Development of Atmospheric Chemistry-Aerosol Transport Model for Bioavailable Iron From Dust and Combustion Source

NASA Astrophysics Data System (ADS)

Ito, A.; Feng, Y.

2009-12-01

An accurate prediction of bioavailable iron fraction for ocean biota is hampered by uncertainties in modeling soluble iron fractions in atmospheric aerosols. It has been proposed that atmospheric processing of mineral aerosols by anthropogenic pollutants may be a key pathway to transform insoluble iron into soluble forms. The dissolution of dust minerals strongly depends on solution pH, which is sensitive to the heterogeneous uptake of soluble gases by the dust particle. Due to the complexity, previous model assessments generally use a common assumption in thermodynamical equilibrium between gas and aerosol phases. Here, we compiled an emission inventory of iron from combustion and dust source, and incorporated a dust iron dissolution scheme in a global chemistry-aerosol transport model (IMPACT). We will examine and discuss the uncertainties in estimation of dissolved iron as well as comparisons of the model results with available observations.

Bounding the heterogeneous gas uptake on aerosols and ground using resistance model

NASA Astrophysics Data System (ADS)

Su, H.; Li, M.; Cheng, Y.

2017-12-01

Heterogeneous uptake on aerosols and ground are potential important atmospheric sinks for gases. Different schemes have been used to characterize the dry deposition and heterogeneous aerosol gas uptake, although they share similar characteristics. In this work, we propose a unified resistance model to compare the uptake flux on both ground and aerosols, to identify the dominate heterogeneous process within the planetary boundary layer (PBL). The Gamma(eq) is introduced to represent the reactive uptake coefficient on aerosols when these two processes are equally important. It's shown that Gamma(eq) is proportional to the dry deposition velocity, inversely proportional to aerosol surface area concentration. Under typical regional background condition, Gamma(eq) vary from 1x10-5 to 4x10-4 with gas species, land-use type and season, which indicates that aerosol gas uptake should be included in atmospheric models when uptake coefficient higher than 10-5. We address the importance of heterogeneous gas uptake on aerosols over ground especially for ozone uptake on liquid organic aerosols and for marine PBL atmosphere.

When the Sun's Away, N2O5 Comes Out to Play: An Updated Analysis of Ambient N2O5 Heterogeneous Chemistry

NASA Astrophysics Data System (ADS)

McDuffie, E. E.; Brown, S. S.

2017-12-01

The heterogeneous chemistry of N2O5 impacts the budget of tropospheric oxidants, which directly controls air quality at Earth's surface. The reaction between gas-phase N2O5 and aerosol particles occurs largely at night, and is therefore more important during the less-intensively-studied winter season. Though N2O5-aerosol interactions are vital for the accurate understanding and simulation of tropospheric chemistry and air quality, many uncertainties persist in our understanding of how various environmental factors influence the reaction rate and probability. Quantitative and accurate evaluation of these factors directly improves the predictive capabilities of atmospheric models, used to inform mitigation strategies for wintertime air pollution. In an update to last year's presentation, The Wintertime Fate of N2O5: Observations and Box Model Analysis for the 2015 WINTER Aircraft Campaign, this presentation will focus on recent field results regarding new information about N2O5 heterogeneous chemistry and future research directions.

Challenges to producing a long-term stratospheric aerosol climatology for chemistry and climate

NASA Astrophysics Data System (ADS)

Thomason, Larry; Vernier, Jean-Paul; Bourassa, Adam; Rieger, Landon; Luo, Beiping; Peter, Thomas; Arfeuille, Florian

2016-04-01

Stratospheric aerosol data sets are key inputs for climate models (GCMs, CCMs) particularly for understanding the role of volcanoes on climate and as a surrogate for understanding the potential of human-derived stratospheric aerosol as mitigation for global warming. In addition to supporting activities of individual climate models, the data sets also act as a historical input to the activities of SPARC's Chemistry-Climate Model Initiative (CCMI) and the World Climate Research Programme's Coupled Model Intercomparison Project (CMIP). One such data set was produced in 2004 as a part of the SPARC Assessment of Stratospheric Aerosol Properties (ASAP), extending from 1979 and 2004. It was primarily constructed from the Stratospheric Aerosol and Gas Experiment series of instruments but supplemented by data from other space-based sources and a number of ground-based and airborne instruments. Updates to this data set have expanded the timeframe to span from 1850 through 2014 through the inclusion of data from additional sources, such as photometer data and ice core analyses. Fundamentally, there are limitations to the reliability of the optical properties of aerosol inferred from even the most complete single instrument data sets. At the same time, the heterogeneous nature of the underlying data to this historical data set produces considerable challenges to the production of a climate data set which is both homogeneous and reliable throughout its timespan. In this presentation, we will discuss the impact of this heterogeneity showing specific examples such as the SAGE II to OSIRIS/CALIPSO transition in 2005. Potential solutions to these issues will also be discussed.

Nighttime chemical evolution of aerosol and trace gases in a power plant plume: Implications for secondary organic nitrate and organosulfate aerosol formation, NO3 radical chemistry, and N2O5 heterogeneous hydrolysis

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

Zaveri, R.A.; Kleinman, L.; Berkowitz, C. M.

2010-06-01

Nighttime chemical evolution of aerosol and trace gases in a coal-fired power plant plume was monitored with the Department of Energy Grumman Gulfstream-1 aircraft during the 2002 New England Air Quality Study field campaign. Quasi-Lagrangian sampling in the plume at increasing downwind distances and processing times was guided by a constant-volume balloon that was released near the power plant at sunset. While no evidence of fly ash particles was found, concentrations of particulate organics, sulfate, and nitrate were higher in the plume than in the background air. The enhanced sulfate concentrations were attributed to direct emissions of gaseous H{sub 2}SO{submore » 4}, some of which had formed new particles as evidenced by enhanced concentrations of nucleation-mode particles in the plume. The aerosol species were internally mixed and the particles were acidic, suggesting that particulate nitrate was in the form of organic nitrate. The enhanced particulate organic and nitrate masses in the plume were inferred as secondary organic aerosol, which was possibly formed from NO{sub 3} radical-initiated oxidation of isoprene and other trace organic gases in the presence of acidic sulfate particles. Microspectroscopic analysis of particle samples suggested that some sulfate was in the form of organosulfates. Microspectroscopy also revealed the presence of sp{sup 2} hybridized C = C bonds, which decreased with increasing processing time in the plume, possibly because of heterogeneous chemistry on particulate organics. Constrained plume modeling analysis of the aircraft and tetroon observations showed that heterogeneous hydrolysis of N{sub 2}O{sub 5} was negligibly slow. These results have significant implications for several issues related to the impacts of power plant emissions on air quality and climate.« less

Characterizing physical properties and heterogeneous chemistry of single particles in air using optical trapping-Raman spectroscopy

NASA Astrophysics Data System (ADS)

Gong, Z.; Wang, C.; Pan, Y. L.; Videen, G.

2017-12-01

Heterogeneous reactions of solid particles in a gaseous environment are of increasing interest; however, most of the heterogeneous chemistry studies of airborne solids were conducted on particle ensembles. A close examination on the heterogeneous chemistry between single particles and gaseous-environment species is the key to elucidate the fundamental mechanisms of hydroscopic growth, cloud nuclei condensation, secondary aerosol formation, etc., and reduce the uncertainty of models in radiative forcing, climate change, and atmospheric chemistry. We demonstrate an optical trapping-Raman spectroscopy (OT-RS) system to study the heterogeneous chemistry of the solid particles in air at single-particle level. Compared to other single-particle techniques, optical trapping offers a non-invasive, flexible, and stable method to isolate single solid particle from substrates. Benefited from two counter-propagating hollow beams, the optical trapping configuration is adaptive to trap a variety of particles with different materials from inorganic substitution (carbon nanotubes, silica, etc.) to organic, dye-doped polymers and bioaerosols (spores, pollen, etc.), with different optical properties from transparent to strongly absorbing, with different sizes from sub-micrometers to tens of microns, or with distinct morphologies from loosely packed nanotubes to microspheres and irregular pollen grains. The particles in the optical trap may stay unchanged, surface degraded, or optically fragmented according to different laser intensity, and their physical and chemical properties are characterized by the Raman spectra and imaging system simultaneously. The Raman spectra is able to distinguish the chemical compositions of different particles, while the synchronized imaging system can resolve their physical properties (sizes, shapes, morphologies, etc.). The temporal behavior of the trapped particles also can be monitored by the OT-RS system at an indefinite time with a resolution from

Heterogeneous chemistry: a mechanism missing in current models to explain secondary inorganic aerosol formation during the January 2013 haze episode in North China

DOE PAGES

Zheng, B.; Zhang, Q.; Zhang, Y.; ...

2015-02-25

Severe regional haze pollution events occurred in eastern and central China in January 2013, which had adverse effects on the environment and public health. Extremely high levels of particulate matter with aerodynamic diameter of 2.5 μm or less (PM 2.5) with dominant components of sulfate and nitrate are responsible for the haze pollution. Although heterogeneous chemistry is thought to play an important role in the production of sulfate and nitrate during haze episodes, few studies have comprehensively evaluated the effect of heterogeneous chemistry on haze formation in China by using the 3-D models due to of a lack of treatmentsmore » for heterogeneous reactions in most climate and chemical transport models. In this work, the WRF-CMAQ model with newly added heterogeneous reactions is applied to East Asia to evaluate the impacts of heterogeneous chemistry and the meteorological anomaly during January 2013 on regional haze formation. As the parameterization of heterogeneous reactions on different types of particles is not well established yet, we arbitrarily selected the uptake coefficients from reactions on dust particles and then conducted several sensitivity runs to find the value that can best match observations. The revised CMAQ with heterogeneous chemistry not only captures the magnitude and temporal variation of sulfate and nitrate, but also reproduces the enhancement of relative contribution of sulfate and nitrate to PM 2.5 mass from clean days to polluted haze days. Finally, these results indicate the significant role of heterogeneous chemistry in regional haze formation and improve the understanding of the haze formation mechanisms during the January 2013 episode.« less

Probing functional groups at the gas-aerosol interface using heterogeneous titration reactions: a tool for predicting aerosol health effects?

PubMed

Setyan, Ari; Sauvain, Jean-Jacques; Guillemin, Michel; Riediker, Michael; Demirdjian, Benjamin; Rossi, Michel J

2010-12-17

The complex chemical and physical nature of combustion and secondary organic aerosols (SOAs) in general precludes the complete characterization of both bulk and interfacial components. The bulk composition reveals the history of the growth process and therefore the source region, whereas the interface controls--to a large extent--the interaction with gases, biological membranes, and solid supports. We summarize the development of a soft interrogation technique, using heterogeneous chemistry, for the interfacial functional groups of selected probe gases [N(CH(3))(3), NH(2)OH, CF(3)COOH, HCl, O(3), NO(2)] of different reactivity. The technique reveals the identity and density of surface functional groups. Examples include acidic and basic sites, olefinic and polycyclic aromatic hydrocarbon (PAH) sites, and partially and completely oxidized surface sites. We report on the surface composition and oxidation states of laboratory-generated aerosols and of aerosols sampled in several bus depots. In the latter case, the biomarker 8-hydroxy-2'-deoxyguanosine, signaling oxidative stress caused by aerosol exposure, was isolated. The increase in biomarker levels over a working day is correlated with the surface density N(i)(O3) of olefinic and/or PAH sites obtained from O(3) uptakes as well as with the initial uptake coefficient, γ(0), of five probe gases used in the field. This correlation with γ(0) suggests the idea of competing pathways occurring at the interface of the aerosol particles between the generation of reactive oxygen species (ROS) responsible for oxidative stress and cellular antioxidants.

Modeling the Relationships Between Aerosol Properties and the Direct and Indirect Effects of Aerosols on Climate

NASA Technical Reports Server (NTRS)

Toon, Owen B.

1994-01-01

Aerosols may affect climate directly by scattering and absorbing visible and infrared energy, They may also affect climate indirectly by modifying the properties of clouds through microphysical processes, and by altering abundances of radiatively important gases through heterogeneous chemistry. Researchers understand which aerosol properties control the direct effect of aerosols on the radiation budget. Unfortunately, despite an abundance of data on certain types of aerosols, much work remains to be done to determine the values of these properties. For instance we have little idea about the global distribution, seasonal variation, or interannual variability of the aerosol optical depth. Also we do not know the visible light absorption properties of tropical aerosols which may contain much debris from slash and burn agriculture. A positive correlation between aerosol concentrations and albedos of marine stratus clouds is observed, and the causative microphysics is understood. However, models suggest that it is difficult to produce new particles in the marine boundary layer. Some modelers have suggested that the particles in the marine boundary layer may originate in the free troposphere and be transported into the boundary layer. Others argue that the aerosols are created in the marine boundary layer. There are no data linking aerosol concentration and cirrus cloud albedo, and models suggest cirrus properties may not be very sensitive to aerosol abundance. There is clear evidence of a radiatively significant change in the global lower stratospheric ozone abundance during the past few decades. These changes are caused by heterogeneous chemical reactions occurring on the surfaces of particles. The rates of these reactions depend upon the chemical composition of the particles. Although rapid advances in understanding heterogeneous chemistry have been made, much remains to be done.

Impacts of Mt Pinatubo volcanic aerosol on the tropical stratosphere in chemistry-climate model simulations using CCMI and CMIP6 stratospheric aerosol data

NASA Astrophysics Data System (ADS)

Revell, Laura E.; Stenke, Andrea; Luo, Beiping; Kremser, Stefanie; Rozanov, Eugene; Sukhodolov, Timofei; Peter, Thomas

2017-11-01

To simulate the impacts of volcanic eruptions on the stratosphere, chemistry-climate models that do not include an online aerosol module require temporally and spatially resolved aerosol size parameters for heterogeneous chemistry and aerosol radiative properties as a function of wavelength. For phase 1 of the Chemistry-Climate Model Initiative (CCMI-1) and, later, for phase 6 of the Coupled Model Intercomparison Project (CMIP6) two such stratospheric aerosol data sets were compiled, whose functional capability and representativeness are compared here. For CCMI-1, the SAGE-4λ data set was compiled, which hinges on the measurements at four wavelengths of the SAGE (Stratospheric Aerosol and Gas Experiment) II satellite instrument and uses ground-based lidar measurements for gap-filling immediately after the 1991 Mt Pinatubo eruption, when the stratosphere was too optically opaque for SAGE II. For CMIP6, the new SAGE-3λ data set was compiled, which excludes the least reliable SAGE II wavelength and uses measurements from CLAES (Cryogenic Limb Array Etalon Spectrometer) on UARS, the Upper Atmosphere Research Satellite, for gap-filling following the Mt Pinatubo eruption instead of ground-based lidars. Here, we performed SOCOLv3 (Solar Climate Ozone Links version 3) chemistry-climate model simulations of the recent past (1986-2005) to investigate the impact of the Mt Pinatubo eruption in 1991 on stratospheric temperature and ozone and how this response differs depending on which aerosol data set is applied. The use of SAGE-4λ results in heating and ozone loss being overestimated in the tropical lower stratosphere compared to observations in the post-eruption period by approximately 3 K and 0.2 ppmv, respectively. However, less heating occurs in the model simulations based on SAGE-3λ, because the improved gap-filling procedures after the eruption lead to less aerosol loading in the tropical lower stratosphere. As a result, simulated tropical temperature anomalies in

Tropospheric Trace Gas Interactions with Aerosols

NASA Technical Reports Server (NTRS)

Penner, Joyce E.; Maddrea, George L., Jr. (Technical Monitor)

2002-01-01

Tropospheric aerosols are of considerable environmental importance. They modify the radiative budget of Earth by scattering and absorbing radiation, and by providing nuclei for cloud formation. Additionally, they provide surfaces for heterogeneous and multiphase reactions that affect tropospheric chemistry. For example, Dentener and Crutzen (1993) showed that reactions of N2O5 and NO3 with sulfate aerosols may significantly alter the tropospheric concentrations of NO(x), O3, and OH by converting NOx to HNO3 which is rapidly removed by precipitation. Zhang et al. (1994) assumed these same reactions would occur on dust aerosols and showed that dust outbreaks may reduce NO(x) levels by up to 50%. Dentener et al. (1996) studied the possible effect of reactions on dust on sulfate, nitrate, and O3 concentration. Heterogeneous and multiphase reactions on aerosols may also perturb the sulfur cycle the chlorine cycle and the bromine cycle. Because these reactions can release free chlorine and free bromine they might lead to the destruction of ozone in the marine boundary layer that may be important to include in models of tropospheric chemistry. The goal of our proposed work is to examine the role of heterogeneous and multiphase reactions in the tropospheric cycles of reactive nitrogen and sulfur.

Heterogeneous Chemistry of HONO on Liquid Sulfuric Acid: A New Mechanism of Chlorine Activation on Stratospheric Sulfate Aerosols

NASA Technical Reports Server (NTRS)

Zhang, Renyi; Leu, Ming-Taun; Keyser, Leon F.

1996-01-01

Heterogeneous chemistry of nitrous acid (HONO) on liquid sulfuric acid (H2SO4) Was investigated at conditions that prevail in the stratosphere. The measured uptake coefficient (gamma) of HONO on H2SO4 increased with increasing acid content, ranging from 0.03 for 65 wt % to about 0.1 for 74 wt %. In the aqueous phase, HONO underwent irreversible reaction with H2SO4 to form nitrosylsulfuric acid (NO(+)HSO4(-). At temperatures below 230 K, NO(+)HSO4(-) was observed to be stable and accumulated in concentrated solutions (less than 70 wt % H2SO4) but was unstable and quickly regenerated HONO in dilute solutions (less than 70 wt %). HCl reacted with HONO dissolved in sulfuric acid, releasing gaseous nitrosyl chloride (ClNO). The reaction probability between HCl and HONO varied from 0.01 to 0.02 for 60-72 wt % H2SO4. In the stratosphere, ClNO photodissociates rapidly to yield atomic chlorine, which catalytically destroys ozone. Analysis of the laboratory data reveals that the reaction of HCl with HONO on sulfate aerosols can affect stratospheric ozone balance during elevated sulfuric acid loadings after volcanic eruptions or due to emissions from the projected high-speed civil transport (HSCT). The present results may have important implications on the assessment of environmental acceptability of HSCT.

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.

Importance of Unimolecular HO 2 Elimination in the Heterogeneous OH Reaction of Highly Oxygenated Tartaric Acid Aerosol

DOE PAGES

Cheng, Chiu Tung; Chan, Man Nin; Wilson, Kevin R.

2016-07-09

Oxygenated organic molecules are abundant in atmospheric aerosols and are transformed by oxidation reactions near the aerosol surface by gas-phase oxidants such as hydroxyl (OH) radicals. To gain better insights into how the structure of an organic molecule, particularly in the presence of hydroxyl groups, controls the heterogeneous reaction mechanisms of oxygenated organic compounds, this paper investigates the OH-radical initiated oxidation of aqueous tartaric acid (C 4H 6O 6) droplets using an aerosol flow tube reactor. The molecular composition of the aerosols before and after reaction is characterized by a soft atmospheric pressure ionization source (Direct Analysis in Real Time)more » coupled with a high-resolution mass spectrometer. The aerosol mass spectra reveal that four major reaction products are formed: a single C 4 functionalization product (C 4H 4O 6) and three C 3 fragmentation products (C 3H 4O 4, C 3H 2O 4, and C 3H 2O 5). The C 4 functionalization product does not appear to originate from peroxy radical self-reactions but instead forms via an α-hydroxylperoxy radical produced by a hydrogen atom abstraction by OH at the tertiary carbon site. The proximity of a hydroxyl group to peroxy group enhances the unimolecular HO 2 elimination from the α-hydroxylperoxy intermediate. This alcohol-to-ketone conversion yields 2-hydroxy-3-oxosuccinic acid (C 4H 4O 6), the major reaction product. While in general, C–C bond scission reactions are expected to dominate the chemistry of organic compounds with high average carbon oxidation states (OS C), our results show that molecular structure can play a larger role in the heterogeneous transformation of tartaric acid (OS C = 1.5). Finally, these results are also compared with two structurally related dicarboxylic acids (succinic acid and 2,3-dimethylsuccinic acid) to elucidate how the identity and location of functional groups (methyl and hydroxyl groups) alter heterogeneous reaction mechanisms.« less

Chemistry of Atmospheric Aerosols at Pacifichem 2015 Congress

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

Nizkorodov, Sergey

This grant was used to provide participant support for a symposium entitled “Chemistry of Atmospheric Aerosols” at the 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem) that took place in Honolulu, Hawaii, USA, on December 15-20, 2015. The objective was to help attract both distinguished scientists as well as more junior researchers, including graduate students, to this international symposium by reducing the financial barrier for its attendance. It was the second time a symposium devoted to Atmospheric Aerosols was part of the Pacifichem program. This symposium provided a unique opportunity for the scientists from different countries to gather inmore » one place and discuss the cutting edge advances in the cross-disciplinary areas of aerosol research. To achieve the highest possible impact, the PI and the symposium co-organizers actively advertised the symposium by e-mail and by announcements at other conferences. A number of people responded, and the end result was a very busy program with about 100 oral and poster presentation described in the attached PDF file. Presentations by invited speakers occupied approximately 30% of time in each of the sessions. In addition to the invited speakers, each session also had contributed presentations, including those by graduate students and postdoctoral researchers. This symposium gathered established aerosol chemists from a number of countries including United States, Canada, China, Japan, Korea, Australia, Brazil, Hongkong, Switzerland, France, and Germany. There were plenty of time for the attendees to discuss new ideas and potential collaborations both during the oral sessions and at the poster sessions of the symposium. The symposium was very beneficial to graduate student researchers, postdoctoral fellows, and junior researchers whose prior exposure to international aerosol chemistry science had been limited. The symposium provided junior researchers with a much broader perspective of

Laboratory studies of stratospheric aerosol chemistry

NASA Technical Reports Server (NTRS)

Molina, Mario J.

1996-01-01

In this report we summarize the results of the two sets of projects funded by the NASA grant NAG2-632, namely investigations of various thermodynamic and nucleation properties of the aqueous acid system which makes up stratospheric aerosols, and measurements of reaction probabilities directly on ice aerosols with sizes corresponding to those of polar stratospheric cloud particles. The results of these investigations are of importance for the assessment of the potential stratospheric effects of future fleets of supersonic aircraft. In particular, the results permit to better estimate the effects of increased amounts of water vapor and nitric acid (which forms from nitrogen oxides) on polar stratospheric clouds and on the chemistry induced by these clouds.

Gaseous Chemistry and Aerosol Mechanism Developments for Version 3.5.1 of the Online Regional Model, WRF-Chem

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

Archer-Nicholls, Scott; Lowe, Douglas; Utembe, Steve

We have made a number of developments in the regional coupled model WRF-Chem, with the aim of making the model more suitable for prediction of atmospheric composition and of interactions between air quality and weather. We have worked on the European domain, with a particular focus on making the model suitable for the study of night time chemistry and oxidation by the nitrate radical in the UK atmosphere. A reduced form of the Common Reactive Intermediates gas-phase chemical mechanism (CRIv2-R5) has been implemented to enable more explicit simulation of VOC degradation. N2O5 heterogeneous chemistry has been added to the existingmore » sectional MOSAIC aerosol module, and coupled to both the CRIv2-R5 and existing CBM-Z gas phase scheme. Modifications have also been made to the sea-spray aerosol emission representation, allowing the inclusion of primary organic material in sea-spray aerosol. Driven by appropriate emissions, wind fields and chemical boundary conditions, implementation of the different developments is illustrated in order to demonstrate the impact that these changes have in the North-West European domain. These developments are now part of the freely available WRF-Chem distribution.« less

WRF-Chem model predictions of the regional impacts of N2O5 heterogeneous processes on night-time chemistry over north-western Europe

NASA Astrophysics Data System (ADS)

Lowe, D.; Archer-Nicholls, S.; Morgan, W.; Allan, J.; Utembe, S.; Ouyang, B.; Aruffo, E.; Le Breton, M.; Zaveri, R. A.; Di Carlo, P.; Percival, C.; Coe, H.; Jones, R.; McFiggans, G.

2015-02-01

Chemical modelling studies have been conducted over north-western Europe in summer conditions, showing that night-time dinitrogen pentoxide (N2O5) heterogeneous reactive uptake is important regionally in modulating particulate nitrate and has a~modest influence on oxidative chemistry. Results from Weather Research and Forecasting model with Chemistry (WRF-Chem) model simulations, run with a detailed volatile organic compound (VOC) gas-phase chemistry scheme and the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) sectional aerosol scheme, were compared with a series of airborne gas and particulate measurements made over the UK in July 2010. Modelled mixing ratios of key gas-phase species were reasonably accurate (correlations with measurements of 0.7-0.9 for NO2 and O3). However modelled loadings of particulate species were less accurate (correlation with measurements for particulate sulfate and ammonium were between 0.0 and 0.6). Sulfate mass loadings were particularly low (modelled means of 0.5-0.7 μg kg-1air, compared with measurements of 1.0-1.5 μg kg-1air). Two flights from the campaign were used as test cases - one with low relative humidity (RH) (60-70%), the other with high RH (80-90%). N2O5 heterogeneous chemistry was found to not be important in the low-RH test case; but in the high-RH test case it had a strong effect and significantly improved the agreement between modelled and measured NO3 and N2O5. When the model failed to capture atmospheric RH correctly, the modelled NO3 and N2O5 mixing ratios for these flights differed significantly from the measurements. This demonstrates that, for regional modelling which involves heterogeneous processes, it is essential to capture the ambient temperature and water vapour profiles. The night-time NO3 oxidation of VOCs across the whole region was found to be 100-300 times slower than the daytime OH oxidation of these compounds. The difference in contribution was less for alkenes (× 80) and

WRF-Chem model predictions of the regional impacts of N 2O 5 heterogeneous processes on night-time chemistry over north-western Europe

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

Lowe, Douglas; Archer-Nicholls, Scott; Morgan, Will

Chemical modelling studies have been conducted over north-western Europe in summer conditions, showing that night-time dinitrogen pentoxide (N 2O 5) heterogeneous reactive uptake is important regionally in modulating particulate nitrate and has a~modest influence on oxidative chemistry. Results from Weather Research and Forecasting model with Chemistry (WRF-Chem) model simulations, run with a detailed volatile organic compound (VOC) gas-phase chemistry scheme and the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) sectional aerosol scheme, were compared with a series of airborne gas and particulate measurements made over the UK in July 2010. Modelled mixing ratios of key gas-phase species were reasonablymore » accurate (correlations with measurements of 0.7–0.9 for NO 2 and O 3). However modelled loadings of particulate species were less accurate (correlation with measurements for particulate sulfate and ammonium were between 0.0 and 0.6). Sulfate mass loadings were particularly low (modelled means of 0.5–0.7 μg kg −1 air, compared with measurements of 1.0–1.5 μg kg −1 air). Two flights from the campaign were used as test cases – one with low relative humidity (RH) (60–70%), the other with high RH (80–90%). N 2O 5 heterogeneous chemistry was found to not be important in the low-RH test case; but in the high-RH test case it had a strong effect and significantly improved the agreement between modelled and measured NO 3 and N 2O 5. When the model failed to capture atmospheric RH correctly, the modelled NO 3 and N 2O 5 mixing ratios for these flights differed significantly from the measurements. This demonstrates that, for regional modelling which involves heterogeneous processes, it is essential to capture the ambient temperature and water vapour profiles. The night-time NO 3 oxidation of VOCs across the whole region was found to be 100–300 times slower than the daytime OH oxidation of these compounds. The difference in

WRF-Chem model predictions of the regional impacts of N 2O 5 heterogeneous processes on night-time chemistry over north-western Europe

DOE PAGES

Lowe, Douglas; Archer-Nicholls, Scott; Morgan, Will; ...

