Sample records for aerosol organic carbon

  1. SAMPLING DURATION DEPENDENCE OF SEMI-CONTINUOUS ORGANIC CARBON MEASUREMENTS ON STEADY STATE SECONDARY ORGANIC AEROSOLS

    EPA Science Inventory

    Semi-continuous organic carbon concentrations were measured through several experiments of statically generated secondary organic aerosol formed by hydrocarbon + NOx irradiations. Repeated, randomized measurements of these steady state aerosols reveal decreases in the observed c...

  2. Organic carbon content of marine aerosols collected on Bermuda

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hoffman, E.J.; Duce, R.A.

    1974-01-01

    The concentration of total organic carbon in marine aerosols collected from a 20-m tower on the Southwest Coast of Bermuda ranged from 0.15 to 0.47 microgram/M/sup 3/ STP under onshore wind conditions. The mass of the organic carbon ranged from 1 to 19% of the mass of sea salt in the particles in Bermuda, and the percentage decreased with increasing salt content.

  3. Direct radiative effect due to brownness in organic carbon aerosols generated from biomass combustion

    NASA Astrophysics Data System (ADS)

    Rathod, T. D.; Sahu, S. K.; Tiwari, M.; Pandit, G. G.

    2016-12-01

    We report the enhancement in the direct radiative effect due the presence of Brown carbon (BrC) as a part of organic carbon aerosols. The optical properties of organic carbon aerosols generated from pyrolytic combustion of mango tree wood (Magnifera Indica) and dung cake at different temperatures were considered. Mie codes were used to calculate absorption and scattering coefficients coupled with experimentally derived imaginary complex refractive index. The direct radiative effect (DRE) for sampled organic carbon aerosols was estimated using a wavelength dependent radiative transfer equation. The BrC DRE was estimated taking virtually non absorbing organic aerosols as reference. The BrC DRE from wood and dung cake was compared at different combustion temperatures and conditions. The BrC contributed positively to the direct top of the atmosphere radiative effect. Dung cake generated BrC aerosols were found to be strongly light absorbing as compared to BrC from wood combustion. It was noted that radiative effects of BrC from wood depended on its generation temperature and conditions. For BrC aerosols from dung cake such strong dependence was not observed. The average BrC aerosol DRE values were 1.53±0.76 W g-1 and 17.84±6.45 W g-1 for wood and dung cake respectively. The DRE contribution of BrC aerosols came mainly (67-90%) from visible light absorption though they exhibited strong absorption in shorter wavelengths of the UV-visible spectrum.

  4. Methods of analysis for complex organic aerosol mixtures from urban emission sources of particulate carbon

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mazurek, M.A.; Hildemann, L.M.; Cass, G.R.

    1990-04-01

    Extractable organic compounds having between 6 to 40 carbon atoms comprise an important mass fraction of the fine particulate matter samples from major urban emission sources. Depending on the emission source type, this solvent-soluble fraction accounts for <20% to 100% of the total organic aerosol mass, as measured by quantitative high-resolution has chromatography (HRGC) with flame ionization detection. In addition to total extract quantitation, HRGC can be applied to further analyses of the mass distributions of elutable organics present in the complex aerosol extract mixtures, thus generating profiles that serve as fingerprints'' for the sources of interest. This HRGC analyticalmore » method is applied to emission source samples that contain between 7 to 12,000 {mu}g/filter organic carbon. It is shown to be a sensitive technique for analysis of carbonaceous aerosol extract mixtures having diverse mass loadings and species distributions. This study describes the analytical chemical methods that have been applied to: the construction of chemical mass balances based on the mass of fine organic aerosol emitted for major urban sources of particulate carbon; and the generation of discrete emission source chemical profiles derived from chromatographic characteristics of the organic aerosol components. 21 refs., 1 fig., 2 tabs.« less

  5. Wet Removal of Organic and Black Carbon Aerosols

    NASA Astrophysics Data System (ADS)

    Torres, A.; Bond, T. C.; Lehmann, C.

    2012-12-01

    Organic carbon (OC) and black carbon (BC) aerosols derived from the combustion of fossil fuels and biomass are significant atmospheric pollutants that alter the Earth's radiation balance and affect human health. Carbonaceous aerosol lifetime and extent of its effects are mainly controlled by its wet removal, especially by rain. Limited work has been done to measure both BC and OC from rain events even though these aerosols are co-emitted and exist together in the atmosphere. The choices of analytical techniques for measuring OC and BC in water are limited, and researchers often employ the same techniques used for measuring atmospheric carbon particles. There is no agreement in the methods employed for monitoring carbon concentration in precipitation. As part of the method development, the Single Particle Soot Photometer (SP2), Thermal-Optical Analysis (TOA), Ultraviolet/Visible (UV/VIS) Spectrophotometer, and the Total Organic Carbon (TOC) Analyzer were evaluated for measuring BC suspended in water, water insoluble OC (WIOC) and dissolved OC (DOC). The study also monitored the concentration of BC, WIOC, and DOC in rainwater collected at Bondville (Illinois) for 18 months. Results indicated that 34% (±3%) of the BC mass was lost in the SP2 analysis, most probably during the nebulization process. Filtration required for TOA also had large losses (>75%) because quartz fiber filters were ineffective for capturing BC particles from water. Addition of NH4H2PO4 as a coagulant improved (>95%) the capture efficiency of the filters. UV/VIS spectrophotometry had good linearity, but the sensitivity for detecting BC particles (±20 μg/L) suspended in water was inadequate. TOC analysis was a robust technique for measuring both DOC and total carbon (BC + OC). The chosen techniques were TOC analysis for DOC, and TOA with an optimized filtration procedure for BC and WIOC. The mean concentrations in rainwater were 8.72 (±9.84) μg/L of BC, 88.97 (±62.64) μg/L of WIOC, and 1

  6. Elucidating secondary organic aerosol from diesel and gasoline vehicles through detailed characterization of organic carbon emissions

    PubMed Central

    Gentner, Drew R.; Isaacman, Gabriel; Worton, David R.; Chan, Arthur W. H.; Dallmann, Timothy R.; Davis, Laura; Liu, Shang; Day, Douglas A.; Russell, Lynn M.; Wilson, Kevin R.; Weber, Robin; Guha, Abhinav; Harley, Robert A.; Goldstein, Allen H.

    2012-01-01

    Emissions from gasoline and diesel vehicles are predominant anthropogenic sources of reactive gas-phase organic carbon and key precursors to secondary organic aerosol (SOA) in urban areas. Their relative importance for aerosol formation is a controversial issue with implications for air quality control policy and public health. We characterize the chemical composition, mass distribution, and organic aerosol formation potential of emissions from gasoline and diesel vehicles, and find diesel exhaust is seven times more efficient at forming aerosol than gasoline exhaust. However, both sources are important for air quality; depending on a region’s fuel use, diesel is responsible for 65% to 90% of vehicular-derived SOA, with substantial contributions from aromatic and aliphatic hydrocarbons. Including these insights on source characterization and SOA formation will improve regional pollution control policies, fuel regulations, and methodologies for future measurement, laboratory, and modeling studies. PMID:23091031

  7. Elucidating secondary organic aerosol from diesel and gasoline vehicles through detailed characterization of organic carbon emissions.

    PubMed

    Gentner, Drew R; Isaacman, Gabriel; Worton, David R; Chan, Arthur W H; Dallmann, Timothy R; Davis, Laura; Liu, Shang; Day, Douglas A; Russell, Lynn M; Wilson, Kevin R; Weber, Robin; Guha, Abhinav; Harley, Robert A; Goldstein, Allen H

    2012-11-06

    Emissions from gasoline and diesel vehicles are predominant anthropogenic sources of reactive gas-phase organic carbon and key precursors to secondary organic aerosol (SOA) in urban areas. Their relative importance for aerosol formation is a controversial issue with implications for air quality control policy and public health. We characterize the chemical composition, mass distribution, and organic aerosol formation potential of emissions from gasoline and diesel vehicles, and find diesel exhaust is seven times more efficient at forming aerosol than gasoline exhaust. However, both sources are important for air quality; depending on a region's fuel use, diesel is responsible for 65% to 90% of vehicular-derived SOA, with substantial contributions from aromatic and aliphatic hydrocarbons. Including these insights on source characterization and SOA formation will improve regional pollution control policies, fuel regulations, and methodologies for future measurement, laboratory, and modeling studies.

  8. Radiocarbon-based Source Apportionment of Organic, Elemental and Water-soluble Organic Carbon Aerosols and the Light Absorption of Water-soluble Organic Carbon Aerosols in the East Asia High-intensity Winter Campaigns in 2014

    NASA Astrophysics Data System (ADS)

    Fang, W.; Andersson, A.; Zheng, M.; Lee, M.; Kim, S. W.; Du, K.; Gustafsson, O.

    2016-12-01

    Improved understanding of anthropogenic aerosol effects on atmospheric chemistry and climate as well as efficient mitigation actions are hampered by the limited comprehension of the relative contributions of different sources of carbonaceous aerosols and of their subsequent atmospheric processing. Here, we present dual carbon isotope constrained source apportionment and optical properties of carbonaceous aerosols simultaneously both at urban and rural receptor sites, includes North China Plain (NCP, Beijing and Tianjin), Yangtze River Delta (YRD, Shanghai, Zhejiang), and Jeju Island (Korea Climate Observatory at Gosan) during January 2014 field campaigns. The radiocarbon (Δ14C) data show that fossil combustions contribute equally ˜80 ± 5% to elemental carbon (EC) aerosol in Beijing, Tianjin, and Shanghai, and 66 ± 9% to Gosan-EC aerosol, while the specific sources of the dominant fossil fuel component were dramatically different among these sites. The mean fraction coal combustion of Beijing-EC, Tianjin-EC, and Gosan-EC is double that of Shanghai-EC. The other large fraction (72―92%) of carbonaceous aerosol is organic carbon (OC) aerosol which contains water soluble and water insoluble organic carbon (WSOC and WISOC). OC, WISOC, and WSOC in Beijing and Gosan sites were still observed largely from fossil sources (53―75%). The more 13C-enriched signature of Gosan-WSOC (-22.8 ± 0.2‰) compared to Gosan-EC (-23.9 ± 0.4‰) and Beijing-WSOC (-23.5 ± 0.7‰) reflects that WSOC is likely more affected by atmospheric aging during long-rang transport than is EC. The high light absorption coefficients of PM2.5, PM1, and TSP were observed at Gosan during this study and was frequently reaching 20―60 Mm-1 by aethalometer and continuous light absorption photometer. The mass absorption cross section of WSOC (MAC365) for above sites is high (1.5 ± 0.8 m2/g), accounted for ˜14 ± 5% of the total direct absorbance relative to EC, which is significantly higher than

  9. Technical note: Relating functional group measurements to carbon types for improved model-measurement comparisons of organic aerosol composition

    NASA Astrophysics Data System (ADS)

    Takahama, Satoshi; Ruggeri, Giulia

    2017-04-01

    Functional group (FG) analysis provides a means by which functionalization in organic aerosol can be attributed to the abundances of its underlying molecular structures. However, performing this attribution requires additional, unobserved details about the molecular mixture to provide constraints in the estimation process. We present an approach for conceptualizing FG measurements of organic aerosol in terms of its functionalized carbon atoms. This reformulation facilitates estimation of mass recovery and biases in popular carbon-centric metrics that describe the extent of functionalization (such as oxygen to carbon ratio, organic mass to organic carbon mass ratio, and mean carbon oxidation state) for any given set of molecules and FGs analyzed. Furthermore, this approach allows development of parameterizations to more precisely estimate the organic carbon content from measured FG abundance. We use simulated photooxidation products of α-pinene secondary organic aerosol previously reported by Ruggeri et al. (2016) and FG measurements by Fourier transform infrared (FT-IR) spectroscopy in chamber experiments by Sax et al. (2005) to infer the relationships among molecular composition, FG composition, and metrics of organic aerosol functionalization. We find that for this simulated system, ˜ 80 % of the carbon atoms should be detected by FGs for which calibration models are commonly developed, and ˜ 7 % of the carbon atoms are undetectable by FT-IR analysis because they are not associated with vibrational modes in the infrared. Estimated biases due to undetected carbon fraction for these simulations are used to make adjustments in these carbon-centric metrics such that model-measurement differences are framed in terms of unmeasured heteroatoms (e.g., in hydroperoxide and nitrate groups for the case studied in this demonstration). The formality of this method provides framework for extending FG analysis to not only model-measurement but also instrument

  10. Size distributions of organic nitrogen and carbon in remote marine aerosols: Evidence of marine biological origin based on their isotopic ratios

    NASA Astrophysics Data System (ADS)

    Miyazaki, Yuzo; Kawamura, Kimitaka; Sawano, Maki

    2010-03-01

    Size-segregated aerosol samples were collected over the western North Pacific in summer 2008 for the measurements of organic nitrogen (ON) and organic carbon (OC). ON and OC showed bimodal size distributions. Their concentrations showed positive correlation with those of biogenic tracers, methanesulfonic acid (MSA) and azelaic acid (C9). We found that average ON and OC concentrations were twice greater in aerosols collected in the oceanic region with higher biological productivity than in the regions with lower productivity. The average ON/OC ratios are higher (0.49 ± 0.11) in more biologically influenced aerosols than those (0.35 ± 0.10) in less influenced aerosols. Stable carbon isotopic analysis indicates that marine-derived carbon accounted for ˜46-72% of total carbon in more biologically influenced aerosols. These results provide evidence that organic aerosols in this region are enriched in ON that is linked to oceanic biological activity and the subsequent emissions to the atmosphere.

  11. Black carbon aerosol mixing state, organic aerosols and aerosol optical properties over the UK

    NASA Astrophysics Data System (ADS)

    McMeeking, G. R.; Morgan, W. T.; Flynn, M.; Highwood, E. J.; Turnbull, K.; Haywood, J.; Coe, H.

    2011-05-01

    Black carbon (BC) aerosols absorb sunlight thereby leading to a positive radiative forcing and a warming of climate and can also impact human health through their impact on the respiratory system. The state of mixing of BC with other aerosol species, particularly the degree of internal/external mixing, has been highlighted as a major uncertainty in assessing its radiative forcing and hence its climate impact, but few in situ observations of mixing state exist. We present airborne single particle soot photometer (SP2) measurements of refractory BC (rBC) mass concentrations and mixing state coupled with aerosol composition and optical properties measured in urban plumes and regional pollution over the UK. All data were obtained using instrumentation flown on the UK's BAe-146-301 large Atmospheric Research Aircraft (ARA) operated by the Facility for Airborne Atmospheric Measurements (FAAM). We measured sub-micron aerosol composition using an aerosol mass spectrometer (AMS) and used positive matrix factorization to separate hydrocarbon-like (HOA) and oxygenated organic aerosols (OOA). We found a higher number fraction of thickly coated rBC particles in air masses with large OOA relative to HOA, higher ozone-to-nitrogen oxides (NOx) ratios and large concentrations of total sub-micron aerosol mass relative to rBC mass concentrations. The more ozone- and OOA-rich air masses were associated with transport from continental Europe, while plumes from UK cities had higher HOA and NOx and fewer thickly coated rBC particles. We did not observe any significant change in the rBC mass absorption efficiency calculated from rBC mass and light absorption coefficients measured by a particle soot absorption photometer despite observing significant changes in aerosol composition and rBC mixing state. The contributions of light scattering and absorption to total extinction (quantified by the single scattering albedo; SSA) did change for different air masses, with lower SSA observed in

  12. Polar and non-polar organic aerosols from large-scale agricultural-waste burning emissions in Northern India: Implications to organic mass-to-organic carbon ratio.

    PubMed

    Rajput, Prashant; Sarin, M M

    2014-05-01

    This study focuses on characteristics of organic aerosols (polar and non-polar) and total organic mass-to-organic carbon ratio (OM/OC) from post-harvest agricultural-waste (paddy- and wheat-residue) burning emissions in Northern India. Aerosol samples from an upwind location (Patiala: 30.2°N, 76.3°E) in the Indo-Gangetic Plain were analyzed for non-polar and polar fractions of organic carbon (OC1 and OC2) and their respective mass (OM1 and OM2). On average, polar organic aerosols (OM2) contribute nearly 85% of the total organic mass (OM) from the paddy- and wheat-residue burning emissions. The water-soluble-OC (WSOC) to OC2 ratio, within the analytical uncertainty, is close to 1 from both paddy- and wheat-residue burning emissions. However, temporal variability and relatively low WSOC/OC2 ratio (Av: 0.67±0.06) is attributed to high moisture content and poor combustion efficiency during paddy-residue burning, indicating significant contribution (∼30%) of aromatic carbon to OC2. The OM/OC ratio for non-polar (OM1/OC1∼1.2) and polar organic aerosols (OM2/OC2∼2.2), hitherto unknown for open agricultural-waste burning emissions, is documented in this study. The total OM/OC ratio is nearly identical, 1.9±0.2 and 1.8±0.2, from paddy- and wheat-residue burning emissions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. Carbon content of common airborne fungal species and fungal contribution to aerosol organic carbon in a subtropical city

    NASA Astrophysics Data System (ADS)

    Cheng, Jessica Y. W.; Chan, Chak K.; Lee, C.-T.; Lau, Arthur P. S.

    Interest in the role and contribution of fungi to atmospheric aerosols and processes grows in the past decade. Substantial data or information such as fungal mass or carbon loading to ambient aerosols is however still lacking. This study aimed to quantify the specific organic carbon content (OC per spore) of eleven fungal species commonly found airborne in the subtropics, and estimated their contribution to organic carbon in aerosols. The specific OC contents showed a size-dependent relationship ( r = 0.64, p < 0.05) and ranged from 3.6 to 201.0 pg carbon per spore or yeast cell, giving an average of 6.0 pg carbon per spore (RSD 51%) for spore or cell size less than 10 μm. In accounting for natural variations in the composition and abundance of fungal population, weighted-average carbon content for field samples was adopted using the laboratory determined specific OC values. An average of 5.97 pg carbon per spore (RSD 3.8%) was enumerated from 28 field samples collected at the university campus. The mean fungal OC concentration was 3.7, 6.0 and 9.7 ng m -3 in PM 2.5, PM 2.5-10 and PM 10, respectively. These corresponded to 0.1%, 1.2% and 0.2% of the total OC in PM 2.5, PM 2.5-10 and PM 10, respectively. In the study period, rain provided periods with low total OC but high fungal prevalence and fungi contributed 7-32% OC in PM 2.5-10 or 2.4-7.1% OC in PM 10. More extensive studies are deserved to better understand the spatial-, temporal- and episodic dependency on the fungal OC contribution to the atmospheric aerosols.

  14. Mechanism of organic aerosol formation and aging: Role of the precursor carbon skeleton

    NASA Astrophysics Data System (ADS)

    Hunter, J. F.; Carrasquillo, A. J.; Daumit, K. E.; Cross, E. S.; Worsnop, D. R.; Kroll, J. H.

    2012-12-01

    Oxidative aging of organic aerosol consists of a complex set of reactions coupled with gas-particle partitioning processes. Functionalization reactions involve adding oxygen containing functional groups onto a molecule, leading to reduced vapor pressures and promoting aerosol formation. In fragmentation reactions carbon-carbon bonds are broken as oxygen containing functional groups are added, which generally splits the parent molecule into two smaller and more volatile products. The initial structure of an aerosol-forming precursor molecule may influence what chemistry will occur both by changing the branching between fragmentation and functionalization processes as well as changing the effects of those processes. The fate of early generation oxidation products upon further aging is dependent on this initial chemistry, leading to a persistent effect of the precursor carbon skeleton. Aging experiments have been conducted using a high NOx smog chamber based aging technique. Long residence times and modestly elevated OH concentrations lead to typical maximum OH exposure of 3e11 molecule*seconds/cc, approaching several days equivalent exposure to ambient OH concentrations. A broad set of linear, branched and cyclic aliphatic hydrocarbons has been oxidized to determine the effects of carbon skeleton on the relative importance of fragmentation and functionalization and impacts on aerosol formation chemistry. Relative degree of fragmentation and functionalization is constrained by mass spectrometry of both the gas and particle phase. Measurements of the aerosol oxygen content and mass yield are reported, and structural effects on these properties are determined. Degree of unsaturation is hypothesized to have a significant impact on the effect of fragmentation reactions and to promote additional aerosol formation, extended aging and more oxygenated aerosol.

  15. Black carbon aerosol mixing state, organic aerosols and aerosol optical properties over the United Kingdom

    NASA Astrophysics Data System (ADS)

    McMeeking, G. R.; Morgan, W. T.; Flynn, M.; Highwood, E. J.; Turnbull, K.; Haywood, J.; Coe, H.

    2011-09-01

    Black carbon (BC) aerosols absorb sunlight thereby leading to a positive radiative forcing and a warming of climate and can also impact human health through their impact on the respiratory system. The state of mixing of BC with other aerosol species, particularly the degree of internal/external mixing, has been highlighted as a major uncertainty in assessing its radiative forcing and hence its climate impact, but few in situ observations of mixing state exist. We present airborne single particle soot photometer (SP2) measurements of refractory BC (rBC) mass concentrations and mixing state coupled with aerosol composition and optical properties measured in urban plumes and regional pollution over the United Kingdom. All data were obtained using instrumentation flown on the UK's BAe-146-301 large Atmospheric Research Aircraft (ARA) operated by the Facility for Airborne Atmospheric Measurements (FAAM). We measured sub-micron aerosol composition using an aerosol mass spectrometer (AMS) and used positive matrix factorization to separate hydrocarbon-like (HOA) and oxygenated organic aerosols (OOA). We found a higher number fraction of thickly coated rBC particles in air masses with large OOA relative to HOA, higher ozone-to-nitrogen oxides (NOx) ratios and large concentrations of total sub-micron aerosol mass relative to rBC mass concentrations. The more ozone- and OOA-rich air masses were associated with transport from continental Europe, while plumes from UK cities had higher HOA and NOx and fewer thickly coated rBC particles. We did not observe any significant change in the rBC mass absorption efficiency calculated from rBC mass and light absorption coefficients measured by a particle soot absorption photometer despite observing significant changes in aerosol composition and rBC mixing state. The contributions of light scattering and absorption to total extinction (quantified by the single scattering albedo; SSA) did change for different air masses, with lower SSA

  16. Large contribution of fossil fuel derived secondary organic carbon to water soluble organic aerosols in winter haze in China

    NASA Astrophysics Data System (ADS)

    Zhang, Yan-Lin; El-Haddad, Imad; Huang, Ru-Jin; Ho, Kin-Fai; Cao, Jun-Ji; Han, Yongming; Zotter, Peter; Bozzetti, Carlo; Daellenbach, Kaspar R.; Slowik, Jay G.; Salazar, Gary; Prévôt, André S. H.; Szidat, Sönke

    2018-03-01

    Water-soluble organic carbon (WSOC) is a large fraction of organic aerosols (OA) globally and has significant impacts on climate and human health. The sources of WSOC remain very uncertain in polluted regions. Here we present a quantitative source apportionment of WSOC, isolated from aerosols in China using radiocarbon (14C) and offline high-resolution time-of-flight aerosol mass spectrometer measurements. Fossil emissions on average accounted for 32-47 % of WSOC. Secondary organic carbon (SOC) dominated both the non-fossil and fossil derived WSOC, highlighting the importance of secondary formation to WSOC in severe winter haze episodes. Contributions from fossil emissions to SOC were 61 ± 4 and 50 ± 9 % in Shanghai and Beijing, respectively, significantly larger than those in Guangzhou (36 ± 9 %) and Xi'an (26 ± 9 %). The most important primary sources were biomass burning emissions, contributing 17-26 % of WSOC. The remaining primary sources such as coal combustion, cooking and traffic were generally very small but not negligible contributors, as coal combustion contribution could exceed 10 %. Taken together with earlier 14C source apportionment studies in urban, rural, semi-urban and background regions in Asia, Europe and the USA, we demonstrated a dominant contribution of non-fossil emissions (i.e., 75 ± 11 %) to WSOC aerosols in the Northern Hemisphere; however, the fossil fraction is substantially larger in aerosols from East Asia and the eastern Asian pollution outflow, especially during winter, due to increasing coal combustion. Inclusion of our findings can improve a modelling of effects of WSOC aerosols on climate, atmospheric chemistry and public health.

  17. 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.

  18. Formation of secondary organic aerosol coating on black carbon particles near vehicular emissions

    NASA Astrophysics Data System (ADS)

    Lee, Alex K. Y.; Chen, Chia-Li; Liu, Jun; Price, Derek J.; Betha, Raghu; Russell, Lynn M.; Zhang, Xiaolu; Cappa, Christopher D.

    2017-12-01

    Black carbon (BC) emitted from incomplete combustion can result in significant impacts on air quality and climate. Understanding the mixing state of ambient BC and the chemical characteristics of its associated coatings is particularly important to evaluate BC fate and environmental impacts. In this study, we investigate the formation of organic coatings on BC particles in an urban environment (Fontana, California) under hot and dry conditions using a soot-particle aerosol mass spectrometer (SP-AMS). The SP-AMS was operated in a configuration that can exclusively detect refractory BC (rBC) particles and their coatings. Using the -log(NOx / NOy) ratio as a proxy for photochemical age of air masses, substantial formation of secondary organic aerosol (SOA) coatings on rBC particles was observed due to active photochemistry in the afternoon, whereas primary organic aerosol (POA) components were strongly associated with rBC from fresh vehicular emissions in the morning rush hours. There is also evidence that cooking-related organic aerosols were externally mixed from rBC. Positive matrix factorization and elemental analysis illustrate that most of the observed SOA coatings were freshly formed, providing an opportunity to examine SOA coating formation on rBCs near vehicular emissions. Approximately 7-20 wt % of secondary organic and inorganic species were estimated to be internally mixed with rBC on average, implying that rBC is unlikely the major condensation sink of SOA in this study. Comparison of our results to a co-located standard high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) measurement suggests that at least a portion of SOA materials condensed on rBC surfaces were chemically different from oxygenated organic aerosol (OOA) particles that were externally mixed with rBC, although they could both be generated from local photochemistry.

  19. Semi-continuous measurement and characteristics of water-soluble organic carbon and ions of PM2.5 aerosol with PILS-TOC-IC in Baengnyeong Island

    NASA Astrophysics Data System (ADS)

    Kang, S.; Kim, K.; Park, G.; Ban, J.; Park, D.; Bae, M. S.; Shin, H. J.; Lee, M.; Seo, Y.; Choi, J.; Jung, D.; Seo, S.; Lee, T.; Kim, D. S.

    2016-12-01

    Aerosols have an important effect from scattering and absorbing the solar energy and indirectly by acting as cloud condensation nuclei and also some of the effects of aerosols are reduction in visibility, deterioration of human health, and deposition of pollutants to ecosystems. In various experimental results were showed that organic compounds have an important fraction from 10 to 70% of the total aerosol mass. Organic carbon contains water-soluble organic carbon (WSOC) and water insoluble organic carbon. WSOC are involved in the most unknown liquid-phase chemistry of wet aerosol and clouds. It is also worked as cloud condensation nuclei (CCN). Formation of secondary organic aerosol by chemical reaction of hydrocarbon compounds is a source of main pollution of WSOC compounds. Study of pollution source of WSOC is important method for creation process of secondary organic aerosol that completely has not studied.Analysis of WSOC is important and need to real-time measurement system for definition of chemical cause and sources. In this study, Particle-into-liquid sampler (PILS) coupled with total organic carbon (TOC) analyser and ion chromatography (PILS-TOC-IC), was used for semi-continuous measurement of WSOC and ionic compounds of PM2.5 during April-June 2016 at Baengnyeong Island Atmospheric Research Center, operated by the Korea National Institute of Environmental Research (NIER). PILS-TOC-IC can provide chemical information about real-time changes from ions composition and concentrations of WSOC and ionic compounds.

  20. Fluorescent water-soluble organic aerosols in the High Arctic atmosphere

    PubMed Central

    Fu, Pingqing; Kawamura, Kimitaka; Chen, Jing; Qin, Mingyue; Ren, Lujie; Sun, Yele; Wang, Zifa; Barrie, Leonard A.; Tachibana, Eri; Ding, Aijun; Yamashita, Youhei

    2015-01-01

    Organic aerosols are ubiquitous in the earth’s atmosphere. They have been extensively studied in urban, rural and marine environments. However, little is known about the fluorescence properties of water-soluble organic carbon (WSOC) or their transport to and distribution in the polar regions. Here, we present evidence that fluorescent WSOC is a substantial component of High Arctic aerosols. The ratios of fluorescence intensity of protein-like peak to humic-like peak generally increased from dark winter to early summer, indicating an enhanced contribution of protein-like organics from the ocean to Arctic aerosols after the polar sunrise. Such a seasonal pattern is in agreement with an increase of stable carbon isotope ratios of total carbon (δ13CTC) from −26.8‰ to −22.5‰. Our results suggest that Arctic aerosols are derived from a combination of the long-range transport of terrestrial organics and local sea-to-air emission of marine organics, with an estimated contribution from the latter of 8.7–77% (mean 45%). PMID:25920042

  1. Dependency of black-carbon-induced atmospheric warming on the concentration of sulphate and organic aerosols

    NASA Astrophysics Data System (ADS)

    Kim, S.; Yoon, S.; in-Jin, C.; Ramanathan, V.; Ramana, M.

    2010-12-01

    Previous modeling studies have showed that the net radiative effect of black carbon (BC) and organic aerosols generated by fossil-fuel combustion and biomass-fuel cooking contribute to a warming by absorbing solar radiation, and the warming effect of fossil-fuel BC is larger than that of biomass-fuel cooking [Ramana et al., Nature Geoscience, 2010]. However, the extent of BC warming is regulated by the ambient concentrations of sulphate and organic carbon (OC) aerosols, which reflect the solar radiation and cool the surface, thus enhancing the net warming caused by BC and GHGs. This is because the major sources of BC also emit CO2 and other greenhouse gases (GHGs) (that warm the climate), and sulfates, nitrates, organics and other particles (that cool the climate). In this study, we present the impact of BC-to-sulphate and BC-to-OC ratios on atmospheric warming on the basis of surface-based filter and in-situ measurements at Gosan climate observatory in Jeju, South Korea and radiative transfer calculations with AERONET Cimel sun/sky radiometer and micro-pulse lidar measurements as a model input. We investigate (1) BC-to-sulphate and BC-to-OC ratios, (2) aerosol solar-absorption efficiency (i.e., co-single scattering albedo) and (3) corresponding atmospheric direct radiative forcing and heating rate of aerosol plumes from N. China (Beijing), S. China (Shanghai) and clean marine sources during ACE-Asia (April-May 2001), ABC-EAREX2005 (March-April 2005) and CAMPEX (August-September 2008), and discuss their relationships.

  2. PRIMARY AND SECONDARY ORGANIC AEROSOLS OVER THE UNITED STATES: ESTIMATES ON THE BASIS OF OBSERVED ORGANIC CARBON (OC) AND ELEMENTAL CARBON (EC), AND AIR QUALITY MODELED PRIMARY (OC/EC) RATIOS

    EPA Science Inventory

    The temporal and spatial distributions of primary and secondary organic carbon aerosols (OC) over the continental US during June 15 to August 31, 1999, were estimated by using observational OC and elemental carbon (EC) data from Interagency Monitoring of Protected Visual Environm...

  3. Chemical Properties of Brown Carbon Aerosol Generated at the Missoula Fire Sciences Laboratory

    NASA Astrophysics Data System (ADS)

    Washenfelder, R. A.; Womack, C.; Franchin, A.; Middlebrook, A. M.; Wagner, N.; Manfred, K.

    2017-12-01

    Aerosol scattering and absorption are still among the largest uncertainties in quantifying radiative forcing. Biomass burning is a major source of light-absorbing carbonaceous aerosol in the United States. These aerosol are generally classified into two categories: black carbon (graphitic-like aerosol that absorbs broadly across the ultraviolet and visible spectral regions) and brown carbon (organic aerosol that absorbs strongly in the ultraviolet and near-visible spectral regions). The composition, volatility, and chemical aging of brown carbon are poorly known, but are important to understanding its radiative effects. We deployed three novel instruments to the Missoula Fire Sciences Laboratory in 2016 to measure brown carbon absorption: a photoacoustic spectrometer, broadband cavity enhanced spectrometer, and particle-into-liquid sampler coupled to a liquid waveguide capillary cell. The instruments sampled from a shared inlet with well-characterized dilution and thermal denuding. We sampled smoke from 32 controlled burns of fuels relevant to western U.S. wildfires. We use these measurements to determine the volatility of water-soluble brown carbon, and compare this to the volatility of water-soluble organic aerosol and total organic aerosol. We further examine the wavelength-dependence of the water-soluble brown carbon absorption as a function of denuder temperature. Together this gives new information about the solubility, volatility, and chemical composition of brown carbon.

  4. Marine biogenic sources of organic nitrogen and water-soluble organic aerosols over the western North Pacific in summer

    NASA Astrophysics Data System (ADS)

    Miyazaki, Y.; Kawamura, K.; Sawano, M.

    2009-12-01

    Size-segregated aerosol samples of organic nitrogen (ON) as well as water-soluble organic compounds were obtained over the western North Pacific in the summer of 2008. Mass contributions of organics to the total aerosol mass were 20-40% in the supermicron mode and 45-60% in the submicron mode. ON as well as diacids and water-soluble organic carbon (WSOC) showed bimodal size distributions over the remote ocean, where high values of chlorophyll-a concentrations and depth-integrated primary production were observed. The ON concentrations increased with increasing biogenic tracer compounds such as methanesulfuric acid (MSA) and azelaic acid (C9). The average concentrations of ON and organic carbon (OC) in aerosols more influenced by marine biological activity were found to be about two times greater than those in biologically less influenced aerosols. These results provide evidence of marine biogenic sources of ON as well as OC. An average ON/OC ratio in biologically more influenced aerosols was as high as 0.49±0.11, which is higher than that in biologically less influenced aerosols (0.35±0.10). This result indicates that organic aerosol in this region is enriched in organic nitrogen, which linked to oceanic biological activity and comparable in magnitude to the marine biogenic OC source. We discuss possible processes for primary and secondary production of ON and OC in these samples, and stable nitrogen and carbon isotope ratios for total nitrogen (TN) and total carbon (TC).

  5. Water-soluble organic carbon, dicarboxylic acids, ketoacids, and α-dicarbonyls in the tropical Indian aerosols

    NASA Astrophysics Data System (ADS)

    Pavuluri, Chandra Mouli; Kawamura, Kimitaka; Swaminathan, T.

    2010-06-01

    Tropical aerosol (PM10) samples (n = 49) collected from southeast coast of India were studied for water-soluble dicarboxylic acids (C2-C12), ketocarboxylic acids (C2-C9), and α-dicarbonyls (glyoxal and methylglyoxal), together with analyses of total carbon (TC) and water-soluble organic carbon (WSOC). Their distributions were characterized by a predominance of oxalic acid followed by terephthalic (t-Ph), malonic, and succinic acids. Total concentrations of diacids (227-1030 ng m-3), ketoacids (16-105 ng m-3), and dicarbonyls (4-23 ng m-3) are comparative to those from other Asian megacities such as Tokyo and Hong Kong. t-Ph acid was found as the second most abundant diacid in the Chennai aerosols. This feature has not been reported previously in atmospheric aerosols. t-Ph acid is most likely derived from the field burning of plastics. Water-soluble diacids were found to contribute 0.4%-3% of TC and 4%-11% of WSOC. Based on molecular distributions and backward air mass trajectories, we found that diacids and related compounds in coastal South Indian aerosols are influenced by South Asian and Indian Ocean monsoons. Organic aerosols are also suggested to be significantly transported long distances from North India and the Middle East in early winter and from Southeast Asia in late winter, but some originate from photochemical reactions over the Bay of Bengal. In contrast, the Arabian Sea, Indian Ocean, and South Indian continent are suggested as major source regions in summer. We also found daytime maxima of most diacids, except for C9 and t-Ph acids, which showed nighttime maxima in summer. Emissions from marine and terrestrial plants, combined with land/sea breezes and in situ photochemical oxidation, are suggested especially in summer as an important factor that controls the composition of water-soluble organic aerosols over the southeast coast of India. Regional emissions from anthropogenic sources are also important in megacity Chennai, but their influence is

  6. Using radiocarbon to constrain black and organic carbon aerosol sources in Salt Lake City

    NASA Astrophysics Data System (ADS)

    Mouteva, Gergana O.; Randerson, James T.; Fahrni, Simon M.; Bush, Susan E.; Ehleringer, James R.; Xu, Xiaomei; Santos, Guaciara M.; Kuprov, Roman; Schichtel, Bret A.; Czimczik, Claudia I.

    2017-09-01

    Black carbon (BC) and organic carbon (OC) aerosols are important components of fine particulate matter (PM2.5) in polluted urban environments. Quantifying the contribution of fossil fuel and biomass combustion to BC and OC concentrations is critical for developing and validating effective air quality control measures and climate change mitigation policy. We used radiocarbon (14C) to measure fossil and contemporary biomass contributions to BC and OC at three locations in Salt Lake City, Utah, USA, during 2012-2014, including during winter inversion events. Aerosol filters were analyzed with the Swiss_4S thermal-optical protocol to isolate BC. We measured fraction modern (fM) of BC and total carbon in PM2.5 with accelerator mass spectrometry and derived the fM of OC using isotope mass balance. Combined with 14C information of end-member composition, our data set of 31 14C aerosol measurements provided a baseline of the fossil and contemporary biomass components of carbonaceous aerosol. We show that fossil fuels were the dominant source of carbonaceous aerosol during winter, contributing 88% (80-98%) of BC and 58% (48-69%) of OC. While the concentration of both BC and OC increased during inversion events, the relative source contributions did not change. The sources of BC also did not vary throughout the year, while OC had a considerably higher contemporary biomass component in summer at 62% (49-76%) and was more variable. Our results suggest that in order to reduce PM2.5 levels in Salt Lake City to meet national standards, a more stringent policy targeting mobile fossil fuel sources may be necessary.

  7. Organic and inorganic markers and stable C-, N-isotopic compositions of tropical coastal aerosols from megacity Mumbai: sources of organic aerosols and atmospheric processing

    NASA Astrophysics Data System (ADS)

    Aggarwal, S. G.; Kawamura, K.; Umarji, G. S.; Tachibana, E.; Patil, R. S.; Gupta, P. K.

    2012-08-01

    To better understand the sources of PM10 samples from Mumbai, India, aerosol chemical compositions, i.e. total carbon (TC), organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and inorganic ions were studied together with specific markers such as methanesulfonate (MSA), oxalic acid (C2), azelaic acid (C9), and levoglucosan. The results revealed that biofuel/biomass burning and fossil fuel combustion are the major sources of the Mumbai aerosols. Nitrogen-isotopic (δ15N) composition of aerosol total nitrogen, which ranged from 18.1 to 25.4‰, also suggest that biofuel/biomass burning is the dominant source in both summer and winter seasons. Aerosol mass concentrations of major species increased 3-4 times in winter compared to summer, indicating an enhanced emission from these sources in winter season. Photochemical production tracers, C2 diacid and nssSO42- do not show diurnal changes. Concentrations of C2 diacid and WSOC show a strong correlation (r2 = 0.95). In addition, WSOC to OC (or TC) ratios remain almost constant for day- (0.37 ± 0.06 (0.28 ± 0.04)) and nighttime (0.38 ± 0.07 (0.28 ± 0.06)), suggesting that mixing of fresh secondary organic aerosols is not significant rather the Mumbai aerosols are photochemically well processed. Concentrations of MSA and C9 diacid present a positive correlation (r2 = 0.75), indicating a marine influence on Mumbai aerosols in addition to local/regional influence. Backward air mass trajectory analyses further suggested that the Mumbai aerosols are largely influenced by long-range continental and regional transport. Stable C-isotopic ratios (δ13C) of TC ranged from -27.0 to -25.4‰ with slightly lower average (-26.5 ± 0.3‰) in summer than in winter (-25.9 ± 0.3‰). Positive correlation between WSOC/TC ratios and δ13C values suggested that the increment in δ13C of wintertime TC may be caused by prolonged photochemical processing of organic aerosols in this season. This study suggests

  8. Secondary formation of water-soluble organic acids and α-dicarbonyls and their contributions to total carbon and water-soluble organic carbon: Photochemical aging of organic aerosols in the Arctic spring

    NASA Astrophysics Data System (ADS)

    Kawamura, Kimitaka; Kasukabe, Hideki; Barrie, Leonard A.

    2010-11-01

    Water-soluble dicarboxylic acids (C2-C12), ketocarboxylic acids (C2-C6, C9), and α-dicarbonyls (glyoxal and methylglyoxal) were determined in the Arctic aerosols collected in winter to early summer, as well as aerosol total carbon (TC) and water-soluble organic carbon (WSOC). Concentrations of TC and WSOC gradually decreased from late February to early June with a peak in spring, indicating a photochemical formation of water-soluble organic aerosols at a polar sunrise. We found that total (C2-C11) diacids (7-84 ng m-3) increased at polar sunrise by a factor of 4 and then decreased toward summer. Their contributions to TC (average 4.0%) peaked in early April and mid-May. The contribution of total diacids to WSOC was on average 7.1%. It gradually increased from February (5%) to a maximum in April (12.7%) with a second peak in mid-May (10.4%). Although oxalic acid (C2) is the dominant diacid until April, its predominance was replaced by succinic acid (C4) after polar sunrise. This may indicate that photochemical production of C2 was overwhelmed by its degradation when solar radiation was intensified and the atmospheric transport of its precursors from midlatitudes to the Arctic was ended in May. Interestingly, the contributions of azelaic (C9) and ω-oxobutanoic acids to WSOC increased in early summer possibly due to an enhanced emission of biogenic unsaturated fatty acids from the ocean followed by photochemical oxidation in the atmosphere. An enhanced contribution of diacids to TC and WSOC at polar sunrise may significantly alter the hygroscopic properties of organic aerosols in the Arctic.

  9. Formation of brown carbon via reactions of ammonia with secondary organic aerosols from biogenic and anthropogenic precursors

    NASA Astrophysics Data System (ADS)

    Updyke, Katelyn M.; Nguyen, Tran B.; Nizkorodov, Sergey A.

    2012-12-01

    Filter samples of secondary organic aerosols (SOA) generated from the ozone (O3)- and hydroxyl radical (OH)-initiated oxidation of various biogenic (isoprene, α-pinene, limonene, α-cedrene, α-humulene, farnesene, pine leaf essential oils, cedar leaf essential oils) and anthropogenic (tetradecane, 1,3,5-trimethylbenzene, naphthalene) precursors were exposed to humid air containing approximately 100 ppb of gaseous ammonia (NH3). Reactions of SOA compounds with NH3 resulted in production of light-absorbing "brown carbon" compounds, with the extent of browning ranging from no observable change (isoprene SOA) to visible change in color (limonene SOA). The aqueous phase reactions with dissolved ammonium (NH4+) salts, such as ammonium sulfate, were equally efficient in producing brown carbon. Wavelength-dependent mass absorption coefficients (MAC) of the aged SOA were quantified by extracting known amounts of SOA material in methanol and recording its UV/Vis absorption spectra. For a given precursor, the OH-generated SOA had systematically lower MAC compared to the O3-generated SOA. The highest MAC values, for brown carbon from SOA resulting from O3 oxidation of limonene and sesquiterpenes, were comparable to MAC values for biomass burning particles but considerably smaller than MAC values for black carbon aerosols. The NH3/NH4+ + SOA brown carbon aerosol may contribute to aerosol optical density in regions with elevated concentrations of NH3 or ammonium sulfate and high photochemical activity.

  10. Semicontinuous measurements of organic carbon and acidity during the Pittsburgh air quality study: implications for acid-catalyzed organic aerosol formation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    S. Takahama; C.I. Davidson; S.N. Pandis

    2006-04-01

    Laboratory evidence suggests that inorganic acid seed particles may increase secondary organic aerosol yields secondary organic aerosol (SOA) through heterogeneous chemistry. Additional laboratory studies, however, report that organic acidity generated in the same photochemical process by which SOA is formed may be sufficient to catalyze these heterogeneous reactions. Understanding the interaction between inorganic acidity and SOA mass is important when evaluating emission controls to meet PM2.5 regulations. Semicontinuous measurements of organic carbon (OC), elemental carbon (EC), and inorganic species from the Pittsburgh Air Quality Study were examined to determine if coupling in the variations of inorganic acidity and OC couldmore » be detected. Significant enhancements of SOA production could not be detected due to inorganic acidity in Western Pennsylvania most of the time, but its signal might have been lost in the noise. If a causal relationship between inorganic acidity and OC is assumed, reductions in OC for Western Pennsylvania that might result from drastic reductions in inorganic acidity were estimated to be 2 {+-} 4% by a regression technique, and an upper bound for this geographic area was estimated to be 5 {+-} 8% based on calculations from laboratory measurements. 48 refs., 7 figs., 3 tabs.« less

  11. AN INITIAL ASSESSMENT OF THE CLIMATE IMPACT OF SECONDARY ORGANIC AEROSOLS

    NASA Astrophysics Data System (ADS)

    O'Donnell, D.; Feichter, J.

    2009-12-01

    Atmospheric aerosols influence the Earth’s climate by absorbing and scattering solar radiation (the direct effect) and by altering the properties of clouds (indirect effects). Measurements have shown that a substantial fraction of the tropospheric aerosol burden consists of organic compounds. Hundreds of different organic species have been identified. While progress has been made in the understanding of the role of certain aerosol types in the climate system, that of organic aerosols remains poorly understood and the climate influences resulting from their presence poorly constrained. Organic aerosols are emitted directly from the surface (primary organic aerosols, POA) and are also formed in the atmosphere from gaseous precursors by oxidation reactions (secondary organic aerosols, SOA). Both biogenic and anthropogenic precursors have been identified. Biogenic emissions of aerosol precursors are known to be climate-dependent. Thus, a bi-directional dependency exists between the biosphere and the atmosphere, whereby aerosols of biogenic origin influence the climate system, which in turn affects biogenic aerosol precursor production. This study builds upon the global aerosol-climate model ECHAM5/HAM and adds techniques to model SOA as well as the necessary global emission inventories. Emission of biogenic precursors is calculated online. Formation of SOA is modeled by the well-known two-product model of SOA formation. SOA is subject to the same aerosol microphysics and sink processes as other modeled species (sulphate, black carbon, primary organic carbon, sea salt and dust). The aerosol radiative effects are calculated on a size resolved basis, and the aerosol scheme is coupled to the model cloud microphysics, permitting estimation of both direct and indirect aerosol effects. The following results will be discussed: (i) Estimation of the direct and indirect effects of biogenic and anthropogenic SOA, (ii) Estimation of the sign and magnitude of the biospheric

  12. Ubiquitous influence of wildfire emissions and secondary organic aerosol on summertime atmospheric aerosol in the forested Great Lakes region

    NASA Astrophysics Data System (ADS)

    Gunsch, Matthew J.; May, Nathaniel W.; Wen, Miao; Bottenus, Courtney L. H.; Gardner, Daniel J.; VanReken, Timothy M.; Bertman, Steven B.; Hopke, Philip K.; Ault, Andrew P.; Pratt, Kerri A.

    2018-03-01

    Long-range aerosol transport affects locations hundreds of kilometers from the point of emission, leading to distant particle sources influencing rural environments that have few major local sources. Source apportionment was conducted using real-time aerosol chemistry measurements made in July 2014 at the forested University of Michigan Biological Station near Pellston, Michigan, a site representative of the remote forested Great Lakes region. Size-resolved chemical composition of individual 0.5-2.0 µm particles was measured using an aerosol time-of-flight mass spectrometer (ATOFMS), and non-refractory aerosol mass less than 1 µm (PM1) was measured with a high-resolution aerosol mass spectrometer (HR-AMS). The field site was influenced by air masses transporting Canadian wildfire emissions and urban pollution from Milwaukee and Chicago. During wildfire-influenced periods, 0.5-2.0 µm particles were primarily aged biomass burning particles (88 % by number). These particles were heavily coated with secondary organic aerosol (SOA) formed during transport, with organics (average O/C ratio of 0.8) contributing 89 % of the PM1 mass. During urban-influenced periods, organic carbon, elemental carbon-organic carbon, and aged biomass burning particles were identified, with inorganic secondary species (ammonium, sulfate, and nitrate) contributing 41 % of the PM1 mass, indicative of atmospheric processing. With current models underpredicting organic carbon in this region and biomass burning being the largest combustion contributor to SOA by mass, these results highlight the importance for regional chemical transport models to accurately predict the impact of long-range transported particles on air quality in the upper Midwest, United States, particularly considering increasing intensity and frequency of Canadian wildfires.

  13. Organic and inorganic markers and stable C-, N-isotopic compositions of tropical coastal aerosols from megacity Mumbai: sources of organic aerosols and atmospheric processing

    NASA Astrophysics Data System (ADS)

    Aggarwal, S. G.; Kawamura, K.; Umarji, G. S.; Tachibana, E.; Patil, R. S.; Gupta, P. K.

    2013-05-01

    To better understand the sources of PM10 samples in Mumbai, India, aerosol chemical composition, i.e., total carbon (TC), organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and inorganic ions were studied together with specific markers such as methanesulfonate (MSA), oxalic acid (C2), azelaic acid (C9), and levoglucosan. The results revealed that biofuel/biomass burning and fossil fuel combustion are the major sources of the Mumbai aerosols. Nitrogen-isotopic (δ15N) composition of aerosol total nitrogen, which ranged from 18.1 to 25.4‰, also suggests that biofuel/biomass burning is a predominate source in both the summer and winter seasons. Aerosol mass concentrations of major species increased 3-4 times in winter compared to summer, indicating enhanced emission from these sources in the winter season. Photochemical production tracers, C2 diacid and nssSO42-, do not show diurnal changes. Concentrations of C2 diacid and WSOC show a strong correlation (r2 = 0.95). In addition, WSOC to OC (or TC) ratios remain almost constant for daytime (0.37 ± 0.06 (0.28 ± 0.04)) and nighttime (0.38 ± 0.07 (0.28 ± 0.06)), suggesting that mixing of fresh secondary organic aerosols is not significant and the Mumbai aerosols are photochemically well processed. Concentrations of MSA and C9 diacid present a positive correlation (r2 = 0.75), indicating a marine influence on Mumbai aerosols in addition to local/regional influence. Backward air mass trajectory analyses further suggested that the Mumbai aerosols are largely influenced by long-range continental and regional transport. Stable C-isotopic ratios (δ13C) of TC ranged from -27.0 to -25.4‰, with slightly lower average (-26.5 ± 0.3‰) in summer than in winter (-25.9 ± 0.3‰). Positive correlation between WSOC/TC ratios and δ13C values suggested that the relative increment in 13C of wintertime TC may be caused by prolonged photochemical processing of organic aerosols in this season. This

  14. Refractive Index and Absorption Attribution of Highly Absorbing Brown Carbon Aerosols from an Urban Indian City-Kanpur.

    PubMed

    Shamjad, P M; Tripathi, S N; Thamban, Navaneeth M; Vreeland, Heidi

    2016-11-24

    Atmospheric aerosols influence Earth's radiative balance, having both warming and cooling effects. Though many aerosols reflect radiation, carbonaceous aerosols such as black carbon and certain organic carbon species known as brown carbon have the potential to warm the atmosphere by absorbing light. Black carbon absorbs light over the entire solar spectrum whereas brown carbon absorbs near-UV wavelengths and, to a lesser extent, visible light. In developing countries, such as India, where combustion sources are prolific, the influence of brown carbon on absorption may be significant. In order to better characterize brown carbon, we present experimental and modeled absorption properties of submicron aerosols measured in an urban Indian city (Kanpur). Brown carbon here is found to be fivefold more absorbing at 365 nm wavelength compared to previous studies. Results suggest ~30% of total absorption in Kanpur is attributed to brown carbon, with primary organic aerosols contributing more than secondary organics. We report the spectral brown carbon refractive indices along with an experimentally constrained estimate of the influence of aerosol mixing state on absorption. We conclude that brown carbon in Kanpur is highly absorbing in nature and that the mixing state plays an important role in light absorption from volatile species.

  15. Refractive Index and Absorption Attribution of Highly Absorbing Brown Carbon Aerosols from an Urban Indian City-Kanpur

    PubMed Central

    Shamjad, P. M.; Tripathi, S. N.; Thamban, Navaneeth M.; Vreeland, Heidi

    2016-01-01

    Atmospheric aerosols influence Earth’s radiative balance, having both warming and cooling effects. Though many aerosols reflect radiation, carbonaceous aerosols such as black carbon and certain organic carbon species known as brown carbon have the potential to warm the atmosphere by absorbing light. Black carbon absorbs light over the entire solar spectrum whereas brown carbon absorbs near-UV wavelengths and, to a lesser extent, visible light. In developing countries, such as India, where combustion sources are prolific, the influence of brown carbon on absorption may be significant. In order to better characterize brown carbon, we present experimental and modeled absorption properties of submicron aerosols measured in an urban Indian city (Kanpur). Brown carbon here is found to be fivefold more absorbing at 365 nm wavelength compared to previous studies. Results suggest ~30% of total absorption in Kanpur is attributed to brown carbon, with primary organic aerosols contributing more than secondary organics. We report the spectral brown carbon refractive indices along with an experimentally constrained estimate of the influence of aerosol mixing state on absorption. We conclude that brown carbon in Kanpur is highly absorbing in nature and that the mixing state plays an important role in light absorption from volatile species. PMID:27883083

  16. Aerosol carbon isotope composition over Baltic Sea

    NASA Astrophysics Data System (ADS)

    Garbaras, Andrius; Pabedinskas, Algirdas; Masalaite, Agne; Petelski, Tomasz; Gorokhova, Elena; Sapolaite, Justina; Ezerinskis, Zilvinas; Remeikis, Vidmantas

    2017-04-01

    Particulate carbonaceous matter is significant contributor to ambient particulate matter originating from intervening sources which contribution is difficult to quantify due to source diversity, chemical complexity and processes during atmospheric transport. Carbon isotope analysis can be extremely useful in source apportionment of organic matter due to the unique isotopic signatures associated with anthropocentric (fossil fuel), continental (terrestrial plants) and marine sources, and is particularly effective when these sources are mixed (Ceburnis et al., 2011;Ceburnis et al., 2016). We will present the isotope ratio measurement results of aerosol collected during the cruise in the Baltic Sea. Sampling campaign of PM10 and size segregated aerosol particles was performed on the R/V "Oceania" in October 2015. Air mass back trajectories were prevailing both from the continental and marine areas during the sampling period. The total carbon concentration varied from 1 µg/m3 to 8 µg/m3. Two end members (δ13C = -25‰ and δ13C = -28 ‰ ) were established from the total stable carbon isotope analysis in PM10 fraction. δ13C analysis in size segregated aerosol particles revealed δ13C values being highest in the 1 - 2.5 µm range (δ13C = -24.9 ‰ ) during continental transport, while lowest TC δ13C values (δ13C ≈ -27 ‰ ) were detected in the size range D50 <1 µm during stormy weather when air mass trajectory prevailed from the western direction. These measurements revealed that simplified isotope mixing model can not be applied for the aerosol source apportionment (Masalaite et al., 2015) in the perturbed marine environment. Additionally, concentration of bacteria and fungi were measured in size segregated and PM10 aerosol fraction. We were able to relate aerosol source δ13C end members with the abundance of bacteria and fungi over Baltic Sea combining air mass trajectories, stable isotope data, fungi and bacteria concentrations. Ceburnis, D., Garbaras, A

  17. Hygroscopic Characteristics of Organic Laden Ambient Aerosols in Yosemite National Park

    NASA Astrophysics Data System (ADS)

    Malm, W. C.; Day, D. E.; Kreidenweis, S. M.; Collett, J. L.; Carrico, C. M.; Lee, T.; Bench, G.; Carrillo, J.

    2003-12-01

    Water absorption by inorganic compounds can be modeled with some degree of certainty; however, water uptake by ambient organic aerosols remains speculative. To improve the understanding of organic hygroscopicity, an aerosol characterization study was conducted at Yosemite National Park, California, starting in July and ending in the first week of September 2002. High time resolution measurement (15-minute time increments) of PM2.5 ionic species (Cl-, SO42-, NO3-, Na+, NH4+, K+, Mg2+, and Ca2+) were measured using PILS (Particle-Into-Liquid-System)/IC (Ion Chromatography). Commercially available annular denuders and a PM2.5 cyclone (URG) were used upstream of the PILS/IC to remove particles greater than 2.5 μm and acidic and basic gases. A dual wavelength aethalometer and an R&P particulate carbon monitor were used to measure carbon on a semi-continuous basis while a DRUM sampler allowed for semi-continuous estimates of concentrations of elements associated with crustal material. Standard IMPROVE type samplers were used to measure 24-hr integrated samples of these same aerosols. Two nephelometers operated in tandem, one dry and the other with a controlled humidity environment, were used to measure f(RH) = bscat(RH)/bscat,dry, where bscat(RH) is the scattering coefficient measured at some relative humidity and bscat,dry is the scattering coefficient measured at RH <10%. The aerosol composition was highly variable in time, with a strong diurnal cycle. Organic carbon mass was observed to be, on the average, 70% of the fine mass with days where its contribution was well over 95% of the mass. Measurements of carbon isotopes revealed the fraction of carbon from biogenic sources to range from approximately 73 to 95%. Water soluble potassium was highly correlated with carbon mass, suggesting the influence of wood smoke. The ionic fraction of the aerosol consisted primarily of ammonium sulfate and in most cases nitrate was in the form of sodium nitrate. Fine soil mass was

  18. Seasonal and spatial variability of the organic matter-to-organic carbon mass ratios in Chinese urban organic aerosols and a first report of high correlations between aerosol oxalic acid and zinc

    NASA Astrophysics Data System (ADS)

    Xing, L.; Fu, T.-M.; Cao, J. J.; Lee, S. C.; Wang, G. H.; Ho, K. F.; Cheng, M.-C.; You, C.-F.; Wang, T. J.

    2013-01-01

    We calculated the organic matter to organic carbon mass ratios (OM/OC mass ratios) in PM2.5 collected from 14 Chinese cities during summer and winter of 2003 and analyzed the causes for their seasonal and spatial variability. The OM/OC mass ratios were calculated two ways. Using a mass balance method, the calculated OM/OC mass ratios averaged 1.92 ± 0.39 yr-round, with no significant seasonal or spatial variation. The second calculation was based on chemical species analyses of the organic compounds extracted from the PM2.5 samples using dichloromethane/methanol and water. The calculated OM/OC mass ratio in summer was relatively high (1.75 ± 0.13) and spatially-invariant, due to vigorous photochemistry and secondary OA production throughout the country. The calculated OM/OC mass ratio in winter (1.59 ± 0.18) was significantly lower than that in summer, with lower values in northern cities (1.51 ± 0.07) than in southern cities (1.65 ± 0.15). This likely reflects the wider usage of coal for heating purposes in northern China in winter, in contrast to the larger contributions from biofuel and biomass burning in southern China in winter. On average, organic matters constituted 36% and 34% of Chinese urban PM2.5 mass in summer and winter, respectively. We reported, for the first time, high correlations between Zn and oxalic acid in Chinese urban aerosols in summer. This is consistent with the formation of stable Zn oxalate complex in the aerosol phase previously proposed by Furukawa and Takahashi (2011). We found that many other dicarboxylic acids were also highly correlated with Zn in the summer Chinese urban aerosol samples, suggesting that they may also form stable organic complexes with Zn. Such formation may have profound implications for the atmospheric abundance and hygroscopic property of aerosol dicarboxylic acids.

  19. Stable carbon isotopic compositions of total carbon, dicarboxylic acids and glyoxylic acid in the tropical Indian aerosols: Implications for sources and photochemical processing of organic aerosols

    NASA Astrophysics Data System (ADS)

    Pavuluri, Chandra Mouli; Kawamura, Kimitaka; Swaminathan, T.; Tachibana, Eri

    2011-09-01

    The tropical Indian aerosols (PM10) collected on day- and nighttime bases in winter and summer, 2007 from Chennai (13.04°N; 80.17°E) were studied for stable carbon isotopic compositions (δ13C) of total carbon (TC), individual dicarboxylic acids (C2-C9) and glyoxylic acid (ωC2). δ13C values of TC ranged from -23.9‰ to -25.9‰ (-25.0 ± 0.6‰; n = 49). Oxalic (C2) (-17.1 ± 2.5‰), malonic (C3) (-20.8 ± 1.8‰), succinic (C4) (-22.5 ± 1.5‰) and adipic (C6) (-20.6 ± 4.1‰) acids and ωC2 acid (-22.4 ± 5.5‰) were found to be more enriched with 13C compared to TC. In contrast, suberic (C8) (-29.4 ± 1.8‰), phthalic (Ph) (-30.1 ± 3.5‰) and azelaic (C9) (-28.4 ± 5.8‰) acids showed smaller δ13C values than TC. Based on comparisons of δ13C values of TC in Chennai aerosols to those (-24.7 ± 2.2‰) found in unburned cow-dung samples collected from Chennai and isotopic signatures of the particles emitted from point sources, we found that biofuel/biomass burning are the major sources of carbonaceous aerosols in South and Southeast Asia. The decrease in δ13C values of C9 diacid by about 5‰ from winter to summer suggests that tropical plant emissions also significantly contribute to organic aerosol in this region. Significant increase in δ13C values from C4 to C2 diacids in Chennai aerosols could be attributed for their photochemical processing in the tropical atmosphere during long-range transport from source regions.

  20. Inorganic markers, carbonaceous components and stable carbon isotope from biomass burning aerosols in northeast China

    NASA Astrophysics Data System (ADS)

    Cao, F.; Zhang, Y.; Kawamura, K.

    2015-12-01

    To better characterize the sources of fine particulate matter (i.e. PM2.5) in Sanjiang Plain, Northeast China, aerosol chemical composition such total carbon (TC), organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and inorganic ions were studied as well as stable carbon isotopic composition (δ13C) of TC. Intensively open biomass burning episodes were identified from late September to early October by satellite fire and aerosol optical depth maps. During the biomass burning episodes, concentrations of PM2.5, OC, EC, and WSOC increased by a factor of 4-12 compared to non-biomass-burning periods. Non-sea-salt potassium is strongly correlated with PM2.5, OC, EC and WSOC, suggesting an important contribution of biomass burning emission. The enrichment in both the non-sea-salt potassium and chlorine is significantly larger than other inorganic species, indicating that biomass burning aerosols in Sanjiang Plain is mostly fresh and less aged. In addition, WSOC to OC ratio is relatively lower compared to that reported in biomass burning aerosols in tropical regions, supporting that biomass burning aerosols in Sanjiang Plain is mostly primary and secondary organic aerosols is not significant. A lower average δ13C value (-26.2‰) is found for the biomass-burning aerosols, suggesting a dominant contribution from combustion of C3 plants in the studied region.

  1. Improving organic aerosol treatments in CESM/CAM5: Development, application, and evaluation

    NASA Astrophysics Data System (ADS)

    Glotfelty, Timothy; He, Jian; Zhang, Yang

    2017-06-01

    New treatments for organic aerosol (OA) formation have been added to a modified version of the CESM/CAM5 model (CESM-NCSU). These treatments include a volatility basis set treatment for the simulation of primary and secondary organic aerosols (SOAs), a simplified treatment for organic aerosol (OA) formation from glyoxal, and a parameterization representing the impact of new particle formation (NPF) of organic gases and sulfuric acid. With the inclusion of these new treatments, the concentration of oxygenated organic aerosol increases by 0.33 µg m-3 and that of primary organic aerosol (POA) decreases by 0.22 µg m-3 on global average. The decrease in POA leads to a reduction in the OA direct effect, while the increased OOA increases the OA indirect effects. Simulations with the new OA treatments show considerable improvement in simulated SOA, oxygenated organic aerosol (OOA), organic carbon (OC), total carbon (TC), and total organic aerosol (TOA), but degradation in the performance of HOA. In simulations of the current climate period, despite some deviations from observations, CESM-NCSU with the new OA treatments significantly improves the magnitude, spatial pattern, seasonal pattern of OC and TC, as well as, the speciation of TOA between POA and OOA. Sensitivity analysis reveals that the inclusion of the organic NPF treatment impacts the OA indirect effects by enhancing cloud properties. The simulated OA level and its impact on the climate system are most sensitive to choices in the enthalpy of vaporization and wet deposition of SVOCs, indicating that accurate representations of these parameters are critical for accurate OA-climate simulations.

  2. Seasonal variation of marine organic aerosols in the North Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Fu, P.; Kawamura, K.

    2017-12-01

    Atmospheric aerosols were collected in the marine boundary layer during five marine cruises in the northern Pacific Ocean from October 1996 to July 1997. Organic molecular compositions of the marine aerosols were measured using gas chromatography/mass spectrometry (GC/MS). Higher concentrations of levoglucosan and its isomers, the biomass-burning tracers, were observed in the coastal regions than those in the central north Pacific. Seasonal trends of biomass burning tracers were found to be higher in fall-winter-spring than in summer, suggesting an enhanced influence of continental aerosols to the marine atmosphere during cold seasons when the westerlies prevail. However, the atmospheric levels of secondary organic aerosol (SOA) tracers from the photooxidation of isoprene and monoterpenes were higher in warm seasons than cold seasons, which are in accordance with the enhanced emissions of biogenic volatile organic compounds (BVOCs) in summer. Stable C isotope ratios of total carbon (δ13CTC) in the marine aerosols ranged from -28.5‰ to -23.6‰ (mean -26.4‰), suggesting an important input of terrestrial/continental aerosol particles. Stable N isotope ratios (2.6‰ to 12.9‰, mean 7.1‰) were found to be higher in the coastal regions than those in the open oceans, suggesting an enhanced emission of marine aerosols in the open oceans. The fluorescence properties of the water-soluble organic carbon (WSOC) in the marine aerosols conform the importance of marine emitted organics in the open ocean, especially during the high biological activity periods.

  3. Measurements of Organic Composition of Aerosol and Rainwater Samples Using Offline Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    OBrien, R. E.; Ridley, K. J.; Canagaratna, M. R.; Croteau, P.; Budisulistiorini, S. H.; Cui, T.; Green, H. S.; Surratt, J. D.; Jayne, J. T.; Kroll, J. H.

    2016-12-01

    A thorough understanding of the sources, evolution, and budgets of atmospheric organic aerosol requires widespread measurements of the amount and chemical composition of atmospheric organic carbon in the condensed phase (within particles and water droplets). Collecting such datasets requires substantial spatial and temporal (long term) coverage, which can be challenging when relying on online measurements by state-of-the-art research-grade instrumentation (such as those used in atmospheric chemistry field studies). Instead, samples are routinely collected using relatively low-cost techniques, such as aerosol filters, for offline analysis of their chemical composition. However, measurements made by online and offline instruments can be fundamentally different, leading to disparities between data from field studies and those from more routine monitoring. To better connect these two approaches, and take advantage of the benefits of each, we have developed a method to introduce collected samples into online aerosol instruments using nebulization. Because nebulizers typically require tens to hundreds of milliliters of solution, limiting this technique to large samples, we developed a new, ultrasonic micro-nebulizer that requires only small volumes (tens of microliters) of sample for chemical analysis. The nebulized (resuspended) sample is then sent into a high-resolution Aerosol Mass Spectrometer (AMS), a widely-used instrument that provides key information on the chemical composition of aerosol particulate matter (elemental ratios, carbon oxidation state, etc.), measurements that are not typically made for collected atmospheric samples. Here, we compare AMS data collected using standard on-line techniques with our offline analysis, demonstrating the utility of this new technique to aerosol filter samples. We then apply this approach to organic aerosol filter samples collected in remote regions, as well as rainwater samples from across the US. This data provides

  4. Quality assurance and quality control for thermal/optical analysis of aerosol samples for organic and elemental carbon.

    PubMed

    Chow, Judith C; Watson, John G; Robles, Jerome; Wang, Xiaoliang; Chen, L-W Antony; Trimble, Dana L; Kohl, Steven D; Tropp, Richard J; Fung, Kochy K

    2011-12-01

    Accurate, precise, and valid organic and elemental carbon (OC and EC, respectively) measurements require more effort than the routine analysis of ambient aerosol and source samples. This paper documents the quality assurance (QA) and quality control (QC) procedures that should be implemented to ensure consistency of OC and EC measurements. Prior to field sampling, the appropriate filter substrate must be selected and tested for sampling effectiveness. Unexposed filters are pre-fired to remove contaminants and acceptance tested. After sampling, filters must be stored in the laboratory in clean, labeled containers under refrigeration (<4 °C) to minimize loss of semi-volatile OC. QA activities include participation in laboratory accreditation programs, external system audits, and interlaboratory comparisons. For thermal/optical carbon analyses, periodic QC tests include calibration of the flame ionization detector with different types of carbon standards, thermogram inspection, replicate analyses, quantification of trace oxygen concentrations (<100 ppmv) in the helium atmosphere, and calibration of the sample temperature sensor. These established QA/QC procedures are applicable to aerosol sampling and analysis for carbon and other chemical components.

  5. The characteristics of brown carbon aerosol during winter in Beijing

    NASA Astrophysics Data System (ADS)

    Cheng, Yuan; He, Ke-bin; Du, Zhen-yu; Engling, Guenter; Liu, Jiu-meng; Ma, Yong-liang; Zheng, Mei; Weber, Rodney J.

    2016-02-01

    Brown carbon (i.e., light-absorbing organic carbon, or BrC) exerts important effects on the environment and on climate in particular. Based on spectrophotometric absorption measurements on extracts of bulk aerosol samples, this study investigated the characteristics of BrC during winter in Beijing, China. Organic compounds extractable by methanol contributed approximately 85% to the organic carbon (OC) mass. Light absorption by the methanol extracts exhibited a strong wavelength dependence, with an average absorption Ångström exponent of 7.10 (fitted between 310 and 450 nm). Normalizing the absorption coefficient (babs) measured at 365 nm to the extractable OC mass yielded an average mass absorption efficiency (MAE) of 1.45 m2/g for the methanol extracts. This study suggests that light absorption by BrC could be comparable with black carbon in the spectral range of near-ultraviolet light. Our results also indicate that BrC absorption and thus BrC radiative forcing could be largely underestimated when using water-soluble organic carbon (WSOC) as a surrogate for BrC. Compared to previous work relying only on WSOC, this study provides a more comprehensive understanding of BrC aerosol based on methanol extraction.

  6. Improving organic aerosol treatments in CESM/CAM5: Development, application, and evaluation

    PubMed Central

    Glotfelty, Timothy; He, Jian

    2017-01-01

    Abstract New treatments for organic aerosol (OA) formation have been added to a modified version of the CESM/CAM5 model (CESM‐NCSU). These treatments include a volatility basis set treatment for the simulation of primary and secondary organic aerosols (SOAs), a simplified treatment for organic aerosol (OA) formation from glyoxal, and a parameterization representing the impact of new particle formation (NPF) of organic gases and sulfuric acid. With the inclusion of these new treatments, the concentration of oxygenated organic aerosol increases by 0.33 µg m−3 and that of primary organic aerosol (POA) decreases by 0.22 µg m−3 on global average. The decrease in POA leads to a reduction in the OA direct effect, while the increased OOA increases the OA indirect effects. Simulations with the new OA treatments show considerable improvement in simulated SOA, oxygenated organic aerosol (OOA), organic carbon (OC), total carbon (TC), and total organic aerosol (TOA), but degradation in the performance of HOA. In simulations of the current climate period, despite some deviations from observations, CESM‐NCSU with the new OA treatments significantly improves the magnitude, spatial pattern, seasonal pattern of OC and TC, as well as, the speciation of TOA between POA and OOA. Sensitivity analysis reveals that the inclusion of the organic NPF treatment impacts the OA indirect effects by enhancing cloud properties. The simulated OA level and its impact on the climate system are most sensitive to choices in the enthalpy of vaporization and wet deposition of SVOCs, indicating that accurate representations of these parameters are critical for accurate OA‐climate simulations. PMID:29104733

  7. Formation of Oxidized Organic Aerosol (OOA) through Fog Processing in the Po Valley

    NASA Astrophysics Data System (ADS)

    Gilardoni, S.; Paglione, M.; Rinaldi, M.; Giulianelli, L.; Massoli, P.; Hillamo, R. E.; Carbone, S.; Lanconelli, C.; Laaksonen, A. J.; Russell, L. M.; Poluzzi, V.; Fuzzi, S.; Facchini, C.

    2014-12-01

    Aqueous phase chemistry might be responsible for the formation of a significant fraction of the organic aerosol (OA) observed in the atmosphere, and could explain some of the discrepancies between OA concentration and properties predicted by models and observed in the environment. Aerosol - fog interaction and its effect on submicron aerosol properties were investigated in the Po Valley (northern Italy) during fall 2011, in the framework of the Supersite project (ARPA Emilia Romagna). Composition and physical properties of submicron aerosol were measured online by a High Resolution- Time of Flight - Aerosol Mass Spectrometer (HR-TOF-AMS), a Soot Photometer - Aerosol Mass Spectrometer (SP-AMS), and a Tandem Differential Mobility Particle Sizer (TDMPS). Organic functional group analysis was performed off-line by Hydrogen - Nuclear Magnetic Resonance (H-NMR) spectrometry and by Fourier Transform Infrared (FTIR) spectrometry. Aerosol absorption, scattering, and total extinction were measured simultaneously with a Particle Soot Absorption Photometer (PSAP), a Nephelometer, and a Cavity Attenuated Phase Shift Spectrometer particle extinction monitor (CAPS PMex), respectively. Water-soluble organic carbon in fog-water was characterized off-line by HR-TOF-AMS. Fourteen distinct fog events were observed. Fog dissipation left behind an aerosol enriched in particles larger than 400 nm, typical of fog and cloud processing, and dominated by secondary species, including ammonium nitrate, ammonium sulfate and oxidized OA (OOA). Source apportionment of OA allowed us to identify OOA as the difference between total OA and primary OA (hydrocarbon like OA and biomass burning OA). The formation of OOA through fog processing is proved by the correlation of OOA concentration with hydroxyl methyl sulfonate signal and by the similarity of OOA spectra with organic mass spectra obtained by re-aerosolization of fog water samples. The oxygen to carbon ratio and the hydrogen to carbon ratio of

  8. Organic molecular composition of marine aerosols over the Arctic Ocean in summer: contributions of primary emission and secondary aerosol formation

    NASA Astrophysics Data System (ADS)

    Fu, P. Q.; Kawamura, K.; Chen, J.; Charrière, B.; Sempéré, R.

    2013-02-01

    Organic molecular composition of marine aerosol samples collected during the MALINA cruise in the Arctic Ocean was investigated by gas chromatography/mass spectrometry. More than 110 individual organic compounds were determined in the samples and were grouped into different compound classes based on the functionality and sources. The concentrations of total quantified organics ranged from 7.3 to 185 ng m-3 (mean 47.6 ng m-3), accounting for 1.8-11.0% (4.8%) of organic carbon in the marine aerosols. Primary saccharides were found to be dominant organic compound class, followed by secondary organic aerosol (SOA) tracers formed from the oxidation of biogenic volatile organic compounds (VOCs) such as isoprene, α-pinene and β-caryophyllene. Mannitol, the specific tracer for airborne fungal spores, was detected as the most abundant organic species in the samples with a concentration range of 0.052-53.3 ng m-3 (9.2 ng m-3), followed by glucose, arabitol, and the isoprene oxidation products of 2-methyltetrols. Biomass burning tracers such as levoglucosan are evident in all samples with trace levels. On the basis of the tracer-based method for the estimation of fungal-spore OC and biogenic secondary organic carbon (SOC), we estimate that an average of 10.7% (up to 26.2%) of the OC in the marine aerosols was due to the contribution of fungal spores, followed by the contribution of isoprene SOC (mean 3.8%) and α-pinene SOC (2.9%). In contrast, only 0.19% of the OC was due to the photooxidation of β-caryophyllene. This study indicates that primary organic aerosols from biogenic emissions, both from long-range transport of mid-latitude aerosols and from sea-to-air emission of marine organics, as well as secondary organic aerosols formed from the photooxidation of biogenic VOCs are important factors controlling the organic chemical composition of marine aerosols in the Arctic Ocean.

  9. Organic molecular composition of marine aerosols over the Arctic Ocean in summer: contributions of primary emission and secondary aerosol formation

    NASA Astrophysics Data System (ADS)

    Fu, P. Q.; Kawamura, K.; Chen, J.; Charrière, B.; Sempéré, R.

    2012-08-01

    Organic molecular composition of marine aerosol samples collected during the MALINA cruise in the Arctic Ocean was investigated by gas chromatography/mass spectrometry. More than 110 individual organic compounds were determined in the samples and were grouped into different compound classes based on the functionality and sources. The concentrations of total quantified organics ranged from 7.3 to 185 ng m-3 (mean 47.6 ng m-3), accounting for 1.8-11.0% (4.8%) of organic carbon in the marine aerosols. Primary saccharides were found to be dominant organic compound class, followed by secondary organic aerosol (SOA) tracers formed from the oxidation of biogenic volatile organic compounds (VOCs) such as isoprene, α-pinene and β-caryophyllene. Mannitol, the specific tracer for airborne fungal spores, was detected as the most abundant organic species in the samples with a concentration range of 0.052-53.3 ng m-3 (9.2 ng m-3), followed by glucose, arabitol, and the isoprene oxidation products of 2-methyltetrols. Biomass burning tracers such as levoglucosan are evident in all samples with trace levels. On the basis of the tracer-based method for the estimation of fungal-spore OC and biogenic secondary organic carbon (SOC), we estimate that an average of 10.7% (up to 26.2%) of the OC in the marine aerosols was due to the contribution of fungal spores, followed by the contribution of isoprene SOC (mean 3.8%) and α-pinene SOC (2.9%). In contrast, only 0.19% of the OC was due to the photooxidation of β-caryophyllene. This study indicates that primary organic aerosols from biogenic emissions, both from long-range transport of mid-latitude aerosols and from sea-to-air emission of marine organics, as well as secondary organic aerosols formed from the photooxidation of biogenic VOCs are important factors controlling the organic chemical composition of marine aerosols in the Arctic Ocean.

  10. Secondary sulfate is internally mixed with sea spray aerosol and organic aerosol in the winter Arctic

    NASA Astrophysics Data System (ADS)

    Kirpes, Rachel M.; Bondy, Amy L.; Bonanno, Daniel; Moffet, Ryan C.; Wang, Bingbing; Laskin, Alexander; Ault, Andrew P.; Pratt, Kerri A.

    2018-03-01

    Few measurements of aerosol chemical composition have been made during the winter-spring transition (following polar sunrise) to constrain Arctic aerosol-cloud-climate feedbacks. Herein, we report the first measurements of individual particle chemical composition near Utqiaġvik (Barrow), Alaska, in winter (seven sample days in January and February 2014). Individual particles were analyzed by computer-controlled scanning electron microscopy with energy dispersive X-ray spectroscopy (CCSEM-EDX, 24 847 particles), Raman microspectroscopy (300 particles), and scanning transmission X-ray microscopy with near-edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS, 290 particles). Sea spray aerosol (SSA) was observed in all samples, with fresh and aged SSA comprising 99 %, by number, of 2.5-7.5 µm diameter particles, 65-95 % from 0.5-2.5 µm, and 50-60 % from 0.1-0.5 µm, indicating SSA is the dominant contributor to accumulation and coarse-mode aerosol during the winter. The aged SSA particles were characterized by reduced chlorine content with 94 %, by number, internally mixed with secondary sulfate (39 %, by number, internally mixed with both nitrate and sulfate), indicative of multiphase aging reactions during transport. There was a large number fraction (40 % of 1.0-4.0 µm diameter particles) of aged SSA during periods when particles were transported from near Prudhoe Bay, consistent with pollutant emissions from the oil fields participating in atmospheric processing of aerosol particles. Organic carbon and sulfate particles were observed in all samples and comprised 40-50 %, by number, of 0.1-0.4 µm diameter particles, indicative of Arctic haze influence. Soot was internally mixed with organic and sulfate components. All sulfate was mixed with organic carbon or SSA particles. Therefore, aerosol sources in the Alaskan Arctic and resulting aerosol chemical mixing states need to be considered when predicting aerosol climate effects, particularly cloud

  11. Laboratory and field measurements of organic aerosols with the photoionization aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Dreyfus, Matthew A.

    . The high-time resolution data shows that rapid concentration changes of a common individual species can be lost with traditional bulk sampling, and a time resolution of 30 minutes is suggested to accurately represent these changes. Using the mass spectra collected from the extended sampling campaign, source apportionment was performed with positive matrix factorization (PMF). The resulting model features six factors either correlated to specific sources (meat cooking, car emissions/road dust, diesel exhaust) or types of compounds (phthalates, alkanes/alkanoic acids, PAHs). The high-time resolution data allowed for the observation of specific trends in each factor's behavior as a function of time and wind direction relative to the receptor site. Elemental carbon/organic carbon (EC/OC) data is used to calculate the percentages of primary and secondary organic aerosol. Primary organic aerosol (POA) constituted the vast majority of the total carbon at 91% (an average of 2.8 +/- 1.1mug/m 3); 30% of which came from combustion, and 70% from non-combustion sources. These results can be explained by the PIAMS data: the diesel factor contributes to the combustion-related POA; the car/road dust, meat cooking, and alkane/alkanoic acid factors contribute the majority of non-combustion POA. The remaining factors represent <5% of the remaining OC. Considering the compatibility of data from the EC/OC and PIAMS, the ability of PIAMS to yield molecular species information to further define the primary and secondary organic aerosol factions is a distinct advantage in describing the behavior of the Wilmington organic aerosol. PIAMS was also applied to laboratory experiments. These experiments simulated complex environmental processes in order to focus on answering a central question. By mixing cholesterol aerosol with ozone in a smog chamber, and monitoring the concentration of cholesterol with PIAMS, the rate of reaction was determined. This rate indicates that cholesterol aerosol

  12. Size distributions and chemical characterization of water-soluble organic aerosols over the western North Pacific in summer

    NASA Astrophysics Data System (ADS)

    Miyazaki, Yuzo; Kawamura, Kimitaka; Sawano, Maki

    2010-12-01

    Size-segregated aerosol samples were collected over the western North Pacific in summer 2008 to investigate marine biological contribution to organic aerosols. The samples were analyzed for organic carbon (OC), water-soluble organic carbon (WSOC), and water-soluble organic compounds including diacids (C2-C9), ω-oxocarboxylic acids, and α-dicarbonyls as well as methanesulfonic acid (MSA). The average concentrations of OC and oxalic acid (C2) were approximately two to three times larger in marine biologically more influenced aerosols, defined by the concentrations of MSA and azelaic acid (C9), than in less influenced aerosols. WSOC, which showed a statistically significant correlation with MSA, accounted for 15-21% of total mass of the components determined in the submicrometer range of biologically more influenced aerosols. These values are comparable to those of water-insoluble organic carbon (WIOC) (˜14-23%), suggesting that organic aerosols in this region are enriched in secondary organic aerosols (SOA) linked to oceanic biological activity. In these aerosols, substantial fractions of C2-C4 diacids were found in the submicrometer size range. Positive correlations of oxalic acid with C3-C5 diacids and glyoxylic acid suggest that secondary production of oxalic acid occurs possibly in the aqueous aerosol phase via the oxidation of longer-chain diacids and glyoxylic acid in the oceanic region with higher biological productivity. We found similar concentration levels and size distributions of methylglyoxal between the two types of aerosols, suggesting that formation of oxalic acid via the oxidation of methylglyoxal from marine isoprene is insignificant in the study region.

  13. Inferring Absorbing Organic Carbon Content from AERONET Data

    NASA Technical Reports Server (NTRS)

    Arola, A.; Schuster, G.; Myhre, G.; Kazadzis, S.; Dey, S.; Tripathi, S. N.

    2011-01-01

    Black carbon, light-absorbing organic carbon (often called brown carbon) and mineral dust are the major light-absorbing aerosols. Currently the sources and formation of brown carbon aerosol in particular are not well understood. In this study we estimated globally the amount of light absorbing organic carbon and black carbon from AERONET measurements. We find that the columnar absorbing organic carbon (brown carbon) levels in biomass burning regions of South-America and Africa are relatively high (about 15-20 magnesium per square meters during biomass burning season), while the concentrations are significantly lower in urban areas in US and Europe. However, we estimated significant absorbing organic carbon amounts from the data of megacities of newly industrialized countries, particularly in India and China, showing also clear seasonality with peak values up to 30-35 magnesium per square meters during the coldest season, likely caused by the coal and biofuel burning used for heating. We also compared our retrievals with the modeled organic carbon by global Oslo CTM for several sites. Model values are higher in biomass burning regions than AERONET-based retrievals, while opposite is true in urban areas in India and China.

  14. Applications of High-Resolution Electrospray Ionization Mass Spectrometry to Measurements of Average Oxygen to Carbon Ratios in Secondary Organic Aerosols

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bateman, Adam P.; Laskin, Julia; Laskin, Alexander

    2012-07-02

    The applicability of high resolution electrospray ionization mass spectrometry (HR ESI-MS) to measurements of the average oxygen to carbon ratio (O/C) in organic aerosols was investigated. Solutions with known average O/C containing up to 10 standard compounds representative of secondary organic aerosol (SOA) were analyzed and corresponding electrospray ionization efficiencies were quantified. The assumption of equal ionization efficiency commonly used in estimating O/C ratios of organic aerosols was found to be reasonably accurate. We found that the accuracy of the measured O/C ratios increases by averaging the values obtained from both (+) and (-) modes. A correlation was found betweenmore » the ratio of the ionization efficiencies in the positive and negative ESI modes with the octanol-water partition constant, and more importantly, with the compound's O/C. To demonstrate the utility of this correlation for estimating average O/C values of unknown mixtures, we analyzed the ESI (+) and ESI (-) data for SOA produced by oxidation of limonene and isoprene and compared to online O/C measurements using an aerosol mass spectrometer (AMS). This work demonstrates that the accuracy of the HR ESI-MS methods is comparable to that of the AMS, with the added benefit of molecular identification of the aerosol constituents.« less

  15. Historical emissions of black and organic carbon aerosol from energy-related combustion, 1850-2000

    NASA Astrophysics Data System (ADS)

    Bond, Tami C.; Bhardwaj, Ekta; Dong, Rong; Jogani, Rahil; Jung, Soonkyu; Roden, Christoph; Streets, David G.; Trautmann, Nina M.

    2007-06-01

    We present an emission inventory of primary black carbon (BC) and primary organic carbon (OC) aerosols from fossil fuel and biofuel combustion between 1850 and 2000. We reconstruct fossil fuel consumption and represent changes in technology on a national and sectoral basis. Our estimates rely on new estimates of biofuel consumption, and updated emission factors for old technologies. Emissions of black carbon increase almost linearly, totaling about 1000 Gg in 1850, 2200 Gg in 1900, 3000 Gg in 1950, and 4400 Gg in 2000. Primary organic carbon shows a similar pattern, with emissions of 4100 Gg, 5800 Gg, 6700 Gg, and 8700 Gg in 1850, 1900, 1950, and 2000, respectively. Biofuel is responsible for over half of BC emission until about 1890, and dominates energy-related primary OC emission throughout the entire period. Coal contributes the greatest fraction of BC emission between 1880 and 1975, and is overtaken by emissions from biofuel around 1975, and by diesel engines around 1990. Previous work suggests a rapid rise in BC emissions between 1950 and 2000. This work supports a more gradual increase between 1950 and 2000, similar to the increase between 1850 and 1925; implementation of clean technology is a primary reason.

  16. Evaluating Organic Aerosol Model Performance: Impact of two Embedded Assumptions

    NASA Astrophysics Data System (ADS)

    Jiang, W.; Giroux, E.; Roth, H.; Yin, D.

    2004-05-01

    Organic aerosols are important due to their abundance in the polluted lower atmosphere and their impact on human health and vegetation. However, modeling organic aerosols is a very challenging task because of the complexity of aerosol composition, structure, and formation processes. Assumptions and their associated uncertainties in both models and measurement data make model performance evaluation a truly demanding job. Although some assumptions are obvious, others are hidden and embedded, and can significantly impact modeling results, possibly even changing conclusions about model performance. This paper focuses on analyzing the impact of two embedded assumptions on evaluation of organic aerosol model performance. One assumption is about the enthalpy of vaporization widely used in various secondary organic aerosol (SOA) algorithms. The other is about the conversion factor used to obtain ambient organic aerosol concentrations from measured organic carbon. These two assumptions reflect uncertainties in the model and in the ambient measurement data, respectively. For illustration purposes, various choices of the assumed values are implemented in the evaluation process for an air quality model based on CMAQ (the Community Multiscale Air Quality Model). Model simulations are conducted for the Lower Fraser Valley covering Southwest British Columbia, Canada, and Northwest Washington, United States, for a historical pollution episode in 1993. To understand the impact of the assumed enthalpy of vaporization on modeling results, its impact on instantaneous organic aerosol yields (IAY) through partitioning coefficients is analysed first. The analysis shows that utilizing different enthalpy of vaporization values causes changes in the shapes of IAY curves and in the response of SOA formation capability of reactive organic gases to temperature variations. These changes are then carried into the air quality model and cause substantial changes in the organic aerosol modeling

  17. Follow the Carbon: Isotopic Labeling Studies of Early Earth Aerosol.

    PubMed

    Hicks, Raea K; Day, Douglas A; Jimenez, Jose L; Tolbert, Margaret A

    2016-11-01

    Despite the faint young Sun, early Earth might have been kept warm by an atmosphere containing the greenhouse gases CH 4 and CO 2 in mixing ratios higher than those found on Earth today. Laboratory and modeling studies suggest that an atmosphere containing these trace gases could lead to the formation of organic aerosol haze due to UV photochemistry. Chemical mechanisms proposed to explain haze formation rely on CH 4 as the source of carbon and treat CO 2 as a source of oxygen only, but this has not previously been verified experimentally. In the present work, we use isotopically labeled precursor gases and unit-mass resolution (UMR) and high-resolution (HR) aerosol mass spectrometry to examine the sources of carbon and oxygen to photochemical aerosol formed in a CH 4 /CO 2 /N 2 atmosphere. UMR results suggest that CH 4 contributes 70-100% of carbon in the aerosol, while HR results constrain the value from 94% to 100%. We also confirm that CO 2 contributes approximately 10% of the total mass to the aerosol as oxygen. These results have implications for the geochemical interpretations of inclusions found in Archean rocks on Earth and for the astrobiological potential of other planetary atmospheres. Key Words: Atmosphere-Early Earth-Planetary atmospheres-Carbon dioxide-Methane. Astrobiology 16, 822-830.

