spectrometry, differential optical absorption spectrometry coupled with a multi-reflection cell and gas chromatography of hydrocarbon tracers for Cl and OH, employing cryogenic preconcentration and flame ionization detection). Measurements are compared to calculations by the CAABA/MECCA 0-D box model, which was adapted to the chamber conditions and took the aerosol liquid water content and composition into account. The model results agree reasonably with the observations and provide important information about the prerequisites for halogen release, such as the time profiles of the aerosol bromide and chloride contents as well as the aerosol pH.

  5. Determination of Aerosol Oxidative Activity using Silver Nanoparticle Aggregation on Paper-Based Analytical Devices

    PubMed Central

    Dungchai, Wijitar; Sameenoi, Yupaporn; Chailapakul, Orawon; Volckens, John; Henry, Charles S.

    2013-01-01

    Airborne particulate matter (PM) pollution significantly impacts human health, but the cellular mechanisms of PM-induced toxicity remain poorly understood. A leading hypothesis on the effects of inhaled PM involves the generation of cellular oxidative stress. To investigate PM-induced oxidative stress, analytical methods have been developed to study the chemical oxidation of dithiothreitol (DTT) in the presence of PM. Although DTT readily reacts with several forms of reactive oxygen species, this molecule is not endogenously produced in biological systems. Glutathione (GSH), on the other hand, is an endogenous antioxidant that is produced throughout the body and is directly involved in combating oxidative stress in the lungs and other tissues. We report here a new method for measuring aerosol oxidative activity that uses silver nanoparticle (AgNP) aggregation coupled to glutathione (GSH) oxidation in a paper-based analytical device. In this assay, the residual reduced GSH from the oxidation of reduced GSH to its disulfide induces the aggregation of AgNPs on a paper-based analytical device, which produces a reddish-brown product. Two methods for aerosol oxidative reactivity are presented: one based on change in color intensity using a traditional paper-based techniques and one based on the length of the color product formed using a distance-based device. These methods were validated against traditional spectroscopic assays for DTT and GSH that employ Elman’s reagent. No significant difference was found between the levels measured by all three GSH methods (our two paper-based devices and the traditional method) at the 95% confidence level. PM reactivity towards GSH was less than towards DTT most likely due to the difference in the oxidation potential between the two molecules. PMID:24067623

  6. Laboratory Studies of Processing of Carbonaceous Aerosols by Atmospheric Oxidants/Hygroscopicity and CCN Activity of Secondary & Processed Primary Organic Aerosols

    SciTech Connect

    Ziemann, P.J.; Arey, J.; Atkinson, R.; Kreidenweis, S.M.; Petters, M.D.

    2012-06-13

    The atmosphere is composed of a complex mixture of gases and suspended microscopic aerosol particles. The ability of these particles to take up water (hygroscopicity) and to act as nuclei for cloud droplet formation significantly impacts aerosol light scattering and absorption, and cloud formation, thereby influencing air quality, visibility, and climate in important ways. A substantial, yet poorly characterized component of the atmospheric aerosol is organic matter. Its major sources are direct emissions from combustion processes, which are referred to as primary organic aerosol (POA), or in situ processes in which volatile organic compounds (VOCs) are oxidized in the atmosphere to low volatility reaction products that subsequent condense to form particles that are referred to as secondary organic aerosol (SOA). POA and VOCs are emitted to the atmosphere from both anthropogenic and natural (biogenic) sources. The overall goal of this experimental research project was to conduct laboratory studies under simulated atmospheric conditions to investigate the effects of the chemical composition of organic aerosol particles on their hygroscopicity and cloud condensation nucleation (CCN) activity, in order to develop quantitative relationships that could be used to more accurately incorporate aerosol-cloud interactions into regional and global atmospheric models. More specifically, the project aimed to determine the products, mechanisms, and rates of chemical reactions involved in the processing of organic aerosol particles by atmospheric oxidants and to investigate the relationships between the chemical composition of organic particles (as represented by molecule sizes and the specific functional groups that are present) and the hygroscopicity and CCN activity of oxidized POA and SOA formed from the oxidation of the major classes of anthropogenic and biogenic VOCs that are emitted to the atmosphere, as well as model hydrocarbons. The general approach for this project was

  7. Impacts of organic aerosols and its oxidation level on CCN activity from measurement at a suburban site in China

    NASA Astrophysics Data System (ADS)

    Zhang, Fang; Li, Zhanqing; Li, Yanan; Sun, Yele; Wang, Zhenzhu; Li, Ping; Sun, Li; Wang, Pucai; Cribb, Maureen; Zhao, Chuanfeng; Fan, Tianyi; Yang, Xin; Wang, Qingqing

    2016-05-01

    This study is concerned with the impacts of organic aerosols on cloud condensation nuclei (CCN) activity based on field measurements made at a suburban site in Northern China. The sensitivity of the estimated CCN number concentration (NCCN) to both volume fraction of organic material (xorg) and aerosol oxidation level (using f44, the fraction of m/z 44 in aerosol organic material) are examined. A strong dependence of CCN number concentration (NCCN) on the xorg and f44 was noted. The sensitivity of NCCN to volume fraction of organics increased with increasing xorg. The impacts of the aerosol particles oxidization or aging level on estimating NCCN were also very significant. When the particles were mostly composed of organics (xorg > 60 %), the NCCN at the supersaturation of 0.075 and 0.13 % was underestimated by 46 and 44 %, respectively, if aerosol particles were freshly emitted with primary organics (f44 < 11 %); the underestimation decreased to 32 and 23 % at the corresponding supersaturations, however, if the particles were with more hygroscopic secondary organics (f44 > 15 %). The NCCN at the supersaturation of 0.76 % was underestimated by 11 and 4 %, respectively, at f44 < 11 and f44 > 15 %. However, for the particles composed of low organics (e.g., xorg < 40 %), the effect caused by the f44 was quite insignificant both at high and low supersaturations. This is because the overall hygroscopicity of the particles is dominated by inorganics such as sulfate and nitrate, which are more hygroscopic than organic compounds. Our results indicated that it would decrease the uncertainties in estimating NCCN and lead to a more accurate estimation of NCCN to increase the proportion of secondary organics, especially when the composition of the aerosols is dominated by organics. The applicability of the CCN activation spectrum obtained at Xinzhou to the Xianghe site, about 400 km to the northeast of Xinzhou, was investigated, with the aim of further examining the

  8. Aerosol palladium activation for electroless copper deposition and heat treatment with NO injection to fabricate Cu oxide/carbon fibre

    NASA Astrophysics Data System (ADS)

    Byeon, Jeong Hoon; Lee, Ryang Hwa; Hwang, Jungho

    2009-03-01

    This paper introduces a novel method for fabricating copper (Cu) oxide/activated carbon fibre (ACF) through the aerosol palladium (Pd) activation for use in electroless Cu deposition and heat treatment of Cu deposited ACF with nitric monoxide (NO) gas injection. Electroless Cu deposition was initiated by catalytically activating the ACF surface with spark generated Pd aerosol nanoparticles. The catalytically activated ACF was placed into a solution used for the electroless Cu deposition. Subjecting the Cu deposited ACF to a heat treatment in a NO/nitrogen (N2) gas injection (1000 ppm NO) resulted in changes to the morphology of the Cu particles. As the temperature increased from 100 to 500 °C, the relative mass fraction of oxygen in the Cu particles increased from 3.6% to 14.2% and the fraction of Cu decreased from 41.2% to 34.1%, which was caused by the formation of Cu oxides (Cu2O and CuO). The corresponding surface area and pore volume of the ACF decreased from 1019 m2 g-1 to 401 m2 g-1 and from 0.40 cm3 g-1 to 0.18 cm3 g-1, respectively. The morphological evolution and decrease in porosity were attributed to volume expansion of Cu particles during oxidation.

  9. Copper oxide aerosol: generation and characterization.

    PubMed

    Peoples, S M; McCarthy, J F; Chen, L C; Eppelsheimer, D; Amdur, M O

    1988-06-01

    Effluent gases from high temperature systems such as fossil fuel combustion and pyrometallurgical processes contain inorganic material which has the potential to interact with sulfur dioxide (SO2) on the surface of particles to form an irritant aerosol. The submicron fraction of this inorganic material is especially important as the fine particles may penetrate deep into the lung and cause serious health effects. A laboratory furnace was designed to produce a submicrometer copper oxide aerosol to stimulate emissions from copper smelters and other pyrometallurgical operations. The ultimate aim of this research is to investigate the interaction of SO2 and the copper oxide aerosol at different temperatures and humidities in order to determine the reaction products and their potential health effects upon inhalation. The initial work, as presented in this paper, was to reproducibly generate a submicrometer copper oxide aerosol and to characterize it in terms of size, morphology and composition. Two experimental regimes were set up. One admitted filtered air, without water vapor, into the furnace, and the other admitted filtered air and water vapor. The size and morphology of the aerosols were determined using an electrical aerosol analyzer and transmission electron microscopy. The particles appear as chain aggregates with a count median diameter of 0.026 micron when no water vapor was added and 0.031 micron when water vapor was added into the furnace. Composition of the aerosol was determined using x-ray photoelectron spectroscopy. The aerosol, with or without water in the furnace, consists of a mixture of copper(I) oxide and copper(II) hydroxide. PMID:3400592

  10. 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.

  11. Heterogeneous oxidation of unsaturated organic aerosols

    NASA Astrophysics Data System (ADS)

    Nah, T.; Kessler, S. H.; Daumit, K. E.; Kroll, J. H.; Leone, S.; Wilson, K. R.

    2011-12-01

    A significant mass fraction of atmospheric aerosols is composed of a variety of oxidized organic compounds with varying functional groups that may affect the rate at which they chemically age. Here we study the heterogeneous reaction of OH radicals with different sub-micron, alkenoic acid particles: Oleic acid (OA), Linoleic acid (LA), and Linolenic acid (LNA), in the presence of H2O2 and O2. This work explores how OH addition reactions initiate chain reactions that rapidly transform the chemical composition of an organic particle. Particles are chemically aged in a photochemical flow tube reactor where they are exposed to OH radicals (~ 1E11 molecule cm-3 s) that are produced by the photolysis of H2O2 at 254 nm. The aerosols are then sized and their composition analyzed via Atmospheric Pressure Chemical Ionization mass spectrometry (APCI-MS). Kinetic measurements, done by tracking the decay of the alkenoic acid parent ion with increasing OH exposure, show that the reactive uptake coefficient, which is defined as the fraction of gas-phase collisions that result in a reaction, is larger than 1, indicating the presence of secondary chain chemistry occurring within the aerosol. The reactive uptake coefficient is found to scale linearly with the number of double bonds present in the molecule. In addition, the reactive uptake coefficient is found to depend sensitively upon the concentrations of O2 and H2O2 in the photochemical flow tube reactor, indicating that O2 and H2O2 play roles as propagators and terminators in the secondary chain reactions. Elemental analysis and mechanistic pathways will also be presented herein.

  12. 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.

  13. Redox activity of naphthalene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    McWhinney, R. D.; Zhou, S.; Abbatt, J. P. D.

    2013-04-01

    Chamber secondary organic aerosol (SOA) from low-NOx photooxidation of naphthalene by hydroxyl radical was examined with respect to its redox cycling behaviour using the dithiothreitol (DTT) assay. Naphthalene SOA was highly redox active, consuming DTT at an average rate of 118 ± 14 pmol per minute per μg of SOA material. Measured particle-phase masses of the major previously identified redox active products, 1,2- and 1,4-naphthoquinone, accounted for only 21 ± 3% of the observed redox cycling activity. The redox-active 5-hydroxy-1,4-naphthoquinone was identified as a new minor product of naphthalene oxidation, and including this species in redox activity predictions increased the predicted DTT reactivity to 30 ± 5% of observations. Similar attempts to predict redox behaviour of oxidised two-stroke engine exhaust particles by measuring 1,2-naphthoquinone, 1,4-naphthoquinone and 9,10-phenanthrenequinone predicted DTT decay rates only 4.9 ± 2.5% of those observed. Together, these results suggest that there are substantial unidentified redox-active SOA constituents beyond the small quinones that may be important toxic components of these particles. A gas-to-SOA particle partitioning coefficient was calculated to be (7.0 ± 2.5) × 10-4 m3 μg-1 for 1,4-naphthoquinone at 25 °C. This value suggests that under typical warm conditions, 1,4-naphthoquinone is unlikely to contribute strongly to redox behaviour of ambient particles, although further work is needed to determine the potential impact under conditions such as low temperatures where partitioning to the particle is more favourable. As well, higher order oxidation products that likely account for a substantial fraction of the redox cycling capability of the naphthalene SOA are likely to partition much more strongly to the particle phase.

  14. Heterogeneous Chemistry: Understanding Aerosol/Oxidant Interactions

    SciTech Connect

    Joyce E. Penner

    2005-03-14

    Global radiative forcing of nitrate and ammonium aerosols has mostly been estimated from aerosol concentrations calculated at thermodynamic equilibrium or using approximate treatments for their uptake by aerosols. In this study, a more accurate hybrid dynamical approach (DYN) was used to simulate the uptake of nitrate and ammonium by aerosols and the interaction with tropospheric reactive nitrogen chemistry in a three-dimensional global aerosol and chemistry model, IMPACT, which also treats sulfate, sea salt and mineral dust aerosol. 43% of the global annual average nitrate aerosol burden, 0.16 TgN, and 92% of the global annual average ammonium aerosol burden, 0.29 TgN, exist in the fine mode (D<1.25 {micro}m) that scatters most efficiently. Results from an equilibrium calculation differ significantly from those of DYN since the fraction of fine-mode nitrate to total nitrate (gas plus aerosol) is 9.8%, compared to 13% in DYN. Our results suggest that the estimates of aerosol forcing from equilibrium concentrations will be underestimated. We also show that two common approaches used to treat nitrate and ammonium in aerosol in global models, including the first-order gas-to-particle approximation based on uptake coefficients (UPTAKE) and a hybrid method that combines the former with an equilibrium model (HYB), significantly overpredict the nitrate uptake by aerosols especially that by coarse particles, resulting in total nitrate aerosol burdens higher than that in DYN by +106% and +47%, respectively. Thus, nitrate aerosol in the coarse mode calculated by HYB is 0.18 Tg N, a factor of 2 more than that in DYN (0.086 Tg N). Excessive formation of the coarse-mode nitrate in HYB leads to near surface nitrate concentrations in the fine mode lower than that in DYN by up to 50% over continents. In addition, near-surface HNO{sub 3} and NO{sub x} concentrations are underpredicted by HYB by up to 90% and 5%, respectively. UPTAKE overpredicts the NO{sub x} burden by 56% and near

  15. Rapid changes in biomass burning aerosols by atmospheric oxidation

    NASA Astrophysics Data System (ADS)

    Vakkari, Ville; Kerminen, Veli-Matti; Beukes, Johan Paul; Tiitta, Petri; Zyl, Pieter G.; Josipovic, Miroslav; Venter, Andrew D.; Jaars, Kerneels; Worsnop, Douglas R.; Kulmala, Markku; Laakso, Lauri

    2014-04-01

    Primary and secondary aerosol particles originating from biomass burning contribute significantly to the atmospheric aerosol budget and thereby to both direct and indirect radiative forcing. Based on detailed measurements of a large number of biomass burning plumes of variable age in southern Africa, we show that the size distribution, chemical composition, single-scattering albedo, and hygroscopicity of biomass burning particles change considerably during the first 2-4 h of their atmospheric transport. These changes, driven by atmospheric oxidation and subsequent secondary aerosol formation, may reach a factor of 6 for the aerosol scattering coefficient and a factor >10 for the cloud condensation nuclei concentration. Since the observed changes take place over the spatial and temporal scales that are neither covered by emission inventories nor captured by large-scale model simulations, the findings reported here point out a significant gap in our understanding on the climatic effects of biomass burning aerosols.

  16. Secondary Organic Aerosol Formation in the Captive Aerosol Growth and Evolution (CAGE) Chambers during the Southern Oxidant and Aerosol Study (SOAS) in Centreville, AL

    NASA Astrophysics Data System (ADS)

    Leong, Y.; Karakurt Cevik, B.; Hernandez, C.; Griffin, R. J.; Taylor, N.; Matus, J.; Collins, D. R.

    2013-12-01

    Secondary organic aerosol (SOA) represents a large portion of sub-micron particulate matter on a global scale. The composition of SOA and its formation processes are heavily influenced by anthropogenic and biogenic activity. Volatile organic compounds (VOCs) that are emitted naturally from forests or from human activity serve as precursors to SOA formation. Biogenic SOA (BSOA) is formed from biogenic VOCs and is prevalent in forested regions like the Southeastern United States. The formation and enhancement of BSOA under anthropogenic influences such as nitrogen oxides (NOx), sulfur dioxide (SO2), and oxygen radicals are still not well understood. The lack of information on anthropogenic BSOA enhancement and the reversibility of SOA formation could explain the underprediction of SOA in current models. To address some of these gaps in knowledge, this study was conducted as part of the Southern Oxidant and Aerosol Study (SOAS) in Centreville, AL during the summer of 2013. SOA growth experiments were conducted in two Captive Aerosol Growth and Evolution (CAGE) outdoor chambers located at the SEARCH site. Ambient trace gas concentrations were maintained in these chambers using semi-permeable gas-exchange membranes, while studying the growth of injected monodisperse seed aerosol. The control chamber was operated under ambient conditions; the relative humidity and oxidant and NOx levels were perturbed in the second chamber. This design allows experiments to capture the natural BSOA formation processes in the southeastern atmosphere and to study the influence of anthropogenic activity on aerosol chemistry. Chamber experiments were periodically monitored with physical and chemical instrumentation including a scanning mobility particle sizer (SMPS), a cloud condensation nuclei counter (CCNC), a humidified tandem differential mobility analyzer (H-TDMA), and an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). The CAGE experiments focused on SOA

  17. Formation and growth of indoor air aerosol particles as a result of D-limonene oxidation

    NASA Astrophysics Data System (ADS)

    Vartiainen, E.; Kulmala, M.; Ruuskanen, T. M.; Taipale, R.; Rinne, J.; Vehkamäki, H.

    Oxidation of D-limonene, which is a common monoterpene, can lead to new aerosol particle formation in indoor environments. Thus, products containing D-limonene, such as citrus fruits, air refresheners, household cleaning agents, and waxes, can act as indoor air aerosol particle sources. We released D-limonene into the room air by peeling oranges and measured the concentration of aerosol particles of three different size ranges. In addition, we measured the concentration of D-limonene, the oxidant, and the concentration of ozone, the oxidizing gas. Based on the measurements we calculated the growth rate of the small aerosol particles, which were 3-10 nm in diameter, to be about 6300nmh-1, and the losses of the aerosol particles that were due to the coagulation and condensation processes. From these, we further approximated the concentration of the condensable vapour and its source rate and then calculated the formation rate of the small aerosol particles. For the final result, we calculated the nucleation rate and the maximum number of molecules in a critical cluster. The nucleation rate was in the order of 105cm-3s-1 and the number of molecules in a critical-sized cluster became 1.2. The results were in agreement with the activation theory.

  18. Effects of aerosol phase and water uptake for understanding organic aerosol oxidation

    NASA Astrophysics Data System (ADS)

    Fitzgerald, C.; Gallimore, P. J.; Fuller, S.; Lee, J.; Garrascon, V.; Achakulwisut, P.; Björkegren, A.; Spring, D. R.; Pope, F. D.; Kalberer, M.

    2012-04-01

    Oxidation reactions of atmospheric organic aerosols strongly influence many important processes in the atmosphere such as aerosol-cloud interactions or heterogeneous chemistry. We present results of an experimental laboratory study with three organic model aerosol systems (maleic, arachidonic and oleic acid) investigating the effect of particle phase and humidity on the oxidative processing of the particle. Two experimental techniques are combined in this investigation. An electrodynamic balance is used to levitate single particles and assess changes in particle size and mass (due to water uptake and/or loss of volatile oxidation products) and phase (liquid or solid) during and after chemical processing with ozone. An aerosol flow tube was used to investigate the detailed chemical composition of the oxidized aerosol with offline ultra-high resolution mass spectrometry. The role of water (i.e., relative humidity) in the oxidation scheme of the three carboxylic acids is very compound specific and the particle phase has a strong effect on the particle processing. Relative humidity was observed to have a major influence on the oxidation scheme of maleic acid and arachidonic acid, whereas no dependence was observed for the oxidation of oleic acid. In both, maleic acid and arachidonic acid, an evaporation of volatile oxidation products could only be observed when the particle was exposed to high relative humidities. Maleic and arachidonic acid change their phase from liquid to solid upon oxidation or upon changes in humidity and efficient oxidative processing of the particle bulk can only occur when the particle is in liquid form. A detailed oxidation mechanism for maleic acid is presented taking the strong effects of water into account. In contrast, oleic acid is liquid under all conditions at room temperature (dry or elevated humidity, pure or oxidized particle). Thus ozone can easily diffuse into the bulk of the particle irrespective of the oxidation conditions. In

  19. OH-initiated heterogeneous aging of highly oxidized organic aerosol

    SciTech Connect

    Kessler, Sean H.; Nah, Theodora; Daumit, Kelly E.; Smith, Jared D.; Leone, Stephen R.; Kolb, Charles E.; Worsnop, Douglas R.; Wilson, Kevin R.; Kroll, Jesse H.

    2011-12-05

    The oxidative evolution (“aging”) of organic species in the atmosphere is thought to have a major influence on the composition and properties of organic particulate matter, but remains poorly understood, particularly for the most oxidized fraction of the aerosol. Here we measure the kinetics and products of the heterogeneous oxidation of highly oxidized organic aerosol, with an aim of better constraining such atmospheric aging processes. Submicron particles composed of model oxidized organics—1,2,3,4-butanetetracarboxylic acid (C{sub 8}H{sub 10}O{sub 8}), citric acid (C{sub 6}H{sub 8}O{sub 7}), tartaric acid (C{sub 4}H{sub 6}O{sub 6}), and Suwannee River fulvic acid—were oxidized by gas-phase OH in a flow reactor, and the masses and elemental composition of the particles were monitored as a function of OH exposure. In contrast to our previous studies of less-oxidized model systems (squalane, erythritol, and levoglucosan), particle mass did not decrease significantly with heterogeneous oxidation. Carbon content of the aerosol always decreased somewhat, but this mass loss was approximately balanced by an increase in oxygen content. The estimated reactive uptake coefficients of the reactions range from 0.37 to 0.51 and indicate that such transformations occur at rates corresponding to 1-2 weeks in the atmosphere, suggesting their importance in the atmospheric lifecycle of organic particulate matter.

  20. Linkages Between Ozone-depleting Substances, Tropospheric Oxidation and Aerosols

    NASA Technical Reports Server (NTRS)

    Voulgarakis, A.; Shindell, D. T.; Faluvegi, G.

    2013-01-01

    Coupling between the stratosphere and the troposphere allows changes in stratospheric ozone abundances to affect tropospheric chemistry. Large-scale effects from such changes on chemically produced tropospheric aerosols have not been systematically examined in past studies. We use a composition-climate model to investigate potential past and future impacts of changes in stratospheric ozone depleting substances (ODS) on tropospheric oxidants and sulfate aerosols. In most experiments, we find significant responses in tropospheric photolysis and oxidants, with small but significant effects on methane radiative forcing. The response of sulfate aerosols is sizeable when examining the effect of increasing future nitrous oxide (N2O) emissions. We also find that without the regulation of chlorofluorocarbons (CFCs) through the Montreal Protocol, sulfate aerosols could have increased by 2050 by a comparable amount to the decreases predicted due to relatively stringent sulfur emissions controls. The individual historical radiative forcings of CFCs and N2O through their indirect effects on methane (-22.6mW/sq. m for CFCs and -6.7mW/sq. m for N2O) and sulfate aerosols (-3.0mW/sq. m for CFCs and +6.5mW/sq. m for N2O when considering the direct aerosol effect) discussed here are non-negligible when compared to known historical ODS forcing. Our results stress the importance of accounting for stratosphere-troposphere, gas-aerosol and composition-climate interactions when investigating the effects of changing emissions on atmospheric composition and climate.

  1. Linkages between ozone-depleting substances, tropospheric oxidation and aerosols

    NASA Astrophysics Data System (ADS)

    Voulgarakis, A.; Shindell, D. T.; Faluvegi, G.

    2013-05-01

    Coupling between the stratosphere and the troposphere allows changes in stratospheric ozone abundances to affect tropospheric chemistry. Large-scale effects from such changes on chemically produced tropospheric aerosols have not been systematically examined in past studies. We use a composition-climate model to investigate potential past and future impacts of changes in stratospheric ozone depleting substances (ODS) on tropospheric oxidants and sulfate aerosols. In most experiments, we find significant responses in tropospheric photolysis and oxidants, with small but significant effects on methane radiative forcing. The response of sulfate aerosols is sizeable when examining the effect of increasing future nitrous oxide (N2O) emissions. We also find that without the regulation of chlorofluorocarbons (CFCs) through the Montreal Protocol, sulfate aerosols could have increased by 2050 by a comparable amount to the decreases predicted due to relatively stringent sulfur emissions controls. The individual historical radiative forcings of CFCs and N2O through their indirect effects on methane (-22.6 mW m-2 for CFCs and -6.7 mW m-2 for N2O) and sulfate aerosols (-3.0 mW m-2 for CFCs and +6.5 mW m-2 for N2O when considering the direct aerosol effect) discussed here are non-negligible when compared to known historical ODS forcing. Our results stress the importance of accounting for stratosphere-troposphere, gas-aerosol and composition-climate interactions when investigating the effects of changing emissions on atmospheric composition and climate.

  2. 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).

  3. Characterization of the Changes in Hygroscopicity of Ambient Organic Aerosol due to Oxidation by Gas Phase OH

    NASA Astrophysics Data System (ADS)

    Wong, J. P.; McWhinney, R. D.; Slowik, J. G.; Abbatt, J.

    2011-12-01

    Despite the ubiquitous nature of organic aerosols and their importance in climate forcing, the influence of chemical processes on their ability to act as cloud condensation nuclei (CCN) in the atmosphere remains uncertain. Changes to the hygroscopicity of ambient organic aerosol due to OH oxidation were explored at a remote forested (Whistler, British Columbia) and an urban (Toronto, Ontario) site. Organic aerosol was exposed to controlled levels of OH radicals in a portable flow tube reactor, the Toronto Photo-Oxidation Tube (TPOT). An Aerodyne Aerosol Mass Spectrometer (AMS) monitored the changes in the chemical composition due to OH-initiated oxidation. The CCN activity of size-selected particles was measured with a DMT Cloud Condensation Nuclei Counter (CCNc) to determine the hygroscopicity parameter, κ. Preliminary results suggest that gas phase OH oxidation increases the degree of oxygenation of organic aerosol, leading to increases in hygroscopicity. These results yield insights into the mechanism by which oxidation affects the hygroscopicity of ambient aerosol of various sources, and to constrain the main aging process that leads to the observation of increasing hygroscopicity with increasing oxidation of organic aerosol.

  4. Enhancement of aerosol responses to changes in emissions over East Asia by gas-oxidant-aerosol coupling and detailed aerosol processes

    NASA Astrophysics Data System (ADS)

    Matsui, H.; Koike, M.

    2016-06-01

    We quantify the responses of aerosols to changes in emissions (sulfur dioxide, black carbon (BC), primary organic aerosol, nitrogen oxides (NOx), and volatile organic compounds) over East Asia by using simulations including gas-oxidant-aerosol coupling, organic aerosol (OA) formation, and BC aging processes. The responses of aerosols to NOx emissions are complex and are dramatically changed by simulating gas-phase chemistry and aerosol processes online. Reduction of NOx emissions by 50% causes a 30-40% reduction of oxidant (hydroxyl radical and ozone) concentrations and slows the formation of sulfate and OA by 20-30%. Because the response of OA to changes in NOx emissions is sensitive to the treatment of emission and oxidation of semivolatile and intermediate volatility organic compounds, reduction of the uncertainty in these processes is necessary to evaluate gas-oxidant-aerosol coupling accurately. Our simulations also show that the sensitivity of aerosols to changes in emissions is enhanced by 50-100% when OA formation and BC aging processes are resolved in the model. Sensitivity simulations show that the increase of NOx emissions from 1850 to 2000 explains 70% (40%) of the enhancement of aerosol mass concentrations (direct radiative effects) over East Asia during that period through enhancement of oxidant concentrations and that this estimation is sensitive to the representation of OA formation and BC aging processes. Our results demonstrate the importance of simultaneous simulation of gas-oxidant-aerosol coupling and detailed aerosol processes. The impact of NOx emissions on aerosol formation will be a key to formulating effective emission reduction strategies such as BC mitigation and aerosol reduction policies in East Asia.

  5. Oxidation enhancement of submicron organic aerosols by fog processing

    NASA Astrophysics Data System (ADS)

    Zhang, Q.; Ge, X.; Collier, S.; Setyan, A.; Xu, J.; Sun, Y.

    2011-12-01

    During 2010 wintertime, a measurement study was carried out at Fresno, California, using an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) combined with a Scanning Mobility Particle Sizer (SMPS). Four fog events occurred during the first week of the campaign. While ambient aerosol was sampled into the HR-ToF-AMS, fog water samples were collected, and were later aerosolized and analyzed via HR-TOF-AMS in the laboratory. We performed Positive Matrix Factorization (PMF) on the AMS ambient organic mass spectra, and identified four OA factors: hydrocarbon-like OA (HOA) likely from vehicle emissions, cooking influenced OA (COA), biomass burning OA (BBOA) representing residential wood combustion, and an oxygenated OA (OOA) that has an average O/C ratio of 0.42. The time series of the OOA factor correlates best with that of sulfate (R2 =0.54 ) during fog events, suggesting that aqueous phase processing may have strongly affected OOA production during wintertime in Fresno. We further investigate the OOA compositions and elemental ratios before, during, and after the fog events, as well as those of dissolved organic matter (DOM) in fog waters to study the influence of aqueous phase processing on OA compositions. Results of fog sample analysis shows an enhancement of oxidation of DOM in 11 separate fog samples. Further factor analysis of the fog DOM data will elucidate the possible mechanisms by which fog processing enhances oxidation of aerosol. In addition, in order to investigate the influence of aqueous processing on OA, we used the Extended Aerosol Inorganic Model (E-AIM) (http://www.aim.env.uea.ac.uk/aim/aim.php) to estimate aerosol phase water contents based on the AMS measured aerosol composition. The predicted water content has a good correlation with sulfate and OOA . We will further explore the correlations between particle phase water with organic aerosol characteristics to discuss the influence of aqueous phase processing on

  6. Molecular Characterization of Secondary Aerosol from Oxidation of Cyclic Methylsiloxanes

    NASA Astrophysics Data System (ADS)

    Wu, Yue; Johnston, Murray V.

    2016-03-01

    Cyclic volatile methylsiloxanes (cVMS) have been identified as important gas-phase atmospheric contaminants, but knowledge of the molecular composition of secondary aerosol derived from cVMS oxidation is incomplete. Here, the chemical composition of secondary aerosol produced from the OH-initiated oxidation of decamethylcyclopentasiloxane (D5, C10H30O5Si5) is characterized by high performance mass spectrometry. ESI-MS reveals a large number of monomeric (300 < m/z < 470) and dimeric (700 < m/z < 870) oxidation products. With the aid of high resolution and MS/MS, it is shown that oxidation leads mainly to the substitution of a CH3 group by OH or CH2OH, and that a single molecule can undergo many CH3 group substitutions. Dimers also exhibit OH and CH2OH substitutions and can be linked by O, CH2, and CH2CH2 groups. GC-MS confirms the ESI-MS results. Oxidation of D4 (C8H24O4Si4) exhibits similar substitutions and oligomerizations to D5, though the degree of oxidation is greater under the same conditions and there is direct evidence for the formation of peroxy groups (CH2OOH) in addition to OH and CH2OH.

  7. Molecular Characterization of Secondary Aerosol from Oxidation of Cyclic Methylsiloxanes.

    PubMed

    Wu, Yue; Johnston, Murray V

    2016-03-01

    Cyclic volatile methylsiloxanes (cVMS) have been identified as important gas-phase atmospheric contaminants, but knowledge of the molecular composition of secondary aerosol derived from cVMS oxidation is incomplete. Here, the chemical composition of secondary aerosol produced from the OH-initiated oxidation of decamethylcyclopentasiloxane (D5, C10H30O5Si5) is characterized by high performance mass spectrometry. ESI-MS reveals a large number of monomeric (300 < m/z < 470) and dimeric (700 < m/z < 870) oxidation products. With the aid of high resolution and MS/MS, it is shown that oxidation leads mainly to the substitution of a CH3 group by OH or CH2OH, and that a single molecule can undergo many CH3 group substitutions. Dimers also exhibit OH and CH2OH substitutions and can be linked by O, CH2, and CH2CH2 groups. GC-MS confirms the ESI-MS results. Oxidation of D4 (C8H24O4Si4) exhibits similar substitutions and oligomerizations to D5, though the degree of oxidation is greater under the same conditions and there is direct evidence for the formation of peroxy groups (CH2OOH) in addition to OH and CH2OH. PMID:26729452

  8. 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.

  9. Uranium oxide and sodium oxide aerosol experiments: NSPP mixed-oxide tests 303-307, data record report. [LMFBR

    SciTech Connect

    Adams, R.E.; Kress, T.S.; Tobias, M.L.

    1982-10-01

    This data record report summarizes five tests, involving mixtures of uranium oxide and sodium oxide aerosols, conducted in the Nuclear Safety Pilot Plant project at Oak Ridge National Laboratory. The goal of this project is to establish the validity (or level of conservatism) of the aerosol behavioral code, HAARM-3, and follow-on codes under development at Battelle Columbus Laboratories for the US Nuclear Regulatory Commission. Descriptions of the five tests with tables and graphs summarizing the results are included.

  10. Cloud condensation nuclei activity of aliphatic amine secondary aerosol

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g. hydroxyl radical and nitrate radical). The resulting particle composition can contain both secondary organic aerosol (SOA) and inorganic salts. The fraction of organic to inorganic materials in the particulate ...

  11. Uranium Oxide Aerosol Transport in Porous Graphite

    SciTech Connect

    Blanchard, Jeremy; Gerlach, David C.; Scheele, Randall D.; Stewart, Mark L.; Reid, Bruce D.; Gauglitz, Phillip A.; Bagaasen, Larry M.; Brown, Charles C.; Iovin, Cristian; Delegard, Calvin H.; Zelenyuk, Alla; Buck, Edgar C.; Riley, Brian J.; Burns, Carolyn A.

    2012-01-23

    The objective of this paper is to investigate the transport of uranium oxide particles that may be present in carbon dioxide (CO2) gas coolant, into the graphite blocks of gas-cooled, graphite moderated reactors. The transport of uranium oxide in the coolant system, and subsequent deposition of this material in the graphite, of such reactors is of interest because it has the potential to influence the application of the Graphite Isotope Ratio Method (GIRM). The GIRM is a technology that has been developed to validate the declared operation of graphite moderated reactors. GIRM exploits isotopic ratio changes that occur in the impurity elements present in the graphite to infer cumulative exposure and hence the reactor’s lifetime cumulative plutonium production. Reference Gesh, et. al., for a more complete discussion on the GIRM technology.

  12. Exposure assessment of oxidant gases and acidic aerosols

    SciTech Connect

    Lioy, P.J.

    1989-01-01

    Clearly the presence of high ozone and acidic species in North America is primarily dependent upon photochemical air pollution. Evidence shows, however, that high acid exposures may occur in specific types of areas of high sulfur fuel use during the winter. At the present time, our concerns about exposure to local populations and regional populations should be directed primarily toward the outdoor activity patterns of individuals in the summer, and how those activity patterns relate to the location, duration, and concentrations of ozone and acid aerosol in photochemical air pollution episodes. Lioy Dyba and Mage et al have examined the activity patterns of children in summer camps. Because they spend more time outside than the normal population, these children form an important group of exercising individuals subject to photochemical pollution exposures. The dose of ozone inhaled by the children in the two camps was within 50% and 25% of the dose inhaled by adults in controlled clinical situations that produced clinically significant decrements in pulmonary function and increased the symptoms after 6.6 hr exposure in a given day. The chamber studies have used only ozone, whereas in the environment this effect may be enhanced by the presence of a complex mixture. The work of Lioy et al in Mendham, New Jersey found that hydrogen ion seemed to play a role in the inability of the children to return immediately to their normal peak expiratory flow rate after exposure. The camp health study conducted in Dunsville, Ontario suggested that children participating in a summer camp where moderate levels of ozone (100 ppb) but high levels of acid (46 micrograms/m3) occurred during an episode had a similar response. Thus, for children or exercising adults who are outdoors for at least one hour or more during a given day, the presence and persistence of oxidants in the environment are of particular concern. 63 references.

  13. Aerosol-spray diverse mesoporous metal oxides from metal nitrates

    PubMed Central

    Kuai, Long; Wang, Junxin; Ming, Tian; Fang, Caihong; Sun, Zhenhua; Geng, Baoyou; Wang, Jianfang

    2015-01-01

    Transition metal oxides are widely used in solar cells, batteries, transistors, memories, transparent conductive electrodes, photocatalysts, gas sensors, supercapacitors, and smart windows. In many of these applications, large surface areas and pore volumes can enhance molecular adsorption, facilitate ion transfer, and increase interfacial areas; the formation of complex oxides (mixed, doped, multimetallic oxides and oxide-based hybrids) can alter electronic band structures, modify/enhance charge carrier concentrations/separation, and introduce desired functionalities. A general synthetic approach to diverse mesoporous metal oxides is therefore very attractive. Here we describe a powerful aerosol-spray method for synthesizing various mesoporous metal oxides from low-cost nitrate salts. During spray, thermal heating of precursor droplets drives solvent evaporation and induces surfactant-directed formation of mesostructures, nitrate decomposition and oxide cross-linking. Thirteen types of monometallic oxides and four groups of complex ones are successfully produced, with mesoporous iron oxide microspheres demonstrated for photocatalytic oxygen evolution and gas sensing with superior performances. PMID:25897988

  14. Aerosol-spray diverse mesoporous metal oxides from metal nitrates.

    PubMed

    Kuai, Long; Wang, Junxin; Ming, Tian; Fang, Caihong; Sun, Zhenhua; Geng, Baoyou; Wang, Jianfang

    2015-01-01

    Transition metal oxides are widely used in solar cells, batteries, transistors, memories, transparent conductive electrodes, photocatalysts, gas sensors, supercapacitors, and smart windows. In many of these applications, large surface areas and pore volumes can enhance molecular adsorption, facilitate ion transfer, and increase interfacial areas; the formation of complex oxides (mixed, doped, multimetallic oxides and oxide-based hybrids) can alter electronic band structures, modify/enhance charge carrier concentrations/separation, and introduce desired functionalities. A general synthetic approach to diverse mesoporous metal oxides is therefore very attractive. Here we describe a powerful aerosol-spray method for synthesizing various mesoporous metal oxides from low-cost nitrate salts. During spray, thermal heating of precursor droplets drives solvent evaporation and induces surfactant-directed formation of mesostructures, nitrate decomposition and oxide cross-linking. Thirteen types of monometallic oxides and four groups of complex ones are successfully produced, with mesoporous iron oxide microspheres demonstrated for photocatalytic oxygen evolution and gas sensing with superior performances. PMID:25897988

  15. Combined effects of organic aerosol loading and fog processing on organic aerosols oxidation and composition

    NASA Astrophysics Data System (ADS)

    Chakraborty, Abhishek; Tripathi, Sachchida; Gupta, Tarun

    2016-04-01

    Fog is a natural meteorological phenomenon that occurs throughout the world, it contains substantial quantity of liquid water and generally seen as a natural cleansing agent but it also has the potential to form highly oxidized secondary organic aerosols (SOA) via aqueous processing of ambient aerosols. On the other hand higher organic aerosols (OA) loading tend to decrease the overall oxidation level (O/C) of the particle phase organics, due to enhanced partitioning of less oxidized organics from gas to particle phase. However, combined impact of these two parameters; aqueous oxidation and OA loading, on the overall oxidation ratio (O/C) of ambient OA has never been studied. To assess this, real time ambient sampling using HR-ToF-AMS was carried out at Kanpur, India from 15 December 2014 - 10 February 2015. In first 3 weeks of this campaign, very high OA loading is (134 ± 42 μg/m3) observed (termed as high loading or HL period) while loading is substantially reduced from 2nd January, 2016 (56 ± 20 μg/m3, termed as low loading or LL period) . However, both the loading period was affected by several fog episodes (10 in HL and 7 in LL), thus providing the opportunity of studying the combined effects of fog and OA loading on OA oxidation. It is found that O/C ratio is very strongly anti-correlated with OA loading in both the loading period, however, slope of this ant-correlation is much steep during HL period than in LL period. Source apportionment of OA revealed that there is drastic change in the types of OA from HL to LL period, clearly indicating difference in OA composition from HL to LL period. During foggy night continuous oxidation of OA is observed from early evening to early morning with 15-20% enhancement in O/C ratio, while the same is absent during non-foggy period, clearly indicating the efficient fog processing of ambient OA. It is also found that night time fog aqueous oxidation can be as effective as daytime photo chemistry in oxidation of OA. Fog

  16. Limited Effect of Anthropogenic Nitrogen Oxides on Secondary Organic Aerosol Formation

    NASA Astrophysics Data System (ADS)

    Zheng, Y.; Unger, N.; Hodzic, A.; Knote, C. J.; Tilmes, S.; Emmons, L. K.; Lamarque, J. F.; Yu, P.

    2014-12-01

    Globally secondary organic aerosol (SOA) is mostly formed from biogenic vegetation emissions and as such is regarded as natural aerosol that cannot be reduced by emission control legislation. However, recent research implies that human activities facilitate SOA formation by affecting the amount of precursor emission, the chemical processing and the partitioning into the aerosol phase. Among the multiple human influences, nitrogen oxides (NO + NO2 = NOx) have been assumed to play a critical role in the chemical formation of low volatile compounds. The goal of this study is to improve the SOA scheme in the global NCAR Community Atmospheric Model version 4 with chemistry (CAM4-Chem) by implementing an updated 4-product Volatility Basis Set (VBS) scheme, and apply it to investigate the impact of anthropogenic NOx on SOA. We first compare three different SOA parameterizations: a 2-product model and the updated VBS model both with and without a SOA aging parameterization. Secondly we evaluate predicted organic aerosol amounts against surface measurement from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network and Aerosol Mass Spectrometer (AMS) measurements from 13 aircraft-based field campaigns. We then perform sensitivity experiments to examine how the SOA loading responds to a 50% reduction in anthropogenic NOx in different regions. We find limited SOA reductions of -2.3%, -5.6% and -4.0% for global, southeastern U.S. and Amazon NOx perturbations, respectively. To investigate the chemical processes in more detail, we also use a simplified box model with the same gas-phase chemistry and gas-aerosol partitioning mechanism as in CAM4-Chem to examine the SOA yields dependence on initial precursor emissions and background NOx level. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to buffering in chemical pathways (low- versus high-NOx pathways, OH versus NO3-initiated oxidation) and to offsetting

  17. Importance of relative humidity in the oxidative ageing of organic aerosols: case study of the ozonolysis of maleic acid aerosol

    NASA Astrophysics Data System (ADS)

    Gallimore, P. J.; Achakulwisut, P.; Pope, F. D.; Davies, J. F.; Spring, D. R.; Kalberer, M.

    2011-12-01

    Many important atmospheric aerosol processes depend on the chemical composition of the aerosol, e.g. water uptake and particle cloud interactions. Atmospheric ageing processes, such as oxidation reactions, significantly and continuously change the chemical composition of aerosol particles throughout their lifetime. These ageing processes are often poorly understood. In this study we utilize an aerosol flow tube set up and an ultra-high resolution mass spectrometer to explore the effect of relative humidity (RH) in the range of <5-90% on the ozonolysis of maleic acid aerosol which is employed as model organic aerosol system. Due to the slow reaction kinetics relatively high ozone concentrations of 160-200 ppm were used to achieve an appreciable degree of oxidation of maleic acid. The effect of oxidative ageing on the hygroscopicity of maleic acid particles is also investigated using an electrodynamic balance and thermodynamic modelling. RH has a profound effect on the oxidation of maleic acid particles. Very little oxidation is observed at RH < 50% and the only observed reaction products are glyoxylic acid and formic acid. In comparison, when RH > 50% there are about 15 oxidation products identified. This increased oxidation was observed even when the particles were exposed to high humidities long after a low RH ozonolysis reaction. This result might have negative implications for the use of water as an extraction solvent for the analysis of oxidized organic aerosols. These humidity-dependent differences in the composition of the ozonolyzed aerosol demonstrate that water is both a key reactant in the oxidation scheme and a determinant of particle phase and hence diffusivity. The measured chemical composition of the processed aerosol is used to model the hygroscopic growth, which compares favourably with water uptake results from the electrodynamic balance measurements. A reaction mechanism is presented which takes into account the RH dependent observations. This

  18. Stochastic methods for aerosol chemistry: a compact molecular description of functionalization and fragmentation in the heterogeneous oxidation of squalane aerosol by OH radicals.

    PubMed

    Wiegel, A A; Wilson, K R; Hinsberg, W D; Houle, F A

    2015-02-14

    The heterogeneous oxidation of organic aerosol by hydroxyl radicals (OH) can proceed through two general pathways: functionalization, in which oxygen functional groups are added to the carbon skeleton, and fragmentation, in which carbon-carbon bonds are broken, producing higher volatility, lower molecular weight products. An ongoing challenge is to develop a quantitative molecular description of these pathways that connects the oxidative evolution of the average aerosol properties (e.g. size and hygroscopicity) to the transformation of free radical intermediates. In order to investigate the underlying molecular mechanism of aerosol oxidation, a relatively compact kinetics model is developed for the heterogeneous oxidation of squalane particles by OH using free radical intermediates that convert reactive hydrogen sites into oxygen functional groups. Stochastic simulation techniques are used to compare calculated system properties over ten oxidation lifetimes with the same properties measured in experiment. The time-dependent average squalane aerosol mass, volume, density, carbon number distribution of scission products, and the average elemental composition are predicted using known rate coefficients. For functionalization, the calculations reveal that the distribution of alcohol and carbonyl groups is controlled primarily by the initial OH abstraction rate and to lesser extent by the branching ratio between secondary peroxy radical product channels. For fragmentation, the calculations reveal that the formation of activated alkoxy radicals with neighboring functional groups controls the molecular decomposition, particularly at high O/C ratios. This kinetic scheme provides a framework for understanding the oxidation chemistry of a model organic aerosol and informs parameterizations of more complex systems. PMID:25578323

  19. Water Activity Limits the Hygroscopic Growth Factor of Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Rodriguez, L. I.; Cabrera, J. A.; Golden, D.; Tabazadeh, A.

    2007-12-01

    In this work we study the hygroscopic behavior of organic aerosols, which has important implications for Earth's climate. The hygroscopic growth factor (HGF) is defined as the ratio of the diameter of a spherical particle when it is exposed to dry conditions to that at humid conditions. We present a new formulation to express the HGF of an aerosol particle as a function of water activity (aw) in the aqueous phase. This new formulation matches reported HGFs for common inorganic salts and water-miscible organic particles that are known to deliquesce into aqueous drops at high relative humidities (RH). Many studies use tandem differential mobility analyzers (TDMA) to determine the HGF of organic aerosols. For example, Brooks et al. used a TDMA to measure a HGF of 1.2 for 2 μm phthalic acid (PA) particles at 90% RH (aw= 0.9). However, water activity limits the growth of a particle that can be attributed to water uptake. We have assembled a vapor pressure apparatus to measure aw of aqueous solutions at room temperature. Measured water activities for PA, used in our growth formulation, yield a HGF of ~ 1.0005 for 2 μm PA particles at 90% RH. Comparing our results against Brooks et al. suggests that TDMA experiments may grossly overestimate the HGF of PA particles since water activity limits this growth to below 1.0005. Alternatively, we suggest that the adsorption of a negligible mass of water by a highly porous PA particle can lead to an apparent growth in particle size by changing its morphology. Other studies also use TDMAs to measure HGFs of secondary organic aerosols (SOAs). HGFs reported for SOAs are very similar to PA, suggesting that the observed growth may be due to morphological changes in particle size rather than water uptake as commonly assumed. We built a smog chamber where an organic precursor, such as d-limonene, reacts with nitrogen oxides under UV radiation to produce SOAs. We compare the HGFs for SOAs obtained with our method to those obtained with

  20. Formation of secondary organic aerosol from isoprene oxidation over Europe

    NASA Astrophysics Data System (ADS)

    Karl, M.; Tsigaridis, K.; Vignati, E.; Dentener, F.

    2009-01-01

    The role of isoprene as a precursor to secondary organic aerosol (SOA) over Europe is studied with the two-way nested global chemistry transport model TM5. The inclusion of the formation of SOA from isoprene oxidation in our model almost doubles the atmospheric burden of SOA over Europe compared to SOA formation from terpenes and aromatics. The reference simulation, which considers SOA formation from isoprene, terpenes and aromatics, predicts a yearly European production rate of 1.0 Tg SOA yr-1 and an annual averaged atmospheric burden of about 50 Gg SOA over Europe. A fraction of 35% of the SOA produced in the boundary layer over Europe is transported to higher altitudes or to other world regions. Summertime measurements of particulate organic matter (POM) during the extensive EMEP OC/EC campaign 2002/2003 are better reproduced when SOA formation from isoprene is taken into account, reflecting also the strong seasonality of isoprene and other biogenic volatile organic compounds (BVOC) emissions from vegetation. However, during winter, our model strongly underestimates POM, likely caused by missing wood burning in the emission inventories. Uncertainties in the parameterisation of isoprene SOA formation have been investigated. Maximum SOA production is found for irreversible sticking (non-equilibrium partitioning) of condensable vapours on particles, with tropospheric SOA production over Europe increased by a factor of 4 in summer compared to the reference case. Completely neglecting SOA formation from isoprene results in the lowest estimate (0.51 Tg SOA yr-1). The amount and the nature of the absorbing matter are shown to be another key uncertainty when predicting SOA levels. Tropospheric isoprene SOA production over Europe in summer more than doubles when, in addition to pre-existing carbonaceous aerosols, condensation of semi volatile vapours on ammonium and sulphate aerosols is considered. Consequently, smog chamber experiments on SOA formation should be

  1. A Computational Approach to Understanding Aerosol Formation and Oxidant Chemistry in the Troposphere

    SciTech Connect

    Francisco, Joseph S.; Kathmann, Shawn M.; Schenter, Gregory K.; Dang, Liem X.; Xantheas, Sotiris S.; Garrett, Bruce C.; Du, Shiyu; Dixon, David A.; Bianco, Roberto; Wang, Shuzhi; Hynes, James T.; Morita, Akihiro; Peterson, Kirk A.

    2006-04-18

    four times higher than expected from the commonly assumed primary sources. Such elevated abundances of HOx imply a more photochemically active troposphere than previously thought. This implies that rates of ozone formation in the lower region of the atmosphere and the oxidation of SO? can be enhanced, thus promoting the formation of new aerosol properties. Central to unraveling this chemistry is the ability to assess the photochemical product distributions resulting from the photodissociation of by-products of VOC oxidation. We propose to use state-of-the-art theoretical techniques to develop a detailed understanding of the mechanisms of aerosol formation in multicomponent (mixed chemical) systems and the photochemistry of atmospheric organic species. The aerosol studies involve an approach that determines homogeneous gas-particle nucleation rates from knowledge of the molecular interactions that are used to define properties of molecular clusters. Over the past several years we developed Dynamical Nucleation Theory (DNT), a novel advance in the theoretical description of homogeneous gas-liquid nucleation, and applied it to gas-liquid nucleation of a single component system (e.g., water). The goal of the present research is to build upon these advances by extending the theory to multicomponent systems important in the atmosphere (such as clusters containing sulfuric acid, water, ions, ammonia, and organics). In addition, high-level ab initio electronic structure calculations will be used to unravel the chemical reactivity of the OH radical and water clusters.

  2. Influence of Surface Seawater and Atmospheric Conditions on the Ccn Activity of Ocean-Derived Aerosol

    NASA Astrophysics Data System (ADS)

    Quinn, P.; Bates, T. S.; Russell, L. M.; Frossard, A. A.; Keene, W. C.; Kieber, D. J.; Hakala, J. P.

    2012-12-01

    Ocean-derived aerosols are produced from direct injection into the atmosphere (primary production) and gas-to-particle conversion in the atmosphere (secondary production). These different production mechanisms result in a broad range of particle sizes that has implications for the impact of ocean-derived aerosol on climate. The chemical composition of ocean-derived aerosols is a result of a complex mixture of inorganic sea salt and organic matter including polysaccharides, proteins, amino acids, microorganisms and their fragments, and secondary oxidation products. Both production mechanisms and biological processes in the surface ocean impact the ability of ocean-derived aerosol to act as cloud condensation nuclei (CCN). In addition, CCN activity can be impacted by atmospheric processing that modifies particle size and composition after the aerosol is emitted from the ocean. To understand relationships between production mechanism, surface ocean biology, and atmospheric processing, measurements were made of surface ocean chlorophyll and dissolved organic matter; nascent sea spray aerosol freshly emitted from the ocean surface; and ambient marine aerosol. These measurements were made along the coast of California and in the North Atlantic between the northeast US and Bermuda. These regions include both eutrophic and oligotraphic waters and, thus, provide for observations over a wide range of ocean conditions.

  3. Relationship between volatility, hygroscopicity, and CCN activity of winter aerosols: Kanpur, Indo-Gangetic Basin

    NASA Astrophysics Data System (ADS)

    Bhattu, Deepika; Tripathi, Sachchida

    2016-04-01

    Aerosol volatility is one of the key property in deciding their lifetime and fate. The volatile species have the potential to affect SOA estimation, so their characterization and establishment of relationship with mass loading, chemical composition, hygroscopicity and CCN activity is required. A 42 days long winter campaign was conducted in an anthropogenically polluted location (Kanpur, India) where CCN activity of both ambient and thermally treated aerosols was characterized. Enhanced partitioning of semi-volatile molecules into particle phase at higher loading conditions was observed. Unexpectedly, the most oxidized organic factor was observed both least volatile and hygroscopic in nature. Lower

  4. Active oxide nanophotonics

    NASA Astrophysics Data System (ADS)

    Dicken, Matthew J.

    Materials that can be manipulated electrically or mechanically to induce a change in their intrinsic properties are highly relevant when suitably integrated with current technologies. These "active" materials, such as oxide-based ferroelectrics or materials with easily accessible changes of phase, find extensive use as mechanical resonators, solid-state memories, and optical modulators. Barium titanate, a tetragonal ferroelectric at room temperature, is a prime example of a material both mechanically and optically active. This thesis deals primarily with the deposition of active, oxide-based materials and their integration into device structures where either the mechanical or optical properties are exploited. The technologically interesting paradigms within which these active oxide materials have been investigated are microelectromechanical systems, plasmonics, and metamaterials. Microelectromechanical systems are devices that have been micromachined and rely on an applied voltage to induce a mechanical response. Mechanically active materials, such as piezoelectrics or ferroelectrics, can increase the response of these devices. Plasmonics deals with electromagnetic waves resonantly coupled into free electron oscillations at a metal-dielectric interface or metal nanoparticle. Coupling to these resonant modes allows surface plasmon polaritons to propagate along the metal with a nonlinear dispersion. Metamaterials are ordered, subwavelength, metal inclusions in a dielectric, which respond collectively to electromagnetic radiation. This response can yield a material permittivity or permeability not found in nature. The optical properties of metamaterials lead to effects such as negative index response and super lensing, and can be used to design optical cloaking structures. Here, devices utilizing these effects are investigated with an eye toward tuning or switching their resonant response using optically active oxide thin films. This manuscript follows the evolution

  5. Parameterization of the Cloud Nucleating Activity of Fresh, Aged, and Internally-Mixed Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Kreidenweis, S.; Petters, M.; Demott, P.; Prenni, A.; Ziemann, P.

    2006-12-01

    Carbonaceous particle types affect global climate, visibility, and human health, but their primary and secondary sources, sinks, and tropospheric lifetimes are highly uncertain. The size and hygroscopicity of particles, and in particular their activity as cloud condensation nuclei (CCN), plays a large role in determining their atmospheric impacts and lifetimes. However, hygroscopicity is difficult to parameterize for many organic species for which no thermodynamic data exist, and for complex, multicomponent aerosols of undefined composition. We propose a simple method to describe the relationship between dry particle diameter and CCN activity using a single hygroscopicity parameter, κ. We derive values of κ from fitting of experimental CCN-activity data from the literature and from recent experiments, including oxidation-aged organic particles and secondary organic aerosols. Values of κ are between 0.5 and 2 for highly-CCN- active salts such as sodium chloride, between 0.01 and 0.5 for slightly to very hygroscopic organic aerosols such as those produced in biomass burning and as secondary organic aerosols, and 0 for nonhygroscopic components. The hygroscopicity of internal mixtures can be calculated as a volume fraction weighted average of the hygroscopicity parameters of the individual species comprising the mixture. Aging of aerosol, understood as changes in hygroscopicity due to condensation of hydrophilic species, coagulation of aerosol populations, or heterogeneous chemical reactions, are described conveniently by changes in κ. Our studies show that oxidative aging that proceeds by addition of functional groups to the CHx carbon backbone leads to only small changes in κ, and thus the process alone is inefficient at rendering small, initially- hydrophobic primary organic particles capable of being scavenged by cloud-drop nucleation. Other processes, such as coagulation and condensation, control the rate of hydrophobic-to-hydrophilic conversion of primary

  6. Models to support active sensing of biological aerosol clouds

    NASA Astrophysics Data System (ADS)

    Brown, Andrea M.; Kalter, Jeffrey M.; Corson, Elizabeth C.; Chaudhry, Zahra; Boggs, Nathan T.; Brown, David M.; Thomas, Michael E.; Carter, Christopher C.

    2013-05-01

    Elastic backscatter LIght Detection And Ranging (LIDAR) is a promising approach for stand-off detection of biological aerosol clouds. Comprehensive models that explain the scattering behavior from the aerosol cloud are needed to understand and predict the scattering signatures of biological aerosols under varying atmospheric conditions and against different aerosol backgrounds. Elastic signatures are dependent on many parameters of the aerosol cloud, with two major components being the size distribution and refractive index of the aerosols. The Johns Hopkins University Applied Physics Laboratory (JHU/APL) has been in a unique position to measure the size distributions of released biological simulant clouds using a wide assortment of aerosol characterization systems that are available on the commercial market. In conjunction with the size distribution measurements, JHU/APL has also been making a dedicated effort to properly measure the refractive indices of the released materials using a thin-film absorption technique and laboratory characterization of the released materials. Intimate knowledge of the size distributions and refractive indices of the biological aerosols provides JHU/APL with powerful tools to build elastic scattering models, with the purpose of understanding, and ultimately, predicting the active signatures of biological clouds.

  7. The ice nucleation activity of biological aerosols

    NASA Astrophysics Data System (ADS)

    Grothe, H.; Pummer, B.; Bauer, H.; Bernardi, J.

    2012-04-01

    Primary Biological Aerosol Particles (PBAPs), including bacteria, spores and pollen may be important for several atmospheric processes. Particularly, the ice nucleation caused by PBAPs is a topic of growing interest, since their impact on ice cloud formation and thus on radiative forcing, an important parameter in global climate is not yet fully understood. In laboratory model studies we investigated the ice nucleation activity of selected PBAPs. We studied the immersion mode freezing using water-oil emulsion, which we observed by optical microscopy. We particularly focused on pollen. We show that pollen of different species strongly differ in their ice nucleation behavior. The average freezing temperatures in laboratory experiments range from 240 K to 255 K. As the most efficient nuclei (silver birch, Scots pine and common juniper pollen) have a distribution area up to the Northern timberline, their ice nucleation activity might be a cryoprotective mechanism. For comparison the ice nucleation activity of Snomax, fungal spores, and mushrooms will be discussed as well. In the past, pollen have been rejected as important atmospheric IN, as they are not as abundant in the atmosphere as bacteria or mineral dust and are too heavy to reach higher altitudes. However, in our experiments (Pummer et al. 2011) it turned out that water, which had been in contact with pollen and then been separated from the bodies, nucleates as good as the pollen grains themselves. So the ice nuclei have to be easily-suspendable macromolecules (100-300 kDa) located on the pollen. Once extracted, they can be distributed further through the atmosphere than the heavy pollen grains and so augment the impact of pollen on ice cloud formation even in the upper troposphere. It is widely known, that material from the pollen, like allergens and sugars, can indeed leave the pollen body and be distributed independently. The most probable mechanism is the pollen grain bursting by rain, which releases

  8. Heterogeneous oxidation of saturated organic aerosols by hydroxyl radicals: uptake kinetics, condensed-phase products, and particle size change

    NASA Astrophysics Data System (ADS)

    George, I. J.; Vlasenko, A.; Slowik, J. G.; Broekhuizen, K.; Abbatt, J. P. D.

    2007-08-01

    The kinetics and reaction mechanism for the heterogeneous oxidation of saturated organic aerosols by gas-phase OH radicals were investigated under NOx-free conditions. The reaction of 150 nm diameter Bis(2-ethylhexyl) sebacate (BES) particles with OH was studied as a proxy for chemical aging of atmospheric aerosols containing saturated organic matter. An aerosol reactor flow tube combined with an Aerodyne time-of-flight aerosol mass spectrometer (ToF-AMS) and scanning mobility particle sizer (SMPS) was used to study this system. Hydroxyl radicals were produced by 254 nm photolysis of O3 in the presence of water vapour. The kinetics of the heterogeneous oxidation of the BES particles was studied by monitoring the loss of a mass fragment of BES with the ToF-AMS as a function of OH exposure. We measured an initial OH uptake coefficient of γ0=1.3 (±0.4), confirming that this reaction is highly efficient. The density of BES particles increased by up to 20% of the original BES particle density at the highest OH exposure studied, consistent with the particle becoming more oxidized. Electrospray ionization mass spectrometry analysis showed that the major particle-phase reaction products are multifunctional carbonyls and alcohols with higher molecular weights than the starting material. Volatilization of oxidation products accounted for a maximum of 17% decrease of the particle volume at the highest OH exposure studied. Tropospheric organic aerosols will become more oxidized from heterogeneous photochemical oxidation, which may affect not only their physical and chemical properties, but also their hygroscopicity and cloud nucleation activity.

  9. Alpha-Pinene Oxidation and Aerosols: Mechanism Development

    NASA Astrophysics Data System (ADS)

    Capouet, M.; Fantechi, G.; Vereecken, L.; Muller, J.; Peeters, J.

    2001-12-01

    Vegetation releases substantial amounts of reactive volatile organic compounds (VOCs), predominantly isoprene and the monoterpenes, to the atmosphere. The atmospheric chemistry of these VOCs has received particular attention because of the large quantities emitted globally in comparison to the anthropogenic releases on one hand, and because of their ability to form aerosols on the other hand. The reactions of (mono)terpenes with ozone and OH are known to be the two main competing daytime loss processes for these species in the atmosphere. It is established that some of their products can form secondary organic aerosols. Fairly recently, products of alpha- and beta-pinene which included pinonaldehyde, nopinone, pinonic acid and pinic acid have been detected in aerosol samples collected in the atmosphere and chamber experiments. The role played by (mono)terpenes in tropospheric chemistry cannot be assessed if (1) the gas-particle partitioning of their degradation products and (2) the gas-phase chemical pathways leading to the formation of condensable products are not determined. Gas-particle partitioning is expected to depend on temperature, organic aerosol mass, and the nature of the low-volatility molecule. The formation of condensables depends on various environmental conditions (NOx, radiation, ozone, etc.) which determine the nature of the major degradation products (e.g. nitrates, hydroperoxides, carbonyls). Whereas many laboratory studies providing insights on the product yields have been conducted, they are not sufficient to constrain a general model for product formation. In the present study, we present a comprehensive kinetic mechanism representing the gas-phase reactions and the gas-particle partitioning of the semivolatile products generated in the gaseous phase. A detailed degradation scheme for the degradation of alpha-pinene by reaction with O3 and with OH in the presence of NOx has been constructed on the basis of experimental data and structure-activity

  10. Formation of secondary organic aerosol from isoprene oxidation over Europe

    NASA Astrophysics Data System (ADS)

    Karl, M.; Tsigaridis, K.; Vignati, E.; Dentener, F.

    2009-09-01

    The role of isoprene as a precursor to secondary organic aerosol (SOA) over Europe is studied with the two-way nested global chemistry transport model TM5. The inclusion of the formation of SOA from isoprene oxidation in our model almost doubles the atmospheric burden of SOA over Europe compared to SOA formation from terpenes and aromatics. The reference simulation, which considers SOA formation from isoprene, terpenes and aromatics, predicts a yearly European production rate of 1.0 Tg SOA yr-1 and an annual averaged atmospheric burden of about 50 Gg SOA over Europe. A fraction of 35% of the SOA produced in the boundary layer over Europe is transported to higher altitudes or to other world regions. Summertime measurements of organic matter (OM) during the extensive EMEP OC/EC campaign 2002/2003 are better reproduced when SOA formation from isoprene is taken into account, reflecting also the strong seasonality of isoprene and other biogenic volatile organic compounds (BVOC) emissions from vegetation. However, during winter, our model strongly underestimates OM, likely caused by missing wood burning in the emission inventories. Uncertainties in the parameterisation of isoprene SOA formation have been investigated. Maximum SOA production is found for irreversible sticking (non-equilibrium partitioning) of condensable vapours on particles, with tropospheric SOA production over Europe increased by a factor of 4 in summer compared to the reference case. Completely neglecting SOA formation from isoprene results in the lowest estimate (0.51 Tg SOA yr-1). The amount and the nature of the absorbing matter are shown to be another key uncertainty when predicting SOA levels. Consequently, smog chamber experiments on SOA formation should be performed with different types of seed aerosols and without seed aerosols in order to derive an improved treatment of the absorption of SOA in the models. Consideration of a number of recent insights in isoprene SOA formation mechanisms

  11. Heterogeneous oxidation of pesticides on aerosol condensed phase

    NASA Astrophysics Data System (ADS)

    Socorro, Joanna; Durand, Amandine; Temime-Roussel, Brice; Ravier, Sylvain; Gligorovski, Sasho; Wortham, Henri; Quivet, Etienne

    2015-04-01

    Pesticides are widely used all over the world. It is known that they exhibit adverse health effects and environmental risks due to their physico-chemical properties and their extensive use which is growing every year. They are distributed in the atmosphere, an important vector of dissemination, over long distances away from the target area. The partitioning of pesticides between the gas and particulate phases influences their atmospheric fate. Most of the pesticides are semi-volatile compounds, emphasizing the importance of assessing their heterogeneous reactivity towards atmospheric oxidants. These reactions are important because they are involved in, among others, direct and indirect climate changes, adverse health effects from inhaled particles, effects on cloud chemistry and ozone production. In this work, the importance of atmospheric degradation of pesticides is evaluated on the surface of aerosol deliquescent particles. The photolysis processing and heterogeneous reactivity towards O3 and OH, was evaluated of eight commonly used pesticides (cyprodinil, deltamethrin, difenoconazole, fipronil, oxadiazon, pendimethalin, permethrin, tetraconazole) adsorbed on silica particles. Silicate particles are present in air-borne mineral dust in atmospheric aerosols, and heterogeneous reactions can be different in the presence of these mineral particles. Depending on their origin and conditioning, aerosol particles containing pesticides can have complex and highly porous microstructures, which are influenced by electric charge effects and interaction with water vapour. Therefore, the kinetic experiments and consecutive product studies were performed at atmospherically relevant relative humidity (RH) of 55 %. The identification of surface bound products was performed using GC-(QqQ)-MS/MS and LC-(Q-ToF)-MS/MS and the gas-phase products were on-line monitored by PTR-ToF-MS. Based on the detected and identified reaction products, it was observed that water plays a crucial

  12. Sodium oxide and uranium oxide aerosol experiments: NSPP Tests 106-108 and Tests 204-207, data record report

    SciTech Connect

    Adams, R.E.; Kress, T.S.; Tobias, M.L.

    1981-03-01

    This data record report describes three sodium oxide aerosol tests and four uranium oxide aerosol tests conducted in the Nuclear Safety Pilot Plant project at Oak Ridge National Laboratory. The goal of this project is to establish the validity (or level of conservatism) of the aerosol behavioral code, HAARM-3, and follow-on codes under development at the Battelle Columbus Laboratories for the US Nuclear Regulatory Commission. Descriptions of the seven tests with tables and graphs summarizing the results are included. 92 figs.

  13. Wintertime Secondary Organic Aerosol (SOA) Formation from Oxidation of Volatile Organic Compounds (VOCs) Associated with Oil and Gas Extraction

    NASA Astrophysics Data System (ADS)

    Murphy, S. M.; Soltis, J.; Field, R. A.; Bates, T. S.; Quinn, P.; De Gouw, J. A.; Veres, P. R.; Warneke, C.; Graus, M.; Gilman, J.; Lerner, B. M.; Koss, A.

    2013-12-01

    The Uintah Basin is located in a lightly populated area of Northeastern Utah near Dinosaur National Monument. Oil and gas extraction activities in the basin have dramatically increased in recent years due to the application of hydraulic fracturing. The Uintah Basin has experienced numerous high-ozone events during the past several winters with concentrations often exceeding 100 ppb. PM 2.5 monitoring by the city of Vernal, located at the edge of the basin, have shown wintertime concentrations in excess of the EPA 8-hour national standard, though the source and composition of particulates during these events is unclear. The Energy and Environment - Uintah Basin Winter Ozone Study (E&E UBWOS) was conducted during the winters of 2012 and 2013. During the study, intensive measurements of aerosol composition and speciated VOCs were made at a monitoring site near oil and gas extraction activities. Organic aerosol was found to be a major component of PM 2.5 and organic aerosol formation was highly correlated with the production of secondary VOC's. This correlation suggests that the organic aerosol is secondary in nature even though O:C ratios suggest a less oxidized aerosol than often observed in summertime SOA. The ozone levels and organic aerosol mass during 2012 were much lower than those observed in 2013. Calculations of the aerosol yield during both years will be presented along with an analysis of how well observed yields match predictions based on smog-chamber data. The potential for additional aerosol formation in the system will also be discussed.

  14. Limited effect of anthropogenic nitrogen oxides on secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

    2015-12-01

    Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but it can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR (National Center for Atmospheric Research) Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product volatility basis set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. Small differences are found for the no-aging VBS and 2-product schemes; large increases in SOA production and the SOA-to-OA ratio are found for the aging scheme. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of 2 compared to aerosol mass spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different regions and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9-5.6, 6.4-12.0 and 0.9-2.8 % for global, southeast US and Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to a limited shift in chemical regime, to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.

  15. Limited effect of anthropogenic nitrogen oxides on secondary organic aerosol formation

    DOE PAGESBeta

    Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

    2015-12-08

    Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but it can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR (National Center for Atmospheric Research) Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product volatility basis set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. Small differences are found for themore » no-aging VBS and 2-product schemes; large increases in SOA production and the SOA-to-OA ratio are found for the aging scheme. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of 2 compared to aerosol mass spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different regions and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9–5.6, 6.4–12.0 and 0.9–2.8 % for global, southeast US and Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to a limited shift in chemical regime, to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.« less

  16. Limited effect of anthropogenic nitrogen oxides on Secondary Organic Aerosol formation

    DOE PAGESBeta

    Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

    2015-08-28

    Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product Volatility Basis Set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. The predicted organic aerosol amounts capture both the magnitude and distribution ofmore » US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of two compared to Aerosol Mass Spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different region and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9 to 5.6, 6.4 to 12.0 and 0.9 to 2.8 % for global, the southeast US and the Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.« less

  17. Limited effect of anthropogenic nitrogen oxides on Secondary Organic Aerosol formation

    NASA Astrophysics Data System (ADS)

    Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

    2015-08-01

    Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product Volatility Basis Set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of two compared to Aerosol Mass Spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different region and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9 to 5.6, 6.4 to 12.0 and 0.9 to 2.8 % for global, the southeast US and the Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.

  18. Parameterization of the influence of organic surfactants on aerosol activation

    NASA Astrophysics Data System (ADS)

    Abdul-Razzak, Hayder; Ghan, Steven J.

    2004-02-01

    Surface-active organic compounds, or surfactants, can affect aerosol activation by two mechanisms: lowering surface tension and altering the bulk hygroscopicity of the particles. A numerical model has been developed to predict the activation of aerosol particles consisting of an internally uniform chemical mixture of organic surfactants and inorganic salts in a parcel of air rising adiabatically at constant speed. Equations reflecting water balance of the air parcel were used together with a modified form of Köhler theory to model droplet nucleation while considering surface effects. We also extend a parametric representation of aerosol activation to the case of a mixture of inorganic salts and organic surfactants by modifying the Raoult term in Köhler theory (assuming additive behavior) and using a simplified relationship between surface tension and surfactant molar concentration to account for surface effects at the critical radius for activation. The close agreement (to within 10% for most and 20% for almost all conditions) between numerical and parametric results validates our modifications. Moreover, the form of the relationship is identical to an empirical relationship between surface tension and organic carbon concentration. Thus the modified form of the parameterization provides a framework that can account for the influence of observed organics on the activation of other salts. The modified form of the parameterization is tested successfully with the Po Valley model both for single aerosol size distribution and three-mode size distributions for marine, rural, and urban aerosols. Further measurements are required to extend the parameterization to other organic surfactants.

  19. Products of BVOC oxidation: ozone and organic aerosols

    NASA Astrophysics Data System (ADS)

    Wildt, Jürgen; Andres, Stefanie; Carriero, Giulia; Ehn, Mikael; Fares, Silvano; Hoffmann, Thorsten; Hacker, Lina; Kiendler-Scharr, Astrid; Kleist, Einhard; Paoletti, Elena; Pullinen, Iida; Rohrer, Franz; Rudich, Yinon; Springer, Monika; Tillmann, Ralf; Wahner, Andreas; Wu, Cheng; Mentel, Thomas

    2015-04-01

    Biogenic Volatile Organic Compounds (BVOC) are important precursors in photochemical O3 and secondary organic aerosol (SOA) formation. We conducted a series of laboratory experiments with OH-induced oxidation of monoterpenes to elucidate pathways and efficiencies of O3 and SOA formation. At high NOx conditions ([BVOC] / [NOx] < 7 ppbC / ppb) photochemical ozone formation was observed. For -pinene as individual BVOC as well as for the monoterpene mixes emitted from different plant species we observed increasing ozone formation with increasing [NOX]. Between 2 and 3 O3-molecules were formed from 1 monoterpene when ozone formation was BVOC limited. Under such high NOX conditions, new particle formation was suppressed. Increasing [BVOC] / [NOX] ratios caused increasing efficiency of new particle formation indicating that peroxy radicals are the key intermediates in both, photochemical ozone- and new particle formation. The classical chemistry of peroxy radicals is well established (e.g. Master Chemical Mechanism). Peroxy radicals are produced by addition of molecular oxygen to the alkyl radical formed after OH attack at the BVOC. They either react with NO which leads to ozone formation or they react with other peroxy radicals and form chemically stable products (hydroperoxides, alkoholes and ketones). Much less knowledge exists on such reactions for Highly Oxidized Peroxy Radicals, (HOPR). Such HOPR were observed during ozonolysis of several volatiles and, in case of monoterpenes as precursors, they can contain more than 12 Oxygen atoms (Mentel et al., 2015). Although the OH-initiated formation of HOPR is yet not fully understood, their basic gas phase reactions seem to follow classical photochemical rules. In reactions with NO they can act as precursor for O3 and in reactions with other HOPR or with classical less oxidized peroxy radicals they can form highly oxidized stable products and alkoxy radicals. In addition, HOPR-HOPR reactions lead to the formation of

  20. Surface-active and Light-absorbing Secondary Organic Aerosol (SOA) Material

    NASA Astrophysics Data System (ADS)

    McNeill, V. F.; Sareen, N.; Schwier, A. N.; Shapiro, E. L.