2015-02-09

Chemical modelling studies have been conducted over north-western Europe in summer conditions, showing that night-time dinitrogen pentoxide (N 2O 5) heterogeneous reactive uptake is important regionally in modulating particulate nitrate and has a~modest influence on oxidative chemistry. Results from Weather Research and Forecasting model with Chemistry (WRF-Chem) model simulations, run with a detailed volatile organic compound (VOC) gas-phase chemistry scheme and the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) sectional aerosol scheme, were compared with a series of airborne gas and particulate measurements made over the UK in July 2010. Modelled mixing ratios of key gas-phase species were reasonablymore » accurate (correlations with measurements of 0.7–0.9 for NO 2 and O 3). However modelled loadings of particulate species were less accurate (correlation with measurements for particulate sulfate and ammonium were between 0.0 and 0.6). Sulfate mass loadings were particularly low (modelled means of 0.5–0.7 μg kg −1 air, compared with measurements of 1.0–1.5 μg kg −1 air). Two flights from the campaign were used as test cases – one with low relative humidity (RH) (60–70%), the other with high RH (80–90%). N 2O 5 heterogeneous chemistry was found to not be important in the low-RH test case; but in the high-RH test case it had a strong effect and significantly improved the agreement between modelled and measured NO 3 and N 2O 5. When the model failed to capture atmospheric RH correctly, the modelled NO 3 and N 2O 5 mixing ratios for these flights differed significantly from the measurements. This demonstrates that, for regional modelling which involves heterogeneous processes, it is essential to capture the ambient temperature and water vapour profiles. The night-time NO 3 oxidation of VOCs across the whole region was found to be 100–300 times slower than the daytime OH oxidation of these compounds. The difference in

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

NASA Astrophysics Data System (ADS)

Shiraiwa, M.; Garland, R.; Pöschl, U.

2009-04-01

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

Ozone impacts of gas-aerosol uptake in global chemistry transport models

NASA Astrophysics Data System (ADS)

Stadtler, Scarlet; Simpson, David; Schröder, Sabine; Taraborrelli, Domenico; Bott, Andreas; Schultz, Martin

2018-03-01

The impact of six heterogeneous gas-aerosol uptake reactions on tropospheric ozone and nitrogen species was studied using two chemical transport models, the Meteorological Synthesizing Centre-West of the European Monitoring and Evaluation Programme (EMEP MSC-W) and the European Centre Hamburg general circulation model combined with versions of the Hamburg Aerosol Model and Model for Ozone and Related chemical Tracers (ECHAM-HAMMOZ). Species undergoing heterogeneous reactions in both models include N2O5, NO3, NO2, O3, HNO3, and HO2. Since heterogeneous reactions take place at the aerosol surface area, the modelled surface area density (Sa) of both models was compared to a satellite product retrieving the surface area. This comparison shows a good agreement in global pattern and especially the capability of both models to capture the extreme aerosol loadings in east Asia. The impact of the heterogeneous reactions was evaluated by the simulation of a reference run containing all heterogeneous reactions and several sensitivity runs. One reaction was turned off in each sensitivity run to compare it with the reference run. The analysis of the sensitivity runs confirms that the globally most important heterogeneous reaction is the one of N2O5. Nevertheless, NO2, HNO3, and HO2 heterogeneous reactions gain relevance particularly in east Asia due to the presence of high NOx concentrations and high Sa in the same region. The heterogeneous reaction of O3 itself on dust is of minor relevance compared to the other heterogeneous reactions. The impacts of the N2O5 reactions show strong seasonal variations, with the biggest impacts on O3 in springtime when photochemical reactions are active and N2O5 levels still high. Evaluation of the models with northern hemispheric ozone surface observations yields a better agreement of the models with observations in terms of concentration levels, variability, and temporal correlations at most sites when the heterogeneous reactions are

Modeling of meteorology, chemistry and aerosol for the 2017 Utah Winter Fine Particle Study

NASA Astrophysics Data System (ADS)

McKeen, S. A.; Angevine, W. M.; McDonald, B.; Ahmadov, R.; Franchin, A.; Middlebrook, A. M.; Fibiger, D. L.; McDuffie, E. E.; Womack, C.; Brown, S. S.; Moravek, A.; Murphy, J. G.; Trainer, M.

2017-12-01

The Utah Winter Fine Particle Study (UWFPS-17) field project took place during January and February of 2017 within the populated region of the Great Salt Lake, Utah. The study focused on understanding the meteorology and chemistry associated with high particulate matter (PM) levels often observed near Salt Lake City during stable wintertime conditions. Detailed composition and meteorological observations were taken from the NOAA Twin-Otter aircraft and several surface sites during the study period, and extremely high aerosol conditions were encountered for two cold-pool episodes occurring in the last 2 weeks of January. A clear understanding of the photochemical and aerosol processes leading to these high PM events is still lacking. Here we present high spatiotemporal resolution simulations of meteorology, PM and chemistry over Utah from January 13 to February 1, 2017 using the WRF/Chem photochemical model. Correctly characterizing the meteorology is difficult due to the complex terrain and shallow inversion layers. We discuss the approach and limitations of the simulated meteorology, and evaluate low-level pollutant mixing using vertical profiles from missed airport approaches by the NOAA Twin-Otter performed routinely during each flight. Full photochemical simulations are calculated using NOx, ammonia and VOC emissions from the U.S. EPA NEI-2011 emissions inventory. Comparisons of the observed vertical column amounts of NOx, ammonia, aerosol nitrate and ammonium with model results shows the inventory estimates for ammonia emissions are low by a factor of four and NOx emissions are low by nearly a factor of two. The partitioning of both nitrate and NH3 between gas and particle phase depends strongly on the NH3 and NOx emissions to the model and calculated NOx to nitrate conversion rates. These rates are underestimated by gas-phase chemistry alone, even though surface snow albedo increases photolysis rates by nearly a factor of two. Several additional conversion

Using WRF-Chem to investigate the impact of night time nitrate radical chemistry and N2O5 heterogeneous chemistry on the chemical composition of the UK troposphere.

NASA Astrophysics Data System (ADS)

Archer-Nicholls, S.; Lowe, D.; Utembe, S.; McFiggans, G.

2012-04-01

It is believed that NO3 is the primary oxidant at night time, significantly impacting ozone formation, rain acidification and the formation and transformation of aerosols, particularly through the formation of the ammonium nitrate particulate (Allan et. al., 2000). However, many of the basic chemical processes controlling the formation and removal of NO3, in particular, the N2O5 heterogeneous reactions, are often not represented in models, although general parameterisations have been developed (c.f. Bertram & Thornton, 2009). The ROle of Night time chemistry in controlling the Oxidising Capacity of the atmOsphere (RONOCO) campaign is a project being funded by NERC and being carried out by a collaboration of UK Universities. It aims to better understand the role of the NO3 radical on the chemistry of the night time atmosphere, its oxidation capacity and thus its overall effects on the composition of the troposphere. The Weather Research and Forecasting model with Chemistry (WRF-Chem) is a state of the art regional climate model with fully coupled online air quality and meteorological components allowing for better resolution of aerosol and gas-phase chemistry (Grell et. al., 2005). It has been extended to include the Common Representative Intermediates scheme (CRIv2-R5) (Watson et. al., 2008), a reduced chemical scheme designed to simulate the atmospheric degradation of 220 species of hydrocarbons and VOCs. The MOSAIC aerosol scheme (Zaveri et. al., 2008), has been extended to include a reduced complexity condensed organic phase consisting of 13 semi-volatile and 2 involatile species (Topping et. al., 2012), as well as the N2O5 heterogeneous reaction scheme of Bertram & Thornton (2009). We aim to use WRF-Chem to compare the oxidation capacity of nighttime NO3 chemistry with that of daytime OH chemistry. The model was run using two nested grids: a 15km resolution domain over western Europe, containing a 5km resolution domain over the UK. The RONOCO campaign consisted

An Aerosol Physical Chemistry Model for the Upper Troposphere

NASA Technical Reports Server (NTRS)

Lin, Jin-Sheng

2001-01-01

This report is the final report for the Cooperative Agreement NCC2-1000. The tasks outlined in the various proposals are: (1) Development of an aerosol chemistry model; (2) Utilization of satellite measurements of trace gases along with analysis of temperatures and dynamic conditions to understand ice cloud formation, dehydration and sedimentation in the winter polar regions; (3) Comparison of the HALOE and SAGE II time dependencies of the Pinatubo aerosol decay. The publications are attached.

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

Recent Rainfall and Aerosol Chemistry From Bermuda

NASA Astrophysics Data System (ADS)

Landing, W. M.; Shelley, R.; Kadko, D. C.

2014-12-01

This project was devoted to testing the use of Be-7 as a tracer for quantifying trace element fluxes from the atmosphere to the oceans. Rainfall and aerosol samples were collected between June 15, 2011 and July 27, 2013 at the Bermuda Institute of Ocean Sciences (BIOS) located near the eastern end of the island of Bermuda. Collectors were situated near ground level, clear of surrounding vegetation, at a meteorological monitoring station in front of the BIOS laboratory, about 10 m above sea level. This is a Bermuda Air Quality Program site used for ambient air quality monitoring. To quantify the atmospheric deposition of Be-7, plastic buckets were deployed for collection of fallout over ~3 week periods. Wet deposition was collected for trace element analysis using a specially modified "GEOTRACES" N-CON automated wet deposition collector. Aerosol samples were collected with a Tisch TE-5170V-BL high volume aerosol sampler, modified to collect 12 replicate samples on acid-washed 47mm diameter Whatman-41 filters, using procedures identical to those used for the US GEOTRACES aerosol program (Morton et al., 2013). Aerosol and rainfall samples were analyzed for total Na, Mg, Al, P, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Zr, Cd, Sb, Ba, La, Ce, Nd, Pb, Th, and U using ICPMS. Confirming earlier data from Bermuda, strong seasonality in rainfall and aerosol loading and chemistry was observed, particularly for aerosol and rainfall Fe concentrations when Saharan dust arrives in July/August with SE trajectories.

Nighttime chemical evolution of aerosol and trace gases in a power plant plume: Implications for secondary organic nitrate and organosulfate aerosol formation, NO₃ radical chemistry, and N₂O₅ heterogeneous hydrolysis

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

Zaveri, Rahul A.; Berkowitz, Carl M.; Brechtel, Fred J.

Chemical evolution of aerosols and trace gases in the Salem Harbor power plant plume was monitored with the DOE G-1 aircraft on the night of July 30-31, 2002. Quasi-Lagrangian sampling in the plume at increasing downwind distances/processing times was guided by a constant-volume tetroon that was released near the power plant at sunset. While no evidence of fly ash particles was found, concentrations of particulate organics, sulfate, and nitrate were higher in the plume than in the nearby background air. These species were internally mixed and the particles were acidic, suggesting that particulate nitrate was in the form of organicmore » nitrate. The enhanced particulate organic and nitrate masses in the plume were inferred to be as secondary organic aerosol, possibly formed from the NO3 radical-initiated oxidation of isoprene and other trace organic gases in the presence of acidic sulfate particles. The enhanced particulate sulfate concentrations observed in the plume were attributed to direct emissions of gaseous SO3/H2SO4 from the power plant. Furthermore, concentration of nucleation mode particles was significantly higher in the plume than in background air, suggesting that some of the emitted H2SO4 had nucleated to form new particles. Spectromicroscopic analyses of particle samples suggested that some sulfate was likely in the form of organosulfates. Constrained Lagrangian model analysis of the aircraft and tetroon observations showed that heterogeneous hydrolysis of N2O5 was negligibly slow. These results have significant implications for several scientific and regulatory issues related to the impacts of power plant emissions on atmospheric chemistry, air quality, visibility, and climate.« less

Aerosol chemistry during the wet season in central Amazonia - The influence of long-range transport

NASA Technical Reports Server (NTRS)

Talbot, R. W.; Andreae, M. O.; Berresheim, H.; Artaxo, P.; Garstang, M.

1990-01-01

The temporal variation in the concentration and chemistry of the atmospheric aerosol over central Amazonia, Brazil, during the 1987 wet season is discussed based on ground and aircraft collected data obtained during the NASA GTE ABLE 2B expedition conducted in April/May 1987. It is found that wet-season aerosol concentrations and composition are variable in contrast to the more uniform biogenic aerosol observed during the 1985 dry season; four distinct intervals of enhanced aerosol concentration coincided with short periods (3 to 5 d) of extensive rainfall. It is hypothesized that aerosol chemistry in Amazonia during the wet season is strongly influenced by long-range transport of soil dust, marine aerosol, and possibly biomass combustion products advected into the central Basin by large-scale tropospheric circulation, producing periodic pulses of material input to local boundary layer air. The resultant wet-season aerosol regime is dynamic, in contrast to the uniformity of natural biogenic aerosols during the dry season.

Simulation of Aerosols and Chemistry with a Unified Global Model

NASA Technical Reports Server (NTRS)

Chin, Mian

2004-01-01

This project is to continue the development of the global simulation capabilities of tropospheric and stratospheric chemistry and aerosols in a unified global model. This is a part of our overall investigation of aerosol-chemistry-climate interaction. In the past year, we have enabled the tropospheric chemistry simulations based on the GEOS-CHEM model, and added stratospheric chemical reactions into the GEOS-CHEM such that a globally unified troposphere-stratosphere chemistry and transport can be simulated consistently without any simplifications. The tropospheric chemical mechanism in the GEOS-CHEM includes 80 species and 150 reactions. 24 tracers are transported, including O3, NOx, total nitrogen (NOy), H2O2, CO, and several types of hydrocarbon. The chemical solver used in the GEOS-CHEM model is a highly accurate sparse-matrix vectorized Gear solver (SMVGEAR). The stratospheric chemical mechanism includes an additional approximately 100 reactions and photolysis processes. Because of the large number of total chemical reactions and photolysis processes and very different photochemical regimes involved in the unified simulation, the model demands significant computer resources that are currently not practical. Therefore, several improvements will be taken, such as massive parallelization, code optimization, or selecting a faster solver. We have also continued aerosol simulation (including sulfate, dust, black carbon, organic carbon, and sea-salt) in the global model to cover most of year 2002. These results have been made available to many groups worldwide and accessible from the website http://code916.gsfc.nasa.gov/People/Chin/aot.html.

An Aerosol Physical Chemistry Model for the Upper Troposphere

NASA Technical Reports Server (NTRS)

Lin, Jin-Sheng

2001-01-01

This report is the final report for the Cooperative Agreement NCC2-1000. The tasks outlined in the various proposals are listed with a brief comment as to the research performed. The publications titles are: The effects of particle size and nitric acid uptake on the homogenous freezing of sulfate aerosols; Parameterization of an aerosol physical chemistry model (APCM) for the NH3/H2SO4/HNO3/H2O system at cold temperatures; and The onset, extent and duration of dehydration in the Southern Hemisphere polar vortex.

Heterogeneous chemistry of atmospheric mineral dust particles and their resulting cloud-nucleation properties

NASA Astrophysics Data System (ADS)

Sullivan, Ryan Christopher

Mineral dust particles are a major component of tropospheric aerosol mass and affect regional and global atmospheric chemistry and climate. Dust particles experience heterogeneous reactions with atmospheric gases that alter the gas and particle-phase chemistry. These in turn influence the warm and cold cloud nucleation ability and optical properties of the dust particles. This dissertation investigates the atmospheric chemistry of mineral dust particles and their role in warm cloud nucleation through a combination of synergistic field measurements, laboratory experiments, and theoretical modeling. In-situ measurements made with a single-particle mass spectrometer during the ACE-Asia field campaign in 2001 provide the motivation for this work. The observed mixing state of the individual ambient particles with secondary organic and inorganic components is described in Chapter 2. A large Asian dust storm occurred during the campaign and produced dramatic changes in the aerosol's composition and mixing state. The effect of particle size and mineralogy on the atmospheric processing of individual dust particles is explored in Chapters 3 & 4. Sulfate was found to accumulate preferentially in submicron iron and aluminosilicate-rich dust particles, while nitrate and chloride were enriched in supermicron calcite-rich dust. The mineral dust (and sea salt particles) were also enriched in oxalic acid, the dominant component of water soluble organic carbon. Chapter 5 explores the roles of gas-phase photochemistry and partitioning of the diacids to the alkaline particles in producing this unique behavior. The effect of the dust's mixing state with secondary organic and inorganic components on the dust particles' solubility, hygroscopicity, and thus warm cloud nucleation properties is explored experimentally and theoretically in Chapter 6. Cloud condensation nucleation (CCN) activation curves revealed that while calcium nitrate and calcium chloride particles were very hygroscopic

Modification of heterogeneous chemistry by complex substrate morphology

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

Henson, B.F.; Buelow, S.J.; Robinson, J.M.

1998-12-31

This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). Chemistry in many environmental systems is determined at some stage by heterogeneous reaction with a surface. Typically the surface exists as a dispersion or matrix of particulate matter or pores, and a determination of the heterogeneous chemistry of the system must address the extent to which the complexity of the environmental surface affects the reaction rates. Reactions that are of current interest are the series of chlorine nitrate reactions important in polar ozone depletion. The authors have applied surfacemore » spectroscopic techniques developed at LANL to address the chemistry of chlorine nitrate reactions on porous nitric and sulfuric acid ice surfaces as a model study of the measurement of complex, heterogeneous reaction rates. The result of the study is an experimental determination of the surface coverage of one adsorbed reagent and a mechanism of reactivity based on the dependence of this coverage on temperature and vapor pressure. The resulting mechanism allows the first comprehensive modeling of chlorine nitrate reaction probability data from several laboratories.« less

Model development of dust emission and heterogeneous chemistry within the Community Multiscale Air Quality modeling system and its application over East Asia

NASA Astrophysics Data System (ADS)

Dong, X.; Fu, J. S.; Huang, K.; Tong, D.

2015-12-01

The Community Multiscale Air Quality (CMAQ) model has been further developed in terms of simulating natural wind-blown dust in this study, with a series of modifications aimed at improving the model's capability to predict the emission, transport, and chemical reactions of dust aerosols. The default parameterization of threshold friction velocity constants in the CMAQ are revised to avoid double counting of the impact of soil moisture based on the re-analysis of field experiment data; source-dependent speciation profiles for dust emission are derived based on local measurements for the Gobi and Taklamakan deserts in East Asia; and dust heterogeneous chemistry is implemented to simulate the reactions involving dust aerosol. The improved dust module in the CMAQ was applied over East Asia for March and April from 2006 to 2010. Evaluation against observations has demonstrated that simulation bias of PM10 and aerosol optical depth (AOD) is reduced from -55.42 and -31.97 % in the original CMAQ to -16.05 and -22.1 % in the revised CMAQ, respectively. Comparison with observations at the nearby Gobi stations of Duolun and Yulin indicates that applying a source-dependent profile helps reduce simulation bias for trace metals. Implementing heterogeneous chemistry is also found to result in better agreement with observations for sulfur dioxide (SO2), sulfate (SO42-), nitric acid (HNO3), nitrous oxides (NOx), and nitrate (NO3-). Investigation of a severe dust storm episode from 19 to 21 March 2010 suggests that the revised CMAQ is capable of capturing the spatial distribution and temporal variations of dust aerosols. Model evaluation indicates potential uncertainties within the excessive soil moisture fraction used by meteorological simulation. The mass contribution of fine mode aerosol in dust emission may be underestimated by 50 %. The revised revised CMAQ provides a useful tool for future studies to investigate the emission, transport, and impact of wind-blown dust over East

Aerosols in atmospheric chemistry and biogeochemical cycles of nutrients

NASA Astrophysics Data System (ADS)

Kanakidou, Maria; Myriokefalitakis, Stelios; Tsigaridis, Kostas

2018-06-01

Atmospheric aerosols have complex and variable compositions and properties. While scientific interest is centered on the health and climatic effects of atmospheric aerosols, insufficient attention is given to their involvement in multiphase chemistry that alters their contribution as carriers of nutrients in ecosystems. However, there is experimental proof that the nutrient equilibria of both land and marine ecosystems have been disturbed during the Anthropocene period. This review study first summarizes our current understanding of aerosol chemical processing in the atmosphere as relevant to biogeochemical cycles. Then it binds together results of recent modeling studies based on laboratory and field experiments, focusing on the organic and dust components of aerosols that account for multiphase chemistry, aerosol ageing in the atmosphere, nutrient (N, P, Fe) emissions, atmospheric transport, transformation and deposition. The human-driven contribution to atmospheric deposition of these nutrients, derived by global simulations using past and future anthropogenic emissions of pollutants, is put into perspective with regard to potential changes in nutrient limitations and biodiversity. Atmospheric deposition of nutrients has been suggested to result in human-induced ecosystem limitations with regard to specific nutrients. Such modifications favor the development of certain species against others and affect the overall functioning of ecosystems. Organic forms of nutrients are found to contribute to the atmospheric deposition of the nutrients N, P and Fe by 20%–40%, 35%–45% and 7%–18%, respectively. These have the potential to be key components of the biogeochemical cycles since there is initial proof of their bioavailability to ecosystems. Bioaerosols have been found to make a significant contribution to atmospheric sources of N and P, indicating potentially significant interactions between terrestrial and marine ecosystems. These results deserve further

Impact of geoengineered aerosols on the troposphere and stratosphere

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

Tilmes, S.; Garcia, Rolando R.; Kinnison, Douglas E.

2009-06-27

A coupled chemistry climate model, the Whole Atmosphere Community Climate Model was used to perform a transient climate simulation to quantify the impact of geoengineered aerosols on atmospheric processes. In contrast to previous model studies, the impact on stratospheric chemistry, including heterogeneous chemistry in the polar regions, is considered in this simulation. In the geoengineering simulation, a constant stratospheric distribution of volcanic-sized, liquid sulfate aerosols is imposed in the period 2020–2050, corresponding to an injection of 2 Tg S/a. The aerosol cools the troposphere compared to a baseline simulation. Assuming an Intergovernmental Panel on Climate Change A1B emission scenario, globalmore » warming is delayed by about 40 years in the troposphere with respect to the baseline scenario. Large local changes of precipitation and temperatures may occur as a result of geoengineering. Comparison with simulations carried out with the Community Atmosphere Model indicates the importance of stratospheric processes for estimating the impact of stratospheric aerosols on the Earth’s climate. Changes in stratospheric dynamics and chemistry, especially faster heterogeneous reactions, reduce the recovery of the ozone layer in middle and high latitudes for the Southern Hemisphere. In the geoengineering case, the recovery of the Antarctic ozone hole is delayed by about 30 years on the basis of this model simulation. For the Northern Hemisphere, a onefold to twofold increase of the chemical ozone depletion occurs owing to a simulated stronger polar vortex and colder temperatures compared to the baseline simulation, in agreement with observational estimates.« less

Modeling the Explicit Chemistry of Anthropogenic and Biogenic Organic Aerosols

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

Madronich, Sasha

2015-12-09

The atmospheric burden of Secondary Organic Aerosols (SOA) remains one of the most important yet uncertain aspects of the radiative forcing of climate. This grant focused on improving our quantitative understanding of SOA formation and evolution, by developing, applying, and improving a highly detailed model of atmospheric organic chemistry, the Generation of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) model. Eleven (11) publications have resulted from this grant.

AerChemMIP: Quantifying the effects of chemistry and aerosols in CMIP6

DOE PAGES

Collins, William J.; Lamarque, Jean -François; Schulz, Michael; ...