  18. Organic and inorganic components of aerosols over the central Himalayas: winter and summer variations in stable carbon and nitrogen isotopic composition.

    PubMed

    Hegde, Prashant; Kawamura, Kimitaka; Joshi, H; Naja, M

    2016-04-01

    The aerosol samples were collected from a high elevation mountain site, Nainital, in India (1958 m asl) during September 2006 to June 2007 and were analyzed for water-soluble inorganic species, total carbon, nitrogen, and their isotopic composition (δ(13)C and δ(15)N, respectively). The chemical and isotopic composition of aerosols revealed significant anthropogenic influence over this remote free-troposphere site. The amount of total carbon and nitrogen and their isotopic composition suggest a considerable contribution of biomass burning to the aerosols during winter. On the other hand, fossil fuel combustion sources are found to be dominant during summer. The carbon aerosol in winter is characterized by greater isotope ratios (av. -24.0‰), mostly originated from biomass burning of C4 plants. On the contrary, the aerosols in summer showed smaller δ(13)C values (-26.0‰), indicating that they are originated from vascular plants (mostly of C3 plants). The secondary ions (i.e., SO4 (2-), NH4 (+), and NO3 (-)) were abundant due to the atmospheric reactions during long-range transport in both seasons. The water-soluble organic and inorganic compositions revealed that they are aged in winter but comparatively fresh in summer. This study validates that the pollutants generated from far distant sources could reach high altitudes over the Himalayan region under favorable meteorological conditions.

  19. Anthropogenic aerosols as a source of ancient dissolved organic matter in glaciers

    USGS Publications Warehouse

    Stubbins, Aron; Hood, Eran; Raymond, Peter A.; Aiken, George R.; Sleighter, Rachel L.; Hernes, Peter J.; Butman, David; Hatcher, Patrick G.; Striegl, Robert G.; Schuster, Paul F.; Abdulla, Hussain A.N.; Vermilyea, Andrew W.; Scott, Durelle T.; Spencer, Robert G.M.

    2012-01-01

    Glacier-derived dissolved organic matter represents a quantitatively significant source of ancient, yet highly bioavailable carbon to downstream ecosystems. This finding runs counter to logical perceptions of age–reactivity relationships, in which the least reactive material withstands degradation the longest and is therefore the oldest. The remnants of ancient peatlands and forests overrun by glaciers have been invoked as the source of this organic matter. Here, we examine the radiocarbon age and chemical composition of dissolved organic matter in snow, glacier surface water, ice and glacier outflow samples from Alaska to determine the origin of the organic matter. Low levels of compounds derived from vascular plants indicate that the organic matter does not originate from forests or peatlands. Instead, we show that the organic matter on the surface of the glaciers is radiocarbon depleted, consistent with an anthropogenic aerosol source. Fluorescence spectrophotometry measurements reveal the presence of protein-like compounds of microbial or aerosol origin. In addition, ultrahigh-resolution mass spectrometry measurements document the presence of combustion products found in anthropogenic aerosols. Based on the presence of these compounds, we suggest that aerosols derived from fossil fuel burning are a source of pre-aged organic matter to glacier surfaces. Furthermore, we show that the molecular signature of the organic matter is conserved in snow, glacier water and outflow, suggesting that the anthropogenic carbon is exported relatively unchanged in glacier outflows.

  20. Fungal spores overwhelm biogenic organic aerosols in a midlatitudinal forest

    NASA Astrophysics Data System (ADS)

    Zhu, Chunmao; Kawamura, Kimitaka; Fukuda, Yasuro; Mochida, Michihiro; Iwamoto, Yoko

    2016-06-01

    Both primary biological aerosol particles (PBAPs) and oxidation products of biogenic volatile organic compounds (BVOCs) contribute significantly to organic aerosols (OAs) in forested regions. However, little is known about their relative importance in diurnal timescales. Here, we report biomarkers of PBAP and secondary organic aerosols (SOAs) for their diurnal variability in a temperate coniferous forest in Wakayama, Japan. Tracers of fungal spores, trehalose, arabitol and mannitol, showed significantly higher levels in nighttime than daytime (p < 0.05), resulting from the nocturnal sporulation under near-saturated relative humidity. On the contrary, BVOC oxidation products showed higher levels in daytime than nighttime, indicating substantial photochemical SOA formation. Using tracer-based methods, we estimated that fungal spores account for 45 % of organic carbon (OC) in nighttime and 22 % in daytime, whereas BVOC oxidation products account for 15 and 19 %, respectively. To our knowledge, we present for the first time highly time-resolved results that fungal spores overwhelmed BVOC oxidation products in contributing to OA especially in nighttime. This study emphasizes the importance of both PBAPs and SOAs in forming forest organic aerosols.

  1. Inorganic markers, carbonaceous components and stable carbon isotope from biomass burning aerosols in Northeast China.

    PubMed

    Cao, Fang; Zhang, Shi-Chun; Kawamura, Kimitaka; Zhang, Yan-Lin

    2016-12-01

    To better characterize the chemical compositions and sources of fine particulate matter (i.e. PM 2.5 ) in Sanjiang Plain, Northeast China, total carbon (TC), organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and inorganic ions as well as stable carbon isotopic composition (δ 13 C) were measured in this study. Intensively open biomass burning episodes are identified from late September to early October by satellite fire and aerosol optical depth maps. During the biomass-burning episode, concentrations of PM 2.5 , OC, EC, and WSOC are increased by a factor of 4-12 compared to those during the non-biomass-burning period. Non-sea-salt potassium is strongly correlated with PM 2.5 , OC, EC and WSOC, demonstrating an important contribution from biomass-burning emissions. The enrichment in both the non-sea-salt potassium and chlorine is significantly larger than other inorganic species, suggesting that biomass-burning aerosols in Sanjiang Plain are mostly fresh and less aged. In addition, the WSOC-to-OC ratio is lower than that reported in biomass-burning aerosols in tropical regions, further supporting that biomass-burning aerosols in Sanjiang Plain are mostly primary and secondary organic aerosols may be not significant. A lower average δ 13 C value (-26.2‰) is observed during the biomass-burning period, indicating a dominant contribution from combustion of C3 plants in the studied region. Copyright © 2015. Published by Elsevier B.V.

  2. Persistence of organic carbon in heated aerosol residuals measured during Tropical Composition Cloud and Climate Coupling (TC4)

    NASA Astrophysics Data System (ADS)

    Thornberry, T.; Froyd, K. D.; Murphy, D. M.; Thomson, D. S.; Anderson, B. E.; Thornhill, K. L.; Winstead, E. L.

    2010-05-01

    The Particle Analysis by Laser Mass Spectrometry (PALMS) single particle mass spectrometer was used to analyze the composition of the nonvolatile fraction of atmospheric aerosol in a number of different environments. The mass spectra of individual particles sampled through an inlet section heated to 300°C were compared to unheated particles during flights of the NASA DC-8 aircraft during the Tropical Composition Cloud and Climate Coupling (TC4) mission. Comparisons are presented of measurements made in the marine boundary layer, the free troposphere, and the continental boundary layer over the Colombian jungle. The heated section completely removed sulfate from the aerosols except for sodium sulfate and related compounds in sea salt particles. Organic material in sea salt particles was observed to be less volatile than chlorine. Biomass burning particles were more likely to survive heating than other mixed sulfate-organic particles. For all particle types, there was a significant contribution to the residues from carbonaceous material other than elemental carbon. These results demonstrate the remaining compositional complexity of aerosol residuals that survive heating in a thermal denuder.

  3. Estimation of black carbon content for biomass burning aerosols from multi-channel Raman lidar data

    NASA Astrophysics Data System (ADS)

    Talianu, Camelia; Marmureanu, Luminita; Nicolae, Doina

    2015-04-01

    Biomass burning due to natural processes (forest fires) or anthropical activities (agriculture, thermal power stations, domestic heating) is an important source of aerosols with a high content of carbon components (black carbon and organic carbon). Multi-channel Raman lidars provide information on the spectral dependence of the backscatter and extinction coefficients, embedding information on the black carbon content. Aerosols with a high content of black carbon have large extinction coefficients and small backscatter coefficients (strong absorption), while aerosols with high content of organic carbon have large backscatter coefficients (weak absorption). This paper presents a method based on radiative calculations to estimate the black carbon content of biomass burning aerosols from 3b+2a+1d lidar signals. Data is collected at Magurele, Romania, at the cross-road of air masses coming from Ukraine, Russia and Greece, where burning events are frequent during both cold and hot seasons. Aerosols are transported in the free troposphere, generally in the 2-4 km altitude range, and reaches the lidar location after 2-3 days. Optical data are collected between 2011-2012 by a multi-channel Raman lidar and follows the quality assurance program of EARLINET. Radiative calculations are made with libRadTran, an open source radiative model developed by ESA. Validation of the retrievals is made by comparison to a co-located C-ToF Aerosol Mass Spectrometer. Keywords: Lidar, aerosols, biomass burning, radiative model, black carbon Acknowledgment: This work has been supported by grants of the Romanian National Authority for Scientific Research, Programme for Research- Space Technology and Advanced Research - STAR, project no. 39/2012 - SIAFIM, and by Romanian Partnerships in priority areas PNII implemented with MEN-UEFISCDI support, project no. 309/2014 - MOBBE

  4. Chemical and microphysical properties of the aerosol during foggy and nonfoggy episodes: a relationship between organic and inorganic content of the aerosol

    NASA Astrophysics Data System (ADS)

    Kaul, D. S.; Gupta, T.; Tripathi, S. N.

    2012-06-01

    An extensive field measurement during winter was carried out at a site located in the Indo-Gangetic Plain (IGP) which gets heavily influenced by the fog during winter almost every year. The chemical and microphysical properties of the aerosols during foggy and nonfoggy episodes and chemical composition of the fogwater are presented. Positive matrix factorization (PMF) as a tool for the source apportionment was employed to understand the sources of pollution. Four major sources viz. biomass burning, refractory, secondary and mineral dust were identified. Aerosols properties during foggy episodes were heavily influenced by almost all the sources and they caused considerable loading of almost all the organic and inorganic species during the period. The biomass generated aerosols were removed from the atmosphere by scavenging during foggy episodes. The wet removal of almost all the species by the fog droplets was observed. The K+, water soluble organic carbon (WSOC), water soluble inorganic carbon (WSIC) and NO3- were most heavily scavenged among the species and their concentrations consequently became lower than the nonfoggy episode concentrations. The production of secondary inorganic aerosol, mainly sulfate and ammonium, during foggy episodes was considerably higher than nitrate which was rather heavily scavenged and removed by the fog droplets. The fogwater analysis showed that dissolved inorganic species play a vital role in processing of organic carbon such as the formation of organo-sulfate and organo-nitrate inside the fog droplets. The formation of organo-sulfate and organo-nitrate in aerosol and the influence of acidity on the secondary organic aerosol (SOA) formation were rather found to be negligible. The study average inorganic component of the aerosol was considerably higher than the carbonaceous component during both foggy and nonfoggy episode. The secondary production of the aerosol changed the microphysical properties of aerosol which was reflected by

  5. Fog scavenging of organic and inorganic aerosol in the Po Valley

    NASA Astrophysics Data System (ADS)

    Gilardoni, S.; Massoli, P.; Giulianelli, L.; Rinaldi, M.; Paglione, M.; Pollini, F.; Lanconelli, C.; Poluzzi, V.; Carbone, S.; Hillamo, R.; Russell, L. M.; Facchini, M. C.; Fuzzi, S.

    2014-07-01

    The interaction of aerosol with atmospheric water affects the processing and wet removal of atmospheric particles. Understanding such interaction is mandatory to improve model description of aerosol lifetime and ageing. We analyzed the aerosol-water interaction at high relative humidity during fog events in the Po Valley within the framework of the Agenzia Regionale per la Prevenzione e l'Ambiente (ARPA) - Emilia Romagna supersite project. For the first time in this area, the changes in particle chemical composition caused by fog are discussed along with changes in particle microphysics. During the experiment, 14 fog events were observed. The average mass scavenging efficiency was 70% for nitrate, 68% for ammonium, 61% for sulfate, 50% for organics, and 39% for black carbon. After fog formation, the interstitial aerosol was dominated by particles smaller than 200 nm Dva (vacuum aerodynamic diameter) and enriched in carbonaceous aerosol, mainly black carbon and water-insoluble organic aerosol. For each fog event, the size-segregated scavenging efficiency of nitrate and organic aerosol (OA) was calculated by comparing chemical species size distribution before and after fog formation. For both nitrate and OA, the size-segregated scavenging efficiency followed a sigmoidal curve, with values close to zero below 100 nm Dva and close to 1 above 700 nm Dva. OA was able to affect scavenging efficiency of nitrate in particles smaller than 300 nm Dva. A linear correlation between nitrate scavenging and particle hygroscopicity (κ) was observed, indicating that 44-51% of the variability of nitrate scavenging in smaller particles (below 300 nm Dva) was explained by changes in particle chemical composition. The size-segregated scavenging curves of OA followed those of nitrate, suggesting that organic scavenging was controlled by mixing with water-soluble species. In particular, functional group composition and OA elemental analysis indicated that more oxidized OA was scavenged

  6. Contribution of dissolved organic matter to submicron water-soluble organic aerosols in the marine boundary layer over the eastern equatorial Pacific

    NASA Astrophysics Data System (ADS)

    Miyazaki, Yuzo; Coburn, Sean; Ono, Kaori; Ho, David T.; Pierce, R. Bradley; Kawamura, Kimitaka; Volkamer, Rainer

    2016-06-01

    Stable carbon isotopic compositions of water-soluble organic carbon (WSOC) and organic molecular markers were measured to investigate the relative contributions of the sea surface sources to the water-soluble fraction of submicron organic aerosols collected over the eastern equatorial Pacific during the Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOCs (TORERO)/KA-12-01 cruise. On average, the water-soluble organic fraction of the total carbon (TC) mass in submicron aerosols was ˜ 30-35 % in the oceans with the low chlorophyll a (Chl a) concentrations, whereas it was ˜ 60 % in the high-Chl a regions. The average stable carbon isotope ratio of WSOC (δ13CWSOC) was -19.8 ± 2.0 ‰, which was systematically higher than that of TC (δ13CTC) (-21.8 ± 1.4 ‰). We found that in the oceans with both high and low Chl a concentrations the δ13CWSOC was close to the typical values of δ13C for dissolved organic carbon (DOC), ranging from -22 to -20 ‰ in surface seawater of the tropical Pacific Ocean. This suggests an enrichment of marine biological products in WSOC aerosols in the study region regardless of the oceanic area. In particular, enhanced levels of WSOC and biogenic organic marker compounds together with high values of WSOC / TC ( ˜ 60 %) and δ13CWSOC were observed over upwelling areas and phytoplankton blooms, which was attributed to planktonic tissues being more enriched in δ13C. The δ13C analysis estimated that, on average, marine sources contribute ˜ 90 ± 25 % of the aerosol carbon, indicating the predominance of marine-derived carbon in the submicron WSOC. This conclusion is supported by Lagrangian trajectory analysis, which suggests that the majority of the sampling points on the ship had been exposed to marine boundary layer (MBL) air for more than 80 % of the time during the previous 7 days. The combined analysis of the δ13C and monosaccharides, such as glucose and fructose, demonstrated that DOC concentration was

  7. Functional characterization of the water-soluble organic carbon of size fractionated aerosol in the Southern Mississippi Valley

    NASA Astrophysics Data System (ADS)

    Chalbot, M.-C. G.; Brown, J.; Chitranshi, P.; Gamboa da Costa, G.; Pollock, E. D.; Kavouras, I. G.

    2014-02-01

    The chemical content of the water soluble organic carbon (WSOC) as a function of particle size was characterized in Little Rock, Arkansas in winter and spring 2013. The objectives of this study were to: (i) compare the functional characteristics of coarse, fine and ultrafine WSOC and (ii) reconcile the sources of WSOC for the period when carbonaceous aerosol was the most abundant particulate component. The WSOC accounted for 5% of particle mass for particles with dp > 0.96 μm and 10% of particle mass for particles with dp < 0.96 μm. Non-exchangeable aliphatic (H-C), unsaturated aliphatic (H-C-C=), oxygenated saturated aliphatic (H-C-O), acetalic (O-CH-O) and aromatic (Ar-H) protons were determined by proton nuclear magnetic resonance. The total non-exchangeable organic hydrogen concentrations varied from 4.1 ± 0.1 nmol m-3 for particles with 0.96 < dp < 1.5 μm to 73.9 ± 12.3 nmol m-3 for particles with dp < 0.49 μm, resulting in molar H / C ratios of 0.48 ± 0.05 to 0.92 ± 0.09 observed in combustion-related organic aerosol. The R-H was the most abundant group representing about 45% of measured total non-exchangeable organic hydrogen concentration followed by H-C-O (27%) and H-C-C= (26%). Levoglucosan, amines, ammonium and methanosulfonate were tentatively identified in NMR fingerprints of fine particles. Sucrose, fructose, glucose, formate and acetate were associated with coarse particles. These qualitative differences of 1H-NMR profiles for different particle sizes indicated the possible contribution of biological aerosol and a mixture of aliphatic and oxygenated compounds from biomass burning and traffic exhausts. The concurrent presence of ammonium and amines also suggested the presence of ammonium/aminium nitrate and sulfate secondary aerosol. The size-dependent origin of WSOC was further corroborated by the increasing δ13C abundance from -26.81 ± 0.18‰ for the smallest particles to -25.93 ± 0.31‰ for the largest particles and the relative

  8. Functional characterization of the water-soluble organic carbon of size-fractionated aerosol in the southern Mississippi Valley

    NASA Astrophysics Data System (ADS)

    Chalbot, M.-C. G.; Brown, J.; Chitranshi, P.; Gamboa da Costa, G.; Pollock, E. D.; Kavouras, I. G.

    2014-06-01

    The chemical content of water-soluble organic carbon (WSOC) as a function of particle size was characterized in Little Rock, Arkansas in winter and spring 2013. The objectives of this study were to (i) compare the functional characteristics of coarse, fine and ultrafine WSOC and (ii) reconcile the sources of WSOC for periods when carbonaceous aerosol was the most abundant particulate component. The WSOC accounted for 5% of particle mass for particles with dp > 0.96 μm and 10% of particle mass for particles with dp < 0.96 μm. Non-exchangeable aliphatic (H-C), unsaturated aliphatic (H-C-C=), oxygenated saturated aliphatic (H-C-O), acetalic (O-CH-O) and aromatic (Ar-H) protons were determined by proton nuclear magnetic resonance (1H-NMR). The total non-exchangeable organic hydrogen concentrations varied from 4.1 ± 0.1 nmol m-3 for particles with 1.5 < dp < 3.0 μm to 73.9 ± 12.3 nmol m-3 for particles with dp < 0.49 μm. The molar H / C ratios varied from 0.48 ± 0.05 to 0.92 ± 0.09, which were comparable to those observed for combustion-related organic aerosol. The R-H was the most abundant group, representing about 45% of measured total non-exchangeable organic hydrogen concentrations, followed by H-C-O (27%) and H-C-C= (26%). Levoglucosan, amines, ammonium and methanesulfonate were identified in NMR fingerprints of fine particles. Sucrose, fructose, glucose, formate and acetate were associated with coarse particles. These qualitative differences of 1H-NMR profiles for different particle sizes indicated the possible contribution of biological aerosols and a mixture of aliphatic and oxygenated compounds from biomass burning and traffic exhausts. The concurrent presence of ammonium and amines also suggested the presence of ammonium/aminium nitrate and sulfate secondary aerosol. The size-dependent origin of WSOC was further corroborated by the increasing δ13C abundance from -26.81 ± 0.18‰ for the smallest particles to -25.93 ± 0.31‰ for the largest

  9. Size-Resolved Composition of Organic Aerosol on the California Central Coast

    NASA Astrophysics Data System (ADS)

    Babila, J. E.; Depew, C. J.; Heinrich, S. E.; Zoerb, M.

    2016-12-01

    Organic compounds represent a significant mass fraction of submicrometer aerosol and can influence properties such as radiative forcing and cloud formation. Despite their broad importance, a complete description of particle sources and composition is lacking. Here we present measurements of solvent-extracted organic compounds in ambient aerosol in San Luis Obispo, CA. Ambient particles were sampled and size segregated with a micro-orifice uniform deposit impactor (MOUDI). Water and methanol soluble organic carbon was characterized with electrospray ionization mass spectrometry (ESI-MS) and UV/Vis spectroscopy. Particle composition and influences from local and regional sources on the organic fraction will be discussed.

  10. An aerosol climatology for a rapidly growing arid region (southern Arizona): Major aerosol species and remotely sensed aerosol properties

    NASA Astrophysics Data System (ADS)

    Sorooshian, Armin; Wonaschütz, Anna; Jarjour, Elias G.; Hashimoto, Bryce I.; Schichtel, Bret A.; Betterton, Eric A.

    2011-10-01

    This study reports a comprehensive characterization of atmospheric aerosol particle properties in relation to meteorological and back trajectory data in the southern Arizona region, which includes two of the fastest growing metropolitan areas in the United States (Phoenix and Tucson). Multiple data sets (MODIS, AERONET, OMI/TOMS, MISR, GOCART, ground-based aerosol measurements) are used to examine monthly trends in aerosol composition, aerosol optical depth (AOD), and aerosol size. Fine soil, sulfate, and organics dominate PM2.5 mass in the region. Dust strongly influences the region between March and July owing to the dry and hot meteorological conditions and back trajectory patterns. Because monsoon precipitation begins typically in July, dust levels decrease, while AOD, sulfate, and organic aerosol reach their maximum levels because of summertime photochemistry and monsoon moisture. Evidence points to biogenic volatile organic compounds being a significant source of secondary organic aerosol in this region. Biomass burning also is shown to be a major contributor to the carbonaceous aerosol budget in the region, leading to enhanced organic and elemental carbon levels aloft at a sky-island site north of Tucson (Mt. Lemmon). Phoenix exhibits different monthly trends for aerosol components in comparison with the other sites owing to the strong influence of fossil carbon and anthropogenic dust. Trend analyses between 1988 and 2009 indicate that the strongest statistically significant trends are reductions in sulfate, elemental carbon, and organic carbon, and increases in fine soil during the spring (March-May) at select sites. These results can be explained by population growth, land-use changes, and improved source controls.

  11. Black carbon in aerosol during BIBLE B

    NASA Astrophysics Data System (ADS)

    Liley, J. Ben; Baumgardner, D.; Kondo, Y.; Kita, K.; Blake, D. R.; Koike, M.; Machida, T.; Takegawa, N.; Kawakami, S.; Shirai, T.; Ogawa, T.

    2003-02-01

    The Biomass Burning and Lightning Experiment (BIBLE) A and B campaigns over the tropical western Pacific during springtime deployed a Gulfstream-II aircraft with systems to measure ozone and numerous precursor species. Aerosol measuring systems included a MASP optical particle counter, a condensation nucleus (CN) counter, and an absorption spectrometer for black carbon. Aerosol volume was very low in the middle and upper troposphere during both campaigns, and during BIBLE A, there was little aerosol enhancement in the boundary layer away from urban areas. In BIBLE B, there was marked aerosol enhancement in the lowest 3 km of the atmosphere. Mixing ratios of CN in cloud-free conditions in the upper troposphere were in general higher than in the boundary layer, indicating new particle formation from gaseous precursors. High concentrations of black carbon were observed during BIBLE B, with mass loadings up to 40 μg m-3 representing as much as one quarter of total aerosol mass. Strong correlations with hydrocarbon enhancement allow the determination of a black carbon emission ratio for the fires at that time. Expressed as elemental carbon, it is about 0.5% of carbon dioxide and 6% of carbon monoxide emissions from the same fires, comparable to methane production, and greater than that of other hydrocarbons.

  12. Black carbon in aerosol during BIBLE B

    NASA Astrophysics Data System (ADS)

    Liley, J. Ben; Baumgardner, D.; Kondo, Y.; Kita, K.; Blake, D. R.; Koike, M.; Machida, T.; Takegawa, N.; Kawakami, S.; Shirai, T.; Ogawa, T.

    2002-02-01

    The Biomass Burning and Lightning Experiment (BIBLE) A and B campaigns over the tropical western Pacific during springtime deployed a Gulfstream-II aircraft with systems to measure ozone and numerous precursor species. Aerosol measuring systems included a MASP optical particle counter, a condensation nucleus (CN) counter, and an absorption spectrometer for black carbon. Aerosol volume was very low in the middle and upper troposphere during both campaigns, and during BIBLE A, there was little aerosol enhancement in the boundary layer away from urban areas. In BIBLE B, there was marked aerosol enhancement in the lowest 3 km of the atmosphere. Mixing ratios of CN in cloud-free conditions in the upper troposphere were in general higher than in the boundary layer, indicating new particle formation from gaseous precursors. High concentrations of black carbon were observed during BIBLE B, with mass loadings up to 40 μg m-3 representing as much as one quarter of total aerosol mass. Strong correlations with hydrocarbon enhancement allow the determination of a black carbon emission ratio for the fires at that time. Expressed as elemental carbon, it is about 0.5% of carbon dioxide and 6% of carbon monoxide emissions from the same fires, comparable to methane production, and greater than that of other hydrocarbons.

  13. 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.

    2014-11-01

    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+ per m3 air sample volume) and the percent change of 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, as well as extending 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 three 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%.

  14. 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%.

  15. New insights into modeling an organic mass fraction of sea spray aerosol

    NASA Astrophysics Data System (ADS)

    Meskhidze, N.; Gantt, B.

    2010-12-01

    As the study of climate change progresses, a need to separate the effects of natural and anthropogenic processes becomes essential in order to correctly forecast the future climate. Due to their massive source regions underlying an atmosphere with low aerosol concentration, marine aerosols derived from sea spray and ocean emitted biogenic volatile organic compounds (BVOCs) are extremely important for the Earth’s radiative budget, regional air quality and biogeochemical cycling of elements. Measurements of freshly-emitted sea spray have revealed that bubble bursting processes, largely responsible for the production of sea salt aerosol, also control sea-to-air transfer of marine organic matter. It has been established that the organic mass fraction of sea spray can be a function of sea-water composition (e.g., concentrations of Chlorophyll-a, [Chl-a], dissolved organic carbon, [DOC], particulate organic carbon, [POC], types of organic carbon, and the amount of surfactants). Current paramaterizations of marine primary organic aerosol emissions use remotely sensed [Chl-a] data as a proxy for oceanic biological activity. However, it has also been shown that the path length, size, and lifetime of bubbles in seawater as well as spatial coverage of seawater surface by streaks or slicks (visible film of a roughly 50 μm thick layer, highly enriched in organics) can have dramatic effect on organic mass fraction of sea spray (OCss). Dynamics of bubble entrainment and the level of microlayer enrichment by organics relative to the underlying bulk water can be controlled by surface wind speed. For bubble entrainment, high winds can increase rising bubble path length and therefore the amount of organics scavenged by the bubble. However, when the surface wind speeds exceed 8 m s-1 breaking of ocean waves can entirely destroy surface organic films and diminish the amount of organics leaving the sea. Despite the probable impact of wind speed, existing parameterizations do not

  16. Identifying Aerosol Type/Mixture from Aerosol Absorption Properties Using AERONET

    NASA Technical Reports Server (NTRS)

    Giles, D. M.; Holben, B. N.; Eck, T. F.; Sinyuk, A.; Dickerson, R. R.; Thompson, A. M.; Slutsker, I.; Li, Z.; Tripathi, S. N.; Singh, R. P.; hide

    2010-01-01

    Aerosols are generated in the atmosphere through anthropogenic and natural mechanisms. These sources have signatures in the aerosol optical and microphysical properties that can be used to identify the aerosol type/mixture. Spectral aerosol absorption information (absorption Angstrom exponent; AAE) used in conjunction with the particle size parameterization (extinction Angstrom exponent; EAE) can only identify the dominant absorbing aerosol type in the sample volume (e.g., black carbon vs. iron oxides in dust). This AAE/EAE relationship can be expanded to also identify non-absorbing aerosol types/mixtures by applying an absorption weighting. This new relationship provides improved aerosol type distinction when the magnitude of absorption is not equal (e.g, black carbon vs. sulfates). The Aerosol Robotic Network (AERONET) data provide spectral aerosol optical depth and single scattering albedo - key parameters used to determine EAE and AAE. The proposed aerosol type/mixture relationship is demonstrated using the long-term data archive acquired at AERONET sites within various source regions. The preliminary analysis has found that dust, sulfate, organic carbon, and black carbon aerosol types/mixtures can be determined from this AAE/EAE relationship when applying the absorption weighting for each available wavelength (Le., 440, 675, 870nm). Large, non-spherical dust particles absorb in the shorter wavelengths and the application of 440nm wavelength absorption weighting produced the best particle type definition. Sulfate particles scatter light efficiently and organic carbon particles are small near the source and aggregate over time to form larger less absorbing particles. Both sulfates and organic carbon showed generally better definition using the 870nm wavelength absorption weighting. Black carbon generation results from varying combustion rates from a number of sources including industrial processes and biomass burning. Cases with primarily black carbon showed

  17. The impact of biogenic carbon emissions on aerosol absorption inMexico City

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Marley, N; Gaffney, J; Tackett, M J

    2009-02-24

    In order to determine the wavelength dependence of atmospheric aerosol absorption in the Mexico City area, the absorption angstrom exponents (AAEs) were calculated from aerosol absorption measurements at seven wavelengths obtained with a seven-channel aethalometer during two field campaigns, the Mexico City Metropolitan Area study in April 2003 (MCMA 2003) and the Megacity Initiative: Local and Global Research Observations in March 2006 (MILAGRO). The AAEs varied from 0.76 to 1.56 in 2003 and from 0.54 to 1.52 in 2006. The AAE values determined in the afternoon were consistently higher than the corresponding morning values, suggesting the photochemical formation of absorbingmore » secondary organic aerosols (SOA) in the afternoon. The AAE values were compared to stable and radiocarbon isotopic measurements of aerosol samples collected at the same time to determine the sources of the aerosol carbon. The fraction of modern carbon (fM) in the aerosol samples, as determined from {sup 14}C analysis, showed that 70% of the carbonaceous aerosols in Mexico City were from modern sources, indicating a significant impact from biomass burning during both field campaigns. The {sup 13}C/{sup 12}C ratios of the aerosol samples illustrate the significant impact of Yucatan forest fires (C-3 plants) in 2003 and local grass fires (C-4 plants) at site T1 in 2006. A direct comparison of the fM values, stable carbon isotope ratios, and calculated aerosol AAEs suggested that the wavelength dependence of the aerosol absorption was controlled by the biogenically derived aerosol components.« less

  18. MATRIX-VBS Condensing Organic Aerosols in an Aerosol Microphysics Model

    NASA Technical Reports Server (NTRS)

    Gao, Chloe Y.; Tsigaridis, Konstas; Bauer, Susanne E.

    2015-01-01

    The condensation of organic aerosols is represented in a newly developed box-model scheme, where its effect on the growth and composition of particles are examined. We implemented the volatility-basis set (VBS) framework into the aerosol mixing state resolving microphysical scheme Multiconfiguration Aerosol TRacker of mIXing state (MATRIX). This new scheme is unique and advances the representation of organic aerosols in models in that, contrary to the traditional treatment of organic aerosols as non-volatile in most climate models and in the original version of MATRIX, this new scheme treats them as semi-volatile. Such treatment is important because low-volatility organics contribute significantly to the growth of particles. The new scheme includes several classes of semi-volatile organic compounds from the VBS framework that can partition among aerosol populations in MATRIX, thus representing the growth of particles via condensation of low volatility organic vapors. Results from test cases representing Mexico City and a Finish forrest condistions show good representation of the time evolutions of concentration for VBS species in the gas phase and in the condensed particulate phase. Emitted semi-volatile primary organic aerosols evaporate almost completely in the high volatile range, and they condense more efficiently in the low volatility range.

  19. Heterogeneous Oxidation of Atmospheric Organic Aerosol: Kinetics of Changes to the Amount and Oxidation State of Particle-Phase Organic Carbon.

    PubMed

    Kroll, Jesse H; Lim, Christopher Y; Kessler, Sean H; Wilson, Kevin R

    2015-11-05

    Atmospheric oxidation reactions are known to affect the chemical composition of organic aerosol (OA) particles over timescales of several days, but the details of such oxidative aging reactions are poorly understood. In this study we examine the rates and products of a key class of aging reaction, the heterogeneous oxidation of particle-phase organic species by the gas-phase hydroxyl radical (OH). We compile and reanalyze a number of previous studies from our laboratories involving the oxidation of single-component organic particles. All kinetic and product data are described on a common basis, enabling a straightforward comparison among different chemical systems and experimental conditions. Oxidation chemistry is described in terms of changes to key ensemble properties of the OA, rather than to its detailed molecular composition, focusing on two quantities in particular, the amount and the oxidation state of the particle-phase carbon. Heterogeneous oxidation increases the oxidation state of particulate carbon, with the rate of increase determined by the detailed chemical mechanism. At the same time, the amount of particle-phase carbon decreases with oxidation, due to fragmentation (C-C scission) reactions that form small, volatile products that escape to the gas phase. In contrast to the oxidation state increase, the rate of carbon loss is nearly uniform among most systems studied. Extrapolation of these results to atmospheric conditions indicates that heterogeneous oxidation can have a substantial effect on the amount and composition of atmospheric OA over timescales of several days, a prediction that is broadly in line with available measurements of OA evolution over such long timescales. In particular, 3-13% of particle-phase carbon is lost to the gas phase after one week of heterogeneous oxidation. Our results indicate that oxidative aging represents an important sink for particulate organic carbon, and more generally that fragmentation reactions play a major

  20. Field and Laboratory Studies of Atmospheric Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Coggon, Matthew Mitchell

    these conditions to all measurements conducted during E-PEACE demonstrated that a large fraction of cloud droplet (72%) and dry aerosol mass (12%) sampled in the California coastal study region was heavily or moderately influenced by ship emissions. Another study investigated the chemical and physical evolution of a controlled organic plume emitted from the R/V Point Sur. Under sunny conditions, nucleated particles composed of oxidized organic compounds contributed nearly an order of magnitude more cloud condensation nuclei (CCN) than less oxidized particles formed under cloudy conditions. The processing time necessary for particles to become CCN active was short ( 4 hr). Laboratory chamber experiments were also conducted to evaluate particle-phase processes influencing aerosol phase and composition. In one study, ammonium sulfate seed was coated with a layer of secondary organic aerosol (SOA) from toluene oxidation followed by a layer of SOA from α-pinene oxidation. The system exhibited different evaporative properties than ammonium sulfate seed initially coated with α-pinene SOA followed by a layer of toluene SOA. This behavior is consistent with a shell-and-core model and suggests limited mixing among different SOA types. Another study investigated the reactive uptake of isoprene epoxy diols (IEPOX) onto non-acidified aerosol. It was demonstrated that particle acidity has limited influence on organic aerosol formation onto ammonium sulfate seed, and that the chemical system is limited by the availability of nucleophiles such as sulfate. Flow tube experiments were conducted to examine the role of iron in the reactive uptake and chemical oxidation of glycolaldehyde. Aerosol particles doped with iron and hydrogen peroxide were mixed with gas-phase glycolaldehyde and photochemically aged in a custom-built flow reactor. Compared to particles free of iron, iron-doped aerosols significantly enhanced the oxygen to carbon (O/C) ratio of accumulated organic mass. The primary

  1. Causes and consequences of decreasing atmospheric organic aerosol in the United States.

    PubMed

    Ridley, D A; Heald, C L; Ridley, K J; Kroll, J H

    2018-01-09

    Exposure to atmospheric particulate matter (PM) exacerbates respiratory and cardiovascular conditions and is a leading source of premature mortality globally. Organic aerosol contributes a significant fraction of PM in the United States. Here, using surface observations between 1990 and 2012, we show that organic carbon has declined dramatically across the entire United States by 25-50%; accounting for more than 30% of the US-wide decline in PM. The decline is in contrast with the increasing organic aerosol due to wildfires and no clear trend in biogenic emissions. By developing a carbonaceous emissions database for the United States, we show that at least two-thirds of the decline in organic aerosol can be explained by changes in anthropogenic emissions, primarily from vehicle emissions and residential fuel burning. We estimate that the decrease in anthropogenic organic aerosol is responsible for averting 180,000 (117,000-389,000) premature deaths between 1990 and 2012. The unexpected decrease in organic aerosol, likely a consequence of the implementation of Clean Air Act Amendments, results in 84,000 (30,000-164,000) more lives saved than anticipated by the EPA between 2000 and 2010.

  2. Causes and consequences of decreasing atmospheric organic aerosol in the United States

    NASA Astrophysics Data System (ADS)

    Ridley, D. A.; Heald, C. L.; Ridley, K. J.; Kroll, J. H.

    2018-01-01

    Exposure to atmospheric particulate matter (PM) exacerbates respiratory and cardiovascular conditions and is a leading source of premature mortality globally. Organic aerosol contributes a significant fraction of PM in the United States. Here, using surface observations between 1990 and 2012, we show that organic carbon has declined dramatically across the entire United States by 25–50%; accounting for more than 30% of the US-wide decline in PM. The decline is in contrast with the increasing organic aerosol due to wildfires and no clear trend in biogenic emissions. By developing a carbonaceous emissions database for the United States, we show that at least two-thirds of the decline in organic aerosol can be explained by changes in anthropogenic emissions, primarily from vehicle emissions and residential fuel burning. We estimate that the decrease in anthropogenic organic aerosol is responsible for averting 180,000 (117,000–389,000) premature deaths between 1990 and 2012. The unexpected decrease in organic aerosol, likely a consequence of the implementation of Clean Air Act Amendments, results in 84,000 (30,000–164,000) more lives saved than anticipated by the EPA between 2000 and 2010.

  3. Sources of primary and secondary organic aerosol and their diurnal variations.

    PubMed

    Zheng, Mei; Zhao, Xiuying; Cheng, Yuan; Yan, Caiqing; Shi, Wenyan; Zhang, Xiaolu; Weber, Rodney J; Schauer, James J; Wang, Xinming; Edgerton, Eric S

    2014-01-15

    PM(2.5), as one of the criteria pollutants regulated in the U.S. and other countries due to its adverse health impacts, contains more than hundreds of organic pollutants with different sources and formation mechanisms. Daytime and nighttime PM2.5 samples from the August Mini-Intensive Gas and Aerosol Campaign (AMIGAS) in the southeastern U.S. were collected during summer 2008 at one urban site and one rural site, and were analyzed for organic carbon (OC), elemental carbon (EC), water soluble organic carbon (WSOC), and various individual organic compounds including some important tracers for carbonaceous aerosol sources by gas chromatography-mass spectrometry. Most samples exhibited higher daytime OC concentration, while higher nighttime OC was found in a few events at the urban site. Sources, formation mechanisms and composition of organic aerosol are complicated and results of this study showed that it exhibited distinct diurnal variations. With detailed organic tracer information, sources contributing to particulate OC were identified: higher nighttime OC concentration occurring in several occasions was mainly contributed by the increasing primary emissions at night, especially diesel exhaust and biomass burning; whereas sources responsible for higher daytime OC concentration included secondary organic aerosol (SOA) formation (e.g., cis-pinonic acid and non-biomass burning WSOC) together with traffic emissions especially gasoline engine exhaust. Primary tracers from combustion related sources such as EC, polycyclic aromatic hydrocarbons, and hopanes and steranes were significantly higher at the urban site with an urban to rural ratio between 5 and 8. However, this urban-rural difference for secondary components was less significant, indicating a relatively homogeneous distribution of SOA spatially. We found cholesterol concentrations, a typical tracer for meat cooking, were consistently higher at the rural site especially during the daytime, suggesting the likely

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

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

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

  5. Determination of the organic aerosol mass to organic carbon ratio in IMPROVE samples.

    PubMed

    El-Zanan, Hazem S; Lowenthal, Douglas H; Zielinska, Barbara; Chow, Judith C; Kumar, Naresh

    2005-07-01

    The ratio of organic mass (OM) to organic carbon (OC) in PM(2.5) aerosols at US national parks in the IMPROVE network was estimated experimentally from solvent extraction of sample filters and from the difference between PM(2.5) mass and chemical constituents other than OC (mass balance) in IMPROVE samples from 1988 to 2003. Archived IMPROVE filters from five IMPROVE sites were extracted with dichloromethane (DCM), acetone and water. The extract residues were weighed to determine OM and analyzed for OC by thermal optical reflectance (TOR). On average, successive extracts of DCM, acetone, and water contained 64%, 21%, and 15%, respectively, of the extractable OC, respectively. On average, the non-blank-corrected recovery of the OC initially measured in these samples by TOR was 115+/-42%. OM/OC ratios from the combined DCM and acetone extracts averaged 1.92 and ranged from 1.58 at Indian Gardens, AZ in the Grand Canyon to 2.58 at Mount Rainier, WA. The average OM/OC ratio determined by mass balance was 2.07 across the IMPROVE network. The sensitivity of this ratio to assumptions concerning sulfate neutralization, water uptake by hygroscopic species, soil mass, and nitrate volatilization were evaluated. These results suggest that the value of 1.4 for the OM/OC ratio commonly used for mass and light extinction reconstruction in IMPROVE is too low.

  6. Annual cycle of size-resolved organic aerosol characterization in an urbanized desert environment

    NASA Astrophysics Data System (ADS)

    Cahill, Thomas M.

    2013-06-01

    Studies of size-resolved organic speciation of aerosols are still relatively rare and are generally only conducted over short durations. However, size-resolved organic data can both suggest possible sources of the aerosols and identify the human exposure to the chemicals since different aerosol sizes have different lung capture efficiencies. The objective of this study was to conduct size-resolved organic aerosol speciation for a calendar year in Phoenix, Arizona to determine the seasonal variations in both chemical concentrations and size profiles. The results showed large seasonal differences in combustion pollutants where the highest concentrations were observed in winter. Summertime aerosols have a greater proportion of biological compounds (e.g. sugars and fatty acids) and the biological compounds represent the largest fraction of the organic compounds detected. These results suggest that standard organic carbon (OC) measurements might be heavily influenced by primary biological compounds particularly if the samples are PM10 and TSP samples. Several large dust storms did not significantly alter the organic aerosol profile since Phoenix resides in a dusty desert environment, so the soil and plant tracer of trehalose was almost always present. The aerosol size profiles showed that PAHs were generally most abundant in the smallest aerosol size fractions, which are most likely to be captured by the lung, while the biological compounds were almost exclusively found in the coarse size fraction.

  7. Absorption and scattering properties of organic carbon vs. sulfate dominant aerosols at Gosan climate observatory in Northeast Asia

    NASA Astrophysics Data System (ADS)

    Lim, S.; Lee, M.; Kim, S.-W.; Yoon, S.-C.; Lee, G.; Lee, Y.

    2013-12-01

    Carbonaceous and soluble ionic species of PM1.0 and PM10 were measured along with the absorption and scattering properties and aerosol number size distributions at Gosan climate observatory (GCO) from January to September 2008. The daily averaged equivalent black carbon (EBC) measured as aerosol absorption exhibited two types of spectral dependence with a distinct maximum (peak) at either 370 nm or 880 nm, by which two subsets were extracted and classified into the respective groups (370 nm and 880 nm). The 370 nm group was distinguished by high organic carbon (OC) concentrations relative to elemental carbon (EC) and sulfate, but sulfate was predominant for the 880 nm group. The PM1.0 OC of the 370 nm group was mainly composed of refractory and pyrolized components that correlated well with PM1.0 EC1, referred to as char EC, which suggests biofuel and biomass combustion as the source of these OC fractions, particularly during winter. The scanning electron microscope (SEM) images and the number size distributions implied that aerosols of the 370 nm group were externally mixed upon transport in fast-moving air masses that passed through the Beijing area in about one day. In contrast, the aerosols of the 880 nm group were characterized by high sulfate concentrations, and seemed to be internally mixed during slow transport over the Yellow Sea region over approximately two to four days. The absorption and scattering coefficients of the 880 nm group were noticeably higher compared to those of the 370 nm group. The average absorption ångström exponent (AAE) was estimated to be 1.29 and 1.0 for the 370 nm and 880 nm groups, respectively, in the range 370-950 nm. These results demonstrated that the optical properties of aerosols were intimately linked to chemical composition and mixing state, characteristics determined both by source and atmospheric aging processes. In OC dominant aerosols, absorption was enhanced in the UV region, which was possibly due to refractory and

  8. Absorption and scattering properties of organic carbon versus sulfate dominant aerosols at Gosan climate observatory in Northeast Asia

    NASA Astrophysics Data System (ADS)

    Lim, S.; Lee, M.; Kim, S.-W.; Yoon, S.-C.; Lee, G.; Lee, Y. J.

    2014-08-01

    Carbonaceous and soluble ionic species of PM1.0 and PM10 were measured along with the absorption and scattering properties and aerosol number size distributions at Gosan Climate Observatory (GCO) from January to September 2008. The daily averaged equivalent black carbon (EBC) measured as aerosol absorption exhibited two types of spectral dependence with a distinct maximum (peak) at either 370 nm or 880 nm, by which two subsets were extracted and classified into the respective groups (370 and 880 nm). The 370 nm group was distinguished by high organic carbon (OC) concentrations relative to elemental carbon (EC) and sulfate, but sulfate was predominant for the 880 nm group. The PM1.0 OC of the 370 nm group was mainly composed of refractory and pyrolized components that correlated well with PM1.0 EC1, referred to as char EC, which suggests biofuel and biomass combustion as the source of these OC fractions, particularly during winter. The scanning electron microscope (SEM) images and the number size distributions implied that aerosols of the 370 nm group were externally mixed upon transport in fast-moving air masses that passed through the Beijing area in about one day. In contrast, the aerosols of the 880 nm group were characterized by high sulfate concentrations, and seemed to be internally mixed during slow transport over the Yellow Sea region over approximately 2 to 4 days. The absorption and scattering coefficients of the 880 nm group were noticeably higher compared to those of the 370 nm group. The average absorption ångström exponent (AAE) was estimated to be 1.29 and 1.0 for the 370 and 880 nm groups, respectively, in the range 370-950 nm. These results demonstrated that the optical properties of aerosols were intimately linked to chemical composition and mixing state, characteristics determined both by source and atmospheric aging processes. In OC dominant aerosols, absorption was enhanced in the UV region, which was possibly due to refractory and pyrolized

  9. Chemical and Optical Properties of Water-Soluble Organic Aerosols from Biomass Burning Emissions

    NASA Astrophysics Data System (ADS)

    Yu, J. M.; Park, S.; Cho, S. Y.

    2016-12-01

    Light absorption property by organic aerosols is an important parameter to determine their radiative forcing on global and regional scales. However, the optical measurements by light absorbing aerosols from biomass burning emissions are rather lacking. This study explored the chemical and light-absorption properties of humic-like substances (HULIS) from biomass burning aerosols of three types; rice straw (RS), pine needles (PN), and sesame stem (SS). Water-soluble organic carbon (WSOC) contributed 42.5, 42.0, and 57.0% to the OC concentrations of the RS, PN, and SS emissions, respectively. Respective HULIS (=1.94´HULIS-C) concentrations accounted for 29.5±2.0, 15.3±3.1, and 25.8±4.0% of PM2.5, and contributed 63±5, 36±10, and 51±8% to WSOC concentration. Absorption Ångström exponents (AAEs) of the WSOC fitted between 300 and 400 nm wavelengths were 7.4-8.3, indicating no significant differences among the biomass types. These AAEs are similar to those reported for aqueous extracts of biomass burning HULIS and fresh secondary organic aerosols from ozonolysis of terpenes. HULIS, which is a hydrophobic part of WSOC and a significant fraction of brown carbon, showed absorption spectra similar to brown carbon. WSOC mass absorption efficiency (MAE365) at 365 nm were 1.37, 0.86, and 1.38 m2/g×C for RS, PN, and SS burning aerosols, respectively. The MAE values by WSOC were less than 10% of MAE caused by light-absorbing black carbon. The light absorption of the water extracts at 365 nm indicated that light absorption was more strongly associated with HULIS from biomass burning emissions than with the hydrophilic WSOC fraction.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Song, Chen; Gyawali, Madhu; Zaveri, Rahul A.

    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 + O 3 and α-pinene + NO x + O 3 systems in the presence ofmore » 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 + O 3 + NO 3 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 + O 3 and α-pinene + NO x + O 3 systems do not form light-absorbing SOA under typical atmospheric conditions.« less

  11. Radiative absorption enhancement from coatings on black carbon aerosols.

    PubMed

    Cui, Xinjuan; Wang, Xinfeng; Yang, Lingxiao; Chen, Bing; Chen, Jianmin; Andersson, August; Gustafsson, Örjan

    2016-05-01

    The radiative absorption enhancement of ambient black carbon (BC), by light-refractive coatings of atmospheric aerosols, constitutes a large uncertainty in estimates of climate forcing. The direct measurements of radiative absorption enhancement require the experimentally-removing the coating materials in ambient BC-containing aerosols, which remains a challenge. Here, the absorption enhancement of the BC core by non-absorbing aerosol coatings was quantified using a two-step removal of both inorganic and organic matter coatings of ambient aerosols. The mass absorption cross-section (MAC) of decoated/pure atmospheric BC aerosols of 4.4±0.8m(2)g(-1) was enhanced to 9.6±1.8m(2)g(-1) at 678-nm wavelength for ambiently-coated BC aerosols at a rural Northern China site. The enhancement of MAC (EMAC) rises from 1.4±0.3 in fresh combustion emissions to ~3 for aged ambient China aerosols. The three-week high-intensity campaign observed an average EMAC of 2.25±0.55, and sulfates were primary drivers of the enhanced BC absorption. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Towards a quasi-complete reconstruction of past atmospheric aerosol load and composition (organic and inorganic) over Europe since 1920 inferred from Alpine ice cores

    NASA Astrophysics Data System (ADS)

    Preunkert, S.; Legrand, M.

    2013-07-01

    Seasonally resolved chemical ice core records available from the Col du Dôme glacier (4250 m elevation, French Alps), are here used to reconstruct past aerosol load and composition of the free European troposphere from before World War II to present. Available ice core records include inorganic (Na+, Ca2+, NH4+, Cl-, NO3-, and SO42-) and organic (carboxylates, HCHO, humic-like substances, dissolved organic carbon, water-insoluble organic carbon, and black carbon) compounds and fractions that permit reconstructing the key aerosol components and their changes over the past. It is shown that the atmospheric load of submicron aerosol has been increased by a factor of 3 from the 1921-1951 to 1971-1988 years, mainly as a result of a large increase of sulfate (a factor of 5), ammonium and water-soluble organic aerosol (a factor of 3). Thus, not only growing anthropogenic emissions of sulfur dioxide and ammonia have caused the enhancement of the atmospheric aerosol load but also biogenic emissions producing water-soluble organic aerosol. This unexpected change of biospheric source of organic aerosol after 1950 needs to be considered and further investigated in scenarios dealing with climate forcing by atmospheric aerosol.

  13. Aqueous aerosol SOA formation: impact on aerosol physical properties.

    PubMed

    Woo, Joseph L; Kim, Derek D; Schwier, Allison N; Li, Ruizhi; McNeill, V Faye

    2013-01-01

    Organic chemistry in aerosol water has recently been recognized as a potentially important source of secondary organic aerosol (SOA) material. This SOA material may be surface-active, therefore potentially affecting aerosol heterogeneous activity, ice nucleation, and CCN activity. Aqueous aerosol chemistry has also been shown to be a potential source of light-absorbing products ("brown carbon"). We present results on the formation of secondary organic aerosol material in aerosol water and the associated changes in aerosol physical properties from GAMMA (Gas-Aerosol Model for Mechanism Analysis), a photochemical box model with coupled gas and detailed aqueous aerosol chemistry. The detailed aerosol composition output from GAMMA was coupled with two recently developed modules for predicting a) aerosol surface tension and b) the UV-Vis absorption spectrum of the aerosol, based on our previous laboratory observations. The simulation results suggest that the formation of oligomers and organic acids in bulk aerosol water is unlikely to perturb aerosol surface tension significantly. Isoprene-derived organosulfates are formed in high concentrations in acidic aerosols under low-NO(x) conditions, but more experimental data are needed before the potential impact of these species on aerosol surface tension may be evaluated. Adsorption of surfactants from the gas phase may further suppress aerosol surface tension. Light absorption by aqueous aerosol SOA material is driven by dark glyoxal chemistry and is highest under high-NO(x) conditions, at high relative humidity, in the early morning hours. The wavelength dependence of the predicted absorption spectra is comparable to field observations and the predicted mass absorption efficiencies suggest that aqueous aerosol chemistry can be a significant source of aerosol brown carbon under urban conditions.

  14. Aerosol generation and measurement of multi-wall carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Myojo, Toshihiko; Oyabu, Takako; Nishi, Kenichiro; Kadoya, Chikara; Tanaka, Isamu; Ono-Ogasawara, Mariko; Sakae, Hirokazu; Shirai, Tadashi

    2009-01-01

    Mass production of some kinds of carbon nanotubes (CNT) is now imminent, but little is known about the risk associated with their exposure. It is important to assess the propensity of the CNT to release particles into air for its risk assessment. In this study, we conducted aerosolization of a multi-walled CNT (MWCNT) to assess several aerosol measuring instruments. A Palas RBG-1000 aerosol generator applied mechanical stress to the MWCNT by a rotating brush at feed rates ranging from 2 to 20 mm/h, which the MWCNT was fed to a two-component fluidized bed. The fluidized bed aerosol generator was used to disperse the MWCNT aerosol once more. We monitored the generated MWCNT aerosol concentrations based on number, area, and mass using a condensation particle counter and nanoparticle surface area monitor. Also we quantified carbon mass in MWCNT aerosol samples by a carbon monitor. The shape of aerosolized MWCNT fibers was observed by a scanning electron microscope (SEM). The MWCNT was well dispersed by our system. We found isolated MWCNT fibers in the aerosols by SEM and the count median lengths of MWCNT fibers were 4-6 μm. The MWCNT was quantified by the carbon monitor with a modified condition based on the NIOSH analytical manual. The MWCNT aerosol concentration (EC mass base) was 4 mg/m3 at 2 mm/h in this study.

  15. Molecular Markers of Secondary Organic Aerosol in Mumbai, India.

    PubMed

    Fu, Pingqing; Aggarwal, Shankar G; Chen, Jing; Li, Jie; Sun, Yele; Wang, Zifa; Chen, Huansheng; Liao, Hong; Ding, Aijun; Umarji, G S; Patil, R S; Chen, Qi; Kawamura, Kimitaka

    2016-05-03

    Biogenic secondary organic aerosols (SOA) are generally considered to be more abundant in summer than in winter. Here, polar organic marker compounds in urban background aerosols from Mumbai were measured using gas chromatography-mass spectrometry. Surprisingly, we found that concentrations of biogenic SOA tracers at Mumbai were several times lower in summer (8-14 June 2006; wet season; n = 14) than in winter (13-18 February 2007; dry season; n = 10). Although samples from less than 10% of the season are extrapolated to the full season, such seasonality may be explained by the predominance of the southwest summer monsoon, which brings clean marine air masses to Mumbai. While heavy rains are an important contributor to aerosol removal during the monsoon season, meteorological data (relative humidity and T) suggest no heavy rains occurred during our sampling period. However, in winter, high levels of SOA and their day/night differences suggest significant contributions of continental aerosols through long-range transport together with local sources. The winter/summer pattern of SOA loadings was further supported by results from chemical transport models (NAQPMS and GEOS-Chem). Furthermore, our study suggests that monoterpene- and sesquiterpene-derived secondary organic carbon (SOC) were more significant than those of isoprene- and toluene-SOC at Mumbai.

  16. Characterization of water-soluble organic aerosol in coastal New England: Implications of variations in size distribution

    NASA Astrophysics Data System (ADS)

    Ziemba, L. D.; Griffin, R. J.; Whitlow, S.; Talbot, R. W.

    2011-12-01

    Size distributions up to 10-micron aerosol diameter ( DP) of organic carbon (OC) and water-soluble organic carbon (WSOC) were measured at two sites in coastal New England, slightly inland at Thompson Farm (TF) and offshore at Isles of Shoals (IOS). Significant OC concentrations were measured across the full size distribution at TF and IOS, respectively. The WSOC fraction (WSOC/OC) was largest in the accumulation mode with values of 0.86 and 0.93 and smallest in the coarse mode with values of 0.61 and 0.79 at TF and IOS, respectively. Dicarboxylic acids containing up to five carbon atoms (C 5) were concentrated in droplet and accumulation mode aerosol with only minor contributions in the coarse mode. C 1-C 3 monocarboxylic acids were generally near or below detection limits. Results from proton nuclear magnetic resonance (H +-NMR) spectroscopy analyses showed that the organic functional group characterized by protons in the alpha position to an unsaturated carbon atoms ([H-C-C dbnd ]) was the dominant WSOC functionality at both TF and IOS, constituting 34 and 43% of carbon-weighted H +-NMR signal, respectively. Size distributions of each H +-NMR-resolved organic functionality are presented. Source apportionment using H +-NMR fingerprints is also presented, and results indicate that nearly all of the WSOC at TF and IOS spectroscopically resembled secondary organic aerosol, regardless of DP.

  17. EVALUATION OF SECONDARY ORGANIC AEROSOL FORMATION IN WINTER. (R823514)

    EPA Science Inventory

    Three different methods are used to predict secondary organic aerosol (SOA)
    concentrations in the San Joaquin Valley of California during the winter of 1995-1996 [Integrated
    Monitoring Study, (IMS95)]. The first of these methods estimates SOA by using elemental carbon as

  18. Light absorption of organic aerosol from pyrolysis of corn stalk

    NASA Astrophysics Data System (ADS)

    Li, Xinghua; Chen, Yanju; Bond, Tami C.

    2016-11-01

    Organic aerosol (OA) can absorb solar radiation in the low-visible and ultra-violet wavelengths thereby modifying radiative forcing. Agricultural waste burning emits a large quantity of organic carbon in many developing countries. In this work, we improved the extraction and analysis method developed by Chen and Bond, and extended the spectral range of OC absorption. We examined light absorbing properties of primary OA from pyrolysis of corn stalk, which is a major type of agricultural wastes. Light absorption of bulk liquid extracts of OA was measured using a UV-vis recording spectrophotometer. OA can be extracted by methanol at 95%, close to full extent, and shows polar character. Light absorption of organic aerosol has strong spectral dependence (Absorption Ångström exponent = 7.7) and is not negligible at ultra-violet and low-visible regions. Higher pyrolysis temperature produced OA with higher absorption. Imaginary refractive index of organic aerosol (kOA) is 0.041 at 400 nm wavelength and 0.005 at 550 nm wavelength, respectively.

  19. Secondary organic aerosol formation through cloud processing of aromatic VOCs

    NASA Astrophysics Data System (ADS)

    Herckes, P.; Hutchings, J. W.; Ervens, B.

    2010-12-01

    Field observations have shown substantial concentrations (20-5,500 ng L-1) of aromatic volatile organic compounds (VOC) in cloud droplets. The potential generation of secondary organic aerosol mass through the processing of these anthropogenic VOCs was investigated through laboratory and modeling studies. Under simulated atmospheric laboratory conditions, in idealized solutions, benzene, toluene, ethylbenzene, and xylene (BTEX) degraded quickly in the aqueous phase. The degradation process yielded less volatile products which would contribute to new aerosol mass upon cloud evaporation. However, when realistic cloud solutions containing natural organic matter were used in the experiments, the reaction rates decreased with increasing organic carbon content. Kinetic data derived from these experiments were used as input to a multiphase box model in order to evaluate the secondary organic aerosol (SOA) mass formation potential of cloud processing of BTEX. Model results will be presented that quantify the SOA amounts from these aqueous phase pathways. The efficiency of this multiphase SOA source will be compared to SOA yields from the same aromatics as treated in traditional SOA models that are restricted to gas phase oxidation and subsequent condensation on particles.

  20. SECONDARY ORGANIC CARBON AND AEROSOL YIELDS FROM THE IRRADIATIONS OF ISOPRENE AND á-PINENE IN THE PRESENCE OF NO X AND SO 2

    EPA Science Inventory

    A laboratory study was carried out to investigate the secondary organic carbon (SOC) yields of a-pinene and isoprene in the presence of SO2, which produces acidic aerosol in the system. Experiments were based on irradiating each hydrocarbon (HC) with NOx in ...

  1. Modelling organic aerosol concentrations and properties during ChArMEx summer campaigns of 2012 and 2013 in the western Mediterranean region

    NASA Astrophysics Data System (ADS)

    Chrit, Mounir; Sartelet, Karine; Sciare, Jean; Pey, Jorge; Marchand, Nicolas; Couvidat, Florian; Sellegri, Karine; Beekmann, Matthias

    2017-10-01

    In the framework of the Chemistry-Aerosol Mediterranean Experiment, a measurement site was set up at a remote site (Ersa) on Corsica Island in the northwestern Mediterranean Sea. Measurement campaigns performed during the summers of 2012 and 2013 showed high organic aerosol concentrations, mostly from biogenic origin. This work aims to represent the organic aerosol concentrations and properties (oxidation state and hydrophilicity) using the air-quality model Polyphemus with a surrogate approach for secondary organic aerosol (SOA) formation. Biogenic precursors are isoprene, monoterpenes and sesquiterpenes. In this work, the following model oxidation products of monoterpenes are added: (i) a carboxylic acid (MBTCA) to represent multi-generation oxidation products in the low-NOx regime, (ii) organic nitrate chemistry and (iii) extremely low-volatility organic compounds (ELVOCs) formed by ozonolysis. The model shows good agreement of measurements of organic concentrations for both 2012 and 2013 summer campaigns. The modelled oxidation property and hydrophilic organic carbon properties of the organic aerosols also agree reasonably well with the measurements. The influence of the different chemical processes added to the model on the oxidation level of organics is studied. Measured and simulated water-soluble organic carbon (WSOC) concentrations show that even at a remote site next to the sea, about 64 % of the organic carbon is soluble. The concentrations of WSOC vary with the origins of the air masses and the composition of organic aerosols. The marine organic emissions only contribute to a few percent of the organic mass in PM1, with maxima above the sea.

  2. Towards a quasi-complete reconstruction of past atmospheric aerosol load and composition (organic and inorganic) over Europe since 1920 inferred from Alpine ice cores

    NASA Astrophysics Data System (ADS)

    Preunkert, S.; Legrand, M.

    2013-02-01

    Seasonally resolved chemical ice core records available from the Col du Dôme glacier (4250 m elevation, French Alps) are here revisited in view to reconstruct past aerosol load of the free European troposphere from prior World War II to present. The extended array of inorganic (Na+, Ca2+, NH4+, Cl-, NO3-, and SO42-) and organic (carboxylates, HCHO, HUmic LIke Substances, dissolved organic carbon, water insoluble organic carbon, and black carbon) compounds and fractions already investigated permit to examine the overall aerosol composition and its change over the past. It is shown that the atmospheric load of submicron aerosol has been increased by a factor of 3 from the 1921-1951 to 1971-1988 years, mainly as a result of a large increase of sulfate (a factor of 5), ammonium and water-soluble organic aerosol (a factor of 3). It is shown that not only growing anthropogenic emissions of sulfur dioxide and ammonia have caused the enhancement of the atmospheric aerosol load but also biogenic emissions producing water soluble organic aerosol. This unexpected change of biospheric source of organic aerosol after 1950 needs to be considered and further investigated in scenarii dealing with climate forcing by atmospheric aerosol.

  3. Time-resolved analysis of particle emissions from residential biomass combustion - Emissions of refractory black carbon, PAHs and organic tracers

    NASA Astrophysics Data System (ADS)

    Nielsen, Ingeborg E.; Eriksson, Axel C.; Lindgren, Robert; Martinsson, Johan; Nyström, Robin; Nordin, Erik Z.; Sadiktsis, Ioannis; Boman, Christoffer; Nøjgaard, Jacob K.; Pagels, Joakim

    2017-09-01

    Time-resolved particle emissions from a conventional wood stove were investigated with aerosol mass spectrometry to provide links between combustion conditions, emission factors, mixing state of refractory black carbon and implications for organic tracer methods. The addition of a new batch of fuel results in low temperature pyrolysis as the fuel heats up, resulting in strong, short-lived, variable emission peaks of organic aerosol-containing markers of anhydrous sugars, such as levoglucosan (fragment at m/z 60). Flaming combustion results in emissions dominated by refractory black carbon co-emitted with minor fractions of organic aerosol and markers of anhydrous sugars. Full cycle emissions are an external mixture of larger organic aerosol-dominated and smaller thinly coated refractory black carbon particles. A very high burn rate results in increased full cycle mass emission factors of 66, 2.7, 2.8 and 1.3 for particulate polycyclic aromatic hydrocarbons, refractory black carbon, total organic aerosol and m/z 60, respectively, compared to nominal burn rate. Polycyclic aromatic hydrocarbons are primarily associated with refractory black carbon-containing particles. We hypothesize that at very high burn rates, the central parts of the combustion zone become air starved, leading to a locally reduced combustion temperature that reduces the conversion rates from polycyclic aromatic hydrocarbons to refractory black carbon. This facilitates a strong increase of polycyclic aromatic hydrocarbons emissions. At nominal burn rates, full cycle emissions based on m/z 60 correlate well with organic aerosol, refractory black carbon and particulate matter. However, at higher burn rates, m/z 60 does not correlate with increased emissions of polycyclic aromatic hydrocarbons, refractory black carbon and organic aerosol in the flaming phase. The new knowledge can be used to advance source apportionment studies, reduce emissions of genotoxic compounds and model the climate impacts of

  4. Characterization of polar organic compounds and source analysis of fine organic aerosols in Hong Kong

    NASA Astrophysics Data System (ADS)

    Li, Yunchun

    Organic aerosols, as an important fraction of airborne particulate mass, significantly affect the environment, climate, and human health. Compared with inorganic species, characterization of individual organic compounds is much less complete and comprehensive because they number in thousands or more and are diverse in chemical structures. The source contributions of organic aerosols are far from being well understood because they can be emitted from a variety of sources as well as formed from photochemical reactions of numerous precursors. This thesis work aims to improve the characterization of polar organic compounds and source apportionment analysis of fine organic carbon (OC) in Hong Kong, which consists of two parts: (1) An improved analytical method to determine monocarboxylic acids, dicarboxylic acids, ketocarboxylic acids, and dicarbonyls collected on filter substrates has been established. These oxygenated compounds were determined as their butyl ester or butyl acetal derivatives using gas chromatography-mass spectrometry. The new method made improvements over the original Kawamura method by eliminating the water extraction and evaporation steps. Aerosol materials were directly mixed with the BF 3/BuOH derivatization agent and the extracting solvent hexane. This modification improves recoveries for both the more volatile and the less water-soluble compounds. This improved method was applied to study the abundances and sources of these oxygenated compounds in PM2.5 aerosol samples collected in Hong Kong under different synoptic conditions during 2003-2005. These compounds account for on average 5.2% of OC (range: 1.4%-13.6%) on a carbon basis. Oxalic acid was the most abundant species. Six C2 and C3 oxygenated compounds, namely oxalic, malonic, glyoxylic, pyruvic acids, glyoxal, and methylglyoxal, dominated this suite of oxygenated compounds. More efforts are therefore suggested to focus on these small compounds in understanding the role of oxygenated

  5. Real time in situ detection of organic nitrates in atmospheric aerosols.

    PubMed

    Rollins, Andrew W; Smith, Jared D; Wilson, Kevin R; Cohen, Ronald C

    2010-07-15

    A novel instrument is described that quantifies total particle-phase organic nitrates in real time with a detection limit of 0.11 microg m(-3) min(-1), 45 ppt min(-1) (-ONO(2)). Aerosol nitrates are separated from gas-phase nitrates with a short residence time activated carbon denuder. Detection of organic molecules containing -ONO(2) subunits is accomplished using thermal dissociation coupled to laser induced fluorescence detection of NO(2). This instrument is capable of high time resolution (seconds) measurements of particle-phase organic nitrates, without interference from inorganic nitrate. Here we use it to quantify organic nitrates in secondary organic aerosol generated from high-NO(x) photooxidation of limonene, alpha-pinene, Delta-3-carene, and tridecane. In these experiments the organic nitrate moiety is observed to be 6-15% of the total SOA mass.

  6. A Monte-Carlo Analysis of Organic Aerosol Volatility with Aerosol Microphysics

    NASA Astrophysics Data System (ADS)

    Gao, C. Y.; Tsigaridis, K.; Bauer, S. E.

    2016-12-01

    A newly developed box model scheme, MATRIX-VBS, includes the volatility-basis set (VBS) framework in an aerosol microphysical scheme MATRIX (Multiconfiguration Aerosol TRacker of mIXing state), which resolves aerosol mass and number concentrations and aerosol mixing state. The new scheme advanced the representation of organic aerosols in Earth system models by improving the traditional and simplistic treatment of organic aerosols as non-volatile and with a fixed size distribution. Further development includes adding the condensation of organics on coarse mode aerosols - dust and sea salt, thus making all organics in the system semi-volatile. To test and simplify the model, a Monte-Carlo analysis is performed to pin point which processes affect organics the most under which chemical and meteorological conditions. Since the model's parameterizations have the ability to capture a very wide range of conditions, from very clean to very polluted and for a wide range of meteorological conditions, all possible scenarios on Earth across the whole parameter space, including temperature, location, emissions and oxidant levels, are examined. The Monte-Carlo simulations provide quantitative information on the sensitivity of the newly developed model and help us understand how organics are affecting the size distribution, mixing state and volatility distribution at varying levels of meteorological conditions and pollution levels. In addition, these simulations give information on which parameters play a critical role in the aerosol distribution and evolution in the atmosphere and which do not, that will facilitate the simplification of the box model, an important step in its implementation in the global model.

  7. Improving source identification of Atlanta aerosol using temperature resolved carbon fractions in positive matrix factorization

    NASA Astrophysics Data System (ADS)

    Kim, Eugene; Hopke, Philip K.; Edgerton, Eric S.

    Daily integrated PM 2.5 (particulate matter ⩽2.5 μm in aerodynamic diameter) composition data including eight individual carbon fractions collected at the Jefferson Street monitoring site in Atlanta were analyzed with positive matrix factorization (PMF). Particulate carbon was analyzed using the thermal optical reflectance method that divides carbon into four organic carbon (OC), pyrolized organic carbon (OP), and three elemental carbon (EC) fractions. A total of 529 samples and 28 variables were measured between August 1998 and August 2000. PMF identified 11 sources in this study: sulfate-rich secondary aerosol I (50%), on-road diesel emissions (11%), nitrate-rich secondary aerosol (9%), wood smoke (7%), gasoline vehicle (6%), sulfate-rich secondary aerosol II (6%), metal processing (3%), airborne soil (3%), railroad traffic (3%), cement kiln/carbon-rich (2%), and bus maintenance facility/highway traffic (2%). Differences from previous studies using only the traditional OC and EC data (J. Air Waste Manag. Assoc. 53(2003a)731; Atmos Environ. (2003b)) include four traffic-related combustion sources (gasoline vehicle, on-road diesel, railroad, and bus maintenance facility) containing carbon fractions whose abundances were different between the various sources. This study indicates that the temperature resolved fractional carbon data can be utilized to enhance source apportionment study, especially with respect to the separation of diesel emissions from gasoline vehicle sources. Conditional probability functions using surface wind data and identified source contributions aid the identifications of local point sources.

  8. Burning of olive tree branches: a major organic aerosol source in the Mediterranean

    NASA Astrophysics Data System (ADS)

    Kostenidou, E.; Kaltsonoudis, C.; Tsiflikiotou, M.; Louvaris, E.; Russell, L. M.; Pandis, S. N.

    2013-09-01

    Aerosol produced during the burning of olive tree branches was characterized with both direct source sampling (using a mobile smog chamber) and with ambient measurements during the burning season. The fresh particles were composed of 80% organic matter, 8-10% black carbon (BC), 5% potassium, 3-4% sulfate, 2-3% nitrate and 0.8% chloride. Almost half of the fresh olive tree branches burning organic aerosol (otBB-OA) consisted of alkane groups. Their mode diameter was close to 70 nm. The oxygen to carbon (O : C) ratio of the fresh otBB-OA was 0.29 ± 0.04. The mass fraction of levoglucosan in PM1 was 0.034-0.043, relatively low in comparison with most fuel types. This may lead to an underestimation of the otBB-OA contribution if levoglucosan is being used as a wood burning tracer. Chemical aging was observed during smog chamber experiments, as f44 and O : C ratio increased, due to reactions with OH radicals and O3. The otBB-OA AMS mass spectrum differs from the other published biomass burning spectra, with a main difference at m/z 60, used as levoglucosan tracer. In addition to particles, volatile organic compounds (VOCs) such as methanol, acetonitrile, acrolein, benzene, toluene and xylenes are also emitted. Positive matrix factorization (PMF) was applied to the ambient organic aerosol data and 3 factors could be identified: OOA (oxygenated organic aerosol, 55%), HOA (hydrocarbon-like organic aerosol, 11.3%) and otBB-OA 33.7%. The fresh chamber otBB-OA AMS spectrum is close to the PMF otBB-OA spectrum and resembles the ambient mass spectrum during olive tree branches burning periods. We estimated an otBB-OA emission factor of 3.5 ± 0.9 g kg-1. Assuming that half of the olive tree branches pruned is burned in Greece, 2300 ± 600 tons of otBB-OA are emitted every year. This activity is one of the most important fine aerosol sources during the winter months in Mediterranean countries.

  9. Burning of olive tree branches: a major organic aerosol source in the Mediterranean

    NASA Astrophysics Data System (ADS)

    Kostenidou, E.; Kaltsonoudis, C.; Tsiflikiotou, M.; Louvaris, E.; Russell, L. M.; Pandis, S. N.

    2013-03-01

    Aerosol produced during the burning of olive tree branches was characterized with both direct source-sampling (using a mobile smog chamber) and with ambient measurements during the burning season. The fresh particles were composed of 80% organic matter, 8-10% black carbon (BC), 5% potassium, 3-4% sulfate, 2-3% nitrate and 0.8% chloride. Almost half of the fresh olive tree branches burning organic aerosol (otBB-OA) consisted of alkane groups. Their mode diameter was close to 70 nm. The oxygen to carbon (O:C) ratio of the fresh otBB-OA was 0.29 ± 0.04. The mass fraction of levoglucosan in PM1 was 0.034-0.043, relatively low in comparison with most fuel types. This may lead to an underestimation of the otBB-OA contribution if levoglucosan is being used as a wood burning tracer. Chemical aging was observed during smog chamber experiments, as f44 and O:C ratio increased, due to reactions with OH radicals and O3. The otBB-OA AMS mass spectrum differs from the other published biomass burning spectra, with a main difference at m/z 60, used as levoglucosan tracer. In addition to particles, volatile organic compounds (VOCs) such as methanol, acetonitrile, acrolein, benzene, toluene and xylenes are also emitted. Positive matrix factorization (PMF) was applied to the ambient organic aerosol data and 3 factors could be identified: OOA (oxygenated organic aerosol, 55%), HOA (hydrocarbon-like organic aerosol, 11.3%) and otBB-OA 33.7%. The fresh chamber otBB-OA AMS spectrum is close to the PMF otBB-OA spectrum and resembles the ambient mass spectrum during olive tree branches burning periods. We estimated an otBB-OA emission factor of 3.5 ± 0.2 g kg-1. Assuming that half of the olive tree branches pruned is burned in Greece 2280 ± 140 tons of otBB-OA are emitted every year. This activity is one of the most important fine aerosol sources during the winter months in the Mediterranean countries.

  10. Reactivity of liquid and semisolid secondary organic carbon with chloride and nitrate in atmospheric aerosols

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wang, Bingbing; O'Brien, Rachel E.; Univ. of the Pacific, Stockton, CA

    2015-05-14

    Constituents of secondary organic carbon (SOC) in atmospheric aerosols are often mixed with inorganic components and compose a significant mass fraction of fine particulate matter in the atmosphere. Interactions between SOC and other condensed-phase species are not well understood. Here, we investigate the reactions of liquid-like and semi-solid SOC from ozonolysis of limonene (LSOC) and α-pinene (PSOC) with NaCl using a set of complementary micro-spectroscopic analyses. These reactions result in chloride depletion in the condensed phase, release of gaseous HCl, and formation of organic salts. The reactions attributed to acid displacement by SOC acidic components are driven by the highmore » volatility of HCl. Similar reactions can take place in SOC/NaNO₃ particles. The results show that an increase in SOC mass fraction in the internally mixed SOC/NaCl particles leads to higher chloride depletion. Glass transition temperatures and viscosity of PSOC were estimated for atmospherically relevant conditions. Data show that the reaction extent depends on SOC composition, particle phase state and viscosity, mixing state, temperature, relative humidity (RH), and reaction time. LSOC shows slightly higher potential to deplete chloride than PSOC. Higher particle viscosity at low temperatures and RH can hinder these acid displacement reactions. Formation of organic salts from these overlooked reactions can alter particle physiochemical properties and may affect their reactivity and ability to act as cloud condensation and ice nuclei. The release and potential recycling of HCl and HNO₃ from reacted aerosol particles may have important implications for atmospheric chemistry.« less

  11. Reactivity of liquid and semisolid secondary organic carbon with chloride and nitrate in atmospheric aerosols.

    PubMed

    Wang, Bingbing; O'Brien, Rachel E; Kelly, Stephen T; Shilling, John E; Moffet, Ryan C; Gilles, Mary K; Laskin, Alexander

    2015-05-14

    Constituents of secondary organic carbon (SOC) in atmospheric aerosols are often mixed with inorganic components and compose a significant mass fraction of fine particulate matter in the atmosphere. Interactions between SOC and other condensed-phase species are not well understood. Here, we investigate the reactions of liquid-like and semisolid SOC from ozonolysis of limonene (LSOC) and α-pinene (PSOC) with NaCl using a set of complementary microspectroscopic analyses. These reactions result in chloride depletion in the condensed phase, release of gaseous HCl, and formation of organic salts. The reactions attributed to acid displacement by SOC acidic components are driven by the high volatility of HCl. Similar reactions can take place in SOC/NaNO3 particles. The results show that an increase in SOC mass fraction in the internally mixed SOC/NaCl particles leads to higher chloride depletion. Glass transition temperatures and viscosity of PSOC were estimated for atmospherically relevant conditions. Data show that the reaction extent depends on SOC composition, particle phase state and viscosity, mixing state, temperature, relative humidity (RH), and reaction time. LSOC shows slightly higher potential to deplete chloride than PSOC. Higher particle viscosity at low temperatures and RH can hinder these acid displacement reactions. Formation of organic salts from these overlooked reactions can alter particle physiochemical properties and may affect their reactivity and ability to act as cloud condensation and ice nuclei. The release and potential recycling of HCl and HNO3 from reacted aerosol particles may have important implications for atmospheric chemistry.

  12. Organic compounds in aerosols from selected European sites - Biogenic versus anthropogenic sources

    NASA Astrophysics Data System (ADS)

    Alves, Célia; Vicente, Ana; Pio, Casimiro; Kiss, Gyula; Hoffer, Andras; Decesari, Stefano; Prevôt, André S. H.; Minguillón, María Cruz; Querol, Xavier; Hillamo, Risto; Spindler, Gerald; Swietlicki, Erik

    2012-11-01

    Atmospheric aerosol samples from a boreal forest (Hyytiälä, April 2007), a rural site in Hungary (K-puszta, summer 2008), a polluted rural area in Italy (San Pietro Capofiume, Po Valley, April 2008), a moderately polluted rural site in Germany located on a meadow (Melpitz, May 2008), a natural park in Spain (Montseny, March 2009) and two urban background locations (Zurich, December 2008, and Barcelona, February/March 2009) were collected. Aliphatics, polycyclic aromatic hydrocarbons, carbonyls, sterols, n-alkanols, acids, phenolic compounds and anhydrosugars in aerosols were chemically characterised by gas chromatography-mass spectrometry, along with source attribution based on the carbon preference index (CPI), the ratios between the unresolved and the chromatographically resolved aliphatics, the contribution of wax n-alkanes, n-alkanols and n-alkanoic acids from plants, diagnostic ratios of individual target compounds and source-specific markers to organic carbon ratios. In spite of transboundary pollution episodes, Hyytiälä registered the lowest levels among all locations. CPI values close to 1 for the aliphatic fraction of the Montseny aerosol suggest that the anthropogenic input may be associated with the transport of aged air masses from the surrounding industrial/urban areas, which superimpose the locally originated hydrocarbons with biogenic origin. Aliphatic and aromatic hydrocarbons in samples from San Pietro Capofiume reveal that fossil fuel combustion is a major source influencing the diel pattern of concentrations. This source contributed to 25-45% of the ambient organic carbon (OC) at the Po Valley site. Aerosols from the German meadow presented variable contributions from both biogenic and anthropogenic sources. The highest levels of vegetation wax components and biogenic secondary organic aerosol (SOA) products were observed at K-puszta, while anthropogenic SOA compounds predominated in Barcelona. The primary vehicular emissions in the Spanish

  13. Method for characterization of low molecular weight organic acids in atmospheric aerosols using ion chromatography mass spectrometry.

    PubMed

    Brent, Lacey C; Reiner, Jessica L; Dickerson, Russell R; Sander, Lane C

    2014-08-05

    The structural composition of PM2.5 monitored in the atmosphere is usually divided by the analysis of organic carbon, black (also called elemental) carbon, and inorganic salts. The characterization of the chemical composition of aerosols represents a significant challenge to analysts, and studies are frequently limited to determination of aerosol bulk properties. To better understand the potential health effects and combined interactions of components in aerosols, a variety of measurement techniques for individual analytes in PM2.5 need to be implemented. The method developed here for the measurement of organic acids achieves class separation of aliphatic monoacids, aliphatic diacids, aromatic acids, and polyacids. The selective ion monitoring capability of a triple quadropole mass analyzer was frequently capable of overcoming instances of incomplete separations. Standard Reference Material (SRM) 1649b Urban Dust was characterized; 34 organic acids were qualitatively identified, and 6 organic acids were quantified.

  14. Technical note: Aerosol light absorption measurements with a carbon analyser - Calibration and precision estimates

    NASA Astrophysics Data System (ADS)

    Ammerlaan, B. A. J.; Holzinger, R.; Jedynska, A. D.; Henzing, J. S.

    2017-09-01

    Equivalent Black Carbon (EBC) and Elemental Carbon (EC) are different mass metrics to quantify the amount of combustion aerosol. Both metrics have their own measurement technique. In state-of-the-art carbon analysers, optical measurements are used to correct for organic carbon that is not evolving because of pyrolysis. These optical measurements are sometimes used to apply the technique of absorption photometers. Here, we use the transmission measurements of our carbon analyser for simultaneous determination of the elemental carbon concentration and the absorption coefficient. We use MAAP data from the CESAR observatory, the Netherlands, to correct for aerosol-filter interactions by linking the attenuation coefficient from the carbon analyser to the absorption coefficient measured by the MAAP. Application of the calibration to an independent data set of MAAP and OC/EC observations for the same location shows that the calibration is applicable to other observation periods. Because of simultaneous measurements of light absorption properties of the aerosol and elemental carbon, variation in the mass absorption efficiency (MAE) can be studied. We further show that the absorption coefficients and MAE in this set-up are determined within a precision of 10% and 12%, respectively. The precisions could be improved to 4% and 8% when the light transmission signal in the carbon analyser is very stable.

  15. Predicting ambient aerosol thermal-optical reflectance (TOR) measurements from infrared spectra: organic carbon

    NASA Astrophysics Data System (ADS)

    Dillner, A. M.; Takahama, S.

    2015-03-01

    Organic carbon (OC) can constitute 50% or more of the mass of atmospheric particulate matter. Typically, organic carbon is measured from a quartz fiber filter that has been exposed to a volume of ambient air and analyzed using thermal methods such as thermal-optical reflectance (TOR). Here, methods are presented that show the feasibility of using Fourier transform infrared (FT-IR) absorbance spectra from polytetrafluoroethylene (PTFE or Teflon) filters to accurately predict TOR OC. This work marks an initial step in proposing a method that can reduce the operating costs of large air quality monitoring networks with an inexpensive, non-destructive analysis technique using routinely collected PTFE filter samples which, in addition to OC concentrations, can concurrently provide information regarding the composition of organic aerosol. This feasibility study suggests that the minimum detection limit and errors (or uncertainty) of FT-IR predictions are on par with TOR OC such that evaluation of long-term trends and epidemiological studies would not be significantly impacted. To develop and test the method, FT-IR absorbance spectra are obtained from 794 samples from seven Interagency Monitoring of PROtected Visual Environment (IMPROVE) sites collected during 2011. Partial least-squares regression is used to calibrate sample FT-IR absorbance spectra to TOR OC. The FTIR spectra are divided into calibration and test sets by sampling site and date. The calibration produces precise and accurate TOR OC predictions of the test set samples by FT-IR as indicated by high coefficient of variation (R2; 0.96), low bias (0.02 μg m-3, the nominal IMPROVE sample volume is 32.8 m3), low error (0.08 μg m-3) and low normalized error (11%). These performance metrics can be achieved with various degrees of spectral pretreatment (e.g., including or excluding substrate contributions to the absorbances) and are comparable in precision to collocated TOR measurements. FT-IR spectra are also

  16. The link between organic aerosol mass loading and degree of oxygenation: an α-pinene photooxidation study

    NASA Astrophysics Data System (ADS)

    Pfaffenberger, L.; Barmet, P.; Slowik, J. G.; Praplan, A. P.; Dommen, J.; Prévôt, A. S. H.; Baltensperger, U.

    2013-07-01

    A series of smog chamber (SC) experiments was conducted to identify factors responsible for the discrepancy between ambient and SC aerosol degree of oxygenation. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer is used to compare mass spectra from α-pinene photooxidation with ambient aerosol. Composition is compared in terms of the fraction of particulate CO2+, a surrogate for carboxylic acids, vs. the fraction of C2H3O+, a surrogate for aldehydes, alcohols and ketones, as well as in the Van Krevelen space, where the evolution of the atomic hydrogen-to-carbon ratio (H : C) vs. the atomic oxygen-to-carbon ratio (O : C) is investigated. Low (near-ambient) organic mass concentrations were found to be necessary to obtain oxygenation levels similar to those of low-volatility oxygenated organic aerosol (LV-OOA) commonly identified in ambient measurements. The effects of organic mass loading and OH (hydroxyl radical) exposure were decoupled by inter-experiment comparisons at the same integrated OH concentration. An OH exposure between 3 and 25 × 107 cm-3 h is needed to increase O : C by 0.05 during aerosol aging. For the first time, LV-OOA-like aerosol from the abundant biogenic precursor α-pinene was produced in a smog chamber by oxidation at typical atmospheric OH concentrations. Significant correlation between measured secondary organic aerosol (SOA) and reference LV-OOA mass spectra is shown by Pearson's R2 values larger than 0.90 for experiments with low organic mass concentrations between 1.2 and 18 μg m-3 at an OH exposure of 4 × 107 cm-3 h, corresponding to about two days of oxidation time in the atmosphere, based on a global mean OH concentration of ~ 1 × 106 cm-3. α-Pinene SOA is more oxygenated at low organic mass loadings. Because the degree of oxygenation influences the chemical, volatility and hygroscopic properties of ambient aerosol, smog chamber studies must be performed at near-ambient concentrations to accurately simulate

  17. On the Complex Coupling Between the Production of Ozone and Secondary Organic Aerosol in Polluted Urban Regions

    NASA Astrophysics Data System (ADS)

    Stewart, D. R.; Stockwell, W. R.; Morris, V. R.; Fitzgerald, R. M.

    2016-12-01

    The major photochemical processes that produce ozone and aerosols are coupled together strongly in the polluted urban atmosphere. Aerosols are either directly emitted or formed through the same kind of chemistry that leads to the production of ozone. The aerosols produced through atmospheric chemistry are known as secondary aerosols and they may be composed of inorganic (nitrates, sulfates) or organic compounds. Wind blown dust and soot are two examples of primary aerosols. The component of secondary inorganic aerosols includes compounds such as ammonium nitrate, ammonium bisulfate and ammonium sulfate. Secondary organic aerosols are a very important component of PM with strong implications for health. The formation of secondary organic aerosol is linked with ozone photochemistry through the reactions of volatile organic compounds (VOC). The oxidation of VOC produces radicals that convert nitric oxide to nitrogen dioxide that photolyze to produce ozone. Larger VOC (those with more carbon atoms) undergo a number of oxidation cycles that add oxygen atoms to large organic molecules. The vapor pressure of many of these highly oxidized compounds is sufficiently low that they condense to produce secondary organic aerosols. The Community Multi-scale Air Quality model (CMAQ) and other chemical simulations have been made to quantify the relationship between varying emissions of VOC and NOx and the production of inorganic and secondary organic aerosols. The results from this analysis will be presented.