    2009-12-01

    We have observed the formation of light-absorbing, high-molecular-weight, and surface-active organics from methylgyloxal interacting with ammonium salts in aqueous aerosol mimics. Mixtures of methylglyoxal and glyoxal also form light-absorbing products and exhibit surface tension depression with a Langmuir-like dependence on initial methylglyoxal concentration. We used chemical ionization mass spectrometry with a volatilization flow tube inlet (Aerosol-CIMS) to characterize the product species. The results are consistent with aldol condensation products, carbon-nitrogen species, sulfur-containing compounds, and oligomeric species up to 759 amu. These observations have potentially significant implications for our understanding of the effects of SOA on climate, since a) SOA are typically treated as non-absorbing in climate models, and b) surface tension depression in aqueous aerosols by SOA material may result in increased cloud condensation nucleus (CCN) activity. Furthermore, surface film formation could affect aerosol heterogeneous chemistry. We will also discuss aerosol flow tube O3 oxidation experiments designed to determine the atmospheric lifetimes of the observed product compounds.

  1. Late-occurring pulmonary pathologies following inhalation of mixed oxide (uranium + plutonium oxide) aerosol in the rat.

    PubMed

    Griffiths, N M; Van der Meeren, A; Fritsch, P; Abram, M-C; Bernaudin, J-F; Poncy, J L

    2010-09-01

    Accidental exposure by inhalation to alpha-emitting particles from mixed oxide (MOX: uranium and plutonium oxide) fuels is a potential long-term health risk to workers in nuclear fuel fabrication plants. For MOX fuels, the risk of lung cancer development may be different from that assigned to individual components (plutonium, uranium) given different physico-chemical characteristics. The objective of this study was to investigate late effects in rat lungs following inhalation of MOX aerosols of similar particle size containing 2.5 or 7.1% plutonium. Conscious rats were exposed to MOX aerosols and kept for their entire lifespan. Different initial lung burdens (ILBs) were obtained using different amounts of MOX. Lung total alpha activity was determined by external counting and at autopsy for total lung dose calculation. Fixed lung tissue was used for anatomopathological, autoradiographical, and immunohistochemical analyses. Inhalation of MOX at ILBs ranging from 1-20 kBq resulted in lung pathologies (90% of rats) including fibrosis (70%) and malignant lung tumors (45%). High ILBs (4-20 kBq) resulted in reduced survival time (N = 102; p < 0.05) frequently associated with lung fibrosis. Malignant tumor incidence increased linearly with dose (up to 60 Gy) with a risk of 1-1.6% Gy for MOX, similar to results for industrial plutonium oxide alone (1.9% Gy). Staining with antibodies against Surfactant Protein-C, Thyroid Transcription Factor-1, or Oct-4 showed differential labeling of tumor types. In conclusion, late effects following MOX inhalation result in similar risk for development of lung tumors as compared with industrial plutonium oxide. PMID:20699696

  2. Atmospheric oxidation of isoprene and 1,3-butadiene: influence of aerosol acidity and relative humidity on secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Lewandowski, M.; Jaoui, M.; Offenberg, J. H.; Krug, J. D.; Kleindienst, T. E.

    2015-04-01

    The effects of acidic seed aerosols on the formation of secondary organic aerosol (SOA) have been examined in a number of previous studies, several of which have observed strong linear correlations between the aerosol acidity (measured as nmol H+ m-3 air sample volume) and the percent change in secondary organic carbon (SOC). The measurements have used several precursor compounds representative of different classes of biogenic hydrocarbons including isoprene, monoterpenes, and sesquiterpenes. To date, isoprene has displayed the most pronounced increase in SOC, although few measurements have been conducted with anthropogenic hydrocarbons. In the present study, we examine several aspects of the effect of aerosol acidity on the secondary organic carbon formation from the photooxidation of 1,3-butadiene, and extend the previous analysis of isoprene. The photooxidation products measured in the absence and presence of acidic sulfate aerosols were generated either through photochemical oxidation of SO2 or by nebulizing mixtures of ammonium sulfate and sulfuric acid into a 14.5 m3 smog chamber system. The results showed that, like isoprene and β-caryophyllene, 1,3-butadiene SOC yields linearly correlate with increasing acidic sulfate aerosol. The observed acid sensitivity of 0.11% SOC increase per nmol m-3 increase in H+ was approximately a factor of 3 less than that measured for isoprene. The results also showed that the aerosol yield decreased with increasing humidity for both isoprene and 1,3-butadiene, although to different degrees. Increasing the absolute humidity from 2 to 12 g m-3 reduced the 1,3-butadiene yield by 45% and the isoprene yield by 85%.

  3. 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.

  4. Reconciling Organic Aerosol Volatility, Hygroscopicity, and Oxidation State During the Colorado DISCOVER-AQ Deployment

    NASA Astrophysics Data System (ADS)

    Hite, J. R.; Moore, R.; Martin, R.; Thornhill, K. L., II; Winstead, E.; Anderson, B. E.; Nenes, A.

    2014-12-01

    The organic fraction of submicron aerosol can profoundly impact radiative forcing on climate directly, through enhancement of extinction, or indirectly through modulation of cloud formation. Semi-volatile constituents of organic ambient aerosol are of particular interest as their partitioning between the vapor and aerosol phases is not well constrained by current atmospheric models and appears to play an important role in the formation of cloud condensation nuclei (CCN) as suggested by recent research. An experimental setup consisting of a DMT CCN counter and SMPS downstream of a custom-built thermodenuder assembly was deployed during the summer 2014 DISCOVER-AQ field campaign to retrieve simultaneous, size-resolved volatility and hygroscopicity - through the use of scanning mobility CCN analysis (SMCA). Housed in the NASA Langley mobile laboratory, a suite of complimentary measurements were made available onboard including submicron aerosol composition and oxidation state provided by an HR-ToF-AMS, and aerosol optical properties provided by a range of other instruments including an SP2. Air masses sampled from locations across the Central Colorado region include influences from regional aerosol nucleation/growth events, long-range transport of Canadian biomass burning aerosols, cattle feedlot emissions and influences of the Denver urban plume - amidst a backdrop of widespread oil and gas exploration. The analysis focuses on the reconciliation of the retrieved aerosol volatility distributions and corresponding hygroscopicity and oxidation state observations, including the use of AMS factor analysis.

  5. On the effectiveness of nitrogen oxide reductions as a control over ammonium nitrate aerosol

    NASA Astrophysics Data System (ADS)

    Pusede, S. E.; Duffey, K. C.; Shusterman, A. A.; Saleh, A.; Laughner, J. L.; Wooldridge, P. J.; Zhang, Q.; Parworth, C. L.; Kim, H.; Capps, S. L.; Valin, L. C.; Cappa, C. D.; Fried, A.; Walega, J.; Nowak, J. B.; Hoff, R. M.; Berkoff, T. A.; Beyersdorf, A. J.; Olson, J.; Crawford, J. H.; Cohen, R. C.

    2015-10-01

    Nitrogen oxides (NOx) have fallen steadily across the US over the last fifteen years. At the same time, due to patterns diesel truck activities, NOx concentrations decrease on weekends relative to weekdays, largely without co-occurring changes in other gas-phase emissions. These trends taken together provide two independent constraints on the role of NOx in the nonlinear chemistry of atmospheric oxidation. In this context, we interpret interannual trends in wintertime ammonium nitrate (NH4NO3) in the San Joaquin Valley of California, a location with the worst aerosol pollution in the US and where a large portion of aerosol mass is NH4NO3. Here, we show that NOx reductions have simultaneously decreased nighttime and increased daytime NH4NO3 production over the last decade. We find a substantial decrease in NH4NO3 since 2000 and conclude that this decrease is due to reduced nitrate radical-initiated production at night in residual layers that are decoupled from fresh emissions at the surface. Further reductions in NOx are imminent in California, and nationwide, and we make a quantitative prediction of the response of NH4NO3. We show that the combination of rapid chemical production and efficient NH4NO3 loss via deposition of gas-phase nitric acid implies high aerosol days in cities in the San Joaquin Valley air basin are responsive to local changes in NOx within those individual cities. Our calculations indicate that large decreases in NOx in the future will not only lower wintertime NH4NO3 concentrations, they will also cause a transition in the dominant NH4NO3 source from nighttime to daytime chemistry.

  6. On the effectiveness of nitrogen oxide reductions as a control over ammonium nitrate aerosol

    NASA Astrophysics Data System (ADS)

    Pusede, S. E.; Duffey, K. C.; Shusterman, A. A.; Saleh, A.; Laughner, J. L.; Wooldridge, P. J.; Zhang, Q.; Parworth, C. L.; Kim, H.; Capps, S. L.; Valin, L. C.; Cappa, C. D.; Fried, A.; Walega, J.; Nowak, J. B.; Weinheimer, A. J.; Hoff, R. M.; Berkoff, T. A.; Beyersdorf, A. J.; Olson, J.; Crawford, J. H.; Cohen, R. C.

    2016-03-01

    Nitrogen oxides (NOx) have fallen steadily across the US over the last 15 years. At the same time, NOx concentrations decrease on weekends relative to weekdays, largely without co-occurring changes in other gas-phase emissions, due to patterns of diesel truck activities. These trends taken together provide two independent constraints on the role of NOx in the nonlinear chemistry of atmospheric oxidation. In this context, we interpret interannual trends in wintertime ammonium nitrate (NH4NO3) in the San Joaquin Valley of California, a location with the worst aerosol pollution in the US and where a large portion of aerosol mass is NH4NO3. Here, we show that NOx reductions have simultaneously decreased nighttime and increased daytime NH4NO3 production over the last decade. We find a substantial decrease in NH4NO3 since 2000 and conclude that this decrease is due to reduced nitrate radical-initiated production at night in residual layers that are decoupled from fresh emissions at the surface. Further reductions in NOx are imminent in California, and nationwide, and we make a quantitative prediction of the response of NH4NO3. We show that the combination of rapid chemical production and efficient NH4NO3 loss via deposition of gas-phase nitric acid implies that high aerosol days in cities in the San Joaquin Valley air basin are responsive to local changes in NOx within those individual cities. Our calculations indicate that large decreases in NOx in the future will not only lower wintertime NH4NO3 concentrations but also cause a transition in the dominant NH4NO3 source from nighttime to daytime chemistry.

  7. Lightning activity and aerosols in the Mediterranean region

    NASA Astrophysics Data System (ADS)

    Proestakis, E.; Kazadzis, S.; Lagouvardos, K.; Kotroni, V.; Kazantzidis, A.

    2016-03-01

    In the framework of this study, the effect of aerosols on lightning activity has been investigated for the first time over the broader Mediterranean Sea. Atmospheric optical depth data retrieved by MODIS on board Aqua satellite and cloud to ground lightning activity data provided by ZEUS network operated by the National Observatory of Athens were analyzed for a time period spanning from 01/01/2005 up to 31/12/2013. The results indicate the importance of aerosols in lightning modulation. The mean aerosol optical depth (AOD) values of the days with lightning activity were found to be higher than the mean seasonal AOD in 90% of the under study domain. Furthermore, the increasing rate of lightning activity with increasing aerosol loading was found to be more pronounced during summertime and for AOD values up to 0.4. Additionally, the spatial analysis showed that the percentage of days with lightning activity during summertime is increasing with increasing AOD. Finally, time series showed similar temporal behavior between AOD seasonal anomalies and days with lightning activity differences. Both the spatial and temporal analysis showed that lightning activity is correlated to AOD, a characteristic consistent for all seasons.

  8. CCN activation of fumed silica aerosols mixed with soluble pollutants

    NASA Astrophysics Data System (ADS)

    Dalirian, M.; Keskinen, H.; Ahlm, L.; Ylisirniö, A.; Romakkaniemi, S.; Laaksonen, A.; Virtanen, A.; Riipinen, I.

    2014-09-01

    Particle-water interactions of completely soluble or insoluble particles are fairly well understood but less is known of aerosols consisting of mixtures of soluble and insoluble components. In this study, laboratory measurements were performed to investigate cloud condensation nuclei (CCN) activity of silica particles coated with ammonium sulphate (a salt), sucrose (a sugar) and bovine serum albumin known as BSA (a protein). In addition, the agglomerated structure of the silica particles was investigated by estimating the surface equivalent diameter based on measurements with a Differential Mobility Analyzer (DMA) and an Aerosol Particle Mass Analyzer (APM). By using the surface equivalent diameter the non-sphericity of the particles containing silica was accounted for when estimating CCN activation. Furthermore, characterizing critical supersaturations of particles consisting of pure soluble on insoluble compounds using existing frameworks showed that the CCN activation of single component particles was in good agreement with Köhler and adsorption theory based models when the agglomerated structure was accounted for. For mixed particles the CCN activation was governed by the soluble components, and the soluble fraction varied considerably with particle size for our wet-generated aerosols. Our results confirm the hypothesis that knowing the soluble fraction is the key parameter needed for describing the CCN activation of mixed aerosols, and highlight the importance of controlled coating techniques for acquiring a detailed understanding of the CCN activation of atmospheric insoluble particles mixed with soluble pollutants.

  9. CCN activation of fumed silica aerosols mixed with soluble pollutants

    NASA Astrophysics Data System (ADS)

    Dalirian, M.; Keskinen, H.; Ahlm, L.; Ylisirniö, A.; Romakkaniemi, S.; Laaksonen, A.; Virtanen, A.; Riipinen, I.

    2015-04-01

    Particle-water interactions of completely soluble or insoluble particles are fairly well understood but less is known of aerosols consisting of mixtures of soluble and insoluble components. In this study, laboratory measurements were performed to investigate cloud condensation nuclei (CCN) activity of silica particles mixed with ammonium sulfate (a salt), sucrose (a sugar) and bovine serum albumin known as BSA (a protein). The agglomerated structure of the silica particles was investigated using measurements with a differential mobility analyser (DMA) and an aerosol particle mass analyser (APM). Based on these data, the particles were assumed to be compact agglomerates when studying their CCN activation capabilities. Furthermore, the critical supersaturations of particles consisting of pure and mixed soluble and insoluble compounds were explored using existing theoretical frameworks. These results showed that the CCN activation of single-component particles was in good agreement with Köhler- and adsorption theory based models when the agglomerated structure was accounted for. For mixed particles the CCN activation was governed by the soluble components, and the soluble fraction varied considerably with particle size for our wet-generated aerosols. Our results confirm the hypothesis that knowing the soluble fraction is the key parameter needed for describing the CCN activation of mixed aerosols, and highlight the importance of controlled coating techniques for acquiring a detailed understanding of the CCN activation of atmospheric insoluble particles mixed with soluble pollutants.

  10. Calculating Capstone depleted uranium aerosol concentrations from beta activity measurements.

    PubMed

    Szrom, Frances; Falo, Gerald A; Parkhurst, Mary Ann; Whicker, Jeffrey J; Alberth, David P

    2009-03-01

    Beta activity measurements were used as surrogate measurements of uranium mass in aerosol samples collected during the field testing phase of the Capstone Depleted Uranium (DU) Aerosol Study. These aerosol samples generated by the perforation of armored combat vehicles were used to characterize the DU source term for the subsequent Human Health Risk Assessment (HHRA) of Capstone aerosols. Establishing a calibration curve between beta activity measurements and uranium mass measurements is straightforward if the uranium isotopes are in equilibrium with their immediate short-lived, beta-emitting progeny. For DU samples collected during the Capstone study, it was determined that the equilibrium between the uranium isotopes and their immediate short-lived, beta-emitting progeny had been disrupted when penetrators had perforated target vehicles. Adjustments were made to account for the disrupted equilibrium and for wall losses in the aerosol samplers. Values for the equilibrium fraction ranged from 0.16 to 1, and the wall loss correction factors ranged from 1 to 1.92. This paper describes the process used and adjustments necessary to calculate uranium mass from proportional counting measurements. PMID:19204483

  11. Calculating Capstone Depleted Uranium Aerosol Concentrations from Beta Activity Measurements

    SciTech Connect

    Szrom, Fran; Falo, Gerald A.; Parkhurst, MaryAnn; Whicker, Jeffrey J.; Alberth, David P.

    2009-03-01

    Beta activity measurements were used as surrogate measurements of uranium mass in aerosol samples collected during the field testing phase of the Capstone Depleted Uranium (DU) Aerosol Study. These aerosol samples generated by the perforation of armored combat vehicles were used to characterize the depleted uranium (DU) source term for the subsequent human health risk assessment (HHRA) of Capstone aerosols. Establishing a calibration curve between beta activity measurements and uranium mass measurements is straightforward if the uranium isotopes are in equilibrium with their immediate short-lived, beta-emitting progeny. For DU samples collected during the Capstone study, it was determined that the equilibrium between the uranium isotopes and their immediate short lived, beta-emitting progeny had been disrupted when penetrators had perforated target vehicles. Adjustments were made to account for the disrupted equilibrium and for wall losses in the aerosol samplers. Correction factors for the disrupted equilibrium ranged from 0.16 to 1, and the wall loss correction factors ranged from 1 to 1.92.

  12. Toward new techniques to measure heterogeneous oxidation of aerosol: Electrodynamic Balance-Mass Spectrometry (EDB-MS) and Aerosol X-ray Photoelectron Spectroscopy

    NASA Astrophysics Data System (ADS)

    Jacobs, M. I.; Heine, N.; Xu, B.; Davies, J. F.; Kirk, B. B.; Kostko, O.; Alayoglu, S.; Wilson, K. R.; Ahmed, M.

    2015-12-01

    The chemical composition and physical properties of aerosol can be changed via heterogeneous oxidation with the OH radical. However, the physical state of the aerosol influences the kinetics of this reaction; liquid particles with a high diffusion coefficient are expected to be well mixed and homogenously oxidized, while oxidation of solid, diffusion-limited aerosol is expected to occur primarily on the surface, creating steep chemical gradients within the particle. We are working to develop several new techniques to study the heterogeneous oxidation of different types of aerosol. We are developing a "modular" electrodynamic balance (EDB) that will enable us to study heterogeneous oxidation at aqueous interfaces using a mass-spectrometer (and potentially other detection techniques). Using a direct analysis in real time (DART) interface, preliminary droplet train measurements have demonstrated single-droplet mass spectrometry to be possible. With long reaction times in our EDB, we will be able to study heterogeneous oxidation of a wide variety of organic species in aqueous droplets. Additionally, we are working to use aerosol photoemission and velocity map imaging (VMI) to study the surface of aerosol particles as they undergo heterogeneous oxidation. With VMI, we're able to collect electrons with a 4π collection efficiency over conventional electron energy analyzers. Preliminary results looking at the ozonolysis of squalene using ultraviolet photoelectron spectroscopy (UPS) show that heterogeneous oxidation kinetic data can be extracted from photoelectron spectra. By moving to X-ray photoemission spectroscopy (XPS), we will determine elemental and chemical composition of the aerosol surface. Thus, aerosol XPS will provide information on the steep chemical gradients that form as diffusion-limited aerosol undergo heterogeneous oxidation.

  13. Influence of crustal dust and sea spray supermicron particle concentrations and acidity on inorganic NO3- aerosol during the 2013 Southern Oxidant and Aerosol Study

    SciTech Connect

    Allen, Hannah M.; Draper, Danielle C.; Ayres, Benjamin R.; Ault, Andrew P.; Bondy, Amy L.; Takahama, S.; Modini, Robert; Baumann, K.; Edgerton, Eric S.; Knote, Christoph; Laskin, Alexander; Wang, Bingbing; Fry, Juliane L.

    2015-09-25

    The inorganic aerosol composition was measured in the southeastern United States, a region that exhibits high aerosol mass loading during the summer, as part of the 1 June to 15 July 2013 Southern Oxidant and Aerosol Study (SOAS) campaign. Measurements using a Monitor for AeRosols and GAses (MARGA), an ion chromatograph coupled with a wet rotating denuder and a steam-jet aerosol collector for monitoring of ambient inorganic gas and aerosol species, revealed two periods of high aerosol nitrate (NO3 ) concentrations during the campaign. These periods of high nitrate were correlated with increased concentrations of coarse mode mineral or sea spray aerosol species, particularly Na+ and Ca2+, and with a shift towards aerosol with larger (1 to 2.5 um) diameters. We suggest this nitrate aerosol forms by multiphase reactions of HNO3 and particles, reactions that are facilitated by transport of mineral dust and sea spray aerosol from a source within the United States. The observed high aerosol acidity prevents the formation of NH4NO3, the inorganic nitrogen species often dominant in fine-mode aerosol at higher pH. Calculation of the rate of the heterogeneous uptake of HNO3 on mineral aerosol supports the conclusion that aerosol NO3 is produced primarily by this process, and is likely limited by the availability of mineral dust surface area. Modeling of NO3 and HNO3 by thermodynamic equilibrium models (ISORROPIA II and E-AIM) reveals the importance of including mineral cations in the southeastern United States to accurately balance ion species and predict gas/aerosol phase partitioning.

  14. Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products.

    PubMed

    Aljawhary, Dana; Zhao, Ran; Lee, Alex K Y; Wang, Chen; Abbatt, Jonathan P D

    2016-03-10

    Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (±0.5) × 10(9) and 3.1 (±0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation. PMID:26299576

  15. Quantifying the Relationship between Organic Aerosol Composition and Hygroscopicity/CCN Activity

    SciTech Connect

    Ziemann, Paul J.; Kreidenweis, Sonia M.; Petters, Markus D.

    2013-06-30

    The overall objective for this project was to provide the data and underlying process level understanding necessary to facilitate the dynamic treatment of organic aerosol CCN activity in future climate models. The specific objectives were as follows: (1) employ novel approaches to link organic aerosol composition and CCN activity, (2) evaluate the effects of temperature and relative humidity on organic aerosol CCN activity, and (3) develop parameterizations to link organic aerosol composition and CCN activity.

  16. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

    SciTech Connect

    Massachusetts Institute of Technology; Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.; Kessler, Sean H.; Canagaratna, Manjula R.; Wilson, Kevin R.; Altieri, Katye E.; Mazzoleni, Lynn R.; Wozniak, Andrew S.; Bluhm, Hendrik; Mysak, Erin R.; Smith, Jared D.; Kolb, Charles E.; Worsnop, Douglas R.

    2010-11-05

    A detailed understanding of the sources, transformations, and fates of organic species in the environment is crucial because of the central roles that organics play in human health, biogeochemical cycles, and Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of OSC , using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number (nC).

  17. Heterogeneous oxidation of atmospheric aerosol particles by gas-phase radicals

    NASA Astrophysics Data System (ADS)

    George, I. J.; Abbatt, J. P. D.

    2010-09-01

    Atmospheric aerosol particles play pivotal roles in climate and air quality. Just as chemically reduced gases experience oxidation in the atmosphere, it is now apparent that solid and liquid atmospheric particulates are also subject to similar oxidative processes. The most reactive atmospheric gas-phase radicals, in particular the hydroxyl radical, readily promote such chemistry through surficial interactions. This Review looks at progress made in this field, discussing the radical-initiated heterogeneous oxidation of organic and inorganic constituents of atmospheric aerosols. We focus on the kinetics and reaction mechanisms of such processes as well as how they can affect the physico-chemical properties of particles, such as their composition, size, density and hygroscopicity. Potential impacts on the atmosphere include the release of chemically reactive gases such as halogens, aldehydes and organic acids, reactive loss of particle-borne molecular tracer and toxic species, and enhanced hygroscopic properties of aerosols that may improve their ability to form cloud droplets.

  18. Antiviral activity of oxidized polyamines.

    PubMed

    Bachrach, U

    2007-08-01

    Polyamines, oxidized by serum amine oxidase, yield aminoaldehydes and hydrogen peroxide. Acrolein may be formed from the aminoaldehydes by a spontaneous beta-elimination process. These oxidation products "oxidized polyamines" inhibit bacterial growth and exhibit anticancer activity. The antimicrobial activity of oxidized polyamines is not limited to bacteria; and the inactivation of bacterial viruses, plant viruses and animal viruses, was also reported. Bacteriophages of the T-odd series are permeable and were inactivated by oxidized polyamines. The inactive phages absorb to their bacterial host and injected their DNA, which formed a stable inactive complex with the aminoaldehydes. Aminoaldehydes, synthesized chemically, also inactivated viruses. The growth of the plant viruses: Tobacco mosaic virus, Potato virus X and Alfalfa mosaic virus was also inhibited by oxidized polyamines. The animal viruses, which were inactivated by oxidized polyamines included Myxoviruses (influenza and Newcastle disease viruses), West Nile, vaccinia and Sindbis viruses. These findings may have practical implications. PMID:17429570

  19. CCN Activity, Hygroscopicity, and Droplet Activation Kinetics of Secondary Organic Aerosol Resulting from the 2010 Gulf Oil Spill

    NASA Astrophysics Data System (ADS)

    Moore, R.; Lathem, T. L.; Cerully, K.; Bahreini, R.; Brock, C. A.; Langridge, J. M.; Middlebrook, A. M.; Nenes, A.; Calnex Science Team

    2010-12-01

    We present an analysis of the hygroscopicity and droplet activation kinetics of cloud condensation nuclei (CCN) sampled onboard the National Oceanic and Atmospheric Administration WP-3D aircraft downwind of the Deepwater Horizon oil spill site on June 8th and 10th, 2010. This set of measurements provides a unique case study for assessing in-situ the impact of fresh, hydrocarbonlike aerosols, which are expected to be formed via gas-to-particle conversion of the semi-volatile vapors released from oil evaporation. Similar hydrocarbon-rich aerosols constitute an important local emissions source in urban areas, but often coexist as an external/partially-internal mixture with more-oxidized, aged organic and sulfate aerosol. The DWH site provides the means to study the hygroscopic properties of these less-oxidized organic aerosols above a cleaner environmental background typical of marine environments in order to better discern their contribution to CCN activity and droplet growth. Measurements were performed with a Droplet Measurement Technologies Streamwise, Thermal-Gradient CCN counter, operating both as a counter (s=0.3%) and as a spectrometer (s=0.2-0.6%) using the newly-developed Scanning Flow CCN Analysis (SFCA) technique [1]. The instrument measures both the number concentration of particles able to nucleate droplets and also their resulting droplet sizes. The measured size information combined with a comprehensive computational fluid dynamics instrument model enables us to determine the rate of water uptake onto the particles and parameterize it in terms of an effective mass transfer coefficient [2], a key parameter needed to predict the number of activated droplets in ambient clouds. Non-refractory aerosol chemical composition was measured with an Aerodyne compact time-of-flight aerosol mass spectrometer. It was observed that the aerosols sampled downwind of the site on both days were composed predominantly of organics with a low degree of oxidation and low

  20. Hygroscopic properties of aerosol formed by oxidation of limonene, α-pinene, and β-pinene

    NASA Astrophysics Data System (ADS)

    Virkkula, Aki; van Dingenen, Rita; Raes, Frank; Hjorth, Jens

    1999-02-01

    The hygroscopic properties of aerosol formed by oxidation of three monoterpenes, limonene, α-pinene, and β-pinene, were measured using a tandem differential mobility analyzer (TDMA). The experiments were performed in the European Photoreactor (EUPHORE) in Valencia, Spain. The experiments included ozonolysis and photooxidation with and without ammonium sulfate seed aerosol. Pure organic particles, formed by oxidation of the terpenes in the absence of the seed aerosol, proved to be slightly hygroscopic. The hygroscopic growth factor (G) was close to 1.10 at relative humidity 84% ± 1%, which is often observed as the G of the less hygroscopic mode of atmospheric aerosol in field measurements. In the experiments with ammonium sulfate seed aerosol G decreased from approximately 1.5 before the start of terpene oxidation to approximately 1.1 as the oxidation products condensed on the particles. G was not proportional to the organic layer thickness but decreased with increasing organic volume fraction. Our analysis shows that in the internally mixed particles, ammonium sulfate and the organic products take up water independently of one another.

  1. Secondary aerosol formation from the oxidation of biogenic hydrocarbons by chlorine atoms

    NASA Astrophysics Data System (ADS)

    Cai, Xuyi; Griffin, Robert J.

    2006-07-01

    The chlorine atom (Cl) is a potential oxidant of volatile organic compounds (VOCs) in the atmosphere and is hypothesized to lead to secondary organic aerosol (SOA) formation in coastal and industrialized areas. The purpose of this paper is to test this hypothesis and to quantify the SOA formation potentials of the common monoterpenes α-pinene, β-pinene, and d-limonene when oxidized by Cl in laboratory chamber experiments. Results indicate that the oxidation of these monoterpenes generates significant amounts of aerosol. The SOA yields of α-pinene, β-pinene, and d-limonene in this study are comparable to those when they are oxidized by ozone, by nitrate radical, and in photooxidation scenarios. For aerosol mass up to 30.0 μg m-3, their yields reach approximately 0.20, 0.20, and 0.30, respectively. For d-limonene, data indicate two yield curves that depend on the initial concentration ratio of Cl precursor to d-limonene. It is argued theoretically that multiple SOA yield curves may be common for VOCs, depending on the initial concentration ratio of oxidant to VOC. SOA formation from the three typical monoterpenes when oxidized by Cl in the marine boundary layer, coastal areas, and inland industrialized areas could be a source of organic aerosol in the early morning.

  2. Ice Nucleation Activity of Various Agricultural Soil Dust Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Schiebel, Thea; Höhler, Kristina; Funk, Roger; Hill, Thomas C. J.; Levin, Ezra J. T.; Nadolny, Jens; Steinke, Isabelle; Suski, Kaitlyn J.; Ullrich, Romy; Wagner, Robert; Weber, Ines; DeMott, Paul J.; Möhler, Ottmar

    2016-04-01

    Recent investigations at the cloud simulation chamber AIDA (Aerosol Interactions and Dynamics in the Atmosphere) suggest that agricultural soil dust has an ice nucleation ability that is enhanced up to a factor of 10 compared to desert dust, especially at temperatures above -26 °C (Steinke et al., in preparation for submission). This enhancement might be caused by the contribution of very ice-active biological particles. In addition, soil dust aerosol particles often contain a considerably higher amount of organic matter compared to desert dust particles. To test agricultural soil dust as a source of ice nucleating particles, especially for ice formation in warm clouds, we conducted a series of laboratory measurements with different soil dust samples to extend the existing AIDA dataset. The AIDA has a volume of 84 m3 and operates under atmospherically relevant conditions over wide ranges of temperature, pressure and humidity. By controlled adiabatic expansions, the ascent of an air parcel in the troposphere can be simulated. As a supplement to the AIDA facility, we use the INKA (Ice Nucleation Instrument of the KArlsruhe Institute of Technology) continuous flow diffusion chamber based on the design by Rogers (1988) to expose the sampled aerosol particles to a continuously increasing saturation ratio by keeping the aerosol temperature constant. For our experiments, soil dust was dry dispersed into the AIDA vessel. First, fast saturation ratio scans at different temperatures were performed with INKA, sampling soil dust aerosol particles directly from the AIDA vessel. Then, we conducted the AIDA expansion experiment starting at a preset temperature. The combination of these two different methods provides a robust data set on the temperature-dependent ice activity of various agriculture soil dust aerosol particles with a special focus on relatively high temperatures. In addition, to extend the data set, we investigated the role of biological and organic matter in more

  3. Reactive Uptake of Dinitrogen Pentoxide on Aqueous Ammonium Nitrate Aerosols: Dependence on the Nitrate Activity

    NASA Astrophysics Data System (ADS)

    Wahner, A.; Folkers, M.; Mentel, T. F.; Sebald, H.; ten Brink, H. M.; Jongejan, P. A.

    2001-12-01

    The heterogeneous conversion of N2O_5 to HNO3 is an important step in the removal of nitrogen oxides from the atmosphere. In the planetary boundary layer this heterogeneous process occurs on the surfaces of aqueous aerosols. The fraction of NH4NO_3 in secondary inorganic aerosols in western Europe and in the United States is increasing, due to decreasing SO2 emissions at nearly constant NOX source strength. This may become of importance, since increasing nitrate concentrations in aerosols can reduce the reaction probability γ N2O5 by up to an order of magnitude ("nitrate effect" [1,2]). We measured γ N2O5 on NH4NO_3, (NH4)_2SO_4 and NH4HSO_4 aerosols in the large aerosol chamber at the FZ-Jülich. The decrease of N2O_5 and the formation of gas-phase HNO3 was monitored by high resolution FTIR spectroscopy. Simultaneously, the aerosol composition was determined on-line by Steam Jet Aerosol Collection/Ion Chromatography. The aerosol surface area was calculated from measured size distributions in the range of 20 nm to 5 μ m. The γ N2O5 of 0.02(+/- 0.003) on (NH4)_2SO_4 and NH4HSO_4 droplets are independent of the relative humidity (RH), like for the corresponding sodium salts at similar conditions. The γ N2O5 on NH4NO_3 aerosol is decreasing from 0.02 at 80% RH to 0.007 at 60% RH with decreasing relative humidity, thus increasing nitrate concentration. The functional dependence of γ N2O5 on the RH or on the ionic strength is different for NH4NO_3 and NaNO3. However it can be unified by supposing direct dependence of γ N2O5 on the mean nitrate activity. [1] A. Wahner, Th. F. Mentel, M. Sohn, J. Stier , J. Geophys. Res., 103 (1999), 31,103 [2] Th. F. Mentel, M. Sohn, A. Wahner , Phys. Chem. Chem. Phys. 1 (1999), 5451

  4. Secondary Aerosol Formation from Oxidation of Aromatics Hydrocarbons by Cl atoms

    NASA Astrophysics Data System (ADS)

    Cai, X.; Griffin, R.

    2006-12-01

    Aerosol Formation From the Oxidation of Aromatic Hydrocarbons by Chlorine Atmospheric secondary organic aerosol (SOA) affects regional and global air quality. The formation mechanisms of SOA via the oxidation of volatile organic compounds by hydroxyl radicals, ozone, and nitrate radicals have been studied intensively during the last decade. Chlorine atoms (Cl) also have been hypothesized to be effective oxidants in marine and industrially influenced areas. Recent work by the authors has indicated that significant amounts of SOA are formed from the oxidation of monoterpenes by Cl. Aromatic hydrocarbons are important for generation of both SOA and ozone in urban areas because of their large emission rates and high reactivity. The goal of this work was to quantify the SOA formation potentials of two representative aromatic hydrocarbons through laboratory chamber experiments in which oxidation was initiated by Cl. The system constructed for this study includes an experimental chamber, a gas chromatograph for quantification of aromatic mixing ratios, a Scanning Mobility Particle Spectrometer to measure SOA size distributions, a zero air generator, and an illuminating system. The model aromatic hydrocarbons chosen for this study are toluene and m-xylene. Aerosol yields are estimated based on measured aerosol volume concentration, the concentration of consumed hydrocarbon, and estimation of wall loss of the newly formed aerosol. Toluene and m-xylene exhibit similar SOA yields from the oxidation initiated by Cl. The toluene SOA yield from Cl-initiated oxidation, however, depends on the ratio between the mixing ratios of the initial chlorine source and toluene in the chamber. For toluene experiments with higher such ratios, SOA yields vary from 0.05 to 0.079 for generated aerosol ranging from 4.2 to12.0 micrograms per cubic meter. In the lower ratio experiments, SOA yields are from 0.033 to 0.064, corresponding to generated aerosol from 3.0 to 11.0 micrograms per cubic

  5. Secondary Organic Aerosol (SOA) Formation from Hydroxyl Radical Oxidation and Ozonolysis of Monoterpenes

    NASA Astrophysics Data System (ADS)

    Zhao, Defeng; Kaminski, Martin; Schlag, Patrick; Fuchs, Hendrik; Acir, Ismail-Hakki; Bohn, Birger; Haeseler, Rolf; Kiendler-Scharr, Astrid; Rohrer, Franz; Tillmann, Ralf; Wang, Mingjin; Wegner, Robert; Wahner, Andreas; Mentel, Thomas

    2014-05-01

    Hydroxyl radical (OH) oxidation and ozonolysis are the two major pathways of daytime biogenic volatile organic compounds (VOCs) oxidation and secondary organic aerosol (SOA) formation. The pure OH oxidation of monoterpenes, an important biogenic VOC class, has seldom been investigated. In order to elucidate the importance of the reaction pathyways of the OH oxidation and ozonolysis and their roles in particle formation and growth, we investigated the particle formation of several common monoterpenes (alpha-pinene, beta-pinene, and limonene) in the large atmosphere simulation chamber SAPHIR in Juelich, Germany. The experiments were conducted for both OH dominant and pure ozonolysis case (in the presence of CO as OH scavenger) at ambient relevant conditions (low OA, low VOC and low NOx concentration). OH and ozone (O3) concentrations were measured so that the oxidation rates of OH and O3 with precursors were quantified. The particle formation and growth, aerosol yield, multi-generation reaction process and aerosol composition were analyzed. Pure ozonolysis generated a large amount of particles indicating ozonolysis plays an important role in particle formation as well as OH oxidation. In individual experiments, particle growth rates did not necessarily correlate with OH or O3 oxidation rates. However, comparing the growth rates at similar OH or O3 oxidation rates shows that generally, OH oxidation and ozonolysis have similar efficiency in particle growth. Multi-generation products are shown to be important in the OH oxidation experiment based on aerosol yield "growth curve" (Ng et al., 2006). The reaction process of OH oxidation experiments was analyzed as a function of OH dose to elucidate the role of functionalization and fragmentation. A novel analysis was developed to link the particle formation with the reaction with OH, which was also used to examine the role of functionalization and fragmentation in the particle formation by OH oxidation. These analyses show

  6. La-oxides as tracers for PuO{sub 2} to simulate contaminated aerosol behavior

    SciTech Connect

    Meyer, L.C.; Newton, G.J.; Cronenberg, A.W.; Loomis, G.G.

    1994-04-01

    An analytical and experimental study was performed on the use of lanthanide oxides (La-oxides) as surrogates for plutonium oxides (PuO{sub 2}) during simulated buried waste retrieval. This study determined how well the La-oxides move compared to PuO{sub 2} in aerosolized soils during retrieval scenarios. As part of the analytical study, physical properties of La-oxides and PuO{sub 2}, such as molecular diameter, diffusivity, density, and molecular weight are compared. In addition, an experimental study was performed in which Idaho National Engineering Laboratory (INEL) soil, INEL soil with lanthanides, and INEL soil with plutonium were aerosolized and collected in filters. Comparison of particle size distribution parameters from this experimental study show similarity between INEL soil, INEL soil with lanthanides, and INEL soil with plutonium.

  7. Characterization of Highly Oxidized Molecules in Fresh and Aged Biogenic Secondary Organic Aerosol.

    PubMed

    Tu, Peijun; Hall, Wiley A; Johnston, Murray V

    2016-04-19

    In this work, highly oxidized multifunctional molecules (HOMs) in fresh and aged secondary organic aerosol (SOA) derived from biogenic precursors are characterized with high-resolution mass spectrometry. Fresh SOA was generated by mixing ozone with a biogenic precursor (β-pinene, limonene, α-pinene) in a flow tube reactor. Aging was performed by passing the fresh SOA through a photochemical reactor where it reacted with hydroxyl radicals. Although these aerosols were as a whole not highly oxidized, molecular analysis identified a significant number of HOMs embedded within it. HOMs in fresh SOA consisted mostly of monomers and dimers, which is consistent with condensation of extremely low-volatility organic compounds (ELVOCs) that have been detected in the gas phase in previous studies and linked to SOA particle formation. Aging caused an increase in the average number of carbon atoms per molecule of the HOMs, which is consistent with particle phase oxidation of (less oxidized) oligomers already existing in fresh SOA. HOMs having different combinations of oxygen-to-carbon ratio, hydrogen-to-carbon ratio and average carbon oxidation state are discussed and compared to low volatility oxygenated organic aerosol (LVOOA), which has been identified in ambient aerosol based on average elemental composition but not fully understood at a molecular level. For the biogenic precursors and experimental conditions studied, HOMs in fresh biogenic SOA have molecular formulas more closely resembling LVOOA than HOMs in aged SOA, suggesting that aging of biogenic SOA is not a good surrogate for ambient LVOOA. PMID:27000653

  8. New tracer compounds for secondary organic aerosol formation from β-caryophyllene oxidation

    NASA Astrophysics Data System (ADS)

    van Eijck, Anna; Opatz, Till; Taraborrelli, Domenico; Sander, Rolf; Hoffmann, Thorsten

    2013-12-01

    Five products from β-caryophyllene oxidation (β-caryophyllonic acid (I), 3,3-dimethyl-2-(3-oxobutyl)cyclobutanecarboxylic acid (βCA198) (II), β-nocaryophyllonic acid (III), β-caryophyllinic acid (IV), and 2-(2-carboxyethyl)-3,3-dimethylcyclobutanecarboxylic acid (βCA200) (V)) were synthesized and their structures confirmed by nuclear magnetic resonance spectroscopy. Reaction chamber experiments with β-caryophyllene at two different ozone mixing ratios were performed and the carboxylic acid oxidation products in the particle phase were characterized by APCI-MS and HPLC-ESI-MS. All five synthesized acids were found as β-caryophyllene oxidation products in the reaction chamber aerosol. The main oxidation products of the reaction chamber experiments were β-14-hydroxynocaryophyllonic acid, β-nocaryophyllonic acid (III) and βCA198 (II). Product yields of the acids were estimated based on the chamber experiments and the application of the atmospheric chemistry box model CAABA/MECCA. Finally, ambient aerosol samples taken during the HUMPPA campaign in Hyytiälä, Finland in summer 2010 were analysed for the carboxylic acid β-caryophyllene oxidation products. All five synthesized compounds were detected and were quantified in the ambient aerosol samples. The major β-caryophyllene carboxylic acid oxidation products in the ambient air samples were β-nocaryophyllonic acid (III) and βCA198 (II) with concentrations in the range of about 0.2-14 ng m-3 and 0.8-6.8 ng m-3. The fact that the concentrations of these two acids in ambient aerosol are generally higher than the concentration of β-caryophyllinic acid (IV) (often used in previous studies as oxidation tracer) with a concentration of about 0.16 ng m-3 leads to the conclusion that these two acids are better suited as tracer compounds for β-caryophyllene secondary organic aerosol formation.

  9. Laboratory investigation of photochemical oxidation of organic aerosol from wood fires Part 2: Analysis of aerosol mass spectrometer data

    NASA Astrophysics Data System (ADS)

    Grieshop, A. P.; Donahue, N. M.; Robinson, A. L.

    2008-09-01

    Experiments were conducted to investigate the effects of photo-oxidation on organic aerosol (OA) in dilute wood smoke by exposing emissions from soft- and hard-wood fires to UV light in a smog chamber. This paper focuses on changes in OA composition measured using a unit mass resolution quadrupole Aerosol Mass Spectrometer (AMS). The results highlight how photochemical processing can lead to considerable evolution of the mass, the volatility and the level of oxygenation of biomass-burning OA. Photochemical oxidation produced substantial new OA, more than doubling the primary contribution after a few hours of aging under typical summertime conditions. Aging decreased the OA volatility of the total OA as measured with a thermodenuder; it also made the OA progressively more oxygenated in every experiment. With explicit knowledge of the condensed-phase mass spectrum (MS) of the primary emissions from each fire, each MS can be decomposed into primary and residual spectra throughout the experiment. The residual spectra provide an estimate of the composition of the photochemically produced OA. These spectra are also very similar to those of the oxygenated OA that dominates ambient AMS datasets. In addition, aged wood smoke spectra are shown to be similar to those from OA created by photo-oxidized dilute diesel exhaust and aged biomass-burning OA measured in urban and remote locations. This demonstrates that the oxygenated OA observed in the atmosphere can be produced by photochemical aging of dilute emissions from combustion of fuels containing both modern and fossil carbon.

  10. Biological aerosol detection with combined passive-active infrared measurements

    NASA Astrophysics Data System (ADS)

    Ifarraguerri, Agustin I.; Vanderbeek, Richard G.; Ben-David, Avishai

    2004-12-01

    A data collection experiment was performed in November of 2003 to measure aerosol signatures using multiple sensors, all operating in the long-wave infrared. The purpose of this data collection experiment was to determine whether combining passive hyperspectral and LIDAR measurements can substantially improve biological aerosol detection performance. Controlled releases of dry aerosols, including road dust, egg albumin and two strains of Bacillus Subtilis var. Niger (BG) spores were performed using the ECBC/ARTEMIS open-path aerosol test chamber located in the Edgewood Area of Aberdeen Proving Grounds, MD. The chamber provides a ~ 20' path without optical windows. Ground truth devices included 3 aerodynamic particle sizers, an optical particle size spectrometer, 6 nephelometers and a high-volume particle sampler. Two sensors were used to make measurements during the test: the AIRIS long-wave infrared imaging spectrometer and the FAL CO2 LIDAR. The AIRIS and FAL data sets were analyzed for detection performance relative to the ground truth. In this paper we present experimental results from the individual sensors as well as results from passive-active sensor fusion. The sensor performance is presented in the form of receiver operating characteristic curves.

  11. Laboratory investigation of photochemical oxidation of organic aerosol from wood fires 1: measurement and simulation of organic aerosol evolution

    NASA Astrophysics Data System (ADS)

    Grieshop, A. P.; Logue, J. M.; Donahue, N. M.; Robinson, A. L.

    2009-02-01

    Experiments were conducted to investigate the effects of photo-oxidation on organic aerosol (OA) emissions from flaming and smoldering hard- and soft-wood fires under plume-like conditions. This was done by exposing the dilute emissions from a small wood stove to UV light in a smog chamber and measuring the gas- and particle-phase pollutant concentrations with a suite of instruments including a Proton Transfer Reaction Mass Spectrometer (PTR-MS), an Aerosol Mass Spectrometer (AMS) and a thermodenuder. The measurements highlight how atmospheric processing can lead to considerable evolution of the mass and volatility of biomass-burning OA. Photochemical oxidation produced substantial new OA, increasing concentrations by a factor of 1.5 to 2.8 after several hours of exposure to typical summertime hydroxyl radical (OH) concentrations. Less than 20% of this new OA could be explained using a state-of-the-art secondary organic aerosol model and the measured decay of traditional SOA precursors. The thermodenuder data indicate that the primary OA is semivolatile; at 50°C between 50 and 80% of the fresh primary OA evaporated. Aging reduced the volatility of the OA; at 50°C only 20 to 40% of aged OA evaporated. The predictions of a volatility basis-set model that explicitly tracks the partitioning and aging of low-volatility organics was compared to the chamber data. The OA production can be explained by the oxidation of low-volatility organic vapors; the model can also reproduce observed changes in OA volatility and composition. The model was used to investigate the competition between photochemical processing and dilution on OA concentrations in plumes.

  12. Multiphase processing of organic hydroxynitrates in secondary organic aerosol from the radical-initiated oxidation of multi-olefinic monoterpenes

    NASA Astrophysics Data System (ADS)

    Slade, J. H.; Lee, L. S.; Shepson, P. B.; De Perre, C.

    2015-12-01

    One of the greatest challenges facing atmospheric and climate science is understanding the impacts human activities have on the natural environment and atmospheric chemistry. The production of condensable organic compounds due to interactions between atmospheric oxidants, nitrogenous pollutants, and biogenic volatile organic compounds (BVOCs) emitted from the terrestrial biosphere can contribute significantly to the formation and growth of secondary organic aerosol (SOA). Aerosol particles influence atmospheric radiative transfer, cloud formation, and thus atmospheric temperatures. Due to their solubility in water and adsorptive nature, hydroxylated organic nitrates (HORONO2) may contribute significantly to the formation and chemical aging of SOA, and serve as an important sink for NOx (NO+NO2). We recently observed that a monoterpene β-hydroxy-organic nitrate (C10H17NO4), produced from the OH oxidation of α-pinene in the presence of NOx, undergoes rapid processing in the aerosol phase via an acid-catalyzed and pH-dependent hydrolysis mechanism, potentially impacting SOA growth and molecular composition. Further processing in the aerosol phase via polymerization and formation of organosulfates is expected, yet studies related to product identification and their formation mechanisms are limited. In this presentation, I will discuss recent laboratory-based reaction chamber studies of gas-phase organic nitrate production, SOA formation, and acidity-dependent aerosol-phase processing of organic nitrates produced from the NO3 oxidation of γ-terpinene. This BVOC is a diolefin, which as modeling studies suggest, may be an important nighttime organic nitrate precursor. Gas-phase organic nitrate compounds resulting from NO3 oxidation were qualitatively identified applying I- chemical ionization mass spectrometry (CIMS) and quantified via calibration using synthetic standards generated in our laboratory. Aerosol-phase analysis was carried out employing Fourier transform

  13. Experimental Measurements of the Effects of Photo-chemical Oxidation on Aerosol Emissions in Aircraft Exhaust

    NASA Astrophysics Data System (ADS)

    Miracolo, M. A.; Presto, A. A.; Hennigan, C. J.; Nguyen, N.; Ranjan, M.; Reeder, A.; Lipsky, E.; Donahue, N. M.; Robinson, A. L.

    2009-12-01

    Many military and commercial airfields are located in non-attainment areas for particulate matter (PM2.5), but the contribution of emissions from in-use aircraft to local and regional PM2.5 concentrations is uncertain. In collaboration with the Pennsylvania Air National Guard 171st Air Refueling Wing, the Carnegie Mellon University (CMU) Mobile Laboratory was deployed to measure fresh and aged emissions from a CFM56-2B1 gas-turbine engine mounted on a KC-135 Stratotanker airframe. The CFM-56 family of engine powers many different types of military and civilian aircraft, including the Boeing 737 and several Airbus models. It is one of the most widely deployed models of engines in the world. The goal of this work was to measure the gas-particle partitioning of the fresh emissions at atmospherically relevant conditions and to investigate the effect of atmospheric oxidation on aerosol loadings as the emissions age. Emissions were sampled from an inlet installed one meter downstream of the engine exit plane and transferred into a portable smog chamber via a heated inlet line. Separate experiments were conducted at different engine loads ranging from ground idle to take-off rated thrust. During each experiment, some diluted exhaust was added to the chamber and the volatility of the fresh emissions was then characterized using a thermodenuder. After this characterization, the chamber was exposed to either ambient sunlight or UV lights to initiate photochemical oxidation, which produced secondary aerosol and ozone. A suite of gas and particle-phase instrumentation was used to characterize the evolution of the gas and particle-phase emissions, including an aerosol mass spectrometer (AMS) to measure particle size and composition distributions. Fresh emissions of fine particles varied with engine load with peak emission factors at low and high loads. At high engine loads, the fresh emissions were dominated by black carbon; at low loads volatile organic carbon emissions were

  14. [Investigation of Aerosol Mixed State and CCN Activity in Nanjing].

    PubMed

    Zhu, Lin; Ma, Yan; Zheng, Jun; Li, Shi-zheng; Wang, Li-peng

    2016-04-15

    During 11-18 September 2014, the size-resolved aerosol Cloud Condensation Nuclei (CCN) activity and mixing state were measured using Cloud Condensation Nuclei Counter (CCNC), Aerosol Particle Mass (APM) and Scanning Mobility Particle Sizer (SMPS). The results showed that aerosols mainly existed as an internal mixture. For 76, 111, 138 and 181 nm particles, black carbon (BC) accounted for 5.4%, 10%, l0.7% and 6.7% of the particle mass, but as high as 51%, 57%, 70% and 59% of the particle number concentrations, respectively, suggesting that BC was a type of important condensation nuclei in the atmosphere and made significant contributions to particle numbers. The occasionally observed external mixtures were mainly present in 111 and 138 nm particles. The critical supersaturation was 0.25%, 0.13%, 0.06% and 0.015% for 76, 111, 138 and 181 nm particles, respectively. Precipitation and haze had significant effects on the particle CCN activity. The hygroscopicity parameter K was 0.37, 0.29 and 0.39 in rainy, clear and hazy days, respectively. Particle density and CCN activity were impacted by chemical compositions. Compared with clear days, higher contents of inorganic salts and lower contents of organics were found on hazy days, accompanied by lower particle density and higher CCN activity. PMID:27548938

  15. Physicochemical Characterization of Capstone Depleted Uranium Aerosols III: Morphologic and Chemical Oxide Analyses

    SciTech Connect

    Krupka, Kenneth M.; Parkhurst, MaryAnn; Gold, Kenneth; Arey, Bruce W.; Jenson, Evan D.; Guilmette, Raymond A.

    2009-03-01

    The impact of depleted uranium (DU) penetrators against an armored target causes erosion and fragmentation of the penetrators, the extent of which is dependent on the thickness and material composition of the target. Vigorous oxidation of the DU particles and fragments creates an aerosol of DU oxide particles and DU particle agglomerations combined with target materials. Aerosols from the Capstone DU aerosol study, in which vehicles were perforated by DU penetrators, were evaluated for their oxidation states using X-ray diffraction (XRD) and particle morphologies using scanning electron microscopy/energy dispersive spectrometry (SEM/EDS). The oxidation state of a DU aerosol is important as it offers a clue to its solubility in lung fluids. The XRD analysis showed that the aerosols evaluated were a combination primarily of U3O8 (insoluble) and UO3 (relatively more soluble) phases, though intermediate phases resembling U4O9 and other oxides were prominent in some samples. Analysis of particle residues in the micrometer-size range by SEM/EDS provided microstructural information such as phase composition and distribution, fracture morphology, size distribution, and material homogeneity. Observations from SEM analysis show a wide variability in the shapes of the DU particles. Some of the larger particles appear to have been fractured (perhaps as a result of abrasion and comminution); others were spherical, occasionally with dendritic or lobed surface structures. Amorphous conglomerates containing metals other than uranium were also common, especially with the smallest particle sizes. A few samples seemed to contain small chunks of nearly pure uranium metal, which were verified by EDS to have a higher uranium content exceeding that expected for uranium oxides. Results of the XRD and SEM/EDS analyses were used in other studies described in this issue of The Journal of Health Physics to interpret the results of lung solubility studies and in selecting input parameters for

  16. Physicochemical characterization of Capstone depleted uranium aerosols III: morphologic and chemical oxide analyses.

    PubMed

    Krupka, Kenneth M; Parkhurst, Mary Ann; Gold, Kenneth; Arey, Bruce W; Jenson, Evan D; Guilmette, Raymond A

    2009-03-01

    The impact of depleted uranium (DU) penetrators against an armored target causes erosion and fragmentation of the penetrators, the extent of which is dependent on the thickness and material composition of the target. Vigorous oxidation of the DU particles and fragments creates an aerosol of DU oxide particles and DU particle agglomerations combined with target materials. Aerosols from the Capstone DU aerosol study, in which vehicles were perforated by DU penetrators, were evaluated for their oxidation states using x-ray diffraction (XRD), and particle morphologies were examined using scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS). The oxidation state of a DU aerosol is important as it offers a clue to its solubility in lung fluids. The XRD analysis showed that the aerosols evaluated were a combination primarily of U3O8 (insoluble) and UO3 (relatively more soluble) phases, though intermediate phases resembling U4O9 and other oxides were prominent in some samples. Analysis of particle residues in the micrometer-size range by SEM/EDS provided microstructural information such as phase composition and distribution, fracture morphology, size distribution, and material homogeneity. Observations from SEM analysis show a wide variability in the shapes of the DU particles. Some of the larger particles were spherical, occasionally with dendritic or lobed surface structures. Others appear to have fractures that perhaps resulted from abrasion and comminution, or shear bands that developed from plastic deformation of the DU material. Amorphous conglomerates containing metals other than uranium were also common, especially with the smallest particle sizes. A few samples seemed to contain small bits of nearly pure uranium metal, which were verified by EDS to have a higher uranium content exceeding that expected for uranium oxides. Results of the XRD and SEM/EDS analyses were used in other studies described in this issue of Health Physics to interpret the

  17. Oxidation of depleted uranium penetrators and aerosol dispersal at high temperatures

    SciTech Connect

    Elder, J.C.; Tinkle, M.C.

    1980-12-01

    Aerosols dispersed from depleted uranium penetrators exposed to air and air-CO/sub 2/ mixtures at temperatures ranging from 500 to 1000/sup 0/C for 2- or 4-h periods were characterized. These experiments indicated dispersal of low concentrations of aerosols in the respirable size range (typically <10/sup -3/% of penetrator mass at 223 cm/s (5 mph) windspeed). Oxidation was maximum at 700/sup 0/C in air and 800/sup 0/C in 50% air-50% CO/sub 2/, indicating some self-protection developed at higher temperatures. No evidence of self-sustained burning was observed, although complete oxidation can be expected in fires significantly exceeding 4 h, the longest exposure of this series. An outdoor burning experiment using 10 batches of pine wood and paper packing material as fuel caused the highest oxidation rate, probably accelerated by disruption of the oxide layer accompanying broad temperature fluctuation as each fuel batch was added.

  18. Massive Volcanic SO2 Oxidation and Sulphate Aerosol Deposition in Cenozoic North America

    EPA Science Inventory

    Volcanic eruptions release a large amount of sulphur dioxide (SO2) into the atmosphere. SO2 is oxidized to sulphate and can subsequently form sulphate aerosol, which can affect the Earth's radiation balance, biologic productivity and high-altitude ozone co...

  19. Probing aerosol formation by comprehensive measurements of gas phase oxidation products

    NASA Astrophysics Data System (ADS)

    Ehn, Mikael; Kleist, Einhard; Junninen, Heikki; Sipilä, Mikko; Petäjä, Tuukka; Pullinen, Iida; Springer, Monika; Andres, Stefanie; Rissanen, Matti; Kontkanen, Jenni; Schobesberger, Siegfried; Rubach, Florian; Tillman, Ralf; Lee, Ben H.; Lopez-Hilfiker, Felipe; Kerminen, Veli-Matti; Kulmala, Markku; Worsnop, Douglas R.; Thornton, Joel; Wildt, Jürgen; Mentel, Thomas F.

    2013-05-01

    A comprehensive suite of chemical ionization mass spectrometers (CIMS) were deployed for chamber studies of monoterpene oxidation. The CIMS instruments were able to detect several different groups of compounds ranging from volatile to practically non-volatile. The compound groups showed very different behavior and correlations with aerosol number and mass. Results suggest that major gas phase contributors are not considered in current models.

  20. THE EFFECTS OF INHALED OXIDANTS AND ACID AEROSOLS ON PULMONARY FUNCTION

    EPA Science Inventory

    Drs. Koenig and Utell each conducted studies in which human volunteers received either combined or sequential exposures to oxidant gases and acid aerosols. In each case, standard pulmonary function tests were performed and symptoms were recorded. Dr. Koenig exposed 28 adole...

  1. Large enhancement in the heterogeneous oxidation rate of organic aerosols by hydroxyl radicals in the presence of nitric oxide

    SciTech Connect

    Richards-Henderson, Nicole K.; Goldstein, Allen H.; Wilson, Kevin R.

    2015-10-27

    In this paper we report an unexpectedly large acceleration in the effective heterogeneous OH reaction rate in the presence of NO. This 10–50 fold acceleration originates from free radical chain reactions, propagated by alkoxy radicals that form inside the aerosol by the reaction of NO with peroxy radicals, which do not appear to produce chain terminating products (e.g., alkyl nitrates), unlike gas phase mechanisms. Lastly, a kinetic model, constrained by experiments, suggests that in polluted regions heterogeneous oxidation plays a much more prominent role in the daily chemical evolution of organic aerosol than previously believed.

  2. Inhaled aerosolized prostacyclin and nitric oxide as selective pulmonary vasodilators in ARDS--a pilot study.

    PubMed

    Van Heerden, P V; Blythe, D; Webb, S A

    1996-10-01

    Nitric oxide 10 ppm and inhaled aerosolized prostacyclin 50 ng/kg/min were compared as selective pulmonary vasodilators in five patients with hypoxaemia secondary to acute respiratory distress syndrome. Neither agent resulted in systemic haemodynamic changes, indicating true pulmonary selectivity. Inhaled aerolized prostacyclin improved oxygenation to a degree comparable to nitric oxide, as measured by the arterial alveolar oxygen partial pressure gradient and shunt fraction. PMID:8909667

  3. Secondary organic aerosol formation and primary organic aerosol oxidation from biomass burning smoke in a flow reactor during FLAME-3

    NASA Astrophysics Data System (ADS)

    Ortega, A. M.; Day, D. A.; Cubison, M. J.; Brune, W. H.; Bon, D.; de Gouw, J. A.; Jimenez, J. L.

    2013-05-01

    We report the physical and chemical effects of photochemically aging dilute biomass-burning smoke. A potential aerosol mass "PAM" flow reactor was used with analysis by a high-resolution aerosol mass spectrometer and a proton-transfer reaction ion-trap mass spectrometer during the FLAME-3 campaign. Hydroxyl (OH) radical concentrations in the reactor reached up to ~ 1000 times average tropospheric levels, producing effective OH exposures equivalent to up to 5 days aging in the atmosphere. VOC observations show aromatics and terpenes decrease with aging, while formic acid and other unidentified oxidation products increase. Unidentified gas-phase oxidation products, previously observed in atmospheric and laboratory measurements, were observed here, including evidence of multiple generations of photochemistry. Substantial new organic aerosol (OA) mass ("net SOA"; secondary OA) was observed from aging biomass-burning smoke, resulting in an total OA average of 1.42 ± 0.36 times the initial primary OA (POA) after oxidation. This study confirms that the net SOA to POA ratio of biomass burning smoke is far lower on average than that observed for urban emissions. Although most fuels were very reproducible, significant differences were observed among the biomasses, with some fuels resulting in a doubling of the OA mass, while for others a very small increase or even a decrease was observed. Net SOA formation in the photochemical reactor increased with OH exposure (OHexp), typically peaking around three days of equivalent atmospheric photochemical age (OHexp ~ 3.9 × 1011 molecules cm-3 s-1), then leveling off at higher exposures. The amount of additional OA mass added from aging is positively correlated with initial POA concentration, but not with the total VOC concentration or the concentration of known SOA precursors. The mass of SOA formed often exceeds the mass of the known VOC precursors, indicating the likely importance of primary semivolatile/intermediate volatility

  4. What is the real role of iron oxides in the optical properties of dust aerosols?

    NASA Astrophysics Data System (ADS)

    Zhang, X. L.; Wu, G. J.; Zhang, C. L.; Xu, T. L.; Zhou, Q. Q.

    2015-11-01

    Iron oxide compounds constitute an important component of mineral dust aerosols. Several previous studies have shown that these minerals are strong absorbers at visible wavelengths and thus that they play a critical role in the overall climate perturbation caused by dust aerosols. When compiling a database of complex refractive indices of possible mineral species of iron oxides to study their optical properties, we found that uniformly continuous optical constants for a single type of iron oxide in the wavelength range between 0.2 and 50 μm are very scarce, and that the use of hematite to represent all molecular or mineral iron-oxides types is a popular hypothesis. However, the crucial problem is that three continuous data sets for complex refractive indices of hematite are employed in climate models, but there are significant differences between them. Thus, the real role of iron oxides in the optical properties of dust aerosols becomes a key scientific question, and we address this problem by considering different refractive indices, size distributions and more logical weight fractions and mixing states of hematite. Based on the microscopic observations, a semi-external mixture that employs an external mixture between Fe aggregates and other minerals and partly internal mixing between iron oxides and aluminosilicate particles is advised as the optimal approximation. The simulations demonstrate that hematite with a spectral refractive index from Longtin et al. (1988) shows approximately equal absorbing capacity to the mineral illite over the whole wavelength region from 0.55 to 2.5 μm, and only enhances the optical absorption of aerosol mixture at λ < 0.55 μm. Using the data set from Querry (1985) may overestimate the optical absorption of hematite at both visible and near-infrared wavelengths. More laboratory measurements of the refractive index of iron oxides, especially for hematite and goethite in the visible spectrum, should therefore be taken into account

  5. Laboratory investigation of photochemical oxidation of organic aerosol from wood fires 2: analysis of aerosol mass spectrometer data

    NASA Astrophysics Data System (ADS)

    Grieshop, A. P.; Donahue, N. M.; Robinson, A. L.

    2009-03-01

    Experiments were conducted to investigate the effects of photo-oxidation on organic aerosol (OA) in dilute wood smoke by exposing emissions from soft- and hard-wood fires to UV light in a smog chamber. This paper focuses on changes in OA composition measured using a unit-mass-resolution quadrupole Aerosol Mass Spectrometer (AMS). The results highlight how photochemical processing can lead to considerable evolution of the mass, volatility and level of oxygenation of biomass-burning OA. Photochemical oxidation produced substantial new OA, more than doubling the OA mass after a few hours of aging under typical summertime conditions. Aging also decreased the volatility of the OA and made it progressively more oxygenated. The results also illustrate strengths of, and challenges with, using AMS data for source apportionment analysis. For example, the mass spectra of fresh and aged BBOA are distinct from fresh motor-vehicle emissions. The mass spectra of the secondary OA produced from aging wood smoke are very similar to those of the oxygenated OA (OOA) that dominates ambient AMS datasets, further reinforcing the connection between OOA and OA formed from photo-chemistry. In addition, aged wood smoke spectra are similar to those from OA created by photo-oxidizing dilute diesel exhaust. This demonstrates that the OOA observed in the atmosphere can be produced by photochemical aging of dilute emissions from different types of combustion systems operating on fuels with modern or fossil carbon. Since OOA is frequently the dominant component of ambient OA, the similarity of spectra of aged emissions from different sources represents an important challenge for AMS-based source apportionment studies.

  6. Observational Evidence of Aerosol Enhancement of Lightning Activity and Convective Invigoration

    NASA Technical Reports Server (NTRS)

    Yuan, Tianle; Remer, Lorraine A.; Pickering, Kenneth E.; Yu, Hongbin

    2011-01-01

    Lightning activity over the West Pacific Ocean east of the Philippines is usually much less frequent than over the nearby maritime continents. However, in 2005 the Lightning Imaging Sensor (LIS) aboard the TRMM satellite observed anomalously high lightning activity in that area. In the same year the Moderate resolution Imaging Spectroradiometer (MODIS) measured anomalously high aerosol loading. The high aerosol loading was traced to volcanic activity, and not to any factor linked to meteorology, disentangling the usual convolution between aerosols and meteorology. We show that in general lightning activity is tightly correlated with aerosol loadings at both inter-annual and biweekly time scales. We estimate that a approximately 60% increase in aerosol loading leads to more than 150% increase in lightning flashes. Aerosols increase lightning activity through modification of cloud microphysics. Cloud ice particle sizes are reduced and cloud glaciation is delayed to colder temperature when aerosol loading is increased. TRMM precipitation radar measurements indicate that anomalously high aerosol loading is associated with enhanced cloud mixed phase activity and invigorated convection over the maritime ocean. These observed associations between aerosols, cloud microphysics, morphology and lightning activity are not related to meteorological variables or ENSO events. The results have important implications for understanding the variability of lightning and resulting aerosol-chemistry interactions.

  7. Secondary organic aerosols over oceans via oxidation of isoprene and monoterpenes from Arctic to Antarctic

    PubMed Central

    Hu, Qi-Hou; Xie, Zhou-Qing; Wang, Xin-Ming; Kang, Hui; He, Quan-Fu; Zhang, Pengfei

    2013-01-01

    Isoprene and monoterpenes are important precursors of secondary organic aerosols (SOA) in continents. However, their contributions to aerosols over oceans are still inconclusive. Here we analyzed SOA tracers from isoprene and monoterpenes in aerosol samples collected over oceans during the Chinese Arctic and Antarctic Research Expeditions. Combined with literature reports elsewhere, we found that the dominant tracers are the oxidation products of isoprene. The concentrations of tracers varied considerably. The mean average values were approximately one order of magnitude higher in the Northern Hemisphere than in the Southern Hemisphere. High values were generally observed in coastal regions. This phenomenon was ascribed to the outflow influence from continental sources. High levels of isoprene could emit from oceans and consequently have a significant impact on marine SOA as inferred from isoprene SOA during phytoplankton blooms, which may abruptly increase up to 95 ng/m3 in the boundary layer over remote oceans. PMID:23880782

  8. Laboratory studies of oxidation of primary emissions: Oxidation of organic molecular markers and secondary organic aerosol production

    NASA Astrophysics Data System (ADS)

    Weitkamp, Emily A.

    Particulate matter (PM) is solid particles and liquid droplets of complex composition suspended in the atmosphere. In 1997, the National Ambient Air Quality Standards (NAAQS) for PM was modified to include new standards for fine particulate (particles smaller than 2.5mum, PM2.5) because of their association with adverse health effects, mortality and visibility reduction. Fine PM may also have large impacts on the global climate. Chemically, fine particulate is a complex mixture of organic and inorganic material, from both natural and anthropogenic sources. A large fraction of PM2.5 is organic. The first objective was to investigate heterogeneous oxidation of condensed-phase molecular markers for two major organic source categories, meat-cooking emissions and motor vehicle exhaust. Effective reaction rate constants of key molecular markers were measured over a range of atmospherically relevant experimental conditions, including a range of concentrations and relative humidities, and with SOA condensed on the particles. Aerosolized meat grease was reacted with ozone to investigate the oxidation of molecular markers for meat-cooking emissions. Aerosolized motor oil, which is chemically similar to vehicle exhaust aerosol and contains the molecular markers used in source apportionment, was reacted with the hydroxyl radical (OH) to investigate oxidation of motor vehicle molecular markers. All molecular markers of interest - oleic acid, palmitoleic acid, and cholesterol for meat-cooking emissions, and hopanes and steranes for vehicle exhaust - reacted at rates that are significant for time scales on the order of days assuming typical summertime oxidant concentrations. Experimental conditions influenced the reaction rate constants. For both systems, experiments conducted at high relative humidity (RH) had smaller reaction rate constants than those at low RH. SOA coating slowed the reaction rate constants for meat-cooking markers, but had no effect on the oxidation of

  9. Secondary organic aerosol formation from the photo-oxidation of benzene

    NASA Astrophysics Data System (ADS)

    Borrás, Esther; Tortajada-Genaro, Luis Antonio

    2012-02-01

    The production of condensate compounds from the degradation of benzene by OH radical chemistry was studied. Secondary organic aerosol (SOA) formation was investigated in the EUPHORE ( European Photoreactor) simulation chambers. Experiments were performed under different OH-production conditions - addition of H 2O 2, NO or HONO -, in a high-volume reactor, with natural light and in the absence of seed aerosols. The consumption of precursor/reagents, the formation of gas-phase and particulate-phase products and the temporal evolution of aerosol were monitored. Several aerosol physical properties - mass concentration, overall aerosol yield, particle size distribution and density - were determined and found to be clearly dependent on OH radical production and NO x concentrations. Furthermore, the use of one and/or two products gas-particle partitioning absorption models allowed us to determine the aerosol yield curves. The SOA yield ranged from 1.6 to 9.7 %, with higher SOA formation under low-NO x conditions. Chemical characterization of the SOA was carried out, determining multi-oxygenated condensed organic compounds by a method based on the gas chromatography-mass spectrometry technique. Several ring-retaining and ring-cleavage products were identified and quantified. The compounds with the highest percentage contribution to the total aerosol mass were 4-nitrobenzene-1,2-diol, butenedioic acid, succinic acid and trans-trans-muconic. In addition, a multigenerational study was performed comparing with the photo-oxidations of phenol and catechol. The results showed that although the mass concentration of SOA produced was different, the physical and chemical properties were quite similar. Finally, we suggest a general mechanism to describe how changes in benzene degradation pathways - rate of OH generation and concentration of NO x - could justify the variation in SOA production and properties.

  10. Measurement of fragmentation and functionalization pathways in the multistep heterogeneous oxidation of organic aerosol

    SciTech Connect

    Kroll, Jesse H.; Smith, Jared D.; Che, Dung L.; Kessler, Sean H.; Worsnop, Douglas R.; Wilson, Kevin R.

    2009-03-10

    The competition between the addition of polar, oxygen-containing functional groups (functionalization) and the cleavage of C-C bonds (fragmentation) has a governing influence on the change in volatility of organic species upon atmospheric oxidation, and hence on the loading of tropospheric organic aerosol. However the branching between these two channels is generally poorly constrained for oxidized organics. Here we determine functionalization/fragmentation branching ratios for organics spanning a range of oxidation levels, using the heterogeneous oxidation of squalane (C30H62) as a model system. Squalane particles are exposed to high concentrations of OH in a flow reactor, and measurements of particle mass and elemental ratios enable the determination of absolute elemental composition (number of oxygen, carbon, and hydrogen atoms) of the oxidized particles. At low OH exposures, the oxygen content of the organics increases, indicating that functionalization dominates, whereas at higher exposures the amount of carbon in the particles decreases, indicating the increasing importance of fragmentation processes. Once the organics are moderately oxidized (O/C~;;0.4), fragmentation completely dominates, and the increase in O/C ratio upon further oxidation is due to the loss of carbon rather than the addition of oxygen. These results suggest that fragmentation reactions may be key steps in the atmospheric formation and evolution of oxygenated organic aerosol (OOA).

  11. Characterization of Electronic Cigarette Aerosol and Its Induction of Oxidative Stress Response in Oral Keratinocytes

    PubMed Central

    Zhao, Tongke; Shu, Shi; Chang, Chong Hyun; Messadi, Diana; Xia, Tian; Zhu, Yifang; Hu, Shen

    2016-01-01

    In this study, we have generated and characterized Electronic Cigarette (EC) aerosols using a combination of advanced technologies. In the gas phase, the particle number concentration (PNC) of EC aerosols was found to be positively correlated with puff duration whereas the PNC and size distribution may vary with different flavors and nicotine strength. In the liquid phase (water or cell culture media), the size of EC nanoparticles appeared to be significantly larger than those in the gas phase, which might be due to aggregation of nanoparticles in the liquid phase. By using in vitro high-throughput cytotoxicity assays, we have demonstrated that EC aerosols significantly decrease intracellular levels of glutathione in NHOKs in a dose-dependent fashion resulting in cytotoxicity. These findings suggest that EC aerosols cause cytotoxicity to oral epithelial cells in vitro, and the underlying molecular mechanisms may be or at least partially due to oxidative stress induced by toxic substances (e.g., nanoparticles and chemicals) present in EC aerosols. PMID:27223106

  12. Droplet activation properties of organic aerosols observed at an urban site during CalNex-LA

    SciTech Connect

    Mei, Fan; Hayes, Patrick L.; Ortega, Amber; Taylor, Jonathan W.; Allan, James D.; Gilman, Jessica; Kuster, William; de Gouw, Joost; Jimenez, Jose L.; Wang, Jian

    2013-04-11

    Size-resolved cloud condensation nuclei (CCN) spectra and aerosol chemical composition were characterized at an urban supersite in Pasadena, California, from 15 May to 4 June 2010, during the CalNex campaign. The derived hygroscopicity (κCCN) of CCN-active particles with diameter between 97 and 165 nm ranged from 0.05 to 0.4. Diurnal variation showed a slight decrease of κCCN from 8:00 to 16:00 (from 0.24 to 0.20), which is attributed to increasing organics volume fraction resulted from secondary organic aerosol (SOA) formation. The derived hygroscopicity distribution and maximum activated fraction of the size selected particles were examined as functions of photochemical age. The result indicates that condensation of secondary species (e.g., SOA and sulfate) quickly converted hydrophobic particles to hydrophilic ones, and during daytime, nearly every particle became a CCN at ~0.4% in just a few hours. Based on κCCN and aerosol chemical composition, the organic hygroscopicity (κorg) was derived, and ranged from 0.05 to 0.23 with an average value of 0.13, consistent with the results from earlier studies. The derived κorg generally increased with the organic oxidation level, and most of the variation in κorg could be explained by the variation of the organic O : C atomic ratio alone. The least squares fit of the data yielded κorg = (0.83 ± 0.06) × (O:C) + (-0.19 ± 0.02). Compared to previous results based on CCN measurements of laboratory generated aerosols, κorg derived from measurements during the CalNex campaign exhibited stronger increase with O : C atomic ratio and therefore substantially higher values for organics with average O : C greater than 0.5.