2017-02-09

The Aerosol Chemistry Model Intercomparison Project (AerChemMIP) is endorsed by the Coupled-Model Intercomparison Project 6 (CMIP6) and is designed to quantify the climate and air quality impacts of aerosols and chemically reactive gases. These are specifically near-term climate forcers (NTCFs: methane, tropospheric ozone and aerosols, and their precursors), nitrous oxide and ozone-depleting halocarbons. The aim of AerChemMIP is to answer four scientific questions. 1. How have anthropogenic emissions contributed to global radiative forcing and affected regional climate over the historical period? 2. How might future policies (on climate, air quality and land use) affect the abundances of NTCFs and theirmore » climate impacts? 3.How do uncertainties in historical NTCF emissions affect radiative forcing estimates? 4. How important are climate feedbacks to natural NTCF emissions, atmospheric composition, and radiative effects? These questions will be addressed through targeted simulations with CMIP6 climate models that include an interactive representation of tropospheric aerosols and atmospheric chemistry. These simulations build on the CMIP6 Diagnostic, Evaluation and Characterization of Klima (DECK) experiments, the CMIP6 historical simulations, and future projections performed elsewhere in CMIP6, allowing the contributions from aerosols and/or chemistry to be quantified. As a result, specific diagnostics are requested as part of the CMIP6 data request to highlight the chemical composition of the atmosphere, to evaluate the performance of the models, and to understand differences in behaviour between them.« less

AerChemMIP: Quantifying the effects of chemistry and aerosols in CMIP6

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

Collins, William J.; Lamarque, Jean -François; Schulz, Michael

The Aerosol Chemistry Model Intercomparison Project (AerChemMIP) is endorsed by the Coupled-Model Intercomparison Project 6 (CMIP6) and is designed to quantify the climate and air quality impacts of aerosols and chemically reactive gases. These are specifically near-term climate forcers (NTCFs: methane, tropospheric ozone and aerosols, and their precursors), nitrous oxide and ozone-depleting halocarbons. The aim of AerChemMIP is to answer four scientific questions. 1. How have anthropogenic emissions contributed to global radiative forcing and affected regional climate over the historical period? 2. How might future policies (on climate, air quality and land use) affect the abundances of NTCFs and theirmore » climate impacts? 3.How do uncertainties in historical NTCF emissions affect radiative forcing estimates? 4. How important are climate feedbacks to natural NTCF emissions, atmospheric composition, and radiative effects? These questions will be addressed through targeted simulations with CMIP6 climate models that include an interactive representation of tropospheric aerosols and atmospheric chemistry. These simulations build on the CMIP6 Diagnostic, Evaluation and Characterization of Klima (DECK) experiments, the CMIP6 historical simulations, and future projections performed elsewhere in CMIP6, allowing the contributions from aerosols and/or chemistry to be quantified. As a result, specific diagnostics are requested as part of the CMIP6 data request to highlight the chemical composition of the atmosphere, to evaluate the performance of the models, and to understand differences in behaviour between them.« less

Aerosol chemistry in Titan's ionosphere: simultaneous growth and etching processes

NASA Astrophysics Data System (ADS)

Carrasco, Nathalie; Cernogora, Guy; Jomard, François; Etcheberry, Arnaud; Vigneron, Jackie

2016-10-01

Since the Cassini-CAPS measurements, organic aerosols are known to be present and formed at high altitudes in the diluted and partially ionized medium that is Titan's ionosphere [1]. This unexpected chemistry can be further investigated in the laboratory with plasma experiments simulating the complex ion-neutral chemistry starting from N2-CH4 [2]. Two sorts of solid organic samples can be produced in laboratory experiments simulating Titan's atmospheric reactivity: grains in the volume and thin films on the reactor walls. We expect that grains are more representative of Titan's atmospheric aerosols, but films are used to provide optical indices for radiative models of Titan's atmosphere.The aim of the present study is to address if these two sorts of analogues are chemically equivalent or not, when produced in the same N2-CH4 plasma discharge. The chemical compositions of both these materials are measured by using elemental analysis, XPS analysis and Secondary Ion Mass Spectrometry. We find that films are homogeneous but significantly less rich in nitrogen and hydrogen than grains produced in the same experimental conditions. This surprising difference in their chemical compositions is explained by the efficient etching occurring on the films, which stay in the discharge during the whole plasma duration, whereas the grains are ejected after a few minutes [3]. The impact for our understanding of Titan's aerosols chemical composition is important. Our study shows that chemical growth and etching process are simultaneously at stake in Titan's ionosphere. The more the aerosols stay in the ionosphere, the more graphitized they get through etching process. In order to infer Titan's aerosols composition, our work highlights a need for constraints on the residence time of aerosols in Titan's ionosphere. [1] Waite et al. (2009) Science , 316, p. 870[2] Szopa et al. (2006) PSS, 54, p. 394[3] Carrasco et al. (2016) PSS, 128, p. 52

Session on coupled atmospheric/chemistry coupled models

NASA Technical Reports Server (NTRS)

Thompson, Anne

1993-01-01

The session on coupled atmospheric/chemistry coupled models is reviewed. Current model limitations, current issues and critical unknowns, and modeling activity are addressed. Specific recommendations and experimental strategies on the following are given: multiscale surface layer - planetary boundary layer - chemical flux measurements; Eulerian budget study; and Langrangian experiment. Nonprecipitating cloud studies, organized convective systems, and aerosols - heterogenous chemistry are also discussed.

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

NASA Technical Reports Server (NTRS)

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

2011-01-01

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

Single Aerosol Particle Studies Using Optical Trapping Raman And Cavity Ringdown Spectroscopy

NASA Astrophysics Data System (ADS)

Gong, Z.; Wang, C.; Pan, Y. L.; Videen, G.

2017-12-01

Due to the physical and chemical complexity of aerosol particles and the interdisciplinary nature of aerosol science that involves physics, chemistry, and biology, our knowledge of aerosol particles is rather incomplete; our current understanding of aerosol particles is limited by averaged (over size, composition, shape, and orientation) and/or ensemble (over time, size, and multi-particles) measurements. Physically, single aerosol particles are the fundamental units of any large aerosol ensembles. Chemically, single aerosol particles carry individual chemical components (properties and constituents) in particle ensemble processes. Therefore, the study of single aerosol particles can bridge the gap between aerosol ensembles and bulk/surface properties and provide a hierarchical progression from a simple benchmark single-component system to a mixed-phase multicomponent system. A single aerosol particle can be an effective reactor to study heterogeneous surface chemistry in multiple phases. Latest technological advances provide exciting new opportunities to study single aerosol particles and to further develop single aerosol particle instrumentation. We present updates on our recent studies of single aerosol particles optically trapped in air using the optical-trapping Raman and cavity ringdown spectroscopy.

Accounting for Heterogeneous-Phase Chemistry in Air Quality Models - Research Needs and Applications

EPA Science Inventory

Understanding the extent to which heterogeneous chemical reactions affect the burden and distribution of atmospheric pollutants is important because heterogeneous surfaces are ubiquitous throughout our environment. They include materials such as aerosol particles, clouds and fog,...

The Physics and Chemistry of Marine Aerosols

NASA Astrophysics Data System (ADS)

Russell, Lynn M.

Understanding the physics and chemistry of the marine atmosphere requires both predicting the evolution of its gas and aerosol phases and making observations that reflect the processes in that evolution. This work presents a model of the most fundamental physical and chemical processes important in the marine atmosphere, and discusses the current uncertainties in our theoretical understanding of those processes. Backing up these predictions with observations requires improved instrumentation for field measurements of aerosol. One important advance in this instrumentation is described for accelerating the speed of size distribution measurements. Observations of aerosols in the marine boundary layer during the Atlantic Stratocumulus Transition Experiment (ASTEX) provide an illustration of the impact of cloud processing in marine stratus. More advanced measurements aboard aircraft were enabled by redesigning the design of the system for separating particles by differential mobility and counting them by condensational growth. With this instrumentation, observations made during the Monterey Area Ship Tracks (MAST) Experiment have illustrated the role of aerosol emissions of ships in forming tracks in clouds. High-resolution gas chromatography and mass spectrometry was used with samples extracted by supercritical fluid extraction in order to identify the role of combustion organics in forming ship tracks. The results illustrate the need both for more sophisticated models incorporating organic species in cloud activation and for more extensive boundary layer observations.

Aerosols, Chemistry, and Radiative Forcing: A 3-D Model Analysis of Satellite and ACE-Asia data (ACMAP)

NASA Technical Reports Server (NTRS)

Chin, Mian; Ginoux, Paul; Torres, Omar; Zhao, Xue-Peng

2005-01-01

We propose a research project to incorporate a global 3-D model and satellite data into the multi-national Aerosol Characterization Experiment-Asia (ACE-Asia) mission. Our objectives are (1) to understand the physical, chemical, and optical properties of aerosols and the processes that control those properties over the Asian-Pacific region, (2) to investigate the interaction between aerosols and tropospheric chemistry, and (3) to determine the aerosol radiative forcing over the Asia-Pacific region. We will use the Georgia TecWGoddard Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) model to link satellite observations and the ACE-Asia measurements. First, we will use the GOCART model to simulate aerosols and related species, and evaluate the model with satellite and in-situ observations. Second, the model generated aerosol vertical profiles and compositions will be used to validate the satellite products; and the satellite data will be used for during- and post- mission analysis. Third, we will use the model to analyze and interpret both satellite and ACE- Asia field campaign data and investigate the aerosol-chemistry interactions. Finally, we will calculate aerosol radiative forcing over the Asian-Pacific region, and assess the influence of Asian pollution in the global atmosphere. We propose a research project to incorporate a global 3-D model and satellite data into

Heterogeneous Chemistry Involving Methanol in Tropospheric Clouds

NASA Technical Reports Server (NTRS)

Tabazadeh, A.; Yokelson, R. J.; Singh, H. B.; Hobbs, P. V.; Crawford, J. H.; Iraci, L. T.

2004-01-01

In this report we analyze airborne measurements to suggest that methanol in biomass burning smoke is lost heterogeneously in clouds. When a smoke plume intersected a cumulus cloud during the SAFARI 2000 field project, the observed methanol gas phase concentration rapidly declined. Current understanding of gas and aqueous phase chemistry cannot explain the loss of methanol documented by these measurements. Two plausible heterogeneous reactions are proposed to explain the observed simultaneous loss and production of methanol and formaldehyde, respectively. If the rapid heterogeneous processing of methanol, seen in a cloud impacted by smoke, occurs in more pristine clouds, it could affect the oxidizing capacity of the troposphere on a global scale.

Simulation of tropospheric chemistry and aerosols with the climate model EC-Earth

NASA Astrophysics Data System (ADS)

van Noije, T. P. C.; Le Sager, P.; Segers, A. J.; van Velthoven, P. F. J.; Krol, M. C.; Hazeleger, W.

2014-03-01

We have integrated the atmospheric chemistry and transport model TM5 into the global climate model EC-Earth version 2.4. We present an overview of the TM5 model and the two-way data exchange between TM5 and the integrated forecasting system (IFS) model from the European Centre for Medium-Range Weather Forecasts (ECMWF), the atmospheric general circulation model of EC-Earth. In this paper we evaluate the simulation of tropospheric chemistry and aerosols in a one-way coupled configuration. We have carried out a decadal simulation for present-day conditions and calculated chemical budgets and climatologies of tracer concentrations and aerosol optical depth. For comparison we have also performed offline simulations driven by meteorological fields from ECMWF's ERA-Interim reanalysis and output from the EC-Earth model itself. Compared to the offline simulations, the online-coupled system produces more efficient vertical mixing in the troposphere, which likely reflects an improvement of the treatment of cumulus convection. The chemistry in the EC-Earth simulations is affected by the fact that the current version of EC-Earth produces a cold bias with too dry air in large parts of the troposphere. Compared to the ERA-Interim driven simulation, the oxidizing capacity in EC-Earth is lower in the tropics and higher in the extratropics. The methane lifetime is 7% higher in EC-Earth, but remains well within the range reported in the literature. We evaluate the model by comparing the simulated climatologies of surface carbon monoxide, tropospheric and surface ozone, and aerosol optical depth against observational data. The work presented in this study is the first step in the development of EC-Earth into an Earth system model with fully interactive atmospheric chemistry and aerosols.

Simulation of tropospheric chemistry and aerosols with the climate model EC-Earth

NASA Astrophysics Data System (ADS)

van Noije, T. P. C.; Le Sager, P.; Segers, A. J.; van Velthoven, P. F. J.; Krol, M. C.; Hazeleger, W.; Williams, A. G.; Chambers, S. D.

2014-10-01

We have integrated the atmospheric chemistry and transport model TM5 into the global climate model EC-Earth version 2.4. We present an overview of the TM5 model and the two-way data exchange between TM5 and the IFS model from the European Centre for Medium-Range Weather Forecasts (ECMWF), the atmospheric general circulation model of EC-Earth. In this paper we evaluate the simulation of tropospheric chemistry and aerosols in a one-way coupled configuration. We have carried out a decadal simulation for present-day conditions and calculated chemical budgets and climatologies of tracer concentrations and aerosol optical depth. For comparison we have also performed offline simulations driven by meteorological fields from ECMWF's ERA-Interim reanalysis and output from the EC-Earth model itself. Compared to the offline simulations, the online-coupled system produces more efficient vertical mixing in the troposphere, which reflects an improvement of the treatment of cumulus convection. The chemistry in the EC-Earth simulations is affected by the fact that the current version of EC-Earth produces a cold bias with too dry air in large parts of the troposphere. Compared to the ERA-Interim driven simulation, the oxidizing capacity in EC-Earth is lower in the tropics and higher in the extratropics. The atmospheric lifetime of methane in EC-Earth is 9.4 years, which is 7% longer than the lifetime obtained with ERA-Interim but remains well within the range reported in the literature. We further evaluate the model by comparing the simulated climatologies of surface radon-222 and carbon monoxide, tropospheric and surface ozone, and aerosol optical depth against observational data. The work presented in this study is the first step in the development of EC-Earth into an Earth system model with fully interactive atmospheric chemistry and aerosols.

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

Complex Coupling of Air Quality and Climate-Relevant Aerosols in a Chemistry-Aerosol Microphysics Model

NASA Astrophysics Data System (ADS)

Yoshioka, M.; Carslaw, K. S.; Reddington, C.; Mann, G.

2013-12-01

Controlling emissions of aerosols and their precursors to improve air quality will impact the climate through direct and indirect radiative forcing. We have investigated the impacts of changes in a range of aerosol and gas-phase emission fluxes and changes in temperature on air quality and climate change metrics using a global aerosol microphysics and chemistry model, GLOMAP. We investigate how the responses of PM2.5 and cloud condensation nuclei (CCN) are coupled, and how attempts to improve air quality could have inadvertent effects on CCN, clouds and climate. The parameter perturbations considered are a 5°C increase in global temperature, increased or decreased precursor emissions of anthropogenic SO2, NH3, and NOx, and biogenic monoterpenes, and increased or decreased primary emissions of organic and black carbon aerosols from wildfire, fossil fuel, and biofuel. To quantify the interactions, we define a new sensitivity metric in terms of the response of CCN divided by the response of PM in different regions. .Our results show that the coupled chemistry and aerosol processes cause complex responses that will make any co-benefit policy decision problematic. In particular, we show that reducing SO2 emissions effectively reduces surface-level PM2.5 over continental regions in summer when background PM2.5 is high, with a relatively small reduction in marine CCN (and hence indirect radiative cooling over ocean), which is beneficial for near-term climate. Reducing NOx emissions does not improve summertime air quality very effectively but leads to a relatively high reduction of marine CCN. Reducing NH3 emissions has moderate effects on both PM2.5 and CCN. These three species are strongly coupled chemically and microphysically and the effects of changing emissions of one species on mass and size distributions of aerosols are very complex and spatially and temporally variable. For example, reducing SO2 emissions leads to reductions in sulphate and ammonium mass

Stratospheric Sulfuric Acid and Black Carbon Aerosol Measured During POLARIS and its Role in Ozone Chemistry

NASA Technical Reports Server (NTRS)

Strawa, Anthony W.; Pueschel, R. F.; Drdla, K.; Verma, S.; Gore, Warren J. (Technical Monitor)

1998-01-01

Stratospheric aerosol can affect the environment in three ways. Sulfuric acid aerosol have been shown to act as sites for the reduction of reactive nitrogen and chlorine and as condensation sites to form Polar Stratospheric Clouds, under very cold conditions, which facilitate ozone depletion. Recently, modeling studies have suggested a link between BCA (Black Carbon Aerosol) and ozone chemistry. These studies suggest that HNO3, NO2, and O3 may be reduced heterogeneously on BCA particles. The ozone reaction converts ozone to oxygen molecules, while HNO3 and NO2 react to form NOx. Finally, a buildup of BCA could reduce the single-scatter albedo of aerosol below a value of 0.98, a critical value that has been postulated to change the effect of stratospheric aerosol from cooling to warming. Correlations between measured BCA amounts and aircraft usage have been reported. Attempts to link BCA to ozone chemistry and other stratospheric processes have been hindered by questions concerning the amount of BCA that exists in the stratosphere, the magnitude of reaction probabilities, and the scarcity of BCA measurements. The Ames Wire Impactors (AWI) participated in POLARIS as part of the complement of experiments on the NASA ER-2. One of our main objectives was to determine the amount of aerosol surface area, particularly BCA, available for reaction with stratospheric constituents and assess if possible, the importance of these reactions. The AWI collects aerosol and BCA particles on thin Palladium wires that are exposed to the ambient air in a controlled manner. The samples are returned to the laboratory for subsequent analysis. The product of the AWI analysis is the size, surface area, and volume distributions, morphology and elemental composition of aerosol and BCA. This paper presents results from our experiments during POLARIS and puts these measurements in the context of POLARIS and other missions in which we have participated. It describes modifications to the AWI data

Description and Evaluation of IAP-AACM: A Global-regional Aerosol Chemistry Model for the Earth System Model CAS-ESM

NASA Astrophysics Data System (ADS)

Wei, Y.; Chen, X.

2017-12-01

We present a first description and evaluation of the IAP Atmospheric Aerosol Chemistry Model (IAP-AACM) which has been integrated into the earth system model CAS-ESM. In this way it is possible to research into interaction of clouds and aerosol by its two-way coupling with the IAP Atmospheric General Circulation Model (IAP-AGCM). The model has a nested global-regional grid based on the Global Environmental Atmospheric Transport Model (GEATM) and the Nested Air Quality Prediction Modeling System (NAQPMS). The AACM provides two optional gas chemistry schemes, the CBM-Z gas chemistry as well as a sulfur oxidize box designed specifically for the CAS-ESM. Now the model driven by AGCM has been applied to a 1-year simulation of tropospheric chemistry both on global and regional scales for 2014, and been evaluated against various observation datasets, including aerosol precursor gas concentration, aerosol mass and number concentrations. Furthermore, global budgets in AACM are compared with other global aerosol models. Generally, the AACM simulations are within the range of other global aerosol model predictions, and the model has a reasonable agreement with observations of gases and particles concentration both on global and regional scales.

Observational Insights into N2O5 Heterogeneous Chemistry: Influencing Factors and Contribution to Wintertime Air Pollution

NASA Astrophysics Data System (ADS)

McDuffie, E. E.; Fibiger, D. L.; Womack, C.; Dube, W. P.; Lopez-Hilfiker, F.; Goldberger, L.; Thornton, J. A.; Shah, V.; Jaegle, L.; Guo, H.; Weber, R. J.; Schroder, J. C.; Campuzano Jost, P.; Jimenez, J. L.; Franchin, A.; Middlebrook, A. M.; Baasandorj, M.; Brown, S. S.

2017-12-01

Chemical mechanisms that underlie wintertime air pollution, including tropospheric ozone and aerosol nitrate, are poorly characterized. Due to colder temperatures and fewer hours of solar radiation, nocturnal heterogeneous uptake of N2O5 plays a relatively larger role during wintertime in controlling the oxidation of NOx (=NO+NO2) and its influence on ozone and soluble nitrate. After uptake to aerosol, N2O5 can act as both a nocturnal NOx reservoir and sink depending on the partitioning between its nitric acid and photo labile, ClNO2 reaction products. In addition, N2O5 itself can act as a NOx reservoir if the aerosol uptake coefficient is small. As a result, the nocturnal fate of N2O5 dictates the amount of NOx in an air parcel and the subsequent formation of aerosol nitrate and following-day ozone. Models of winter air pollution therefore require accurate parameterization of the N2O5 uptake coefficient, as well as factors that control its magnitude and N2O5 product partitioning. There are currently only a small number of ambient N2O5 and ClNO2 observations during the winter season concurrent with measurements of relevant variables such as aerosol size distributions and composition. The Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) campaign conducted 10 nighttime research flights with the NCAR C-130 over the eastern U.S. during February and March, 2015. The more recent Utah Wintertime Fine Particulate Study (UWFPS) conducted over 20 research flights with the NOAA twin otter aircraft during January-February 2017 in three mountain basins near and including Salt Lake City, Utah. The two campaigns were similarly instrumented and have provided the first aircraft observations of N2O5, ClNO2, and aerosol composition in the wintertime boundary layer in these urban-influenced regions. Analysis of heterogeneous chemistry under a wide range of real environmental conditions provides insight into the factors controlling the N2O5 uptake coefficient

Heterogeneous Reduction Pathways for Hg(II) Species on Dry Aerosols: A First-Principles Computational Study

DOE PAGES

Tacey, Sean A.; Xu, Lang; Mavrikakis, Manos; ...

2016-03-25

Here, the atmospheric lifetime of mercury is greatly impacted by redox chemistry resulting from the high deposition rate of reactive mercury (Hg(II)) compared to elemental mercury (Hg 0). Recent laboratory and field studies have observed the reduction of Hg(II) but the chemical mechanism for this reaction has not been identified. Recent laboratory studies have shown that the reduction reaction is heterogeneous and can occur on iron and sodium chloride aerosol surfaces. This study explores the use of density functional theory calculations to discern the reduction pathways of HgCl 2, HgBr 2, Hg(NO 3) 2, and HgSO 4 on clean Fe(110),more » NaCl(100), and NaCl(111) Na surfaces. In doing so, potential energy surfaces have been prepared for the various reduction pathways, indicating that the reduction pathway leading to the production of gas-phase elemental mercury is highly favorable on Fe(110) and NaCl(111) Na. Moreover, the Fe(110) surface requires an external energy source of approximately 0.5 eV to desorb the reduced mercury, whereas the NaCl(111) Na surface requires no energy input. The results indicate that a number of mercury species can be reduced on metallic iron and sodium chloride surfaces, which are known aerosol components, and that a photochemical reaction involving the aerosol surface is likely needed for the reaction to be catalytic.« less

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.

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.

Importance of sulfate radical anion formation and chemistry in heterogeneous OH oxidation of sodium methyl sulfate, the smallest organosulfate

DOE PAGES

Kwong, Kai Chung; Chim, Man Mei; Davies, James F.; ...

2018-02-27

Organosulfates are important organosulfur compounds present in atmospheric particles. While the abundance, composition, and formation mechanisms of organosulfates have been extensively investigated, it remains unclear how they transform and evolve throughout their atmospheric lifetime. To acquire a fundamental understanding of how organosulfates chemically transform in the atmosphere, this study investigates the heterogeneous OH radical-initiated oxidation of sodium methyl sulfate (CH 3SO 4Na) droplets, the smallest organosulfate detected in atmospheric particles, using an aerosol flow tube reactor at a high relative humidity (RH) of 85%. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (direct analysis in real time,more » DART) coupled with a high-resolution mass spectrometer showed that neither functionalization nor fragmentation products are detected. Instead, the ion signal intensity of the bisulfate ion (HSO 4 -) has been found to increase significantly after OH oxidation. We postulate that sodium methyl sulfate tends to fragment into a formaldehyde (CH 2O) and a sulfate radical anion (SO 4 .-) upon OH oxidation. The formaldehyde is likely partitioned back to the gas phase due to its high volatility. The sulfate radical anion, similar to OH radical, can abstract a hydrogen atom from neighboring sodium methyl sulfate to form the bisulfate ion, contributing to the secondary chemistry. Kinetic measurements show that the heterogeneous OH reaction rate constant, k, is (3.79 ± 0.19) × 10 -13cm 3molecule -1s -1 with an effective OH uptake coefficient, γ eff, of 0.17 ± 0.03. While about 40% of sodium methyl sulfate is being oxidized at the maximum OH exposure (1.27 × 10 12molecule cm -3s), only a 3% decrease in particle diameter is observed. This can be attributed to a small fraction of particle mass lost via the formation and volatilization of formaldehyde. Overall, we firstly demonstrate that the heterogeneous OH oxidation of an

Importance of sulfate radical anion formation and chemistry in heterogeneous OH oxidation of sodium methyl sulfate, the smallest organosulfate

NASA Astrophysics Data System (ADS)

Chung Kwong, Kai; Chim, Man Mei; Davies, James F.; Wilson, Kevin R.; Nin Chan, Man

2018-02-01

Organosulfates are important organosulfur compounds present in atmospheric particles. While the abundance, composition, and formation mechanisms of organosulfates have been extensively investigated, it remains unclear how they transform and evolve throughout their atmospheric lifetime. To acquire a fundamental understanding of how organosulfates chemically transform in the atmosphere, this work investigates the heterogeneous OH radical-initiated oxidation of sodium methyl sulfate (CH3SO4Na) droplets, the smallest organosulfate detected in atmospheric particles, using an aerosol flow tube reactor at a high relative humidity (RH) of 85 %. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (direct analysis in real time, DART) coupled with a high-resolution mass spectrometer showed that neither functionalization nor fragmentation products are detected. Instead, the ion signal intensity of the bisulfate ion (HSO4-) has been found to increase significantly after OH oxidation. We postulate that sodium methyl sulfate tends to fragment into a formaldehyde (CH2O) and a sulfate radical anion (SO4 ṡ -) upon OH oxidation. The formaldehyde is likely partitioned back to the gas phase due to its high volatility. The sulfate radical anion, similar to OH radical, can abstract a hydrogen atom from neighboring sodium methyl sulfate to form the bisulfate ion, contributing to the secondary chemistry. Kinetic measurements show that the heterogeneous OH reaction rate constant, k, is (3.79 ± 0.19) × 10-13 cm3 molecule-1 s-1 with an effective OH uptake coefficient, γeff, of 0.17 ± 0.03. While about 40 % of sodium methyl sulfate is being oxidized at the maximum OH exposure (1.27 × 1012 molecule cm-3 s), only a 3 % decrease in particle diameter is observed. This can be attributed to a small fraction of particle mass lost via the formation and volatilization of formaldehyde. Overall, we firstly demonstrate that the heterogeneous OH oxidation of an

Importance of sulfate radical anion formation and chemistry in heterogeneous OH oxidation of sodium methyl sulfate, the smallest organosulfate

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

Kwong, Kai Chung; Chim, Man Mei; Davies, James F.

Organosulfates are important organosulfur compounds present in atmospheric particles. While the abundance, composition, and formation mechanisms of organosulfates have been extensively investigated, it remains unclear how they transform and evolve throughout their atmospheric lifetime. To acquire a fundamental understanding of how organosulfates chemically transform in the atmosphere, this study investigates the heterogeneous OH radical-initiated oxidation of sodium methyl sulfate (CH 3SO 4Na) droplets, the smallest organosulfate detected in atmospheric particles, using an aerosol flow tube reactor at a high relative humidity (RH) of 85%. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (direct analysis in real time,more » DART) coupled with a high-resolution mass spectrometer showed that neither functionalization nor fragmentation products are detected. Instead, the ion signal intensity of the bisulfate ion (HSO 4 -) has been found to increase significantly after OH oxidation. We postulate that sodium methyl sulfate tends to fragment into a formaldehyde (CH 2O) and a sulfate radical anion (SO 4 .-) upon OH oxidation. The formaldehyde is likely partitioned back to the gas phase due to its high volatility. The sulfate radical anion, similar to OH radical, can abstract a hydrogen atom from neighboring sodium methyl sulfate to form the bisulfate ion, contributing to the secondary chemistry. Kinetic measurements show that the heterogeneous OH reaction rate constant, k, is (3.79 ± 0.19) × 10 -13cm 3molecule -1s -1 with an effective OH uptake coefficient, γ eff, of 0.17 ± 0.03. While about 40% of sodium methyl sulfate is being oxidized at the maximum OH exposure (1.27 × 10 12molecule cm -3s), only a 3% decrease in particle diameter is observed. This can be attributed to a small fraction of particle mass lost via the formation and volatilization of formaldehyde. Overall, we firstly demonstrate that the heterogeneous OH oxidation of an

Real-Time Characterization of Aerosol Particle Composition above the Urban Canopy in Beijing: Insights into the Interactions between the Atmospheric Boundary Layer and Aerosol Chemistry.