  18. Physical properties of ambient and laboratory-generated secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    O'Brien, Rachel E.; Neu, Alexander; Epstein, Scott A.; MacMillan, Amanda C.; Wang, Bingbing; Kelly, Stephen T.; Nizkorodov, Sergey A.; Laskin, Alexander; Moffet, Ryan C.; Gilles, Mary K.

    2014-06-01

    The size and thickness of organic aerosol particles collected by impaction in five field campaigns were compared to those of laboratory-generated secondary organic aerosols (SOA). Scanning transmission X-ray microscopy was used to measure the total carbon absorbance (TCA) by individual particles as a function of their projection areas on the substrate. Particles with higher viscosity/surface tension can be identified by a steeper slope on a plot of TCA versus size because they flatten less upon impaction. The slopes of the ambient data are statistically similar indicating a small range of average viscosities/surface tensions across five field campaigns. Steeper slopes were observed for the plots corresponding to ambient particles, while smaller slopes were indicative of the laboratory-generated SOA. This comparison indicates that ambient organic particles have higher viscosities/surface tensions than those typically generated in laboratory SOA studies.

  19. Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation

    PubMed Central

    Shiraiwa, Manabu; Yee, Lindsay D.; Schilling, Katherine A.; Loza, Christine L.; Craven, Jill S.; Zuend, Andreas; Ziemann, Paul J.; Seinfeld, John H.

    2013-01-01

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process. PMID:23818634

  20. Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation.

    PubMed

    Shiraiwa, Manabu; Yee, Lindsay D; Schilling, Katherine A; Loza, Christine L; Craven, Jill S; Zuend, Andreas; Ziemann, Paul J; Seinfeld, John H

    2013-07-16

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process.

  1. Final Report, The Influence of Organic-Aerosol Emissions and Aging on Regional and Global Aerosol Size Distributions and the CCN Number Budget

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Donahue, Neil M.

    We conducted laboratory experiments and analyzed data on aging of organic aerosol and analysis of field data on volatility and CCN activity. With supplemental ASR funding we participated in the FLAME-IV campaign in Missoula MT in the Fall of 2012, deploying a two-chamber photochemical aging system to enable experimental exploration of photochemical aging of biomass burning emissions. Results from that campaign will lead to numerous publications, including demonstration of photochemical production of Brown Carbon (BrC) from secondary organic aerosol associated with biomass burning emissions as well as extensive characterization of the effect of photochemical aging on the overall concentrations ofmore » biomass burning organic aerosol. Excluding publications arising from the FLAME-IV campaign, project research resulted in 8 papers: [11, 5, 3, 10, 12, 4, 8, 7], including on in Nature Geoscience addressing the role of organic compounds in nanoparticle growth [11]« less

  2. Quantification of black carbon mixing state from traffic: Implications for aerosol optical properties

    DOE PAGES

    Willis, Megan D.; Healy, Robert M.; Riemer, Nicole; ...

    2016-04-14

    The climatic impacts of black carbon (BC) aerosol, an important absorber of solar radiation in the atmosphere, remain poorly constrained and are intimately related to its particle-scale physical and chemical properties. Using particle-resolved modelling informed by quantitative measurements from a soot-particle aerosol mass spectrometer, we confirm that the mixing state (the distribution of co-emitted aerosol amongst fresh BC-containing particles) at the time of emission significantly affects BC-aerosol optical properties even after a day of atmospheric processing. Both single particle and ensemble aerosol mass spectrometry observations indicate that BC near the point of emission co-exists with hydrocarbon-like organic aerosol (HOA) inmore » two distinct particle types: HOA-rich and BC-rich particles. The average mass fraction of black carbon in HOA-rich and BC-rich particle classes was < 0.1 and 0.8, respectively. Notably, approximately 90 % of BC mass resides in BC-rich particles. This new measurement capability provides quantitative insight into the physical and chemical nature of BC-containing particles and is used to drive a particle-resolved aerosol box model. Lastly, significant differences in calculated single scattering albedo (an increase of 0.1) arise from accurate treatment of initial particle mixing state as compared to the assumption of uniform aerosol composition at the point of BC injection into the atmosphere.« less

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  4. Seasonal variation of organic aerosol in PM2.5 at Anmyeondo, a background site in Korea

    NASA Astrophysics Data System (ADS)

    Lee, J.; Kim, E. S.; Kim, Y. P.; Jung, C. H.; Lee, J.

    2016-12-01

    Routine measurements of PM2.5 and chemical speciation for 100 individual organic compounds were carried out to understand seasonal variation of organic compounds at a background area in Korea between 2015 and 2016. Organic compounds analyzed in this study were classified into five groups, n-alkanes, polycyclic aromatic hydrocarbons (PAHs), fatty acids (FA), dicarboxylic acids (DCAs), and sugar. Further, organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC) and Humic Like Substance-Carbon (HULIS-C) in PM2.5 were simultaneously analyzed to make mass balance of carbonaceous aerosol in PM2.5 at a background site in Korea. PAHs concentrations at this site was lower than that at Seoul, a representative urban site in Korea. PAHs and n-Alkanes concentrations showed clear seasonal variation with summer minimum and winter maximum, while, seasonal variation of DCAs and Sugars were different with PAHs and n-Alkanes.WSOC concentrations were highly correlated with SOC (Secondary Organic Carbon) concentrations which were estimated by the EC tracer method. The results indicate the formation of secondary organic aerosol (SOA) is major factor for the determination of WSOC concentrations in this region. HULIS-C as known one of brown carbon was major component of WSOC which accounts for 39 to 99% in WSOC. The average concentrations of HULIS-C was 2.02±1.42 and the highest concentration was observed in fall.

  5. Characterization of Ambient Black Carbon Aerosols

    NASA Astrophysics Data System (ADS)

    Zhang, R.; Levy, M. E.; Zheng, J.; Molina, L. T.

    2013-12-01

    Because of the strong absorption over a broad range of the electromagnetic spectra, black carbon (BC) is a key short-lived climate forcer, which contributes significantly to climate change by direct radiative forcing and is the second most important component causing global warming after carbon dioxide. The impact of BC on the radiative forcing of the Earth-Atmosphere system is highly dependent of the particle properties. In this presentation, emphasis will be placed on characterizing BC containing aerosols in at the California-Mexico border to obtain a greater understanding of the atmospheric aging and properties of ambient BC aerosols. A comprehensive set of directly measured aerosol properties, including the particle size distribution, effective density, hygroscopicity, volatility, and several optical properties, will be discussed to quantify the mixing state and composition of ambient particles. In Tijuana, Mexico, submicron aerosols are strongly influenced by vehicle emissions; subsequently, the BC concentration in Tijuana is considerably higher than most US cities with an average BC concentration of 2.71 × 2.65 g cm-3. BC accounts for 24.75 % × 9.44 of the total submicron concentration on average, but periodically accounts for over 50%. This high concentration of BC strongly influences many observed aerosol properties such as single scattering albedo, hygroscopicity, effective density, and volatility.

  6. Role of organic aerosols in CCN activation and closure over a rural background site in Western Ghats, India

    NASA Astrophysics Data System (ADS)

    Singla, V.; Mukherjee, S.; Safai, P. D.; Meena, G. S.; Dani, K. K.; Pandithurai, G.

    2017-06-01

    The cloud condensation nuclei (CCN) closure study was performed to exemplify the effect of aerosol chemical composition on the CCN activity of aerosols at Mahabaleshwar, a high altitude background site in the Western Ghats, India. For this, collocated aerosol, CCN, Elemental Carbon (EC), Organic Carbon (OC), sub-micron aerosol chemical speciation for the period from 3rd June to 19th June 2015 was used. The chemical composition of non-refractory particulate matter (<1 μm) as measured by Time of Flight - Aerosol Chemical Speciation Monitor (ToF-ACSM) was dominated by organics with average concentration of 3.81 ± 1.6, 0.32 ± 0.06, 0.15 ± 0.02, 0.13 ± 0.03 and 0.95 ± 0.12 μg m-3 for organics, ammonium, chloride, nitrate and sulphate, respectively. The PM1 number concentration as obtained by Wide Range Aerosol Spectrometer (WRAS) varied from 750 to 6480 cm-3. The average mass concentration of elemental carbon (EC) as measured by OC-EC analyzer was 1.16 ± 0.4 μg m-3. The average CCN concentrations obtained from CCN counter (CCNC) at five super-saturations (SS's) was 118 ± 58 cm-3 (0.1% SS), 873 ± 448 cm-3 (0.31% SS), 1308 ± 603 cm-3 (0.52% SS), 1610 ± 838 cm-3 (0.73% SS) and 1826 ± 985 cm-3 (0.94% SS). The CCN concentrations were predicted using Köhler theory on the basis of measured aerosol particle number size distribution, size independent NR-PM1 chemical composition and calculated hygroscopicity. The CCN closure study was evaluated for 3 scenarios, B-I (all soluble inorganics), B-IO (all soluble organics and inorganics) and B-IOOA (all soluble inorganic and soluble oxygenated organic aerosol, OOA). OOA component was derived from the positive matrix factorization (PMF) analysis of organic aerosol mass spectra. Considering the bulk composition as internal mixture, CCN closure study was underestimated by 16-39% for B-I and overestimated by 47-62% for B-IO. The CCN closure result was appreciably improved for B-IOOA where the knowledge of OOA fraction was

  7. A contribution of black and brown carbon to the aerosol light absorption

    NASA Astrophysics Data System (ADS)

    Kim, Sang-Woo; Cho, Chaeyoon; Jo, Duseong; Park, Rokjin

    2017-04-01

    Black carbon (BC) is functionally defined as the absorbing component of atmospheric total carbonaceous aerosols and is typically dominated by soot-like elemental carbon (EC). Organic carbon (OC) has also been shown to absorb strongly at visible to UV wavelengths and the absorbing organics are referred to as brown carbon (BrC; Alexander et al., 2008). These two aerosols contribute to solar radiative forcing through absorption of solar radiation and heating of the absorbing aerosol layer, but most optical instruments that quantify light absorption are unable to distinguish one type of absorbing aerosol from another (Moosmüller et al. 2009). In this study, we separate total aerosol absorption from these two different light absorbers from co-located simultaneous in-situ measurements, such as Continuous Soot Monitoring System (COSMOS), Continuous Light Absorption Photometer (CLAP) and Sunset EC/OC analyzer, at Gosan climate observatory, Korea. We determine the mass absorption cross-section (MAC) of BC, and then estimate the contribution of BC and BrC on aerosol light absorption, together with a global 3-D chemical transport model (GEOS-Chem) simulation. At 565 nm wavelength, BC MAC is found to be about 5.4±2.8 m2 g-1 from COSMOS and Sunset EC/OC analyzer measurements during January-May 2012. This value is similar to those from Alexander et al. (2008; 4.3 ˜ 4.8 m2 g-1 at 550 nm) and Chung et al. (2012; 5.1 m2 g-1 at 520 nm), but slightly lower than Bond and Bergstrom (2006; 7.5±1.2 m2 g-1 at 550 nm). The COMOS BC mass concentration calculated with 5.4 m2 g-1 of BC MAC shows a good agreement with thermal EC concentration, with a good slope (1.1). Aerosol absorption coefficient and BC mass concentration from COSMOS, meanwhile, are approximately 25 ˜ 30 % lower than those of CLAP. This difference can be attributable to the contribution of volatile light-absorbing aerosols (i.e., BrC). The absorption coefficient of BrC, which is determined by the difference of

  8. Aerosol characterization over the southeastern United States using high resolution aerosol mass spectrometry: spatial and seasonal variation of aerosol composition, sources, and organic nitrates

    NASA Astrophysics Data System (ADS)

    Xu, L.; Suresh, S.; Guo, H.; Weber, R. J.; Ng, N. L.

    2015-04-01

    We deployed a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and an Aerosol Chemical Speciation Monitor (ACSM) to characterize the chemical composition of submicron non-refractory particles (NR-PM1) in the southeastern US. Measurements were performed in both rural and urban sites in the greater Atlanta area, GA and Centreville, AL for approximately one year, as part of Southeastern Center of Air Pollution and Epidemiology study (SCAPE) and Southern Oxidant and Aerosol Study (SOAS). Organic aerosol (OA) accounts for more than half of NR1 mass concentration regardless of sampling sites and seasons. Positive matrix factorization (PMF) analysis of HR-ToF-AMS measurements identified various OA sources, depending on location and season. Hydrocarbon-like OA (HOA) and cooking OA (COA) have important but not dominant contributions to total OA in urban sites. Biomass burning OA (BBOA) concentration shows a distinct seasonal variation with a larger enhancement in winter than summer. We find a good correlation between BBOA and brown carbon, indicating biomass burning is an important source for brown carbon, although an additional, unidentified brown carbon source is likely present at the rural Yorkville site. Isoprene-derived OA (Isoprene-OA) is only deconvolved in warmer months and contributes 18-36% of total OA. The presence of Isoprene-OA factor in urban sites is more likely from local production in the presence of NOx than transport from rural sites. More-oxidized and less-oxidized oxygenated organic aerosol (MO-OOA and LO-OOA, respectively) are dominant fractions (47-79%) of OA in all sites. MO-OOA correlates well with ozone in summer, but not in winter, indicating MO-OOA sources may vary with seasons. LO-OOA, which reaches a daily maximum at night, correlates better with estimated nitrate functionality from organic nitrates than total nitrates. Based on the HR-ToF-AMS measurements, we estimate that the nitrate functionality from organic nitrates

  9. Functional group composition of organic aerosol from combustion emissions and secondary processes at two contrasted urban environments

    NASA Astrophysics Data System (ADS)

    El Haddad, Imad; Marchand, Nicolas; D'Anna, Barbara; Jaffrezo, Jean Luc; Wortham, Henri

    2013-08-01

    The quantification of major functional groups in atmospheric organic aerosol (OA) provides a constraint on the types of compounds emitted and formed in atmospheric conditions. This paper presents functional group composition of organic aerosol from two contrasted urban environments: Marseille during summer and Grenoble during winter. Functional groups were determined using a tandem mass spectrometry approach, enabling the quantification of carboxylic (RCOOH), carbonyl (RCOR‧), and nitro (RNO2) functional groups. Using a multiple regression analysis, absolute concentrations of functional groups were combined with those of organic carbon derived from different sources in order to infer the functional group contents of different organic aerosol fractions. These fractions include fossil fuel combustion emissions, biomass burning emissions and secondary organic aerosol (SOA). Results clearly highlight the differences between functional group fingerprints of primary and secondary OA fractions. OA emitted from primary sources is found to be moderately functionalized, as about 20 carbons per 1000 bear one of the functional groups determined here, whereas SOA is much more functionalized, as in average 94 carbons per 1000 bear a functional group under study. Aging processes appear to increase both RCOOH and RCOR‧ functional group contents by nearly one order of magnitude. Conversely, RNO2 content is found to decrease with photochemical processes. Finally, our results also suggest that other functional groups significantly contribute to biomass smoke and SOA. In particular, for SOA, the overall oxygen content, assessed using aerosol mass spectrometer measurements by an O:C ratio of 0.63, is significantly higher than the apparent O:C* ratio of 0.17 estimated based on functional groups measured here. A thorough examination of our data suggests that this remaining unexplained oxygen content can be most probably assigned to alcohol (ROH), organic peroxides (ROOH

  10. Secondary organic aerosol: a comparison between foggy and nonfoggy days.

    PubMed

    Kaul, D S; Gupta, Tarun; Tripathi, S N; Tare, V; Collett, J L

    2011-09-01

    Carbonaceous species, meteorological parameters, trace gases, and fogwater chemistry were measured during winter in the Indian city of Kanpur to study secondary organic aerosol (SOA) during foggy and clear (nonfoggy) days. Enhanced SOA production was observed during fog episodes. It is hypothesized that aqueous phase chemistry in fog drops is responsible for increasing SOA production. SOA concentrations on foggy days exceeded those on clear days at all times of day; peak foggy day SOA concentrations were observed in the evening vs peak clear day SOA concentrations which occurred in the afternoon. Changes in biomass burning emissions on foggy days were examined because of their potential to confound estimates of SOA production based on analysis of organic to elemental carbon (OC/EC) ratios. No evidence of biomass burning influence on SOA during foggy days was found. Enhanced oxidation of SO(2) to sulfate during foggy days was observed, possibly causing the regional aerosol to become more acidic. No evidence was found in this study, either, for effects of temperature or relative humidity on SOA production. In addition to SOA production, fogs can also play an important role in cleaning the atmosphere of carbonaceous aerosols. Preferential scavenging of water-soluble organic carbon (WSOC) by fog droplets was observed. OC was found to be enriched in smaller droplets, limiting the rate of OC deposition by droplet sedimentation. Lower EC concentrations were observed on foggy days, despite greater stagnation and lower mixing heights, suggesting fog scavenging and removal of EC was active as well.

  11. Cloud processing of organic compounds: Secondary organic aerosol and nitrosamine formation

    NASA Astrophysics Data System (ADS)

    Hutchings, James W., III

    Cloud processing of atmospheric organic compounds has been investigated through field studies, laboratory experiments, and numerical modeling. Observational cloud chemistry studies were performed in northern Arizona and fog studies in central Pennsylvania. At both locations, the cloud and fogs showed low acidity due to neutralization by soil dust components (Arizona) and ammonia (Pennsylvania). The field observations showed substantial concentrations (20-5500 ng•L -1) of volatile organic compounds (VOC) in the cloud droplets. The potential generation of secondary organic aerosol mass through the processing of these anthropogenic VOCs was investigated through laboratory and modeling studies. Under simulated atmospheric conditions, in idealized solutions, benzene, toluene, ethylbenzene, and xylene (BTEX) degraded quickly in the aqueous phase with half lives of approximately three hours. The degradation process yielded less volatile products which would contribute to new aerosol mass upon cloud evaporation. However, when realistic cloud solutions containing natural organic matter were used in the experiments, the reaction kinetics decreased with increasing organic carbon content, resulting in half lives of approximately 7 hours. The secondary organic aerosol (SUA) mass formation potential of cloud processing of BTEX was evaluated. SOA mass formation by cloud processing of BTEX, while strongly dependent on the atmospheric conditions, could contribute up to 9% of the ambient atmospheric aerosol mass, although typically ˜1% appears realistic. Field observations also showed the occurrence of N-nitrosodimethylamine (NDMA), a potent carcinogen, in fogs and clouds (100-340 ng•L -1). Laboratory studies were conducted to investigate the formation of NDMA from nitrous acid and dimethylamine in the homogeneous aqueous phase within cloud droplets. While NDMA was produced in the cloud droplets, the low yields (<1%) observed could not explain observational concentrations

  12. Light Absorption of Brown Carbon Aerosol in the Pearl River Delta Region of China

    NASA Astrophysics Data System (ADS)

    Huang, X.

    2015-12-01

    X.F. Huang, J.F. Yuan, L.M. Cao, J. Cui, C.N. Huang, Z.J. Lan and L.Y. He Key Laboratory for Urban Habitat Environmental Science and Technology, School of Environment and Energy, Peking University Shenzhen Graduate School, Shenzhen 518055, ChinaCorresponding author. Tel.: +86 755 26032532; fax: +86 755 26035332. E-mail address: huangxf@pku.edu.cn (X. F. Huang). Abstract: The strong spectral dependence of light absorption of brown carbon (BrC) aerosol has been recognized in recent decades. The Absorption Angstrom Exponent (AAE) of ambient aerosol was widely used in previous studies to attribute light absorption of brown carbon at shorter wavelengths, with a theoretical assumption that the AAE of black carbon (BC) aerosol equals to unit. In this study, the AAE method was improved by statistical extrapolation based on ambient measurements in the polluted seasons in typical urban and rural areas in the Pearl River Delta (PRD) region of China. A three-wavelength photoacoustic soot spectrometer (PASS-3) and an aerosol mass spectrometer (AMS) were used to explore the relationship between the ambient measured AAE and the ratio of organic aerosol to BC aerosol, in order to extract the more realistic AAE by pure BC aerosol, which were found to be 0.86, 0.82 and 1.02 at 405nm and 0.70, 0.71, and 0.86 at 532nm in the campaigns of urban-winter, urban-fall, and rural-fall, respectively. Roadway tunnel experiment results further supported the effectiveness of the obtained AAE for pure BC aerosol. In addition, biomass burning experiments proved higher spectral dependence of more-BrC environment and further verified the reliability of the instruments' response. Then, the average light absorption contribution of BrC aerosol was calculated to be 11.7, 6.3 and 12.1% (with total relative uncertainty of 7.5, 6.9 and 10.0%) at 405nm and 10.0, 4.1 and 5.5% (with total relative uncertainty of 6.5, 8.6 and 15.4%) at 532nm of the three campaigns, respectively. These results indicate that the

  13. Small molecules as tracers in atmospheric secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Yu, Ge

    Secondary organic aerosol (SOA), formed from in-air oxidation of volatile organic compounds, greatly affects human health and climate. Although substantial research has been devoted to SOA formation and evolution, the modeled and lab-generated SOA are still low in mass and degree of oxidation compared to ambient measurements. In order to compensate for these discrepancies, the aqueous processing pathway has been brought to attention. The atmospheric waters serve as aqueous reaction media for dissolved organics to undergo further oxidation, oligomerization, or other functionalization reactions, which decreases the vapor pressure while increasing the oxidation state of carbon atoms. Field evidence for aqueous processing requires the identification of tracer products such as organosulfates. We synthesized the standards for two organosulfates, glycolic acid sulfate and lactic acid sulfate, in order to measure their aerosol-state concentration from five distinct locations via filter samples. The water-extracted filter samples were analyzed by LC-MS. Lactic acid sulfate and glycolic acid sulfate were detected in urban locations in the United States, Mexico City, and Pakistan with varied concentrations, indicating their potential as tracers. We studied the aqueous processing reaction between glyoxal and nitrogen-containing species such as ammonium and amines exclusively by NMR spectrometry. The reaction products formic acid and several imidazoles along with the quantified kinetics were reported. The brown carbon generated from these reactions were quantified optically by UV-Vis spectroscopy. The organic-phase reaction between oxygen molecule and alkenes photosensitized by alpha-dicarbonyls were studied in the same manner. We observed the fast kinetics transferring alkenes to epoxides under simulated sunlight. Statistical estimations indicate a very effective conversion of aerosol-phase alkenes to epoxides, potentially forming organosulfates in a deliquescence event and

  14. The effect of organic aerosol material on aerosol reactivity towards ozone

    NASA Astrophysics Data System (ADS)

    Batenburg, Anneke; Gaston, Cassandra; Thornton, Joel; Virtanen, Annele

    2015-04-01

    After aerosol particles are formed or emitted into the atmosphere, heterogeneous reactions with gaseous oxidants cause them to 'age'. Aging can change aerosol properties, such as the hygroscopicity, which is an important parameter in how the particles scatter radiation and form clouds. Conversely, heterogeneous reactions on aerosol particles play a significant role in the cycles of various atmospheric trace gases. Organic compounds, a large part of the total global aerosol matter, can exist in liquid or amorphous (semi)solid physical phases. Different groups have shown that reactions with ozone (O3) can be limited by bulk diffusion in organic aerosol, particularly in viscous, (semi)solid materials, and that organic coatings alter the surface interactions between gas and aerosol particles. We aim to better understand and quantify how the viscosity and phase of organic aerosol matter affect gas-particle interactions. We have chosen the reaction of O3 with particles composed of a potassium iodide (KI) core and a variable organic coating as a model system. The reaction is studied in an aerosol flow reactor that consists of a laminar flow tube and a movable, axial injector for the injection of O3. The aerosol-containing air is inserted at the tube's top. The interaction length (and therefore time), between the particles and the O3 can be varied by moving the injector. Alternatively, the production of aerosol particles can be modulated. The remaining O3 concentration is monitored from the bottom of the tube and particle concentrations are measured simultaneously, which allows us to calculate the reactive uptake coefficient γ. We performed exploratory experiments with internally mixed KI and polyethylene glycol (PEG) particles at the University of Washington (UW) in a setup with a residence time around 50 s. Aerosol particles were generated in an atomizer from solutions with varying concentrations of KI and PEG and inserted into the flow tube after they were diluted and

  15. DETERMINATION OF THE ORGANIC MASS TO ORGANIC CARBON RATIO IN IMPROVE SAMPLES. (R831086)

    EPA Science Inventory

    The ratio of organic mass (OM) to organic carbon (OC) in PM2.5 aerosols at US national parks in the IMPROVE network was estimated experimentally from solvent extraction of sample filters and from the difference between PM2.5 mass and chemical constituents...

  16. New insights on aerosol sources and properties of Organics in the west Mediterranean basin

    NASA Astrophysics Data System (ADS)

    Nicolas, José B.; Sciare, Jean; Petit, Jean-Eudes; Bonnaire, Nicolas; Féron, Anais; Dulac, François; Hamonou, Eric; Gros, Valérie; Mallet, Marc; Lambert, Dominique; Sauvage, Stéphane; Léonardis, Thierry; Tison, Emmanuel; Colomb, Aurélie; Fresney, Evelyn; Pichon, Jean-Marc; Bouvier, Laetitia; Bourrianne, Thierry; Roberts, Gregory

    2013-04-01

    The Mediterranean basin exhibits high PM concentrations for a marine area, in particular during the dry season (summer), associated with high photochemistry. The large population of the basin is impacted by both natural and anthropogenic aerosols of various sources from Europe and North Africa. Simulations predict significant climate changes in that area, with less precipitation and hotter temperatures, reinforced by an increasing anthropogenic pressure, which will be linked by higher emissions of pollutants and also by higher impacts on the health. Nevertheless the aerosol models in that area currently suffer from large uncertainties, due to a lack of knowledge in organic aerosol (OA) sources and processes. As part of the French program ChArMEx (The Chemistry-Aerosol Mediterranean Experiment, http://charmex.lsce.ipsl.fr), a 5-week intensive campaign has been performed in June - July 2012 at the new Cape Corsica station (see Dulac et al. in that session), and aiming at a better characterization of anthropogenic versus biogenic aerosols, long range transport versus local influence, with a focus on fine OA. A complete instrumental strategy was deployed thanks to the contribution of a large French community: PM1 concentration every 6 min with a TEOM-FDMS 1405 (Thermo), major aerosol components in PM1 every 30 min (Organics, SO4, NO3, NH4) by Aerosol Chemical Speciation Monitor (Aerodyne), Equivalent Black Carbon every 5 min with a 7-? aethalometer AE31 (Magee Scientific), on-line major anions and cations (incl. light organics like oxalate & MSA) every 10 min with Particle-Into-Liquid Sampler (PILS, Metrohm) coupled with Ion Chromatographs (Dionex), on-line water-soluble organic carbon (WSOC) every 4 min with a PILS (Applikon) coupled with a Total Organic Carbon instrument (Ionics). Filter sampling in PM2.5 and PM10 was also performed every 12h for quality purposes (PM, EC/OC, ions) and for complementary measurements (metals by ICP-MS and organic tracers by LC

  17. Do Regional Aerosols Contribute to the Riverine Export of Dissolved Black Carbon?

    NASA Astrophysics Data System (ADS)

    Jones, M. W.; Quine, T. A.; de Rezende, C. E.; Dittmar, T.; Johnson, B.; Manecki, M.; Marques, J. S. J.; de Aragão, L. E. O. C.

    2017-11-01

    The fate of black carbon (BC), a stable form of thermally altered organic carbon produced during biomass and fuel combustion, remains an area of uncertainty in the global carbon cycle. The transfer of photosynthetically derived BC into extremely long-term oceanic storage is of particular significance and rivers are the key linkage between terrestrial sources and oceanic stores. Significant fluvial fluxes of dissolved BC to oceans result from the slow release of BC from degrading charcoal stocks; however, these fluvial fluxes may also include undetermined contributions of aerosol BC, produced by biomass and fossil fuel combustion, which are deposited in river catchments following atmospheric transport. By investigation of the Paraíba do Sul River catchment in Southeast Brazil we show that aerosol deposits can be substantial contributors to fluvial fluxes of BC. We derived spatial distributions of BC stocks within the catchment associated with soil charcoal and with aerosol from both open biomass burning and fuel combustion. We then modeled the fluvial concentrations of dissolved BC (DBC) in scenarios with varying rates of export from each stock. We analyzed the ability of each scenario to reproduce the variability in DBC concentrations measured in four data sets of river water samples collected between 2010 and 2014 and found that the best performing scenarios included a 5-18% (135-486 Mg DBC year-1) aerosol contribution. Our results suggest that aerosol deposits of BC in river catchments have a shorter residence time in catchments than charcoal BC and, therefore, contribute disproportionately (with respect to stock magnitude) toward fluvial fluxes of BC.

  18. Aerosol characterization over the southeastern United States using high-resolution aerosol mass spectrometry: spatial and seasonal variation of aerosol composition and sources with a focus on organic nitrates

    NASA Astrophysics Data System (ADS)

    Xu, L.; Suresh, S.; Guo, H.; Weber, R. J.; Ng, N. L.

    2015-07-01

    We deployed a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and an Aerosol Chemical Speciation Monitor (ACSM) to characterize the chemical composition of submicron non-refractory particulate matter (NR-PM1) in the southeastern USA. Measurements were performed in both rural and urban sites in the greater Atlanta area, Georgia (GA), and Centreville, Alabama (AL), for approximately 1 year as part of Southeastern Center for Air Pollution and Epidemiology study (SCAPE) and Southern Oxidant and Aerosol Study (SOAS). Organic aerosol (OA) accounts for more than half of NR-PM1 mass concentration regardless of sampling sites and seasons. Positive matrix factorization (PMF) analysis of HR-ToF-AMS measurements identified various OA sources, depending on location and season. Hydrocarbon-like OA (HOA) and cooking OA (COA) have important, but not dominant, contributions to total OA in urban sites (i.e., 21-38 % of total OA depending on site and season). Biomass burning OA (BBOA) concentration shows a distinct seasonal variation with a larger enhancement in winter than summer. We find a good correlation between BBOA and brown carbon, indicating biomass burning is an important source for brown carbon, although an additional, unidentified brown carbon source is likely present at the rural Yorkville site. Isoprene-derived OA factor (isoprene-OA) is only deconvolved in warmer months and contributes 18-36 % of total OA. The presence of isoprene-OA factor in urban sites is more likely from local production in the presence of NOx than transport from rural sites. More-oxidized and less-oxidized oxygenated organic aerosol (MO-OOA and LO-OOA, respectively) are dominant fractions (47-79 %) of OA in all sites. MO-OOA correlates well with ozone in summer but not in winter, indicating MO-OOA sources may vary with seasons. LO-OOA, which reaches a daily maximum at night, correlates better with estimated nitrate functionality from organic nitrates than total nitrates. Based

  19. Recent advances in understanding secondary organic aerosol: Implications for global climate forcing: Advances in Secondary Organic Aerosol

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shrivastava, Manish; Cappa, Christopher D.; Fan, Jiwen

    Anthropogenic emissions and land-use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding pre-industrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features 1) influence estimates of aerosol radiative forcing and 2) can confound estimates of the historical response of climate to increases in greenhouse gases (e.g. the ‘climate sensitivity’). Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron-sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through a combinationmore » of laboratory and field measurements, yet current climate models typically do not comprehensively include all important SOA-relevant processes. Therefore, major gaps exist at present between current measurement-based knowledge on the one hand and model implementation of organic aerosols on the other. The critical review herein summarizes some of the important developments in understanding SOA formation that could potentially have large impacts on our understanding of aerosol radiative forcing and climate. We highlight the importance of some recently discovered processes and properties that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including: formation of extremely low-volatility organics in the gas-phase; isoprene epoxydiols (IEPOX) multi-phase chemistry; particle-phase oligomerization; and physical properties such as viscosity. In addition, this review also highlights some of the important processes that involve interactions between natural biogenic emissions and anthropogenic emissions, such as the role of sulfate and oxides of nitrogen (NOx) on SOA formation from biogenic volatile organic compounds. Studies that relate the observed evolution of organic

  20. Quantifying Wildfire Emissions and associated Aerosol Species using Assimilation of Satellite Carbon Monoxide Retrievals

    NASA Astrophysics Data System (ADS)

    Edwards, David; Barre, Jerome; Worden, Helen; Gaubert, Benjamin

    2017-04-01

    Intense and costly wildfires tend are predicted to increase in frequency under a warming climate. For example, the recent August 2015 Washington State fires were the largest in the state's history. Also in September and October 2015 very intense fires over Indonesia produced some of the highest concentrations of carbon monoxide (CO) ever seen from satellite. Such larges fires impact not only the local environment but also affect air quality far downwind through the long-range transport of pollutants. Global to continental scale coverage showing the evolution of CO resulting from fire emission is available from satellite observations. Carbon monoxide is the only atmospheric trace gas for which satellite multispectral retrievals have demonstrated reliable independent profile information close to the surface and also higher in the free troposphere. The unique CO profile product from Terra/MOPITT clearly distinguishes near-surface CO from the free troposphere CO. Also previous studies have suggested strong correlations between primary emissions of fire organic and black carbon aerosols and CO. We will present results from the Ensemble Adjustement Kalman Filter (DART) system that has been developed to assimilate MOPITT CO in the global-scale chemistry-climate model CAM-Chem. The ensemble technique allows inference on various fire model state variables such as CO emissions, and also aerosol species resulting from fires such as organic and black carbon. The benefit of MOPITT CO profile assimilation for estimating the CO emissions from the Washington and Indonesian fire cases will be discussed, along with the ability of the ensemble approach to infer information on the black and organic carbon aerosol distribution. This study builds on capability to quantitatively integrate satellite observations and models developed in recent years through projects funded by the NASA ACMAP Program.

  1. 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...

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kessler, Sean H.; Nah, Theodora; Daumit, Kelly E.

    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 amore » 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.« less

  3. Fine Aerosol Associated Non-Polar Organics in Jammu, AN Urban Location in the Foothill Region of North Western Himalayas

    NASA Astrophysics Data System (ADS)

    Yadav, S.; Bamotra, S.

    2017-12-01

    A comprehensive study was done on the mass, composition and sources of fine aerosol associated non-polar organics in Jammu, an urban location in the foothill region of North - Western Himalayas. Systematic multi-scale sampling was done from October, 2015 to February, 2017 to collect fine aerosol (PM2.5) samples every week using a Fine Particulate Sampler (Envirotech, APM 550 MFC) which operates at a constant flow rate of 16.7 L/minute. The Non- polar organic compounds comprising of n-alkanes, PAHs, isoprenoid hydrocarbons and nicotine were analyzed using Thermal desorption Gas Chromatography Mass Spectrometry (TD-GC-MS) method. The n-alkane associated diagnostic parameters include—mass weighted Averaged Chain Length (ACL); Carbon number with maximum concentration (Cmax); Petroleum derived n-alkanes (PNA%), Carbon Preference Index (CPI) and the percentage contribution of Wax n-alkanes from plants (WNA%). These diagnostic parameters along with PAH based molecular ratios were used to understand the diurnal and seasonal variations in different biogenic and petrogenic source contributions in this part of Himalayas. The presence of source specific tracers like Levoglucosan, Retene, Isoquinoline and nicotine also corroborated our findings. Further Fine aerosols associated Black Carbon, an important marker for burning was determined using Optical Transmissometer. Significant multiscale variations were found in the Fine aerosol load, associated Non-polar organics, source tracers/contributions and Black Carbon.

  4. 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.

  5. Impacts of springtime biomass burning in the northern Southeast Asia on marine organic aerosols over the Gulf of Tonkin, China.

    PubMed

    Zheng, Lishan; Yang, Xiaoyang; Lai, Senchao; Ren, Hong; Yue, Siyao; Zhang, Yingyi; Huang, Xin; Gao, Yuanguan; Sun, Yele; Wang, Zifa; Fu, Pingqing

    2018-06-01

    Fine particles (PM 2.5 ) samples, collected at Weizhou Island over the Gulf of Tonkin on a daytime and nighttime basis in the spring of 2015, were analyzed for primary and secondary organic tracers, together with organic carbon (OC), elemental carbon (EC), and stable carbon isotopic composition (δ 13 C) of total carbon (TC). Five organic compound classes, including saccharides, lignin/resin products, fatty acids, biogenic SOA tracers and phthalic acids, were quantified by gas chromatography/mass spectrometry (GC/MS). Levoglucosan was the most abundant organic species, indicating that the sampling site was under strong influence of biomass burning. Based on the tracer-based methods, the biomass-burning-derived fraction was estimated to be the dominant contributor to aerosol OC, accounting for 15.7% ± 11.1% and 22.2% ± 17.4% of OC in daytime and nighttime samples, respectively. In two episodes E1 and E2, organic aerosols characterized by elevated concentrations of levoglucosan as well as its isomers, sugar compounds, lignin products, high molecular weight (HMW) fatty acids and β-caryophyllinic acid, were attributed to the influence of intensive biomass burning in the northern Southeast Asia (SEA). However, the discrepancies in the ratios of levoglucosan to mannosan (L/M) and OC (L/OC) as well as the δ 13 C values suggest the type of biomass burning and the sources of organic aerosols in E1 and E2 were different. Hardwood and/or C 4 plants were the major burning materials in E1, while burning of softwood and/or C 3 plants played important role in E2. Furthermore, more complex sources and enhanced secondary contribution were found to play a part in organic aerosols in E2. This study highlights the significant influence of springtime biomass burning in the northern SEA to the organic molecular compositions of marine aerosols over the Gulf of Tonkin. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Strong radiative heating due to the mixing state of black carbon in atmospheric aerosols.

    PubMed

    Jacobson, M Z

    2001-02-08

    Aerosols affect the Earth's temperature and climate by altering the radiative properties of the atmosphere. A large positive component of this radiative forcing from aerosols is due to black carbon--soot--that is released from the burning of fossil fuel and biomass, and, to a lesser extent, natural fires, but the exact forcing is affected by how black carbon is mixed with other aerosol constituents. From studies of aerosol radiative forcing, it is known that black carbon can exist in one of several possible mixing states; distinct from other aerosol particles (externally mixed) or incorporated within them (internally mixed), or a black-carbon core could be surrounded by a well mixed shell. But so far it has been assumed that aerosols exist predominantly as an external mixture. Here I simulate the evolution of the chemical composition of aerosols, finding that the mixing state and direct forcing of the black-carbon component approach those of an internal mixture, largely due to coagulation and growth of aerosol particles. This finding implies a higher positive forcing from black carbon than previously thought, suggesting that the warming effect from black carbon may nearly balance the net cooling effect of other anthropogenic aerosol constituents. The magnitude of the direct radiative forcing from black carbon itself exceeds that due to CH4, suggesting that black carbon may be the second most important component of global warming after CO2 in terms of direct forcing.

  7. Formation of secondary organic aerosols from gas-phase emissions of heated cooking oils

    NASA Astrophysics Data System (ADS)

    Liu, Tengyu; Li, Zijun; Chan, ManNin; Chan, Chak K.

    2017-06-01

    Cooking emissions can potentially contribute to secondary organic aerosol (SOA) but remain poorly understood. In this study, formation of SOA from gas-phase emissions of five heated vegetable oils (i.e., corn, canola, sunflower, peanut and olive oils) was investigated in a potential aerosol mass (PAM) chamber. Experiments were conducted at 19-20 °C and 65-70 % relative humidity (RH). The characterization instruments included a scanning mobility particle sizer (SMPS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS). The efficiency of SOA production, in ascending order, was peanut oil, olive oil, canola oil, corn oil and sunflower oil. The major SOA precursors from heated cooking oils were related to the content of monounsaturated fat and omega-6 fatty acids in cooking oils. The average production rate of SOA, after aging at an OH exposure of 1. 7 × 1011 molecules cm-3 s, was 1. 35 ± 0. 30 µg min-1, 3 orders of magnitude lower compared with emission rates of fine particulate matter (PM2. 5) from heated cooking oils in previous studies. The mass spectra of cooking SOA highly resemble field-derived COA (cooking-related organic aerosol) in ambient air, with R2 ranging from 0.74 to 0.88. The average carbon oxidation state (OSc) of SOA was -1.51 to -0.81, falling in the range between ambient hydrocarbon-like organic aerosol (HOA) and semi-volatile oxygenated organic aerosol (SV-OOA), indicating that SOA in these experiments was lightly oxidized.

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  9. Contrasting diurnal variations in fossil and nonfossil secondary organic aerosol in urban outflow, Japan.

    PubMed

    Morino, Yu; Takahashi, Katsuyuki; Fushimi, Akihiro; Tanabe, Kiyoshi; Ohara, Toshimasa; Hasegawa, Shuichi; Uchida, Masao; Takami, Akinori; Yokouchi, Yoko; Kobayashi, Shinji

    2010-11-15

    Diurnal variations of fossil secondary organic carbon (SOC) and nonfossil SOC were determined for the first time using a combination of several carbonaceous aerosol measurement techniques, including radiocarbon (¹⁴C) determinations by accelerator mass spectrometry, and a receptor model (chemical mass balance, CMB) at a site downwind of Tokyo during the summer of 2007. Fossil SOC showed distinct diurnal variation with a maximum during daytime, whereas diurnal variation of nonfossil SOC was relatively small. This behavior was reproduced by a chemical transport model (CTM). However, the CTM underestimated the concentration of anthropogenic secondary organic aerosol (ASOA) by a factor of 4-7, suggesting that ASOA enhancement during daytime is not explained by production from volatile organic compounds that are traditionally considered major ASOA precursors. This result suggests that unidentified semivolatile organic compounds or multiphase chemistry may contribute largely to ASOA production. As our knowledge of production pathways of secondary organic aerosol (SOA) is still limited, diurnal variations of fossil and nonfossil SOC in our estimate give an important experimental constraint for future development of SOA models.

  10. Comprehensive characterization of atmospheric organic carbon at a forested site

    NASA Astrophysics Data System (ADS)

    Hunter, James F.; Day, Douglas A.; Palm, Brett B.; Yatavelli, Reddy L. N.; Chan, Arthur W. H.; Kaser, Lisa; Cappellin, Luca; Hayes, Patrick L.; Cross, Eben S.; Carrasquillo, Anthony J.; Campuzano-Jost, Pedro; Stark, Harald; Zhao, Yunliang; Hohaus, Thorsten; Smith, James N.; Hansel, Armin; Karl, Thomas; Goldstein, Allen H.; Guenther, Alex; Worsnop, Douglas R.; Thornton, Joel A.; Heald, Colette L.; Jimenez, Jose L.; Kroll, Jesse H.

    2017-10-01

    Atmospheric organic compounds are central to key chemical processes that influence air quality, ecological health, and climate. However, longstanding difficulties in predicting important quantities such as organic aerosol formation and oxidant lifetimes indicate that our understanding of atmospheric organic chemistry is fundamentally incomplete, probably due in part to the presence of organic species that are unmeasured using standard analytical techniques. Here we present measurements of a wide range of atmospheric organic compounds--including previously unmeasured species--taken concurrently at a single site (a ponderosa pine forest during summertime) by five state-of-the-art mass spectrometric instruments. The combined data set provides a comprehensive characterization of atmospheric organic carbon, covering a wide range in chemical properties (volatility, oxidation state, and molecular size), and exhibiting no obvious measurement gaps. This enables the first construction of a measurement-based local organic budget, highlighting the high emission, deposition, and oxidation fluxes in this environment. Moreover, previously unmeasured species, including semivolatile and intermediate-volatility organic species (S/IVOCs), account for one-third of the total organic carbon, and (within error) provide closure on both OH reactivity and potential secondary organic aerosol formation.

  11. Direct observation of aqueous secondary organic aerosol from biomass-burning emissions

    PubMed Central

    Massoli, Paola; Paglione, Marco; Giulianelli, Lara; Carbone, Claudio; Rinaldi, Matteo; Decesari, Stefano; Sandrini, Silvia; Costabile, Francesca; Gobbi, Gian Paolo; Pietrogrande, Maria Chiara; Visentin, Marco; Scotto, Fabiana; Fuzzi, Sandro; Facchini, Maria Cristina

    2016-01-01

    The mechanisms leading to the formation of secondary organic aerosol (SOA) are an important subject of ongoing research for both air quality and climate. Recent laboratory experiments suggest that reactions taking place in the atmospheric liquid phase represent a potentially significant source of SOA mass. Here, we report direct ambient observations of SOA mass formation from processing of biomass-burning emissions in the aqueous phase. Aqueous SOA (aqSOA) formation is observed both in fog water and in wet aerosol. The aqSOA from biomass burning contributes to the “brown” carbon (BrC) budget and exhibits light absorption wavelength dependence close to the upper bound of the values observed in laboratory experiments for fresh and processed biomass-burning emissions. We estimate that the aqSOA from residential wood combustion can account for up to 0.1–0.5 Tg of organic aerosol (OA) per y in Europe, equivalent to 4–20% of the total OA emissions. Our findings highlight the importance of aqSOA from anthropogenic emissions on air quality and climate. PMID:27551086

  12. MATRIX-VBS (v1.0): Implementing an Evolving Organic Aerosol Volatility in an Aerosol Microphysics Model

    NASA Technical Reports Server (NTRS)

    Gao, Chloe Y.; Tsigaridis, Kostas; Bauer, Susanne E.

    2017-01-01

    The gas-particle partitioning and chemical aging of semi-volatile organic aerosol are presented in a newly developed box model scheme, where its effect on the growth, composition, and mixing state of particles is examined. The volatility-basis set (VBS) framework is implemented into the aerosol microphysical scheme MATRIX (Multiconfiguration Aerosol TRacker of mIXing state), which resolves mass and number aerosol concentrations and in multiple mixing-state classes. The new scheme, MATRIX-VBS, has the potential to significantly advance the representation of organic aerosols in Earth system models by improving upon the conventional representation as non-volatile particulate organic matter, often also with an assumed fixed size distribution. We present results from idealized cases representing Beijing, Mexico City, a Finnish forest, and a southeastern US forest, and investigate the evolution of mass concentrations and volatility distributions for organic species across the gas and particle phases, as well as assessing their mixing state among aerosol populations. Emitted semi-volatile primary organic aerosols evaporate almost completely in the intermediate-volatility range, while they remain in the particle phase in the low-volatility range. Their volatility distribution at any point in time depends on the applied emission factors, oxidation by OH radicals, and temperature. We also compare against parallel simulations with the original scheme, which represented only the particulate and non-volatile component of the organic aerosol, examining how differently the condensed-phase organic matter is distributed across the mixing states in the model. The results demonstrate the importance of representing organic aerosol as a semi-volatile aerosol, and explicitly calculating the partitioning of organic species between the gas and particulate phases.

  13. Characterization of urban aerosol using aerosol mass spectrometry and proton nuclear magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Cleveland, M. J.; Ziemba, L. D.; Griffin, R. J.; Dibb, J. E.; Anderson, C. H.; Lefer, B.; Rappenglück, B.

    2012-07-01

    Particulate matter was measured during August and September of 2006 in Houston as part of the Texas Air Quality Study II Radical and Aerosol Measurement Project. Aerosol size and composition were determined using an Aerodyne quadrupole aerosol mass spectrometer. Aerosol was dominated by sulfate (4.1 ± 2.6 μg m-3) and organic material (5.5 ± 4.0 μg m-3), with contributions of organic material from both primary (˜32%) and secondary (˜68%) sources. Secondary organic aerosol appears to be formed locally. In addition, 29 aerosol filter samples were analyzed using proton nuclear magnetic resonance (1H NMR) spectroscopy to determine relative concentrations of organic functional groups. Houston aerosols are less oxidized than those observed elsewhere, with smaller relative contributions of carbon-oxygen double bonds. These particles do not fit 1H NMR source apportionment fingerprints for identification of secondary, marine, and biomass burning organic aerosol, suggesting that a new fingerprint for highly urbanized and industrially influenced locations be established.

  14. Characterization of water-soluble organic matter isolated from atmospheric fine aerosol

    NASA Astrophysics Data System (ADS)

    Kiss, Gyula; Varga, BáLint; Galambos, IstváN.; Ganszky, Ildikó

    2002-11-01

    Atmospheric fine aerosol (dp < 1.5 μm) was collected at a rural site in Hungary from January to September 2000. The total carbon concentration ranged from 5 to 13 μg m-3 and from 3 to 6 μg m-3 in the first three months and the rest of the sampling period, respectively. On average, water-soluble organic carbon (WSOC) accounted for 66% of the total carbon concentration independent of the season. A variable fraction of the water-soluble organic constituents (38-72% of WSOC depending on the sample) was separated from inorganic ions and isolated in pure organic form by using solid phase extraction on a copolymer sorbent. This fraction was experimentally characterized by an organic matter to organic carbon mass ratio of 1.9, and this value did not change with the seasons. Furthermore, the average elemental composition (molar ratio) of C:H:N:O ≈ 24:34:1:14 of the isolated fraction indicated the predominance of oxygenated functional groups, and the low hydrogen to carbon ratio implied the presence of unsaturated or polyconjugated structures. These conclusions were confirmed by UV, fluorescence, and Fourier transform infrared (FTIR) studies. On the basis of theoretical considerations, the organic matter to organic carbon mass ratio was estimated to be 2.3 for the nonisolated water-soluble organic fraction, resulting in an overall ratio of 2.1 for the WSOC. In order to extend the scope of this estimation to the total organic carbon, which is usually required in mass closure calculations, the aqueous extraction was followed by sequential extraction with acetone and 0.01 M NaOH solution. As a result, a total organic matter to total organic carbon mass ratio of 1.9-2.0 was estimated, but largely on the basis of experimental data.

  15. Formation of halogen-induced secondary organic aerosol (XOA)

    NASA Astrophysics Data System (ADS)

    Kamilli, Katharina; Ofner, Johannes; Zetzsch, Cornelius; Held, Andreas

    2013-04-01

    Reactive halogen species (RHS) are very important due to their potential of stratospheric ozone depletion and surface ozone destruction. RHS seem to interact with precursors of secondary organic aerosol (SOA) similarly to common atmospheric oxidants like OH radicals and ozone. The potential interaction of RHS with preformed SOA has recently been studied (Ofner et al., 2012). Although aerosol formation from reaction of RHS with typical SOA precursors was previously studied (e.g. Cai et al., 2006), no data are available on bromine-induced aerosol formation from organic precursors yet. An aerosol smog-chamber was used to examine the halogen-induced secondary organic aerosol (XOA) formation under atmospheric conditions using simulated sunlight. With a concentration of 10 ppb for the organic precursor, 2 ppb for molecular chlorine, and 10 ppb for molecular bromine, the experimental setup is close to ambient conditions. By combined measurements of the aerosol size distribution, ozone and NOx mixing ratios, as well as the decay of the organic precursor, aerosol yields and aerosol growth rates were determined. The decay of the organic precursor was analyzed by capillary gas chromatography coupled with flame-ionization detection (GC-FID) and the aerosol size distribution was measured using a Scanning Mobility Particle Sizer (SMPS). Additionally, with the decay rate of the precursor and the calculated photolysis rates of molecular halogen species, based on the well-known spectrum of the solar simulator, mechanistic details on the XOA formation pathways can be determined. We observed XOA formation even at very low precursor and RHS concentrations with a diameter mode at 10-20 nm and a number concentration up to 1000000 particles cm-3. While the XOA formation from chlorine is very rapid, the interaction of bromine with the organic precursors is about five times slower. The aerosol yield reached maximum values of 0.01 for the reaction of chlorine with α-pinene and 0.0004 for

  16. Carbon Isotopic Measurements and Aerosol Optical Determinations during CARES: Indications of the Importance of Background Biogenic Aerosols

    NASA Astrophysics Data System (ADS)

    Gaffney, J. S.; Marley, N. A.; Begum, M.; Sturchio, N. C.; Guilderson, T. P.

    2011-12-01

    High volume size-fractionated aerosol samples were obtained in Cool, CA during the Carbonaceous Aerosol and Radiative Effects Study (CARES) in June of 2010. This site was chosen to study the regional impacts of carbonaceous aerosols originating from the Sacramento area. Samples were collected for 6 to 24 hour time periods on quartz fiber filters by using slotted impactors to allow for collection of sample size cuts above and below one micron. Both total carbon content and carbon isotopic composition, including 13C/12C and 14C, were determined on the samples. In addition, Ångstrom absorption exponents (AAEs) were determined for the region of 300-900 nm on the sub-micron size cut by using state of the art diffuse reflectance UV-visible spectroscopy with integrating sphere technology. The overall carbonaceous aerosol loadings were found to be quite low and relatively constant during the study, suggesting that most of the aerosols at the site were locally formed background aerosols. The 14C data is consistent with a substantial fraction (~80 %) being from modern carbon sources and 13C/12C results indicate that the carbon source was from C-3 plants. This is consistent with a significant fraction of the aerosols in the area arising from secondary formation from biogenic precursor emissions from trees, most likely mono- and sesquiterpenes. These results are compared to past results obtained in Mexico City and discussed in terms of the potential importance of biogenic emissions to UV absorbing aerosols as these are anticipated to increase with climate change. This work was supported by the Office of Science (BER), U.S. Department of Energy, Grant No. DE-FG02-07ER64328 and Grant No. DE-FG02-07-ER64329 as part of the Atmospheric Systems Research program.

  17. Intercomparison and closure calculations using measurements of aerosol species and optical properties during the Yosemite Aerosol Characterization Study

    NASA Astrophysics Data System (ADS)

    Malm, William C.; Day, Derek E.; Carrico, Christian; Kreidenweis, Sonia M.; Collett, Jeffrey L.; McMeeking, Gavin; Lee, Taehyoung; Carrillo, Jacqueline; Schichtel, Bret

    2005-07-01

    Physical and optical properties of inorganic aerosols have been extensively studied, but less is known about carbonaceous aerosols, especially as they relate to the non-urban settings such as our nation's national parks and wilderness areas. Therefore an aerosol characterization study was conceived and implemented at one national park that is highly impacted by carbonaceous aerosols, Yosemite. The primary objective of the study was to characterize the physical, chemical, and optical properties of a carbon-dominated aerosol, including the ratio of total organic matter weight to organic carbon, organic mass scattering efficiencies, and the hygroscopic characteristics of a carbon-laden ambient aerosol, while a secondary objective was to evaluate a variety of semi-continuous monitoring systems. Inorganic ions were characterized using 24-hour samples that were collected using the URG and Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring systems, the micro-orifice uniform deposit impactor (MOUDI) cascade impactor, as well as the semi-continuous particle-into-liquid sampler (PILS) technology. Likewise, carbonaceous material was collected over 24-hour periods using IMPROVE technology along with the thermal optical reflectance (TOR) analysis, while semi-continuous total carbon concentrations were measured using the Rupprecht and Patashnick (R&P) instrument. Dry aerosol number size distributions were measured using a differential mobility analyzer (DMA) and optical particle counter, scattering coefficients at near-ambient conditions were measured with nephelometers fitted with PM10 and PM2.5 inlets, and "dry" PM2.5 scattering was measured after passing ambient air through Perma Pure Nafion® dryers. In general, the 24-hour "bulk" measurements of various aerosol species compared more favorably with each other than with the semi-continuous data. Semi-continuous sulfate measurements correlated well with the 24-hour measurements, but were biased low by

  18. Can Condensing Organic Aerosols Lead to Less Cloud Particles?

    NASA Astrophysics Data System (ADS)

    Gao, C. Y.; Tsigaridis, K.; Bauer, S.

    2017-12-01

    We examined the impact of condensing organic aerosols on activated cloud number concentration in a new aerosol microphysics box model, MATRIX-VBS. The model includes the volatility-basis set (VBS) framework in an aerosol microphysical scheme MATRIX (Multiconfiguration Aerosol TRacker of mIXing state) that resolves aerosol mass and number concentrations and aerosol mixing state. Preliminary results show that by including the condensation of organic aerosols, the new model (MATRIX-VBS) has less activated particles compared to the original model (MATRIX), which treats organic aerosols as non-volatile. Parameters such as aerosol chemical composition, mass and number concentrations, and particle sizes which affect activated cloud number concentration are thoroughly evaluated via a suite of Monte-Carlo simulations. The Monte-Carlo simulations also provide information on which climate-relevant parameters play a critical role in the aerosol evolution in the atmosphere. This study also helps simplifying the newly developed box model which will soon be implemented in the global model GISS ModelE as a module.

  19. On the implications of aerosol liquid water and phase separation for organic aerosol mass

    EPA Science Inventory

    Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to org...

  20. Observation of hydration of single, modified carbon aerosols

    NASA Technical Reports Server (NTRS)

    Wyslouzil, B. E.; Carleton, K. L.; Sonnenfroh, D. M.; Rawlins, W. T.; Arnold, S.

    1994-01-01

    We have compared the hydration behavior of single carbon particles that have been treated by exposure to gaseous H2SO4 with that of untreated particles. Untreated carbon particles did not hydrate as the relative humidity varied from 0 to 80% at 23 C. In contrast, treated particles hydrated under subsaturation conditions; mass increases of up to 30% were observed. The mass increase is consistent with sulfuric acid equilibration with the ambient relative humidity in the presence of inert carbon. For the samples studied, the average amount of absorbed acid was 14% +/- 6% by weight, which corresponds to a surface coverage of approximately 0.1 monolayer. The mass fraction of surface-absorbed acid is comparable to the soluble mass fraction observed by Whitefield et al. (1993) in jet aircraft engine aerosols. Estimates indicate this mass fraction corresponds to 0.1% of the available SO2 exiting an aircraft engine ending up as H2SO4 on the carbon aerosol. If this heterogeneous process occurs early enough in the exhaust plume, it may compete with homogeneous nucleation as a mechanism for producing sulfuric acid rich aerosols.

  1. Observations and analysis of organic aerosol evolution in some prescribed fire smoke plumes

    NASA Astrophysics Data System (ADS)

    May, A. A.; Lee, T.; McMeeking, G. R.; Akagi, S.; Sullivan, A. P.; Urbanski, S.; Yokelson, R. J.; Kreidenweis, S. M.

    2015-06-01

    Open biomass burning is a significant source of primary air pollutants such as particulate matter (PM) and non-methane organic gases (NMOG). However, the physical and chemical atmospheric processing of these emissions during transport is poorly understood. Atmospheric transformations of biomass burning emissions have been investigated in environmental chambers, but there have been limited opportunities to investigate these transformations in the atmosphere. In this study, we deployed a suite of real-time instrumentation on a Twin Otter aircraft to sample smoke from prescribed fires in South Carolina, conducting measurements at both the source and downwind to characterize smoke evolution with atmospheric aging. Organic aerosol (OA) within the smoke plumes was quantified using an aerosol mass spectrometer (AMS); refractory black carbon (rBC) was quantified using a single-particle soot photometer, and carbon monoxide (CO) and carbon dioxide (CO2) were measured using a cavity ring-down spectrometer. During the two fires for which we were able to obtain aerosol aging data, normalized excess mixing ratios and "export factors" of conserved species (rBC, CO, CO2) suggested that changes in emissions at the source did not account for most of the differences observed in samples of increasing age. An investigation of AMS mass fragments indicated that the in-plume fractional contribution (fm/z) to OA of the primary fragment (m/z 60) decreased downwind, while the fractional contribution of the secondary fragment (m/z 44) increased. Increases in f44 are typically interpreted as indicating chemical aging of OA. Likewise, we observed an increase in the O : C elemental ratio downwind, which is usually associated with aerosol aging. However, the rapid mixing of these plumes into the background air suggests that these chemical transformations may be attributable to the different volatilities of the compounds that fragment to these m/z in the AMS. The gas-particle partitioning behavior

  2. Molecular marker characterization and source appointment of particulate matter and its organic aerosols.

    PubMed

    Choi, Jong-Kyu; Ban, Soo-Jin; Kim, Yong-Pyo; Kim, Yong-Hee; Yi, Seung-Muk; Zoh, Kyung-Duk

    2015-09-01

    This study was carried out to identify possible sources and to estimate their contribution to total suspended particle (TSP) organic aerosol (OA) contents. A total of 120 TSP and PM2.5 samples were collected simultaneously every third day over a one-year period in urban area of Incheon, Korea. High concentration in particulate matters (PM) and its components (NO3(-), water soluble organic compounds (WSOCs), and n-alkanoic acids) were observed during the winter season. Among the organics, n-alkanes, n-alkanoic acids, levoglucosan, and phthalates were major components. Positive matrix factorization (PMF) analysis identified seven sources of organic aerosols including combustion 1 (low molecular weight (LMW)-polycyclic aromatic hydrocarbons (PAHs)), combustion 2 (high molecular weight (HMW)-PAHs), biomass burning, vegetative detritus (n-alkane), secondary organic aerosol 1 (SOA1), secondary organic aerosol 2 (SOA2), and motor vehicles. Vegetative detritus increased during the summer season through an increase in biogenic/photochemical activity, while most of the organic sources were prominent in the winter season due to the increases in air pollutant emissions and atmospheric stability. The correlation factors were high among the main components of the organic carbon (OC) in the TSP and PM2.5. The results showed that TSP OAs had very similar characteristics to the PM2.5 OAs. SOA, combustion (PAHs), and motor vehicle were found to be important sources of carbonaceous PM in this region. Our results imply that molecular markers (MMs)-PMF model can provide useful information on the source and characteristics of PM. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Long-term trends in California mobile source emissions and ambient concentrations of black carbon and organic aerosol.

    PubMed

    McDonald, Brian C; Goldstein, Allen H; Harley, Robert A

    2015-04-21

    A fuel-based approach is used to assess long-term trends (1970-2010) in mobile source emissions of black carbon (BC) and organic aerosol (OA, including both primary emissions and secondary formation). The main focus of this analysis is the Los Angeles Basin, where a long record of measurements is available to infer trends in ambient concentrations of BC and organic carbon (OC), with OC used here as a proxy for OA. Mobile source emissions and ambient concentrations have decreased similarly, reflecting the importance of on- and off-road engines as sources of BC and OA in urban areas. In 1970, the on-road sector accounted for ∼90% of total mobile source emissions of BC and OA (primary + secondary). Over time, as on-road engine emissions have been controlled, the relative importance of off-road sources has grown. By 2010, off-road engines were estimated to account for 37 ± 20% and 45 ± 16% of total mobile source contributions to BC and OA, respectively, in the Los Angeles area. This study highlights both the success of efforts to control on-road emission sources, and the importance of considering off-road engine and other VOC source contributions when assessing long-term emission and ambient air quality trends.

  4. Contrasting Secondary Organic Aerosol Formation in Aerosol Liquid Water During Summer and Winter

    NASA Astrophysics Data System (ADS)

    El-Sayed, M.; Hennigan, C. J.

    2017-12-01

    In this study, we characterize the formation of aqueous secondary organic aerosols (aqSOA) in the eastern United States during summer and winter. The aim was to identify the main factors affecting the reversible and irreversible uptake of water-soluble organic gases to aerosol liquid water under variable influence from biogenic and anthropogenic sources. The reversible and irreversible uptake of water-soluble organic gases to aerosol water was measured in Baltimore, MD using a recently developed on-line method. The formation of aqSOA was observed during the summer and the winter; however, the amount of aqSOA varied significantly between the two seasons, as did the reversible and irreversible nature of the uptake. While the availability of aerosol liquid water (ALW) predominantly controlled aqSOA formation in the summer, wintertime aqSOA formation was limited by precursor VOCs as well. During the summer, aqSOA formation was tightly linked with isoprene oxidation, while the aqSOA formed in the winter was associated with biomass burning. Irreversible aqSOA was formed in both seasons; however, reversible aqSOA was only observed in the summer. Overall, these results demonstrate the importance of multi-phase chemistry in aerosol formation and underscore the significance of soluble organic gases partitioning to aerosol water both reversibly and irreversibly.

  5. Linking Remotely Sensed Aerosol Types to Their Chemical Composition

    NASA Technical Reports Server (NTRS)

    Dawson, Kyle William; Kacenelenbogen, Meloe S.; Johnson, Matthew S.; Burton, Sharon P.; Hostetler, Chris A.; Meskhidze, Nicholas

    2016-01-01

    Aerosol types measured during the Ship-Aircraft Bio-Optical Research (SABOR) experiment are related to GEOS-Chem model chemical composition. The application for this procedure to link model chemical components to aerosol type is desirable for understanding aerosol evolution over time. The Mahalanobis distance (DM) statistic is used to cluster model groupings of five chemical components (organic carbon, black carbon, sea salt, dust and sulfate) in a way analogous to the methods used by Burton et al. [2012] and Russell et al. [2014]. First, model-to-measurement evaluation is performed by collocating vertically resolved aerosol extinction from SABOR High Spectral Resolution LiDAR (HSRL) to the GEOS-Chem nested high-resolution data. Comparisons of modeled-to-measured aerosol extinction are shown to be within 35% +/- 14%. Second, the model chemical components are calculation into five variables to calculate the DM and cluster means and covariances for each HSRL-retrieved aerosol type. The layer variables from the model are aerosol optical depth (AOD) ratios of (i) sea salt and (ii) dust to total AOD, mass ratios of (iii) total carbon (i.e. sum of organic and black carbon) to the sum of total carbon and sulfate (iv) organic carbon to black carbon, and (v) the natural log of the aerosol-to-molecular extinction ratio. Third, the layer variables and at most five out of twenty SABOR flights are used to form the pre-specified clusters for calculating DM and to assign an aerosol type. After determining the pre-specified clusters, model aerosol types are produced for the entire vertically resolved GEOS-Chem nested domain over the United States and the model chemical component distributions relating to each type are recorded. Resulting aerosol types are Dust/Dusty Mix, Maritime, Smoke, Urban and Fresh Smoke (separated into 'dark' and 'light' by a threshold of the organic to black carbon ratio). Model-calculated DM not belonging to a specific type (i.e. not meeting a threshold

  6. Linking remotely sensed aerosol types to their chemical composition

    NASA Astrophysics Data System (ADS)

    Dawson, K. W.; Kacenelenbogen, M. S.; Johnson, M. S.; Burton, S. P.; Hostetler, C. A.; Meskhidze, N.

    2016-12-01

    Aerosol types measured during the Ship-Aircraft Bio-Optical Research (SABOR) experiment are related to GEOS-Chem model chemical composition. The application for this procedure to link model chemical components to aerosol type is desirable for understanding aerosol evolution over time. The Mahalanobis distance (DM) statistic is used to cluster model groupings of five chemical components (organic carbon, black carbon, sea salt, dust and sulfate) in a way analogous to the methods used by Burton et al. [2012] and Russell et al. [2014]. First, model-to-measurement evaluation is performed by collocating vertically resolved aerosol extinction from SABOR High Spectral Resolution LiDAR (HSRL) to the GEOS-Chem nested high-resolution data. Comparisons of modeled-to-measured aerosol extinction are shown to be within 35% ± 14%. Second, the model chemical components are calculation into five variables to calculate the DM and cluster means and covariances for each HSRL-retrieved aerosol type. The layer variables from the model are aerosol optical depth (AOD) ratios of (i) sea salt and (ii) dust to total AOD, mass ratios of (iii) total carbon (i.e. sum of organic and black carbon) to the sum of total carbon and sulfate (iv) organic carbon to black carbon, and (v) the natural log of the aerosol-to-molecular extinction ratio. Third, the layer variables and at most five out of twenty SABOR flights are used to form the pre-specified clusters for calculating DM and to assign an aerosol type. After determining the pre-specified clusters, model aerosol types are produced for the entire vertically resolved GEOS-Chem nested domain over the United States and the model chemical component distributions relating to each type are recorded. Resulting aerosol types are Dust/Dusty Mix, Maritime, Smoke, Urban and Fresh Smoke (separated into `dark' and `light' by a threshold of the organic to black carbon ratio). Model-calculated DM not belonging to a specific type (i.e. not meeting a threshold

  7. Black carbon reduction will weaken the aerosol net cooling effect

    NASA Astrophysics Data System (ADS)

    Wang, Z. L.; Zhang, H.; Zhang, X. Y.

    2014-12-01

    Black carbon (BC), a distinct type of carbonaceous material formed from the incomplete combustion of fossil and biomass based fuels under certain conditions, can interact with solar radiation and clouds through its strong light-absorption ability, thereby warming the Earth's climate system. Some studies have even suggested that global warming could be slowed down in a short term by eliminating BC emission due to its short lifetime. In this study, we estimate the influence of removing some sources of BC and other co-emitted species on the aerosol radiative effect by using an aerosol-climate coupled model BCC_AGCM2.0.1_CUACE/Aero, in combination with the aerosol emissions from the Representative Concentration Pathways (RCPs) scenarios. We find that the global annual mean aerosol net cooling effect at the top of the atmosphere (TOA) will be enhanced by 0.12 W m-2 compared with present-day conditions if the BC emission is reduced exclusively to the level projected for 2100 based on the RCP2.6 scenario. This will be beneficial for the mitigation of global warming. However, the global annual mean aerosol net cooling effect at the TOA will be weakened by 1.7-2.0 W m-2 relative to present-day conditions if emissions of BC and co-emitted sulfur dioxide and organic carbon are simultaneously reduced as the most close conditions to the actual situation to the level projected for 2100 in different ways based on the RCP2.6, RCP4.5, and RCP8.5 scenarios. Because there are no effective ways to remove the BC exclusively without influencing the other co-emitted components, our results therefore indicate that a reduction in BC emission can lead to an unexpected warming on the Earth's climate system in the future.

  8. Brown and black carbon in Beijing aerosol: Implications for the effects of brown coating on light absorption by black carbon.

    PubMed

    Cheng, Yuan; He, Ke-Bin; Engling, Guenter; Weber, Rodney; Liu, Jiu-Meng; Du, Zhen-Yu; Dong, Shu-Ping

    2017-12-01

    Brown carbon (BrC) is increasingly included in climate models as an emerging category of particulate organic compounds that can absorb solar radiation efficiently at specific wavelengths. Water-soluble organic carbon (WSOC) has been commonly used as a surrogate for BrC; however, it only represents a limited fraction of total organic carbon (OC) mass, which could be as low as about 20% in urban atmosphere. Using methanol as the extraction solvent, up to approximately 90% of the OC in Beijing aerosol was isolated and measured for absorption spectra over the ultraviolet-to-visible wavelength range. Compared to methanol-soluble OC (MSOC), WSOC underestimated BrC absorption by about 50% at 365nm. The mass absorption efficiencies measured for BrC in Beijing aerosol were converted to the imaginary refractive indices of BrC and subsequently used to compute BrC coating-induced enhancement of light absorption (E abs ) by black carbon. E abs attributed to lensing was reduced in the case of BrC coating relative to that caused by purely-scattering coating. However, this reduction was overwhelmed by the effect of BrC shell absorption, indicating that the overall effect of BrC coating was an increase in E abs . Methanol extraction significantly reduced charring of OC during thermal-optical analysis, leading to a large increase in the measured elemental carbon (EC) mass and an apparent improvement in the consistency of EC measurements by different thermal-optical methods. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Chemical compositions of black carbon particle cores and coatings via soot particle aerosol mass spectrometry with photoionization and electron ionization.

    PubMed

    Canagaratna, Manjula R; Massoli, Paola; Browne, Eleanor C; Franklin, Jonathan P; Wilson, Kevin R; Onasch, Timothy B; Kirchstetter, Thomas W; Fortner, Edward C; Kolb, Charles E; Jayne, John T; Kroll, Jesse H; Worsnop, Douglas R

    2015-05-14

    Black carbon is an important constituent of atmospheric aerosol particle matter (PM) with significant effects on the global radiation budget and on human health. The soot particle aerosol mass spectrometer (SP-AMS) has been developed and deployed for real-time ambient measurements of refractory carbon particles. In the SP-AMS, black carbon or metallic particles are vaporized through absorption of 1064 nm light from a CW Nd:YAG laser. This scheme allows for continuous "soft" vaporization of both core and coating materials. The main focus of this work is to characterize the extent to which this vaporization scheme provides enhanced chemical composition information about aerosol particles. This information is difficult to extract from standard SP-AMS mass spectra because they are complicated by extensive fragmentation from the harsh 70 eV EI ionization scheme that is typically used in these instruments. Thus, in this work synchotron-generated vacuum ultraviolet (VUV) light in the 8-14 eV range is used to measure VUV-SP-AMS spectra with minimal fragmentation. VUV-SP-AMS spectra of commercially available carbon black, fullerene black, and laboratory generated flame soots were obtained. Small carbon cluster cations (C(+)-C5(+)) were found to dominate the VUV-SP-AMS spectra of all the samples, indicating that the corresponding neutral clusters are key products of the SP vaporization process. Intercomparisons of carbon cluster ratios observed in VUV-SP-AMS and SP-AMS spectra are used to confirm spectral features that could be used to distinguish between different types of refractory carbon particles. VUV-SP-AMS spectra of oxidized organic species adsorbed on absorbing cores are also examined and found to display less thermally induced decomposition and fragmentation than spectra obtained with thermal vaporization at 200 °C (the minimum temperature needed to quantitatively vaporize ambient oxidized organic aerosol with a continuously heated surface). The particle cores

  10. Total Observed Organic Carbon (TOOC): A Synthesis of North American Observations

    NASA Technical Reports Server (NTRS)

    Heald, C. L.; Goldstein, A. H.; Allan, J. D.; Aiken, A. C.; Apel, E.; Atlas, E. L.; Baker, A. K.; Bates, T. S.; Beyersdorf, A. J.; Blake, D. R.; hide

    2007-01-01

    Measurements of organic carbon compounds in both the gas and particle phases made upwind, over and downwind of North America are synthesized to examine the total observed organic carbon (TOOC) in the atmosphere over this region. These include measurements made aboard the NOAA WP-3 and BAe-146 aircraft, the NOAA research vessel Ronald H. Brown, and at the Thompson Farm and Chebogue Point surface sites during the summer 2004 ICARTT campaign. Both winter and summer 2002 measurements during the Pittsburgh Air Quality Study are also included. Lastly, the spring 2002 observations at Trinidad Head, CA, surface measurements made in March 2006 in Mexico City and coincidentally aboard the C-130 aircraft during the MILAGRO campaign and later during the IMPEX campaign off the northwestern United States are incorporated. Concentrations of TOOC in these datasets span more than two orders of magnitude. The daytime mean TOOC ranges from 4.0 to 456 microg C/cubic m from the cleanest site (Trinidad Head) to the most polluted (Mexico City). Organic aerosol makes up 3-17% of this mean TOOC, with highest fractions reported over the northeastern United States, where organic aerosol can comprise up to 50% of TOOC. Carbon monoxide concentrations explain 46 to 86% of the variability in TOOC, with highest TOOC/CO slopes in regions with fresh anthropogenic influence, where we also expect the highest degree of mass closure for TOOC. Correlation with isoprene, formaldehyde, methyl vinyl ketone and methacrolein also indicates that biogenic activity contributes substantially to the variability of TOOC, yet these tracers of biogenic oxidation sources do not explain the variability in organic aerosol observed over North America. We highlight the critical need to develop measurement techniques to routinely detect total gas phase VOCs, and to deploy comprehensive suites of TOOC instruments in diverse environments to quantify the ambient evolution of organic carbon from source to sink.

  11. Physico-Chemical Evolution of Organic Aerosol from Wildfire Emissions

    NASA Astrophysics Data System (ADS)

    Croteau, P.; Jathar, S.; Akherati, A.; Galang, A.; Tarun, S.; Onasch, T. B.; Lewane, L.; Herndon, S. C.; Roscioli, J. R.; Yacovitch, T. I.; Fortner, E.; Xu, W.; Daube, C.; Knighton, W. B.; Werden, B.; Wood, E.

    2017-12-01

    Wildfires are the largest combustion-related source of carbonaceous emissions to the atmosphere; these include direct emissions of black carbon (BC), primary organic aerosol (POA) and semi-volatile, intermediate-volatility, and volatile organic compounds (SVOCs, IVOCs, and VOCs). However, there are large uncertainties surrounding the evolution of these carbonaceous emissions as they are physically and chemically transformed in the atmosphere. To understand these transformations, we performed sixteen experiments using an environmental chamber to simulate day- and night-time chemistry of gas- and aerosol-phase emissions from 6 different fuels at the Fire Laboratory in Missoula, MT. Across the test matrix, the experiments simulated 2 to 8 hours of equivalent day-time aging (with the hydroxyl radical and ozone) or several hours of night-time aging (with the nitrate radical). Aging resulted in an average organic aerosol (OA) mass enhancement of 28% although the full range of OA mass enhancements varied between -10% and 254%. These enhancement findings were consistent with chamber and flow reactor experiments performed at the Fire Laboratory in 2010 and 2012 but, similar to previous studies, offered no evidence to link the OA mass enhancement to fuel type or oxidant exposure. Experiments simulating night-time aging resulted in an average OA mass enhancement of 10% and subsequent day-time aging resulted in a decrease in OA mass of 8%. While small, for the first time, these experiments highlighted the continuous nature of the OA evolution as the wildfire smoke cycled through night- and day-time processes. Ongoing work is focussed on (i) quantifying bulk compositional changes in OA, (ii) comparing the near-field aging simulated in this work with far-field aging simulated during the same campaign (via a mini chamber and flow tube) and (iii) integrating wildfire smoke aging datasets over the past decade to examine the relationship between OA mass enhancement ratios, modified

  12. Aerosol volatility in a boreal forest environment

    NASA Astrophysics Data System (ADS)

    Häkkinen, S. A. K.; ńijälä, M.; Lehtipalo, K.; Junninen, H.; Virkkula, A.; Worsnop, D. R.; Kulmala, M.; Petäjä, T.; Riipinen, I.

    2012-04-01

    Climate and health effects of atmospheric aerosols are determined by their properties such as their chemical composition. Aerosol chemical composition can be studied indirectly by measuring volatility of aerosol particles. The volatility of submicron aerosol particles (20-500 nm) was studied in a boreal forest site at SMEAR II (Station for Measuring Ecosystem-Atmosphere Relations II) station (Vesala et al., 1998) in Hyytiälä, Finland, during 01/2008-05/2010. The instrument used for the measurements was VDMPS (Volatility Differential Mobility Particle Sizer), which consists of two separate instruments: DMPS (Differential Mobility Particle Sizer, Aalto et al., 2001) and TD (Thermodenuder, Wehner et al., 2002). Aerosol evaporation was examined by heating the aerosol and comparing the total aerosol mass before and after heating. In the VDMPS system ambient aerosol sample was heated up to temperatures ranging from 80 °C to 280 °C. The higher the heating temperature was the more aerosol material was evaporated. There was a non-volatile residual present in aerosol particles when heated up to 280 °C. This residual explained (20±8)% of the total aerosol mass. Aerosol non-volatile mass fraction was highest during winter and smallest during summer months. The role of black carbon in the observed non-volatile residual was determined. Black carbon explained 40 to 90% of the non-volatile mass. Especially during colder seasons noticeable amount of non-volatile material, something else than black carbon, was observed. According to Kalberer et al. (2004) some atmospheric organic species can form polymers that have high evaporation temperatures. Also low-volatile organic salts may contribute to the non-volatile aerosol (Smith et al., 2010). Aerosol mass composition measured directly with AMS (Aerosol Mass Spectrometer, Jayne et al., 2000) was analyzed in order to examine the properties of the non-volatile material (other than black carbon). The AMS measurements were performed

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

    EPA Science Inventory

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

  14. Identifying precursors and aqueous organic aerosol formation pathways during the SOAS campaign

    NASA Astrophysics Data System (ADS)

    Sareen, Neha; Carlton, Annmarie G.; Surratt, Jason D.; Gold, Avram; Lee, Ben; Lopez-Hilfiker, Felipe D.; Mohr, Claudia; Thornton, Joel A.; Zhang, Zhenfa; Lim, Yong B.; Turpin, Barbara J.

    2016-11-01

    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, and health. 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 additional precursors and products that may be atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS). Hydroxyl (OH⚫) radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 µM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS). Ultra high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) spectra and tandem MS (MS-MS) fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and complexes). Thus

  15. Molecular-Size-Separated Brown Carbon Absorption for Biomass-Burning Aerosol at Multiple Field Sites.

    PubMed

    Di Lorenzo, Robert A; Washenfelder, Rebecca A; Attwood, Alexis R; Guo, Hongyu; Xu, Lu; Ng, Nga L; Weber, Rodney J; Baumann, Karsten; Edgerton, Eric; Young, Cora J

    2017-03-21

    Biomass burning is a known source of brown carbon aerosol in the atmosphere. We collected filter samples of biomass-burning emissions at three locations in Canada and the United States with transport times of 10 h to >3 days. We analyzed the samples with size-exclusion chromatography coupled to molecular absorbance spectroscopy to determine absorbance as a function of molecular size. The majority of absorption was due to molecules >500 Da, and these contributed an increasing fraction of absorption as the biomass-burning aerosol aged. This suggests that the smallest molecular weight fraction is more susceptible to processes that lead to reduced light absorption, while larger-molecular-weight species may represent recalcitrant brown carbon. We calculate that these large-molecular-weight species are composed of more than 20 carbons with as few as two oxygens and would be classified as extremely low volatility organic compounds (ELVOCs).

  16. Recent advances in understanding secondary organic aerosol: Implications for global climate forcing: Advances in Secondary Organic Aerosol

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shrivastava, Manish; Cappa, Christopher D.; Fan, Jiwen

    Anthropogenic emissions and land use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding preindustrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features (1) influence estimates of aerosol radiative forcing and (2) can confound estimates of the historical response of climate to increases in greenhouse gases. Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron-sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate modelsmore » typically do not comprehensively include all important processes. Our review summarizes some of the important developments during the past decade in understanding SOA formation. We also highlight the importance of some processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including formation of extremely low volatility organics in the gas phase, acid-catalyzed multiphase chemistry of isoprene epoxydiols, particle-phase oligomerization, and physical properties such as volatility and viscosity. Several SOA processes highlighted in this review are complex and interdependent and have nonlinear effects on the properties, formation, and evolution of SOA. Current global models neglect this complexity and nonlinearity and thus are less likely to accurately predict the climate forcing of SOA and project future climate sensitivity to greenhouse gases. Efforts are also needed to rank the most influential processes and nonlinear process-related interactions, so that these processes can be accurately represented in atmospheric chemistry-climate models.« less

  17. Recent advances in understanding secondary organic aerosol: Implications for global climate forcing: Advances in Secondary Organic Aerosol

    DOE PAGES

    Shrivastava, Manish; Cappa, Christopher D.; Fan, Jiwen; ...

    2017-06-15

    Anthropogenic emissions and land use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding preindustrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features (1) influence estimates of aerosol radiative forcing and (2) can confound estimates of the historical response of climate to increases in greenhouse gases. Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron-sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate modelsmore » typically do not comprehensively include all important processes. Our review summarizes some of the important developments during the past decade in understanding SOA formation. We also highlight the importance of some processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including formation of extremely low volatility organics in the gas phase, acid-catalyzed multiphase chemistry of isoprene epoxydiols, particle-phase oligomerization, and physical properties such as volatility and viscosity. Several SOA processes highlighted in this review are complex and interdependent and have nonlinear effects on the properties, formation, and evolution of SOA. Current global models neglect this complexity and nonlinearity and thus are less likely to accurately predict the climate forcing of SOA and project future climate sensitivity to greenhouse gases. Efforts are also needed to rank the most influential processes and nonlinear process-related interactions, so that these processes can be accurately represented in atmospheric chemistry-climate models.« less

  18. Organic Aerosol Formation Photoenhanced by the Formation of Secondary Photo-sensitizers in ageing Aerosols

    NASA Astrophysics Data System (ADS)

    Aregahegn, Kifle; Nozière, Barbara; George, Christian

    2013-04-01

    Humankind is facing a changing environment possibly due to anthropogenic stress on the atmosphere. In this context, aerosols play a key role by affecting the radiative climate forcing, hydrological cycle, and by their adverse effect on health. The role of organic compounds in these processes is however still poorly understood because of their massive chemical complexity and numerous transformations. This is particularly true for Secondary Organic Aerosol (SOA), which are produced in the atmosphere by organic gases. Traditionally, the driving forces for SOA growth is believed to be the partitioning onto aerosol seeds of condensable gases, either emitted primarily or resulting from the gas phase oxidation of organic gases. However, even the most up-to-date models based on such mechanisms can not account for the SOA mass observed in the atmosphere, suggesting the existence of other, yet unknown formation processes. The present study shows experimental evidence that particulate phase chemistry produces photo-sensitizers that lead to photo-induced formation and growth of secondary organic aerosol in the near UV and the presence of volatile organic compounds (VOC) such as terpenes. By means of an aerosol flow tube reactor equipped with Scanning Mobility Particle Sizer (SMPS) having Kr-85 source aerosol neutralizer, Differential Mobility Analyser (DMA) and Condensation Particle Sizer (CPC), we identified that traces of the aerosol phase product of glyoxal chemistry as is explained in Gallway et al., and Yu et al., namely imidazole-2-carboxaldehyde (IC) is a strong photo-sensitizer when irradiated by near-UV in the presence of volatile organic compounds such as terpenes. Furthermore, the influence of pH, type and concentration of VOCs, composition of seed particles, relative humidity and irradiation intensity on particle growth were studied. This novel photo-sensitizer contributed to more than 30% of SOA growth in 19min irradiation time in the presence of terpenes in the

  19. Water soluble organic aerosols in the Colorado Rocky Mountains, USA: composition, sources and optical properties

    PubMed Central

    Xie, Mingjie; Mladenov, Natalie; Williams, Mark W.; Neff, Jason C.; Wasswa, Joseph; Hannigan, Michael P.

    2016-01-01

    Atmospheric aerosols have been shown to be an important input of organic carbon and nutrients to alpine watersheds and influence biogeochemical processes in these remote settings. For many remote, high elevation watersheds, direct evidence of the sources of water soluble organic aerosols and their chemical and optical characteristics is lacking. Here, we show that the concentration of water soluble organic carbon (WSOC) in the total suspended particulate (TSP) load at a high elevation site in the Colorado Rocky Mountains was strongly correlated with UV absorbance at 254 nm (Abs254, r = 0.88 p < 0.01) and organic carbon (OC, r = 0.95 p < 0.01), accounting for >90% of OC on average. According to source apportionment analysis, biomass burning had the highest contribution (50.3%) to average WSOC concentration; SOA formation and motor vehicle emissions dominated the contribution to WSOC in the summer. The source apportionment and backward trajectory analysis results supported the notion that both wildfire and Colorado Front Range pollution sources contribute to the summertime OC peaks observed in wet deposition at high elevation sites in the Colorado Rocky Mountains. These findings have important implications for water quality in remote, high-elevation, mountain catchments considered to be our pristine reference sites. PMID:27991554

  20. A global modeling study on carbonaceous aerosol microphysical characteristics and radiative forcing

    NASA Astrophysics Data System (ADS)

    Bauer, S. E.; Menon, S.; Koch, D.; Bond, T. C.; Tsigaridis, K.

    2010-02-01

    Recently, attention has been drawn towards black carbon aerosols as a short-term climate warming mitigation candidate. However the global and regional impacts of the direct, cloud-indirect and semi-direct forcing effects are highly uncertain, due to the complex nature of aerosol evolution and the way that mixed, aged aerosols interact with clouds and radiation. A detailed aerosol microphysical scheme, MATRIX, embedded within the GISS climate model is used in this study to present a quantitative assessment of the impact of microphysical processes involving black carbon, such as emission size distributions and optical properties on aerosol cloud activation and radiative forcing. Our best estimate for net direct and indirect aerosol radiative forcing between 1750 and 2000 is -0.56 W/m2. However, the direct and indirect aerosol effects are quite sensitive to the black and organic carbon size distribution and consequential mixing state. The net radiative forcing can vary between -0.32 to -0.75 W/m2 depending on these carbonaceous particle properties at emission. Assuming that sulfates, nitrates and secondary organics form a coating around a black carbon core, rather than forming a uniformly mixed particle, changes the overall net aerosol radiative forcing from negative to positive. Taking into account internally mixed black carbon particles let us simulate correct aerosol absorption. Black carbon absorption is amplified by sulfate and nitrate coatings, but even more strongly by organic coatings. Black carbon mitigation scenarios generally showed reduced radiative forcing when sources with a large proportion of black carbon, such as diesel, are reduced; however reducing sources with a larger organic carbon component as well, such as bio-fuels, does not necessarily lead to climate benefits.

  1. The hygroscopicity parameter (κ) of ambient organic aerosol at a field site subject to biogenic and anthropogenic influences: relationship to degree of aerosol oxidation

    NASA Astrophysics Data System (ADS)

    Chang, R. Y.-W.; Slowik, J. G.; Shantz, N. C.; Vlasenko, A.; Liggio, J.; Sjostedt, S. J.; Leaitch, W. R.; Abbatt, J. P. D.