  13. Monoterpene oxidation products and organosulfates in aerosols during BEARPEX 2007 and 2009

    NASA Astrophysics Data System (ADS)

    Glasius, Marianne; Kristensen, Kasper; Worton, David R.; Goldstein, Allen H.

    2010-05-01

    Organosulfate esters of oxidation products of monoterpenes and isoprene have been identified in aerosols from both laboratory and field studies. While the exact route of formation of organosulfates is still ambiguous, these compounds pose an interesting coupling between anthropogenic emissions and biogenic oxidation products in secondary organic aerosols (SOA). We present measurements of monoterpene oxidation products, organosulfates and nitroxy organosulfates in aerosols collected during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) in California during late summer 2007 and summer 2009. The study site was located in a Ponderosa pine plantation affected by regional transport of air pollutants. Particles (PM2.5) were collected as one night-time and two daytime samples per day using a high volume sampler. After extraction of filters, polar organic compounds were analysed by HPLC coupled through an electrospray inlet to a quadrupole time-of-flight mass spectrometer (qTOF-MS). Standards of adipic, cis-pinic and pinonic acids were used for quantification, while camphor sulphonic acid was used as a surrogate standard for organosulfate compounds. Organosulfate esters can be identified from their MS-fragments (HSO4- and SO3-) and the isotopic pattern of sulphur. Concentrations of adipic acid and the terpene oxidation products cis-pinic acid and pinonic acid (from α- and β-pinene) were quantified. The relative concentrations between samples of terpenylic acid, diterpenylic acid and 2-hydroxyterpenylic acid were also investigated. Organosulfate esters and nitroxy organosulfate esters of α-pinene, β-pinene, limonene and isoprene, as well as their oxidation products, were identified based on their molecular mass and fragmentation patterns. Concentrations of some nitroxy organosulfate esters generally increased during night compared to day-time. Their formation thus seems to be related to reactions involving nitrate radicals at night-time.

  14. Determination of minimum mass and spatial location of initiator for detonation of propylene oxide aerosols

    NASA Astrophysics Data System (ADS)

    Apparao, A.; Saji, J.; Balaji, M.; Devangan, A. K.; Rao, C. R.

    2016-06-01

    The mishandling of liquid fuels during production, processing or transportation can lead to the formation of combustible two-phase mixtures. These mixtures, with the availability of a suitable energy source, may be ignited generating a deflagration, or even a detonation wave. For military applications, unconfined fuel aerosols are created and detonated with the help of a strong shock generated by a powerful energy source. The minimum energy requirement is expressed in terms of the shock strength, or mass of the high-explosive-based initiator. In this study, the detonability of unconfined aerosols of 4.3 kg propylene oxide was studied by positioning different quantities of cylindrical-shaped initiators of RDX/wax (95/5) at a fixed spatial location in the aerosol cloud, and the minimum mass of the initiator required for detonation initiation was determined. The effect of spatial location and the requirement of initiator mass, especially at farther locations where the fuel concentration is likely to be lower and closer to the lower explosive limit, was also investigated. The experimental findings help identify the detonable zone in unconfined propylene oxide aerosol clouds for different combinations of spatial location and mass of initiator.

  15. Characterization of indoor cooking aerosol using neutron activation analysis

    SciTech Connect

    Wu, D.; Landsberger, S.; Larson, S. )

    1993-01-01

    Suspended particles in air are potentially harmful to human health, depending on their sizes and chemical composition. Residential indoor particles mainly come from (a) outdoor sources that are transported indoors, (b) indoor dust that is resuspended, and (c) indoor combustion sources, which include cigarette smoking, cooking, and heating. Jedrychowski stated that chronic phlegm in elderly women was strongly related to the cooking exposure. Kamens et al. indicated that cooking could generate small particles (<0.1 [mu]m), and cooking one meal could contribute [approximately]5 to 18% of total daytime particle volume exposure. Although cooking is a basic human activity, there are not many data available on the properties of particles generated by this activity. Some cooking methods, such as stir-frying and frying, which are the most favored for Chinese and other Far East people, generate a large quantity of aerosols. This research included the following efforts: 1. investigating particle number concentrations, distributions, and their variations with four different cooking methods and ventilation conditions; 2. measuring the chemical composition of cooking aerosol samples by instrumental neutron activation analysis.

  16. Assessing the oxidative potential of isoprene-derived epoxides and secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Kramer, Amanda J.; Rattanavaraha, Weruka; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.; Lin, Ying-Hsuan

    2016-04-01

    Fine particulate matter (PM2.5) is known to contribute to adverse health effects, such as asthma, cardiopulmonary disease, and lung cancer. Secondary organic aerosol (SOA) is a major component of PM2.5 and can be enhanced by atmospheric oxidation of biogenic volatile organic compounds in the presence of anthropogenic pollutants, such as nitrogen oxides (NOx) and sulfur dioxide. However, whether biogenic SOA contributes to adverse health effects remains unclear. The objective of this study was to assess the potential of isoprene-derived epoxides and SOA for generating reactive oxygen species (ROS) in light of the recent recognition that atmospheric oxidation of isoprene in the presence of acidic sulfate aerosol is a major contributor to the global SOA burden. The dithiothreitol (DTT) assay was used to characterize the ROS generation by the isoprene-derived epoxides, trans-β-isoprene epoxydiol (trans-β-IEPOX) and methacrylic acid epoxide (MAE), and their hydrolysis products, the 2-methyltetrol diastereomers (2-MT), 2-methylglyceric acid (2-MG), their organosulfate derivatives, as well as an isoprene-derived hydroxyhydroperoxide (ISOPOOH). In addition, ROS generation potential was evaluated for total SOA produced from photooxidation of isoprene and methacrolein (MACR) as well as from the reactive uptake of trans-β-IEPOX and MAE onto acidified sulfate aerosol. The high-NOx regime, which yields 2-MG-, MAE- and MACR-derived SOA has a higher ROS generation potential than the low-NOx regime, which yields 2-MT, IEPOX- and isoprene-derived SOA. ISOPOOH has an ROS generation potential similar to 1,4-naphthoquinone (1,4-NQ), suggesting a significant contribution of aerosol-phase organic peroxides to PM oxidative potential. MAE- and MACR-derived SOA show equal or greater ROS generation potential than reported in studies on diesel exhaust PM, highlighting the importance of a comprehensive investigation of the toxicity of isoprene-derived SOA.

  17. Aerosol synthesis of nano and micro-scale zero valent metal particles from oxide precursors

    SciTech Connect

    Phillips, Jonathan; Luhrs, Claudia; Lesman, Zayd; Soliman, Haytham; Zea, Hugo

    2010-01-01

    In this work a novel aerosol method, derived form the batch Reduction/Expansion Synthesis (RES) method, for production of nano / micro-scale metal particles from oxides and hydroxides is presented. In the Aerosol-RES (A-RES) method, an aerosol, consisting of a physical mixture of urea and metal oxide or hydroxides, is passed through a heated oven (1000 C) with a residence time of the order of 1 second, producing pure (zero valent) metal particles. It appears that the process is flexible regarding metal or alloy identity, allows control of particle size and can be readily scaled to very large throughput. Current work is focused on creating nanoparticles of metal and metal alloy using this method. Although this is primarily a report on observations, some key elements of the chemistry are clear. In particular, the reducing species produced by urea decomposition are the primary agents responsible for reduction of oxides and hydroxides to metal. It is also likely that the rapid expansion that takes place when solid/liquid urea decomposes to form gas species influences the final morphology of the particles.

  18. A highly sensitive technique for detecting catalytically active nanoparticles against a background of general workplace aerosols

    NASA Astrophysics Data System (ADS)

    Neubauer, N.; Weis, F.; Binder, A.; Seipenbusch, M.; Kasper, G.

    2011-07-01

    A new measurement technique was studied using catalysis to specifically detect airborne nanoparticles in presence of background particles in the workplace air. Catalytically active nanoparticles produced by spark discharge were used as aerosol catalysts. According to these particles suitable catalytic test reactions were chosen and investigated by two different approaches: catalysis on airborne nanoparticles and catalysis on deposited nanoparticles. The results indicate that catalysis is applicable for the specific measurement of nanoparticles in the workplace air. Catalysis on airborne particles is suitable for the specific detection of very active nanoparticles, e.g. platinum or nickel, at high concentrations of about 107 #/cm3. The approach of catalysis on deposited particles is better suited for nanoparticle aerosols at low concentrations, for slow catalytic reactions or less active nanoparticles like iron oxide (Fe2O3). On the basis of the experimental results detection limits in the range of μg or even ng were calculated which assure the good potential of catalysis for the specific detection of nanoparticles in the workplace air based on their catalytic activity.

  19. Activating Nonreducible Oxides via Doping.

    PubMed

    Nilius, Niklas; Freund, Hans-Joachim

    2015-05-19

    Nonreducible oxides are characterized by large band gaps and are therefore unable to exchange electrons or to form bonds with surface species, explaining their chemical inertness. The insertion of aliovalent dopants alters this situation, as new electronic states become available in the gap that may be involved in charge-transfer processes. Consequently, the adsorption and reactivity pattern of doped oxides changes with respect to their nondoped counterparts. This Account describes scanning tunneling microscopy (STM) and photoelectron spectroscopy (XPS) experiments that demonstrate the impact of dopants on the physical and chemical properties of well-defined crystalline oxide films. For this purpose, MgO and CaO as archetypical rocksalt oxides have been loaded either with high-valence (Mo, Cr) or low-valence dopants (Li). While the former generate filled states in the oxide band gap and serve as electron donors, the latter produce valence-band holes and give rise to an acceptor response. The dopant-related electronic states and their polarization effect on the surrounding host material are explored with XPS and STM spectroscopy on nonlocal and local scales. Moreover, charge-compensating defects were found to develop in the oxide lattice, such as Ca and O vacancies in Mo- and Li-doped CaO films, respectively. These native defects are able to trap the excess charges of the impurities and therefore diminish the desired doping effect. If noncompensated dopants reside in the host lattice, electron exchange with surface species is observed. Mo ions in CaO, for example, were found to donate electrons to surface Au atoms. The anionic Au strongly binds to the CaO surface and nucleates in the form of monolayer islands, in contrast to the 3D growth prevailing on pristine oxides. Charge transfer is also revealed for surface O2 that traps one Mo electron by forming a superoxo-species. The activated oxygen is characterized by a reinforced binding to the surface, an elongated O

  20. Cardiac and pulmonary oxidative stress in rats exposed to realistic emissions of source aerosols

    PubMed Central

    Lemos, Miriam; Diaz, Edgar A.; Gupta, Tarun; Kang, Choong-Min; Ruiz, Pablo; Coull, Brent A.; Godleski, John J.; Gonzalez-Flecha, Beatriz

    2013-01-01

    In vivo chemiluminescence (CL) is a measure of reactive oxygen species in tissues. CL was used to assess pulmonary and cardiac responses to inhaled aerosols derived from aged emissions of three coal-fired power plants in the USA. Sprague–Dawley rats were exposed to either filtered air or: (1) primary emissions (P); (2) ozone oxidized emissions (PO); (3) oxidized emissions + secondary organic aerosol (SOA) (POS); (4) neutralized oxidized emissions + SOA (PONS); and (5) control scenarios: oxidized emissions + SOA in the absence of primary particles (OS), oxidized emissions alone (O), and SOA alone (S). Immediately after 6 hours of exposure, CL in the lung and heart was measured. Tissues were also assayed for thiobarbituric acid reactive substances (TBARS). Exposure to P or PO aerosols led to no changes compared to filtered air in lung or heart CL at any individual plant or when all data were combined. POS caused significant increases in lung CL and TBARS at only one plant, and not in combined data from all plants; PONS resulted in increased lung CL only when data from all plants were combined. Heart CL was also significantly increased with exposure to POS only when data from all plants were combined. PONS increased heart CL significantly in one plant with TBARS accumulation, but not in combined data. Exposure to O, OS, and S had no CL effects. Univariate analyses of individual measured components of the exposure atmospheres did not identify any component associated with increased CL. These data suggest that coal-fired power plant emissions combined with other atmospheric constituents produce limited pulmonary and cardiac oxidative stress. PMID:21913821

  1. Stable carbon isotope composition of secondary organic aerosol from β-pinene oxidation

    NASA Astrophysics Data System (ADS)

    Fisseha, Rebeka; Spahn, Holger; Wegener, Robert; Hohaus, Thorsten; Brasse, Gregor; Wissel, Holger; Tillmann, Ralf; Wahner, Andreas; Koppmann, Ralf; Kiendler-Scharr, Astrid

    2009-01-01

    A chamber study was carried out to investigate the stable carbon isotopic composition (δ13C) of secondary organic aerosol (SOA) formed from ozonolysis of β-pinene. β-Pinene (600 ppb) with a known δ13C value (-30.1‰) and 500 ppb ozone were injected into the chamber in the absence of light and the resulting SOA was collected on preheated quartz fiber filters. Furthermore, δ13C values of the gas-phase β-pinene and one of its oxidation products, nopinone, were measured using a gas chromatograph coupled to an isotope ratio mass spectrometer (GC-IRMS). β-Pinene was progressively enriched with the heavy carbon isotope due to the kinetic isotope effect (KIE). The KIE of the reaction of β-pinene with ozone was measured to be 1.0026 ? 2.6 ± 1.5‰). The δ13C value of total secondary organic aerosol was very similar to that of its precursor (average = -29.6 ± 0.2‰) independent of experiment time. Nopinone, one of the major oxidation products of β-pinene, was found in both the gas and aerosol phases. The gas-phase nopinone was heavier than the initial β-pinene by 1.3‰ but lighter than the corresponding aerosol-phase nopinone. On average, the gas-phase nopinone was lighter by 2.3‰ than the corresponding aerosol-phase nopinone. The second product found in the SOA was detected as acetone, but it desorbed from the filter at a higher temperature than nopinone, which indicates that it is a pyrolysis product. The acetone showed a much lower δ13C (-36.6‰) compared to the initial β-pinene δ13C.

  2. SECONDARY ORGANIC AEROSOL FORMATION FROM THE OXIDATION OF AROMATIC HYDROCARBONS IN THE PRESENCE OF DRY SUBMICRON AMMONIUM SULFATE AEROSOL

    EPA Science Inventory

    A laboratory study was conducted to examine formation of secondary organic aerosols. A smog chamber system was developed for studying gas-aerosol interactions in a dynamic flow reactor. These experiments were conducted to investigate the fate of gas and aerosol phase compounds ...

  3. Atmospheric oxidation of isoprene and 1,3-Butadiene: influence of aerosol acidity and Relative humidity on secondary organic aerosol

    EPA Science Inventory

    The effects of acidic seed aerosols on the formation of secondary organic aerosol (SOA)have been examined in a number of previous studies, several of which have observed strong linear correlations between the aerosol acidity (measured as nmol H+ per m3 air s...

  4. Relationship between Oxidation Level and Optical Properties of Secondary Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Lambe, A. T.; Cappa, C. D.; Massoli, P.; Onasch, T. B.; Forestieri, S.; Martin, A. T.; Cummings, M. J.; Croasdale, D. R.; Brune, W. H.; Worsnop, D. R.; Davidovits, P.

    2013-12-01

    Brown carbon (BrC), which may include secondary organic aerosol (SOA), can be a significant climate-forcing agent via its optical absorption properties. However, the overall contribution of SOA to BrC remains poorly understood. Here, correlations between oxidation level and optical properties of SOA are examined. SOA was generated in a flow reactor in the absence of NOx by OH oxidation of gas-phase precursors used as surrogates for anthropogenic (naphthalene, tricyclo-[5.2.1.02,6]decane), biomass burning (guaiacol), and biogenic (α-pinene) emissions. SOA chemical composition was characterized with a time-of-flight aerosol mass spectrometer. SOA mass-specific absorption cross sections (MAC) and refractive indices were calculated from real-time cavity ring-down photoacoustic spectrometry measurements at 405 and 532 nm and from UV-vis spectrometry measurements of methanol extracts of filter-collected particles (300 to 600 nm). At 405 nm, SOA MAC values and imaginary refractive indices increased with increasing oxidation level and decreased with increasing wavelength, leading to negligible absorption at 532 nm. Real refractive indices of SOA decreased with increasing oxidation level. Comparison with literature studies suggests that under typical polluted conditions the effect of NOx on SOA absorption is small. SOA may contribute significantly to atmospheric BrC, with the magnitude dependent on both precursor type and oxidation level. Mass-specific absorption cross sections (MAC) of SOA at λ = 405 nm as a function of the O/C ratio

  5. Relationship between oxidation level and optical properties of secondary organic aerosol.

    PubMed

    Lambe, Andrew T; Cappa, Christopher D; Massoli, Paola; Onasch, Timothy B; Forestieri, Sara D; Martin, Alexander T; Cummings, Molly J; Croasdale, David R; Brune, William H; Worsnop, Douglas R; Davidovits, Paul

    2013-06-18

    Brown carbon (BrC), which may include secondary organic aerosol (SOA), can be a significant climate-forcing agent via its optical absorption properties. However, the overall contribution of SOA to BrC remains poorly understood. Here, correlations between oxidation level and optical properties of SOA are examined. SOA was generated in a flow reactor in the absence of NOx by OH oxidation of gas-phase precursors used as surrogates for anthropogenic (naphthalene, tricyclo[5.2.1.0(2,6)]decane), biomass burning (guaiacol), and biogenic (α-pinene) emissions. SOA chemical composition was characterized with a time-of-flight aerosol mass spectrometer. SOA mass-specific absorption cross sections (MAC) and refractive indices were calculated from real-time cavity ring-down photoacoustic spectrometry measurements at 405 and 532 nm and from UV-vis spectrometry measurements of methanol extracts of filter-collected particles (300 to 600 nm). At 405 nm, SOA MAC values and imaginary refractive indices increased with increasing oxidation level and decreased with increasing wavelength, leading to negligible absorption at 532 nm. Real refractive indices of SOA decreased with increasing oxidation level. Comparison with literature studies suggests that under typical polluted conditions the effect of NOx on SOA absorption is small. SOA may contribute significantly to atmospheric BrC, with the magnitude dependent on both precursor type and oxidation level. PMID:23701291

  6. Aerosol activation properties and CCN closure during TCAP

    NASA Astrophysics Data System (ADS)

    Mei, F.; Tomlinson, J. M.; Shilling, J. E.; Wilson, J. M.; Zelenyuk, A.; Chand, D.; Comstock, J. M.; Hubbe, J.; Berg, L. K.; Schmid, B.

    2013-12-01

    The indirect effects of atmospheric aerosols currently remain the most uncertain components in forcing of climate change over the industrial period (IPCC, 2007). This large uncertainty is partially due to our incomplete understanding of the ability of particles to form cloud droplets under atmospherically relevant supersaturation. In addition, there is a large uncertainty in the aerosol optical depth (AOD) simulated by climate models near the North American coast and a wide variety in the types of clouds are observed over this region. The goal of the US Department of Energy Two Column Aerosol Project (TCAP) is to understand the processes responsible for producing and maintaining aerosol distributions and associated radiative and cloud forcing off the coast of North America. During the TCAP study, aerosol total number concentration, cloud condensation nuclei (CCN) spectra and aerosol chemical composition were in-situ measured from the DOE Gulfstream 1 (G-1) research aircraft during two Intensive Operations Periods (IOPs), one conducted in July 2012 and the other in February 2013. An overall aerosol size distribution was achieved by merging the observations from several instruments, including Ultra High Sensitivity Aerosol Spectrometer - Airborne (UHSAS-A, DMT), Passive Cavity Aerosol Spectrometer Probe (PCASP-200, DMT), and Cloud Aerosol Spectrometer (CAS, DMT). Aerosol chemical composition was characterized using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS, Aerodyne Inc.) and single particle mass spectrometer, mini-SPLAT. Based on the aerosol size distribution, CCN number concentration (characterized by a DMT dual column CCN counter with a range from 0.1% to 0.4%), and chemical composition, a CCN closure was obtained. The sensitivity of CCN closure to organic hygroscopicity was investigated. The differences in aerosol/CCN properties between two columns, and between two phases, will be discussed.

  7. Photo-oxidation of pinonaldehyde at low NOx: from chemistry to organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Chacon-Madrid, H. J.; Henry, K. M.; Donahue, N. M.

    2013-03-01

    Pinonaldehyde oxidation by OH radicals under low-NOx conditions produces significant secondary organic aerosol (SOA) mass yields. Under concurrent UV illumination, mass yields are lower than high-NOx yields published earlier by our group. However, when OH radicals are produced via dark ozonolysis the SOA mass yields are comparable at high and low NOx. Because pinonaldehyde is a major first-generation gas-phase product of α-pinene oxidation by either ozone or OH radicals, its potential to form SOA serves as a molecular counterpoint to bulk SOA aging experiments involving SOA formed from α-pinene. Both the general tendency for aging reactions to produce more SOA and the sensitivity of the low-NOx products to UV photolysis observed in the bulk clearly occur for this single species as well. Photochemical oxidation of pinonaldehye and analogous first-generation terpene oxidation products are potentially a significant source of additional SOA in biogenically influenced air masses.

  8. Aqueous secondary organic aerosol (SOA) production from the oxidation of phenols by triplet excited state organics

    NASA Astrophysics Data System (ADS)

    Smith, J.; Yu, L.; Zhang, Q.; Anastasio, C.

    2011-12-01

    Recent literature has shown that atmospheric condensed-phase chemistry can play a significant role in the evolution of organic aerosols, including the formation of secondary organic aerosol (SOA). SOA formation from the oxidation of volatile organic compounds (VOCs) in the aqueous phase has largely focused on oxidations involving the hydroxyl radical and other oxidants, such as photochemically created triplet excited states, have not been fully investigated. Phenolic compounds are one of the primary carbon emission classes from biomass and wood combustion and have significant water solubility. Once in the aqueous phase, phenolic compounds can react with the triplet excited states of non-phenolic aromatic carbonyls (NPCs), particle-bound organics that are also emitted in large quantities from wood combustion. The oxidation of phenolic species in the condensed phase by triplet excited states can result in the production of SOA. A main goal of this study was to investigate bulk solution reaction kinetics under atmospherically relevant conditions in order to ascertain how these reactions can impact aqueous-phase SOA production. In our experiments, we studied the reactions of five phenols (phenol, guaiacol, syringol, catechol, and resorcinol) with the triplet state of 3,4-dimethoxybenzaldehyde (34-DMB) during simulated solar radiation. We have characterized the impacts of pH, ionic strength and reactant concentrations on the reaction behavior of this system. In addition, we analyzed the SOA formed using high-resolution aerosol mass spectrometry, ion chromatography, and liquid chromatography-mass spectrometry to infer the reaction mechanisms. Our evidence suggests that under atmospherically relevant conditions, triplet excited states can be the dominant oxidant of phenolics and contribute significantly to the total SOA budget.

  9. Atmospheric Aerosols: Cloud Condensation Nucleus Activity of Selected Organic Molecules

    NASA Astrophysics Data System (ADS)

    Rosenorn, T.; Henning, S.; Hartz, K. H.; Kiss, G.; Pandis, S.; Bilde, M.

    2005-12-01

    Gas/particle partitioning of vapors in the atmosphere plays a major role in both climate through micro meteorology and in the physical and chemical processes of a single particle. This work has focused on the cloud droplet activation of a number of pure and mixed compounds. The means used to investigate these processes have been the University of Copenhagen cloud condensation nucleus counter setup and the Carnegie Mellon University CCNC setup. The importance of correct water activity modeling has been addressed and it has been pointed out that the molecular mass is an important parameter to consider when choosing model compounds for cloud activation models. It was shown that both traditional Kohler theory and Kohler theory modified to account for limited solubility reproduce measurements of soluble compounds well. For less soluble compounds it is necessary to use Kohler theory modified to account for limited solubility. It was also shown that this works for mixtures of compounds containing both inorganic salts and dicarboxylic acids. It has also been shown that particle phase and humidity history is important for activation behavior of particles consisting of two slightly soluble organic substances (succinic and adipic acid) and a soluble salt (NaCl). Model parameters for terpene oxidation product cloud activation have been derived. These are based on two sets of average parameters covering monoterpene oxidation products and sesquiterpene oxidation products. All parameters except the solubility were estimated and an effective solubility was calculated as the fitting parameter. The average solubility of the model compound found for mono terpene oxidation products is similar to those of sodium chloride and ammonium sulfate; however the higher molecular weight leads to a slightly higher activation diameter at fixed supersaturation. On a molar basis the monoterpene oxidation products show a 1.5 times higher effective solubility than the sesquiterpene oxidation products.

  10. Chemical Aging and Cloud Condensation Nuclei Activity of Biomass Burning Aerosol Proxies in the Presence of OH Radicals

    NASA Astrophysics Data System (ADS)

    Slade, Jonathan H., Jr.

    Biomass burning aerosol (BBA) can adversely impact regional and global air quality and represents a significant source of organic aerosol (OA) to the atmosphere that can affect climate. Aerosol particles can alter the transfer of radiation in earth's atmosphere directly by scattering and absorbing radiation or indirectly via cloud formation. Gas-to-particle, also termed heterogeneous, oxidation reactions can significantly alter the particle's physical and chemical properties. In turn, this can lead to the degradation of biomolecular markers for air quality-related aerosol source apportionment studies, the particles' lifetime, and modify the particles' abilities to serve as cloud condensation nuclei (CCN). However, the rates, mechanisms, and conditions by which these multiphase oxidation reactions occur and influence the CCN activity of OA is not well understood. The work presented here aims to determine the reactivity and products from the interaction of BBA surrogate-particles and trace gas-phase oxidants and to link the effects of OA chemical aging on the particles' ability to nucleate clouds. The reactive uptake of OH by BBA surrogate-substrates and particles, including levoglucosan, nitroguaiacol, abietic acid, and methyl-nitrocatechol, was determined as a function of both OH concentration and relative humidity (RH) using chemical ionization mass spectrometry coupled to various flow reactors. OH reactive uptake decreased with increasing OH concentration, indicative of OH adsorption followed by reaction. OH oxidation led to significant volatilization, i.e. mass loss of the organic material, as determined by application of high resolution proton transfer reaction time-of-flight mass spectrometry. Volatilized reaction products were identified, providing mechanistic insight of the chemical pathways in the heterogeneous OH oxidation of BBA. The reactive uptake of OH by levoglucosan particles increased with RH due to enhanced OH and organic bulk diffusivity. In

  11. [Exogenous fibrosing alveolitis due to the condensation aerosol (smoke) of zinc oxide].

    PubMed

    Voznesenskiĭ, N K

    2004-01-01

    Clinical-and-biological, biochemical, immunological, histomorphological; X-ray and functional examinations of workers of an electric-melting shop manufacturing brass alloys, who had contacts with condensation aerosol with a high zinc oxide concentrations, were used to detect in them pneumoconiosis with the exogenous fibrosing alveolitis (ZEFA). Some workers had acute conditions, i.e. "foundry fever" speaking in clinical terms, which was followed by a period of "visible improvement" lasting on the average for 8.6 +/- 0.8 years. The latter was described by the autoimmune activation of B-lymphocytes accompanied by an intensified formation of circulating immune complexes with a sharp reduction of the DR-cell content. The disease onset is gradual with the below signs: increasing dyspnea, cough and cyanosis of the lips due to the developing hypoxemia with decreasing PO2 (below 80 mm Hg); it can also be displayed through a mixed type of respiratory insufficiency with a lower PO2 and a higher PCO2 (above 40 mm Hg)-X-ray showed reticular changes in the pulmonary pattern. Generation of a high-above-norm quantity of active forms of oxygen and nitrogen by alveolar macrophages and neutrophils in their contacts with cellular membranes is the key mechanism triggering the pathological process like it happens in all cases of pneumoconiosis. Transformation of the mentioned products of free-radical oxygenation into hydroxyl radicals in the catalytic centers of the dust-particle borders containing zinc (which is, like iron, a metal with transient valence) is ZEFA specificity. The factor draws together ZEFA with pathological processes caused by asbestos-fiber dust, which have iron ions in their catalytic centers. PMID:15108372

  12. Secondary organic aerosol formation and composition from the photo-oxidation of methyl chavicol (estragole)

    NASA Astrophysics Data System (ADS)

    Pereira, K. L.; Hamilton, J. F.; Rickard, A. R.; Bloss, W. J.; Alam, M. S.; Camredon, M.; Muñoz, A.; Vásquez, M.; Borrás, E.; Ródenas, M.

    2013-12-01

    The increasing demand for palm oil for uses in biofuel and food products is leading to rapid expansion of oil palm agriculture. Methyl chavicol (also known as estragole and 1-allyl-4-methoxybenzene) is an oxygenated biogenic volatile organic compound that was recently identified as the main floral emission from an oil palm plantation in Malaysian Borneo. The emissions of methyl chavicol observed may impact regional atmospheric chemistry, but little is known of its ability to form secondary organic aerosol (SOA). The photo-oxidation of methyl chavicol was investigated at the European Photoreactor chamber as a part of the atmospheric chemistry of methyl chavicol (ATMECH) project. Aerosol samples were collected using a particle into liquid sampler (PILS) and analysed offline using an extensive range of instruments including; high performance liquid chromatography mass spectrometry (HPLC-ITMS), high performance liquid chromatography quadrupole time-of-flight mass spectrometry (HPLC-QTOFMS) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The SOA yield was determined as 18-29% depending on initial precursor (VOC : NOx) mixing ratios. In total, 59 SOA compounds were observed and the structures of 10 compounds have been identified using high resolution tandem mass spectrometry. The addition of hydroxyl and/or nitro functional groups to the aromatic ring appears to be an important mechanistic pathway for aerosol formation. This results in the formation of compounds with both low volatility and high O : C ratios, where functionalisation rather than fragmentation is mainly observed as a~result of the stability of the ring. The SOA species observed can be characterized as semi-volatile to low volatile oxygenated organic aerosol (SVOOA and LVOOA) components and therefore may be important in aerosol formation and growth.

  13. Secondary organic aerosol formation and composition from the photo-oxidation of methyl chavicol (estragole)

    NASA Astrophysics Data System (ADS)

    Pereira, K. L.; Hamilton, J. F.; Rickard, A. R.; Bloss, W. J.; Alam, M. S.; Camredon, M.; Muñoz, A.; Vázquez, M.; Borrás, E.; Ródenas, M.

    2014-06-01

    The increasing demand for palm oil for uses in biofuel and food products is leading to rapid expansion of oil palm agriculture. Methyl chavicol (also known as estragole and 1-allyl-4-methoxybenzene) is an oxygenated biogenic volatile organic compound (VOC) that was recently identified as the main floral emission from an oil palm plantation in Malaysian Borneo. The emissions of methyl chavicol observed may impact regional atmospheric chemistry, but little is known of its ability to form secondary organic aerosol (SOA). The photo-oxidation of methyl chavicol was investigated at the European Photoreactor chamber as a part of the atmospheric chemistry of methyl chavicol (ATMECH) project. Aerosol samples were collected using a particle into liquid sampler (PILS) and analysed offline using an extensive range of instruments including; high-performance liquid chromatography mass spectrometry (HPLC-ITMS), high-performance liquid chromatography quadrupole time-of-flight mass spectrometry (HPLC-QTOFMS) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The SOA yield was determined as 18 and 29% for an initial VOC mixing ratio of 212 and 460 ppbv (parts per billion by volume) respectively; using a VOC:NOx ratio of ~5:1. In total, 59 SOA compounds were observed and the structures of 10 compounds have been identified using high-resolution tandem mass spectrometry. The addition of hydroxyl and/or nitro-functional groups to the aromatic ring appears to be an important mechanistic pathway for aerosol formation. This results in the formation of compounds with both low volatility and high O:C ratios, where functionalisation rather than fragmentation is mainly observed as a result of the stability of the ring. The SOA species observed can be characterised as semi-volatile to low-volatility oxygenated organic aerosol (SVOOA and LVOOA) components and therefore may be important in aerosol formation and growth.

  14. Polarity and oxidation level of visible absorbers in model organic aerosol

    NASA Astrophysics Data System (ADS)

    Rifkha Kameel, F.; Lee, S. H.; Hoffmann, M. R.; Colussi, A. J.

    2014-05-01

    How to parametrize the absorptivity of organic aerosols in atmospheric radiative models remains uncertain. Here we report that the λ = 400 nm absorbers in model aerosol mixtures elute as weakly polar species in reversed-phase chromatography. Typical among them, the m/z = 269 (C12H13O7-, O/C = 0.58) isomers detected by mass spectrometry possess Cdbnd O groups linked by Cdbnd C bridges. More polar species, such as the m/z = 289 (C11H13O9-, O/C = 0.82) polyacids, are instead colorless. On this basis we argue that visible absorptivity, which develops from extended conjugation among chromophores, may not increase monotonically with oxidation level.

  15. Oxidative Aging and Secondary Organic Aerosol Formation from Simulated Wildfire Emissions

    NASA Astrophysics Data System (ADS)

    Hennigan, C. J.; Miracolo, M. A.; Engelhart, G. J.; May, A. A.; Wold, C. E.; Hao, W. M.; Lee, T.; Sullivan, A. P.; Gilman, J. B.; Kuster, W. C.; de Gouw, J. A.; Collett, J. L.; Kreidenweis, S. M.; Robinson, A. L.

    2010-12-01

    Wildfires are a significant fraction of global biomass burning and a major source of trace gas and particle emissions in the atmosphere. Understanding the air quality and climate implications of wildfires is difficult since the emissions undergo complex transformations due to aging processes during transport away from the source. As part of the third Fire Lab at Missoula Experiment (FLAME III), we investigated the oxidative aging of smoke from combustion of 12 different types of vegetation commonly burned in North American wildfires. In these photochemical chamber experiments, we quantified the evolution of reactive trace gases and particles, with a focus on the chemistry contributing to changes in the organic aerosol (OA) concentration. Factors such as precursor VOC concentrations, oxidant exposure, and the role of NOx were considered. The results illustrate the complex and variable nature of biomass burning emissions, since none of these factors alone account for the wide range of OA enhancements that were observed. For example, in some experiments, a net decrease of up to 30% in the OA concentration was observed, while in others, the OA concentration increased by a factor of three over the course of aging due to secondary OA (SOA) production. Despite this variability, all experiments showed significant physical (e.g., changes in aerosol volatility) and chemical (e.g., changes in oxidation) transformations in the OA due to oxidation. Overall, the results demonstrate that traditional definitions of POA and SOA continue to blur in many systems, and that processes like partitioning and heterogeneous chemistry can have the most significant effect on the evolution of biomass burning aerosol.

  16. Chemical aging of single and multicomponent biomass burning aerosol surrogate particles by OH: implications for cloud condensation nucleus activity

    DOE PAGESBeta

    Slade, J. H.; Thalman, R.; Wang, J.; Knopf, D. A.

    2015-09-14

    Multiphase OH and O3 oxidation reactions with atmospheric organic aerosol (OA) can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low-soluble single-component OA by OH and O3 can increase their water solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN) and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA) surrogate particles exposed tomore » OH and O3 is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type, mixing state, and OH and O3 exposure applying a CCN counter (CCNc) coupled to an aerosol flow reactor (AFR). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O3 exposure. Following exposure to OH, κ of MNC was enhanced by an order of magnitude, from 0.009 to ~ 0.1, indicating that chemically aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in κ was observed for pure LEV particles following OH exposure. κ of the internally mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH-exposed MNC-coated KS particles is similar to the OH unexposed atomized 1 : 1 by mass MNC : KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC) or inorganic ions

  17. Chemical aging of single and multicomponent biomass burning aerosol surrogate-particles by OH: implications for cloud condensation nucleus activity

    DOE PAGESBeta

    Slade, J. H.; Thalman, R.; Wang, J.; Knopf, D. A.

    2015-03-06

    Multiphase OH and O3 oxidation reactions with atmospheric organic aerosol (OA) can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low soluble single-component OA by OH and O3 can increase their water-solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN) and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water-solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA) surrogate-particles exposed to OH andmore » O3 is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type, mixing state, and OH/O3 exposure applying a CCN counter (CCNc) coupled to an aerosol flow reactor (AFR). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O3 exposure. Following exposure to OH, κ of MNC was enhanced by an order of magnitude, from 0.009 to ~0.1, indicating that chemically-aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in κ was observed for pure LEV particles following OH exposure. κ of the internally-mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH exposed MNC-coated KS particles is similar to the OH unexposed atomized 1 : 1 by mass MNC : KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC) or inorganic ions, chemical

  18. Chemical aging of single and multicomponent biomass burning aerosol surrogate-particles by OH: implications for cloud condensation nucleus activity

    NASA Astrophysics Data System (ADS)

    Slade, J. H.; Thalman, R.; Wang, J.; Knopf, D. A.

    2015-03-01

    Multiphase OH and O3 oxidation reactions with atmospheric organic aerosol (OA) can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low soluble single-component OA by OH and O3 can increase their water-solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN) and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water-solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA) surrogate-particles exposed to OH and O3 is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type, mixing state, and OH/O3 exposure applying a CCN counter (CCNc) coupled to an aerosol flow reactor (AFR). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O3 exposure. Following exposure to OH, κ of MNC was enhanced by an order of magnitude, from 0.009 to ~0.1, indicating that chemically-aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in κ was observed for pure LEV particles following OH exposure. κ of the internally-mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH exposed MNC-coated KS particles is similar to the OH unexposed atomized 1 : 1 by mass MNC : KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC) or inorganic ions, chemical aging

  19. Chemical aging of single and multicomponent biomass burning aerosol surrogate particles by OH: implications for cloud condensation nucleus activity

    NASA Astrophysics Data System (ADS)

    Slade, J. H.; Thalman, R.; Wang, J.; Knopf, D. A.

    2015-09-01

    Multiphase OH and O3 oxidation reactions with atmospheric organic aerosol (OA) can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low-soluble single-component OA by OH and O3 can increase their water solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN) and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA) surrogate particles exposed to OH and O3 is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type, mixing state, and OH and O3 exposure applying a CCN counter (CCNc) coupled to an aerosol flow reactor (AFR). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O3 exposure. Following exposure to OH, κ of MNC was enhanced by an order of magnitude, from 0.009 to ~ 0.1, indicating that chemically aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in κ was observed for pure LEV particles following OH exposure. κ of the internally mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH-exposed MNC-coated KS particles is similar to the OH unexposed atomized 1 : 1 by mass MNC : KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC) or inorganic ions, chemical

  20. Measurements of secondary organic aerosol formed from OH-initiated photo-oxidation of isoprene using online photoionization aerosol mass spectrometry.

    PubMed

    Fang, Wenzheng; Gong, Lei; Zhang, Qiang; Cao, Maoqi; Li, Yuquan; Sheng, Liusi

    2012-04-01

    Isoprene is a significant source of atmospheric organic aerosol; however, the secondary organic aerosol (SOA) formation and involved chemical reaction pathways have remained to be elucidated. Recent works have shown that the photo-oxidation of isoprene leads to form SOA. In this study, the chemical composition of SOA from the OH-initiated photo-oxidation of isoprene, in the absence of seed aerosols, was investigated through the controlled laboratory chamber experiments. Thermal desorption/tunable vacuum-ultraviolet photoionization time-of-flight aerosol mass spectrometry (TD-VUV-TOF-PIAMS) was used in conjunction with the environmental chamber to study SOA formation. The mass spectra obtained at different photon energies and the photoionization efficiency (PIE) spectra of the SOA products can be obtained in real time. Aided by the ionization energies (IE) either from the ab initio calculations or the literatures, a number of SOA products were proposed. In addition to methacrolein, methyl vinyl ketone, and 3-methyl-furan, carbonyls, hydroxycarbonyls, nitrates, hydroxynitrates, and other oxygenated compounds in SOA formed in laboratory photo-oxiadation experiments were identified, some of them were investigated for the first time. Detailed chemical identification of SOA is crucial for understanding the photo-oxidation mechanisms of VOCs and the eventual formation of SOA. Possible reaction mechanisms will be discussed. PMID:22397593

  1. Secondary Organic Aerosol (SOA) formation from hydroxyl radical oxidation and ozonolysis of monoterpenes

    NASA Astrophysics Data System (ADS)

    Zhao, D. F.; Kaminski, M.; Schlag, P.; Fuchs, H.; Acir, I.-H.; Bohn, B.; Häseler, R.; Kiendler-Scharr, A.; Rohrer, F.; Tillmann, R.; Wang, M. J.; Wegener, R.; Wildt, J.; Wahner, A.; Mentel, T. F.

    2014-05-01

    Oxidation by hydroxyl radical (OH) and ozonolysis are the two major pathways of daytime biogenic volatile organic compounds (VOCs) oxidation and secondary organic aerosol (SOA) formation. In this study, we investigated the particle formation of several common monoterpenes (α-pinene, β-pinene, and limonene) by OH dominated oxidation, which has seldom been investigated. OH oxidation experiments were carried out in the SAPHIR chamber in Jülich, Germany, at low NOx (0.01-1 ppbV) and low ozone (O3) concentration. OH concentration and OH reactivity were measured directly so that the overall reaction rates of organic compounds with OH were quantified. Multi-generation reaction process, particle growth, new particle formation, particle yield, and chemical composition were analyzed and compared with that of monoterpene ozonolysis. Multi-generation products were found to be important in OH dominated SOA formation. The relative role of functionalization and fragmentation in the reaction process of OH oxidation was analyzed by examining the particle mass and the particle size as a function of OH dose. We developed a novel method which quantitatively links particle growth to the reaction of OH with organics in a reaction system. This method was also used to analyze the evolution of functionalization and fragmentation of organics in the particle formation by OH oxidation. It shows that functionalization of organics was dominant in the beginning of the reaction (within two lifetimes of the monoterpene) and fragmentation started to be dominant after that. We compared particle formation from OH oxidation with that from pure ozonolysis. In individual experiments, growth rates of the particle size did not necessarily correlate with the reaction rate of monoterpene with OH and O3. Comparing the size growth rates at the similar reaction rates of monoterpene with OH or O3 indicates that generally, OH oxidation and ozonolysis had similar efficiency in particle growth. The SOA yield of

  2. Secondary organic aerosol formation from hydroxyl radical oxidation and ozonolysis of monoterpenes

    NASA Astrophysics Data System (ADS)

    Zhao, D. F.; Kaminski, M.; Schlag, P.; Fuchs, H.; Acir, I.-H.; Bohn, B.; Häseler, R.; Kiendler-Scharr, A.; Rohrer, F.; Tillmann, R.; Wang, M. J.; Wegener, R.; Wildt, J.; Wahner, A.; Mentel, Th. F.

    2015-01-01

    Oxidation by hydroxyl radical (OH) and ozonolysis are the two major pathways of daytime biogenic volatile organic compound (BVOC) oxidation and secondary organic aerosol (SOA) formation. In this study, we investigated the particle formation of several common monoterpenes (α-pinene, β-pinene and limonene) by OH-dominated oxidation, which has seldom been investigated. OH oxidation experiments were carried out in the SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction) chamber in Jülich, Germany, at low NOx (0.01 ~ 1 ppbV) and low ozone (O3) concentration (< 20 ppbV). OH concentration and total OH reactivity (kOH) were measured directly, and through this the overall reaction rate of total organics with OH in each reaction system was quantified. Multi-generation reaction process, particle growth, new particle formation (NPF), particle yield and chemical composition were analyzed and compared with that of monoterpene ozonolysis. Multi-generation products were found to be important in OH-dominated SOA formation. The relative role of functionalization and fragmentation in the reaction process of OH oxidation was analyzed by examining the particle mass and the particle size as a function of OH dose. We developed a novel method which quantitatively links particle growth to the reaction rate of OH with total organics in a reaction system. This method was also used to analyze the evolution of functionalization and fragmentation of organics in the particle formation by OH oxidation. It shows that functionalization of organics was dominant in the beginning of the reaction (within two lifetimes of the monoterpene) and fragmentation started to play an important role after that. We compared particle formation from OH oxidation with that from pure ozonolysis. In individual experiments, growth rates of the particle size did not necessarily correlate with the reaction rate of monoterpene with OH and O3. Comparing the size growth rates at the similar reaction rates

  3. Development and Validation of a Model to Predict Aerosol Breathing Zone Concentrations During Common Outdoor Activities

    EPA Science Inventory

    Research has been conducted on aerosol emission rates during various activities as well as aerosol transport into the breathing zone under idealized conditions. However, there has been little effort to link the two into a model for predicting a person’s breathing zone concentrat...

  4. DEVELOPMENT OF AN RH -DENUDED MIE ACTIVE SAMPLING SYSTEM AND TARGETED AEROSOL CALIBRATION

    EPA Science Inventory

    The MIE pDR 1200 nephelometer provides time resolved aerosol concentrations during personal and fixed-site sampling. Active (pumped) operation allows defining an upper PM2.5 particle size, however, this dramatically increases the aerosol mass passing through the phot...

  5. Gas-Phase Oxidation Kinetics and Organic Aerosol Products of Ethanolamine

    NASA Astrophysics Data System (ADS)

    Borduas, N.; Abbatt, J.; Murphy, J. G.

    2012-12-01

    Ethanolamine is currently the solvent of choice in carbon capture and storage technology (CCS) which aims to reduce CO2 emissions to the atmosphere in coal powered pilot plants. CCS technology represents an unprecedented large scale application of ethanolamine and little is known of its fate if it was unintentionally released into the atmosphere. Relative kinetic experiments were conducted in a 1m3 smog chamber using online proton-transfer-reaction mass spectrometry. The kinetics of oxidation with hydroxyl radicals from light and dark sources converge to a value of (7.6 ± 1.1) x 10-11 cm3 molec-1 s-1. The reaction of ethanolamine with ozone was determined to be (1.05 ± 0.08) x 10-18 cm3 molec-1 s-1. We find that ethanolamine has a short lifetime in the atmosphere and readily deposits onto wall and particle surfaces, as observed by considerable formation of organonitrogen aerosol products. An investigation into the oxidation product formation using a combination of reagent ions with online chemical ionization mass spectrometry approaches lead to the detection of higher order products. The formation of these high molecular weight products is simultaneous with the oxidation of ethanolamine and implies substantial organic aerosol chemistry.

  6. Aerosol composition, oxidation properties, and sources in Beijing: results from the 2014 Asia-Pacific Economic Cooperation summit study

    NASA Astrophysics Data System (ADS)

    Xu, W. Q.; Sun, Y. L.; Chen, C.; Du, W.; Han, T. T.; Wang, Q. Q.; Fu, P. Q.; Wang, Z. F.; Zhao, X. J.; Zhou, L. B.; Ji, D. S.; Wang, P. C.; Worsnop, D. R.

    2015-12-01

    The mitigation of air pollution in megacities remains a great challenge because of the complex sources and formation mechanisms of aerosol particles. The 2014 Asia-Pacific Economic Cooperation (APEC) summit in Beijing serves as a unique experiment to study the impacts of emission controls on aerosol composition, size distributions, and oxidation properties. Herein, a high-resolution time-of-flight aerosol mass spectrometer was deployed in urban Beijing for real-time measurements of size-resolved non-refractory submicron aerosol (NR-PM1) species from 14 October to 12 November 2014, along with a range of collocated measurements. The average (±σ) PM1 was 41.6 (±38.9) μg m-3 during APEC, which was decreased by 53 % compared with that before APEC. The aerosol composition showed substantial changes owing to emission controls during APEC. Secondary inorganic aerosol (SIA: sulfate + nitrate + ammonium) showed significant reductions of 62-69 %, whereas organics presented much smaller decreases (35 %). The results from the positive matrix factorization of organic aerosol (OA) indicated that highly oxidized secondary organic aerosol (SOA) showed decreases similar to those of SIA during APEC. However, primary organic aerosol (POA) from cooking, traffic, and biomass-burning sources were comparable to those before APEC, indicating the presence of strong local source emissions. The oxidation properties showed corresponding changes in response to OA composition. The average oxygen-to-carbon level during APEC was 0.36 (±0.10), which is lower than the 0.43 (±0.13) measured before APEC, demonstrating a decrease in the OA oxidation degree. The changes in size distributions of primary and secondary species varied during APEC. SIA and SOA showed significant reductions in large accumulation modes with peak diameters shifting from ~ 650 to 400 nm during APEC, whereas those of POA remained relatively unchanged. The changes in aerosol composition, size distributions, and oxidation

  7. Removal of sulphur from the marine boundary layer by ozone oxidation in sea-salt aerosols

    NASA Astrophysics Data System (ADS)

    Sievering, H.; Boatman, J.; Gorman, E.; Kim, Y.; Anderson, L.; Ennis, G.; Luria, M.; Pandis, S.

    1992-12-01

    The contribution of ozone oxidation in sea-salt aerosols to the cycling of sulfur in the marine boundary layer (MBL) is assessed. It is shown that, due to the effects of mass transfer, the non-sea-salt SO4(2-) so generated will be predominantly associated with particles 2-9 microns in diameter and will accordingly dry-deposit at a rapid rate. Because part of the dimethyl sulfide emitted by marine organisms is converted to SO2 in the MBL, this additional removal pathway for sulfur may markedly reduce the proposed feedback between greenhouse warming, oceanic DMS emissions, and sulfate haze albedos.

  8. Biogenic VOC oxidation and organic aerosol formation in an urban nocturnal boundary layer: aircraft vertical profiles in Houston, TX

    NASA Astrophysics Data System (ADS)

    Brown, S. S.; Dubé, W. P.; Bahreini, R.; Middlebrook, A. M.; Brock, C. A.; Warneke, C.; de Gouw, J. A.; Washenfelder, R. A.; Atlas, E.; Peischl, J.; Ryerson, T. B.; Holloway, J. S.; Schwarz, J. P.; Spackman, R.; Trainer, M.; Parrish, D. D.; Fehshenfeld, F. C.; Ravishankara, A. R.

    2013-11-01

    Organic compounds are a large component of aerosol mass, but organic aerosol (OA) sources remain poorly characterized. Recent model studies have suggested nighttime oxidation of biogenic hydrocarbons as a potentially large OA source, but analysis of field measurements to test these predictions is sparse. We present nighttime vertical profiles of nitrogen oxides, ozone, VOCs and aerosol composition measured during low approaches of the NOAA P-3 aircraft to airfields in Houston, TX. This region has large emissions of both biogenic hydrocarbons and nitrogen oxides. The latter category serves as a source of the nitrate radical, NO3, a key nighttime oxidant. Biogenic VOCs (BVOC) and urban pollutants were concentrated within the nocturnal boundary layer (NBL), which varied in depth from 100-400 m. Despite concentrated NOx at low altitude, ozone was never titrated to zero, resulting in rapid NO3 radical production rates of 0.2-2.7 ppbv h-1 within the NBL. Monoterpenes and isoprene were frequently present within the NBL and underwent rapid oxidation (up to 1 ppbv h-1), mainly by NO3 and to a lesser extent O3. Concurrent enhancement in organic and nitrate aerosol on several profiles was consistent with primary emissions and with secondary production from nighttime BVOC oxidation, with the latter equivalent to or slightly larger than the former. Some profiles may have been influenced by biomass burning sources as well, making quantitative attribution of organic aerosol sources difficult. Ratios of organic aerosol to CO within the NBL ranged from 14 to 38 μg m-3 OA/ppmv CO. A box model simulation incorporating monoterpene emissions, oxidant formation rates and monoterpene SOA yields suggested overnight OA production of 0.5 to 9 μg m-3.

  9. Secondary Organic Aerosol Formation and Organic Nitrate Yield from NO3 Oxidation of Biogenic Hydrocarbons

    PubMed Central

    2014-01-01

    The secondary organic aerosol (SOA) mass yields from NO3 oxidation of a series of biogenic volatile organic compounds (BVOCs), consisting of five monoterpenes and one sesquiterpene (α-pinene, β-pinene, Δ-3-carene, limonene, sabinene, and β-caryophyllene), were investigated in a series of continuous flow experiments in a 10 m3 indoor Teflon chamber. By making in situ measurements of the nitrate radical and employing a kinetics box model, we generate time-dependent yield curves as a function of reacted BVOC. SOA yields varied dramatically among the different BVOCs, from zero for α-pinene to 38–65% for Δ-3-carene and 86% for β-caryophyllene at mass loading of 10 μg m–3, suggesting that model mechanisms that treat all NO3 + monoterpene reactions equally will lead to errors in predicted SOA depending on each location’s mix of BVOC emissions. In most cases, organonitrate is a dominant component of the aerosol produced, but in the case of α-pinene, little organonitrate and no aerosol is formed. PMID:25229208

  10. Transboundary secondary organic aerosol in western Japan: An observed limitation of the f44 oxidation indicator

    NASA Astrophysics Data System (ADS)

    Irei, Satoshi; Takami, Akinori; Sadanaga, Yasuhiro; Miyoshi, Takao; Arakaki, Takemitsu; Sato, Kei; Kaneyasu, Naoki; Bandow, Hiroshi; Hatakeyama, Shiro

    2015-11-01

    To obtain evidence for secondary organic aerosol formation during the long-range transport of air masses over the East China Sea, we conducted field measurements in March 2012 at the Fukue atmospheric monitoring station, Nagasaki, in western Japan. The relative abundance of m/z 44 in fine organic aerosol (f44) was measured by an Aerodyne aerosol chemical speciation monitor. The stable carbon isotope ratio (δ13C) of low-volatile water-soluble organic carbon (LV-WSOC) in the daily filter samples of total suspended particulate matter was also analyzed using an elemental-analyzer coupled with an isotope ratio mass spectrometer. Additionally, in situ measurements of NOx and NOy were performed using NOx and NOy analyzers. The measurements showed that, unlike the systematic trends observed in a previous field study, a scatter plot for δ13C of LV-WSOC versus f44 indicated a random variation. Comparison of f44 with the estimated photochemical age by the NOx/NOy ratio revealed that the random distribution of f44 values near 0.2 is likely an indication of saturation already. Such f44 values were significantly lower than the observed f44 (∼0.3) at Hedo in the previous study. These findings imply that the saturation point of f44, and the use of f44 as an oxidation indicator, is case dependent.

  11. Modeling aerosol surface chemistry and gas-particle interaction kinetics with K2-SURF: PAH oxidation

    NASA Astrophysics Data System (ADS)

    Shiraiwa, M.; Garland, R.; Pöschl, U.

    2009-04-01

    Atmospheric aerosols are ubiquitous in the atmosphere. They have the ability to impact cloud properties, radiative balance and provide surfaces for heterogeneous reactions. The uptake of gaseous species on aerosol surfaces impacts both the aerosol particles and the atmospheric budget of trace gases. These subsequent changes to the aerosol can in turn impact the aerosol chemical and physical properties. However, this uptake, as well as the impact on the aerosol, is not fully understood. This uncertainty is due not only to limited measurement data, but also a dearth of comprehensive and applicable modeling formalizations used for the analysis, interpretation and description of these heterogeneous processes. Without a common model framework, comparing and extrapolating experimental data is difficult. In this study, a novel kinetic surface model (K2-SURF) [Ammann & Pöschl, 2007; Pöschl et al., 2007] was used to describe the oxidation of a variety of polycyclic aromatic hydrocarbons (PAHs). Integrated into this consistent and universally applicable kinetic and thermodynamic process model are the concepts, terminologies and mathematical formalizations essential to the description of atmospherically relevant physicochemical processes involving organic and mixed organic-inorganic aerosols. Within this process model framework, a detailed master mechanism, simplified mechanism and parameterizations of atmospheric aerosol chemistry are being developed and integrated in analogy to existing mechanisms and parameterizations of atmospheric gas-phase chemistry. One of the key aspects to this model is the defining of a clear distinction between various layers of the particle and surrounding gas phase. The processes occurring at each layer can be fully described using known fluxes and kinetic parameters. Using this system there is a clear separation of gas phase, gas-surface and surface bulk transport and reactions. The partitioning of compounds can be calculated using the flux

  12. Cloud — Aerosol interaction during lightning activity over land and ocean: Precipitation pattern assessment

    NASA Astrophysics Data System (ADS)

    Pal, Jayanti; Chaudhuri, Sutapa; Chowdhury, Arumita Roy; Bandyopadhyay, Tanuka

    2016-06-01

    The present study attempts to identify the land - ocean contrast in cloud - aerosol relation during lightning and non-lightning days and its effect on subsequent precipitation pattern. The thermal hypothesis in view of Convective Available Potential Energy (CAPE) behind the land - ocean contrast is observed to be insignificant in the present study region. The result shows that the lightning activities are significantly and positively correlated with aerosols over both land and ocean in case of low aerosol loading whereas for high aerosol loading the correlation is significant but, only over land. The study attempts to comprehend the mechanism through which the aerosol and lightning interact using the concept of aerosol indirect effect that includes the study of cloud effective radius, cloud fraction and precipitation rate. The result shows that the increase in lightning activity over ocean might have been caused due to the first aerosol indirect effect, while over land the aerosol indirect effect might have been suppressed due to lightning. Thus, depending on the region and relation between cloud parameters it is observed that the precipitation rate decreases (increases) over ocean during lightning (non-lightning) days. On the other hand during non-lightning days, the precipitation rate decreases over land.

  13. Light absorption by secondary organic aerosol from α-pinene: Effects of oxidants, seed aerosol acidity, and relative humidity

    SciTech Connect

    Song, Chen; Gyawali, Madhu; Zaveri, Rahul A.; Shilling, John E.; Arnott, W. Patrick

    2013-10-25

    It is well known that light absorption from dust and black carbon aerosols has a warming effect on climate while light scattering from sulfate, nitrate, and sea salt aerosols has a cooling effect. However, there are large uncertainties associated with light absorption and scattering by different types of organic aerosols, especially in the near-UV and UV spectral regions. In this paper, we present the results from a systematic laboratory study focused on measuring light absorption by secondary organic aerosols (SOAs) generated from dark α-pinene + O3 and α-pinene + NOx + O3 systems in the presence of neutral and acidic sulfate seed aerosols. Light absorption was monitored using photoacoustic spectrometers at four different wavelengths: 355, 405, 532, and 870 nm. Significant light absorption at 355 and 405 nm was observed for the SOA formed from α-pinene + O3 + NO3 system only in the presence of highly acidic sulfate seed aerosols under dry conditions. In contrast, no absorption was observed when the relative humidity was elevated to greater than 27% or in the presence of neutral sulfate seed aerosols. Organic nitrates in the SOA formed in the presence of neutral sulfate seed aerosols were found to be nonabsorbing, while the light-absorbing compounds are speculated to be aldol condensation oligomers with nitroxy organosulfate groups that are formed in highly acidic sulfate aerosols. Finally and overall, these results suggest that dark α-pinene + O3 and α-pinene + NOx + O3 systems do not form light-absorbing SOA under typical atmospheric conditions.

  14. Light absorption by secondary organic aerosol from α-pinene: Effects of oxidants, seed aerosol acidity, and relative humidity

    NASA Astrophysics Data System (ADS)

    Song, Chen; Gyawali, Madhu; Zaveri, Rahul A.; Shilling, John E.; Arnott, W. Patrick

    2013-10-01

    is well known that light absorption from dust and black carbon aerosols has a warming effect on climate while light scattering from sulfate, nitrate, and sea salt aerosols has a cooling effect. However, there are large uncertainties associated with light absorption and scattering by different types of organic aerosols, especially in the near-UV and UV spectral regions. In this paper, we present the results from a systematic laboratory study focused on measuring light absorption by secondary organic aerosols (SOAs) generated from dark α-pinene + O3 and α-pinene + NOx + O3 systems in the presence of neutral and acidic sulfate seed aerosols. Light absorption was monitored using photoacoustic spectrometers at four different wavelengths: 355, 405, 532, and 870 nm. Significant light absorption at 355 and 405 nm was observed for the SOA formed from α-pinene + O3 + NO3 system only in the presence of highly acidic sulfate seed aerosols under dry conditions. In contrast, no absorption was observed when the relative humidity was elevated to greater than 27% or in the presence of neutral sulfate seed aerosols. Organic nitrates in the SOA formed in the presence of neutral sulfate seed aerosols were found to be nonabsorbing, while the light-absorbing compounds are speculated to be aldol condensation oligomers with nitroxy organosulfate groups that are formed in highly acidic sulfate aerosols. Overall, these results suggest that dark α-pinene + O3 and α-pinene + NOx + O3 systems do not form light-absorbing SOA under typical atmospheric conditions.

  15. Sources and evolution of cloud-active aerosol in California's Sierra Nevada Mountains

    NASA Astrophysics Data System (ADS)

    Roberts, G. C.; Corrigan, C.; Noblitt, S.; Creamean, J.; Collins, D. B.; Cahill, J. F.; Prather, K. A.; Collett, J. L.; Henry, C.

    2011-12-01

    To assess the sources of cloud-active aerosol and their influence on the hydrological cycle in California, the CalWater Experiment took place in winter 2011 in the foothills of the Sierra Nevada Mountains. During this experiment, we coupled the capabilities of demonstrated miniaturized instrumentation - cloud condensation nuclei (CCN), water condensation nuclei (WCN) and microchip capillary electrophoresis (MCE) - to provide direct chemical measurements of cloud active aerosols. Ion concentrations of CCN droplets attribute the anthropogenic, marine and secondary organic contributions to cloud-active aerosols. Detailed spectra from an Aerosol-Time-of-Flight Mass Spectrometer provide additional information on the sources of aerosol. Storm fronts and changes in atmospheric boundary layer brought aerosol and anions associated with Central Valley pollution to the field site with CCN concentrations reaching several thousand cm-3. Hygroscopicity parameters indicate aging of the organic fraction during aerosol transport from the Central Valley to the mountains. Otherwise, CCN concentrations were low when high pressure systems prevented boundary layer development and intrusion of the Central Valley pollution to the site. MCE results show that nitrates and sulfates comprise most of the fraction of the aerosol anion mass (PM1). During the passage of storm fronts, which transported pollution from the Central Valley upslope, nitrate concentrations peaked at several μ g m-3. Low supersaturation CCN concentrations coincide with increases in aerosol nitrate, which suggests that nitrate has a role in cloud formation of giant CCN and, furthermore, in precipitation processes in the Sierra Nevada. CCN spectra show large variations depending on the aerosol sources and sometimes exhibit bi-modal distributions with minima at 0.3% Sc -- similar to the so-called 'Hoppel minima' associated to number size distributions. During these bi-modal events, sulfate also increases supporting the

  16. Heterogeneous oxidation reactions relevant to tropospheric aerosol chemistry studied by sum frequency generation

    NASA Astrophysics Data System (ADS)

    Stokes, Grace; Buchbinder, Avram; Gibbs-Davis, Julianne; Scheidt, Karl; Geiger, Franz

    2008-03-01

    Unsaturated organic molecules (terpenes) that commonly form molecular films on tropospheric aerosols can be oxidized by ozone, influencing the microphysics of cloud formation and thus the earth's climate. Using a laboratory approach that combines organic synthesis with surface spectroscopy, we track the ozone oxidation reactions of tropospherically relevant terpenes bound to glass surfaces that serve as mimics for mineral dust. Specifically, vibrational broadband sum frequency generation (SFG) is used to study a number of tailor-made terpene-modified glass surfaces and to track their interactions with ozone in real time. Exposure of these surfaces to ppm levels of ozone at 1 atm and 300 K yield initial reaction probabilities that are significantly higher than corresponding gas phase reactions. SFG spectra help elucidate the molecular orientations of the surface-bound terpenes and the accessibility of reactive C=C bonds. Our work shows the successful use of SFG spectroscopy to determine heterogeneous atmospheric reaction probabilities and bridges the gap between atmospheric aerosol science and surface spectroscopy.

  17. Spectroscopic analysis of iron-oxide minerals in aerosol particles from northern China.

    PubMed

    Shen, Z X; Cao, J J; Zhang, X Y; Arimoto, R; Ji, J F; Balsam, W L; Wang, Y Q; Zhang, R J; Li, X X

    2006-08-31

    Diffuse reflectance spectrometry was used to study iron-oxide minerals and to investigate the reflectance characteristics of eolian dust collected during the spring of 2001 and 2002 on bulk filters from three sites in northern China. The first derivatives of the reflectance spectra were consistent with signals from two iron-oxide minerals, hematite and goethite, at wavelengths of 565 and 435 nm, respectively, and these values varied with the iron concentrations in the samples. The percent reflectances for the yellow, orange and red bands increased with the iron concentrations and with the first derivative values representing hematite and goethite while those for violet, blue and green bands decreased correspondingly. The results show that iron-oxide minerals play an important role in determining the aerosol particles' color and reflectance properties. Moreover, the relative amounts of the two iron-oxides in Asian dust apparently differ from those in African dust, suggesting that the iron-oxides may provide another tool for tracing the origins of eolian dust on a global scale. PMID:16487575

  18. LABORATORY EVALUATION OF A MICROFLUIDIC ELECTROCHEMICAL SENSOR FOR AEROSOL OXIDATIVE LOAD

    PubMed Central

    Koehler, Kirsten; Shapiro, Jeffrey; Sameenoi, Yupaporn; Henry, Charles; Volckens, John

    2014-01-01

    Human exposure to particulate matter (PM) air pollution is associated with human morbidity and mortality. The mechanisms by which PM impacts human health are unresolved, but evidence suggests that PM intake leads to cellular oxidative stress through the generation of reactive oxygen species (ROS). Therefore, reliable tools are needed for estimating the oxidant generating capacity, or oxidative load, of PM at high temporal resolution (minutes to hours). One of the most widely reported methods for assessing PM oxidative load is the dithiothreitol (DTT) assay. The traditional DTT assay utilizes filter-based PM collection in conjunction with chemical analysis to determine the oxidation rate of reduced DTT in solution with PM. However, the traditional DTT assay suffers from poor time resolution, loss of reactive species during sampling, and high limit of detection. Recently, a new DTT assay was developed that couples a Particle-Into-Liquid-Sampler with microfluidic-electrochemical detection. This ‘on-line’ system allows high temporal resolution monitoring of PM reactivity with improved detection limits. This study reports on a laboratory comparison of the traditional and on-line DTT approaches. An urban dust sample was aerosolized in a laboratory test chamber at three atmospherically-relevant concentrations. The on-line system gave a stronger correlation between DTT consumption rate and PM mass (R2 = 0.69) than the traditional method (R2 = 0.40) and increased precision at high temporal resolution, compared to the traditional method. PMID:24711675

  19. Volatility and oxidative aging of aqueous maleic acid aerosol droplets and the dependence on relative humidity.

    PubMed

    Dennis-Smither, Benjamin J; Marshall, Frances H; Miles, Rachael E H; Preston, Thomas C; Reid, Jonathan P

    2014-07-31

    The microphysical structure and heterogeneous oxidation by ozone of single aerosol particles containing maleic acid (MA) has been studied using aerosol optical tweezers and cavity enhanced Raman spectroscopy. The evaporation rate of MA from aqueous droplets has been measured over a range of relative humidities and the pure component vapor pressure determined to be (1.7 ± 0.2) × 10(-3) Pa. Variation in the refractive index (RI) of an aqueous MA droplet with relative humidity (RH) allowed the subcooled liquid RI of MA to be estimated as 1.481 ± 0.001. Measurements of the hygroscopic growth are shown to be consistent with equilibrium model predictions from previous studies. Simultaneous measurements of the droplet composition, size, and refractive index have been made during ozonolysis at RHs in the range 50-80%, providing insight into the volatility of organic products, changes in the droplet hygroscopicity, and optical properties. Exposure of the aqueous droplets to ozone leads to the formation of products with a wide range of volatilities spanning from involatile to volatile. Reactive uptake coefficients show a weak dependence on ozone concentration, but no dependence on RH or salt concentration. The time evolving RI depends significantly on the RH at which the oxidation proceeds and can even show opposing trends; while the RI increases with ozone exposure at low relative humidity, the RI decreases when the oxidation proceeds at high relative humidity. The variations in RI are broadly consistent with a framework for predicting RIs for organic components published by Cappa et al. ( J. Geophys. Res. 2011 , 116 , D15204 ). Once oxidized, particles are shown to form amorphous phases on drying rather than crystallization, with slow evaporation kinetics of residual water. PMID:25003240

  20. Apparatus having reduced background for measuring radiation activity in aerosol particles

    DOEpatents

    Rodgers, John C.; McFarland, Andrew R.; Oritz, Carlos A.; Marlow, William H.

    1992-01-01

    Apparatus having reduced background for measuring radiation activity in aerosol particles. A continuous air monitoring sampler is described for use in detecting the presence of alpha-emitting aerosol particles. An inlet fractionating screen has been demonstrated to remove about 95% of freshly formed radon progeny from the aerosol sample, and approximately 33% of partially aged progeny. Addition of an electrical condenser and a modified dichotomous virtual impactor are expected to produce considerable improvement in these numbers, the goal being to enrich the transuranic (TRU) fraction of the aerosols. This offers the possibility of improving the signal-to-noise ratio for the detected alpha-particle energy spectrum in the region of interest for detecting TRU materials associated with aerosols, thereby enhancing the performance of background-compensation algorithms for improving the quality of alarm signals intended to warn personnel of potentially harmful quantities of TRU materials in the ambient air.

  1. Aerosol measurements at a high-elevation site: composition, size, and cloud condensation nuclei activity

    SciTech Connect

    Friedman, Beth; Zelenyuk, Alla; Beranek, Josef; Kulkarni, Gourihar R.; Pekour, Mikhail S.; Hallar, Anna G.; McCubbin, Ian; Thornton, Joel A.; Cziczo, D. J.

    2013-12-09

    We present measurements of CCN concentrations and associated aerosol composition and size properties at a high-elevation research site in March 2011. CCN closure and aerosol hygroscopicity were assessed using simplified assumptions of bulk aerosol properties as well as a new method utilizing single particle composition and size to assess the importance of particle mixing state in CCN activation. Free troposphere analysis found no significant difference between the CCN activity of free tropospheric aerosol and boundary layer aerosol at this location. Closure results indicate that using only size and number information leads to adequate prediction, in the majority of cases within 50%, of CCN concentrations, while incorporating the hygroscopicity parameters of the individual aerosol components measured by single particle mass spectrometry adds to the agreement, in most cases within 20%, between predicted and measured CCN concentrations. For high-elevation continental sites, with largely aged aerosol and low amounts of local area emissions, a lack of chemical knowledge and hygroscopicity may not hinder models in predicting CCN concentrations. At sites influenced by fresh emissions or more heterogeneous particle types, single particle composition information may be more useful in predicting CCN concentrations and understanding the importance of particle mixing state on CCN activation.

  2. Biogenic VOC oxidation and organic aerosol formation in an urban nocturnal boundary layer: aircraft vertical profiles in Houston, TX

    NASA Astrophysics Data System (ADS)

    Brown, S. S.; Dubé, W. P.; Bahreini, R.; Middlebrook, A. M.; Brock, C. A.; Warneke, C.; de Gouw, J. A.; Washenfelder, R. A.; Atlas, E.; Peischl, J.; Ryerson, T. B.; Holloway, J. S.; Schwarz, J. P.; Spackman, R.; Trainer, M.; Parrish, D. D.; Fehshenfeld, F. C.; Ravishankara, A. R.

    2013-05-01

    Organic compounds are a large component of aerosol mass, but organic aerosol (OA) sources remain poorly characterized. Recent model studies have suggested nighttime oxidation of biogenic hydrocarbons as a potentially large OA source, but analysis of field measurements to test these predictions is sparse. We present nighttime vertical profiles of nitrogen oxides, ozone, VOCs and aerosol composition measured during low approaches of the NOAA P-3 aircraft to airfields in Houston, TX. This region has large emissions of both biogenic hydrocarbons and nitrogen oxides. The latter serves as a source of the nitrate radical, NO3, a key nighttime oxidant. Biogenic VOCs (BVOC) and urban pollutants were concentrated within the nocturnal boundary layer (NBL), which varied in depth from 100-400 m. Despite concentrated NOx at low altitude, ozone was never titrated to zero, resulting in rapid NO3 radical production rates of 0.2-2.7ppbv h-1 within the NBL. Monoterpenes and isoprene were frequently present within the NBL and underwent rapid oxidation (up to 1ppbv h-1), mainly by NO3 and to a lesser extent O3. Concurrent enhancement in organic and nitrate aerosol on several profiles was consistent with primary emissions and with secondary production from nighttime BVOC oxidation, with the latter equivalent to or slightly larger than the former. Ratios of organic aerosol to CO within the NBL ranged from 14 to 38 μg m-3 OA/ppmv CO. A box model simulation incorporating monoterpene emissions, oxidant formation rates and monoterpene SOA yields suggested overnight OA production of 0.5 to 9 μg m-3.

  3. Aerosol composition, oxidative properties, and sources in Beijing: results from the 2014 Asia-Pacific Economic Cooperation Summit study

    NASA Astrophysics Data System (ADS)

    Xu, W. Q.; Sun, Y. L.; Chen, C.; Du, W.; Han, T. T.; Wang, Q. Q.; Fu, P. Q.; Wang, Z. F.; Zhao, X. J.; Zhou, L. B.; Ji, D. S.; Wang, P. C.; Worsnop, D. R.

    2015-08-01

    The mitigation of air pollution in megacities remains a great challenge because of the complex sources and formation mechanisms of aerosol particles. The 2014 Asia- Pacific Economic Cooperation (APEC) summit in Beijing serves as a unique experiment to study the impacts of emission controls on aerosol composition, size distributions, and oxidative properties. Herein, a high-resolution time-of-flight aerosol mass spectrometer was deployed in urban Beijing for real-time measurements of size-resolved non-refractory submicron aerosol (NR-PM1) species from 14 October to 12 November 2014, along with a range of collocated measurements. The average (±σ) PM1 was 41.6 (±38.9) μg m-3 during APEC, which was decreased by 53 % compared with that before APEC. The aerosol composition showed substantial changes owing to emission controls during APEC. Secondary inorganic aerosols (SIA = sulfate + nitrate + ammonium) showed significant reductions of 62-69 %, whereas organics presented much smaller decreases (35 %). The results from the positive matrix factorization of organic aerosols (OA) indicated that highly oxidized secondary OA (SOA) showed decreases similar to those of SIA during APEC. However, primary OA (POA) from cooking, traffic, and biomass burning sources were comparable to those before APEC, indicating the presence of strong local source emissions. The oxidation properties showed corresponding changes in response to OA composition. The average oxygen-to-carbon level during APEC was 0.36 (±0.10), which is lower than the 0.43 (±0.13) measured before APEC, demonstrating a decrease in the OA oxidation degree. The changes in size distributions of primary and secondary species varied during APEC. SIA and SOA showed significant reductions in large accumulation modes with peak diameters shifting from ~ 650 to 400 nm during APEC, whereas those of POA remained relatively unchanged. The changes in aerosol composition, size distributions, and oxidation degrees during the aging

  4. Examining the Effects of Anthropogenic Emissions on Isoprene-Derived Secondary Organic Aerosol Formation During the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee, Ground Site

    EPA Science Inventory

    A suite of offline and real-time gas- and particle-phase measurements was deployed atLook Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formatio...