PubMed

Sun, Yele; Du, Wei; Wang, Qingqing; Zhang, Qi; Chen, Chen; Chen, Yong; Chen, Zhenyi; Fu, Pingqing; Wang, Zifa; Gao, Zhiqiu; Worsnop, Douglas R

2015-10-06

Despite extensive efforts into the characterization of air pollution during the past decade, real-time characterization of aerosol particle composition above the urban canopy in the megacity Beijing has never been performed to date. Here we conducted the first simultaneous real-time measurements of aerosol composition at two different heights at the same location in urban Beijing from December 19, 2013 to January 2, 2014. The nonrefractory submicron aerosol (NR-PM1) species were measured in situ by a high-resolution aerosol mass spectrometer at near-ground level and an aerosol chemical speciation monitor at 260 m on a 325 m meteorological tower in Beijing. Secondary aerosol showed similar temporal variations between ground level and 260 m, whereas much weaker correlations were found for the primary aerosol. The diurnal evolution of the ratios and correlations of aerosol species between 260 m and the ground level further illustrated a complex interaction between vertical mixing processes and local source emissions on aerosol chemistry in the atmospheric boundary layer. As a result, the aerosol compositions at the two heights were substantially different. Organic aerosol (OA), mainly composed of primary OA (62%), at the ground level showed a higher contribution to NR-PM1 (65%) than at 260 m (54%), whereas a higher concentration and contribution (15%) of nitrate was observed at 260 m, probably due to the favorable gas-particle partitioning under lower temperature conditions. In addition, two different boundary layer structures were observed, each interacting differently with the evolution processes of aerosol chemistry.

International Workshop on Stratospheric Aerosols: Measurements, Properties, and Effects

NASA Technical Reports Server (NTRS)

Pueschel, Rudolf F. (Editor)

1991-01-01

Following a mandate by the International Aerosol Climatology Program under the auspices of International Association of Meteorology and Atmospheric Physics International Radiation Commission, 45 scientists from five nations convened to discuss relevant issues associated with the measurement, properties, and effects of stratospheric aerosols. A summary is presented of the discussions on formation and evolution, transport and fate, effects on climate, role in heterogeneous chemistry, and validation of lidar and satellite remote sensing of stratospheric aerosols. Measurements are recommended of the natural (background) and the volcanically enhanced aerosol (sulfuric acid and silica particles), the exhaust of shuttle, civil aviation and supersonic aircraft operations (alumina, soot, and ice particles), and polar stratospheric clouds (ice, condensed nitric and hydrochloric acids).

Heterogenous uptake of gaseous N(sub 2)O(sub 5) by sulfate aerosols

NASA Technical Reports Server (NTRS)

Leu, M. -T.; Kane, S. M.; Caloz, F.

2001-01-01

The heterogeneous uptake of gaseous N sub 2 O sub 5 by ammonium sulfate, ammonium bisulfate, and sulfuric acid aerosols as a function of relative humididty has been investigated at room temperature and atmsopheric pressure.

Heterogeneous interaction of SiO2 with N2O5: aerosol flow tube and single particle optical levitation-Raman spectroscopy studies.

PubMed

Tang, M J; Camp, J C J; Rkiouak, L; McGregor, J; Watson, I M; Cox, R A; Kalberer, M; Ward, A D; Pope, F D

2014-09-25

Silica (SiO2) is an important mineral present in atmospheric mineral dust particles, and the heterogeneous reaction of N2O5 on atmospheric aerosol is one of the major pathways to remove nitrogen oxides from the atmosphere. The heterogeneous reaction of N2O5 with SiO2 has only been investigated by two studies previously, and the reported uptake coefficients differ by a factor of >10. In this work two complementary laboratory techniques were used to study the heterogeneous reaction of SiO2 particles with N2O5 at room temperature and at different relative humidities (RHs). The uptake coefficients of N2O5, γ(N2O5), were determined to be (7.2 ± 0.6) × 10(-3) (1σ) at 7% RH and (5.3 ± 0.8) × 10(-3) (1σ) at 40% RH for SiO2 particles, using the aerosol flow tube technique. We show that γ(N2O5) determined in this work can be reconciled with the two previous studies by accounting for the difference in geometric and BET derived aerosol surface areas. To probe the particle phase chemistry, individual micrometer sized SiO2 particles were optically levitated and exposed to a continuous flow of N2O5 at different RHs, and the composition of levitated particles was monitored online using Raman spectroscopy. This study represents the first investigation into the heterogeneous reactions of levitated individual SiO2 particles as a surrogate for mineral dust. Relative humidity was found to play a critical role: while no significant change of particle composition was observed by Raman spectroscopy during exposure to N2O5 at RH of <2%, increasing the RH led to the formation of nitrate species on the particle surface which could be completely removed after decreasing the RH back to <2%. This can be explained by the partitioning of HNO3 between the gas and adsorbed phases. The atmospheric implications of this work are discussed.

Surface Chemistry in Heterogeneous Catalysis: An Emerging Discipline.

ERIC Educational Resources Information Center

White, J. M.; Campbell, Charles T.

1980-01-01

Provides background data on surface chemistry as an emerging discipline. Highlights the important role which surfaces play in catalysis by focusing on the catalyzed oxidation of carbon monoxide. Provides a demonstration of how surfaces exert their influences in heterogeneous phenomena and illustrates how experimental problems in this field are…

Development and evaluation of the aerosol dynamics and gas phase chemistry model ADCHEM

NASA Astrophysics Data System (ADS)

Roldin, P.; Swietlicki, E.; Schurgers, G.; Arneth, A.; Lehtinen, K. E. J.; Boy, M.; Kulmala, M.

2011-06-01

The aim of this work was to develop a model suited for detailed studies of aerosol dynamics, gas and particle phase chemistry within urban plumes, from local scale (1 × 1 km2) to regional scale. This article describes and evaluates the trajectory model for Aerosol Dynamics, gas and particle phase CHEMistry and radiative transfer (ADCHEM). The model treats both vertical and horizontal dispersion perpendicular to an air mass trajectory (2-space dimensions). The Lagrangian approach enables a more detailed representation of the aerosol dynamics, gas and particle phase chemistry and a finer spatial and temporal resolution compared to that of available regional 3D-CTMs. These features make it among others well suited for urban plume studies. The aerosol dynamics model includes Brownian coagulation, dry deposition, wet deposition, in-cloud processing, condensation, evaporation, primary particle emissions and homogeneous nucleation. The organic mass partitioning was either modeled with a 2-dimensional volatility basis set (2D-VBS) or with the traditional two-product model approach. In ADCHEM these models consider the diffusion limited and particle size dependent condensation and evaporation of 110 and 40 different organic compounds respectively. The gas phase chemistry model calculates the gas phase concentrations of 61 different species, using 130 different chemical reactions. Daily isoprene and monoterpene emissions from European forests were simulated separately with the vegetation model LPJ-GUESS, and included as input to ADCHEM. ADCHEM was used to simulate the ageing of the urban plumes from the city of Malmö in southern Sweden (280 000 inhabitants). Several sensitivity tests were performed concerning the number of size bins, size structure method, aerosol dynamic processes, vertical and horizontal mixing, coupled or uncoupled condensation and the secondary organic aerosol formation. The simulations show that the full-stationary size structure gives accurate results

Development and evaluation of the aerosol dynamic and gas phase chemistry model ADCHEM

NASA Astrophysics Data System (ADS)

Roldin, P.; Swietlicki, E.; Schurgers, G.; Arneth, A.; Lehtinen, K. E. J.; Boy, M.; Kulmala, M.

2010-08-01

The aim of this work was to develop a model ideally suited for detailed studies on aerosol dynamics, gas and particle phase chemistry within urban plumes, from local scale (1×1 km2) to regional or global scale. This article describes and evaluates the trajectory model for Aerosol Dynamics, gas and particle phase CHEMistry and radiative transfer (ADCHEM), which has been developed and used at Lund University since 2007. The model treats both vertical and horizontal dispersion perpendicular to an air mass trajectory (2-space dimensions), which is not treated in Lagrangian box-models (0-space dimensions). The Lagrangian approach enables a more detailed representation of the aerosol dynamics, gas and particle phase chemistry and a finer spatial and temporal resolution compared to that of available regional 3D-CTMs. These features make it among others ideally suited for urban plume studies. The aerosol dynamics model includes Brownian coagulation, dry deposition, wet deposition, in-cloud processing, condensation, evaporation, primary particle emissions and homogeneous nucleation. The gas phase chemistry model calculates the gas phase concentrations of 63 different species, using 119 different chemical reactions. Daily isoprene and monoterpene emissions from European forests were simulated separately with the vegetation model LPJ-GUESS, and included as input to ADCHEM. ADCHEM was used to simulate the ageing of the urban plumes from the city of Malmö in Southern Sweden (280 000 inhabitants). Several sensitivity tests were performed concerning the number of size bins, size structure method, coupled or uncoupled condensation, the volatility basis set (VBS) or traditional 2-product model for secondary organic aerosol formation, different aerosol dynamic processes and vertical and horizontal mixing. The simulations show that the full-stationary size structure gives accurate results with little numerical diffusion when more than 50 size bins are used between 1.5 and 2500 nm

Photochemical Formation of Aerosol in Planetary Atmospheres: Photon and Water Mediated Chemistry of SO_2

NASA Astrophysics Data System (ADS)

Kroll, Jay A.; Donaldson, D. J.; Vaida, Veronica

2016-06-01

Sulfur compounds have been observed in a number of planetary atmospheres throughout our solar system. Our current understanding of sulfur chemistry explains much of what we observe in Earth's atmosphere. However, several discrepancies between modeling and observations of the Venusian atmosphere show there are still problems in our fundamental understanding of sulfur chemistry. This is of particular concern due to the important role sulfur compounds play in the formation of aerosols, which have a direct impact on planetary climates, including Earth's. We investigate the role of water complexes in the hydration of sulfur oxides and dehydration of sulfur acids and will present spectroscopic studies to document such effects. I will present recent work investigating mixtures of SO_2 and water that generate large quantities of aerosol when irradiated with solar UV light, even in the absence of traditional OH chemistry. I will discuss a proposed mechanism for the formation of sulfurous acid (H_2SO_3) and present recent experimental work that supports this proposed mechanism. Additionally, the implications that photon-induced hydration of SO_2 has for aerosol formation in the atmosphere of earth as well as other planetary atmospheres will be discussed.

Spatial heterogeneities in aerosol size distribution over Bay of Bengal during Winter-ICARB Experiment

NASA Astrophysics Data System (ADS)

Sinha, P. R.; Manchanda, R. K.; Kaskaoutis, D. G.; Sreenivasan, S.; Krishna Moorthy, K.; Suresh Babu, S.

2011-09-01

This work examines the aerosol physical properties and size distribution measured in the Marine Atmospheric Boundary Layer (MABL) over entire Bay of Bengal (BoB) and Northern Indian Ocean (NIO) during the Winter Integrated Campaign on Aerosols, Gases and Radiation Budget (W-ICARB). The measurements were taken using the GRIMM optical particle counter from 27th December 2008 to 30th January 2009. The results show large spatial heterogeneities regarding both the total aerosol number concentrations ( N T) and the size distributions over BoB, which in turn indicates the variations in the source strength or advection from different regions. The aerosol number size distribution seems to be bi-modal in the 72% of the cases and can also be parameterized by uni-modal or by a combination of power-law and uni-modal distributions for the rest of the cases. The mode radius for accumulation and coarse-mode particles ranges from ˜0.1-0.2 μm and ˜0.6-0.8 μm, respectively. In the northern BoB and along the Indian coast, the aerosols are mainly of sub-micron size with effective radius ( Reff) ranging between 0.25 and 0.3 μm highlighting the strong anthropogenic influence, while in the open oceanic areas they are much higher (0.4-0.6 μm). It was also found that the sea-surface wind plays a considerable role in the super-micron number concentration, Reff and mode radius for coarse-mode aerosols. Using the relation between N T and columnar AOD from Terra and Aqua-MODIS we found that the majority of the aerosols are within the lower MABL, while in some areas vertical heterogeneities also exist.

Evidence of Aerosols as a Media for Rapid Daytime HONO Production over China

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

Liu, Zhen; Wang, Yuhang; Costabile, Francesa

Current knowledge of daytime HONO sources remains incomplete. A large missing daytime HONO source has been found in many places around the world, including polluted regions in China. Conventional understanding and recent studies attributed this missing source mainly to ground surface processes or gas-phase chemistry, while assuming aerosols to be an insignificant media for HONO production. We analyze in situ observations of HONO and its precursors at an urban site in Beijing, China, and report an apparent dependence of the missing HONO source strength on aerosol surface area and solar ultraviolet radiation. Based on extensive correlation analysis and process-modeling, wemore » propose that the rapid daytime HONO production in Beijing can be explained by enhanced hydrolytic disproportionation of NO2 on aqueous aerosol surfaces due to catalysis by dicarboxylic acid anions. The combination of high abundance of NO2, aromatic hydrocarbons, and aerosols over broad regions in China likely leads to elevated HONO levels, rapid OH production, and enhanced oxidizing capacity on a regional basis. Our findings call for attention to aerosols as a media for daytime heterogeneous HONO production in polluted regions like Beijing. This study also highlights the complex and uncertain heterogeneous chemistry in China, which merits future efforts of reconciling regional modeling and laboratory experiments, in order to understand and mitigate the regional particulate and O3 pollutions over China.« less

Aerosol Chemistry over a High Altitude Station at Northeastern Himalayas, India

PubMed Central

Chatterjee, Abhijit; Adak, Anandamay; Singh, Ajay K.; Srivastava, Manoj K.; Ghosh, Sanjay K.; Tiwari, Suresh; Devara, Panuganti C. S.; Raha, Sibaji

2010-01-01

Background There is an urgent need for an improved understanding of the sources, distributions and properties of atmospheric aerosol in order to control the atmospheric pollution over northeastern Himalayas where rising anthropogenic interferences from rapid urbanization and development is becoming an increasing concern. Methodology/Principal Findings An extensive aerosol sampling program was conducted in Darjeeling (altitude ∼2200 meter above sea level (masl), latitude 27°01′N and longitude 88°15′E), a high altitude station in northeastern Himalayas, during January–December 2005. Samples were collected using a respirable dust sampler and a fine dust sampler simultaneously. Ion chromatograph was used to analyze the water soluble ionic species of aerosol. The average concentrations of fine and coarse mode aerosol were found to be 29.5±20.8 µg m−3 and 19.6±11.1 µg m−3 respectively. Fine mode aerosol dominated during dry seasons and coarse mode aerosol dominated during monsoon. Nitrate existed as NH4NO3 in fine mode aerosol during winter and as NaNO3 in coarse mode aerosol during monsoon. Gas phase photochemical oxidation of SO2 during premonsoon and aqueous phase oxidation during winter and postmonsoon were the major pathways for the formation of SO4 2− in the atmosphere. Long range transport of dust aerosol from arid regions of western India was observed during premonsoon. The acidity of fine mode aerosol was higher in dry seasons compared to monsoon whereas the coarse mode acidity was higher in monsoon compared to dry seasons. Biomass burning, vehicular emissions and dust particles were the major types of aerosol from local and continental regions whereas sea salt particles were the major types of aerosol from marine source regions. Conclusions/Significance The year-long data presented in this paper provide substantial improvements to the heretofore poor knowledge regarding aerosol chemistry over northeastern Himalayas, and should be useful to

Aerosol chemistry over a high altitude station at northeastern Himalayas, India.

PubMed

Chatterjee, Abhijit; Adak, Anandamay; Singh, Ajay K; Srivastava, Manoj K; Ghosh, Sanjay K; Tiwari, Suresh; Devara, Panuganti C S; Raha, Sibaji

2010-06-16

There is an urgent need for an improved understanding of the sources, distributions and properties of atmospheric aerosol in order to control the atmospheric pollution over northeastern Himalayas where rising anthropogenic interferences from rapid urbanization and development is becoming an increasing concern. An extensive aerosol sampling program was conducted in Darjeeling (altitude approximately 2200 meter above sea level (masl), latitude 27 degrees 01'N and longitude 88 degrees 15'E), a high altitude station in northeastern Himalayas, during January-December 2005. Samples were collected using a respirable dust sampler and a fine dust sampler simultaneously. Ion chromatograph was used to analyze the water soluble ionic species of aerosol. The average concentrations of fine and coarse mode aerosol were found to be 29.5+/-20.8 microg m(-3) and 19.6+/-11.1 microg m(-3) respectively. Fine mode aerosol dominated during dry seasons and coarse mode aerosol dominated during monsoon. Nitrate existed as NH(4)NO(3) in fine mode aerosol during winter and as NaNO(3) in coarse mode aerosol during monsoon. Gas phase photochemical oxidation of SO(2) during premonsoon and aqueous phase oxidation during winter and postmonsoon were the major pathways for the formation of SO(4)(2-) in the atmosphere. Long range transport of dust aerosol from arid regions of western India was observed during premonsoon. The acidity of fine mode aerosol was higher in dry seasons compared to monsoon whereas the coarse mode acidity was higher in monsoon compared to dry seasons. Biomass burning, vehicular emissions and dust particles were the major types of aerosol from local and continental regions whereas sea salt particles were the major types of aerosol from marine source regions. The year-long data presented in this paper provide substantial improvements to the heretofore poor knowledge regarding aerosol chemistry over northeastern Himalayas, and should be useful to policy makers in making control

Creating Aerosol Types from CHemistry (CATCH): A New Algorithm to Extend the Link Between Remote Sensing and Models

NASA Astrophysics Data System (ADS)

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

2017-11-01

Current remote sensing methods can identify aerosol types within an atmospheric column, presenting an opportunity to incrementally bridge the gap between remote sensing and models. Here a new algorithm was designed for Creating Aerosol Types from CHemistry (CATCH). CATCH-derived aerosol types—dusty mix, maritime, urban, smoke, and fresh smoke—are based on first-generation airborne High Spectral Resolution Lidar (HSRL-1) retrievals during the Ship-Aircraft Bio-Optical Research (SABOR) campaign, July/August 2014. CATCH is designed to derive aerosol types from model output of chemical composition. CATCH-derived aerosol types are determined by multivariate clustering of model-calculated variables that have been trained using retrievals of aerosol types from HSRL-1. CATCH-derived aerosol types (with the exception of smoke) compare well with HSRL-1 retrievals during SABOR with an average difference in aerosol optical depth (AOD) <0.03. Data analysis shows that episodic free tropospheric transport of smoke is underpredicted by the Goddard Earth Observing System- with Chemistry (GEOS-Chem) model. Spatial distributions of CATCH-derived aerosol types for the North American model domain during July/August 2014 show that aerosol type-specific AOD values occurred over representative locations: urban over areas with large population, maritime over oceans, smoke, and fresh smoke over typical biomass burning regions. This study demonstrates that model-generated information on aerosol chemical composition can be translated into aerosol types analogous to those retrieved from remote sensing methods. In the future, spaceborne HSRL-1 and CATCH can be used to gain insight into chemical composition of aerosol types, reducing uncertainties in estimates of aerosol radiative forcing.

An SOA model for toluene oxidation in the presence of inorganic aerosols.

PubMed

Cao, Gang; Jang, Myoseon

2010-01-15

A predictive model for secondary organic aerosol (SOA) formation including both partitioning and heterogeneous reactions is explored for the SOA produced from the oxidation of toluene in the presence of inorganic seed aerosols. The predictive SOA model comprises the explicit gas-phase chemistry of toluene, gas-particle partitioning, and heterogeneous chemistry. The resulting products from the explicit gas phase chemistry are lumped into several classes of chemical species based on their vapor pressure and reactivity for heterogeneous reactions. Both the gas-particle partitioning coefficient and the heterogeneous reaction rate constant of each lumped gas-phase product are theoretically determined using group contribution and molecular structure-reactivity. In the SOA model, the predictive SOA mass is decoupled into partitioning (OM(P)) and heterogeneous aerosol production (OM(H)). OM(P) is estimated from the SOA partitioning model developed by Schell et al. (J. Geophys. Res. 2001, 106, 28275-28293 ) that has been used in a regional air quality model (CMAQ 4.7). OM(H) is predicted from the heterogeneous SOA model developed by Jang et al. (Environ. Sci. Technol. 2006, 40, 3013-3022 ). The SOA model is evaluated using a number of the experimental SOA data that are generated in a 2 m(3) indoor Teflon film chamber under various experimental conditions (e.g., humidity, inorganic seed compositions, NO(x) concentrations). The SOA model reasonably predicts not only the gas-phase chemistry, such as the ozone formation, the conversion of NO to NO(2), and the toluene decay, but also the SOA production. The model predicted that the OM(H) fraction of the total toluene SOA mass increases as NO(x) concentrations decrease: 0.73-0.83 at low NO(x) levels and 0.17-0.47 at middle and high NO(x) levels for SOA experiments with high initial toluene concentrations. Our study also finds a significant increase in the OM(H) mass fraction in the SOA generated with low initial toluene

Heterogeneous chemistry of alkylamines with sulfuric acid: implications for atmospheric formation of alkylaminium sulfates.

PubMed

Wang, Lin; Lal, Vinita; Khalizov, Alexei F; Zhang, Renyi

2010-04-01

The heterogeneous interaction of alkylamines with sulfuric acid has been investigated to assess the role of amines in aerosol growth through the formation of alkylaminium sulfates. The kinetic experiments were conducted in a low-pressure fast flow reactor coupled to an ion drift-chemical ionization mass spectrometer (ID-CIMS). The measurements of heterogeneous uptake of methylamine, dimethylamine, and trimethylamine were performed in the acidity range of 59-82 wt % H(2)SO(4) and between 243 and 283 K. Irreversible reactive uptakes were observed for all three alkylamines, with comparable uptake coefficients (gamma) in the range of 2.0 x 10(-2) to 4.4 x 10(-2). The measured gamma value was slightly higher in more concentrated sulfuric acid and at lower temperatures. The results imply that the heterogeneous reactions of alkylamines contribute effectively to the growth of atmospheric acidic particles and, hence, secondary organic aerosol formation.

Heterogeneous photochemistry of imidazole-2-carboxaldehyde: HO2 radical formation and aerosol growth

NASA Astrophysics Data System (ADS)

González Palacios, Laura; Corral Arroyo, Pablo; Aregahegn, Kifle Z.; Steimer, Sarah S.; Bartels-Rausch, Thorsten; Nozière, Barbara; George, Christian; Ammann, Markus; Volkamer, Rainer

2016-09-01

The multiphase chemistry of glyoxal is a source of secondary organic aerosol (SOA), including its light-absorbing product imidazole-2-carboxaldehyde (IC). IC is a photosensitizer that can contribute to additional aerosol ageing and growth when its excited triplet state oxidizes hydrocarbons (reactive uptake) via H-transfer chemistry. We have conducted a series of photochemical coated-wall flow tube (CWFT) experiments using films of IC and citric acid (CA), an organic proxy and H donor in the condensed phase. The formation rate of gas-phase HO2 radicals (PHO2) was measured indirectly by converting gas-phase NO into NO2. We report on experiments that relied on measurements of NO2 formation, NO loss and HONO formation. PHO2 was found to be a linear function of (1) the [IC] × [CA] concentration product and (2) the photon actinic flux. Additionally, (3) a more complex function of relative humidity (25 % < RH < 63 %) and of (4) the O2 / N2 ratio (15 % < O2 / N2 < 56 %) was observed, most likely indicating competing effects of dilution, HO2 mobility and losses in the film. The maximum PHO2 was observed at 25-55 % RH and at ambient O2 / N2. The HO2 radicals form in the condensed phase when excited IC triplet states are reduced by H transfer from a donor, CA in our system, and subsequently react with O2 to regenerate IC, leading to a catalytic cycle. OH does not appear to be formed as a primary product but is produced from the reaction of NO with HO2 in the gas phase. Further, seed aerosols containing IC and ammonium sulfate were exposed to gas-phase limonene and NOx in aerosol flow tube experiments, confirming significant PHO2 from aerosol surfaces. Our results indicate a potentially relevant contribution of triplet state photochemistry for gas-phase HO2 production, aerosol growth and ageing in the atmosphere.

Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China

NASA Astrophysics Data System (ADS)

Cheng, Yafang; Zheng, Guangjie; Wei, Chao; Mu, Qing; Zheng, Bo; Wang, Zhibin; Gao, Meng; Zhang, Qiang; Wang, Kebin; Carmichael, Gregory; Pöschl, Ulrich; Su, Hang

2017-04-01

Fine-particle pollution associated with winter haze threatens the health of more than 400 million people in the North China Plain. Sulfate is a major component of fine haze particles. Record sulfate concentrations of up to 300 μg m-3 were observed during the January 2013 winter haze event in Beijing. State-of-the-art air quality models that rely on sulfate production mechanisms requiring photochemical oxidants cannot predict these high levels because of the weak photochemistry activity during haze events. We find that the missing source of sulfate and particulate matter can be explained by reactive nitrogen chemistry in aerosol water. The aerosol water serves as a reactor, where the alkaline aerosol components trap SO2, which is oxidized by NO2 to form sulfate, whereby high reaction rates are sustained by the high neutralizing capacity of the atmosphere in northern China. This mechanism is self-amplifying because higher aerosol mass concentration corresponds to higher aerosol water content, leading to faster sulfate production and more severe haze pollution. Reference: Cheng, Y., Zheng, G., Wei, C., Mu, Q., Zheng, B., Wang, Z., Gao, M., Zhang, Q., He, K., Carmichael, G., Pöschl, U., and Su, H.: Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China, Science Advances, 2, 10.1126/sciadv.1601530, 2016.

Reactive Nitrogen Chemistry in Aerosol Water as a Source of Sulfate during Haze Events in China

NASA Astrophysics Data System (ADS)

Su, H.; Zheng, G.; Wei, C.; Mu, Q.; Zheng, B.; Wang, Z.; Zhang, Q.; Gao, M.; He, K.; Carmichael, G. R.; Poeschl, U.; Cheng, Y.

2017-12-01

Fine particle pollution associated with winter haze threatens the health of over 400 million people in the North China Plain. Sulfate is a major component of fine haze particles. Record sulfate concentrations up to 300 μg m-3 were observed during the January 2013 winter haze event in Beijing. State-of-the-art air quality models relying on sulfate production mechanisms that require photochemical oxidants, cannot predict these high levels due to the weak photochemistry activity during haze events. We find that the missing source of sulfate and particulate matter can be explained by reactive nitrogen chemistry in aerosol water. The aerosol water serves as a reactor where the alkaline aerosol components trap SO2, which is oxidized by NO2 to form sulfate, whereby high reaction rates are sustained by the high neutralizing capacity of the atmosphere in northern China. This mechanism is self-amplifying because higher aerosol mass concentration corresponds to higher aerosol water content leading to faster sulfate production and more severe haze pollution. Reference: Cheng, Y., Zheng, G., Wei, C., Mu, Q., Zheng, B., Wang, Z., Gao, M., Zhang, Q., He, K., Carmichael, G., Pöschl, U., and Su, H.: Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China, Science Advances, 2, 10.1126/sciadv.1601530, 2016.

Effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events

DOE PAGES

Quan, Jiannong; Liu, Yangang; Liu, Quan; ...