    2010-06-01

    Cloud condensation nuclei (CCN) concentrations were measured at Egbert, a rural site in Ontario, Canada during the spring of 2007. The CCN concentrations were compared to values predicted from the aerosol chemical composition and size distribution using κ-Köhler theory, with the specific goal of this work being to determine the hygroscopic parameter (κ) of the oxygenated organic component of the aerosol, assuming that oxygenation drives the hygroscopicity for the entire organic fraction of the aerosol. The hygroscopicity of the oxygenated fraction of the organic component, as determined by an Aerodyne aerosol mass spectrometer (AMS), was characterised by two methods. First, positive matrix factorization (PMF) was used to separate oxygenated and unoxygenated organic aerosol factors. By assuming that the unoxygenated factor is completely non-hygroscopic and by varying κ of the oxygenated factor so that the predicted and measured CCN concentrations are internally consistent and in good agreement, κ of the oxygenated organic factor was found to be 0.22±0.04 for the suite of measurements made during this five-week campaign. In a second, equivalent approach, we continue to assume that the unoxygenated component of the aerosol, with a mole ratio of atomic oxygen to atomic carbon (O/C) ≈ 0, is completely non-hygroscopic, and we postulate a simple linear relationship between κorg and O/C. Under these assumptions, the κ of the entire organic component for bulk aerosols measured by the AMS can be parameterised as κorg=(0.29±0.05)·(O/C), for the range of O/C observed in this study (0.3 to 0.6). These results are averaged over our five-week study at one location using only the AMS for composition analysis. Empirically, our measurements are consistent with κorg generally increasing with increasing particle oxygenation, but high uncertainties preclude us from testing this hypothesis. Lastly, we examine select periods of different aerosol composition, corresponding

  2. Quantifying fire emissions and associated aerosols species using assimilation of satellite carbon monoxide retrievals.

    NASA Astrophysics Data System (ADS)

    Barre, J.; Edwards, D. P.; Worden, H. M.

    2016-12-01

    Wildfires tend to be more intense and hence costly and are predicted to increase in frequency under a warming climate. For example, the recent August 2015 Washington State fires were the largest in the state's history. Also in September and October 2015 very intense fires over Indonesia produced some of the highest concentration of carbon monoxide (CO) ever seen from space. Such larges fires impact not only the local environment but also affects air quality far downwind through the long-range transport of pollutants. Global to continental scale coverage showing the evolution of CO resulting from fire emission is available from satellite observations. Carbon monoxide is the only atmospheric trace gas for which satellite multispectral retrievals have demonstrated reliable independent profile information close to the surface and also higher in the free troposphere. The unique CO profile product from Terra/MOPITT clearly distinguishes near-surface CO from the free troposphere CO. Also previous studies have suggested strong correlations between primary emissions of fire organic and black carbon aerosols and CO. We will present results from the Ensemble Adjustement Kalman Filter (DART) system that has been developed to assimilate MOPITT CO in the global scale chemistry-climate model CAM-Chem. The ensemble technique allows inference on various fire model state variables such as CO emissions and also aerosol species resulting from fires such as organic and black carbon. The benefit of MOPITT CO assimilation on the Washington and Indonesian fire cases studies will be diagnosed regarding the CO fire emissions, black and organic carbon inference using the ensemble information.

  3. Primary and secondary organic aerosols in Fresno, California during wintertime: Results from high resolution aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Ge, Xinlei; Setyan, Ari; Sun, Yele; Zhang, Qi

    2012-10-01

    Organic aerosols (OA) were studied in Fresno, California, in winter 2010 with an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). OA dominated the submicron aerosol mass (average = 67%) with an average concentration of 7.9μg m-3 and a nominal formula of C1H1.59N0.014O0.27S0.00008, which corresponds to an average organic mass-to-carbon ratio of 1.50. Three primary OA (POA) factors and one oxygenated OA factor (OOA) representative of secondary OA (SOA) were identified via Positive Matrix Factorization of the high-resolution mass spectra. The three POA factors, which include a traffic-related hydrocarbon-like OA (HOA), a cooking OA (COA), and a biomass burning OA (BBOA) released from residential heating, accounted for an average 57% of the OA mass and up to 80% between 6 - 9 P.M., during which enhanced emissions from evening rush hour traffic, dinner cooking, and residential wood burning were exacerbated by low mixed layer height. The mass-based size distributions of the OA factors were estimated based on multilinear analysis of the size-resolved mass spectra of organics. Both HOA and BBOA peaked at ˜140 nm in vacuum aerodynamic diameter (Dva) while OOA peaked at an accumulation mode of ˜460 nm. COA exhibited a unique size distribution with two size modes centering at ˜200 nm and 450 nm respectively. This study highlights the leading roles played by anthropogenic POA emissions, primarily from traffic, cooking and residential heating, in aerosol pollution in Fresno in wintertime.

  4. Effect of the secondary organic aerosol coatings on black carbon water uptake, cloud condensation nuclei activity, and particle collapse

    EPA Science Inventory

    The ability of black carbon aerosols to absorb water and act as a cloud condensation nuclei (CCN) directly controls their lifetime in the atmosphere as well as their impact on cloud formation, thus impacting the earth’s climate. Black carbon emitted from most combustion pro...

  5. INVESTIGATION OF A SYSTEMATIC OFFSET IN THE MEASUREMENT OF ORGANIC CARBON WITH A SEMI-CONTINUOUS ANALYZER

    EPA Science Inventory

    Organic carbon was measured semi-continuously in laboratory experiments of steady-state secondary organic aerosol formed by hydrocarbon + NOx irradiations. Examination of the mass of carbon measured on the filter for various sample volumes reveals a systematic offset that is not...

  6. Smoke aerosol chemistry and aging of Siberian biomass burning emissions in a large aerosol chamber

    NASA Astrophysics Data System (ADS)

    Kalogridis, A.-C.; Popovicheva, O. B.; Engling, G.; Diapouli, E.; Kawamura, K.; Tachibana, E.; Ono, K.; Kozlov, V. S.; Eleftheriadis, K.

    2018-07-01

    Vegetation open fires constitute a significant source of particulate pollutants on a global scale and play an important role in both atmospheric chemistry and climate change. To better understand the emission and aging characteristics of smoke aerosols, we performed small-scale fire experiments using the Large Aerosol Chamber (LAC, 1800 m3) with a focus on biomass burning from Siberian boreal coniferous forests. A series of burn experiments were conducted with typical Siberian biomass (pine and debris), simulating separately different combustion conditions, namely, flaming, smoldering and mixed phase. Following smoke emission and dispersion in the combustion chamber, we investigated aging of aerosols under dark conditions. Here, we present experimental data on emission factors of total, elemental and organic carbon, as well as individual organic compounds, such as anhydrosugars, phenolic and dicarboxylic acids. We found that total carbon accounts for up to 80% of the fine mode (PM2.5) smoke aerosol. Higher PM2.5 emission factors were observed in the smoldering compared to flaming phase and in pine compared to debris smoldering phase. For low-temperature combustion, organic carbon (OC) contributed to more than 90% of total carbon, whereas elemental carbon (EC) dominated the aerosol composition in flaming burns with a 60-70% contribution to the total carbon mass. For all smoldering burns, levoglucosan (LG), a cellulose decomposition product, was the most abundant organic species (average LG/OC = 0.26 for pine smoldering), followed by its isomer mannosan or dehydroabietic acid (DA), an important constituent of conifer resin (DA/OC = 0.033). A levoglucosan-to-mannosan ratio of about 3 was observed, which is consistent with ratios reported for coniferous biomass and more generally softwood. The rates of aerosol removal for OC and individual organic compounds were investigated during aging in the chamber in terms of mass concentration loss rates over time under dark

  7. Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets

    PubMed Central

    Mohr, Claudia; Lopez-Hilfiker, Felipe D.; Lutz, Anna; Hallquist, Mattias; Lee, Lance; Romer, Paul; Cohen, Ronald C.; Iyer, Siddharth; Kurtén, Theo; Hu, Weiwei; Day, Douglas A.; Campuzano-Jost, Pedro; Jimenez, Jose L.; Xu, Lu; Ng, Nga Lee; Guo, Hongyu; Weber, Rodney J.; Wild, Robert J.; Brown, Steven S.; Koss, Abigail; de Gouw, Joost; Olson, Kevin; Goldstein, Allen H.; Seco, Roger; Kim, Saewung; McAvey, Kevin; Shepson, Paul B.; Starn, Tim; Baumann, Karsten; Edgerton, Eric S.; Liu, Jiumeng; Shilling, John E.; Miller, David O.; Brune, William; Schobesberger, Siegfried; D'Ambro, Emma L.; Thornton, Joel A.

    2016-01-01

    Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas–particle equilibrium and (ii) have a short particle-phase lifetime (∼2–4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment. PMID:26811465

  8. Atmospheric aerosol brown carbon in the high Himalayas

    NASA Astrophysics Data System (ADS)

    Kirillova, Elena; Decesari, Stefano; Marinoni, Angela; Bonasoni, Paolo; Vuillermoz, Elisa; Facchini, M. Cristina; Fuzzi, Sandro

    2016-04-01

    Anthropogenic light-absorbing atmospheric aerosol can reach very high concentrations in the planetary boundary layer in South-East Asia ("brown clouds"), affecting atmospheric transparency and generating spatial gradients of temperature over land with a possible impact on atmospheric dynamics and monsoon circulation. Besides black carbon (BC), an important light-absorbing component of anthropogenic aerosols is the organic carbon component known as 'brown carbon' (BrC). In this research, we provided first measurements of atmospheric aerosol BrC in the high Himalayas during different seasons. Aerosol sampling was conducted at the GAW-WMO Global station "Nepal Climate Observatory-Pyramid" (NCO-P) located in the high Khumbu valley at 5079 m a.s.l. in the foothills of Mt. Everest. PM10 aerosol samples were collected from July 2013 to November 2014. The sampling strategy was set up in order to discriminate the daytime valley breeze bringing polluted air masses up to the observatory and free tropospheric air during nighttime. Water-soluble BrC (WS-BrC) and methanol-soluble BrC (MeS-BrC) were extracted and analyzed using a UV/VIS spectrophotometer equipped with a 50 cm liquid waveguide capillary cell. In the polluted air masses, the highest levels of the BrC light absorption coefficient at 365 nm (babs365) were observed during the pre-monsoon season (1.83±1.46 Mm-1 for WS-BrC and 2.86±2.49 Mm-1 for MeS-BrC) and the lowest during the monsoon season (0.21±0.22 Mm-1 for WS-BrC and 0.32±0.29 Mm-1 for MeS-BrC). The pre-monsoon season is the most frequently influenced by a strong atmospheric brown cloud (ABC) transport to NCO-P due to increased convection and mixing layer height over South Asia combined with the highest up-valley wind speed and the increase of the emissions from open fires due to the agricultural practice along the Himalayas foothills and the Indo-Gangetic Plain. In contrast, the monsoon season is characterized by a weakened valley wind regime and an

  9. Biogenic-Anthropogenic Interactions in Secondary Organic Aerosol Formation and Health Effects of Atmospheric Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Ye, Jianhuai

    Secondary organic aerosol (SOA) formed from oxidation of volatile organic compounds (VOCs), comprises a major fraction of atmospheric submicron particulate matter, which is crucial for global climate change and human health. While biogenic VOCs are naturally emitted and cannot be directly controlled, field measurements and satellite observations have shown that biogenic SOA (BSOA) formation correlates well with anthropogenic pollutants and may be anthropogenically controlled. In this work, the formation of the "anthropogenically controllable BSOA" was examined. BSOA from alpha-pinene ozonolysis was investigated in the presence of laboratory-generated or ambient organic aerosol such as Toronto ambient particles. It is shown that SOA was not equally miscible with all organic species. Aerosol mixing thermodynamics in the atmosphere is composition dependent. Based on laboratory observations, an empirical framework using bulk elemental ratios was developed to predict atmospheric organic miscibility and SOA yield enhancements. Besides organic aerosol, interactions between BSOA formation and SO2 was also examined. Synergistic effects were observed between BSOA formation and SO2 oxidation through Criegee and peroxide chemistry under atmospherically relevant RH conditions. In addition to the physicochemical properties of SOA, health impacts of SOA were examined. An atmospheric simulation reactor (ASR) was developed to investigate the health effects of air pollutants by permitting controlled chronic in vivo exposure of mice to combine particulate and gaseous pollutants at 'real-life' concentrations. Results show that daily exposure to SOA from naphthalene photooxidation led to increased airway hyperresponsiveness (AHR) to methacholine in a dose-dependent manner. Multi-pollutant exposures with ozone and/or NO2 in conjunction with a sub-toxic concentration of SOA resulted in additive effects on AHR to methacholine. Inflammatory cell recruitment to the airways was not observed

  10. Characterization of urban aerosol in Cork city (Ireland) using aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Dall'Osto, M.; Ovadnevaite, J.; Ceburnis, D.; Martin, D.; Healy, R. M.; O'Connor, I. P.; Kourtchev, I.; Sodeau, J. R.; Wenger, J. C.; O'Dowd, C.

    2013-05-01

    Ambient wintertime background urban aerosol in Cork city, Ireland, was characterized using aerosol mass spectrometry. During the three-week measurement study in 2009, 93% of the ca. 1 350 000 single particles characterized by an Aerosol Time-of-Flight Mass Spectrometer (TSI ATOFMS) were classified into five organic-rich particle types, internally mixed to different proportions with elemental carbon (EC), sulphate and nitrate, while the remaining 7% was predominantly inorganic in nature. Non-refractory PM1 aerosol was characterized using a High Resolution Time-of-Flight Aerosol Mass Spectrometer (Aerodyne HR-ToF-AMS) and was also found to comprise organic aerosol as the most abundant species (62%), followed by nitrate (15%), sulphate (9%) and ammonium (9%), and chloride (5%). Positive matrix factorization (PMF) was applied to the HR-ToF-AMS organic matrix, and a five-factor solution was found to describe the variance in the data well. Specifically, "hydrocarbon-like" organic aerosol (HOA) comprised 20% of the mass, "low-volatility" oxygenated organic aerosol (LV-OOA) comprised 18%, "biomass burning" organic aerosol (BBOA) comprised 23%, non-wood solid-fuel combustion "peat and coal" organic aerosol (PCOA) comprised 21%, and finally a species type characterized by primary {m/z} peaks at 41 and 55, similar to previously reported "cooking" organic aerosol (COA), but possessing different diurnal variations to what would be expected for cooking activities, contributed 18%. Correlations between the different particle types obtained by the two aerosol mass spectrometers are also discussed. Despite wood, coal and peat being minor fuel types used for domestic space heating in urban areas, their relatively low combustion efficiencies result in a significant contribution to PM1 aerosol mass (44% and 28% of the total organic aerosol mass and non-refractory total PM1, respectively).

  11. Characterization of urban aerosol in Cork City (Ireland) using aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Dall'Osto, M.; Ovadnevaite, J.; Ceburnis, D.; Martin, D.; Healy, R. M.; O'Connor, I. P.; Sodeau, J. R.; Wenger, J. C.; O'Dowd, C.

    2012-11-01

    Ambient wintertime background urban aerosol in Cork City, Ireland, was characterized using aerosol mass spectrometry. During the three-week measurement study in 2009, 93% of the 1 200 000 single particles characterized by an Aerosol Time-Of-Flight Mass Spectrometer (TSI ATOFMS) were classified into five organic-rich particle types, internally-mixed to different proportions with Elemental Carbon (EC), sulphate and nitrate while the remaining 7% was predominantly inorganic in nature. Non-refractory PM1 aerosol was also characterized using a High Resolution Time-Of-Flight Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS) and was also found to comprise organic matter as the most abundant species (62%), followed by nitrate (15%), sulphate (9%) and ammonium (9%), and then chloride (5%). Positive matrix factorization (PMF) was applied to the HR-ToF-AMS organic matrix and a five-factor solution was found to describe the variance in the data well. Specifically, "Hydrocarbon-like" Organic Aerosol (HOA) comprised 19% of the mass, "Oxygenated low volatility" Organic Aerosols (LV-OOA) comprised 19%, "Biomass wood Burning" Organic Aerosol (BBOA) comprised 23%, non-wood solid-fuel combustion "Peat and Coal" Organic Aerosol (PCOA) comprised 21%, and finally, a species type characterized by primary m/z peaks at 41 and 55, similar to previously-reported "Cooking" Organic Aerosol (COA) but possessing different diurnal variations to what would be expected for cooking activities, contributed 18%. Despite wood, cool and peat being minor fuel types used for domestic space heating in urban areas, their relatively low combustion efficiencies result in a significant contribution to PM1 aerosol mass (44% and 28% of the total organic aerosols mass and non refractory PM1, respectively).

  12. The Composition of Organic Aerosols in Southeast Asia During The 2006 Haze Episode

    NASA Astrophysics Data System (ADS)

    Jun, H.; Zielinska, B.; Balasubramanian, R.

    2007-12-01

    The regional smoke haze in Southeast Asia is a recurring air pollution problem. Uncontrolled forest fires from land-clearing activities in Sumatra and Borneo, and to a lesser extent Malaysia, have occurred almost every dry season since the late 1990s. The smoke haze that took place in October 2006 shrouded an estimated 215,000 square miles of land on Indonesia's islands of Sumatra and Borneo, and persisted for several weeks. Satellite pictures showed numerous hotspots in both Sumatra and Kalimantan. The prevailing, South-Southwesterly, winds blew smoke from land and forest fires in central and south Sumatra to Singapore, affecting the regional air quality significantly and reducing atmospheric visibility. During this haze episode, we carried out an intensive field study in Singapore to characterize the composition of organic aerosols, which usually account for a large fraction of airborne particulate matter (PM). A total of 17 PM samples were collected while the hazy atmospheric conditions persisted in Singapore, and subjected to accelerated solvent extraction with dichloromethane and acetone. The extracted compounds were grouped into three major fractions (n-alkanes, polycyclic aromatic hydrocarbons, and polar organic compounds). More than 180 particulate-bound organic compounds were determined using gas chromatography/mass spectrometry (GC-MS). In order to investigate the origin of organic species, the carbon preference indexes as well as diagnostic ratios were used. The compositional differences of organic aerosols between the haze- and non- haze periods will be presented. The atmospheric implications of the composition of organic aerosols of biomass burning origin will be discussed. Keywords: smoke haze, organic aerosols, n-alkanes, polycyclic aromatic hydrocarbons, polar organic compounds

  13. A Global Modeling Study on Carbonaceous Aerosol Microphysical Characteristics and Radiative Effects

    NASA Technical Reports Server (NTRS)

    Bauer, S. E.; Menon, S.; Koch, D.; Bond, T. C.; Tsigaridis, K.

    2010-01-01

    Recently, attention has been drawn towards black carbon aerosols as a short-term climate warming mitigation candidate. However the global and regional impacts of the direct, indirect and semi-direct aerosol effects are highly uncertain, due to the complex nature of aerosol evolution and the way that mixed, aged aerosols interact with clouds and radiation. A detailed aerosol microphysical scheme, MATRIX, embedded within the GISS climate model is used in this study to present a quantitative assessment of the impact of microphysical processes involving black carbon, such as emission size distributions and optical properties on aerosol cloud activation and radiative effects. Our best estimate for net direct and indirect aerosol radiative flux change between 1750 and 2000 is -0.56 W/m2. However, the direct and indirect aerosol effects are quite sensitive to the black and organic carbon size distribution and consequential mixing state. The net radiative flux change can vary between -0.32 to -0.75 W/m2 depending on these carbonaceous particle properties at emission. Taking into account internally mixed black carbon particles let us simulate correct aerosol absorption. Absorption of black carbon aerosols is amplified by sulfate and nitrate coatings and, even more strongly, by organic coatings. Black carbon mitigation scenarios generally showed reduced radiative fluxeswhen sources with a large proportion of black carbon, such as diesel, are reduced; however reducing sources with a larger organic carbon component as well, such as bio-fuels, does not necessarily lead to a reduction in positive radiative flux.

  14. A global modeling study on carbonaceous aerosol microphysical characteristics and radiative effects

    NASA Astrophysics Data System (ADS)

    Bauer, S. E.; Menon, S.; Koch, D.; Bond, T. C.; Tsigaridis, K.

    2010-08-01

    Recently, attention has been drawn towards black carbon aerosols as a short-term climate warming mitigation candidate. However the global and regional impacts of the direct, indirect and semi-direct aerosol effects are highly uncertain, due to the complex nature of aerosol evolution and the way that mixed, aged aerosols interact with clouds and radiation. A detailed aerosol microphysical scheme, MATRIX, embedded within the GISS climate model is used in this study to present a quantitative assessment of the impact of microphysical processes involving black carbon, such as emission size distributions and optical properties on aerosol cloud activation and radiative effects. Our best estimate for net direct and indirect aerosol radiative flux change between 1750 and 2000 is -0.56 W/m2. However, the direct and indirect aerosol effects are quite sensitive to the black and organic carbon size distribution and consequential mixing state. The net radiative flux change can vary between -0.32 to -0.75 W/m2 depending on these carbonaceous particle properties at emission. Taking into account internally mixed black carbon particles let us simulate correct aerosol absorption. Absorption of black carbon aerosols is amplified by sulfate and nitrate coatings and, even more strongly, by organic coatings. Black carbon mitigation scenarios generally showed reduced radiative fluxeswhen sources with a large proportion of black carbon, such as diesel, are reduced; however reducing sources with a larger organic carbon component as well, such as bio-fuels, does not necessarily lead to a reduction in positive radiative flux.

  15. Radiocarbon (14C) Constraints On The Fraction Of Refractory Dissolved Organic Carbon In Primary Marine Aerosol From The Northwest Atlantic

    NASA Astrophysics Data System (ADS)

    Beaupre, S. R.; Kieber, D. J.; Keene, W. C.; Long, M. S.; Frossard, A. A.; Kinsey, J. D.; Duplessis, P.; Chang, R.; Maben, J. R.; Lu, X.; Zhu, Y.; Bisgrove, J.

    2017-12-01

    Nearly all organic carbon in seawater is dissolved (DOC), with more than 95% considered refractory based on modeled average lifetimes ( 16,000 years) and characteristically old bulk radiocarbon (14C) ages (4000 - 6000 years) that exceed the timescales of overturning circulation. Although this refractory dissolved organic carbon (RDOC) is present throughout the oceans as a major reservoir of the global carbon cycle, its sources and sinks are poorly constrained. Recently, RDOC was proposed to be removed from the oceans through adsorption onto the surfaces of rising bubble plumes produced by breaking waves, ejection into the atmosphere via bubble bursting as a component of primary marine aerosol (PMA), and subsequent oxidation in the atmosphere. To test this mechanism, we used natural abundance 14C (5730 ± 40 yr half-life) to trace the fraction of RDOC in PMA produced in a high capacity generator at two biologically-productive and two oligotrophic hydrographic stations in the Northwest Atlantic Ocean during a research cruise aboard the R/V Endeavor (Sep - Oct 2016). The 14C signatures of PMA separately generated day and night from near-surface (5 m) and deep (2500 m) seawater were compared with corresponding 14C signatures in seawater of near-surface dissolved inorganic carbon (DIC, a proxy for recently produced organic matter), bulk deep DOC (a proxy for RDOC), and near-surface bulk DOC. Results constrain the selectivity of PMA formation from RDOC in natural mixtures of recently produced and refractory DOC. The implications of these results for PMA formation and RDOC biogeochemistry will be discussed.

  16. Quantification of Semi-Volatile gas-phase Organic Compounds (SVOCs) & Organic Aerosol species and the role of SVOCs in Secondary Organic Aerosol formation

    NASA Astrophysics Data System (ADS)

    Khan, M. H.; Holzinger, R.

    2013-12-01

    A Thermal-Desorption Proton-Transfer-Reaction Mass-Spectrometer (TD-PTR-MS) with different sampling systems (multi-stage denuder for gas phase and impact on a collector for aerosol phase) has been deployed in summer 2013 during the Southern Oxidant and Aerosol Study (SOAS) at the SEARCH ground site, Centreville, Alabama for in-situ gas phase and aerosol measurements on an hourly time resolution. A bunch of DB-1 column (0.53 mm x 5.0 μm) is used in the denuder for capturing the bulk of SVOCs and a collection-thermal-desorption (CTD) cell is used for collecting aerosol particles. Several hundreds semivolatile organic compounds (SVOCs) in gas phase and aerosol phases have been detected. The high mass resolution capabilities of ~5000, low detection limit (<0.05 pptv for gas species, <0.01 ng m-3 for aerosol species) and good physical and chemical characterization of SVOCs with the TD-PTR-MS allows constraining both, the quantity and the chemical composition. The SEARCH site was highly impacted by Biogenic Volatile Organic Compounds (BVOCs) and occasionally influenced by anthropogenic pollution. BVOCs and their oxidation products are capable of partitioning into the particle phase, so their simultaneous quantification in both phases has been used to determine the gas/particle-phase partitioning. Our results show the expected diurnal variation based on the changes of air temperature for many species. The results from this study give valuable insights into sources and processing of Secondary Organic Aerosols (SOAs) that can be used to improve parameterization algorithms in regional and global climate models.

  17. A large source of low-volatility secondary organic aerosol.

    PubMed

    Ehn, Mikael; Thornton, Joel A; Kleist, Einhard; Sipilä, Mikko; Junninen, Heikki; Pullinen, Iida; Springer, Monika; Rubach, Florian; Tillmann, Ralf; Lee, Ben; Lopez-Hilfiker, Felipe; Andres, Stefanie; Acir, Ismail-Hakki; Rissanen, Matti; Jokinen, Tuija; Schobesberger, Siegfried; Kangasluoma, Juha; Kontkanen, Jenni; Nieminen, Tuomo; Kurtén, Theo; Nielsen, Lasse B; Jørgensen, Solvejg; Kjaergaard, Henrik G; Canagaratna, Manjula; Maso, Miikka Dal; Berndt, Torsten; Petäjä, Tuukka; Wahner, Andreas; Kerminen, Veli-Matti; Kulmala, Markku; Worsnop, Douglas R; Wildt, Jürgen; Mentel, Thomas F

    2014-02-27

    Forests emit large quantities of volatile organic compounds (VOCs) to the atmosphere. Their condensable oxidation products can form secondary organic aerosol, a significant and ubiquitous component of atmospheric aerosol, which is known to affect the Earth's radiation balance by scattering solar radiation and by acting as cloud condensation nuclei. The quantitative assessment of such climate effects remains hampered by a number of factors, including an incomplete understanding of how biogenic VOCs contribute to the formation of atmospheric secondary organic aerosol. The growth of newly formed particles from sizes of less than three nanometres up to the sizes of cloud condensation nuclei (about one hundred nanometres) in many continental ecosystems requires abundant, essentially non-volatile organic vapours, but the sources and compositions of such vapours remain unknown. Here we investigate the oxidation of VOCs, in particular the terpene α-pinene, under atmospherically relevant conditions in chamber experiments. We find that a direct pathway leads from several biogenic VOCs, such as monoterpenes, to the formation of large amounts of extremely low-volatility vapours. These vapours form at significant mass yield in the gas phase and condense irreversibly onto aerosol surfaces to produce secondary organic aerosol, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies. We further demonstrate how these low-volatility vapours can enhance, or even dominate, the formation and growth of aerosol particles over forested regions, providing a missing link between biogenic VOCs and their conversion to aerosol particles. Our findings could help to improve assessments of biosphere-aerosol-climate feedback mechanisms, and the air quality and climate effects of biogenic emissions generally.

  18. A large source of low-volatility secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Ehn, Mikael; Thornton, Joel A.; Kleist, Einhard; Sipilä, Mikko; Junninen, Heikki; Pullinen, Iida; Springer, Monika; Rubach, Florian; Tillmann, Ralf; Lee, Ben; Lopez-Hilfiker, Felipe; Andres, Stefanie; Acir, Ismail-Hakki; Rissanen, Matti; Jokinen, Tuija; Schobesberger, Siegfried; Kangasluoma, Juha; Kontkanen, Jenni; Nieminen, Tuomo; Kurtén, Theo; Nielsen, Lasse B.; Jørgensen, Solvejg; Kjaergaard, Henrik G.; Canagaratna, Manjula; Maso, Miikka Dal; Berndt, Torsten; Petäjä, Tuukka; Wahner, Andreas; Kerminen, Veli-Matti; Kulmala, Markku; Worsnop, Douglas R.; Wildt, Jürgen; Mentel, Thomas F.

    2014-02-01

    Forests emit large quantities of volatile organic compounds (VOCs) to the atmosphere. Their condensable oxidation products can form secondary organic aerosol, a significant and ubiquitous component of atmospheric aerosol, which is known to affect the Earth's radiation balance by scattering solar radiation and by acting as cloud condensation nuclei. The quantitative assessment of such climate effects remains hampered by a number of factors, including an incomplete understanding of how biogenic VOCs contribute to the formation of atmospheric secondary organic aerosol. The growth of newly formed particles from sizes of less than three nanometres up to the sizes of cloud condensation nuclei (about one hundred nanometres) in many continental ecosystems requires abundant, essentially non-volatile organic vapours, but the sources and compositions of such vapours remain unknown. Here we investigate the oxidation of VOCs, in particular the terpene α-pinene, under atmospherically relevant conditions in chamber experiments. We find that a direct pathway leads from several biogenic VOCs, such as monoterpenes, to the formation of large amounts of extremely low-volatility vapours. These vapours form at significant mass yield in the gas phase and condense irreversibly onto aerosol surfaces to produce secondary organic aerosol, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies. We further demonstrate how these low-volatility vapours can enhance, or even dominate, the formation and growth of aerosol particles over forested regions, providing a missing link between biogenic VOCs and their conversion to aerosol particles. Our findings could help to improve assessments of biosphere-aerosol-climate feedback mechanisms, and the air quality and climate effects of biogenic emissions generally.

  19. Implementing marine organic aerosols into the GEOS-Chem model

    DOE PAGES

    Gantt, B.; Johnson, M. S.; Crippa, M.; ...

    2015-03-17

    Marine-sourced organic aerosols (MOAs) have been shown to play an important role in tropospheric chemistry by impacting surface mass, cloud condensation nuclei, and ice nuclei concentrations over remote marine and coastal regions. In this work, an online marine primary organic aerosol emission parameterization, designed to be used for both global and regional models, was implemented into the GEOS-Chem (Global Earth Observing System Chemistry) model. The implemented emission scheme improved the large underprediction of organic aerosol concentrations in clean marine regions (normalized mean bias decreases from -79% when using the default settings to -12% when marine organic aerosols are added). Modelmore » predictions were also in good agreement (correlation coefficient of 0.62 and normalized mean bias of -36%) with hourly surface concentrations of MOAs observed during the summertime at an inland site near Paris, France. Our study shows that MOAs have weaker coastal-to-inland concentration gradients than sea-salt aerosols, leading to several inland European cities having >10% of their surface submicron organic aerosol mass concentration with a marine source. The addition of MOA tracers to GEOS-Chem enabled us to identify the regions with large contributions of freshly emitted or aged aerosol having distinct physicochemical properties, potentially indicating optimal locations for future field studies.« less

  20. Implementing Marine Organic Aerosols Into the GEOS-Chem Model

    NASA Technical Reports Server (NTRS)

    Johnson, Matthew S.

    2015-01-01

    Marine-sourced organic aerosols (MOA) have been shown to play an important role in tropospheric chemistry by impacting surface mass, cloud condensation nuclei, and ice nuclei concentrations over remote marine and coastal regions. In this work, an online marine primary organic aerosol emission parameterization, designed to be used for both global and regional models, was implemented into the GEOS-Chem model. The implemented emission scheme improved the large under-prediction of organic aerosol concentrations in clean marine regions (normalized mean bias decreases from -79% when using the default settings to -12% when marine organic aerosols are added). Model predictions were also in good agreement (correlation coefficient of 0.62 and normalized mean bias of -36%) with hourly surface concentrations of MOA observed during the summertime at an inland site near Paris, France. Our study shows that MOA have weaker coastal-to-inland concentration gradients than sea-salt aerosols, leading to several inland European cities having > 10% of their surface submicron organic aerosol mass concentration with a marine source. The addition of MOA tracers to GEOS-Chem enabled us to identify the regions with large contributions of freshly-emitted or aged aerosol having distinct physicochemical properties, potentially indicating optimal locations for future field studies.

  1. 403 nm cavity ring-down measurements of brown carbon aerosol

    NASA Astrophysics Data System (ADS)

    Kwon, D.; Grassian, V. H.; Kleiber, P.; Young, M. A.

    2017-12-01

    Atmospheric aerosol influences Earth's climate by absorbing and scattering incoming solar radiation and outgoing terrestrial radiation. One class of secondary organic aerosol (SOA), called brown carbon (BrC), has attracted attention for its wavelength dependent light absorbing properties with absorption coefficients that generally increase from the visible (Vis) to ultraviolet (UV) regions. Here we report results from our investigation of the optical properties of BrC aerosol products from the aqueous phase reaction of ammonium sulfate (AS) with methylglyoxal (MG) using cavity ring-down spectroscopy (CRDS) at 403 nm wavelength. We have measured the optical constants of BrC SOA from the AS/MG reaction as a function of reaction time. Under dry flow conditions, we observed no apparent variation in the BrC refractive index with aging over the course of 22 days. The retrieved BrC optical constants are similar to those of AS with n = 1.52 for the real component. Despite significant UV absorption observed from the bulk BrC solution, the imaginary index value at 403 nm is below our minimum detection limit which puts an upper bound of k as 0.03. These observations are in agreement with results from our recent studies of the light scattering properties of this BrC aerosol.

  2. Predicting ambient aerosol Thermal Optical Reflectance (TOR) measurements from infrared spectra: organic carbon

    NASA Astrophysics Data System (ADS)

    Dillner, A. M.; Takahama, S.

    2014-11-01

    Organic carbon (OC) can constitute 50% or more of the mass of atmospheric particulate matter. Typically, the organic carbon concentration is measured using thermal methods such as Thermal-Optical Reflectance (TOR) from quartz fiber filters. Here, methods are presented whereby Fourier Transform Infrared (FT-IR) absorbance spectra from polytetrafluoroethylene (PTFE or Teflon) filters are used to accurately predict TOR OC. Transmittance FT-IR analysis is rapid, inexpensive, and non-destructive to the PTFE filters. To develop and test the method, FT-IR absorbance spectra are obtained from 794 samples from seven Interagency Monitoring of PROtected Visual Environment (IMPROVE) sites sampled during 2011. Partial least squares regression is used to calibrate sample FT-IR absorbance spectra to artifact-corrected TOR OC. The FTIR spectra are divided into calibration and test sets by sampling site and date which leads to precise and accurate OC predictions by FT-IR as indicated by high coefficient of determination (R2; 0.96), low bias (0.02 μg m-3, all μg m-3 values based on the nominal IMPROVE sample volume of 32.8 m-3), low error (0.08 μg m-3) and low normalized error (11%). These performance metrics can be achieved with various degrees of spectral pretreatment (e.g., including or excluding substrate contributions to the absorbances) and are comparable in precision and accuracy to collocated TOR measurements. FT-IR spectra are also divided into calibration and test sets by OC mass and by OM / OC which reflects the organic composition of the particulate matter and is obtained from organic functional group composition; this division also leads to precise and accurate OC predictions. Low OC concentrations have higher bias and normalized error due to TOR analytical errors and artifact correction errors, not due to the range of OC mass of the samples in the calibration set. However, samples with low OC mass can be used to predict samples with high OC mass indicating that the

  3. Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols

    NASA Astrophysics Data System (ADS)

    Chim, Man Mei; Cheng, Chiu Tung; Davies, James F.; Berkemeier, Thomas; Shiraiwa, Manabu; Zuend, Andreas; Nin Chan, Man

    2017-12-01

    Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C5H8O4) droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART) coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C5) hydroxyl functionalization product (C5H8O5) and a C4 fragmentation product (C4H6O3). These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon-carbon bond scission) of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model) coupled with the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase from 0.362 to 0.424; however, the

  4. Single-particle characterization of biomass burning organic aerosol (BBOA): evidence for non-uniform mixing of high molecular weight organics and potassium

    NASA Astrophysics Data System (ADS)

    Lee, Alex K. Y.; Willis, Megan D.; Healy, Robert M.; Wang, Jon M.; Jeong, Cheol-Heon; Wenger, John C.; Evans, Greg J.; Abbatt, Jonathan P. D.

    2016-05-01

    Biomass burning organic aerosol (BBOA) can be emitted from natural forest fires and human activities such as agricultural burning and domestic energy generation. BBOA is strongly associated with atmospheric brown carbon (BrC) that absorbs near-ultraviolet and visible light, resulting in significant impacts on regional visibility degradation and radiative forcing. The mixing state of BBOA can play a critical role in the prediction of aerosol optical properties. In this work, single-particle measurements from a Soot-Particle Aerosol Mass Spectrometer coupled with a light scattering module (LS-SP-AMS) were performed to examine the mixing state of BBOA, refractory black carbon (rBC), and potassium (K, a tracer for biomass burning aerosol) in an air mass influenced by wildfire emissions transported from northern Québec to Toronto, representing aged biomass burning plumes. Cluster analysis of single-particle measurements identified five BBOA-related particle types. rBC accounted for 3-14 wt % of these particle types on average. Only one particle type exhibited a strong ion signal for K+, with mass spectra characterized by low molecular weight organic species. The remaining four particle types were classified based on the apparent molecular weight of the BBOA constituents. Two particle types were associated with low potassium content and significant amounts of high molecular weight (HMW) organic compounds. Our observations indicate non-uniform mixing of particles within a biomass burning plume in terms of molecular weight and illustrate that HMW BBOA can be a key contributor to low-volatility BrC observed in BBOA particles. The average mass absorption efficiency of low-volatility BBOA is about 0.8-1.1 m2 g-1 based on a theoretical closure calculation. Our estimates indicate that low-volatility BBOA contributes ˜ 33-44 % of thermo-processed particle absorption at 405 nm; and almost all of the BBOA absorption was associated with low-volatility organics.

  5. Seasonal variations of stable carbon isotopic composition of bulk aerosol carbon from Gosan site, Jeju Island in the East China Sea

    NASA Astrophysics Data System (ADS)

    Kundu, Shuvashish; Kawamura, Kimitaka

    2014-09-01

    This study explores the usefulness of stable isotopic composition (δ13C) along with other chemical tracers and air mass trajectory to identify the primary and secondary sources of carbonaceous aerosols. Aerosol samples (n = 84) were collected continuously from April 2003 to April 2004 at Gosan site in Jeju Island, South Korea. The concentrations of total carbon (TC), HCl fumed carbonate-free total carbon (fumed-TC) and their δ13C were measured online using elemental analyzer interfaced to isotope ratio mass spectrometer (EA-IRMS). Similar concentrations of TC and fumed-TC and their similar δ13C values suggest the insignificant contribution of inorganic carbon to Gosan aerosols. The monthly averaged δ13CTC showed the lowest in April/May (-24.2 to -24.4‰), which is related with the highest concentrations of oxalic acid (a secondary tracer). The result indicates an enhanced contribution of TC from secondary sources. The monthly averaged δ13CTC in July/August (-23.0 to -22.5‰) were similar to those in January/February (-23.1‰ to -22.7‰). However, chemical tracers and air mass transport pattern suggest that the pollution source regions in January/February are completely different from those in July/August. Higher δ13C values in July/August are aligned with higher concentration ratios of marine tracers (azelaic acid/TC and methanesulfonate/TC), suggesting an enhanced contribution of marine organic matter to the aerosol loading. Higher δ13C values in January/February are associated with higher concentrations of phthalic acid and K+/TC, indicating more contributions of carbonaceous aerosols from fossil fuel and C4-plant biomass combustion. This study demonstrates that δ13CTC, along with other chemical tracers and air mass trajectory, can be used as a tracer to understand the importance of primary versus secondary pollution sources of carbonaceous aerosols in the atmosphere.

  6. Apportionment of Primary and Secondary Organic Aerosols in Southern California During the 2005 Study of Organic Aerosols in Riverside (SOAR-1)

    EPA Science Inventory

    Ambient sampling was conducted in Riverside, California during the 2005 Study of Organic Aerosols in Riverside to characterize the composition and sources of organic aerosol using a variety of state-of-the-art instrumentation and source apportionment techniques.

  7. Seasonal and spatial trends in the sources of fine particle organic carbon in Israel, Jordan, and Palestine

    NASA Astrophysics Data System (ADS)

    von Schneidemesser, Erika; Zhou, Jiabin; Stone, Elizabeth A.; Schauer, James J.; Qasrawi, Radwan; Abdeen, Ziad; Shpund, Jacob; Vanger, Arye; Sharf, Geula; Moise, Tamar; Brenner, Shmuel; Nassar, Khaled; Saleh, Rami; Al-Mahasneh, Qusai M.; Sarnat, Jeremy A.

    2010-09-01

    A study of carbonaceous particulate matter (PM) was conducted in the Middle East at sites in Israel, Jordan, and Palestine. The sources and seasonal variation of organic carbon, as well as the contribution to fine aerosol (PM 2.5) mass, were determined. Of the 11 sites studied, Nablus had the highest contribution of organic carbon (OC), 29%, and elemental carbon (EC), 19%, to total PM 2.5 mass. The lowest concentrations of PM 2.5 mass, OC, and EC were measured at southern desert sites, located in Aqaba, Eilat, and Rachma. The OC contribution to PM 2.5 mass at these sites ranged between 9.4% and 16%, with mean annual PM 2.5 mass concentrations ranging from 21 to 25 ug m -3. These sites were also observed to have the highest OC to EC ratios (4.1-5.0), indicative of smaller contributions from primary combustion sources and/or a higher contribution of secondary organic aerosol. Biomass burning and vehicular emissions were found to be important sources of carbonaceous PM in this region at the non-southern desert sites, which together accounted for 30%-55% of the fine particle organic carbon at these sites. The fraction of measured OC unapportioned to primary sources (1.4 μgC m -3 to 4.9 μgC m -3; 30%-74%), which has been shown to be largely from secondary organic aerosol, is relatively constant at the sites examined in this study. This suggests that secondary organic aerosol is important in the Middle East during all seasons of the year.

  8. Characterization of fresh and aged organic aerosol emissions from meat charbroiling

    NASA Astrophysics Data System (ADS)

    Kaltsonoudis, Christos; Kostenidou, Evangelia; Louvaris, Evangelos; Psichoudaki, Magda; Tsiligiannis, Epameinondas; Florou, Kalliopi; Liangou, Aikaterini; Pandis, Spyros N.

    2017-06-01

    Cooking emissions can be a significant source of fine particulate matter in urban areas. In this study the aerosol- and gas-phase emissions from meat charbroiling were characterized. Greek souvlakia with pork were cooked using a commercial charbroiler and a fraction of the emissions were introduced into a smog chamber where after a characterization phase they were exposed to UV illumination and oxidants. The particulate and gas phases were characterized by a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a proton-transfer-reaction mass spectrometer (PTR-MS) correspondingly. More than 99 % of the aerosol emitted was composed of organic compounds, while black carbon (BC) contributed 0.3 % and the inorganic species less than 0.5 % of the total aerosol mass. The initial O : C ratio was approximately 0.09 and increased up to 0.30 after a few hours of chemical aging (exposures of 1010 molecules cm-3 s for OH and 100 ppb h for ozone). The initial and aged AMS spectra differed considerably (θ = 27°). Ambient measurements were also conducted during Fat Thursday in Patras, Greece, when traditionally meat is charbroiled everywhere in the city. Positive matrix factorization (PMF) revealed that cooking organic aerosol (COA) reached up to 85 % of the total OA from 10:00 to 12:00 LST that day. The ambient COA factor in two major Greek cities had a mass spectrum during spring and summer similar to the aged meat charbroiling emissions. In contrast, the ambient COA factor during winter resembled strongly the fresh laboratory meat charbroiling emissions.

  9. Organic aerosols and inorganic species from post-harvest agricultural-waste burning emissions over northern India: impact on mass absorption efficiency of elemental carbon.

    PubMed

    Rajput, Prashant; Sarin, M M; Sharma, Deepti; Singh, Darshan

    2014-01-01

    Atmospheric PM2.5 (particulate matter with aerodynamic diameter of ≤ 2.5 μm), collected from a source region [Patiala: 30.2 °N; 76.3 °E; 250 m above mean sea level] of emissions from post-harvest agricultural-waste (paddy-residue) burning in the Indo-Gangetic Plain (IGP), North India, has been studied for its chemical composition and impact on regional atmospheric radiative forcing. On average, organic aerosol mass accounts for 63% of PM2.5, whereas the contribution of elemental carbon (EC) is ∼3.5%. Sulphate, nitrate and ammonium contribute up to ∼85% of the total water-soluble inorganic species (WSIS), which constitutes ∼23% of PM2.5. The potassium-to-organic carbon ratio from paddy-residue burning emissions (KBB(+)/OC: 0.05 ± 0.01) is quite similar to that reported from Amazonian and Savanna forest-fires; whereas non-sea-salt-sulphate-to-OC ratio (nss-SO4(2-)/OC: 0.21) and nss-SO4(2-)/EC ratio of 2.6 are significantly higher (by factor of 5 to 8). The mass absorption efficiency of EC (3.8 ± 1.3 m(2) g(-1)) shows significant decrease with a parallel increase in the concentrations of organic aerosols and scattering species (sulphate and nitrate). A cross plot of OC/EC and nss-SO4(2-)/EC ratios show distinct differences for post-harvest burning emissions from paddy-residue as compared to those from fossil-fuel combustion sources in south-east Asia.

  10. Emissions of Black Carbon, Organic, and Inorganic Aerosols From Biomass Burning in North America and Asia in 2008

    NASA Technical Reports Server (NTRS)

    Kondo, Y.; Matsui, H.; Moteki, N.; Sahu, L.; Takegawa, N.; Kajino, M.; Zhao, Y.; Cubison, M. J.; Jimenez, J. L.; Vay, S.; hide

    2011-01-01

    Reliable assessment of the impact of aerosols emitted from boreal forest fires on the Arctic climate necessitates improved understanding of emissions and the microphysical properties of carbonaceous (black carbon (BC) and organic aerosols (OA)) and inorganic aerosols. The size distributions of BC were measured by an SP2 based on the laser-induced incandescence technique on board the DC-8 aircraft during the NASA ARCTAS campaign. Aircraft sampling was made in fresh plumes strongly impacted by wildfires in North America (Canada and California) in summer 2008 and in those transported from Asia (Siberia in Russia and Kazakhstan) in spring 2008. We extracted biomass burning plumes using particle and tracer (CO, CH3CN, and CH2Cl2) data. OA constituted the dominant fraction of aerosols mass in the submicron range. The large majority of the emitted particles did not contain BC. We related the combustion phase of the fire as represented by the modified combustion efficiency (MCE) to the emission ratios between BC and other species. In particular, we derived the average emission ratios of BC/CO = 2.3 +/- 2.2 and 8.5 +/- 5.4 ng/cu m/ppbv for BB in North America and Asia, respectively. The difference in the BC/CO emission ratios is likely due to the difference in MCE. The count median diameters and geometric standard deviations of the lognormal size distribution of BC in the BB plumes were 136-141 nm and 1.32-1.36, respectively, and depended little on MCE. These BC particles were thickly coated, with shell/core ratios of 1.3-1.6. These parameters can be used directly for improving model estimates of the impact of BB in the Arctic.

  11. Light absorbing organic carbon from prescribed and laboratory biomass burning and gasoline vehicle emissions

    EPA Science Inventory

    The light absorption of carbonaceous aerosols plays an important role in the atmospheric radiation balance. Light-absorbing organic carbon (OC), also called brown carbon (BrC), from laboratory-based biomass burning (BB) has been studied intensively to understand the contribution ...

  12. Wet Deposition Flux of Reactive Organic Carbon

    NASA Astrophysics Data System (ADS)

    Safieddine, S.; Heald, C. L.

    2016-12-01

    Reactive organic carbon (ROC) is the sum of non-methane volatile organic compounds (NMVOCs) and primary and secondary organic aerosols (OA). ROC plays a key role in driving the chemistry of the atmosphere, affecting the hydroxyl radical concentrations, methane lifetime, ozone formation, heterogeneous chemical reactions, and cloud formation, thereby impacting human health and climate. Uncertainties on the lifecycle of ROC in the atmosphere remain large. In part this can be attributed to the large uncertainties associated with the wet deposition fluxes. Little is known about the global magnitude of wet deposition as a sink of both gas and particle phase organic carbon, making this an important area for research and sensitivity testing in order to better understand the global ROC budget. In this study, we simulate the wet deposition fluxes of the reactive organic carbon of the troposphere using a global chemistry transport model, GEOS-Chem. We start by showing the current modeled global distribution of ROC wet deposition fluxes and investigate the sensitivity of these fluxes to variability in Henry's law solubility constants and spatial resolution. The average carbon oxidation state (OSc) is a useful metric that depicts the degree of oxidation of atmospheric reactive carbon. Here, we present for the first time the simulated gas and particle phase OSc of the global troposphere. We compare the OSc in the wet deposited reactive carbon flux and the dry deposited reactive carbon flux to the OSc of atmospheric ROC to gain insight into the degree of oxidation in deposited material and, more generally, the aging of organic material in the troposphere.

  13. Vertical dependence of black carbon, sulphate and biomass burning aerosol radiative forcing

    NASA Astrophysics Data System (ADS)

    Samset, Bjørn H.; Myhre, Gunnar

    2011-12-01

    A global radiative transfer model is used to calculate the vertical profile of shortwave radiative forcing from a prescribed amount of aerosols. We study black carbon (BC), sulphate (SO4) and a black and organic carbon mixture typical of biomass burning (BIO), by prescribing aerosol burdens in layers between 1000 hPa and 20 hPa and calculating the resulting direct radiative forcing divided by the burden (NDRF). We find a strong sensitivity in the NDRF for BC with altitude, with a tenfold increase between BC close to the surface and the lower part of the stratosphere. Clouds are a major contributor to this dependence with altitude, but other factors also contribute. We break down and explain the different physical contributors to this strong sensitivity. The results show a modest regional dependence of the altitudinal dependence of BC NDRF between industrial regions, while for regions with properties deviating from the global mean NDRF variability is significant. Variations due to seasons and interannual changes in cloud conditions are found to be small. We explore the effect that large altitudinal variation in NDRF may have on model estimates of BC radiative forcing when vertical aerosol distributions are insufficiently constrained, and discuss possible applications of the present results for reducing inter-model differences.

  14. Light-absorbing oligomer formation in secondary organic aerosol from reactive uptake of isoprene epoxydiols.

    PubMed

    Lin, Ying-Hsuan; Budisulistiorini, Sri Hapsari; Chu, Kevin; Siejack, Richard A; Zhang, Haofei; Riva, Matthieu; Zhang, Zhenfa; Gold, Avram; Kautzman, Kathryn E; Surratt, Jason D

    2014-10-21

    Secondary organic aerosol (SOA) produced from reactive uptake and multiphase chemistry of isoprene epoxydiols (IEPOX) has been found to contribute substantially (upward of 33%) to the fine organic aerosol mass over the Southeastern U.S. Brown carbon (BrC) in rural areas of this region has been linked to secondary sources in the summer when the influence of biomass burning is low. We demonstrate the formation of light-absorbing (290 < λ < 700 nm) SOA constituents from reactive uptake of trans-β-IEPOX onto preexisting sulfate aerosols as a potential source of secondary BrC. IEPOX-derived BrC generated in controlled chamber experiments under dry, acidic conditions has an average mass absorption coefficient of ∼ 300 cm(2) g(-1). Chemical analyses of SOA constituents using UV-visible spectroscopy and high-resolution mass spectrometry indicate the presence of highly unsaturated oligomeric species with molecular weights separated by mass units of 100 (C5H8O2) and 82 (C5H6O) coincident with the observations of enhanced light absorption, suggesting such oligomers as chromophores, and potentially explaining one source of humic-like substances (HULIS) ubiquitously present in atmospheric aerosol. Similar light-absorbing oligomers were identified in fine aerosol collected in the rural Southeastern U.S., supporting their atmospheric relevance and revealing a previously unrecognized source of oligomers derived from isoprene that contributes to ambient fine aerosol mass.

  15. Comparison of methods for the quantification of the different carbon fractions in atmospheric aerosol samples

    NASA Astrophysics Data System (ADS)

    Nunes, Teresa; Mirante, Fátima; Almeida, Elza; Pio, Casimiro

    2010-05-01

    Atmospheric carbon consists of: organic carbon (OC, including various organic compounds), elemental carbon (EC, or black carbon [BC]/soot, a non-volatile/light-absorbing carbon), and a small quantity of carbonate carbon. Thermal/optical methods (TOM) have been widely used for quantifying total carbon (TC), OC, and EC in ambient and source particulate samples. Unfortunately, the different thermal evolution protocols in use can result in a wide elemental carbon-to-total carbon variation. Temperature evolution in thermal carbon analysis is critical to the allocation of carbon fractions. Another critical point in OC and EC quantification by TOM is the interference of carbonate carbon (CC) that could be present in the particulate samples, mainly in the coarse fraction of atmospheric aerosol. One of the methods used to minimize this interference consists on the use of a sample pre-treatment with acid to eliminate CC prior to thermal analysis (Chow et al., 2001; Pio et al., 1994). In Europe, there is currently no standard procedure for determining the carbonaceous aerosol fraction, which implies that data from different laboratories at various sites are of unknown accuracy and cannot be considered comparable. In the framework of the EU-project EUSAAR, a comprehensive study has been carried out to identify the causes of differences in the EC measured using different thermal evolution protocols. From this study an optimised protocol, the EUSAAR-2 protocol, was defined (Cavali et al., 2009). During the last two decades thousands of aerosol samples have been taken over quartz filters at urban, industrial, rural and background sites, and also from plume forest fires and biomass burning in a domestic closed stove. These samples were analysed for OC and EC, by a TOM, similar to that in use in the IMPROVE network (Pio et al., 2007). More recently we reduced the number of steps in thermal evolution protocols, without significant repercussions in the OC/EC quantifications. In order

  16. Hygroscopic growth of water soluble organic carbon isolated from atmospheric aerosol collected at US national parks and Storm Peak Laboratory

    NASA Astrophysics Data System (ADS)

    Taylor, Nathan F.; Collins, Don R.; Lowenthal, Douglas H.; McCubbin, Ian B.; Gannet Hallar, A.; Samburova, Vera; Zielinska, Barbara; Kumar, Naresh; Mazzoleni, Lynn R.

    2017-02-01

    Due to the atmospheric abundance and chemical complexity of water soluble organic carbon (WSOC), its contribution to the hydration behavior of atmospheric aerosol is both significant and difficult to assess. For the present study, the hygroscopicity and CCN activity of isolated atmospheric WSOC particulate matter was measured without the compounding effects of common, soluble inorganic aerosol constituents. WSOC was extracted with high purity water from daily high-volume PM2.5 filter samples and separated from water soluble inorganic constituents using solid-phase extraction. The WSOC filter extracts were concentrated and combined to provide sufficient mass for continuous generation of the WSOC-only aerosol over the combined measurement time of the tandem differential mobility analyzer and coupled scanning mobility particle sizer-CCN counter used for the analysis. Aerosol samples were taken at Great Smoky Mountains National Park during the summer of 2006 and fall-winter of 2007-2008; Mount Rainier National Park during the summer of 2009; Storm Peak Laboratory (SPL) near Steamboat Springs, Colorado, during the summer of 2010; and Acadia National Park during the summer of 2011. Across all sampling locations and seasons, the hygroscopic growth of WSOC samples at 90 % RH, expressed in terms of the hygroscopicity parameter, κ, ranged from 0.05 to 0.15. Comparisons between the hygroscopicity of WSOC and that of samples containing all soluble materials extracted from the filters implied a significant modification of the hydration behavior of inorganic components, including decreased hysteresis separating efflorescence and deliquescence and enhanced water uptake between 30 and 70 % RH.

  17. Photochemical Aging of Organic Aerosols: A Laboratory Study

    NASA Astrophysics Data System (ADS)

    Papanastasiou, Dimitrios K.; Kostenidou, Evangelia; Gkatzelis, Georgios I.; Psichoudaki, Magdalini; Louvaris, Evangelos; Pandis, Spyros N.

    2014-05-01

    Organic aerosols (OA) are either emitted directly (primary OA) or formed (secondary OA) in the atmosphere and consist of an extremely complex mixture of thousands of organic compounds. Although the scientific community has put significant effort, in the past few decades, to understand organic aerosol (OA) formation, evolution and fate in the atmosphere, traditional models often fail to reproduce the ambient OA levels. Secondary organic aerosol (SOA) formed, in traditional laboratory chamber experiments, from the gas phase oxidation of known precursors, such as α-pinene, is semi-volatile and with an O:C ratio of around 0.4. In contrast, OA found in the atmosphere is significantly less volatile, while the O:C ratio often ranges from 0.5 to 1. In conclusion, there is a significant gap of knowledge in our understanding of OA formation and photochemical transformation in the atmosphere. There is increased evidence that homogeneous gas phase aging by OH radicals might be able to explain, at least in part, the significantly higher OA mass loadings observed and also the oxidation state and volatility of OA in the atmosphere. In this study, laboratory chamber experiments were performed to study the role of the continued oxidation of first generation volatile and semi-volatile species by OH radicals in the evolution of the SOA characteristics (mass concentration, volatility, and oxidation state). Ambient air mixtures or freshly formed SOA from α-pinene ozonolysis were used as the source of organic aerosols and semi-volatile species. The initial mixture of organic aerosols and gas phase species (volatile and semi-volatile) was then exposed to atmospheric concentrations of OH radicals to study the aging of aerosols. Experiments were performed with various OH radical sources (H2O2 or HONO) and under various NOx conditions. A suite of instruments was employed to characterize both the gas and the aerosol phase. A Scanning Mobility Particle Sizer (SMPS) and a High

  18. The Chemical Composition and Mixing State of Sea Spray Aerosol and Organic Aerosol in the Winter-Spring Arctic

    NASA Astrophysics Data System (ADS)

    Kirpes, R.; Bondy, A. L.; Bonanno, D.; Moffet, R.; Wang, B.; Laskin, A.; Ault, A. P.; Pratt, K.

    2016-12-01

    The Arctic region is undergoing rapid transformations and loss of sea ice due to climate change. With increased sea ice fracturing resulting in greater open ocean surface, winter emissions of sea spray aerosol (SSA) are expected to be increasing. Additionally, during the winter-spring transition, Arctic haze contributes to the Arctic aerosol budget. The magnitude of aerosol climate effects depends on the aerosol composition and mixing state (distribution of chemical species within and between particles). However, few studies of aerosol chemistry have been conducted in the winter Arctic, despite it being a time when aerosol impacts on clouds are expected to be significant. To study aerosol composition and mixing state in the winter Arctic, atmospheric particles were collected near Barrow, Alaska in January and February 2014 for off-line individual particle chemical analysis. SSA was the most prevalent particle type observed. Sulfate and nitrate were observed to be internally mixed with SSA and organic aerosol. Greater than 98% of observed SSA particles contained organic content, with 15-35% organic volume fraction on average for individual particles. The SSA organic compounds consisted of carbohydrates, lipids, and fatty acids found in the seawater surface microlayer. SSA was determined to be emitted from open leads, while transported sulfate and nitrate contributed to aging of SSA and organic aerosol. Determining the aerosol chemical composition and mixing state in the winter Arctic will further the understanding of how individual aerosol particles impact climate through radiative effects and cloud formation.

  19. Evaluations of tropospheric aerosol properties simulated by the community earth system model with a sectional aerosol microphysics scheme

    PubMed Central

    Toon, Owen B.; Bardeen, Charles G.; Mills, Michael J.; Fan, Tianyi; English, Jason M.; Neely, Ryan R.

    2015-01-01

    Abstract A sectional aerosol model (CARMA) has been developed and coupled with the Community Earth System Model (CESM1). Aerosol microphysics, radiative properties, and interactions with clouds are simulated in the size‐resolving model. The model described here uses 20 particle size bins for each aerosol component including freshly nucleated sulfate particles, as well as mixed particles containing sulfate, primary organics, black carbon, dust, and sea salt. The model also includes five types of bulk secondary organic aerosols with four volatility bins. The overall cost of CESM1‐CARMA is approximately ∼2.6 times as much computer time as the standard three‐mode aerosol model in CESM1 (CESM1‐MAM3) and twice as much computer time as the seven‐mode aerosol model in CESM1 (CESM1‐MAM7) using similar gas phase chemistry codes. Aerosol spatial‐temporal distributions are simulated and compared with a large set of observations from satellites, ground‐based measurements, and airborne field campaigns. Simulated annual average aerosol optical depths are lower than MODIS/MISR satellite observations and AERONET observations by ∼32%. This difference is within the uncertainty of the satellite observations. CESM1/CARMA reproduces sulfate aerosol mass within 8%, organic aerosol mass within 20%, and black carbon aerosol mass within 50% compared with a multiyear average of the IMPROVE/EPA data over United States, but differences vary considerably at individual locations. Other data sets show similar levels of comparison with model simulations. The model suggests that in addition to sulfate, organic aerosols also significantly contribute to aerosol mass in the tropical UTLS, which is consistent with limited data. PMID:27668039

  20. Global Impacts of Gas-Phase Chemistry-Aerosol Interactions on Direct Radiative Forcing by Anthropogenic Aerosols and Ozone

    NASA Technical Reports Server (NTRS)

    Liao, Hong; Seinfeld, John H.

    2005-01-01

    We present here a first global modeling study on the influence of gas-phase chemistry/aerosol interactions on estimates of anthropogenic forcing by tropospheric O3 and aerosols. Concentrations of gas-phase species and sulfate, nitrate, ammonium, black carbon, primary organic carbon, secondary organic carbon, sea salt, and mineral dust aerosols in the preindustrial, present-day, and year 2100 (IPCC SRES A2) atmospheres are simulated online in the Goddard Institute for Space Studies general circulation model II' (GISS GCM II'). With fully coupled chemistry and aerosols, the preindustrial, presentday, and year 2100 global burdens of tropospheric ozone are predicted to be 190, 319, and 519 Tg, respectively. The burdens of sulfate, nitrate, black carbon, and organic carbon are predicted respectively to be 0.32. 0.18, 0.01, 0.33 Tg in preindustrial time, 1.40, 0.48, 0.23, 1.60 Tg in presentday, and 1.37, 1.97, 0.54, 3.31 Tg in year 2100. Anthropogenic O3 is predicted to have a globally and annually averaged present-day forcing of +0.22 W m(sup -2) and year 2100 forcing of +0.57 W m(sup -2) at the top of the atmosphere (TOA). Net anthropogenic TOA forcing by internally mixed sulfate, nitrate, organic carbon, and black carbon aerosols is estimated to be virtually zero in the present-day and +0.34 W m(sup -2) in year 2100, whereas it is predicted to be -0.39 W m(sup -2) in present-day and -0.61 W m(sup -2) in year 2100 if the aerosols are externally mixed. Heterogeneous reactions are shown to be important in affecting anthropogenic forcing. When reactions of N2O5, NO3, NO2, and HO2 on aerosols are accounted for, TOA anthropogenic O3 forcing is less by 20-45% in present-day and by 20-32% in year 2100 at mid to high latitudes in the Northern Hemisphere, as compared with values predicted in the absence of heterogeneous gas aerosol reactions. Mineral dust uptake of HNO3 and O3 is shown to have practically no influence on anthropogenic O3 forcing. Heterogeneous reactions of N2Os

  1. Black Carbon Concentration from Worldwide Aerosol Robotic Network (AERONET)

    NASA Technical Reports Server (NTRS)

    Schuster, Greg; Dubovik, Oleg; Holben, Brent; Clothiaux, Eugene

    2008-01-01

    Worldwide black carbon concentration measurements are needed to assess the efficacy of the carbon emissions inventory and transport model output. This requires long-term measurements in many regions, as model success in one region or season does not apply to all regions and seasons. AERONET is an automated network of more than 180 surface radiometers located throughout the world. The sky radiance measurements obtained by AERONET are inverted to provide column-averaged aerosol refractive indices and size distributions for the AERONET database, which we use to derive column-averaged black carbon concentrations and specific absorptions that are constrained by the measured radiation field. This provides a link between AERONET sky radiance measurements and the elemental carbon concentration of transport models without the need for an optics module in the transport model. Knowledge of both the black carbon concentration and aerosol absorption optical depth (i.e., input and output of the optics module) will enable improvements to the transport model optics module.

  2. Formation and aging of secondary organic aerosol from toluene: Changes in chemical composition, volatility, and hygroscopicity

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.

    Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NO x under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OS c), and mass yield. The OA oxidation state generallymore » increased during photo-oxidation, and the final OA OS c ranged from –0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. In conclusion, there was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

  3. Formation and aging of secondary organic aerosol from toluene: Changes in chemical composition, volatility, and hygroscopicity

    DOE PAGES

    Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.; ...

    2015-07-24

    Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NO x under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OS c), and mass yield. The OA oxidation state generallymore » increased during photo-oxidation, and the final OA OS c ranged from –0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. In conclusion, there was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

  4. A Monte-Carlo Analysis of Organic Volatility with Aerosol Microphysics

    NASA Astrophysics Data System (ADS)

    Gao, Chloe; Tsigaridis, Kostas; Bauer, Susanne E.

    2017-04-01

    A newly developed box model, MATRIX-VBS, includes the volatility-basis set (VBS) framework in an aerosol microphysical scheme MATRIX (Multiconfiguration Aerosol TRacker of mIXing state), which resolves aerosol mass and number concentrations and aerosol mixing state. The new scheme advanced the representation of organic aerosols in models by improving the traditional and simplistic treatment of organic aerosols as non-volatile and with a fixed size distribution. Further development includes adding the condensation of organics on coarse mode aerosols - dust and sea salt, thus making all organics in the system semi-volatile. To test and simplify the model, a Monte-Carlo analysis is performed to pin point which processes affect organics the most under varied chemical and meteorological conditions. Since the model's parameterizations have the ability to capture a very wide range of conditions, all possible scenarios on Earth across the whole parameter space, including temperature, humidity, location, emissions and oxidant levels, are examined. The Monte-Carlo simulations provide quantitative information on the sensitivity of the newly developed model and help us understand how organics are affecting the size distribution, mixing state and volatility distribution at varying levels of meteorological conditions and pollution levels. In addition, these simulations give information on which parameters play a critical role in the aerosol distribution and evolution in the atmosphere and which do not, that will facilitate the simplification of the box model, an important step in its implementation in the global model GISS ModelE as a module.

  5. Effects of morphology on the radiative properties of internally mixed light absorbing carbon aerosols with different aging status.

    PubMed

    Cheng, Tianhai; Wu, Yu; Chen, Hao

    2014-06-30

    Light absorbing carbon aerosols play a substantial role in climate change through radiative forcing, which is the dominant absorber of solar radiation. Radiative properties of light absorbing carbon aerosols are strongly dependent on the morphological factors and the mixing mechanism of black carbon with other aerosol components. This study focuses on the morphological effects on the optical properties of internally mixed light absorbing carbon aerosols using the numerically exact superposition T-matrix method. Three types aerosols with different aging status such as freshly emitted BC particles, thinly coated light absorbing carbon aerosols, heavily coated light absorbing carbon aerosols are studied. Our study showed that morphological factors change with the aging of internally mixed light absorbing carbon aerosols to result in a dramatic change in their optical properties. The absorption properties of light absorbing carbon aerosols can be enhanced approximately a factor of 2 at 0.67 um, and these enhancements depend on the morphological factors. A larger shell/core diameter ratio of volume-equivalent shell-core spheres (S/C), which indicates the degree of coating, leads to stronger absorption. The enhancement of absorption properties accompanies a greater enhancement of scattering properties, which is reflected in an increase in single scattering albedo (SSA). The enhancement of single scattering albedo due to the morphological effects can reach a factor of 3.75 at 0.67 μm. The asymmetry parameter has a similar yet smaller enhancement. Moreover, the corresponding optical properties of shell-and-core model determined by using Lorenz -Mie solutions are presented for comparison. We found that the optical properties of internally mixed light absorbing carbon aerosol can differ fundamentally from those calculated for the Mie theory shell-and-core model, particularly for thinly coated light absorbing carbon aerosols. Our studies indicate that the complex morphology

  6. What Aerosol Water do Organic Compounds See?

    EPA Science Inventory

    Large amounts of aerosol water are associated with inorganic salts such as ammonium sulfate with generally smaller but important contributions from hydrophilic organics. Ambient aerosols can be externally or internally mixed in addition to containing one or multiple phases. The d...

  7. Field Studies for Secondary Organic Aerosol in the Transboundary Air

    NASA Astrophysics Data System (ADS)

    Irei, S.; Takami, A.; Sadanaga, Y.; Nozoe, S.; Hayashi, M.; Hara, K.; Arakaki, T.; Hatakeyama, S.; Miyoshi, T.; Yokouchi, Y.; Bandow, H.

    2014-12-01

    To study formation of secondary organic aerosol (SOA) in the air outflowed from the Chinese continent and its fraction in an urban city located in downwind, we have conducted field studies at two background sites and one urban site in the western Japan: the Cape Hedo Aerosol and Atmospheric Monitoring Station (26.9˚N, 128.3˚E), the Fukue Atmospheric Monitoring Station (32.8˚N, 128.7˚E), and Fukuoka University (33.6˚N, 130.4˚E), respectively. During the studies, stable carbon isotope ratio (δ13C) of low-volatile water-soluble organic carbon (LV-WSOC) was measured in 24 h collected filter samples of total suspended particulate matter. Concentration of fine organic aerosol and the proportion of the signal at m/z 44 (ions from the carboxyl group) in the organic mass spectra (f44) were also measured by Aerodyne aerosol mass spectrometers. Limited to the Fukue site only, mixing ratios of trace gas species, such as aromatic hydrocarbons, NOx, and NOy, were also measured using GC-FID and NOx and NOyanalyzers for estimation of photochemical age (t[OH]). A case study in December 2010 showed that plots of δ13C versus f44 showed systematic variations at Hedo and Fukue. However, their trends were opposite. At Fukue the trend was consistent in the plot of δ13C of LV-WSOC versus t[OH] estimated by the NOx/NOy or the hydrocarbon ratios, indicating influence of SOA. The systematic trends aforementioned qualitatively agreed with a binary mixture model of SOA with background LV-WSOC having the f44 of ~0.06 and the δ13C of -17‰ or higher, implication of some influence of primary emission associated with C4plants. Given that the LV-WSOC at the urban Fukuoka site was a binary mixture, a mass balance for δ13C was constructed below. In the equation, δ13CMix, δ13CLocal, δ13CTrans, and FLocal are δ13C of binary LV-WSOC mixture, δ13C of LV-WSOC from local emission origin, δ13C of LV-WSOC from transboundary pollution origin, and a fraction of LV-WSOC from local emission

  8. Influence of Aerosol Acidity on the Formation of Secondary Organic Aerosol from Biogenic Precursor Hydrocarbons

    EPA Science Inventory

    Secondary organic aerosol (SOA) formation and dynamics may be important factors for the role of aerosols in adverse health effects, visibility and climate change. Formation of SOA occurs when a parent volatile organic compound is oxidized to create products that form in a conden...

  9. Carbonaceous Aerosol Removal During Precipitation Events: Climate Implications

    NASA Astrophysics Data System (ADS)

    Gaffney, J. S.; Marley, N. A.; Bridges, G. L.; Marchany-Rivera, A.; Begum, M.

    2009-12-01

    Atmospheric aerosols and their links to clouds are one of the main focus areas of the Department of Energy’s Atmospheric Systems Research, due to the fact that aerosols and clouds constitute the major uncertainties in radiative forcing that need to be reduced for more accurate modeling of climate, particularly regional climate. The impact of absorbing aerosols on radiative balance of the atmosphere will depend on their atmospheric lifetimes as well as their UV-visible absorption profiles. Aerosol lifetimes depend on the aerosols ability to take up water and grow to sufficient size to be either removed by gravitational settling or to act as cloud condensation nuclei and be removed by precipitation scavenging. The investigation of uv-visible absorbing aerosols is underway using a seven-channel aethalometer to evaluate the change in aerosol optical absorption during precipitation events. Angstrom absorption exponents (AAEs) are determined before, during, and after rain events to examine the impact on the aerosol absorption profiles anticipated by removal of the water soluble short-wave absorbing species (i.e. HULIS) that can be produced by photochemical oxidation of biogenic emissions (isoprene, monoterpenes, sesquiterpenes). Aerosol absorption data are presented from observations made at the University of Arkansas at Little Rock and other sites, which clearly show that a significant amount of absorbing carbon is not removed during rain events, and that the organic matter removed is likely secondary organics produced from biogenic precursors. The dissolved organic carbon measured in precipitation samples along with determinations of natural radionuclide tracers are also used to help examine the extent of carbonaceous aerosol removal by precipitation. The data are discussed in terms of the potential impacts of anthropogenic enhancement of aerosol absorption by secondary organic aerosols adding to atmospheric heating and changes in atmospheric dynamics. The potential

  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. The effects of isoprene and NOx on secondary organic aerosols formed through reversible and irreversible uptake to aerosol water

    NASA Astrophysics Data System (ADS)

    El-Sayed, Marwa M. H.; Ortiz-Montalvo, Diana L.; Hennigan, Christopher J.

    2018-01-01

    Isoprene oxidation produces water-soluble organic gases capable of partitioning to aerosol liquid water. The formation of secondary organic aerosols through such aqueous pathways (aqSOA) can take place either reversibly or irreversibly; however, the split between these fractions in the atmosphere is highly uncertain. The aim of this study was to characterize the reversibility of aqSOA formed from isoprene at a location in the eastern United States under substantial influence from both anthropogenic and biogenic emissions. The reversible and irreversible uptake of water-soluble organic gases to aerosol water was characterized in Baltimore, Maryland, USA, using measurements of particulate water-soluble organic carbon (WSOCp) in alternating dry and ambient configurations. WSOCp evaporation with drying was observed systematically throughout the late spring and summer, indicating reversible aqSOA formation during these times. We show through time lag analyses that WSOCp concentrations, including the WSOCp that evaporates with drying, peak 6 to 11 h after isoprene concentrations, with maxima at a time lag of 9 h. The absolute reversible aqSOA concentrations, as well as the relative amount of reversible aqSOA, increased with decreasing NOx / isoprene ratios, suggesting that isoprene epoxydiol (IEPOX) or other low-NOx oxidation products may be responsible for these effects. The observed relationships with NOx and isoprene suggest that this process occurs widely in the atmosphere, and is likely more important in other locations characterized by higher isoprene and/or lower NOx levels. This work underscores the importance of accounting for both reversible and irreversible uptake of isoprene oxidation products to aqueous particles.

  12. Time-resolved molecular characterization of organic aerosols by PILS + UPLC/ESI-Q-TOFMS

    NASA Astrophysics Data System (ADS)

    Zhang, X.; Dalleska, N. F.; Huang, D. D.; Bates, K. H.; Sorooshian, A.; Flagan, R. C.; Seinfeld, J. H.

    2016-04-01

    Real-time and quantitative measurement of particulate matter chemical composition represents one of the most challenging problems in the field of atmospheric chemistry. In the present study, we integrate the Particle-into-Liquid Sampler (PILS) with Ultra Performance Liquid Chromatography/Electrospray ionization Quadrupole Time-of-Flight High-Resolution/Mass Spectrometry (UPLC/ESI-Q-TOFMS) for the time-resolved molecular speciation of chamber-derived secondary organic aerosol (SOA). The unique aspect of the combination of these two well-proven techniques is to provide quantifiable molecular-level information of particle-phase organic compounds on timescales of minutes. We demonstrate that the application of the PILS + UPLC/ESI-Q-TOFMS method is not limited to water-soluble inorganic ions and organic carbon, but is extended to slightly water-soluble species through collection efficiency calibration together with sensitivity and linearity tests. By correlating the water solubility of individual species with their O:C ratio, a parameter that is available for aerosol ensembles as well, we define an average aerosol O:C ratio threshold of 0.3, above which the PILS overall particulate mass collection efficiency approaches ∼0.7. The PILS + UPLC/ESI-Q-TOFMS method can be potentially applied to probe the formation and evolution mechanism of a variety of biogenic and anthropogenic SOA systems in laboratory chamber experiments. We illustrate the application of this method to the reactive uptake of isoprene epoxydiols (IEPOX) on hydrated and acidic ammonium sulfate aerosols.

  13. Influence of local production and vertical transport on the organic aerosol budget over Paris

    NASA Astrophysics Data System (ADS)

    Janssen, R. H. H.; Tsimpidi, A. P.; Karydis, V. A.; Pozzer, A.; Lelieveld, J.; Crippa, M.; Prévôt, A. S. H.; Ait-Helal, W.; Borbon, A.; Sauvage, S.; Locoge, N.

    2017-08-01

    We performed a case study of the organic aerosol (OA) budget during the MEGAPOLI campaign during summer 2009 in Paris. We combined aerosol mass spectrometer, gas phase chemistry, and atmospheric boundary layer (ABL) data and applied the MXL/MESSy column model. We find that during daytime, vertical mixing due to ABL growth has opposing effects on secondary organic aerosol (SOA) and primary organic aerosol (POA) concentrations. POA concentrations are mainly governed by dilution due to boundary layer expansion and transport of POA-depleted air from aloft, while SOA concentrations are enhanced by entrainment of SOA-rich air from the residual layer (RL). Further, local emissions and photochemical production control the diurnal cycle of SOA. SOA from intermediate volatility organic compounds constitutes about half of the locally formed SOA mass. Other processes that previously have been shown to influence the urban OA budget, such as aging of semivolatile and intermediate volatility organic compounds (S/IVOC), dry deposition of S/IVOCs, and IVOC emissions, are found to have minor influences on OA. Our model results show that the modern carbon content of the OA is driven by vertical and long-range transport, with a minor contribution from local cooking emissions. SOA from regional sources and resulting from aging and long-lived precursors can lead to high SOA concentrations above the ABL, which can strongly influence ground-based observations through downward transport. Sensitivity analysis shows that modeled SOA concentrations in the ABL are equally sensitive to ABL dynamics as to SOA concentrations transported from the RL.

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

    EPA Science Inventory

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

  15. Mercury bonds with carbon (OC and EC) in small aerosols (PM1) in the urbanized coastal zone of the Gulf of Gdansk (southern Baltic).

    PubMed

    Lewandowska, A U; Bełdowska, M; Witkowska, A; Falkowska, L; Wiśniewska, K

    2018-08-15

    PM1 aerosols were collected at the coastal station in Gdynia between 1st January and 31st December 2012. The main purpose of the study was to determine the variability in concentrations of mercury Hg(p), organic carbon (OC) and elemental carbon (EC) in PM1 aerosols under varying synoptic conditions in heating and non-heating periods. Additionally, sources of origin and bonds of mercury with carbon species were identified. The highest concentrations of Hg(p), OC and EC were found during the heating period. Then all analyzed PM1 components had a common, local origin related to the consumption of fossil fuels for heating purposes under conditions of lower air temperatures and poor dispersion of pollutants. Long periods without precipitation also led to the increase in concentration of all measured PM1 compounds. In heating period mercury correlated well with elemental carbon and primary and secondary organic carbon when air masses were transported from over the land. At that time, the role of transportation was of minor importance. In the non-heating period, the concentration of all analyzed compounds were lower than in the heating period, which could be associated with the reduced influence of combustion processes, higher precipitation and, in the case of mercury, also the evaporation of aerosols at higher air temperatures. However, when air masses were transported from over the sea or from the port/shipyard areas the mercury concentration increased significantly. In the first case higher air humidity, solar radiation and ozone concentration as well as the presence of marine aerosols could further facilitate the conversion of gaseous mercury into particulate mercury and its concentration increase. In the second case Hg(p) could be adsorbed on particles rich in elemental carbon and primary organic carbon emitted from ships. Copyright © 2018 Elsevier Inc. All rights reserved.

  16. EVIDENCE FOR ORGANOSULFATES IN SECONDARY ORGANIC AEROSOL

    EPA Science Inventory

    Recent work has shown that particle-phase reactions contribute to the formation of secondary organic aerosol (SOA), with enhancements of SOA yields in the presence of acidic seed aerosol. In this study, the chemical composition of SOA from the photooxidations of α-pinene and isop...

  17. Estimation of atmospheric columnar organic matter (OM) mass concentration from remote sensing measurements of aerosol spectral refractive indices

    NASA Astrophysics Data System (ADS)

    Zhang, Ying; Li, Zhengqiang; Sun, Yele; Lv, Yang; Xie, Yisong

    2018-04-01

    Aerosols have adverse effects on human health and air quality, changing Earth's energy balance and lead to climate change. The components of aerosol are important because of the different spectral characteristics. Based on the low hygroscopic and high scattering properties of organic matter (OM) in fine modal atmospheric aerosols, we develop an inversion algorithm using remote sensing to obtain aerosol components including black carbon (BC), organic matter (OM), ammonium nitrate-like (AN), dust-like (DU) components and aerosol water content (AW). In the algorithm, the microphysical characteristics (i.e. volume distribution and complex refractive index) of particulates are preliminarily separated to fine and coarse modes, and then aerosol components are retrieved using bimodal parameters. We execute the algorithm using remote sensing measurements of sun-sky radiometer at AERONET site (Beijing RADI) in a period from October of 2014 to January of 2015. The results show a reasonable distribution of aerosol components and a good fit for spectral feature calculations. The mean OM mass concentration in atmospheric column is account for 14.93% of the total and 56.34% of dry and fine-mode aerosol, being a fairly good correlation (R = 0.56) with the in situ observations near the surface layer.

  18. Molecular Diversity of Brown Carbon Chromophores in Biomass Burning Aerosol

    NASA Astrophysics Data System (ADS)

    Lin, P.; Laskin, A.; Laskin, J.; Fleming, L.; Nizkorodov, S.

    2017-12-01

    Brown carbon (BrC) is ubiquitous in the atmosphere and significant contributor to climate forcing. Understanding the environmental effects of BrC, its sources, formation, and atmospheric transformation mechanisms requires identification of BrC chromophores and characterization of their light-absorption properties. In this study, we investigate the chemical composition, molecular identity and optical properties of BrC chromophores associated with biomass burning aerosols emitted from burns of different biofuels during the NOAA FIREX/FireLab experiment. The results show that BrC in the biomass burning smoke contains organic compounds of various molecular structures, polarities, and volatilities. The relative contributions to light absorption from different classes of chromophores such as nitro-phenols, polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs and heterocyclic PAHs are quantified and are shown to be diverse among aerosol samples from different biofuel sources. Despite complexity of BrC, grouping its chromophores according to their polarity and volatility may simplify the parameters for modelling input.

  19. Sources of Water-soluble Organic Aerosol in the Southeastern United States - Evidence of SOA Formed Through Heterogeneous Reactions

    NASA Astrophysics Data System (ADS)

    Zhang, X.; Weber, R. J.

    2010-12-01

    Recent laboratory studies suggest partitioning of semi-volatile organic compounds (SVOCs) to liquid water followed by heterogeneous chemical transformation as a possible route to forming secondary organic aerosol (SOA). This paper will present results from observational studies of SOA formation using Water-Soluble Organic Carbon (WSOC) fraction of SOA, soluble brown carbon (e.g., light absorption spectra), organic acids and a number of aerosol source tracers in the Southeastern U.S., a region known for extensive biogenic and anthropogenic VOC emissions. Based on 24-h integrated filter measurements at 15 sites in the southeast throughout the year of 2007, a PMF analysis identified a factor characterized by the co-abundance of WSOC (58 percent of the total), oxalate (51 percent) and brown carbon (Abs365) (44 percent), which is consistent with the aqueous phase SOA formation mechanism in which water-soluble organic products from gas-phase photochemistry dissolve in liquid (fog/cloud droplets or particle water) and react further to form oligomers, light absorbing compounds, and light-weight organic acids, with oxalic acid being the most abundant one [Hecobian et al., 2010; Zhang et al., 2010]. The temporal variability of this factor correlated well with ambient temperature, possibly owing to the large impact from biogenic emissions, which are dependent on temperature and known to be significant over the southeast. PMF analysis of other data sets collected in Atlanta with online instruments during summer support these findings; as do other studies based on different data sets and data-analysis methods [Hennigan et al., 2008a; Hennigan et al., 2008b; Hennigan et al., 2008c; Hennigan et al., 2009]. Overall, we find that WSOC is largely secondary (roughly 75 to 85 percent) and estimate that 65 to 75 percent of the secondary WSOC formed in the southeast involves some form of aqueous phase chemical process. Hecobian, A., X. Zhang, M. Zheng, N. Frank, E. S. Edgerton, and R. J

  20. Primary sources and secondary formation of organic aerosols in Beijing, China.

    PubMed

    Guo, Song; Hu, Min; Guo, Qingfeng; Zhang, Xin; Zheng, Mei; Zheng, Jun; Chang, Chih Chung; Schauer, James J; Zhang, Renyi

    2012-09-18

    Ambient aerosol samples were collected at an urban site and an upwind rural site of Beijing during the CAREBEIJING-2008 (Campaigns of Air quality REsearch in BEIJING and surrounding region) summer field campaign. Contributions of primary particles and secondary organic aerosols (SOA) were estimated by chemical mass balance (CMB) modeling and tracer-yield method. The apportioned primary and secondary sources explain 73.8% ± 9.7% and 79.6% ± 10.1% of the measured OC at the urban and rural sites, respectively. Secondary organic carbon (SOC) contributes to 32.5 ± 15.9% of the organic carbon (OC) at the urban site, with 17.4 ± 7.6% from toluene, 9.7 ± 5.4% from isoprene, 5.1 ± 2.0% from α-pinene, and 2.3 ± 1.7% from β-caryophyllene. At the rural site, the secondary sources are responsible for 38.4 ± 14.4% of the OC, with the contributions of 17.3 ± 6.9%, 13.9 ± 9.1%, 5.6 ± 1.9%, and 1.7 ± 1.0% from toluene, isoprene, α-pinene, and β-caryophyllene, respectively. Compared with other regions in the world, SOA in Beijing is less aged, but the concentrations are much higher; between the sites, SOA is more aged and affected by regional transport at the urban site. The high SOA loading in Beijing is probably attributed to the high regional SOC background (~2 μg m(-3)). The toluene SOC concentration is high and comparable at the two sites, implying that some anthropogenic components, at least toluene SOA, are widespread in Beijing and represents a major factor in affecting the regional air quality. The aerosol gaseous precursor concentrations and temperature correlate well with SOA, both affecting SOA formation. The significant SOA enhancement with increasing water uptake and acidification indicates that the aqueous-phase reactions are largely responsible SOA formation in Beijing.

  1. Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chim, Man Mei; Cheng, Chiu Tung; Davies, James F.

    Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C 5Hmore » 8O 4) droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART) coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C 5) hydroxyl functionalization product (C 5H 8O 5) and a C 4 fragmentation product (C 4H 6O 3). These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon–carbon bond scission) of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model) coupled with the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase

  2. Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols

    DOE PAGES

    Chim, Man Mei; Cheng, Chiu Tung; Davies, James F.; ...

    2017-12-05

    Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C 5Hmore » 8O 4) droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART) coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C 5) hydroxyl functionalization product (C 5H 8O 5) and a C 4 fragmentation product (C 4H 6O 3). These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon–carbon bond scission) of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model) coupled with the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase

  3. A Global Assessment of Rain-Dissolved Organic Carbon

    NASA Astrophysics Data System (ADS)

    Safieddine, S.; Heald, C. L.

    2017-12-01

    Precipitation is the largest physical removal pathway of atmospheric organic carbon from the atmosphere. The removed carbon is transferred to the land and ocean in the form of dissolved organic carbon (DOC). Limited measurements have hindered efforts to characterize global DOC. In this poster presentation, we show the first simulated global DOC distribution based on a GEOS-Chem model simulation of the atmospheric reactive carbon budget. Over the ocean, simulated DOC concentrations are between 0.1 to 1 mgCL-1 with a total of 85 TgCyr-1 deposited. DOC concentrations are higher inland, ranging between 1 and 10 mgCL-1, producing a total of 188 TgCyr-1 terrestrial organic wet deposition. We compare the 2010 simulated DOC to a 30-year synthesis of available DOC measurements over different environments. Despite imperfect matching of observational and simulated time intervals, the model is able to reproduce much of the spatial variability of DOC (r= 0.63), with a low bias of 35%. We compare the global average carbon oxidation state (OSc) of both atmospheric and dissolved organic carbon, as a simple metric for describing the chemical composition of organics. In the global atmosphere reactive organic carbon (ROC) is dominated by hydrocarbons and ketones, and OSc, ranges from -1.8 to -0.6. In the dissolved form, formaldehyde, formic acid, primary and secondary semi-volatiles organic aerosol dominate the DOC concentrations. The increase in solubility upon oxidation leads to a global increase in OSc in rainwater with -0.6<=OSc <=0. This simulation provides new insight into the current model representation of the flow of atmospheric and rain-dissolved organic carbon, and new opportunities to use observations and simulations to understand the DOC reaching land and ocean.

  4. High Altitude Emissions of Black Carbon Aerosols: Potential Climate Implications

    NASA Astrophysics Data System (ADS)

    Satheesh, S. K.

    2017-12-01

    Synthesizing a series of ground-based and airborne measurements of aerosols over the Indian region during summer and pre-monsoon seasons have revealed the persistence of elevated absorbing aerosol layers over most of the Indian region; more than 50% of which located above clouds. Subsequent, in situ measurements of black carbon (BC) using high-altitude balloons, showed surprising layers with high concentrations in the middle and upper troposphere even at an altitude of 8 to 10 kms. Simultaneous measurements of the vertical thermal structure have shown localized warming due to BC absorption leading to large reduction in lapse rate and sharp temperature inversion, which in turn increases the atmospheric stability. This aerosol-induced stable layer is conducive for maintaining the black carbon layer longer at that level, leading thereby to further solar absorption and subsequently triggering dry convection. These observations support the `solar escalator' concept through which absorption-warming-convection cycles lead to self-lifting of BC to upper troposphere or even to lower stratosphere under favorable conditions in a matter of a few days. Employing an on-line regional chemistry transport model (WRF-Chem), incorporating aircraft emissions, it is shown that emissions from high-flying aircrafts as the most likely source of these elevated black carbon layers. These in-situ injected particles, produce significant warming of the thin air in those heights and lift these layers to even upper tropospheric/lower stratospheric heights, aided by the strong monsoonal convection occurring over the region, which are known to overshoot the tropical tropopause leading to injection of tropospheric air mass (along with its constituent aerosols) into the stratosphere, especially during monsoon season when the tropical tropopause layer is known to be thinnest. These simulations are further supported by the CALIPSO space-borne LIDAR derived extinction coefficient profiles. Based on

  5. SEASONAL AND REGIONAL VARIATIONS OF PRIMARY AND SECONDARY ORGANIC AEROSOLS OVER THE CONTINENTAL UNITED STATES: SEMI-EMPIRICAL ESTIMATES AND MODEL EVALUATION

    EPA Science Inventory

    Seasonal and regional variations of primary (OCpri) and secondary (OCsec) organic carbon aerosols across the continental U.S. for the year 2001 were examined by a semi-empirical technique using observed OC and elemental carbon (EC) data from 142 routine moni...