  5. In vitro dissolution of respirable aerosols of industrial uranium and plutonium mixed-oxide nuclear fuels.

    PubMed

    Eidson, A F; Mewhinney, J A

    1983-12-01

    Dissolution characteristics of mixed-oxide nuclear fuels are important considerations for prediction of biological behavior of inhaled particles. Four representative industrial mixed-oxide powders were obtained from fuel fabrication enclosures. Studies of the dissolution of Pu, Am and U from aerosol particles of these materials in a serum simulant solution and in 0.1M HCl showed: (1) dissolution occurred at a rapid rate initially and slowed at longer times, (2) greater percentages of U dissolved than Pu or Am: with the dissolution rates of U and Pu generally reflecting the physical nature of the UO2-PuO2 matrix, (3) the temperature history of industrial mixed-oxides could not be reliably related to Pu dissolution except for a 3-5% increase when incorporated into a solid solution by sintering at 1750 degrees C, and (4) dissolution in the serum simulant agreed with the in vivo UO2 dissolution rate and suggested the dominant role of mechanical processes in PuO2 clearance from the lung. The rapid initial dissolution rate was shown to be related, in part, to an altered surface layer. The advantages and uses of in vitro solubility data for estimation of biological behavior of inhaled industrial mixed oxides, such as assessing the use of chelation therapy and interpretation of urinary excretion data, are discussed. It was concluded that in vitro solubility tests were useful, simple and easily applied to individual materials potentially inhaled by humans. PMID:6643070

  6. The Statistical Evolution of Multiple Generations of Oxidation Products in the Photochemical Aging of Chemically Reduced Organic Aerosol

    SciTech Connect

    Wilson, Kevin R.; Smith, Jared D.; Kessler, Sean; Kroll, Jesse H.

    2011-10-03

    The heterogeneous reaction of hydroxyl radicals (OH) with squalane and bis(2-ethylhexyl) sebacate (BES) particles are used as model systems to examine how distributions of reactionproducts evolve during the oxidation of chemically reduced organic aerosol. A kinetic model of multigenerational chemistry, which is compared to previously measured (squalane) and new(BES) experimental data, reveals that it is the statistical mixtures of different generations of oxidation products that control the average particle mass and elemental composition during thereaction. The model suggests that more highly oxidized reaction products, although initially formed with low probability, play a large role in the production of gas phase reaction products.In general, these results highlight the importance of considering atmospheric oxidation as a statistical process, further suggesting that the underlying distribution of molecules could playimportant roles in aerosol formation as well as in the evolution of key physicochemical properties such as volatility and hygroscopicity.

  7. Aerosol identification using a hybrid active/passive system

    NASA Astrophysics Data System (ADS)

    D'Amico, Francis M.; Moon, Raphael P.; Davidson, Charles E.

    2005-08-01

    Recent experimental work has shown that passive systems such as hyperspectral FTIR and frequency-tunable IR cameras have application in detection of biological aerosols. This provided the motivation for a new detection technique, which we call Aerosol Ranging Spectroscopy (ARS), whereby a scattering LIDAR is used to augment passive spectrometer data to determine the location and optical depth of the aerosol plume. When the two systems are co-aligned or boresighted, the hybrid data product provides valuable enhancements for signal exploitation of the passive spectral data. This paper presents the motivation and theoretical basis for the ARS technique. A prototype implementation of an ARS system will also be described, along with preliminary results from recent outdoor field experiments.

  8. Cloud condensation nuclei activity, droplet growth kinetics, and hygroscopicity of biogenic and anthropogenic secondary organic aerosol (SOA)

    NASA Astrophysics Data System (ADS)

    Zhao, D. F.; Buchholz, A.; Kortner, B.; Schlag, P.; Rubach, F.; Fuchs, H.; Kiendler-Scharr, A.; Tillmann, R.; Wahner, A.; Watne, Å. K.; Hallquist, M.; Flores, J. M.; Rudich, Y.; Kristensen, K.; Hansen, A. M. K.; Glasius, M.; Kourtchev, I.; Kalberer, M.; Mentel, Th. F.

    2016-02-01

    Interaction of biogenic volatile organic compounds (VOCs) with Anthropogenic VOC (AVOC) affects the physicochemical properties of secondary organic aerosol (SOA). We investigated cloud droplet activation (CCN activity), droplet growth kinetics, and hygroscopicity of mixed anthropogenic and biogenic SOA (ABSOA) compared to pure biogenic SOA (BSOA) and pure anthropogenic SOA (ASOA). Selected monoterpenes and aromatics were used as representative precursors of BSOA and ASOA, respectively.

    We found that BSOA, ASOA, and ABSOA had similar CCN activity despite the higher oxygen to carbon ratio (O/C) of ASOA compared to BSOA and ABSOA. For individual reaction systems, CCN activity increased with the degree of oxidation. Yet, when considering all different types of SOA together, the hygroscopicity parameter, κCCN, did not correlate with O/C. Droplet growth kinetics of BSOA, ASOA, and ABSOA were comparable to that of (NH4)2SO4, which indicates that there was no delay in the water uptake for these SOA in supersaturated conditions.

    In contrast to CCN activity, the hygroscopicity parameter from a hygroscopic tandem differential mobility analyzer (HTDMA) measurement, κHTDMA, of ASOA was distinctively higher (0.09-0.10) than that of BSOA (0.03-0.06), which was attributed to the higher degree of oxidation of ASOA. The ASOA components in mixed ABSOA enhanced aerosol hygroscopicity. Changing the ASOA fraction by adding biogenic VOC (BVOC) to ASOA or vice versa (AVOC to BSOA) changed the hygroscopicity of aerosol, in line with the change in the degree of oxidation of aerosol. However, the hygroscopicity of ABSOA cannot be described by a simple linear combination of pure BSOA and ASOA systems. This indicates that additional processes, possibly oligomerization, affected the hygroscopicity.

    Closure analysis of CCN and HTDMA data showed κHTDMA was lower than κCCN by 30-70 %. Better closure was achieved for ASOA compared to BSOA. This

  9. Dependence of Heterogeneous OH Kinetics with Biomass Burning Aerosol Proxies on Oxidant Concentration and Relative Humidity

    NASA Astrophysics Data System (ADS)

    Slade, J. H.; Knopf, D. A.

    2013-12-01

    Chemical transformations of aerosol particles by heterogeneous reactions with trace gases such as OH radicals can influence particle physicochemical properties and lifetime, affect cloud formation, light scattering, and human health. Furthermore, OH oxidation can result in degradation of particle mass by volatilization reactions, altering the budget of volatile organic compounds (VOCs). However, the reactive uptake coefficient (γ) and particle oxidation degree can vary depending on several factors including oxidant concentration and relative humidity (RH). While RH can influence the extent of dissociation/ionization, it can also affect particle phase and thus oxidant diffusivity. Only one study so far has investigated the effect of RH on the rate of OH uptake to organic surfaces; however, the underlying processes affecting OH reactivity with organic aerosol under humidified conditions still remains elusive. Here, we determine the effect of RH on OH reactivity with laboratory-generated biomass burning aerosol (BBA) surrogate particles: levoglucosan and 4-methyl-5-nitrocatechol. The effect of OH concentration on γ for three common BBA molecular markers (levoglucosan, abietic acid, and nitroguaiacol) under dry conditions was investigated from [OH]≈107-1011 molecule cm-3, covering both [OH] in biomass burning plumes and [OH] commonly used in particle aging studies. Furthermore, key VOC reaction products and their production pathways resulting from BBA volatilization by OH were identified. OH radicals are produced using a microwave induced plasma (MIP) of H2 in He or Ar followed by reaction with O2, or by photolysis of O3 in the presence of H2O. A cylindrical rotating wall flow-tube reactor and fast-flow aerosol flow reactor are used for conducting kinetic studies. OH is detected using a Chemical Ionization Mass Spectrometer (CIMS) and a Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS) is employed for VOC analysis. γ decreases from 0.2-0.5 at

  10. In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

    NASA Astrophysics Data System (ADS)

    Palm, Brett B.; Campuzano-Jost, Pedro; Ortega, Amber M.; Day, Douglas A.; Kaser, Lisa; Jud, Werner; Karl, Thomas; Hansel, Armin; Hunter, James F.; Cross, Eben S.; Kroll, Jesse H.; Peng, Zhe; Brune, William H.; Jimenez, Jose L.

    2016-03-01

    An oxidation flow reactor (OFR) is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen-Rocky Mountain Biogenic Aerosol Study) field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowed for semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs) onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m-3 when LVOC fate corrected) compared to daytime (average 0.9 µg m-3 when LVOC fate corrected), with maximum formation observed at 0.4-1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic

  11. In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

    DOE PAGESBeta

    Palm, Brett B.; Campuzano-Jost, Pedro; Ortega, Amber M.; Day, Douglas A.; Kaser, Lisa; Jud, Werner; Karl, Thomas; Hansel, Armin; Hunter, James F.; Cross, Eben S.; et al

    2016-03-08

    An oxidation flow reactor (OFR) is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen–Rocky Mountain Biogenic Aerosol Study) field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowed formore » semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs) onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m–3 when LVOC fate corrected) compared to daytime (average 0.9 µg m–3 when LVOC fate corrected), with maximum formation observed at 0.4–1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (>10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small

  12. In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

    DOE PAGESBeta

    Palm, Brett B.; Campuzano-Jost, Pedro; Ortega, Amber M.; Day, Douglas A.; Kaser, Lisa; Jud, Werner; Karl, Thomas; Hansel, Armin; Hunter, James F.; Cross, Eben S.; et al

    2016-03-08

    An oxidation flow reactor (OFR) is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen–Rocky Mountain Biogenic Aerosol Study) field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowed formore » semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs) onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m−3 when LVOC fate corrected) compared to daytime (average 0.9 µg m−3 when LVOC fate corrected), with maximum formation observed at 0.4–1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of

  13. In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

    SciTech Connect

    Palm, Brett B.; Campuzano-Jost, Pedro; Ortega, Amber M.; Day, Douglas A.; Kaser, Lisa; Jud, Werner; Karl, Thomas; Hansel, Armin; Hunter, James F.; Cross, Eben S.; Kroll, Jesse H.; Peng, Zhe; Brune, William H.; Jimenez, Jose L.

    2016-01-01

    An oxidation flow reactor (OFR) is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen–Rocky Mountain Biogenic Aerosol Study) field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowed for semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs) onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m−3 when LVOC fate corrected) compared to daytime (average 0.9 µg m−3 when LVOC fate corrected), with maximum formation observed at 0.4–1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the

  14. AMS+ALS: Kinetic and Product Studies of the Heterogeneous Oxidation of Organic Aerosol at the Advanced Light Source

    NASA Astrophysics Data System (ADS)

    Kroll, J. H.; Wilson, K. R.; Kessler, S. H.; Browne, E. C.; Nah, T.; Smith, J.; Worsnop, D. R.

    2014-12-01

    The atmospheric oxidation of condensed-phase organic species can have a major influence on the composition, properties, and impacts of organic aerosol (OA); however the rates and products of such "aging" reactions are poorly constrained. Here we describe a series of laboratory experiments aimed at better understanding one class of aging reactions, the heterogeneous oxidation of OA by gas-phase oxidants. Central to these experiments is the availability of vacuum ultraviolet (VUV) light at the Chemical Dynamics Beamline of the Advanced Light Source at LBNL, which enables the implementation of VUV photoionization aerosol mass spectrometry. This technique allows for the real-time, speciated measurement of OA composition, yielding molecular information that is highly complementary to ensemble data from electron-impact ionization. OA composition is measured with both ionization schemes as a function of oxidant exposure within a flow reactor, providing detailed information on the kinetics and products of heterogeneous oxidation over multiple generations of oxidation. Specific topics investigated include the branching between functionalization and fragmentation of OA components, the formation of secondary organic aerosol from photolytically-generated radical species, and the heterogeneous aging of soot-associated organic species.

  15. Compositional changes in neurotoxins and their oxidative derivatives from the dinoflagellate, Karenia brevis, in seawater and marine aerosol

    PubMed Central

    Pierce, Richard H.; Henry, Michael S.; Blum, Patricia C.; Osborn, Shannon E.; Cheng, Yung-Sung; Zhou, Yue; Irvin, Clinton M.; Bourdelais, Andrea J.; Naar, Jerome; Baden, Daniel G.

    2011-01-01

    The harmful alga, Karenia brevis, produces a suite of polyether neurotoxins, brevetoxins or PbTx, that cause marine animal mortality and neurotoxic shellfish poisoning (NSP). A characteristic of K. brevis blooms is associated airborne toxins that result in severe respiratory problems. This study was undertaken to determine the composition of aerosolized brevetoxins and oxidative derivatives to which beachgoers are exposed during a K. brevis bloom. The suite of brevetoxins and derivatives in seawater is comprised of intra-cellular (IC) and extra-cellular (EC) compounds. We hypothesized that aerosolized compounds are generated primarily from EC, hydrophobic compounds in seawater by bubble-mediated transport. Thus the composition of aerosolized brevetoxins and derivatives, to which beachgoers are exposed, would reflect the EC composition of the source matrix (the local surf zone). Brevetoxins were extracted from water collected along the shore and from marine aerosols along Siesta Beach and Lido Beach in Sarasota, FL, USA, during K. brevis blooms. Water samples were further processed into IC and EC components. The primary brevetoxins observed in water and air included PbTx-1, -2, -3, -PbTx-2-carboxylic acid, and brevenal. Oxidation and/or hydrolysis products of PbTx-1, -2, -3 and -7 were also found in EC water and in aerosol, but not IC. PMID:21191552

  16. Application of FIGAERO (Filter Inlet for Gases and AEROsol) coupled to a high resolution time of flight chemical ionization mass spectrometer to field and chamber organic aerosol: Implications for carboxylic acid formation and gas-particle partitioning from monoterpene oxidation

    NASA Astrophysics Data System (ADS)

    Lopez-Hilfiker, F.; Mohr, C.; Ehn, M.; Rubach, F.; Mentel, T. F.; Kleist, E.; Wildt, J.; Thornton, J. A.

    2013-12-01

    We present measurements of a large suite of gas and particle phase carboxylic acid containing compounds made with a Filter Inlet for Gas and AEROsol (FIGAERO) coupled to a high resolution time of flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. A prototype operated with acetate negative ion proton transfer chemistry was deployed on the Julich Plant Atmosphere Chamber to study a-pinene oxidation, and a modified version was deployed at the SMEAR II forest station in Hyytiälä, Finland and SOAS, in Brent Alabama. We focus here on results from JPAC and Hyytiälä, where we utilized the same ionization method most selective towards carboxylic acids. In all locations, 100's of organic acid compounds were observed in the gas and particles and many of the same composition acids detected in the gas-phase were detected in the particles upon temperature programmed thermal desorption. Particulate organics detected by FIGAERO are highly correlated with organic aerosol mass measured by an AMS, providing additional volatility and molecular level information about collected aerosol. The fraction of a given compound measured in the particle phase follows expected trends with elemental composition, but many compounds would not be well described by an absorptive partitioning model assuming unity activity coefficients. Moreover the detailed structure in the thermal desorption signals reveals a contribution from thermal decomposition of large molecular weight organics and or oligomers with implications for partitioning measurements and model validation

  17. Reduction of photosynthetically active radiation under extreme stratospheric aerosol loads

    SciTech Connect

    Gerstl, S.A.W.; Zardecki, A.

    1981-08-01

    The recently published hypothesis that the Cretaceous-Tertiary extinctions might be caused by an obstruction of sunlight is tested by model calculations. First we compute the total mass of stratospheric aerosols under normal atmospheric conditions for four different (measured) aerosol size distributions and vertical profiles. For comparison, the stratospheric dust masses after four volcanic eruptions are also evaluated. Detailed solar radiative transfer calculations are then performed for artificially increased aerosol amounts until the postulated darkness scenario is obtained. Thus we find that a total stratospheric aerosol mass between 1 and 4 times 10/sup 1/ g is sufficient to reduce photosynthesis to 10/sup -3/ of normal. We also infer from this result tha the impact of a 0.4- to 3-km-diameter asteroid or a close encounter with a Halley-size comet may deposit that amount of particulates into the stratosphere. The darkness scenario of Alvarez et al. is thus shown to be a possible extinction mechanism, even with smaller size asteroids of comets than previously estimated.

  18. The optical constants of several atmospheric aerosol species - Ammonium sulfate, aluminum oxide, and sodium chloride

    NASA Technical Reports Server (NTRS)

    Toon, O. B.; Pollack, J. B.; Khare, B. N.

    1976-01-01

    An investigation is conducted of problems which are related to a use of measured optical constants in the simulation of the optical constants of real atmospheric aerosols. The techniques of measuring optical constants are discussed, taking into account transmission measurements through homogeneous and inhomogeneous materials, the immersion of a material in a liquid of a known refractive index, the consideration of the minimum deviation angle of prism measurement, the interference of multiply reflected light, reflectivity measurements, and aspects of mathematical analysis. Graphs show the real and the imaginary part of the refractive index as a function of wavelength for aluminum oxide, NaCl, and ammonium sulfate. Tables are provided for the dispersion parameters and the optical constants.

  19. Comparative Antimicrobial Activities of Aerosolized Sodium Hypochlorite, Chlorine Dioxide, and Electrochemically Activated Solutions Evaluated Using a Novel Standardized Assay

    PubMed Central

    Thorn, R. M. S.; Robinson, G. M.

    2013-01-01

    The main aim of this study was to develop a standardized experimental assay to enable differential antimicrobial comparisons of test biocidal aerosols. This study represents the first chlorine-matched comparative assessment of the antimicrobial activities of aerosolized sodium hypochlorite, chlorine dioxide, and electrochemically activated solution (ECAS) to determine their relative abilities to decontaminate various surface-associated health care-relevant microbial challenges. Standard microbiological challenges were developed by surface-associating typed Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus subtilis spores, or a clinical methicillin-resistant S. aureus (MRSA) strain on stainless steel, polypropylene, or fabric. All test coupons were subjected to 20-min biocidal aerosols of chlorine-matched (100 ppm) sodium hypochlorite, chlorine dioxide, or ECAS within a standard aerosolization chamber using a commercial humidifier under defined conditions. Biocidal treatment type and material surface had a significant effect on the number of microorganisms recovered from various material surfaces following treatment exposure. Under the conditions of the assay, the order of antimicrobial efficacy of biocidal aerosol treatment was as follows: ECAS > chlorine dioxide > sodium hypochlorite. For all biocides, greater antimicrobial reductions were seen when treating stainless steel and fabric than when treating plastic-associated microorganisms. The experimental fogging system and assay protocol designed within this study were shown capable of differentiating the comparative efficacies of multiple chlorine-matched biocidal aerosols against a spectrum of target organisms on a range of test surface materials and would be appropriate for testing other biocidal aerosol treatments or material surfaces. PMID:23459480

  20. Photodegradation of secondary organic aerosol generated from limonene oxidation by ozone studied with chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pan, X.; Underwood, J. S.; Xing, J.-H.; Mang, S. A.; Nizkorodov, S. A.

    2009-06-01

    Photodegradation of secondary organic aerosol (SOA) prepared by ozone-initiated oxidation of D-limonene is studied with an action spectroscopy approach, which relies on detection of volatile photoproducts with chemical ionization mass-spectrometry as a function of the UV irradiation wavelength. Efficient photodegradation is observed for a broad range of ozone (0.1-300 ppm) and D-limonene (0.02-3 ppm) concentrations used in the preparation of SOA. The observed photoproducts are dominated by oxygenated C1-C3 compounds such as methanol, formic acid, acetaldehyde, acetic acid, and acetone. The irradiation wavelength dependence of the combined yield of the photoproducts closely tracks the absorption spectrum of the SOA material suggesting that photodegradation is not limited to the UV wavelengths. Kinetic simulations suggest that RO2+HO2/RO2 reactions represent the dominant route to photochemically active carbonyl and peroxide species in the limonene SOA prepared in these experiments. Similar photodegradation processes are likely to occur in realistic SOA produced by OH- or O3-initiated oxidation of biogenic volatile organic compounds in clean air.

  1. Photodegradation of secondary organic aerosol generated from limonene oxidation by ozone studied with chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pan, X.; Underwood, J. S.; Xing, J.-H.; Mang, S. A.; Nizkorodov, S. A.

    2009-02-01

    Photodegradation of secondary organic aerosol (SOA) prepared by ozone-initiated oxidation of D-limonene is studied with an action spectroscopy approach, which relies on detection of volatile photoproducts with chemical ionization mass-spectrometry as a function of the UV irradiation wavelength. Efficient photodegradation is observed for a broad range of ozone and D-limonene concentrations (0.1-300 ppm) used in the preparation of SOA. The observed photoproducts are dominated by oxygenated C1-C3 compounds such as methanol, formic acid, acetaldehyde, acetic acid, and acetone. The irradiation wavelength dependence of the combined yield of the photoproducts closely tracks the absorption spectrum of the SOA material suggesting that photodegradation is not limited to the UV wavelengths. Kinetic simulations suggest that RO2+HO2/RO2 reactions represent the dominant route to photochemically active carbonyl and peroxide species in the limonene SOA material. Similar photodegradation processes are likely to occur in realistic SOA produced by OH- or O3-initiated oxidation of biogenic volatile organic compounds in clean air.

  2. Carboxylic acids in secondary aerosols from oxidation of cyclic monoterpenes by ozone

    SciTech Connect

    Glasius, M.; Lahaniati, M.; Calogirou, A.; Di Bella, D.; Jensen, N.R.; Hjorth, J.; Kotzias, D.; Larsen, B.R.

    2000-03-15

    A series of smog chamber experiments have been conducted in which five cyclic monoterpenes were oxidized by ozone. The evolved secondary aerosol was analyzed by GC-MS and HPLC-MS for nonvolatile polar oxidation products with emphasis on the identification of carboxylic acids. Three classes of compounds were determined at concentration levels corresponding to low percentage molar yields: i.e., dicarboxylic acids, oxocarboxylic acids, and hydroxyketocarboxylic acids. Carboxylic acids are highly polar and have lower vapor pressures than their corresponding aldehydes and may thus play an important role in secondary organic aerosol formation processes. The most abundant carboxylic acids were the following: cis-pinic acid AB1(cis-3-carboxy-2,2-dimethylcyclobutylethanoic acid) from {alpha} and {beta}-pinene; cis-pinonic acid A3 (cis-3-acetyl-2,2-dimethylcyclobutylethanoic acid) and cis-10-hydroxypinonic acid Ab6 (cis-2,2-dimethyl-3-hydroxyacetylcyclobutyl-ethanoic acid) from {alpha}-pinene and {beta}-pinene; cis-3-caric acid C1 (cis-2,2-dimethyl-1,3-cyclopropyldiethanoic acid), cis-3-caronic acid C3 (2,2-dimethyl-3-(2-oxopropyl)cyclopropanylethanoic acid), and cis-10-hydroxy-3-caronic acid C6 (cis-2,2-dimethyl-3(hydroxy-2-oxopropyl)cyclopropanylethanoic acid) from 3-carene; cis-sabinic acid S1 (cis-2-carboxy-1-isopropylcyclopropylethanoic acid) from sabinene; limonic acid L1 (3-isopropenylhexanedioic acid), limononic acid L3 (3-isopropenyl-6-oxo-heptanoic acid), 7-hydroxy-limononic acid L6 (3-isopropenyl-7-hydroxy-6-oxoheptanoic acid), and 7-hydroxylimononic acid Lg{prime} (7-hydroxy-3-isopropenyl-6-oxoheptanoic acid) from limonene.

  3. Regional Biases in Droplet Activation Parameterizations: Strong Influence on Aerosol Second Indirect Effect in the Community Atmosphere Model v5.

    NASA Astrophysics Data System (ADS)

    Morales, R.; Nenes, A.

    2014-12-01

    Aerosol-cloud interactions constitute one of the most uncertain aspects of anthropogenic climate change estimates. The magnitude of these interactions as represented in climate models strongly depends on the process of aerosol activation. This process is the most direct physical link between aerosols and cloud microphysical properties. Calculation of droplet number in GCMs requires the computation of new droplet formation (i.e., droplet activation), through physically based activation parameterizations. Considerable effort has been placed in ensuring that droplet activation parameterizations have a physically consistent response to changes in aerosol number concentration. However, recent analyses using an adjoint sensitivity approach showed that parameterizations can exhibit considerable biases in their response to other aerosol properties, such as aerosol modal diameter or to the aerosol chemical composition. This is a potentially important factor in estimating aerosol indirect effects since changes in aerosol properties from pre-industrial times to present day exhibit a very strong regional signature. In this work we use the Community Atmosphere Model (CAM5) to show that the regional imprint of the changes in aerosol properties during the last century interacts with the droplet activation parameterization in a way that these biases are amplified over climatically relevant regions. Two commonly used activation routines, the CAM5 default, Abdul-Razzak and Ghan parameterization, as well as the Fountoukis and Nenes parameterization are used in this study. We further explored the impacts of Nd parameterization biases in the first and second aerosol indirect effects separately, by performing simulations were droplet number was not allowed to intervene in the precipitation initiation process. The simulations performed show that an unphysical response to changes in the diameter of accumulation mode aerosol translates into extremely high Nd concentrations over South

  4. Composition of Secondary Organic Aerosols Produced by Photo-Oxidation of Biomass Burning Emissions in a Smog Chamber

    NASA Astrophysics Data System (ADS)

    Desyaterik, Y.; Sullivan, A.; Hennigan, C. J.; Robinson, A. L.; Collett, J. L.

    2009-12-01

    Knowledge of the chemical composition of atmospheric organic aerosols (OA) is essential for accurate representation of OA in air quality and climate models. Both the sources of OA and their properties and effects remain poorly understood. In particular, we still know relatively little about the atmospheric formation of secondary organic aerosols (SOA). There is growing interest in the impact of biomass burning emissions on air quality, human health, and radiative forcing. Through a series of experiments, we are working to quantify changes in the chemical composition of wood smoke particles as a result of photochemical aging under well-controlled laboratory conditions. One specific objective of this study is to identify markers for biomass burning SOA and test whether these markers can be used in atmospheric samples to quantify SOA formation from aging of biomass burning emissions. We analyzed SOA generated in a smog chamber by photooxidation of smoke produced by burning oak wood. In order to initiate photochemistry, the chamber was irradiated with UV light. Aqueous extracts of collected aerosol samples were analyzed with Electrospray Ionization Time-of-Flight Mass Spectrometry. The high mass accuracy of these measurements reduces ambiguity in the assignment of elemental compositions for observed ions. Analysis has shown that primary oak smoke aerosol includes products of the thermal decomposition of cellulose (levoglucosan, cyclotene etc.) and lignin (guaiacol and syringol derivatives, mostly aldehydes and alcohols). After 2 hours of aging at typical summertime hydroxyl radical concentrations, the aerosol mass increased 2.5 fold due to the production of secondary organic aerosol. Mass spectra of the secondary organic aerosol formed are dominated by organic nitrates (nitrophenol, nitrocresol, nitrocatechol, and nitroguaiacol) and aromatic acids (benzoic acid, mono and di-hydroxybenzoic acid). Both nitrates and acids most likely are formed due to oxidation of the

  5. In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

    NASA Astrophysics Data System (ADS)

    Palm, B. B.; Campuzano-Jost, P.; Ortega, A. M.; Day, D. A.; Kaser, L.; Jud, W.; Karl, T.; Hansel, A.; Hunter, J. F.; Cross, E. S.; Kroll, J. H.; Peng, Z.; Brune, W. H.; Jimenez, J. L.

    2015-11-01

    Ambient air was oxidized by OH radicals in an oxidation flow reactor (OFR) located in a montane pine forest during the BEACHON-RoMBAS campaign to study biogenic secondary organic aerosol (SOA) formation and aging. High OH concentrations and short residence times allowed for semi-continuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative time scales of condensation of low volatility organic compounds (LVOCs) onto particles, condensational loss to the walls, and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 4 μg m-3 when LVOC fate corrected) compared to daytime (average 1 μg m-3 when LVOC fate corrected), with maximum formation observed at 0.4-1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene + p-cymene concentrations, including a substantial increase just after sunrise at 07:00 LT. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic compounds, and net production at lower ages followed by net consumption of terpenoid oxidation products as photochemical age increased. New particle formation was observed in the reactor after oxidation, especially during times when precursor gas concentrations and SOA formation were largest. Approximately 6 times more SOA was formed in the reactor from OH oxidation than

  6. Fabrication of porous materials (metal, metal oxide and semiconductor) through an aerosol-assisted route

    NASA Astrophysics Data System (ADS)

    Sohn, Hiesang

    Porous materials have gained attraction owing to their vast applications in catalysts, sensors, energy storage devices, bio-devices and other areas. To date, various porous materials were synthesized through soft and hard templating approaches. However, a general synthesis method for porous non-oxide materials, metal alloys and semiconductors with tunable structure, composition and morphology has not been developed yet. To address this challenge, this thesis presents an aerosol method towards the synthesis of such materials and their applications for catalysis, hydrogen storage, Li-batteries and photo-catalysis. The first part of this thesis presents the synthesis of porous metals, metal oxides, and semiconductors with controlled pore structure, crystalline structure and morphology. In these synthesis processes, metal salts and organic ligands were employed as precursors to create porous metal-carbon frameworks. During the aerosol process, primary metal clusters and nanoparticles were formed, which were coagulated/ aggregated forming the porous particles. Various porous particles, such as those of metals (e.g., Ni, Pt, Co, Fe, and Ni xPt(1-x)), metal oxides (e.g., Fe3O4 and SnO2) and semiconductors (e.g., CdS, CuInS2, CuInS 2x-ZnS(1-x), and CuInS2x-TiO2(1-x)) were synthesized. The morphology, porous structure and crystalline structure of the particles were regulated through both templating and non-templating methods. The second part of this thesis explores the applications of these materials, including propylene hydrogenation and H2 uptake capacity of porous Ni, NiPt alloys and Ni-Pt composites, Li-storage of Fe3O4 and SnO2, photodegradation of CuInS2-based semiconductors. The effects of morphology, compositions, and porous structure on the device performance were systematically investigated. Overall, this dissertation work unveiled a simple synthesis approach for porous particles of metals, metal alloys, metal oxides, and semiconductors with controlled

  7. Calibration correction of an active scattering spectrometer probe to account for refractive index of stratospheric aerosols

    NASA Technical Reports Server (NTRS)

    Pueschel, R. F.; Overbeck, V. R.; Snetsinger, K. G.; Russell, P. B.; Ferry, G. V.

    1990-01-01

    The use of the active scattering spectrometer probe (ASAS-X) to measure sulfuric acid aerosols on U-2 and ER-2 research aircraft has yielded results that are at times ambiguous due to the dependence of particles' optical signatures on refractive index as well as physical dimensions. The calibration correction of the ASAS-X optical spectrometer probe for stratospheric aerosol studies is validated through an independent and simultaneous sampling of the particles with impactors; sizing and counting of particles on SEM images yields total particle areas and volumes. Upon correction of calibration in light of these data, spectrometer results averaged over four size distributions are found to agree with similarly averaged impactor results to within a few percent: indicating that the optical properties or chemical composition of the sample aerosol must be known in order to achieve accurate optical aerosol spectrometer size analysis.

  8. The Effect of Methyl, Hydroxyl, and Ketone Functional Groups on the Heterogeneous Oxidation of Succinic Acid Aerosol by OH Radicals

    NASA Astrophysics Data System (ADS)

    Chan, M.; Zhang, H.; Wilson, K. R.

    2013-12-01

    The heterogeneous oxidation of atmospheric organic aerosols can influence their effects on climate, human health, and visibility. During oxidation, functionalization occurs when an oxygenated functional group is added to a molecule, leaving the carbon skeleton intact. Fragmentation involves carbon-carbon bond cleavage and produces two products with smaller carbon numbers than the parent compound. To gain better insights into how the molecular structure of more oxygenated organic compounds affects heterogeneous reactivity, succinic acid aerosols are photo-oxidized in an aerosol flow tube reactor, and the reaction products are analyzed using Direct Analysis in Real Time Mass Spectrometry for online chemical analysis. The effect of various functional groups (CH3, OH, C=O) along the carbon backbone on the heterogeneous reaction mechanisms are also investigated using model compounds. For this series of compounds, the formation of more oxygenated products through functionalization can be explained by well-known condensation-phase reactions such as Russell and Bennett and Summers. The number of fragmentation products is found to increase with the presence of OH and CH3 groups. This can be attributed to the increased number of tertiary carbons, enhancing the fragmentation after multiple oxidation steps. Smaller dicaids (oxalic acid and malonic acid) can be formed through the fragmentation processes in the heterogeneous oxidation of succinic acid. The effect of molecular structure on reaction kinetics, volatilization, and the relative importance of functionalization and fragmentation pathways will be discussed.

  9. Secondary organic aerosol formation and primary organic aerosol oxidation from biomass-burning smoke in a flow reactor during FLAME-3

    NASA Astrophysics Data System (ADS)

    Ortega, A. M.; Day, D. A.; Cubison, M. J.; Brune, W. H.; Bon, D.; de Gouw, J. A.; Jimenez, J. L.

    2013-11-01

    We report the physical and chemical effects of photochemically aging dilute biomass-burning smoke. A "potential aerosol mass" (PAM) flow reactor was used with analysis by a high-resolution aerosol mass spectrometer and a proton-transfer-reaction ion-trap mass spectrometer during the FLAME-3 campaign. Hydroxyl (OH) radical concentrations in the reactor reached up to ~1000 times average tropospheric levels, producing effective OH exposures equivalent to up to 5 days of aging in the atmosphere, and allowing for us to extend the investigation of smoke aging beyond the oxidation levels achieved in traditional smog chambers. Volatile organic compound (VOC) observations show aromatics and terpenes decrease with aging, while formic acid and other unidentified oxidation products increase. Unidentified gas-phase oxidation products, previously observed in atmospheric and laboratory measurements, were observed here, including evidence of multiple generations of photochemistry. Substantial new organic aerosol (OA) mass ("net SOA"; secondary OA) was observed from aging biomass-burning smoke, resulting in total OA average of 1.42 ± 0.36 times the initial primary OA (POA) after oxidation. This study confirms that the net-SOA-to-POA ratio of biomass-burning smoke is far lower on average than that observed for urban emissions. Although most fuels were very reproducible, significant differences were observed among the biomasses, with some fuels resulting in a doubling of the OA mass, while for others a very small increase or even a decrease was observed. Net SOA formation in the photochemical reactor increased with OH exposure (OHexp), typically peaking around three days of equivalent atmospheric photochemical age (OHexp~3.9 × 1011 molecules cm-3 s), then leveling off at higher exposures. The amount of additional OA mass added from aging is positively correlated with initial POA concentration, but not with the total VOC concentration or the concentration of known SOA precursors

  10. Global modelling of secondary organic aerosol from α-pinene oxidation using a parameterization based on a detailed chemical mechanism

    NASA Astrophysics Data System (ADS)

    Ceulemans, Karl; Müller, Jean-Francois; Compernolle, Steven; Stavrakou, Jenny

    2010-05-01

    Monoterpenes are oxidized in the atmosphere by ozone and the hydroxyl and nitrate radicals. The condensable products resulting from these reactions contribute to Secondary Organic Aerosol (SOA). We have developed a detailed α-pinene chemical mechanism BOREAM (Capouet et al. 2008), in which the primary gas phase chemistry is based on quantum-chemical results, structure activity relationships and experimental data. The secondary chemistry of the most important products is treated explicitly, while further chemistry is reduced by the aid of generic species classes. The partitioning between gas phase and SOA is modeled using Pankow's partitioning approach (Pankow 1994), with vapor pressures (Capouet and Müller 2006) and activity coefficients (Compernolle et al. 2009) obtained from group contribution methods. We will discuss the performance of BOREAM through comparison of model predictions for SOA formation with experimental SOA yields for a large number (>150) of photo-oxidation and dark ozonolysis experiments (Ceulemans et al. 2009). Although the BOREAM SOA yields are significantly higher than in several previous box modeling studies, a reasonable agreement is found in comparison with most laboratory measurements. For use in a global model, the detailed BOREAM chemistry is replaced by a parameterized scheme based on the two-product approach (Odum et al. 1996) with parameters obtained through regressions of full model simulations. The reduced scheme accounts for the dependence of SOA yield on the oxidant (ozone, OH or NO3) and the NOx regime. For example, the reaction of alpha-pinene with OH generates a peroxy radical which, upon reaction with either NO or HO2 leads to the formation of two condensable products. The branching ratios and partitioning coefficients are temperature dependent. We inserted the obtained parameterized scheme in the global model IMAGES, where it is used to represent the SOA formation due to the monoterpenes. For aromatics, isoprene and

  11. LC-MS analysis of aerosol particles from the oxidation of α-pinene by ozone and OH-radicals

    NASA Astrophysics Data System (ADS)

    Winterhalter, R.; van Dingenen, R.; Larsen, B. R.; Jensen, N. R.; Hjorth, J.

    2003-01-01

    The time resolved chemical composition of aerosol particles, formed by the oxidation of alpha-pinene has been investigated by liquid chromatography/mass spectrometry (LC-MS) using negative and positive ionisation methods (ESI(-) and APCI(+)). The experiments were performed at the EUPHORE facility in Valencia (Spain) under various experimental conditions, including dark ozone reactions, photosmog experiments with low NOx mixing ratios and reaction with OH radicals in the absence of NOx (H2O2-photolysis). Particles were sampled on PTFE f ilters at different stages of the reaction and extracted with methanol. The predominant products from alpha-pinene in the particulate phase are cis-pinic acid, cis-pinonic acid and hydroxy-pinonic acid isomers. Another major compound with molecular weight 172 was detected, possibly a hydroxy-carboxylic acid. These major compounds account for 50% to 80% of the identified aerosol products, depending on the time of sampling and type of experiment. In addition, more than 20 different products have been detected and structures have been tentatively assigned based on their molecular weight and responses to the different ionisation modes. The different experiments performed showed that the aerosol formation is mainly caused by the ozonolysis reaction. The highest aerosol yields were observed in the dark ozone experiments, for which also the highest ratios of mass of identified products to the formed aerosol mass were found (30% to 50%, assuming a density of 1 g cm-3).

  12. Formation of Low Volatility Organic Compounds and Secondary Organic Aerosol from Isoprene Hydroxyhydroperoxide Low-NO Oxidation.

    PubMed

    Krechmer, Jordan E; Coggon, Matthew M; Massoli, Paola; Nguyen, Tran B; Crounse, John D; Hu, Weiwei; Day, Douglas A; Tyndall, Geoffrey S; Henze, Daven K; Rivera-Rios, Jean C; Nowak, John B; Kimmel, Joel R; Mauldin, Roy L; Stark, Harald; Jayne, John T; Sipilä, Mikko; Junninen, Heikki; Clair, Jason M St; Zhang, Xuan; Feiner, Philip A; Zhang, Li; Miller, David O; Brune, William H; Keutsch, Frank N; Wennberg, Paul O; Seinfeld, John H; Worsnop, Douglas R; Jimenez, Jose L; Canagaratna, Manjula R

    2015-09-01

    Gas-phase low volatility organic compounds (LVOC), produced from oxidation of isoprene 4-hydroxy-3-hydroperoxide (4,3-ISOPOOH) under low-NO conditions, were observed during the FIXCIT chamber study. Decreases in LVOC directly correspond to appearance and growth in secondary organic aerosol (SOA) of consistent elemental composition, indicating that LVOC condense (at OA below 1 μg m(-3)). This represents the first simultaneous measurement of condensing low volatility species from isoprene oxidation in both the gas and particle phases. The SOA formation in this study is separate from previously described isoprene epoxydiol (IEPOX) uptake. Assigning all condensing LVOC signals to 4,3-ISOPOOH oxidation in the chamber study implies a wall-loss corrected non-IEPOX SOA mass yield of ∼4%. By contrast to monoterpene oxidation, in which extremely low volatility VOC (ELVOC) constitute the organic aerosol, in the isoprene system LVOC with saturation concentrations from 10(-2) to 10 μg m(-3) are the main constituents. These LVOC may be important for the growth of nanoparticles in environments with low OA concentrations. LVOC observed in the chamber were also observed in the atmosphere during SOAS-2013 in the Southeastern United States, with the expected diurnal cycle. This previously uncharacterized aerosol formation pathway could account for ∼5.0 Tg yr(-1) of SOA production, or 3.3% of global SOA. PMID:26207427

  13. Activity size distribution and residence time of 7Be aerosols in the Arctic atmosphere

    NASA Astrophysics Data System (ADS)

    Ioannidou, Alexandra; Paatero, Jussi

    2014-05-01

    The activity size distributions of the natural radionuclide tracer 7Be in different size range fractions (<0.39 μm, 0.39-0.69 μm, 0.69-1.3 μm, 1.3-2.1 μm, 2.1-4.2 μm, 4.2-10.2 μm and >10.2 μm) were determined in the boreal atmosphere in the Arctic Research Centre of the Finnish Meteorological Institute (FMI) at Sodankylä, Finland (67°22‧ N, 26°38‧ E, 180 m asl). The activity median aerodynamic diameter (AMAD) ranged from 0.54 μm to 1.05 μm (average 0.83 μm). A residence time of about 8 days applies to aerosols of 0.83 μm diameter, representing the residence of aerosol particles in arctic environment. The observed positive correlation between AMAD values and RH% can be explained by the fact that condensation during high relative humidity conditions becomes more intense, resulting in increased particle sizes of atmospheric aerosols. However, greater aerosol particle sizes means higher wet scavenging rate of aerosols and as a result lower activity concentration of 7Be in the atmosphere, explaining the anti-correlation between the AMAD values and activity concentrations of 7Be. But this associated with possibly higher scavenging rates of aerosols does not necessarily alone explain the anti-correlation between the AMAD and the 7Be activities. The air mass origin associated with synoptic scale weather phenomena may contribute to that too. The Flextra model was used to assess the transport pattern and to explain the deviation in radionuclide activity concentrations and AMAD values observed in the site of investigation.

  14. Aerosol mixing state, hygroscopic growth and cloud activation efficiency during MIRAGE 2006

    NASA Astrophysics Data System (ADS)

    Lance, S.; Raatikainen, T.; Onasch, T. B.; Worsnop, D. R.; Yu, X.-Y.; Alexander, M. L.; Stolzenburg, M. R.; McMurry, P. H.; Smith, J. N.; Nenes, A.

    2013-05-01

    Observations of aerosol hygroscopic growth and CCN activation spectra for submicron particles are reported for the T1 ground site outside of Mexico City during the MIRAGE 2006 campaign. κ-Köhler theory is used to evaluate the characteristic hygroscopicity parameter, κ*, for the CCN active aerosol population using both size-resolved HTMDA and size-resolved CCNc measurements. Organic mass fractions (forg) are evaluated from size-resolved aerosol mass spectrometer (AMS) measurements, from which predictions of the hygroscopicity parameter are compared against κ*. Strong diurnal changes in aerosol water uptake parameters and aerosol composition are observed. We find that new particle formation (NPF) events are correlated with an increased κ* and CCN-active fraction during the daytime, with greater impact on smaller particles. During NPF events, the number concentration of 40 nm particles acting as CCN at 0.51% ± 0.06% supersaturation can surpass by more than a factor of two the corresponding concentrations of 100 nm particles. We also find that at 06:00-08:00 LT throughout the campaign, fresh traffic emissions result in substantial changes to the chemical distribution of the aerosol, with on average 65% externally mixed fraction for 40 nm particles and 30% externally mixed fraction for 100 nm particles, whereas at midday nearly all particles of both sizes can be described as "internally mixed". Average activation spectra and growth factor distributions are analyzed for different time periods characterizing the daytime (with and without NPF events), the early morning "rush hour" and the entire campaign. We show that κ* derived from CCNc measurements decreases as a function of size during all time periods, while the CCN-active fraction increases as a function of size. Size-resolved AMS measurements do not predict the observed trend for κ* versus particle size, which can be attributed to unresolved mixing state and the presence of refractory material not measured

  15. Characterization and parameterization of aerosol cloud condensation nuclei activation under different pollution conditions.

    PubMed

    Che, H C; Zhang, X Y; Wang, Y Q; Zhang, L; Shen, X J; Zhang, Y M; Ma, Q L; Sun, J Y; Zhang, Y W; Wang, T T

    2016-01-01

    To better understand the cloud condensation nuclei (CCN) activation capacity of aerosol particles in different pollution conditions, a long-term field experiment was carried out at a regional GAW (Global Atmosphere Watch) station in the Yangtze River Delta area of China. The homogeneity of aerosol particles was the highest in clean weather, with the highest active fraction of all the weather types. For pollution with the same visibility, the residual aerosol particles in higher relative humidity weather conditions were more externally mixed and heterogeneous, with a lower hygroscopic capacity. The hygroscopic capacity (κ) of organic aerosols can be classified into 0.1 and 0.2 in different weather types. The particles at ~150 nm were easily activated in haze weather conditions. For CCN predictions, the bulk chemical composition method was closer to observations at low supersaturations (≤0.1%), whereas when the supersaturation was ≥0.2%, the size-resolved chemical composition method was more accurate. As for the mixing state of the aerosol particles, in haze, heavy haze, and severe haze weather conditions CCN predictions based on the internal mixing assumption were robust, whereas for other weather conditions, predictions based on the external mixing assumption were more accurate. PMID:27075947

  16. Characterization and parameterization of aerosol cloud condensation nuclei activation under different pollution conditions

    NASA Astrophysics Data System (ADS)

    Che, H. C.; Zhang, X. Y.; Wang, Y. Q.; Zhang, L.; Shen, X. J.; Zhang, Y. M.; Ma, Q. L.; Sun, J. Y.; Zhang, Y. W.; Wang, T. T.

    2016-04-01

    To better understand the cloud condensation nuclei (CCN) activation capacity of aerosol particles in different pollution conditions, a long-term field experiment was carried out at a regional GAW (Global Atmosphere Watch) station in the Yangtze River Delta area of China. The homogeneity of aerosol particles was the highest in clean weather, with the highest active fraction of all the weather types. For pollution with the same visibility, the residual aerosol particles in higher relative humidity weather conditions were more externally mixed and heterogeneous, with a lower hygroscopic capacity. The hygroscopic capacity (κ) of organic aerosols can be classified into 0.1 and 0.2 in different weather types. The particles at ~150 nm were easily activated in haze weather conditions. For CCN predictions, the bulk chemical composition method was closer to observations at low supersaturations (≤0.1%), whereas when the supersaturation was ≥0.2%, the size-resolved chemical composition method was more accurate. As for the mixing state of the aerosol particles, in haze, heavy haze, and severe haze weather conditions CCN predictions based on the internal mixing assumption were robust, whereas for other weather conditions, predictions based on the external mixing assumption were more accurate.

  17. Characterization and parameterization of aerosol cloud condensation nuclei activation under different pollution conditions

    PubMed Central

    Che, H. C.; Zhang, X. Y.; Wang, Y. Q.; Zhang, L.; Shen, X. J.; Zhang, Y. M.; Ma, Q. L.; Sun, J. Y.; Zhang, Y. W.; Wang, T. T.

    2016-01-01

    To better understand the cloud condensation nuclei (CCN) activation capacity of aerosol particles in different pollution conditions, a long-term field experiment was carried out at a regional GAW (Global Atmosphere Watch) station in the Yangtze River Delta area of China. The homogeneity of aerosol particles was the highest in clean weather, with the highest active fraction of all the weather types. For pollution with the same visibility, the residual aerosol particles in higher relative humidity weather conditions were more externally mixed and heterogeneous, with a lower hygroscopic capacity. The hygroscopic capacity (κ) of organic aerosols can be classified into 0.1 and 0.2 in different weather types. The particles at ~150 nm were easily activated in haze weather conditions. For CCN predictions, the bulk chemical composition method was closer to observations at low supersaturations (≤0.1%), whereas when the supersaturation was ≥0.2%, the size-resolved chemical composition method was more accurate. As for the mixing state of the aerosol particles, in haze, heavy haze, and severe haze weather conditions CCN predictions based on the internal mixing assumption were robust, whereas for other weather conditions, predictions based on the external mixing assumption were more accurate. PMID:27075947

  18. Dimers and organosulfates derived from biogenic oxidation products in aerosols during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) in California 2007 and 2009 (Invited)

    NASA Astrophysics Data System (ADS)

    Glasius, M.; Worton, D. R.; Kristensen, K.; Nguyen, Q.; Surratt, J.; Enggrob, K. L.; Bouvier-Brown, N. C.; Farmer, D.; Docherty, K. S.; Platt, S.; Bilde, M.; Nøjgaard, J. K.; Seinfeld, J.; Jimenez, J. L.; Goldstein, A.

    2010-12-01

    Oxidation products of biogenic volatile organic compounds, such as monoterpenes and isoprene, contribute to biogenic secondary organic aerosol (BSOA). The organosulfate derivatives of these compounds are formed through heterogeneous reactions involving sulphur compounds, with a considerable contribution from anthropogenic sources. Organosulfate derivatives of biogenic oxidation products thus belong to a new group of anthropogenic enhanced biogenic SOA (ABSOA). The Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) during summers of 2007 and 2009 provided an excellent platform at Blodgett Forest, California (a ponderosa pine plantation) for studying ABSOA. Typically, polluted air masses were transported upslope from the California Central Valley during day, while night conditions were influenced by downslope transport of air masses, low local atmospheric mixing and formation of a shallow boundary layer. We collected particle samples (PM2.5) as one nighttime and two daytime samples per day. After extraction of filters in polar organic solvents (i.e. acetonitrile or methanol), organic aerosol constituents were analyzed by HPLC coupled through an electrospray inlet to a quadrupole time-of-flight mass spectrometer (qTOF-MS). Organosulfates and nitrooxy organosulfates derived from oxidation products of α-pinene, β-pinene, limonene and isoprene were identified based on their molecular mass and MS fragmentation patterns. Measurements by High Resolution Time of Flight Aerosol Mass Spectrometry (HR-ToF-AMS) show high mass loadings of nitrate in the night and morning samples with highest levels of the nitrooxy organosulfates with MW 295 and MW 297. This may indicate that elevated levels of nitrate and nitrooxy organosulfates are formed in the same polluted air mass, probably through nitrate radical reactions. Terpenylic acid, diterpenylic acid acetate, and methylbutane tricarboxylic acid were found at concentrations comparable to pinic acid. A dimer of

  19. Comparison of the cloud activation potential of open ocean and coastal aerosol in the Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Vidaurre, G.; Brooks, S. D.; Thornton, D. C.

    2010-12-01

    Continuous measurements of aerosol concentration, particle size distribution, and cloud activation potential between 0.15 and 1.2% supersaturation were performed for open ocean and coastal air during the Halocarbon Air Sea Transect - Pacific (HalocAST) campaign. The nearly 7000 mile transect, aboard the R/V Thomas G. Thompson, started in Punta Arenas, Chile and ended in Seattle, Washington. Air mass source regions were identified on the basis of air mass back trajectories. For air masses in the southern hemisphere, aerosols sampled over the open ocean acted as cloud condensation nuclei at supersaturations between 0.5 and 1%, while coastal aerosols required higher supersaturations. In the pristine open ocean, observed aerosol concentrations were very low, typically below 200 cm-3, with an average particle diameter of approximately 0.4 μm. On the other hand, coastal aerosol concentrations were above 1000 cm-3 with an average particle diameter of 0.7 μm. Air masses originating in the northern hemisphere had much higher aerosol loads, between 500 and 2000 cm-3 over the ocean and above 4000 cm-3 at the coast. In both cases, the average particle diameters were approximately 0.5 μm. Measurements suggest that the northern hemisphere, substantially more polluted than the southern hemisphere, is characterized by alternating regions of high and medium aerosol number concentration. In addition, measurements of microorganism and organic matter concentration in the surface layer of the ocean water were conducted along the cruise track, to test the hypothesis that biogenic aerosol containing marine organic matter contribute to cloud activation potential. There was a significant correlation between mean aerosol diameter and prokaryote concentration in surface waters (r = 0.585, p < 0.01, n = 24), and between critical supersaturation and prokaryote concentration in surface waters (r = 0.538, p < 0.01, n = 24). This correlation indicates that larger aerosols occurred over water

  20. Active Oxidation of SiC

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan S.; Myers,Dwight L.; Harder, Bryan J.

    2011-01-01

    The high temperature oxidation of silicon carbide occurs in either a passive or active mode, depending on temperature and oxygen potential. Passive oxidation forms a protective oxide film which limits attack of the SiC:SiC(s) + 3/2 O2(g) = SiO2(s) + CO(g.) Active oxidation forms a volatile oxide and leads to extensive attack of the SiC: SiC(s) + O2(g) = SiO(g) + CO(g). The transition points and rates of active oxidation are a major issue. Previous studies are reviewed and the leading theories of passive/active transitions summarized. Comparisons are made to the active/passive transitions in pure Si, which are relatively well-understood. Critical questions remain about the difference between the active-to-passive transition and passive-to-active transition. For Si, Wagner [2] points out that the active-to-passive transition is governed by the criterion for a stable Si/SiO2 equilibria and the passive-to-active transition is governed by the decomposition of the SiO2 film. This suggests a significant oxygen potential difference between these two transitions and our experiments confirm this. For Si, the initial stages of active oxidation are characterized by the formation of SiO(g) and further oxidation to SiO2(s) as micron-sized rods, with a distinctive morphology. SiC shows significant differences. The active-to-passive and the passive-to-active transitions are close. The SiO2 rods only appear as the passive film breaks down. These differences are explained in terms of the reactions at the SiC/SiO2 interface. In order to understand the breakdown of the passive film, pre-oxidation experiments are conducted. These involve forming dense protective scales of 0.5, 1, and 2 microns and then subjecting the samples with these scales to a known active oxidation environment. Microstructural studies show that SiC/SiO2 interfacial reactions lead to a breakdown of the scale with a distinct morphology.

  1. 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.

  2. Black-carbon-surface oxidation and organic composition of beech-wood soot aerosols

    NASA Astrophysics Data System (ADS)

    Corbin, J. C.; Lohmann, U.; Sierau, B.; Keller, A.; Burtscher, H.; Mensah, A. A.

    2015-03-01

    Soot particles are the most strongly light-absorbing particles commonly found in the atmosphere. They are major contributors to the radiative budget of the Earth and to the toxicity of atmospheric pollution. Atmospheric aging of soot may change its health- and climate-relevant properties by oxidizing the primary black carbon (BC) or organic particulate matter (OM) which, together with ash, comprise soot. This atmospheric aging, which entails the condensation of secondary particulate matter as well as the oxidation of the primary OM and BC emissions, is currently poorly understood. In this study, atmospheric aging of wood-stove soot aerosols was simulated in a continuous-flow reactor. The composition of fresh and aged soot particles was measured in real time by a dual-vaporizer aerosol-particle mass spectrometer (SP-AMS). The SP-AMS provided information on the OM, BC, and surface composition of the soot. The OM appeared to be generated largely by cellulose and/or hemicellulose pyrolysis, and was only present in large amounts when new wood was added to the stove. BC signals otherwise dominated the mass spectrum. These signals consisted of ions related to refractory BC (rBC, C+1-5), oxygenated surface groups (CO+1-2), potassium (K+) and water (H+2O and related fragments). The C+4 : C+3 ratio, but not the C+1 : C+3 ratio, was consistent with the BC-structure trends of Corbin et al. (2015c). The CO+1-2 signals likely originated from BC surface groups: upon aging, both CO+ and CO+2 increased relative to C+1-3 while CO+2 simultaneously increased relative to CO+. Factor analysis (PMF) of SP-AMS and AMS data, using a new error model to account for peak-integration uncertainties, indicated that the surface composition of the BC was approximately constant across all stages of combustion for both fresh and aged samples. These results represent the first time-resolved measurements of in-situ BC-surface aging and suggest that the surface of beech-wood BC may be modelled as a

  3. Black carbon surface oxidation and organic composition of beech-wood soot aerosols

    NASA Astrophysics Data System (ADS)

    Corbin, J. C.; Lohmann, U.; Sierau, B.; Keller, A.; Burtscher, H.; Mensah, A. A.

    2015-10-01

    Soot particles are the most strongly light-absorbing particles commonly found in the atmosphere. They are major contributors to the radiative budget of the Earth and to the toxicity of atmospheric pollution. Atmospheric aging of soot may change its health- and climate-relevant properties by oxidizing the primary black carbon (BC) or organic particulate matter (OM) which, together with ash, comprise soot. This atmospheric aging, which entails the condensation of secondary particulate matter as well as the oxidation of the primary OM and BC emissions, is currently poorly understood. In this study, atmospheric aging of wood-stove soot aerosols was simulated in a continuous-flow reactor. The composition of fresh and aged soot particles was measured in real time by a dual-vaporizer aerosol-particle mass spectrometer (SP-AMS). The dual-vaporizer SP-AMS provided information on the OM and BC components of the soot as well as on refractory components internally mixed with BC. By switching the SP-AMS laser vaporizer off and using only the AMS thermal vaporizer (at 600 °C), information on the OM component only was obtained. In both modes, OM appeared to be generated largely by cellulose and/or hemicellulose pyrolysis and was only present in large amounts when new wood was added to the stove. In SP-AMS mode, BC signals otherwise dominated the mass spectrum. These signals consisted of ions related to refractory BC (rBC, C1-5+), oxygenated carbonaceous ions (CO1-2+), potassium (K+), and water (H2O+ and related fragments). The C4+ : C3+ ratio, but not the C1+ : C3+ ratio, was consistent with the BC-structure trends of Corbin et al. (2015c). The CO1-2+ signals likely originated from BC surface groups: upon aging, both CO+ and CO2+ increased relative to C1-3+ while CO2+ simultaneously increased relative to CO+. Factor analysis (positive matrix factorization) of SP-AMS and AMS data, using a modified error model to address peak-integration uncertainties, indicated that the surface

  4. Environmental Health Hazards of e-Cigarettes and their Components: Oxidants and Copper in e-cigarette aerosols

    PubMed Central

    Lerner, Chad A.; Sundar, Isaac K.; Watson, Richard M.; Elder, Alison; Jones, Ryan; Done, Douglas; Kurtzman, Rachel; Ossip, Deborah J.; Robinson, Risa; McIntosh, Scott; Rahman, Irfan

    2014-01-01

    To narrow the gap in our understanding of potential oxidative properties associated with Electronic Nicotine Delivery systems (ENDS) i.e. e-cigarettes, we employed semi-quantitative methods to detect oxidant reactivity in disposable components of ENDS/e-cigarettes (batteries and cartomizers) using a fluorescein indicator. These components exhibit oxidants/reactive oxygen species reactivity similar to used conventional cigarette filters. Oxidants/reactive oxygen species reactivity in e-cigarette aerosols was also similar to oxidant reactivity in cigarette smoke. A cascade particle impactor allowed sieving of a range of particle size distributions between 0.450 and 2.02 μm in aerosols from an e-cigarette. Copper, being among these particles, is 6.1 times higher per puff than reported previously for conventional cigarette smoke. The detection of a potentially cytotoxic metal as well as oxidants from e-cigarette and its components raises concern regarding the safety of e-cigarettes use and the disposal of e-cigarette waste products into the environment. PMID:25577651

  5. Effects of flame made zinc oxide particles in human lung cells - a comparison of aerosol and suspension exposures

    PubMed Central

    2012-01-01

    Background Predominantly, studies of nanoparticle (NPs) toxicology in vitro are based upon the exposure of submerged cell cultures to particle suspensions. Such an approach however, does not reflect particle inhalation. As a more realistic simulation of such a scenario, efforts were made towards direct delivery of aerosols to air-liquid-interface cultivated cell cultures by the use of aerosol exposure systems. This study aims to provide a direct comparison of the effects of zinc oxide (ZnO) NPs when delivered as either an aerosol, or in suspension to a triple cell co-culture model of the epithelial airway barrier. To ensure dose–equivalence, ZnO-deposition was determined in each exposure scenario by atomic absorption spectroscopy. Biological endpoints being investigated after 4 or 24h incubation include cytotoxicity, total reduced glutathione, induction of antioxidative genes such as heme-oxygenase 1 (HO–1) as well as the release of the (pro)-inflammatory cytokine TNFα. Results Off-gases released as by-product of flame ZnO synthesis caused a significant decrease of total reduced GSH and induced further the release of the cytokine TNFα, demonstrating the influence of the gas phase on aerosol toxicology. No direct effects could be attributed to ZnO particles. By performing suspension exposure to avoid the factor “flame-gases”, particle specific effects become apparent. Other parameters such as LDH and HO–1 were not influenced by gaseous compounds: Following aerosol exposure, LDH levels appeared elevated at both timepoints and the HO–1 transcript correlated positively with deposited ZnO-dose. Under submerged conditions, the HO–1 induction scheme deviated for 4 and 24h and increased extracellular LDH was found following 24h exposure. Conclusion In the current study, aerosol and suspension-exposure has been compared by exposing cell cultures to equivalent amounts of ZnO. Both exposure strategies differ fundamentally in their dose–response pattern

  6. Multi-generational oxidation model to simulate secondary organic aerosol in a 3-D air quality model

    NASA Astrophysics Data System (ADS)

    Jathar, S. H.; Cappa, C. D.; Wexler, A. S.; Seinfeld, J. H.; Kleeman, M. J.

    2015-08-01

    Multi-generational gas-phase oxidation of organic vapors can influence the abundance, composition and properties of secondary organic aerosol (SOA). Only recently have SOA models been developed that explicitly represent multi-generational SOA formation. In this work, we integrated the statistical oxidation model (SOM) into SAPRC-11 to simulate the multi-generational oxidation and gas/particle partitioning of SOA in the regional UCD/CIT (University of California, Davis/California Institute of Technology) air quality model. In the SOM, evolution of organic vapors by reaction with the hydroxyl radical is defined by (1) the number of oxygen atoms added per reaction, (2) the decrease in volatility upon addition of an oxygen atom and (3) the probability that a given reaction leads to fragmentation of the organic molecule. These SOM parameter values were fit to laboratory smog chamber data for each precursor/compound class. SOM was installed in the UCD/CIT model, which simulated air quality over 2-week periods in the South Coast Air Basin of California and the eastern United States. For the regions and episodes tested, the two-product SOA model and SOM produce similar SOA concentrations but a modestly different SOA chemical composition. Predictions of the oxygen-to-carbon ratio qualitatively agree with those measured globally using aerosol mass spectrometers. Overall, the implementation of the SOM in a 3-D model provides a comprehensive framework to simulate the atmospheric evolution of organic aerosol.

  7. Oxidative potential of secondary organic aerosols produced from photooxidation of different hydrocarbons using outdoor chamber under ambient sunlight

    NASA Astrophysics Data System (ADS)

    Jiang, Huanhuan; Jang, Myoseon; Sabo-Attwood, Tara; Robinson, Sarah E.

    2016-04-01

    The oxidative potential of various secondary organic aerosols (SOA) was measured using dithiothreitol (DTT) assay to understand how organic aerosols react with cellular materials. SOA was produced via the photooxidation of four different hydrocarbons (toluene, 1,3,5-trimethylbenzene, isoprene and α-pinene) in the presence of NOx using a large outdoor photochemical smog chamber. The DTT consumption rate was normalized by the aerosol mass, which is expressed as DTTmass. Toluene SOA and isoprene SOA yielded higher DTTmass than 1,3,5-trimethylbenzene SOA or α-pinene SOA. In order to discover the correlation between the molecular structure and oxidative potential, the DTT responses of selected model compounds were also measured. Among them, conjugated aldehydes, quinones, and H2O2 showed considerable DTT response. To investigate the correlation between DTT response and cell responses in vitro, the expression of biological markers, i.e. IL-6, IL-8, and HMOX-1 were studied using small airway epithelial cells. Higher cellular expression of IL-8 was observed with toluene SOA exposure compared to 1,3,5-trimethylbenzene SOA exposure, which aligned with the results from DTT assay. Our study also suggests that within the urban atmosphere, the contribution of toluene SOA and isoprene SOA to the oxidative potential of ambient SOA will be more significant than that of α-pinene SOA.

  8. Aerosol synthesis and electrochemical analysis of niobium mixed-metal oxides for the ethanol oxidation reaction in acid and alkaline electrolyte

    NASA Astrophysics Data System (ADS)

    Konopka, Daniel A.

    Direct ethanol fuel cells are especially important among emerging electrochemical power systems with the potential to offset a great deal of the energy demand currently met through the use of fossil fuels. Ethanol can be refined from petroleum sources or attained from renewable biomass, and is more easily and safely stored and transported than hydrogen, methanol or gasoline. The full energy potential of ethanol in fuel cells can only be realized if the reaction follows a total oxidation pathway to produce CO2. This must be achieved by the development of advanced catalysts that are electrically conductive, stable in corrosive environments, contain a high surface area on which the reaction can occur, and exhibit a bi-functional effect for the ethanol oxidation reaction (EOR). The latter criterion is achievable in mixed-metal systems. Platinum is an effective metal for catalyzing surface reactions of many adsorbates and is usually implemented in the form of Pt nanoparticles supported on inexpensive carbon. This carbon is believed to be neutral in the catalysis of Pt. Instead, carbon can be replaced with carefully designed metals and metal oxides as co-catalysis or support structures that favorably alter the electronic structure of Pt slightly through a strong metal support interaction, while also acting as an oxygen source near adsorbates to facilitate the total oxidation pathway. Niobium mixed-metal-oxides were explored in this study as bi-functional catalyst supports to Pt nanoparticles. We developed a thermal aerosol synthesis process by which mesoporous powders of mixed-metal-oxides decorated with Pt nanoparticles could be obtained from liquid precursors within ˜5 seconds or less, followed by carefully refined chemical and thermal post-treatments. Exceptionally high surface areas of 170--180m2/g were achieved via a surfactant-templated 3D wormhole-type porosity, comparable on a per volume basis to commercial carbon blacks and high surface area silica supports

  9. Exploring Atmospheric Aqueous Chemistry (and Secondary Organic Aerosol Formation) through OH Radical Oxidation Experiments, Droplet Evaporation and Chemical Modeling

    NASA Astrophysics Data System (ADS)

    Turpin, B. J.; Kirkland, J. R.; Lim, Y. B.; Ortiz-Montalvo, D. L.; Sullivan, A.; Häkkinen, S.; Schwier, A. N.; Tan, Y.; McNeill, V. F.; Collett, J. L.; Skog, K.; Keutsch, F. N.; Sareen, N.; Carlton, A. G.; Decesari, S.; Facchini, C.

    2013-12-01

    Gas phase photochemistry fragments and oxidizes organic emissions, making water-soluble organics ubiquitous in the atmosphere. My group and others have found that several water-soluble compounds react further in the aqueous phase forming low volatility products under atmospherically-relevant conditions (i.e., in clouds, fogs and wet aerosols). Thus, secondary organic aerosol can form as a result of gas followed by aqueous chemistry (aqSOA). We have used aqueous OH radical oxidation experiments coupled with product analysis and chemical modeling to validate and refine the aqueous chemistry of glyoxal, methylglyoxal, glycolaldehyde, and acetic acid. The resulting chemical model has provided insights into the differences between oxidation chemistry in clouds and in wet aerosols. Further, we conducted droplet evaporation experiments to characterize the volatility of the products. Most recently, we have conducted aqueous OH radical oxidation experiments with ambient mixtures of water-soluble gases to identify additional atmospherically-important precursors and products. Specifically, we scrubbed water-soluble gases from the ambient air in the Po Valley, Italy using four mist chambers in parallel, operating at 25-30 L min-1. Aqueous OH radical oxidation experiments and control experiments were conducted with these mixtures (total organic carbon ≈ 100 μM-C). OH radicals (3.5E-2 μM [OH] s-1) were generated by photolyzing H2O2. Precursors and products were characterized using electrospray ionization mass spectrometry (ESI-MS), ion chromatography (IC), IC-ESI-MS, and ultra high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Chemical modeling suggests that organic acids (e.g., oxalate, pyruvate, glycolate) are major products of OH radical oxidation at cloud-relevant concentrations, whereas organic radical - radical reactions result in the formation of oligomers in wet aerosols. Products of cloud chemistry and droplet evaporation have

  10. Understanding the anthropogenic influence on formation of biogenic secondary organic aerosols via analysis of organosulfates and related oxidation products

    NASA Astrophysics Data System (ADS)

    Nguyen, Q. T.; Christensen, M. K.; Cozzi, F.; Zare, A.; Hansen, A. M. K.; Kristensen, K.; Tulinius, T. E.; Madsen, H. H.; Christensen, J. H.; Brandt, J.; Massling, A.; Nøjgaard, J. K.; Glasius, M.

    2014-01-01

    Anthropogenic emissions of sulfur dioxide (SO2) and nitrogen oxides (NOx) may affect concentration levels and composition of biogenic secondary organic aerosols (BSOA) through photochemical reactions with biogenic organic precursors to form organosulfates and nitrooxy organosulfates. We investigated this influence in a field study from 19 May-22 June 2011 at two sampling sites in Denmark. Within the study, we identified a substantial number of organic acids, organosulfates and nitrooxy organosulfates in the ambient urban curbside and semi-rural background air. A high degree of correlation in concentrations was found among a group of specific organic acids, organosulfates and nitrooxy organosulfates, which may originate from various precursors, suggesting a common mechanism or factor affecting their concentration levels at the sites. It was proposed that the formation of those species most likely occurred on a larger spatial scale with the compounds being long-range transported to the sites on the days with highest concentrations. The origin of the long-range transported aerosols was investigated using the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model in addition to modeled emissions of related precursors including isoprene and monoterpenes using the global Model of Emissions of Gases and Aerosols from Nature (MEGAN) and SO2 emissions using the European Monitoring and Evaluation Program (EMEP) database. The local impacts were also studied by examining the correlation between selected species which showed significantly enhanced concentrations at the urban curbside site and the local concentrations of various gases including SO2, ozone (O3), carbon monoxide (CO), NOx, aerosol acidity and other meteorological conditions. This investigation showed that an inter-play of the local parameters such as the aerosol acidity, NOx, relative humidity (RH), temperature and global radiation seemed to influence the concentration level of those species, via

  11. Mesoscale modeling of combined aerosol and photo-oxidant processes in the eastern Mediterranean

    NASA Astrophysics Data System (ADS)

    Lazaridis, M.; Spyridaki, A.; Solberg, S.; Smolík, J.; Ždímal, V.; Eleftheriadis, K.; Aleksandropoulou, V.; Hov, O.; Georgopoulos, P. G.

    2004-09-01

    Particulate matter and photo-oxidant processes in the Eastern Mediterranean have been studied using the UAM-AERO mesoscale air quality model in conjunction with the NILU-CTM regional model. Meteorological data were obtained from the RAMS prognostic meteorological model. The modeling domain includes the eastern Mediterranean area between the Greek mainland and the island of Crete. The modeling system is applied to study the atmospheric processes in three periods, i.e. 13-16 July 2000, 26-30 July 2000 and 7-14 January 2001. The spatial and temporal distributions of both gaseous and particulate matter pollutants have been extensively studied together with the identification of major emission sources in the area. The modeling results were compared with field data obtained in the same period. Comparison of the modeling results with measured data was performed for a number of gaseous and aerosol species. The UAM-AERO model underestimates the PM10 measured concentrations during summer but better comparison has been obtained for the winter data.

  12. Mesoscale modeling of combined aerosol and photo-oxidant processes in the Eastern Mediterranean

    NASA Astrophysics Data System (ADS)

    Lazaridis, M.; Spyridaki, A.; Solberg, S.; Smolík, J.; Zdímal, V.; Eleftheriadis, K.; Aleksanropoulou, V.; Hov, O.; Georgopoulos, P. G.

    2005-03-01

    Particulate matter and photo-oxidant processes in the Eastern Mediterranean have been studied using the UAM-AERO mesoscale air quality model in conjunction with the NILU-CTM regional model. Meteorological data were obtained from the RAMS prognostic meteorological model. The modeling domain includes the eastern Mediterranean area between the Greek mainland and the island of Crete. The modeling system is applied to study the atmospheric processes in three periods, i.e. 13-16 July 2000, 26-30 July 2000 and 7-14 January 2001. The spatial and temporal distributions of both gaseous and particulate matter pollutants have been extensively studied together with the identification of major emission sources in the area. The modeling results were compared with field data obtained in the same period. The objective of the current modeling work was mainly to apply the UAM-AERO mesoscale model in the eastern Mediterranean in order to assess the performed field campaigns and determine that the applied mesoscale model is fit for this purpose. Comparison of the modeling results with measured data was performed for a number of gaseous and aerosol species. The UAM-AERO model underestimates the PM10 measured concentrations during summer and winter campaigns. Discrepancies between modeled and measured data are attributed to unresolved particulate matter emissions. Particulate matter in the area is mainly composed by sulphate, sea salt and crustal materials, and with significant amounts of nitrate, ammonium and organics. During winter the particulate matter and oxidant concentrations were lower than the summer values.

  13. Secondary organic aerosols formed from oxidation of biogenic volatile organic compounds in the Sierra Nevada Mountains of California

    NASA Astrophysics Data System (ADS)

    Cahill, Thomas M.; Seaman, Vincent Y.; Charles, M. Judith; Holzinger, Rupert; Goldstein, Allen H.

    2006-08-01

    Biogenic volatile organic compound (BVOC) emissions, such as isoprene and terpenes, can be oxidized to form less volatile carbonyls, acids, and multifunctional oxygenated products that may condense to form secondary organic aerosols (SOA). This research was designed to assess the contribution of oxidized BVOC emissions to SOA in coniferous forests by collecting high-volume particulate samples for 6 days and 5 nights in the summer of 2003. The samples were analyzed for acids, carbonyls, polyols and alkanes to quantify oxidized BVOCs. Terpene and isoprene oxidation products were among the most abundant chemical species detected with the exception of hexadecanoic acid, octadecanoic acid and two butyl esters of unknown origin. The terpene oxidation products of pinonic acid, pinic acid, nopinone and pinonaldehyde showed clear diurnal cycles with concentrations two- to eight-fold higher at night. These cycles resulted from the diurnal cycles in gaseous terpene concentrations and lower temperatures that enhanced condensation of semivolatile chemicals onto aerosols. The terpene-derived compounds averaged 157 ± 118 ng/m3 of particulate organic matter while the isoprene oxidation compounds, namely the 2-methyltetrols and 2-methylglyceric acid, accounted for 53 ± 19 ng/m3. Together, the terpene and isoprene oxidation products represented 36.9% of the identified organic mass of 490 ± 95 ng/m3. PM10 organic matter loadings in the region were approximately 2.1 ± 1.2 μg/m3, so about 23% of the organic matter was identified and at least 8.6% was oxidized BVOCs. The BVOC oxidation products we measured were significant, but not dominant, contributors to the regional SOA only 75 km downwind of the Sacramento urban area.

  14. Oxidative potential of size-fractionated atmospheric aerosol in urban and rural sites across Europe.

    PubMed

    Shafer, Martin M; Hemming, Jocelyn D C; Antkiewicz, Dagmara S; Schauer, James J

    2016-07-18

    In this study we applied several assays, an in vitro rat alveolar macrophage model, a chemical ROS probe (DTT, dithiothreitol), and cytokine induction (TNFα) to examine relationships between PM-induced generation of reactive oxygen species (ROS) and PM composition, using a unique set of size-resolved PM samples obtained from urban and rural 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 and from three rural sites spanning the continent. A Hi-Vol sampler was used to collect PM in three size classes (PM>7, PM7-3, PM3) and PM was characterized for total elements, and oxidative activity quantified in unfiltered and filtered PM extracts. We measured a remarkable uniformity in air concentrations of ROS and especially DTT activity across the continent. Only a 4-fold difference was documented for DTT across the urban sites and a similar variance was documented for ROS, implying that chemical drivers of oxidative activity are relatively similar between sites. The ROS and DTT specific activity was greater at urban background sites (and also rural sites) than at urban canyon locations. PM3 dominated the size distribution of both ROS activity (86% of total) and DTT activity (76% of total), reflecting both the large contribution of PM3 to total PM mass levels and importantly the higher specific oxidative activity of the PM3 in comparison with the larger particles. The soluble fraction of total activity was very high for DTT (94%) as well as for ROS (64%) in the PM3. However in the larger PM size fractions the contributions of the insoluble components became increasingly significant. The dominance of the insoluble PM drivers of activity was particularly evident in the TNFα data, where the insoluble contribution to cytokine production could be 100-fold greater than that from soluble components. ROS and DTT activity were strongly correlated in the PM3 (r = 0

  15. Effects of precursor concentration and acidic sulfate in aqueous glyoxal-OH radical oxidation and implications for secondary organic aerosol.