2015-09-30

In this study, the effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events was investigated by analysis of comprehensive measurements of aerosol composition and concentrations [e.g., particular matters (PM 2.5), nitrate (NO 3), sulfate (SO 4), ammonium (NH 4)], gas-phase precursors [e.g., nitrogen oxides (NOx), sulfur dioxide (SO 2), and ozone (O 3)], and relevant meteorological parameters [e.g., visibility and relative humidity (RH)]. The measurements were conducted in Beijing, China from Sep. 07, 2012 to Jan. 16, 2013. The results show that the conversion ratios of N from NOx to nitrate (N ratio) andmore » S from SO 2 to sulfate (S ratio) both significantly increased in haze events, suggesting enhanced conversions from NOx and SO 2 to their corresponding particle phases in the late haze period. Further analysis shows that N ratio and S ratio increased with increasing RH, with N ratio and S ratio being only 0.04 and 0.03, respectively, when RH < 40%, and increasing up to 0.16 and 0.12 when RH reached 60–80%, respectively. The enhanced conversion ratios of N and S in the late haze period is likely due to heterogeneous aqueous reactions, because solar radiation and thus the photochemical capacity are reduced by the increases in aerosols and RH. This point was further affirmed by the relationships of N ratio and S ratio to O 3: the conversion ratios increase with decreasing O 3 concentration when O 3 concentration is lower than <15 ppb but increased with increasing O 3 when O 3 concentration is higher than 15 ppb. The results suggest that heterogeneous aqueous reactions likely changed aerosols and their precursors during the haze events: in the beginning of haze events, the precursor gases accumulated quickly due to high emission and low reaction rate; the occurrence of heterogeneous aqueous reactions in the late haze period, together with the accumulated high concentrations of precursor gases such as SO 2 and

The Effect of Aerosols on Pluto's C2 Hydrocarbon Chemistry

NASA Astrophysics Data System (ADS)

Luspay-Kuti, Adrienn; Mandt, Kathleen; Jessup, Kandis-Lea; Hue, Vincent; Kammer, Joshua; Filwett, Rachael; Hamel, Mark

2017-10-01

On July 14, 2015 the New Horizons spacecraft flew through the Pluto system, providing critical details about Pluto’s atmosphere. The vertical profiles of N2 and CH4, C2H2, C2H4, and C2H6 derived from New Horizons Alice transmission data allow the more accurate modeling of Pluto’s atmosphere than in the pre-New Horizons era, and help better understand the physical and photochemical processes in Pluto’s atmosphere. All the measured C2 hydrocarbon densities showed an unexpected inversion between ~100 and 400 km, which suggests that processes other than chemistry play an important role in shaping their vertical profiles. We present here a state-of-the-art Pluto Ion-Neutral-Photochemistry (Pluto INP) model that includes the condensation onto and incorporation into aerosol particles, and evaluate the dominant production and loss processes of C2 hydrocarbons with a special emphasis on the role of aerosol interaction. We found that in order to reproduce the C2 profiles measured by New Horizons, they must stick to and be permanently removed by aerosols - a process different from condensation. We determined through empirical fits to the New Horizons data that the sticking efficiency of C2 hydrocarbons and the stickiness of the aerosol particles are inversely related to the available aerosol surface area, which has been inferred from observation to increase as altitude decreases. This counterintuitive relationship between sticking efficiency and available aerosol surfaces indicates that similarly to Titan, Pluto’s aerosols must harden and become less sticky as they age. Such hardening with ageing is both necessary and sufficient to explain the vertical profiles of C2 hydrocarbons in Pluto’s atmosphere.

Sulfuric Acid Monohydrate: Formation and Heterogeneous Chemistry in the Stratosphere

NASA Technical Reports Server (NTRS)

Zhang, Renyi; Leu, Ming-Taun; Keyser, Leon F.

1995-01-01

We have investigated some thermodynamic properties (i.e., freezing/melting points) and heterogeneous chemistry of sulfuric acid monohydrate (SAM, H2SO4.H2O), using a fast flow reactor coupled to a quadrupole mass spectrometer. The freezing point observations of thin liquid sulfuric acid films show that for acid contents between 75 and 85 wt % the monohydrate crystallizes readily at temperatures between 220 and 240 K on a glass substrate. Once formed, SAM can be thermodynamically stable in the H2O partial pressure range of (1-4) x 10(exp -4) torr and in the temperature range of 220-240 K. For a constant H2O partial pressure, lowering the temperature causes SAM to melt when the temperature and water partial pressure conditions are out of its stability regime. The reaction probability measurements indicate that the hydrolysis of N2O5 is significantly suppressed owing to the formation of crystalline SAM: The reaction probability on water-rich SAM (with higher relative humidity, or RH) is of the order of 10(exp -3) at 210 K and decreases by more than an order of magnitude for the acid-rich form (with lower RH). The hydrolysis rate of ClONO2 on water-rich SAM is even smaller, of the order of 10(exp -4) at 195 K. These reported values on crystalline SAM are much smaller than those on liquid solutions. No enhancement of these reactions is observed in the presence of HCl vapor at the stratospheric concentrations. In addition, Brunauer, Emmett, and Teller analysis of gas adsorption isotherms and photomicrography have been performed to characterize the surface roughness and porosities of the SAM substrate. The results suggest the possible formation of SAM in some regions of the middle- or low-latitude stratosphere and, consequently, much slower heterogeneous reactions on the frozen aerosols.

Heterogeneous Ice Nucleation Ability of NaCl and Sea Salt Aerosol Particles at Cirrus Temperatures

NASA Astrophysics Data System (ADS)

Wagner, Robert; Kaufmann, Julia; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin; Ullrich, Romy; Leisner, Thomas

2018-03-01

In situ measurements of the composition of heterogeneous cirrus ice cloud residuals have indicated a substantial contribution of sea salt in sampling regions above the ocean. We have investigated the heterogeneous ice nucleation ability of sodium chloride (NaCl) and sea salt aerosol (SSA) particles at cirrus cloud temperatures between 235 and 200 K in the Aerosol Interaction and Dynamics in the Atmosphere aerosol and cloud chamber. Effloresced NaCl particles were found to act as ice nucleating particles in the deposition nucleation mode at temperatures below about 225 K, with freezing onsets in terms of the ice saturation ratio, Sice, between 1.28 and 1.40. Above 225 K, the crystalline NaCl particles deliquesced and nucleated ice homogeneously. The heterogeneous ice nucleation efficiency was rather similar for the two crystalline forms of NaCl (anhydrous NaCl and NaCl dihydrate). Mixed-phase (solid/liquid) SSA particles were found to act as ice nucleating particles in the immersion freezing mode at temperatures below about 220 K, with freezing onsets in terms of Sice between 1.24 and 1.42. Above 220 K, the SSA particles fully deliquesced and nucleated ice homogeneously. Ice nucleation active surface site densities of the SSA particles were found to be in the range between 1.0 · 1010 and 1.0 · 1011 m-2 at T < 220 K. These values are of the same order of magnitude as ice nucleation active surface site densities recently determined for desert dust, suggesting a potential contribution of SSA particles to low-temperature heterogeneous ice nucleation in the atmosphere.

"Sizing" Heterogeneous Chemistry in the Conversion of Gaseous Dimethyl Sulfide to Atmospheric Particles.

PubMed

Enami, Shinichi; Sakamoto, Yosuke; Hara, Keiichiro; Osada, Kazuo; Hoffmann, Michael R; Colussi, Agustín J

2016-02-16

The oxidation of biogenic dimethyl sulfide (DMS) emissions is a global source of cloud condensation nuclei. The amounts of the nucleating H2SO4(g) species produced in such process, however, remain uncertain. Hydrophobic DMS is mostly oxidized in the gas phase into H2SO4(g) + DMSO(g) (dimethyl sulfoxide), whereas water-soluble DMSO is oxidized into H2SO4(g) in the gas phase and into SO4(2-) + MeSO3(-) (methanesulfonate) on water surfaces. R = MeSO3(-)/(non-sea-salt SO4(2-)) ratios would therefore gauge both the strength of DMS sources and the extent of DMSO heterogeneous oxidation if Rhet = MeSO3(-)/SO4(2-) for DMSO(aq) + ·OH(g) were known. Here, we report that Rhet = 2.7, a value obtained from online electrospray mass spectra of DMSO(aq) + ·OH(g) reaction products that quantifies the MeSO3(-) produced in DMSO heterogeneous oxidation on aqueous aerosols for the first time. On this basis, the inverse R dependence on particle radius in size-segregated aerosol collected over Syowa station and Southern oceans is shown to be consistent with the competition between DMSO gas-phase oxidation and its mass accommodation followed by oxidation on aqueous droplets. Geographical R variations are thus associated with variable contributions of the heterogeneous pathway to DMSO atmospheric oxidation, which increase with the specific surface area of local aerosols.

Observations of Ozone-aerosol Correlated Behaviour in the Lower Stratosphere During the EASOE Campaign

NASA Technical Reports Server (NTRS)

Digirolamo, P.; Cacciani, M.; Disarra, A.; Fiocco, G.; Fua, D.; Joergensen, T. S.; Knudsen, B.; Larsen, N.

1992-01-01

The question of possible interactions between ozone and stratospheric aerosol has been open for a long time. Measurements carried out after the Mt. Agung and El Chicon eruptions showed evidence of negative correlations between the presence of volcanic stratospheric aerosols and ozone concentration. Evidence for negative correlations in the polar winter has been also found. It is only after the discovery of the Antarctic ozone hole that catalytic effects related to low temperature heterogeneous chemistry have become the object of much investigation, now extended to the role of volcanic aerosol in the ozone reduction. These phenomena can be the object of various interpretations, not mutually exclusive, including the effect of transport, diffuse radiation as well as heterogeneous chemistry. The present paper provides preliminary results of simultaneous measurements of ozone and aerosol, carried out at Thule, Greenland, during the winter 1991-92. The European Stratospheric Ozone Experiment (EASOE) was aimed at monitoring the winter Arctic stratosphere in order to obtain a deeper insight of the ozone destruction processes taking place in the polar regions. A large amount of aerosol was injected into the lower stratosphere by the recent eruption of Volcano Pinatubo. A lidar system, already operational in Thule since November 1990, has provided detailed measurements of the stratospheric aerosol concentration during EASOE. In the same period, a large number of ozonesondes were launched. Although no PSC formation was detected over Thule, the simultaneous measurement of the stratospheric aerosol and ozone profiles give the possibility to study interactions occurring in the stratosphere between these two constituents.

Stratospheric ion and aerosol chemistry and possible links with cirrus cloud microphysics - A critical assessment

NASA Technical Reports Server (NTRS)

Mohnen, Volker A.

1990-01-01

Aspects of stratospheric ion chemistry and physics are assessed as they relate to aerosol formation and the transport of aerosols to upper tropospheric regions to create conditions favorable for cirrus cloud formation. It is found that ion-induced nucleation and other known phase transitions involving ions and sulfuric acid vapor are probably not efficient processes for stratospheric aerosol formation, and cannot compete with condensation of sulfuric acid on preexisting particles of volcanic or meteoritic origin which are larger than about 0.15 micron in radius. Thus, galactic cosmic rays cannot have a significant impact on stratospheric aerosol population. Changes in the stratospheric aerosol burden due to volcanos are up to two orders of magnitude larger than changes in ion densities. Thus, volcanic activity may modulate the radiative properties of cirrus clouds.

Aerosol chemistry in GLOBE

NASA Technical Reports Server (NTRS)

Clarke, Antony D.; Rothermel, Jeffry; Jarzembski, Maurice A.

1993-01-01

This task addresses the measurement and understanding of the physical and chemical properties of aerosol in remote regions that are responsible for aerosol backscatter at infrared wavelengths. Because it is representative of other clean areas, the remote Pacific is of extreme interest. Emphasis is on the determination size dependent aerosol properties that are required for modeling backscatter at various wavelengths and upon those features that may be used to help understand the nature, origin, cycling and climatology of these aerosols in the remote troposphere. Empirical relationships will be established between lidar measurements and backscatter derived from the aerosol microphysics as required by the NASA Doppler Lidar Program. This will include the analysis of results from the NASA GLOBE Survey Mission Flight Program. Additional instrument development and deployment will be carried out in order to extend and refine this data base. Identified activities include participation in groundbased and airborne experiments. Progress to date includes participation in, analysis of, and publication of results from Mauna Loa Backscatter Intercomparison Experiment (MABIE) and Global Backscatter Experiment (GLOBE).

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%.

Climatology of the Aerosol Optical Depth by Components from the Multi-Angle Imaging Spectroradiometer (MISR) and Chemistry Transport Models

NASA Technical Reports Server (NTRS)

Lee, Huikyo; Kalashnikova, Olga V.; Suzuki, Kentaroh; Braverman, Amy; Garay, Michael J.; Kahn, Ralph A.

2016-01-01

The Multi-angle Imaging Spectroradiometer (MISR) Joint Aerosol (JOINT_AS) Level 3 product has provided a global, descriptive summary of MISR Level 2 aerosol optical depth (AOD) and aerosol type information for each month over 16+ years since March 2000. Using Version 1 of JOINT_AS, which is based on the operational (Version 22) MISR Level 2 aerosol product, this study analyzes, for the first time, characteristics of observed and simulated distributions of AOD for three broad classes of aerosols: spherical nonabsorbing, spherical absorbing, and nonspherical - near or downwind of their major source regions. The statistical moments (means, standard deviations, and skew-nesses) and distributions of AOD by components derived from the JOINT_AS are compared with results from two chemistry transport models (CTMs), the Goddard Chemistry Aerosol Radiation and Transport (GOCART) and SPectral RadIatioN-TrAnSport (SPRINTARS). Overall, the AOD distributions retrieved from MISR and modeled by GOCART and SPRINTARS agree with each other in a qualitative sense. Marginal distributions of AOD for each aerosol type in both MISR and models show considerable high positive skewness, which indicates the importance of including extreme AOD events when comparing satellite retrievals with models. The MISR JOINT_AS product will greatly facilitate comparisons between satellite observations and model simulations of aerosols by type.

The chemistry-climate model ECHAM6.3-HAM2.3-MOZ1.0

NASA Astrophysics Data System (ADS)

Schultz, Martin G.; Stadtler, Scarlet; Schröder, Sabine; Taraborrelli, Domenico; Franco, Bruno; Krefting, Jonathan; Henrot, Alexandra; Ferrachat, Sylvaine; Lohmann, Ulrike; Neubauer, David; Siegenthaler-Le Drian, Colombe; Wahl, Sebastian; Kokkola, Harri; Kühn, Thomas; Rast, Sebastian; Schmidt, Hauke; Stier, Philip; Kinnison, Doug; Tyndall, Geoffrey S.; Orlando, John J.; Wespes, Catherine

2018-05-01

The chemistry-climate model ECHAM-HAMMOZ contains a detailed representation of tropospheric and stratospheric reactive chemistry and state-of-the-art parameterizations of aerosols using either a modal scheme (M7) or a bin scheme (SALSA). This article describes and evaluates the model version ECHAM6.3-HAM2.3-MOZ1.0 with a focus on the tropospheric gas-phase chemistry. A 10-year model simulation was performed to test the stability of the model and provide data for its evaluation. The comparison to observations concentrates on the year 2008 and includes total column observations of ozone and CO from IASI and OMI, Aura MLS observations of temperature, HNO3, ClO, and O3 for the evaluation of polar stratospheric processes, an ozonesonde climatology, surface ozone observations from the TOAR database, and surface CO data from the Global Atmosphere Watch network. Global budgets of ozone, OH, NOx, aerosols, clouds, and radiation are analyzed and compared to the literature. ECHAM-HAMMOZ performs well in many aspects. However, in the base simulation, lightning NOx emissions are very low, and the impact of the heterogeneous reaction of HNO3 on dust and sea salt aerosol is too strong. Sensitivity simulations with increased lightning NOx or modified heterogeneous chemistry deteriorate the comparison with observations and yield excessively large ozone budget terms and too much OH. We hypothesize that this is an impact of potential issues with tropical convection in the ECHAM model.

Ozone loss in the lower stratosphere over the United States in 1992-1993: Evidence for heterogeneous chemistry on the Pinatubo aerosol

NASA Technical Reports Server (NTRS)

Hofmann, D. J.; Oltmans, S. J.; Komhyr, W. D.; Harris, J. M.; Lathrop, J. A.; Langford, A. O.; Deshler, T.; Johnson, B. J.; Torres, A.; Matthews, W. A.

1994-01-01

Ozone profiles obtained at Boulder, Colorado and Wallops Island, Virginia indicate that ozone was about 25% below normal during the winter and spring of 1992-93 in the 12-22 km region. This large ozone reduction in the lower stratosphere, though sometimes partially compensated by higher than normal ozone above 24 km, was responsible for the low total column ozone values observed across the United States during this period. Normal temperatures throughout the low ozone region suggest that transport-related effects are probably not the most important cause of the ozone deficits. This region of low ozone at Boulder corresponds closely with the location of the enhanced H2SO4/H2O aerosol from the Pinatubo eruption of 1991 as measured near Boulder and at Laramie, Wyoming. Trajectory analyses suggest that except at low altitudes in spring, air parcels on the days of the ozone measurements generally arrived at Boulder from higher latitude, although seldom higher than 60 deg N, and hence may have been subjected to heterogeneous chemical processing on the surface of Pinatubo aerosol droplets resulting in chlorine-catalyzed ozone destruction, a process which is believed to be more effective under the lower winter temperatures and sunlight levels of higher latitudes.

Trace Chemistry

NASA Technical Reports Server (NTRS)

Radhakrishnan, Krishnan; Whitefield, Philip

1999-01-01

The goals of the trace chemistry group were to identify the processes relevant to aerosol and aerosol precursor formation occurring within aircraft gas turbine engines; that is, within the combustor, turbine, and nozzle. The topics of discussion focused on whether the chemistry of aerosol formation is homogeneous or heterogeneous; what species are important for aerosol and aerosol precursor formation; what modeling/theoretical activities to pursue; what experiments to carry out that both support modeling activities and elucidate fundamental processes; and the role of particulates in aerosol and aerosol precursor formation. The consensus of the group was that attention should be focused on SO2, SO3, and aerosols. Of immediate concern is the measurement of the concentration of the species SO3, SO2, H2SO4 OH, HO2, H2O2, O, NO, NO2, HONO, HNO3, CO, and CO2 and particulates in various engines, both those currently in use and those in development. The recommendation was that concentration measurements should be made at both the combustor exit and the engine exit. At each location the above species were classified into one of four categories of decreasing importance, Priority I through IV, as follows: Combustor exit: Priority I species - SO3:SO2 ratio, SO3, SO2, and particulates; Priority II species: OH and O; Priority III species - NO and NO2; and Priority IV species - CO and CO2. For the Engine exit: Priority I species - SO3:SO2 ratio, SO3, SO2,H2SO4, and particulates; Priority II species: OH,HO2, H2O2, and O; Priority III species - NO, NO2, HONO, and HNO3; and Priority IV species - CO and CO2. Table I summarizes the anticipated concentration range of each of these species. For particulate matter, the quantities of interest are the number density, size distribution, and composition. In order to provide data for validating multidimensional reacting flow models, it would be desirable to make 2-D, time-resolved measurements of the concentrations of the above species and

Aerosol modelling and validation during ESCOMPTE 2001

NASA Astrophysics Data System (ADS)

Cousin, F.; Liousse, C.; Cachier, H.; Bessagnet, B.; Guillaume, B.; Rosset, R.

The ESCOMPTE 2001 programme (Atmospheric Research. 69(3-4) (2004) 241) has resulted in an exhaustive set of dynamical, radiative, gas and aerosol observations (surface and aircraft measurements). A previous paper (Atmospheric Research. (2004) in press) has dealt with dynamics and gas-phase chemistry. The present paper is an extension to aerosol formation, transport and evolution. To account for important loadings of primary and secondary aerosols and their transformation processes in the ESCOMPTE domain, the ORISAM aerosol module (Atmospheric Environment. 35 (2001) 4751) was implemented on-line in the air-quality Meso-NH-C model. Additional developments have been introduced in ORganic and Inorganic Spectral Aerosol Module (ORISAM) to improve the comparison between simulations and experimental surface and aircraft field data. This paper discusses this comparison for a simulation performed during one selected day, 24 June 2001, during the Intensive Observation Period IOP2b. Our work relies on BC and OCp emission inventories specifically developed for ESCOMPTE. This study confirms the need for a fine resolution aerosol inventory with spectral chemical speciation. BC levels are satisfactorily reproduced, thus validating our emission inventory and its processing through Meso-NH-C. However, comparisons for reactive species generally denote an underestimation of concentrations. Organic aerosol levels are rather well simulated though with a trend to underestimation in the afternoon. Inorganic aerosol species are underestimated for several reasons, some of them have been identified. For sulphates, primary emissions were introduced. Improvement was obtained too for modelled nitrate and ammonium levels after introducing heterogeneous chemistry. However, no modelling of terrigeneous particles is probably a major cause for nitrates and ammonium underestimations. Particle numbers and size distributions are well reproduced, but only in the submicrometer range. Our work points out

Heterogeneous reactions in aircraft gas turbine engines

NASA Astrophysics Data System (ADS)

Brown, R. C.; Miake-Lye, R. C.; Lukachko, S. P.; Waitz, I. A.

2002-05-01

One-dimensional flow models and unity probability heterogeneous rate parameters are used to estimate the maximum effect of heterogeneous reactions on trace species evolution in aircraft gas turbines. The analysis includes reactions on soot particulates and turbine/nozzle material surfaces. Results for a representative advanced subsonic engine indicate the net change in reactant mixing ratios due to heterogeneous reactions is <10-6 for O2, CO2, and H2O, and <10-10 for minor combustion products such as SO2 and NO2. The change in the mixing ratios relative to the initial values is <0.01%. Since these estimates are based on heterogeneous reaction probabilities of unity, the actual changes will be even lower. Thus, heterogeneous chemistry within the engine cannot explain the high conversion of SO2 to SO3 which some wake models require to explain the observed levels of volatile aerosols. Furthermore, turbine heterogeneous processes will not effect exhaust NOx or NOy levels.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Developing a new parameterization framework for the heterogeneous ice nucleation of atmospheric aerosol particles

NASA Astrophysics Data System (ADS)

Ullrich, Romy; Hiranuma, Naruki; Hoose, Corinna; Möhler, Ottmar; Niemand, Monika; Steinke, Isabelle; Wagner, Robert

2014-05-01

Developing a new parameterization framework for the heterogeneous ice nucleation of atmospheric aerosol particles Ullrich, R., Hiranuma, N., Hoose, C., Möhler, O., Niemand, M., Steinke, I., Wagner, R. Aerosols of different nature induce microphysical processes of importance for the Earth's atmosphere. They affect not only directly the radiative budget, more importantly they essentially influence the formation and life cycles of clouds. Hence, aerosols and their ice nucleating ability are a fundamental input parameter for weather and climate models. During the previous years, the AIDA (Aerosol Interactions and Dynamics in the Atmosphere) cloud chamber was used to extensively measure, under nearly realistic conditions, the ice nucleating properties of different aerosols. Numerous experiments were performed with a broad variety of aerosol types and under different freezing conditions. A reanalysis of these experiments offers the opportunity to develop a uniform parameterization framework of ice formation for many atmospherically relevant aerosols in a broad temperature and humidity range. The analysis includes both deposition nucleation and immersion freezing. The aim of this study is to develop this comprehensive parameterization for heterogeneous ice formation mainly by using the ice nucleation active site (INAS) approach. Niemand et al. (2012) already developed a temperature dependent parameterization for the INAS- density for immersion freezing on desert dust particles. In addition to a reanalysis of the ice nucleation behaviour of desert dust (Niemand et al. (2012)), volcanic ash (Steinke et al. (2010)) and organic particles (Wagner et al. (2010,2011)) this contribution will also show new results for the immersion freezing and deposition nucleation of soot aerosols. The next step will be the implementation of the parameterizations into the COSMO- ART model in order to test and demonstrate the usability of the framework. Hoose, C. and Möhler, O. (2012) Atmos

OCEANFILMS-2: Representing coadsorption of saccharides in marine films and potential impacts on modeled marine aerosol chemistry

NASA Astrophysics Data System (ADS)

Burrows, Susannah M.; Gobrogge, Eric; Fu, Li; Link, Katie; Elliott, Scott M.; Wang, Hongfei; Walker, Rob

2016-08-01

Here we show that the addition of chemical interactions between soluble monosaccharides and an insoluble lipid surfactant monolayer improves agreement of modeled sea spray chemistry with observed marine aerosol chemistry. In particular, the alkane:hydroxyl mass ratio in modeled sea spray organic matter is reduced from a median of 2.73 to a range of 0.41-0.69, reducing the discrepancy with previous Fourier transform infrared spectroscopy (FTIR) observations of clean marine aerosol (ratio: 0.24-0.38). The overall organic fraction of submicron sea spray also increases, allowing organic mass fractions in the range 0.5-0.7 for submicron sea spray particles over highly active phytoplankton blooms. Sum frequency generation experiments support the modeling approach by demonstrating that soluble monosaccharides can strongly adsorb to a lipid monolayer likely via Coulomb interactions under appropriate conditions. These laboratory findings motivate further research to determine the relevance of coadsorption mechanisms for real-world, sea spray aerosol production.

Effects of synoptic patterns on atmospheric chemistry and aerosols during the Arctic Ocean Expedition 1996

NASA Astrophysics Data System (ADS)

Nilsson, E. Douglas; Barr, Sumner

2001-12-01

The atmospheric program on the Arctic Ocean Expedition of July through September 1996 (AOE-96) was focused on aerosol climate feedback. The expedition took place close to the saddle point between a semipersistent anticyclonic ridge from near Scandinavia to the Arctic coast of eastern Siberia and a trough from the Canadian archipelago across the pole to north central Siberia. The weather varied from anticyclonic clear-sky conditions to cyclonic cloudy conditions, and 13 identifiable migratory features (frontal bands, wave disturbances) clearly influenced local weather, clouds, atmospheric transport, and chemistry. This includes an explosive polar cyclone, born at the lateral heat gradient between Greenland and the pack ice rather than between open sea and the pack ice. The synoptic scale weather systems caused the strongest variability in trace gases (O3 in particular) and aerosols, and also strong variability in the cloud cover. The formation of air masses over the pack ice primarily depends on if there is cyclonic (convergent) or anticyclonic (divergent) flow. Cyclonic flow resulted in a modified marine air mass loaded with vapor, but with low aerosol number concentrations owing to frequent clouds and fogs and efficient cloud scavenging of the aerosol. Anticyclonic flow resulted in almost continental air masses with clear sky, long residence time over the pack ice and subsidence slowly replacing the boundary layer with free tropospheric air, low vapor concentrations, but large aerosol number in lack of efficient cloud scavenging. The synoptic variability and advection from south of the ice edge were weaker than during the predecessor International Arctic Ocean Expedition in 1991 (IAOE-91), when on average the sampled air spent 55 hours over the pack ice compared to more than 120 hours during AOE-96, owing to exceptionally high cyclone activity in 1991. This caused a large difference in atmospheric transport, chemistry, and aerosols between the two expeditions.