  6. Molecular distributions and stable carbon isotopic compositions of dicarboxylic acids and related compounds in aerosols from Sapporo, Japan: Implications for photochemical aging during long-range atmospheric transport

    NASA Astrophysics Data System (ADS)

    Aggarwal, Shankar G.; Kawamura, Kimitaka

    2008-07-01

    Molecular and stable carbon isotopic (δ13C value) compositions of dicarboxylic acids, ketoacids, and dicarbonyls in aerosol samples (i.e., total suspended particles) collected in Sapporo, northern Japan during spring and summer were determined to better understand the photochemical aging of organic aerosols during long-range transport from East Asia and Siberia. Their molecular distributions were characterized by the predominance of oxalic acid (C2) followed by malonic (C3) or occasionally succinic (C4) acids. Concentrations of total diacids ranged from 106-787 ng m-3 with ketoacids (13-81 ng m-3) and dicarbonyls (2.6-28 ng m-3) being less abundant. Water-soluble organic carbon (WSOC) comprised 23-69% of aerosol organic carbon (OC). OC to elemental carbon (EC) ratios were high (3.6-19, mean: 8.7). The ratios of C3/C4 and WSOC/OC did not show significant diurnal changes, suggesting that the Sapporo aerosols were not seriously affected by local photochemical processes and instead they were already aged. δ13C values of the dominant diacids (C2 - C4) ranged from -14.0 to -25.3‰. Largest δ13C values (-14.0 to -22.4‰, mean: -18.8‰) were obtained for C2, whereas smallest values (-25.1 to -31.4‰, mean: -28.1‰) were for azelaic acid (C9). In general, δ13C values of C2 - C4 diacids became less negative with aerosol aging (i.e., WSOC/OC), presumably due to isotopic fractionation during photochemical degradation of diacids. By comparing the δ13C values of diacids in the Sapporo aerosols with different air mass source regions, we suggest that although initial δ13C values of diacids depend on their precursor sources, the enrichment in 13C can be ascribed to aerosol photochemical aging.

  7. Fossil and contemporary sources of organic and elemental carbon at a rural and an urban site in the Netherlands

    NASA Astrophysics Data System (ADS)

    Dusek, U.; Monaco, M.; Weijers, E.; Röckmann, T.

    2012-04-01

    Measurement of the radioactive carbon isotope 14C in aerosols can provide a direct estimate of the contribution of fossil fuel sources to aerosol carbon. In aerosol science, measurements of 14C/12C ratios are usually reported as fraction modern (fm), relative to an oxalic acid standard that, by definition, has fm=1. The radiocarbon signature gives a clear distinction between 'modern' carbon sources (fm around 1.1-1.2 for biomass burning and around 1.05 for biogenic secondary organic aerosol) and 'fossil' carbon sources (fm =0 for primary and secondary formation from fossil fuel combustion). High volume filter samples have been collected since February 2011 at Cabauw, a rural location in the Netherlands, and additionally in May and June at two suburban locations around Rotterdam. We report measurements of fm for total carbon (TC), organic carbon (OC), water insoluble OC (WIOC) and thermally refractory carbon (RC) as a proxy for elemental carbon. The carbon fractions are isolated by combusting TC at 650 °C, OC and WIOC at 360 °C. Refractory carbon is defined as the carbon remaining on the filter after water extraction, combustion at 360 °C for 15 min and at 450 °C for 2 minutes. The method has been tested with test substances and real aerosol filters and shows little charring for water-extracted filters. First results of 7 filter samples taken from February - Mai 2011 show fm(OC) generally larger than 0.86 at the rural site, except for one case, when a strongly polluted air mass originating in Eastern Europe reached the site. This indicates a strong contribution of natural sources to OC, even in the Netherlands, a very densely populated country with one of the highest levels of aerosol pollution in Western Europe. In particular, WSOC in the rural springtime aerosol seems to originate almost entirely from contemporary sources. Refractory carbon also showed relatively high fm, generally between 0.3-0.5, except in two cases, when marine air masses reached the site

  8. Spatial variability of carbonaceous aerosol concentrations in East and West Jerusalem.

    PubMed

    von Schneidemesser, Erika; Zhou, Iiabin; Stone, Elizabeth A; Schauer, James I; Shpund, Jacob; Brenner, Shmuel; Qasrawi, Radwan; Abdeen, Ziad; Sarnat, Jeremy A

    2010-03-15

    Carbonaceous aerosol concentrations and sources were compared during a year long study at two sites in East and West Jerusalem that were separated by a distance of approximately 4 km. One in six day 24-h PM(2.5) elemental and organic carbon concentrations were measured, along with monthly average concentrations of particle-phase organic compound tracers for primary and secondary organic aerosol sources.Tracer compounds were used in a chemical mass balance ICMB) model to determine primary and secondary source contributions to organic carbon. The East Jerusalem sampling site at Al Quds University experienced higher concentrations of organic carbon (OC) and elemental carbon (EC) compared to the West Jerusalem site at Hebrew University. The annual average concentrations of OC and EC at the East Jerusalem site were 5.20 and 2.19 μg m(-3), respectively, and at the West Jerusalem site were 4.03 and 1.14 μg m(-3), respectively. Concentrations and trends of secondary organic aerosol and vegetative detritus were similar at both sites, but large differences were observed in the concentrations of organic aerosol from fossil fuel combustion and biomass burning, which was the cause of the large differences in OC and EC concentrations observed at the two sites.

  9. Light-Absorbing Brown Carbon Aerosol Constituents from Combustion of Indonesian Peat and Biomass.

    PubMed

    Budisulistiorini, Sri Hapsari; Riva, Matthieu; Williams, Michael; Chen, Jing; Itoh, Masayuki; Surratt, Jason D; Kuwata, Mikinori

    2017-04-18

    Light-absorbing brown carbon (BrC) constituents of organic aerosol (OA) have been shown to significantly absorb ultraviolet (UV) and visible light and thus impact radiative forcing. However, molecular identification of the BrC constituents is still limited. In this study, we characterize BrC constituents at the molecular level in (i) aerosols emitted by combustion of peat, fern/leaf, and charcoal from Indonesia and (ii) ambient aerosols collected in Singapore during the 2015 haze episode. Aerosols were analyzed using ultra performance liquid chromatography instrument interfaced to a diode array detector and electrospray ionization high-resolution quadrupole time-of-flight mass spectrometer operated in the negative ion mode. In the laboratory-generated aerosols, we identified 41 compounds that can potentially absorb near-UV and visible wavelengths, such as oxygenated-conjugated compounds, nitroaromatics, and S-containing compounds. The sum of BrC constituents in peat, fern/leaf, and charcoal burning aerosols are 16%, 35%, and 28% of the OA mass, respectively, giving an average contribution of 24%. On average, the BrC constituents account for 0.4% of the ambient OA mass; however, large uncertainties in mass closure remain because of the lack of authentic standards. This study highlights the potential of light-absorbing BrC OA constituents from peat, fern/leaf, and charcoal burning and their importance in the atmosphere.

  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. Biomass burning dominates brown carbon absorption in the rural southeastern United States

    NASA Astrophysics Data System (ADS)

    Washenfelder, R. A.; Attwood, A. R.; Brock, C. A.; Guo, H.; Xu, L.; Weber, R. J.; Ng, N. L.; Allen, H. M.; Ayres, B. R.; Baumann, K.; Cohen, R. C.; Draper, D. C.; Duffey, K. C.; Edgerton, E.; Fry, J. L.; Hu, W. W.; Jimenez, J. L.; Palm, B. B.; Romer, P.; Stone, E. A.; Wooldridge, P. J.; Brown, S. S.

    2015-01-01

    carbon aerosol consists of light-absorbing organic particulate matter with wavelength-dependent absorption. Aerosol optical extinction, absorption, size distributions, and chemical composition were measured in rural Alabama during summer 2013. The field site was well located to examine sources of brown carbon aerosol, with influence by high biogenic organic aerosol concentrations, pollution from two nearby cities, and biomass burning aerosol. We report the optical closure between measured dry aerosol extinction at 365 nm and calculated extinction from composition and size distribution, showing agreement within experiment uncertainties. We find that aerosol optical extinction is dominated by scattering, with single-scattering albedo values of 0.94 ± 0.02. Black carbon aerosol accounts for 91 ± 9% of the total carbonaceous aerosol absorption at 365 nm, while organic aerosol accounts for 9 ± 9%. The majority of brown carbon aerosol mass is associated with biomass burning, with smaller contributions from biogenically derived secondary organic aerosol.

  12. Fine Mode Aerosol over the United Arab Emirates

    NASA Astrophysics Data System (ADS)

    Ross, K. E.; Piketh, S. J.; Reid, J. S.; Reid, E. A.

    2005-12-01

    The aerosol loading of the atmosphere over the Arabian Gulf region is extremely diverse and is composed not only of dust, but also of pollution that is derived largely from oil-related activities. Fine mode pollution particles are most efficient at scattering incoming solar radiation and have the potential to act as cloud condensation nuclei (CCN), and may therefore have implications for climate change. The smaller aerosols may also pose a health hazard if present in high concentrations. The United Arab Emirates Unified Aerosol Experiment (UAE2) was designed to investigate aerosol and meteorological characteristics over the region using ground-based, aircraft and satellite measurements, and was conducted in August and September 2004. Aerosol chemical composition has been obtained from filters that were collected at the site of the Mobile Atmospheric Aerosol and Radiation Characterization Observatory (MAARCO) on the coast of the UAE between Abu Dhabi and Dubai. Filter samples were also collected on an airborne platform in order to assess how aerosol chemical composition varies across the region and throughout the depth of the boundary layer. Results of the analysis of the PM2.5 coastal samples show that ammonium sulphate is the most prevalent constituent of the fine mode aerosol in the region (>50% of the mass), followed by organic matter, alumino-silicates, calcium carbonate and black carbon. Source apportionment indicates that most of the fine aerosol mass is derived from fossil fuel combustion, while mineral dust and local vehicle emissions also contribute to the fine aerosol loading. The organic carbon-to-total carbon ratio of the aerosol is 0.65, which is typical of fossil fuel combustion. The dominance of sulphates means that the fine mode aerosol in the region is probably responsible for a negative radiative forcing, and that the polluting emissions significantly elevate the concentration of CCN.

  13. Remote sensing of soot carbon - Part 1: Distinguishing different absorbing aerosol species

    NASA Astrophysics Data System (ADS)

    Schuster, G. L.; Dubovik, O.; Arola, A.

    2016-02-01

    We describe a method of using the Aerosol Robotic Network (AERONET) size distributions and complex refractive indices to retrieve the relative proportion of carbonaceous aerosols and free iron minerals (hematite and goethite). We assume that soot carbon has a spectrally flat refractive index and enhanced imaginary indices at the 440 nm wavelength are caused by brown carbon or hematite. Carbonaceous aerosols can be separated from dust in imaginary refractive index space because 95 % of biomass burning aerosols have imaginary indices greater than 0.0042 at the 675-1020 nm wavelengths, and 95 % of dust has imaginary refractive indices of less than 0.0042 at those wavelengths. However, mixtures of these two types of particles can not be unambiguously partitioned on the basis of optical properties alone, so we also separate these particles by size. Regional and seasonal results are consistent with expectations. Monthly climatologies of fine mode soot carbon are less than 1.0 % by volume for West Africa and the Middle East, but the southern African and South American biomass burning sites have peak values of 3.0 and 1.7 %. Monthly averaged fine mode brown carbon volume fractions have a peak value of 5.8 % for West Africa, 2.1 % for the Middle East, 3.7 % for southern Africa, and 5.7 % for South America. Monthly climatologies of free iron volume fractions show little seasonal variability, and range from about 1.1 to 1.7 % for coarse mode aerosols in all four study regions. Finally, our sensitivity study indicates that the soot carbon retrieval is not sensitive to the component refractive indices or densities assumed for carbonaceous and free iron aerosols, and the retrieval differs by only 15.4 % when these parameters are altered from our chosen baseline values. The total uncertainty of retrieving soot carbon mass is ˜ 50 % (when uncertainty in the AERONET product and mixing state is included in the analysis).

  14. Atmospheric Carbon Dioxide and Aerosols: Effects of Large Increases on Global Climate

    ERIC Educational Resources Information Center

    Science, 1971

    1971-01-01

    Mathematical models indicate increasing atmospheric carbon dioxide causes an increase in surface temperature at a decreasing rate, and the rate of temperature decrease caused by increasing aerosols increases with aerosol concentration. (AL)

  15. Simulating the effect of photochemical aging on the oxidation state and hygroscopicity of organic aerosol

    NASA Astrophysics Data System (ADS)

    Tsimpidi, A.; Karydis, V.; Pandis, S. N.; Lelieveld, J.

    2016-12-01

    Hygroscopicity is an important property of aerosols which describes their propensity to absorb water vapor. The hygroscopicity of organic aerosol (OA) can change during its atmospheric aging affecting the total aerosol hygroscopicity. A more hygroscopic particle will grow more rapidly under humid conditions, scatter incident sunlight more efficiently; and it will more likely form cloud droplets. Both phenomena strongly influence the radiative forcing of climate through the direct and indirect effects of aerosols. Therefore, taking into account the hygrscopicity changes of OA during its atmospheric aging is of prime importance to accurately estimate the aerosol climatic impact. Here, we use a computationally efficient module for the description of OA composition and evolution in the atmosphere (ORACLE) (Tsimpidi et al., 2014) in the frame of the global chemistry climate model EMAC to simulate the global distribution of the OA oxidation state and hygroscopicity. To track the evolution of the OA oxidation state during its atmospheric aging, ORACLE is modified to include the description of the OA oxygen content change when mass from any OA surrogate species reacts with the OH radical. Subsequently, it is assumed that the cloud condensation nuclei (CCN) activity of OA, expressed in the form of the hygroscopicity parameter κ, will increase with increasing oxygen content (expressed by the oxygen per carbon ratio, O:C) and will range from κ = 0 (for O:C ≤ 0.2) to κ = 0.35 (for O:C = 1). The exact relationship between O:C and κ is determined based on aerosol mass spectrometer (AMS) and continuous flow CCN (CCNC) measurements of SOA (Lambe et al., 2011). Following a straightforward mixing rule, the hygroscopicity and oxygen content of total OA is calculated based on the hygroscopicities of the individual OA compounds and their degree of oxidation. A global dataset of O:C measurements is used to validate the model results. ReferencesLambe, A. T., et al. : Laboratory

  16. Urban organic aerosols measured by single particle mass spectrometry in the megacity of London

    NASA Astrophysics Data System (ADS)

    Dall'Osto, M.; Harrison, R. M.

    2012-05-01

    During the month of October 2006, as part of the REPARTEE-I experiment (Regent's Park and Tower Environmental Experiment) an Aerosol Time-Of-Flight Mass Spectrometer (ATOFMS) was deployed at an urban background location in the city of London, UK. Fifteen particle types were classified, some of which were already discussed (Dall'Osto et al., 2009a,b; Harrison et al., 2012). In this manuscript the origins and properties of four unreported particle types postulated to be due to locally generated aerosols, independent of the air mass type advected into London, are examined. One particle type, originating from lubricating oil (referred to as Ca-EC), was associated with morning rush hour traffic emissions. A second particle type, composed of both inorganic and organic species (called Na-EC-OC), was found enhanced in particle number concentration during evening time periods, and is likely to originate from a source operating at this time of day, or more probably from condensation of semi-volatile species. A third class, internally mixed with organic carbon and sulphate (called OC), was found to spike both in the morning and evenings although it could not unambiguously associated with a specific source or atmospheric process. The fourth class (Secondary Organic Aerosols - Polycyclic Aromatic Hydrocarbon; SOA-PAH) exhibited maximum frequency during the warmest part of the day, and a number of factors point towards secondary aerosol production from traffic-related volatile aromatic compounds. Single particle mass spectra of this particle type showed an oxidized polycyclic aromatic compound signature. A comparison of ATOFMS particle class data is then made with factors obtained by Positive Matrix Factorization and PAH signatures obtained from Aerosol Mass Spectrometer (AMS) data (Allan et al., 2010). Both the Ca-EC and OC particle types correlate with primary Hydrocarbon-like Organic Aerosol (HOA, R2 = 0.65 and 0.50 respectively), and Na-EC-OC correlates weakly with the AMS

  17. Assessing the Dynamics of Organic Aerosols over the North Atlantic Ocean

    PubMed Central

    Kasparian, Jérôme; Hassler, Christel; Ibelings, Bas; Berti, Nicolas; Bigorre, Sébastien; Djambazova, Violeta; Gascon-Diez, Elena; Giuliani, Grégory; Houlmann, Raphaël; Kiselev, Denis; de Laborie, Pierric; Le, Anh-Dao; Magouroux, Thibaud; Neri, Tristan; Palomino, Daniel; Pfändler, Stéfanie; Ray, Nicolas; Sousa, Gustavo; Staedler, Davide; Tettamanti, Federico; Wolf, Jean-Pierre; Beniston, Martin

    2017-01-01

    The influence of aerosols on climate is highly dependent on the particle size distribution, concentration, and composition. In particular, the latter influences their ability to act as cloud condensation nuclei, whereby they impact cloud coverage and precipitation. Here, we simultaneously measured the concentration of aerosols from sea spray over the North Atlantic on board the exhaust-free solar-powered vessel “PlanetSolar”, and the sea surface physico-chemical parameters. We identified organic-bearing particles based on individual particle fluorescence spectra. Organic-bearing aerosols display specific spatio-temporal distributions as compared to total aerosols. We propose an empirical parameterization of the organic-bearing particle concentration, with a dependence on water salinity and sea-surface temperature only. We also show that a very rich mixture of organic aerosols is emitted from the sea surface. Such data will certainly contribute to providing further insight into the influence of aerosols on cloud formation, and be used as input for the improved modeling of aerosols and their role in global climate processes. PMID:28361985

  18. An interfacial mechanism for cloud droplet formation on organic aerosols

    DOE PAGES

    Ruehl, C. R.; Davies, J. F.; Wilson, K. R.

    2016-03-25

    Accurate predictions of aerosol/cloud interactions require simple, physically accurate parameterizations of the cloud condensation nuclei (CCN) activity of aerosols. Current models assume that organic aerosol species contribute to CCN activity by lowering water activity. We measured droplet diameters at the point of CCN activation for particles composed of dicarboxylic acids or secondary organic aerosol and ammonium sulfate. Droplet activation diameters were 40 to 60% larger than predicted if the organic was assumed to be dissolved within the bulk droplet, suggesting that a new mechanism is needed to explain cloud droplet formation. A compressed film model explains how surface tension depressionmore » by interfacial organic molecules can alter the relationship between water vapor supersaturation and droplet size (i.e., the Köhler curve), leading to the larger diameters observed at activation.« less

  19. An interfacial mechanism for cloud droplet formation on organic aerosols

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ruehl, C. R.; Davies, J. F.; Wilson, K. R.

    Accurate predictions of aerosol/cloud interactions require simple, physically accurate parameterizations of the cloud condensation nuclei (CCN) activity of aerosols. Current models assume that organic aerosol species contribute to CCN activity by lowering water activity. We measured droplet diameters at the point of CCN activation for particles composed of dicarboxylic acids or secondary organic aerosol and ammonium sulfate. Droplet activation diameters were 40 to 60% larger than predicted if the organic was assumed to be dissolved within the bulk droplet, suggesting that a new mechanism is needed to explain cloud droplet formation. A compressed film model explains how surface tension depressionmore » by interfacial organic molecules can alter the relationship between water vapor supersaturation and droplet size (i.e., the Köhler curve), leading to the larger diameters observed at activation.« less

  20. Anomalies of the Asian Monsoon Induced by Aerosol Forcings

    NASA Technical Reports Server (NTRS)

    Lau, William K. M.; Kim, M. K.

    2004-01-01

    Impacts of aerosols on the Asian summer monsoon are studied using the NASA finite volume General Circulation Model (fvGCM), with radiative forcing derived from three-dimensional distributions of five aerosol species i.e., black carbon, organic carbon, soil dust, and sea salt from the Goddard Chemistry Aerosol Radiation and Transport Model (GOCART). Results show that absorbing aerosols, i.e., black carbon and dust, induce large-scale upper-level heating anomaly over the Tibetan Plateau in April and May, ushering in & early onset of the Indian summer monsoon. Absorbing aerosols also I i enhance lower-level heating and anomalous ascent over northern India, intensifying the Indian monsoon. Overall, the aerosol-induced large-scale surface' temperature cooling leads to a reduction of monsoon rainfall over the East Asia continent, and adjacent oceanic regions.

  1. Open burning of rice, corn and wheat straws: primary emissions, photochemical aging, and secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Fang, Zheng; Deng, Wei; Zhang, Yanli; Ding, Xiang; Tang, Mingjin; Liu, Tengyu; Hu, Qihou; Zhu, Ming; Wang, Zhaoyi; Yang, Weiqiang; Huang, Zhonghui; Song, Wei; Bi, Xinhui; Chen, Jianmin; Sun, Yele; George, Christian; Wang, Xinming

    2017-12-01

    Agricultural residues are among the most abundant biomass burned globally, especially in China. However, there is little information on primary emissions and photochemical evolution of agricultural residue burning. In this study, indoor chamber experiments were conducted to investigate primary emissions from open burning of rice, corn and wheat straws and their photochemical aging as well. Emission factors of NOx, NH3, SO2, 67 non-methane hydrocarbons (NMHCs), particulate matter (PM), organic aerosol (OA) and black carbon (BC) under ambient dilution conditions were determined. Olefins accounted for > 50 % of the total speciated NMHCs emission (2.47 to 5.04 g kg-1), indicating high ozone formation potential of straw burning emissions. Emission factors of PM (3.73 to 6.36 g kg-1) and primary organic carbon (POC, 2.05 to 4.11 gC kg-1), measured at dilution ratios of 1300 to 4000, were lower than those reported in previous studies at low dilution ratios, probably due to the evaporation of semi-volatile organic compounds under high dilution conditions. After photochemical aging with an OH exposure range of (1.97-4.97) × 1010 molecule cm-3 s in the chamber, large amounts of secondary organic aerosol (SOA) were produced with OA mass enhancement ratios (the mass ratio of total OA to primary OA) of 2.4-7.6. The 20 known precursors could only explain 5.0-27.3 % of the observed SOA mass, suggesting that the major precursors of SOA formed from open straw burning remain unidentified. Aerosol mass spectrometry (AMS) signaled that the aged OA contained less hydrocarbons but more oxygen- and nitrogen-containing compounds than primary OA, and carbon oxidation state (OSc) calculated with AMS resolved O / C and H / C ratios increased linearly (p < 0.001) with OH exposure with quite similar slopes.

  2. Simulating Aerosol Optical Properties With the Aerosol Simulation Program (ASP): Closure Studies Using ARCTAS Data

    NASA Astrophysics Data System (ADS)

    Alvarado, M. J.; Macintyre, H. L.; Bian, H.; Chin, M.; Wang, C.

    2012-12-01

    The scattering and absorption of ultraviolet and visible radiation by aerosols can significantly alter actinic fluxes and photolysis rates. Accurate modeling of aerosol optical properties is thus essential to simulating atmospheric chemistry, air quality, and climate. Here we evaluate the aerosol optical property predictions of the Aerosol Simulation Program (ASP) with in situ data on aerosol scattering and absorption gathered during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) campaign. The model simulations are initialized with in situ data on the aerosol size distribution and composition. We perform a set of sensitivity studies (e.g., internal vs. external mixture, core-in-shell versus Maxwell-Garnett, fraction of the organic carbon mass that is light-absorbing "brown carbon," etc.) to determine the model framework and parameters most consistent with the observations. We compare the ASP results to the aerosol optical property lookup tables in FAST-JX and suggest improvements that will better enable FAST-JX to simulate the impact of aerosols on photolysis rates and atmospheric chemistry.

  3. Urban organic aerosols measured by single particle mass spectrometry in the megacity of London

    NASA Astrophysics Data System (ADS)

    Dall'Osto, M.; Harrison, R. M.

    2011-02-01

    During the month of October 2006, as part of the REPARTEE-I experiment (Regent's Park and Tower Environmental Experiment) an Aerosol Time-Of-Flight Mass Spectrometer (ATOFMS) was deployed at an urban background location in the city of London, UK. Fifteen particle types were classified, some of which were accompanied by Aerosol Mass Spectrometer (AMS) quantitative aerosol mass loading measurements (Dall'Osto et al., 2009a, b). In this manuscript the origins and properties of four particle types associated with locally generated aerosols, independent of the air mass type advected into London, are examined. One particle type, originating from lubricating oil (referred to as Ca-EC), was associated with morning rush hour traffic emissions. A second particle type, composed of both inorganic and organic species (called Na-EC-OC), was found enhanced in particle number concentration during evening time periods, and is likely to originate from a source operating at this time of day, or more probably from condensation of semi-volatile species, and contains both primary and secondary components. A third class, internally mixed with organic carbon and sulphate (called OC), was found to spike both in the morning and evenings. The fourth class (SOA-PAH) exhibited maximum frequency during the warmest part of the day, and a number of factors point towards secondary production from traffic-related volatile aromatic compounds. Single particle mass spectra of this particle type showed an oxidized polycyclic aromatic compound signature. Finally, a comparison of ATOFMS particle class data is made with factors obtained by Positive Matrix Factorization from AMS data.. Both the Ca-EC and OC particle types correlate with the AMS HOA primary organic fraction (R2 = 0.65 and 0.50 respectively), and Na-EC-OC, but not SOA-PAH, which correlates weakly with the AMS OOA secondary organic aerosol factor (R2 = 0.35). A detailed analysis was conducted to identify ATOFMS particle type(s) representative

  4. Springtime carbon episodes at Gosan background site revealed by total carbon, stable carbon isotopic composition, and thermal characteristics of carbonaceous particles

    NASA Astrophysics Data System (ADS)

    Jung, J.; Kawamura, K.

    2011-05-01

    In order to investigate the carbon episodes at Gosan background super-site (33.17° N, 126.10° E) in East Asia during spring of 2007 and 2008, total suspended particles (TSP) were collected and analyzed for particulate organic carbon, elemental carbon, total carbon (TC), total nitrogen (TN), and stable carbon isotopic composition (δ13C) of TC. The carbon episodes at the Gosan site were categorized as long-range transported anthropogenic pollutant (LTP) from Asian continent, Asian dust (AD) accompanying with LTP, and local pollen episodes. The stable carbon isotopic composition of TC (δ13CTC) was found to be lowest during the pollen episodes (range: -26.2 ‰ to -23.5 ‰, avg.: -25.2 ± 0.9 ‰), followed by the LTP episodes (range: -23.5 ‰ to -23.0 ‰, avg.: -23.3 ± 0.3 ‰) and the AD episodes (range: -23.3 to -20.4 %, avg.: -21.8 ± 2.0 ‰). The δ13CTC of the airborne pollens (-28.0 ‰) collected at the Gosan site showed value similar to that of tangerine fruit (-28.1 ‰) produced from Jeju Island. Based on the carbon isotope mass balance equation and the TN and TC regression approach, we found that ∼40-45 % of TC in the TSP samples during the pollen episodes was attributed to airborne pollens from Japanese cedar trees planted around tangerine farms in Jeju Island. The δ13C of citric acid in the airborne pollens (-26.3 ‰) collected at the Gosan site was similar to that in tangerine fruit (-27.4 ‰). The negative correlation between the citric acid-carbon/TC ratios and δ13CTC were obtained during the pollen episodes. These results suggest that citric acid emitted from tangerine fruit may be adsorbed on the airborne pollens and then transported to the Gosan site. Based on the thermal evolution pattern of organic aerosols during the carbon episodes, we found that organic aerosols originated from East China are more volatile on heating and are more likely to form pyrolized organic carbon than the pollen-enriched organic aerosols and organic

  5. Black and Brown Carbon in Biogenic Settings with Different Levels of Anthropogenic Influence, and The Effect of Semivolatile Compounds on Aerosol Optical Properties

    NASA Astrophysics Data System (ADS)

    Tasoglou, A.; Ramachandran, S.; Khlystov, A.; Saha, P.; Grieshop, A. P.; Pandis, S. N.

    2015-12-01

    Secondary organic aerosol (SOA) is a major contributor to the global aerosol burden. Black carbon (BC) is a significant climate warming agent, while light-absorbing organic carbon (brown carbon, BrC), also impacts the atmospheric radiative balance. The optical properties of ambient aerosols can be affected by biogenic SOA through the lensing effect (coating of BC cores by semivolatile SOA), and by the potential formation of BrC from biogenic sources influenced by anthropogenic sources. To evaluate these effects, measurements of ambient aerosol optical properties and BC concentrations were made in rural Centreville, AL (a remote site with little anthropogenic influence) in summer 2013 and at Duke Forest in Chapel Hill, NC (a site close to high density vehicular traffic and industrial sources), during summer 2015. Photoacoustic extinctiometers (PAX, 405 nm and 532 nm) measured particulate light absorption and a single particle soot photometer (SP2) measured BC mass at both locations. A seven-wavelength Aethalometer and a three-wavelength nephelometer were also deployed at Duke Forest. A third PAX (870 nm) was deployed at Centreville. For absorption and BC measurements, the sample was cycled between a dry line and a dry/thermally-denuded line. Hourly samples were collected with a steam jet aerosol collector (SJAC) for online (2013) and offline (2015) chemical composition analysis. BC concentrations were generally higher at Duke Forest compared to the rural Centreville site. The Aethalometer readings at Duke Forest show greater absorption at the shorter wavelengths (370 nm and 470 nm) than expected from the absorption at 880 nm coupled with an inverse wavelength dependence, suggesting the presence of brown carbon. This presentation will examine the evidence for brown carbon at the two sites, as well as the effect of non-BC coatings on BC light absorption (the lensing effect.)

  6. Organic Aerosols from SÃO Paulo and its Relationship with Aerosol Absorption and Scattering Properties

    NASA Astrophysics Data System (ADS)

    Artaxo, P.; Brito, J. F.; Rizzo, L. V.

    2012-12-01

    The megacity of São Paulo with its 19 million people and 7 million cars is a challenge from the point of view of air pollution. High levels of organic aerosols, PM10, black carbon and ozone and the peculiar situation of the large scale use of ethanol fuel makes it a special case. Little is known about the impact of ethanol on air quality and human health and the increase of ethanol as vehicle fuel is rising worldwide An experiment was designed to physico-chemical properties of aerosols in São Paulo, as well as their optical properties. Aerosol size distribution in the size range of 1nm to 10 micrometers is being measured with a Helsinki University SMPS (Scanning Mobility Particle Sizer), an NAIS (Neutral ion Spectrometer) and a GRIMM OPC (Optical Particle Counter). Optical properties are being measured with a TSI Nephelometer and a Thermo MAAP (Multi Angle Absorption Photometer). A CIMEL sunphotometer from the AERONET network measure the aerosol optical depth. Furthermore, a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS) and an Aerosol Chemical Speciation Monitor (ACSM) are used to real-time VOC analysis and aerosol composition, respectively. The ACSM was operated for 3 months continuosly during teh wintertime of 2012. The measured total particle concentration typically varies between 10,000 and 30,000 cm-3 being the lowest late in the night and highest around noon and frequently exceeding 50,000 cm-3. Clear diurnal patterns in aerosol optical properties were observed. Scattering and absorption coefficients typically range between 20 and 100 Mm-1 at 450 nm, and between 10 to 40 Mm-1 at 637 nm, respectively, both of them peaking at 7:00 local time, the morning rush hour. The corresponding single scattering albedo varies between 0.50 and 0.85, indicating a significant contribution of primary absorbing particles to the aerosol population. During the first month a total of seven new particle formation events were observed with growth rates ranging from 9 to 25

  7. Springtime carbon emission episodes at the Gosan background site revealed by total carbon, stable carbon isotopic composition, and thermal characteristics of carbonaceous particles

    NASA Astrophysics Data System (ADS)

    Jung, J.; Kawamura, K.

    2011-11-01

    In order to investigate the emission of carbonaceous aerosols at the Gosan background super-site (33.17° N, 126.10° E) in East Asia, total suspended particles (TSP) were collected during spring of 2007 and 2008 and analyzed for particulate organic carbon, elemental carbon, total carbon (TC), total nitrogen (TN), and stable carbon isotopic composition (δ13C) of TC. The stable carbon isotopic composition of TC (δ13CTC) was found to be lowest during pollen emission episodes (range: -26.2‰ to -23.5‰, avg. -25.2 ± 0.9‰), approaching those of the airborne pollen (-28.0‰) collected at the Gosan site. Based on a carbon isotope mass balance equation, we found that ~42% of TC in the TSP samples during the pollen episodes was attributed to airborne pollen from Japanese cedar trees planted around tangerine farms in Jeju Island. A negative correlation between the citric acid-carbon/TC ratios and δ13CTC was obtained during the pollen episodes. These results suggest that citric acid emitted from tangerine fruit may be adsorbed on the airborne pollen and then transported to the Gosan site. Thermal evolution patterns of organic carbon during the pollen episodes were characterized by high OC evolution in the OC2 temperature step (450 °C). Since thermal evolution patterns of organic aerosols are highly influenced by their molecular weight, they can be used as additional information on the formation of secondary organic aerosols and the effect of aging of organic aerosols during the long-range atmospheric transport and sources of organic aerosols.

  8. Enhanced UV Absorption in Carbonaceous Aerosols during MILAGRO and Identification of Potential Organic Contributors.

    NASA Astrophysics Data System (ADS)

    Mangu, A.; Kelley, K. L.; Marchany-Rivera, A.; Kilaparty, S.; Gunawan, G.; Gaffney, J. S.; Marley, N. A.

    2007-12-01

    ), and nitrated PAH compounds for comparison. Potential organic aerosol components are identified which contribute to the enhanced absorption observed in the field. The wavelength dependence of the mass specific absorption is obtained from these spectra and total carbon measurements. The wavelength dependence of the aerosol complex refractive index (m = n +ik) in the UV-visible spectral region is determined by application of the Kramers Kronig function. The importance of the aerosol absorption in the infrared spectral region to radiative forcing will be discussed. 1. Marley, N.A., J.S. Gaffney, J.C. Baird, C.A. Blazer, P.J. Drayton, and J.E. Frederick, Aerosol Sci. Technol., 34, 535-549, (2001). 2. N.A. Marley, J.S. Gaffney, and K.A. Orlandini, Chapter 7 in Humic/Fulvic Acids and Organic Colloidal Materials in the Environment, ACS Symposium Series 651, American Chemical Society, Washington, D.C., pp. 96-107, 1996. This work was conducted as part of the Department of Energy's Atmospheric Science Program as part of the Megacity Aerosol Experiment - Mexico City during MILAGRO. This research was supported by the Office of Science (BER), U.S. Department of Energy Grant No. DE-FG02-07ER64329. We also wish to thank Mexican Scientists and students for their assistance from the Instituto Mexicano de Petroleo (IMP) and CENICA.

  9. An interfacial mechanism for cloud droplet formation on organic aerosols.

    PubMed

    Ruehl, Christopher R; Davies, James F; Wilson, Kevin R

    2016-03-25

    Accurate predictions of aerosol/cloud interactions require simple, physically accurate parameterizations of the cloud condensation nuclei (CCN) activity of aerosols. Current models assume that organic aerosol species contribute to CCN activity by lowering water activity. We measured droplet diameters at the point of CCN activation for particles composed of dicarboxylic acids or secondary organic aerosol and ammonium sulfate. Droplet activation diameters were 40 to 60% larger than predicted if the organic was assumed to be dissolved within the bulk droplet, suggesting that a new mechanism is needed to explain cloud droplet formation. A compressed film model explains how surface tension depression by interfacial organic molecules can alter the relationship between water vapor supersaturation and droplet size (i.e., the Köhler curve), leading to the larger diameters observed at activation. Copyright © 2016, American Association for the Advancement of Science.

  10. Changes in organic aerosol composition with aging inferred from aerosol mass spectra

    NASA Astrophysics Data System (ADS)

    Ng, N. L.; Canagaratna, M. R.; Jimenez, J. L.; Chhabra, P. S.; Seinfeld, J. H.; Worsnop, D. R.

    2011-07-01

    Organic aerosols (OA) can be separated with factor analysis of aerosol mass spectrometer (AMS) data into hydrocarbon-like OA (HOA) and oxygenated OA (OOA). We develop a new method to parameterize H:C of OOA in terms of f43 (ratio of m/z 43, mostly C2H3O+, to total signal in the component mass spectrum). Such parameterization allows for the transformation of large database of ambient OOA components from the f44 (mostly CO2+, likely from acid groups) vs. f43 space ("triangle plot") (Ng et al., 2010) into the Van Krevelen diagram (H:C vs. O:C) (Van Krevelen, 1950). Heald et al. (2010) examined the evolution of total OA in the Van Krevelen diagram. In this work total OA is deconvolved into components that correspond to primary (HOA and others) and secondary (OOA) organic aerosols. By deconvolving total OA into different components, we remove physical mixing effects between secondary and primary aerosols which allows for examination of the evolution of OOA components alone in the Van Krevelen space. This provides a unique means of following ambient secondary OA evolution that is analogous to and can be compared with trends observed in chamber studies of secondary organic aerosol formation. The triangle plot in Ng et al. (2010) indicates that f44 of OOA components increases with photochemical age, suggesting the importance of acid formation in OOA evolution. Once they are transformed with the new parameterization, the triangle plot of the OOA components from all sites occupy an area in Van Krevelen space which follows a ΔH:C/ΔO:C slope of ~ -0.5. This slope suggests that ambient OOA aging results in net changes in chemical composition that are equivalent to the addition of both acid and alcohol/peroxide functional groups without fragmentation (i.e. C-C bond breakage), and/or the addition of acid groups with fragmentation. These results provide a framework for linking the bulk aerosol chemical composition evolution to molecular-level studies.

  11. Refractive indices of Early Earth organic aerosol analogs

    NASA Astrophysics Data System (ADS)

    Gavilan, L.; Carrasco, N.; Fleury, B.; Vettier, L.

    2017-09-01

    Organic hazes in the early Earth atmosphere are hypothesized to provide additional shielding to solar radiation. We simulate the conditions of this primitive atmosphere by adding CO2 to a N2:CH4 gas mixture feeding a plasma. In this plasma, solid organic films were produced simulating early aerosols. We performed ellipsometry on these films from the visible to the near-ultraviolet range. Such measurements reveal how organic aerosols in the early Earth atmosphere preferentially absorb photons of shorter wavelengths than typical Titan tholins, suggesting a coolant role in the early Earth.

  12. Stable carbon and nitrogen isotopic compositions of ambient aerosols collected from Okinawa Island in the western North Pacific Rim, an outflow region of Asian dusts and pollutants

    NASA Astrophysics Data System (ADS)

    Kunwar, Bhagawati; Kawamura, Kimitaka; Zhu, Chunmao

    2016-04-01

    Stable carbon (δ13C) and nitrogen (δ15N) isotope ratios were measured for total carbon (TC) and nitrogen (TN), respectively, in aerosol (TSP) samples collected at Cape Hedo, Okinawa, an outflow region of Asian pollutants, during 2009-2010. The averaged δ13C and δ15N ratios are -22.2‰ and +12.5‰, respectively. The δ13C values are similar in both spring (-22.5‰) and winter (-22.5‰), suggesting the similar sources and/or source regions. We found that δ13C from Okinawa aerosols are ca. 2‰ higher than those reported from Chinese megacities probably due to photochemical aging of organic aerosols. A strong correlation (r = 0.81) was found between nss-Ca and TSP, suggesting that springtime aerosols are influenced from Asian dusts. However, carbonates in the Asian dusts were titrated with acidic species such as sulfuric acid and oxalic acid during atmospheric transport although two samples suggested the presence of remaining carbonate. No correlations were found between δ13C and tracer compounds (levoglucosan, elemental carbon, oxalic acid, and Na+). During winter and spring, coal burning is significant source in China. Based on isotopic mass balance, contribution of coal burning origin particles to total aerosol carbon was estimated as ca. 97% in winter, which is probably associated with the high emissions in China. Contribution of NO3- to TN was on average 45% whereas that of NH4+ was 18%. These results suggest that vehicular exhaust is an important source of TN in Okinawa aerosols. Concentration of water-soluble organic nitrogen (WSON) is higher in summer, suggesting that WSON is more emitted from the ocean in warmer season whereas inorganic nitrogen is more emitted in winter and spring from pollution sources in the Asian continent.

  13. Impact of aftertreatment devices on primary emissions and secondary organic aerosol formation potential from in-use diesel vehicles: results from smog chamber experiments

    NASA Astrophysics Data System (ADS)

    Chirico, R.; Decarlo, P. F.; Heringa, M. F.; Tritscher, T.; Richter, R.; Prévôt, A. S. H.; Dommen, J.; Weingartner, E.; Wehrle, G.; Gysel, M.; Laborde, M.; Baltensperger, U.

    2010-12-01

    Diesel particulate matter (DPM) is a significant source of aerosol in urban areas and has been linked to adverse health effects. Although newer European directives have introduced increasingly stringent standards for primary PM emissions, gaseous organics emitted from diesel cars can still lead to large amounts of secondary organic aerosol (SOA) in the atmosphere. Here we present results from smog chamber investigations characterizing the primary organic aerosol (POA) and the corresponding SOA formation at atmospherically relevant concentrations for three in-use diesel vehicles with different exhaust aftertreatment systems. One vehicle lacked exhaust aftertreatment devices, one vehicle was equipped with a diesel oxidation catalyst (DOC) and the third vehicle used both a DOC and diesel particulate filter (DPF). The experiments presented here were obtained from the vehicles at conditions representative of idle mode, and for one car in addition at a speed of 60 km/h. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was used to measure the organic aerosol (OA) concentration and to obtain information on the chemical composition. For the conditions explored in this paper, primary aerosols from vehicles without a particulate filter consisted mainly of black carbon (BC) with a low fraction of organic matter (OM, OM/BC < 0.5), while the subsequent aging by photooxidation resulted in a consistent production of SOA only for the vehicles without a DOC and with a deactivated DOC. After 5 h of aging ~80% of the total organic aerosol was on average secondary and the estimated "emission factor" for SOA was 0.23-0.56 g/kg fuel burned. In presence of both a DOC and a DPF, only 0.01 g SOA per kg fuel burned was produced within 5 h after lights on. The mass spectra indicate that POA was mostly a non-oxidized OA with an oxygen to carbon atomic ratio (O/C) ranging from 0.10 to 0.19. Five hours of oxidation led to a more oxidized OA with an O/C range of 0

  14. Contribution of Black Carbon Aerosol to Drying of the Mediterranean

    NASA Astrophysics Data System (ADS)

    Tang, T.; Shindell, D. T.; Samset, B. H.; Boucher, O.; Forster, P.; Hodnebrog, Ø.; Myhre, G.; Sillmann, J.; Voulgarakis, A.; Andrews, T.; Faluvegi, G.; Fläschner, D.; Iverson, T.; Kasoar, M.; Kharin, V. V.; Kirkevag, A.; Lamarque, J. F.; Olivié, D.; Richardson, T.; Stjern, C.; Takemura, T.; Zwiers, F. W.

    2017-12-01

    Atmospheric aerosols affect cloud properties, radiative balance and thus, the hydrological cycle. Many studies have reported that precipitation has decreased in the Mediterranean since the mid-20th century, and investigated possible mechanisms. So far, however, the effects of aerosol forcing on Mediterranean precipitation remain largely unknown. Here we compare observed Mediterranean precipitation trends during 1951-2010 with responses to individual forcing in a set of state-of-the-art global climate models. Our analyses suggest that nearly one-third (30%) of the observed precipitation decrease may be attributable to black carbon forcing. The remainder is most strongly linked to forcing of well-mixed greenhouse gases (WMGHGs), with scattering sulfate aerosols having negligible impacts. Black carbon caused an enhanced positive North Atlantic Oscillation (NAO)/Arctic Oscillation (AO)-like sea level pressure (SLP) pattern, characterized by higher SLP at mid-latitudes and lower SLP at high-latitudes. This SLP change diverted the jet stream and storm tracks further northward, reducing precipitation in the Mediterranean while increasing precipitation in Northern Europe. The results from this study suggest that future black carbon emissions may significantly affect regional water resources, agricultural practices, ecosystems, and economy in the Mediterranean region.

  15. Molecular structure impacts on secondary organic aerosol formation from glycol ethers

    NASA Astrophysics Data System (ADS)

    Li, Lijie; Cocker, David R.

    2018-05-01

    Glycol ethers, a class of widely used solvents in consumer products, are often considered exempt as volatile organic compounds based on their vapor pressure or boiling points by regulatory agencies. However, recent studies found that glycol ethers volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents indicating the potential of glycol ethers to form secondary organic aerosol (SOA). This is the first work on SOA formation from glycol ethers. The impact of molecular structure, specifically -OH, on SOA formation from glycol ethers and related ethers are investigated in the work. Ethers with and without -OH, with methyl group hindrance on -OH and with -OH at different location are studied in the presence of NOX and under "NOX free" conditions. Photooxidation experiments under different oxidation conditions confirm that the processing of ethers is a combination of carbonyl formation, cyclization and fragmentation. Bulk SOA chemical composition analysis and oxidation products identified in both gas and particle phase suggests that the presence and location of -OH in the carbon bond of ethers determine the occurrence of cyclization mechanism during ether oxidation. The cyclization is proposed as a critical SOA formation mechanism to prevent the formation of volatile compounds from fragmentation during the oxidation of ethers. Glycol ethers with -CH2-O-CH2CH2OH structure is found to readily form cyclization products, especially with the presence of NOx, which is more relevant to urban atmospheric conditions than without NOx. Glycol ethers are evaluated as dominating SOA precursors among all ethers studied. It is estimated that the contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources. The contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources and will play a more important role in future anthropogenic SOA

  16. Broadband optical properties of biomass-burning aerosol and identification of brown carbon chromophores: OPTICAL AND CHEMICAL PROPERTIES OF BROWN CARBON AEROSOLS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bluvshtein, Nir; Lin, Peng; Flores, J. Michel

    The radiative effects of biomass burning aerosols on regional and global scale is substantial. Accurate modeling of the radiative effects of smoke aerosols require wavelength-dependent measurements and parameterizations of their optical properties in the UV and visible spectral ranges along with improved description of their chemical composition. To address this issue, we used a recently developed approach to retrieve the time- and spectral-dependent optical properties of ambient biomass burning aerosols between 300 and 650 nm wavelength during a regional bonfire festival in Israel. During the biomass burning event, the overall absorption at 400 nm increased by about two orders ofmore » magnitude, changing the size-weighted single scattering albedo from a background level of 0.95 to 0.7. Based on the new retrieval method, we provide parameterizations of the wavelength-dependent effective complex refractive index from 350 to 650 nm for freshly emitted and aged biomass burning aerosols. In addition, PM2.5 filter samples were collected for detailed off-line chemical analysis of the water soluble organics that contribute to light absorption. Nitrophenols were identified as the main organic species responsible for the increased absorption at 400-500 nm. These include species such as 4- nitrocatechol, 4-nitrophenol, nitro-syringol and nitro-guaiacol; oxidation-nitration products of methoxyphenols, known products of lignin pyrolysis. Our findings emphasize the importance of both primary and secondary organic aerosol from biomass burning in absorption of solar radiation and in effective radiative forcing.« less

  17. 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

  18. Source contributions to black carbon mass fractions in aerosol particles over the northwestern Pacific

    NASA Astrophysics Data System (ADS)

    Koga, Seizi; Maeda, Takahisa; Kaneyasu, Naoki

    Aerosol particle number size distributions above 0.3 μm in diameter and black carbon mass concentrations in aerosols were observed on Chichi-jima of the Ogasawara Islands in the northwestern Pacific from January 2000 to December 2002. Chichi-jima is suitable to observe polluted air masses from East Asia in winter and clean air masses over the western North Pacific in summer. In winter, aerosols over Chichi-jima were strongly affected by anthropogenic emissions in East Asia. The form of energy consumption in East Asia varies in various regions. Hence, each source region is expected to be characterized by an individual black carbon mass fraction. A three-dimensional Eulerian transport model was used to estimate contribution rates to air pollutants from each source region in East Asia. Because the Miyake-jima eruption began at the end of June 2000, the influence of smokes from Miyake-jima was also considered in the model calculation. The results of model calculations represent what must be noticed about smokes from volcanoes including Miyake-jima to interpret temporal variations of sulfur compounds over the northwestern Pacific. To evaluate black carbon mass fractions in anthropogenic aerosols as a function of source region, the relationships between the volume concentration of aerosol particles and the black carbon mass concentration in the winter were classified under each source region in East Asia. Consequently, the black carbon mass fractions in aerosols from China, Japan and the Korean Peninsula, and other regions were estimated to be 9-13%, 5-7%, and 4-5%, respectively.

  19. THERMODYNAMIC MODELING OF LIQUID AEROSOLS CONTAINING DISSOLVED ORGANICS AND ELECTROLYTES

    EPA Science Inventory

    Many tropospheric aerosols contain large fractions of soluble organic material, believed to derive from the oxidation of precursors such alpha-pinene. The chemical composition of aerosol organic matter is complex and not yet fully understood.

    The key properties of solu...

  20. Review of brown carbon aerosols: Recent progress and perspectives.

    PubMed

    Yan, Juping; Wang, Xiaoping; Gong, Ping; Wang, Chuanfei; Cong, Zhiyuan

    2018-09-01

    Brown carbon (BrC), a carbonaceous aerosol which absorbs solar radiation over a broad range of wavelengths, is beginning to be seen as an important contributor to global warming. BrC absorbs both inorganic and organic pollutants, leading to serious effects on human health. We review the fundamental features of BrC, including its sources, chemical composition, optical properties and radiative forcing effects. We detail the importance of including photochemical processes related to BrC in the GEOS-Chem transport model for the estimation of aerosol radiative forcing. Calculation methods for BrC emission factors are examined, including the problems and limitations of current measurement methods. We provide some insight into existing publications and recommend areas for future research, such as further investigations into the reaction mechanisms of the aging of secondary BrC, calculations of the emission factors for BrC from different sources, the absorption of large and long-lived BrC molecules and the construction of an enhanced model for the simulation of radiative forcing. This review will improve our understanding of the climatic and environmental effects of BrC. Copyright © 2018 Elsevier B.V. All rights reserved.

  1. Contribution of bioaerosols to the global organic aerosol budget

    NASA Astrophysics Data System (ADS)

    Janssen, R.; Heald, C. L.

    2017-12-01

    Bioaerosols are ubiquitous in the atmosphere and may contribute significantly to cloud condensation and ice nuclei populations, and consequently to formation of clouds and precipitation. However, quantifying the contribution of bioaerosols to the global organic aerosol budget is a challenge, since bioaerosol sources are poorly constrained on the global scale. Previous global estimates of global primary biological aerosol particle (PBAP) emissions, including bacteria, fungal spores and pollen, range from 78-296 Tg/year. Over the past several years, size-resolved measurements of fluorescent biological aerosol particles have been made in tropical, temperate and boreal ecosystems. Besides, single particle mass spectroscopy has been used to quantify bioaerosol concentrations at various locations in the US. We use these observations to develop and evaluate a bioaerosol emission scheme that describes both the biological production of bioaerosols and the meteorological drivers of the emission of these particles into the atmosphere. Then, we implement this scheme in the GEOS-Chem global chemical transport model to estimate the emission, burden and lifetime of bioaerosols. Finally, we evaluate the contribution of bioaerosols to the total organic aerosol budget, which further consists of primary and secondary organic aerosol.

  2. Assessment of the Aerosol Generation and Toxicity of Carbon Nanotubes

    PubMed Central

    O’Shaughnessy, Patrick T.; Adamcakova-Dodd, Andrea; Altmaier, Ralph; Thorne, Peter S.

    2014-01-01

    Current interest in the pulmonary toxicity of carbon nanotubes (CNTs) has resulted in a need for an aerosol generation system that is capable of consistently producing a CNT aerosol at a desired concentration level. This two-part study was designed to: (1) assess the properties of a commercially-available aerosol generator when producing an aerosol from a purchased powder supply of double-walled carbon nanotubes (DWCNTs); and (2) assess the pulmonary sub-acute toxicity of DWCNTs in a murine model during a 5-day (4 h/day) whole-body exposure. The aerosol generator, consisting of a novel dustfeed mechanism and venturi ejector was determined to be capable of producing a DWCNT consistently over a 4 h exposure period at an average level of 10.8 mg/m3. The count median diameter was 121 nm with a geometric standard deviation of 2.04. The estimated deposited dose was 32 µg/mouse. The total number of cells in bronchoalveolar lavage (BAL) fluid was significantly (p < 0.01) increased in exposed mice compared to controls. Similarly, macrophages in BAL fluid were significantly elevated in exposed mice, but not neutrophils. All animals exposed to CNT and euthanized immediately after exposure had changes in the lung tissues showing acute inflammation and injury; however these pathological changes resolved two weeks after the exposure. PMID:28344231

  3. Assessment of the Aerosol Generation and Toxicity of Carbon Nanotubes.

    PubMed

    O'Shaughnessy, Patrick T; Adamcakova-Dodd, Andrea; Altmaier, Ralph; Thorne, Peter S

    2014-06-12

    Current interest in the pulmonary toxicity of carbon nanotubes (CNTs) has resulted in a need for an aerosol generation system that is capable of consistently producing a CNT aerosol at a desired concentration level. This two-part study was designed to: (1) assess the properties of a commercially-available aerosol generator when producing an aerosol from a purchased powder supply of double-walled carbon nanotubes (DWCNTs); and (2) assess the pulmonary sub-acute toxicity of DWCNTs in a murine model during a 5-day (4 h/day) whole-body exposure. The aerosol generator, consisting of a novel dustfeed mechanism and venturi ejector was determined to be capable of producing a DWCNT consistently over a 4 h exposure period at an average level of 10.8 mg/m³. The count median diameter was 121 nm with a geometric standard deviation of 2.04. The estimated deposited dose was 32 µg/mouse. The total number of cells in bronchoalveolar lavage (BAL) fluid was significantly ( p < 0.01) increased in exposed mice compared to controls. Similarly, macrophages in BAL fluid were significantly elevated in exposed mice, but not neutrophils. All animals exposed to CNT and euthanized immediately after exposure had changes in the lung tissues showing acute inflammation and injury; however these pathological changes resolved two weeks after the exposure.

  4. Towards the isolation and estimation of elemental carbon in atmospheric aerosols using supercritical fluid extraction and thermo-optical analysis.

    PubMed

    Azeem, Hafiz Abdul; Martinsson, Johan; Stenström, Kristina Eriksson; Swietlicki, Erik; Sandahl, Margareta

    2017-07-01

    Air-starved combustion of biomass and fossil fuels releases aerosols, including airborne carbonaceous particles, causing negative climatic and health effects. Radiocarbon analysis of the elemental carbon (EC) fraction can help apportion sources of its emission, which is greatly constrained by the challenges in isolation of EC from organic compounds in atmospheric aerosols. The isolation of EC using thermo-optical analysis is however biased by the presence of interfering compounds that undergo pyrolysis during the analysis. EC is considered insoluble in all acidic, basic, and organic solvents. Based on the property of insolubility, a sample preparation method using supercritical CO 2 and methanol as co-solvent was developed to remove interfering organic compounds. The efficiency of the method was studied by varying the density of supercritical carbon dioxide by means of temperature and pressure and by varying the methanol content. Supercritical CO 2 with 10% methanol by volume at a temperature of 60 °C, a pressure of 350 bar and 20 min static mode extraction were found to be the most suitable conditions for the removal of 59 ± 3% organic carbon, including compounds responsible for pyrolysis with 78 ± 16% EC recovery. The results indicate that the method has potential for the estimation and isolation of EC from OC for subsequent analysis methods and source apportionment studies.

  5. Investigating water soluble organic aerosols: Sources and evolution

    NASA Astrophysics Data System (ADS)

    Hecobian, Arsineh N.

    Many studies are being conducted on the different properties of organic aerosols (OA-s) as it is first emitted into the atmosphere and the consequent changes in these characteristics as OA-s age and secondary organic aerosol (SOA) is produced and in turn aged. This thesis attempts to address some of the significant and emerging issues that deal with the formation and transformation of water-soluble organic aerosols in the atmosphere. First, a proven method for the measurement of gaseous sulfuric acid, negative ion chemical ionization mass spectrometry (CIMS), has been modified for fast and sensitive measurements of particulate phase sulfuric acid (i.e. sulfate). The modifications implemented on this system have also been the subject of preliminary verifications for measurements of aerosol phase oxalic acid (an organic acid). Second, chemical and physical characteristics of a wide range of biomass-burning plumes intercepted by the NASA DC-8 research aircraft during the three phases of the ARCTAS experiment are presented here. A statistical summary of the emission (or enhancement) ratios relative to carbon monoxide is presented for various gaseous and aerosol species. Extensive investigations of fire plume evolutions were undertaken during the second part of this field campaign. For four distinct Boreal fires, where plumes were intercepted by the aircraft over a wide range of down-wind distances, emissions of various compounds and the effect of aging on them were investigated in detail. No clear evidence of production of secondary compounds (e.g., WSOC and OA) was observed. High variability in emissions between the different plumes may have obscured any clear evidence of changes in the mass of various species with increasing plume age. Also, the lack if tropospheric oxidizing species (e.g., O3 and OH) may have contributed to the lack of SOA formation. Individual intercepts of smoke plumes in this study were segregated by source regions. The normalized excess mixing

  6. Evaluation of Organic Aerosol Formation and Apportionment in a polluted Megacity

    NASA Astrophysics Data System (ADS)

    Tsimpidi, A. P.; Karydis, V. A.; Zavala, M.; Lei, W.; Decarlo, P. F.; Ulbrich, I.; Jimenez, J. L.; Molina, L. T.; Pandis, S. N.

    2009-04-01

    Pollution from megacities and large urban areas is important not only for local effects on health, visibility, and ecosystems but also because of their collective influence on atmospheric chemistry and radiative forcing in regional and global scale. Organic species account for a large fraction of the submicron aerosol mass at most megacities. Urban areas are large sources of organic aerosols and their precursors. Nevertheless, the contributions of primary (POA) and secondary organic aerosol (SOA) have been difficult to quantify. In this study, new primary and secondary organic aerosol modules were added to PMCAMx, a three dimensional chemical transport model (Gaydos et al., 2007). The new modeling framework is based on the volatility basis-set approach (Lane et al., 2007): both primary and secondary organic components are assumed to be semivolatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. The emission inventory is modified and the POA emissions are distributed by volatility based on dilution experiments (Robinson et al., 2007). PMCAMx is applied in the Mexico City Metropolitan Area during April 2003 and March 2006. The model predictions are compared with Aerodyne's Aerosol Mass Spectrometer (AMS) observations from the MCMA and MILAGRO campaigns respectively. Furthermore, the predicted concentrations over Mexico City are compared against measurements from a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) which was onboard the NSF/NCAR C-130 aircraft as part of the MILAGRO field campaign (DeCarlo et al., 2008). The organic aerosol (OA) to CO ratio is used as an indicator in order to evaluate the photo-oxidation of the predicted OA after its horizontal and vertical advection. References Gaydos, T.M.; Pinder, R.W.; Koo, B.; Fahey, K.M.; Pandis, S.N., 2007. Development and application of a three-dimensional aerosol chemical transport model, PMCAMx. Atmospheric Environment 41, 2594-2611. Lane, T

  7. Seasonal dependence of aerosol processing in urban Philadelphia

    NASA Astrophysics Data System (ADS)

    Avery, A. M.; Waring, M. S.; DeCarlo, P. F.

    2017-12-01

    Urban aerosols pose an important threat to human health due to the conflation of emissions and concentrated population exposed. Winter and summer aerosol and trace gas measurements were taken in downtown Philadelphia in 2016. Measurements included aerosol composition and size with an Aerodyne Aerosol Mass Spectrometer (AMS), particle size distributions with an SMPS, and an aethalometer. Trace gas measurements of O3, NO, CH4, CO, and CO2 were taken concurrently. Sampling in seasonal extremes provided contrast in aerosol and trace gas composition, aerosol processing, and emission factors. Inorganic aerosol components contributed approximately 60% of the submicron aerosol mass, while summertime aerosol composition was roughly 70% organic matter. Positive Matrix Factorization (PMF) on the organic aerosol (OA) matrix revealed three factors in common in each season, including an oxygenated organic aerosol (OOA) factor with different temporal behavior in each season. In summertime, OOA varied diurnally with ozone and daytime temperature, but in the wintertime, it was anti-correlated with ozone and temperature, and instead trended with calculated liquid water, indicating a seasonally-dependent processing of organic aerosol in Philadelphia's urban environment. Due to the inorganic dominant winter aerosol, liquid water much higher (2.65 μg/m3) in winter than in summer (1.54 μg/m3). Diurnally varying concentrations of background gas phase species (CH4, CO2) were higher in winter and varied less as a result of boundary layer conditions; ozone was also higher in background in winter than summer. Winter stagnation events with low windspeed showed large buildup of trace gases CH4, CO, CO2, and NO. Traffic related aerosol was also elevated with black carbon and hydrocarbon-like OA (HOA) plumes of each at 3-5 times higher than the winter the average value for each. Winter ratios of HOA to black carbon were significantly higher in the winter than the summer due to lower

  8. Organic nitrogen in aerosols at a forest site in southern Appalachia

    EPA Science Inventory

    This study investigates the composition of organic particulate matter (PM2.5) in a remote montane forest in the southeastern U.S., focusing on the role of organic nitrogen (N) in sulfur-containing secondary organic aerosol (SOA) and aerosols associated with biomass burning. Meas...

  9. Snow Impurities on Central Asian Glaciers: Mineral Dust, Organic & Elemental Carbon

    NASA Astrophysics Data System (ADS)

    Schmale, J.; Kang, S.; Peltier, R.; Sprenger, M.; Guo, J.; Li, Y.; Zhang, Q.

    2014-12-01

    In Central Asia, 90 % of the population depend on water stored in glaciers and mountain snow cover. Accelerated melting can be induced by the deposition of e.g., mineral dust and black carbon that reduce the surface albedo. Data on source regions and chemical characteristics of snow impurities are however scarce in Central Asia. We studied aerosol deposited between summers of 2012 and 2013on three different glaciers in the Kyrgyz Republic. Samples were taken from two snow pits on the glacier Abramov in the northern Pamir and from one snow pit on Ak-Shiirak and Suek in the central Tien Shan. The snow was analyzed for elemental and total organic carbon, major ions and mineral dust. In addition, dissolved organic carbon was speciated by using the Aerodyne high-resolution time-of-flight aerosol spectrometer. Elevated mineral dust concentrations were found on all glaciers during summer and winter with lower annual average concentrations (20 mg l-1)in the northern Pamir (factor 5 to 6). Correlations between dust tracers varied, indicating different source regions. Average EC concentrations showed seasonal variation in the northern Pamir (> 100 μg l-1 in summer, < 30 μg l-1 in winter) while there was little variation throughout the year in the central Tien Shan (~ 200 μg l-1). Similarly, OC:EC ratios showed no seasonal cycle in that region averaging around 3. On Abramov, the ratio was significantly higher in winter (> 12) than in summer (< 4). The average O:C ratios across all glaciers ranged between 0.65 and 1.09, indicating a high degree of oxygenation which suggests long-range transport of the organic snow impurities. Marker substances such as potassium and mercury and their correlations suggest contribution from biomass burning emissions. Atmospheric measurements in August 2013 were conducted to obtain information on background aerosol characteristics in the remote high mountain areas. The average black carbon concentration was 0.26 μg/m³ (± 0.24 μg/m³).

  10. The validation of the Yonsei CArbon Retrieval algorithm with improved aerosol information using GOSAT measurements

    NASA Astrophysics Data System (ADS)

    Jung, Yeonjin; Kim, Jhoon; Kim, Woogyung; Boesch, Hartmut; Goo, Tae-Young; Cho, Chunho

    2017-04-01

    Although several CO2 retrieval algorithms have been developed to improve our understanding about carbon cycle, limitations in spatial coverage and uncertainties due to aerosols and thin cirrus clouds are still remained as a problem for monitoring CO2 concentration globally. Based on an optimal estimation method, the Yonsei CArbon Retrieval (YCAR) algorithm was developed to retrieve the column-averaged dry-air mole fraction of carbon dioxide (XCO2) using the Greenhouse Gases Observing SATellite (GOSAT) measurements with optimized a priori CO2 profiles and aerosol models over East Asia. In previous studies, the aerosol optical properties (AOP) are the most important factors in CO2 retrievals since AOPs are assumed as fixed parameters during retrieval process, resulting in significant XCO2 retrieval error up to 2.5 ppm. In this study, to reduce these errors caused by inaccurate aerosol optical information, the YCAR algorithm improved with taking into account aerosol optical properties as well as aerosol vertical distribution simultaneously. The CO2 retrievals with two difference aerosol approaches have been analyzed using the GOSAT spectra and have been evaluated throughout the comparison with collocated ground-based observations at several Total Carbon Column Observing Network (TCCON) sites. The improved YCAR algorithm has biases of 0.59±0.48 ppm and 2.16±0.87 ppm at Saga and Tsukuba sites, respectively, with smaller biases and higher correlation coefficients compared to the GOSAT operational algorithm. In addition, the XCO2 retrievals will be validated at other TCCON sites and error analysis will be evaluated. These results reveal that considering better aerosol information can improve the accuracy of CO2 retrieval algorithm and provide more useful XCO2 information with reduced uncertainties. This study would be expected to provide useful information in estimating carbon sources and sinks.

  11. 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.

  12. Investigation of a systematic offset in the measurement of organic carbon with a semicontinuous analyzer.

    PubMed

    Offenberg, John H; Lewandowski, Michael; Edney, Edward O; Kleindienst, Tadeusz E; Jaoui, Mohammed

    2007-05-01

    Organic carbon (OC) was measured semicontinuously in laboratory experiments of steady-state secondary organic aerosol formed by hydrocarbon + nitrogen oxide irradiations. Examination of the mass of carbon measured on the filter for various sample volumes reveals a systematic offset that is not observed when performing an instrumental blank. These findings suggest that simple subtraction of instrumental blanks determined as the standard analysis without sample collection (i.e., by cycling the pump and valves yet filtering zero liters of air followed by routine chemical analysis) from measured concentrations may be inadequate. This may be especially true for samples collected through the filtration of small air volumes wherein the influence of the systematic offset is greatest. All of the experiments show that filtering a larger volume of air minimizes the influence of contributions from the systematic offset. Application of these results to measurements of ambient concentrations of carbonaceous aerosol suggests a need for collection of sufficient carbon mass to minimize the relative influence of the offset signal.

  13. Contributions of Organic Sources to Atmospheric Aerosol Particle Concentrations and Growth

    NASA Astrophysics Data System (ADS)

    Russell, L. M.

    2017-12-01

    Organic molecules are important contributors to aerosol particle mass and number concentrations through primary emissions as well as secondary growth in the atmosphere. New techniques for measuring organic aerosol components in atmospheric particles have improved measurements of this contribution in the last 20 years, including Scanning Transmission X-ray Microscopy Near Edge X-ray Absorption Fine Structure (STXM-NEXAFS), Fourier Transform Infrared spectroscopy (FTIR), and High-Resolution Aerosol Mass Spectrometry (AMS). STXM-NEXAFS individual aerosol particle composition illustrated the variety of morphology of organic components in marine aerosols, the inherent relationships between organic composition and shape, and the links between atmospheric aerosol composition and particles produced in smog chambers. This type of single particle microscopy has also added to size distribution measurements by providing evidence of how surface-controlled and bulk-controlled processes contribute to the growth of particles in the atmosphere. FTIR analysis of organic functional groups are sufficient to distinguish combustion, marine, and terrestrial organic particle sources and to show that each of those types of sources has a surprisingly similar organic functional group composition over four different oceans and four different continents. Augmenting the limited sampling of these off-line techniques with side-by-side inter-comparisons to online AMS provides complementary composition information and consistent quantitative attribution to sources (despite some clear method differences). Single-particle AMS techniques using light scattering and event trigger modes have now also characterized the types of particles found in urban, marine, and ship emission aerosols. Most recently, by combining with off-line techniques, single particle composition measurements have separated and quantified the contributions of organic, sulfate and salt components from ocean biogenic and sea spray

  14. Brown Carbon Production in Ammonium- or Amine-Containing Aerosol Particles by Reactive Uptake of Methylglyoxal and Photolytic Cloud Cycling.

    PubMed

    De Haan, David O; Hawkins, Lelia N; Welsh, Hannah G; Pednekar, Raunak; Casar, Jason R; Pennington, Elyse A; de Loera, Alexia; Jimenez, Natalie G; Symons, Michael A; Zauscher, Melanie; Pajunoja, Aki; Caponi, Lorenzo; Cazaunau, Mathieu; Formenti, Paola; Gratien, Aline; Pangui, Edouard; Doussin, Jean-François

    2017-07-05

    The effects of methylglyoxal uptake on the physical and optical properties of aerosol containing amines or ammonium sulfate were determined before and after cloud processing in a temperature- and RH-controlled chamber. The formation of brown carbon was observed upon methylglyoxal addition, detected as an increase in water-soluble organic carbon mass absorption coefficients below 370 nm and as a drop in single-scattering albedo at 450 nm. The imaginary refractive index component k 450 reached a maximum value of 0.03 ± 0.009 with aqueous glycine aerosol particles. Browning of solid particles occurred at rates limited by chamber mixing (<1 min), and in liquid particles occurred more gradually, but in all cases occurred much more rapidly than in bulk aqueous studies. Further browning in AS and methylammonium sulfate seeds was triggered by cloud events with chamber lights on, suggesting photosensitized brown carbon formation. Despite these changes in optical aerosol characteristics, increases in dried aerosol mass were rarely observed (<1 μg/m 3 in all cases), consistent with previous experiments on methylglyoxal. Under dry, particle-free conditions, methylglyoxal reacted (presumably on chamber walls) with methylamine with a rate constant k = (9 ± 2) × 10 -17 cm 3 molecule -1 s -1 at 294 K and activation energy E a = 64 ± 37 kJ/mol.

  15. Organic condensation: A vital link connecting aerosol formation to climate forcing (Invited)

    NASA Astrophysics Data System (ADS)

    Riipinen, I.; Pierce, J. R.; Yli-Juuti, T.; Nieminen, T.; Häkkinen, S.; Ehn, M.; Junninen, H.; Lehtipalo, K.; Petdjd, T. T.; Slowik, J. G.; Chang, R. Y.; Shantz, N. C.; Abbatt, J.; Leaitch, W. R.; Kerminen, V.; Worsnop, D. R.; Pandis, S. N.; Donahue, N. M.; Kulmala, M. T.

    2010-12-01

    Aerosol-cloud interactions represent the largest uncertainty in calculations of Earth’s radiative forcing. Number concentrations of atmospheric aerosol particles are in the core of this uncertainty, as they govern the numbers of cloud condensation nuclei (CCN) and influence the albedo and lifetime of clouds. Aerosols also impair air quality through their adverse effects on atmospheric visibility and human health. The ultrafine fraction (<100 nm) of atmospheric aerosol particles often dominates the total aerosol numbers, and nucleation of atmospheric vapours is one of the most important sources of these particles. To have climatic relevance, however, the freshly-nucleated particles need to grow in size, and consequently their climatic importance remains to be quantified (see Fig. 1). We combine observations from two continental sites (Egbert, Canada and Hyytiälä, Finland) to show that condensation of organic vapours is a crucial factor governing the lifetimes and climatic importance of the smallest atmospheric particles. We demonstrate that state-of-the-science organic gas-particle partitioning models fail to reproduce the observations; we propose a new modelling approach that is consistent with the measurements. Finally, we demonstrate the large sensitivity of climatic forcing of atmospheric aerosols to these interactions between organic vapours and the smallest atmospheric nanoparticles - highlighting the need for representing this process in global climate models. Figure 1. Organic emissions and the dynamic processes governing the climatic importance of ultrafine aerosol. Condensable vapours are produced upon oxidation of volatile organic compounds (VOCs) and can 1) nucleate to form new small particles; 2) grow freshly formed particles to larger sizes and increase their probability to serve as CCN; 3) condense on the background aerosol (> 100 nm) and enhance the loss of ultrafine particles. Primary organic aerosol (POA) contributes to the large end of the

  16. Role of Climate Change in Global Predictions of Future Tropospheric Ozone and Aerosols

    NASA Technical Reports Server (NTRS)

    Liao, Hong; Chen, Wei-Ting; Seinfeld, John H.

    2006-01-01

    A unified tropospheric chemistry-aerosol model within the Goddard Institute for Space Studies general circulation model II is applied to simulate an equilibrium CO2-forced climate in the year 2100 to examine the effects of climate change on global distributions of tropospheric ozone and sulfate, nitrate, ammonium, black carbon, primary organic carbon, secondary organic carbon, sea salt, and mineral dust aerosols. The year 2100 CO2 concentration as well as the anthropogenic emissions of ozone precursors and aerosols/aerosol precursors are based on the Intergovernmental Panel on Climate Change Special Report on Emissions Scenarios (SRES) A2. Year 2100 global O3 and aerosol burdens predicted with changes in both climate and emissions are generally 5-20% lower than those simulated with changes in emissions alone; as exceptions, the nitrate burden is 38% lower, and the secondary organic aerosol burden is 17% higher. Although the CO2-driven climate change alone is predicted to reduce the global O3 concentrations over or near populated and biomass burning areas because of slower transport, enhanced biogenic hydrocarbon emissions, decomposition of peroxyacetyl nitrate at higher temperatures, and the increase of O3 production by increased water vapor at high NOx levels. The warmer climate influences aerosol burdens by increasing aerosol wet deposition, altering climate-sensitive emissions, and shifting aerosol thermodynamic equilibrium. Climate change affects the estimates of the year 2100 direct radiative forcing as a result of the climate-induced changes in burdens and different climatological conditions; with full gas-aerosol coupling and accounting for ozone and direct radiative forcings by the O2, sulfate, nitrate, black carbon, and organic carbon are predicted to be +0.93, -0.72, -1.0, +1.26, and -0.56 W m(exp -2), respectively, using present-day climate and year 2100 emissions, while they are predicted to be +0.76, -0.72, 0.74, +0.97, and -0.58 W m(exp -2

  17. A Physically Based Framework for Modelling the Organic Fractionation of Sea Spray Aerosol from Bubble Film Langmuir Equilibria

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Burrows, Susannah M.; Ogunro, O.; Frossard, Amanda

    2014-12-19

    The presence of a large fraction of organic matter in primary sea spray aerosol (SSA) can strongly affect its cloud condensation nuclei activity and interactions with marine clouds. Global climate models require new parameterizations of the SSA composition in order to improve the representation of these processes. Existing proposals for such a parameterization use remotely-sensed chlorophyll-a concentrations as a proxy for the biogenic contribution to the aerosol. However, both observations and theoretical considerations suggest that existing relationships with chlorophyll-a, derived from observations at only a few locations, may not be representative for all ocean regions. We introduce a novel frameworkmore » for parameterizing the fractionation of marine organic matter into SSA based on a competitive Langmuir adsorption equilibrium at bubble surfaces. Marine organic matter is partitioned into classes with differing molecular weights, surface excesses, and Langmuir adsorption parameters. The classes include a lipid-like mixture associated with labile dissolved organic carbon (DOC), a polysaccharide-like mixture associated primarily with semi-labile DOC, a protein-like mixture with concentrations intermediate between lipids and polysaccharides, a processed mixture associated with recalcitrant surface DOC, and a deep abyssal humic-like mixture. Box model calculations have been performed for several cases of organic adsorption to illustrate the underlying concepts. We then apply the framework to output from a global marine biogeochemistry model, by partitioning total dissolved organic carbon into several classes of macromolecule. Each class is represented by model compounds with physical and chemical properties based on existing laboratory data. This allows us to globally map the predicted organic mass fraction of the nascent submicron sea spray aerosol. Predicted relationships between chlorophyll-\\textit{a} and organic fraction are similar to existing empirical

  18. Molecular characterization of urban organic aerosol in tropical India: contributions of biomass/biofuel burning, plastic burning, and fossil fuel combustion

    NASA Astrophysics Data System (ADS)

    Fu, P. Q.; Kawamura, K.; Pavuluri, C. M.; Swaminathan, T.

    2009-10-01

    Organic molecular composition of PM10 samples, collected at Chennai in tropical India, was studied using capillary gas chromatography/mass spectrometry. Twelve organic compound classes were detected in the aerosols, including aliphatic lipids, sugar compounds, lignin products, terpenoid biomarkers, sterols, aromatic acids, phthalates, hopanes, and polycyclic aromatic hydrocarbons (PAHs). At daytime, phthalates was found to be the most abundant compound class; while at nighttime, fatty acids was the dominant one. Concentrations of total quantified organics were higher in summer (611-3268 ng m-3, average 1586 ng m-3) than in winter (362-2381 ng m-3, 1136 ng m-3), accounting for 11.5±1.93% and 9.35±1.77% of organic carbon mass in summer and winter, respectively. Di-(2-ethylhexyl) phthalate, C16 fatty acid, and levoglucosan were identified as the most abundant single compounds. The nighttime maxima of most organics in the aerosols indicate a land/sea breeze effect in tropical India, although some other factors such as local emissions and long-range transport may also influence the composition of organic aerosols. The abundances of anhydrosugars (e.g., levoglucosan), lignin and resin products, hopanes and PAHs in the Chennai aerosols suggest that biomass burning and fossil fuel combustion are significant sources of organic aerosols in tropical India. Interestingly, terephthalic acid was maximized at nighttime, which is different from those of phthalic and isophthalic acids. A positive correlation was found between the concentration of 1,3,5-triphenylbenzene (a tracer for plastic burning) and terephthalic acid, suggesting that field burning of municipal solid wastes including plastics is a significant source of terephthalic acid. This study demonstrates that, in addition to biomass burning and fossil fuel combustion, the open-burning of plastics also contributes to the organic aerosols in South Asia.

  19. Differences in the OC/EC Ratios that Characterize Ambient and Source Aerosols due to Thermal-Optical Analysis

    EPA Science Inventory

    Thermal-optical analysis (TOA) is typically used to measure the OC/EC (organic carbon/elemental carbon) and EC/TC (elemental carbon/total carbon) ratios in source and atmospheric aerosols. The present study utilizes a dual-optical carbon aerosol analyzer to examine the effects of...

  20. Formation of carbon allotrope aerosol by colliding plasmas in an inertial fusion reactor

    NASA Astrophysics Data System (ADS)

    Hirooka, Y.; Sato, H.; Ishihara, K.; Yabuuchi, T.; Tanaka, K. A.

    2014-02-01

    Along with repeated implosions, the interior of an inertial fusion target chamber is exposed to short pulses of high-energy x-ray, unburned DT-fuel particles, He-ash and pellet debris. As a result, chamber wall materials are subjected to ablation, emitting particles in the plasma state. Ablated particles will either be re-deposited elsewhere or collide with each other, perhaps in the centre-of-symmetry region of the chamber volume. Colliding ablation plasma particles can lead to the formation of clusters to grow into aerosol, possibly floating thereafter, which can deteriorate the subsequent implosion performance via laser scattering, etc. In a laboratory-scale YAG laser setup, the formation of nano-scale aerosol has been demonstrated in vacuum at irradiation power densities of the orders of 108-10 W cm-2 at 10 Hz, each 6 ns long, simulating the high-repetition rate inertial fusion reactor situation. Interestingly, carbon aerosol formation has been observed in the form of fullerene onion, nano- and micro-tubes when laser-ablated plasma plumes of carbon collide with each other. In contrast, colliding plasma plumes of metals tend to generate aerosol in the form of droplets under identical laser irradiation conditions. An atomic and molecular reaction model is proposed to interpret the process of carbon allotrope aerosol formation.

  1. Testing of an automated online EA-IRMS method for fast and simultaneous carbon content and stable isotope measurement of aerosol samples

    NASA Astrophysics Data System (ADS)

    Major, István; Gyökös, Brigitta; Túri, Marianna; Futó, István; Filep, Ágnes; Hoffer, András; Molnár, Mihály

    2016-04-01

    Comprehensive atmospheric studies have demonstrated that carbonaceous aerosol is one of the main components of atmospheric particulate matter over Europe. Various methods, considering optical or thermal properties, have been developed for quantification of the accurate amount of both organic and elemental carbon constituents of atmospheric aerosol. The aim of our work was to develop an alternative fast and easy method for determination of the total carbon content of individual aerosol samples collected on prebaked quartz filters whereby the mass and surface concentration becomes simply computable. We applied the conventional "elemental analyzer (EA) coupled online with an isotope ratio mass spectrometer (IRMS)" technique which is ubiquitously used in mass spectrometry. Using this technique we are able to measure simultaneously the carbon stable isotope ratio of the samples, as well. During the developing process, we compared the EA-IRMS technique with an off-line catalytic combustion method worked out previously at Hertelendi Laboratory of Environmental Studies (HEKAL). We tested the combined online total carbon content and stable isotope ratio measurement both on standard materials and real aerosol samples. Regarding the test results the novel method assures, on the one hand, at least 95% of carbon recovery yield in a broad total carbon mass range (between 100 and 3000 ug) and, on the other hand, a good reproducibility of stable isotope measurements with an uncertainty of ± 0.2 per mill. Comparing the total carbon results obtained by the EA-IRMS and the off-line catalytic combustion method we found a very good correlation (R2=0.94) that proves the applicability of both preparation method. Advantages of the novel method are the fast and simplified sample preparation steps and the fully automated, simultaneous carbon stable isotope ratio measurement processes. Furthermore stable isotope ratio results can effectively be applied in the source apportionment

  2. Primary to secondary organic aerosol: evolution of organic emissions from mobile combustion sources

    NASA Astrophysics Data System (ADS)

    Presto, A. A.; Gordon, T. D.; Robinson, A. L.

    2014-05-01

    A series of smog chamber experiments were conducted to investigate the transformation of primary organic aerosol (POA) and formation of secondary organic aerosol (SOA) during the photooxidation of dilute exhaust from a fleet of gasoline and diesel motor vehicles and two gas-turbine engines. In experiments where POA was present in the chamber at the onset of photooxidation, positive matrix factorization (PMF) was used to determine separate POA and SOA factors from aerosol mass spectrometer data. A 2-factor solution, with one POA factor and one SOA factor, was sufficient to describe the organic aerosol for gasoline vehicles, diesel vehicles, and one of the gas-turbine engines. Experiments with the second gas-turbine engine required a 3-factor PMF solution with a POA factor and two SOA factors. Results from the PMF analysis were compared to the residual method for determining SOA and POA mass concentrations. The residual method apportioned a larger fraction of the organic aerosol mass as POA because it assumes that all mass at m / z 57 is associated with POA. The POA mass spectrum for the gasoline and diesel vehicles exhibited high abundances of the CnH2n+1 series of ions (m / z 43, 57, etc.) and was similar to the mass spectra of the hydrocarbon-like organic aerosol factor determined from ambient data sets with one exception, a diesel vehicle equipped with a diesel oxidation catalyst. POA mass spectra for the gas-turbine engines are enriched in the CnH2n-1 series of ions (m / z 41, 55, etc.), consistent with the composition of the lubricating oil used in these engines. The SOA formed from the three sources exhibits high abundances of m / z 44 and 43, indicative of mild oxidation. The SOA mass spectra are consistent with less-oxidized ambient SV-OOA (semivolatile oxygenated organic aerosols) and fall within the triangular region of f44 versus f43 defined by ambient measurements. However there is poor absolute agreement between the experimentally derived SOA mass

  3. Amphiphobic Polytetrafluoroethylene Membranes for Efficient Organic Aerosol Removal.

    PubMed

    Feng, Shasha; Zhong, Zhaoxiang; Zhang, Feng; Wang, Yong; Xing, Weihong

    2016-04-06

    Polytetrafluoroethylene (PTFE) membrane is an extensively used air filter, but its oleophilicity leads to severe fouling of the membrane surface due to organic aerosol deposition. Herein, we report the fabrication of a new amphiphobic 1H,1H,2H,2H-perfluorodecyl acrylate (PFDAE)-grafted ZnO@PTFE membrane with enhanced antifouling functionality and high removal efficiency. We use atomic-layer deposition (ALD) to uniformly coat a layer of nanosized ZnO particles onto porous PTFE matrix to increase surface area and then subsequently graft PFDAE with plasma. Consequently, the membrane surface showed both superhydrophobicity and oleophobicity with a water contact angle (WCA) and an oil contact angle (OCA) of 150° and 125°, respectively. The membrane air permeation rate of 513 (m(3) m(-2) h(-1) kPa(-1)) was lower than the pristine membrane rate of 550 (m(3) m(-2) h(-1) kPa(-1)), which indicates the surface modification slightly decreased the membrane air permeation. Significantly, the filtration resistance of this amphiphobic membrane to the oil aerosol system was much lower than the initial one. Moreover, the filter exhibited exceptional organic aerosol removal efficiencies that were greater than 99.5%. These results make the amphiphobic PTFE membranes very promising for organic aerosol-laden air-filtration applications.

  4. Formation of nitrogenated organic aerosols in the Titan upper atmosphere.

    PubMed

    Imanaka, Hiroshi; Smith, Mark A

    2010-07-13

    Many aspects of the nitrogen fixation process by photochemistry in the Titan atmosphere are not fully understood. The recent Cassini mission revealed organic aerosol formation in the upper atmosphere of Titan. It is not clear, however, how much and by what mechanism nitrogen is incorporated in Titan's organic aerosols. Using tunable synchrotron radiation at the Advanced Light Source, we demonstrate the first evidence of nitrogenated organic aerosol production by extreme ultraviolet-vacuum ultraviolet irradiation of a N(2)/CH(4) gas mixture. The ultrahigh-mass-resolution study with laser desorption ionization-Fourier transform-ion cyclotron resonance mass spectrometry of N(2)/CH(4) photolytic solid products at 60 and 82.5 nm indicates the predominance of highly nitrogenated compounds. The distinct nitrogen incorporations at the elemental abundances of H(2)C(2)N and HCN, respectively, are suggestive of important roles of H(2)C(2)N/HCCN and HCN/CN in their formation. The efficient formation of unsaturated hydrocarbons is observed in the gas phase without abundant nitrogenated neutrals at 60 nm, and this is confirmed by separately using (13)C and (15)N isotopically labeled initial gas mixtures. These observations strongly suggest a heterogeneous incorporation mechanism via short lived nitrogenated reactive species, such as HCCN radical, for nitrogenated organic aerosol formation, and imply that substantial amounts of nitrogen is fixed as organic macromolecular aerosols in Titan's atmosphere.

  5. Aqueous-phase mechanism for secondary organic aerosol ...

    EPA Pesticide Factsheets

    Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx  ≡  NO + NO2) over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA) and formaldehyde (a product of isoprene oxidation). Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NOx pathway and glyoxal (28 %) from both low- and high-NOx pathways. This speciation is consistent with observati

  6. Quantifying organic aerosol single scattering albedo over tropical biomass burning regions using ground-based observation

    NASA Astrophysics Data System (ADS)

    Chu, J. E.

    2016-12-01

    Despite growing evidence of light-absorbing organic aerosols (OAs), OA light absorption has been poorly understood due to difficulties in aerosol light absorption measurements. In this study, we developed an empirical method to quantify OA single scattering albedo (SSA), the ratio of light scattering to extinction, using ground-based Aerosol Robotic Network (AERONET) observation. Our method includes partitioning fine-mode aerosol optical depth (fAOD) to individual aerosol's optical depth (AOD), separating black carbon and OA absorption aerosol optical depths, and finally binding OA SSA and sulfate+nitrate AOD. Our best estimate of OA SSA over tropical biomass burning region is 0.91 at 550nm with a range of 0.82-0.93. It implies the common OA SSA values of 0.96-1.0 in aerosol CTMs and GCMs significantly underrepresent OA light absorption. Model experiments with prescribed OA SSA showed that the enhanced absorption of solar radiation due to light absorbing OA yields global mean radiative forcing is +0.09 Wm-2 at the TOA, +0.21 Wm-2 at the atmosphere, and -0.12 Wm-2 at the surface. Compared to the previous assessment of OA radiative forcing reported in AeroCom II project, our result indicate that OA light absorption causes TOA radiative forcing by OA to change from negative (i.e., cooling effect) to positive (warming effect).

  7. CHEMICAL ANALYSIS METHODS FOR ATMOSPHERIC AEROSOL COMPONENTS

    EPA Science Inventory

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

  8. Multi-walled carbon nanotubes: sampling criteria and aerosol characterization

    PubMed Central

    Chen, Bean T.; Schwegler-Berry, Diane; McKinney, Walter; Stone, Samuel; Cumpston, Jared L.; Friend, Sherri; Porter, Dale W.; Castranova, Vincent; Frazer, David G.