    PubMed

    Tan, Yi; Perri, Mark J; Seitzinger, Sybil P; Turpin, Barbara J

    2009-11-01

    Previous experiments demonstrated that aqueous OH radical oxidation of glyoxal yields low-volatility compounds. When this chemistry takes place in clouds and fogs, followed by droplet evaporation (or if it occurs in aerosol water), the products are expected to remain partially in the particle phase, forming secondary organic aerosol (SOA). Acidic sulfate exists ubiquitously in atmospheric water and has been shown to enhance SOA formation through aerosol phase reactions. In this work, we investigate how starting concentrations of glyoxal (30-3000 microM) and the presence of acidic sulfate (0-840 microM) affect product formation in the aqueous reaction between glyoxal and OH radical. The oxalic acid yield decreased with increasing precursor concentrations, and the presence of sulfuric acid did not alter oxalic acid concentrations significantly. A dilute aqueous chemistry model successfully reproduced oxalic acid concentrations, when the experiment was performed at cloud-relevant concentrations (glyoxal <300 microM), but predictions deviated from measurements at increasing concentrations. Results elucidate similarities and differences in aqueous glyoxal chemistry in clouds and in wet aerosols. They validate for the first time the accuracy of model predictions at cloud-relevant concentrations. These results suggest that cloud processing of glyoxal could be an important source of SOA. PMID:19924930

  16. Organic Aerosol Formation in the Humid, Photochemically-Active Southeastern US: SOAS Experiments and Simulations

    NASA Astrophysics Data System (ADS)

    Sareen, N.; Lim, Y. B.; Carlton, A. G.; Turpin, B. J.

    2013-12-01

    Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized low volatility organic aerosol and, in some cases, light absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, health, and the environment. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols) leading to the formation of secondary organic aerosol (SOAAQ). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify other precursors that are atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere at Brent, Alabama during the Southern Oxidant and Aerosol Study (SOAS). Four mist chambers in parallel collected ambient gases in a DI water medium at 20-25 LPM with a 4 hr collection time. Total organic carbon (TOC) values in daily composited samples were 64-180 μM. Aqueous OH radical oxidation experiments were conducted with these mixtures in a newly designed cuvette chamber to understand the formation of SOA through gas followed by aqueous chemistry. OH radicals (3.5E-2 μM [OH] s-1) were formed in-situ in the chamber, continuously by H2O2 photolysis. Precursors and products of these aqueous OH experiments were characterized using ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS), and IC-ESI-MS. ESI-MS results from a June 12th, 2013 sample showed precursors to be primarily odd, positive mode ions, indicative of the presence of non-nitrogen containing alcohols, aldehydes, organic peroxides, or epoxides. Products were seen in the negative mode and included organic acid ions like pyruvate

  17. Evolution of the Physicochemical and Activation Properties of Aerosols within Smoke Plumes during the Biomass Burning Observation Project (BBOP)

    NASA Astrophysics Data System (ADS)

    Tomlinson, J. M.; Mei, F.; Wang, J.; Comstock, J. M.; Hubbe, J. M.; Pekour, M. S.; Shilling, J. E.; Fortner, E.; Chand, D.; Sedlacek, A. J., III; Kleinman, L. I.; Senum, G.; Schmid, B.

    2014-12-01

    Biomass burning from wildfires and controlled agricultural burns are known to be a major source of fine particles and organic aerosols at northern temperate latitudes during the summer months. However, the evolution of the physicochemical properties of the aerosol during transport and the potential impact of this evolution on cloud condensation nuclei (CCN) activity has rarely been studied for these events. During the DOE-sponsored Biomass Burning Observation Project (BBOP) conducted in the summer and fall of 2013, over 30 research flights sampled biomass burning plumes from wildfires in the Northwestern United States and agricultural burns in the Mid-South region of the United States. A large suite of instruments aboard the DOE G-1 (Gulfstream-1) measured the chemical, physical, and optical properties of biomass burning aerosol with an emphasis on black carbon. A Fast Integrated Mobility Spectrometer (FIMS), Ultra High Sensitivity Aerosol Spectrometer - Airborne (UHSAS-A), and Passive Cavity Aerosol Spectrometer (PCASP) were used to measure the aerosol size distribution from 15 - 3,000 nm at 1-Hz. A dual column CCN counter measured the CCN number concentration at supersaturations of 0.25% and 0.50% at a time resolution of 1-Hz and the aerosol chemical composition was measured using a soot particle aerosol mass spectrometer (SP-AMS, Aerodyne, Inc). The SP-AMS was operated in two modes: (i) as a traditional high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS, Aerodyne Inc.), which measured chemical composition of non-refractory aerosols and (ii) as the SP-AMS which measured chemical composition of the refractory black carbon-containing (rBC) particle coating and rBC aerosol mass. Utilizing the aforementioned measurements, a CCN closure study is used to investigate the emitted aerosol hygroscopicity, the evolution of the physicochemical properties of the aerosol, and the potential impacts on cloud microphysics from the different fuel sources.

  18. The effect of phase partitioning of semivolatile compounds on the measured CCN activity of aerosol particles

    NASA Astrophysics Data System (ADS)

    Romakkaniemi, S.; Jaatinen, A.; Laaksonen, A.; Nenes, A.; Raatikainen, T.

    2013-09-01

    The effect of inorganic semivolatile aerosol compounds on the CCN activity of aerosol particles was studied by using a computational model for a DMT-CCN counter, a cloud parcel model for condensation kinetics and experiments to quantify the modelled results. Concentrations of water vapour and semivolatiles as well as aerosol trajectories in the CCN column were calculated by a computational fluid dynamics model. These trajectories and vapour concentrations were then used as an input for the cloud parcel model to simulate mass transfer kinetics of water and semivolatiles between aerosol particles and the gas phase. Two different questions were studied: (1) how big fraction of semivolatiles is evaporated from particles before activation in the CCN counter? (2) How much the CCN activity can be increased due to condensation of semivolatiles prior to the maximum water supersaturation in the case of high semivolatile concentration in the gas phase? The results show that, to increase the CCN activity of aerosol particles, a very high gas phase concentration (as compared to typical ambient conditions) is needed. We used nitric acid as a test compound. A concentration of several ppb or higher is needed for measurable effect. In the case of particle evaporation, we used ammonium nitrate as a test compound and found that it partially evaporates before maximum supersaturation is reached in the CCN counter, thus causing an underestimation of CCN activity. The effect of evaporation is clearly visible in all supersaturations, leading to an underestimation of the critical dry diameter by 10 to 15 nanometres in the case of ammonium nitrate particles in different supersaturations. This result was also confirmed by measurements in supersaturations between 0.1 and 0.7%.

  19. Deriving aerosol hygroscopic mixing state from size-resolved CCN activity and HR-ToF-AMS measurements

    NASA Astrophysics Data System (ADS)

    Bhattu, Deepika; Tripathi, S. N.; Chakraborty, Abhishek

    2016-10-01

    The ability of a particle to uptake water and form a cloud droplet depends on its hygroscopicity. To understand its impact on cloud properties and ultimately radiative forcing, knowledge of chemically-resolved mixing state information or the one based on hygroscopic growth is crucial. Typically, global models assume either pure internal or external mixing state which might not be true for all conditions and sampling locations. To investigate into this, the current study employed an indirect approach to infer the probable mixing state. The hygroscopic parameters derived from κ-Kohler theory using size-resolved CCN measurements (κCCN) and bulk/size-resolved aerosol mass spectrometer (AMS) measurements (κAMS) were compared. The accumulation mode particles were found to be more hygroscopic (κCCN = 0.24) than Aitken mode (κCCN = 0.13), perhaps due to increased ratio of inorganic to organic mass fraction. The activation diameter calculated from size-resolved CCN activity measurements at 5 different supersaturation (SS) levels varied in the range of 115 nm-42 nm with κCCN = 0.13-0.23 (avg = 0.18 ± 0.10 (±1σ)). Further, κAMS>κCCN was observed possibly due to the fact that organic and inorganic mass present in the Aitken mode was not correctly represented by bulk chemical composition and size-resolved fractional contribution of oxidized OA was not accurately accounted. Better correlation of organic fraction (forg) and κCCN at lower SS explained this behaviour. The decrease in κCCN with the time of the day was more pronounced at lower SS because of the relative mass reduction of soluble inorganic species by ∼17%. Despite the large differences between κ measured from two approaches, less over-prediction (up to 18%) between measured and predicted CCN concentration suggested lower impact of chemical composition and mixing state at higher SS. However, at lower SS, presences of externally mixed CCN-inactive aerosols lead to CCN over-prediction reflecting the

  20. Anticandidal activity of pomegranate peel extract aerosol as an applicable sanitizing method.

    PubMed

    Tayel, Ahmed A; El-Tras, Wael F

    2010-03-01

    Pomegranate is a wonderful fruit from the paradise which contains a wide variety of precious phytochemical compounds applicable in the fields of therapeutics and health care. Candida albicans is the most common etiological agent for many clinical mycoses which could lead to human and animal death. Determination of the anticandidal activity of pomegranate peel extracts (PPE), and application of PPE aerosol as sanitizer agent against C. albicans contamination were investigated. Agar diffusion assay and broth microdilution susceptibility test were applied for qualitative and quantitative determining the PPE anticandidal activity, respectively, versus commonly used fungicides. Aerosolization of PPE using an experimentally designed sanitizer room was applied for examining C. albicans sanitation potentiality of extract. PPE exhibited potent anticandidal activity against C. albicans strains comparing with standard fungicides in both used susceptibility techniques. Methanol, ethanol and water extracts were the most effective for inhibiting C. albicans growth. PPE aerosol was an efficient method for complete sanitizing of semi-closed places against C. albicans growth. Application of PPE aerosol is a proper sanitizing method for preventing C. albicans contamination and growth in suspected places. PMID:19207830

  1. Modeling Secondary Organic Aerosols over Europe: Impact of Activity Coefficients and Viscosity

    NASA Astrophysics Data System (ADS)

    Kim, Y.; Sartelet, K.; Couvidat, F.

    2014-12-01

    Semi-volatile organic species (SVOC) can condense on suspended particulate materials (PM) in the atmosphere. The modeling of condensation/evaporation of SVOC often assumes that gas-phase and particle-phase concentrations are at equilibrium. However, recent studies show that secondary organic aerosols (SOA) may not be accurately represented by an equilibrium approach between the gas and particle phases, because organic aerosols in the particle phase may be very viscous. The condensation in the viscous liquid phase is limited by the diffusion from the surface of PM to its core. Using a surrogate approach to represent SVOC, depending on the user's choice, the secondary organic aerosol processor (SOAP) may assume equilibrium or model dynamically the condensation/evaporation between the gas and particle phases to take into account the viscosity of organic aerosols. The model is implemented in the three-dimensional chemistry-transport model of POLYPHEMUS. In SOAP, activity coefficients for organic mixtures can be computed using UNIFAC for short-range interactions between molecules and AIOMFAC to also take into account the effect of inorganic species on activity coefficients. Simulations over Europe are performed and POLYPHEMUS/SOAP is compared to POLYPHEMUS/H2O, which was previously used to model SOA using the equilibrium approach with activity coefficients from UNIFAC. Impacts of the dynamic approach on modeling SOA over Europe are evaluated. The concentrations of SOA using the dynamic approach are compared with those using the equilibrium approach. The increase of computational cost is also evaluated.

  2. Characterization of iron oxides in mineral dust aerosols: Implications for light absorption

    NASA Astrophysics Data System (ADS)

    Lafon, Sandra; Sokolik, Irina N.; Rajot, Jean Louis; Caquineau, Sandrine; Gaudichet, Annie

    2006-11-01

    We report on measurements that were specifically designed to determine iron oxides in mineral dust aerosols needed for improved optical modeling. Atmospheric dust samples as well as samples generated in a wind tunnel from soils were analyzed by a number of analytical techniques for their total and free iron content (bulk and size resolved), hematite and goethite, mineralogy, and size distribution. These samples are representative of several important dust sources in East Asia and northern Africa. A novel data set generated from these measurements enables us to perform an in-depth modeling study of dust optical properties in the solar spectrum. We modeled the iron oxide-clay aggregates, which are the key light-absorbing species, as well as their mixtures with nonabsorbing minerals. A volume fraction of iron oxide in aggregates was determined from measurements. Significant differences in the single-scattering albedo, ω0, were found between hematite- and goethite-clay aggregates, although these calculations involved several important assumptions about the partition of hematite and goethite in size-resolved aggregates. Furthermore, we found that variability of the free iron content is large enough to cause important differences in ω0 of mineral dust originating from different sources. In contrast, this variability has little effect on the extinction coefficient and optical depth. We demonstrate that for the same size distribution, ω0 calculated from data obtained for Chinese and Tunisian samples show higher values and more distinct wavelength dependence than those of Niger dust. All the above ω0 differ from ones calculated using the refractive indices of Patterson et al. (1977) or the OPAC model (Hess et al., 1998), which are often used in radiative transfer studies. We conclude that information on a size-resolved content of free iron and a fraction of hematite and goethite in aggregates will need to be known on a regional basis to improve the prediction of the

  3. Leukocytic oxygen activation and microbicidal oxidative toxins.

    PubMed

    Hurst, J K; Barrette, W C

    1989-01-01

    Following a brief introduction of cellular response to stimulation comprising leukocyte activation, three major areas are discussed: (1) the neutrophil oxidase; (2) myeloperoxidase (MPO)-dependent oxidative microbicidal reactions; and (3) MPO-independent oxidative reactions. Topics included in section (A) are current views on the activation mechanism, redox composition, structural and topographic organization of the oxidase, and its respiratory products. In section (B), emphasis is placed on recent research on cidal mechanisms of HOCl, including the oxidative biochemistry of active chlorine compounds, identification of sites of lesions in bacteria, and attendant metabolic consequences. In section (C), we review the (bio)chemistry of H2O2 and .OH microbicidal reactions, with particular attention being given to addressing the controversial issue of probe methods to identify .OH radical and critical assessment of the recent proposal that MPO-independent killing arises from site-specific metal-catalyzed Fenton-type chemistry. PMID:2548810

  4. Initiation of depleted uranium oxide and spent fuel testing for the spent fuel sabotage aerosol ratio program.

    SciTech Connect

    Gregson, Michael Warren; Mo, Tin; Sorenson, Ken Bryce; Loiseau, Olivier; Nolte, Oliver; Hibbs, Russell S.; Molecke, Martin Alan; Slater-Thompson, Nancy; Autrusson, Bruno A.; Koch, Wolfgang; Pretzsch, Gunter Guido; Tsai, Han-Chung; Billone, Michael C.; Lange, Florentin; Young, Francis I.

    2004-08-01

    The authors provide a detailed overview of an on-going, multinational test program that is developing aerosol data for some spent fuel sabotage scenarios on spent fuel transport and storage casks. Experiments are being performed to quantify the aerosolized materials plus volatilized fission products generated from actual spent fuel and surrogate material test rods, due to impact by a high-energy-density device. The program participants in the United States plus Germany, France and the United Kingdom, part of the international Working Group for Sabotage Concerns of Transport and Storage Casks (WGSTSC) have strongly supported and coordinated this research program. Sandia National Laboratories has the lead role for conducting this research program; test program support is provided by both the US Department of Energy and the US Nuclear Regulatory Commission. The authors provide a summary of the overall, multiphase test design and a description of all explosive containment and aerosol collection test components used. They focus on the recently initiated tests on 'surrogate' spent fuel, unirradiated depleted uranium oxide and forthcoming actual spent fuel tests, and briefly summarize similar results from completed surrogate tests that used non-radioactive, sintered cerium oxide ceramic pellets in test rods.

  5. The Active Oxidation of Silicon Carbide

    NASA Technical Reports Server (NTRS)

    Jacobson, Nathan S.; Myers, Dwight L.

    2009-01-01

    The high temperature oxidation of silicon carbide occurs in two very different modes. Passive oxidation forms a protective oxide film which limits further attack of the SiC: SiC(s) + 3/2 O2(g) = SiO2(s) + CO(g) Active oxidation forms a volatile oxide and may lead to extensive attack of the SiC: SiC(s) + O2(g) = SiO(g) + CO(g) Generally passive oxidation occurs at higher oxidant pressures and active oxidation occurs at lower oxidant pressures and elevated temperatures. Active oxidation is a concern for reentry, where the flight trajectory involves the latter conditions. Thus the transition points and rates of active oxidation are a major concern. Passive/active transitions have been studied by a number of investigators. An examination of the literature indicates many questions remain regarding the effect of impurity, the hysteresis of the transition (i.e. the difference between active-to-passive and passive-toactive), and the effect of total pressure. In this study we systematically investigate each of these effects. Experiments were done in both an alumina furnace tube and a quartz furnace tube. It is known that alumina tubes release impurities such as sodium and increase the kinetics in the passive region [1]. We have observed that the active-to-passive transition occurs at a lower oxygen pressure when the experiment is conducted in alumina tubes and the resultant passive silica scale contains sodium. Thus the tests in this study are conducted in quartz tubes. The hysteresis of the transition has been discussed in the detail in the original theoretical treatise of this problem for pure silicon by Wagner [2], yet there is little mention of it in subsequent literature. Essentially Wagner points out that the active-to-passive transition is governed by the criterion for a stable Si/SiO2 equilibria and the passive-to-active transition is governed by the decomposition of the SiO2 film. A series of experiments were conducted for active-to-passive and passive-to-active

  6. Effect of oxidant concentration, exposure time, and seed particles on secondary organic aerosol chemical composition and yield

    DOE PAGESBeta

    Lambe, A. T.; Chhabra, P. S.; Onasch, T. B.; Brune, W. H.; Hunter, J. F.; Kroll, J. H.; Cummings, M. J.; Brogan, J. F.; Parmar, Y.; Worsnop, D. R.; et al

    2015-03-18

    We performed a systematic intercomparison study of the chemistry and yields of secondary organic aerosol (SOA) generated from OH oxidation of a common set of gas-phase precursors in a Potential Aerosol Mass (PAM) continuous flow reactor and several environmental chambers. In the flow reactor, SOA precursors were oxidized using OH concentrations ranging from 2.0 × 108 to 2.2 × 1010 molec cm-3 over exposure times of 100 s. In the environmental chambers, precursors were oxidized using OH concentrations ranging from 2 × 106 to 2 × 107 molec cm-3 over exposure times of several hours. The OH concentration in themore » chamber experiments is close to that found in the atmosphere, but the integrated OH exposure in the flow reactor can simulate atmospheric exposure times of multiple days compared to chamber exposure times of only a day or so. In most cases, for a specific SOA type the most-oxidized chamber SOA and the least-oxidized flow reactor SOA have similar mass spectra, oxygen-to-carbon and hydrogen-to-carbon ratios, and carbon oxidation states at integrated OH exposures between approximately 1 × 1011 and 2 × 1011 molec cm-3 s, or about 1–2 days of equivalent atmospheric oxidation. This observation suggests that in the range of available OH exposure overlap for the flow reactor and chambers, SOA elemental composition as measured by an aerosol mass spectrometer is similar whether the precursor is exposed to low OH concentrations over long exposure times or high OH concentrations over short exposure times. This similarity in turn suggests that both in the flow reactor and in chambers, SOA chemical composition at low OH exposure is governed primarily by gas-phase OH oxidation of the precursors rather than heterogeneous oxidation of the condensed particles. In general, SOA yields measured in the flow reactor are lower than measured in chambers for the range of equivalent OH exposures that can be measured in both the flow reactor and chambers. The influence of

  7. Modeling Aerosol Effects on Shallow Cumuli and Turbulent Activities Under Various Meteorological Conditions

    NASA Astrophysics Data System (ADS)

    Wang, H.; McFarquhar, G. M.

    2007-12-01

    To determine conditions over the Indian Ocean for which cloud fields are most susceptible to modification from aerosols and to study how turbulent activities and shallow cumuli vary for different meteorological scenarios, the National Center for Atmospheric Research Eulerian-semi-Lagrangian (EULAG) three-dimensional large-eddy simulation model was initialized using data collected during the Indian Ocean Experiment (INDOEX). Radiosonde data were used to construct 6 soundings encompassing the range of temperature and humidity observed in the trade-wind boundary layer. By then adding the characteristics (height, depth and strength) of either a typical transition layer (TL), a strong inversion layer (IL) or no stable layer a total of 18 meteorological scenarios were produced. Separate simulations were conducted using EULAG assuming pristine and polluted conditions (i.e., cloud droplet number concentrations, aerosol extinction profiles and single-scattering albedos) using INDOEX observations. For the range of meteorological conditions observed during INDOEX, sensitivity studies showed that the semi- direct effect always dominated indirect effects, producing a positive daytime mean net indirect forcing varying between 0.2 and 4.5 W m-2. The simulations showed that changes in the environmental relative humidity (RH) and the presence of the TL had critical impacts on the cloud properties, turbulence and lateral detrainment rates, and on how aerosols affect these quantities. The net indirect forcing was larger when the RH was higher and in the absence of any dry and stable layers. It was reduced to less than 1.2 W m-2 when the TL was present. The impact of the IL was dependent on convective strength which increases with increasing RH. In fact, changes in meteorological factors had larger impacts on the simulated cloud properties than did the presence of anthropogenic aerosols, indicating large uncertainties can be introduced when solely using observations of aerosols and

  8. Process for preparing active oxide powders

    DOEpatents

    Berard, Michael F.; Hunter, Jr., Orville; Shiers, Loren E.; Dole, Stephen L.; Scheidecker, Ralph W.

    1979-02-20

    An improved process for preparing active oxide powders in which cation hydroxide gels, prepared in the conventional manner are chemically dried by alternately washing the gels with a liquid organic compound having polar characteristics and a liquid organic compound having nonpolar characteristics until the mechanical water is removed from the gel. The water-free cation hydroxide is then contacted with a final liquid organic wash to remove the previous organic wash and speed drying. The dried hydroxide treated in the conventional manner will form a highly sinterable active oxide powder.

  9. Oxidation of ketone groups in transported biomass burning aerosol from the 2008 Northern California Lightning Series fires

    NASA Astrophysics Data System (ADS)

    Hawkins, Lelia N.; Russell, Lynn M.

    2010-11-01

    Submicron particles were collected from June to September 2008 in La Jolla, California to investigate the composition and sources of atmospheric aerosol in an anthropogenically-influenced coastal site. Factor analysis of aerosol mass spectrometry (AMS) and Fourier transform infrared (FTIR) spectroscopy measurements revealed that the two largest sources of submicron organic mass (OM) at the sampling site were (1) fossil fuel combustion associated with ship and diesel truck emissions near the ports of Los Angeles and Long Beach and (2) aged smoke from large wildfires burning in central and northern California. During non-fire periods, fossil fuel combustion contributed up to 95% of FTIR OM, correlated to sulfur, and consisted mostly of alkane (86%) and carboxylic acid groups (9%). During fire periods, biomass burning contributed up to 74% of FTIR OM, consisted mostly of alkane (48%), ketone (25%), and carboxylic acid groups (17%), and correlated to AMS-derived factors resembling brush fire smoke, wood smoldering and flaming particles, and biogenic secondary organic aerosol. The two AMS-derived biomass burning factors were identified as oxygenated and hydrocarbon biomass burning aerosol on the basis of spectral similarities to smoldering and flaming smoke particles, respectively. In addition, the ratio of oxygenated to hydrocarbon biomass burning OM shows a clear diurnal trend with an afternoon peak, consistent with photochemical oxidation. Back trajectory analysis indicates that 2-4-day old forest fire emissions include substantial ketone groups, which have both lower O/C and lower m/ z 44/OM fraction than carboxylic acid groups. Air masses with more than 4-day old emissions have higher carboxylic acid/ketone group ratios, showing that atmospheric processing of these ketone-containing organic aerosol particles results in increased m/ z 44 and O/C. These observations may provide functionally-specific evidence for the type of chemical processing that is responsible for

  10. Characterization of Isoprene-Derived Secondary Organic Aerosol Formation at the Look Rock Site during the 2013 Southern Oxidant and Aerosol Study (SOAS)

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S.; Li, X.; Bairai, S. T.; Hicks, W.; Renfro, J.; Corrigan, A. L.; Guzman, J. M.; Russell, L. M.; Liu, Y.; McKinney, K. A.; Zhang, X.; Cappa, C. D.; Zimmermann, K.; Bertram, T. H.; Canagaratna, M. R.; Croteau, D.; Worsnop, D. R.; Jayne, J. T.; Zhang, Z.; Gold, A.; Surratt, J. D.

    2013-12-01

    Although isoprene is considered as the single largest source of secondary organic aerosol (SOA), the exact manner in which it forms remains unclear. Improving our fundamental understanding of isoprene-derived SOA will be key to improving existing air quality models, especially in the southeastern U.S. where models currently underestimate observations. Reactive epoxides, which include methacrylic acid epoxide (MAE) and isomeric isoprene epoxydiols (IEPOX), produced from the oxidation of isoprene have recently been demonstrated to lead to SOA through heterogeneous chemistry. Anthropogenic pollutants (NOx and SO2) have been shown to enhance isoprene-derived epoxides as a source of SOA. One of the major aims during SOAS was to examine how anthropogenic pollutants impact isoprene SOA formation and its climate-relevant properties. To address this aim, we deployed both an Aerodyne aerosol chemical speciation monitor (ACSM) and a chemical ionization high-resolution time-of-flight mass spectrometer (CI-HR-TOFMS) at the Look Rock (LRK) site in the Great Smoky Mountains National Park, TN, from June 1 to July 15, 2013. In addition, high-volume PM2.5 samplers collected daily (8AM-7AM), day (8AM-7PM), and night (8PM-7AM) samples onto quartz filters. On days that LRK was forecasted to have high isoprene, SO4 (sulfate), and NOx levels, PM2.5 were collected more frequently (8AM-11AM, 12PM-3PM, 4PM-7PM, and 8PM-7AM). Filters were analyzed for known isoprene-derived SOA tracers (2-methyltetrols, 2-methylglyceric acid, C5-alkene triols, 3-methyltetrahydrofuran-3,4-diols, and organosulfates) by gas chromatography/mass spectrometry and ultra performance liquid chromatography coupled to diode array detection and electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry. The average non-refractory PM1 mass measured by the ACSM was 3.87 μg m-3, with organic, sulfate, ammonium, nitrate and chloride contributing 64.4%, 24.1%, 7.6%, 3.8%, and 0.1%, respectively

  11. Measurement of sub-2 nm clusters of pristine and composite metal oxides during nanomaterial synthesis in flame aerosol reactors.

    PubMed

    Fang, Jiaxi; Wang, Yang; Attoui, Michel; Chadha, Tandeep S; Ray, Jessica R; Wang, Wei-Ning; Jun, Young-Shin; Biswas, Pratim

    2014-08-01

    Measuring stable clusters to understand particle inception will aid the synthesis of well-controlled nanoparticles via gas-phase aerosol routes. Using a Half Mini differential mobility analyzer, the presence of monomers, dimers, trimers, and tetramers was detected for the first time in a flame aerosol reactor during the synthesis of pristine TiO2 and TiO2/SiO2 nanocomposites. Atomic force microscopy confirmed the presence and the size of sub-2 nm clusters. The detection of these clusters elucidated the initial stages of particle formation during combustion synthesis and supported previous hypotheses that collisional growth from stable monomers of metal oxides is the first step of particle growth. PMID:24968004

  12. Fluorescence spectra and biological activity of aerosolized bacillus spores and MS2 bacteriophage exposed to ozone at different relative humidities in a rotating drum

    SciTech Connect

    Ratnesar-Shumate, Shanna; Pan, Yong-Le; Hill, Steven C.; Kinahan, Sean; Corson, Elizabeth; Eshbaugh, Jonathan; Santarpia, Joshua L.

    2015-10-14

    Biological aerosols (bioaerosols) released into the environment may undergo physical and chemical transformations when exposed to atmospheric constituents such as solar irradiation, reactive oxygenated species, ozone, free radicals, water vapor and pollutants. Aging experiments were performed in a rotating drum chamber subjecting bioaerosols, Bacillus thuringiensis Al Hakam (BtAH) spores and MS2 bacteriophages to ozone at 0 and 150 ppb, and relative humidities (RH) at 10%, 50%, and 80+%. Fluorescence spectra and intensities of the aerosols as a function of time in the reaction chamber were measured with a single particle fluorescence spectrometer (SPFS) and an Ultra-Violet Aerodynamic Particle Sizer® Spectrometer (UV-APS). Losses in biological activity were measured by culture and quantitative polymerase chain reaction (q-PCR) assay. For both types of aerosols the largest change in fluorescence emission was between 280 and 400 nm when excited at 263 nm followed by fluorescence emission between 380 and 700 nm when excited at 351 nm. The fluorescence for both BtAH and MS2 were observed to decrease significantly at high ozone concentration and high RH when excited at 263 nm excitation. The decreases in 263 nm excited fluorescence are indicative of hydrolysis and oxidation of tryptophan in the aerosols. Fluorescence measured with the UV-APS (355-nm excitation) increased with time for both BtAH and MS2 aerosols. A two log loss of MS2 bacteriophage infectivity was observed in the presence of ozone at ~50% and 80% RH when measured by culture and normalized for physical losses by q-PCR. Viability of BtAH spores after exposure could not be measured due to the loss of genomic material during experiments, suggesting degradation of extracelluar DNA attributable to oxidation. The results of these studies indicate that the physical and biological properties of bioaerosols change significantly after exposure to ozone and water vapor.

  13. Fluorescence spectra and biological activity of aerosolized bacillus spores and MS2 bacteriophage exposed to ozone at different relative humidities in a rotating drum

    DOE PAGESBeta

    Ratnesar-Shumate, Shanna; Pan, Yong-Le; Hill, Steven C.; Kinahan, Sean; Corson, Elizabeth; Eshbaugh, Jonathan; Santarpia, Joshua L.

    2015-10-14

    Biological aerosols (bioaerosols) released into the environment may undergo physical and chemical transformations when exposed to atmospheric constituents such as solar irradiation, reactive oxygenated species, ozone, free radicals, water vapor and pollutants. Aging experiments were performed in a rotating drum chamber subjecting bioaerosols, Bacillus thuringiensis Al Hakam (BtAH) spores and MS2 bacteriophages to ozone at 0 and 150 ppb, and relative humidities (RH) at 10%, 50%, and 80+%. Fluorescence spectra and intensities of the aerosols as a function of time in the reaction chamber were measured with a single particle fluorescence spectrometer (SPFS) and an Ultra-Violet Aerodynamic Particle Sizer® Spectrometermore » (UV-APS). Losses in biological activity were measured by culture and quantitative polymerase chain reaction (q-PCR) assay. For both types of aerosols the largest change in fluorescence emission was between 280 and 400 nm when excited at 263 nm followed by fluorescence emission between 380 and 700 nm when excited at 351 nm. The fluorescence for both BtAH and MS2 were observed to decrease significantly at high ozone concentration and high RH when excited at 263 nm excitation. The decreases in 263 nm excited fluorescence are indicative of hydrolysis and oxidation of tryptophan in the aerosols. Fluorescence measured with the UV-APS (355-nm excitation) increased with time for both BtAH and MS2 aerosols. A two log loss of MS2 bacteriophage infectivity was observed in the presence of ozone at ~50% and 80% RH when measured by culture and normalized for physical losses by q-PCR. Viability of BtAH spores after exposure could not be measured due to the loss of genomic material during experiments, suggesting degradation of extracelluar DNA attributable to oxidation. The results of these studies indicate that the physical and biological properties of bioaerosols change significantly after exposure to ozone and water vapor.« less

  14. Fluorescence spectra and biological activity of aerosolized bacillus spores and MS2 bacteriophage exposed to ozone at different relative humidities in a rotating drum

    NASA Astrophysics Data System (ADS)

    Ratnesar-Shumate, Shanna; Pan, Yong-Le; Hill, Steven C.; Kinahan, Sean; Corson, Elizabeth; Eshbaugh, Jonathan; Santarpia, Joshua L.

    2015-03-01

    Biological aerosols (bioaerosols) released into the environment may undergo physical and chemical transformations when exposed to atmospheric constituents such as solar irradiation, reactive oxygenated species, ozone, free radicals, water vapor and pollutants. Aging experiments were performed in a rotating drum chamber subjecting bioaerosols, Bacillus thuringiensis Al Hakam (BtAH) spores and MS2 bacteriophages to ozone at 0 and 150 ppb, and relative humidities (RH) at 10%, 50%, and 80+%. Fluorescence spectra and intensities of the aerosols as a function of time in the reaction chamber were measured with a single particle fluorescence spectrometer (SPFS) and an Ultra-Violet Aerodynamic Particle Sizer® Spectrometer (UV-APS). Losses in biological activity were measured by culture and quantitative polymerase chain reaction (q-PCR) assay. For both types of aerosols the largest change in fluorescence emission was between 280 and 400 nm when excited at 263 nm followed by fluorescence emission between 380 and 700 nm when excited at 351 nm. The fluorescence for both BtAH and MS2 were observed to decrease significantly at high ozone concentration and high RH when excited at 263 nm excitation. The decreases in 263 nm excited fluorescence are indicative of hydrolysis and oxidation of tryptophan in the aerosols. Fluorescence measured with the UV-APS (355-nm excitation) increased with time for both BtAH and MS2 aerosols. A two log loss of MS2 bacteriophage infectivity was observed in the presence of ozone at ~50% and 80% RH when measured by culture and normalized for physical losses by q-PCR. Viability of BtAH spores after exposure could not be measured due to the loss of genomic material during experiments, suggesting degradation of extracelluar DNA attributable to oxidation. The results of these studies indicate that the physical and biological properties of bioaerosols change significantly after exposure to ozone and water vapor.

  15. 3rd hand smoking; heterogeneous oxidation of nicotine and secondary aerosol formation in the indoor environment

    NASA Astrophysics Data System (ADS)

    Petrick, Lauren; Dubowski, Yael

    2010-05-01

    Tobacco smoking is well known as a significant source of primary indoor air pollutants. However, only recently has it been recognized that the impact of Tobacco smoking may continue even after the cigarette has been extinguished (i.e., third hand smoke) due to the effect of indoor surfaces. These surfaces may affect the fate of tobacco smoke in the form of secondary reactions and pollutants, including secondary organic aerosol (SOA) formation. Fourier Transform Infrared spectrometry with Attenuated Total Reflection (FTIR-ATR) in tandem with a Scanning Mobility Particle Sizing (SMPS) system was used to monitor the ozonation of cellulose sorbed nicotine and resulting SOA formation. SOA formation began at onset of ozone introduction ([O3] = 60 ± 5 ppb) with a size distribution of dp ≤ 25 nm, and was determined to be a result of heterogeneous reaction (opposed to homogeneous). SOA yield from reacted surface nicotine was on the order of 10 %. Simultaneous to SOA monitoring, FTIR-ATR spectra showed surface changes in the nicotine film as the reaction progressed, revealing a pseudo first-order surface reaction rate of 0.0026 ± 0.0008 min-1. Identified surface oxidation products included: cotinine, myosmine, methylnicotinamide and nicotyrine. Surface reaction rate was found to be partially inhibited at high relative humidity. Given the toxicity of some of the identified products (e.g., cotinine has shown potential mutagenicity and teratogenicity) and that small particles may contribute to adverse health effects, the present study indicates that exposure to 3rd hand smoke ozonation products may pose additional health risks.

  16. Aerosol and product yields from NO{sub 3} radical-initiated oxidation o/f selected monoterpenes

    SciTech Connect

    Hallquist, M.; Ljungstroem, E.; Waengberg, I.; Barnes, I.; Becker, K.H.

    1999-02-15

    Atmospheric transformation of monoterpenes gives products that may cause environmental consequences. In this work the NO{sub 3} radical-initiated oxidation of the monoterpenes {alpha}-pinene, {beta}-pinene, {Delta}{sup 3}-carene, and limonene has been investigated. All experiments were conducted in EUPHORE, the EUropean PHOto REactor facility in Valencia, Spain. The aerosol and product yields were measured in experiments with a conversion of the terpenes in the interval from 7 to 400 ppb. The lower end of the concentrations used are close to those measured in ambient pine forest air. Products were measured using long path in situ FTIR. Aerosol yields were obtained using a DMA-CPC system. The aerosol mass yields measured at low concentrations were <1, 10, 15, and 17% for {alpha}-pinene, {beta}-pinene, {Delta}{sup 3}-carene, and limonene, respectively. The total molar alkylnitrate yields were calculated to be 19, 61, 66, and 48%, and molar carbonyl compound yields were estimated to be 71, 14, 29, and 69% for {alpha}-pinene, {beta}-pinene, {Delta}{sup 3}-carene, and limonene, respectively. The aerosol yields were strongly dependent on the amounts of terpene reacted, whereas the nitrate and carbonyl yields do not depend on the amount of terpene converted. The principal carbonyl compound from {alpha}pinene oxidation was pinonaldehyde. In the case of limonene, endolim was tentatively identified and appears to be a major product. The reactions with {beta}-pinene and {Delta}{sup 3}-carene yielded 1--2% of nopinone and 2--3% caronaldehyde, respectively. The results show that it is not possible to use generalized descriptions of terpene chemistry, e.g., in mathematical models.

  17. Gas-particle partitioning of organic acids during the Southern Oxidant and Aerosol Study (SOAS): measurements and modeling

    NASA Astrophysics Data System (ADS)

    Thompson, S.; Yatavelli, R.; Stark, H.; Kimmel, J.; Krechmer, J.; Day, D. A.; Isaacman, G. A.; Goldstein, A. H.; Khan, M. A. H.; Holzinger, R.; Lopez-Hilfiker, F.; Mohr, C.; Thornton, J. A.; Jayne, J. T.; Worsnop, D. R.; Jimenez, J. L.

    2014-12-01

    Gas-Particle partitioning measurements of organic acids were carried out during the Southern Oxidant and Aerosol Study (SOAS, June-July 2013) at the Centerville, AL Supersite in the Southeast US, a region with significant isoprene and terpene emissions. Organic acid measurements were made with a Chemical Ionization High Resolution Time-of-Flight Mass Spectrometer (HRToF-CIMS) with a Filter Inlet for Gases and AEROsols (FIGAERO) and acetate (CH3COO-) as the reagent ion. We investigate both individual species and bulk organic acids and partitioning to organic and water phases in the aerosol. Measured partitioning is compared to data from three other instruments that can also quantify gas-particle partitioning with high time resolution: another HRToF-CIMS using iodide (I-) as the reagent ion to ionize acids and other highly oxidized compounds, a Semivolatile Thermal Desorption Aerosol GC/MS (SV-TAG), and a Thermal Desorption Proton Transfer Time-of-Flight Mass Spectrometer (TD-PTRMS The partitioning measurements for three of the instruments are generally consistent, with results in the same range for most species and following similar temporal trends and diurnal cycles. The TD-PTRMS measures on average ½ the partitioning to the particle phase of the acetate CIMS. Both the measurements and the model of partitioning to the organic phase respond quickly to temperature, and the model agrees with the measured partitioning within the error of the measurement for multiple compounds, although many compounds do not match the modeled partitioning, especially at lower m/z. This discrepancy may be due to thermal decomposition of larger molecules into smaller ones when heated.

  18. A modeling perspective of the ChArMEx intensive campaign: origin of photo-oxidant and organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Cholakian, Arineh; Beekmann, Matthias; Siour, Guillaume; Coll, Isabelle; Colette, Augustin; Gros, Valerie; Marchand, Nicolas; Sciare, Jean; Colomb, Aurélie; Gheusi, François; Sauvage, Stéphane

    2016-04-01

    During the summers of 2013 and 2014, two three-week intensive campaigns took place over the western Mediterranean in order to investigate the origins of photo-oxidants as well as the sources and processes of formation of organic aerosols in this region. Within the frame of the MISTRAL/ChArMEx program, an extensive number of chemical compounds were investigated by means of ground-based and also airborne measurements. In this paper, a modeling perspective of the 2013 campaign is given, using the CHIMERE chemistry-transport model, dealing with two aspects: 1) representativeness of the simulations with respect to the complex orography of Cape Corsica, 2) evaluation of secondary organic aerosol simulations in the western Mediterranean region with different model configurations using a variety of experimental data. The model has been configured in a way to fit the specificities of this unique region. The base simulations are performed in a domain covering the entire Europe as well as the northern Africa with a low resolution (30 km). In order to take into account the orographic complexity of the area where the ground-based measurements were performed (Ersa, Cape Corsica), nested simulations with a high resolution (1km horizontal resolution) focused on this site were performed with the goal of increasing the representativeness of the simulations. Still, this resolution does not allow to correctly represent the altitude of the Cape Corsica measurement site (533 m asl). To solve this problem, a large number of grid cells in the vicinity of the measurements site, all having different altitudes, were used to find the extrapolated concentration of an indicative list of species towards the exact altitude of the aforementioned site and to estimate an orographic representativeness error, which was shown to be less important for organic aerosols among said species. Alongside the base simulations, other series of simulations using multiple configurations of the Volatility Basis Set

  19. Incorporating an advanced aerosol activation parameterization into WRF-CAM5: Model evaluation and parameterization intercomparison

    SciTech Connect

    Zhang, Yang; Zhang, Xin; Wang, Kai; He, Jian; Leung, Lai-Yung R.; Fan, Jiwen; Nenes, Athanasios

    2015-07-22

    Aerosol activation into cloud droplets is an important process that governs aerosol indirect effects. The advanced treatment of aerosol activation by Fountoukis and Nenes (2005) and its recent updates, collectively called the FN series, have been incorporated into a newly developed regional coupled climate-air quality model based on the Weather Research and Forecasting model with the physics package of the Community Atmosphere Model version 5 (WRF-CAM5) to simulate aerosol-cloud interactions in both resolved and convective clouds. The model is applied to East Asia for two full years of 2005 and 2010. A comprehensive model evaluation is performed for model predictions of meteorological, radiative, and cloud variables, chemical concentrations, and column mass abundances against satellite data and surface observations from air quality monitoring sites across East Asia. The model performs overall well for major meteorological variables including near-surface temperature, specific humidity, wind speed, precipitation, cloud fraction, precipitable water, downward shortwave and longwave radiation, and column mass abundances of CO, SO2, NO2, HCHO, and O3 in terms of both magnitudes and spatial distributions. Larger biases exist in the predictions of surface concentrations of CO and NOx at all sites and SO2, O3, PM2.5, and PM10 concentrations at some sites, aerosol optical depth, cloud condensation nuclei over ocean, cloud droplet number concentration (CDNC), cloud liquid and ice water path, and cloud optical thickness. Compared with the default Abdul-Razzack Ghan (2000) parameterization, simulations with the FN series produce ~107–113% higher CDNC, with half of the difference attributable to the higher aerosol activation fraction by the FN series and the remaining half due to feedbacks in subsequent cloud microphysical processes. With the higher CDNC, the FN series are more skillful in simulating cloud water path, cloud optical thickness, downward shortwave radiation

  20. N(2)O(5) reaction on submicron sea salt aerosol: kinetics, products, and the effect of surface active organics.

    PubMed

    Thornton, Joel A; Abbatt, Jonathan P D

    2005-11-10

    The reaction of N(2)O(5) on sea salt aerosol is a sink for atmospheric nitrogen oxides and a source of the Cl radical. We present room-temperature measurements of the N(2)O(5) loss rate on submicron artificial seawater (ASW) aerosol, performed with an entrained aerosol flow tube coupled to a chemical ionization mass spectrometer, as a function of aerosol phase (aqueous or partially crystalline), liquid water content, and size. We also present an analysis of the product growth kinetics showing that ClNO(2) is produced at a rate equal to N(2)O(5) loss, with an estimated lower limit yield of 50% at 50% relative humidity (RH). The reaction probability for N(2)O(5), gamma(N(2)(O)(5)), depends strongly on the particle phase, being 0.005 +/- 0.004 on partially crystalline ASW aerosol at 30% RH and 0.03 +/- 0.008 on aqueous ASW aerosol at 65% RH. At 50% RH, N(2)O(5) loss is relatively insensitive to particle size for radii greater than 100 nm, and gamma(N(2)(O)(5)) displays a statistically insignificant increase from 0.022 to approximately 0.03 for aqueous ASW aerosol over the RH range of 43-70%. We find that the presence of millimolar levels of hexanoic acid in the aerosol bulk decreases the gamma(N(2)(O)(5)) at 70% RH by a factor of 3-4 from approximately 0.025 to 0.008 +/- 0.004. This reduction is likely due to the partitioning of hexanoic acid to the gas-aerosol interface at a surface coverage that we estimate to be equivalent to a monolayer. This result is the first evidence that a monolayer coating of aqueous organic surfactant can slow the reactive uptake of atmospheric trace gases to aerosol. PMID:16838918

  1. Survival and ice nucleation activity of bacteria as aerosols in a cloud simulation chamber

    NASA Astrophysics Data System (ADS)

    Amato, P.; Joly, M.; Schaupp, C.; Attard, E.; Möhler, O.; Morris, C. E.; Brunet, Y.; Delort, A.-M.

    2015-06-01

    The residence time of bacterial cells in the atmosphere is predictable by numerical models. However, estimations of their aerial dispersion as living entities are limited by a lack of information concerning survival rates and behavior in relation to atmospheric water. Here we investigate the viability and ice nucleation (IN) activity of typical atmospheric ice nucleation active bacteria (Pseudomonas syringae and P. fluorescens) when airborne in a cloud simulation chamber (AIDA, Karlsruhe, Germany). Cell suspensions were sprayed into the chamber and aerosol samples were collected by impingement at designated times over a total duration of up to 18 h, and at some occasions after dissipation of a cloud formed by depressurization. Aerosol concentration was monitored simultaneously by online instruments. The cultivability of airborne cells decreased exponentially over time with a half-life time of 250 ± 30 min (about 3.5 to 4.5 h). In contrast, IN activity remained unchanged for several hours after aerosolization, demonstrating that IN activity was maintained after cell death. Interestingly, the relative abundance of IN active cells still airborne in the chamber was strongly decreased after cloud formation and dissipation. This illustrates the preferential precipitation of IN active cells by wet processes. Our results indicate that from 106 cells aerosolized from a surface, one would survive the average duration of its atmospheric journey estimated at 3.4 days. Statistically, this corresponds to the emission of 1 cell that achieves dissemination every ~ 33 min m-2 of cultivated crops fields, a strong source of airborne bacteria. Based on the observed survival rates, depending on wind speed, the trajectory endpoint could be situated several hundreds to thousands of kilometers from the emission source. These results should improve the representation of the aerial dissemination of bacteria in numeric models.

  2. Survival and ice nucleation activity of bacteria as aerosols in a cloud simulation chamber

    NASA Astrophysics Data System (ADS)

    Amato, P.; Joly, M.; Schaupp, C.; Attard, E.; Möhler, O.; Morris, C. E.; Brunet, Y..; Delort, A.-M.

    2015-02-01

    The residence time of bacterial cells in the atmosphere is predictable by numerical models. However, estimations of their aerial dispersion as living entities are limited by lacks of information concerning survival rates and behavior in relation to atmospheric water. Here we investigate the viability and ice nucleation (IN) activity of typical atmospheric ice nucleation active bacteria (Pseudomonas syringae and P. fluorescens) when airborne in a cloud simulation chamber (AIDA, Karlsruhe, Germany). Cell suspensions were sprayed into the chamber and aerosol samples were collected by impingement at designated times over a total duration of up to 18 h, and at some occasions after dissipation of a cloud formed by depressurization. Aerosol concentration was monitored simultaneously by online instruments. The cultivability of airborne cells decreased exponentially over time with a half-life time of 250 ± 30 min (about 3.5 to 4.5 h). In contrast, IN activity remained unchanged for several hours after aerosolization, demonstrating that IN activity was maintained after cell death. Interestingly, the relative abundance of IN active cells still airborne in the chamber was strongly decreased after cloud formation and dissipation. This illustrates the preferential precipitation of IN active cells by wet processes. Our results indicate that from 106 = cells aerosolized from a surface, one would survive the average duration of its atmospheric journey estimated at 3.4 days. Statistically, this corresponds to the emission of 1 cell that achieves dissemination every ~33 min per m2 of cultivated crops fields, a strong source of airborne bacteria. Based on the observed survival rates, depending on wind speed, the trajectory endpoint could be situated several hundreds to thousands of kilometers from the emission source. These results should improve the representation of the aerial dissemination of bacteria in numeric models.

  3. Anti-tumor activity of CpG-ODN aerosol in mouse lung metastases.

    PubMed

    Sfondrini, Lucia; Sommariva, Michele; Tortoreto, Monica; Meini, Alessandra; Piconese, Silvia; Calvaruso, Marco; Van Rooijen, Nick; Bonecchi, Raffaella; Zaffaroni, Nadia; Colombo, Mario P; Tagliabue, Elda; Balsari, Andrea

    2013-07-15

    Studies in preclinical models have demonstrated the superior anti-tumor effect of CpG oligodeoxynucleotides (CpG-ODN) when administered at the tumor site rather than systemically. We evaluated the effect of aerosolized CpG-ODN on lung metastases in mice injected with immunogenic N202.1A mammary carcinoma cells or weakly immunogenic B16 melanoma cells. Upon reaching the bronchoalveolar space, aerosolized CpG-ODN activated a local immune response, as indicated by production of IL-12p40, IFN-γ and IL-1β and by recruitment and maturation of DC cells in bronchoalveolar lavage fluid of mice. Treatment with aerosolized CpG-ODN induced an expansion of CD4+ cells in lung and was more efficacious than systemic i.p. administration against experimental lung metastases of immunogenic N202.1A mammary carcinoma cells, whereas only i.p. delivery of CpG-ODN provided anti-tumor activity, which correlated with NK cell expansion in the lung, against lung metastases of the poorly immunogenic B16 melanoma. The inefficacy of aerosol therapy to induce NK expansion was related to the presence of immunosuppressive macrophages in B16 tumor-bearing lungs, as mice depleted of these cells by clodronate treatment responded to aerosol CpG-ODN through expansion of the NK cell population and significantly reduced numbers of lung metastases. Our results indicate that tumor immunogenicity and the tumor-induced immunosuppressive environment are critical factors to the success of CpG therapy in the lung, and point to the value of routine sampling of the lung immune environment in defining an optimal immunotherapeutic strategy. PMID:23319306

  4. Delivery of Highly Active Noble-Metal Nanoparticles into Microspherical Supports by an Aerosol-Spray Method.

    PubMed

    Kan, Erjie; Kuai, Long; Wang, Wenhai; Geng, Baoyou

    2015-09-14

    Noble metal nanoparticles (NPs) with 1-5 nm diameter obtained from NaHB4 reduction possess high catalytic activity. However, they are rarely used directly. This work presents a facile, versatile, and efficient aerosol-spray approach to deliver noble-metal NPs into metal oxide supports, while maintaining the size of the NPs and the ability to easily adjust the loading amount. In comparison with the conventional spray approach, the size of the loaded noble-metal nanoparticles can be significantly decreased. An investigation of the 4-nitrophenol hydrogenation reaction catalyzed by these materials suggests that the NPs/oxides catalysts have high activity and good endurance. For 1 % Au/CeO2 and Pd/Al2 O3 catalysts, the rate constants reach 2.03 and 1.46 min(-1) , which is much higher than many other reports with the same noble-metal loading scale. Besides, the thermal stability of catalysts can be significantly enhanced by modifying the supports. Therefore, this work contributes an efficient method as well as some guidance on how to produce highly active and stable supported noble-metal catalysts. PMID:26234910

  5. Active and passive smoking - New insights on the molecular composition of different cigarette smoke aerosols by LDI-FTICRMS

    NASA Astrophysics Data System (ADS)

    Schramm, Sébastien; Carré, Vincent; Scheffler, Jean-Luc; Aubriet, Frédéric

    2014-08-01

    The aerosol generated when a cigarette is smoked is a significant indoor contaminant. Both smokers and non-smokers can be exposed to this class of pollutants. Nevertheless, they are not exposed to the same kind of smoke. The active smoker breathes in the mainstream smoke (MSS) during a puff, whereas the passive smoker inhales not only the smoke generated by the lit cigarette between two puffs (SSS) but also the smoke exhaled by active smokers (EXS). The aerosol fraction of EXS has until now been poorly documented; its composition is expected to be different from MSS. This study aims to investigate the complex composition of aerosol from EXS to better understand the difference in exposure between active and passive smokers. To address this, the in-situ laser desorption ionisation Fourier transform ion cyclotron mass spectrometry (LDI-FTICRMS) was used to characterise the aerosol composition of EXS from two different smokers. Results clearly indicated many similarities between EXS samples but also significant differences with MSS and SSS aerosol. The comparison of MSS and EXS aerosol allowed the chemicals retained by the active smoker's lungs to be identified, whereas the convolution of the EXS and SSS aerosol compositions were considered relevant to the exposition of a passive smoker. As a consequence, active smokers are thought to be mainly exposed to polar and poorly unsaturated oxygenated and nitrogenated organics, compared with poorly oxygenated but highly unsaturated compounds in passive smokers.

  6. Secondary Organic Aerosol Formation from Ambient Air in an Oxidation Flow Reactor at GoAmazon2014/5

    NASA Astrophysics Data System (ADS)

    Palm, Brett B.; de Sa, Suzane S.; Campuzano-Jost, Pedro; Day, Douglas A.; Hu, Weiwei; Seco, Roger; Park, Jeong-Hoo; Guenther, Alex; Kim, Saewung; Brito, Joel; Wurm, Florian; Artaxo, Paulo; Yee, Lindsay; Isaacman-VanWertz, Gabrial; Goldstein, Allen; Newburn, Matt K.; Lizabeth Alexander, M.; Martin, Scot T.; Brune, William H.; Jimenez, Jose L.

    2016-04-01

    During GoAmazon2014/5, ambient air was exposed to controlled concentrations of OH or O3 in situ using an oxidation flow reactor (OFR). Oxidation ranged from hours-several weeks of aging. Oxidized air was sampled by several instruments (e.g., HR-AMS, ACSM, PTR-TOF-MS, SMPS, CCN) at both the T3 site (IOP1: Feb 1-Mar 31, 2014, and IOP2: Aug 15-Oct 15, 2014) and T2 site (between IOPs and into 2nd IOP). The oxidation of ambient air in the OFR led to substantial and variable secondary organic aerosol (SOA) formation from any SOA-precursor gases, known and unknown, that entered the OFR. In general, more SOA was produced during the nighttime than daytime, suggesting that SOA-precursor gases were found in relatively higher concentrations at night. Similarly, more SOA was formed in the dry season (IOP2) than wet season (IOP1). The maximum amount of SOA produced during nighttime from OH oxidation ranged from less than 1 μg/m3 on some nights to greater than 10 μg/m3 on other nights. O3 oxidation of ambient air also led to SOA formation, although several times less than from OH oxidation. The amount of SOA formation sometimes, but not always, correlated with measured gas-phase biogenic and/or anthropogenic SOA precursors (e.g., SV-TAG sesquiterpenes, PTR-TOFMS aromatics, isoprene, and monoterpenes). The SOA mass formed in the OFR from OH oxidation was up to an order of magnitude larger than could be explained from aerosol yields of measured primary VOCs. This along with measurements from previous campaigns suggests that most SOA was formed from intermediate S/IVOC sources (e.g., VOC oxidation products, evaporated POA, or direct emissions). To verify the SOA yields of VOCs under OFR experimental conditions, atmospherically-relevant concentrations of several VOCs were added individually into ambient air in the OFR and oxidized by OH or O3. SOA yields in the OFR were similar to published chamber yields. Preliminary PMF factor analysis showed production of secondary factors in

  7. Secondary organic aerosol formation from isoprene photo-oxidation during cloud condensation-evaporation cycles (CUMULUS project)

    NASA Astrophysics Data System (ADS)

    Brégonzio-Rozier, Lola; Siekmann, Frank; Giorio, Chiara; Temime-Roussel, Brice; Pangui, Edouard; Morales, Sébastien; Gratien, Aline; Ravier, Sylvain; Monod, Anne; Doussin, Jean-Francois

    2014-05-01

    It is acknowledged that atmospheric photo-oxidation of Volatile Organic Compounds (VOC) leads to the formation of less volatile oxidized species. These compounds can undergo gas-to-particle conversion, leading to the formation of Secondary Organic Aerosols (SOA) in the atmosphere. Nevertheless, some of these oxidized species are water soluble and could also partition into cloud droplets. Higher molecular weight and less volatile compounds could be produced in the aqueous phase and remain in the particle phase after water evaporation (Ervens et al., 2011). The aim of the present work is to study SOA formation in the presence of cloud droplets during isoprene photo-oxidation. To this end, an original multiphase approach in a simulation chamber was set up in order to investigate the chemistry occurring in the gaseous, particulate and aqueous phases, and the exchange between these phases. Experiments were performed, within the CUMULUS project (CloUd MULtiphase chemistry of organic compoUndS in the troposphere), in the CESAM chamber (Wang et al., 2011). This chamber was designed to investigate multiphase processes under realistic actinic flux, and accurate control of both temperature and relative humidity. A specific protocol was set up to produce cloud events in the simulation chamber exhibiting a significant lifetime in the presence of light (10-12 minutes). By using this protocol, many clouds could be generated in a single experiment. In each experiment, around 800 ppb of isoprene was injected in the chamber together with HONO under dry conditions before irradiation. A Fourier Transform Infrared Spectrometer (FTIR), a Proton Transfer Reaction Mass Spectrometer (PTR-TOF-MS) and NOx and O3 analyzers were used to analyze gas-phase composition. Dried SOA size distributions and total concentrations were measured by a Scanning Mobility Particle Sizer (SMPS). An Aerodyne High Resolution Time-Of-Flight Aerosol Mass Spectrometer (HR-TOF-AMS) was also used to investigate

  8. Multi-generational oxidation model to simulate secondary organic aerosol in a 3-D air quality model

    NASA Astrophysics Data System (ADS)

    Jathar, S. H.; Cappa, C. D.; Wexler, A. S.; Seinfeld, J. H.; Kleeman, M. J.

    2015-02-01

    Multi-generational gas-phase oxidation of organic vapors can influence the abundance, composition and properties of secondary organic aerosol (SOA). Only recently have SOA models been developed that explicitly represent multi-generational SOA formation. In this work, we integrated the statistical oxidation model (SOM) into SAPRC-11 to simulate the multi-generational oxidation and gas/particle partitioning of SOA in the regional UCD/CIT air quality model. In SOM, evolution of organic vapors by reaction with the hydroxyl radical is defined by (1) the number of oxygen atoms added per reaction, (2) the decrease in volatility upon addition of an oxygen atom and (3) the probability that a given reaction leads to fragmentation of the organic molecule. These SOM parameter values were fit to laboratory "smog chamber" data for each precursor/compound class. The UCD/CIT model was used to simulate air quality over two-week periods in the South Coast Air Basin of California and the eastern United States. For the regions and episodes tested, the traditional two-product SOA model and SOM produce similar SOA concentrations but a modestly different SOA chemical composition. Predictions of the oxygen-to-carbon ratio qualitatively agree with those measured globally using aerosol mass spectrometers. Overall, the implementation of the SOM in a 3-D model provides a comprehensive framework to simulate the atmospheric evolution of OA.

  9. Aerosol mixing-state, hygroscopic growth and cloud activation efficiency during MIRAGE 2006

    NASA Astrophysics Data System (ADS)

    Lance, S.; Raatikainen, T.; Onasch, T.; Worsnop, D. R.; Yu, X.-Y.; Alexander, M. L.; Stolzenburg, M. R.; McMurry, P. H.; Smith, J. N.; Nenes, A.

    2012-06-01

    Observations of aerosol hygroscopic growth and CCN activation spectra for submicron particles are reported for the T1 ground site outside of Mexico City during the MIRAGE 2006 campaign. κ-Köhler theory is used to evaluate the characteristic water uptake coefficient, κ*, for the CCN active aerosol population using both size-resolved HTDMA and size-resolved CCNc measurements. Organic mass fractions, forg, are evaluated from size-resolved aerosol mass spectrometer (AMS) measurements, from which κAMS is inferred and compared against κ*. Strong diurnal profiles of aerosol water uptake parameters and aerosol composition are observed. We find that new particle formation (NPF) events are correlated with an increased κ* and CCN-active fraction during the daytime, with greater impact on smaller particles. During NPF events, the number concentration of 40 nm particles acting as CCN can surpass by more than a factor of two the concentrations of 100 nm particles acting as CCN, at supersaturations of 0.51% ± 0.06%. We also find that at 06:00-08:00 in the morning throughout the campaign, fresh traffic emissions result in substantial changes to the chemical distribution of the aerosol, with on average 65% externally-mixed fraction for 40 nm particles and 30% externally-mixed fraction for 100 nm particles, whereas at midday nearly all particles of both sizes can be described as internally-mixed. Average activation spectra and growth factor distributions are analyzed for different time periods characterizing the daytime (with and without NPF events), the early morning "rush hour", and the entire campaign. We show that κ* derived from CCNc measurements decreases as a function of size during all time periods, while the CCN-active fraction increases as a function of size. Size-resolved AMS measurements do not predict the observed trend for κ* versus particle size, which can be attributed to unresolved mixing-state and the presence of refractory material not measured by the AMS

  10. Aerosol mixingstate, hygroscopic growth and cloud activation efficiency during MIRAGE 2006

    SciTech Connect

    Lance, Sara; Raatikainen, T.; Onasch, Timothy B.; Worsnop, Douglas R.; Yu, Xiao-Ying; Alexander, M. L.; Stolzenberg, Mark; McMurry, Peter; Smith, James N.; Nenes, Athanasios

    2013-05-15

    Observations of aerosol hygroscopic growth and CCN activation spectra for submicron particles are reported for the T1 ground site outside of Mexico City during the MIRAGE 2006 campaign. K¨ohler theory is used to evaluate the characteristic water uptake coefficient, k*, for the CCN active aerosol population using both size-resolved HTMDA and size-resolved CCNc measurements. Organic mass fractions, (forg), are evaluated from size-resolved aerosol mass spectrometer (AMS) measurements, from which kAMS is inferred and compared against k*. Strong diurnal profiles of aerosol water uptake parameters and aerosol composition are observed. We find that new particle formation (NPF) events are correlated with an increased k* and CCN-active fraction during the daytime, with greater impact on smaller particles. During NPF events, the number concentration of 40 nm particles acting as CCN can surpass by more than a factor of two the concentrations of 100 nm particles acting as CCN, at supersaturations of 0.51% +/- 0.06%. We also find that at 0600-0800 in the morning throughout the campaign, fresh traffic emissions result in substantial changes to the chemical distribution of the aerosol, with on average 65% externally-mixed fraction for 40 nm particles and 30% externally-mixed fraction for 100 nm particles, whereas at midday nearly all particles of both sizes can be described as “internally-mixed”. Average activation spectra and growth factor distributions are analyzed for different time periods characterizing the daytime (with and without NPF events), the early morning “rush hour”, and the entire campaign. We show that k* derived from CCNc measurements decreases as a function of size during all time periods, while the CCN-active fraction increases as a function of size. Size-resolved AMS measurements do not predict the observed trend for k* versus particle size, which can be attributed to unresolved mixing-state and the presence of refractory material not measured by the

  11. A New Method for Multicomponent Activity Coefficients of Electrolytes in Aqueous Atmospheric Aerosols

    SciTech Connect

    Zaveri, Rahul A.; Easter, Richard C.; Wexler, Anthony S.

    2005-01-21

    Three-dimensional models of atmospheric inorganic aerosols need an accurate yet computationally efficient parameterization of activity coefficients of various electrolytes in multicomponent aqueous solutions. This paper describes the development and application of a new mixing rule for calculating activity coefficients of electrolytes typically found in atmospheric aerosol systems containing H+, NH4+, Na+, Ca2+ SO42-, HSO4-, NO3-, and Cl- ions. The new mixing rule, called MTEM (Multicomponent Taylor Expansion Model), estimates the mean activity coefficient of an electrolyte in a multicomponent solution based on its values in binary solutions of all the electrolytes present in the mixture at the solution water activity aw, assuming aw is equal to the ambient relative humidity. The aerosol water content is calculated using the Zdanovskii-Stokes-Robinson method. For self-consistency, most of the MTEM and Zdanovskii-Stokes-Robinson parameters are derived using the comprehensive Pitzer-Simonson-Clegg model at 298.15 K. MTEM is evaluated for several multicomponent systems representing various continental and marine aerosols, and is contrasted against the mixing rule of Kusik and Meissner and the newer approach of Metzger et al. [2002]. Predictions of MTEM are found to be generally within a factor of 0.8 to 1.25 of the comprehensive Pitzer-Simonson-Clegg model, and are shown to be significantly more accurate than predictions of the other two methods. MTEM also yields a non-iterative solution of the bisulfate ion dissociation in sulfate-rich systems – a major computational advantage over other iterative methods. CPU time requirements of MTEM relative to other methods for sulfate-poor and sulfate-rich systems are also discussed.

  12. Aerosol hygroscopicity and CCN activity during the AC3Exp campaign: Implications for CCN parameterization

    NASA Astrophysics Data System (ADS)

    Zhang, Fang; Li, Yanan; Li, Zhanqing

    2015-04-01

    Atmospheric aerosol particles acting as CCN are pivotal elements of the hydrological cycle and climate change. In this study, we measured and characterized NCCN in relatively clean and polluted air during the AC3Exp campaign conducted at Xianghe, China during summer 2013. The aim was to examine CCN activation properties under high aerosol loading conditions in a polluted region and to assess the impacts of particle size and chemical composition on the CCN AR which acts as a proxy of the total number of aerosol particles in the atmosphere. A gradual increase in size-resolved AR with particle diameter suggests that aerosol particles have different hygroscopicities. For particles in the accumulation mode, values of κapa range from 0.31-0.38 under background conditions, which is about 20% higher than that derived under polluted conditions. For particles in the nucleation or Aitken mode, κ range from 0.20-0.34 under both background and polluted conditions. Larger particles were on average more hygroscopic than smaller particles. However, the case is more complex for particles originating from heavy pollution due to the diversity in particle composition and mixing state. The low R2 for the NPO CCN closure test suggests a 30%-40% uncertainty in total NCCN estimation. Using bulk chemical composition data from ACSM measurements, the relationship between bulk AR and the physical and chemical properties of atmospheric aerosols is investigated. Based on a case study, it has been concluded that one cannot use a parameterized formula using only total NCN to estimate total NCCN. Our results showed a possibility of using bulk κchem and f44 in combination with bulk NCN > 100 nm to parameterize CCN number concentrations.

  13. Modeling secondary organic aerosol formation from oxidation of α-pinene, β-pinene, and d-limonene

    NASA Astrophysics Data System (ADS)

    Chen, Jianjun; Griffin, Robert J.

    The biogenic species α-pinene, β-pinene, and d-limonene are among the most abundant monoterpenes emitted globally. They are also important precursors to secondary organic aerosol (SOA) formation in the atmosphere. This study involves the development of proposed oxidation mechanisms for these three species. Semi- and non-volatile oxidation products with the potential to lead to SOA formation are predicted explicitly. Simulation code that describes the gas-phase oxidation mechanisms including reactions that lead to ozone (O 3) formation is coupled to an equilibrium absorptive partitioning code. The coupled model is used to simulate both gas-phase chemistry and SOA formation associated with oxidation of these three species in chamber experiments involving single as well as multiple oxidants. For the partitioning model, required molecular properties of the oxidation products are taken from the literature or estimated based on structural characteristics. The predicted O 3 and SOA concentrations are typically within ±50% of measured values for most of the experiments except for the experiments with low initial hydrocarbon concentrations and the nitrate radical experiments with α-pinene. The developed model will be used to update a gas-phase chemical mechanism and a SOA formation module used in a three-dimensional air quality model.

  14. Global and Regional Decreases in Tropospheric Oxidants from Photochemical Effects of Aerosols

    NASA Technical Reports Server (NTRS)

    Martin, Randall V.; Jacob, Daniel J.; Yantosca, Robert M.; Chin, Mian; Ginoux, Paul

    2003-01-01

    We evaluate the sensitivity of tropospheric OH, O3, and O3 precursors to photochemical effects of aerosols not usually included in global models: (1) aerosol scattering and absorption of ultraviolet radiation and (2) reactive uptake of HO', NO2, and NO3. Our approach is to couple a global 3-D model of tropospheric chemistry (GEOS- CHEM) with aerosol fields from a global 3-D aerosol model (GOCART). Reactive uptake by aerosols is computed using reaction probabilities from a recent review (gamma(sub HO2) = 0.2, gamma(sub NO2) = 10(exp -4), gamma(sub NO3) = l0(exp -3). Aerosols decrease the O3 - O((sup 1)D) photolysis frequency by 5-20% at the surface throughout the Northern Hemisphere (largely due to mineral dust) and by a factor of 2 in biomass burning regions (largely due to black carbon). Aerosol uptake of HO2 accounts for 10-40% of total HOx radical ((triple bonds)OH + peroxy) loss in the boundary layer over polluted continental regions (largely due to sulfate and organic carbon) and for more than 70% over tropical biomass burning regions (largely due to organic carbon). Uptake of NO2 and NO3 accounts for 10-20% of total HNO3 production over biomass burning regions and less elsewhere. Annual mean OH concentrations decrease by 9% globally and by 5-35% in the boundary layer over the Northern Hemisphere. Simulated CO increases by 5- 15 ppbv in the remote Northern Hemisphere, improving agreement with observations. Simulated boundary layer O3 decreases by 15- 45 ppbv over India during the biomass burning season in March and by 5-9 ppbv over northern Europe in August, again improving comparison with observations. We find that particulate matter controls would increase surface O3 over Europe and other industrial regions.

  15. Temporal variations of 7Be and 210Pb activity in aerosols at Xiamen, China

    NASA Astrophysics Data System (ADS)

    Huang, Dekun

    2016-04-01

    The radionuclides serve as powerful tracers to identify and quantify several atmospheric processes, such as source, transport and mixing of air masses, air masses exchanging between various atmospheric layers, residence times of atmospheric gasses and pollutants. 7Be and 210Pb activities in aerosols were measurement from October, 2013 to September, 2015 at Xiamen (24°26'7.44″N, 118°5'31.30″N) in South China. The activity of 7Be and 210Pb in aerosols from 2013 to 2015 in Xiamen ranged from 0.26 to 9.05 (mean:4.15) mBq m-3 and from 0.14 to 2.64 (mean:1.05) mBq m-3, respectively. The mean activity of 7Be was comparable with the activities of other places in the same latitude, while the mean activity of 210Pb was lower than the activity of the locations at high altitudes. The possible reason is that Xiamen is a coastal city located on southwest Pacific. The activities of 7Be and 210Pb had a commonly low value in summer (July-September) and a high value in autumn (October-December), it may be controlled by the rainfall. There is significant relationship between the monthly 210Pb activities and the concentration of PM 2.5 and PM 10. In contrast, monthly 7Be activities only show significant correlation with the concentration of PM 10, which implies that 7Be and 210Pb can be used to trace the different sources of the aerosols. And the dry 7Be depositional fluxes increased with latitude along the coast of China (R2=0.92, n=8).

  16. Evidence for an unrecognized secondary anthropogenic source of organosulfates and sulfonates: gas-phase oxidation of polycyclic aromatic hydrocarbons in the presence of sulfate aerosol.

    PubMed

    Riva, Matthieu; Tomaz, Sophie; Cui, Tianqu; Lin, Ying-Hsuan; Perraudin, Emilie; Gold, Avram; Stone, Elizabeth A; Villenave, Eric; Surratt, Jason D

    2015-06-01

    In the present study, formation of aromatic organosulfates (OSs) from the photo-oxidation of polycyclic aromatic hydrocarbons (PAHs) was investigated. Naphthalene (NAP) and 2-methylnaphthalene (2-MeNAP), two of the most abundant gas-phase PAHs and thought to represent "missing" sources of urban SOA, were photochemically oxidized in an outdoor smog chamber facility in the presence of nonacidified and acidified sulfate seed aerosol. Effects of seed aerosol composition, acidity and relative humidity on OS formation were examined. Chemical characterization of SOA extracts by ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry revealed the formation of OSs and sulfonates from photo-oxidation in the presence of sulfate seed aerosol. Many of the organosulfur compounds identified in the smog chamber extracts were also measured in urban fine aerosol collected at Lahore, Pakistan, and Pasadena, USA, demonstrating that PAH photo-oxidation in the presence of sulfate aerosol is a hitherto unrecognized source of anthropogenic secondary organosulfur compounds, and providing new PAH SOA tracers. PMID:25879928

  17. Synthesis and Analysis of Putative Terpene Oxidation Products and the Secondary Organic Aerosol Particles that Form from Them

    NASA Astrophysics Data System (ADS)

    Ebben, C. J.; Strick, B. F.; Upshur, M.; Shrestha, M.; Velarde, L.; Lu, Z.; Wang, H.; Xiao, D.; Batista, V. S.; Martin, S. T.; Thomson, R. J.; Geiger, F. M.

    2013-12-01

    The terpenes isoprene and α-pinene are abundant volatile organic compounds (VOCs) that are emitted by trees and oxidized in the atmosphere. However, the chemical processes involved in the formation of secondary organic aerosol (SOA) particles from VOCs are not well understood. In this work, we use a combined synthetic, analytical, and theoretical approach to gain a molecular level understanding of the chemistry involved in the formation of SOA particles from VOC precursors. To this end, we have synthesized putative products of isoprene and α-pinene oxidation and the oligomers that form from them. Specifically, we have focused on the epoxide and 2-methyltetraols that form from isoprene oxidation by hydroxyl radicals, as well as products of α-pinene ozonolysis. In our analysis, we utilize a spectroscopic technique called sum frequency generation (SFG). SFG is a coherent, surface-specific, vibrational spectroscopy that uses infrared and visible laser light fields, overlapped spatially and temporally at a surface, to probe vibrational transitions within molecules. Our use of this technique allows us to assess the chemical identity of aerosol-forming components at their surfaces, where interactions with the gas phase occur. The spectral responses from these compounds are compared to those of synthetic isoprene- and α-pinene-derived aerosol particles, as well as natural aerosol particles collected in tropical and boreal forests to begin to predict the constituents that may be present at the surfaces of these particles. In addition, isotope editing is utilized to gain a better understanding of α-pinene. The rigidity of this molecule makes it difficult to understand spectroscopically. The combination of synthesis with deuterium labeling, theory, and broadband and high-resolution SFG spectroscopy in the C-H and C-D stretching regions allow us to determine the orientation of this important molecule on a surface, which could have implications for its reactivity in the

  18. The influence of marine microbial activities on aerosol production: A laboratory mesocosm study

    NASA Astrophysics Data System (ADS)

    Alpert, Peter A.; Kilthau, Wendy P.; Bothe, Dylan W.; Radway, JoAnn C.; Aller, Josephine Y.; Knopf, Daniel A.