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

DOE PAGES

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

2015-10-27

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

Sulfate aerosols and polar stratospheric cloud formation

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

Tolbert, M.A.

Before the discovery of the Antarctic ozone hole, it was generally assumed that gas-phase chemical reactions controlled the abundance of stratospheric ozone. However, the massive springtime ozone losses over Antarctica first reported by Farman et al in 1985 could not be explained on the basis of gas-phase chemistry alone. In 1986, Solomon et al suggested that chemical reactions occurring on the surfaces of polar stratospheric clouds (PSCs) could be important for the observed ozone losses. Since that time, an explosion of laboratory, field, and theoretical research in heterogeneous atmospheric chemistry has occurred. Recent work has indicated that the most importantmore » heterogeneous reaction on PSCs is ClONO[sub 2] + HCl [yields] Cl[sub 2] + HNO[sub 3]. This reaction converts inert chlorine into photochemically active Cl[sub 2]. Photolysis of Cl[sub 2] then leads to chlorine radicals capable of destroying ozone through very efficient catalytic chain reactions. New observations during the second Airborne Arctic Stratospheric Expedition found stoichiometric loss of ClONO[sub 2] and HCl in air processed by PSCs in accordance with reaction 1. Attention is turning toward understanding what kinds of aerosols form in the stratospheric, their formation mechanism, surface area, and specific chemical reactivity. Some of the latest findings, which underline the importance of aerosols, were presented at a recent National Aeronautics and Space Administration workshop in Boulder, Colorado.« less

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

Modelling of strong heterogeneities in aerosol single scattering albedos over a polluted region

NASA Astrophysics Data System (ADS)

Mallet, M.; Pont, V.; Liousse, C.

2005-05-01

To date, most models dedicated to the investigation of aerosol direct or semi-direct radiative forcings have assumed the various aerosol components to be either completely externally mixed or homogeneously internally mixed. Some recent works have shown that a core-shell treatment of particles should be more realistic, leading to significant differences in the radiative impact as compared to only externally or well-internally mixed states. To account for these studies, an optical module, ORISAM-RAD, has been developed for computing aerosol radiative properties under the hypothesis of internally mixed particles with a n-layer spherical concentric structure. Mesoscale simulations using ORISAM-RAD, coupled with the 3D mesoscale model Meso-NH-C, have been performed for one selected day (06/24/2001) during the ESCOMPTE experiment in the Marseilles-Fos/Berre region, which illustrate the ability of this new module to reproduce spatial heterogeneities of measured single scattering albedo (ωo), due to industrial and/or urban pollution plumes.

Diffusive confinement of free radical intermediates in the OH radical oxidation of semisolid aerosols

DOE PAGES

Wiegel, Aaron A.; Liu, Matthew J.; Hinsberg, William D.; ...

2017-02-07

Multiphase chemical reactions (gas + solid/liquid) involve a complex interplay between bulk and interface chemistry, diffusion, evaporation, and condensation. Reactions of atmospheric aerosols are an important example of this type of chemistry: the rich array of particle phase states and multiphase transformation pathways produce diverse but poorly understood interactions between chemistry and transport. Their chemistry is of intrinsic interest because of their role in controlling climate. Their characteristics also make them useful models for the study of principles of reactivity of condensed materials under confined conditions. Previously, we have reported a computational study of the oxidation chemistry of a liquidmore » aliphatic aerosol. In this study, we extend the calculations to investigate nearly the same reactions at a semisolid gas-aerosol interface. A reaction-diffusion model for heterogeneous oxidation of triacontane by hydroxyl radicals (OH) is described, and its predictions are compared to measurements of aerosol size and composition, which evolve continuously during oxidation. Our results are also explicitly compared to those obtained for the corresponding liquid system, squalane, to pinpoint salient elements controlling reactivity. The diffusive confinement of the free radical intermediates at the interface results in enhanced importance of a few specific chemical processes such as the involvement of aldehydes in fragmentation and evaporation, and a significant role of radical-radical reactions in product formation. The simulations show that under typical laboratory conditions semisolid aerosols have highly oxidized nanometer-scale interfaces that encapsulate an unreacted core and may confer distinct optical properties and enhanced hygroscopicity. This highly oxidized layer dynamically evolves with reaction, which we propose to result in plasticization. The validated model is used to predict chemistry under atmospheric conditions, where the OH

Examining the impact of nitryl chloride chemistry on summertime air quality

NASA Astrophysics Data System (ADS)

Sarwar, G.; Simon, H. A.; Bhave, P.; Hutzell, W. T.

2011-12-01

Results of recent field campaigns suggest that heterogeneous reactions can form nitryl chloride (ClNO2) at night. ClNO2 photodissociates into nitrogen dioxide and chlorine radicals during the day. Subsequent photolysis of nitrogen dioxide and reactions of chlorine radicals with volatile organic compounds increase ozone production. Thus, the presence of ClNO2 in the atmosphere can enhance ozone. In this study, the impact of the heterogeneous production of ClNO2 on summertime air quality in the United States is examined by using the Community Multiscale Air Quality (CMAQ) model. Laboratory chamber experimental studies have parameterized the yield of ClNO2 and the heterogeneous uptake of dinitrogen pentoxide on aerosols. We implement these parameterizations into the CMAQ model. In addition to the typical emissions, the model also includes emissions of sea-salt, anthropogenic particulate chloride, anthropogenic hydrochloric acid and molecular chlorine from the National Emissions Inventory. Model simulations are conducted without and with the heterogeneous ClNO2 formation reaction for September 1-10, 2006. The results of the study suggest that the heterogeneous reaction produces ClNO2 in many coastal areas as well as inland locations in the United States. The ClNO2 increase in coastal areas is caused by chloride emissions from sea-salt and in inland-areas by chloride emissions from fire and anthropogenic sources. Predicted ClNO2 levels reach nighttime peaks of up to 4.0 ppb in the Los Angeles area and up to 1.2 ppb near Houston, similar to the measured values reported in the literature. The ClNO2 chemistry decreases nitric acid as well as particulate nitrate by a large margin; consequently it changes composition of NOz. It increases hourly and daily maximum 8-hr ozone by up to 9 ppbv and 6 ppbv, respectively. It increases aerosol sulfate while decreasing aerosol nitrate and ammonium. The accompanying presentation identifies predicted spatial patterns of ClNO2

Heterogeneous reaction of N2O5 with airborne TiO2 particles and its implication for stratospheric particle injection

NASA Astrophysics Data System (ADS)

Tang, M. J.; Telford, P. J.; Pope, F. D.; Rkiouak, L.; Abraham, N. L.; Archibald, A. T.; Braesicke, P.; Pyle, J. A.; McGregor, J.; Watson, I. M.; Cox, R. A.; Kalberer, M.

2014-06-01

Injection of aerosol particles (or their precursors) into the stratosphere to scatter solar radiation back into space has been suggested as a solar-radiation management scheme for the mitigation of global warming. TiO2 has recently been highlighted as a possible candidate particle because of its high refractive index, but its impact on stratospheric chemistry via heterogeneous reactions is as yet unknown. In this work the heterogeneous reaction of airborne sub-micrometre TiO2 particles with N2O5 has been investigated for the first time, at room temperature and different relative humidities (RH), using an atmospheric pressure aerosol flow tube. The uptake coefficient of N2O5 onto TiO2, γ(N2O5), was determined to be ~1.0 × 10-3 at low RH, increasing to ~3 × 10-3 at 60% RH. The uptake of N2O5 onto TiO2 is then included in the UKCA chemistry-climate model to assess the impact of this reaction on stratospheric chemistry. While the impact of TiO2 on the scattering of solar radiation is chosen to be similar to the aerosol from the Mt Pinatubo eruption, the impact of TiO2 injection on stratospheric N2O5 is much smaller.

Heterogeneous Uptake of HO2 Radicals onto Submicron Atmospheric Aerosols

NASA Astrophysics Data System (ADS)

Matthews, P. S.; George, I. J.; Brooks, B.; Whalley, L. K.; Baeza-Romero, M. T.; Heard, D. E.

2012-12-01

OH and HO2 (HOx) radicals are closely coupled and OH is responsible for the majority of the oxidation in the troposphere and controls the concentrations of many trace species. Therefore, it is important to be able to accurately predict HOx concentrations. However, some field measurement studies have reported significantly lower HO2 radical concentrations than calculated by constrained box models using detailed chemical mechanisms. Although the inclusion of halogen chemistry into the mechanisms can explain much of the differences in the marine boundary layer (MBL) (1,2), HO2 uptake by aerosols has been suggested as a possible sink in the MBL (2), the Arctic troposphere (3) and the upper troposphere (4). There have been very few laboratory studies (5,6) on HO2 uptake by aerosols and the rates and mechanism is still uncertain. The HO2 uptake coefficients were measured for a variety of atmospherically relevant inorganic and organic aerosols. The measurements were performed using an aerosol flow tube combined with a Fluorescence Assay by Gas Expansion (FAGE) detector. The sensitive FAGE cell allowed low HO2 concentrations (108-109 molecule cm-3) to be injected into the flow tube using a moveable injector. By moving the injector along the flow tube, position dependent HO2 decays were able to be recorded which when plotted against the total aerosol surface area allowed an uptake coefficient to be obtained. The aerosols were generated using an atomiser or by homogeneous nucleation and the total aerosol surface area was measured using a Scanning Mobility Particle Sizer. The HO2 uptake coefficient (γ) was measured at room temperature for dry inorganic salts and dry organics (γ< 0.004), wet inorganic salts and wet organics (γ= 0.002-0.005), wet copper doped ammonium sulfate aerosols (γ= 0.28± 0.05) and ammonium sulfate aerosols doped with different molar amounts of iron (γ= 0.003-0.06). The pH dependence of the HO2 uptake coefficient was investigated, however no

Model analysis of secondary organic aerosol formation by glyoxal in laboratory studies: the case for photoenhanced chemistry.

PubMed

Sumner, Andrew J; Woo, Joseph L; McNeill, V Faye

2014-10-21

The reactive uptake of glyoxal by atmospheric aerosols is believed to be a significant source of secondary organic aerosol (SOA). Several recent laboratory studies have been performed with the goal of characterizing this process, but questions remain regarding the effects of photochemistry on SOA growth. We applied GAMMA (McNeill et al. Environ. Sci. Technol. 2012, 46, 8075-8081), a photochemical box model with coupled gas-phase and detailed aqueous aerosol-phase chemistry, to simulate aerosol chamber studies of SOA formation by the uptake of glyoxal by wet aerosol under dark and irradiated conditions (Kroll et al. J. Geophys. Res. 2005, 110 (D23), 1-10; Volkamer et al. Atmos. Chem. Phys. 2009, 9, 1907-1928; Galloway et al. Atmos. Chem. Phys. 2009, 9, 3331- 306 3345 and Geophys. Res. Lett. 2011, 38, L17811). We find close agreement between simulated SOA growth and the results of experiments conducted under dark conditions using values of the effective Henry's Law constant of 1.3-5.5 × 10(7) M atm(-1). While irradiated conditions led to the production of some organic acids, organosulfates, and other oxidation products via well-established photochemical mechanisms, these additional product species contribute negligible aerosol mass compared to the dark uptake of glyoxal. Simulated results for irradiated experiments therefore fell short of the reported SOA mass yield by up to 92%. This suggests a significant light-dependent SOA formation mechanism that is not currently accounted for by known bulk photochemistry, consistent with recent laboratory observations of SOA production via photosensitizer chemistry.

OCEANFILMS-2: Representing coadsorption of saccharides in marine films and potential impacts on modeled marine aerosol chemistry

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

Burrows, Susannah M.; Gobrogge, Eric; Fu, Li

Here we show that the addition of chemical interactions of soluble polysaccharides with a surfactant monolayer improves agreement of modeled sea spray chemistry with observed marine aerosol chemistry. In particular, the fraction of hydroxyl functional groups in modeled sea spray organic matter is increased, improving agreement with FTIR observations of marine aerosol composition. The overall organic fraction of submicron sea spray also increases, allowing organic mass fractions in the range 0.5 – 0.7 for submicron sea spray particles over highly active phytoplankton blooms. We show results from Sum Frequency Generation (SFG) experiments that support the modeling approach, by demonstrating thatmore » soluble polysaccharides can strongly adsorb to a lipid monolayer via columbic interactions under appropriate conditions.« less

Radical loss in the atmosphere from Cu-Fe redox coupling in aerosols

NASA Astrophysics Data System (ADS)

Mao, J.; Fan, S.; Jacob, D. J.; Travis, K.; Naik, V.; Horowitz, L. W.

2012-12-01

The hydroperoxyl radical (HO2) is a major precursor of OH and tropospheric ozone. OH is the main atmospheric oxidant, while tropospheric ozone is an important surface pollutant and greenhouse gas. Standard gas-phase models for atmospheric chemistry tend to overestimate observed HO2 concentrations, and this has been tentatively attributed to heterogeneous uptake by aerosol particles. It is generally assumed that HO2 uptake by aerosol involves conversion to H2O2, but this is of limited efficacy as an HO2 sink because H2O2 can photolyze to regenerate OH and from there HO2. Joint atmospheric observations of HO2 and H2O2 suggest that HO2 uptake by aerosols may in fact not produce H2O2. Here we propose a catalytic mechanism involving coupling of the transition metal ions (TMI) Cu(I)/Cu(II) and Fe(II)/Fe(III) to rapidly convert HO2 to H2O in aerosols. The implied HO2 uptake significantly affects global model predictions of tropospheric OH, ozone, and other species, improving comparisons to observations, and may have a major and previously unrecognized impact on atmospheric oxidant chemistry.

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

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

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

The SOA formation model combined with semiempirical quantum chemistry for predicting UV-Vis absorption of secondary organic aerosols.

PubMed

Zhong, Min; Jang, Myoseon; Oliferenko, Alexander; Pillai, Girinath G; Katritzky, Alan R

2012-07-07

A new model for predicting the UV-visible absorption spectra of secondary organic aerosols (SOA) has been developed. The model consists of two primary parts: a SOA formation model and a semiempirical quantum chemistry method. The mass of SOA is predicted using the PHRCSOA (Partitioning Heterogeneous Reaction Consortium Secondary Organic Aerosol) model developed by Cao and Jang [Environ. Sci. Technol., 2010, 44, 727]. The chemical composition is estimated using a combination of the kinetic model (MCM) and the PHRCSOA model. The absorption spectrum is obtained by taking the sum of the spectrum of each SOA product calculated using a semiempirical NDDO (Neglect of Diatomic Differential Overlap)-based method. SOA was generated from the photochemical reaction of toluene or α-pinene at different NO(x) levels (low NO(x): 24-26 ppm, middle NO(x): 49 ppb, high NO(x): 104-105 ppb) using a 2 m(3) indoor Teflon film chamber. The model simulation reasonably agrees with the measured absorption spectra of α-pinene SOA but underestimates toluene SOA under high and middle NO(x) conditions. The absorption spectrum of toluene SOA is moderately enhanced with increasing NO(x) concentrations, while that of α-pinene SOA is not affected. Both measured and calculated UV-visible spectra show that the light absorption of toluene SOA is much stronger than that of α-pinene SOA.

The Impact of Organic Surfactants and Coatings in Regulating Heterogeneous N2O5 Reaction Kinetics on Nascent Marine Aerosol

NASA Astrophysics Data System (ADS)

Ryder, O. S.; Campbell, N.; Schill, S.; Pöhlker, C.; Andreae, M. O.; Bertram, T. H.

2013-12-01

The heterogeneous reaction of N2O5 on aerosol particles impacts both the lifetime of nitrogen oxides, and the production rate of chlorine radicals following the activation of particulate chloride to nitryl chloride in both coastal and continental regions. The extent to which N2O5 reactivity impacts oxidant loadings depends on the heterogeneous reaction rate, which is directly influenced by aerosol chemical composition, morphology, and physical phase state. In the marine environment, the chemical composition of aerosol particles produced via wave induced bubble bursting mechanisms varies greatly and is influenced by the composition of the sea surface microlayer . Here, we present direct measurements of N2O5 reaction kinetics determined using model sea-spray particles generated in a novel Marine Aerosol Reference Tank (MART), capable of generating accurate mimics of ambient sea spray particles, in a lab environment. Here, a synthetic sea salt ocean was sequentially doped with organic molecules chosen to mimic organic species present in natural sea water over the course of a phytoplankton bloom in the open ocean. These included sterol, galactose, lippolysaccharide, BSA protein, and 1,2-dipalmitoyl-sn-glycero-3-phosphate (DPPA). These observations permit discussion of the role of marine organics in regulating heterogeneous reaction kinetics, as well a re-evaluation of potential organic lab proxies for marine organics.

Stratospheric aerosol acidity, density, and refractive index deduced from SAGE 2 and NMC temperature data

NASA Technical Reports Server (NTRS)

Yue, G. K.; Poole, L. R.; Wang, P.-H.; Chiou, E. W.

1994-01-01

Water vapor concentrations obtained by the Stratospheric Aerosol and Gas Experiment 2 (SAGE 2) and collocated temperatures provided by the National Meteorological Center (NMC) from 1986 to 1990 are used to deduce seasonally and zonally averaged acidity, density, and refractive index of stratospheric aerosols. It is found that the weight percentage of sulfuric acid in the aerosols increases from about 60 just above the tropopause to about 86 at 35 km. The density increases from about 1.55 to 1.85 g/cu cm between the same altitude limits. Some seasonal variations of composition and density are evident at high latitudes. The refractive indices at 1.02, 0.694, and 0.532 micrometers increase, respectively, from about 1.425, 1.430, and 1.435 just above the tropopause to about 1.445, 1.455, and 1.458 at altitudes above 27 km, depending on the season and latitude. The aerosol properties presented can be used in models to study the effectiveness of heterogeneous chemistry, the mass loading of stratospheric aerosols, and the extinction and backscatter of aerosols at different wavelengths. Computed aerosol surface areas, rate coefficients for the heterogeneous reaction ClONO2 + H2O yields HOCl + HNO3 and aerosol mass concentrations before and after the Pinatubo eruption in June 1991 are shown as sample applications.

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

NASA Astrophysics Data System (ADS)

Tabazadeh, Azadeh

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

Homogeneous and heterogeneous chemistry along air parcel trajectories

NASA Technical Reports Server (NTRS)

Jones, R. L.; Mckenna, D. L.; Poole, L. R.; Solomon, S.

1990-01-01

The study of coupled heterogeneous and homogeneous chemistry due to polar stratospheric clouds (PSC's) using Lagrangian parcel trajectories for interpretation of the Airborne Arctic Stratosphere Experiment (AASE) is discussed. This approach represents an attempt to quantitatively model the physical and chemical perturbation to stratospheric composition due to formation of PSC's using the fullest possible representation of the relevant processes. Further, the meteorological fields from the United Kingdom Meteorological office global model were used to deduce potential vorticity and inferred regions of PSC's as an input to flight planning during AASE.

Modeling Gas-Aerosol Processes during MILAGRO 2006

NASA Astrophysics Data System (ADS)

Zaveri, R. A.; Chapman, E. G.; Easter, R. C.; Fast, J. D.; Flocke, F.; Kleinman, L. I.; Madronich, S.; Springston, S. R.; Voss, P. B.; Weinheimer, A.

2007-12-01

Significant gas-aerosol interactions are expected in the Mexico City outflow due to formation of various semi- volatile secondary inorganic and organic gases that can partition into the particulate phase and due to various heterogeneous chemical processes. A number of T0-T1-T2 Lagrangian transport episodes during the MILAGRO campaign provide focused modeling opportunities to elucidate the roles of various chemical and physical processes in the evolution of the primary trace gases and aerosol particles emitted in Mexico City over a period of 4-8 hours. Additionally, one long-range Lagrangian transport episode on March 18-19, 2006, as characterized by the Controlled Meteorological (CMET) balloon trajectories, presents an excellent opportunity to model evolution of Mexico City pollutants over 26 hours. The key tools in our analysis of these Lagrangian episodes include a comprehensive Lagrangian box-model and the WRF-chem model based on the new Model for Simulating Aerosol Interactions and Chemistry (MOSAIC), which simulates gas-phase photochemistry, heterogeneous reactions, equilibrium particulate phase-state and water content, and dynamic gas-particle partitioning for size- resolved aerosols. Extensive gas, aerosol, and meteorological measurements onboard the G1 and C130 aircraft and T0, T1, and T2 ground sites will be used to initialize, constrain, and evaluate the models. For the long-range transport event, in-situ vertical profiles of wind vectors from repeated CMET balloon soundings in the Mexico City outflow will be used to nudge the winds in the WRF-chem simulation. Preliminary model results will be presented with the intention to explore further collaborative opportunities to use additional gas and particulate measurements to better constrain and evaluate the models.

Aerosol Chemistry of Furfural and Sugars

NASA Astrophysics Data System (ADS)

Srithawirat, T.; Brimblecombe, P.

2008-12-01

Furfural and sugars (as levoglucosan equivalent) are derived from biomass burning and contribute to aerosol composition. This study examined the potential of furfural and levoglucosan to be tracers of biomass burning. Furfural is likely to be oxidized quickly so comparison with levoglucosan may give a sense of the age of the aerosols in forest fire smoke. However, few furfural emissions are available for biomass combustion. Furfural and sugars were determined in coarse aerosols (>2.4μm aerodynamic diameter) and fine aerosols (<2.4μm aerodynamic diameter) collected in 24 hour periods during different seasons in the United Kingdom and PM10 collected from Thailand and Malaysia including haze episodes. Also total suspended particulate matter (TSP) samples were collected from Taiwan. Furfural and sugars dominated in fine fractions, especially in the UK autumn. Sugars were found at 5.96-18.37 nmol m-3 in fine mode and 1.36-5.75 nmol m-3 in coarse mode aerosols in the UK. Furfural was found at 0.18-0.91 nmol m-3 and 0.05-0.51 nmol m-3 respectively in the same aerosols. Sugars were a dominant contributor to aerosol derived from biomass burning. Sugars and furfural were about 10 and 20 times higher during haze episodes in Malaysia. Laboratory experimental simulation suggested furfural is more rapid destroyed by UV and sunlight than levoglucosan.

Comprehensive modeling study of ozonolysis of oleic acid aerosol based on real-time, online measurements of aerosol composition

NASA Astrophysics Data System (ADS)

Gallimore, P. J.; Griffiths, P. T.; Pope, F. D.; Reid, J. P.; Kalberer, M.

2017-04-01

The chemical composition of organic aerosols profoundly influences their atmospheric properties, but a detailed understanding of heterogeneous and in-particle reactivity is lacking. We present here a combined experimental and modeling study of the ozonolysis of oleic acid particles. An online mass spectrometry (MS) method, Extractive Electrospray Ionization (EESI), is used to follow the composition of the aerosol at a molecular level in real time; relative changes in the concentrations of both reactants and products are determined during aerosol aging. The results show evidence for multiple non-first-order reactions involving stabilized Criegee intermediates, including the formation of secondary ozonides and other oligomers. Offline liquid chromatography MS is used to confirm the online MS assignment of the monomeric and dimeric products. We explain the observed EESI-MS chemical composition changes, and chemical and physical data from previous studies, using a process-based aerosol chemistry simulation, the Pretty Good Aerosol Model (PG-AM). In particular, we extend previous studies of reactant loss by demonstrating success in reproducing the time dependence of product formation and the evolving particle size. This advance requires a comprehensive chemical scheme coupled to the partitioning of semivolatile products; relevant reaction and evaporation parameters have been refined using our new measurements in combination with PG-AM.

Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China

PubMed Central

Cheng, Yafang; Zheng, Guangjie; Wei, Chao; Mu, Qing; Zheng, Bo; Wang, Zhibin; Gao, Meng; Zhang, Qiang; He, Kebin; Carmichael, Gregory; Pöschl, Ulrich; Su, Hang

2016-01-01

Fine-particle pollution associated with winter haze threatens the health of more than 400 million people in the North China Plain. Sulfate is a major component of fine haze particles. Record sulfate concentrations of up to ~300 μg m−3 were observed during the January 2013 winter haze event in Beijing. State-of-the-art air quality models that rely on sulfate production mechanisms requiring photochemical oxidants cannot predict these high levels because of the weak photochemistry activity during haze events. We find that the missing source of sulfate and particulate matter can be explained by reactive nitrogen chemistry in aerosol water. The aerosol water serves as a reactor, where the alkaline aerosol components trap SO2, which is oxidized by NO2 to form sulfate, whereby high reaction rates are sustained by the high neutralizing capacity of the atmosphere in northern China. This mechanism is self-amplifying because higher aerosol mass concentration corresponds to higher aerosol water content, leading to faster sulfate production and more severe haze pollution. PMID:28028539

Cloud processing of gases and aerosols in the Community Multiscale Air Quality (CMAQ) model: Impacts of extended chemistry

EPA Science Inventory

Clouds and fogs can significantly impact the concentration and distribution of atmospheric gases and aerosols through chemistry, scavenging, and transport. This presentation summarizes the representation of cloud processes in the Community Multiscale Air Quality (CMAQ) modeling ...

The primary volcanic aerosol emission from Mt Etna: Size-resolved particles with SO2 and role in plume reactive halogen chemistry

NASA Astrophysics Data System (ADS)

Roberts, T. J.; Vignelles, D.; Liuzzo, M.; Giudice, G.; Aiuppa, A.; Coltelli, M.; Salerno, G.; Chartier, M.; Couté, B.; Berthet, G.; Lurton, T.; Dulac, F.; Renard, J.-B.

2018-02-01

Volcanoes are an important source of aerosols to the troposphere. Within minutes after emission, volcanic plume aerosol catalyses conversion of co-emitted HBr, HCl into highly reactive halogens (e.g. BrO, OClO) through chemical cycles that cause substantial ozone depletion in the dispersing downwind plume. This study quantifies the sub-to-supramicron primary volcanic aerosol emission (0.2-5 μm diameter) and its role in this process. An in-situ ground-based study at Mt Etna (Italy) during passive degassing co-deployed an optical particle counter and Multi-Gas SO2 sensors at high time resolution (0.1 Hz) enabling to characterise the aerosol number, size-distribution and emission flux. A tri-modal volcanic aerosol size distribution was found, to which lognormal distributions are fitted. Total particle volume correlates to SO2 (as a plume tracer). The measured particle volume:SO2 ratio equates to a sulfate:SO2 ratio of 1-2% at the observed meteorological conditions (40% Relative Humidity). A particle mass flux of 0.7 kg s-1 is calculated for the measured Mt Etna SO2 flux of 1950 tonnes/day. A numerical plume atmospheric chemistry model is used to simulate the role of the hygroscopic primary aerosol surface area and its humidity dependence on volcanic plume BrO and OClO chemistry. As well as predicting volcanic BrO formation and O3 depletion, the model achieves OClO/SO2 in broad quantitative agreement with recently reported Mt Etna observations, with a predicted maximum a few minutes downwind. In addition to humidity - that enhances aerosols surface area for halogen cycling - background ozone is predicted to be an important control on OClO/SO2. Dependence of BrO/SO2 on ambient humidity is rather low near-to-source but increases further downwind. The model plume chemistry also exhibits strong across-plume spatial variations between plume edge and centre.