    2015-01-01

    This study intends to develop protocols for sampling and characterizing multi-walled carbon nanotube (MWCNT) aerosols in workplaces or during inhalation studies. Manufactured dry powder containing MWCNT’s, combined with soot and metal catalysts, form complex morphologies and diverse shapes. The aerosols, examined in this study, were produced using an acoustical generator. Representative samples were collected from an exposure chamber using filters and a cascade impactor for microscopic and gravimetric analyses. Results from filters showed that a density of 0.008–0.10 particles per µm2 filter surface provided adequate samples for particle counting and sizing. Microscopic counting indicated that MWCNT’s, resuspended at a concentration of 10 mg/m3, contained 2.7 × 104 particles/cm3. Each particle structure contained an average of 18 nanotubes, resulting in a total of 4.9 × 105 nanotubes/cm3. In addition, fibrous particles within the aerosol had a count median length of 3.04 µm and a width of 100.3 nm, while the isometric particles had a count median diameter of 0.90 µm. A combination of impactor and microscopic measurements established that the mass median aerodynamic diameter of the mixture was 1.5 µm. It was also determined that the mean effective density of well-defined isometric particles was between 0.71 and 0.88 g/cm3, and the mean shape factor of individual nanotubes was between 1.94 and 2.71. The information obtained from this study can be used for designing animal inhalation exposure studies and adopted as guidance for sampling and characterizing MWCNT aerosols in workplaces. The measurement scheme should be relevant for any carbon nanotube aerosol. PMID:23033994

  9. Updating CMAQ secondary organic aerosol properties relevant for aerosol water interactions

    EPA Science Inventory

    Properties of secondary organic aerosol (SOA) compounds in CMAQ are updated with state-of-the-science estimates from structure activity relationships to provide consistency among volatility, molecular weight, degree of oxygenation, and solubility/hygroscopicity. These updated pro...

  10. Modeling regional air quality and climate: improving organic aerosol and aerosol activation processes in WRF/Chem version 3.7.1

    NASA Astrophysics Data System (ADS)

    Yahya, Khairunnisa; Glotfelty, Timothy; Wang, Kai; Zhang, Yang; Nenes, Athanasios

    2017-06-01

    Air quality and climate influence each other through the uncertain processes of aerosol formation and cloud droplet activation. In this study, both processes are improved in the Weather, Research and Forecasting model with Chemistry (WRF/Chem) version 3.7.1. The existing Volatility Basis Set (VBS) treatments for organic aerosol (OA) formation in WRF/Chem are improved by considering the following: the secondary OA (SOA) formation from semi-volatile primary organic aerosol (POA), a semi-empirical formulation for the enthalpy of vaporization of SOA, and functionalization and fragmentation reactions for multiple generations of products from the oxidation of VOCs. Over the continental US, 2-month-long simulations (May to June 2010) are conducted and results are evaluated against surface and aircraft observations during the Nexus of Air Quality and Climate Change (CalNex) campaign. Among all the configurations considered, the best performance is found for the simulation with the 2005 Carbon Bond mechanism (CB05) and the VBS SOA module with semivolatile POA treatment, 25 % fragmentation, and the emissions of semi-volatile and intermediate volatile organic compounds being 3 times the original POA emissions. Among the three gas-phase mechanisms (CB05, CB6, and SAPRC07) used, CB05 gives the best performance for surface ozone and PM2. 5 concentrations. Differences in SOA predictions are larger for the simulations with different VBS treatments (e.g., nonvolatile POA versus semivolatile POA) compared to the simulations with different gas-phase mechanisms. Compared to the simulation with CB05 and the default SOA module, the simulations with the VBS treatment improve cloud droplet number concentration (CDNC) predictions (normalized mean biases from -40.8 % to a range of -34.6 to -27.7 %), with large differences between CB05-CB6 and SAPRC07 due to large differences in their OH and HO2 predictions. An advanced aerosol activation parameterization based on the Fountoukis and Nenes

  11. On the mixing and evaporation of secondary organic aerosol components.

    PubMed

    Loza, Christine L; Coggon, Matthew M; Nguyen, Tran B; Zuend, Andreas; Flagan, Richard C; Seinfeld, John H

    2013-06-18

    The physical state and chemical composition of an organic aerosol affect its degree of mixing and its interactions with condensing species. We present here a laboratory chamber procedure for studying the effect of the mixing of organic aerosol components on particle evaporation. The procedure is applied to the formation of secondary organic aerosol (SOA) from α-pinene and toluene photooxidation. SOA evaporation is induced by heating the chamber aerosol from room temperature (25 °C) to 42 °C over 7 h and detected by a shift in the peak diameter of the SOA size distribution. With this protocol, α-pinene SOA is found to be more volatile than toluene SOA. When SOA is formed from the two precursors sequentially, the evaporation behavior of the SOA most closely resembles that of SOA from the second parent hydrocarbon, suggesting that the structure of the mixed SOA resembles a core of SOA from the initial precursor coated by a layer of SOA from the second precursor. Such a core-and-shell configuration of the organic aerosol phases implies limited mixing of the SOA from the two precursors on the time scale of the experiments, consistent with a high viscosity of at least one of the phases.

  12. SECONDARY ORGANIC AEROSOL FORMATION FROM THE IRRADIATION OF SIMULATED AUTOMOBILE EXHAUST

    EPA Science Inventory

    A laboratory study was conducted to evaluate the potential for secondary organic aerosol formation from emissions from automotive exhaust. The goal was to determine to what extent photochemical oxidation products of these hydrocarbons contribute to secondary organic aerosol (SO...

  13. Gas/Particle Partitioning of Organic Acids and Organic Aerosols in a Ponderosa Pine Forest in Colorado during BEACHON-RoMBAS 2011

    NASA Astrophysics Data System (ADS)

    Jimenez, J. L.; Yatavelli, L.; Stark, H.; Hayes, P. L.; Campuzano-Jost, P.; Thompson, S.; Kimmel, J. R.; Day, D. A.; Cubison, M. J.; Thornton, J. A.; Jayne, J.; Worsnop, D. R.

    2012-12-01

    The Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) took place at Manitou Forest, CO, during July-Aug. 2011. Gas and particle-phase organic acids were analyzed in real time using a micro-orifice volatilization impactor chemical ionization high-resolution time-of-flight mass spectrometer (MOVI-HRToF-CIMS; Yatavelli et al., AS&T 2012; Yatavelli & Thornton, AS&T 2010) with acetate as the reagent ion. During the gas sampling phase (when the MOVI was at room temperature) aerosol was collected on the MOVI impactor, and was subsequently thermally desorbed over 10 min. under nitrogen, allowing the collection of temperature-programmed thermal desorption (TPTD) mass spectra of particle-phase species. The high resolution of the instrument allows the determination of the elemental composition of most detected ions. Positive Matrix Factorization (PMF) is shown to be very useful to quantify the CIMS backgrounds during the different phases of operation. Two methods were used to estimate the volatility of the detected species. First, the fraction of each species in the particle phase (Fp) vs carbon number was found to approximately follow partitioning theory, both for the alkanoic acids and also for the total acid signal, after accounting for the effect of the oxidation state on vapor pressure. Fp was found to respond on timescales of ~1 h to changes in ambient temperature, indicating that diffusion limitations to evaporation are not major for the aerosol at this site. Preliminary results suggest that Fp depends more strongly on vapor pressure and temperature than on RH, suggesting preferential partitioning for the organic phase rather than the water phase. Secondly, the volatility of individual or groups of acids can be quantified based on the TPTD signal based on calibration with multiple acids of known vapor pressure at concentrations similar to ambient, analogous to the methods of

  14. Understanding the interacted mechanism between carbonation and chloride aerosol attack in ordinary Portland cement concrete

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Liu, Jun; Qiu, Qiwen; Chen, Xiaochi

    An experimental study is carried out with the aim to understand the interacted mechanism between carbonation and chloride aerosol attack in ordinary Portland cement (OPC) concrete. Effects of carbonation on the chloride profile, the chloride binding capacity and the chloride diffusion coefficient are evaluated. Besides, effect of chloride aerosol attack on the carbonation rate is investigated. Concrete specimens with three water-to-cement ratios (0.38, 0.47 and 0.53) are fabricated in this work. Tested results demonstrate that carbonation remarkably affects the chloride profile, reduces the chloride binding capacity, and also accelerates the rate of chloride ion diffusion of concrete. Besides, the presencemore » of chloride aerosol can lead to lower the carbonation depth and increase the pH value of carbonated concrete. Microscopic properties such as morphology, porosity, and pore size distribution for the contaminated concretes are explored by scanning electron microscope and mercury intrusion porosimetry, which provide strong evidence to these research findings.« less

  15. First Quantification of Imidazoles in Ambient Aerosol Particles: Potential Photosensitizers, Brown Carbon Constituents, and Hazardous Components.

    PubMed

    Teich, Monique; van Pinxteren, Dominik; Kecorius, Simonas; Wang, Zhibin; Herrmann, Hartmut

    2016-02-02

    Imidazoles are widely discussed in recent literature. They have been studied as a secondary product of the reaction of dicarbonyls with nitrogen containing compounds in a number of laboratory studies, potentially acting as photosensitizers triggering secondary organic aerosol growth and are forming constituents of light absorbing brown carbon. Despite the knowledge from laboratory studies, no quantitative information about imidazoles in ambient aerosol particles is available. Within the present study, five imidazoles (1-butylimidazole, 1-ethylimidazole, 2-ethylimidazole, imidazol-2-carboxaldehyde, and 4(5)-methylimidazole) were successfully identified and quantified for the first time in ambient aerosol samples from different environments in Europe and China. Their concentrations range between 0.2 and 14 ng/m(3). 4(5)-Methylimidazole was found to be the most abundant imidazole. The occurrence of imidazoles seems to be favored at sites with strong biomass burning influence or connected to more polluted air masses. No connection was found between aerosol particle pH and imidazole concentration. Our work corroborates the laboratory studies by showing that imidazoles are present in ambient aerosol samples in measurable amounts. Moreover, it further motivates to explore the potential photosensitizing properties of small alkyl-substituted imidazoles.

  16. Sources and composition of submicron organic mass in marine aerosol particles

    NASA Astrophysics Data System (ADS)

    Frossard, Amanda A.; Russell, Lynn M.; Burrows, Susannah M.; Elliott, Scott M.; Bates, Timothy S.; Quinn, Patricia K.

    2014-11-01

    The sources and composition of atmospheric marine aerosol particles (aMA) have been investigated with a range of physical and chemical measurements from open-ocean research cruises. This study uses the characteristic functional group composition (from Fourier transform infrared spectroscopy) of aMA from five ocean regions to show the following: (i) The organic functional group composition of aMA that can be identified as mainly atmospheric primary marine (ocean derived) aerosol particles (aPMA) is 65 ± 12% hydroxyl, 21 ± 9% alkane, 6 ± 6% amine, and 7 ± 8% carboxylic acid functional groups. Contributions from photochemical reactions add carboxylic acid groups (15%-25%), shipping effluent in seawater and ship emissions add additional alkane groups (up to 70%), and coastal or continental emissions mix in alkane and carboxylic acid groups. (ii) The organic composition of aPMA is nearly identical to model-generated primary marine aerosol particles from bubbled seawater (gPMA, which has 55 ± 14% hydroxyl, 32 ± 14% alkane, and 13 ± 3% amine functional groups), indicating that its overall functional group composition is the direct consequence of the organic constituents of the seawater source. (iii) While the seawater organic functional group composition was nearly invariant across all three ocean regions studied and the ratio of organic carbon to sodium (OC/Na+) in the gPMA remained nearly constant over a broad range of chlorophyll a concentrations, the gPMA alkane group fraction appeared to increase with chlorophyll a concentrations (r = 0.66). gPMA from productive seawater had a larger fraction of alkane functional groups (42 ± 9%) compared to gPMA from nonproductive seawater (22 ± 10%), perhaps due to the presence of surfactants in productive seawater that stabilize the bubble film and lead to preferential drainage of the more soluble (lower alkane group fraction) organic components. gPMA has a hydroxyl group absorption peak location characteristic of

  17. Effects of post-sampling conditions on ambient carbon aerosol filter measurements

    NASA Astrophysics Data System (ADS)

    Dillner, Ann M.; Phuah, Chin H.; Turner, Jay R.

    2009-12-01

    Ambient carbonaceous material collected on quartz filters is prone to measurement artifacts due to material gained or lost during post-sampling field latency, shipping, and storage. In seventeen sampling events over a one year period, ambient PM 2.5 aerosols were collected on quartz filters (without denuders) and subjected to various filter treatments to assess the potential for and extent of artifacts. The filter treatments simulated post-sampling environments that filters may be exposed to and included: storage at 40 °C for up to 96 h, storage at -16 °C for 48 h, and storage at room temperature (˜21 °C) for 48 h. Carbon mass on the filters was measured using a thermal-optical method. The total carbon (TC), total organic carbon (TOC) and total elemental carbon (TEC) as well as carbon thermal fraction masses were obtained. Statistical analyses were performed to identify significant differences in carbon fraction concentrations between filters analyzed immediately after sampling and after being subjected to treatment. TOC and TC concentrations decreased by on average 15 ± 5% and 10 ± 4%, respectively, for filters maintained at 40 °C for 96 h but did not change for filters stored at room temperature or frozen for 48 h. TEC did not change for any of the filter treatments. The mass concentration for the organic carbon thermal fraction that evolves at the lowest temperature step (OC1) decreased with increasing storage time at 40 °C with average losses of 70 ± 7% after 96 h. Therefore, OC1 is not a stable measurement due to post-sampling conditions that may be encountered. This work demonstrates that TOC and TC can have substantial measurement artifacts on filters subjected to field latency and other non-temperature controlled post-sampling handling, compared to the carbon loadings on the filter at the end of the sampling period.

  18. Effect of phytoplackton-derived organic matter on the behavior of marine aerosols

    NASA Astrophysics Data System (ADS)

    Fuentes, E.; Coe, H.; McFiggans, G.; Green, D.

    2009-04-01

    The presence of significant concentrations of organic material in marine aerosols has been appreciated for several decades; however, only recently has significant progress been made towards demonstrating that this organic content is biogenically formed. Biogenic organics of placktonic life origin are incorporated in marine aerosol composition as a result of bubble bursting/breaking waves mechanisms that occur at the ocean surface. The presence of organic surfactants in the marine aerosol composition might have a significant impact on the properties of the generated aerosols by affecting the particles surface tension and solution balance properties. Nevertheless, it remains uncertain the role of such organics on the physical-chemical behavior of marine aerosols. In this work an experimental study was performed in order to determine the influence of biogenic marine organic compounds on the size distribution, hygroscopicity and cloud-nucleating properties of marine aerosols. For the experimental study a laboratory water recirculation system (bubble tank), designed for the simulation of bubble-burst aerosol formation, was used as marine aerosol generator. The bubble spectra produced by such system was characterized by means of an optical bubble measuring device (BMS) and it was found to be consistent with oceanic bubble spectra properties. Seawater proxy solutions were prepared from laboratory biologically-synthesized exudates produced by oceanic representative algal species and introduced in the tank for the generation of marine aerosol by bubble bursting. Two experimental methods were employed for seawater proxies preparation: the formation of surface monolayers from the biogenic surfactants extracted by a solid phase extraction technique (monolayer method) and the mixing of the exudates in the sea salt water bulk (bulk mixing method). Particle size distribution, hygroscopicity and cloud condensation nuclei experiments for different monolayers, and exudate mixtures

  19. Trends in sulfate and organic aerosol mass in the Southeast U.S.: Impact on aerosol optical depth and radiative forcing

    NASA Astrophysics Data System (ADS)

    Attwood, A. R.; Washenfelder, R. A.; Brock, C. A.; Hu, W.; Baumann, K.; Campuzano-Jost, P.; Day, D. A.; Edgerton, E. S.; Murphy, D. M.; Palm, B. B.; McComiskey, A.; Wagner, N. L.; Sá, S. S.; Ortega, A.; Martin, S. T.; Jimenez, J. L.; Brown, S. S.

    2014-11-01

    Emissions of SO2 in the United States have declined since the early 1990s, resulting in a decrease in aerosol sulfate mass in the Southeastern U.S. of -4.5(±0.9)% yr-1 between 1992 and 2013. Organic aerosol mass, the other major aerosol component in the Southeastern U.S., has decreased more slowly despite concurrent emission reductions in anthropogenic precursors. Summertime measurements in rural Alabama quantify the change in aerosol light extinction as a function of aerosol composition and relative humidity. Application of this relationship to composition data from 2001 to 2013 shows that a -1.1(±0.7)% yr-1 decrease in extinction can be attributed to decreasing aerosol water mass caused by the change in aerosol sulfate/organic ratio. Calculated reductions in extinction agree with regional trends in ground-based and satellite-derived aerosol optical depth. The diurnally averaged summertime surface radiative effect has changed by 8.0 W m-2, with 19% attributed to the decrease in aerosol water.

  20. Organic Aerosols as Cloud Condensation Nuclei

    NASA Astrophysics Data System (ADS)

    Hudson, J. G.

    2002-05-01

    The large organic component of the atmospheric aerosol contributes to both natural and anthropogenic cloud condensation nuclei (CCN). Moreover, some organic substances may reduce droplet surface tension (Facchini et al. 1999), while others may be partially soluble (Laaksonen et al. 1998), and others may inhibit water condensation. The interaction of organics with water need to be understood in order to better understand the indirect aerosol effect. Therefore, laboratory CCN spectral measurements of organic aerosols are presented. These are measurements of the critical supersaturation (Sc), the supersaturation needed to produce an activated cloud droplet, as a function of the size of the organic particles. Substances include sodium lauryl (dodecyl) sulfate, oxalic, adipic, pinonic, hexadecanedioic, glutaric, stearic, succinic, phthalic, and benzoic acids. These size-Sc relationships are compared with theoretical and measured size-Sc relationships of common inorganic compounds (e.g., NaCl, KI, ammonium and calcium sulfate). Unlike most inorganics some organics display variations in solubility per unit mass as a function of particle size. Those showing relatively greater solubility at smaller sizes may be attributable to surface tension reduction, which is greater for less water dilution, as is the case for smaller particles, which are less diluted at the critical sizes. This was the case for sodium dodecyl sulfate, which does reduce surface tension. Relatively greater solubility for larger particles may be caused by greater dissolution at the higher dilutions that occur with larger particles; this is partial solubility. Measurements are also presented of internal mixtures of various organic and inorganic substances. These measurements were done with two CCN spectrometers (Hudson 1989) operating simultaneously. These two instruments usually displayed similar results in spite of the fact that they have different flow rates and supersaturation profiles. The degree of

  1. Impact of aftertreatment devices on primary emissions and secondary organic aerosol formation potential from in-use diesel vehicles: results from smog chamber experiments

    NASA Astrophysics Data System (ADS)

    Chirico, R.; Decarlo, P. F.; Heringa, M. F.; Tritscher, T.; Richter, R.; Prevot, A. S. H.; Dommen, J.; Weingartner, E.; Wehrle, G.; Gysel, M.; Laborde, M.; Baltensperger, U.

    2010-06-01

    Diesel particulate matter (DPM) is a significant source of aerosol in urban areas and has been linked to adverse health effects. Although newer European directives have introduced increasingly stringent standards for primary PM emissions, gaseous organics emitted from diesel cars can still lead to large amounts of secondary organic aerosol (SOA) in the atmosphere. Here we present results from smog chamber investigations characterizing the primary organic aerosol (POA) and the corresponding SOA formation at atmospherically relevant concentrations for three in-use diesel vehicles with different exhaust aftertreatment systems. One vehicle lacked exhaust aftertreatment devices, one vehicle was equipped with a diesel oxidation catalyst (DOC) and the final vehicle used both a DOC and diesel particulate filter (DPF). The experiments presented here were obtained from the vehicles at conditions representative of idle mode, and for one car in addition at a speed of 60 km/h. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was used to measure the organic aerosol (OA) concentration and to obtain information on the chemical composition. For the conditions explored in this paper, primary aerosols from vehicles without a particulate filter consisted mainly of black carbon (BC) with a low fraction of organic matter (OM, OM/BC<0.5), while the subsequent aging by photooxidation resulted in a consistent production of SOA only for the vehicles without a DOC and with a deactivated DOC. After 5 h of aging ~80% of the total organic aerosol was on average secondary and the estimated "emission factor" for SOA was 0.23-0.56 g/kg fuel burned. In presence of both a DOC and a DPF, primary particles with a mobility diameter above 5 nm were 300±19 cm-3, and only 0.01 g SOA per kg fuel burned was produced within 5 h after lights on. The mass spectra indicate that POA was mostly a non-oxidized OA with an oxygen to carbon atomic ratio (O/C) ranging from 0.097 to 0

  2. Black carbon aerosol size in snow.

    PubMed

    Schwarz, J P; Gao, R S; Perring, A E; Spackman, J R; Fahey, D W

    2013-01-01

    The effect of anthropogenic black carbon (BC) aerosol on snow is of enduring interest due to its consequences for climate forcing. Until now, too little attention has been focused on BC's size in snow, an important parameter affecting BC light absorption in snow. Here we present first observations of this parameter, revealing that BC can be shifted to larger sizes in snow than are typically seen in the atmosphere, in part due to the processes associated with BC removal from the atmosphere. Mie theory analysis indicates a corresponding reduction in BC absorption in snow of 40%, making BC size in snow the dominant source of uncertainty in BC's absorption properties for calculations of BC's snow albedo climate forcing. The shift reduces estimated BC global mean snow forcing by 30%, and has scientific implications for our understanding of snow albedo and the processing of atmospheric BC aerosol in snowfall.

  3. Emission of intermediate, semi and low volatile organic compounds from traffic and their impact on secondary organic aerosol concentrations over Greater Paris

    NASA Astrophysics Data System (ADS)

    Sartelet, K.; Zhu, S.; Moukhtar, S.; André, M.; André, J. M.; Gros, V.; Favez, O.; Brasseur, A.; Redaelli, M.

    2018-05-01

    Exhaust particle emissions are mostly made of black carbon and/or organic compounds, with some of these organic compounds existing in both the gas and particle phases. Although emissions of volatile organic compounds (VOC) are usually measured at the exhaust, emissions in the gas phase of lower volatility compounds (POAvapor) are not. However, these gas-phase emissions may be oxidised after emission and enhance the formation of secondary organic aerosols (SOA). They are shown here to contribute to most of the SOA formation in Central Paris. POAvapor emissions are usually estimated from primary organic aerosol emissions in the particle phase (POA). However, they could also be estimated from VOC emissions for both gasoline and diesel vehicles using previously published measurements from chamber measurements. Estimating POAvapor from VOC emissions and ageing exhaust emissions with a simple model included in the Polyphemus air-quality platform compare well to measurements of SOA formation performed in chamber experiments. Over Greater Paris, POAvapor emissions estimated using POA and VOC emissions are compared using the HEAVEN bottom-up traffic emissions model. The impact on the simulated atmospheric concentrations is then assessed using the Polyphemus/Polair3D chemistry-transport model. Estimating POAvapor emissions from VOC emissions rather than POA emissions lead to lower emissions along motorway axes (between -50% and -70%) and larger emissions in urban areas (up to between +120% and +140% in Central Paris). The impact on total organic aerosol concentrations (gas plus particle) is lower than the impact on emissions: between -8% and 25% along motorway axes and in urban areas respectively. Particle-phase organic concentrations are lower when POAvapor emissions are estimated from VOC than POA emissions, even in Central Paris where the total organic aerosol concentration is higher, because of different assumptions on the emission volatility distribution, stressing the

  4. Fossil and Nonfossil Sources of Organic and Elemental Carbon Aerosols in the Outflow from Northeast China.

    PubMed

    Zhang, Yan-Lin; Kawamura, Kimitaka; Agrios, Konstantinos; Lee, Meehye; Salazar, Gary; Szidat, Sönke

    2016-06-21

    Source quantification of carbonaceous aerosols in the Chinese outflow regions still remains uncertain despite their high mass concentrations. Here, we unambiguously quantified fossil and nonfossil contributions to elemental carbon (EC) and organic carbon (OC) of total suspended particles (TSP) from a regional receptor site in the outflow of Northeast China using radiocarbon measurement. OC and EC concentrations were lower in summer, representing mainly marine air, than in other seasons, when air masses mostly traveled over continental regions in Mongolia and northeast China. The annual-mean contribution from fossil-fuel combustion to EC was 76 ± 11% (0.1-1.3 μg m(-3)). The remaining 24 ± 11% (0.03-0.42 μg m(-3)) was attributed to biomass burning, with slightly higher contribution in the cold period (∼31%) compared to the warm period (∼21%) because of enhanced emissions from regional biomass combustion sources in China. OC was generally dominated by nonfossil sources, with an annual average of 66 ± 11% (0.5-2.8 μg m(-3)), approximately half of which was apportioned to primary biomass-burning sources (34 ± 6%). In winter, OC almost equally originated from primary OC (POC) emissions and secondary OC (SOC) formation from fossil fuel and biomass-burning sources. In contrast, summertime OC was dominated by primary biogenic emissions as well as secondary production from biogenic and biomass-burning sources, but fossil-derived SOC was the smallest contributor. Distinction of POC and SOC was performed using primary POC-to-EC emission ratios separated for fossil and nonfossil emissions.

  5. Chemical Composition of African Biomass Burning Aerosols Over the Southeast Atlantic: Aerosol Mass Spectrometer Results from the 2016 and 2017 ORACLES Field Campaigns.

    NASA Astrophysics Data System (ADS)

    Dobracki, A. N.; Howell, S. G.; Freitag, S.; Smirnow, N.; Podolske, J. R.

    2017-12-01

    Biomass burning (BB) is one of the largest contributors of anthropogenic aerosols in the atmosphere. During BB events, organic and inorganic gases and particles are emitted into the atmosphere. Because of their abundance, particle size, and radiative properties, BB aerosols play an important role in global climate. Southern Africa produces 30% of the Earth's BB aerosol particles. Organics, Nitrates, sulfates, and refractory black carbon, along with other chemical species are lofted into the free troposphere and transported over the Southeast Atlantic Ocean. However, considerate uncertainty remains in the chemical composition of these plumes with its large variety of organic and inorganic species. As part of the NASA ORACLES (ObseRvations of Aerosols above CLouds and their intEractionS) 2016 and 2017 airborne field campaigns, an Aerosol Mass Spectrometer (AMS) was used to sample the chemical composition and chemical structure of the aerosol in this region. Results show constant vertical stratification within the plume over the course of the campaign (August 2017 / September 2016). Using nitrate (NO3) and organic carbon (OC) as two tracers, the structure of the September 2016 plume had a ratio of 1:8 (NO3:OC) in the upper plume (3km-5km), while the lower plume (1km-2.5km) had a ratio of 1:12 (NO3:OC). AMS measurements were supported by carbon monoxide (CO) and carbon dioxide (CO2) measurements. This data revealed a modified combustion efficiency (MCE= ΔCO2/ΔCO2 + ΔCO) of <0.97 in the upper plume, and a higher MCE > 0.97 in the lower plume. An MCE above 0.9 represents efficient burning processes. Additionally, concentrations of C2(H2O)2 (m/z60), a common chemical fragment from breaking up carbohydrates (primarily levoglucosan) emitted by burning biomass only represented <1% of total organics throughout the campaign. These low concentrations are due to efficient combustion rather than oxidation during transport. These results are consistent with earlier studies of

  6. Chemical transport model simulations of organic aerosol in ...

    EPA Pesticide Factsheets

    Gasoline- and diesel-fueled engines are ubiquitous sources of air pollution in urban environments. They emit both primary particulate matter and precursor gases that react to form secondary particulate matter in the atmosphere. In this work, we updated the organic aerosol module and organic emissions inventory of a three-dimensional chemical transport model, the Community Multiscale Air Quality Model (CMAQ), using recent, experimentally derived inputs and parameterizations for mobile sources. The updated model included a revised volatile organic compound (VOC) speciation for mobile sources and secondary organic aerosol (SOA) formation from unspeciated intermediate volatility organic compounds (IVOCs). The updated model was used to simulate air quality in southern California during May and June 2010, when the California Research at the Nexus of Air Quality and Climate Change (CalNex) study was conducted. Compared to the Traditional version of CMAQ, which is commonly used for regulatory applications, the updated model did not significantly alter the predicted organic aerosol (OA) mass concentrations but did substantially improve predictions of OA sources and composition (e.g., POA–SOA split), as well as ambient IVOC concentrations. The updated model, despite substantial differences in emissions and chemistry, performed similar to a recently released research version of CMAQ (Woody et al., 2016) that did not include the updated VOC and IVOC emissions and SOA data

  7. Application of the integrating sphere method to separate the contributions of brown and black carbon in atmospheric aerosols.

    PubMed

    Wonaschütz, Anna; Hitzenberger, Regina; Bauer, Heidi; Pouresmaeil, Parissa; Klatzer, Barbara; Caseiro, Alexandre; Puxbaum, Hans

    2009-02-15

    Until about a decade ago, black carbon (BC) was thought to be the only light absorbing substance in the atmospheric aerosol except for soil or desert dust In more recent years, light absorbing polymeric carbonaceous material was found in atmospheric aerosols. Absorption increases appreciably toward short wavelengths, so this fraction was called brown carbon. Because brown carbon is thermally rather refractory, it influences the split between organic carbon (OC) and elemental carbon (EC) in thermal methods and, through its light absorption characteristics, leads to overestimations of BC concentrations. The goal of the present study was to extend the integrating sphere method to correct the BC signal for the contribution of brown carbon and to obtain an estimate of brown carbon concentrations. Humic acid sodium salt was used as proxy for brown carbon. The extended method is first tested on mixtures of test substances and then applied to atmospheric samples collected during biomass smoke episodes (Easter bonfires) in Austria. The resulting concentrations of black and brown carbon are compared to EC obtained with a widely used thermal method, the Cachier method (Cachier et al. Tellus 1989, 41B, 379-390) and a thermal-optical method (Schmid et al. Atmos. Environ. 2001, 35, 2111-2121), as well as to concentrations of humic like substances (HULIS) and to biomass smoke POM (particulate organic matter). Both the thermal methods were found to overestimate BC on days with large contributions of woodsmoke, which agrees with the findings of the method intercomparison study by Reisinger et at. (Environ. Sci. Technol. 2008, 42, 884-889). During the days of the bonfires, the Cachier method gave EC concentrations that were higher by a factor of 3.8 than the BC concentrations, while the concentrations obtained with the thermal-optical method were higher by a factor of 2.6.

  8. Desert dust and anthropogenic aerosol interactions in the Community Climate System Model coupled-carbon-climate model

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mahowald, Natalie; Rothenberg, D.; Lindsay, Keith

    2011-02-01

    Coupled-carbon-climate simulations are an essential tool for predicting the impact of human activity onto the climate and biogeochemistry. Here we incorporate prognostic desert dust and anthropogenic aerosols into the CCSM3.1 coupled carbon-climate model and explore the resulting interactions with climate and biogeochemical dynamics through a series of transient anthropogenic simulations (20th and 21st centuries) and sensitivity studies. The inclusion of prognostic aerosols into this model has a small net global cooling effect on climate but does not significantly impact the globally averaged carbon cycle; we argue that this is likely to be because the CCSM3.1 model has a small climatemore » feedback onto the carbon cycle. We propose a mechanism for including desert dust and anthropogenic aerosols into a simple carbon-climate feedback analysis to explain the results of our and previous studies. Inclusion of aerosols has statistically significant impacts on regional climate and biogeochemistry, in particular through the effects on the ocean nitrogen cycle and primary productivity of altered iron inputs from desert dust deposition.« less

  9. Formation of nitrogenated organic aerosols in the Titan upper atmosphere

    PubMed Central

    Imanaka, Hiroshi; Smith, Mark A.

    2010-01-01

    Many aspects of the nitrogen fixation process by photochemistry in the Titan atmosphere are not fully understood. The recent Cassini mission revealed organic aerosol formation in the upper atmosphere of Titan. It is not clear, however, how much and by what mechanism nitrogen is incorporated in Titan’s organic aerosols. Using tunable synchrotron radiation at the Advanced Light Source, we demonstrate the first evidence of nitrogenated organic aerosol production by extreme ultraviolet–vacuum ultraviolet irradiation of a N2/CH4 gas mixture. The ultrahigh-mass-resolution study with laser desorption ionization-Fourier transform-ion cyclotron resonance mass spectrometry of N2/CH4 photolytic solid products at 60 and 82.5 nm indicates the predominance of highly nitrogenated compounds. The distinct nitrogen incorporations at the elemental abundances of H2C2N and HCN, respectively, are suggestive of important roles of H2C2N/HCCN and HCN/CN in their formation. The efficient formation of unsaturated hydrocarbons is observed in the gas phase without abundant nitrogenated neutrals at 60 nm, and this is confirmed by separately using 13C and 15N isotopically labeled initial gas mixtures. These observations strongly suggest a heterogeneous incorporation mechanism via short lived nitrogenated reactive species, such as HCCN radical, for nitrogenated organic aerosol formation, and imply that substantial amounts of nitrogen is fixed as organic macromolecular aerosols in Titan’s atmosphere. PMID:20616074

  10. Aerosol transport from Chiang Mai, Thailand to Mt. Lulin, Taiwan - Implication of aerosol aging during long-range transport

    NASA Astrophysics Data System (ADS)

    Chuang, Ming-Tung; Lee, Chung-Te; Chou, Charles C.-K.; Engling, Guenter; Chang, Shih-Yu; Chang, Shuenn-Chin; Sheu, Guey-Rong; Lin, Neng-Huei; Sopajaree, Khajornsak; Chang, You-Jia; Hong, Guo-Jun

    2016-07-01

    The transport of biomass burning (BB) aerosol from Indochina may cause a potential effect on climate change in Southeast Asia, East Asia, and the Western Pacific. Up to now, the understanding of BB aerosol composition modification during long-range transport (LRT) is still very limited due to the lack of observational data. In this study, atmospheric aerosols were collected at the Suthep/Doi Ang Khang (DAK) mountain sites in Chiang Mai, Thailand and the Lulin Atmospheric Background Station (Mt. Lulin) in central Taiwan from March to April 2010 and from February to April 2013, respectively. During the study period, an upwind and downwind relationship between the Suthep/DAK and Lulin sites (2400 km apart) was validated by backward trajectories. Comprehensive aerosol properties were resolved for PM2.5 water-soluble inorganic ions, carbonaceous content, water-soluble/insoluble organic carbon (WSOC/WIOC), dicarboxylic acids and their salts (DCAS), and anhydrosugars. A Modification Factor (MF) is proposed by employing non-sea-salt potassium ion (nss-K+) or fractionalized elemental carbon evolved at 580 °C after pyrolized OC correction (EC1-OP) as a BB aerosol tracer to evaluate the mass fraction changes of aerosol components from source to receptor regions during LRT. The MF values of nss-SO42-, NH4+, NO3-, OC1 (fractionalized organic carbon evolved from room temperature to 140 °C), OP (pyrolized OC fraction), DCAS, and WSOC were above unity, which indicated that these aerosol components were enhanced during LRT as compared with those in the near-source region. In contrast, the MF values of anhydrosugars ranged from 0.1 to 0.3, indicating anhydrosugars have degraded during LRT.

  11. On the implications of aerosol liquid water and phase ...

    EPA Pesticide Factsheets

    Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to organic carbon (OM ∕ OC) ratios are high such that separation relative humidities (SRH) are below the ambient relative humidity (RH). As OM ∕ OC ratios in the SE US are often between 1.8 and 2.2, organic aerosol experiences both mixing with inorganic water and separation from it. Regional chemical transport model simulations including inorganic water (but excluding water uptake by organic compounds) in the partitioning medium for secondary organic aerosol (SOA) when RH  >  SRH led to increased SOA concentrations, particularly at night. Water uptake to the organic phase resulted in even greater SOA concentrations as a result of a positive feedback in which water uptake increased SOA, which further increased aerosol water and organic aerosol. Aerosol properties, such as the OM ∕ OC and hygroscopicity parameter (κorg), were captured well by the model compared with measurements during the Southern Oxidant and Aerosol Study (SOAS) 2013. Organic nitrates from monoterpene oxidation were predicted to be the least water-soluble semivolatile species in the model, but most biogenically derived semivolatile species in the Community Multiscale Air Quality (CMAQ) model were hig

  12. Secondary organic aerosol formation from isoprene photooxidation

    NASA Astrophysics Data System (ADS)

    Kroll, J. H.; Ng, N. L.; Murphy, S. M.; Flagan, R. C.; Seinfeld, J. H.

    2005-12-01

    We report chamber studies of the formation of secondary organic aerosol (SOA) from the oxidation of isoprene (2-methyl-1,3-butadiene). Isoprene is the most abundant non-methane hydrocarbon emitted into the troposphere (source strength of ~500 Tg/year), so even small SOA yields may have a large impact on global SOA production. Reactions are carried out in Caltech's dual 28 m3 Teflon chambers, and aerosol growth is monitored by a differential mobility analyzer (DMA) and an Aerodyne time-of-flight aerosol mass spectrometer (AMS). Isoprene oxidation is initiated by the UV irradiation of isoprene in the presence of hydrogen peroxide, with NO added for high-NOx experiments. These conditions ensure that isoprene oxidation is initiated by reaction with the OH radical, with negligible interference from other oxidants (ozone, nitrate radicals, and O atoms). Aerosol growth is observed under both high-NOx and low-NOx conditions, at isoprene concentrations lower than measured in previous studies (down to 8 ppb). SOA yields are found to be in the range of 1-2%. Yields exhibit a complex dependence on NOx concentration, likely a result of changes in the chemistry of organic peroxy radicals. It is shown that condensable compounds are formed from further reactions of first-generation isoprene oxidation products; the rates and products of such gas-phase reactions are at present poorly understood. Additionally, measurements of SOA composition indicate that these products undergo reactions in the aerosol phase, leading to the formation of low-volatility oligomeric products.

  13. Aerosol Modeling for the Global Model Initiative

    NASA Technical Reports Server (NTRS)

    Weisenstein, Debra K.; Ko, Malcolm K. W.

    2001-01-01

    The goal of this project is to develop an aerosol module to be used within the framework of the Global Modeling Initiative (GMI). The model development work will be preformed jointly by the University of Michigan and AER, using existing aerosol models at the two institutions as starting points. The GMI aerosol model will be tested, evaluated against observations, and then applied to assessment of the effects of aircraft sulfur emissions as needed by the NASA Subsonic Assessment in 2001. The work includes the following tasks: 1. Implementation of the sulfur cycle within GMI, including sources, sinks, and aqueous conversion of sulfur. Aerosol modules will be added as they are developed and the GMI schedule permits. 2. Addition of aerosol types other than sulfate particles, including dust, soot, organic carbon, and black carbon. 3. Development of new and more efficient parameterizations for treating sulfate aerosol nucleation, condensation, and coagulation among different particle sizes and types.

  14. Steady increase of secondary organic aerosol mass concentration and light extinction during the CARES 2010 Field Campaign

    NASA Astrophysics Data System (ADS)

    Gyawali, M. S.; Arnott, W. P.; Flowers, B. A.; Dubey, M. K.; Atkinson, D. B.; Song, C.; Zaveri, R. A.; Setyan, A.; Zhang, Q.; Mazzoleni, C.; Gorkowski, K.

    2011-12-01

    We present multispectral (355, 375, 405, 532, 870, 781, and 1047 nm) aerosol light absorption and scattering measurements for the 2010 Carbonaceous Aerosols and Radiative Effects (CARES) campaign in Sacramento, CA and the Sierra Nevada foothills. The short wavelength scattering at both sites gradually increased during the last 10 days of the campaign as diagnosed by a systematic increase in the Ångström exponent of scattering. The UV and near UV enhanced scattering was likely a consequence of the ultra and sub-micron aerosol which began to grow vigorously in the size range where scattering at shorter wavelengths begins to increase. Multispectral aerosol light absorption coefficients suggest the absence of short wavelength light absorption by brown carbon. Aerosol mass spectrometer data also shows the steady increase of secondary organic aerosol during the last 10 days of CARES. The time series of the measurements made between the two sites (T0 and T1) separated by the slope of the foothills are strikingly similar, except for isolated night time episodes of enhanced absorption at T0. This is possibly due to paving events or other nocturnal emissions markers

  15. Wet scavenging of organic and elemental carbon during summer monsoon and winter monsoon seasons

    NASA Astrophysics Data System (ADS)

    Sonwani, S.; Kulshrestha, U. C.

    2017-12-01

    In the era of rapid industrialization and urbanization, atmospheric abundance of carbonaceous aerosols is increasing due to more and more fossil fuel consumption. Increasing levels of carbonaceous content have significant adverse effects on air quality, human health and climate. The present study was carried out at Delhi covering summer monsoon (July -Sept) and winter monsoon (Dec-Jan) seasons as wind and other meteorological factors affect chemical composition of precipitation in different manner. During the study, the rainwater and PM10 aerosols were collected in order to understand the scavenging process of elemental and organic carbon. The Rain water samples were collected on event basis. PM10 samples were collected before rain (PR), during rain (DR) and after rain (AR) during 2016-2017. The collected samples were analysed by the thermal-optical reflectance method using IMPROVE-A protocol. In PM10, the levels of organic carbon (OC) and its fractions (OC1, OC2, OC3 and OC4) were found significantly lower in the AR samples as compared to PR and DR samples. A significant positive correlation was noticed between scavenging ratios of organic carbon and rain intensity indicating an efficient wet removal of OC. In contrast to OCs, the levels of elemental carbon and its fractions (EC1, EC2, and EC3) in AR were not distinct during PR and DR. The elemental carbon showed very week correlation with rain intensity in Delhi region which could be explained on the basis of hydrophobic nature of freshly emitted carbon soot. The detailed results will be discussed during the conference.

  16. Numerical Investigation on Absorption Enhancement of Black Carbon Aerosols Partially Coated With Nonabsorbing Organics

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaolin; Mao, Mao; Yin, Yan; Wang, Bin

    2018-01-01

    This study numerically evaluates the effects of aerosol microphysics, including coated volume fraction of black carbon (BC), shell/core ratio, and size distribution, on the absorption enhancement (Eab) of polydisperse BC aggregates partially coated by organics, which is calculated by the exact multiple-sphere T-matrix method. The coated volume fraction of BC plays a substantial role in determining the absorption enhancement of partially coated BC aggregates, which typically have an Eab in the range of 1.0-2.0 with a larger value for larger coated volume fraction of BC as the shell/core ratio, BC geometry, and size distribution are fixed. The shell/core ratio, BC geometry, and size distribution have little impact on the Eab of coated BC with small coated volume fraction of BC, while they become significant for large coated volume fraction of BC. The Eab of partially coated BC particles can be slightly less than 1.0 for the large BC in the accumulation mode exhibiting large shell/core ratio and small coated volume fraction of BC, indicating that the absorption shows even slight decrease relative to uncoated BC particles. For partially coated BC aggregates in the accumulation and coarse modes, the refractive index uncertainties of BC result in the Eab differences of less than 9% and 2%, respectively, while those of organics can induce larger variations with the maximum differences up to 22% and 18%, respectively. Our study indicates that accounting for particle coating microphysics, particularly the coated volume fraction of BC, can potentially help to understand the differences in observations of largely variable absorption enhancements over various regions.

  17. Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

    2015-08-01

    This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOAs). Typically only photolysis of smaller organic molecules (e.g., formaldehyde) for which explicit data exist is included in chemistry-climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low and high NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after 4 days of chemical aging under those conditions (equivalent to 8 days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields, i.e., ~15 % (low NOx) to ~45 % (high NOx) for α-pinene, ~15 % for toluene, ~25 % for C12 n-alkane, and ~10 % for C16 n-alkane. The small effect of gas-phase photolysis on low-volatility n-alkanes such as C16 n-alkane is due to the rapid partitioning of early-generation products to the particle phase, where they are protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass is increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an empirically estimated SOA photolysis rate of JSOA

  18. Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

    2015-03-01

    This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOA). Typically only photolysis of smaller organic molecules (e.g. formaldehyde) for which explicit data exist is included in chemistry-climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low- and high-NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after four days of chemical aging under those conditions (equivalent to eight days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields i.e ~15% (low-NOx) to ~45% (high-NOx) for α-pinene, ~15% for toluene, ~25% for C12-alkane, and ~10% for C16-alkane. The small effect on low volatility n-alkanes such as C16-alkane is due to the rapid partitioning of early-generation products to the particle phase where they are assumed to be protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass seems increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas-phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an estimated SOA photolysis rate of JSOA=4 x 10-4JNO2. Modeling

  19. Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

    DOE PAGES

    Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; ...

    2015-08-20

    This paper presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOAs). Typically only photolysis of smaller organic molecules (e.g., formaldehyde) for which explicit data exist is included in chemistry–climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C 12 and C 16 n-alkane reactions with OH at low and high NO x. Simulations are conducted formore » typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after 4 days of chemical aging under those conditions (equivalent to 8 days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields, i.e., ~15 % (low NO x) to ~45 % (high NO x) for α-pinene, ~15 % for toluene, ~25 % for C 12 n-alkane, and ~10 % for C 16 n-alkane. The small effect of gas-phase photolysis on low-volatility n-alkanes such as C 16 n-alkane is due to the rapid partitioning of early-generation products to the particle phase, where they are protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass is increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an empirically estimated SOA

  20. A new method to discriminate secondary organic aerosols from different sources using high-resolution aerosol mass spectra

    NASA Astrophysics Data System (ADS)

    Heringa, M. F.; Decarlo, P. F.; Chirico, R.; Tritscher, T.; Clairotte, M.; Mohr, C.; Crippa, M.; Slowik, J. G.; Pfaffenberger, L.; Dommen, J.; Weingartner, E.; Prévôt, A. S. H.; Baltensperger, U.

    2011-10-01

    Organic aerosol (OA) represents a significant and often major fraction of the non-refractory PM1 (particulate matter with an aerodynamic diameter da < 1 μm) mass. Secondary organic aerosol (SOA) is an important contributor to the OA and can be formed from biogenic and anthropogenic precursors. Here we present results from the characterization of SOA produced from the emissions of three different anthropogenic sources. SOA from a log wood burner, a Euro 2 diesel car and a two-stroke Euro 2 scooter were characterized with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and compared to SOA from α-pinene. The emissions were sampled from the chimney/tailpipe by a heated inlet system and filtered before injection into a smog chamber. The gas phase emissions were irradiated by xenon arc lamps to initiate photo-chemistry which led to nucleation and subsequent particle growth by SOA production. Duplicate experiments were performed for each SOA type, with the averaged organic mass spectra in the m/z range 12-250 showing Pearson's r values >0.94 for the correlations between the different SOA types after 5 h of aging. High-resolution mass spectra (HR-MS) showed that the dominant peaks in the MS, m/z 43 and 44, are dominated by the oxygenated ions C2H3O+ and CO2+, respectively, similarly to the relatively fresh semi-volatile oxidized OA (SV-OOA) observed in the ambient aerosol. The atomic O : C ratios were found to be in the range of 0.25-0.55 with no major increase during the first 5 h of aging. On average, the diesel SOA showed the lowest O : C ratio followed by SOA from wood burning, α-pinene and the scooter emissions. Grouping the fragment ions based on their carbon number revealed that the SOA source with the highest O : C ratio had the largest fraction of small ions. Fragment ions containing up to 3 carbon atoms accounted for 66%, 68%, 72% and 76% of the organic spectrum of the SOA produced by the diesel car, wood burner, α-pinene and

  1. NMOC, ozone, and organic aerosol in the southeastern United States, 1999-2007: 3. Origins of organic aerosol in Atlanta, Georgia, and surrounding areas

    NASA Astrophysics Data System (ADS)

    Blanchard, C. L.; Hidy, G. M.; Tanenbaum, S.; Edgerton, E. S.

    2011-02-01

    Carbonaceous compounds constitute a major fraction of the fine particle mass at locations throughout North America; much of the condensed-phase organic carbon (OC) is produced in the atmosphere from NMOC reactions as "secondary" OC (SOC). Ten years of particulate carbon and speciated non-methane organic compound (NMOC) data combined with other measurements from Southeastern Aerosol Research and Characterization (SEARCH) and other sites provide insight into the association between elemental carbon (EC), OC and NMOCs. Data are analyzed to characterize the OC and SOC contrasts between urban Atlanta, Georgia, and nearby non-urban conditions in the Southeast. Analysis of the monitoring record indicates that the mean Atlanta urban excess of total carbon (TC) is 2.1-2.8 μg m -3. The OC/EC ratio of the Atlanta urban excess is in the range 1.3 to 1.8, consistent with OC/EC ratios observed in motor vehicle emissions and a fossil carbon source of urban excess TC. Carbon isotope analysis of a subset of particle samples demonstrates that the urban excess is mainly fossil in origin, even though the majority of the TC is modern at both urban and non-urban sites. Temperature-dependent partitioning of OC between gas and condensed phases cannot explain the observed diurnal and seasonal variations of OC/CO, EC/CO, and OC/EC ratios. Alternatively, a hypothesis involving vertical mixing of OC-enriched air from aloft is supported by the seasonal and diurnal OC, isopentane, aromatic and isoprene observations at the ground. A statistical model is applied to indicate the relative significance of aerometric factors affecting OC and EC concentrations, including meteorological and pollutant associations. The model results demonstrate strong linkages between fine particle carbon and pollutant indicators of source emissions compared with meteorological factors; the model results show weaker dependence of OC on meteorological factors than is the case for ozone (O 3) concentrations.

  2. Optical properties and aging of light-absorbing secondary organic aerosol

    DOE PAGES

    Liu, Jiumeng; Lin, Peng; Laskin, Alexander; ...

    2016-10-14

    The light-absorbing organic aerosol (OA) commonly referred to as “brown carbon” (BrC) has attracted considerable attention in recent years because of its potential to affect atmospheric radiation balance, especially in the ultraviolet region and thus impact photochemical processes. A growing amount of data has indicated that BrC is prevalent in the atmosphere, which has motivated numerous laboratory and field studies; however, our understanding of the relationship between the chemical composition and optical properties of BrC remains limited. We conducted chamber experiments to investigate the effect of various volatile organic carbon (VOC) precursors, NO x concentrations, photolysis time, and relative humidity (RH) on the lightmore » absorption of selected secondary organic aerosols (SOA). Light absorption of chamber-generated SOA samples, especially aromatic SOA, was found to increase with NO x concentration, at moderate RH, and for the shortest photolysis aging times. The highest mass absorption coefficient (MAC) value is observed from toluene SOA products formed under high-NO x conditions at moderate RH, in which nitro-aromatics were previously identified as the major light-absorbing compounds. BrC light absorption is observed to decrease with photolysis time, correlated with a decline of the organic nitrate fraction of SOA. SOA formed from mixtures of aromatics and isoprene absorb less visible (Vis) and ultraviolet (UV) light than SOA formed from aromatic precursors alone on a mass basis. However, the mixed SOA absorption was underestimated when optical properties were predicted using a two-product SOA formation model, as done in many current climate models. Further investigation, including analysis on detailed mechanisms, are required to explain the discrepancy.« less

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

    NASA Astrophysics Data System (ADS)

    Collier, K.; Brooks, S. D.

    2014-12-01

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

  4. THERMAL PROPERTIES OF SECONDARY ORGANIC AEROSOLS

    EPA Science Inventory

    Volume concentrations of steady-state secondary organic aerosol (SOA) were measured in several hydrocarbon/NOx irradiation experiments. These measurements were used to estimate the thermal behavior of the particles that may be formed in the atmosphere. These laborator...

  5. SEASONAL AND REGIONAL VARIATIONS OF PRIMARY AND SECONDARY ORGANIC AEROSOLS OVER THE CONTINENTAL UNITED STATES: OBSERVATION-BASED ESTIMATES AND MODEL EVALUATION

    EPA Science Inventory

    Due to the lack of an analytical technique for directly quantifying the atmospheric concentrations of primary (OCpri) and secondary (OCsec) organic carbon aerosols, different indirect methods have been developed to estimate their concentrations. In this stu...

  6. Middle Adriatic Study of the Sea Surface Films as a Sink and Source of Trace Organics of Marine Aerosols

    NASA Astrophysics Data System (ADS)

    Frka Milosavljevic, S.; Cvitešić, A.; Kroflič, A.; Šala, M.; Ciglenečki, I.; Grgic, I.

    2016-02-01

    Properties, (trans)formation, and removal of organic particles remain the least understood aspects of atmospheric chemistry despite the importance of organic aerosol (OA) for both human health and climate change. Recently, organosulfur compounds (OS) have come into the focus of atmospheric research as significant reservoirs of S in the atmosphere, being potentially important components of gas-to-particle conversion and formation of secondary organic aerosol (SOA) especially in the oceanic region. Moreover, nitroaromatic compounds (NAC), as (methyl)nitrocatehols recently reported as potentially toxic constituents of aerosol water soluble organic matter (WSOM) and significant SOA tracers, have not been studied over marine atmosphere till now. A range of global exchange processes between the sea and the atmosphere is hindered by the sea surface microlayer (SML) generally enriched in surface active organics which form films and serve both as a sink and a source of marine OA. To better understand the role of surfactant films at the air-sea interface in global biogeochemistry as well as the sources and transport pathways of marine OA and to estimate their importance in global climate, it is necessary to study chemical composition and properties of trace organics, OS and NAC, in both the SML and marine aerosols as an integrated whole. We will present the first attempt to study marine aerosol WSOM as well as the SML collected in the Middle Adriatic with a special emphasis on its total S and OS content as well as on specific NAC. For that purpose a novel methodological approach capable of their quantification as well as determination of their surfactant nature is applied by combining liquid chromatography mass spectrometry, ion chromatography, inductively coupled plasma mass spectrometry, and electrochemistry. The obtained data are correlated with those for dissolved and particulate organic carbon, water soluble anions and cations, chlorophyll a, nutrients, and surfactants.

  7. Aerosol Absorption in the Atmosphere: Perspectives from Global Model, Ground-Based Measurements, and Field Observations

    NASA Technical Reports Server (NTRS)

    Chin, Mian; Dubovik, Oleg; Holben, Brent; Torres, Omar; Anderson, Tad; Quinn, Patricia; Ginoux, Paul

    2004-01-01

    Aerosol absorption in the atmosphere poses a major uncertainty in assessing the aerosol climate effects. This uncertainty arises from the poorly quantified aerosol sources, especially black carbon emissions, and our limited knowledge of aerosol mixing state and optical properties. Here we use a global model GOCART to simulate atmospheric aerosols, including sulfate, black carbon, organic carbon, dust, and sea salt. We compare the model calculated total aerosol optical thickness, extinction, and absorption with those quantities from the ground-based sun photometer measurements from AERONET, satellite retrievals from the TOMS instrument, and field observations from ACE-Asia. We will examine the most sensitive factors in determining the aerosol absorption. and the consequences of assessing the aerosol radiative forcing and atmospheric heating associated with those factors.

  8. Aerosol Absorption in the Atmosphere: Perspectives from Global Model, Ground-Based Measurements, and Field Observations

    NASA Technical Reports Server (NTRS)

    Chin, Mian; Dubovik, Oleg; Holben, Brent; Anderson, Tad; Quinn, Patricia; Duncan, Bryan; Ginoux, Paul

    2003-01-01

    Aerosol absorption in the atmosphere poses a major uncertainty in assessing the aerosol climate effects. This uncertainty arises from the poorly quantified aerosol sources, especially black carbon emissions, and our limited knowledge of aerosol mixing state and optical properties. Here we use a global model GOCART to simulate atmospheric aerosols, including sulfate, black carbon, organic carbon, dust, and sea salt. We compare the model calculated total aerosol optical thickness, extinction, and absorption with those quantities from the ground-based sun photometer measurements from AERONET at several different wavelengths and the field observations from ACE-Asia. We will examine what are the most sensitive factors in determining the aerosol absorption, and the consequences of assessing the aerosol radiative forcing and atmospheric heating associated with those factors.

  9. Aerosol Absorption in the Atmosphere: Perspectives from Global Model, Ground-Based Measurements, and Field Observations

    NASA Technical Reports Server (NTRS)

    Chin, Main; Dubovik, Oleg; Holben, Brent; Anderson, Tad; Quinn, Patricia; Duncan, Bryan; Ginoux, Paul

    2004-01-01

    Aerosol absorption in the atmosphere poses a major uncertainty in assessing the aerosol climate effects. This uncertainty arises from the poorly quantified aerosol sources, especially black carbon emissions, and our limited knowledge of aerosol mixing state and optical properties. Here we use a global model GOCART to simulate atmospheric aerosols, including sulfate, black carbon, organic carbon, dust, and sea salt. We compare the model calculated total aerosol optical thickness, extinction, and absorption with those quantities from the ground-based sun photometer measurements from AERONET at several different wavelengths and the field observations from ACE-Asia. We will examine the most sensitive factors in determining the aerosol absorption, and the consequences of assessing the aerosol radiative forcing and atmospheric heating associated with those factors.

  10. Probing into the aging dynamics of biomass burning aerosol by using satellite measurements of aerosol optical depth and carbon monoxide

    NASA Astrophysics Data System (ADS)

    Konovalov, Igor B.; Beekmann, Matthias; Berezin, Evgeny V.; Formenti, Paola; Andreae, Meinrat O.

    2017-04-01

    Carbonaceous aerosol released into the atmosphere from open biomass burning (BB) is known to undergo considerable chemical and physical transformations (aging). However, there is substantial controversy about the nature and observable effects of these transformations. A shortage of consistent observational evidence on BB aerosol aging processes under different environmental conditions and at various temporal scales hinders development of their adequate representations in chemistry transport models (CTMs). In this study, we obtain insights into the BB aerosol dynamics by using available satellite measurements of aerosol optical depth (AOD) and carbon monoxide (CO). The basic concept of our method is to consider AOD as a function of the BB aerosol photochemical age (that is, the time period characterizing the exposure of BB aerosol emissions to atmospheric oxidation reactions) predicted by means of model tracers. We evaluate the AOD enhancement ratio (ER) defined as the ratio of optical depth of actual BB aerosol with respect to that of a modeled aerosol tracer that is assumed to originate from the same fires as the real BB aerosol but that is not affected by any aging processes. To limit possible effects of model transport errors, the AOD measurements are normalized to CO column amounts that are also retrieved from satellite measurements. The method is applied to the analysis of the meso- and synoptic-scale evolution of aerosol in smoke plumes from major wildfires that occurred in Siberia in summer 2012. AOD and CO retrievals from MODIS and IASI measurements, respectively, are used in combination with simulations performed with the CHIMERE CTM. The analysis indicates that aging processes strongly affected the evolution of BB aerosol in the situation considered, especially in dense plumes (with spatial average PM2. 5 concentration exceeding 100 µg m-3). For such plumes, the ER is found to increase almost 2-fold on the scale of ˜ 10 h of daytime aerosol

  11. Influence of metal-mediated aerosol-phase oxidation on secondary organic aerosol formation from the ozonolysis and OH-oxidation of α-pinene

    PubMed Central

    Chu, Biwu; Liggio, John; Liu, Yongchun; He, Hong; Takekawa, Hideto; Li, Shao-Meng; Hao, Jiming

    2017-01-01

    The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9 m3 smog chamber. The presence of FeSO4 or Fe2(SO4)3 seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of α-pinene compared to that in the presence of ZnSO4 or (NH4)2SO4. These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO4 or Fe2(SO4)3 seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation. PMID:28059151

  12. Influence of metal-mediated aerosol-phase oxidation on secondary organic aerosol formation from the ozonolysis and OH-oxidation of α-pinene.

    PubMed

    Chu, Biwu; Liggio, John; Liu, Yongchun; He, Hong; Takekawa, Hideto; Li, Shao-Meng; Hao, Jiming

    2017-01-06

    The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9 m 3 smog chamber. The presence of FeSO 4 or Fe 2 (SO 4 ) 3 seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of α-pinene compared to that in the presence of ZnSO 4 or (NH 4 ) 2 SO 4 . These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO 4 or Fe 2 (SO 4 ) 3 seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation.

  13. Sensitivity of Stratospheric Geoengineering with Black Carbon to Aerosol Size and Altitude of Injection

    NASA Technical Reports Server (NTRS)

    Kravitz, Ben; Robock, Alan; Shindell, Drew T.; Miller, Mark A.

    2012-01-01

    Simulations of stratospheric geoengineering with black carbon (BC) aerosols using a general circulation model with fixed sea surface temperatures show that the climate effects strongly depend on aerosol size and altitude of injection. 1 Tg BC/a injected into the lower stratosphere would cause little surface cooling for large radii but a large amount of surface cooling for small radii and stratospheric warming of over 60 C. With the exception of small particles, increasing the altitude of injection increases surface cooling and stratospheric warming. Stratospheric warming causes global ozone loss by up to 50% in the small radius case. The Antarctic shows less ozone loss due to reduction of polar stratospheric clouds, but strong circumpolar winds would enhance the Arctic ozone hole. Using diesel fuel to produce the aerosols is likely prohibitively expensive and infeasible. Although studying an absorbing aerosol is a useful counterpart to previous studies involving sulfate aerosols, black carbon geoengineering likely carries too many risks to make it a viable option for deployment.

  14. Effects of continental anthropogenic sources on organic aerosols in the coastal atmosphere of East China.

    PubMed

    Shang, Dongjie; Hu, Min; Guo, Qingfeng; Zou, Qi; Zheng, Jing; Guo, Song

    2017-10-01

    Although organic compounds in marine atmospheric aerosols have significant effects on climate and marine ecosystems, they have rarely been studied, especially in the coastal regions of East China. To assess the origins of the organic aerosols in the East China coastal atmosphere, PM 2.5 samples were collected from the atmospheres of the Yellow Sea, the East China Sea, and Changdao Island during the CAPTAIN (Campaign of Air PolluTion At INshore Areas of Eastern China) field campaign in the spring of 2011. The marine atmospheric aerosol samples that were collected were grouped based on the backward trajectories of their air masses. The organic carbon concentrations in the PM 2.5 samples from the marine and Changdao Island atmospheres were 5.5 ± 3.1 μgC/m 3 and 6.9 ± 2.4 μgC/m 3 , respectively, which is higher than in other coastal water atmospheres. The concentration of polycyclic aromatic hydrocarbons (PAHs) in the marine atmospheric PM 2.5 samples was 17.0 ± 20.2 ng/m 3 , indicating significant continental anthropogenic influences. The influences of fossil fuels and biomass burning on the composition of organic aerosols in the coastal atmosphere of East China were found to be highly dependent on the origins of the air masses. Diesel combustion had a strong impact on air masses from the Yangtze River Delta (YRD), and gasoline emissions had a more significant impact on the "North China" marine atmospheric samples. The "Northeast China" marine atmospheric samples were most impacted by biomass burning. Coal combustion contributed significantly to the compositions of all of the atmospheric samples. The proportions of secondary compounds increased as samples aged in the marine atmosphere indicating that photochemical oxidation occured during transport. Our results quantified ecosystem effects on marine atmospheric aerosols and highlighted the uncertainties that arise when modeling marine atmospheric PM 2.5 without considering high spatial resolution source

  15. 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 ...

  16. Highly Oxygenated Multifunctional Compounds in α-Pinene Secondary Organic Aerosol.

    PubMed

    Zhang, Xuan; Lambe, Andrew T; Upshur, Mary Alice; Brooks, William A; Gray Bé, Ariana; Thomson, Regan J; Geiger, Franz M; Surratt, Jason D; Zhang, Zhenfa; Gold, Avram; Graf, Stephan; Cubison, Michael J; Groessl, Michael; Jayne, John T; Worsnop, Douglas R; Canagaratna, Manjula R

    2017-06-06

    Highly oxygenated multifunctional organic compounds (HOMs) originating from biogenic emissions constitute a widespread source of organic aerosols in the pristine atmosphere. However, the molecular forms in which HOMs are present in the condensed phase upon gas-particle partitioning remain unclear. In this study, we show that highly oxygenated molecules that contain multiple peroxide functionalities are readily cationized by the attachment of Na + during electrospray ionization operated in the positive ion mode. With this method, we present the first identification of HOMs characterized as C 8-10 H 12-18 O 4-9 monomers and C 16-20 H 24-36 O 8-14 dimers in α-pinene derived secondary organic aerosol (SOA). Simultaneous detection of these molecules in the gas phase provides direct evidence for their gas-to-particle conversion. Molecular properties of particulate HOMs generated from ozonolysis and OH oxidation of unsubstituted (C 10 H 16 ) and deuterated (C 10 H 13 D 3 ) α-pinene are investigated using coupled ion mobility spectrometry with mass spectrometry. The systematic shift in the mass of monomers in the deuterated system is consistent with the decomposition of isomeric vinylhydroperoxides to release vinoxy radical isotopologues, the precursors to a sequence of autoxidation reactions that ultimately yield HOMs in the gas phase. The remarkable difference observed in the dimer abundance under O 3 - versus OH-dominant environments underlines the competition between intramolecular hydrogen migration of peroxy radicals and their bimolecular termination reactions. Our results provide new and direct molecular-level information for a key component needed for achieving carbon mass closure of α-pinene SOA.

  17. Carbon Dioxide Removal by Salty Aerosols

    NASA Astrophysics Data System (ADS)

    Gokturk, H.

    2016-12-01

    Aerosols consisting of salt ions dissolved in water are observed in nature as sea spray particles generated by breaking waves. Such aerosols can be also generated artificially by spraying seawater to the atmosphere to create clouds, which was suggested as a method of solar radiation management (SRM). Salty aerosols can be utilized not only for SRM, but also for carbon dioxide removal from the atmosphere, if salt ions carrying charges -2 or more negative are added to the seawater. CO2 is a very stable molecule where carbon to oxygen double bond has a bond strength of 8.3 eV (190 kcal/mol). Therefore the approach chosen here to modify CO2 is to further oxidize it to CO3. Quantum mechanical calculations indicate that CO2 reacts readily with hydroxyl minus ion (OH-) or oxygen double minus ion (O-) to form HCO3- or CO3-, respectively. What is studied in this paper is the utilization of hydrated negative salt ions to create OH- and possibly even O-. The negative ions chosen are chlorine minus ion (Cl-), sulfate double minus ion (SO4-), phosphate triple minus ion (PO4--) and silicate quadruple minus ion (SiO4--). The former two ions exist in seawater, but the latter two ions do not, though they are available as part of water soluble salts such as potassium phosphate. Using quantum mechanical calculations, following reactions were investigated: R1: (Cl-) + H2O => HCl + (OH-), R2: (SO4-) + H2O => (HSO4-) + (OH-), R3: (PO4--) + H2O => (HPO4-) + (OH-), R4: (SiO4--) + H2O => (HSiO4--) + (OH-), R5: (HPO4-) + H2O => (H2PO4-) + (OH-), R6: (HSiO4--) + H2O => (H2SiO4-) + (OH-), R7: (H2SiO4-) + H2O => (H3SiO4-) + (OH-), R8: (SiO4--) + H2O => (H2SiO4-) + (O-). Results indicate that singly charged negative salt ions, such as Cl- in R1, cannot create OH-. Doubly charged negative salt ions, such as SO4- in R2, can create OH-, though the amount of SO4- in seawater is relatively small. Triply or quadruply charged negative ions are even more favorable than doubly charged ions in creating

  18. On the Implications of aerosol liquid water and phase separation for modeled organic aerosol mass

    EPA Science Inventory

    Current chemical transport models assume that organic aerosol (OA)-forming compounds partition mostly to a water-poor, organic-rich phase in accordance with their vapor pressures. However, in the southeast United States, a significant fraction of ambient organic compounds are wat...

  19. Broadband optical properties of biomass burning aerosol and identification of brown carbon chromophores

    NASA Astrophysics Data System (ADS)

    Rudich, Y.; Bluvshtein, N.; Lin, P.; Flores, J. M.; Segey, L.; Tas, E.; Snider, G.; Weagle, C. L. M.; Brown, S. S.; Laskin, J.; Laskin, A.

    2017-12-01

    Accurate modeling of the radiative effects of smoke aerosols requires wavelength-dependent measurements and parameterizations of their optical properties in the UV and visible spectral ranges along with improved description of their chemical composition. To address this issue, we used a recently developed approach to retrieve the time- and spectral-dependent optical properties of ambient biomass burning aerosols from 300 to 650 nm wavelengths during a regional nighttime bonfire festival in Israel. During the biomass burning event, the overall absorption at 400 nm increased by about two orders of magnitude, changing the single scattering albedo from a background level of 0.95 to 0.7. In addition, PM2.5 filter samples were collected for detailed chemical analysis of the water soluble organics that contribute to light absorption. Nitroaromatic compounds were identified as major organic species responsible for the 50-80% of the total visible light absorption (> 400 nm). Typical chromophores include 4-nitrocatechol, 4-nitrophenol, nitro-syringol and nitro-guaiacol; oxidation-nitration products of methoxyphenols, and known products of lignin pyrolysis. Our results suggests that night time chemistry of nitrogen oxides with particles may play a significant role in atmospheric transformations of brown carbon.

  20. Chemical, microphysical and optical properties of the aerosols during foggy and nonfoggy day over a typical location in Indo-Gangetic Plain

    NASA Astrophysics Data System (ADS)

    Kaul, D. S.; Tripathi, S. N.; Gupta, T.

    2012-04-01

    An extensive experimental measurement was carried out from January 16, 2010 to February 20, 2010 at Kanpur to study the chemical, microphysical and optical properties of the aerosols. A Micro-Pulse Lidar Network (MPLNET), a part of National Aeronautic Space Administration (NASA), was used for identification of fog duration. PM1 samples and fogwater were collected to examine the organic and inorganic species of aerosol and fogwater. Organic Carbon (OC), Elemental Carbon (EC) and water soluble organic carbon analysis were carried out by an EC-OC analyzer and a TOC analyzer, respectively. Trace gases and solar flux measurement were carried out by gas analyzers and a pyranometer (a part of NASA Aeronet), respectively, to identify the photo-chemical activity. Meteorological data were measured by atmospheric weather station. The microphysical properties such as aerosol size distribution were measured using a scanning mobility particle sizer (SMPS). Optical properties were measured by a photo-acoustic soot spectrometer (PASS). Organic and inorganic species are processed by fog droplets such as production of secondary organic aerosol through aqueous mechanism (Kaul et al., 2011) and scavenging of various water soluble species. The concentrations of almost all the ionic species and organic carbon were higher in aerosols during foggy day. Presence of numerous ionic species and organic carbon in the fogwater indicates their wet scavenging and removal from the atmosphere by the fog droplets. Most of the aerosol is composed of inorganic component, ~80% during foggy day and ~85.5 % during clear day. Biomass burning contribution to PM1 mass concentration was considerably higher during clear days and lower during foggy days; lower concentration during foggy day could be due to wet scavenging of biomass generated aerosols. The study average higher number concentration of aerosol during foggy day during late evening and overnight was due to lower boundary layer height and subsequent

  1. Atmospheric aerosol composition and source apportionments to aerosol in southern Taiwan

    NASA Astrophysics Data System (ADS)

    Tsai, Ying I.; Chen, Chien-Lung

    In this study, the chemical characteristics of winter aerosol at four sites in southern Taiwan were determined and the Gaussian Trajectory transfer coefficient model (GTx) was then used to identify the major air pollutant sources affecting the study sites. Aerosols were found to be acidic at all four sites. The most important constituents of the particulate matter (PM) by mass were SO 42-, organic carbon (OC), NO 3-, elemental carbon (EC) and NH 4+, with SO 42-, NO 3-, and NH 4+ together constituting 86.0-87.9% of the total PM 2.5 soluble inorganic salts and 68.9-78.3% of the total PM 2.5-10 soluble inorganic salts, showing that secondary photochemical solution components such as these were the major contributors to the aerosol water-soluble ions. The coastal site, Linyuan (LY), had the highest PM mass percentage of sea salts, higher in the coarse fraction, and higher sea salts during daytime than during nighttime, indicating that the prevailing daytime sea breeze brought with it more sea-salt aerosol. Other than sea salts, crustal matter, and EC in PM 2.5 at Jenwu (JW) and in PM 2.5-10 at LY, all aerosol components were higher during nighttime, due to relatively low nighttime mixing heights limiting vertical and horizontal dispersion. At JW, a site with heavy traffic loadings, the OC/EC ratio in the nighttime fine and coarse fractions of approximately 2.2 was higher than during daytime, indicating that in addition to primary organic aerosol (POA), secondary organic aerosol (SOA) also contributed to the nighttime PM 2.5. This was also true of the nighttime coarse fraction at LY. The GTx produced correlation coefficients ( r) for simulated and observed daily concentrations of PM 10 at the four sites (receptors) in the range 0.45-0.59 and biases from -6% to -20%. Source apportionment indicated that point sources were the largest PM 10 source at JW, LY and Daliao (DL), while at Meinung (MN), a suburban site with less local PM 10, SO x and NO x emissions, upwind

  2. Biogenic influence on the composition and growth of summertime Arctic aerosol

    NASA Astrophysics Data System (ADS)

    Willis, M. D.; Burkart, J.; Thomas, J. L.; Koellner, F.; Schneider, J.; Bozem, H.; Hoor, P. M.; Aliabadi, A. A.; Schulz, H.; Herber, A. B.; Leaitch, R.; Abbatt, J.

    2016-12-01

    The summertime Arctic lower troposphere is a relatively pristine background aerosol environment dominated by nucleation and Aitken mode particles. Understanding the mechanisms that control the formation and growth of aerosol is crucial for our ability to predict cloud properties and therefore radiative balance and climate. We present aircraft-based observations of submicron aerosol composition from an aerosol mass spectrometer made during the NETCARE 2014 summertime arctic campaign, based in the Canadian High Arctic, at Resolute Bay, NU (74°N). Under stable and regionally influenced atmospheric conditions with low carbon monoxide and black carbon concentrations (< 100 ppbv and < 50 ng/m3, respectively), we observed organic aerosol (OA)-to-sulfate ratios ranging from 0.5 to > 6 with evidence for enhancement within the lower boundary layer. Methanesulfonic acid (MSA), a marker for the contribution of ocean-derived biogenic sulphur, was also observed in submicron aerosol. MSA-to-sulfate ratios ranged from near zero to 0.3 and tended to increase within the lower boundary layer, suggesting a contribution to aerosol loading from the ocean. In one notable case while flying in the lower boundary layer above open water in Lancaster Sound, we observed growth of small particles, <20 nm in diameter, into sizes above 50 nm. Aerosol growth was correlated with the presence of organic species, trimethylamine, and MSA in particles 80 nm and larger, where the organics were similar to those previously observed in marine settings. The organic-rich aerosol contributed significantly to particles active as cloud condensation nuclei (CCN, supersaturation = 0.6%). Our results highlight the potential importance of secondary organic aerosol formation and its role in growing nucleation mode aerosol into CCN-active sizes in this remote marine environment.

  3. Optical Properties of Black and Brown Carbon Aerosols from Laboratory Combustion of Wildland Fuels

    NASA Astrophysics Data System (ADS)

    Beres, N. D.; Molzan, J.

    2015-12-01

    Aerosol light absorption in the solar spectral region (300 nm - 2300 nm) of the atmosphere is key for the direct aerosol radiative forcing, which is determined by aerosol single scattering albedo (SSA), asymmetry parameter, and by the albedo of the underlying surface. SSA is of key importance for the sign and quantity of aerosol direct radiative forcing; that is, does the aerosol make the earth look darker (heating) or whiter (cooling)? In addition, these optical properties are needed for satellite retrievals of aerosol optical depth and properties. During wildland fires, aerosol optical absorption is largely determined by black carbon (BC) and brown carbon (BrC) emissions. BC is strongly absorbing throughout the solar spectrum, while BrC absorption strongly increases toward shorter wavelength and can be neglected in the red and infrared. Optical properties of BrC emitted from wildland fires are poorly understood and need to be studied as function of fuel type and moisture content and combustion conditions. While much more is known about BC optical properties, knowledge for the ultraviolet (UV) spectral region is still lacking and critically needed for satellite remote sensing (e.g., TOMS, OMI) and for modeling of tropospheric photochemistry. Here, a project to better characterize biomass burning aerosol optical properties is described. It utilizes a laboratory biomass combustion chamber to generate aerosols through combustion of different wildland fuels of global and regional importance. Combustion aerosol optics is characterized with an integrating nephelometer to measure aerosol light scattering and a photoacoustic instrument to measure aerosol light absorption. These measurements will yield optical properties that are needed to improve qualitative and quantitative understanding of aerosol radiative forcing and satellite retrievals for absorbing carbonaceous aerosols from combustion of wildland fuels.

  4. Source apportionment of organic compounds in Berlin using positive matrix factorization - assessing the impact of biogenic aerosol and biomass burning on urban particulate matter.

    PubMed

    Wagener, Sandra; Langner, Marcel; Hansen, Ute; Moriske, Heinz-Jörn; Endlicher, Wilfried R

    2012-10-01

    Source apportionment of 13 organic compounds, elemental carbon and organic carbon of ambient PM(10) and PM(1) was performed with positive matrix factorization (PMF). Samples were collected at three sites characterized by different vegetation influences in Berlin, Germany in 2010. The aim was to determine organic, mainly biogenic sources and their impact on urban aerosol collected in a densely populated region. A 6-factor solution provided the best data fit for both PM-fractions, allowing the sources isoprene- and α-pinene-derived secondary organic aerosol (SOA), bio primary, primarily attributable to fungal spores, bio/urban primary including plant fragments in PM(10) and cooking and traffic emissions in PM(1), biomass burning and combustion fossil to be identified. With mean concentrations up to 2.6 μg Cm(-3), biomass burning dominated the organic fraction in cooler months. Concentrations for α-pinene-derived SOA exceeded isoprene-derived concentrations. Estimated secondary organic carbon contributions to total organic carbon (OC) were between 7% and 42% in PM(10) and between 11% and 60% in PM(1), which is slightly lower than observed for US- or Asian cities. Primary biogenic emissions reached up to 33% of OC in the PM(10)-fraction in the late summer and autumn months. Temperature-dependence was found for both SOA-factors, correlations with ozone and mix depth only for the α-pinene-derived SOA-factor. Latter indicated input of α-pinene from the borders, highlighting differences in the origin of the precursors of both factors. Most factors were regionally distributed. High regional distribution was found to be associated with stronger influence of ambient parameters and higher concentrations at the background station. A significant contribution of biogenic emissions and biomass burning to urban organic aerosol could be stated. This indicates a considerable impact on PM concentrations also in cities in a densely populated area, and should draw the attention

  5. Gas and aerosol fluxes. [emphasizing sulfur, nitrogen, and carbon

    NASA Technical Reports Server (NTRS)

    Martens, C. S.

    1980-01-01

    The development of remote sensing techniques to address the global need for accurate distribution and flux determinations of both man made and natural materials which affect the chemical composition of the atmosphere, the heat budget of the Earth, and the depletion, of stratospheric ozone is considered. Specifically, trace gas fluxes, sea salt aerosol production, and the effect of sea surface microlayer on gas and aerosol fluxes are examined. Volatile sulfur, carbon, nitrogen, and halocarbon compounds are discussed including a statement of the problem associated with each compound or group of compounds, a brief summary of current understanding, and suggestions for needed research.

  6. Composition and physical properties of the Asian Tropopause Aerosol Layer and the North American Tropospheric Aerosol Layer: Composition of ATAL and NATAL

    DOE PAGES

    Yu, Pengfei; Toon, Owen B.; Neely, Ryan R.; ...

    2015-04-10

    Recent studies revealed layers of enhanced aerosol scattering in the upper troposphere and lower stratosphere over Asia (Asian Tropopause Aerosol Layer (ATAL)) and North America (North American Tropospheric Aerosol Layer (NATAL)). We use a sectional aerosol model (Community Aerosol and Radiation Model for Atmospheres (CARMA)) coupled with the Community Earth System Model version 1 (CESM1) to explore the composition and optical properties of these aerosol layers. The observed aerosol extinction enhancement is reproduced by CESM1/CARMA. Both model and observations indicate a strong gradient of the sulfur-to-carbon ratio from Europe to the Asia on constant pressure surfaces. We found that themore » ATAL is mostly composed of sulfates, surface-emitted organics, and secondary organics; the NATAL is mostly composed of sulfates and secondary organics. In conclusion, the model also suggests that emission increases in Asia between 2000 and 2010 led to an increase of aerosol optical depth of the ATAL by 0.002 on average which is consistent with observations.« less

  7. Composition and physical properties of the Asian Tropopause Aerosol Layer and the North American Tropospheric Aerosol Layer: Composition of ATAL and NATAL

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yu, Pengfei; Toon, Owen B.; Neely, Ryan R.

    Recent studies revealed layers of enhanced aerosol scattering in the upper troposphere and lower stratosphere over Asia (Asian Tropopause Aerosol Layer (ATAL)) and North America (North American Tropospheric Aerosol Layer (NATAL)). We use a sectional aerosol model (Community Aerosol and Radiation Model for Atmospheres (CARMA)) coupled with the Community Earth System Model version 1 (CESM1) to explore the composition and optical properties of these aerosol layers. The observed aerosol extinction enhancement is reproduced by CESM1/CARMA. Both model and observations indicate a strong gradient of the sulfur-to-carbon ratio from Europe to the Asia on constant pressure surfaces. We found that themore » ATAL is mostly composed of sulfates, surface-emitted organics, and secondary organics; the NATAL is mostly composed of sulfates and secondary organics. In conclusion, the model also suggests that emission increases in Asia between 2000 and 2010 led to an increase of aerosol optical depth of the ATAL by 0.002 on average which is consistent with observations.« less

  8. High-Resolution Electrospray Ionization Mass Spectrometry Analysis of Water- Soluble Organic Aerosols Collected with a Particle into Liquid Sampler

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bateman, Adam P.; Nizkorodov, Serguei; Laskin, Julia

    2010-10-01

    This work demonstrates the utility of a particle-into-liquid sampler (PILS) a technique traditionally used for identification of inorganic ions present in ambient or laboratory aerosols for the analysis of water soluble organic aerosol (OA) using high resolution electrospray ionization mass spectrometry (HR ESI-MS). Secondary organic aerosol (SOA) was produced from 0.5 ppm mixing ratios of limonene and ozone in a 5 m3 Teflon chamber. SOA was collected simultaneously using a traditional filter sampler and a PILS. The filter samples were later extracted with either water or acetonitrile, while the aqueous PILS samples were analyzed directly. In terms of peak intensities,more » types of detectable compounds, average O:C ratios, and organic mass to organic carbon ratios, the resulting high resolution mass spectra were essentially identical for the PILS and filter based samples. SOA compounds extracted from both filter/acetonitrile extraction and PILS/water extraction accounted for >95% of the total ion current in ESI mass spectra. This similarity was attributed to high solubility of limonene SOA in water. In contrast, significant differences in detected ions and peak abundances were observed for pine needle biomass burning organic aerosol (BBOA) collected with PILS and filter sampling. The water soluble fraction of BBOA is considerably smaller than for SOA, and a number of unique peaks were detectable only by the filter/acetonitrile method. The combination of PILS collection with HR-ESI-MS analysis offers a new approach for molecular analysis of the water-soluble organic fraction in biogenic SOA, aged photochemical smog, and BBOA.« less

  9. Black carbon mixing state impacts on cloud microphysical properties: effects of aerosol plume and environmental conditions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ching, Ping Pui; Riemer, Nicole; West, Matthew

    2016-05-27

    Black carbon (BC) is usually mixed with other aerosol species within individual aerosol particles. This mixture, along with the particles' size and morphology, determines the particles' optical and cloud condensation nuclei properties, and hence black carbon's climate impacts. In this study the particle-resolved aerosol model PartMC-MOSAIC was used to quantify the importance of black carbon mixing state for predicting cloud microphysical quantities. Based on a set of about 100 cloud parcel simulations a process level analysis framework was developed to attribute the response in cloud microphysical properties to changes in the underlying aerosol population ("plume effect") and the cloud parcelmore » cooling rate ("parcel effect"). It shows that the response of cloud droplet number concentration to changes in BC emissions depends on the BC mixing state. When the aerosol population contains mainly aged BC particles an increase in BC emission results in increasing cloud droplet number concentrations ("additive effect"). In contrast, when the aerosol population contains mainly fresh BC particles they act as sinks for condensable gaseous species, resulting in a decrease in cloud droplet number concentration as BC emissions are increased ("competition effect"). Additionally, we quantified the error in cloud microphysical quantities when neglecting the information on BC mixing state, which is often done in aerosol models. The errors ranged from -12% to +45% for the cloud droplet number fraction, from 0% to +1022% for the nucleation-scavenged black carbon (BC) mass fraction, from -12% to +4% for the effective radius, and from -30% to +60% for the relative dispersion.« less

  10. Equilibrium climate response of the East Asian summer monsoon to forcing of anthropogenic aerosol species

    NASA Astrophysics Data System (ADS)

    Wang, Zhili; Wang, Qiuyan; Zhang, Hua

    2017-12-01

    We used an online aerosol-climate model to study the equilibrium climate response of the East Asian summer monsoon (EASM) to increases in anthropogenic emissions of sulfate, organic carbon, and black carbon aerosols from 1850 to 2000. Our results show that each of these aerosol species has a different effect on the EASM as a result of changes in the local sea-land thermal contrast and atmospheric circulation. The increased emission of sulfate aerosol leads to a decrease in the thermal contrast between the land and ocean, a southward shift of the East Asian subtropical jet, and significant northerly wind anomalies at 850 hPa over eastern China and the ambient oceans, markedly dampening the EASM. An increase in organic carbon aerosol results in pronounced surface cooling and the formation of an anomalous anticyclone over the oceans north of 30°N. These effects cause a slight increase in the sea-land thermal contrast and southerly flow anomalies to the west of the anticyclonic center, strengthening the northern EASM. An increase in organic carbon emission decreases the sea-land thermal contrast over southern China, which weakens the southern EASM. The response of the summer 850-hPa winds and rainfall over the East Asian monsoon region to an increase in black carbon emission is generally consistent with the response to an increase in organic carbon. The increase in black carbon emission leads to a strengthening of the northern EASM north of 35°N and a slight weakening of the southern EASM south of 35°N. The simulated response of the EASM to the increase in black carbon emission is unchanged when the emission of black carbon is scaled up by five times its year 2000 levels, although the intensities of the response is enhanced. The increase in sulfate emission primarily weakens the EASM, whereas the increases in black carbon and organic carbon emissions mitigate weakening of the northern EASM.

  11. 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...

  12. Aerosol Absorption by Black Carbon and Dust: Implications of Climate Change and Air Quality in Asia

    NASA Technical Reports Server (NTRS)

    Chin, Mian

    2010-01-01

    Atmospheric aerosol distributions from 2000 to 2007 are simulated with the global model GOCART to attribute light absorption by aerosol to its composition and sources. We show the seasonal and interannual variations of absorbing aerosols in the atmosphere over Asia, mainly black carbon and dust. and their linkage to the changes of anthropogenic and dust emissions in the region. We compare our results with observations from satellite and ground-based networks, and estimate the importance of black carbon and dust on regional climate forcing and air quality.

  13. A smog chamber study coupling a photoionization aerosol electron/ion spectrometer to VUV synchrotron radiation: organic and inorganic-organic mixed aerosol analysis

    NASA Astrophysics Data System (ADS)

    Baeza-Romero, María Teresa; Gaie-Levrel, Francois; Mahjoub, Ahmed; López-Arza, Vicente; Garcia, Gustavo A.; Nahon, Laurent

    2016-07-01

    A reaction chamber was coupled to a photoionization aerosol time-of-flight mass spectrometer based on an electron/ion coincidence scheme and applied for on-line analysis of organic and inorganic-organic mixed aerosols using synchrotron tunable vacuum ultraviolet (VUV) photons as the ionization source. In this proof of principle study, both aerosol and gas phase were detected simultaneously but could be differentiated. Present results and perspectives for improvement for this set-up are shown in the study of ozonolysis ([O3] = 0.13-3 ppm) of α-pinene (2-3 ppm), and the uptake of glyoxal upon ammonium sulphate. In this work the ozone concentration was monitored in real time, together with the particle size distributions and chemical composition, the latter taking advantage of the coincidence spectrometer and the tuneability of the synchrotron radiation as a soft VUV ionization source.

  14. Sulfur Dioxide Accelerates the Heterogeneous Oxidation Rate of Organic Aerosol by Hydroxyl Radicals

    DOE PAGES

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

    2016-03-08

    There remains considerable uncertainty in how anthropogenic gas phase emissions alter the oxidative aging of organic aerosols in the troposphere. Here we observe a 10-20 fold acceleration in the effective heterogeneous OH oxidation rate of organic aerosol in the presence of SO 2. This acceleration originates from the radical chain reactions propagated by alkoxy radicals, which are formed efficiently inside the particle by the reaction of peroxy radicals with SO 2. As the OH approaches atmospheric concentrations, the radical chain length increases, transforming the aerosol at rates predicted to be up to 10 times the OH-aerosol collision frequency. Model predictions,more » constrained by experiments over orders of magnitude changes in [OH] and [SO 2], suggest that in polluted regions the heterogeneous processing of organic aerosols by OH ([SO 2] ≥ 40 ppb) occur on similar time scales as analogous gas-phase oxidation reactions. These results provide evidence for a previously unidentified mechanism by which organic aerosol oxidation is enhanced by anthropogenic gas phase emissions. (Chemical Equation Presented).« less

  15. [Research progress and direction of atmospheric brown carbon].