    2015-09-01

    The oceans cover most of the Earth's surface, contain nearly half the total global primary biomass productivity, and are a major source of atmospheric aerosol particles. Here we experimentally investigate links between biological activity in seawater and sea spray aerosol (SSA) flux, a relationship of potential significance for organic aerosol loading and cloud formation over the oceans and thus for climate globally. Bubbles were generated in laboratory mesocosm experiments either by recirculating impinging water jets or glass frits. Experiments were conducted with Atlantic Ocean seawater collected off the eastern end of Long Island, NY, and with artificial seawater containing cultures of bacteria and phytoplankton Thalassiosira pseudonana, Emiliania huxleyi, and Nannochloris atomus. Changes in SSA size distributions occurred during all phases of bacterial and phytoplankton growth, as characterized by cell concentrations, dissolved organic carbon, total particulate carbon, and transparent exopolymer particles (gel-forming polysaccharides representing a major component of biogenic exudate material). Over a 2 week growth period, SSA particle concentrations increased by a factor of less than 2 when only bacteria were present and by a factor of about 3 when bacteria and phytoplankton were present. Production of jet-generated SSA particles of diameter less than 200 nm increased with time, while production of all particle diameters increased with time when frits were used. The implications of a marine biological activity dependent SSA flux are discussed.

  19. Differences between the activity size distributions of the different natural radionuclide aerosols in outdoor air

    NASA Astrophysics Data System (ADS)

    Gründel, M.; Porstendörfer, J.

    The results of the activity size distribution of the short-lived ( 218Po, 214Bi/ 214Po) and long-lived ( 210Pb, 210Po) radon decay product aerosols, the thoron decay product aerosols ( 212Pb, 212Po) and 7Be of the outdoor atmosphere are presented. The results were obtained from measurements averaged over an extended period (4 weeks) and were carried out with a low-pressure On-Line Alpha Cascade Impactor (OLACI). The size distributions of the radionuclides were obtained from the same measurement run with the OLACI, so that the size classification technique and the atmospheric and weather conditions for all radionuclides were identical. This measurement technique made it possible to measure the correct differences between the size distributions of the different natural radionuclides in the environmental air. The differences between the activity size distributions of the long- and short-lived radionuclides could be explained by coagulation with aerosol particles of the atmosphere as for instance 210Pb was shown.

  20. The dynamic surface tension of atmospheric aerosol surfactants reveals new aspects of cloud activation

    PubMed Central

    Nozière, Barbara; Baduel, Christine; Jaffrezo, Jean-Luc

    2014-01-01

    The activation of aerosol particles into cloud droplets in the Earth’s atmosphere is both a key process for the climate budget and a main source of uncertainty. Its investigation is facing major experimental challenges, as no technique can measure the main driving parameters, the Raoult’s term and surface tension, σ, for sub-micron atmospheric particles. In addition, the surfactant fraction of atmospheric aerosols could not be isolated until recently. Here we present the first dynamic investigation of the total surfactant fraction of atmospheric aerosols, evidencing adsorption barriers that limit their gradient (partitioning) in particles and should enhance their cloud-forming efficiency compared with current models. The results also show that the equilibration time of surfactants in sub-micron atmospheric particles should be beyond the detection of most on-line instruments. Such instrumental and theoretical shortcomings would be consistent with atmospheric and laboratory observations and could have limited the understanding of cloud activation until now. PMID:24566451

  1. Sun-Sky Radiometer Synthesis of Interplay Between Aerosols and Monsoon Activity Over Pune, India

    NASA Astrophysics Data System (ADS)

    Devara, P. C. S.; Kumar, Sumit; Vijayakumar, K.; Pandithurai, G.

    2014-09-01

    Besides several thematic campaigns, utilizing a variety of platforms including satellites, ground-based networks have been established to improve our understanding of the role of aerosols in the changing monsoon climate. Two such widely known networks over the globe are `SKYNET' and `AERONET' with sun-sky radiometers as the principal equipment that characterizes aerosols and gases over different geographical locations under varied air mass conditions. Pune (18°43'N, 73°51'E, 559 m above mean sea level), a fast growing low-latitude, urban city in India, is one of the sites where Prede (POM-01L, SKYNET) and Cimel (CE-318, AERONET) Sun-sky radiometers have been in operation since 2004. These radiometers have been extensively used in several studies related to stand-alone and coupled aerosol-cloud-climate processes. The Prede instrument at this site is being augmented for the network of the Global Atmospheric Watch program of the World Meteorological Organization to facilitate data coordination through the World Data Center for Aerosols. The present study envisages understanding the response of atmospheric constituents, through simultaneous operation of the radiometers amongst others, for the rainfall activity over Pune during two contrasting monsoon years of 2008 (active, 98 % of long period average (LPA) rainfall over the whole country) and 2009 (weak, 78 % of LPA). The synthesis of data indicates that, apart from excellent agreement between the direct Sun observations, both radiometers capture well the monsoon features within the instrument density and efficacy of data retrieval algorithms involved. The meteorological fields from the ECMWF re-analysis and NOAA-HYSPLIT air-mass back-trajectory analysis during the study period have been utilized to explain the variations observed in the radiometer products.

  2. Hygroscopicity and CCN activity of atmospheric aerosol particles and their relation to organics: Characteristics of urban aerosols in Nagoya, Japan

    NASA Astrophysics Data System (ADS)

    Kawana, Kaori; Nakayama, Tomoki; Mochida, Michihiro

    2016-04-01

    The size-resolved distributions of hygroscopic growth factor g and the ratios of cloud condensation nuclei (CCN) to condensation nuclei of atmospheric aerosols were investigated in Nagoya, Japan. The average of the distributions of g at 85% relative humidity was bimodal. The size-resolved mean κ derived from g showed an increasing trend with diameter: 0.17-0.33 at 24-359 nm. The κ values calculated from CCN activation curves were 37% higher than those derived from g. Only 9% of the 37% difference is explained by the difference in the κ of inorganics under subsaturated and supersaturated conditions, suggesting a contribution of organics to the remaining 28% difference. The size-averaged κ of organics (κorg) was calculated as 0.14 and 0.19 by two different methods. The number fractions of CCN predicted from the hygroscopicity data over the range of 24-359 nm are loosely consistent with those observed if the size- and time-averaged g is applied to all particles (differences: -30% to +10%). This consistency improves if size- and time-resolved g and g distribution are used (differences: -19% to -3%). Whereas the number fractions of CCN predicted from the composition data are greatly underestimated if organics are assumed to be insoluble (differences: -64% to -45%), they are more consistent if κorg of 0.14 or 0.19 is applied (differences: -10% to +14%). The results demonstrate the importance of the dependence of the g of particles on time and particle size and the hygroscopicity of organics for CCN number concentrations in the urban atmosphere.

  3. A full mass spectrum evaluation of semivolatile organic compounds measured during the Southern Oxidant and Aerosol Study in Alabama, USA, 2013

    NASA Astrophysics Data System (ADS)

    Holzinger, Rupert; Khan, Anwar; Misztal, Pawel; Goldstein, Allen

    2016-04-01

    A serial 3-stage denuder system has been developed and for the first time deployed during the Southern Oxidant and Aerosol Study (SOAS) in Centreville, Alabama, USA, for one month during the summer of 2013. Volatile organic compounds (VOCs) were collected on an activated carbon denuder and thermally desorbed to be measured with PTR-MS (PTR-TOF800, Ionicon Analytik GmbH). Comparison with a second PTR-MS instrument operated under standard conditions at the same site revealed poor recovery for the majority of the VOCs while individual species measured by the different PTR-MS systems still exhibited excellent correlation. Semivolatile organic compounds (SVOCs) in the gas phase were collected and thermally desorbed on a denuder coated with Methylsiloxane (Agilent DB-1). More than 100 SVOCs have been detected at levels in the range 0.05-3 pmmol/mol and only a few species exhibited maximum mixing ratios above 5 pmol/mol. Many of the detected species exhibited a clear diurnal profile while the concentration of some was clearly dominated by pollution events. Carboxylic acids, (oxidized) polycyclic aromatic compounds, and monoterpene oxidation products were compound groups that provided most of the mass and a typical total concentration of the measured burden of SVOCs was 5 microgram per cubic meter.

  4. Study of Heterogeneouse Processes Related to the Chemistry of Tropospheric Oxidants and Aerosols

    SciTech Connect

    Davidovits, Paul; Worsnop, D R; Jayne, J T; Colb, C E

    2013-02-13

    The objective of the studies was to elucidate the heterogeneous chemistry of tropospheric aerosols. Experiments were designed to measure both specifically needed parameters, and to obtain systematic data required to build a fundamental understanding of the nature of gas-surface physical and chemical interactions

  5. On the Water Uptake and CCN Activation of Tropospheric Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Rastak, Narges; Pajunoja, Aki; Acosta Navarro, Juan-Camilo; Leong, Yu Jun; Cerully, Kate M.; Nenes, Athanasios; Kirkevåg, Alf; Topping, David; Virtanen, Annele; Riipinen, Ilona

    2016-04-01

    Aerosol particles introduce high uncertainties to radiative climate forcing. If exposed to a given relative humidity (RH), aerosol particles containing soluble material can absorb water and grow in size (hygroscopic growth). If RH is increased further beyond supersaturation (RH >100%) the particles can act as cloud condensation nuclei (CCN). Aerosol particles interactions with water vapour determine to a large extent their influence on climate. Organic aerosols (OA) contribute a large fraction (20-90%) of atmospheric submicron particulate mass, on the other hand they often consist of thousands of compounds with different properties. One of these properties is solubility, which affects the hygroscopic growth and cloud condensation nucleus (CCN) activation of the organic particles. We investigate the hygroscopic behaviour of complex organic aerosols accounting for the distribution of solubilities present in these mixtures. We use the SPARC method to estimate the solubility distributions of isoprene (IP) and monoterpene (MT) SOA based on their chemical composition, as predicted by the Master Chemical Mechanism (MCM). Combining these solubility distributions with the adsorption theory along with the non-ideal behaviour of organic mixtures, we predict the expected hygroscopic growth factors (HGFs), CCN activation behaviour and the related hygroscopicity parameters kappa for these mixtures. The predictions are compared to laboratory measurements as well as field data from MT- and IP-dominated measurement sites. The predicted solubility distributions do a good job in explaining the water uptake of these two mixture types at high relative humidities (RH around 90%), as well as their CCN activation - including the potential differences between the kappa values derived from HGF vs. CCN data. At lower relative humidities, however, the observed water uptake is higher than predicted on solubility alone, particularly for the MT-derived SOA. The data from the low RHs are further

  6. Characterization of ambient aerosols during the Southern Oxidant and Aerosol Study (SOAS) in Centreville, AL with a high-resolution time-of-flight aerosol mass spectrometer Basak Karakurt Cevik1, Yu Jun Leong1, Carlos Hernandez1, Robert Griffin1 1 Rice University, CEE Department, 6100 Main St., Houston, TX 77005, USA

    NASA Astrophysics Data System (ADS)

    Karakurt Cevik, B.; Leong, Y.; Hernandez, C.; Griffin, R. J.

    2013-12-01

    An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a Brechtel Manufacturing, Inc. particle-into-liquid sampler (PILS) were deployed at a rural location in Centreville, AL, from 1 June to 15 July 2013 as a part of the Southern Oxidant and Aerosol Study (SOAS). PILS samples were analyzed with Dionex ion chromatographs. The data will allow us to characterize the temporal characteristics of the concentrations and size distributions of non-refractory (NR) chemical species in the ambient submicron particles. Preliminary analysis of the data indicates that the sub-micron particulate matter is highly dominated by organic matter with a relatively high state of oxidation and it is followed by smaller contributions from sulfate and ammonium. In order to investigate the processes and sources that lead to observed aerosol concentrations at the site, the time series will be analyzed in conjunction with additional trace gas, aerosol, and meteorological measurements. The region is known to have high biogenic volatile organic compounds (VOCs) emissions and many of these biogenic VOCs (BVOCs) are important secondary organic aerosol (SOA) precursors. Preliminary data from the HR-ToF-AMS indicates the importance of oxidized organic aerosol during SOAS. The study will also focus on the importance of the SOA in the total organic fraction and the effect of atmospheric processing on the chemical composition of the organic fraction.

  7. Organosulfates and oxidation products from biogenic hydrocarbons in fine aerosols from a forest in North West Europe during spring

    NASA Astrophysics Data System (ADS)

    Kristensen, Kasper; Glasius, Marianne

    2011-09-01

    Organosulfates of monoterpenes and isoprene, as well as their oxidation products have been identified in biogenic secondary organic aerosols (BSOA) from both laboratory and field studies. Organosulfates provide an interesting coupling between air pollution and formation of low-volatility BSOA. HPLC quadrupole time-of-flight mass spectrometry was used to study polar acidic monoterpene and isoprene oxidation products including pinic acid, pinonic and terpenylic acid along with organosulfates and nitrooxy organosulfates in aerosols from ambient air. The method was first validated by analysis of spiked quartz filters, which showed acceptable recoveries >74% for pinic acid, pinonic acid, camphor sulphonic acid and adipic acid. Acetonitrile was identified as a better solvent than methanol for extraction and analysis of pinonic acid and adipic acid, due to improved analytical sensitivity and prevention of methyl ester formation during sample extraction. PM 1 (i.e, aerosols with an aerodynamic diameter ≤1 μm) were collected during spring 2008 in a forest in Denmark with mixed deciduous and coniferous trees. Average concentrations of the most abundant compounds were: pinic acid: 1.5 ng m -3, pinonic acid: 3.0 ng m -3, terpenylic acid: 0.8 ng m -3 and 3-methyl-1,2,3-butanetricarboxylic acid: 3.0 ng m -3. Organosulfates and nitrooxy organosulfates were identified in a majority of the daily samples and the highest levels were observed during a warm period in late spring. As a first approach, due to the lack of authentic standards, organosulfates and nitrooxy organosulfates were tentatively quantified based on the analytical response of camphor sulphonic acid. Generally the concentrations of organosulfates and nitrooxy organosulfates were lower than first generation oxidation products. The maximum concentration of a total of 10 organosulfates and nitrooxy organosulfates were found to be about three times lower than pinonic acid with a maximum concentration of 8 ng m -3. A

  8. Evaluating nitrogen oxide sources and oxidation pathways impacting aerosol production on the Southern Ute Indian Reservation and Navajo Nation using geochemical isotopic analysis

    NASA Astrophysics Data System (ADS)

    King, Michael Z.

    Increased emissions of nitrogen oxides (NOx = NO + NO 2) as a result of the development of oil, gas and coal resources in the Four Corners region of the United States have caused concern for area American Indian tribes that levels of ozone, acid rain, and aerosols or particulate matter (PM) may increase on reservation lands. NOx in the atmosphere plays an important role in the formation of these pollutants and high levels are indicators of poor air quality and exposure to them has been linked to a host of human health effects and environmental problems facing today's society. Nitrogen oxides are eventually oxidized in the atmosphere to form nitrate and nitric acid which falls to earth's surface by way of dry or wet deposition. In the end, it is the removal of NOx from the atmosphere by chemical conversion to nitrate that halts this production of oxidants, acids, and aerosols. Despite the importance of understanding atmospheric nitrate (NO3- = HNO3-(g), NO3-(aq), NO3-(s)) production there remains major deficiencies in estimating the significant key reactions that transform NOx into atmospheric nitrate. Stable isotope techniques have shown that variations in oxygen (16O, 17O, 18O) and nitrogen (14N, 15N) isotope abundances in atmospheric nitrate provide significant insight to the sources and oxidation pathways that transform NOx. Therefore, this project applied this resolution using high pressure liquid chromatography and isotope ratio mass spectrometry to determine the chemical and isotopic composition of particulate nitrate (PM2.5 and PM10), collected on the Southern Ute Indian Reservation and Navajo Nation. It was determined that the observed particulate nitrate concentrations on tribal lands were likely linked to seasonal changes in boundary layer height (BLH), local sources, meteorology, photochemistry and increases in windblown crustal material. The Southern Ute Indian Reservation indicated higher delta15N values in comparison to the Navajo Nation study site

  9. Aerosol-assisted chemical vapor deposition of tungsten oxide films and nanorods from oxo tungsten(VI) fluoroalkoxide precursors.

    PubMed

    Kim, Hankook; Bonsu, Richard O; O'Donohue, Christopher; Korotkov, Roman Y; McElwee-White, Lisa; Anderson, Timothy J

    2015-02-01

    Aerosol-assisted chemical vapor deposition (AACVD) of WOx was demonstrated using the oxo tungsten(VI) fluoroalkoxide single-source precursors, WO[OCCH3(CF3)2]4 and WO[OC(CH3)2CF3]4. Substoichiometric amorphous tungsten oxide thin films were grown on indium tin oxide (ITO) substrates in nitrogen at low deposition temperature (100-250 °C). At growth temperatures above 300 °C, the W18O49 monoclinic crystalline phase was observed. The surface morphology and roughness, visible light transmittance, electrical conductivity, and work function of the tungsten oxide materials are reported. The solvent and carrier gas minimally affected surface morphology and composition at low deposition temperature; however, material crystallinity varied with solvent choice at higher temperatures. The work function of the tungsten oxide thin films grown between 150 and 250 °C was determined to be in the range 5.0 to 5.7 eV, according to ultraviolet photoelectron spectroscopy (UPS). PMID:25569472

  10. Particulate oxidative burden associated with firework activity.

    PubMed

    Godri, Krystal J; Green, David C; Fuller, Gary W; Dall'Osto, Manuel; Beddows, David C; Kelly, Frank J; Harrison, Roy M; Mudway, Ian S

    2010-11-01

    Firework events are capable of inducing particulate matter (PM) episodes that lead to exceedances of regulatory limit values. As short-term peaks in ambient PM concentration have been associated with negative impacts on respiratory and cardiovascular health, we performed a detailed study of the consequences of firework events in London on ambient air quality and PM composition. These changes were further related to the oxidative activity of daily PM samples by assessing their capacity to drive the oxidation of physiologically important lung antioxidants including ascorbate, glutathione and urate (oxidative potential, OP). Twenty-four hour ambient PM samples were collected at the Marylebone Road sampling site in Central London over a three week period, including two major festivals celebrated with pyrotechnic events: Guy Fawkes Night and Diwali. Pyrotechnic combustion events were characterized by increased gas phase pollutants levels (NO(x) and SO(2)), elevated PM mass concentrations, and trace metal concentrations (specifically Sr, Mg, K, Ba, and Pb). Relationships between NO(x), benzene, and PM(10) were used to apportion firework and traffic source fractions. A positive significant relationship was found between PM oxidative burden and individual trace metals associated with each of these apportioned source fractions. The level of exposure to each source fraction was significantly associated with the total OP. The firework contribution to PM total OP, on a unit mass basis, was greater than that associated with traffic sources: a 1 μg elevation in firework and traffic PM fraction concentration was associated with a 6.5 ± 1.5 OP(T) μg(-1) and 5.2 ± 1.4 OP(T) μg(-1) increase, respectively. In the case of glutathione depletion, firework particulate OP (3.5 ± 0.8 OP(GSH) μg(-1)) considerably exceeded that due to traffic particles (2.2 ± 0.8 OP(GSH) μg(-1)). Therefore, in light of the elevated PM concentrations caused by firework activity and the increased

  11. Reactivity of polycyclic aromatic compounds (PAHs, NPAHs and OPAHs) adsorbed on natural aerosol particles exposed to atmospheric oxidants

    NASA Astrophysics Data System (ADS)

    Ringuet, Johany; Albinet, Alexandre; Leoz-Garziandia, Eva; Budzinski, Hélène; Villenave, Eric

    2012-12-01

    Reactivity of polycyclic aromatic compounds (PACs) adsorbed on natural aerosol particles exposed to different atmospheric oxidants (O3, OH and NO2/O3 mixture) was studied. Decay of polycyclic aromatic hydrocarbons (PAHs) and formation/decay of oxygenated PAHs (OPAHs) and nitrated PAHs (NPAHs) were monitored. Overall, benzo[a]pyrene appeared to be the most reactive PAH (degradation of 50%). Only its nitrated derivative, 6-nitrobenzo[a]pyrene, was significantly formed explaining just 0.4% of reacted benzo[a]pyrene. No other nitrated or oxygenated benzo[a]pyrene derivatives were detected. Interestingly, B[e]P and In[1,2,3,c,d]P, which are usually considered as quite stable PAHs, also underwent decay in all experiments. In presence of O3, ketones were significantly formed but their amount was not totally explained by decay of parent PAH. These results suggest that PAH derivatives could be formed from the reaction of other compounds than their direct parent PAHs and raise the question to know if the oxidation of methyl-PAHs, identified in vehicle-exhausts, could constitute this missing source of OPAHs. NPAHs were significantly formed in presence of O3/NO2 and OH. Surprisingly, NPAH formation was clearly observed during O3 experiments. Nitrated species, already associated with aerosol particles (NO3-, NO2-) or formed by ozonation of particulate nitrogen organic matter, could react with PAHs to form NPAHs. Heterogeneous formation of 2-nitropyrene from pyrene oxidation was for the first time observed, questioning its use as an indicator of NPAH formation in gaseous phase. Equally, formation of 2-nitrofluoranthene by heterogeneous reaction of fluoranthene with O3/NO2 was clearly shown, while only its formation by homogeneous processes (gaseous phase) is reported in the literature. Finally, results obtained highlighted the dependence of heterogeneous PAH reactivity with the substrate nature and the importance to focus reactivity studies on natural particles, whatever the

  12. Characterization and quantification of the oxides of sulfur and nitrogen and associated compounds in their gaseous, aerosol, and dissolved states

    SciTech Connect

    Newman, L

    1980-05-01

    The needs and problems associated with the characterization and quantification of the oxides of sulfur and nitrogen and associated compounds in their gaseous, aerosol, and dissolved states are discussed. Illustrations are given of the techniques in present usage for the determination of the substances of interest to investigators concerned with the effects of air pollutants on the terrestrial ecosystem. The value and utility of the newer techniques employing real time continuous instrumentation are presented and compared with the more traditional approaches utilizing sampling collection. A plea is made to provide resources for data reduction especially in order to obtain constructive utilization of continuous instrumentation. It is asserted that real time instrumentation is best utilized during campaign measurement programs where short time resolution is required and that collection techniques still have a place, especially in long term monitoring efforts. Special attention was directed at, and the problems highlighted that are associated with, the utilization of the real time instruments available for the flame photometric determination of the oxides of sulfur and the chemiluminescent measurement of the oxides of nitrogen. The newer methods proposed for their use in the determination of sulfate and nitric acid respectively are presented. The difficulties associated with the determination of nitrate are enunciated and attention focused on the problems of obtaining a sample due to the variation of the vapor pressure of gaseous nitric acid and ammonia above solid ammonium nitrate which is in association with an acidic aerosol containing sulfate. The utility of measurements of the composition of rainwater is discussed in light of its application to determine the mechanisms through which rain derives its chemical composition.

  13. Cardioprotective activity of iron oxide nanoparticles

    PubMed Central

    Xiong, Fei; Wang, Hao; Feng, Yidong; Li, Yunman; Hua, Xiaoqing; Pang, Xingyun; Zhang, Song; Song, Lina; Zhang, Yu; Gu, Ning

    2015-01-01

    Iron oxide nanoparticles (IONPs) are chemically inert materials and have been mainly used for imaging applications and drug deliveries. However, the possibility whether they can be used as therapeutic drugs themselves has not yet been explored. We reported here that Fe2O3 nanoparticles (NPs) can protect hearts from ischemic damage at the animal, tissue and cell level. The cardioprotective activity of Fe2O3 NPs requires the integrity of nanoparticles and is not dependent upon their surface charges and molecules that were integrated into nanoparticles. Also, Fe2O3 NPs showed no significant toxicity towards normal cardiomyocytes, indicative of their potential to treat cardiovascular diseases. PMID:25716309

  14. Aerosol from Organic Nitrogen in the Southeast United States

    EPA Science Inventory

    Biogenic volatile organic compounds (BVOCs) contribute significantly to organic aerosol in the southeastern United States. During the Southern Oxidant and Aerosol Study (SOAS), a portion of ambient organic aerosol was attributed to isoprene oxidation and organic nitrogen from BVO...

  15. Hygroscopic growth and activation of HULIS particles: experimental data and a new iterative parameterization scheme for complex aerosol particles

    NASA Astrophysics Data System (ADS)

    Ziese, M.; Wex, H.; Nilsson, E.; Salma, I.; Ocskay, R.; Hennig, T.; Massling, A.; Stratmann, F.

    2007-09-01

    The hygroscopic growth and activation of two HULIS and one Aerosol-Water-Extract sample, prepared from urban-type aerosol, were investigated. All samples were extracted from filters, redissolved in water and atomized for the investigations presented here. The hygroscopic growth measurements were done using LACIS (Leipzig Aerosol Cloud Interaction Simulator) together with a HH-TDMA (High Humidity Tandem Differential Mobility Analyzer). Hygroscopic growth was determined for relative humidities up to 99.75%. The critical diameters for activation were measured using LACIS for supersaturations between 2 and 10 per mill. All three samples showed a similar hygroscopic growth behaviour, and the two HULIS samples also were similar in their activation behavior, while the Aerosol-Water-Extract turned out to be more CCN active than the HULIS samples. The experimental data was used to derive parameterizations for the hygroscopic growth and activation of HULIS particles. The concept of ρion (Wex et al., 2007a) and the Szyszkowski-equation (Szyszkowski, 1908; Facchini et al., 1999) were used for parameterizing the Raoult and the Kelvin (surface tension) terms of the Köhler equation, respectively. This concept proved to be very successful for the HULIS samples in the saturation range from relative humidities larger than 98% up to activation. However it failed for the Aerosol-Water extract.

  16. Analysis of CCN activity of Arctic aerosol and Canadian biomass burning during summer 2008

    NASA Astrophysics Data System (ADS)

    Lathem, T. L.; Beyersdorf, A. J.; Thornhill, K. L.; Winstead, E. L.; Cubison, M. J.; Hecobian, A.; Jimenez, J. L.; Weber, R. J.; Anderson, B. E.; Nenes, A.

    2013-03-01

    The NASA DC-8 aircraft characterized the aerosol properties, chemical composition, and cloud condensation nuclei (CCN) concentrations of the summertime Arctic during the 2008 NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) campaign. Air masses characteristic of fresh and aged biomass burning, boreal forest, Arctic background, and anthropogenic industrial pollution were sampled. Observations were spatially extensive (50-85° N and 40-130° W) and exhibit significant variability in aerosol and CCN concentrations. The chemical composition was dominated by highly oxidized organics (66-94% by volume), with a water-soluble mass fraction of more than 50%. The aerosol hygroscopicity parameter, κ, ranged between κ = 0.08-0.32 for all air mass types. Industrial pollution had the lowest κ of 0.08 ± 0.01, while the Arctic background had the highest and most variable κ of 0.32 ± 0.21, resulting from a lower and more variable organic fraction. Both fresh and aged (long-range transported) biomass burning air masses exhibited remarkably similar κ (0.18 ± 0.13), consistent with observed rapid chemical and physical aging of smoke emissions in the atmosphere, even in the vicinity of fresh fires. The organic hygroscopicity (κorg) was parameterized by the volume fraction of water-soluble organic matter (ɛWSOM), with a κ = 0.12, such that κorg = 0.12ɛWSOM. Assuming bulk (size-independent) composition and including the κorg parameterization enabled CCN predictions to within 30% accuracy for nearly all environments sampled. The only exception was for industrial pollution from Canadian oil sands exploration, where an external mixture and size-dependent composition was required. Aerosol mixing state assumptions (internal vs. external) in all other environments did not significantly affect CCN predictions; however, the external mixing assumption provided the best results, even though the available observations could not determine

  17. CCN activation and hygroscopic growth measurements of secondary organic aerosols from tree emissions

    NASA Astrophysics Data System (ADS)

    Buchholz, Angela; Mentel, Thomas F.; Kiendler-Scharr, Astrid; Spindler, Christian; Tillmann, Ralf; Kleist, Einhard; Wildt, Juergen

    2010-05-01

    Plant emitted volatile organic compounds (VOCs) are a major precursor of secondary organic aerosols (SOA), an important constituent of atmospheric aerosols. We used the Juelich Plant Atmosphere Chamber (JPAC) at the Research Center Juelich to investigate the microphysical properties of aerosols. SOA particles were produced from the ozonolysis and reaction of OH radicals with the complex VOC mixture emitted from trees typical for the boreal forest. Hygroscopic growth factors (GF) were determined with a humidity tandem differential mobility analyzer (HTDMA) for different particle sizes at RH = 2 - 97%. Cloud condensation nuclei (CCN) activation was measured with a continuous flow CCN counter (DMT). Additionally, the chemical composition, size distribution and number concentration of the particles were measured. The gas phase was monitored with GC-MS and PTR-MS. Changing the emission pattern of the trees changed the measured GF and the diameter of the dry particles that were activated (Dcrit). However, below 80% RH the GF changes are within the range of the measurement error. The GF (RH = 95%) are between 1.11 and 1.19 and the Dcrit(SS = 0.4%) in a range of 93 - 100nm. Koehler theory was applied to achieve closure between CCN activation and GF measurements. The κ parameter according to Petters and Kreidenweis (2007) was calculated for all SS (κ(CCN)) and RH (κ(GF)). The κ(GF) decrease with increasing RH but levels off at RH > 95%. Assuming the surface tension of pure water, κ(GF, RH>95%) would be by a factor of 2 lower than κ(CCN). Closure between the HTDMA and CCN measurement requires the use of either a lower surface tension or a limited solubility of the organic material. Reference: Petters, M. D. and Kreidenweis, S. M. (2007). Atmos. Chem. Phys., 7, 1961-1971.

  18. Circular Polarimetry: Diagnostic of Magnetic Fields, Atmospheric Aerosols and Biologic Activity

    NASA Astrophysics Data System (ADS)

    Yanamandra-Fisher, P. A.

    2013-12-01

    The overarching goals for the remote sensing and robotic exploration of planetary systems are: (1) understanding the formation of planetary systems and their diversity; and (2) search for habitability. Our solar system is a dynamic laboratory with unique linear and circular polarimetric signatures of planets, satellites, comets, asteroids, dust, etc.. The study of both linear and circular polarization of a given system, therefore, provides insight into its origin and physical properties. Specifically, linear and circular polarimetric signatures of the object arise from different physical processes. Additionally, spectral dependence of polarization is important to separate the macroscopic (bulk) properties of the scattering medium from the microscopic (particulate) properties of the scattering medium. Linear polarization of reflected light by various solar system objects provides insight into the scattering characteristics of atmospheric aerosols and hazes; and surficial properties of atmosphereless bodies. Measurements of linear limb polarization characterizes the variation of aerosol properties across the planetary disk. Many optically active materials are anisotropic and so their scattering properties differ with the object's principal axes (such as dichroic or birefringent materials) and are crystalline in structure instead of amorphous, eg., the presence of olivines and silicates in cometary dust and circumstellar disks; Titan, etc.). Ices (water and other species) are abundant in the system indicated in their near-infrared spectra. Gas giants form outside the frost line (where ices condense), and their satellites and ring systems exhibit signature of water ice; clathrates, non-ices (Si, C, Fe) in their NIR spectra and spectral dependence of linear polarization. Circular polarization is diagnostic of magnetic fields, atmospheric aerosols and biologic activity. Aurorae occur in response to changing local magnetic fields (Earth, Jupiter, Ganymede, etc.). Biologic

  19. Aqueous-phase OH oxidation of glyoxal: application of a novel analytical approach employing aerosol mass spectrometry and complementary off-line techniques.

    PubMed

    Lee, Alex K Y; Zhao, R; Gao, S S; Abbatt, J P D

    2011-09-29

    Aqueous-phase chemistry of glyoxal may play an important role in the formation of highly oxidized secondary organic aerosol (SOA) in the atmosphere. In this work, we use a novel design of photochemical reactor that allows for simultaneous photo-oxidation and atomization of a bulk solution to study the aqueous-phase OH oxidation of glyoxal. By employing both online aerosol mass spectrometry (AMS) and offline ion chromatography (IC) measurements, glyoxal and some major products including formic acid, glyoxylic acid, and oxalic acid in the reacting solution were simultaneously quantified. This is the first attempt to use AMS in kinetics studies of this type. The results illustrate the formation of highly oxidized products that likely coexist with traditional SOA materials, thus, potentially improving model predictions of organic aerosol mass loading and degree of oxidation. Formic acid is the major volatile species identified, but the atmospheric relevance of its formation chemistry needs to be further investigated. While successfully quantifying low molecular weight organic oxygenates and tentatively identifying a reaction product formed directly from glyoxal and hydrogen peroxide, comparison of the results to the offline total organic carbon (TOC) analysis clearly shows that the AMS is not able to quantitatively monitor all dissolved organics in the bulk solution. This is likely due to their high volatility or low stability in the evaporated solution droplets. This experimental approach simulates atmospheric aqueous phase processing by conducting oxidation in the bulk phase, followed by evaporation of water and volatile organics to form SOA. PMID:21854005

  20. Marine organic aerosol and oceanic biological activity: what we know and what we need (Invited)

    NASA Astrophysics Data System (ADS)

    Facchini, M.

    2009-12-01

    Observations carried out in the North Atlantic as well as in other marine locations evidenced a seasonal dependence of sub micron particle chemical composition on biological oceanic activity and a potentially important marine aerosol organic component from primary and/or secondary formation processes associated to marine vegetation and its seasonal cycle. Primary organics generated by bubble bursting in high biological activity periods are almost entirely water insoluble (WIOM up to 96 ± 2 % )and are constituted by aggregation of lipopolysaccharides exuded by phytoplankton with dominant surface tension character. In many marine environments the secondary organic fraction is dominated by MSA and by several oxygenated species (mainly carboxylic acids). New measurements also show the potential importance of secondary organic N species (biogenic amine salts ). However a large fraction of the secondary organic fraction (SOA) is still not characterized and the precursors are not identified. For modeling marine organics, besides reducing the uncertainty in the knowledge of the chemical composition and new precursors, it is of crucial importance to link marine aerosol organic composition to satellite products that could be better proxy for marine biological activity and of its decomposition products than chlorophyll-a.

  1. A kinetic mechanism for predicting secondary organic aerosol formation from toluene oxidation in the presence of NO x and natural sunlight

    NASA Astrophysics Data System (ADS)

    Hu, Di; Tolocka, Michael; Li, Qianfeng; Kamens, Richard M.

    A kinetic mechanism to predict secondary organic aerosol (SOA) formation from the photo-oxidation of toluene was developed. Aerosol phase chemistry that includes nucleation, gas-particle partitioning and particle-phase reactions as well as the gas-phase chemistry of toluene and its degradation products were represented. The mechanism was evaluated against experimental data obtained from the University of North Carolina (UNC) 270 m 3 dual outdoor aerosol smog chamber facility. The model adequately simulates the decay of toluene, the nitric oxide (NO) to nitrogen dioxide (NO 2) conversion and ozone formation. It also provides a reasonable prediction of SOA production under different conditions that range from 15 to 300 μg m -3. Speciation of simulated aerosol material shows that up to 70% of the aerosol mass comes from oligomers and polymers depending on initial reactant concentrations. The dominant particle-phase species predicted by the mechanism are glyoxal oligomers, ketene oligomers from the photolysis of the toluene OH reaction product 2-methyl-2,4-hexadienedial, organic nitrates, methyl nitro-phenol analogues, C7 organic peroxides, acylperoxy nitrates and for the low-concentration experiments, unsaturated hydroxy nitro acids.

  2. 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.

  3. Parameterization of thermal properties of aging secondary organic aerosol produced by photo-oxidation of selected terpene mixtures.

    PubMed

    Emanuelsson, Eva U; Mentel, Thomas F; Watne, Agot K; Spindler, Christian; Bohn, Birger; Brauers, Theo; Dorn, Hans-Peter; Hallquist, Asa M; Häseler, Rolf; Kiendler-Scharr, Astrid; Müller, Klaus-Peter; Pleijel, Håkan; Rohrer, Franz; Rubach, Florian; Schlosser, Eric; Tillmann, Ralf; Hallquist, Mattias

    2014-06-01

    Formation and evolution of secondary organic aerosols (SOA) from biogenic VOCs influences the Earth's radiative balance. We have examined the photo-oxidation and aging of boreal terpene mixtures in the SAPHIR simulation chamber. Changes in thermal properties and chemical composition, deduced from mass spectrometric measurements, were providing information on the aging of biogenic SOA produced under ambient solar conditions. Effects of precursor mixture, concentration, and photochemical oxidation levels (OH exposure) were evaluated. OH exposure was found to be the major driver in the long term photochemical transformations, i.e., reaction times of several hours up to days, of SOA and its thermal properties, whereas the initial concentrations and terpenoid mixtures had only minor influence. The volatility distributions were parametrized using a sigmoidal function to determine TVFR0.5 (the temperature yielding a 50% particle volume fraction remaining) and the steepness of the volatility distribution. TVFR0.5 increased by 0.3±0.1% (ca. 1 K), while the steepness increased by 0.9±0.3% per hour of 1×10(6) cm(-3) OH exposure. Thus, aging reduces volatility and increases homogeneity of the vapor pressure distribution, presumably because highly volatile fractions become increasingly susceptible to gas phase oxidation, while less volatile fractions are less reactive with gas phase OH. PMID:24810838

  4. CCN activity and volatility of β-caryophyllene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Frosch, M.; Bilde, M.; Nenes, A.; Praplan, A. P.; Jurányi, Z.; Dommen, J.; Gysel, M.; Weingartner, E.; Baltensperger, U.

    2012-08-01

    In a series of smog chamber experiments, the Cloud Condensation Nuclei (CCN) activity of Secondary Organic Aerosol (SOA) generated from ozonolysis of β-caryophyllene was characterized by determining the CCN derived hygroscopicity parameter, κCCN, from experimental data. Two types of CCN counters, operating at different temperatures, were used. The effect of semi-volatile organic compounds on the CCN activity of SOA was studied using a thermodenuder. Overall, SOA was only slightly CCN active (with κCCN in the range 0.001-0.16), and in dark experiments with no OH scavenger present, κCCN decreased when particles were sent through the thermodenuder (with a temperature up to 50 °C). SOA was generated under different experimental conditions: in some experiments, an OH scavenger (2-butanol) was added. SOA from these experiments was less CCN active than SOA produced in experiments without an OH scavenger (i.e. where OH was produced during ozonolysis). In other experiments, lights were turned on, either without or with the addition of HONO (OH source). This led to the formation of more CCN active SOA. SOA was aged up to 30 h through exposure to ozone and (in experiments with no OH scavenger present) to OH. In all experiments, the derived κCCN consistently increased with time after initial injection of β-caryophyllene, showing that chemical ageing increases the CCN activity of β-caryophyllene SOA. κCCN was also observed to depend on supersaturation, which was explained either as an evaporation artifact from semi-volatile SOA (only observed in experiments lacking light exposure) or, alternatively, by effects related to chemical composition depending on dry particle size. Using the method of Threshold Droplet Growth Analysis it was also concluded that the activation kinetics of the SOA do not differ significantly from calibration ammonium sulphate aerosol.

  5. CCN activity and volatility of β-caryophyllene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Frosch, M.; Bilde, M.; Nenes, A.; Praplan, A. P.; Jurányi, Z.; Dommen, J.; Gysel, M.; Weingartner, E.; Baltensperger, U.

    2013-02-01

    In a series of smog chamber experiments, the cloud condensation nuclei (CCN) activity of secondary organic aerosol (SOA) generated from ozonolysis of β-caryophyllene was characterized by determining the CCN derived hygroscopicity parameter, κCCN, from experimental data. Two types of CCN counters, operating at different temperatures, were used. The effect of semi-volatile organic compounds on the CCN activity of SOA was studied using a thermodenuder. Overall, SOA was only slightly CCN active (with κCCN in the range 0.001-0.16), and in dark experiments with no OH scavenger present, κCCN decreased when particles were sent through the thermodenuder (with a temperature up to 50 °C). SOA was generated under different experimental conditions: In some experiments, an OH scavenger (2-butanol) was added. SOA from these experiments was less CCN active than SOA produced in experiments without an OH scavenger (i.e. where OH was produced during ozonolysis). In other experiments, lights were turned on, either without or with the addition of HONO (OH source). This led to the formation of more CCN active SOA. SOA was aged up to 30 h through exposure to ozone and (in experiments with no OH scavenger present) to OH. In all experiments, the derived κCCN consistently increased with time after initial injection of β-caryophyllene, showing that chemical ageing increases the CCN activity of β-caryophyllene SOA. κCCN was also observed to depend on supersaturation, which was explained either as an evaporation artifact from semi-volatile SOA (only observed in experiments lacking light exposure) or, alternatively, by effects related to chemical composition depending on dry particle size. Using the method of Threshold Droplet Growth Analysis it was also concluded that the activation kinetics of the SOA do not differ significantly from calibration ammonium sulphate aerosol for particles aged for several hours.

  6. A kinetic mechanism for predicting secondary aerosol formation from the reactions of d-limonene in the presence of oxides of nitrogen and natural sunlight

    NASA Astrophysics Data System (ADS)

    Leungsakul, Sirakarn; Jeffries, Harvey E.; Kamens, Richard M.

    Among the monoterpenes, d-limonene is one of the most reactive, and has one of the highest particle formation potentials. Chamber experiments with d-limonene, nitric oxide, nitrogen dioxide, and diurnal natural sunlight are compared with simulation results from a first generation semi-explicit d-limonene daytime mechanism. The d-limonene model adequately predicts the timing of NO-NO 2 crossover, d-limonene decay, and the general trend of ozone formation, and particle mass accumulation. When experimental secondary organic aerosol (SOA) masses were greater than 1 mg m -3 the simulations tended to agree closely with the measured aerosol maxima. At lower SOA concentrations, the simulations tended to overpredict measured aerosol maxima by 25-50%. FTIR analysis and GC-ECD measurements indicate particle phase nitrates and peroxyacetyl nitrate (PAN) formation in the system. In the afternoon when temperatures are highest in the outdoor chambers, the slow rise of continuous ozone measurements suggests that PAN type compounds were decomposing to "bleed" NO 2 into the gas phase. Partitioning calculations also suggest that these types of compounds are off-gassing from the particle phase later in the afternoon as well, and provide an additional source of NO 2. Predicted aerosol yields with a commonly used two-parameter aerosol yield model are compared with experimental aerosol yields. The parameritized aerosol yield model had difficulty predicting most of the UNC chamber data. The explicit d-limonene mechanism developed in this study could reasonably simulate the aerosol formation trend in the Caltech chambers, but tended to overpredict SOA maxima.

  7. Experimental determination of the partitioning coefficient and volatility of important BVOC oxidation products using the Aerosol Collection Module (ACM) coupled to a PTR-ToF-MS

    NASA Astrophysics Data System (ADS)

    Gkatzelis, G.; Hohaus, T.; Tillmann, R.; Schmitt, S. H.; Yu, Z.; Schlag, P.; Wegener, R.; Kaminski, M.; Kiendler-Scharr, A.

    2015-12-01

    Atmospheric aerosol can alter the Earth's radiative budget and global climate but can also affect human health. A dominant contributor to the submicrometer particulate matter (PM) is organic aerosol (OA). OA can be either directly emitted through e.g. combustion processes (primary OA) or formed through the oxidation of organic gases (secondary organic aerosol, SOA). A detailed understanding of SOA formation is of importance as it constitutes a major contribution to the total OA. The partitioning between the gas and particle phase as well as the volatility of individual components of SOA is yet poorly understood adding uncertainties and thus complicating climate modelling. In this work, a new experimental methodology was used for compound-specific analysis of organic aerosol. The Aerosol Collection Module (ACM) is a newly developed instrument that deploys an aerodynamic lens to separate the gas and particle phase of an aerosol. The particle phase is directed to a cooled sampling surface. After collection particles are thermally desorbed and transferred to a detector for further analysis. In the present work, the ACM was coupled to a Proton Transfer Reaction-Time of Flight-Mass Spectrometer (PTR-ToF-MS) to detect and quantify organic compounds partitioning between the gas and particle phase. This experimental approach was used in a set of experiments at the atmosphere simulation chamber SAPHIR to investigate SOA formation. Ozone oxidation with subsequent photochemical aging of β-pinene, limonene and real plant emissions from Pinus sylvestris (Scots pine) were studied. Simultaneous measurement of the gas and particle phase using the ACM-PTR-ToF-MS allows to report partitioning coefficients of important BVOC oxidation products. Additionally, volatility trends and changes of the SOA with photochemical aging are investigated and compared for all systems studied.

  8. REPEATED REDUCTIVE AND OXIDATIVE TREATMENTS ON GRANULAR ACTIVATED CARBON

    EPA Science Inventory

    Fenton oxidation and Fenton oxidation preceded by reduction solutions were applied to granular activated carbon (GAC) to chemically regenerate the adsorbent. No adsorbate was present on the GAC so physicochemical effects from chemically aggressive regeneration of the carbon coul...

  9. Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee ground site

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S. H.; Li, X.; Bairai, S. T.; Renfro, J.; Liu, Y.; Liu, Y. J.; McKinney, K. A.; Martin, S. T.; McNeill, V. F.; Pye, H. O. T.; Nenes, A.; Neff, M. E.; Stone, E. A.; Mueller, S.; Knote, C.; Shaw, S. L.; Zhang, Z.; Gold, A.; Surratt, J. D.

    2015-08-01

    A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time-resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~ 9 % (up to 28 %) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~ 97 % of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2 > 0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~ 26 % (up to 49 %) of the IEPOX-OA factor mass, which accounted for 32 % of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO ~ 0.03 ppb), carbon monoxide (CO ~ 116 ppb), and black

  10. A thermodynamic model of mixed organic-inorganic aerosols to predict activity coefficients

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Luo, B. P.; Peter, T.

    2008-08-01

    Tropospheric aerosols contain mixtures of inorganic salts, acids, water, and a large variety of organic compounds. Interactions between these substances in liquid mixtures lead to discrepancies from ideal thermodynamic behaviour. By means of activity coefficients, non-ideal behaviour can be taken into account. We present here a thermodynamic model named AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) that is able to calculate activity coefficients covering inorganic, organic, and organic-inorganic interactions in aqueous solutions over a wide concentration range. This model is based on the activity coefficient model LIFAC by Yan et al. (1999) that we modified and reparametrised to better describe atmospherically relevant conditions and mixture compositions. Focusing on atmospheric applications we considered H+, Li+, Na+, K+, NH+4, Mg2+, Ca2+, Cl-, Br-, NO-3, HSO-4, and SO2-4 as cations and anions and a wide range of alcohols/polyols composed of the functional groups CHn and OH as organic compounds. With AIOMFAC, the activities of the components within an aqueous electrolyte solution are well represented up to high ionic strength. Most notably, a semi-empirical middle-range parametrisation of direct organic-inorganic interactions in alcohol+water+salt solutions strongly improves the agreement between experimental and modelled activity coefficients. At room temperature, this novel thermodynamic model offers the possibility to compute equilibrium relative humidities, gas/particle partitioning and liquid-liquid phase separations with high accuracy. In further studies, other organic functional groups will be introduced. The model framework is not restricted to specific ions or organic compounds and is therefore also applicable for other research topics.

  11. A thermodynamic model of mixed organic-inorganic aerosols to predict activity coefficients

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Luo, B. P.; Peter, Th.

    2008-03-01

    Tropospheric aerosols contain mixtures of inorganic salts, acids, water, and a large variety of organic compounds. Interactions between these substances in liquid mixtures lead to discrepancies from ideal thermodynamic behaviour. By means of activity coefficients, non-ideal behaviour can be taken into account. We present here a thermodynamic model named AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) that is able to calculate activity coefficients covering inorganic, organic, and organic-inorganic interactions in aqueous solutions over a wide concentration range. This model is based on the activity coefficient model LIFAC by Yan et al. (1999) that we modified and reparametrised to better describe atmospherically relevant conditions and mixture compositions. Focusing on atmospheric applications we considered H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl-, Br-, NO3-, HSO4-, and SO42- as cations and anions and a wide range of alcohols/polyols composed of the functional groups CHn and OH as organic compounds. With AIOMFAC, the activities of the components within an aqueous electrolyte solution are well represented up to high ionic strength. Most notably, a semi-empirical middle-range parametrisation of direct organic-inorganic interactions in alcohol + water + salt solutions strongly improves the agreement between experimental and modelled activity coefficients. At room temperature, this novel thermodynamic model offers the possibility to compute equilibrium relative humidities, gas/particle partitioning and liquid-liquid phase separations with high accuracy. In further studies, other organic functional groups will be introduced. The model framework is not restricted to specific ions or organic compounds and is therefore also applicable for other research topics.

  12. Soot Aerosol Particles as Cloud Condensation Nuclei: from Ice Nucleation Activity to Ice Crystal Morphology

    NASA Astrophysics Data System (ADS)

    Pirim, Claire; Ikhenazene, Raouf; Ortega, Isamel Kenneth; Carpentier, Yvain; Focsa, Cristian; Chazallon, Bertrand; Ouf, François-Xavier

    2016-04-01

    Emissions of solid-state particles (soot) from engine exhausts due to incomplete fuel combustion is considered to influence ice and liquid water cloud droplet activation [1]. The activity of these aerosols would originate from their ability to be important centers of ice-particle nucleation, as they would promote ice formation above water homogeneous freezing point. Soot particles are reported to be generally worse ice nuclei than mineral dust because they activate nucleation at higher ice-supersaturations for deposition nucleation and at lower temperatures for immersion freezing than ratios usually expected for homogeneous nucleation [2]. In fact, there are still numerous opened questions as to whether and how soot's physico-chemical properties (structure, morphology and chemical composition) can influence their nucleation ability. Therefore, systematic investigations of soot aerosol nucleation activity via one specific nucleation mode, here deposition nucleation, combined with thorough structural and compositional analyzes are needed in order to establish any association between the particles' activity and their physico-chemical properties. In addition, since the morphology of the ice crystals can influence their radiative properties [3], we investigated their morphology as they grow over both soot and pristine substrates at different temperatures and humidity ratios. In the present work, Combustion Aerosol STandart soot samples were produced from propane using various experimental conditions. Their nucleation activity was studied in deposition mode (from water vapor), and monitored using a temperature-controlled reactor in which the sample's relative humidity is precisely measured with a cryo-hygrometer. Formation of water/ice onto the particles is followed both optically and spectroscopically, using a microscope coupled to a Raman spectrometer. Vibrational signatures of hydroxyls (O-H) emerge when the particle becomes hydrated and are used to characterize ice

  13. Discernible signals of aerosol effects on the diurnal, weekly and decadal variations in thunderstorm activities

    NASA Astrophysics Data System (ADS)

    Li, Z.

    2015-12-01

    Aerosol can affect atmospheric convection, cloud and precipitation in a variety of means by altering energy balance at the surface and in the atmospheric column, and by altering cloud micro- and macro-physical properties. The effects are often contingent upon meteorological variables and aerosol properties. By reducing surface energy budget, aerosol tends to suppress convection, but aerosol-induced heating in the lower atmosphere can destabilize the upper atmosphere and strengthen convection. Aerosol-induced altering cloud microphysics may also suppress or invigorate cloud development pending on various factors. In this talk, I will illustrate how aerosols likely contribute to the thunderstorm variability on three distinct time scales from diurnal, weekly to decadal and how different types of aerosols and varying meteorological conditions may affect with the observed trends. I will first demonstrate the opposite effects of conservative scattering and hygroscopic aerosols versus absorbing and hydrophobic aerosol on the long-term trends of thunderstorms. I will then illustrate that aerosol can have a discernible effect on the weekly cycle of thunderstorms and there is the dependence of the phase of the weekly cycle on aerosol types. Last, I will show how aerosol delays the occurrence of thunderstorms. Of course, the plausible connections are subject to various uncertainties that should be tackled with more rigorous modeling and extensive observation studies.

  14. Do aerosols act as catalysts in the OH radical initiated atmospheric oxidation of volatile organic compounds?

    NASA Astrophysics Data System (ADS)

    Sørensen, M.; Hurley, M. D.; Wallington, T. J.; Dibble, T. S.; Nielsen, O. J.

    Smog chamber/FTIR techniques were used to study the relative reactivity of OH radicals with methanol, ethanol, phenol, C 2H 4, C 2H 2, and p-xylene in 750 Torr of air diluent at 296±2 K. Experiments were performed with, and without, 500-8000 μg m -3 (4000-50 000 μm 2 cm -3 surface area per volume) of NaCl, (NH 4) 2SO 4 or NH 4NO 3 aerosol. In contrast to the recent findings of Oh and Andino (Atmospheric Environment 34 (2000) 2901, 36 (2002) 149; International Journal of Chemical Kinetics 33 (2001) 422) there was no discernable effect of aerosol on the rate of loss of the organic compounds via reaction with OH radicals. Gas kinetic theory arguments cast doubt upon the findings of Oh and Andino. The available data suggest that the answer to the title question is "No". As part of this work the rate constants for reactions of OH radicals with methanol, ethanol, and phenol in 750 Torr of air at 296 K were determined to be: kOH+CH 3OH =(8.12±0.54)×10 -13, kOH+C 2H 5OH =(3.47±0.32)×10 -12 and kOH+phenol=(3.27±0.31)×10 -11 cm 3 molecule -1 s -1.

  15. CCN Activity of Organic Aerosols Observed Downwind of Urban Emissions during CARES

    SciTech Connect

    Mei, Fan; Setyan, Ari; Zhang, Qi; Wang, J. X.

    2013-12-17

    During the Carbonaceous Aerosols and Radiative Effects Study (CARES), activation fraction of size-resolved aerosol particles and aerosol chemical composition were characterized at the T1 site (~60 km downwind of Sacramento, California) from 10 June to 28 June 2010. The hygroscopicity of CCN-active particles (KCCN) with diameter from 100 to 170 nm, derived from the size-resolved activated fraction, varied from 0.10 to 0.21, with an average of 0.15, which was substantially lower than that proposed for continental sites in earlier studies. The low KCCN value was due to the high organic volume fraction, averaged over 80% at the T1 site. The derived KCCN exhibited little diurnal variation, consistent with the relatively constant organic volume fraction observed. At any time, over 90% of the size selected particles with diameter between 100 and 171nm were CCN active, suggesting most particles within this size range were aged background particles. Due to the large organic volume fraction, organic hygroscopicity (Korg) strongly impacted particle hygroscopicity and therefore calculated CCN concentration. For vast majority of the cases, an increase of Korg from 0.03 to 0.18, which are within the typical range, doubled the calculated CCN concentration. Organic hygroscopicity was derived from KCCN and aerosol chemical composition, and its variations with the fraction of total organic mass spectral signal at m/z 44 (f44) and O:C were compared to results from previous studies. Overall, the relationships between Korg and f44 are quite consistent for organic aerosol (OA) observed during field studies and those formed in smog chamber. Compared to the relationship between Korg and f44, the relationship between Korg and O:C exhibits more significant differences among different studies, suggesting korg may be better parameterized using f44. A

  16. Atmospheric DMS and Biogenic Sulfur aerosol measurements in the Arctic

    NASA Astrophysics Data System (ADS)

    Ghahremaninezhadgharelar, R.; Norman, A. L.; Wentworth, G.; Burkart, J.; Leaitch, W. R.; Abbatt, J.; Sharma, S.; Desiree, T. S.

    2014-12-01

    Dimethyl Sulfide (DMS) and its oxidation products were measured on the board of the Canadian Coast Guard Ship (CCGS) Amundsen and above melt ponds in the Arctic during July 2014 in the context of the NETCARE study which seeks to understand the effect of DMS and its oxidation products with respect to aerosol nucleation, as well as its effect on cloud and precipitation properties. The objective of this study is to quantify the role of DMS in aerosol growth and activation in the Arctic atmosphere. Atmospheric DMS samples were collected from different altitudes, from 200 to 9500 feet, aboard the POLAR6 aircraft expedition to determine variations in the DMS concentration and a comparison was made to shipboard DMS measurements and its effects on aerosol size fractions. The chemical and isotopic composition of sulfate aerosol size fractions was studied. Sulfur isotope ratios (34S/32S) offer a way to determine the oceanic DMS contribution to aerosol growth. The results are expected to address the contribution of anthropogenic as well as biogenic sources of aerosols to the growth of the different aerosol size fractions. In addition, aerosol sulfate concentrations were measured at the same time within precipitation and fogs to compare with the characteristics of aerosols in each size fraction with the characteristics of the sulfate in each medium. This measurement is expected to explain the contribution of DMS oxidation in aerosol activation in the Arctic summer. Preliminary results from the measurement campaign for DMS and its oxidation products in air, fog and precipitation will be presented.

  17. OH- Initiated Heterogeneous Oxidation of Saturated Organic Aerosols in the Presence of SO2: Uptake Kinetics and Product Identification.

    NASA Astrophysics Data System (ADS)

    Richards-Henderson, N. K.; Ward, M.; Goldstein, A. H.; Wilson, K. R.

    2014-12-01

    Gas-phase oxidation mechanisms for organic gases are often used as a starting point to understand heterogeneous oxidation. The reaction of a simple alkane hydrocarbon by OH proceeds through hydrogen abstraction and under ambient conditions leads to peroxy radical (RO2) formation. RO2 can further react to form: (1) smaller molecular weight products (i.e. fragmentation) via alkoxy radical formation and dissociation and/or (2) higher molecular weight products with oxygenated functional groups (i.e. functionalization). The ability to perturb these two pathways (functionalization vs. fragmentation) is critical for understanding the detailed reaction mechanism that control atmospheric aging chemistry of particles. At high temperatures the presence of sulfur dioxide (SO2) during organic-OH gas-phase oxidation enhances the fragmentation pathway leading to increased alkoxy formation. It is unknown if a comparative affect occurs at room temperature during a heterogeneous reaction. We used the heterogeneous reaction of OH radicals with sub-micron squalane particles in the presence and absence of SO2 as a model system to explore changes in individual mechanistic pathways. Detailed kinetic measurements were made in a flow tube reactor using a vacuum ultraviolet (VUV) photoionization aerosol mass spectrometer and oxidation products are identified from samples collected on quartz filters using thermal desorption two-dimensional chromatographic separation and ionization by either VUV (10.5 eV) or electron impact (70 eV), with detection by high resolution time of flight mass spectrometry (GCxGC-VUV/EI-HRTOFMS). In the presence of SO2 the yields of alcohols were enhanced compared to without SO2, suggesting that the alkoxy formation pathway was dominant. The results from this work will provide an experimentally-confirmed kinetic framework that could be used to model atmospheric aging mechanisms.

  18. Electrochromic and colorimetric properties of nickel(II) oxide thin films prepared by aerosol-assisted chemical vapor deposition.

    PubMed

    Sialvi, Muhammad Z; Mortimer, Roger J; Wilcox, Geoffrey D; Teridi, Asri Mat; Varley, Thomas S; Wijayantha, K G Upul; Kirk, Caroline A

    2013-06-26

    Aerosol-assisted chemical vapor deposition (AACVD) was used for the first time in the preparation of thin-film electrochromic nickel(II) oxide (NiO). The as-deposited films were cubic NiO, with an octahedral-like grain structure, and an optical band gap that decreased from 3.61 to 3.48 eV on increase in film thickness (in the range 500-1000 nm). On oxidative voltammetric cycling in aqueous KOH (0.1 mol dm(-3)) electrolyte, the morphology gradually changed to an open porous NiO structure. The electrochromic properties of the films were investigated as a function of film thickness, following 50, 100, and 500 conditioning oxidative voltammetric cycles in aqueous KOH (0.1 mol dm(-3)). Light modulation of the films increased with the number of conditioning cycles. The maximum coloration efficiency (CE) for the NiO (transmissive light green, the "bleached" state) to NiOOH (deep brown, the colored state) electrochromic process was found to be 56.3 cm(2) C(-1) (at 450 nm) for films prepared by AACVD for 15 min followed by 100 "bleached"-to-colored conditioning oxidative voltammetric cycles. Electrochromic response times were <10 s and generally longer for the coloration than the bleaching process. The films showed good stability when tested for up to 10 000 color/bleach cycles. Using the CIE (Commission Internationale de l'Eclairage) system of colorimetry the color stimuli of the electrochromic NiO films and the changes that take place on reversibly oxidatively switching to the NiOOH form were calculated from in situ visible spectra recorded under electrochemical control. Reversible changes in the hue and saturation occur on oxidation of the NiO (transmissive light green) form to the NiOOH (deep brown) form, as shown by the track of the CIE 1931 xy chromaticity coordinates. As the NiO film is oxidized, a sharp decrease in luminance was observed. CIELAB L*a*b* coordinates were also used to quantify the electrochromic color states. A combination of a low L* and positive a

  19. Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee, ground site

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S. H.; Li, X.; Bairai, S. T.; Renfro, J.; Liu, Y.; Liu, Y. J.; McKinney, K. A.; Martin, S. T.; McNeill, V. F.; Pye, H. O. T.; Nenes, A.; Neff, M. E.; Stone, E. A.; Mueller, S.; Knote, C.; Shaw, S. L.; Zhang, Z.; Gold, A.; Surratt, J. D.

    2015-03-01

    A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~9% (up to 26%) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~97% of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2>0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~25% (up to 47%) of the IEPOX-OA factor mass, which accounted for 32% of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO~0.03ppb), carbon monoxide (CO~116 ppb), and black carbon (BC~0

  20. Effect of aerosols on solar UV irradiances during the Photochemical Activity and Solar Ultraviolet Radiation Campaign

    NASA Astrophysics Data System (ADS)

    Kylling, A.; Bais, A. F.; Blumthaler, M.; Schreder, J.; Zerefos, C. S.; Kosmidis, E.

    1998-10-01

    Surface UV irradiances were measured at two different sites in Greece during June 1996 under noncloudy conditions. The measured UV irradiances are simulated by a radiative transfer model using measured ozone density and aerosol optical depth profiles. The absolute difference between model and measurements ranges between -5% and +5% with little dependence on wavelength. The temporal and solar zenith angle dependence in the difference between model and measurement suggests that part of this difference may be explained by assumptions made about the aerosol single-scattering albedo and phase function. Simulated spectra including aerosols are compared with calculated spectra excluding aerosols. It is found that for otherwise similar atmospheric conditions the UVB irradiance is reduced with respect to aerosol free conditions by 5% to 35% depending on the aerosol optical depth and single-scattering albedo. For the campaign period, changes in the aerosol loading gave larger variations in the surface UV irradiances than the changes seen in the ozone column.

  1. Detection and quantification of water-based aerosols using active open-path FTIR

    NASA Astrophysics Data System (ADS)

    Kira, Oz; Linker, Raphael; Dubowski, Yael

    2016-04-01

    Aerosols have a leading role in many eco-systems and knowledge of their properties is critical for many applications. This study suggests using active Open-Path Fourier Transform Infra-Red (OP-FTIR) spectroscopy for quantifying water droplets and solutes load in the atmosphere. The OP-FTIR was used to measure water droplets, with and without solutes, in a 20 m spray tunnel. Three sets of spraying experiments generated different hydrosols clouds: (1) tap water only, (2) aqueous ammonium sulfate (0.25–3.6%wt) and (3) aqueous ethylene glycol (0.47–2.38%wt). Experiment (1) yielded a linear relationship between the shift of the extinction spectrum baseline and the water load in the line-of-sight (LOS) (R2 = 0.984). Experiment (2) also yielded a linear relationship between the integrated extinction in the range of 880–1150 cm‑1 and the ammonium sulfate load in the LOS (R2 = 0.972). For the semi-volatile ethylene glycol (experiment 3), present in the gas and condense phases, quantification was much more complex and two spectral approaches were developed: (1) according to the linear relationship from the first experiment (determination error of 8%), and (2) inverse modeling (determination error of 57%). This work demonstrates the potential of the OP-FTIR for detecting clouds of water-based aerosols and for quantifying water droplets and solutes at relatively low concentrations.

  2. Detection and quantification of water-based aerosols using active open-path FTIR.

    PubMed

    Kira, Oz; Linker, Raphael; Dubowski, Yael

    2016-01-01

    Aerosols have a leading role in many eco-systems and knowledge of their properties is critical for many applications. This study suggests using active Open-Path Fourier Transform Infra-Red (OP-FTIR) spectroscopy for quantifying water droplets and solutes load in the atmosphere. The OP-FTIR was used to measure water droplets, with and without solutes, in a 20 m spray tunnel. Three sets of spraying experiments generated different hydrosols clouds: (1) tap water only, (2) aqueous ammonium sulfate (0.25-3.6%wt) and (3) aqueous ethylene glycol (0.47-2.38%wt). Experiment (1) yielded a linear relationship between the shift of the extinction spectrum baseline and the water load in the line-of-sight (LOS) (R(2) = 0.984). Experiment (2) also yielded a linear relationship between the integrated extinction in the range of 880-1150 cm(-1) and the ammonium sulfate load in the LOS (R(2) = 0.972). For the semi-volatile ethylene glycol (experiment 3), present in the gas and condense phases, quantification was much more complex and two spectral approaches were developed: (1) according to the linear relationship from the first experiment (determination error of 8%), and (2) inverse modeling (determination error of 57%). This work demonstrates the potential of the OP-FTIR for detecting clouds of water-based aerosols and for quantifying water droplets and solutes at relatively low concentrations. PMID:27121498

  3. VEGF neutralizing aerosol therapy in primary pulmonary adenocarcinoma with K-ras activating-mutations.

    PubMed

    Hervé, Virginie; Rabbe, Nathalie; Guilleminault, Laurent; Paul, Flora; Schlick, Laurène; Azzopardi, Nicolas; Duruisseaux, Michael; Fouquenet, Delphine; Montharu, Jérôme; Redini, Françoise; Paintaud, Gilles; Lemarié, Etienne; Cadranel, Jacques; Wislez, Marie; Heuzé-Vourc'h, Nathalie

    2014-01-01

    K-ras mutations promote angiogenesis in lung cancer and contribute to the drug resistance of cancer cells. It is not clear whether K-ras mutated adenocarcinomas are sensitive to anti-angiogenic therapy with monoclonal antibodies (mAbs) that target vascular endothelial growth factor (VEGF). Anti-angiogenic mAbs are usually delivered systemically, but only a small proportion reaches the lung after intravenous injection. We investigated the relevance of a non-invasive pulmonary route for the delivery of anti-VEGF mAbs in the mouse K-ras(LA1) model. We found that pulmonary delivery of these mAbs significantly reduced the number of tumor lesions and inhibited malignant progression. The antitumor effect involves the VEGFR2-dependent inhibition of blood vessel growth, which impairs tumor proliferation. Pharmacokinetic analysis of aerosolized anti-VEGF showed its low rate of passage into the bloodstream, suggesting that this delivery route is associated with reduced systemic side effects. Our findings highlight the value of the aerosol route for administration of anti-angiogenic mAbs in pulmonary adenocarcinoma with K-ras activating-mutations. PMID:25484066

  4. Oxidative stress-mediated antibacterial activity of graphene oxide and reduced graphene oxide in Pseudomonas aeruginosa

    PubMed Central

    Gurunathan, Sangiliyandi; Han, Jae Woong; Dayem, Ahmed Abdal; Eppakayala, Vasuki; Kim, Jin-Hoi

    2012-01-01

    Background Graphene holds great promise for potential use in next-generation electronic and photonic devices due to its unique high carrier mobility, good optical transparency, large surface area, and biocompatibility. The aim of this study was to investigate the antibacterial effects of graphene oxide (GO) and reduced graphene oxide (rGO) in Pseudomonas aeruginosa. In this work, we used a novel reducing agent, betamercaptoethanol (BME), for synthesis of graphene to avoid the use of toxic materials. To uncover the impacts of GO and rGO on human health, the antibacterial activity of two types of graphene-based material toward a bacterial model P. aeruginosa was studied and compared. Methods The synthesized GO and rGO was characterized by ultraviolet-visible absorption spectroscopy, particle-size analyzer, X-ray diffraction, scanning electron microscopy and Raman spectroscopy. Further, to explain the antimicrobial activity of graphene oxide and reduced graphene oxide, we employed various assays, such as cell growth, cell viability, reactive oxygen species generation, and DNA fragmentation. Results Ultraviolet-visible spectra of the samples confirmed the transition of GO into graphene. Dynamic light-scattering analyses showed the average size among the two types of graphene materials. X-ray diffraction data validated the structure of graphene sheets, and high-resolution scanning electron microscopy was employed to investigate the morphologies of prepared graphene. Raman spectroscopy data indicated the removal of oxygen-containing functional groups from the surface of GO and the formation of graphene. The exposure of cells to GO and rGO induced the production of superoxide radical anion and loss of cell viability. Results suggest that the antibacterial activities are contributed to by loss of cell viability, induced oxidative stress, and DNA fragmentation. Conclusion The antibacterial activities of GO and rGO against P. aeruginosa were compared. The loss of P

  5. Photochemical Aging of α-pinene and β-pinene Secondary Organic Aerosol formed from Nitrate Radical Oxidation.

    PubMed

    Nah, Theodora; Sanchez, Javier; Boyd, Christopher M; Ng, Nga Lee

    2016-01-01

    The nitrate radical (NO3) is the dominant nighttime oxidant in most urban and rural environments and reacts rapidly with biogenic volatile organic compounds to form secondary organic aerosol (SOA) and organic nitrates (ON). Here, we study the formation of SOA and ON from the NO3 oxidation of two monoterpenes (α-pinene and β-pinene) and investigate how they evolve during photochemical aging. High SOA mass loadings are produced in the NO3+β-pinene reaction, during which we detected 41 highly oxygenated gas- and particle-phase ON possessing 4 to 9 oxygen atoms. The fraction of particle-phase ON in the β-pinene SOA remains fairly constant during photochemical aging. In contrast to the NO3+β-pinene reaction, low SOA mass loadings are produced during the NO3+α-pinene reaction, during which only 5 highly oxygenated gas- and particle-phase ON are detected. The majority of the particle-phase ON evaporates from the α-pinene SOA during photochemical aging, thus exhibiting a drastically different behavior from that of β-pinene SOA. Our results indicate that nighttime ON formed by NO3+monoterpene chemistry can serve as either permanent or temporary NOx sinks depending on the monoterpene precursor. PMID:26618657

  6. Observational Constraints on Glyoxal Production from Isoprene Oxidation and Its Contribution to Organic Aerosol Over the Southeast United States

    NASA Astrophysics Data System (ADS)

    Li, J.; Mao, J.; Min, K. E.; Washenfelder, R. A.; Brown, S. S.; Kaiser, J.; Keutsch, F. N.; Wolfe, G. M.; Hanisco, T. F.; Pollack, I. B.; Ryerson, T. B.; Graus, M.; Gilman, J.; Lerner, B. M.; Warneke, C.; De Gouw, J. A.; Middlebrook, A. M.; Henderson, B. H.; Paulot, F.; Horowitz, L. W.; Liao, J.; Welti, A.

    2015-12-01

    We use observations from the NOAA Southeast Nexus (SENEX) aircraft campaign, evaluated with a nudged global chemistry-climate model, to better understand the sources and sinks of glyoxal over the Southeast United States. We find that the model with an isoprene oxidation mechanism that does not account for δ-hydroxyl peroxy radicals (δ-ISOPO2), can better reproduce the observed vertical profiles of glyoxal and HCHO, as well as their correlation (RGF) in the continental boundary layer. The suppression of δ-ISOPO2 is consistent with recent theoretical and laboratory studies, reflecting different fates of δ-ISOPO2 under chamber conditions (NO > 100 ppbv) vs. ambient conditions (NO ~ 0.1 ppbv). By including a reactive uptake of glyoxal in the model (γglyx=2.9×10-3), we find that this improves modeled glyoxal in the surface layer but leads to an underestimate of glyoxal above the surface. We estimate an upper limit (1.0 μg/m3) for SOA contributed by glyoxal uptake by aerosols and clouds in the boundary layer of this region. Our work highlights several uncertainties in current chemical mechanisms on glyoxal production from isoprene oxidation under high and low NOx conditions, which may lead to large biases in the estimates of its contribution to SOA formation. Further investigation on these pathways is warranted to quantify the sources and sinks of glyoxal in regional and global scales.

  7. Effect of Slow Aging Reactions on Optical Properties of Secondary Organic Aerosol Prepared by Oxidation of Selected Monoterpenes

    NASA Astrophysics Data System (ADS)

    Nizkorodov, S. A.; Bones, D. L.; Henricksen, D. K.; Mang, S. A.; Bateman, A. P.; Pan, X.; Nguyen, T. B.; Gonsior, M.; Cooper, W.; Laskin, J.; Laskin, A.

    2009-05-01

    Organic particulate matter (PM) has a major impact on atmospheric chemistry, climate, and human health. Secondary organic aerosol (SOA) accounts for a rather significant fraction of organic PM; this includes SOA produced by oxidation of biogenically emitted monoterpenes. Once such SOA is formed, it is believed to undergo slow aging processes, which may have large effects on the physical and chemical properties of the particles. This presentation focuses on the effect of slow chemical aging on optical properties of SOA formed from the ozone-induced oxidation of limonene, myrcene, and other selected monoterpenes. Several complementary techniques including high resolution electrospray ionization mass spectrometry, FTIR spectroscopy, UV/vis spectroscopy, NMR spectroscopy, 3D-fluorescence spectroscopy, and photodissociation spectroscopy are used to probe the aging-induced changes in physical properties and chemical composition of laboratory generated SOA. Limonene SOA appears to undergo a dramatic change in its absorption spectrum on a time scale of hours; it develops strong visible bands in the 400-500 nm region, and becomes fluorescent. This transformation is catalyzed by ammonium sulfate and certain amino acids. This rather unusual aging process can potentially contribute to the formation of brown carbon in biogenic SOA.

  8. A Computational Approach to Understanding Oxidant Chemistry and Aerosol Formation in the Troposphere

    SciTech Connect

    Garrett, Bruce C.; Bianco, Roberto; Dang, Liem X.; Dixon, David A.; Dupuis, Michel; Francisco, Joseph; Gertner, Bradley; Hynes, James T.; Kathmann, Shawn M.; Lee, Timothy J.; Morita, Akihiro; Peterson, Kirk A.; Schenter, Gregory K.; Seinfeld, John H.; Xantheas, Sotiris S.

    2002-08-01

    Ozone production and aerosol formation in the troposphere are recognized as two major effects of energy-related air pollutants. Tropospheric ozone is of concern primarily because of its impact on health. Ozone levels are controlled by NOx and by volatile organic compounds (VOCs) in the lower troposphere. The VOCs can either be from natural emissions from such sources as vegetation and phytoplankton or from anthropogenic sources such as automobiles and oil-fueled power production plants. It is of critical importance to the Department of Energy (DOE) in developing national energy use policies to understand the role of VOCs in determining air quality and how VOC emission or NOx emission control strategies should be designed.

  9. Kinetics and Products of Heterogeneous Oxidation of Oleic acid, Linoleic acid and Linolenic acid in Aerosol Particles by Hydroxyl radicals

    NASA Astrophysics Data System (ADS)

    Nah, T.; Leone, S. R.; Wilson, K. R.