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system a review

NASA Astrophysics Data System (ADS)

Zahardis, J.; Petrucci, G. A.

2006-11-01

The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the primary products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. Anomalies in the relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide polymers. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei. The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, a series of atmospheric implications of oxidative processing of particulate containing fatty acids is presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semisolids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed particulate may contribute to indirect forcing of radiation. Other effects, including the potential role of aldehydic

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system - a review

NASA Astrophysics Data System (ADS)

Zahardis, J.; Petrucci, G. A.

2007-02-01

The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the commonly observed aldehyde and organic acid products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. The relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide oligomers and polymers, and their formation is in accord with solution and liquid-phase ozonolysis. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei (CCN). The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, the main atmospheric implications of oxidative processing of particulate containing fatty acids are presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semi-solids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas-phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed

Evaluating Ammonium, Nitrate and Sulfate Aerosols in 3-Dimensions

NASA Technical Reports Server (NTRS)

Mezuman, Keren; Bauer, Susanne E.; Tsigaridis, Kostas

2015-01-01

The effect aerosols have on climate and air quality is a func-on of their chemical composi-on, concentra-on and spa-al distribu-on. These parameters are controlled by emissions, heterogeneous and homogeneous chemistry, where thermodynamics plays a key role, transport, which includes stratospheric-­- tropospheric exchange, and deposi-onal sinks. In this work we demonstrate the effect of some of these processes on the SO4-NH4­-NO3 system using the GISS ModelE2 Global Circula-on Model (GCM).

A parameterization of the heterogeneous hydrolysis of N2O5 for mass-based aerosol models: improvement of particulate nitrate prediction

NASA Astrophysics Data System (ADS)

Chen, Ying; Wolke, Ralf; Ran, Liang; Birmili, Wolfram; Spindler, Gerald; Schröder, Wolfram; Su, Hang; Cheng, Yafang; Tegen, Ina; Wiedensohler, Alfred

2018-01-01

The heterogeneous hydrolysis of N2O5 on the surface of deliquescent aerosol leads to HNO3 formation and acts as a major sink of NOx in the atmosphere during night-time. The reaction constant of this heterogeneous hydrolysis is determined by temperature (T), relative humidity (RH), aerosol particle composition, and the surface area concentration (S). However, these parameters were not comprehensively considered in the parameterization of the heterogeneous hydrolysis of N2O5 in previous mass-based 3-D aerosol modelling studies. In this investigation, we propose a sophisticated parameterization (NewN2O5) of N2O5 heterogeneous hydrolysis with respect to T, RH, aerosol particle compositions, and S based on laboratory experiments. We evaluated closure between NewN2O5 and a state-of-the-art parameterization based on a sectional aerosol treatment. The comparison showed a good linear relationship (R = 0.91) between these two parameterizations. NewN2O5 was incorporated into a 3-D fully online coupled model, COSMO-MUSCAT, with the mass-based aerosol treatment. As a case study, we used the data from the HOPE Melpitz campaign (10-25 September 2013) to validate model performance. Here, we investigated the improvement of nitrate prediction over western and central Europe. The modelled particulate nitrate mass concentrations ([NO3-]) were validated by filter measurements over Germany (Neuglobsow, Schmücke, Zingst, and Melpitz). The modelled [NO3-] was significantly overestimated for this period by a factor of 5-19, with the corrected NH3 emissions (reduced by 50 %) and the original parameterization of N2O5 heterogeneous hydrolysis. The NewN2O5 significantly reduces the overestimation of [NO3-] by ˜ 35 %. Particularly, the overestimation factor was reduced to approximately 1.4 in our case study (12, 17-18 and 25 September 2013) when [NO3-] was dominated by local chemical formations. In our case, the suppression of organic coating was negligible over western and central Europe

Aircraft-based investigation of Dynamics-Aerosol-Chemistry-Cloud Interactions in Southern West Africa

NASA Astrophysics Data System (ADS)

Flamant, Cyrille

2017-04-01

The EU-funded project DACCIWA (Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa, http://www.dacciwa.eu) is investigating the relationship between weather, climate and air pollution in southern West Africa. The air over the coastal region of West Africa is a unique mixture of natural and anthropogenic gases, liquids and particles, emitted in an environment, in which multi-layer cloud decks frequently form. These exert a large influence on the local weather and climate, mainly due to their impact on radiation, the surface energy balance and thus the diurnal cycle of the atmospheric boundary layer. The main objective for the aircraft detachment was to build robust statistics of cloud properties in southern West Africa in different chemical landscapes to investigate the physical processes involved in their life cycle in such a complex chemical environment. As part of the DACCIWA field campaigns, three European aircraft (the German DLR Falcon 20, the French SAFIRE ATR 42 and the British BAS Twin Otter) conducted a total of 50 research flights across Ivory Coast, Ghana, Togo, and Benin from 27 June to 16 July 2016 for a total of 155 flight hours, including hours sponsored through 3 EUFAR projects. The aircraft were used in different ways based on their strengths, but all three had comparable instrumentation with the the capability to do gas-phase chemistry, aerosol and clouds, thereby generating a rich dataset of atmospheric conditions across the region. Eight types of flight objectives were conducted to achieve the goals of the DACCIWA: (i) Stratus clouds, (ii) Land-sea breeze clouds, (iii) Mid-level clouds, (iv) Biogenic emission, (v) City emissions, (vi) Flaring and ship emissions, (vii) Dust and biomass burning aerosols, and (viii) air-sea interactions. An overview of the DACCIWA aircraft campaign as well as first highlights from the airborne observations will be presented.

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

Heterogeneous reactions in a stratospheric box model: A sensitivity study

NASA Astrophysics Data System (ADS)

Danilin, Michael Y.; McConnell, John C.

1994-12-01

Recent laboratory data concerning the reactions of HCl and HOx on/in sulfuric acid aerosol (Hanson et al., 1994), N2O5 and ClONO2 hydrolysis on the frozen aerosol (Hanson and Ravishankara, 1993a) and the temperature dependence of the HNO3 absorption cross section (Burkholder et al., 1993) indicate that a reevaluation of the role of heterogeneous reactions in the chemical balance of the stratosphere is required. A chemical module prepared for a three-dimensional (3-D) global chemistry transport model (CTM) and a general circulation model (GCM) has been used to carry out a sensitivity study of the effects of heterogeneous reactions on/in the sulfate aerosol and on the polar stratospheric cloud (PSC) particles. We present here results for the latitudes 60°S, 70°S and 75°S at the 50-mbar level. Our findings indicate that (1) the new values of the HNO3 cross sections result in lower mixing ratios for NOx and make ozone more vulnerable to catalytic destruction by ClOx; (2) the effect of the heterogeneous reactions OH + HNO3(a) → H2O + NO3 and HO2 +HO2(a) → H2O2 + O2 are small in comparison with the same gas phase reactions and play a negligible role for the ozone balance; (3) the HCl reactions in the sulfuric acid aerosol at 60°S and 70°S increase the chlorine activation up to 0.53 parts per billion by volume (ppbv) and 0.72 ppbv, respectively, for liquid aerosol and up to 0.87 ppbv for frozen aerosol at 70°S for volcanic conditions and this results in considerable ozone depletion at these latitudes; (4) studying the ozone "hole" phenomenon, we have considered the different initial ratios of ClONO2/HCl, of N2O5, galactic cosmic rays (GCRs), and longer lifetimes for the PSC. We have speculated an existence of the reaction N2O5 + HCl(a) → ClNO2 + HNO3.

Puerto Rico - 2002 : field studies to resolve aerosol processes.

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

Gaffney, J. S.; Marley, N. A.; Ravelo, R.

1999-10-05

A number of questions remain concerning homogeneous aerosol formation by natural organics interacting with anthropogenic pollutants. For example, chlorine has been proposed as a potential oxidant in the troposphere because of its very high reactivity with a wide range of organics (Finlayson-Pitts, 1993). Indeed, sea salt aerosol in the presence of ozone has been shown to produce chlorine atoms in heterogeneous photochemical reactions under laboratory conditions. Whether chlorine can initiate oxidation of natural organics such as monoterpene hydrocarbons and can generate homogeneous nucleation or condensable material that contributes to aerosol loadings needs to be assessed. The nighttime reactions of ozonemore » and nitrate radical can also result in monoterpene reactions that contribute to aerosol mass. We are currently planning field studies in Puerto Rico to assess these aerosol issues and other atmospheric chemistry questions. Puerto Rico has a number of key features that make it very attractive for a field study of this sort. The principal feature is the island's very regular meteorology and its position in the Caribbean Sea relative to the easterly trade winds. This meteorology and the island's rectangular shape (100 x 35 miles) make it highly suitable for simplification of boundary layer conditions. In addition, the long stretch between Puerto Rico and the nearest pollution sources in Africa and southern Europe make the incoming background air relatively clean and constant. Furthermore, Puerto Rico has approximately 3.5 million people with a very well defined source region and a central area of rain forest vegetation. These features make Puerto Rico an ideal locale for assessing aerosol processes. The following sections describe specific areas of atmospheric chemistry that can be explored during the proposed field study.« less

Overview of the Chemistry-Aerosol Mediterranean Experiment/Aerosol Direct Radiative Forcing on the Mediterranean Climate (ChArMEx/ADRIMED) summer 2013 campaign

NASA Astrophysics Data System (ADS)

Mallet, M.; Dulac, F.; Formenti, P.; Nabat, P.; Sciare, J.; Roberts, G.; Pelon, J.; Ancellet, G.; Tanré, D.; Parol, F.; di Sarra, A.; Alados, L.; Arndt, J.; Auriol, F.; Blarel, L.; Bourrianne, T.; Brogniez, G.; Chazette, P.; Chevaillier, S.; Claeys, M.; D'Anna, B.; Denjean, C.; Derimian, Y.; Desboeufs, K.; Di Iorio, T.; Doussin, J.-F.; Durand, P.; Féron, A.; Freney, E.; Gaimoz, C.; Goloub, P.; Gómez-Amo, J. L.; Granados-Muñoz, M. J.; Grand, N.; Hamonou, E.; Jankowiak, I.; Jeannot, M.; Léon, J.-F.; Maillé, M.; Mailler, S.; Meloni, D.; Menut, L.; Momboisse, G.; Nicolas, J.; Podvin, J.; Pont, V.; Rea, G.; Renard, J.-B.; Roblou, L.; Schepanski, K.; Schwarzenboeck, A.; Sellegri, K.; Sicard, M.; Solmon, F.; Somot, S.; Torres, B.; Totems, J.; Triquet, S.; Verdier, N.; Verwaerde, C.; Wenger, J.; Zapf, P.

2015-07-01

The Chemistry-Aerosol Mediterranean Experiment (ChArMEx; http://charmex.lsce.ipsl.fr) is a collaborative research program federating international activities to investigate Mediterranean regional chemistry-climate interactions. A special observing period (SOP-1a) including intensive airborne measurements was performed in the framework of the Aerosol Direct Radiative Forcing on the Mediterranean Climate (ADRIMED) project during the Mediterranean dry season over the western and central Mediterranean basins, with a focus on aerosol-radiation measurements and their modeling. The SOP-1a took place from 11 June to 5 July 2013. Airborne measurements were made by both the ATR-42 and F-20 French research aircraft operated from Sardinia (Italy) and instrumented for in situ and remote-sensing measurements, respectively, and by sounding and drifting balloons, launched in Minorca. The experimental set-up also involved several ground-based measurement sites on islands including two ground-based reference stations in Corsica and Lampedusa and secondary monitoring sites in Minorca and Sicily. Additional measurements including lidar profiling were also performed on alert during aircraft operations at EARLINET/ACTRIS stations at Granada and Barcelona in Spain, and in southern Italy. Remote sensing aerosol products from satellites (MSG/SEVIRI, MODIS) and from the AERONET/PHOTONS network were also used. Dedicated meso-scale and regional modelling experiments were performed in relation to this observational effort. We provide here an overview of the different surface and aircraft observations deployed during the ChArMEx/ADRIMED period and of associated modeling studies together with an analysis of the synoptic conditions that determined the aerosol emission and transport. Meteorological conditions observed during this campaign (moderate temperatures and southern flows) were not favorable to produce high level of atmospheric pollutants nor

Aerosol Variations in Boundary Atmospheres: Review and Prospect

NASA Astrophysics Data System (ADS)

Chen, Bin; Shi, Guangyu

Atmospheric aerosols play important roles in climate and atmospheric chemistry: They scatter sunlight, provide condensation nuclei for cloud droplets, and participate in heterogeneous chemical reactions. To enable better understanding of the vertical physical, chemical and optical feathers of the aerosols in East Asia, using some atmospheric and aerosol measurement instruments on board a kind of tethered-balloon system, a series of measurements were operated in some typical areas of East Asia, including Dunhuang, which is located in the source origin district of Asian dust and Beijing, which is the representative of large inland city during the years of 2002-2011. Mineral compositions carried by the airborne particles were analyzed as well as the microbial components, meanwhile the Lidar data were compared to the direct measurements in order to get the correlation between the optical properties of the particles and their physical and chemical variations in the boundary atmosphere. Moreover, the simultaneous observations over the districts of China, Japan and Korea, and even Pakistan supported by an international cooperative project are highly expected, in order to know the changes of the chemical, physical and even optical and radiation properties of the atmospheric aerosols during their long-range transport.

A simple parameterization of aerosol emissions in RAMS

NASA Astrophysics Data System (ADS)

Letcher, Theodore

Throughout the past decade, a high degree of attention has been focused on determining the microphysical impact of anthropogenically enhanced concentrations of Cloud Condensation Nuclei (CCN) on orographic snowfall in the mountains of the western United States. This area has garnered a lot of attention due to the implications this effect may have on local water resource distribution within the Region. Recent advances in computing power and the development of highly advanced microphysical schemes within numerical models have provided an estimation of the sensitivity that orographic snowfall has to changes in atmospheric CCN concentrations. However, what is still lacking is a coupling between these advanced microphysical schemes and a real-world representation of CCN sources. Previously, an attempt to representation the heterogeneous evolution of aerosol was made by coupling three-dimensional aerosol output from the WRF Chemistry model to the Colorado State University (CSU) Regional Atmospheric Modeling System (RAMS) (Ward et al. 2011). The biggest problem associated with this scheme was the computational expense. In fact, the computational expense associated with this scheme was so high, that it was prohibitive for simulations with fine enough resolution to accurately represent microphysical processes. To improve upon this method, a new parameterization for aerosol emission was developed in such a way that it was fully contained within RAMS. Several assumptions went into generating a computationally efficient aerosol emissions parameterization in RAMS. The most notable assumption was the decision to neglect the chemical processes in formed in the formation of Secondary Aerosol (SA), and instead treat SA as primary aerosol via short-term WRF-CHEM simulations. While, SA makes up a substantial portion of the total aerosol burden (much of which is made up of organic material), the representation of this process is highly complex and highly expensive within a numerical

Global Atmospheric Aerosol Modeling

NASA Technical Reports Server (NTRS)

Hendricks, Johannes; Aquila, Valentina; Righi, Mattia

2012-01-01

Global aerosol models are used to study the distribution and properties of atmospheric aerosol particles as well as their effects on clouds, atmospheric chemistry, radiation, and climate. The present article provides an overview of the basic concepts of global atmospheric aerosol modeling and shows some examples from a global aerosol simulation. Particular emphasis is placed on the simulation of aerosol particles and their effects within global climate models.

Proceedings of a Workshop on Research Needs in Heterogeneous Tropospheric Chemistry

NASA Technical Reports Server (NTRS)

1983-01-01

The role of heterogeneous reactions and processes in the troposphere is critically assessed. The results of this assessment, including identification and prioritization of a number of important and scientifically tractable processes, as well as recommendations of ways in which they can be incorporated into the existing NASA tropospheric chemistry program are presented. Also presented is a detailed summary of the considerations that led to the group's recommendations.

Reconciling the aerosol-liquid water path relationship in the ECHAM6-HAM GCM and the Aerosol_cci/Cloud_cci (A)ATSR dataset by minimizing the effect of aerosol swelling

NASA Astrophysics Data System (ADS)

Neubauer, D.; Christensen, M.; Lohmann, U.; Poulsen, C. A.

2016-12-01

Studies using present day variability to assess statistical relationships between aerosol and cloud properties find different strengths of these relationships between satellite data and general circulation model (GCM) data. This discrepancy can be explained by structural uncertainties due to differences in the analysis/observational scale and the process scale or spurious relationships between aerosol and cloud properties. Such spurious relationships are the growth of aerosol particles in the humid environment surrounding clouds, misclassification of partly cloudy satellite pixels as cloud free pixels, brightening of aerosol particles by sunlight reflected at cloud edges, or effects of clouds on aerosol like processing of aerosol particles in clouds by nucleation or impact scavenging and subsequent growth by heterogeneous chemistry and release by cloud droplet evaporation or wet scavenging of aerosol particles. To minimize the effects of spatial aggregation and spurious relationships we apply a new nearest neighbour approach to high resolution (A)ATSR datasets from the Aerosol_cci and Cloud_cci projects of the Climate Change Initiative (CCI) programme of ESA. For the ECHAM6-HAM GCM we quantify the impact of using dry aerosol (without aerosol water) in the analysis to mimic the effect of the nearest neighbour approach. The aerosol-liquid water path relationship in ECHAM6-HAM is systematically stronger than in (A)ATSR data and cannot be explained by an overestimation of autoconversion when using diagnostic precipitation but rather by aerosol swelling in regions where humidity is high and clouds are present. When aerosol water is removed from the analysis in ECHAM6-HAM the strength of the aerosol-liquid water path relationship agrees much better with the ones of (A)ATSR or MODIS. We further find that while the observed relationships of different satellite sensors ((A)ATSR vs. MODIS) are not always consistent for tested environmental conditions the relationships in

Direct radiative effect by multicomponent aerosol over China

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

Huang, Xin; Song, Yu; Zhao, Chun

The direct radiative effect (DRE) of multiple aerosol species (sulfate, nitrate, ammonium, black carbon (BC), organic carbon (OC), and mineral aerosol) and their spatiotemporal variations over China were investigated using a fully coupled meteorology–chemistry model (WRF-Chem) for the entire year of 2006. We made modifications to improve model performance, including updating land surface parameters, improving the calculation of transition metal-catalyzed oxidation of SO 2, and adding in heterogeneous reactions between mineral aerosol and acid gases. The modified model well reproduced the magnitude, seasonal pattern, and spatial distribution of the measured meteorological conditions, concentrations of PM 10 and its components, andmore » aerosol optical depth (AOD). A diagnostic iteration method was used to estimate the overall DRE of aerosols and contributions from different components. At the land surface, all kinds of aerosol species reduced the incident net radiation flux with a total DRE of 10.2 W m -2 over China. Aerosols significantly warm the atmosphere with the national mean DRE of +10.8 W m -2. BC was the leading radiative-heating component (+8.7 W m -2), followed by mineral aerosol (+1.1 W m -2). At the top of the atmosphere (TOA), BC introduced the largest radiative perturbation (+4.5 W m -2), followed by sulfate (-1.4 W m -2). The overall perturbation of aerosols on radiation transfer is quite small over China, demonstrating the counterbalancing effect between scattering and adsorbing aerosols. Aerosol DRE at the TOA had distinct seasonality, generally with a summer maximum and winter minimum, mainly determined by mass loadings, hygroscopic growth, and incident radiation flux.« less

Forcing of stratospheric chemistry and dynamics during the Dalton Minimum

NASA Astrophysics Data System (ADS)

Anet, J. G.; Muthers, S.; Rozanov, E.; Raible, C. C.; Peter, T.; Stenke, A.; Shapiro, A. I.; Beer, J.; Steinhilber, F.; Brönnimann, S.; Arfeuille, F.; Brugnara, Y.; Schmutz, W.

2013-06-01

The response of atmospheric chemistry and climate to volcanic eruptions and a decrease in solar activity during the Dalton Minimum is investigated with the fully coupled atmosphere-ocean-chemistry general circulation model SOCOL-MPIOM covering the time period 1780 to 1840 AD. We carried out several sensitivity ensemble experiments to separate the effects of (i) reduced solar ultra-violet (UV) irradiance, (ii) reduced solar visible and near infrared irradiance, (iii) enhanced galactic cosmic ray intensity as well as less intensive solar energetic proton events and auroral electron precipitation, and (iv) volcanic aerosols. The introduced changes of UV irradiance and volcanic aerosols significantly influence stratospheric climate in the early 19th century, whereas changes in the visible part of the spectrum and energetic particles have smaller effects. A reduction of UV irradiance by 15% causes global ozone decrease below the stratopause reaching 8% in the midlatitudes at 5 hPa and a significant stratospheric cooling of up to 2 °C in the midstratosphere and to 6 °C in the lower mesosphere. Changes in energetic particle precipitation lead only to minor changes in the yearly averaged temperature fields in the stratosphere. Volcanic aerosols heat the tropical lower stratosphere allowing more water vapor to enter the tropical stratosphere, which, via HOx reactions, decreases upper stratospheric and mesospheric ozone by roughly 4%. Conversely, heterogeneous chemistry on aerosols reduces stratospheric NOx leading to a 12% ozone increase in the tropics, whereas a decrease in ozone of up to 5% is found over Antarctica in boreal winter. The linear superposition of the different contributions is not equivalent to the response obtained in a simulation when all forcing factors are applied during the DM - this effect is especially well visible for NOx/NOy. Thus, this study highlights the non-linear behavior of the coupled chemistry-climate system. Finally, we conclude that

Applicability of the Effective-Medium Approximation to Heterogeneous Aerosol Particles.

NASA Technical Reports Server (NTRS)

Mishchenko, Michael I.; Dlugach, Janna M.; Liu, Li

2016-01-01

The effective-medium approximation (EMA) is based on the assumption that a heterogeneous particle can have a homogeneous counterpart possessing similar scattering and absorption properties. We analyze the numerical accuracy of the EMA by comparing superposition T-matrix computations for spherical aerosol particles filled with numerous randomly distributed small inclusions and Lorenz-Mie computations based on the Maxwell-Garnett mixing rule. We verify numerically that the EMA can indeed be realized for inclusion size parameters smaller than a threshold value. The threshold size parameter depends on the refractive-index contrast between the host and inclusion materials and quite often does not exceed several tenths, especially in calculations of the scattering matrix and the absorption cross section. As the inclusion size parameter approaches the threshold value, the scattering-matrix errors of the EMA start to grow with increasing the host size parameter and or the number of inclusions. We confirm, in particular, the existence of the effective-medium regime in the important case of dust aerosols with hematite or air-bubble inclusions, but then the large refractive-index contrast necessitates inclusion size parameters of the order of a few tenths. Irrespective of the highly restricted conditions of applicability of the EMA, our results provide further evidence that the effective-medium regime must be a direct corollary of the macroscopic Maxwell equations under specific assumptions.

Impact of OH Heterogenous Oxidation on the Evolution of Brown Carbon Aerosol Optical Properties

NASA Astrophysics Data System (ADS)

Schnitzler, E.; Abbatt, J.

2017-12-01

The effects of varying relative humidity (RH) on the evolution of brown carbon (BrC) optical properties induced by heterogeneous OH oxidation were investigated in a series of photooxidation chamber experiments. A BrC surrogate was generated from aqueous 1,3-dihydroxybenzene (10 mM) and H2O2 (10 mM) exposed to >300 nm radiation, atomized, passed through a series of trace gas denuders, and injected into the chamber, which was conditioned to about 10 or 60% RH. Following aerosol injection, H2O2 was continuously bubbled into the chamber; an hour later, the chamber was irradiated with black-lights (UV-B) to produce OH. Before irradiation, aerosol absorption and scattering at 405 nm, measured using a photoacoustic spectrometer, decreased due only to deposition and dilution, and single scattering albedo (SSA) was relatively steady. In the presence of gas-phase OH, absorption first increased, despite continued particle losses, and SSA decreased. Subsequently, absorption decreased faster than scattering, and SSA increased uniformly. At 60% RH, colour enhancement, likely associated with functionalization, was greatest after only minutes of reaction. In contrast, at 10% RH, peak colour enhancement occurred after about two hours of reaction, indicating that the decrease in RH and the attendant increase in particle viscosity significantly impeded heterogeneous OH oxidation of the BrC surrogate.

Heterogeneous ice nucleation of viscous secondary organic aerosol produced from ozonolysis of α-pinene

NASA Astrophysics Data System (ADS)

Ignatius, Karoliina; Kristensen, Thomas B.; Järvinen, Emma; Nichman, Leonid; Fuchs, Claudia; Gordon, Hamish; Herenz, Paul; Hoyle, Christopher R.; Duplissy, Jonathan; Garimella, Sarvesh; Dias, Antonio; Frege, Carla; Höppel, Niko; Tröstl, Jasmin; Wagner, Robert; Yan, Chao; Amorim, Antonio; Baltensperger, Urs; Curtius, Joachim; Donahue, Neil M.; Gallagher, Martin W.; Kirkby, Jasper; Kulmala, Markku; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin; Tomé, Antonio; Virtanen, Annele; Worsnop, Douglas; Stratmann, Frank

2016-05-01

There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate heterogeneous ice nucleation and thus influence cloud properties. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles. The SOA particles were produced from the ozone initiated oxidation of α-pinene in an aerosol chamber at temperatures in the range from -38 to -10 °C at 5-15 % relative humidity with respect to water to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. The ice nucleation ability of SOA particles with different sizes was investigated with a new continuous flow diffusion chamber. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA for ice saturation ratios between 1.3 and 1.4 significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between -39.0 and -37.2 °C ranged from 6 to 20 % and did not depend on the particle surface area. Global modelling of monoterpene SOA particles suggests that viscous biogenic SOA particles are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle budget.

Changes in Reactivity as Chemistry Becomes Confined to an Interface. The Case of Free Radical Oxidation of C 30H 62 Alkane by OH

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

Houle, Frances A.; Wiegel, Aaron A.; Wilson, Kevin R.