    PubMed

    Yan, Cai-Qing; Zheng, Mei; Zhang, Yuan-Hang

    2014-11-01

    Organic aerosol is one of the most important components of atmospheric aerosols. In recent years, organic aerosol has been found and proved to be light absorbing in UV-Visible region. Light absorbing organic carbon (also named as brown carbon) has been one of the forefronts in the field of atmospheric research. Its light absorption contributions to radiative forcing, regional air quality, and global climate change have drawn much attention. Regional air pollution is complex in China. Frequent visibility decline and severe regional haze episodes occurred since January 2013. Previous studies showed high amount of estimated columnar light-absorbing organic carbon in China, and according to current research findings, major sources of fine particulate matter in China (e. g. biomass burning and fossil fuel combustion) were also recognized as the main sources for brown carbon. Considering the high abundance of brown carbon in atmosphere, there is a great need to reconsider and reevaluate contributions of organic aerosol to light absorption, especially its role in haze formation and radiative forcing. However, up to now, basic researches on light absorbing organic carbon are still limited in China. This study aimed to elucidate the need for basic research on brown carbon, summarize previous studies and research progress from different aspects such as sources, composition, measurement, mass concentration distribution, optical property, radiative forcing of brown carbon, point out the existing problems and deficiencies, and put forward suggestions for future study.

  16. Springtime variations of organic and inorganic constituents in submicron aerosols (PM1.0) from Cape Hedo, Okinawa

    NASA Astrophysics Data System (ADS)

    Kunwar, Bhagawati; Torii, K.; Zhu, Chunmao; Fu, Pingqing; Kawamura, Kimitaka

    2016-04-01

    During the spring season with enhanced Asian outflow, we collected submicron aerosol (PM1.0) samples at Cape Hedo, Okinawa Island in the western North Pacific Rim. We analyzed the filter samples for diacids, oxoacids, pyruvic acid, α-dicarbonyls and fatty acids to better understand the sources and atmospheric processes in the outflow regions of Asian pollutants. Molecular distributions of diacids show a predominance of oxalic acid (C2) followed by malonic (C3) and succinic (C4) acids. Total diacids strongly correlated with secondary source tracers such as SO42- (r = 0.87), NH4+ (0.90) and methanesulfonate (MSA-) (0.84), suggesting that diacids are secondarily formed from their precursor compounds. We also found good correlations among C2, organic carbon (OC) and elemental carbon (EC) in the Okinawa aerosols, suggesting that diacids are mainly derived from anthropogenic sources. However, a weak correlation of diacids with levoglucosan, a biomass burning tracer, suggests that biomass buring is not the main source of diacids, rather diacids are secondarily formed by photochemical oxidation of organic precursors derived from fossil fuel combustion. We found a strong correlation (r = 0.98) between inorganic nitrogen (NO3-N + NH4-N) and total nitrogen (TN), to which organic nitrogen (ON) contributed 23%. Fatty acids were characterized by even carbon number predominance, suggesting that they are derived from biogenic sources. The higher abundances of short chain fatty acids (C20) further suggest that fatty acids are largely derived from marine phytoplankton during spring bloom.

  17. Lubricating oil dominates primary organic aerosol emissions from motor vehicles.

    PubMed

    Worton, David R; Isaacman, Gabriel; Gentner, Drew R; Dallmann, Timothy R; Chan, Arthur W H; Ruehl, Christopher; Kirchstetter, Thomas W; Wilson, Kevin R; Harley, Robert A; Goldstein, Allen H

    2014-04-01

    Motor vehicles are major sources of primary organic aerosol (POA), which is a mixture of a large number of organic compounds that have not been comprehensively characterized. In this work, we apply a recently developed gas chromatography mass spectrometry approach utilizing "soft" vacuum ultraviolet photoionization to achieve unprecedented chemical characterization of motor vehicle POA emissions in a roadway tunnel with a mass closure of >60%. The observed POA was characterized by number of carbon atoms (NC), number of double bond equivalents (NDBE) and degree of molecular branching. Vehicular POA was observed to predominantly contain cycloalkanes with one or more rings and one or more branched alkyl side chains (≥80%) with low abundances of n-alkanes and aromatics (<5%), similar to "fresh" lubricating oil. The gas chromatography retention time data indicates that the cycloalkane ring structures are most likely dominated by cyclohexane and cyclopentane rings and not larger cycloalkanes. High molecular weight combustion byproducts, that is, alkenes, oxygenates, and aromatics, were not present in significant amounts. The observed carbon number and chemical composition of motor vehicle POA was consistent with lubricating oil being the dominant source from both gasoline and diesel-powered vehicles, with an additional smaller contribution from unburned diesel fuel and a negligible contribution from unburned gasoline.

  18. The Correlation of Secondary Organic Aerosol with Odd Oxygen in Mexico City

    EPA Science Inventory

    Data from a mountain location intercepting the Mexico City emission plume demonstrate a strong correlation between secondary organic aerosol and odd-oxygen (O3 + NO2). The measured oxygenated-organic aerosol correlates with odd-oxygen measurements with an a...

  19. Nonequilibrium atmospheric secondary organic aerosol formation and growth

    PubMed Central

    Perraud, Véronique; Bruns, Emily A.; Ezell, Michael J.; Johnson, Stanley N.; Yu, Yong; Alexander, M. Lizabeth; Zelenyuk, Alla; Imre, Dan; Chang, Wayne L.; Dabdub, Donald; Pankow, James F.; Finlayson-Pitts, Barbara J.

    2012-01-01

    Airborne particles play critical roles in air quality, health effects, visibility, and climate. Secondary organic aerosols (SOA) formed from oxidation of organic gases such as α-pinene account for a significant portion of total airborne particle mass. Current atmospheric models typically incorporate the assumption that SOA mass is a liquid into which semivolatile organic compounds undergo instantaneous equilibrium partitioning to grow the particles into the size range important for light scattering and cloud condensation nuclei activity. We report studies of particles from the oxidation of α-pinene by ozone and NO3 radicals at room temperature. SOA is primarily formed from low-volatility ozonolysis products, with a small contribution from higher volatility organic nitrates from the NO3 reaction. Contrary to expectations, the particulate nitrate concentration is not consistent with equilibrium partitioning between the gas phase and a liquid particle. Rather the fraction of organic nitrates in the particles is only explained by irreversible, kinetically determined uptake of the nitrates on existing particles, with an uptake coefficient that is 1.6% of that for the ozonolysis products. If the nonequilibrium particle formation and growth observed in this atmospherically important system is a general phenomenon in the atmosphere, aerosol models may need to be reformulated. The reformulation of aerosol models could impact the predicted evolution of SOA in the atmosphere both outdoors and indoors, its role in heterogeneous chemistry, its projected impacts on air quality, visibility, and climate, and hence the development of reliable control strategies. PMID:22308444

  20. Chemically-resolved volatility measurements of organic aerosol fom different sources.

    PubMed

    Huffman, J A; Docherty, K S; Mohr, C; Cubison, M J; Ulbrich, I M; Ziemann, P J; Onasch, T B; Jimenez, J L

    2009-07-15

    A newly modified fast temperature-stepping thermodenuder (TD) was coupled to a High Resolution Time-of-Flight Aerosol Mass Spectrometer for rapid determination of chemically resolved volatility of organic aerosols (OA) emitted from individual sources. The TD-AMS system was used to characterize primary OA (POA) from biomass burning, trash burning surrogates (paper and plastic), and meat cooking as well as chamber-generated secondary OA (SOA) from alpha-pinene and gasoline vapor. Almost all atmospheric models represent POA as nonvolatile, with no allowance for evaporation upon heating or dilution, or condensation upon cooling. Our results indicate that all OAs observed show semivolatile behavior and that most POAs characterized here were at least as volatile as SOA measured in urban environments. Biomass-burning OA (BBOA) exhibited a wide range of volatilities, but more often showed volatility similar to urban OA. Paper-burning resembles some types of BBOA because of its relatively high volatility and intermediate atomic oxygen-to-carbon (O/C) ratio, while meat-cooking OAs (MCOA) have consistently lower volatility than ambient OA. Chamber-generated SOA under the relatively high concentrations used intraditional experiments was significantly more volatile than urban SOA, challenging extrapolation of traditional laboratory volatility measurements to the atmosphere. Most OAs sampled show increasing O/C ratio and decreasing H/C (hydrogen-to-carbon) ratio with temperature, further indicating that more oxygenated OA components are typically less volatile. Future experiments should systematically explore a wider range of mass concentrations to more fully characterize the volatility distributions of these OAs.

  1. Reactive Heterogeneous Chemistry on Organic Aerosols: Two Case Studies

    NASA Astrophysics Data System (ADS)

    Abbatt, J.; Braban, C.; Broekhuizen, K.; Thornberry, T.; Thornton, J.

    2003-12-01

    Two sets of laboratory studies will be discussed to illustrate the impact that heterogeneous chemistry involving tropospheric organic aerosols may have on both the gas-phase composition of the atmosphere and the chemical nature of the particles themselves. In the first case, the reactive uptake coefficient for the hydrolysis of dinitrogen pentoxide (N2O5) on organic aerosols has been measured in an entrained aerosol flow tube coupled to a Chemical-Ionization Mass Spectrometer (CIMS). The general observation is that the reaction on aqueous malonic acid aerosols behaves in an analogous manner to that on aqueous inorganic salts, i.e. the uptake coefficient shows a linear dependence on the particle water content up to 50% relative humidity (RH), at which point the effect saturates. In addition, there is evidence for the kinetics being dependent on both the size of the particles and the levels of dissolved nitrate. By contrast, the N2O5 hydrolysis kinetics on solid azelaic acid particles are too slow to be atmospherically significant, even at 85% RH. In the second case, the kinetics and product yields from the oxidation of liquid oleic acid by ozone have been studied in considerable detail, with emphasis on the quantification of gas-phase products (nonanal) by CIMS and water-soluble species by HPLC/Electrospray-Ionization Mass Spectrometry (azelaic acid, nonanoic acid). The atmospheric importance of these results will be discussed, in particular with respect to the role of organic aerosol oxidation as a source of cloud condensation nuclei.

  2. Organics, Meteoritic Material, and other Elements in High Altitude Aerosols

    NASA Technical Reports Server (NTRS)

    Mahoney, M.; Murphy, D. M.; Thomson, D. S.

    1998-01-01

    Recent in situ measurements of the chemical composition of single aerosol particles at altitudes up to 19 km have revealed a number of surprising features about ambient particles. Upper tropospheric aerosols in the study region often contained more organic material than sulfate.

  3. EFFECT OF ACIDITY ON SECONDARY ORGANIC AEROSOL FORMATION FROM ISOPRENE

    EPA Science Inventory

    The effect of particle-phase acidity on secondary organic aerosol (SOA) formation from isoprene is investigated in a laboratory chamber study, in which the acidity of the inorganic seed aerosol was controlled systematically. The observed enhancement in SOA mass concentration is c...

  4. Seasonal variations in elemental carbon aerosol, carbon monoxide and sulfur dioxide: Implications for sources

    NASA Astrophysics Data System (ADS)

    Antony Chen, L.-W.; Doddridge, Bruce G.; Dickerson, Russell R.; Chow, Judith C.; Mueller, Peter K.; Quinn, John; Butler, William A.

    As part of Maryland Aerosol Research and CHaracterization (MARCH-Atlantic) study, measurements of 24-hr average elemental carbon (EC) aerosol concentration were made at Fort Meade, Maryland, USA, a suburban site within the Baltimore-Washington corridor during July 1999, October 1999, January 2000, April 2000 and July 2000. Carbon monoxide (CO) and sulfur dioxide (SO2) were also measured nearly continuously over the period. Tight correlation between EC and CO in every month suggests common or proximate sources, likely traffic emissions. The EC versus CO slope varies in different seasons and generally increases with ambient temperature. The temperature dependence of EC/CO ratios suggests that EC source strength peaks in summer. By using the well established emission inventory for CO, and EC/CO ratio found in this study, EC emission over North America is estimated at 0.31±0.12 Tg yr-1, on the low end but in reasonable agreement with prior inventories based on emission factors and fuel consumption.

  5. Seasonal variations in elemental carbon aerosol, carbon monoxide and sulfur dioxide: Implications for sources

    NASA Astrophysics Data System (ADS)

    Chen, L.-W. Antony; Doddridge, Bruce G.; Dickerson, Russell R.; Chow, Judith C.; Mueller, Peter K.; Quinn, John; Butler, William A.

    2001-05-01

    As part of Maryland Aerosol Research and CHaracterization (MARCH-Atlantic) study, measurements of 24-hr average elemental carbon (EC) aerosol concentration were made at Fort Meade, Maryland, USA, a suburban site within the Baltimore-Washington corridor during July 1999, October 1999, January 2000, April 2000 and July 2000. Carbon monoxide (CO) and sulfur dioxide (SO2) were also measured nearly continuously over the period. Tight correlation between EC and CO in every month suggests common or proximate sources, likely traffic emissions. The EC versus CO slope varies in different seasons and generally increases with ambient temperature. The temperature dependence of EC/CO ratios suggests that EC source strength peaks in summer. By using the well established emission inventory for CO, and EC/CO ratio found in this study, EC emission over North America is estimated at 0.31+/-0.12Tgyr-1, on the low end but in reasonable agreement with prior inventories based on emission factors and fuel consumption.

  6. Stable Carbon Fractionation In Size Segregated Aerosol Particles Produced By Controlled Biomass Burning

    NASA Astrophysics Data System (ADS)

    Masalaite, Agne; Garbaras, Andrius; Garbariene, Inga; Ceburnis, Darius; Martuzevicius, Dainius; Puida, Egidijus; Kvietkus, Kestutis; Remeikis, Vidmantas

    2014-05-01

    Biomass burning is the largest source of primary fine fraction carbonaceous particles and the second largest source of trace gases in the global atmosphere with a strong effect not only on the regional scale but also in areas distant from the source . Many studies have often assumed no significant carbon isotope fractionation occurring between black carbon and the original vegetation during combustion. However, other studies suggested that stable carbon isotope ratios of char or BC may not reliably reflect carbon isotopic signatures of the source vegetation. Overall, the apparently conflicting results throughout the literature regarding the observed fractionation suggest that combustion conditions may be responsible for the observed effects. The purpose of the present study was to gather more quantitative information on carbonaceous aerosols produced in controlled biomass burning, thereby having a potential impact on interpreting ambient atmospheric observations. Seven different biomass fuel types were burned under controlled conditions to determine the effect of the biomass type on the emitted particulate matter mass and stable carbon isotope composition of bulk and size segregated particles. Size segregated aerosol particles were collected using the total suspended particle (TSP) sampler and a micro-orifice uniform deposit impactor (MOUDI). The results demonstrated that particle emissions were dominated by the submicron particles in all biomass types. However, significant differences in emissions of submicron particles and their dominant sizes were found between different biomass fuels. The largest negative fractionation was obtained for the wood pellet fuel type while the largest positive isotopic fractionation was observed during the buckwheat shells combustion. The carbon isotope composition of MOUDI samples compared very well with isotope composition of TSP samples indicating consistency of the results. The measurements of the stable carbon isotope ratio in

  7. Thermodynamic Modeling of Organic-Inorganic Aerosols with the Group-Contribution Model AIOMFAC

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

    Liquid aerosol particles are - from a physicochemical viewpoint - mixtures of inorganic salts, acids, water and a large variety of organic compounds (Rogge et al., 1993; Zhang et al., 2007). Molecular interactions between these aerosol components lead to deviations from ideal thermodynamic behavior. Strong non-ideality between organics and dissolved ions may influence the aerosol phases at equilibrium by means of liquid-liquid phase separations into a mainly polar (aqueous) and a less polar (organic) phase. A number of activity models exists to successfully describe the thermodynamic equilibrium of aqueous electrolyte solutions. However, the large number of different, often multi-functional, organic compounds in mixed organic-inorganic particles is a challenging problem for the development of thermodynamic models. The group-contribution concept as introduced in the UNIFAC model by Fredenslund et al. (1975), is a practical method to handle this difficulty and to add a certain predictability for unknown organic substances. We present the group-contribution model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients), which explicitly accounts for molecular interactions between solution constituents, both organic and inorganic, to calculate activities, chemical potentials and the total Gibbs energy of mixed systems (Zuend et al., 2008). This model enables the computation of vapor-liquid (VLE), liquid-liquid (LLE) and solid-liquid (SLE) equilibria within one framework. Focusing on atmospheric applications we considered eight different cations, five anions and a wide range of alcohols/polyols as organic compounds. With AIOMFAC, the activities of the components within an aqueous electrolyte solution are very well represented up to high ionic strength. We show that the semi-empirical middle-range parametrization of direct organic-inorganic interactions in alcohol-water-salt solutions enables accurate computations of vapor-liquid and liquid

  8. Aerosol Sources, Absorption, and Intercontinental Transport: Synergies among Models, Remote Sensing, and Atmospheric Measurements

    NASA Technical Reports Server (NTRS)

    Chin, Mian; Ginoux, Paul; Dubovik, Oleg; Holben, Brent; Kaufman, Yoram; chu, Allen; Anderson, Tad; Quinn, Patricia

    2003-01-01

    Aerosol climate forcing is one of the largest uncertainties in assessing the anthropogenic impact on the global climate system. This uncertainty arises from the poorly quantified aerosol sources, especially black carbon emissions, our limited knowledge of aerosol mixing state and optical properties, and the consequences of intercontinental transport of aerosols and their precursors. Here we use a global model GOCART to simulate atmospheric aerosols, including sulfate, black carbon, organic carbon, dust, and sea salt, from anthropogenic, biomass burning, and natural sources. We compare the model calculated aerosol extinction and absorption with those quantities from the ground-based sun photometer measurements from AERONET at several different wavelengths and the field observations from ACE-Asia, and model calculated total aerosol optical depth and fine mode fractions with the MODIS satellite retrieval. We will also estimate the intercontinental transport of pollution and dust aerosols from their source regions to other areas in different seasons.

  9. Aerosol Sources, Absorption, and Intercontinental Transport: Synergies Among Models, Remote Sensing, and Atmospheric Measurements

    NASA Technical Reports Server (NTRS)

    Chin, Mian; Chu, Allen; Levy, Robert; Remer, Lorraine; Kaufman, Yoram; Dubovik, Oleg; Holben, Brent; Eck, Tom; Anderson, Tad; Quinn, Patricia

    2004-01-01

    Aerosol climate forcing is one of the largest uncertainties in assessing the anthropogenic impact on the global climate system. This uncertainty arises from the poorly quantified aerosol sources, especially black carbon emissions, our limited knowledge of aerosol mixing state and optical properties, and the consequences of intercontinental transport of aerosols and their precursors. Here we use a global model GOCART to simulate atmospheric aerosols, including sulfate, black carbon, organic carbon, dust, and sea salt, from anthropogenic, .biomass burning, and natural sources. We compare the model calculated aerosol extinction and absorption with those quantities from the ground-based sun photometer measurements from AERON" at several different wavelengths and the field observations from ACE-Asia, and model calculated total aerosol optical depth and fine mode fractions with the MODIS satellite retrieval. We will also estimate the intercontinental transport of pollution and dust aerosols from their source regions to other areas in different seasons.

  10. Evaluation of biomass burning aerosols in the HadGEM3 climate model with observations from the SAMBBA field campaign

    NASA Astrophysics Data System (ADS)

    Johnson, Ben T.; Haywood, James M.; Langridge, Justin M.; Darbyshire, Eoghan; Morgan, William T.; Szpek, Kate; Brooke, Jennifer K.; Marenco, Franco; Coe, Hugh; Artaxo, Paulo; Longo, Karla M.; Mulcahy, Jane P.; Mann, Graham W.; Dalvi, Mohit; Bellouin, Nicolas

    2016-11-01

    We present observations of biomass burning aerosol from the South American Biomass Burning Analysis (SAMBBA) and other measurement campaigns, and use these to evaluate the representation of biomass burning aerosol properties and processes in a state-of-the-art climate model. The evaluation includes detailed comparisons with aircraft and ground data, along with remote sensing observations from MODIS and AERONET. We demonstrate several improvements to aerosol properties following the implementation of the Global Model for Aerosol Processes (GLOMAP-mode) modal aerosol scheme in the HadGEM3 climate model. This predicts the particle size distribution, composition, and optical properties, giving increased accuracy in the representation of aerosol properties and physical-chemical processes over the Coupled Large-scale Aerosol Scheme for Simulations in Climate Models (CLASSIC) bulk aerosol scheme previously used in HadGEM2. Although both models give similar regional distributions of carbonaceous aerosol mass and aerosol optical depth (AOD), GLOMAP-mode is better able to capture the observed size distribution, single scattering albedo, and Ångström exponent across different tropical biomass burning source regions. Both aerosol schemes overestimate the uptake of water compared to recent observations, CLASSIC more so than GLOMAP-mode, leading to a likely overestimation of aerosol scattering, AOD, and single scattering albedo at high relative humidity. Observed aerosol vertical distributions were well captured when biomass burning aerosol emissions were injected uniformly from the surface to 3 km. Finally, good agreement between observed and modelled AOD was gained only after scaling up GFED3 emissions by a factor of 1.6 for CLASSIC and 2.0 for GLOMAP-mode. We attribute this difference in scaling factor mainly to different assumptions for the water uptake and growth of aerosol mass during ageing via oxidation and condensation of organics. We also note that similar agreement

  11. Effect of Heterogeneous Chemical Reactions on the Köhler Activation of Aqueous Organic Aerosols.

    PubMed

    Djikaev, Yuri S; Ruckenstein, Eli

    2018-05-03

    We study some thermodynamic aspects of the activation of aqueous organic aerosols into cloud droplets considering the aerosols to consist of liquid solution of water and hydrophilic and hydrophobic organic compounds, taking into account the presence of reactive species in the air. The hydrophobic (surfactant) organic molecules on the surface of such an aerosol can be processed by chemical reactions with some atmospheric species; this affects the hygroscopicity of the aerosol and hence its ability to become a cloud droplet either via nucleation or via Köhler activation. The most probable pathway of such processing involves atmospheric hydroxyl radicals that abstract hydrogen atoms from hydrophobic organic molecules located on the aerosol surface (first step), the resulting radicals being quickly oxidized by ubiquitous atmospheric oxygen molecules to produce surface-bound peroxyl radicals (second step). These two reactions play a crucial role in the enhancement of the Köhler activation of the aerosol and its evolution into a cloud droplet. Taking them and a third reaction (next in the multistep chain of relevant heterogeneous reactions) into account, one can derive an explicit expression for the free energy of formation of a four-component aqueous droplet on a ternary aqueous organic aerosol as a function of four independent variables of state of a droplet. The results of numerical calculations suggest that the formation of cloud droplets on such (aqueous hydrophilic/hydrophobic organic) aerosols is most likely to occur as a Köhler activation-like process rather than via nucleation. The model allows one to determine the threshold parameters of the system necessary for the Köhler activation of such aerosols, which are predicted to be very sensitive to the equilibrium constant of the chain of three heterogeneous reactions involved in the chemical aging of aerosols.

  12. Secondary organic aerosol from atmospheric photooxidation of indole

    NASA Astrophysics Data System (ADS)

    Montoya-Aguilera, Julia; Horne, Jeremy R.; Hinks, Mallory L.; Fleming, Lauren T.; Perraud, Véronique; Lin, Peng; Laskin, Alexander; Laskin, Julia; Dabdub, Donald; Nizkorodov, Sergey A.

    2017-09-01

    Indole is a heterocyclic compound emitted by various plant species under stressed conditions or during flowering events. The formation, optical properties, and chemical composition of secondary organic aerosol (SOA) formed by low-NOx photooxidation of indole were investigated. The SOA yield (1. 3 ± 0. 3) was estimated from measuring the particle mass concentration with a scanning mobility particle sizer (SMPS) and correcting it for wall loss effects. The high value of the SOA mass yield suggests that most oxidized indole products eventually end up in the particle phase. The SOA particles were collected on filters and analysed offline with UV-vis spectrophotometry to measure the mass absorption coefficient (MAC) of the bulk sample. The samples were visibly brown and had MAC values of ˜ 2 m2 g-1 at λ = 300 nm and ˜ 0. 5 m2 g-1 at λ = 400 nm, comparable to strongly absorbing brown carbon emitted from biomass burning. The chemical composition of SOA was examined with several mass spectrometry methods. Direct analysis in real-time mass spectrometry (DART-MS) and nanospray desorption electrospray high-resolution mass spectrometry (nano-DESI-HRMS) were both used to provide information about the overall distribution of SOA compounds. High-performance liquid chromatography, coupled to photodiode array spectrophotometry and high-resolution mass spectrometry (HPLC-PDA-HRMS), was used to identify chromophoric compounds that are responsible for the brown colour of SOA. Indole derivatives, such as tryptanthrin, indirubin, indigo dye, and indoxyl red, were found to contribute significantly to the visible absorption spectrum of indole SOA. The potential effect of indole SOA on air quality was explored with an airshed model, which found elevated concentrations of indole SOA during the afternoon hours contributing considerably to the total organic aerosol under selected scenarios. Because of its high MAC values, indole SOA can contribute to decreased visibility and poor air

  13. Predicting Thermal Behavior of Secondary Organic Aerosols

    EPA Science Inventory

    Volume concentrations of steady-state secondary organic aerosol (SOA) were measured in 139 steadystate single precursor hydrocarbon oxidation experiments after passing through a temperature controlled inlet tube. Higher temperatures resulted in greater loss of particle volume, wi...

  14. Evaluation of atmospheric aerosol and tropospheric ozone effects on global terrestrial ecosystem carbon dynamics

    NASA Astrophysics Data System (ADS)

    Chen, Min

    The increasing human activities have produced large amounts of air pollutants ejected into the atmosphere, in which atmospheric aerosols and tropospheric ozone are considered to be especially important because of their negative impacts on human health and their impacts on global climate through either their direct radiative effect or indirect effect on land-atmosphere CO2 exchange. This dissertation dedicates to quantifying and evaluating the aerosol and tropospheric ozone effects on global terrestrial ecosystem dynamics using a modeling approach. An ecosystem model, the integrated Terrestrial Ecosystem Model (iTem), is developed to simulate biophysical and biogeochemical processes in terrestrial ecosystems. A two-broad-band atmospheric radiative transfer model together with the Moderate-Resolution Imaging Spectroradiometer (MODIS) measured atmospheric parameters are used to well estimate global downward solar radiation and the direct and diffuse components in comparison with observations. The atmospheric radiative transfer modeling framework were used to quantify the aerosol direct radiative effect, showing that aerosol loadings cause 18.7 and 12.8 W m -2 decrease of direct-beam Photosynthetic Active Radiation (PAR) and Near Infrared Radiation (NIR) respectively, and 5.2 and 4.4 W m -2 increase of diffuse PAR and NIR, respectively, leading to a total 21.9 W m-2 decrease of total downward solar radiation over the global land surface during the period of 2003-2010. The results also suggested that the aerosol effect may be overwhelmed by clouds because of the stronger extinction and scattering ability of clouds. Applications of the iTem with solar radiation data and with or without considering the aerosol loadings shows that aerosol loading enhances the terrestrial productions [Gross Primary Production (GPP), Net Primary Production (NPP) and Net Ecosystem Production (NEP)] and carbon emissions through plant respiration (RA) in global terrestrial ecosystems over the

  15. Characterization of Secondary Organic Aerosol Precursors Using Two-Dimensional Gas-Chromatography

    NASA Astrophysics Data System (ADS)

    Roskamp, M.; Lou, W.; Pankow, J. F.; Harley, P. C.; Turnipseed, A.; Barsanti, K. C.

    2012-12-01

    The oxidation of volatile organic compounds (VOCs) plays a role in both regional and global air quality. However, field and laboratory research indicate that the body of knowledge around the identities, quantities and oxidation processes of these compounds in the ambient atmosphere is still incomplete (e.g., Goldstein & Galbally, 2007; Robinson et al., 2009). VOCs emitted to the atmosphere largely are of biogenic origin (Guenther et al., 2006), and many studies of ambient secondary organic aerosol (SOA) suggest that SOA is largely of biogenic origin (albeit closely connected to anthropogenic activities, e.g., de Gouw and Jimenez, 2009). Accurate modeling of SOA levels and properties will require a more complete understanding of biogenic VOCs (BOCs) and their atmospheric oxidation products. For example, satellite measurements indicate that biogenic VOC emissions are two to three times greater than levels currently included in models (Heald et al., 2010). Two-dimensional gas chromatography (GC×GC) is a powerful analytical technique that shows much promise in advancing the state-of-knowledge regarding BVOCs and their role in SOA formation. In this work, samples were collected during BEACHON-RoMBAS (Bio-hydro-atmosphere Interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Biogenic Aerosol Study) in July and August of 2011. The field site was a Ponderosa Pine forest near Woodland, CO, inside the Manitou Experimental Forest, which is operated by the US Forest Service. The area is characteristic of the central Rocky Mountains and trace gas monitoring indicates that little anthropogenic pollution is transported from the nearby urban areas (Kim et al. 2010 and references therein). Ambient and enclosure samples were collected on ATD (adsorption/thermal desorption) cartridges and analyzed for BVOCs using two-dimensional gas chromatography (GC×GC) with time of flight mass spectrometry (TOFMS) and flame ionized detection (FID). Measurements of

  16. Measurement of the temperature dependent partitioning of semi-volatile organics onto aerosol near roadways

    NASA Astrophysics Data System (ADS)

    Wentzell, J. J.; Liggio, J.; Li, S.; Brook, J.; Staebler, R. M.; Evans, G. J.; Jeong, C.; Sheppard, A.; Lu, G.; Gordon, M.; Mihele, C.

    2010-12-01

    The volatility of the organic aerosol fraction has received a great deal of attention recently in light of new volatility-based modelling approaches and due to the inability of current models to fully account for secondary organic aerosol (SOA). In this regard, evaporation of primary organic aerosol species and their subsequent oxidation may contribute significantly to SOA downwind of sources. This implies that moderate ambient temperature fluctuations can significantly increase or decrease the aerosol bound fraction of semi-volatile and intermediate volatility (SVOC + IVOC) compounds. In order to examine the importance of these more volatile organic components, a temperature controlled inlet was developed with the ability to heat and cool the aerosol in 2 C increments to 15 C above or below ambient temperature. The inlet was coupled to an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and deployed on a mobile platform upwind and downwind of a major Southern Ontario highway as part of the Fast Evolution of Vehicle Emissions near Roadways (FEVER 2010) campaign. Preliminary results suggest that changes in temperature of 5-10 C can alter the partitioning of volatile organic aerosol components by up to 30%. Although the largest affect was observed 10-13 meters downwind of the vehicle emissions, a measurable affect was observed beyond 500 m and in aerosol upwind of the highway. These results suggest that a significant pool of semi-volatile organics exist, which can condense onto particles at slightly lower temperatures or evaporate to the gas phase and be further oxidized. The nature of these organic species at locations upwind and downwind of vehicle emissions will be discussed.

  17. Quantifying the effect of organic aerosol aging and intermediate-volatility emissions on regional-scale aerosol pollution in China

    PubMed Central

    Zhao, Bin; Wang, Shuxiao; Donahue, Neil M.; Jathar, Shantanu H.; Huang, Xiaofeng; Wu, Wenjing; Hao, Jiming; Robinson, Allen L.

    2016-01-01

    Secondary organic aerosol (SOA) is one of the least understood constituents of fine particles; current widely-used models cannot predict its loadings or oxidation state. Recent laboratory experiments demonstrated the importance of several new processes, including aging of SOA from traditional precursors, aging of primary organic aerosol (POA), and photo-oxidation of intermediate volatility organic compounds (IVOCs). However, evaluating the effect of these processes in the real atmosphere is challenging. Most models used in previous studies are over-simplified and some key reaction trajectories are not captured, and model parameters are usually phenomenological and lack experimental constraints. Here we comprehensively assess the effect of organic aerosol (OA) aging and intermediate-volatility emissions on regional-scale OA pollution with a state-of-the-art model framework and experimentally constrained parameters. We find that OA aging and intermediate-volatility emissions together increase OA and SOA concentrations in Eastern China by about 40% and a factor of 10, respectively, thereby improving model-measurement agreement significantly. POA and IVOCs both constitute over 40% of OA concentrations, and IVOCs constitute over half of SOA concentrations; this differs significantly from previous apportionment of SOA sources. This study facilitates an improved estimate of aerosol-induced climate and health impacts, and implies a shift from current fine-particle control policies. PMID:27350423

  18. Characterization of a large biogenic secondary organic aerosol event from eastern Canadian forests

    NASA Astrophysics Data System (ADS)

    Slowik, J. G.; Stroud, C.; Bottenheim, J. W.; Brickell, P. C.; Chang, R. Y.-W.; Liggio, J.; Makar, P. A.; Martin, R. V.; Moran, M. D.; Shantz, N. C.; Sjostedt, S. J.; van Donkelaar, A.; Vlasenko, A.; Wiebe, H. A.; Xia, A. G.; Zhang, J.; Leaitch, W. R.; Abbatt, J. P. D.

    2010-03-01

    Measurements of aerosol composition, volatile organic compounds, and CO are used to determine biogenic secondary organic aerosol (SOA) concentrations at a rural site 70 km north of Toronto. These biogenic SOA levels are many times higher than past observations and occur during a period of increasing temperatures and outflow from Northern Ontario and Quebec forests in early summer. A regional chemical transport model approximately predicts the event timing and accurately predicts the aerosol loading, identifying the precursors as monoterpene emissions from the coniferous forest. The agreement between the measured and modeled biogenic aerosol concentrations contrasts with model underpredictions for polluted regions. Correlations of the oxygenated organic aerosol mass with tracers such as CO support a secondary aerosol source and distinguish biogenic, pollution, and biomass burning periods during the field campaign. Using the Master Chemical Mechanism, it is shown that the levels of CO observed during the biogenic event are consistent with a photochemical source arising from monoterpene oxidation. The biogenic aerosol mass correlates with satellite measurements of regional aerosol optical depth, indicating that the event extends across the eastern Canadian forest. This regional event correlates with increased temperatures, indicating that temperature-dependent forest emissions can significantly affect climate through enhanced direct optical scattering and higher cloud condensation nuclei numbers.

  19. Biomass Burning Dominates Brown Carbon Absorption in the Rural Southeastern U.S.

    NASA Astrophysics Data System (ADS)

    Washenfelder, R. A.; Attwood, A. R.; Brock, C. A.; Brown, S. S.; Guo, H.; Weber, R. J. J.; Xu, L.; Ng, N. L.; Stone, E. A.; Edgerton, E. S.; Baumann, K.; Hu, W.; Palm, B. B.; Jimenez, J. L.; Fry, J.; Ayres, B. R.; Draper, D.; Allen, H.

    2014-12-01

    Aerosol scattering and absorption are still among the largest uncertainties in quantifying radiative forcing. Brown carbon has a wavelength-dependent absorption that increases in the UV spectral region, and its major atmospheric sources include biomass burning, anthropogenic combustion of fossil fuels, and secondary organic aerosol. The rural Southeastern U.S. is influenced by high isoprene concentrations and varying concentrations of biomass burning aerosol, making it an ideal place to compare the relative contributions of these two sources to the brown carbon absorption budget. During the Southern Oxidant and Aerosol Study in summer 2013, we deployed a new field instrument that uses cavity enhanced spectroscopy with a broadband light source to measure aerosol optical extinction as a function of wavelength. The instrument consists of two broadband channels which span the 360-390 and 385-420 nm spectral regions using two light emitting diodes (LED) and a grating spectrometer with charge-coupled device (CCD) detector. We combine these data with direct absorption measurements of water-soluble organic carbon obtained from a novel UV/VIS-WSOC instrument, and with aerosol composition measurements. We examine these data sets to determine: 1) the optical closure between measured dry aerosol extinction and values calculated from aerosol composition and size distribution; 2) the magnitude of brown and black carbon absorption; 3) the relative contributions of biomass burning, anthropogenic, and secondary organic aerosol contributions to brown carbon absorption in the Southeast U.S. during the summer. We conclude that biomass burning is a major contributor to optical absorption by organic aerosol in the rural southeastern U.S.

  20. Carbonaceous aerosols from prescribed burning of a boreal forest ecosystem

    NASA Technical Reports Server (NTRS)

    Mazurek, Monica A.; Cofer, Wesley R., III; Levine, Joel S.

    1991-01-01

    During the boreal forest burn studied, the ambient concentrations for the particle carbon smoke aerosol are highest for the full-fire burn conditions and vary significantly throughout the burn. Collection strategies must accordingly define ranges in the smoke aerosol concentrations produced. While the highest elemental C concentrations are observed during full-fire conditions, the great majority of smoke aerosol particles are in the form of organic C particles irrespective of fire temperature. The formation of organic C light-scattering particles was a significant process in the burn studied.

  1. Introduction of the new concept: Potential Aerosol Mass (PAM) for Inorganic and Organic Secondary Aerosol

    NASA Astrophysics Data System (ADS)

    Kang, E.; Root, M. J.; Brune, W. H.

    2006-12-01

    A new concept, the Potential Aerosol Mass (PAM), is being developed and tested in the laboratory with the goal of deploying instruments to measure PAM in the atmosphere. PAM can be defined as the maximum aerosol mass that precursor gases can be oxidized to form. In the PAM concept, all precursor gases are oxidized to low volatile compounds with excessive amount of oxidants in a small continuous-flow Teflon cylinder, resulting in aerosol formation. Excessive amounts of OH and O3 are produced by a UV light that shines into the Teflon chamber. For our studies, the aerosol mass is then detected with a real-time aerosol mass measurement instrument, the Rupprecht and Patashnick Tapered Element Oscillating Microbalance (TEOM) and Filter Dynamic Measurement System (FDMS). As a test of the system, SO2 was oxidized to sulfate; the measured and calculated conversion ratios of sulfate aerosol mass to SO2 mass agree to within 10%. We will discuss the results of a series of laboratory tests that have been conducted with α-pinene to determine the variables that most affect its Secondary Organic Aerosol (SOA) yield. We will also discuss the results of some atmospheric measurement tests made at a site on the Penn State University campus.

  2. Preliminary characterization of submicron secondary aerosol in the amazon forest - ATTO station

    NASA Astrophysics Data System (ADS)

    Carbone, S.; Ferreira De Brito, J.; Andreae, M. O.; Pöhlker, C.; Chi, X.; Saturno, J.; Barbosa, H. M.; Artaxo, P.

    2014-12-01

    Biogenic secondary organic aerosol particles are investigated in the Amazon in the context of the GoAmazon Project. The forest naturally emits a large number of gaseous compounds; they are called the volatile organic compounds (VOCs). They are emitted through processes that are not totally understood. Part of those gaseous compounds are converted into aerosol particles, which affect the biogeochemical cycles, the radiation balance, the mechanisms involving cloud formation and evolution, among few other important effects. In this study the aerosol life-cycle is investigated at the ATTO station, which is located about 150 km northeast of Manaus, with emphasis on the natural organic component and its impacts in the ecosystem. To achieve these objectives physical and chemical aerosol properties have been investigated, such as the chemical composition with aerosol chemical speciation monitor (ACSM), nanoparticle size distribution (using the SMPS - Scanning Mobility Particle Sizer), optical properties with measurements of scattering and absorption (using nephelometers and aethalometers). Those instruments have been operating continuously since February 2014 together with trace gases (O3, CO2, CO, SO2 and NOx) analyzers and additional meteorological instruments. On average PM1 (the sum of black carbon, organic and inorganic ions) totalized 1.0±0.3 μg m-3, where the organic fraction was dominant (75%). During the beginning of the dry season (July/August) the organic aerosol presented a moderate oxygenated character with the oxygen to carbon ratio (O:C) of 0.7. In the wet season some episodes containing significant amount of chloride and backward wind trajectories suggest aerosol contribution from the Atlantic Ocean. A more comprehensive analysis will include an investigation of the different oxidized fractions of the organic aerosol and optical properties.

  3. 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

  4. OZONE-ISOPRENE REACTION: RE-EXAMINATION OF THE FORMATION OF SECONDARY ORGANIC AEROSOL

    EPA Science Inventory

    The reaction of ozone and isoprene has been studied to examine physical and chemical characteristics of the secondary organic aerosol formed. Using a scanning mobility particle sizer, the volume distribution of the aerosol was found in the range 0.05 - 0.2 µm. The aerosol yield w...

  5. Reactive intermediates revealed in secondary organic aerosol formation from isoprene

    PubMed Central

    Surratt, Jason D.; Chan, Arthur W. H.; Eddingsaas, Nathan C.; Chan, ManNin; Loza, Christine L.; Kwan, Alan J.; Hersey, Scott P.; Flagan, Richard C.; Wennberg, Paul O.; Seinfeld, John H.

    2010-01-01

    Isoprene is a significant source of atmospheric organic aerosol; however, the oxidation pathways that lead to secondary organic aerosol (SOA) have remained elusive. Here, we identify the role of two key reactive intermediates, epoxydiols of isoprene (IEPOX = β-IEPOX + δ-IEPOX) and methacryloylperoxynitrate (MPAN), which are formed during isoprene oxidation under low- and high-NOx conditions, respectively. Isoprene low-NOx SOA is enhanced in the presence of acidified sulfate seed aerosol (mass yield 28.6%) over that in the presence of neutral aerosol (mass yield 1.3%). Increased uptake of IEPOX by acid-catalyzed particle-phase reactions is shown to explain this enhancement. Under high-NOx conditions, isoprene SOA formation occurs through oxidation of its second-generation product, MPAN. The similarity of the composition of SOA formed from the photooxidation of MPAN to that formed from isoprene and methacrolein demonstrates the role of MPAN in the formation of isoprene high-NOx SOA. Reactions of IEPOX and MPAN in the presence of anthropogenic pollutants (i.e., acidic aerosol produced from the oxidation of SO2 and NO2, respectively) could be a substantial source of “missing urban SOA” not included in current atmospheric models. PMID:20080572

  6. Organosulfate Formation in Biogenic Secondary Organic Aerosol

    EPA Science Inventory

    Organosulfates of isoprene, α-pinene, and β-pinene have recently been identified in both laboratory-generated and ambient secondary organic aerosol (SOA). In this study, the mechanism and ubiquity of organosulfate formation in biogenic SOA is investigated by a comprehensive seri...

  7. Nanoporous mannitol carrier prepared by non-organic solvent spray drying technique to enhance the aerosolization performance for dry powder inhalation

    PubMed Central

    Peng, Tingting; Zhang, Xuejuan; Huang, Ying; Zhao, Ziyu; Liao, Qiuying; Xu, Jing; Huang, Zhengwei; Zhang, Jiwen; Wu, Chuan-yu; Pan, Xin; Wu, Chuanbin

    2017-01-01

    An optimum carrier rugosity is essential to achieve a satisfying drug deposition efficiency for the carrier based dry powder inhalation (DPI). Therefore, a non-organic spray drying technique was firstly used to prepare nanoporous mannitol with small asperities to enhance the DPI aerosolization performance. Ammonium carbonate was used as a pore-forming agent since it decomposed with volatile during preparation. It was found that only the porous structure, and hence the specific surface area and carrier density were changed at different ammonium carbonate concentration. Furthermore, the carrier density was used as an indication of porosity to correlate with drug aerosolization. A good correlation between the carrier density and fine particle fraction (FPF) (r2 = 0.9579) was established, suggesting that the deposition efficiency increased with the decreased carrier density. Nanoporous mannitol with a mean pore size of about 6 nm exhibited 0.24-fold carrier density while 2.16-fold FPF value of the non-porous mannitol. The enhanced deposition efficiency was further confirmed from the pharmacokinetic studies since the nanoporous mannitol exhibited a significantly higher AUC0-8h value than the non-porous mannitol and commercial product Pulmicort. Therefore, surface modification by preparing nanoporous carrier through non-organic spray drying showed to be a facile approach to enhance the DPI aerosolization performance. PMID:28462948

  8. Speleothem records of acid sulphate deposition and organic carbon mobilisation

    NASA Astrophysics Data System (ADS)

    Wynn, Peter; Fairchild, Ian; Bourdin, Clement; Baldini, James; Muller, Wolfgang; Hartland, Adam; Bartlett, Rebecca

    2017-04-01

    Dramatic increases in measured surface water DOC in recent decades have been variously attributed to either temperature rise, or destabilisation of long-term soil carbon pools following sulphur peak emissions status. However, whilst both drivers of DOC dynamics are plausible, they remain difficult to test due to the restricted nature of the available records of riverine DOC flux (1978 to present), and the limited availability of SO2 emissions inventory data at the regional scale. Speleothems offer long term records of both sulphur and carbon. New techniques to extract sulphur concentrations and isotopes from speleothem calcite have enabled archives of pollution history and environmental acidification to be reconstructed. Due to the large dynamic range in sulphur isotopic values from end member sources (marine aerosol +21 ‰ to continental biogenic emissions -30 ‰) and limited environmental fractionation under oxidising conditions, sulphur isotopes form an ideal tracer of industrial pollution and environmental acidification in the palaeo-record. We couple this acidification history to the carbon record, using organic matter fluorescence and trace metals. Trace metal ratios and abundance can be used to infer the type and size of organic ligand and are therefore sensitive to changes in temperature as a driver of organic carbon processing and biodegradation. This allows fluorescent properties and ratios of trace metals in speleothem carbonate to be used to represent both the flux of organic carbon into the cave as well as the degradation pathway. Here we present some of the first results of this work, exploring sulphur acidification as a mechanistic control on carbon solubility and export throughout the twentieth century.

  9. Unspeciated organic emissions from combustion sources and their influence on the secondary organic aerosol budget in the United States

    EPA Science Inventory

    Secondary organic aerosol (SOA) formed from the atmospheric oxidation of nonmethane organic gases (NMOG) is a major contributor to atmospheric aerosol mass. Emissions and smog chamber experiments were performed to investigate SOA formation from gasoline vehicles, diesel vehicles,...

  10. Uncertainties in global aerosols and climate effects due to biofuel emissions

    NASA Astrophysics Data System (ADS)

    Kodros, J. K.; Scott, C. E.; Farina, S. C.; Lee, Y. H.; L'Orange, C.; Volckens, J.; Pierce, J. R.

    2015-08-01

    Aerosol emissions from biofuel combustion impact both health and climate; however, while reducing emissions through improvements to combustion technologies will improve health, the net effect on climate is largely unconstrained. In this study, we examine sensitivities in global aerosol concentration, direct radiative climate effect, and cloud-albedo aerosol indirect climate effect to uncertainties in biofuel emission factors, optical mixing state, and model nucleation and background secondary organic aerosol (SOA). We use the Goddard Earth Observing System global chemical-transport model (GEOS-Chem) with TwO Moment Aerosol Sectional (TOMAS) microphysics. The emission factors include amount, composition, size, and hygroscopicity, as well as optical mixing-state properties. We also evaluate emissions from domestic coal use, which is not biofuel but is also frequently emitted from homes. We estimate the direct radiative effect assuming different mixing states (homogeneous, core-shell, and external) with and without absorptive organic aerosol (brown carbon). We find the global-mean direct radiative effect of biofuel emissions ranges from -0.02 to +0.06 W m-2 across all simulation/mixing-state combinations with regional effects in source regions ranging from -0.2 to +0.8 W m-2. The global-mean cloud-albedo aerosol indirect effect (AIE) ranges from +0.01 to -0.02 W m-2 with regional effects in source regions ranging from -1.0 to -0.05 W m-2. The direct radiative effect is strongly dependent on uncertainties in emissions mass, composition, emissions aerosol size distributions, and assumed optical mixing state, while the indirect effect is dependent on the emissions mass, emissions aerosol size distribution, and the choice of model nucleation and secondary organic aerosol schemes. The sign and magnitude of these effects have a strong regional dependence. We conclude that the climate effects of biofuel aerosols are largely unconstrained, and the overall sign of the aerosol

  11. The ambient organic aerosol soluble in water: Measurements, chemical characterization, and an investigation of sources

    NASA Astrophysics Data System (ADS)

    Sullivan, Amy P.

    This thesis characterizes the ambient fine organic carbon (OC) aerosol and investigates its sources through the development and deployment of new analytical measurement techniques. Recognizing that OC is highly chemically complex, the approach was to develop methods capable of quantitatively measuring a large chemical fraction of the aerosol instead of specific chemical speciation. The focus is on organic compounds that are soluble in water (WSOC) since little is known about its chemical nature. The results from this thesis show that WSOC has mainly two sources: biomass burning and secondary organic aerosol (SOA). In urban areas, WSOC increases with plume age, and tracks other photochemically produced compounds. Chemical analysis of WSOC suggests that in urban Atlanta, the SOA is mainly small-chain aliphatic compounds indirectly linked to vehicle emissions. A method was first developed for quantitative on-line measurements of WSOC by extending the application of the Particle-into-Liquid Sampler (PILS) from inorganic to organic aerosol measurements. In this approach a PILS captures ambient particles into a flow of purified water, which is then forced through a liquid filter and the carbonaceous content quantified on-line by a Total Organic Carbon (TOC) analyzer. An instrument was first developed for ground-based measurements and then modified for airborne deployment. Ground-based measurements at the St. Louis - Midwest Supersite during the summer of 2003 showed that the fraction of OC that is water-soluble can have a highly diurnal pattern with WSOC to OC ratios reaching 0.80 during the day and lows of 0.40 during the night. During extended periods under stagnation pollution events, this pattern was well correlated with ozone concentrations. The results are consistent with formation of SOA. Airborne PILS-TOC measurements from the NOAA WP-3D during the New England Air Quality Study/Intercontinental Transport and Chemical Transformation (NEAQS/ITCT) 2004 program

  12. Submicron aerosol organic functional groups, ions, and water content at the Centreville SEARCH site (Alabama), during SOAS campaign

    NASA Astrophysics Data System (ADS)

    Ruggeri, G.; Ergin, G.; Modini, R. L.; Takahama, S.

    2013-12-01

    The SOAS campaign was conducted from June 1 to July 15 of 2013 in order to understand the relationship between biogenic and anthropogenic emissions in the South East US1,2. In this study, the organic and inorganic composition of submicron aerosol in the Centreville SEARCH site was measured by Fourier Transform Infrared Spectroscopy (FTIR) and the Ambient Ion Monitor (AIM; URG Corporation), whereas the aerosol water content was measured with a Dry Ambient Aerosol Size Spectrometer (DAASS)3. Organic functional group analysis was performed on PM1 aerosol selected by cyclone and collected on teflon filters with a time resolution of 4-12 hours, using one inlet heated to 50 °C and the other operated either at ambient temperature or 70 °C 4. The AIM measured both condensed and gas phase composition with a time resolution of 1 hour, providing partitioning behavior of inorganic species such as NH3/NH4+, HNO3/NO3-. These measurements collectively permit calculation of pure-component vapor pressures of candidate organic compounds and activity coefficients of interacting components in the condensed phase, using models such as SIMPOL.15, E-AIM6, and AIOMFAC7. From these results, the water content of the aerosol is predicted, and a comparison between modeled and measured partitioning of inorganic compounds and water vapor are discussed, in addition to organic aerosol volatility prediction based on functional group analysis. [1]- Goldstein, A.H., et al., Biogenic carbon and anthropogenic pollutants combine to form a cooling haze over the southeastern United States. Proceedings of the National Academy of Sciences of the United States of America, 2009. 106(22), 8835-8840. [2]- Carlton, A.G., Turpin, B.J., 2013. Particle partitioning potential of organic compounds is highest in the Eastern US and driven by anthropogenic water. Atmospheric Chemistry and Physics Discussions 13, 12743-12770. [3]- Khlystov, A., Stanier, C.O., Takahama, S., Pandis, S.N., 2005. Water content of ambient

  13. Variation in pH of Model Secondary Organic Aerosol during Liquid-Liquid Phase Separation.

    PubMed

    Dallemagne, Magda A; Huang, Xiau Ya; Eddingsaas, Nathan C

    2016-05-12

    The majority of atmospheric aerosols consist of both organic and inorganic components. At intermediate relative humidity (RH), atmospheric aerosol can undergo liquid-liquid phase separation (LLPS) in which the organic and inorganic fractions segregate from each other. We have extended the study of LLPS to the effect that phase separation has on the pH of the overall aerosols and the pH of the individual phases. Using confocal microscopy and pH sensitive dyes, the pH of internally mixed model aerosols consisting of polyethylene glycol 400 and ammonium sulfate as well as the pH of the organic fraction during LLPS have been directly measured. During LLPS, the pH of the organic fraction was observed to increase to 4.2 ± 0.2 from 3.8 ± 0.1 under high RH when the aerosol was internally mixed. In addition, the high spatial resolution of the confocal microscope allowed us to characterize the composition of each of the phases, and we have observed that during LLPS the organic shell still contains large quantities of water and should be characterized as an aqueous organic-rich phase rather than simply an organic phase.

  14. Global distribution of secondary organic aerosol particle phase state

    NASA Astrophysics Data System (ADS)

    Shiraiwa, M.; Li, Y., Sr.; Tsimpidi, A.; Karydis, V.; Berkemeier, T.; Pandis, S. N.; Lelieveld, J.; Koop, T.; Poeschl, U.

    2016-12-01

    Secondary organic aerosols (SOA) account for a large fraction of submicron particles in the atmosphere and play a key role in aerosol effects on climate, air quality and public health. The formation and aging of SOA proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is challenging for the interpretation of field measurements and laboratory experiments as well as accurate representation of SOA evolution in atmospheric aerosol models. SOA particles can adopt liquid, semi-solid and amorphous solid (glassy) phase states depending on chemical composition, relative humidity and temperature. The particle phase state is crucial for various atmospheric gas-particle interactions, including SOA formation, heterogeneous and multiphase reactions and ice nucleation. We found that organic compounds with a wide variety of functional groups fall into molecular corridors, characterized by a tight inverse correlation between molar mass and volatility. Based on the concept of molecular corridors, we develop a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, which is a key property for determination of particle phase state. We use the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the atmospheric SOA phase state. For the planetary boundary layer, global simulations indicate that SOA is mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes, and solid over dry lands. We find that in the middle and upper troposphere (>500 hPa) SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants, and organic molecules could kinetically limit gas-particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded within SOA.

  15. Comprehensive characterization of PM2.5 aerosols in Singapore

    NASA Astrophysics Data System (ADS)

    Balasubramanian, R.; Qian, W.-B.; Decesari, S.; Facchini, M. C.; Fuzzi, S.

    2003-08-01

    A comprehensive characterization of PM2.5 aerosols collected in Singapore from January through December 2000 is presented. The annual average mass concentration of PM2.5 was 27.2 μg/m3. The atmospheric loading of PM2.5 was elevated sporadically from March through May, mainly due to advection of biomass burning (deliberate fires to clear plantation areas) impacted air masses from Sumatra, Indonesia. Satellite images of the area, trajectory calculations, and surface wind direction data are in support of the transport of pyrogenic products from Sumatra toward Singapore. Aerosol samples collected during the dry season were analyzed for water-soluble ions, water-soluble organic compounds (WSOC), elemental carbon (EC), organic carbon, and trace elements using a number of analytical techniques. The major components were sulfate, EC, water-soluble carbonaceous materials, and water-insoluble carbonaceous materials. Aerosol WSOC were characterized based on a combination of chromatographic separations by ion exchange chromatography, functional group investigation by proton nuclear magnetic resonance, and total organic carbon determination. The comprehensive chemical characterization of PM2.5 particles revealed that both non-sea-salt sufate (nss-SO42-) and carbonaceous aerosols mainly contributed to the increase in the mass concentration of aerosols during the smoke haze period. Using a mass closure test (a mass balance), we determined whether the physical measurement of gravimetric fine PM concentration of a sample is equal to the summed concentrations of the individually identified chemical constituents (measured or inferred) in the sample. The sum of the determined groups of aerosol components and the gravimetrically determined mass agreed reasonably well. Principal component analysis was performed from the combined data set, and five factors were observed: a soil dust component, a metallurgical industry factor, a factor representing emissions from biomass burning and

  16. Chemical and cellular oxidant production induced by naphthalene secondary organic aerosol (SOA): effect of redox-active metals and photochemical aging.

    PubMed

    Tuet, Wing Y; Chen, Yunle; Fok, Shierly; Gao, Dong; Weber, Rodney J; Champion, Julie A; Ng, Nga L

    2017-11-09

    Exposure to air pollution is a leading global health risk. Secondary organic aerosol (SOA) constitute a large portion of ambient particulate matter (PM). In this study, the water-soluble oxidative potential (OP) determined by dithiothreitol (DTT) consumption and intracellular reactive oxygen and nitrogen species (ROS/RNS) production was measured for SOA generated from the photooxidation of naphthalene in the presence of iron sulfate and ammonium sulfate seed particles. The measured intrinsic OP varied for aerosol formed using different initial naphthalene concentrations, however, no trends were observed between OP and bulk aerosol composition or seed type. For all experiments, aerosol generated in the presence of iron-containing seed induced higher ROS/RNS production compared to that formed in the presence of inorganic seed. This effect was primarily attributed to differences in aerosol carbon oxidation state [Formula: see text]. In the presence of iron, radical concentrations are elevated via iron redox cycling, resulting in more oxidized species. An exponential trend was also observed between ROS/RNS and [Formula: see text] for all naphthalene SOA, regardless of seed type or aerosol formation condition. This may have important implications as aerosol have an atmospheric lifetime of a week, over which [Formula: see text] increases due to continued photochemical aging, potentially resulting in more toxic aerosol.

  17. 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.

  18. Impacts of Siberian biomass burning on organic aerosols over the North Pacific Ocean and the Arctic: primary and secondary organic tracers.

    PubMed

    Ding, Xiang; Wang, Xinming; Xie, Zhouqing; Zhang, Zhou; Sun, Liguang

    2013-04-02

    During the 2003 Chinese Arctic Research Expedition (CHINARE2003) from the Bohai Sea to the high Arctic (37°N-80°N), filter-based particle samples were collected and analyzed for tracers of primary and secondary organic aerosols (SOA) as well as water-soluble organic carbon (WSOC). Biomass burning (BB) tracer levoglucosan had comparatively much higher summertime average levels (476 ± 367 pg/m(3)) during our cruise due to the influence of intense forest fires then in Siberia. On the basis of 5-day back trajectories, samples with air masses passing through Siberia had organic tracers 1.3-4.4 times of those with air masses transporting only over the oceans, suggesting substantial contribution of continental emissions to organic aerosols in the marine atmosphere. SOA tracers from anthropogenic aromatics were negligible or not detected, while those from biogenic terpenenoids were ubiquitously observed with the sum of SOA tracers from isoprene (623 ± 414 pg/m(3)) 1 order of magnitude higher than that from monoterpenes (63 ± 49 pg/m(3)). 2-Methylglyceric acid as a product of isoprene oxidation under high-NOx conditions was dominant among SOA tracers, implying that these BSOA tracers were not formed over the oceans but mainly transported from the adjacent Siberia where a high-NOx environment could be induced by intense forest fires. The carbon fractions shared by biogenic SOA tracers and levoglucosan in WSOC in our ocean samples were 1-2 orders of magnitude lower than those previously reported in continental samples, BB emissions or chamber simulation samples, largely due to the chemical evolution of organic tracers during transport. As a result of the much faster decline in levels of organic tracers than that of WSOC during transport, the trace-based approach, which could well reconstruct WSOC using biogenic SOA and BB tracers for continental samples, only explained ∼4% of measured WSOC during our expedition if the same tracer-WSOC or tracer-SOC relationships were

  19. Impact of tropospheric sulphate aerosols on the terrestrial carbon cycle

    NASA Astrophysics Data System (ADS)

    Eliseev, Alexey V.

    2015-01-01

    Tropospheric sulphate aerosols (TSAs) may oxidise the photosynthesising tissues if they are taken up by plants. A parameterisation of this impact of tropospheric sulphate aerosols (TSAs) on the terrestrial gross primary production is suggested. This parameterisation is implemented into the global Earth system model developed at the A.M. Obukhov Institute of the Atmospheric Physics, Russian Academy of Sciences (IAP RAS CM). With this coupled model, the simulations are performed which are forced by common anthropogenic and natural climate forcings based on historical reconstructions followed by the RCP 8.5 scenario. The model response to sulphate aerosol loading is subdivided into the climatic (related to the influence of TSA on the radiative transport in the atmosphere) and ecological (related to the toxic influence of sulphate aerosol on terrestrial plants) impacts. We found that the former basically dominates over the latter on a global scale and modifies the responses of the global vegetation and soil carbon stocks to external forcings by 10%. At a regional scale, however, ecological impact may be as much important as the climatic one.

  20. Simultaneous reductions in emissions of black carbon and co-emitted species will weaken the aerosol net cooling effect

    NASA Astrophysics Data System (ADS)

    Wang, Z. L.; Zhang, H.; Zhang, X. Y.

    2015-04-01

    Black carbon (BC), a distinct type of carbonaceous material formed from the incomplete combustion of fossil and biomass based fuels under certain conditions, can interact with solar radiation and clouds through its strong light-absorption ability, thereby warming the Earth's climate system. Some studies have even suggested that global warming could be slowed down in the short term by eliminating BC emission due to its short lifetime. In this study, we estimate the influence of removing some sources of BC and other co-emitted species on the aerosol radiative effect by using an aerosol-climate atmosphere-only model BCC_AGCM2.0.1_CUACE/Aero with prescribed sea surface temperature and sea ice cover, in combination with the aerosol emissions from the Representative Concentration Pathways (RCPs) scenarios. We find that the global annual mean aerosol net cooling effect at the top of the atmosphere (TOA) will be enhanced by 0.12 W m-2 compared with recent past year 2000 levels if the emissions of only BC are reduced to the level projected for 2100 based on the RCP2.6 scenario. This will be beneficial~for the mitigation of global warming. However, both aerosol negative direct and indirect radiative effects are weakened when BC and its co-emitted species (sulfur dioxide and organic carbon) are simultaneously reduced. Relative to year 2000 levels, the global annual mean aerosol net cooling effect at the TOA will be weakened by 1.7-2.0 W m-2 if the emissions of all these aerosols are decreased to the levels projected for 2100 in different ways based on the RCP2.6, RCP4.5, and RCP8.5 scenarios. Because there are no effective ways to remove the BC exclusively without influencing the other co-emitted components, our results therefore indicate that a reduction in BC emission can lead to an unexpected warming on the Earth's climate system in the future.

  1. Where and What Is Pristine Marine Aerosol?

    NASA Astrophysics Data System (ADS)

    Russell, L. M.; Frossard, A. A.; Long, M. S.; Burrows, S. M.; Elliott, S.; Bates, T. S.; Quinn, P.

    2014-12-01

    The sources and composition of atmospheric marine aerosol particles have been measured by functional group composition (from Fourier transform infrared spectroscopy) to identify the organic composition of the pristine primary marine (ocean-derived) particles as 65% hydroxyl, 21% alkane, 6% amine, and 7% carboxylic acid functional groups [Frossard et al., 2014a,b]. Pristine but non-primary components from photochemical reactions (likely from biogenic marine vapor emissions) add carboxylic acid groups. Non-pristine contributions include shipping effluent in seawater and ship emissions, which add additional alkane groups (up to 70%), and coastal or continental emissions mix in alkane and carboxylic acid groups. The pristine primary marine (ocean-derived) organic aerosol composition is nearly identical to model generated primary marine aerosol particles from bubbled seawater, indicating that its overall functional group composition is the direct consequence of the organic constituents of the seawater source. While the seawater organic functional group composition was nearly invariant across all three ocean regions studied and the ratio of organic carbon to sodium (OC/Na+) in the generated primary marine aerosol particles remained nearly constant over a broad range of chlorophyll-a concentrations, the generated primary marine aerosol particle alkane group fraction increased with chlorophyll-a concentrations. In addition, the generated primary marine aerosol particles have a hydroxyl group absorption peak location characteristic of monosaccharides and disaccharides, where the seawater hydroxyl group peak location is closer to that of polysaccharides. References Cited Frossard, Amanda A., Lynn M. Russell, Paola Massoli, Timothy S. Bates, and Patricia K. Quinn, "Side-by-Side Comparison of Four Techniques Explains the Apparent Differences in the Organic Composition of Generated and Ambient Marine Aerosol Particles," Aerosol Science and Technology - Aerosol Research Letter

  2. Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol

    NASA Astrophysics Data System (ADS)

    Ng, Nga Lee; Brown, Steven S.; Archibald, Alexander T.; Atlas, Elliot; Cohen, Ronald C.; Crowley, John N.; Day, Douglas A.; Donahue, Neil M.; Fry, Juliane L.; Fuchs, Hendrik; Griffin, Robert J.; Guzman, Marcelo I.; Herrmann, Hartmut; Hodzic, Alma; Iinuma, Yoshiteru; Jimenez, José L.; Kiendler-Scharr, Astrid; Lee, Ben H.; Luecken, Deborah J.; Mao, Jingqiu; McLaren, Robert; Mutzel, Anke; Osthoff, Hans D.; Ouyang, Bin; Picquet-Varrault, Benedicte; Platt, Ulrich; Pye, Havala O. T.; Rudich, Yinon; Schwantes, Rebecca H.; Shiraiwa, Manabu; Stutz, Jochen; Thornton, Joel A.; Tilgner, Andreas; Williams, Brent J.; Zaveri, Rahul A.

    2017-02-01

    Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry-climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

  3. Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ng, Nga Lee; Brown, Steven S.; Archibald, Alexander T.

    Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO 3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO 3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of importantmore » uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO 3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO 3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO 3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO 3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO 3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.« less

  4. Impact of fog processing on water soluble organic aerosols.

    NASA Astrophysics Data System (ADS)

    Tripathi, S. N.; Chakraborty, A.; Gupta, T.

    2017-12-01

    Fog is a natural meteorological phenomenon that occurs all around the world, and contains a substantial quantity of liquid water. Fog is generally seen as a natural cleansing agent but can also form secondary organic aerosols (SOA) via aqueous processing of ambient organics. Few field studies have reported elevated O/C ratio and SOA mass during or after fog events. However, mechanism behind aqueous SOA formation and its contribution to total organic aerosols (OA) still remains unclear. In this study we have tried to explore the impact of fog/aqueous processing on the characteristics of water soluble organic aerosols (WSOC), which to our knowledge has not been studied before. To assess this, both online (using HR-ToF-AMS) and offline (using a medium volume PM2.5 sampler and quartz filter) aerosol sampling were carried out at Kanpur, India from 15 December 2014 - 10 February 2015. Further, offline analysis of the aqueous extracts of the collected filters were carried out by AMS to characterize the water soluble OA (WSOA). Several (17) fog events occurred during the campaign and high concentrations of OA (151 ± 68 µg/m3) and WSOA (47 ± 19 µg/m3) were observed. WSOA/OA ratios were similar during fog (0.36 ± 0.14) and nofog (0.34 ± 0.15) periods. WSOA concentrations were also similar (slightly higher) during foggy (49 ± 18 µg/m3) and non-foggy periods (46 ± 20 µg/m3), in spite of fog scavenging. However, WSOA was more oxidized during foggy period (average O/C = 0.81) than non foggy periods (average O/C = 0.70). Like WSOA, OA was also more oxidized during foggy periods (average O/C = 0.64) than non foggy periods (average O/C = 0.53). During fog, WSOA to WIOA (water insoluble OA) ratios were higher (0.65 ± 0.16) compared to non foggy periods (0.56 ± 0.15). These observations clearly showed that WSOA become more dominant and processed during fog events, possibly due to the presence of fog droplets. This study highlights that fog processing of soluble organics

  5. Multiphase OH oxidation kinetics of organic aerosol: The role of particle phase state and relative humidity

    NASA Astrophysics Data System (ADS)

    Slade, Jonathan H.; Knopf, Daniel A.

    2014-07-01

    Organic aerosol can exhibit different phase states in response to changes in relative humidity (RH), thereby influencing heterogeneous reaction rates with trace gas species. OH radical uptake by laboratory-generated levoglucosan and methyl-nitrocatechol particles, serving as surrogates for biomass burning aerosol, is determined as a function of RH. Increasing RH lowers the viscosity of amorphous levoglucosan aerosol particles enabling enhanced OH uptake. Conversely, OH uptake by methyl-nitrocatechol aerosol particles is suppressed at higher RH as a result of competitive coadsorption of H2O that occupies reactive sites. This is shown to have substantial impacts on organic aerosol lifetimes with respect to OH oxidation. The results emphasize the importance of organic aerosol phase state to accurately describe the multiphase chemical kinetics and thus chemical aging process in atmospheric models to better represent the evolution of organic aerosol and its role in air quality and climate.

  6. Uncertainties in global aerosols and climate effects due to biofuel emissions

    NASA Astrophysics Data System (ADS)

    Kodros, J. K.; Scott, C. E.; Farina, S. C.; Lee, Y. H.; L'Orange, C.; Volckens, J.; Pierce, J. R.

    2015-04-01

    Aerosol emissions from biofuel combustion impact both health and climate; however, while reducing emissions through improvements to combustion technologies will improve health, the net effect on climate is largely unconstrained. In this study, we examine sensitivities in global aerosol concentration, direct radiative climate effect, and cloud-albedo aerosol indirect climate effect to uncertainties in biofuel emission factors, optical mixing-state, and model nucleation and background SOA. We use the Goddard Earth Observing System global chemical-transport model (GEOS-Chem) with TwO Moment Aerosol Sectional (TOMAS) microphysics. The emission factors include: amount, composition, size and hygroscopicity, as well as optical mixing-state properties. We also evaluate emissions from domestic coal use, which is not biofuel but is also frequently emitted from homes. We estimate the direct radiative effect assuming different mixing states (internal, core-shell, and external) with and without absorptive organic aerosol (brown carbon). We find the global-mean direct radiative effect of biofuel emissions ranges from -0.02 to +0.06 W m-2 across all simulation/mixing state combinations with regional effects in source regions ranging from -0.2 to +1.2 W m-2. The global-mean cloud-albedo aerosol indirect effect ranges from +0.01 to -0.02 W m-2 with regional effects in source regions ranging from -1.0 to -0.05 W m-2. The direct radiative effect is strongly dependent on uncertainties in emissions mass, composition, emissions aerosol size distributions and assumed optical mixing state, while the indirect effect is dependent on the emissions mass, emissions aerosol size distribution and the choice of model nucleation and secondary organic aerosol schemes. The sign and magnitude of these effects have a strong regional dependence. We conclude that the climate effects of biofuel aerosols are largely unconstrained, and the overall sign of the aerosol effects is unclear due to uncertainties

  7. Combustion Organic Aerosol as Cloud Condensation Nuclei in Ship Tracks.

    NASA Astrophysics Data System (ADS)

    Russell, Lynn M.; Noone, Kevin J.; Ferek, Ronald J.; Pockalny, Robert A.; Flagan, Richard C.; Seinfeld, John H.

    2000-08-01

    Polycyclic aromatic hydrocarbons (PAHs) have been sampled in marine stratiform clouds to identify the contribution of anthropogenic combustion emissions in activation of aerosol to cloud droplets. The Monterey Area Ship Track experiment provided an opportunity to acquire data on the role of organic compounds in ambient clouds and in ship tracks identified in satellite images. Identification of PAHs in cloud droplet residual samples indicates that several PAHs are present in cloud condensation nuclei in anthropogenically influenced air and do result in activated droplets in cloud. These results establish the presence of combustion products, such as PAHs, in submicrometer aerosols in anthropogenically influenced marine air, with enhanced concentrations in air polluted by ship effluent. The presence of PAHs in droplet residuals in anthropogenically influenced air masses indicates that some fraction of those combustion products is present in the cloud condensation nuclei that activate in cloud. Although a sufficient mass of droplet residuals was not collected to establish a similar role for organics from measurements in satellite-identified ship tracks, the available evidence from the fraction of organics present in the interstitial aerosol is consistent with part of the organic fraction partitioning to the droplet population. In addition, the probability that a compound will be found in cloud droplets rather than in the unactivated aerosol and the compound's water solubility are compared. The PAHs studied are only weakly soluble in water, but most of the sparse data collected support more soluble compounds having a higher probability of activation.

  8. Size distribution of ions in atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Krivácsy, Z.; Molnár, Á.

    The aim of this paper is to present data about the concentration and size distribution of ions in atmospheric aerosol under slightly polluted urban conditions in Hungary. Concentration of inorganic cations (ammonium, sodium, potassium, calcium, magnesium), inorganic anions (sulfate, nitrate, chloride, carbonate) and organic acids (oxalic, malonic, succinic, formic and acetic acid) for 8 particle size range between 0.0625 and 16 μm were determined. As was the case for ammonium, sulfate and nitrate, the organic acids were mostly found in the fine particle size range. Potassium and chloride were rather uniformly distributed between fine and coarse particles. Sodium, calcium, magnesium and carbonate were practically observed in the coarse mode. The results obtained for the summer and the winter half-year were also compared. The mass concentrations were recalculated in equivalents, and the ion balance was found to be reasonable in most cases. Measurement of the pH of the aerosol extracts indicates that the aerosol is acidic in the fine mode, but alkaline in the coarse particle size range.

  9. Organic aerosol formation in citronella candle plumes.

    PubMed

    Bothe, Melanie; Donahue, Neil McPherson

    2010-09-01

    Citronella candles are widely used as insect repellants, especially outdoors in the evening. Because these essential oils are unsaturated, they have a unique potential to form secondary organic aerosol (SOA) via reaction with ozone, which is also commonly elevated on summer evenings when the candles are often in use. We investigated this process, along with primary aerosol emissions, by briefly placing a citronella tealight candle in a smog chamber and then adding ozone to the chamber. In repeated experiments, we observed rapid and substantial SOA formation after ozone addition; this process must therefore be considered when assessing the risks and benefits of using citronella candle to repel insects.

  10. A dichotomy in primary marine organic aerosol-cloud-climate system

    NASA Astrophysics Data System (ADS)

    Ceburnis, D.; Ovadnevaite, J.; Martucci, G.; Bialek, J.; Monahan, C.; Rinaldi, M.; Facchini, C.; Berresheim, H.; Worsnop, D. R.; O'Dowd, C.

    2011-12-01

    D. Ceburnis1, J. Ovadnevaite1, G. Martucci1, J. Bialek1, C. Monahan1, M. Rinaldi2, M. C. Facchini2, H. Berresheim1, D. R. Worsnop3,4 and C. D. O'Dowd1 1School of Physics & Centre for Climate and Air Pollution Studies, National University of Ireland Galway, University Road, Galway, Ireland 2Institute of Atmospheric Sciences and Climate, National Research Council, Bologna, 20129, Italy. 3 Aerodyne Research, Inc., 45 Manning Road, Billerica, MA 01821-3976, USA 4 Physics Department, University of Helsinki, P.O. Box 64, 00014, Helsinki, Finland Organic matter has been observed to significantly contribute to particulate matter in every environment including pristine remote oceans. A significant if not dominant contribution of insoluble organic matter to marine aerosol has been proved to be of biogenic origin1,2. High time resolution measurements of marine organic matter have demonstrated a dynamic system with regular organic matter plume events occurring during summer3 as well as frequent open ocean particle formation events4. High-time resolution measurements of primary marine organic sea-spray physico-chemical properties reveal an apparent dichotomous behavior in terms of water uptake: specifically sea-spray aerosol enriched in organic matter possesses a low hygroscopic Growth Factor (GF~1.25) while simultaneously having a cloud condensation nucleus/condensation nuclei (CCN/CN) activation efficiency of between 83% at 0.25% supersaturation and 100% at 0.75%5. Simultaneous retrieval of Cloud Droplet Number Concentration (CDNC) during primary organic aerosol plumes reveal CDNC concentrations of 350 cm-3 in newly formed marine stratocumulus cloud for boundary layer organic mass concentrations of 3-4 ug m-36. It is suggested that marine hydrogels are responsible for this dichotomous behavior which has profound impacts to aerosol-cloud-climate system along with a better understood process analysis of aerosol formation by sea-spray7. A hydrophobic character of organic matter

  11. Toward Investigating Optically Trapped Organic Aerosols with CARS Microspectroscopy

    NASA Astrophysics Data System (ADS)

    Voss, L. F.

    2009-12-01

    The Intergovernmental Panel on Climate Change notes the huge uncertainty in the effect that atmospheric aerosols play in determining overall global temperature, specifically in their ability to nucleate clouds. To better understand aerosol chemistry, the novel coupling of gradient force optical trapping with broad bandwidth coherent anti-Stokes Raman scattering (CARS) spectroscopy is being developed to study single particles suspended in air. Building on successful designs employed separately for the techniques, this hybrid technology will be used to explain how the oxidation of organic compounds changes the chemical and physical properties of aerosols. By trapping the particles, an individual aerosol can be studied for up to several days. Using a broad bandwidth pulse for one of the incident beams will result in a Raman vibrational spectrum from every laser pulse. Combined with signal enhancement due to resonance and coherence of nonlinear CARS spectroscopy, this technique will allow for acquisition of data on the millisecond time scale, facilitating the study of dynamic processes. This will provide insights on how aerosols react with and absorb species from the gas phase. These experiments will increase understanding of aerosol oxidation and growth mechanisms and the effects that aerosols have on our atmosphere and climate. Progress in efforts developing this novel technique to study model systems is presented.

  12. 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

  13. A Global Data Assimilation System for Atmospheric Aerosol

    NASA Technical Reports Server (NTRS)

    daSilva, Arlindo

    1999-01-01

    We will give an overview of an aerosol data assimilation system which combines advances in remote sensing of atmospheric aerosols, aerosol modeling and data assimilation methodology to produce high spatial and temporal resolution 3D aerosol fields. Initially, the Goddard Aerosol Assimilation System (GAAS) will assimilate TOMS, AVHRR and AERONET observations; later we will include MODIS and MISR. This data assimilation capability will allows us to integrate complementing aerosol observations from these platforms, enabling the development of an assimilated aerosol climatology as well as a global aerosol forecasting system in support of field campaigns. Furthermore, this system provides an interactive retrieval framework for each aerosol observing satellites, in particular TOMS and AVHRR. The Goddard Aerosol Assimilation System (GAAS) takes advantage of recent advances in constituent data assimilation at DAO, including flow dependent parameterizations of error covariances and the proper consideration of model bias. For its prognostic transport model, GAAS will utilize the Goddard Ozone, Chemistry, Aerosol, Radiation and Transport (GOCART) model developed at NASA/GSFC Codes 916 and 910.3. GOCART includes the Lin-Rood flux-form, semi-Langrangian transport model with parameterized aerosol chemistry and physical processes for absorbing (dust and black carbon) and non-absorbing aerosols (sulfate and organic carbon). Observations and model fields are combined using a constituent version of DAO's Physical-space Statistical Analysis System (PSAS), including its adaptive quality control system. In this talk we describe the main components of this assimilation system and present preliminary results obtained by assimilating TOMS data.

  14. Filterable redox cycling activity: a comparison between diesel exhaust particles and secondary organic aerosol constituents.

    PubMed

    McWhinney, Robert D; Badali, Kaitlin; Liggio, John; Li, Shao-Meng; Abbatt, Jonathan P D

    2013-04-02

    The redox activity of diesel exhaust particles (DEP) collected from a light-duty diesel passenger car engine was examined using the dithiothreitol (DTT) assay. DEP was highly redox-active, causing DTT to decay at a rate of 23-61 pmol min(-1) μg(-1) of particle used in the assay, which was an order of magnitude higher than ambient coarse and fine particulate matter (PM) collected from downtown Toronto. Only 2-11% of the redox activity was in the water-soluble portion, while the remainder occurred at the black carbon surface. This is in contrast to redox-active secondary organic aerosol constituents, in which upward of 90% of the activity occurs in the water-soluble fraction. The redox activity of DEP is not extractable by moderately polar (methanol) and nonpolar (dichloromethane) organic solvents, and is hypothesized to arise from redox-active moieties contiguous with the black carbon portion of the particles. These measurements illustrate that "Filterable Redox Cycling Activity" may therefore be useful to distinguish black carbon-based oxidative capacity from water-soluble organic-based activity. The difference in chemical environment leading to redox activity highlights the need to further examine the relationship between activity in the DTT assay and toxicology measurements across particles of different origins and composition.

  15. Black carbon aerosols and the third polar ice cap

    NASA Astrophysics Data System (ADS)

    Menon, S.; Koch, D.; Beig, G.; Sahu, S.; Fasullo, J.; Orlikowski, D.

    2010-05-01

    Recent thinning of glaciers over the Himalayas (sometimes referred to as the third polar region) have raised concern on future water supplies since these glaciers supply water to large river systems that support millions of people inhabiting the surrounding areas. Black carbon (BC) aerosols, released from incomplete combustion, have been increasingly implicated as causing large changes in the hydrology and radiative forcing over Asia and its deposition on snow is thought to increase snow melt. In India BC emissions from biofuel combustion is highly prevalent and compared to other regions, BC aerosol amounts are high. Here, we quantify the impact of BC aerosols on snow cover and precipitation from 1990 to 2010 over the Indian subcontinental region using two different BC emission inventories. New estimates indicate that Indian BC emissions from coal and biofuel are large and transport is expected to expand rapidly in coming years. We show that over the Himalayas, from 1990 to 2000, simulated snow/ice cover decreases by ~0.9% due to aerosols. The contribution of the enhanced Indian BC to this decline is ~36%, similar to that simulated for 2000 to 2010. Spatial patterns of modeled changes in snow cover and precipitation are similar to observations (from 1990 to 2000), and are mainly obtained with the newer BC estimates.

  16. Black carbon aerosols and the third polar ice cap

    NASA Astrophysics Data System (ADS)

    Menon, S.; Koch, D.; Beig, G.; Sahu, S.; Fasullo, J.; Orlikowski, D.

    2009-12-01

    Recent thinning of glaciers over the Himalayas (sometimes referred to as the third polar region) have raised concern on future water supplies since these glaciers supply water to large river systems that support millions of people inhabiting the surrounding areas. Black carbon (BC) aerosols, released from incomplete combustion, have been increasingly implicated as causing large changes in the hydrology and radiative forcing over Asia and its deposition on snow is thought to increase snow melt. In India BC from biofuel combustion is highly prevalent and compared to other regions, BC aerosol amounts are high. Here, we quantify the impact of BC aerosols on snow cover and precipitation from 1990 to 2010 over the Indian subcontinental region using two different BC emission inventories. New estimates indicate that Indian BC from coal and biofuel are large and transport is expected to expand rapidly in coming years. We show that over the Himalayas, from 1990 to 2000, simulated snow/ice cover decreases by ~0.9% due to aerosols. The contribution of the enhanced Indian BC to this decline is ~30%, similar to that simulated for 2000 to 2010. Spatial patterns of modeled changes in snow cover and precipitation are similar to observations (from 1990 to 2000), and are mainly obtained with the newer BC estimates.

  17. Diffusion Rates of Organic Molecules in Secondary Organic Aerosol Particle

    NASA Astrophysics Data System (ADS)

    Bertram, A. K.; Chenyakin, Y.; Song, M.; Grayson, J. W.; Ullmann, D.; Evoy, E.; Renbaum-Wolff, L.; Liu, P.; Zhang, Y.; Kamal, S.; Martin, S. T.

    2016-12-01

    Information on the diffusion rates of organic molecules in secondary organic aerosol (SOA) particles are needed when predicting their size distribution, growth rates, photochemistry and heterogeneous chemistry. We have used two approaches to determine diffusion rates of organic molecules in SOA particles and proxies of SOA. In the first approach, we measured viscosities and then predicted diffusion rates using the Stokes-Einstein relation. In the second approach, we measured diffusion rates directly using a technique referred to as fluorescence recovery after photobleaching. Results from these measurements, including diffusion coefficients as a function of water activity, will be presented and the implications discussed.

  18. Real-time analysis of ambient organic aerosols using aerosol flowing atmospheric-pressure afterglow mass spectrometry (AeroFAPA-MS)

    NASA Astrophysics Data System (ADS)

    Brüggemann, Martin; Karu, Einar; Stelzer, Torsten; Hoffmann, Thorsten

    2015-04-01

    Organic aerosol accounts for a major fraction of atmospheric aerosols and has implications on the earth's climate and human health. However, due to the chemical complexity its measurement remains a major challenge for analytical instrumentation.1 Here, we present the development, characterization and application of a new soft ionization technique that allows mass spectrometric real-time detection of organic compounds in ambient aerosols. The aerosol flowing atmospheric-pressure afterglow (AeroFAPA) ion source utilizes a helium glow discharge plasma to produce excited helium species and primary reagent ions. Ionization of the analytes occurs in the afterglow region after thermal desorption and results mainly in intact molecular ions, facilitating the interpretation of the acquired mass spectra. In the past, similar approaches were used to detect pesticides, explosives or illicit drugs on a variety of surfaces.2,3 In contrast, the AeroFAPA source operates 'online' and allows the detection of organic compounds in aerosols without a prior precipitation or sampling step. To our knowledge, this is the first application of an atmospheric-pressure glow discharge ionization technique to ambient aerosol samples. We illustrate that changes in aerosol composition and concentration are detected on the time scale of seconds and in the ng-m-3 range. Additionally, the successful application of AeroFAPA-MS during a field study in a mixed forest region in Central Europe is presented. Several oxidation products of monoterpenes were clearly identified using the possibility to perform tandem MS experiments. The acquired data are in agreement with previous studies and demonstrate that AeroFAPA-MS is a suitable tool for organic aerosol analysis. Furthermore, these results reveal the potential of this technique to enable new insights into aerosol formation, growth and transformation in the atmosphere. References: 1) IPCC, 2013: Summary for Policymakers. In: Climate Change 2013: The

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  20. Photosensitized Formation of Secondary Organic Aerosols above the Air/Water Interface

    PubMed Central

    2016-01-01

    In this study, we evaluated photosensitized chemistry at the air–sea interface as a source of secondary organic aerosols (SOA). Our results show that, in addition to biogenic emissions, abiotic processes could also be important in the marine boundary layer. Photosensitized production of marine secondary organic aerosol was studied in a custom-built multiphase atmospheric simulation chamber. The experimental chamber contained water, humic acid (1–10 mg L–1) as a proxy for dissolved organic matter, and nonanoic acid (0.1–10 mM), a fatty acid proxy which formed an organic film at the air–water interface. Dark secondary reaction with ozone after illumination resulted in SOA particle concentrations in excess of 1000 cm–3, illustrating the production of unsaturated compounds by chemical reactions at the air–water interface. SOA numbers via photosensitization alone and in the absence of ozone did not exceed background levels. From these results, we derived a dependence of SOA numbers on nonanoic acid surface coverage and dissolved organic matter concentration. We present a discussion on the potential role of the air–sea interface in the production of atmospheric organic aerosol from photosensitized origins. PMID:27434860

  1. Glyoxal-methylglyoxal cross-reactions in secondary organic aerosol formation.

    PubMed

    Schwier, Allison N; Sareen, Neha; Mitroo, Dhruv; Shapiro, Erica L; McNeill, V Faye

    2010-08-15

    Glyoxal (G) and methylglyoxal (MG) are potentially important secondary organic aerosol (SOA) precursors. Previous studies of SOA formation by G and MG have focused on either species separately; however, G and MG typically coexist in the atmosphere. We studied the formation of secondary organic material in aqueous aerosol mimic mixtures containing G and MG with ammonium sulfate. We characterized the formation of light-absorbing products using UV-vis spectrophotometry. We found that absorption at 280 nm can be described well using models for the formation of light-absorbing products by G and MG in parallel. Pendant drop tensiometry measurements showed that surface tension depression by G and MG in these solutions can be modeled as a linear combination of the effects of G and MG alone. Product species were identified using chemical ionization mass spectrometry with a volatilization flow tube inlet (Aerosol CIMS). Peaks consistent with G-MG cross-reaction products were observed, accounting for a significant fraction of detected product mass, but most peaks could be attributed to self-reaction. We conclude that cross-reactions contribute to SOA mass from uptake of G and MG, but they are not required to accurately model the effects of this process on aerosol surface tension or light absorption.