    2010-12-01

    A significant mass fraction of atmospheric aerosols is composed of a variety of oxidized organic compounds with varying functional groups that may affect the rate at which they chemically age. Here we study the heterogeneous reaction of OH radicals with different sub-micron, alkenoic acid particles: Oleic acid (OA), Linoleic acid (LA), and Linolenic acid (LNA), in the presence of H2O2 and O2. This research explores how OH addition reactions initiate chain reactions that rapidly transform the chemical composition of an organic particle. Particles are chemically aged in a photochemical flow tube reactor where they are exposed to OH radicals (~ 1011 molecule cm-3 s) that are produced by the photolysis of H2O2 at 254 nm. The aerosols are then sized and their composition analyzed via Atmospheric Pressure Chemical Ionization (APCI). Detailed kinetic measurements show that the reactive uptake coefficient is larger than 1, indicating the presence of secondary chemistry occurring in the condensed phase. Reactive uptake coefficient is found to scale linearly with the number of double bonds present in the molecule. In addition, the reactive uptake coefficient is found to depend sensitively upon the concentrations of O2 in the photochemical flow tube reactor, indicating that O2 plays a role in secondary chemistry. In the absence of O2 the reactive uptake coefficient increases to ~ 8, 5 and 3 for LNA, LA, and OA, respectively. The reactive uptake coefficient approaches values of 6, 4 and 2 for LNA, LA, and OA respectively when 18% of the total nitrogen flow is replaced with O2. Mechanistic pathways and products will also be presented herein.

  10. Reaction of oleic acid particles with NO3 radicals: Products, mechanism, and implications for radical-initiated organic aerosol oxidation.

    PubMed

    Docherty, Kenneth S; Ziemann, Paul J

    2006-03-16

    The heterogeneous reaction of liquid oleic acid aerosol particles with NO3 radicals in the presence of NO2, N2O5, and O2 was investigated in an environmental chamber using a combination of on-line and off-line mass spectrometric techniques. The results indicate that the major reaction products, which are all carboxylic acids, consist of hydroxy nitrates, carbonyl nitrates, dinitrates, hydroxydinitrates, and possibly more highly nitrated products. The key intermediate in the reaction is the nitrooxyalkylperoxy radical, which is formed by the addition of NO3 to the carbon-carbon double bond and subsequent addition of O2. The nitrooxyalkylperoxy radicals undergo self-reactions to form hydroxy nitrates and carbonyl nitrates, and may also react with NO2 to form nitrooxy peroxynitrates. The latter compounds are unstable and decompose to carbonyl nitrates and dinitrates. It is noteworthy that in this reaction nitrooxyalkoxy radicals appear not to be formed, as indicated by the absence of the expected products of decomposition or isomerization of these species. This is different from gas-phase alkene-NO3 reactions, in which a large fraction of the products are formed through these pathways. The results may indicate that, for liquid organic aerosol particles in low NOx environments, the major products of the radical-initiated oxidation (including by OH radicals) of unsaturated and saturated organic compounds will be substituted forms of the parent compound rather than smaller decomposition products. These compounds will remain in the particle and can potentially enhance particle hygroscopicity and the ability of particles to act as cloud condensation nuclei. PMID:16526637

  11. Selectivity Across the Interface: A Test of Surface Activity in the Composition of Organic-Enriched Aerosols from Bubble Bursting.

    PubMed

    Cochran, Richard E; Jayarathne, Thilina; Stone, Elizabeth A; Grassian, Vicki H

    2016-05-01

    Although theories have been developed that describe surface activity of organic molecules at the air-water interface, few studies have tested how surface activity impacts the selective transfer of molecules from solution phase into the aerosol phase during bubble bursting. The selective transfer of a series of organic compounds that differ in their solubility and surface activity from solution into the aerosol phase is quantified experimentally for the first time. Aerosol was produced from solutions containing salts and a series of linear carboxlyates (LCs) and dicarboxylates (LDCs) using a bubble bursting process. Surface activity of these molecules dominated the transport across the interface, with enrichment factors of the more surface-active C4-C8 LCs (55 ± 8) being greater than those of C4-C8 LDCs (5 ± 1). Trends in the estimated surface concentrations of LCs at the liquid-air interface agreed well with their relative concentrations in the aerosol phase. In addition, enrichment of LCs was followed by enrichment of calcium with respect to other inorganic cations and depletion of chloride and sulfate. PMID:27093579

  12. Use of active and passive ground based remote sensors to explore cloud droplet modifications in aerosol-cloud interactions

    NASA Astrophysics Data System (ADS)

    Han, Zaw Thet

    We explore the potential aerosol impact on cloud optical properties which is a strong modifier of climate forcing. Previous studies have shown that increased aerosol loading can affect the cloud optical properties such as cloud optical depth and cloud droplet effective radius in rural areas, particularly at the Atmospheric Radiation Measurement, Southern Great Plain site. In this study, we attempt to observe and quantify aerosol-cloud interaction over New York City, using a combination of passive and active radiometric sensors. In particular, we look for signatures of the Twomey indirect effect which states that the droplet size of water phase clouds will decrease with increasing aerosols. We find that under certain conditions, a strong signature is found between the cloud drop effective radius and extinction and this effect is in part due to vertical wind uptake. In demonstrating the Aerosol Cloud Interaction, we use multiple approaches. For example, we derive the integrated liquid water path using both a multiband neural network and dual channel approach and show general agreement between two methods while the DC approach seems more robust. We also find that these measurements are difficult and sensitive to the position of the aerosols relative to the cloud base. As a corollary, we explore whether near surface aerosol loading can effecting the cloud by using particulate matter (PM2.5) and find that the effects are too variable to be given any statistical weight. Finally, we explore the potential of modifying our approach to remove the noisy and difficult measurement of Raman LIDAR derived extinction with calibrated LIDAR backscatter. The results seem to show a general improvement in correlation and offer the possibility of increasing the number of cases observed.

  13. Novel multi-functional europium-doped gadolinium oxide nanoparticle aerosols facilitate the study of deposition in the developing rat lung

    NASA Astrophysics Data System (ADS)

    Das, Gautom K.; Anderson, Donald S.; Wallis, Chris D.; Carratt, Sarah A.; Kennedy, Ian M.; van Winkle, Laura S.

    2016-06-01

    Ambient ultrafine particulate matter (UPM), less than 100 nm in size, has been linked to the development and exacerbation of pulmonary diseases. Age differences in susceptibility to UPM may be due to a difference in delivered dose as well as age-dependent differences in lung biology and clearance. In this study, we developed and characterized aerosol exposures to novel metal oxide nanoparticles containing lanthanides to study particle deposition in the developing postnatal rat lung. Neonatal, juvenile and adult rats (1, 3 and 12 weeks old) were nose only exposed to 380 μg m-3 of ~30 nm europium doped gadolinium oxide nanoparticles (Gd2O3:Eu3+) for 1 h. The deposited dose in the nose, extrapulmonary airways and lungs was determined using inductively-coupled plasma mass spectroscopy. The dose of deposited particles was significantly greater in the juvenile rats at 2.22 ng per g body weight compared to 1.47 ng per g and 0.097 ng per g for the adult and neonate rats, respectively. Toxicity was investigated in bronchoalveolar lavage fluid (BALF) by quantifying recovered cell types, and measuring lactate dehydrogenase activity and total protein. The toxicity data suggests that the lanthanide particles were not acutely toxic or inflammatory with no increase in neutrophils or lactate dehydrogenase activity at any age. Juvenile and adult rats had the same mass of deposited NPs per gram of lung tissue, while neonatal rats had significantly less NPs deposited per gram of lung tissue. The current study demonstrates the utility of novel lanthanide-based nanoparticles to study inhaled particle deposition in vivo and has important implications for nanoparticles delivery to the developing lung either as therapies or as a portion of particulate matter air pollution.Ambient ultrafine particulate matter (UPM), less than 100 nm in size, has been linked to the development and exacerbation of pulmonary diseases. Age differences in susceptibility to UPM may be due to a difference in

  14. CCN activation and efficiency of nucleation and impaction removal process of biomass burning aerosols in Brazil: preliminary results.

    NASA Astrophysics Data System (ADS)

    Sánchez Gácita, Madeleine; Longo, Karla M.; Freitas, Saulo R.; Martin, Scot T.

    2015-04-01

    The biomass burning activity constitutes an important source of aerosols and trace gases to the atmosphere globally. In South America, during the dry season, aerosols prevenient from biomass burning are typically transported to long distances from its sources before being removed though contributing significantly to the aerosol budget on a continental scale. The uncertainties in the magnitude of the impacts on the hydrological cycle, the radiation budget and the biogeochemical cycles on a continental scale are still noteworthy. The still unknowns on the efficiency of biomass burning aerosol to act as cloud condensation nuclei (CCN) and the effectiveness of the nucleation and impaction scavenging mechanisms in removing them from the atmosphere contribute to such uncertainties. In the present work, the explicit modelling of the early stages of cloud development using a parcel model for the typical conditions of the dry season and dry-to-wet transition periods in Amazonia allowed an estimation of the efficiency of nucleation scavenging process and the ability of South American biomass burning aerosol to act as CCN. Additionally, the impaction scavenging was simulated for the same aerosol population following a method based on the widely used concept of the efficiency of collision between a raindrop and an aerosol particle. DMPS and H-TDMA data available in the literature for biomass burning aerosol population in the region indicated the presence of a nearly hydrophobic fraction (on average, with specific hygroscopic parameter κ=0.04, and relative abundance of 73 %) and nearly hygroscopic fraction (κ=0.13, 27 %), externally mixed. The hygroscopic parameters and relative abundances of each hygroscopic group, as well as the weighted average specific hygroscopic parameter for the entire population κ=0.06, were used in calculations of aerosol activation and population mass and number concentration scavenged by nucleation. Results from both groups of simulations are

  15. Novel multi-functional europium-doped gadolinium oxide nanoparticle aerosols facilitate the study of deposition in the developing rat lung.

    PubMed

    Das, Gautom K; Anderson, Donald S; Wallis, Chris D; Carratt, Sarah A; Kennedy, Ian M; Van Winkle, Laura S

    2016-06-01

    Ambient ultrafine particulate matter (UPM), less than 100 nm in size, has been linked to the development and exacerbation of pulmonary diseases. Age differences in susceptibility to UPM may be due to a difference in delivered dose as well as age-dependent differences in lung biology and clearance. In this study, we developed and characterized aerosol exposures to novel metal oxide nanoparticles containing lanthanides to study particle deposition in the developing postnatal rat lung. Neonatal, juvenile and adult rats (1, 3 and 12 weeks old) were nose only exposed to 380 μg m(-3) of ∼30 nm europium doped gadolinium oxide nanoparticles (Gd2O3:Eu(3+)) for 1 h. The deposited dose in the nose, extrapulmonary airways and lungs was determined using inductively-coupled plasma mass spectroscopy. The dose of deposited particles was significantly greater in the juvenile rats at 2.22 ng per g body weight compared to 1.47 ng per g and 0.097 ng per g for the adult and neonate rats, respectively. Toxicity was investigated in bronchoalveolar lavage fluid (BALF) by quantifying recovered cell types, and measuring lactate dehydrogenase activity and total protein. The toxicity data suggests that the lanthanide particles were not acutely toxic or inflammatory with no increase in neutrophils or lactate dehydrogenase activity at any age. Juvenile and adult rats had the same mass of deposited NPs per gram of lung tissue, while neonatal rats had significantly less NPs deposited per gram of lung tissue. The current study demonstrates the utility of novel lanthanide-based nanoparticles to study inhaled particle deposition in vivo and has important implications for nanoparticles delivery to the developing lung either as therapies or as a portion of particulate matter air pollution. PMID:27198643

  16. The standoff aerosol active signature testbed (SAAST) at MIT Lincoln Laboratory

    NASA Astrophysics Data System (ADS)

    Richardson, Jonathan M.; Aldridge, John C.

    2005-11-01

    Standoff LIDAR detection of BW agents depends on accurate knowledge of the infrared and ultraviolet optical elastic scatter (ES) and ultraviolet fluorescence (UVF) signatures of bio-agents and interferents. MIT Lincoln Laboratory has developed the Standoff Aerosol Active Signature Testbed (SAAST) for measuring ES cross sections from BW simulants and interferents at all angles including 180º (direct backscatter). Measurements of interest include the dependence of the ES and UVF signatures on several spore production parameters including growth medium, sporulation protocol, washing protocol, fluidizing additives, and degree of aggregation. Using SAAST, we have made measurements of the ES signature of Bacillus globigii (atropheaus, Bg) spores grown under different growth methods. We have also investigated one common interferent (Arizona Test Dust). Future samples will include pollen and diesel exhaust. This paper presents the details of the SAAST apparatus along with the results of recent measurements.

  17. EFFECT OF AN ACTIVATED SLUDGE WASTEWATER TREATMENT PLANT ON AMBIENT AIR DENSITIES OF AEROSOLS CONTAINING BACTERIA AND VIRUSES

    EPA Science Inventory

    Bacteria and virus-containing aerosols were studied during late summer and fall in a U.S. midwestern suburb before and during the start up and operation of an unenclosed activated sludge wastewater treatment plant. The air in this suburban area contained low-level densities of in...

  18. Hygroscopic growth and activation of HULIS particles: experimental data and a new iterative parameterization scheme for complex aerosol particles

    NASA Astrophysics Data System (ADS)

    Ziese, M.; Wex, H.; Nilsson, E.; Salma, I.; Ocskay, R.; Hennig, T.; Massling, A.; Stratmann, F.

    2008-03-01

    The hygroscopic growth and activation of two HULIS (HUmic LIke Substance) and one Aerosol-Water-Extract sample, prepared from urban-type aerosol, were investigated. All samples were extracted from filters, redissolved in water and atomized for the investigations presented here. The hygroscopic growth measurements were done using LACIS (Leipzig Aerosol Cloud Interaction Simulator) together with a HH-TDMA (High Humidity Tandem Differential Mobility Analyzer). Hygroscopic growth was determined for relative humidities (RHs) up to 99.75%. The critical diameters for activation were measured for supersaturations between 0.2 and 1%. All three samples showed a similar hygroscopic growth behavior, and the two HULIS samples also were similar in their activation behavior, while the Aerosol-Water-Extract turned out to be more CCN active than the HULIS samples. The experimental data was used to derive parameterizations for the hygroscopic growth and activation of HULIS particles. The concept of ρion (Wex et al., 2007a) and the Szyszkowski-equation (Szyszkowski, 1908; Facchini, 1999) were used for parameterizing the Raoult and the Kelvin (surface tension) terms of the Köhler equation, respectively. This concept proved to be very successful for the HULIS samples in the saturation range from RHs larger than 98% up to activation. It was also shown to work well with data on HULIS taken from literature. Here, different atmospheric life-times and/or different sources for the different samples showed up in different coefficients for the parameterization. However, the parameterization did not work out well for the Aerosol-Water-Extract.

  19. Biogenic oxidized organic functional groups in aerosol particles from a mountain forest site and their similarities to laboratory chamber products

    NASA Astrophysics Data System (ADS)

    Schwartz, R. E.; Russell, L. M.; Sjostedt, S. J.; Vlasenko, A.; Slowik, J. G.; Abbatt, J. P. D.; MacDonald, A. M.; Li, S. M.; Liggio, J.; Toom-Sauntry, D.; Leaitch, W. R.

    2010-06-01

    Submicron particles collected at Whistler, British Columbia, at 1020 m a.s.l. during May and June 2008 on Teflon filters were analyzed by Fourier transform infrared (FTIR) and X-ray fluorescence (XRF) techniques for organic functional groups (OFG) and elemental composition. Organic mass (OM) concentrations ranged from less than 0.5 to 3.1 μg m-3, with a project mean and standard deviation of 1.3±1.0 μg m-3 and 0.21±0.16 μg m-3 for OM and sulfate, respectively. On average, organic hydroxyl, alkane, and carboxylic acid groups represented 34%, 33%, and 23% of OM, respectively. Ketone, amine and organosulfate groups constituted 6%, 5%, and <1% of the average organic aerosol composition, respectively. Measurements of volatile organic compounds (VOC), including isoprene and monoterpenes from biogenic VOC (BVOC) emissions and their oxidation products (methyl-vinylketone / methacrolein, MVK/MACR), were made using co-located proton transfer reaction mass spectrometry (PTR-MS). We present chemically-specific evidence of OFG associated with BVOC emissions. Positive matrix factorization (PMF) analysis attributed 65% of the campaign OM to biogenic sources, based on the correlations of one factor to monoterpenes and MVK/MACR. The remaining fraction was attributed to anthropogenic sources based on a correlation to sulfate. The functional group composition of the biogenic factor (consisting of 32% alkane, 25% carboxylic acid, 21% organic hydroxyl, 16% ketone, and 6% amine groups) was similar to that of secondary organic aerosol (SOA) reported from the oxidation of BVOCs in laboratory chamber studies, providing evidence that the magnitude and chemical composition of biogenic SOA simulated in the laboratory is similar to that found in actual atmospheric conditions. The biogenic factor OM is also correlated to dust elements, indicating that dust may act as a non-acidic SOA sink. This role is supported by the organic functional group composition and morphology of single particles

  20. Biogenic oxidized organic functional groups in aerosol particles from a mountain forest site and their similarities to laboratory chamber products

    NASA Astrophysics Data System (ADS)

    Schwartz, R. E.; Russell, L. M.; Sjosted, S. J.; Vlasenko, A.; Slowik, J. G.; Abbatt, J. P. D.; MacDonald, A. M.; Li, S. M.; Liggio, J.; Toom-Sauntry, D.; Leaitch, W. R.

    2010-02-01

    Submicron particles collected at Whistler, British Columbia, at 1020 masl during May and June 2008 on Teflon filters were analyzed by Fourier transform infrared (FTIR) and X-ray fluorescence (XRF) techniques for organic functional groups (OFG) and elemental composition. Organic mass (OM) ranged from less than 0.5 to 3.1μg m-3, with a project mean and standard deviation of 1.3±1.0 μg m-3 and 0.21±0.16 μg m-3 for OM and sulfate, respectively. On average, organic hydroxyl, alkane, and carboxylic acid groups represented 34%, 33%, and 23% of OM, respectively. Ketone, amine and organosulfate groups constituted 6%, 5%, and <1% of the average organic aerosol composition, respectively. Measurements of volatile organic compounds (VOC), including isoprene and monoterpenes from biogenic VOC (BVOC) emissions and their oxidation products (methyl-vinylketone/methacrolein, MVK/MACR), were made using co-located proton transfer reaction mass spectrometry (PTR-MS). We present chemically-specific evidence of OFG associated with BVOC emissions. Positive matrix factorization (PMF) analysis attributed 65% of the campaign OM to biogenic sources, based on the correlations of one factor to monoterpenes and MVK/MACR. The remaining fraction was attributed to anthropogenic sources based on a correlation to sulfate. The functional group composition of the biogenic factor (consisting of 32% alkane, 25% carboxylic acid, 2% organic hydroxyl, 16% ketone, and 6% amine groups) was similar to that of secondary organic aerosol (SOA) reported from the oxidation of BVOCs in laboratory chamber studies, providing evidence that the magnitude and chemical composition of biogenic SOA simulated in the laboratory is similar to that found in actual atmospheric conditions. The biogenic factor OM is also correlated to dust elements, indicating that dust may act as a non-acidic SOA sink. This role is supported by the organic functional group composition and morphology of single particles, which were analyzed

  1. Light activated nitric oxide releasing materials

    NASA Astrophysics Data System (ADS)

    Muizzi Casanas, Dayana Andreina

    The ability to control the location and dosage of biologically active molecules inside the human body can be critical to maximizing effective treatment of cardiovascular diseases like angina. The current standard of treatment relies on the metabolism of organonitrate drugs into nitric oxide (NO), which are not specific, and also show problems with densitization with long-term use. There is a need then to create a treatment method that gives targeted release of NO. Metal-nitrosyl (M-NO) complexes can be used for delivery of NO since the release of NO can be controlled with light. However, the NO-releasing drug must be activated with red light to ensure maximum penetration of light through tissue. However, the release of NO from M-NO complexes with red-light activation is a significant challenge since the energy required to break the metal-NO bond is usually larger than the energy provided by red light. The goal of this project was to create red- sensitive, NO-releasing materials based on Ru-salen-nitrosyl compounds. Our approach was to first modify Ru salen complexes to sensitize the photochemistry for release of NO after red light irradiation. Next, we pursued polymerization of the Ru-salen complexes. We report the synthesis and quantitative photochemical characterization of a series of ruthenium salen nitrosyl complexes. These complexes were modified by incorporating electron donating groups in the salen ligand structure at key locations to increase electron density on the Ru. Complexes with either an --OH or --OCH3 substituent showed an improvement in the quantum yield of release of NO upon blue light irradiation compared to the unmodified salen. These --OH and --OCH3 complexes were also sensitized for NO release after red light activation, however the red-sensitive complexes were unstable and showed ligand substitution on the order of minutes. The substituted complexes remained sensitive for NO release, but only after blue light irradiation. The Ru

  2. Long-term study of cloud condensation nuclei (CCN) activation of the atmospheric aerosol in Vienna

    PubMed Central

    Burkart, J.; Steiner, G.; Reischl, G.; Hitzenberger, R.

    2011-01-01

    During a total of 11 months, cloud condensation nuclei (CCN at super-saturation S 0.5%) and condensation nuclei (CN) concentrations were measured in the urban background aerosol of Vienna, Austria. For several months, number size distributions between 13.22 nm and 929 nm were also measured with a scanning mobility particle spectrometer (SMPS). Activation ratios (i.e. CCN/CN ratios) were calculated and apparent activation diameters obtained by integrating the SMPS size distributions. Variations in all CCN parameters (concentration, activation ratio, apparent activation diameter) are quite large on timescales of days to weeks. Passages of fronts influenced CCN parameters. Concentrations decreased with the passage of a front. No significant differences were found for fronts from different sectors (for Vienna mainly north to west and south to east). CCN concentrations at 0.5% S ranged from 160 cm−3 to 3600 cm−3 with a campaign average of 820 cm−3. Activation ratios were quite low (0.02–0.47, average: 0.13) and comparable to activation ratios found in other polluted regions (e.g. Cubison et al., 2008). Apparent activation diameters were found to be much larger (campaign average: 169 nm, range: (69–370) nm) than activation diameters for single-salt particles (around 50 nm depending on the salt). Contrary to CN concentrations, which are influenced by source patterns, CCN concentrations did not exhibit distinct diurnal patterns. Activation ratios showed diurnal variations counter-current to the variations of CN concentrations. PMID:21977003

  3. Effects of surface-active organic matter on carbon dioxide nucleation in atmospheric wet aerosols: a molecular dynamics study.

    PubMed

    Daskalakis, Vangelis; Charalambous, Fevronia; Panagiotou, Fostira; Nearchou, Irene

    2014-11-21

    Organic matter (OM) uptake in cloud droplets produces water-soluble secondary organic aerosols (SOA) via aqueous chemistry. These play a significant role in aerosol properties. We report the effects of OM uptake in wet aerosols, in terms of the dissolved-to-gas carbon dioxide nucleation using molecular dynamics (MD) simulations. Carbon dioxide has been implicated in the natural rainwater as well as seawater acidity. Variability of the cloud and raindrop pH is assumed in space and time, as regional emissions, local human activities and geophysical characteristics differ. Rain scavenging of inorganic SOx, NOx and NH3 plays a major role in rain acidity in terms of acid-base activity, however carbon dioxide solubility also remains a key parameter. Based on the MD simulations we propose that the presence of surface-active OM promotes the dissolved-to-gas carbon dioxide nucleation in wet aerosols, even at low temperatures, strongly decreasing carbon dioxide solubility. A discussion is made on the role of OM in controlling the pH of a cloud or raindrop, as a consequence, without involving OM ionization equilibrium. The results are compared with experimental and computational studies in the literature. PMID:25272147

  4. Tropospheric Aerosols

    NASA Astrophysics Data System (ADS)

    Buseck, P. R.; Schwartz, S. E.

    2003-12-01

    It is widely believed that "On a clear day you can see forever," as proclaimed in the 1965 Broadway musical of the same name. While an admittedly beautiful thought, we all know that this concept is only figurative. Aside from Earth's curvature and Rayleigh scattering by air molecules, aerosols - colloidal suspensions of solid or liquid particles in a gas - limit our vision. Even on the clearest day, there are billions of aerosol particles per cubic meter of air.Atmospheric aerosols are commonly referred to as smoke, dust, haze, and smog, terms that are loosely reflective of their origin and composition. Aerosol particles have arisen naturally for eons from sea spray, volcanic emissions, wind entrainment of mineral dust, wildfires, and gas-to-particle conversion of hydrocarbons from plants and dimethylsulfide from the oceans. However, over the industrial period, the natural background aerosol has been greatly augmented by anthropogenic contributions, i.e., those produced by human activities. One manifestation of this impact is reduced visibility (Figure 1). Thus, perhaps more than in other realms of geochemistry, when considering the composition of the troposphere one must consider the effects of these activities. The atmosphere has become a reservoir for vast quantities of anthropogenic emissions that exert important perturbations on it and on the planetary ecosystem in general. Consequently, much recent research focuses on the effects of human activities on the atmosphere and, through them, on the environment and Earth's climate. For these reasons consideration of the geochemistry of the atmosphere, and of atmospheric aerosols in particular, must include the effects of human activities. (201K)Figure 1. Impairment of visibility by aerosols. Photographs at Yosemite National Park, California, USA. (a) Low aerosol concentration (particulate matter of aerodynamic diameter less than 2.5 μm, PM2.5=0.3 μg m-3; particulate matter of aerodynamic diameter less than 10

  5. Assessing the impact of anthropogenic pollution on isoprene-derived secondary organic aerosol formation in PM2.5 collected from the Birmingham, Alabama, ground site during the 2013 Southern Oxidant and Aerosol Study

    NASA Astrophysics Data System (ADS)

    Rattanavaraha, Weruka; Chu, Kevin; Hapsari Budisulistiorini, Sri; Riva, Matthieu; Lin, Ying-Hsuan; Edgerton, Eric S.; Baumann, Karsten; Shaw, Stephanie L.; Guo, Hongyu; King, Laura; Weber, Rodney J.; Neff, Miranda E.; Stone, Elizabeth A.; Offenberg, John H.; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.

    2016-04-01

    In the southeastern US, substantial emissions of isoprene from deciduous trees undergo atmospheric oxidation to form secondary organic aerosol (SOA) that contributes to fine particulate matter (PM2.5). Laboratory studies have revealed that anthropogenic pollutants, such as sulfur dioxide (SO2), oxides of nitrogen (NOx), and aerosol acidity, can enhance SOA formation from the hydroxyl radical (OH)-initiated oxidation of isoprene; however, the mechanisms by which specific pollutants enhance isoprene SOA in ambient PM2.5 remain unclear. As one aspect of an investigation to examine how anthropogenic pollutants influence isoprene-derived SOA formation, high-volume PM2.5 filter samples were collected at the Birmingham, Alabama (BHM), ground site during the 2013 Southern Oxidant and Aerosol Study (SOAS). Sample extracts were analyzed by gas chromatography-electron ionization-mass spectrometry (GC/EI-MS) with prior trimethylsilylation and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) to identify known isoprene SOA tracers. Tracers quantified using both surrogate and authentic standards were compared with collocated gas- and particle-phase data as well as meteorological data provided by the Southeastern Aerosol Research and Characterization (SEARCH) network to assess the impact of anthropogenic pollution on isoprene-derived SOA formation. Results of this study reveal that isoprene-derived SOA tracers contribute a substantial mass fraction of organic matter (OM) ( ˜ 7 to ˜ 20 %). Isoprene-derived SOA tracers correlated with sulfate (SO42-) (r2 = 0.34, n = 117) but not with NOx. Moderate correlations between methacrylic acid epoxide and hydroxymethyl-methyl-α-lactone (together abbreviated MAE/HMML)-derived SOA tracers with nitrate radical production (P[NO3]) (r2 = 0.57, n = 40) were observed during nighttime, suggesting a potential role of the NO3 radical in

  6. Detection and quantification of water-based aerosols using active open-path FTIR

    PubMed Central

    Kira, Oz; Linker, Raphael; Dubowski, Yael

    2016-01-01

    Aerosols have a leading role in many eco-systems and knowledge of their properties is critical for many applications. This study suggests using active Open-Path Fourier Transform Infra-Red (OP-FTIR) spectroscopy for quantifying water droplets and solutes load in the atmosphere. The OP-FTIR was used to measure water droplets, with and without solutes, in a 20 m spray tunnel. Three sets of spraying experiments generated different hydrosols clouds: (1) tap water only, (2) aqueous ammonium sulfate (0.25–3.6%wt) and (3) aqueous ethylene glycol (0.47–2.38%wt). Experiment (1) yielded a linear relationship between the shift of the extinction spectrum baseline and the water load in the line-of-sight (LOS) (R2 = 0.984). Experiment (2) also yielded a linear relationship between the integrated extinction in the range of 880–1150 cm−1 and the ammonium sulfate load in the LOS (R2 = 0.972). For the semi-volatile ethylene glycol (experiment 3), present in the gas and condense phases, quantification was much more complex and two spectral approaches were developed: (1) according to the linear relationship from the first experiment (determination error of 8%), and (2) inverse modeling (determination error of 57%). This work demonstrates the potential of the OP-FTIR for detecting clouds of water-based aerosols and for quantifying water droplets and solutes at relatively low concentrations. PMID:27121498

  7. Epoxide as a precursor to secondary organic aerosol formation from isoprene photooxidation in the presence of nitrogen oxides

    PubMed Central

    Lin, Ying-Hsuan; Zhang, Haofei; Pye, Havala O. T.; Zhang, Zhenfa; Marth, Wendy J.; Park, Sarah; Arashiro, Maiko; Cui, Tianqu; Budisulistiorini, Sri Hapsari; Sexton, Kenneth G.; Vizuete, William; Xie, Ying; Luecken, Deborah J.; Piletic, Ivan R.; Edney, Edward O.; Bartolotti, Libero J.; Gold, Avram; Surratt, Jason D.

    2013-01-01

    Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear. We present evidence from controlled smog chamber experiments and field measurements that in the presence of high levels of nitrogen oxides (NOx = NO + NO2) typical of urban atmospheres, 2-methyloxirane-2-carboxylic acid (methacrylic acid epoxide, MAE) is a precursor to known isoprene-derived SOA tracers, and ultimately to SOA. We propose that MAE arises from decomposition of the OH adduct of methacryloylperoxynitrate (MPAN). This hypothesis is supported by the similarity of SOA constituents derived from MAE to those from photooxidation of isoprene, methacrolein, and MPAN under high-NOx conditions. Strong support is further derived from computational chemistry calculations and Community Multiscale Air Quality model simulations, yielding predictions consistent with field observations. Field measurements taken in Chapel Hill, North Carolina, considered along with the modeling results indicate the atmospheric significance and relevance of MAE chemistry across the United States, especially in urban areas heavily impacted by isoprene emissions. Identification of MAE implies a major role of atmospheric epoxides in forming SOA from isoprene photooxidation. Updating current atmospheric modeling frameworks with MAE chemistry could improve the way that SOA has been attributed to isoprene based on ambient tracer measurements, and lead to SOA parameterizations that better capture the dependency of yield on NOx. PMID:23553832

  8. Epoxide as a precursor to secondary organic aerosol formation from isoprene photooxidation in the presence of nitrogen oxides.

    PubMed

    Lin, Ying-Hsuan; Zhang, Haofei; Pye, Havala O T; Zhang, Zhenfa; Marth, Wendy J; Park, Sarah; Arashiro, Maiko; Cui, Tianqu; Budisulistiorini, Sri Hapsari; Sexton, Kenneth G; Vizuete, William; Xie, Ying; Luecken, Deborah J; Piletic, Ivan R; Edney, Edward O; Bartolotti, Libero J; Gold, Avram; Surratt, Jason D

    2013-04-23

    Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear. We present evidence from controlled smog chamber experiments and field measurements that in the presence of high levels of nitrogen oxides (NO(x) = NO + NO2) typical of urban atmospheres, 2-methyloxirane-2-carboxylic acid (methacrylic acid epoxide, MAE) is a precursor to known isoprene-derived SOA tracers, and ultimately to SOA. We propose that MAE arises from decomposition of the OH adduct of methacryloylperoxynitrate (MPAN). This hypothesis is supported by the similarity of SOA constituents derived from MAE to those from photooxidation of isoprene, methacrolein, and MPAN under high-NOx conditions. Strong support is further derived from computational chemistry calculations and Community Multiscale Air Quality model simulations, yielding predictions consistent with field observations. Field measurements taken in Chapel Hill, North Carolina, considered along with the modeling results indicate the atmospheric significance and relevance of MAE chemistry across the United States, especially in urban areas heavily impacted by isoprene emissions. Identification of MAE implies a major role of atmospheric epoxides in forming SOA from isoprene photooxidation. Updating current atmospheric modeling frameworks with MAE chemistry could improve the way that SOA has been attributed to isoprene based on ambient tracer measurements, and lead to SOA parameterizations that better capture the dependency of yield on NO(x). PMID:23553832

  9. A Physically-Based Estimate of Radiative Forcing by Anthropogenic Sulfate Aerosol

    SciTech Connect

    Ghan, Steven J.); Easter, Richard C.); Chapman, Elaine G.); Abdul-Razzak, Hayder; Zhang, Yang ); Leung, Ruby ); Laulainen, Nels S.); Saylor, Rick D.); Zaveri, Rahul A.)

    2001-04-01

    Estimates of direct and indirect radiative forcing by anthropogenic sulfate aerosols from an integrated global aerosol and climate modeling system are presented. A detailed global tropospheric chemistry and aerosol model that predicts concentrations of oxidants as well as aerosols and aerosol precursors, is coupled to a general circulation model that predicts both cloud water mass and cloud droplet number. Both number and mass of several externally-mixed aerosol size modes are predicted, with internal mixing assumed for the different aerosol components within each mode. Predicted aerosol species include sulfate, organic and black carbon, soil dust, and sea salt. The models use physically-based treatments of aerosol radiative properties (including dependence on relative humidity) and aerosol activation as cloud condensation nuclei. Parallel simulations with and without anthropogenic sulfate aerosol are performed for a global domain. The global and annual mean direct and indirect radiative forcing due to anthropogenic sulfate are estimated to be -0.3 to -0.5 and -1.5 to -3.0 W m-2, respectively. The radiative forcing is sensitive to the model's horizontal resolution, the use of predicted vs. analyzed relative humidity, the prediction vs. diagnosis of aerosol number and droplet number, and the parameterization of droplet collision/coalescence. About half of the indirect radiative forcing is due to changes in droplet radius and half to increased cloud liquid water.

  10. Instantaneous nitric oxide effect on secondary organic aerosol formation from m-xylene photooxidation

    NASA Astrophysics Data System (ADS)

    Li, Lijie; Tang, Ping; Cocker, David R.

    2015-10-01

    Secondary organic aerosol (SOA) formation from aromatic hydrocarbon photooxidation is highly sensitive to NO concentration. The instantaneous effect of NO on SOA formation from m-xylene photooxidation is investigated in this work by data mining 10 years of aromatic hydrocarbon chamber experiments conducted in the UC Riverside/CE-CERT chamber. First, the effect of sub-ppb NO concentrations on SOA formation is explored. The relationship of SOA growth rate to 1) NO2/NO ratio; 2) instantaneous HC/NO; 3) absolute NO concentration; 4) peroxy radical reaction branching ratio and 5) hydroxyl radical concentration are illustrated. Second, continuous and stepwise NO, NO2 and HONO injection are applied to m-xylene photooxidation experiments to simulate continuous NO sources in an urban area. The influence of these reaction scenarios on radical concentrations and SOA formation is explored. [HO2rad ]/[RO2rad ] shows a strong correlation with SOA yields in addition to [rad OH]/[HO2rad ], [rad OH], [HO2rad ] and [RO2rad ]. Enhanced SOA formation is observed when low NO levels (<1 ppb) are artificially maintained by continuous or step-wise injection; consistent with earlier research, SOA formation is observed to be suppressed by large initial NO injections. It is proposed that NO at sub-ppb level enhances rad OH formation increasing HO2rad and RO2rad and therefore promoting SOA formation. Further, two NO pathways (one promoting and one suppressing SOA formation) and one extremely low NO phase (NO "free") are used to demonstrate the evolution of NO impact on SOA formation during photooxidation. This study implies that SOA yields from aromatic hydrocarbon and low NOx photooxidation is previously underestimated due to differences between traditional environmental chamber experiments and atmospheric reactivity.

  11. Secondary Organic Aerosol (SOA) Formation From the NO3 Radical Oxidation of Alpha- pinene

    NASA Astrophysics Data System (ADS)

    Perraud, V.; Yu, Y.; Bruns, E.; Ezell, M. J.; Johnson, S. N.; Alexander, M.; Zelenyuk, A.; Imre, D.; Finlayson-Pitts, B. J.

    2008-12-01

    Terpenes such as alpha-pinene, emitted in large quantities from vegetation into the troposphere, are well known to react with O3, OH and NO3 radicals leading to the formation of secondary organic aerosol, SOA. While particle formation and growth from the NO3 reaction with alpha-pinene have been reported by a number of groups, as have the gas phase products of this reaction, little is known about the chemical composition of the particles. We report studies of the composition of particles formed in the NO3 - alpha- pinene reaction using two reactors, a flow tube and a static chamber. Nitrate radicals were generated in the flow tube by the reaction of NO2 with O3 and in the static chamber by the thermal decomposition of N2O5. Particle formation and growth was monitored using SMPS and APS. A variety of analytical techniques were applied to measure the chemical composition, including FTIR of particles collected on ZnSe impactor discs, and GC-MS, ESI-MS, APCI-MS, HPLC-MS and HPLC-UV of samples collected on quartz fiber filters. In addition, particle mass spectrometer techniques including AMS and SPLAT provided real-time analysis. A number of organic nitrates were observed in the particles, along with carbonyl compounds and organic acids. Gas phase products measured using DNPH coated-cartridges included pinonaldehyde, formaldehyde, acetaldehyde and acetone. Results of studies in which concentrations of the reactants were varied will be presented and possible mechanisms and the atmospheric implications will be discussed.

  12. Ozone reactivity of biogenic volatile organic compound (BVOC) emissions during the Southeast Oxidant and Aerosol Study (SOAS)

    NASA Astrophysics Data System (ADS)

    Park, J.; Guenther, A. B.; Helmig, D.

    2013-12-01

    Recent studies on atmospheric chemistry in the forest environment showed that the total reactivity by biogenic volatile organic compound (BVOC) emission is still not well understood. During summer 2013, an intensive field campaign (Southeast Oxidant and Aerosol Study - SOAS) took place in Alabama, U.S.A. In this study, an ozone reactivity measurement system (ORMS) was deployed for the direct determination of the reactivity of foliage emissions. The ORMS is a newly developed measurement approach, in which a known amount of ozone is added to the ozone-free air sample stream, with the ORMS measuring ozone concentration difference between before and after a glass flask flow tube reaction vessel (2-3 minutes of residence time). Emissions were also collected onto adsorbent cartridges to investigate the discrepancy between total ozone reactivity observation and reactivity calculated from identified BVOC. Leaf and canopy level experiments were conducted by deploying branch enclosures on the three dominant tree species at the site (i.e. liquidambar, white oak, loblolly pine) and by sampling ambient air above the forest canopy. For the branch enclosure experiments, BVOC emissions were sampled from a 70 L Teflon bag enclosure, purged with air scrubbed for ozone, nitrogen oxides. Each branch experiment was performed for 3-5 days to collect at least two full diurnal cycle data. In addition, BVOCs were sampled using glass tube cartridges for 2 hours during daytime and 3 - 4 hours at night. During the last week of campaign, the inlet for the ORMS was installed on the top of scaffolding tower (~30m height). The ozone loss in the reactor showed distinct diurnal cycle for all three tree species investigated, and ozone reactivity followed patterns of temperature and light intensity.

  13. Catalytic activity of metal oxides in hydrogen sulfide oxidation by oxygen and sulfur dioxide

    SciTech Connect

    Marshneva, V.I.; Mokrinskii, V.V.

    1989-02-01

    Separate investigations have been made of the catalytic activities of a wide range of oxides by groups I-VIII metals in the Claus reaction and oxidation of H/sub 2/S by oxygen. Only 9 of 21 oxides used in the Claus reaction exhibit stable activity. The remaining oxides are deactivated, mainly by absorbing H/sub 2/S and being converted into sulfides. There are similar tendencies in the changes of sulfur formation specific velocities in both processes in the series of stable oxides V/sub 2/O/sub 5/, TiO/sub 2/, Mn/sub 2/O/sub 3/, Al/sub 2/O/sub 3/, MgO, Cr/sub 2/O/sub 3/. Vanadium pentoxide is the most active catalyst in the total and partial oxidations of H/sub 2/S and the Claus reaction.

  14. Elastolytic activity in the lungs of rats exposed to cadmium aerosolization

    SciTech Connect

    Padmanabhan, R.V.; Gudapaty, S.R.; Liener, I.E.; Hoidal, J.R.

    1982-10-01

    Rats were exposed for 1 hr per day for up to 35 days to an aerosol of 0.1% cadmium chloride. At periodic intervals, animals were sacrificed and their lungs lavaged. The lung lavage fluid was examined for polymorphonuclear leukocytes (PMN) and alveolar macrophages (AM). A portion of the cells of the lavage fluid was lysed, and the remainder of the cells were cultured. The lavage fluids, cell lysates, and conditioned media were assayed for elastolytic activity in the presence and absence of a peptide chloromethyl ketone and EDTA. Exposure to cadmium evoked a biphasic cellular response characterized by an initial influx (1-3 days) of PMN followed by a gradual increase in AM. This biphasic cellular response was accompanied by a shift in the type of elastolytic activity which was present in the lung lavage and its cellular components. The initial PMN phase was accompanied by the enhanced production of an elastase inhibited only by the peptide chloromethyl ketone, while the subsequent AM phase was associated with an elastase activity which was inhibited only by EDTA. The possible implication of these results with respect to the pathogenesis of emphysema is considered.

  15. Spectroscopic investigations of organic aerosol and its reaction with halogens, released by sea-salt activation

    NASA Astrophysics Data System (ADS)

    Ofner, J.; Zetzsch, C.

    2009-04-01

    The release of reactive halogen species from sea-salt aerosol offers a class of reactants for heterogeneous reactions of utmost importance. These heterogeneous reactions have been overlooked so far, although they may occur with internal and external mixtures of sea-salt aerosol and organic aerosol or organic matter. Such reactions might constitute sources of gaseous organohalogen compounds or halogenated organic aerosol in the atmospheric boundary layer. Infrared and UV/VIS spectroscopy provide an insight into chemical processes at reactive sites of the organic phase on a molecular level. Model studies of heterogeneous reactions of halogens with different kinds of (secondary) organic aerosols and organic matter were performed using a 700L smog chamber with a solar simulator. The model compounds alpha-pinene, catechol and humic acid have been chosen as precursors/material for the condensed, organic phase of the aerosol. After formation of the secondary organic aerosol or preparation of the organic material and the sea-salt solution the reaction was carried out using molecular chlorine and bromine in the presence of simulated sunlight. Chemical transformation of the organic material was studied using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) on a ZnSe crystal and diffuse reflectance UV/VIS spectroscopy. An electrostatic precipitator was developed to deposit the aerosol particles on the ATR crystal as a thin film. On the other hand, longpath-FTIR spectroscopy with a 40m White-cell allows us to monitor both the condensed and gas phase of the aerosol in situ in the smog chamber directly. These spectroscopic techniques enable us to characterize different organic aerosol particles and their functional groups at reactive sites on these particles as well as to study aerosol formation and transformation directly. The heterogeneous reaction of reactive halogen species with organic material at atmospheric conditions leads to small reactive

  16. Investigating Types and Sources of Organic Aerosol in Rocky Mountain National Park Using Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Schurman, M. I.; Lee, T.; Sun, Y.; Schichtel, B. A.; Kreidenweis, S. M.; Collett, J. L.

    2011-12-01

    The Rocky Mountain Atmospheric Nitrogen and Sulfur Study (RoMANS) focuses on identifying pathways and sources of nitrogen deposition in Rocky Mountain National Park (RMNP). Past work has combined measurements from a range of instrumentation such as annular denuders, PILS-IC, Hi-Vol samplers, and trace gas analyzers. Limited information from early RoMANS campaigns is available regarding organic aerosol. While prior measurements have produced a measure of total organic carbon mass, high time resolution measures of organic aerosol concentration and speciation are lacking. One area of particular interest is characterizing the types, sources, and amounts of organic nitrogen aerosol. Organic nitrogen measurements in RMNP wet deposition reveal a substantial contribution to the total reactive nitrogen deposition budget. In this study an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed in summer 2010 at RMNP to investigate organic aerosol composition and its temporal variability. The species timeline and diurnal species variations are combined with meteorological data to investigate local transport events and chemistry; transport from the Colorado Front Range urban corridor appears to be more significant for inorganic species than for the overall organic aerosol mass. Considerable variation in organic aerosol concentration is observed (0.5 to 20 μg/m3), with high concentration episodes lasting between hours and two days. High resolution AMS data are analyzed for organic aerosol, including organic nitrogen species that might be expected from local biogenic emissions, agricultural activities, and secondary reaction products of combustion emissions. Positive matrix factorization reveals that semi-volatile oxidized OA, low-volatility oxidized OA, and biomass burning OA comprise most organic mass; the diurnal profile of biomass burning OA peaks at four and nine pm and may arise from local camp fires, while constant concentrations of

  17. Molecular Characterization of Brown Carbon (BrC) Chromophores in Secondary Organic Aerosol Generated From Photo-Oxidation of Toluene

    SciTech Connect

    Lin, Peng; Liu, Jiumeng; Shilling, John E.; Kathmann, Shawn M.; Laskin, Julia; Laskin, Alexander

    2015-09-28

    Atmospheric Brown carbon (BrC) is a significant contributor to light absorption and climate forcing. However, little is known about a fundamental relationship between the chemical composition of BrC and its optical properties. In this work, light-absorbing secondary organic aerosol (SOA) was generated in the PNNL chamber from toluene photo-oxidation in the presence of NOx (Tol-SOA). Molecular structures of BrC components were examined using nanospray desorption electrospray ionization (nano-DESI) and liquid chromatography (LC) combined with UV/Vis spectroscopy and electrospray ionization (ESI) high-resolution mass spectrometry (HRMS). The chemical composition of BrC chromophores and the light absorption properties of toluene SOA (Tol-SOA) depend strongly on the initial NOx concentration. Specifically, Tol-SOA generated under high-NOx conditions (defined here as initial NOx/toluene of 5/1) appears yellow and mass absorption coefficient of the bulk sample (MACbulk@365nm = 0.78 m2 g-1) is nearly 80 fold higher than that measured for the Tol-SOA sample generated under low-NOx conditions (NOx/toluene < 1/300). Fifteen compounds, most of which are nitrophenols, are identified as major BrC chromophores responsible for the enhanced light absorption of Tol-SOA material produced in the presence of NOx. The integrated absorbance of these fifteen chromophores accounts for 40-60% of the total light absorbance by Tol-SOA at wavelengths between 300 nm and 500 nm. The combination of tandem LC-UV/Vis-ESI/HRMS measurements provides an analytical platform for predictive understanding of light absorption properties by BrC and their relationship to the structure of individual chromophores. General trends in the UV/vis absorption by plausible isomers of the BrC chromophores were evaluated using theoretical chemistry calculations. The molecular-level understanding of BrC chemistry is helpful for better understanding the evolution and behavior of light absorbing aerosols in the atmosphere.

  18. Molecular characterization of brown carbon (BrC) chromophores in secondary organic aerosol generated from photo-oxidation of toluene.

    PubMed

    Lin, Peng; Liu, Jiumeng; Shilling, John E; Kathmann, Shawn M; Laskin, Julia; Laskin, Alexander

    2015-09-28

    Atmospheric brown carbon (BrC) is a significant contributor to light absorption and climate forcing. However, little is known about a fundamental relationship between the chemical composition of BrC and its optical properties. In this work, light-absorbing secondary organic aerosol (SOA) was generated in the PNNL chamber from toluene photo-oxidation in the presence of NOx (Tol-SOA). Molecular structures of BrC components were examined using nanospray desorption electrospray ionization (nano-DESI) and liquid chromatography (LC) combined with UV/Vis spectroscopy and electrospray ionization (ESI) high-resolution mass spectrometry (HRMS). The chemical composition of BrC chromophores and the light absorption properties of toluene SOA (Tol-SOA) depend strongly on the initial NOx concentration. Specifically, Tol-SOA generated under high-NOx conditions (defined here as initial NOx/toluene of 5/1) appears yellow and mass absorption coefficient of the bulk sample (MACbulk@365 nm = 0.78 m(2) g(-1)) is nearly 80 fold higher than that measured for the Tol-SOA sample generated under low-NOx conditions (NOx/toluene < 1/300). Fifteen compounds, most of which are nitrophenols, are identified as major BrC chromophores responsible for the enhanced light absorption of Tol-SOA material produced in the presence of NOx. The integrated absorbance of these fifteen chromophores accounts for 40-60% of the total light absorbance by Tol-SOA at wavelengths between 300 nm and 500 nm. The combination of tandem LC-UV/Vis-ESI/HRMS measurements provides an analytical platform for predictive understanding of light absorption properties by BrC and their relationship to the structure of individual chromophores. General trends in the UV/Vis absorption by plausible isomers of the BrC chromophores were evaluated using theoretical chemistry calculations. The molecular-level understanding of BrC chemistry is helpful for better understanding the evolution and behavior of light absorbing aerosols in the

  19. Theoretical investigation on iodine oxides formation and their role in the production of atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Galvez, Óscar; Gomez, Pedro C.; Gomez-Martin, Juan C.; Saiz-Lopez, Alfonso; Pacios, Luis F.

    2013-04-01

    Atmospheric iodine has received considerable attention in the past two decades due to both its potential role in the catalytic destruction of ozone (1) and its contribution to the formation of ultrafine particles (2). Seaweeds, marine phytoplankton, and abiotic processes release iodocarbons and I2 to the atmosphere, which are photo-oxidized giving iodine oxides that polymerize to finally form iodine oxide particles (IOPs). In the last years, some laboratory studies have been carried out to investigate this process (see e.g. (3)), however the complete mechanism of formation of such particles and the role of water, and other condensable vapors, in this process have not yet been elucidated. In this context, quantum calculations could help to unravel essential steps of these processes and to evaluate relevant physicochemical properties that can be incorporated into atmospheric models. In this contribution, we show results of a theoretical study on different reactions that iodine oxides, in the presence of water, can undergo to form IOPs. Thermodynamic and kinetic properties of these reactions have been obtained at high level ab initio correlated calculations that included relativistic corrections. In these calculations, we have used a relativistic effective potential (REP) and REP-optimized basis sets for iodine atom developed in our group, which have previously been employed in a theoretical study about several iodinated species (4). (1) Saiz-Lopez, A.; Mahajan, A.S.; Salmon, R.A.; Bauguitte, J.B.; Jones, A.E.; Roscoe, H.K.; Plane, J.M.C. Science 2007, 317, 348-351 (2) O'Dowd, C.D.; Jimenez, J.L.; Bahreini, R.; Flagan, R.C.; Seinfeld, J.H.; Hämeri, K.; Pirjola, L.; Kulmala, M.; Jennings, S.G.; Hoffmann, T. Nature, 2002, 417, 632-636. (3) Saunders, R.W.; Kumar, R.; Gómez Martin, J.C.; Mahajan, A.S.; Murray, B.J.; Plane, J.M.C. Z. Phys. Chem. 2010, 224, 1095-1117. (4) Pacios, L.F.; Gálvez, O. J. Chem. Theory Comput., 2010, 6, 1738-1752.

  20. Aerosol-Radiation-Cloud Interactions in the South-East Atlantic: Future Suborbital Activities to Address Knowledge Gaps in Satellite and Model Assessments

    NASA Technical Reports Server (NTRS)

    Redemann, Jens; Wood, R.; Zuidema, P.; Haywood, J.; Piketh, S.; Formenti, P.; L'Ecuyer, T.; Kacenelenbogen, M.; Segal-Rosenheimer, M.; Shinozuka, Y.; LeBlanc, S.; Vaughan, M.; Schmidt, S.; Flynn, C.; Schmid, B.; Luna, B.; Abel, S.

    2016-01-01

    Southern Africa produces almost a third of the Earth's biomass burning (BB) aerosol particles. Particles lofted into the mid-troposphere are transported westward over the South-East (SE) Atlantic, home to one of the three permanent subtropical stratocumulus (Sc) cloud decks in the world. The SE Atlantic stratocumulus deck interacts with the dense layers of BB aerosols that initially overlay the cloud deck, but later subside and may mix into the clouds. These interactions include adjustments to aerosol-induced solar heating and microphysical effects, and their global representation in climate models remains one of the largest uncertainties in estimates of future climate. Hence, new observations over the SE Atlantic have significant implications for global climate change scenarios. Our understanding of aerosol-cloud interactions in the SE Atlantic is hindered both by the lack of knowledge on aerosol and cloud properties, as well as the lack of knowledge about detailed physical processes involved. Most notably, we are missing knowledge on the absorptive and cloud nucleating properties of aerosols, including their vertical distribution relative to clouds, on the locations and degree of aerosol mixing into clouds, on the processes that govern cloud property adjustments, and on the importance of aerosol effects on clouds relative to co-varying synoptic scale meteorology. We discuss the current knowledge of aerosol and cloud property distributions based on satellite observations and sparse suborbital sampling. Recent efforts to make full use of A-Train aerosol sensor synergies will be highlighted. We describe planned field campaigns in the region to address the existing knowledge gaps. Specifically, we describe the scientific objectives and implementation of the five synergistic, international research activities aimed at providing some of the key aerosol and cloud properties and a process-level understanding of aerosol-cloud interactions over the SE Atlantic: NASA

  1. Active Oxidation of a UHTC-Based CMC

    NASA Technical Reports Server (NTRS)

    Glass, David E.; Splinter, Scott C.

    2012-01-01

    The active oxidation of ceramic matrix composites (CMC) is a severe problem that must be avoided for multi-use hypersonic vehicles. Much work has been performed studying the active oxidation of silicon-based CMCs such as C/SiC and SiC-coated carbon/carbon (C/C). Ultra high temperature ceramics (UTHC) have been proposed as a possible material solution for high-temperature applications on hypersonic vehicles. However, little work has been performed studying the active oxidation of UHTCs. The intent of this paper is to present test data indicating an active oxidation process for a UHTC-based CMC similar to the active oxidation observed with Si-based CMCs. A UHTC-based CMC was tested in the HyMETS arc-jet facility (or plasma wind tunnel, PWT) at NASA Langley Research Center, Hampton, VA. The coupon was tested at a nominal surface temperature of 3000 F (1650 C), with a stagnation pressure of 0.026 atm. A sudden and large increase in surface temperature was noticed with negligible increase in the heat flux, indicative of the onset of active oxidation. It is shown that the surface conditions, both temperature and pressure, fall within the region for a passive to active transition (PAT) of the oxidation.

  2. Fabrication of a metal membrane on a perforated polymer substrate by palladium aerosol activation and subsequent electroless plating.

    PubMed

    Byeon, Jeong Hoon; Hwang, Jungho

    2009-02-01

    Fabrication of a metal membrane on a perforated flexible poly(tetrafluoroethylene) (PTFE) substrate was developed by employing spark-generated palladium (Pd) aerosol activation and the subsequent electroless plating of Pd. After aerosol activation, Pd agglomerates of spark-generated primary particles (approximately 2.6 nm in diameter) with a face-centered-cubic structure were deposited uniformly on the PTFE substrate. Homogeneous Pd particles with an average size of 188 nm were tightly packed together to form a Pd membrane after Pd plating. The average plating rate of Pd during 30 min of plating at an activation intensity of 25 microg/cm(2) was 14.2 microg/cm(2) x min. PMID:20353212

  3. Interpreting the Ultraviolet Aerosol Index Observed with the OMI Satellite Instrument to Understand Absorption by Organic Carbon Aerosols and Implications for Atmospheric Oxidation

    NASA Astrophysics Data System (ADS)

    Hammer, M. S.; Martin, R.; van Donkelaar, A.; Buchard, V.; Torres, O.; Ridley, D. A.; Spurr, R. J. D.

    2015-12-01

    Absorption of solar radiation by aerosols plays a major role in radiative forcing and atmospheric photochemistry. Many atmospheric chemistry models tend to overestimate tropospheric OH concentrations compared to observations. Accurately representing aerosol absorption in the UV could help rectify the discrepancies between simulated and observed OH concentrations. We develop a simulation of the Ultraviolet Aerosol Index (UVAI), using the 3-D chemical transport model GEOS-Chem coupled with the Vector Linearized Discrete Ordinate Radiative Transfer model (VLIDORT). The simulation is applied to interpret UVAI observations from the Ozone Monitoring Instrument (OMI). Simulated and observed values are highly consistent in regions where mineral dust dominates the UVAI, but a large negative bias (-0.4 to -1.0) exists between simulated and observed values in biomass burning regions. We implement optical properties for absorbing organic aerosol, known as brown carbon (BrC), into GEOS-Chem and evaluate the simulation with observed UVAI values over biomass burning regions. The spectral dependence of absorption after adding BrC to the model is broadly consistent with reported observations for biomass burning aerosol, with Absorbing Angstrom Exponent (AAE) values ranging from 2.7 in the UV to 1.3 across the UV-Near IR spectrum. The addition of absorbing BrC decreases the mean bias between simulated and OMI UVAI values from -0.60 to -0.08 over North Africa in January, from -0.40 to -0.003 over South Asia in April, from -1.0 to -0.24 over southern Africa in July, and from -0.50 to +0.34 over South America in September. We assess the effect of the additional UV absorption by BrC on atmospheric photochemistry by examining ozone photolysis frequencies (J(O(1D))) and tropospheric OH concentrations in GEOS-Chem. The inclusion of BrC decreases J(O(1D)) and OH by up to 35% over biomass burning regions, and reduces the global bias in OH.

  4. Aerosol typing - key information from aerosol studies

    NASA Astrophysics Data System (ADS)

    Mona, Lucia; Kahn, Ralph; Papagiannopoulos, Nikolaos; Holzer-Popp, Thomas; Pappalardo, Gelsomina

    2016-04-01

    Aerosol typing is a key source of aerosol information from ground-based and satellite-borne instruments. Depending on the specific measurement technique, aerosol typing can be used as input for retrievals or represents an output for other applications. Typically aerosol retrievals require some a priori or external aerosol type information. The accuracy of the derived aerosol products strongly depends on the reliability of these assumptions. Different sensors can make use of different aerosol type inputs. A critical review and harmonization of these procedures could significantly reduce related uncertainties. On the other hand, satellite measurements in recent years are providing valuable information about the global distribution of aerosol types, showing for example the main source regions and typical transport paths. Climatological studies of aerosol load at global and regional scales often rely on inferred aerosol type. There is still a high degree of inhomogeneity among satellite aerosol typing schemes, which makes the use different sensor datasets in a consistent way difficult. Knowledge of the 4d aerosol type distribution at these scales is essential for understanding the impact of different aerosol sources on climate, precipitation and air quality. All this information is needed for planning upcoming aerosol emissions policies. The exchange of expertise and the communication among satellite and ground-based measurement communities is fundamental for improving long-term dataset consistency, and for reducing aerosol type distribution uncertainties. Aerosol typing has been recognized as one of its high-priority activities of the AEROSAT (International Satellite Aerosol Science Network, http://aero-sat.org/) initiative. In the AEROSAT framework, a first critical review of aerosol typing procedures has been carried out. The review underlines the high heterogeneity in many aspects: approach, nomenclature, assumed number of components and parameters used for the

  5. The Impact of Atmospheric Aerosols on the Fraction of absorbed Photosynthetically Active Radiation

    NASA Astrophysics Data System (ADS)

    Veroustraete, Frank

    2010-05-01

    Aerosol pollution attracts a growing interest from atmospheric scientists with regard to their impact on health, the global climate and vegetation stress. A hypothesis, less investigated, is whether atmospheric aerosol interactions in the solar radiation field affect the amount of radiation absorbed by vegetation canopies and hence terrestrial vegetation productivity. Typically, aerosols affect vegetation canopy radiation absorption efficiency by altering the physical characteristics of solar radiation incoming on for example a forest canopy. It has been illustrated, that increasing mixing ratio's of atmospheric particulate matter lead to a higher fraction of diffuse sunlight as opposed to direct sunlight. It can be demonstrated, based on the application of atmospheric (MODTRAN) and leaf/canopy radiative transfer (LIBERTY/SPRINT) models, that radiation absorption efficiency in the PAR band of Picea like forests increases with increasing levels of diffuse radiation. It can be documented - on a theoretical basis - as well, that increasing aerosol loads in the atmosphere, induce and increased canopy PAR absorption efficiency. In this paper it is suggested, that atmospheric aerosols have to be taken into account when estimating vegetation gross primary productivity (GPP). The results suggest that Northern hemisphere vegetation CO2 uptake magnitude may increase with increasing atmospheric aerosol loads. Many climate impact scenario's related to vegetation productivity estimates, do not take this phenomenon into account. Boldly speaking, the results suggest a larger sink function for terrestrial vegetation than generally accepted. Keywords: Aerosols, vegetation, fAPAR, CO2 uptake, diffuse radiation.

  6. An inexpensive active optical remote sensing instrument for assessing aerosol distributions.

    PubMed

    Barnes, John E; Sharma, Nimmi C P

    2012-02-01

    Air quality studies on a broad variety of topics from health impacts to source/sink analyses, require information on the distributions of atmospheric aerosols over both altitude and time. An inexpensive, simple to implement, ground-based optical remote sensing technique has been developed to assess aerosol distributions. The technique, called CLidar (Charge Coupled Device Camera Light Detection and Ranging), provides aerosol altitude profiles over time. In the CLidar technique a relatively low-power laser transmits light vertically into the atmosphere. The transmitted laser light scatters off of air molecules, clouds, and aerosols. The entire beam from ground to zenith is imaged using a CCD camera and wide-angle (100 degree) optics which are a few hundred meters from the laser. The CLidar technique is optimized for low altitude (boundary layer and lower troposphere) measurements where most aerosols are found and where many other profiling techniques face difficulties. Currently the technique is limited to nighttime measurements. Using the CLidar technique aerosols may be mapped over both altitude and time. The instrumentation required is portable and can easily be moved to locations of interest (e.g. downwind from factories or power plants, near highways). This paper describes the CLidar technique, implementation and data analysis and offers specifics for users wishing to apply the technique for aerosol profiles. PMID:22442935

  7. Cysteine redox sensor in PKGIa enables oxidant-induced activation.

    PubMed

    Burgoyne, Joseph R; Madhani, Melanie; Cuello, Friederike; Charles, Rebecca L; Brennan, Jonathan P; Schröder, Ewald; Browning, Darren D; Eaton, Philip

    2007-09-01

    Changes in the concentration of oxidants in cells can regulate biochemical signaling mechanisms that control cell function. We have found that guanosine 3',5'-monophosphate (cGMP)-dependent protein kinase (PKG) functions directly as a redox sensor. The Ialpha isoform, PKGIalpha, formed an interprotein disulfide linking its two subunits in cells exposed to exogenous hydrogen peroxide. This oxidation directly activated the kinase in vitro, and in rat cells and tissues. The affinity of the kinase for substrates it phosphorylates was enhanced by disulfide formation. This oxidation-induced activation represents an alternate mechanism for regulation along with the classical activation involving nitric oxide and cGMP. This mechanism underlies cGMP-independent vasorelaxation in response to oxidants in the cardiovascular system and provides a molecular explantion for how hydrogen peroxide can operate as an endothelium-derived hyperpolarizing factor. PMID:17717153

  8. Photochemical aging of light-absorbing secondary organic aerosol material.

    PubMed

    Sareen, Neha; Moussa, Samar G; McNeill, V Faye

    2013-04-11

    Dark reactions of methylglyoxal with NH4(+) in aqueous aerosols yield light-absorbing and surface-active products that can influence the physical properties of the particles. Little is known about how the product mixture and its optical properties will change due to photolysis as well as oxidative aging by O3 and OH in the atmosphere. Here, we report the results of kinetics and product studies of the photochemical aging of aerosols formed by atomizing aqueous solutions of methylglyoxal and ammonium sulfate. Experiments were performed using aerosol flow tube reactors coupled with an aerosol chemical ionization mass spectrometer (Aerosol-CIMS) for monitoring gas- and particle-phase compositions. Particles were also impacted onto quartz windows in order to assess changes in their UV-visible absorption upon oxidation. Photooxidation of the aerosols leads to the formation of small, volatile organic acids including formic acid, acetic acid, and glyoxylic acid. The atmospheric lifetime of these species during the daytime is predicted to be on the order of minutes, with photolysis being an important mechanism of degradation. The lifetime with respect to O3 oxidation was observed to be on the order of hours. O3 oxidation also leads to a net increase in light absorption by the particles due to the formation of additional carbonyl compounds. Our results are consistent with field observations of high brown carbon absorption in the early morning. PMID:23506538

  9. Aerosol Gemcitabine: Preclinical Safety and In Vivo Antitumor Activity in Osteosarcoma-Bearing Dogs

    PubMed Central

    Crabbs, Torrie A.; Wilson, Dennis W.; Cannan, Virginia A.; Skorupski, Katherine A.; Gordon, Nancy; Koshkina, Nadya; Kleinerman, Eugenie; Anderson, Peter M.

    2010-01-01

    Abstract Background Osteosarcoma is the most common skeletal malignancy in the dog and in young humans. Although chemotherapy improves survival time, death continues to be attributed to metastases. Aerosol delivery can provide a strategy with which to improve the lung drug delivery while reducing systemic toxicity. The purpose of this study is to assess the safety of a regional aerosol approach to chemotherapy delivery in osteosarcoma-bearing dogs, and second, to evaluate the effect of gemcitabine on Fas expression in the pulmonary metastasis. Methods We examined the systemic and local effects of aerosol gemcitabine on lung and pulmonary metastasis in this relevant large-animal tumor model using serial laboratory and arterial blood gas analysis and histopathology and immunohistochemistry, respectively. Results and Conclusions Six hundred seventy-two 1-h doses of aerosol gemcitabine were delivered. The treatment was well tolerated by these subjects with osteosarcoma (n = 20). Aerosol-treated subjects had metastatic foci that demonstrated extensive, predominately central, intratumoral necrosis. Fas expression was decreased in pulmonary metastases compared to the primary tumor (p = 0.008). After aerosol gemcitabine Fas expression in the metastatic foci was increased compared to lung metastases before treatment (p = 0.0075), and even was higher than the primary tumor (p = 0.025). Increased apoptosis (TUNEL) staining was also detected in aerosol gemcitabine treated metastasis compared to untreated controls (p = 0.028). The results from this pivotal translational study support the concept that aerosol gemcitabine may be useful against pulmonary metastases of osteosarcoma. Additional studies that evaluate the aerosol route of administration of gemcitabine in humans should be safe and are warranted. PMID:19803732

  10. DIESEL OXIDATION CATALYST CONTROL OF HYDROCARBON AEROSOLS FROM REACTIVITY CONTROLLED COMPRESSION IGNITION COMBUSTION

    SciTech Connect

    Prikhodko, Vitaly Y; Parks, II, James E; Barone, Teresa L; Curran, Scott; Cho, Kukwon; Lewis Sr, Samuel Arthur; Storey, John Morse; Wagner, Robert M

    2011-01-01

    Reactivity Controlled Compression Ignition (RCCI) is a novel combustion process that utilizes two fuels with different reactivity to stage and control combustion and enable homogeneous combustion. The technique has been proven experimentally in previous work with diesel and gasoline fuels; low NOx emissions and high efficiencies were observed from RCCI in comparison to conventional combustion. In previous studies on a multi-cylinder engine, particulate matter (PM) emission measurements from RCCI suggested that hydrocarbons were a major component of the PM mass. Further studies were conducted on this multi-cylinder engine platform to characterize the PM emissions in more detail and understand the effect of a diesel oxidation catalyst (DOC) on the hydrocarbon-dominated PM emissions. Results from the study show that the DOC can effectively reduce the hydrocarbon emissions as well as the overall PM from RCCI combustion. The bimodal size distribution of PM from RCCI is altered by the DOC which reduces the smaller mode 10 nm size particles.

  11. Effect of an activated sludge wastewater treatment plant on ambient air densities of aerosols containing bacteria and viruses.

    PubMed

    Fannin, K F; Vana, S C; Jakubowski, W

    1985-05-01

    Bacteria- and virus-containing aerosols were studied during the late summer and fall seasons in a midwestern suburb of the United States before and during the start-up and operation of an unenclosed activated sludge wastewater treatment plant. The study showed that the air in this suburban area contained low-level densities of indicator microorganisms. After the plant began operating, the densities of total aerobic bacteria-containing particles, standard plate count bacteria, total coliforms, fecal coliforms, fecal streptococci, and coliphages increased significantly in the air within the perimeter of the plant. Before plant operations, bacteria were detected from five genera, Klebsiella, Enterobacter, Serratia, Salmonella, and Aeromonas. During plant operations, the number of genera identified increased to 11. In addition to those genera found before plant operations, Escherichia, Providencia, Citrobacter, Acinetobacter, Pasteurella, and Proteus, were also identified. Enteric viruses were detected in low densities from the air emissions of this plant. Only standard plate count bacteria remained at significantly higher than base-line densities beyond 250 m downwind from the center of the aeration tanks. Fecal streptococci and coliphages appeared to be more stable in aerosols than the other indicator microorganisms studied. In general, the densities of microorganism-containing aerosols were higher at night than during the day. The techniques used in this study may be employed to establish microorganism-containing aerosol exposure during epidemiological investigations. PMID:2988442

  12. Oxidative Regulation of Large Conductance Calcium-Activated Potassium Channels

    PubMed Central

    Tang, Xiang D.; Daggett, Heather; Hanner, Markus; Garcia, Maria L.; McManus, Owen B.; Brot, Nathan; Weissbach, Herbert; Heinemann, Stefan H.; Hoshi, Toshinori

    2001-01-01

    Reactive oxygen/nitrogen species are readily generated in vivo, playing roles in many physiological and pathological conditions, such as Alzheimer's disease and Parkinson's disease, by oxidatively modifying various proteins. Previous studies indicate that large conductance Ca2+-activated K+ channels (BKCa or Slo) are subject to redox regulation. However, conflicting results exist whether oxidation increases or decreases the channel activity. We used chloramine-T, which preferentially oxidizes methionine, to examine the functional consequences of methionine oxidation in the cloned human Slo (hSlo) channel expressed in mammalian cells. In the virtual absence of Ca2+, the oxidant shifted the steady-state macroscopic conductance to a more negative direction and slowed deactivation. The results obtained suggest that oxidation enhances specific voltage-dependent opening transitions and slows the rate-limiting closing transition. Enhancement of the hSlo activity was partially reversed by the enzyme peptide methionine sulfoxide reductase, suggesting that the upregulation is mediated by methionine oxidation. In contrast, hydrogen peroxide and cysteine-specific reagents, DTNB, MTSEA, and PCMB, decreased the channel activity. Chloramine-T was much less effective when concurrently applied with the K+ channel blocker TEA, which is consistent with the possibility that the target methionine lies within the channel pore. Regulation of the Slo channel by methionine oxidation may represent an important link between cellular electrical excitability and metabolism. PMID:11222629

  13. The Formation and Aerosol Uptake of Isoprene Nitrooxyhydroxyepoxide (INHE), a Newly Identified Product from the RO2 + HO2 Pathway of Isoprene NO3 Oxidation

    NASA Astrophysics Data System (ADS)

    Schwantes, R.; Teng, A.; Nguyen, T.; Coggon, M. M.; Zhang, X.; Schilling-Fahnestock, K.; Crounse, J.; St Clair, J. M.; Seinfeld, J.; Wennberg, P. O.

    2014-12-01

    Isoprene (C5H8) reacts with the nitrate radical (NO3) during the night to produce a peroxy nitrate radical (RO2). This RO2 can react with nitrogen oxides (i.e., NO, NO2, or NO3) and other RO2 radicals to form isoprene nitrates or with the hydroperoxyl radical (HO2) to form nitrooxyhydroperoxide (INP). Both model and field studies have found that in the ambient atmosphere much of the RO2 radical reacts with HO2. More specifically, during the 2013 SOAS field campaign, INP was one of the main species that increased at sunset suggesting the RO2 + HO2 pathway from NO3 oxidation is important in the southeastern US and similar areas. However, chamber studies so far have been run under conditions that optimize RO2 + NO3 reactions and/or RO2 + RO2 reactions. In this work, we present a new way to run NO3 oxidation chamber experiments that optimize for the RO2 + HO2 pathway creating a more atmospherically relevant product distribution. The gas phase formation of INP and subsequent oxidation products were monitored using a chemical ionization mass spectrometer (CIMS). Because isoprene nitrates formed from NO3 oxidation react slowly with ozone (O3) and NO3, many of these nitrates will remain in the atmosphere until the sun rises and hydroxyl radical (OH) begins to form. Results from these chamber experiments suggest that OH will react with INP to form nitrooxyhydroxyepoxide (INHE), a newly identified product from INP. We suspect INHE could be important for Secondary Organic Aerosol (SOA) production due to its similarity to isoprene epoxydiol (IEPOX), a product from isoprene OH oxidation that has been shown to be a significant SOA precursor. We studied the uptake of INHE onto various seed types, and found that as expected INHE rapidly partitions to highly acidic seed aerosol due to an acid catalyzed ring opening. A time-of-flight aerosol mass spectrometer (ToF-AMS) was used to understand the chemical composition of the aerosol produced from the various seed types.

  14. Mitochondrial oxidant stress in locus coeruleus is regulated by activity and nitric oxide synthase.

    PubMed

    Sanchez-Padilla, Javier; Guzman, Jaime N; Ilijic, Ema; Kondapalli, Jyothisri; Galtieri, Daniel J; Yang, Ben; Schieber, Simon; Oertel, Wolfgang; Wokosin, David; Schumacker, Paul T; Surmeier, D James

    2014-06-01

    Loss of noradrenergic locus coeruleus (LC) neurons is a prominent feature of aging-related neurodegenerative diseases, such as Parkinson's disease (PD). The basis of this vulnerability is not understood. To explore possible physiological determinants, we studied LC neurons using electrophysiological and optical approaches in ex vivo mouse brain slices. We found that autonomous activity in LC neurons was accompanied by oscillations in dendritic Ca(2+) concentration that were attributable to the opening of L-type Ca(2+) channels. This oscillation elevated mitochondrial oxidant stress and was attenuated by inhibition of nitric oxide synthase. The relationship between activity and stress was malleable, as arousal and carbon dioxide increased the spike rate but differentially affected mitochondrial oxidant stress. Oxidant stress was also increased in an animal model of PD. Thus, our results point to activity-dependent Ca(2+) entry and a resulting mitochondrial oxidant stress as factors contributing to the vulnerability of LC neurons. PMID:24816140

  15. Field and Laboratory Studies of Atmospheric Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Coggon, Matthew Mitchell

    This thesis is the culmination of field and laboratory studies aimed at assessing processes that affect the composition and distribution of atmospheric organic aerosol. An emphasis is placed on measurements conducted using compact and high-resolution Aerodyne Aerosol Mass Spectrometers (AMS). The first three chapters summarize results from aircraft campaigns designed to evaluate anthropogenic and biogenic impacts on marine aerosol and clouds off the coast of California. Subsequent chapters describe laboratory studies intended to evaluate gas and particle-phase mechanisms of organic aerosol oxidation. The 2013 Nucleation in California Experiment (NiCE) was a campaign designed to study environments impacted by nucleated and/or freshly formed aerosol particles. Terrestrial biogenic aerosol with > 85% organic mass was observed to reside in the free troposphere above marine stratocumulus. This biogenic organic aerosol (BOA) originated from the Northwestern United States and was transported to the marine atmosphere during periodic cloud-clearing events. Spectra recorded by a cloud condensation nuclei counter demonstrated that BOA is CCN active. BOA enhancements at latitudes north of San Francisco, CA coincided with enhanced cloud water concentrations of organic species such as acetate and formate. Airborne measurements conducted during the 2011 Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE) were aimed at evaluating the contribution of ship emissions to the properties of marine aerosol and clouds off the coast of central California. In one study, analysis of organic aerosol mass spectra during periods of enhanced shipping activity yielded unique tracers indicative of cloud-processed ship emissions (m/z 42 and 99). The variation of their organic fraction (f42 and f 99) was found to coincide with periods of heavy (f 42 > 0.15; f99 > 0.04), moderate (0.05 < f42 < 0.15; 0.01 < f99 < 0.04), and negligible (f42 < 0.05; f99 < 0.01) ship influence. Application of

  16. Oxidative esterification via photocatalytic C-H activation

    EPA Science Inventory

    Direct oxidative esterification of alcohol via photocatalytic C-H activation has been developed using VO@g-C3N4 catalyst; an expeditious esterification of alcohols occurs under neutral conditions using visible light as the source of energy.