  2. Highly-controlled, reproducible measurements of aerosol emissions from African biomass combustion

    NASA Astrophysics Data System (ADS)

    Haslett, Sophie; Thomas, J. Chris; Morgan, William; Hadden, Rory; Liu, Dantong; Allan, James; Williams, Paul; Sekou, Keïta; Liousse, Catherine; Coe, Hugh

    2017-04-01

    Particulate emissions from biomass burning can alter the atmosphere's radiative balance and cause significant harm to human health. However, the relationship between these emissions and fundamental combustion processes is, to date, poorly characterised. In atmospheric models, aerosol emissions are represented by emission factors based on mass loss, which are averaged over an entire combustion event for each particulate species. This approach, however, masks huge variability in emissions during different phases of the combustion period. Laboratory tests have shown that even small changes to the burning environment can lead to huge variation in observed aerosol emission factors (Akagi et al., 2011). In order to address this gap in understanding, in this study, small wood samples sourced from Côte D'Ivoire were burned in a highly-controlled laboratory environment. The shape and mass of samples, available airflow and surrounding heat were carefully regulated. Organic aerosol and refractory black carbon emissions were measured in real-time using an Aerosol Mass Spectrometer and a Single Particle Soot Photometer, respectively. Both of these instruments are used regularly to measure aerosol concentrations in the field. This methodology produced remarkably repeatable results, allowing three different phases of combustion to be identified by their emissions. Black carbon was emitted predominantly during flaming combustion; organic aerosols were emitted during pyrolysis before ignition and from smouldering-dominated behaviour near the end of combustion. During the flaming period, there was a strong correlation between the emission of black carbon and the rate of mass loss, which suggests there is value in employing a mass-based emission factor for this species. However, very little correlation was seen between organic aerosol and mass loss throughout the tests. As such, results here suggest that emission factors averaged over an entire combustion event are unlikely to be

  3. Radiative effects of interannually varying vs. interannually invariant aerosol emissions from fires

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Grandey, Benjamin S.; Lee, Hsiang-He; Wang, Chien

    Open-burning fires play an important role in the earth's climate system. In addition to contributing a substantial fraction of global emissions of carbon dioxide, they are a major source of atmospheric aerosols containing organic carbon, black carbon, and sulfate. These “fire aerosols” can influence the climate via direct and indirect radiative effects. In this study, we investigate these radiative effects and the hydrological fast response using the Community Atmosphere Model version 5 (CAM5). Emissions of fire aerosols exert a global mean net radiative effect of −1.0 W m −2, dominated by the cloud shortwave response to organic carbon aerosol. The net radiative effectmore » is particularly strong over boreal regions. Conventionally, many climate modelling studies have used an interannually invariant monthly climatology of emissions of fire aerosols. However, by comparing simulations using interannually varying emissions vs. interannually invariant emissions, we find that ignoring the interannual variability of the emissions can lead to systematic overestimation of the strength of the net radiative effect of the fire aerosols. Globally, the overestimation is +23 % (−0.2 W m −2). Regionally, the overestimation can be substantially larger. For example, over Australia and New Zealand the overestimation is +58 % (−1.2 W m −2), while over Boreal Asia the overestimation is +43 % (−1.9 W m −2). The systematic overestimation of the net radiative effect of the fire aerosols is likely due to the non-linear influence of aerosols on clouds. However, ignoring interannual variability in the emissions does not appear to significantly impact the hydrological fast response. In order to improve understanding of the climate system, we need to take into account the interannual variability of aerosol emissions.« less

  4. Radiative effects of interannually varying vs. interannually invariant aerosol emissions from fires

    DOE PAGES

    Grandey, Benjamin S.; Lee, Hsiang-He; Wang, Chien

    2016-11-23

    Open-burning fires play an important role in the earth's climate system. In addition to contributing a substantial fraction of global emissions of carbon dioxide, they are a major source of atmospheric aerosols containing organic carbon, black carbon, and sulfate. These “fire aerosols” can influence the climate via direct and indirect radiative effects. In this study, we investigate these radiative effects and the hydrological fast response using the Community Atmosphere Model version 5 (CAM5). Emissions of fire aerosols exert a global mean net radiative effect of −1.0 W m −2, dominated by the cloud shortwave response to organic carbon aerosol. The net radiative effectmore » is particularly strong over boreal regions. Conventionally, many climate modelling studies have used an interannually invariant monthly climatology of emissions of fire aerosols. However, by comparing simulations using interannually varying emissions vs. interannually invariant emissions, we find that ignoring the interannual variability of the emissions can lead to systematic overestimation of the strength of the net radiative effect of the fire aerosols. Globally, the overestimation is +23 % (−0.2 W m −2). Regionally, the overestimation can be substantially larger. For example, over Australia and New Zealand the overestimation is +58 % (−1.2 W m −2), while over Boreal Asia the overestimation is +43 % (−1.9 W m −2). The systematic overestimation of the net radiative effect of the fire aerosols is likely due to the non-linear influence of aerosols on clouds. However, ignoring interannual variability in the emissions does not appear to significantly impact the hydrological fast response. In order to improve understanding of the climate system, we need to take into account the interannual variability of aerosol emissions.« less

  5. Characterization of the sources and processes of organic and inorganic aerosols in New York City with a high-resolution time-of-flight aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Sun, Y.-L.; Zhang, Q.; Schwab, J. J.; Demerjian, K. L.; Chen, W.-N.; Bae, M.-S.; Hung, H.-M.; Hogrefe, O.; Frank, B.; Rattigan, O. V.; Lin, Y.-C.

    2010-10-01

    Submicron aerosol particles (PM1) were measured in-situ using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) during the summer 2009 Field Intensive Study at Queens College in New York City. Organic aerosol (OA) and sulfate are the two dominant species, accounting for 54% and 24%, respectively, of total PM1 mass on average. The average mass size distribution of OA presents a small mode peaking at ~150 nm (Dva) in addition to an accumulation mode (~550 nm) that is internally mixed with sulfate, nitrate, and ammonium. The diurnal cycles of sulfate and OA both show pronounced peaks between 01:00-02:00 p.m. EST due to photochemical production. The average (±1σ) oxygen-to-carbon (O/C), hydrogen-to-carbon (H/C), and nitrogen-to-carbon (N/C) ratios of OA in NYC are 0.36 (±0.09), 1.49 (±0.08), and 0.012(±0.005), respectively, corresponding to an average organic mass-to-carbon (OM/OC) ratio of 1.62(±0.11). Positive matrix factorization (PMF) of the high resolution mass spectra identified five OA components: a hydrocarbon-like OA (HOA), two types of oxygenated OA (OOA) including a low-volatility OOA (LV-OOA) and a semi-volatile OOA (SV-OOA), a cooking-emission related OA (COA), and a unique nitrogen-enriched OA (NOA). HOA appears to represent primary OA (POA) from urban traffic emissions. It comprises primarily of reduced species (H/C=1.83; O/C=0.06) and shows a mass spectral pattern very similar to those of POA from fossil fuel combustion, and correlates tightly with traffic emission tracers including elemental carbon and NOx. LV-OOA, which is highly oxidized (O/C=0.63) and correlates well with sulfate, appears to be representative for regional, aged secondary OA (SOA). SV-OOA, which is less oxidized (O/C=0.38) and correlates well with non-refractory chloride, likely represents less photo-chemically aged, semi-volatile SOA. COA shows a similar spectral pattern to the reference spectra of POA from cooking emissions and a distinct diurnal pattern

  6. Biogenic contribution to PM-2.5 ambient aerosol from radiocarbon measurements

    NASA Astrophysics Data System (ADS)

    Lewis, C.; Klouda, G.; Ellenson, W.

    2003-04-01

    Knowledge of the relative contributions of biogenic versus anthropogenic sources to ambient aerosol is of great interest in the formulation of strategies to achieve nationally mandated air quality standards. Radiocarbon (14C) measurements provide a means to quantify the biogenic fraction of any carbon-containing sample of ambient aerosol. In the absence of an impact from biomass burning (e.g., during summertime) such measurements can provide an estimate of the contribution of biogenic secondary organic aerosol, from biogenic volatile organic compound precursors. Radiocarbon results for 11.5-h PM-2.5 samples collected near Nashville, Tennessee, USA, during summer 1999 will be presented. On average the measured biogenic fraction was surprisingly large (more than half), with the average biogenic fraction for night samples being only slightly smaller than for day samples. Discussion will include (a) description of the radiocarbon methodology, (b) use of radiocarbon measurements on local vegetation and fuel samples as calibration data, (c) concurrent measurements of organic carbon and elemental carbon ambient concentrations, (d) assessment of organic aerosol sampling artifact through use of organic vapor denuders, variable face velocities, and filter extraction, and (e) comparison with published radiocarbon results obtained in Houston, Texas in a similar study. Disclaimer: This work has been funded wholly or in part by the United States Environmental Protection Agency under Interagency Agreement No. 13937923 to the National Institute of Standards and Technology, and Contract No. 68-D5-0049 to ManTech Environmental Tecnology, Inc. It has been subjected to Agency review and approved for publication.

  7. Spatial variability of aerosol and black carbon concentrations in the troposphere of the Russian Arctic

    NASA Astrophysics Data System (ADS)

    Kozlov, Valerii S.; Panchenko, Mikhail V.; Paris, Jean D.; Nédéléc, Philippe; Chernov, Dmitry G.; Shmargunov, Vladimir P.

    2015-11-01

    A cycle of flights of the Optik TU-134 Flying Laboratory of IAO SB RAS over regions of Western Siberia and the Russian Arctic (55.0-74.8°N, 61.3-82.9°E) was carried out on October 15-17 of 2014 within the framework of the YAK-AEROSIB Russian—French Project. The mass concentrations of submicron aerosol and Black Carbon (BC) in the troposphere up to a height of 8.5 km were measured in the flights. The ranges of variability were 0.3-20 μg/m3 for the aerosol concentration and 0.02-1 μg/m3 for the BC concentration. In the subpolar latitudes of 71-74.8°N, the lower levels of aerosol (0.8-6 μg/m3) and BC (0.02-0.3 μg/m3) were observed. The comparison of the results of airborne sensing in 2008 and 2014 has shown that in the Western Subartic the aerosol and BC concentrations in the vertical profiles up to six times exceeded those observed in the Eastern Subarctic (0.3-1 μg/m3 and 10-50 ng/m3). The excess of the mean integral BC concentrations and the aerosol optical depth was, on average, 2-2.5 times (0.16 mg/m2; 0.02). In the region of the Kara Sea at heights of 0.5-2 and 4-6 km, the excess of the aerosol content in the western sector in comparison with the eastern one was, on average, 2 times, while for the black carbon the excess achieved 7 times at heights of 1-2 km (0.25- 0.035 μg/m3). The mean integral concentrations of aerosol and black carbon ˜ 1.3 times exceeded those in the clearer eastern region of the sea (0.31 mg/m2; 0.049). The obtained estimates indicate the decrease of the aerosol and BC concentrations in the subpolar latitudes of the Russian Federation from the west to the east.

  8. Secondary organic aerosol formation from low-NO(x) photooxidation of dodecane: evolution of multigeneration gas-phase chemistry and aerosol composition.

    PubMed

    Yee, Lindsay D; Craven, Jill S; Loza, Christine L; Schilling, Katherine A; Ng, Nga Lee; Canagaratna, Manjula R; Ziemann, Paul J; Flagan, Richard C; Seinfeld, John H

    2012-06-21

    The extended photooxidation of and secondary organic aerosol (SOA) formation from dodecane (C(12)H(26)) under low-NO(x) conditions, such that RO(2) + HO(2) chemistry dominates the fate of the peroxy radicals, is studied in the Caltech Environmental Chamber based on simultaneous gas and particle-phase measurements. A mechanism simulation indicates that greater than 67% of the initial carbon ends up as fourth and higher generation products after 10 h of reaction, and simulated trends for seven species are supported by gas-phase measurements. A characteristic set of hydroperoxide gas-phase products are formed under these low-NO(x) conditions. Production of semivolatile hydroperoxide species within three generations of chemistry is consistent with observed initial aerosol growth. Continued gas-phase oxidation of these semivolatile species produces multifunctional low volatility compounds. This study elucidates the complex evolution of the gas-phase photooxidation chemistry and subsequent SOA formation through a novel approach comparing molecular level information from a chemical ionization mass spectrometer (CIMS) and high m/z ion fragments from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Combination of these techniques reveals that particle-phase chemistry leading to peroxyhemiacetal formation is the likely mechanism by which these species are incorporated in the particle phase. The current findings are relevant toward understanding atmospheric SOA formation and aging from the "unresolved complex mixture," comprising, in part, long-chain alkanes.

  9. Aerosol Emissions from Great Lakes Harmful Algal Blooms

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    May, Nathaniel W.; Olson, Nicole E.; Panas, Mark

    In freshwater lakes, harmful algal blooms (HABs) of Cyanobacteria (blue-green algae) produce toxins that impact human health. However, little is known about the chemical species present in lake spray aerosol (LSA) produced from wave-breaking in freshwater HABs. In this study, a laboratory LSA generator produced aerosols from freshwater samples collected from Lake Michigan and Lake Erie during HAB and non-bloom conditions. Particles were analyzed for size and chemical composition by single particle mass spectrometry, electron microscopy, and fluorescence microscopy, with three distinct types of LSA identified with varying levels of organic carbon and biological material associated with calcium salts. LSAmore » autofluorescence increases with blue-green algae concentration, showing that organic molecules of biological origin are incorporated in LSA from HABs. The number fraction of LSA with biological mass spectral markers also increases with particle diameter (greater than 0.5 μm), showing that HABs have size-dependent impacts on aerosol composition. The highest number fraction of LSA enriched in organic carbon were observed in particles less than 0.5 μm in diameter. Understanding the transfer of organic and biogenic material from freshwater to the atmosphere via LSA particles is crucial for determining health and climate effects due to HABs.« less

  10. Wildland fire emissions, carbon, and climate: Emission factors

    Treesearch

    Shawn Urbanski

    2014-01-01

    While the vast majority of carbon emitted by wildland fires is released as CO2, CO, and CH4, wildland fire smoke is nonetheless a rich and complex mixture of gases and aerosols. Primary emissions include significant amounts of CH4 and aerosol (organic aerosol and black carbon), which are short-lived climate forcers. In addition to CO2 and short-lived climate forcers,...

  11. Carbonaceous aerosols in fine particulate matter of Santiago Metropolitan Area, Chile.

    PubMed

    Toro Araya, Richard; Flocchini, Robert; Morales Segura, Rául G E; Leiva Guzmán, Manuel A

    2014-01-01

    Measurements of carbonaceous aerosols in South American cities are limited, and most existing data are of short term and limited to only a few locations. For 6 years (2002-2007), concentrations of fine particulate matter and organic and elemental carbon were measured continuously in the capital of Chile. The contribution of carbonaceous aerosols to the primary and secondary fractions was estimated at three different sampling sites and in the warm and cool seasons. The results demonstrate that there are significant differences in the levels in both the cold (March to August) and warm (September to February) seasons at all sites studied. The percent contribution of total carbonaceous aerosol fine particulate matter was greater in the cool season (53 ± 41%) than in the warm season (44 ± 18%). On average, the secondary organic carbon in the city corresponded to 29% of the total organic carbon. In cold periods, this proportion may reach an average of 38%. A comparison of the results with the air quality standards for fine particulate matter indicates that the total carbonaceous fraction alone exceeds the World Health Organization standard (10 µg/m(3)) and the United States Environmental Protection Agency standard (15 µg/m(3)) for fine particulate matter.

  12. Black carbon's contribution to aerosol absorption optical depth over S. Korea

    NASA Astrophysics Data System (ADS)

    Lamb, K.; Perring, A. E.; Beyersdorf, A. J.; Anderson, B. E.; Segal-Rosenhaimer, M.; Redemann, J.; Holben, B. N.; Schwarz, J. P.

    2017-12-01

    Aerosol absorption optical depth (AAOD) monitored by ground-based sites (AERONET, SKYNET, etc.) is used to constrain climate radiative forcing from black carbon (BC) and other absorbing aerosols in global models, but few validation studies between in situ aerosol measurements and ground-based AAOD exist. AAOD is affected by aerosol size distributions, composition, mixing state, and morphology. Megacities provide appealing test cases for this type of study due to their association with very high concentrations of anthropogenic aerosols. During the KORUS-AQ campaign in S. Korea, which took place in late spring and early summer of 2016, in situ aircraft measurements over the Seoul Metropolitan Area and Taehwa Research Forest (downwind of Seoul) were repeated three times per flight over a 6 week period, providing significant temporal coverage of vertically resolved aerosol properties influenced by different meteorological conditions and sources. Measurements aboard the NASA DC-8 by the NOAA Humidified Dual Single Particle Soot Photometers (HD-SP2) quantified BC mass, size distributions, mixing state, and the hygroscopicity of BC containing aerosols. The in situ BC mass vertical profiles are combined with estimated absorption enhancement calculated from observed optical size and hygroscopicity using Mie theory, and then integrated over the depth of the profile to calculate BC's contribution to AAOD. Along with bulk aerosol size distributions and hygroscopicity, bulk absorbing aerosol optical properties, and on-board sky radiance measurements, these measurements are compared with ground-based AERONET site measurements of AAOD to evaluate closure between in situ vertical profiles of BC and AAOD measurements. This study will provide constraints on the relative importance of BC (including lensing and hygroscopicity effects) and non-BC components to AAOD over S. Korea.

  13. Exposure and Emissions Monitoring during Carbon Nanofiber Production—Part I: Elemental Carbon and Iron–Soot Aerosols

    PubMed Central

    Birch, M. Eileen; Ku, Bon-Ki; Evans, Douglas E.; Ruda-Eberenz, Toni A.

    2015-01-01

    Production of carbon nanofibers and nanotubes (CNFs/CNTs) and their composite products is increasing globally. High volume production may increase the exposure risks for workers who handle these materials. Though health effects data for CNFs/CNTs are limited, some studies raise serious health concerns. Given the uncertainty about their potential hazards, there is an immediate need for toxicity data and field studies to assess exposure to CNFs/CNTs. An extensive study was conducted at a facility that manufactures and processes CNFs. Filter, sorbent, cascade impactor, bulk, and microscopy samples, combined with direct-reading instruments, provided complementary information on air contaminants. Samples were analyzed for organic carbon (OC) and elemental carbon (EC), metals, and polycyclic aromatic hydrocarbons (PAHs), with EC as a measure of CNFs. Transmission electron microscopy with energy-dispersive X-ray spectroscopy also was applied. Fine/ultrafine iron-rich soot, PAHs, and carbon monoxide were production byproducts. Direct-reading instrument results were reported previously [Evans DE et al. (Aerosol monitoring during carbon nanofiber production: mobile direct-reading sampling. Ann Occup Hyg 2010;54:514–31.)] Results for time-integrated samples are reported as companion papers in this Issue. OC and EC, metals, and microscopy results are reported here, in Part I, while results for PAHs are reported in Part II [Birch ME. (Exposure and Emissions Monitoring during Carbon Nanofiber Production—Part II: Polycyclic Aromatic Hydrocarbons. Ann. Occup. Hyg 2011; 55: 1037–47.)]. Respirable EC area concentrations inside the facility were about 6–68 times higher than outdoors, while personal breathing zone samples were up to 170 times higher. PMID:21965464

  14. Global Radiative Forcing of Coupled Tropospheric Ozone and Aerosols in a Unified General Circulation Model

    NASA Technical Reports Server (NTRS)

    Liao, Hong; Seinfeld, John H.; Adams, Peter J.; Mickley, Loretta J.

    2008-01-01

    Global simulations of sea salt and mineral dust aerosols are integrated into a previously developed unified general circulation model (GCM), the Goddard Institute for Space Studies (GISS) GCM II', that simulates coupled tropospheric ozone-NOx-hydrocarbon chemistry and sulfate, nitrate, ammonium, black carbon, primary organic carbon, and secondary organic carbon aerosols. The fully coupled gas-aerosol unified GCM allows one to evaluate the extent to which global burdens, radiative forcing, and eventually climate feedbacks of ozone and aerosols are influenced by gas-aerosol chemical interactions. Estimated present-day global burdens of sea salt and mineral dust are 6.93 and 18.1 Tg with lifetimes of 0.4 and 3.9 days, respectively. The GCM is applied to estimate current top of atmosphere (TOA) and surface radiative forcing by tropospheric ozone and all natural and anthropogenic aerosol components. The global annual mean value of the radiative forcing by tropospheric ozone is estimated to be +0.53 W m(sup -2) at TOA and +0.07 W m(sup -2) at the Earth's surface. Global, annual average TOA and surface radiative forcing by all aerosols are estimated as -0.72 and -4.04 W m(sup -2), respectively. While the predicted highest aerosol cooling and heating at TOA are -10 and +12 W m(sup -2) respectively, surface forcing can reach values as high as -30 W m(sup -2), mainly caused by the absorption by black carbon, mineral dust, and OC. We also estimate the effects of chemistry-aerosol coupling on forcing estimates based on currently available understanding of heterogeneous reactions on aerosols. Through altering the burdens of sulfate, nitrate, and ozone, heterogeneous reactions are predicted to change the global mean TOA forcing of aerosols by 17% and influence global mean TOA forcing of tropospheric ozone by 15%.

  15. Characterization of aerosol particles at the forested site in Lithuania

    NASA Astrophysics Data System (ADS)

    Rimselyte, I.; Garbaras, A.; Kvietkus, K.; Remeikis, V.

    2009-04-01

    monitoring station (55˚ 26'26"N; 26˚ 03'60"E) in the eastern part of Lithuania in the Aukštaitija national park during 2-24 July, 2008. The Rugšteliškis station is located in a remote relatively clean forested area. An aerosol mass spectrometer (AMS), developed at Aerodyne Research, was used to obtain real-time quantitative information on particle size-resolved mass loadings for volatile and semi-volatile chemical components present in/on ambient aerosol. The AMS inlet system allows 100 % transmission efficiency for particles with size diameter between 60 to 600 nm and partial transmission down to 20 nm and up to 2000 nm. The aerosol sampling was also carried out using a Micro-Orifice Uniform Deposit Impactor (MOUDI) model 110. The flow rate was 30 l/min, and the 50% aerodynamic cutoff diameters of the 10 stages were 18, 10, 5.6, 3.2, 1.8, 1.0, 0.56, 0.32, 0.18, 0.10 and 0.056 m. Aluminum foil was used as the impaction surface. The aerosol samples were analyzed for total carbon using the elemental analyzer (Flash EA1112). Besides, samples were analyzed for ^13C/12C ratio by the isotopic ratio mass spectrometer (Thermo Finnigan Delta Plus Advantage) (Norman et al., 1999; Garbaras et al., 2008). During campaign the dynamic behavior of aerosols was measured and quantitatively compared with meteorological conditions and air mass transport. The submicron aerosol was predominately sulphate and organic material. The AMS was able to discriminate and quantify mixed organic/inorganic accumulation mode particles (300 - 400 nm), which appeared to be dominated by regional sources and were of the origin similar to those seen in the more remote areas. The particulate organic fraction was also investigated in detail using the mass spectral data. By combining the organic matter size distribution (measured with AMS) with the total carbon (TC) size distribution (measured with MOUDI) we were able to report organic carbon to total carbon (OC/TC) ratio in different size particles

  16. Recent advances in understanding secondary organic aerosol: Implications for global climate forcing

    NASA Astrophysics Data System (ADS)

    Shrivastava, Manish; Cappa, Christopher D.; Fan, Jiwen; Goldstein, Allen H.; Guenther, Alex B.; Jimenez, Jose L.; Kuang, Chongai; Laskin, Alexander; Martin, Scot T.; Ng, Nga Lee; Petaja, Tuukka; Pierce, Jeffrey R.; Rasch, Philip J.; Roldin, Pontus; Seinfeld, John H.; Shilling, John; Smith, James N.; Thornton, Joel A.; Volkamer, Rainer; Wang, Jian; Worsnop, Douglas R.; Zaveri, Rahul A.; Zelenyuk, Alla; Zhang, Qi

    2017-06-01

    Anthropogenic emissions and land use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding preindustrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features (1) influence estimates of aerosol radiative forcing and (2) can confound estimates of the historical response of climate to increases in greenhouse gases. Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron-sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate models typically do not comprehensively include all important processes. This review summarizes some of the important developments during the past decade in understanding SOA formation. We highlight the importance of some processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including formation of extremely low volatility organics in the gas phase, acid-catalyzed multiphase chemistry of isoprene epoxydiols, particle-phase oligomerization, and physical properties such as volatility and viscosity. Several SOA processes highlighted in this review are complex and interdependent and have nonlinear effects on the properties, formation, and evolution of SOA. Current global models neglect this complexity and nonlinearity and thus are less likely to accurately predict the climate forcing of SOA and project future climate sensitivity to greenhouse gases. Efforts are also needed to rank the most influential processes and nonlinear process-related interactions, so that these processes can be accurately represented in atmospheric chemistry-climate models.

  17. Highly controlled, reproducible measurements of aerosol emissions from combustion of a common African biofuel source

    NASA Astrophysics Data System (ADS)

    Haslett, Sophie L.; Thomas, J. Chris; Morgan, William T.; Hadden, Rory; Liu, Dantong; Allan, James D.; Williams, Paul I.; Keita, Sekou; Liousse, Cathy; Coe, Hugh

    2018-01-01

    Particulate emissions from biomass burning can both alter the atmosphere's radiative balance and cause significant harm to human health. However, due to the large effect on emissions caused by even small alterations to the way in which a fuel burns, it is difficult to study particulate production of biomass combustion mechanistically and in a repeatable manner. In order to address this gap, in this study, small wood samples sourced from Côte D'Ivoire in West Africa were burned in a highly controlled laboratory environment. The shape and mass of samples, available airflow and surrounding thermal environment were carefully regulated. Organic aerosol and refractory black carbon emissions were measured in real time using an Aerosol Mass Spectrometer and a Single Particle Soot Photometer, respectively. This methodology produced remarkably repeatable results, allowing aerosol emissions to be mapped directly onto different phases of combustion. Emissions from pyrolysis were visible as a distinct phase before flaming was established. After flaming combustion was initiated, a black-carbon-dominant flame was observed during which very little organic aerosol was produced, followed by a period that was dominated by organic-carbon-producing smouldering combustion, despite the presence of residual flaming. During pyrolysis and smouldering, the two phases producing organic aerosol, distinct mass spectral signatures that correspond to previously reported variations in biofuel emissions measured in the atmosphere are found. Organic aerosol emission factors averaged over an entire combustion event were found to be representative of the time spent in the pyrolysis and smouldering phases, rather than reflecting a coupling between emissions and the mass loss of the sample. Further exploration of aerosol yields from similarly carefully controlled fires and a careful comparison with data from macroscopic fires and real-world emissions will help to deliver greater constraints on the

  18. Molecular Composition and Volatility of Organic Aerosol in the Southeastern U.S.: Implications for IEPOX Derived SOA.

    PubMed

    Lopez-Hilfiker, F D; Mohr, C; D'Ambro, E L; Lutz, A; Riedel, T P; Gaston, C J; Iyer, S; Zhang, Z; Gold, A; Surratt, J D; Lee, B H; Kurten, T; Hu, W W; Jimenez, J; Hallquist, M; Thornton, J A

    2016-03-01

    We present measurements as part of the Southern Oxidant and Aerosol Study (SOAS) during which atmospheric aerosol particles were comprehensively characterized. We present results utilizing a Filter Inlet for Gases and AEROsol coupled to a chemical ionization mass spectrometer (CIMS). We focus on the volatility and composition of isoprene derived organic aerosol tracers and of the bulk organic aerosol. By utilizing the online volatility and molecular composition information provided by the FIGAERO-CIMS, we show that the vast majority of commonly reported molecular tracers of isoprene epoxydiol (IEPOX) derived secondary organic aerosol (SOA) is derived from thermal decomposition of accretion products or other low volatility organics having effective saturation vapor concentrations <10(-3) μg m(-3). In addition, while accounting for up to 30% of total submicrometer organic aerosol mass, the IEPOX-derived SOA has a higher volatility than the remaining bulk. That IEPOX-SOA, and more generally bulk organic aerosol in the Southeastern U.S. is comprised of effectively nonvolatile material has important implications for modeling SOA derived from isoprene, and for mechanistic interpretations of molecular tracer measurements. Our results show that partitioning theory performs well for 2-methyltetrols, once accretion product decomposition is taken into account. No significant partitioning delays due to aerosol phase or viscosity are observed, and no partitioning to particle-phase water or other unexplained mechanisms are needed to explain our results.

  19. Recent advances in understanding secondary organic aerosols: implications for global climate forcing

    NASA Astrophysics Data System (ADS)

    Shrivastava, Manish

    2017-04-01

    Anthropogenic emissions and land-use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding pre-industrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features 1) influence estimates of aerosol radiative forcing and 2) can confound estimates of the historical response of climate to increases in greenhouse gases (e.g. the 'climate sensitivity'). Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, often represents a major fraction of global submicron-sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate models typically do not comprehensively include all important processes. This presentation is based on a US Department of Energy Atmospheric Systems Research sponsored workshop, which highlighted key SOA processes overlooked in climate models that could greatly affect climate forcing estimates. We will highlight the importance of processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including: formation of extremely low-volatility organics in the gas-phase; isoprene epoxydiols (IEPOX) multi-phase chemistry; particle-phase oligomerization; and physical properties such as viscosity. We also highlight some of the recently discovered important processes that involve interactions between natural biogenic emissions and anthropogenic emissions such as effects of sulfur and NOx emissions on SOA. We will present examples of integrated model-measurement studies that relate the observed evolution of organic aerosol mass and number with knowledge of particle properties such as volatility and viscosity. We will also highlight the importance of continuing efforts to rank the most influential SOA processes that affect climate forcing, but are often missing

  20. Aerosol Indirect effect on Stratocumulus Organization

    NASA Astrophysics Data System (ADS)

    Zhou, X.; Heus, T.; Kollias, P.

    2015-12-01

    Large-eddy simulations are used to investigate the role of aerosol loading on organized Stratocumulus. We prescribed the cloud droplet number concentration (Nc) and considered it as the proxy for different aerosol loading. While the presence of drizzle amplifies the mesoscale variability as is in Savic-Jovcic and Stevens (JAS, 2008), two noticeable findings are discussed here: First, the scale of marine boundary layer circulation appears to be independent of aerosol loading, suggesting a major role of the turbulence. The precise role of the turbulence in stratocumulus organization is studied by modifying the large scale fluctuations from the LES domain. Second, while it is commonly thought that the whole circulation needs to be represented for robust cloud development, we find that stratocumulus dynamics, including variables like w'w' and w'w'w', are remarkably robust even if large scales are ignored by simply reducing the domain sizes. The only variable that is sensitive to the change of the scale is the amount of cloudiness. Despite their smaller cloud thickness and inhomogeneous macroscopic structure for low Nc, individual drizzling clouds have sizes that are commensurate with circulation scale. We observe an Nc threshold below which stratocumulus is thin enough so that a little decrease of Nc would lead to great change of cloud fraction. The simulated cloud albedo is more sensitive to in-cloud liquid water content than to the amount of cloudiness since the former decreases at least three times faster than the latter due to drizzle. The main impact of drizzle evaporation is observed to keep the sub-cloud layer moist and as a result to extend the lifetime of stratocumulus by a couple of hours.

  1. Seasonal variability of carbon in humic-like matter of ambient size-segregated water soluble organic aerosols from urban background environment

    NASA Astrophysics Data System (ADS)

    Frka, Sanja; Grgić, Irena; Turšič, Janja; Gini, Maria I.; Eleftheriadis, Konstantinos

    2018-01-01

    Long-term measurements of carbon in HUmic-LIke Substances (HULIS-C) of ambient size-segregated water soluble organic aerosols were performed using a ten-stage low-pressure Berner impactor from December 2014 to November 2015 at an urban background environment in Ljubljana, Slovenia. The mass size distribution patterns of measured species (PM - particulate matter, WSOC - water-soluble organic carbon and HULIS-C) for all seasons were generally tri-modal (primarily accumulation mode) but with significant seasonal variability. HULIS-C was found to have similar distributions as WSOC, with nearly the same mass median aerodynamic diameters (MMADs), except for winter when the HULIS-C size distribution was bimodal. In autumn and winter, the dominant accumulation mode with MMAD at ca. 0.65 μm contributed 83 and 97% to the total HULIS-C concentration, respectively. HULIS-C accounted for a large fraction of WSOC, averaging more than 50% in autumn and 40% in winter. Alternatively, during warmer periods the contributions of ultrafine (27% in summer) and coarse mode (27% in spring) were also substantial. Based on mass size distribution characteristics, HULIS-C was found to be of various sources. In colder seasons, wood burning was confirmed as the most important HULIS source; secondary formation in atmospheric liquid water also contributed significantly, as revealed by the MMADs of the accumulation mode shifting to larger sizes. The distinct difference between the spring and summer ratios of HULIS-C/WSOC in fine particles (ca. 50% in spring, but only 10% in summer) indicated different sources and chemical composition of WSOC in summer (e.g., SOA formation from biogenic volatile organic compounds (BVOCs) via photochemistry). The enlarged amount of HULIS-C in the ultrafine mode in summer suggests that the important contribution was most likely from new particle formation during higher emissions of BVOC due to the vicinity of a mixed deciduous forest; the higher contribution of

  2. Hygroscopicity of organic compounds as a function of carbon chain length, carboxyl, hydroperoxy, and carbonyl functional groups

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Petters, Sarah Suda; Pagonis, Demetrios; Claflin, Megan Suzanne

    The albedo and microphysical properties of clouds are controlled in part by the hygroscopicity of particles serving as cloud condensation nuclei (CCN). Hygroscopicity of complex organic mixtures in the atmosphere varies widely and remains challenging to predict. Here we present new measurements characterizing the CCN activity of pure compounds in which carbon chain length and the number of hydroperoxy, carboxyl, and carbonyl functional groups were systematically varied to establish the contributions of these groups to organic aerosol apparent hygroscopicity. Apparent hygroscopicity decreased with carbon chain length and increased with polar functional groups in the order carboxyl > hydroperoxy > carbonyl.more » Activation diameters at different supersaturations deviated from the -3/2 slope in log-log space predicted by Köhler theory, suggesting that water solubility limits CCN activity of particles composed of weakly functionalized organic compounds. Results are compared to a functional group contribution model that predicts CCN activity of organic compounds. The model performed well for most compounds but under-predicted the CCN activity of hydroperoxy groups. New best-fit hydroperoxy group/water interaction parameters were derived from the available CCN data. Lastly, these results may help improve estimates of the CCN activity of ambient organic aerosols from composition data.« less

  3. Hygroscopicity of organic compounds as a function of carbon chain length, carboxyl, hydroperoxy, and carbonyl functional groups

    DOE PAGES

    Petters, Sarah Suda; Pagonis, Demetrios; Claflin, Megan Suzanne; ...

    2017-06-16

    The albedo and microphysical properties of clouds are controlled in part by the hygroscopicity of particles serving as cloud condensation nuclei (CCN). Hygroscopicity of complex organic mixtures in the atmosphere varies widely and remains challenging to predict. Here we present new measurements characterizing the CCN activity of pure compounds in which carbon chain length and the number of hydroperoxy, carboxyl, and carbonyl functional groups were systematically varied to establish the contributions of these groups to organic aerosol apparent hygroscopicity. Apparent hygroscopicity decreased with carbon chain length and increased with polar functional groups in the order carboxyl > hydroperoxy > carbonyl.more » Activation diameters at different supersaturations deviated from the -3/2 slope in log-log space predicted by Köhler theory, suggesting that water solubility limits CCN activity of particles composed of weakly functionalized organic compounds. Results are compared to a functional group contribution model that predicts CCN activity of organic compounds. The model performed well for most compounds but under-predicted the CCN activity of hydroperoxy groups. New best-fit hydroperoxy group/water interaction parameters were derived from the available CCN data. Lastly, these results may help improve estimates of the CCN activity of ambient organic aerosols from composition data.« less

  4. Water-soluble Organic Components in Aerosols Associated with Savanna Fires in Southern Africa: Identification, Evolution and Distribution

    NASA Technical Reports Server (NTRS)

    Gao, Song; Hegg, Dean A.; Hobbs, Peter V.; Kirchstetter, Thomas W.; Magi, Brian I.; Sadilek, Martin

    2003-01-01

    During the SAFARI 2000 field campaign, both smoke aerosols from savanna fires and haze aerosols in the boundary layer and in the free troposphere were collected from an aircraft in southern Africa. These aerosol samples were analyzed for their water-soluble chemical components, particularly the organic species. A novel technique, electrospray ionization-ion trap mass spectrometry, was used concurrently with an ion chromatography system to analyze for carbohydrate species. Seven carbohydrates, seven organic acids, five metallic elements, and three inorganic anions were identified and quantified. On the average, these 22 species comprised 36% and 27% of the total aerosol mass in haze and smoke aerosols, respectively. For the smoke aerosols, levoglucosan was the most abundant carbohydrate species, while gluconic acid was tentatively identified as the most abundant organic acid. The mass abundance and possible source of each class of identified species are discussed, along with their possible formation pathways. The combustion phase of a fire had an impact on the chemical composition of the emitted aerosols. Secondary formation of sulfate, nitrate, levoglucosan, and several organic acids occurred during the initial aging of smoke aerosols. It is likely that under certain conditions, some carbohydrate species in smoke aerosols, such as levoglucosan, were converted to organic acids during upward transport.

  5. Long-term measurements of aerosols and carbon monoxide at the ZOTTO tall tower to characterize polluted and pristine air in the Siberian Taiga

    NASA Astrophysics Data System (ADS)

    Chi, X.; Winderlich, J.; Mayer, J.-C.; Panov, A. V.; Heimann, M.; Birmili, W.; Heintzenberg, J.; Cheng, Y.; Andreae, M. O.

    2013-07-01

    Siberia is one of few background regions in the Northern Hemisphere where the atmosphere may sometimes approach pristine conditions. We present the time series of aerosol and carbon monoxide (CO) measurements between September~2006 and December 2010 at the Zotino Tall Tower Observatory (ZOTTO) in Central Siberia (61° N; 90° E). We investigate the seasonal, weekly and diurnal variations of aerosol properties (including absorption and scattering coefficients and derived parameters, like equivalent black carbon (BCe), Ångström exponent, single scattering albedo, and backscattering ratio) and the CO mixing ratios. Criteria were established to distinguish polluted and near-pristine air masses and characterize them separately. Depending on the season, 15-47% of the sampling time at ZOTTO was representative of a clean atmosphere. The summer pristine data indicates that primary biogenic and/or secondary organic aerosol formation are quite strong particle sources in the Siberian Taiga. The summer seasons 2007-2008 are dominated by an Aitken mode of 80 nm size, whereas the summer 2009 with prevailing easterly winds produced aerosols in the accumulation mode around 200 nm size. We found these differences mainly related to air temperature, in parallel with production rates of biogenic volatile organic compounds (VOC). In winter, the footprint and aerosol size distribution (with a peak at 160 nm) of the clean background air are characteristic for aged aerosols from anthropogenic sources at great distances from ZOTTO and diluted biofuel burning emissions from heating. The wintertime polluted air originates from the large cities to the south and southwest of the site; these aerosols have a dominant mode around 100 nm, and the Δ BCe/Δ CO ratio of 7-11 ng m-3 ppb-1 suggests dominant contributions from coal and biofuel burning for heating. During summer, anthropogenic emissions are the dominant contributor to the pollution aerosols at ZOTTO, while only 12% of the polluted

  6. Optical Properties and Aging of Light Absorbing Secondary Organic Aerosol

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Liu, Jiumeng; Lin, Peng; Laskin, Alexander

    2016-10-14

    The light-absorbing organic aerosol (OA), commonly referred to as “brown carbon (BrC)”, has attracted considerable attention in recent years because of its potential to affect atmospheric radiation balance, especially in the ultraviolet region and thus impact photochemical processes. A growing amount of data has indicated that BrC is prevalent in the atmosphere, which has motivated numerous laboratory and field studies; however, our understanding of the relationship between the chemical composition and optical properties of BrC remains limited. We conducted chamber experiments to investigate the effect of various VOC precursors, NOx concentrations, photolysis time and relative humidity (RH) on the lightmore » absorption of selected secondary organic aerosols (SOA). Light absorption of chamber generated SOA samples, especially aromatic SOA, was found to increase with NOx concentration, at moderate RH, and for the shortest photolysis aging times. The highest mass absorption coefficients (MAC) value is observed from toluene SOA products formed under high NOx conditions at moderate RH, in which nitro-aromatics were previously identified as the major light absorbing compounds. BrC light absorption is observed to decrease with photolysis time, correlated with a decline of the organonitrate fraction of SOA. SOA formed from mixtures of aromatics and isoprene absorb less visible and UV light than SOA formed from aromatic precursors alone on a mass basis. However, the mixed-SOA absorption was underestimated when optical properties were predicted using a two-product SOA formation model, as done in many current climate models. Further investigation, including analysis on detailed mechanisms, are required to explain the discrepancy.« less

  7. Organic aerosol evaporation and formation in biomass-burning plumes: The competition between dilution and chemistry

    NASA Astrophysics Data System (ADS)

    Pierce, J. R.; Kreidenweis, S. M.; Bian, Q.; Jathar, S.; Kodros, J.; Barsanti, K.; Hatch, L. E.; May, A.

    2017-12-01

    Secondary organic aerosol (SOA) has been shown to form in biomass-burning emissions in laboratory and field studies. However, there is significant variability among studies in mass enhancement, which could be due to differences in fuels, fire conditions, dilution, and/or limitations of laboratory experiments and observations. This study focuses on understanding processes affecting biomass-burning SOA formation in ambient plumes. The plume dilution rate impacts the organic partitioning between the gas and particle phases, which may impact the potential for SOA to form as well as the rate of SOA formation. We use an aerosol microphysics model that includes representations of volatility and oxidation chemistry to estimate SOA formation in the smoke emitted into the atmosphere. We add Gaussian dispersion to our aerosol microphysical model to estimate how SOA formation may vary under different ambient-plume conditions (e.g. fire size, emission mass flux, atmospheric stability). Smoke from small fires, such as typical prescribed burns, dilutes rapidly, which drives evaporation of organic vapor from the particle phase, leading to more effective SOA formation. Emissions from large fires, such as intense wildfires, dilute slowly, suppressing OA evaporation and subsequent SOA formation in the near field. We also demonstrate that different approaches to the calculation of OA enhancement in ambient plumes can lead to different conclusions regarding SOA formation. Normalized OA mass enhancement ratios of around 1 calculated using an inert tracer, such as black carbon or CO, have traditionally been interpreted as exhibiting little or no SOA formation; however, we show that SOA formation may have greatly contributed to the mass in these plumes.

  8. The colors of biomass burning aerosols in the atmosphere.

    PubMed

    Liu, Chao; Chung, Chul Eddy; Zhang, Feng; Yin, Yan

    2016-06-16

    Biomass burning aerosols mainly consist of black carbon (BC) and organic aerosols (OAs), and some of OAs are brown carbon (BrC). This study simulates the colors of BrC, BC and their mixture with scattering OAs in the ambient atmosphere by using a combination of light scattering simulations, a two-stream radiative transfer model and a RGB (Red, Green, Blue) color model. We find that both BCs and tar balls (a class of BrC) appear brownish at small particle sizes and blackish at large sizes. This is because the aerosol absorption Ångström exponent (AAE) largely controls the color and larger particles give smaller AAE values. At realistic size distributions, BCs look more blackish than tar balls, but still exhibit some brown color. However, when the absorptance of aerosol layer at green wavelength becomes larger than approximately 0.8, all biomass burning aerosols look blackish. The colors for mixture of purely scattering and absorptive carbonaceous aerosol layers in the atmosphere are also investigated. We suggest that the brownishness of biomass burning aerosols indicates the amount of BC/BrC as well as the ratio of BC to BrC.

  9. Transitions from functionalization to fragmentation reactions of laboratory secondary organic aerosol (SOA) generated from the OH oxidation of alkane precursors.

    PubMed

    Lambe, Andrew T; Onasch, Timothy B; Croasdale, David R; Wright, Justin P; Martin, Alexander T; Franklin, Jonathan P; Massoli, Paola; Kroll, Jesse H; Canagaratna, Manjula R; Brune, William H; Worsnop, Douglas R; Davidovits, Paul

    2012-05-15

    Functionalization (oxygen addition) and fragmentation (carbon loss) reactions governing secondary organic aerosol (SOA) formation from the OH oxidation of alkane precursors were studied in a flow reactor in the absence of NO(x). SOA precursors were n-decane (n-C10), n-pentadecane (n-C15), n-heptadecane (n-C17), tricyclo[5.2.1.0(2,6)]decane (JP-10), and vapors of diesel fuel and Southern Louisiana crude oil. Aerosol mass spectra were measured with a high-resolution time-of-flight aerosol mass spectrometer, from which normalized SOA yields, hydrogen-to-carbon (H/C) and oxygen-to-carbon (O/C) ratios, and C(x)H(y)+, C(x)H(y)O+, and C(x)H(y)O(2)+ ion abundances were extracted as a function of OH exposure. Normalized SOA yield curves exhibited an increase followed by a decrease as a function of OH exposure, with maximum yields at O/C ratios ranging from 0.29 to 0.74. The decrease in SOA yield correlates with an increase in oxygen content and decrease in carbon content, consistent with transitions from functionalization to fragmentation. For a subset of alkane precursors (n-C10, n-C15, and JP-10), maximum SOA yields were estimated to be 0.39, 0.69, and 1.1. In addition, maximum SOA yields correspond with a maximum in the C(x)H(y)O+ relative abundance. Measured correlations between OH exposure, O/C ratio, and H/C ratio may enable identification of alkane precursor contributions to ambient SOA.

  10. Organic condensation - a vital link connecting aerosol formation to climate forcing

    NASA Astrophysics Data System (ADS)

    Riipinen, I.; Pierce, J. R.; Yli-Juuti, T.; Nieminen, T.; Häkkinen, S.; Ehn, M.; Junninen, H.; Lehtipalo, K.; Petäjä, T.; Slowik, J.; Chang, R.; Shantz, N. C.; Abbatt, J.; Leaitch, W. R.; Kerminen, V.-M.; Worsnop, D. R.; Pandis, S. N.; Donahue, N. M.; Kulmala, M.

    2011-01-01

    Atmospheric aerosol particles influence global climate as well as impair air quality through their effects on atmospheric visibility and human health. Ultrafine (<100 nm) particles often dominate aerosol numbers, and nucleation of atmospheric vapors is an important source of these particles. To have climatic relevance, however, the freshly-nucleated particles need to grow in size. We combine observations from two continental sites (Egbert, Canada and Hyytiälä, Finland) to show that condensation of organic vapors is a crucial factor governing the lifetimes and climatic importance of the smallest atmospheric particles. We demonstrate that state-of-the-science organic gas-particle partitioning models fail to reproduce the observations, and propose a modeling approach that is consistent with the measurements. We demonstrate the large sensitivity of climatic forcing of atmospheric aerosols to these interactions between organic vapors and the smallest atmospheric nanoparticles - highlighting the need for representing this process in global climate models.

  11. Complex refractive indices in the near-ultraviolet spectral region of biogenic secondary organic aerosol aged with ammonia

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Flores, J. M.; Washenfelder, Rebecca; Adler, Gabriela

    2014-05-14

    Atmospheric absorption by brown carbon aerosol may play an important role in global radiative forcing. Brown carbon arises from both primary and secondary sources, but the mechanisms and reactions for the latter are highly uncertain. One proposed mechanism is the reaction of ammonia or amino acids with carbonyl products in secondary organic aerosol (SOA). We generated SOA in situ by reacting biogenic alkenes (α-pinene, limonene, and α-humulene) with excess ozone, humidifying the resulting aerosol, and reacting the humidified aerosol with gaseous ammonia. We determined the complex refractive indices (RI) in the 360 – 420 nm range for these aerosols usingmore » broadband cavity enhanced spectroscopy (BBCES). The average real part (n) of the measured spectral range of the NH3-aged α-pinene SOA increased from n = 1.50 (±0.01) for the unreacted SOA to n = 1.57 (± 0.01) after a 1.5h exposure to 1.9 ppm NH3; whereas,the imaginary component (k) remained below k < 0.001 (± 0.002). For the limonene and α-humulene SOA the real part did not change significantly, and we observed a small change in the imaginary component of the RI. The imaginary component increased from k = 0.0 to an average k= 0.029 (± 0.021) for α-humulene SOA, and from k < 0.001 (± 0.002) to an average k = 0.032 (±0.019) for limonene SOA after a 1.5 h exposure to 1.3 and 1.9 ppm of NH3, respectively. Collected filter samples of the aged and unreacted α-pinene SOA and limonene SOA were analyzed off-line with nanospray desorption electrospray ionization high resolution mass spectrometry (nano-DESI/HR-MS), and in-situ with a Time-of-Fligh Aerosol Mass Spectrometer, confirming that the SOA reacted and that various nitrogen-containing reaction products formed. If we assume that NH3 aging reactions scale linearly with time and concentration, then a 1.5 h reaction with 1 ppm NH3 in the laboratory is equivalent to 24 h reaction with 63 ppbv NH3, indicating that the observed aerosol absorption will be

  12. SOURCES OF ORGANIC AEROSOL: SEMIVOLATILE EMISSIONS AND PHOTOCHEMICAL AGING

    EPA Science Inventory

    The proposed research integrates emissions testing, smog chamber experiments, and regional chemical transport models (CTMs) to investigate the sources of organic aerosol in urban and regional environments.

  13. Nighttime aqueous-phase secondary organic aerosols in Los Angeles and its implication for fine particulate matter composition and oxidative potential

    NASA Astrophysics Data System (ADS)

    Saffari, Arian; Hasheminassab, Sina; Shafer, Martin M.; Schauer, James J.; Chatila, Talal A.; Sioutas, Constantinos

    2016-05-01

    Recent investigations suggest that aqueous phase oxidation of hydrophilic organic compounds can be a significant source of secondary organic aerosols (SOA) in the atmosphere. Here we investigate the possibility of nighttime aqueous phase formation of SOA in Los Angeles during winter, through examination of trends in fine particulate matter (PM2.5) carbonaceous content during two contrasting seasons. Distinctive winter and summer trends were observed for the diurnal variation of organic carbon (OC) and secondary organic carbon (SOC), with elevated levels during the nighttime in winter, suggesting an enhanced formation of SOA during that period. The nighttime ratio of SOC to OC was positively associated with the relative humidity (RH) at high RH levels (above 70%), which is when the liquid water content of the ambient aerosol would be high and could facilitate dissolution of hydrophilic primary organic compounds into the aqueous phase. Time-integrated collection and analysis of wintertime particles at three time periods of the day (morning, 6:00 a.m.-9:00 a.m.; afternoon, 11:00 a.m.-3:00 p.m.; night, 8:00 p.m.-4:00 a.m.) revealed higher levels of water soluble organic carbon (WSOC) and organic acids during the night and afternoon periods compared to the morning period, indicating that the SOA formation in winter continues throughout the nighttime. Furthermore, diurnal trends in concentrations of semi-volatile organic compounds (SVOCs) from primary emissions showed that partitioning of SVOCs from the gas to the particle phase due to the decreased nighttime temperatures cannot explain the substantial OC and SOC increase at night. The oxidative potential of the collected particles (quantified using a biological macrophage-based reactive oxygen species assay, in addition to the dithiothreitol assay) was comparable during afternoon and nighttime periods, but higher (by at least ∼30%) compared to the morning period, suggesting that SOA formation processes possibly

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

    NASA Astrophysics Data System (ADS)

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

    2012-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-03-01

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

  16. Modeling organic aerosols in a megacity: potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Jimenez, J. L.; Madronich, S.; Canagaratna, M. R.; Decarlo, P. F.; Kleinman, L.; Fast, J.

    2010-06-01

    It has been established that observed local and regional levels of secondary organic aerosols (SOA) in polluted areas cannot be explained by the oxidation and partitioning of anthropogenic and biogenic VOC precursors, at least using current mechanisms and parameterizations. In this study, the 3-D regional air quality model CHIMERE is applied to estimate the potential contribution to SOA formation of recently identified semi-volatile and intermediate volatility organic precursors (S/IVOC) in and around Mexico City for the MILAGRO field experiment during March 2006. The model has been updated to include explicitly the volatility distribution of primary organic aerosols (POA), their gas-particle partitioning and the gas-phase oxidation of the vapors. Two recently proposed parameterizations, those of Robinson et al. (2007) ("ROB") and Grieshop et al. (2009) ("GRI") are compared and evaluated against surface and aircraft measurements. The 3-D model results are assessed by comparing with the concentrations of OA components from Positive Matrix Factorization of Aerosol Mass Spectrometer (AMS) data, and for the first time also with oxygen-to-carbon ratios derived from high-resolution AMS measurements. The results show a substantial enhancement in predicted SOA concentrations (2-4 times) with respect to the previously published base case without S/IVOCs (Hodzic et al., 2009), both within and downwind of the city leading to much reduced discrepancies with the total OA measurements. Model improvements in OA predictions are associated with the better-captured SOA magnitude and diurnal variability. The predicted production from anthropogenic and biomass burning S/IVOC represents 40-60% of the total measured SOA at the surface during the day and is somewhat larger than that from commonly measured aromatic VOCs, especially at the T1 site at the edge of the city. The SOA production from the continued multi-generation S/IVOC oxidation products continues actively downwind. Similar

  17. Sources and Removal of Springtime Arctic Aerosol

    NASA Astrophysics Data System (ADS)

    Willis, M. D.; Burkart, J.; Bozem, H.; Kunkel, D.; Schulz, H.; Hanna, S.; Aliabadi, A. A.; Bertram, A. K.; Hoor, P. M.; Herber, A. B.; Leaitch, R.; Abbatt, J.

    2017-12-01

    The sources and removal mechanisms of pollution transported to Arctic regions are key factors in controlling the impact of short-lived climate forcing agents on Arctic climate. We lack a predictive understanding of pollution transport to Arctic regions largely due to poor understanding of removal mechanisms and aerosol chemical and physical processing both within the Arctic and during transport. We present vertically resolved observations of aerosol physical and chemical properties in High Arctic springtime. While much previous work has focused on characterizing episodic events of high pollutant concentrations transported to Arctic regions, here we focus on measurements made under conditions consistent with chronic Arctic Haze, which is more representative of the pollution seasonal maximum observed at long term monitoring stations. On six flights based at Alert and Eureka, Nunavut, Canada, we observe evidence for vertical variations in both aerosol sources and removal mechanisms. With support from model calculations, we show evidence for sources of partially neutralized aerosol with higher organic aerosol (OA) and black carbon content in the middle troposphere, compared to lower tropospheric aerosol with higher amounts of acidic sulfate. Further, we show evidence for aerosol depletion relative to carbon monoxide, both in the mid-to-upper troposphere and within the Arctic Boundary Layer (ABL). Dry deposition, with relatively low removal efficiency, was responsible for aerosol removal in the ABL while ice or liquid-phase scavenging was responsible for aerosol removal at higher altitudes during transport. Overall, we find that vertical variations in both regional and remote aerosol sources, and removal mechanisms, combine with long aerosol residence times to drive the properties of springtime Arctic aerosol.

  18. Optical absorption characteristics of brown carbon aerosols during the KORUS-AQ campaign at an urban site

    NASA Astrophysics Data System (ADS)

    Park, Seungshik; Yu, Geun-Hye; Lee, Sangil

    2018-05-01

    This study investigates the absorption characteristics of brown carbon (BrC) obtained from water and methanol extracts of fine particulate matter measured at an urban site in Gwangju, Korea during the KOREA U.S. - Air Quality campaign (May 2-June 11, 2016). The measurement period was classified into two intervals: biomass burning (BB) and non-BB periods. During the non-BB period, water-soluble organic carbon (WSOC) and humic-like substances (HULIS) primarily resulted from secondary organic aerosol (SOA) formation and primary vehicle emissions. Water-soluble organic aerosols during the BB period, meanwhile, were closely related to SOA formation and regionally transported BB emissions. The light absorption coefficient measured at 365 nm (babs,365) by methanol extracts was 2.6 and 6.1 times higher than the coefficients from the water and HULIS extracts, respectively, indicating the importance of BrC absorption by water-insoluble organic carbon. This was demonstrated by a good correlation between the water-insoluble BrC absorption and the elemental carbon concentration. A comparison of babs,365 between the methanol- and water-extracted BrC indicated that water-insoluble BrC accounted for approximately 61% (33-86%) of the total BrC absorption. The contributions of SOA, primary BB emissions, and traffic emissions to the water extract babs,365 were estimated using a stepwise multiple linear regression (MLR) analysis and found to be 1.17 ± 0.55, 0.65 ± 0.62, and 0.25 ± 0.09 Mm- 1, respectively, accounting for 59.6, 26.1, and 14.3% of the absorption coefficient by the water-soluble BrC. Further, it was determined that the contribution of the BB emissions to the water-soluble BrC absorption was approximately two times higher in the BB period than in the non-BB period. The average absorption Ångstrӧm exponent was 4.8 ± 0.3, 5.3 ± 0.7, and 6.8 ± 0.8 for the methanol, water, and HULIS extracts, respectively. The average mass absorption efficiency (MAE365) of methanol

  19. Sources and atmospheric transformations of semivolatile organic aerosols

    NASA Astrophysics Data System (ADS)

    Grieshop, Andrew P.

    Fine atmospheric particulate matter (PM2.5) is associated with increased mortality, a fact which led the EPA to promulgate a National Ambient Air Quality Standard (NAAQS) for PM2.5 in 1997. Organic material contributes a substantial portion of the PM2.5 mass; organic aerosols (OA) are either directly emitted (primary OA or POA) or formed via the atmospheric oxidation of volatile precursor compounds as secondary OA (SOA). The relative contributions of POA and SOA to atmospheric OA are uncertain, as are the contributions from various source classes (e.g. motor vehicles, biomass burning). This dissertation first assesses the importance of organic PM within the context of current US air pollution regulations. Most control efforts to date have focused on the inorganic component of PM. Although growing evidence strongly implicates OA, especially which from motor vehicles, in the health effects of PM, uncertain and complex source-receptor relationships for OA discourage its direct control for NAAQS compliance. Analysis of both ambient data and chemical transport modeling results indicate that OA does not play a dominant role in NAAQS violations in most areas of the country under current and likely future regulations. Therefore, new regulatory approaches will likely be required to directly address potential health impacts associated with OA. To help develop the scientific understanding needed to better regulate OA, this dissertation examined the evolution of organic aerosol emitted by combustion systems. The current conceptual model of POA is that it is non-volatile and non-reactive. Both of these assumptions were experimental investigated in this dissertation. Novel dilution measurements were carried out to investigate the gas-particle partitioning of OA at atmospherically-relevant conditions. The results demonstrate that POA from combustion sources is semivolatile. Therefore its gas-particle partitioning depends on temperature and atmospheric concentrations; heating and

  20. Hygroscopicity of organic surrogate compounds from biomass burning and their effect on the efflorescence of ammonium sulfate in mixed aerosol particles

    NASA Astrophysics Data System (ADS)

    Lei, Ting; Zuend, Andreas; Cheng, Yafang; Su, Hang; Wang, Weigang; Ge, Maofa

    2018-01-01

    relatively good agreement between models and observed growth factors, as well as ERH of AS in the mixed system. The use of the ZSR relation leads to good agreement with measured diameter growth factors of aerosol particles containing humic acid and ammonium sulfate. Lastly, two distinct mixtures of organic surrogate compounds, including levoglucosan, 4-hydroxybenzoic acid, and humic acid, were used to represent the average water-soluble organic carbon (WSOC) fractions observed during the wet and dry seasons in the central Amazon Basin. A comparison of the organic fraction's hygroscopicity parameter for the simple mixtures, e.g., κ ≈ 0.12 to 0.15 for the wet-season mixture in the 90 to 40 % RH range, shows good agreement with field data for the wet season in the Amazon Basin (WSOC κ ≈ 0.14±0.06 at 90 % RH). This suggests that laboratory-generated mixtures containing organic surrogate compounds and ammonium sulfate can be used to mimic, in a simplified manner, the chemical composition of ambient aerosols from the Amazon Basin for the purpose of RH-dependent hygroscopicity studies.

  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. Comparison of structural features of water-soluble organic matter from atmospheric aerosols with those of aquatic humic substances

    NASA Astrophysics Data System (ADS)

    Duarte, Regina M. B. O.; Santos, Eduarda B. H.; Pio, Casimiro A.; Duarte, Armando C.

    Elemental analysis, Fourier transform infrared coupled to attenuated total reflectance (FTIR-ATR) and solid-state cross polarization with magic angle spinning- 13C-nuclear magnetic resonance (CPMAS 13C NMR) spectroscopies were used to compare the chemical features of water-soluble organic compounds (WSOC) from atmospheric aerosols with those of aquatic humic and fulvic acids. The influence of different meteorological conditions on the structural composition of aerosol WSOC was also evaluated. Prior to the structural characterisation, the WSOC samples were separated into hydrophobic acids and hydrophilic acids fractions by using a XAD-8/XAD-4 isolation procedure. Results showed that WSOC hydrophobic acids are mostly aliphatic (40-62% of total NMR peak area), followed by oxygenated alkyls (15-21%) and carboxylic acid (5.4-13.4%) functional groups. Moreover, the aromatic content of aerosol WSOC samples collected between autumn and winter seasons is higher (˜18-19%) than that of samples collected during warmer periods (˜6-10%). The presence of aromatic signals typical of lignin-derived structures in samples collected during low-temperature conditions highlights the major contribution of wood burning processes in domestic fireplaces into the bulk chemical properties of WSOC from aerosols. According to our investigations, aerosol WSOC hydrophobic acids and aquatic fulvic and humic acids hold similar carbon functional groups; however, they differ in terms of the relative carbon distribution. Elemental analysis indicates that H and N contents of WSOC hydrophobic acids samples surpass those of aquatic fulvic and humic acids. In general, the obtained results suggest that WSOC hydrophobic acids have a higher aliphatic character and a lower degree of oxidation than those of standard fulvic and humic acids. The study here reported suggests that aquatic fulvic and humic acids may not be good models for WSOC from airborne particulate matter.

  3. Impacts of controlling biomass burning emissions on wintertime carbonaceous aerosol in Europe

    NASA Astrophysics Data System (ADS)

    Fountoukis, C.; Butler, T.; Lawrence, M. G.; Denier van der Gon, H. A. C.; Visschedijk, A. J. H.; Charalampidis, P.; Pilinis, C.; Pandis, S. N.

    2014-04-01

    We use a 3-D regional chemical transport model, with the latest advancements in the organic aerosol (OA) treatment, and an updated emission inventory for wood combustion to study the organic aerosol change in response to the replacement of current residential wood combustion technologies with pellet stoves. Simulations show a large decrease of fine organic aerosol (more than 60%) in urban and suburban areas during winter and decreases of 30-50% in elemental carbon levels in large parts of Europe. There is also a considerable decrease (around 40%) of oxidized OA, mostly in rural and remote regions. Total PM2.5 mass is predicted to decrease by 15-40% on average during the winter in continental Europe. Accurate representation of the intermediate volatility precursors of organic aerosol in the emission inventory is crucial in assessing the efficiency of such abatement strategies.

  4. Organic composition and source apportionment of fine aerosol at Monterrey, Mexico, based on organic markers

    NASA Astrophysics Data System (ADS)

    Mancilla, Y.; Mendoza, A.; Fraser, M. P.; Herckes, P.

    2016-01-01

    Primary emissions from anthropogenic and biogenic sources as well as secondary formation are responsible for the pollution levels of ambient air in major urban areas. These sources release fine particles into the air that negatively impact human health and the environment. Organic molecular markers, which are compounds that are unique to specific PM2.5 sources, can be utilized to identify the major emission sources in urban areas. In this study, 43 representative PM2.5 samples, for both daytime and nighttime periods, were built from individual samples collected in an urban site of the Monterrey metropolitan area (MMA) during the spring and fall of 2011 and 2012. The samples were analyzed for organic carbon, elemental carbon, and organic molecular markers. Several diagnostic tools were employed for the preliminary identification of emission sources. Organic compounds for eight compound classes were quantified. The n-alkanoic acids were the most abundant, followed by n-alkanes, wood smoke markers, and levoglucosan/alkenoic acids. Polycyclic aromatic hydrocarbons (PAHs) and hopanes were less abundant. The carbon preference index (0.7-2.6) for n-alkanes indicates a major contribution of anthropogenic and mixed sources during the fall and the spring, respectively. Hopanes levels confirmed the contribution from gasoline and diesel engines. In addition, the contribution of gasoline and diesel vehicle exhaust was confirmed and identified by the PAH concentrations in PM2.5. Diagnostic ratios of PAHs showed emissions from burning coal, wood, biomass, and other fossil fuels. The total PAHs and elemental carbon were correlated (r2 = 0.39-0.70) across the monitoring periods, reinforcing that motor vehicles are the major contributors of PAHs. Cholesterol levels remained constant during the spring and fall, showing evidence of the contribution of meat-cooking operations, while the isolated concentrations of levoglucosan suggested occasional biomass burning events. Finally, source

  5. Dynamic light absorption of biomass-burning organic carbon photochemically aged under natural sunlight

    NASA Astrophysics Data System (ADS)

    Zhong, M.; Jang, M.

    2014-02-01

    Wood-burning aerosol produced under smoldering conditions was photochemically aged with different relative humidity (RH) and NOx conditions using a 104 m3 dual outdoor chamber under natural sunlight. Light absorption of organic carbon (OC) was measured over the course of photooxidation using a UV-visible spectrometer connected to an integrating sphere. At high RH, the color decayed rapidly. NOx slightly prolonged the color of wood smoke, suggesting that NOx promotes the formation of chromophores via secondary processes. Overall, the mass absorption cross section (integrated between 280 and 600 nm) of OC increased by 11-54% (except high RH) in the morning and then gradually decreased by 19-68% in the afternoon. This dynamic change in light absorption of wood-burning OC can be explained by two mechanisms: chromophore formation and sunlight bleaching. To investigate the effect of chemical transformation on light absorption, wood smoke particles were characterized using various spectrometers. The intensity of fluorescence, which is mainly related to polycyclic aromatic hydrocarbons (PAHs), rapidly decreased with time, indicating the potential bleaching of PAHs. A decline of levoglucosan concentrations evinced the change of primary organic aerosol with time. The aerosol water content measured by Fourier transform infrared spectroscopy showed that wood-burning aerosol became less hygroscopic as photooxidation proceeded. A similar trend in light absorption changes has been observed in ambient smoke aerosol originating from the 2012 County Line wildfire in Florida. We conclude that the biomass-burning OC becomes less light absorbing after 8-9 h sunlight exposure compared to fresh wood-burning OC.

  6. Retrieval of Aerosol Absorption Properties from Satellite Observations

    NASA Technical Reports Server (NTRS)

    Torres, Omar; Bhartia, Pawan K.; Jethva, H.; Ahn, Chang-Woo

    2012-01-01

    The Angstrom Absorption Exponent (AAE) is a parameter commonly used to characterize the wavelength-dependence of aerosol absorption optical depth (AAOD). It is closely related to aerosol composition. Black carbon (BC) containing aerosols yield AAE values near unity whereas Organic carbon (OC) aerosol particles are associated with values larger than 2. Even larger AAE values have been reported for desert dust aerosol particles. Knowledge of spectral AAOD is necessary for the calculation of direct radiative forcing effect of aerosols and for inferring aerosol composition. We have developed a satellitebased method of determining the spectral AAOD of absorbing aerosols. The technique uses multi-spectral measurements of upwelling radiation from scenes where absorbing aerosols lie above clouds as indicated by the UV Aerosol Index. For those conditions, the satellite measurement can be explained, using an approximations of Beer's Law (BL), as the upwelling reflectance at the cloud top attenuated by the absorption effects of the overlying aerosol layer. The upwelling reflectance at the cloud-top in an aerosol-free atmospheric column is mainly a function of cloud optical depth (COD). In the proposed method of AAE derivation, the first step is determining COD which is retrieved using a previously developed color-ratio based approach. In the second step, corrections for molecular scattering effects are applied to both the observed ad the calculated cloud reflectance terms, and the spectral AAOD is then derived by an inversion of the BL approximation. The proposed technique will be discussed in detail and application results making use of OMI multi-spectral measurements in the UV-Vis. will be presented.

  7. Secondary organic aerosol origin in an urban environment: influence of biogenic and fuel combustion precursors.

    PubMed

    Minguillón, M C; Pérez, N; Marchand, N; Bertrand, A; Temime-Roussel, B; Agrios, K; Szidat, S; van Drooge, B; Sylvestre, A; Alastuey, A; Reche, C; Ripoll, A; Marco, E; Grimalt, J O; Querol, X

    2016-07-18

    Source contributions of organic aerosol (OA) are still not fully understood, especially in terms of quantitative distinction between secondary OA formed from anthropogenic precursors vs. that formed from natural precursors. In order to investigate the OA origin, a field campaign was carried out in Barcelona in summer 2013, including two periods characterized by low and high traffic conditions. Volatile organic compound (VOC) concentrations were higher during the second period, especially aromatic hydrocarbons related to traffic emissions, which showed a marked daily cycle peaking during traffic rush hours, similarly to black carbon (BC) concentrations. Biogenic VOC (BVOC) concentrations showed only minor changes from the low to the high traffic period, and their intra-day variability was related to temperature and solar radiation cycles, although a decrease was observed for monoterpenes during the day. The organic carbon (OC) concentrations increased from the first to the second period, and the fraction of non-fossil OC as determined by (14)C analysis increased from 43% to 54% of the total OC. The combination of (14)C analysis and Aerosol Chemical Speciation Monitor (ACSM) OA source apportionment showed that the fossil OC was mainly secondary (>70%) except for the last sample, when the fossil secondary OC only represented 51% of the total fossil OC. The fraction of non-fossil secondary OC increased from 37% of total secondary OC for the first sample to 60% for the last sample. This enhanced formation of non-fossil secondary OA (SOA) could be attributed to the reaction of BVOC precursors with NOx emitted from road traffic (or from its nocturnal derivative nitrate that enhances night-time semi-volatile oxygenated OA (SV-OOA)), since NO2 concentrations increased from 19 to 42 μg m(-3) from the first to the last sample.

  8. Seasonality of major aerosol species and their transformations in Cairo megacity

    NASA Astrophysics Data System (ADS)

    Favez, Olivier; Cachier, Hélène; Sciare, Jean; Alfaro, Stéphane C.; El-Araby, Tarek M.; Harhash, Maha A.; Abdelwahab, Magdy M.

    Bulk aerosols sampled on a weekly basis at two Cairo (Egypt) urban sites from January 2003 to May 2006 were analysed for their chemical composition of major aerosol species (elemental carbon, water soluble/insoluble organic carbon, nitrate, sulphate, ammonium, chloride, sodium and calcium). Data subsequently obtained constitute one of the longest and more detailed dataset related to Cairo aerosols, and offer the opportunity to investigate seasonal trends. Dust aerosols (derived from calcium measurements) displayed maximum concentrations in spring and winter, due to frequent dust storms, but also high background concentration levels (˜50 μg m -3) all year long. Within these particles, about 40% on average of Ca 2+ was found to be associated with SO 42-, NO 3- and/or Cl -, pointing out "dust anthropization" processes and their subsequent climatic impact on a regional scale. Seasonal variations of non-dust aerosols, equally distributed between carbonaceous aerosols and ions, were also observed, with concentrations of the order of 100 μg m -3 in autumn and winter, and of 60 μg m -3 in spring and summer. High concentration levels of non-sea-salt chloride (up to 15 μg m -3 on a monthly basis), likely of industrial origin, were observed in autumn and winter. During the autumn "Black Cloud" event, biomass burning aerosols originating from rice straw burning in the Nile Delta have shown to account for 12%, 35% and 50% of Cairo EC, WIOC and WSOC mass concentrations, respectively. Finally, relatively low WSOC/OC ratios (˜1/3) were obtained all the year long, calling for more investigation on the water-solubility of organic aerosols originating from the burning of agricultural waste, and on that of secondary organic aerosols formed in dry urban atmospheres.

  9. Observed secondary organic aerosol (SOA) and organic nitrate yields from NO3 oxidation of isoprene

    NASA Astrophysics Data System (ADS)

    Rollins, A. W.; Fry, J. L.; Kiendler-Scharr, A.; Wooldridge, P. J.; Brown, S. S.; Fuchs, H.; Dube, W.; Mensah, A.; Tillmann, R.; Dorn, H.; Brauers, T.; Cohen, R. C.

    2008-12-01

    Formation of organic nitrates and secondary organic aerosol (SOA) from the NO3 oxidation of isoprene has been studied at atmospheric concentrations of VOC (10 ppb) and oxidant (<100 ppt NO3) in the presence of ammonium sulfate seed aerosol in the atmosphere simulation chamber SAPHIR at Forschungszentrum Jülich. Cavity Ringdown (CaRDS) and thermal dissociation - CaRDS measurements of NO3 and N2O5 as well as Thermal Dissociation - Laser Induced Fluorescence (TD-LIF) detection of alkyl nitrates (RONO2) and Aerodyne Aerosol Mass Spectrometer (AMS) measurements of aerosol composition were all used in comparison to a Master Chemical Mechanism (MCM) based chemical kinetics box model to quantify the product yields from two stages in isoprene oxidation. We find significant yields of organic nitrate formation from both the initial isoprene + NO3 reaction (71%) as well as from the reaction of NO3 with the initial oxidation products (30% - 60%). Under these low concentration conditions (~1 μg / m3), measured SOA production was greater than instrument noise only for the second oxidation step. Based on the modeled chemistry, we estimate an SOA mass yield of 10% (relative to isoprene mass reacted) for the reaction of the initial oxidation products with NO3. This yield is found to be consistent with the estimated saturation concentration (C*) of the presumed gas products of the doubly oxidized isoprene, where both oxidations lead to the addition of nitrate, carbonyl, and hydroxyl groups.

  10. Aerosol Optical Depth Over India

    NASA Astrophysics Data System (ADS)

    David, Liji Mary; Ravishankara, A. R.; Kodros, John K.; Venkataraman, Chandra; Sadavarte, Pankaj; Pierce, Jeffrey R.; Chaliyakunnel, Sreelekha; Millet, Dylan B.

    2018-04-01

    Tropospheric aerosol optical depth (AOD) over India was simulated by Goddard Earth Observing System (GEOS)-Chem, a global 3-D chemical-transport model, using SMOG (Speciated Multi-pOllutant Generator from Indian Institute of Technology Bombay) and GEOS-Chem (GC) (current inventories used in the GEOS-Chem model) inventories for 2012. The simulated AODs were 80% (SMOG) and 60% (GC) of those measured by the satellites (Moderate Resolution Imaging Spectroradiometer and Multi-angle Imaging SpectroRadiometer). There is no strong seasonal variation in AOD over India. The peak AOD values are observed/simulated during summer. The simulated AOD using SMOG inventory has particulate black and organic carbon AOD higher by a factor 5 and 3, respectively, compared to GC inventory. The model underpredicted coarse-mode AOD but agreed for fine-mode AOD with Aerosol Robotic Network data. It captured dust only over Western India, which is a desert, and not elsewhere, probably due to inaccurate dust transport and/or noninclusion of other dust sources. The calculated AOD, after dust correction, showed the general features in its observed spatial variation. Highest AOD values were observed over the Indo-Gangetic Plain followed by Central and Southern India with lowest values in Northern India. Transport of aerosols from Indo-Gangetic Plain and Central India into Eastern India, where emissions are low, is significant. The major contributors to total AOD over India are inorganic aerosol (41-64%), organic carbon (14-26%), and dust (7-32%). AOD over most regions of India is a factor of 5 or higher than over the United States.

  11. Introductory lecture: atmospheric organic aerosols: insights from the combination of measurements and chemical transport models.

    PubMed

    Pandis, Spyros N; Donahue, Neil M; Murphy, Benjamin N; Riipinen, Ilona; Fountoukis, Christos; Karnezi, Eleni; Patoulias, David; Skyllakou, Ksakousti

    2013-01-01

    The formation, atmospheric evolution, properties, and removal of organic particulate matter remain some of the least understood aspects of atmospheric chemistry despite the importance of organic aerosol (OA) for both human health and climate change. Here, we summarize our recent efforts to deal with the chemical complexity of the tens of thousands of organic compounds in the atmosphere using the volatility-oxygen content framework (often called the 2D-Volatility Basis Set, 2D-VBS). Our current ability to measure the ambient OA concentration as a function of its volatility and oxygen to carbon (O:C) ratio is evaluated. The combination of a thermodenuder, isothermal dilution and Aerosol Mass Spectrometry (AMS) together with a mathematical aerosol dynamics model is a promising approach. The development of computational modules based on the 2D-VBS that can be used in chemical transport models (CTMs) is described. Approaches of different complexity are tested against ambient observations, showing the challenge of simulating the complex chemical evolution of atmospheric OA. The results of the simplest approach describing the net change due to functionalization and fragmentation are quite encouraging, reproducing both the observed OA levels and O : C in a variety of conditions. The same CTM coupled with source-apportionment algorithms can be used to gain insights into the travel distances and age of atmospheric OA. We estimate that the average age of OA near the ground in continental locations is 1-2 days and most of it was emitted (either as precursor vapors or particles) hundreds of kilometers away. Condensation of organic vapors on fresh particles is critical for the growth of these new particles to larger sizes and eventually to cloud condensation nuclei (CCN) sizes. The semivolatile organics currently simulated by CTMs are too volatile to condense on these tiny particles with high curvature. We show that chemical aging reactions converting these semivolatile

  12. Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol

    DOE PAGES

    Zaveri, Rahul A.; Shilling, John E.; Zelenyuk, Alla; ...

    2017-12-15

    Low bulk diffusivity inside viscous semisolid atmospheric secondary organic aerosol (SOA) can prolong equilibration time scale, but its broader impacts on aerosol growth and size distribution dynamics are poorly understood. In this article, we present quantitative insights into the effects of bulk diffusivity on the growth and evaporation kinetics of SOA formed under dry conditions from photooxidation of isoprene in the presence of a bimodal aerosol consisting of Aitken (ammonium sulfate) and accumulation (isoprene or α-pinene SOA) mode particles. Aerosol composition measurements and evaporation kinetics indicate that isoprene SOA is composed of several semivolatile organic compounds (SVOCs), with some reversiblymore » reacting to form oligomers. Model analysis shows that liquid-like bulk diffusivities can be used to fit the observed evaporation kinetics of accumulation mode particles but fail to explain the growth kinetics of bimodal aerosol by significantly under-predicting the evolution of the Aitken mode. In contrast, the semisolid scenario successfully reproduces both evaporation and growth kinetics, with the interpretation that hindered partitioning of SVOCs into large viscous particles effectively promotes the growth of smaller particles that have shorter diffusion time scales. This effect has important implications for the growth of atmospheric ultrafine particles to climatically active sizes.« less

  13. Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zaveri, Rahul A.; Shilling, John E.; Zelenyuk, Alla

    Low bulk diffusivity inside viscous semisolid atmospheric secondary organic aerosol (SOA) can prolong equilibration time scale, but its broader impacts on aerosol growth and size distribution dynamics are poorly understood. In this article, we present quantitative insights into the effects of bulk diffusivity on the growth and evaporation kinetics of SOA formed under dry conditions from photooxidation of isoprene in the presence of a bimodal aerosol consisting of Aitken (ammonium sulfate) and accumulation (isoprene or α-pinene SOA) mode particles. Aerosol composition measurements and evaporation kinetics indicate that isoprene SOA is composed of several semivolatile organic compounds (SVOCs), with some reversiblymore » reacting to form oligomers. Model analysis shows that liquid-like bulk diffusivities can be used to fit the observed evaporation kinetics of accumulation mode particles but fail to explain the growth kinetics of bimodal aerosol by significantly under-predicting the evolution of the Aitken mode. In contrast, the semisolid scenario successfully reproduces both evaporation and growth kinetics, with the interpretation that hindered partitioning of SVOCs into large viscous particles effectively promotes the growth of smaller particles that have shorter diffusion time scales. This effect has important implications for the growth of atmospheric ultrafine particles to climatically active sizes.« less

  14. Secondary Organic Aerosol (SOA) from Nitrate Radical Oxidation of Monoterpenes: Effects of Temperature, Dilution, and Humidity on Aerosol Formation, Mixing, and Evaporation.

    PubMed

    Boyd, Christopher M; Nah, Theodora; Xu, Lu; Berkemeier, Thomas; Ng, Nga Lee

    2017-07-18

    Nitrate radical (NO 3 ) oxidation of biogenic volatile organic compounds (BVOC) is important for nighttime secondary organic aerosol (SOA) formation. SOA produced at night may evaporate the following morning due to increasing temperatures or dilution of semivolatile compounds. We isothermally dilute the oxidation products from the limonene+NO 3 reaction at 25 °C and observe negligible evaporation of organic aerosol via dilution. The SOA yields from limonene+NO 3 are approximately constant (∼174%) at 25 °C and range from 81 to 148% at 40 °C. Based on the difference in yields between the two temperatures, we calculated an effective enthalpy of vaporization of 117-237 kJ mol -1 . The aerosol yields at 40 °C can be as much as 50% lower compared to 25 °C. However, when aerosol formed at 25 °C is heated to 40 °C, only about 20% of the aerosol evaporates, which could indicate a resistance to aerosol evaporation. To better understand this, we probe the possibility that SOA from limonene+NO 3 and β-pinene+NO 3 reactions is highly viscous. We demonstrate that particle morphology and evaporation is dependent on whether SOA from limonene is formed before or during the formation of SOA from β-pinene. This difference in particle morphology is present even at high relative humidity (∼70%).

  15. Hygroscopic behavior of atmospheric aerosols containing nitrate salts and water-soluble organic acids

    NASA Astrophysics Data System (ADS)

    Jing, Bo; Wang, Zhen; Tan, Fang; Guo, Yucong; Tong, Shengrui; Wang, Weigang; Zhang, Yunhong; Ge, Maofa

    2018-04-01

    While nitrate salts have critical impacts on environmental effects of atmospheric aerosols, the effects of coexisting species on hygroscopicity of nitrate salts remain uncertain. The hygroscopic behaviors of nitrate salt aerosols (NH4NO3, NaNO3, Ca(NO3)2) and their internal mixtures with water-soluble organic acids were determined using a hygroscopicity tandem differential mobility analyzer (HTDMA). The nitrate salt / organic acid mixed aerosols exhibit varying phase behavior and hygroscopic growth depending upon the type of components in the particles. Whereas pure nitrate salt particles show continuous water uptake with increasing relative humidity (RH), the deliquescence transition is still observed for ammonium nitrate particles internally mixed with organic acids such as oxalic acid and succinic acid with a high deliquescence point. The hygroscopicity of submicron aerosols containing sodium nitrate and an organic acid is also characterized by continuous growth, indicating that sodium nitrate tends to exist in a liquid-like state under dry conditions. It is observed that in contrast to the pure components, the water uptake is hindered at low and moderate RH for calcium nitrate particles containing malonic acid or phthalic acid, suggesting the potential effects of mass transfer limitation in highly viscous mixed systems. Our findings improve fundamental understanding of the phase behavior and water uptake of nitrate-salt-containing aerosols in the atmospheric environment.

  16. Characteristics, sources and evolution of fine aerosol (PM1) at urban, coastal and forest background sites in Lithuania

    NASA Astrophysics Data System (ADS)

    Masalaite, A.; Holzinger, R.; Remeikis, V.; Röckmann, T.; Dusek, U.

    2017-01-01

    The chemical and isotopic composition of organic aerosol (OA) samples collected on PM1 filters was determined as a function of desorption temperature to investigate the main sources of organic carbon and the effects of photochemical processing on atmospheric aerosol. The filter samples were collected at an urban (54°38‧ N, 25°18‧ E), coastal (55°55‧ N, 21°00‧ E) and forest (55°27‧ N, 26°00' E) site in Lithuania in March 2013. They can be interpreted as winter-time samples because the monthly averaged temperature was -4 °C. The detailed chemical composition of organic compounds was analysed with a thermal desorption PTR-MS. The mass concentration of organic aerosol at the forest site was roughly by a factor of 30 lower than at the urban and coastal site. This fact could be an indication that in this cold month the biogenic secondary organic aerosol (SOA) formation was very low. Moreover, the organic aerosol collected at the forest site was more refractory and contained a larger fraction of heavy molecules with m/z > 200. The isotopic composition of the aerosol was used to differentiate the two main sources of organic aerosol in winter, i.e. biomass burning (BB) and fossil fuel (FF) combustion. Organic aerosol from biomass burning is enriched in 13C compared to OA from fossil fuel emissions. δ13COC values of the OA samples showed a positive correlation with the mass fraction of several individual organic compounds. Most of these organic compounds contained nitrogen indicating that organic nitrogen compounds formed during the combustion of biomass may be indicative of BB. Other compounds that showed negative correlations with δ13COC were possibly indicative of FF. These compounds included heavy hydrocarbons and were on the average less oxidized than the bulk organic carbon. The correlation of δ13COC and the O/C ratio was positive at low but negative at high desorption temperatures at the forest site. We propose that this might be due to

  17. Composition and formation of organic aerosol particles in the Amazon

    NASA Astrophysics Data System (ADS)

    Pöhlker, C.; Wiedemann, K.; Sinha, B.; Shiraiwa, M.; Gunthe, S. S.; Artaxo, P.; Gilles, M. K.; Kilcoyne, A. L. D.; Moffet, R. C.; Smith, M.; Weigand, M.; Martin, S. T.; Pöschl, U.; Andreae, M. O.

    2012-04-01

    We applied scanning transmission X-ray microscopy with near edge X-ray absorption fine structure (STXM-NEXAFS) analysis to investigate the morphology and chemical composition of aerosol samples from a pristine tropical environment, the Amazon Basin. The samples were collected in the Amazonian rainforest during the rainy season and can be regarded as a natural background aerosol. The samples were found to be dominated by secondary organic aerosol (SOA) particles in the fine and primary biological aerosol particles (PBAP) in the coarse mode. Lab-generated SOA-samples from isoprene and terpene oxidation as well as pure organic compounds from spray-drying of aqueous solution were measured as reference samples. The aim of this study was to investigate the microphysical and chemical properties of a tropical background aerosol in the submicron size range and its internal mixing state. The lab-generated SOA and pure organic compounds occurred as spherical and mostly homogenous droplet-like particles, whereas the Amazonian SOA particles comprised a mixture of homogeneous droplets and droplets having internal structures due to atmospheric aging. In spite of the similar morphological appearance, the Amazon samples showed considerable differences in elemental and functional group composition. According to their NEXAFS spectra, three chemically distinct types of organic material were found and could be assigned to the following three categories: (1) particles with a pronounced carboxylic acid (COOH) peak similar to those of laboratory-generated SOA particles from terpene oxidation; (2) particles with a strong hydroxy (COH) signal similar to pure carbohydrate particles; and (3) particles with spectra resembling a mixture of the first two classes. In addition to the dominant organic component, the NEXAFS spectra revealed clearly resolved potassium (K) signals for all analyzed particles. During the rainy season and in the absence of anthropogenic influence, active biota is

  18. Source apportionment of submicron organic aerosol collected from Atlanta, Georgia, during 2014-2015 using the aerosol chemical speciation monitor (ACSM)

    NASA Astrophysics Data System (ADS)

    Rattanavaraha, Weruka; Canagaratna, Manjula R.; Budisulistiorini, Sri Hapsari; Croteau, Philip L.; Baumann, Karsten; Canonaco, Francesco; Prevot, Andre S. H.; Edgerton, Eric S.; Zhang, Zhenfa; Jayne, John T.; Worsnop, Douglas R.; Gold, Avram; Shaw, Stephanie L.; Surratt, Jason D.

    2017-10-01

    The Aerodyne Aerosol Chemical Speciation Monitor (ACSM) was redeployed at the Jefferson Street (JST) site in downtown Atlanta, Georgia (GA) for 1 year (March 20, 2014-February 08, 2015) to chemically characterize non-refractory submicron particulate matter (NR-PM1) in near real-time and to assess whether organic aerosol (OA) types and amounts change from year-to-year. Submicron organic aerosol (OA) mass spectra were analyzed by season using multilinear engine (ME-2) to apportion OA subtypes to potential sources and chemical processes. A suite of real-time collocated measurements from the Southeastern Aerosol Research and Characterization (SEARCH) network was compared with ME-2 factor solutions to aid in the interpretation of OA subtypes during each season. OA tracers measured from high-volume filter samples using gas chromatography interfaced with electron ionization-mass spectrometry (GC/EI-MS) also aided in identifying OA sources. The initial application of ME-2 to the yearlong ACSM dataset revealed that OA source apportionment by season was required to better resolve sporadic OA types. Spring and fall OA mass spectral datasets were separated into finer periods to capture potential OA sources resulting from non-homogeneous emissions during transitioning periods. NR-PM1 was highest in summer (16.7 ± 8.4 μg m-3) and lowest in winter (8.0 ± 5.7 μg m-3), consistent with prior studies. OA dominated NR-PM1 mass (56-74% on average) in all seasons. Hydrocarbon-like OA (HOA) from primary emissions was observed in all seasons, averaging 5-22% of total OA mass. Strong correlations of HOA with carbon monoxide (CO) (R = 0.71-0.88) and oxides of nitrogen (NOx) (R = 0.55-0.79) indicated that vehicular traffic was the likely source. Biomass burning OA (BBOA) was observed in all seasons, with lower contributions (2%) in summer and higher in colder seasons (averaging 8-20% of total OA mass). BBOA correlated strongly with levoglucosan (R = 0.78-0.95) during colder seasons

  19. Molecular Characterization of Brown Carbon (BrC) Chromophores in Secondary Organic Aerosol Generated From Photo-Oxidation of Toluene

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lin, Peng; Liu, Jiumeng; Shilling, John E.

    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) dependmore » 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

  20. Direct Aqueous Photochemistry of Isoprene High-NOx Secondary Organic Aerosol

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Nguyen, Tran B.; Laskin, Alexander; Laskin, Julia

    2012-05-17

    Secondary organic aerosol (SOA) generated from the high-NOx photooxidation of isoprene was dissolved in water and irradiated with {lambda} > 290 nm light to simulate direct photolytic processing of organics in atmospheric water droplets. High-resolution mass spectrometry was used to characterize the composition at four time intervals (0, 1, 2, and 4 h). Photolysis resulted in the decomposition of high molecular weight (MW) oligomers, reducing the average length of organics by 2 carbon units. Approximately 65% by count of SOA molecules decomposed during photolysis, accompanied by the formation of new products. An average of 30 % of the organic massmore » was modified after 4 h of direct photolysis. In contrast, only a small fraction of the mass (<2 %), belonging primarily to organic nitrates, decomposed in the absence of irradiation by hydrolysis. We observed a statistically-significant increase in average O/C, decrease in H/C, and increase in N/C ratios resulting from photolysis. Furthermore, the concentration of aromatic compounds increased significantly during photolysis. Approximately 10 % of photodegraded compounds and 50 % of the photoproducts contain nitrogen. Organic nitrates and multifunctional oligomers were identified as compounds degraded by photolysis. Low-MW 0N (compounds with 0 nitrogen atoms in their structure) and 2N compounds were the dominant photoproducts. Fragmentation experiments using tandem mass spectrometry (MSn, n = 2-3) indicate that the 2N products are likely heterocyclic/aromatic and are tentatively identified as furoxans. Although the exact mechanism is unclear, these 2N heterocyclic compounds are produced by reactions between photochemically-formed aqueous NOx species and SOA organics.« less