  17. Phase partitioning and volatility of secondary organic aerosol components formed from α-pinene ozonolysis and OH oxidation: the importance of accretion products and other low volatility compounds

    NASA Astrophysics Data System (ADS)

    Lopez-Hilfiker, F. D.; Mohr, C.; Ehn, M.; Rubach, F.; Kleist, E.; Wildt, J.; Mentel, Th. F.; Carrasquillo, A.; Daumit, K.; Hunter, J.; Kroll, J. H.; Worsnop, D.; Thornton, J. A.

    2015-02-01

    We measured a large suite of gas and particle phase multi-functional organic compounds with a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We focus here on results from experiments utilizing an ionization method most selective towards acids (acetate negative ion proton transfer), but our conclusions are based on more general physical and chemical properties of the SOA. Hundreds of compounds were observed in both gas and particle phases, the latter being detected upon temperature programmed thermal desorption of collected particles. Particulate organic compounds detected by the FIGAERO HR-ToF-CIMS are highly correlated with, and explain at least 25-50% of, the organic aerosol mass measured by an Aerodyne Aerosol Mass Spectrometer (AMS). Reproducible multi-modal structures in the thermograms for individual compounds of a given elemental composition reveal a significant SOA mass contribution from large molecular weight organics and/or oligomers (i.e. multi-phase accretion reaction products). Approximately 50% of the HR-ToF-CIMS particle phase mass is associated with compounds having effective vapor pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. The relative importance of these accretion-type and other extremely low volatility products appears to vary with photochemical conditions. We present a desorption temperature based framework for apportionment of thermogram signals into volatility bins. The volatility-based apportionment greatly improves agreement between measured and modeled gas-particle partitioning for select major and minor components of the SOA, consistent with thermal decomposition during desorption causing the conversion of

  18. Phase partitioning and volatility of secondary organic aerosol components formed from α-pinene ozonolysis and OH oxidation: the importance of accretion products and other low volatility compounds

    NASA Astrophysics Data System (ADS)

    Lopez-Hilfiker, F. D.; Mohr, C.; Ehn, M.; Rubach, F.; Kleist, E.; Wildt, J.; Mentel, Th. F.; Carrasquillo, A. J.; Daumit, K. E.; Hunter, J. F.; Kroll, J. H.; Worsnop, D. R.; Thornton, J. A.

    2015-07-01

    We measured a large suite of gas- and particle-phase multi-functional organic compounds with a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We focus here on results from experiments utilizing an ionization method most selective towards acids (acetate negative ion proton transfer), but our conclusions are based on more general physical and chemical properties of the SOA. Hundreds of compounds were observed in both gas and particle phases, the latter being detected by temperature-programmed thermal desorption of collected particles. Particulate organic compounds detected by the FIGAERO-HR-ToF-CIMS are highly correlated with, and explain at least 25-50 % of, the organic aerosol mass measured by an Aerodyne aerosol mass spectrometer (AMS). Reproducible multi-modal structures in the thermograms for individual compounds of a given elemental composition reveal a significant SOA mass contribution from high molecular weight organics and/or oligomers (i.e., multi-phase accretion reaction products). Approximately 50 % of the HR-ToF-CIMS particle-phase mass is associated with compounds having effective vapor pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. The relative importance of these accretion-type and other extremely low volatility products appears to vary with photochemical conditions. We present a desorption-temperature-based framework for apportionment of thermogram signals into volatility bins. The volatility-based apportionment greatly improves agreement between measured and modeled gas-particle partitioning for select major and minor components of the SOA, consistent with thermal decomposition during desorption causing the conversion of

  19. Phase partitioning and volatility of secondary organic aerosol components formed from α-pinene ozonolysis and OH oxidation: the importance of accretion products and other low volatility compounds

    DOE PAGESBeta

    Lopez-Hilfiker, F. D.; Mohr, C.; Ehn, M.; Rubach, F.; Kleist, E.; Wildt, J.; Mentel, Th. F.; Carrasquillo, A. J.; Daumit, K. E.; Hunter, J. F.; et al

    2015-07-16

    We measured a large suite of gas- and particle-phase multi-functional organic compounds with a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We focus here on results from experiments utilizing an ionization method most selective towards acids (acetate negative ion proton transfer), but our conclusions are based on more general physical and chemical properties of the SOA. Hundreds of compounds were observed in both gas andmore » particle phases, the latter being detected by temperature-programmed thermal desorption of collected particles. Particulate organic compounds detected by the FIGAERO–HR-ToF-CIMS are highly correlated with, and explain at least 25–50 % of, the organic aerosol mass measured by an Aerodyne aerosol mass spectrometer (AMS). Reproducible multi-modal structures in the thermograms for individual compounds of a given elemental composition reveal a significant SOA mass contribution from high molecular weight organics and/or oligomers (i.e., multi-phase accretion reaction products). Approximately 50 % of the HR-ToF-CIMS particle-phase mass is associated with compounds having effective vapor pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. The relative importance of these accretion-type and other extremely low volatility products appears to vary with photochemical conditions. We present a desorption-temperature-based framework for apportionment of thermogram signals into volatility bins. The volatility-based apportionment greatly improves agreement between measured and modeled gas-particle partitioning for select major and minor components of the SOA, consistent with thermal decomposition during desorption causing the

  20. Phase partitioning and volatility of secondary organic aerosol components formed from α-pinene ozonolysis and OH oxidation: the importance of accretion products and other low volatility compounds

    DOE PAGESBeta

    Lopez-Hilfiker, F. D.; Mohr, C.; Ehn, M.; Rubach, F.; Kleist, E.; Wildt, J.; Mentel, Th. F.; Carrasquillo, A.; Daumit, K.; Hunter, J.; et al

    2015-02-18

    We measured a large suite of gas and particle phase multi-functional organic compounds with a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We focus here on results from experiments utilizing an ionization method most selective towards acids (acetate negative ion proton transfer), but our conclusions are based on more general physical and chemical properties of the SOA. Hundreds of compounds were observed in both gasmore » and particle phases, the latter being detected upon temperature programmed thermal desorption of collected particles. Particulate organic compounds detected by the FIGAERO HR-ToF-CIMS are highly correlated with, and explain at least 25–50% of, the organic aerosol mass measured by an Aerodyne Aerosol Mass Spectrometer (AMS). Reproducible multi-modal structures in the thermograms for individual compounds of a given elemental composition reveal a significant SOA mass contribution from large molecular weight organics and/or oligomers (i.e. multi-phase accretion reaction products). Approximately 50% of the HR-ToF-CIMS particle phase mass is associated with compounds having effective vapor pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. The relative importance of these accretion-type and other extremely low volatility products appears to vary with photochemical conditions. We present a desorption temperature based framework for apportionment of thermogram signals into volatility bins. The volatility-based apportionment greatly improves agreement between measured and modeled gas–particle partitioning for select major and minor components of the SOA, consistent with thermal decomposition during desorption causing the

  1. Constraining Predicted Secondary Organic Aerosol Formation and Processing Using Real-Time Observations of Aging Urban Emissions in an Oxidation Flow Reactor

    NASA Astrophysics Data System (ADS)

    Ortega, A. M.; Palm, B. B.; Hayes, P. L.; Day, D. A.; Cubison, M.; Brune, W. H.; Hu, W.; Graus, M.; Warneke, C.; Gilman, J.; De Gouw, J. A.; Jimenez, J. L.

    2014-12-01

    To investigate atmospheric processing of urban emissions, we deployed an oxidation flow reactor with measurements of size-resolved chemical composition of submicron aerosol during CalNex-LA, a field study investigating air quality and climate change at a receptor site in the Los Angeles Basin. The reactor produces OH concentrations up to 4 orders of magnitude higher than in ambient air, achieving equivalent atmospheric aging of hours to ~2 weeks in 5 minutes of processing. The OH exposure (OHexp) was stepped every 20 min to survey the effects of a range of oxidation exposures on gases and aerosols. This approach is a valuable tool for in-situ evaluation of changes in organic aerosol (OA) concentration and composition due to photochemical processing over a range of ambient atmospheric conditions and composition. Combined with collocated gas-phase measurements of volatile organic compounds, this novel approach enables the comparison of measured SOA to predicted SOA formation from a prescribed set of precursors. Results from CalNex-LA show enhancements of OA and inorganic aerosol from gas-phase precursors. The OA mass enhancement from aging was highest at night and correlated with trimethylbenzene, indicating the importance of relatively short-lived VOC (OH lifetime of ~12 hrs or less) as SOA precursors in the LA Basin. Maximum net SOA production is observed between 3-6 days of aging and decreases at higher exposures. Aging in the reactor shows similar behavior to atmospheric processing; the elemental composition of ambient and reactor measurements follow similar slopes when plotted in a Van Krevelen diagram. Additionally, for air processed in the reactor, oxygen-to-carbon ratios (O/C) of aerosol extended over a larger range compared to ambient aerosol observed in the LA Basin. While reactor aging always increases O/C, often beyond maximum observed ambient levels, a transition from net OA production to destruction occurs at intermediate OHexp, suggesting a transition

  2. Surface fractal dimension, water adsorption efficiency, and cloud nucleation activity of insoluble aerosol.

    PubMed

    Laaksonen, Ari; Malila, Jussi; Nenes, Athanasios; Hung, Hui-Ming; Chen, Jen-Ping

    2016-01-01

    Surface porosity affects the ability of a substance to adsorb gases. The surface fractal dimension D is a measure that indicates the amount that a surface fills a space, and can thereby be used to characterize the surface porosity. Here we propose a new method for determining D, based on measuring both the water vapour adsorption isotherm of a given substance, and its ability to act as a cloud condensation nucleus when introduced to humidified air in aerosol form. We show that our method agrees well with previous methods based on measurement of nitrogen adsorption. Besides proving the usefulness of the new method for general surface characterization of materials, our results show that the surface fractal dimension is an important determinant in cloud drop formation on water insoluble particles. We suggest that a closure can be obtained between experimental critical supersaturation for cloud drop activation and that calculated based on water adsorption data, if the latter is corrected using the surface fractal dimension of the insoluble cloud nucleus. PMID:27138171

  3. Surface fractal dimension, water adsorption efficiency, and cloud nucleation activity of insoluble aerosol

    NASA Astrophysics Data System (ADS)

    Laaksonen, Ari; Malila, Jussi; Nenes, Athanasios; Hung, Hui-Ming; Chen, Jen-Ping

    2016-05-01

    Surface porosity affects the ability of a substance to adsorb gases. The surface fractal dimension D is a measure that indicates the amount that a surface fills a space, and can thereby be used to characterize the surface porosity. Here we propose a new method for determining D, based on measuring both the water vapour adsorption isotherm of a given substance, and its ability to act as a cloud condensation nucleus when introduced to humidified air in aerosol form. We show that our method agrees well with previous methods based on measurement of nitrogen adsorption. Besides proving the usefulness of the new method for general surface characterization of materials, our results show that the surface fractal dimension is an important determinant in cloud drop formation on water insoluble particles. We suggest that a closure can be obtained between experimental critical supersaturation for cloud drop activation and that calculated based on water adsorption data, if the latter is corrected using the surface fractal dimension of the insoluble cloud nucleus.

  4. Surface fractal dimension, water adsorption efficiency, and cloud nucleation activity of insoluble aerosol

    PubMed Central

    Laaksonen, Ari; Malila, Jussi; Nenes, Athanasios; Hung, Hui-Ming; Chen, Jen-Ping

    2016-01-01

    Surface porosity affects the ability of a substance to adsorb gases. The surface fractal dimension D is a measure that indicates the amount that a surface fills a space, and can thereby be used to characterize the surface porosity. Here we propose a new method for determining D, based on measuring both the water vapour adsorption isotherm of a given substance, and its ability to act as a cloud condensation nucleus when introduced to humidified air in aerosol form. We show that our method agrees well with previous methods based on measurement of nitrogen adsorption. Besides proving the usefulness of the new method for general surface characterization of materials, our results show that the surface fractal dimension is an important determinant in cloud drop formation on water insoluble particles. We suggest that a closure can be obtained between experimental critical supersaturation for cloud drop activation and that calculated based on water adsorption data, if the latter is corrected using the surface fractal dimension of the insoluble cloud nucleus. PMID:27138171

  5. An Energetic Perspective on Aerosol Radiative Forcing and Interactions with Atmospheric Wave Activity

    NASA Astrophysics Data System (ADS)

    Hosseinpour, F.; Wilcox, E. M.; Colarco, P. R.

    2014-12-01

    Aerosols have the capability to alter regional-scale atmospheric circulations. A better understanding of the contribution of aerosols to multi-scale atmospheric phenomena and their transient changes is crucial for efforts to evaluate climate predictions using next generation climate models. In this study we address the following questions: (1) Is there a mechanistic relationship between variability of oceanic dust aerosol forcing and transient changes in the African easterly jet- African easterly wave (AEJ-AEW) system? (2) What are the long-term impacts of possible aerosol-wave interactions on climate dynamics of eastern tropical Atlantic Ocean and western African monsoon (WAM) region during boreal summer seasons? Our hypothesis is that aerosol radiative forcing may act as additional energy source to fuel the development of African easterly waves on the northern and southern sides of the AEJ. Evidence in support of this hypothesis is presented based on analysis of an ensemble of NASA satellite data sets, including aerosol optical thickness (AOT) observations from the Moderate Resolution Imaging Spectro-radiometer (MODIS) and the Sea-Viewing Wide Field-of-View Sensor (SeaWiFS), as well as an atmospheric reanalysis from the Modern-Era Retrospective Analysis for Research and Applications (MERRA) and a simulation of global aerosol distributions made with the Goddard Earth Observing System Model version 5 (GEOS-5) Earth system model with meteorology constrained by MERRA and an assimilation of MODIS AOT (MERRAero). We propose that the impacts of Saharan aerosols on the regional climate dynamics occur through contributions to the eddy energy of waves with 2—7-day and 7—11-day variability.

  6. Chemical and physical influences on aerosol activation in liquid clouds: a study based on observations from the Jungfraujoch, Switzerland

    SciTech Connect

    Hoyle, Christopher R.; Webster, Clare S.; Rieder, Harald E.; Nenes, Athanasios; Hammer, Emanuel; Herrmann, Erik; Gysel, Martin; Bukowiecki, Nicolas; Weingartner, Ernest; Steinbacher, Martin; Baltensperger, Urs

    2016-01-01

    A simple statistical model to predict the number of aerosols which activate to form cloud droplets in warm clouds has been established, based on regression analysis of data from four summertime Cloud and Aerosol Characterisation Experiments (CLACE) at the high-altitude site Jungfraujoch (JFJ). It is shown that 79 % of the observed variance in droplet numbers can be represented by a model accounting only for the number of potential cloud condensation nuclei (defined as number of particles larger than 80 nm in diameter), while the mean errors in the model representation may be reduced by the addition of further explanatory variables, such as the mixing ratios of O3, CO, and the height of the measurements above cloud base. The statistical model has a similar ability to represent the observed droplet numbers in each of the individual years, as well as for the two predominant local wind directions at the JFJ (northwest and southeast). Given the central European location of the JFJ, with air masses in summer being representative of the free troposphere with regular boundary layer in-mixing via convection, we expect that this statistical model is generally applicable to warm clouds under conditions where droplet formation is aerosol limited (i.e. at relatively high updraught velocities and/or relatively low aerosol number concentrations). A comparison between the statistical model and an established microphysical parametrization shows good agreement between the two and supports the conclusion that cloud droplet formation at the JFJ is predominantly controlled by the number concentration of aerosol particles.

  7. Chemical and physical influences on aerosol activation in liquid clouds: a study based on observations from the Jungfraujoch, Switzerland

    NASA Astrophysics Data System (ADS)

    Hoyle, Christopher R.; Webster, Clare S.; Rieder, Harald E.; Nenes, Athanasios; Hammer, Emanuel; Herrmann, Erik; Gysel, Martin; Bukowiecki, Nicolas; Weingartner, Ernest; Steinbacher, Martin; Baltensperger, Urs

    2016-03-01

    A simple statistical model to predict the number of aerosols which activate to form cloud droplets in warm clouds has been established, based on regression analysis of data from four summertime Cloud and Aerosol Characterisation Experiments (CLACE) at the high-altitude site Jungfraujoch (JFJ). It is shown that 79 % of the observed variance in droplet numbers can be represented by a model accounting only for the number of potential cloud condensation nuclei (defined as number of particles larger than 80 nm in diameter), while the mean errors in the model representation may be reduced by the addition of further explanatory variables, such as the mixing ratios of O3, CO, and the height of the measurements above cloud base. The statistical model has a similar ability to represent the observed droplet numbers in each of the individual years, as well as for the two predominant local wind directions at the JFJ (northwest and southeast). Given the central European location of the JFJ, with air masses in summer being representative of the free troposphere with regular boundary layer in-mixing via convection, we expect that this statistical model is generally applicable to warm clouds under conditions where droplet formation is aerosol limited (i.e. at relatively high updraught velocities and/or relatively low aerosol number concentrations). A comparison between the statistical model and an established microphysical parametrization shows good agreement between the two and supports the conclusion that cloud droplet formation at the JFJ is predominantly controlled by the number concentration of aerosol particles.

  8. Chemical and physical influences on aerosol activation in liquid clouds: a study based on observations from the Jungfraujoch, Switzerland

    DOE PAGESBeta

    Hoyle, Christopher R.; Webster, Clare S.; Rieder, Harald E.; Nenes, Athanasios; Hammer, Emanuel; Herrmann, Erik; Gysel, Martin; Bukowiecki, Nicolas; Weingartner, Ernest; Steinbacher, Martin; et al

    2016-03-29

    In this study, a simple statistical model to predict the number of aerosols which activate to form cloud droplets in warm clouds has been established, based on regression analysis of data from four summertime Cloud and Aerosol Characterisation Experiments (CLACE) at the high-altitude site Jungfraujoch (JFJ). It is shown that 79 % of the observed variance in droplet numbers can be represented by a model accounting only for the number of potential cloud condensation nuclei (defined as number of particles larger than 80 nm in diameter), while the mean errors in the model representation may be reduced by the additionmore » of further explanatory variables, such as the mixing ratios of O3, CO, and the height of the measurements above cloud base. The statistical model has a similar ability to represent the observed droplet numbers in each of the individual years, as well as for the two predominant local wind directions at the JFJ (northwest and southeast). Given the central European location of the JFJ, with air masses in summer being representative of the free troposphere with regular boundary layer in-mixing via convection, we expect that this statistical model is generally applicable to warm clouds under conditions where droplet formation is aerosol limited (i.e. at relatively high updraught velocities and/or relatively low aerosol number concentrations). Finally, a comparison between the statistical model and an established microphysical parametrization shows good agreement between the two and supports the conclusion that cloud droplet formation at the JFJ is predominantly controlled by the number concentration of aerosol particles.« less

  9. Impacts Of Radiatively-Active Aerosols On Mars’ Current Climate: Simulation Results With The NASA ARC Mars GCM

    NASA Astrophysics Data System (ADS)

    Hollingsworth, Jeffery L.; Kahre, M. A.; Haberle, R. M.; Montmessin, F.; Herin, B.; Laamoumi, F.; Wilson, R. J.; Schaeffer, J.

    2010-10-01

    Recent upgrades to the NASA Ames Research Center (ARC) Mars general circulation model (GCM) include a fundamentally new and modernized radiative transfer package which permits radiative effects and interactions of suspended atmospheric aerosols (e.g., water ice clouds, water vapor, dust, and their mutual interactions) to influence the net diabatic heating rate within the atmosphere. Such aerosols are critically important in determining the nature of atmospheric thermal structure and hence the overall climate of the planet. Our Mars GCM simulations indicate that radiatively-active water ice clouds profoundly affect the seasonal and annual mean climate in a variety of ways. In particular, preliminary results suggest that the bulk thermal structure and resultant (i.e., balanced) circulation patterns are strongly modified near the surface and aloft. Generally speaking, we find a bulk warming of the atmosphere in upper layers, a cooling of the atmosphere in the lower and near-surface regions, and, increases in the mean pole-to-equator temperature contrasts (i.e., stronger mean polar vortices). A variety of results from our baseline and control simulations (i.e., where the radiative/physical effects are examined in isolation and when combined) will be presented. Comparisons with MGS/TES and MRO/MCS measurements indicate better agreement between the model's simulated climate compared to that observed. Using a state-of-the-art Mars GCM, these results highlight important effects radiatively-active aerosols have on physical and dynamical processes active in the current climate of Mars.

  10. Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation

    PubMed Central

    Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H.; Navrotsky, Alexandra

    2013-01-01

    Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn3+/Mn4+ ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states. PMID:23667149

  11. 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

  12. Mitochondrial oxidant stress in locus coeruleus is regulated by activity and nitric oxide synthase

    PubMed Central

    Sanchez–Padilla, J.; Guzman, J.N.; Ilijic, E.; Kondapalli, J.; Galtieri, D.J.; Yang, B.; Schieber, S.; Oertel, W.; Wokosin, D.; Schumacker, P. T.; Surmeier, D. J.

    2014-01-01

    Summary Loss of noradrenergic locus coeruleus (LC) neurons is a prominent feature of aging–related neurodegenerative diseases, like Parkinson’s disease (PD). The basis of this vulnerability is not understood. To explore possible physiological determinants, LC neurons were studied using electrophysiological and optical approaches in ex vivo mouse brain slices. These studies revealed that autonomous activity in LC neurons was accompanied by oscillations in dendritic Ca2+ concentration attributable to opening of L–type Ca2+ channels. This oscillation elevated mitochondrial oxidant stress and was attenuated by inhibition of nitric oxide synthase. The relationship between activity and stress was malleable, as arousal and carbon dioxide, each increased the spike rate, but differentially affected mitochondrial oxidant stress. Oxidant stress also was increased in an animal model of PD. Thus, our results point to activity–dependent Ca2+ entry and a resulting mitochondrial oxidant stress as factors contributing to the vulnerability of LC neurons. PMID:24816140

  13. Interpreting the ultraviolet aerosol index observed with the OMI satellite instrument to understand absorption by organic aerosols: implications for atmospheric oxidation and direct radiative effects

    NASA Astrophysics Data System (ADS)

    Hammer, Melanie S.; Martin, Randall V.; van Donkelaar, Aaron; Buchard, Virginie; Torres, Omar; Ridley, David A.; Spurr, Robert J. D.

    2016-03-01

    Satellite observations of the ultraviolet aerosol index (UVAI) are sensitive to absorption of solar radiation by aerosols; this absorption affects photolysis frequencies and radiative forcing. We develop a global simulation of the UVAI using the 3-D chemical transport model GEOS-Chem coupled with the Vector Linearized Discrete Ordinate Radiative Transfer model (VLIDORT). The simulation is applied to interpret UVAI observations from the Ozone Monitoring Instrument (OMI) for the year 2007. Simulated and observed values are highly consistent in regions where mineral dust dominates the UVAI, but a large negative bias (-0.32 to -0.97) exists between simulated and observed values in biomass burning regions. We determine effective optical properties for absorbing organic aerosol, known as brown carbon (BrC), and implement them into GEOS-Chem to better represent observed UVAI values over biomass burning regions. The inclusion of absorbing BrC decreases the mean bias between simulated and OMI UVAI values from -0.57 to -0.09 over West Africa in January, from -0.32 to +0.0002 over South Asia in April, from -0.97 to -0.22 over southern Africa in July, and from -0.50 to +0.33 over South America in September. The spectral dependence of absorption after including BrC in the model is broadly consistent with reported observations for biomass burning aerosol, with absorbing Ångström exponent (AAE) values ranging from 2.9 in the ultraviolet (UV) to 1.3 across the UV-Near IR spectrum. We assess the effect of the additional UV absorption by BrC on atmospheric photochemistry by examining tropospheric hydroxyl radical (OH) concentrations in GEOS-Chem. The inclusion of BrC decreases OH by up to 30 % over South America in September, up to 20 % over southern Africa in July, and up to 15 % over other biomass burning regions. Global annual mean OH concentrations in GEOS-Chem decrease due to the presence of absorbing BrC, increasing the methyl chloroform lifetime from 5.62 to 5.68 years

  14. Interpreting the Ultraviolet Aerosol Index observed with the OMI satellite instrument to understand absorption by organic aerosols: implications for atmospheric oxidation and direct radiative effects

    NASA Astrophysics Data System (ADS)

    Hammer, M. S.; Martin, R. V.; van Donkelaar, A.; Buchard, V.; Torres, O.; Ridley, D. A.; Spurr, R. J. D.

    2015-10-01

    Satellite observations of the Ultraviolet Aerosol Index (UVAI) are sensitive to absorption of solar radiation by aerosols; this absorption affects photolysis frequencies and radiative forcing. We develop a global simulation of the UVAI using the 3-D chemical transport model GEOS-Chem coupled with the Vector Linearized Discrete Ordinate Radiative Transfer model (VLIDORT). The simulation is applied to interpret UVAI observations from the Ozone Monitoring Instrument (OMI) for the year 2007. Simulated and observed values are highly consistent in regions where mineral dust dominates the UVAI, but a large negative bias (-0.32 to -0.97) exists between simulated and observed values in biomass burning regions. We determine effective optical properties for absorbing organic aerosol, known as brown carbon (BrC), and implement them into GEOS-Chem to better represent observed UVAI values over biomass burning regions. The addition of absorbing BrC decreases the mean bias between simulated and OMI UVAI values from -0.57 to -0.09 over West Africa in January, from -0.32 to +0.0002 over South Asia in April, from -0.97 to -0.22 over southern Africa in July, and from -0.50 to +0.33 over South America in September. The spectral dependence of absorption after adding BrC to the model is broadly consistent with reported observations for biomass burning aerosol, with Absorbing Angstrom Exponent (AAE) values ranging from 2.9 in the ultraviolet (UV) to 1.3 across the UV-Near IR spectrum. We assess the effect of the additional UV absorption by BrC on atmospheric photochemistry by examining tropospheric hydroxyl radical (OH) concentrations in GEOS-Chem. The inclusion of BrC decreases OH by up to 35 % over South America in September, up to 25 % over southern Africa in July, and up to 20 % over other biomass burning regions. Global annual mean OH concentrations in GEOS-Chem decrease due to the presence of absorbing BrC, increasing the methyl chloroform lifetime from 5.62 to 5.68 years, thus

  15. Interpreting the Ultraviolet Aerosol Index Observed with the OMI Satellite Instrument to Understand Absorption by Organic Aerosols: Implications for Atmospheric Oxidation and Direct Radiative Effects

    NASA Technical Reports Server (NTRS)

    Hammer, Melanie S.; Martin, Randall V.; Donkelaar, Aaron van; Buchard, Virginie; Torres, Omar; Ridley, David A.; Spurr, Robert J. D.

    2016-01-01

    Satellite observations of the ultraviolet aerosol index (UVAI) are sensitive to absorption of solar radiation by aerosols; this absorption affects photolysis frequencies and radiative forcing. We develop a global simulation of the UVAI using the 3-D chemical transport model GEOSChem coupled with the Vector Linearized Discrete Ordinate Radiative Transfer model (VLIDORT). The simulation is applied to interpret UVAI observations from the Ozone Monitoring Instrument (OMI) for the year 2007. Simulated and observed values are highly consistent in regions where mineral dust dominates the UVAI, but a large negative bias (-0.32 to -0.97) exists between simulated and observed values in biomass burning regions. We determine effective optical properties for absorbing organic aerosol, known as brown carbon (BrC), and implement them into GEOS-Chem to better represent observed UVAI values over biomass burning regions. The inclusion of absorbing BrC decreases the mean bias between simulated and OMI UVAI values from -0.57 to -0.09 over West Africa in January, from -0.32 to +0.0002 over South Asia in April, from -0.97 to -0.22 over southern Africa in July, and from -0.50 to +0.33 over South America in September. The spectral dependence of absorption after including BrC in the model is broadly consistent with reported observations for biomass burning aerosol, with absorbing Angstrom exponent (AAE) values ranging from 2.9 in the ultraviolet (UV) to 1.3 across the UV-Near IR spectrum. We assess the effect of the additional UV absorption by BrC on atmospheric photochemistry by examining tropospheric hydroxyl radical (OH) concentrations in GEOS-Chem. The inclusion of BrC decreases OH by up to 30% over South America in September, up to 20% over southern Africa in July, and up to 15% over other biomass burning regions. Global annual mean OH concentrations in GEOS-Chem decrease due to the presence of absorbing BrC, increasing the methyl chloroform lifetime from 5.62 to 5.68 years, thus

  16. Anionic, Cationic, and Nonionic Surfactants in Atmospheric Aerosols from the Baltic Coast at Askö, Sweden: Implications for Cloud Droplet Activation.

    PubMed

    Gérard, Violaine; Nozière, Barbara; Baduel, Christine; Fine, Ludovic; Frossard, Amanda A; Cohen, Ronald C

    2016-03-15

    Recent analyses of atmospheric aerosols from different regions have demonstrated the ubiquitous presence of strong surfactants and evidenced surface tension values, σ, below 40 mN m(-1), suspected to enhance the cloud-forming potential of these aerosols. In this work, this approach was further improved and combined with absolute concentration measurements of aerosol surfactants by colorimetric titration. This analysis was applied to PM2.5 aerosols collected at the Baltic station of Askö, Sweden, from July to October 2010. Strong surfactants were found in all the sampled aerosols, with σ = (32-40) ± 1 mN m(-1) and concentrations of at least 27 ± 6 mM or 104 ± 21 pmol m(-3). The absolute surface tension curves and critical micelle concentrations (CMC) determined for these aerosol surfactants show that (1) surfactants are concentrated enough in atmospheric particles to strongly depress the surface tension until activation, and (2) the surface tension does not follow the Szyszkowski equation during activation but is nearly constant and minimal, which provides new insights on cloud droplet activation. In addition, both the CMCs determined and the correlation (R(2) ∼ 0.7) between aerosol surfactant concentrations and chlorophyll-a seawater concentrations suggest a marine and biological origin for these compounds. PMID:26895279

  17. Nanostructured manganese oxides as highly active water oxidation catalysts: a boost from manganese precursor chemistry.

    PubMed

    Menezes, Prashanth W; Indra, Arindam; Littlewood, Patrick; Schwarze, Michael; Göbel, Caren; Schomäcker, Reinhard; Driess, Matthias

    2014-08-01

    We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1oxidizing agent. Photocatalytic water oxidation in the presence of [Ru(bpy)3 ](2+) (bpy=2,2'-bipyridine) as a sensitizer and peroxodisulfate as an electron acceptor was carried out for all three manganese oxides including the newly formed amorphous MnOx . Both Mn2 O3 and the amorphous MnOx exhibit tremendous enhancement in oxygen evolution during photocatalysis and are much higher in comparison to so far known bioinspired manganese oxides and calcium-manganese oxides. Also, for the first time, a new approach for the representation of activities of water oxidation catalysts has been proposed by determining the amount of accessible manganese centers. PMID:25044528

  18. Variability of CCN Activation Behaviour of Aerosol Particles in the Marine Boundary Layer of the Northern and Southern Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Henning, Silvia; Dieckmann, Katrin; Hartmann, Susan; Schäfer, Michael; Wu, Zhijun; Merkel, Maik; Wiedensohler, Alfred; Stratmann, Frank

    2013-04-01

    The variability of cloud condensation nucleus (CCN) activation behaviour and total CCN number concentrations was investigated during three ship cruises. Measurements were performed in a mobile laboratory on the German research vessel FS Polarstern cruising between Cape Town and Bremerhaven (April / May and October / November 2011) as well as between Punta Arenas and Bremerhaven (April / May 2012). CCN size distributions were measured for supersaturations between 0.1% and 0.4% using a Cloud Condensation Nucleus Counter (DMT, USA). Aerosol particle and CCN total number concentrations as well as the hygroscopicity parameter κ (Petters and Kreidenweis, 2007) were determined. Furthermore, size distribution data were collected. The hygroscopicity parameter κ featured a high variability during the cruises, with a median κ-value of 0.52 ± 0.26. The κ-values are depended on air mass origin; and are as expected mainly dominated by marine influences, but also long range transport of aerosol particles was detected. In the Celtic Sea, κ was found to be lower than that of clean marine aerosol particles (0.72 ± 0.24; Pringle et al., 2010) with κ-values ~0.2, possibly influenced by anthropogenic emissions from Europe. Close to the West African coast particle hygroscopicity was found to be influenced by the Saharan dust plume, resulting in low κ-values ~0.25. Petters, M.D. and S.M. Kreidenweis (2007), A single parameter representation of hygroscopic growth and cloud condensation nucleus activity, Atmos. Chem. and Phys., 7, 1961-1971. Pringle, K.J., H. Tost, A. Pozzer, U. Pöschl, and J. Lelieveld (2010), Global distribution of the effective aerosol hygroscopicity parameter for CCN activation, Atmos. Chem. Phys., 10, 5241-5255.

  19. A Supramolecularly Activated Radical Cation for Accelerated Catalytic Oxidation.

    PubMed

    Jiao, Yang; Li, Wan-Lu; Xu, Jiang-Fei; Wang, Guangtong; Li, Jun; Wang, Zhiqiang; Zhang, Xi

    2016-07-25

    Tuning the activity of radicals is crucial for radical reactions and radical-based materials. Herein, we report a supramolecular strategy to accelerate the Fenton reaction through the construction of supramolecularly activated radical cations. As a proof of the concept, cucurbit[7]uril (CB[7]) was introduced, through host-guest interactions, onto each side of a derivative of 1,4-diketopyrrolo[3,4-c]pyrrole (DPP), a model dye for Fenton oxidation. The DPP radical cation, the key intermediate in the oxidation process, was activated by the electrostatically negative carbonyl groups of CB[7]. The activation induced a drastic decrease in the apparent activation energy and greatly increased the reaction rate. This facile supramolecular strategy is a promising method for promoting radical reactions. It may also open up a new route for the catalytic oxidation of organic pollutants for water purification and widen the realm of supramolecular catalysis. PMID:27273046

  20. 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

  1. Atmospheric reactivity of hydroxyl radicals with guaiacol (2-methoxyphenol), a biomass burning emitted compound: Secondary organic aerosol formation and gas-phase oxidation products

    NASA Astrophysics Data System (ADS)

    Lauraguais, Amélie; Coeur-Tourneur, Cécile; Cassez, Andy; Deboudt, Karine; Fourmentin, Marc; Choël, Marie

    2014-04-01

    Methoxyphenols are low molecular weight semi-volatile polar aromatic compounds produced from the pyrolysis of wood lignin. The reaction of guaiacol (2-methoxyphenol) with hydroxyl radicals has been studied in the LPCA simulation chamber at (294 ± 2) K, atmospheric pressure, low relative humidity (RH < 1%) and under high-NOx conditions using CH3ONO as OH source. The aerosol production was monitored using a SMPS (Scanning Mobility Particle Sizer); the SOA yields were in the range from 0.003 to 0.87 and the organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. Transmission (TEM) and Scanning (SEM) Electron Microscopy observations were performed to characterize the physical state of SOA produced from the OH reaction with guaiacol; they display both liquid and solid particles (in an amorphous state). GC-FID (Gas Chromatography - Flame Ionization Detection) and GC-MS (Gas Chromatography - Mass Spectrometry) analysis show the formation of nitroguaiacol isomers as main oxidation products in the gas- and aerosol-phases. In the gas-phase, the formation yields were (10 ± 2) % for 4-nitroguaiacol (1-hydroxy-2-methoxy-4-nitrobenzene; 4-NG) and (6 ± 2) % for 3- or 6-nitroguaiacol (1-hydroxy-2-methoxy-3-nitrobenzene or 1-hydroxy-2-methoxy-6-nitrobenzene; 3/6-NG; the standards are not commercially available so both isomers cannot be distinguished) whereas in SOA their yield were much lower (≤0.1%). To our knowledge, this work represents the first identification of nitroguaiacols as gaseous oxidation products of the OH reaction with guaiacol. As the reactivity of nitroguaiacols with atmospheric oxidants is probably low, we suggest using them as biomass burning emission gas tracers. The atmospheric implications of the guaiacol + OH reaction are also discussed.

  2. Comparison of secondary organic aerosol formed with an aerosol flow reactor and environmental reaction chambers: effect of oxidant concentration, exposure time and seed particles on chemical composition and yield

    DOE PAGESBeta

    Lambe, A. T.; Chhabra, P. S.; Onasch, T. B.; Brune, W. H.; Hunter, J. F.; Kroll, J. H.; Cummings, M. J.; Brogan, J. F.; Parmar, Y.; Worsnop, D. R.; et al

    2014-12-02

    We performed a systematic intercomparison study of the chemistry and yields of SOA generated from OH oxidation of a common set of gas-phase precursors in a Potential Aerosol Mass (PAM) continuous flow reactor and several environmental chambers. In the flow reactor, SOA precursors were oxidized using OH concentrations ranging from 2.0×108 to 2.2×1010 molec cm-3 over exposure times of 100 s. In the environmental chambers, precursors were oxidized using OH concentrations ranging from 2×106 to 2×107 molec cm-3 over exposure times of several hours. The OH concentration in the chamber experiments is close to that found in the atmosphere, butmore » the integrated OH exposure in the flow reactor can simulate atmospheric exposure times of multiple days compared to chamber exposure times of only a day or so. A linear correlation analysis of the mass spectra (m=0.91–0.92, r2=0.93–0.94) and carbon oxidation state (m=1.1, r2=0.58) of SOA produced in the flow reactor and environmental chambers for OH exposures of approximately 1011 molec cm-3 s suggests that the composition of SOA produced in the flow reactor and chambers is the same within experimental accuracy as measured with an aerosol mass spectrometer. This similarity in turn suggests that both in the flow reactor and in chambers, SOA chemical composition at low OH exposure is governed primarily by gas-phase OH oxidation of the precursors, rather than heterogeneous oxidation of the condensed particles. In general, SOA yields measured in the flow reactor are lower than measured in chambers for the range of equivalent OH exposures that can be measured in both the flow reactor and chambers. The influence of sulfate seed particles on isoprene SOA yield measurements was examined in the flow reactor. The studies show that seed particles increase the yield of SOA produced in flow reactors by a factor of 3 to 5 and may also account in part for higher SOA yields obtained in the chambers, where seed particles are

  3. Can we better use existing and emerging computing hardware to embed activity coefficient predictions in complex atmospheric aerosol models?

    NASA Astrophysics Data System (ADS)

    Topping, David; Alibay, Irfan; Ruske, Simon; Hindriksen, Vincent; Noisternig, Michael

    2016-04-01

    To predict the evolving concentration, chemical composition and ability of aerosol particles to act as cloud droplets, we rely on numerical modeling. Mechanistic models attempt to account for the movement of compounds between the gaseous and condensed phases at a molecular level. This 'bottom up' approach is designed to increase our fundamental understanding. However, such models rely on predicting the properties of molecules and subsequent mixtures. For partitioning between the gaseous and condensed phases this includes: saturation vapour pressures; Henrys law coefficients; activity coefficients; diffusion coefficients and reaction rates. Current gas phase chemical mechanisms predict the existence of potentially millions of individual species. Within a dynamic ensemble model, this can often be used as justification for neglecting computationally expensive process descriptions. Indeed, on whether we can quantify the true sensitivity to uncertainties in molecular properties, even at the single aerosol particle level it has been impossible to embed fully coupled representations of process level knowledge with all possible compounds, typically relying on heavily parameterised descriptions. Relying on emerging numerical frameworks, and designed for the changing landscape of high-performance computing (HPC), in this study we show that comprehensive microphysical models from single particle to larger scales can be developed to encompass a complete state-of-the-art knowledge of aerosol chemical and process diversity. We focus specifically on the ability to capture activity coefficients in liquid solutions using the UNIFAC method, profiling traditional coding strategies and those that exploit emerging hardware.

  4. Assessment of aerosol-cloud interactions during southern African biomass burning activity, employing cloud parameterizations

    NASA Astrophysics Data System (ADS)

    Wiston, Modise; McFiggans, Gordon; Schultz, David

    2015-04-01

    In this study, we perform a simulation of the spatial distributions of particle and gas concentrations from a significantly large source of pollution event during a dry season in southern Africa and their interactions with cloud processes. Specific focus is on the extent to which cloud-aerosol interactions are affected by various inputs (i.e. emissions) and parameterizations and feedback mechanisms in a coupled mesoscale chemistry-meteorology model -herein Weather Research and Forecasting model with chemistry (WRF-Chem). The southern African dry season (May-Sep) is characterised by biomass burning (BB) type of pollution. During this period, BB particles are frequently observed over the subcontinent, at the same time a persistent deck of stratocumulus covers the south West African coast, favouring long-range transport over the Atlantic Ocean of aerosols above clouds. While anthropogenic pollutants tend to spread more over the entire domain, biomass pollutants are concentrated around the burning areas, especially the savannah and tropical rainforest of the Congo Basin. BB is linked to agricultural practice at latitudes south of 10° N. During an intense burning event, there is a clear signal of strong interactions of aerosols and cloud microphysics. These species interfere with the radiative budget, and directly affect the amount of solar radiation reflected and scattered back to space and partly absorbed by the atmosphere. Aerosols also affect cloud microphysics by acting as cloud condensation nuclei (CCN), modifying precipitation pattern and the cloud albedo. Key area is to understand the role of pollution on convective cloud processes and its impacts on cloud dynamics. The hypothesis is that an environment of potentially high pollution enables the probability of interactions between co-located aerosols and cloud layers. To investigate this hypothesis, we outline an approach to integrate three elements: i) focusing on regime(s) where there are strong indications of

  5. Size-spectra of trace elements in urban aerosol particles by instrumental neutron activation analysis

    SciTech Connect

    Ondov, J.M.; Divita, F. Jr.; Suarez, A.

    1994-12-31

    Knowledge of composition and size of atmospheric aerosol particles is needed to elucidate their sources, atmospheric transformation processes, contributions to visibility reduction, and respiratory and environmental deposition. In a previous communication, we described size spectra and hygroscopic growth of arsenic, selenium, antimony, and zinc in College Park, Maryland, an urban, nonindustrial area located near Washington, D.C., wherein, concentrations of these elements are influenced largely by sulfate-containing aerosol transported from the Ohio River valley region, more than 200 km west of the area, and local coal utility plants and incinerators located 20 to 50 km from the sampling site. At College Park, mass median aerodynamic diameters (mmad) versus relative humidity (RH) data for these elements fell along different curves for samples influenced by local and distant aerosols; i.e., the curve for distant sources lay below the curve for local sources, at larger mmads for the same RH. In this paper we discuss size spectra, distribution parameters, and hygroscopic growth of aerosol particles bearing trace elements in aerosol collected in Camden, New Jersey, a heavily industrial area in which major sources, including an antimony roaster and municipal incinerator, lie in close proximity (i.e., 5 to 15 km) to the site.

  6. Hygroscopicity of aerosol particles and CCN activity of nearly hydrophobic particles in the urban atmosphere over Japan during summer

    NASA Astrophysics Data System (ADS)

    Ogawa, Shuhei; Setoguchi, Yoshitaka; Kawana, Kaori; Nakayama, Tomoki; Ikeda, Yuka; Sawada, Yuuki; Matsumi, Yutaka; Mochida, Michihiro

    2016-06-01

    We investigated the hygroscopicity of 150 nm particles and the number-size distributions and the cloud condensation nuclei (CCN) activity of nearly hydrophobic particles in aerosols over Nagoya, Japan, during summer. We analyzed the correlations between the number concentrations of particles in specific hygroscopic growth factor (g) ranges and the mass concentrations of chemical components. This analysis suggests the association of nearly hydrophobic particles with hydrocarbon-like organic aerosol, elemental carbon and semivolatile oxygenated organic aerosol (SV-OOA), that of less hygroscopic particles with SV-OOA and nitrate and that of more hygroscopic particles with low-volatile oxygenated organic aerosol (LV-OOA) and sulfate. The hygroscopicity parameter (κ) of organics was derived based on the g distributions and chemical composition of 150 nm particles. The κ of the organics correlated positively with the fraction of the total organic mass spectral signal at m/z 44 and the volume fraction of the LV-OOA to the organics, indicating that organics with highly oxygenated structures including carboxylic acid groups contribute to the water uptake. The number-size distributions of the nearly hydrophobic particles with g around 1.0 and 1.1 correlated with the mass concentrations of chemical components. The results show that the chemical composition of the particles with g around 1.0 was different between the Aitken mode and the accumulation mode size ranges. An analysis for a parameter Fmax of the curves fitted to the CCN efficiency spectra of the particles with g around 1.0 suggests that the coating by organics associated with SV-OOA elevated the CCN activity of these particles.

  7. Properties of the stratospheric aerosol layer studied with a one-dimensional computer model

    NASA Technical Reports Server (NTRS)

    Turco, R. P.; Toon, O. B.; Whitten, R. C.; Hamill, P.; Kiang, C. S.

    1978-01-01

    Aerosol particle effects are often neglected in theoretical studies of stratospheric phenomena. In reality, the particulate matter normally found above the tropopause may influence the terrestrial radiation balance, catalyze heterogeneous chemical interactions, and serve as a tracer of atmospheric motions. The paper proposes a one-dimensional model of the stratospheric aerosol layer, and it is used to compare aerosol theory with observational data. The model considers gaseous sulfur photochemistry and the physical aerosol processes of nucleation, coagulation, sedimentation, and diffusion. Calculations of the effects on the aerosol layer of stratospheric injections of aluminum oxide particles by Space Shuttle engines and of sulfur dioxide molecules by volcanic activity are performed. The relation between measured aerosol variability and changes in stratospheric air temperatures and vertical transport rates are discussed.

  8. Tubular solid oxide fuel cell demonstration activities

    SciTech Connect

    Veyo, S.E.

    1995-08-01

    The development of a viable fuel cell driven electrical power generation system involves not only the development of cell and stack technology, but also the development of the overall system concept, the strategy for control, and the ancillary subsystems. The design requirements used to guide system development must reflect a customer focus in order to evolve a commercial product. In order to obtain useful customer feedback, Westinghouse has practiced the deployment with customers of fully integrated, automatically controlled, packaged solid oxide fuel cell power generation systems. These field units have served to demonstrate to customers first hand the beneficial attributes of the SOFC, to expose deficiencies through experience in order to guide continued development, and to garner real world feedback and data concerning not only cell and stack parameters, but also transportation, installation, permitting and licensing, start-up and shutdown, system alarming, fault detection, fault response, and operator interaction.

  9. Contribution of methane to aerosol carbon mass

    NASA Astrophysics Data System (ADS)

    Bianchi, F.; Barmet, P.; Stirnweis, L.; El Haddad, I.; Platt, S. M.; Saurer, M.; Lötscher, C.; Siegwolf, R.; Bigi, A.; Hoyle, C. R.; DeCarlo, P. F.; Slowik, J. G.; Prévôt, A. S. H.; Baltensperger, U.; Dommen, J.

    2016-09-01

    Small volatile organic compounds (VOC) such as methane (CH4) have long been considered non-relevant to aerosol formation due to the high volatility of their oxidation products. However, even low aerosol yields from CH4, the most abundant VOC in the atmosphere, would contribute significantly to the total particulate carbon budget. In this study, organic aerosol (OA) mass yields from CH4 oxidation were evaluated at the Paul Scherrer Institute (PSI) smog chamber in the presence of inorganic and organic seed aerosols. Using labeled 13C methane, we could detect its oxidation products in the aerosol phase, with yields up to 0.09

  10. Chemical and physical transformations of organic aerosol from the photo-oxidation of open biomass burning emissions in an environmental chamber

    NASA Astrophysics Data System (ADS)

    Hennigan, C. J.; Miracolo, M. A.; Engelhart, G. J.; May, A. A.; Presto, A. A.; Lee, T.; Sullivan, A. P.; McMeeking, G. R.; Coe, H.; Wold, C. E.; Hao, W.-M.; Gilman, J. B.; Kuster, W. C.; de Gouw, J.; Schichtel, B. A.; Collett, J. L., Jr.; Kreidenweis, S. M.; Robinson, A. L.

    2011-08-01

    Smog chamber experiments were conducted to investigate the chemical and physical transformations of organic aerosol (OA) during photo-oxidation of open biomass burning emissions. The experiments were carried out at the US Forest Service Fire Science Laboratory as part of the third Fire Lab at Missoula Experiment (FLAME III). We investigated emissions from 12 different fuels commonly burned in North American wildfires. The experiments feature atmospheric and plume aerosol and oxidant concentrations; aging times ranged from 3 to 4.5 h. OA production, expressed as a mass enhancement ratio (ratio of OA to primary OA (POA) mass), was highly variable. OA mass enhancement ratios ranged from 2.9 in experiments where secondary OA (SOA) production nearly tripled the POA concentration to 0.7 in experiments where photo-oxidation resulted in a 30 % loss of the OA mass. The campaign-average OA mass enhancement ratio was 1.7 ± 0.7 (mean ± 1σ); therefore, on average, there was substantial SOA production. In every experiment, the OA was chemically transformed. Even in experiments with net loss of OA mass, the OA became increasingly oxygenated and less volatile with aging, indicating that photo-oxidation transformed the POA emissions. Levoglucosan concentrations were also substantially reduced with photo-oxidation. The transformations of POA were extensive; using levoglucosan as a tracer for POA, unreacted POA only contributed 17 % of the campaign-average OA mass after 3.5 h of exposure to typical atmospheric hydroxyl radical (OH) levels. Heterogeneous reactions with OH could account for less than half of this transformation, implying that the coupled gas-particle partitioning and reaction of semi-volatile vapors is an important and potentially dominant mechanism for POA processing. Overall, the results illustrate that biomass burning emissions are subject to extensive chemical processing in the atmosphere, and the timescale for these transformations is rapid.

  11. Chemical and physical transformations of organic aerosol from the photo-oxidation of open biomass burning emissions in an environmental chamber

    NASA Astrophysics Data System (ADS)

    Hennigan, C. J.; Miracolo, M. A.; Engelhart, G. J.; May, A. A.; Presto, A. A.; Lee, T.; Sullivan, A. P.; McMeeking, G. R.; Coe, H.; Wold, C. E.; Hao, W.-M.; Gilman, J. B.; Kuster, W. C.; de Gouw, J.; Schichtel, B. A.; Collett, J. L., Jr.; Kreidenweis, S. M.; Robinson, A. L.

    2011-04-01

    Smog chamber experiments were conducted to investigate chemical and physical transformations of organic aerosol (OA) during photo-oxidation of open biomass burning emissions. The experiments were carried out at the US Forest Service's Fire Science Laboratory as part of the third Fire Lab at Missoula Experiment (FLAME III). We investigated 12 different fuels commonly burned in North American wildfires. The experiments feature atmospheric and plume aerosol and oxidant concentrations; aging times ranged from 3-4.5 h. OA production, expressed as a mass enhancement ratio (ratio of OA to primary OA (POA) mass), was highly variable. OA mass enhancement ratios ranged from 2.9 in experiments where secondary OA (SOA) production nearly tripled the POA concentration, to 0.7 in experiments where photo-oxidation resulted in a 30% loss of the OA mass. The campaign-average OA mass enhancement ratio was 1.7 ± 0.7 (mean ± 1 σ); therefore, on average, there was substantial SOA production. In every experiment, the OA was chemically transformed. Even in experiments with net loss of OA mass, the OA became increasingly oxygenated and less volatile with aging, indicating that photo-oxidation transformed the POA emissions. Levoglucosan concentrations were also substantially reduced with photo-oxidation. The transformations of POA were extensive; using levoglucosan as a tracer for POA, unreacted POA only contributed 17% of the campaign-average OA mass after 3.5 h of exposure to typical atmospheric hydroxyl radical (OH) levels. Heterogeneous reactions with OH could account for less than half of this transformation, implying that the coupled gas-particle partitioning and reaction of semi-volatile vapors is an important and potentially dominant mechanism for POA processing. Overall, the results illustrate that biomass burning emissions are subject to extensive chemical processing in the atmosphere, and the timescale for these transformations is rapid.

  12. Understanding the anthropogenic influence on formation of biogenic secondary organic aerosols in Denmark via analysis of organosulfates and related oxidation products

    NASA Astrophysics Data System (ADS)

    Nguyen, Q. T.; Christensen, M. K.; Cozzi, F.; Zare, A.; Hansen, A. M. K.; Kristensen, K.; Tulinius, T. E.; Madsen, H. H.; Christensen, J. H.; Brandt, J.; Massling, A.; Nøjgaard, J. K.; Glasius, M.

    2014-09-01

    Anthropogenic emissions of sulfur dioxide (SO2) and nitrogen oxides (NOx) may affect concentration levels and composition of biogenic secondary organic aerosols (BSOA) through photochemical reactions with biogenic organic precursors to form organosulfates and nitrooxy organosulfates. We investigated this influence in a field study from 19 May to 22 June, 2011 at two sampling sites in Denmark. Within the study, we identified a substantial number of organic acids, organosulfates and nitrooxy organosulfates in the ambient urban curbside and semi-rural background air. A high degree of correlation in concentrations was found among a group of specific organic acids, organosulfates and nitrooxy organosulfates, which may originate from various precursors, suggesting a common mechanism or factor affecting their concentration levels at the sites. It was proposed that the formation of those species most likely occurred on a larger spatial scale, with the compounds being long-range transported to the sites on the days with the highest concentrations. The origin of the long-range transported aerosols was investigated using the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model in addition to modeled emissions of related precursors, including isoprene and monoterpenes using the global Model of Emissions of Gases and Aerosols from Nature (MEGAN) and SO2 emissions using the European Monitoring and Evaluation Program (EMEP) database. The local impacts were also studied by examining the correlation between selected species, which showed significantly enhanced concentrations at the urban curbside site and the local concentrations of various gases, including SO2, ozone (O3), NOx, aerosol acidity and other meteorological conditions. This investigation showed that an inter-play of the local parameters such as the aerosol acidity, NOx, SO2, relative humidity (RH), temperature and global radiation seemed to affect the concentration level of those species, suggesting

  13. Paraoxonase Activity and Oxidative Status in Patients with Tinnitus

    PubMed Central

    Akyüz, Servet; Somuk, Battal Tahsin; Soyalic, Harun; Yılmaz, Beyhan; Taskin, Abdullah; Bilinc, Hasan; Aksoy, Nurten

    2016-01-01

    Background and Objectives The aim of this study was to investigate serum paraoxanase-1 (PON) activity, total oxidant status (TOS), total antioxidant status (TAS), and the oxidative stress index (OSI) in tinnitus; and to compare the results with data from healthy subjects. Subjects and Methods A total of 114 subjects-54 patients with tinnitus and 60 healthy controls were enrolled in this study. Serum PON activity, TOS, TAS, and OSI levels were measured. Results In the tinnitus group, TAS, and PON were significantly lower than in the control group (p<0.001). However, the TOS, and OSI levels were significantly higher in the tinnitus group than in the control group (p<0.001). Conclusions According to the data obtained from the present study, patients with tinnitus were exposed to potent oxidative stress. Oxidative stress may be the key contributing factor to the pathogenesis of tinnitus. PMID:27144229

  14. Competing effects of viscosity and surface-tension depression on the hygroscopicity and CCN activity of laboratory surrogates for oligomers in atmospheric aerosol

    NASA Astrophysics Data System (ADS)

    Hodas, N.; Zuend, A.; Shiraiwa, M.; Flagan, R. C.; Seinfeld, J.; Schilling, K.; Berkemeier, T.

    2015-12-01

    The presence of oligomers in biomass burning aerosol, as well as secondary organic aerosol derived from other sources, influences particle viscosity and can introduce kinetic limitations to water uptake. This, in turn, impacts aerosol optical properties and the efficiency with which these particles serve as cloud condensation nuclei (CCN). To explore the influence of organic-component viscosity on aerosol hygroscopicity, the water-uptake behavior of aerosol systems comprised of polyethylene glycol (PEG) and mixtures of PEG and ammonium sulfate (AS) was measured under sub- and supersaturated relative humidity (RH) conditions. Experiments were conducted with systems containing PEG with average molecular weights ranging from 200 to 10,000 g/mol, corresponding to a range in viscosity of 0.004 - 4.5 Pa s under dry conditions. While evidence suggests that viscous aerosol components can suppress water uptake at RH < 90%, under supersaturated conditions (with respect to RH), an increase in CCN activity with increasing PEG molecular weight was observed. We attribute this to an increase in the efficiency with which PEG serves as a surfactant with increasing molecular weight. This effect is most pronounced for PEG-AS mixtures and, in fact, a modest increase in CCN activity is observed for the PEG 10,000-AS mixture as compared to pure AS, as evidenced by a 4% reduction in critical activation diameter. Experimental results are compared with calculations of hygroscopic growth at thermodynamic equilibrium using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients model and the potential influence of kinetic limitations to observed water uptake is further explored with the Kinetic Multi-Layer Model of Gas-Particle Interactions. Results suggest the competing effects of organic-component viscosity and surface-tension depression may lead to RH-dependent differences in hygroscopicity for oligomers and other surface-active compounds present in atmospheric

  15. Chamber Study Exploring Aerosol Formation from NO3 Oxidation of α-pinene and Δ-carene under Varying HO2/RO2/NO3 Regimes

    NASA Astrophysics Data System (ADS)

    Kang, H.; Ayres, B. R.; Fry, J.; Brown, S. S.; Day, D. A.; Thompson, S.; Hu, W.; Campuzano Jost, P.; Stark, H.; Jimenez, J. L.; Ranney, A.; Ziemann, P. J.

    2014-12-01

    Although monoterpenes are pervasive in wooded environments, their reactions with nitrate radicals (NO3, a potent nighttime oxidant downwind of combustion sources) and the resulting secondary aerosol formation are not well characterized. To better understand these reactions, environmental chamber experiments have often been conducted at elevated terpene concentrations and HO2/RO2/NO3 ratios that are not representative of the real atmosphere, resulting in a range of yields. To elucidate the reasons for these varying yields, a new series of experiments were conducted with varying concentration ratios of α-pinene or Δ-carene with N2O5 (source of NO3 radical) and with/without formaldehyde in a 8000 L Teflon chamber. Formaldehyde served as a precursor for HO2 to bias the system towards HO2-RO2 reactions, elevated N2O5 caused NO3-RO2 reactions to dominate, and elevated monoterpene concentrations (but not amount reacted) favored RO2-RO2 reactions. The chamber products in the gaseous and aerosol phase were characterized using an NO3/N2O5 Cavity Ringdown Spectrometer (CRDS), an Aerodyne High-Resolution Aerosol Mass Spectrometer (AMS), a Scanning Mobility Particle Sizer (SMPS), an Ultrafine Condensation Particle Counter (UCPC), an Aerodyne High-Resolution Chemical Ionization Mass Spectrometer using Iodide ion chemistry (I- CIMS), and a chemiluminescence NOx detector. The mechanistic reasons for the starkly different SOA yield from the NO3 + α-pinene vs. NO3 + Δ-carene systems were explored in addition to differences in gas and aerosol-phase composition and yields under the varying conditions of the primary terpene RO2 radical fate.

  16. A review of research on human activity induced climate change I. Greenhouse gases and aerosols

    NASA Astrophysics Data System (ADS)

    Wang, Mingxing; Liu, Qiang; Yang, Xin

    2004-06-01

    Extensive research on the sources and sinks of greenhouse gases, carbon cycle modeling, and the characterization of atmospheric aerosols has been carried out in China during the last 10 years or so. This paper presents the major achievements in the fields of emissions of greenhouse gases from agricultural lands, carbon cycle modeling, the characterization of Asian mineral dust, source identification of the precursors of the tropospheric ozone, and observations of the concentrations of atmospheric organic compounds. Special, more detailed information on the emissions of methane from rice fields and the physical and chemical characteristics of mineral aerosols are presented.

  17. Temperature dependence of bromine activation due to reaction with ozone in a proxy for organic aerosols

    NASA Astrophysics Data System (ADS)

    Edebeli, Jacinta; Ammann, Markus; Gilgen, Anina; Eichler, Anja; Schneebeli, Martin; Bartels-Rausch, Thorsten

    2016-04-01

    The discovery of boundary layer ozone depletion events in the Polar Regions [1] and in the mid-latitudes [2], two areas of very different temperature regimes, begs the question of temperature dependence of reactions responsible for these observations [3]. These ODEs have been attributed to ozone reacting with halides leading to reactive halogens (halogen activation) of which bromide is extensively studied, R1 - R3 [4, 5] (R1 is a multiphase reaction). O3 + Br‑→ O2 + OBr‑ (R1) OBr‑ + H+ ↔ HOBr (R2) HOBr + H+ + Br‑→ Br2 + H2O (R3) Despite extensive studies of ozone-bromide interactions, the temperature dependence of bromine activation is not clear [3]. This limits parameterization of the involved reactions and factors in atmospheric models [3, 6]. Viscosity changes in the matrix (such as organic aerosols) due to temperature have been shown to influence heterogeneous reaction rates and products beyond pure temperature effect [7]. With the application of coated wall flow-tubes, the aim of this study is therefore to investigate the temperature dependence of bromine activation by ozone interaction while attempting to characterize the contributions of the bulk and surface reactions to observed ozone uptake. Citric acid is used in this study as a hygroscopically characterized matrix whose viscosity changes with temperature and humidity. Here, we present reactive ozone uptake measured between 258 and 289 K. The data show high reproducibility. Comparison of measured uptake with modelled bulk uptake at different matrix compositions (and viscosities) indicate that bulk reactive uptake dominates, but there are other factors which still need further consideration in the model. References 1. Barrie, L.A., et al., Nature, 1988. 334: p. 138 - 141. 2. Hebestreit, K., et al., Science, 1999. 283: p. 55-57. 3. Simpson, W.R., et al., Atmospheric Chemistry and Physics, 2007. 7: p. 4375 - 4418. 4. Haag, R.W. and J. Hoigné, Environ Sci Technol, 1983. 17: p. 261-267. 5. Oum

  18. Particulate Matter Oxidative Potential from Waste Transfer Station Activity

    PubMed Central

    Godri, Krystal J.; Duggan, Sean T.; Fuller, Gary W.; Baker, Tim; Green, David; Kelly, Frank J.; Mudway, Ian S.

    2010-01-01

    Background Adverse cardiorespiratory health is associated with exposure to ambient particulate matter (PM). The highest PM concentrations in London occur in proximity to waste transfer stations (WTS), sites that experience high numbers of dust-laden, heavy-duty diesel vehicles transporting industrial and household waste. Objective Our goal was to quantify the contribution of WTS emissions to ambient PM mass concentrations and oxidative potential. Methods PM with a diameter < 10 μm (PM10) samples were collected daily close to a WTS. PM10 mass concentrations measurements were source apportioned to estimate local versus background sources. PM oxidative potential was assessed using the extent of antioxidant depletion from a respiratory tract lining fluid model. Total trace metal and bioavailable iron concentrations were measured to determine their contribution to PM oxidative potential. Results Elevated diurnal PM10 mass concentrations were observed on all days with WTS activity (Monday–Saturday). Variable PM oxidative potential, bioavailable iron, and total metal concentrations were observed on these days. The contribution of WTS emissions to PM at the sampling site, as predicted by microscale wind direction measurements, was correlated with ascorbate (r = 0.80; p = 0.030) and glutathione depletion (r = 0.76; p = 0.046). Increased PM oxidative potential was associated with aluminum, lead, and iron content. Conclusions PM arising from WTS activity has elevated trace metal concentrations and, as a consequence, increased oxidative potential. PM released by WTS activity should be considered a potential health risk to the nearby residential community. PMID:20368130

  19. Aerosol disturbances of the stratosphere over Tomsk according to data of lidar observations in volcanic activity period 2006-2011

    NASA Astrophysics Data System (ADS)

    Makeev, Andrey P.; Burlakov, Vladimir D.; Dolgii, Sergey I.; Nevzorov, Aleksey V.; Trifonov, Dimitar A.

    2012-11-01

    We summarize and analyze the lidar measurements (Tomsk: 56.5°N; 85.0°E) of the optical characteristics of the stratospheric aerosol layer (SAL) in the volcanic activity period 2006-2011. The background SAL state with minimal aerosol content, which was observed since 1997 under the conditions of long-term volcanically quiescent period, was interrupted in October 2006 by a series of explosive eruptions of volcanoes of the Pacific Ring of Fire: Rabaul (October 2006, New Guinea); Okmok and Kasatochi (July-August 2008, Aleutian Islands); Redoubt (March-April 2009, Alaska); Sarychev Peak (June 2009, Kuril Islands), and Grimsvötn (May 2011, Iceland). A short-term and minor disturbance of the lower stratosphere was also observed in April 2010 after eruption of the Icelandic volcano Eyjafjallajokull. The developed regional empirical model of the vertical distribution of background SAL optical characteristics was used to identify the periods of elevated stratospheric aerosol content after each of the volcanic eruptions.

  20. Activation of molecular oxygen and the nature of the active oxygen species for CO oxidation on oxide supported Au catalysts.

    PubMed

    Widmann, D; Behm, R J

    2014-03-18

    Although highly dispersed Au catalysts with Au nanoparticles (NPs) of a few nanometers in diameter are well-known for their high catalytic activity for several oxidation and reduction reactions already at rather low temperatures for almost 30 years, central aspects of the reaction mechanism are still unresolved. While most studies focused on the active site, the active Au species, and the effect of the support material, the most crucial step during oxidation reactions, the activation of molecular oxygen and the nature of the resulting active oxygen species (Oact), received more attention just recently. This is topic of this Account, which focuses on the formation, location, and nature of the Oact species present on metal oxide supported Au catalysts under typical reaction conditions, at room temperature and above. It is mainly based on quantitative temporal analysis of products (TAP) reactor measurements, which different from most spectroscopic techniques are able to detect and quantify these species even at the extremely low concentrations present under realistic reaction conditions. Different types of pulse experiments were performed, during which the highly dispersed, realistic powder catalysts are exposed to very low amounts of reactants, CO and/or O2, in order to form and reactively remove Oact species and gain information on their formation, nature, and the active site for Oact formation. Our investigations have shown that the active oxygen species for CO oxidation on Au/TiO2 for reaction at 80 °C and higher is a highly stable atomic species, which at 80 °C is formed only at the perimeter of the Au-oxide interface and whose reactive removal by CO is activated, but not its formation. From these findings, it is concluded that surface lattice oxygen represents the Oact species for the CO oxidation. Accordingly, the CO oxidation proceeds via a Au-assisted Mars-van Krevelen mechanism, during which surface lattice oxygen close to the Au NPs is removed by reaction

  1. What's Up in the Atmosphere? Exploring How Aerosols Impact Sky Color Through Hands-on Activities with Elementary GLOBE

    NASA Astrophysics Data System (ADS)

    Damadeo, K.; Taylor, J.

    2015-12-01

    What color is the sky today? The GLOBE Kids - Anita, Simon, and Dennis want to know why the sky isn't always the same shade of blue and sometimes isn't even blue. Through the new Elementary GLOBE Aerosols Storybook and Learning Activities, the GLOBE Kids learn that there's a lot more than air in the atmosphere, which can affect the colors we see in the sky. There are four hands-on activities in this unit: 1) Sky Observers - Students make observations of the sky, record their findings and share their observation reports with their peers. The activity promotes active observation and recording skills to help students observe sky color, and recognize that sky color changes; 2) Why (Not) So Blue? - Students make predictions about how drops of milk will affect color and visibility in cups of water representing the atmosphere to help them understand that aerosols in the atmosphere have an effect on sky conditions, including sky color and visibility. The activity also introduces the classification categories for daytime sky color and visibility; 3) See the Light - Students use prisms and glue sticks to explore the properties of light. The activity demonstrates that white light is made up of seven colors that represent different wavelengths, and illustrates why the sky is blue during the day and red at sunset; 4) Up in the Air - Students work in groups to make an aerosol sampler, a simple adhesive tool that allows students to collect data and estimate the extent of aerosols present at their school, understanding that, in fact, there are particles in the air we breathe. NGSS Alignment includes: Disciplinary Core Ideas- ESS2.D: Weather and Climate, ESS3.C: Human Impacts on Earth Systems, PS4.B: Electromagnetic Radiation, ESS3.A: Natural Resources; Science and Engineering Practices- Asking Questions and Defining Problems, Planning and Carrying Out an Investigation, Analyzing and Interpreting Data, Engaging in Argument from Evidence, Obtaining, Evaluating, and Communicating

  2. Nonpolar organic compounds in fine particles: quantification by thermal desorption-GC/MS and evidence for their significant oxidation in ambient aerosols in Hong Kong.

    PubMed

    Yu, Jian Zhen; Huang, X H Hilda; Ho, Steven S H; Bian, Qijing

    2011-12-01

    Nonpolar organic compounds (NPOCs) in ambient particulate matter (PM) commonly include n-alkanes, branched alkanes, hopanes and steranes, and polycyclic aromatic hydrocarbons (PAHs). The recent development of thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) has greatly reduced time and labor in their quantification by eliminating the laborious solvent extraction and sample concentration steps in the traditional approach that relies on solvent extraction. The simplicity of the TD-GCMS methods has afforded us concentration data of NPOCs in more than 90 aerosol samples in two aerosol field studies and 20 vehicular emissions-dominated source samples in Hong Kong over the past few years. In this work, we examine the interspecies relationships between select NPOCs and their concentration ratios to elemental carbon (EC) among the ambient samples and among the source samples. Our analysis indicates that hopanes were mainly from vehicular emissions and they were significantly oxidized in ambient PM. The hopane/EC ratio in ambient samples was on average less than half of the ratio in vehicular emissions-dominated source samples. This highlights the necessity in considering oxidation loss in applying organic tracer data in source apportionment studies. Select PAH/EC ratio-ratio plots reveal that PAHs had diverse sources and vehicular emissions were unlikely a dominant source for PAHs in Hong Kong. Biomass burning and other regional sources likely dominated ambient PAHs in Hong Kong. PMID:21983947

  3. Direct and Semi-direct Effects of Aerosol on the Climate System

    NASA Astrophysics Data System (ADS)

    Mahajan, S.; Evans, K. J.; Hack, J. J.; Truesdale, J.

    2011-12-01

    High-resolution (1x1 degree) global tropospheric aerosol datasets are generated using the atmospheric component of CESM1.0 coupled to an active bulk aerosol model for the 1850's and the period 1960-2000. The interactive aerosol module incorporates surface and elevated emissions of anthropogenic and natural aerosol precursors and oxidants. Experiments performed with the new aerosol datasets in atmosphere only GCM runs reveal that current level of aerosols can cause significant surface cooling and shift precipitation when compared to pre-industrial levels of aerosols. Experiments performed with the atmosphere component coupled to a slab ocean model reveal that aerosols can enhance the land-sea contrast, and cross-equatorial SST gradient leading to enhanced reduction in monsoon and shift in the ITCZ over the tropical Atlantic as compared to the atmosphere only runs. AMIP style experiments with the new aerosol dataset further reveal that aerosols could have had a significant impact on the trends in regional surface temperature and precipitation in the later part of the 20th century.

  4. Biological activity of ellagitannins: Effects as anti-oxidants, pro-oxidants and metal chelators.

    PubMed

    Moilanen, Johanna; Karonen, Maarit; Tähtinen, Petri; Jacquet, Rémi; Quideau, Stéphane; Salminen, Juha-Pekka

    2016-05-01

    Ellagitannins are a subclass of hydrolysable tannins that have been suggested to function as defensive compounds of plants against herbivores. However, it is known that the conditions in the digestive tracts of different herbivores are variable, so it seems reasonable to anticipate that the reactivities and modes of actions of these ingested defensive compounds would also be different. A previous study on a few ellagitannins has shown that these polyphenolic compounds are highly oxidizable at high pH and that their bioactivity can be attributed to certain structural features. Herein, the activities of 13 ellagitannins using the deoxyribose assay were measured. The results provided information about the anti-oxidant, pro-oxidant and metal chelating properties of ellagitannins. Surprisingly, many of the tested ellagitannins exhibited pro-oxidant activities even at neutral pH and only moderate to low radical scavenging activities, although the metal chelating capacities of all tested ellagitannins were relatively high. PMID:26899362

  5. Neural activity triggers neuronal oxidative metabolism followed by astrocytic glycolysis.

    PubMed

    Kasischke, Karl A; Vishwasrao, Harshad D; Fisher, Patricia J; Zipfel, Warren R; Webb, Watt W

    2004-07-01

    We have found that two-photon fluorescence imaging of nicotinamide adenine dinucleotide (NADH) provides the sensitivity and spatial three-dimensional resolution to resolve metabolic signatures in processes of astrocytes and neurons deep in highly scattering brain tissue slices. This functional imaging reveals spatiotemporal partitioning of glycolytic and oxidative metabolism between astrocytes and neurons during focal neural activity that establishes a unifying hypothesis for neurometabolic coupling in which early oxidative metabolism in neurons is eventually sustained by late activation of the astrocyte-neuron lactate shuttle. Our model integrates existing views of brain energy metabolism and is in accord with known macroscopic physiological changes in vivo. PMID:15232110

  6. Ultrasound assisted, thermally activated persulfate oxidation of coal tar DNAPLs.

    PubMed

    Peng, Libin; Wang, Li; Hu, Xingting; Wu, Peihui; Wang, Xueqing; Huang, Chumei; Wang, Xiangyang; Deng, Dayi

    2016-11-15

    The feasibility of ultrasound assisted, thermally activated persulfate for effective oxidation of twenty 2-6 ringed coal tar PAHs in a biphasic tar/water system and a triphasic tar/soil/water system were investigated and established. The results indicate that ultrasonic assistance, persulfate and elevated reaction temperature are all required to achieve effective oxidation of coal tar PAHs, while the heating needed can be provided by ultrasonic induced heating as well. Further kinetic analysis reveals that the oxidation of individual PAH in the biphasic tar/water system follows the first-order kinetics, and individual PAH oxidation rate is primary determined by the mass transfer coefficients, tar/water interfacial areas, the aqueous solubility of individual PAH and its concentration in coal tar. Based on the kinetic analysis and experimental results, the contributions of ultrasound, persulfate and elevated reaction temperature to PAHs oxidation were characterized, and the effects of ultrasonic intensity and oxidant dosage on PAHs oxidation efficiency were investigated. In addition, the results indicate that individual PAH degradability is closely related to its reactivity as well, and the high reactivity of 4-6 ringed PAHs substantially improves their degradability. PMID:27450342

  7. High temperature solid oxide fuel development activities

    SciTech Connect

    Ray, E.R.

    1993-11-01

    This paper presents an overview of the Westinghouse tubular SOFC development activities and current program status. Goal is to develop a cell that can operate for 50,000 to 100,000 h. Test results are presented for multiple single cell tests which have now successfully exceeded 40,000 hours of continuous