Here, we examine in a simple organic aerosol the transition between heterogeneous chemistry under well-mixed conditions to chemistry under interfacial confinement. A single reaction mechanism, shown to reproduce observed OH oxidation chemistry for liquid and semisolid C 30H 62, is used in reaction-diffusion simulations to explore reactivity over a broad viscosity range. The results show that when internal mixing of the aerosol is fast and the particle interface is enriched in C-H groups, ketone and alcohol products, formed via peroxy radical disproportionation, predominate. As viscosity increases the reactions become confined to a shell at the gas-aerosol interface. The confinement ismore » accompanied by emergence of acyloxy reaction pathways that are particularly active when the shell is 1 nm or less. We quantify this trend using a reaction-diffusion index, allowing the parts of the mechanism that control reactivity as viscosity increases to be identified.« less

Changes in Reactivity as Chemistry Becomes Confined to an Interface. The Case of Free Radical Oxidation of C 30H 62 Alkane by OH

DOE PAGES

Houle, Frances A.; Wiegel, Aaron A.; Wilson, Kevin R.

2018-02-14

Here, we examine in a simple organic aerosol the transition between heterogeneous chemistry under well-mixed conditions to chemistry under interfacial confinement. A single reaction mechanism, shown to reproduce observed OH oxidation chemistry for liquid and semisolid C 30H 62, is used in reaction-diffusion simulations to explore reactivity over a broad viscosity range. The results show that when internal mixing of the aerosol is fast and the particle interface is enriched in C-H groups, ketone and alcohol products, formed via peroxy radical disproportionation, predominate. As viscosity increases the reactions become confined to a shell at the gas-aerosol interface. The confinement ismore » accompanied by emergence of acyloxy reaction pathways that are particularly active when the shell is 1 nm or less. We quantify this trend using a reaction-diffusion index, allowing the parts of the mechanism that control reactivity as viscosity increases to be identified.« less

Tracking Transport and Transformation of Aerosols using C and O-triple Isotopic Composition of Carbonates: CSI La Jolla

NASA Astrophysics Data System (ADS)

Thiemens, M. H.; Shaheen, R.; Chong, K.; Hill, A.; Wong, J.; Zhang, Z.; Dominguez, G.

2012-12-01

Aerosols affect climate in numerous ways, including change in the earth's energy balance by absorbing and scattering solar radiations, alteration of the hydrological cycle by serving as cloud condensation nuclei, change in biogeochemical cycles by providing nutrients. Another significant process is the effect on the chemical composition of the atmosphere by providing surfaces for heterogeneous chemical reactions. Fine particles of aerodynamic diameter less than 2.5μm (PM2.5) also impinge upon human health by admission to the respiratory system causing a range of cardiopulmonary diseases. Both climate and public health aspects depend on their physical and chemical properties, therefore, understanding physico-chemical and photochemical transformations on aerosol surfaces is important for predicting their effects on climate change, atmospheric chemistry and human health. Here we present initial findings on the processes occurring on aerosol surfaces using isotopes to delineate day and night time chemistry, thus resolving photochemistry effects, and to identify their sources by way of the carbon isotopes. Aerosols were collected on filter papers for 12h during the day and at night time from June-Dec. 2011in La Jolla, CA., using high volume, multi stage cascade impactors. CO2 released after treating these filter papers with 100% phosphoric acid at 27oC was collected, purified chromatographically and analyzed for both C and O isotopes. Our data indicate that both C and O isotopes can be used to distinguish between heterogeneous and photochemical transformations. Aerosol carbonates collected during the day time were depleted in δ13Cday = -23 to -28‰ and δ18Oday = +3 to +10‰ and were isotopically distinct from the carbonates collected at night time δ13Cnight = 0 to -12‰, δ18Onightnight = +23 to +32‰. Higher chloride concentration in the samples collected at night time indicated the transport of marine air masses whereas higher nitrate and sulfate concentration

Nighttime Lagrangian Measurements of Aerosols and Oxidants in the Boston Urban Plume: Possible Evidence of Heterogeneous Loss of Ozone

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

Zaveri, Rahul A.; Berkowitz, Carl M.; Hubbe, John M.

2004-10-04

Heterogeneous chemical processes involving trace gases and aerosols are poorly understood and are expected to play an important role at night. As part of the 2002 New England Air Quality Study (NEAQS), the Nighttime Aerosol/Oxidant Plume Experiment (NAOPEX) was designed to study the chemical evolution and interaction of ambient urban aerosols and trace gases in the absence of photochemistry. Lagrangian measurements of trace gases (O3, NOx, NOy, VOCs, CO) and aerosols (size distribution and composition) were made with the Department of Energy’s (DOE) G-1 aircraft in the nocturnal residual layer downwind of greater Boston area. On clear nights with offshoremore » flow, a superpressure, constant-volume balloon (tetroon) was launched from a coastal site into the Boston plume around sunset to serve as a Lagrangian marker of urban air parcels as they moved out over the Atlantic Ocean. The tetroon carried an instrument payload of about 2.5 kg that included a GPS receiver, radiosonde and ozonesonde. Latitude, longitude, altitude, temperature, pressure, relative humidity and ozone concentration data were transmitted in real-time to a receiver on the ground as well as one onboard the G-1 aircraft. About an hour after the launch, when the tetroon was outside the restricted Class-B airspace, the G-1 aircraft made the first flight to make more comprehensive measurements in the vicinity of the tetroon. About five hours after the launch, the G-1 made a second flight to make another set of measurements near the tetroon. Here, we report on the two flights made between 20:00 EST July 30 and 02:00 EST July 31. Analyses of the Lagrangian aerosol and trace gases dataset suggest evidence of heterogeneous activity and aging of aerosols. Vertical profiles of Ozone + NOy concentrations in the vicinity of the tetroon were found to be anti-correlated with aerosol number density, and the slope of the linear regression fit decreased as a function of time. These changes could be explained

Describing the direct and indirect radiative effects of atmospheric aerosols over Europe by using coupled meteorology-chemistry simulations: a contribution from the AQMEII-Phase II exercise

NASA Astrophysics Data System (ADS)

Jimenez-Guerrero, Pedro; Balzarini, Alessandra; Baró, Rocío; Curci, Gabriele; Forkel, Renate; Hirtl, Marcus; Honzak, Luka; Langer, Matthias; Pérez, Juan L.; Pirovano, Guido; San José, Roberto; Tuccella, Paolo; Werhahn, Johannes; Zabkar, Rahela

2014-05-01

The study of the response of the aerosol levels in the atmosphere to a changing climate and how this affects the radiative budget of the Earth (direct, semi-direct and indirect effects) is an essential topic to build confidence on climate science, since these feedbacks involve the largest uncertainties nowadays. Air quality-climate interactions (AQCI) are, therefore, a key, but uncertain contributor to the anthropogenic forcing that remains poorly understood. To build confidence in the AQCI studies, regional-scale integrated meteorology-atmospheric chemistry models (i.e., models with on-line chemistry) that include detailed treatment of aerosol life cycle and aerosol impacts on radiation (direct effects) and clouds (indirect effects) are in demand. In this context, the main objective of this contribution is the study and definition of the uncertainties in the climate-chemistry-aerosol-cloud-radiation system associated to the direct radiative forcing and the indirect effect caused by aerosols over Europe, using an ensemble of fully-coupled meteorology-chemistry model simulations with the WRF-Chem model run under the umbrella of AQMEII-Phase 2 international initiative. Simulations were performed for Europe for the entire year 2010. According to the common simulation strategy, the year was simulated as a sequence of 2-day time slices. For better comparability, the seven groups applied the same grid spacing of 23 km and shared common processing of initial and boundary conditions as well as anthropogenic and fire emissions. With exception of a simulation with different cloud microphysics, identical physics options were chosen while the chemistry options were varied. Two model set-ups will be considered here: one sub-ensemble of simulations not taking into account any aerosol feedbacks (the baseline case) and another sub-ensemble of simulations which differs from the former by the inclusion of aerosol-radiation feedback. The existing differences for meteorological

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.

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.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Fast Airborne Aerosol Size and Chemistry Measurements with the High Resolution Aerosol Mass Spectrometer during the MILAGRO Campaign

NASA Technical Reports Server (NTRS)

DeCarlo, P. F.; Dunlea, E. J.; Kimmel, J. R.; Aiken, A. C.; Sueper, D.; Crounse, J.; Wennberg, P. O.; Emmons, L.; Shinozuka, Y.; Clarke, A.;

Atmospheric Chemistry and Air Pollution

DOE PAGES

Gaffney, Jeffrey S.; Marley, Nancy A.

2003-01-01

Atmospheric chemistry is an important discipline for understanding air pollution and its impacts. This mini-review gives a brief history of air pollution and presents an overview of some of the basic photochemistry involved in the production of ozone and other oxidants in the atmosphere. Urban air quality issues are reviewed with a specific focus on ozone and other oxidants, primary and secondary aerosols, alternative fuels, and the potential for chlorine releases to amplify oxidant chemistry in industrial areas. Regional air pollution issues such as acid rain, long-range transport of aerosols and visibility loss, and the connections of aerosols to ozonemore » and peroxyacetyl nitrate chemistry are examined. Finally, the potential impacts of air pollutants on the global-scale radiative balances of gases and aerosols are discussed briefly.« less

Theoretical Investigations of Clouds and Aerosols in the Stratosphere and Upper Troposphere

NASA Technical Reports Server (NTRS)

Toon, Owen B.

2005-01-01

support of the Atmospheric Chemistry Modeling and Data Analysis Program. We investigated a wide variety of issues involving ambient stratospheric aerosols, polar stratospheric clouds or heterogeneous chemistry, analysis of laboratory data, and particles in the upper troposphere. The papers resulting from these studies are listed below. In addition, I participated in the 1999-2000 SOLVE mission as one of the project scientists and in the 2002 CRYSTAL field mission as one of the project scientists. Several CU graduate students and research associates also participated in these mission, under support from the ACMAP program, and worked to interpret data. During the past few years my group has completed a number of projects under the

Can a coupled meteorology–chemistry model reproduce the historical trend in aerosol direct radiative effects over the Northern Hemisphere?

EPA Science Inventory

The ability of a coupled meteorology–chemistry model, i.e., Weather Research and Forecast and Community Multiscale Air Quality (WRF-CMAQ), to reproduce the historical trend in aerosol optical depth (AOD) and clear-sky shortwave radiation (SWR) over the Northern Hemisphere h...

Aerosol chemistry and the effect of aerosol water content on visibility impairment and radiative forcing in Guangzhou during the 2006 Pearl River Delta campaign.

PubMed

Jung, Jinsang; Lee, Hanlim; Kim, Young J; Liu, Xingang; Zhang, Yuanhang; Gu, Jianwei; Fan, Shaojia

2009-08-01

Optical and chemical aerosol measurements were obtained from 2 to 31 July 2006 at an urban site in the metropolitan area of Guangzhou (China) as part of the Program of Regional Integrated Experiment of Air Quality over Pearl River Delta (PRIDE-PRD2006) to investigate aerosol chemistry and the effect of aerosol water content on visibility impairment and radiative forcing. During the PRIDE-PRD2006 campaign, the average contributions of ammonium sulfate, organic mass by carbon (OMC), elemental carbon (EC), and sea salt (SS) to total PM(2.5) mass were measured to be 36.5%, 5.7%, 27.1%, 7.8%, and 3.7%, respectively. Compared with the clean marine period, (NH(4))(2)SO(4), NH(4)NO(3), and OMC were all greatly enhanced (by up to 430%) during local haze periods via the accumulation of a secondary aerosol component. The OMC dominance increased when high levels of biomass burning influenced the measurement site while (NH(4))(2)SO(4) and OMC did when both biomass burning and industrial emissions influenced it. The effect of aerosol water content on the total light-extinction coefficient was estimated to be 34.2%, of which 25.8% was due to aerosol water in (NH(4))(2)SO(4), 5.1% that in NH(4)NO(3), and 3.3% that in SS. The average mass-scattering efficiency (MSE) of PM(10) particles was determined to be 2.2+/-0.6 and 4.6+/-1.7m(2)g(-1) under dry (RH<40%) and ambient conditions, respectively. The average single-scattering albedo (SSA) was 0.80+/-0.08 and 0.90+/-0.04 under dry and ambient conditions, respectively. Not only are the extinction and scattering coefficients greatly enhanced by aerosol water content, but MSE and SSA are also highly sensitive. It can be concluded that sulfate and carbonaceous aerosol, as well as aerosol water content, play important roles in the processes that determine visibility impairment and radiative forcing in the ambient atmosphere of the Guangzhou urban area.

Synergistic effect among Cl2, SO2 and NO2 in their heterogeneous reactions on gamma-alumina

NASA Astrophysics Data System (ADS)

Huang, Zhenling; Zhang, Zhaohui; Kong, Weiheng; Feng, Shuo; Qiu, Ye; Tang, Siqun; Xia, Chuanqin; Ma, Lingling; Luo, Min; Xu, Diandou

2017-10-01

Severe haze in China has been a global concern in recent years. Most studies about the mechanism of haze formation mare only focused on the heterogeneous reactions of SO2 and NO2 on mineral aerosols. However, little is known about the role of molecular chlorine (Cl2) in those reactions. Here, we investigated the heterogeneous uptake of Cl2, SO2 and NO2 on γ-Al2O3 particles under different conditions using a quartz-based flow reactor. We found that the existence of γ-Al2O3 seed aerosols significantly promotes the formation of secondary chloride, sulfate and nitrate aerosols, and Cl2, NO2 and SO2 have synergistic effects when they react on γ-Al2O3 surface under humid condition. The results also shows that Cl2 can promote the formation of secondary sulfate and nitrate aerosols on γ-Al2O3 surface. Moreover, Cl2 is much easier to react with the surface of γ-Al2O3 and form secondary Cl- aerosol when comparing with NO2 and SO2, suggesting that Cl2 is of great importance in atmospheric chemistry, it has the potential to alter the surface properties (e.g., chemical composition and fraction) of mineral aerosol, enhance the production of secondary inorganic aerosols in the troposphere, and thus cause adverse effects on the climate and human health.

Computation of Phase Equilibria, State Diagrams and Gas/Particle Partitioning of Mixed Organic-Inorganic Aerosols

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Peter, T.

2009-04-01

The chemical composition of organic-inorganic aerosols is linked to several processes and specific topics in the field of atmospheric aerosol science. Photochemical oxidation of organics in the gas phase lowers the volatility of semi-volatile compounds and contributes to the particulate matter by gas/particle partitioning. Heterogeneous chemistry and changes in the ambient relative humidity influence the aerosol composition as well. Molecular interactions between condensed phase species show typically non-ideal thermodynamic behavior. Liquid-liquid phase separations into a mainly polar, aqueous and a less polar, organic phase may considerably influence the gas/particle partitioning of semi-volatile organics and inorganics (Erdakos and Pankow, 2004; Chang and Pankow, 2006). Moreover, the phases present in the aerosol particles feed back on the heterogeneous, multi-phase chemistry, influence the scattering and absorption of radiation and affect the CCN ability of the particles. Non-ideal thermodynamic behavior in mixtures is usually described by an expression for the excess Gibbs energy, enabling the calculation of activity coefficients. We use the group-contribution model AIOMFAC (Zuend et al., 2008) to calculate activity coefficients, chemical potentials and the total Gibbs energy of mixed organic-inorganic systems. This thermodynamic model was combined with a robust global optimization module to compute potential liquid-liquid (LLE) and vapor-liquid-liquid equilibria (VLLE) as a function of particle composition at room temperature. And related to that, the gas/particle partitioning of semi-volatile components. Furthermore, we compute the thermodynamic stability (spinodal limits) of single-phase solutions, which provides information on the process type and kinetics of a phase separation. References Chang, E. I. and Pankow, J. F.: Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water - Part

Role of interfacial water in the heterogeneous uptake of glyoxal by mixed glycine and ammonium sulfate aerosols.

PubMed

Trainic, Miri; Riziq, Ali Abo; Lavi, Avi; Rudich, Yinon

2012-06-21

This study focuses on the heterogeneous reactions of gas phase glyoxal with aerosols of glycine, the most abundant amino acid in atmospheric aerosols, as well as with a mixture of glycine and ammonium sulfate (AS) at a molar ratio of 1:100 (glycine-AS 1:100). Aerosols were exposed to varying relative humidity (RH) conditions in the presence of gas phase glyoxal for ∼1 h, followed by drying and efflorescence. The changes in size, chemical composition, and optical properties were consequently measured. The reactions occur over a wide range of relative humidities, from ∼30% up to 90% RH, covering values that are substantially lower as well as above the deliquescence point of the investigated aerosols. The product aerosols exhibit a trend of increasing growth in size, in optical extinction cross sections, and in extinction efficiencies (at λ = 355 nm) with decreasing seed aerosol size, and with decreasing RH values from 90% to ∼50%. For glycine-AS 1:100 particles, the ratio of the geometric cross section of the product aerosol to the original seed aerosol reached a value of ∼3, the optical extinction cross section ratio was up to ∼25, and the Q(ext) ratio was up to ∼8, exceeding those of both AS and glycine separately, suggesting a synergistic effect. Aerosol mass spectrometer analyses show that the main products of all the studied reactions are glyoxal oligomers (light scattering compounds), with a minor contribution from imidazoles (absorbing compounds at λ = 355 nm). These findings imply that the changes in the optical properties are likely due to enhanced scattering by the reaction products. The fraction of absorbing substances in the reacted aerosol increases with increasing RH, suggesting that the absorption component may become more substantial after longer reaction times, possibly in cloud or fog droplets. The results suggest that these reactions are possibly important in low RH regions, plausibly due to the reaction occurring in a few interfacial

Air quality modelling over the Eastern Mediterranean using the WRF/Chem model: Comparison of gas-phase chemistry and aerosol mechanisms

NASA Astrophysics Data System (ADS)

Georgiou, George K.; Christoudias, Theodoros; Proestos, Yiannis; Kushta, Jonilda; Hadjinicolaou, Panos; Lelieveld, Jos

2017-04-01

A comprehensive analysis of the performance of three coupled gas-phase chemistry and aerosol mechanisms included in the WRF/Chem model has been performed over the Eastern Mediterranean focusing on Cyprus during the CYPHEX campaign in 2014, using high temporal and spatial resolution. The model performance was evaluated by comparing calculations to measurements of gas phase species (O3, CO, NOx, SO2) and aerosols (PM10, PM2.5) from 13 ground stations. Initial results indicate that the calculated day-to-day and diurnal variations of the aforementioned species show good agreement with observations. The model was set up with three nested grids, downscaling to 4km over Cyprus. The meteorological boundary conditions were updated every 3 hours throughout the simulation using the Global Forecast System (GFS), while chemical boundary conditions were updated every 6 hours using the MOZART global chemical transport model. Biogenic emissions were calculated online by the the Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1). Anthropogenic emissions were based on the EDGAR HTAP v2 global emission inventory, provided on a horizontal grid resolution of 0.1o × 0.1o. Three simulations were performed employing different chemistry and aerosol mechanisms; i) RADM2 chemical mechanism and MADE/SORGAM aerosols, ii) CBMZ chemical mechanism and MOSAIC aerosols, iii) MOZART chemical mechanism and MOSAIC aerosols. Results show that the WRF/Chem model satisfactorily estimates the trace gases relative concentrations at the background sites but not at the urban and traffic sites, while some differences appear between the simulated concentrations by the three mechanisms. The resulting discrepancies between the model outcome and measurements, especially at the urban and traffic sites, suggest that a higher resolution anthropogenic emission inventory might help improve fine resolution, regional air quality modelling. Differences in the simulated concentrations by the

Size matters in the water uptake and hygroscopic growth of atmospherically relevant multicomponent aerosol particles.

PubMed

Laskina, Olga; Morris, Holly S; Grandquist, Joshua R; Qin, Zhen; Stone, Elizabeth A; Tivanski, Alexei V; Grassian, Vicki H

2015-05-14

Understanding the interactions of water with atmospheric aerosols is crucial for determining the size, physical state, reactivity, and climate impacts of this important component of the Earth's atmosphere. Here we show that water uptake and hygroscopic growth of multicomponent, atmospherically relevant particles can be size dependent when comparing 100 nm versus ca. 6 μm sized particles. It was determined that particles composed of ammonium sulfate with succinic acid and of a mixture of chlorides typical of the marine environment show size-dependent hygroscopic behavior. Microscopic analysis of the distribution of components within the aerosol particles show that the size dependence is due to differences in the mixing state, that is, whether particles are homogeneously mixed or phase separated, for different sized particles. This morphology-dependent hygroscopicity has consequences for heterogeneous atmospheric chemistry as well as aerosol interactions with electromagnetic radiation and clouds.

Response of an aerosol mass spectrometer to organonitrates and organosulfates and implications for atmospheric chemistry

PubMed Central

Farmer, D. K.; Matsunaga, A.; Docherty, K. S.; Surratt, J. D.; Seinfeld, J. H.; Ziemann, P. J.; Jimenez, J. L.

2010-01-01

Organonitrates (ON) are important products of gas-phase oxidation of volatile organic compounds in the troposphere; some models predict, and laboratory studies show, the formation of large, multifunctional ON with vapor pressures low enough to partition to the particle phase. Organosulfates (OS) have also been recently detected in secondary organic aerosol. Despite their potential importance, ON and OS remain a nearly unexplored aspect of atmospheric chemistry because few studies have quantified particulate ON or OS in ambient air. We report the response of a high-resolution time-of-flight aerosol mass spectrometer (AMS) to aerosol ON and OS standards and mixtures. We quantify the potentially substantial underestimation of organic aerosol O/C, commonly used as a metric for aging, and N/C. Most of the ON-nitrogen appears as ions in the AMS, which are typically dominated by inorganic nitrate. Minor organonitrogen ions are observed although their identity and intensity vary between standards. We evaluate the potential for using fragment ratios, organonitrogen ions, ions, the ammonium balance of the nominally inorganic ions, and comparison to ion-chromatography instruments to constrain the concentrations of ON for ambient datasets, and apply these techniques to a field study in Riverside, CA. OS manifests as separate organic and sulfate components in the AMS with minimal organosulfur fragments and little difference in fragmentation from inorganic sulfate. The low thermal stability of ON and OS likely causes similar detection difficulties for other aerosol mass spectrometers using vaporization and/or ionization techniques with similar or larger energy, which has likely led to an underappreciation of these species. PMID:20194777

New directions: Mineral dust and ozone - Heterogeneous chemistry

NASA Astrophysics Data System (ADS)

Ramachandran, S.

2015-04-01

Aerosols, the tiny solid or liquid particles suspended in air and produced from natural sources and anthropogenic activities, continue to contribute the largest uncertainty to radiative forcing (IPCC, 2013). Aerosol particles give rise to radiative forcing directly through scattering and absorption of solar and infrared radiation in the atmosphere. Aerosols also give rise to indirect radiative forcing by modifying the cloud optical properties and lifetimes. Among the aerosol species mineral dust and black carbon cause a warming (positive forcing) while sulphate and sea salt cause a cooling (negative forcing) of the Earth-atmosphere system. In tropics and sub-tropics mineral dust is a major contributor to aerosol loading and optical thickness. The global source strength of dust aerosol varies significantly on spatial and temporal scales. The source regions of dust are mainly deserts, dry lake beds, and semi-arid regions, in addition to drier regions where vegetation has been reduced or soil surfaces that are disturbed by man made activities. Anthropogenic activities mainly related to agriculture such as harvesting, ploughing, overgrazing, and cement production and transport also produce mineral dust. An estimated 2500 terragram (Tg, 1012 g) of mineral dust is emitted into the atmosphere per year, and dominates the aerosol mass over continental regions in south Asia and China accounting for ∼35% of the total aerosol mass (IPCC, 2013). In India, dust is prevalent throughout the north and western India during the year and peaks during premonsoon season.

Model development of dust emission and heterogeneous chemistry within the Community Multiscale Air Quality modeling system and its application over East Asia

NASA Astrophysics Data System (ADS)

Dong, Xinyi; Fu, Joshua S.; Huang, Kan; Tong, Daniel; Zhuang, Guoshun

2016-07-01

The Community Multiscale Air Quality (CMAQ) model has been further developed in terms of simulating natural wind-blown dust in this study, with a series of modifications aimed at improving the model's capability to predict the emission, transport, and chemical reactions of dust. The default parameterization of initial threshold friction velocity constants are revised to correct the double counting of the impact of soil moisture in CMAQ by the reanalysis of field experiment data; source-dependent speciation profiles for dust emission are derived based on local measurements for the Gobi and Taklamakan deserts in East Asia; and dust heterogeneous chemistry is also implemented. The improved dust module in the CMAQ is applied over East Asia for March and April from 2006 to 2010. The model evaluation result shows that the simulation bias of PM10 and aerosol optical depth (AOD) is reduced, respectively, from -55.42 and -31.97 % by the original CMAQ to -16.05 and -22.1 % by the revised CMAQ. Comparison with observations at the nearby Gobi stations of Duolun and Yulin indicates that applying a source-dependent profile helps reduce simulation bias for trace metals. Implementing heterogeneous chemistry also results in better agreement with observations for sulfur dioxide (SO2), sulfate (SO42-), nitric acid (HNO3), nitrous oxides (NOx), and nitrate (NO3-). The investigation of a severe dust storm episode from 19 to 21 March 2010 suggests that the revised CMAQ is capable of capturing the spatial distribution and temporal variation of dust. The model evaluation also indicates potential uncertainty within the excessive soil moisture used by meteorological simulation. The mass contribution of fine-mode particles in dust emission may be underestimated by 50 %. The revised CMAQ model provides a useful tool for future studies to investigate the emission, transport, and impact of wind-blown dust over East Asia and elsewhere.

Overview of the Chemistry-Aerosol Mediterranean Experiment/Aerosol Direct Radiative Forcing on the Mediterranean Climate (ChArMEx/ADRIMED) summer 2013 campaign

NASA Astrophysics Data System (ADS)

Mallet, M.; Dulac, F.; Formenti, P.; Nabat, P.; Sciare, J.; Roberts, G.; Pelon, J.; Ancellet, G.; Tanré, D.; Parol, F.; Denjean, C.; Brogniez, G.; di Sarra, A.; Alados-Arboledas, L.; Arndt, J.; Auriol, F.; Blarel, L.; Bourrianne, T.; Chazette, P.; Chevaillier, S.; Claeys, M.; D'Anna, B.; Derimian, Y.; Desboeufs, K.; Di Iorio, T.; Doussin, J.-F.; Durand, P.; Féron, A.; Freney, E.; Gaimoz, C.; Goloub, P.; Gómez-Amo, J. L.; Granados-Muñoz, M. J.; Grand, N.; Hamonou, E.; Jankowiak, I.; Jeannot, M.; Léon, J.-F.; Maillé, M.; Mailler, S.; Meloni, D.; Menut, L.; Momboisse, G.; Nicolas, J.; Podvin, T.; Pont, V.; Rea, G.; Renard, J.-B.; Roblou, L.; Schepanski, K.; Schwarzenboeck, A.; Sellegri, K.; Sicard, M.; Solmon, F.; Somot, S.; Torres, B.; Totems, J.; Triquet, S.; Verdier, N.; Verwaerde, C.; Waquet, F.; Wenger, J.; Zapf, P.

2016-01-01

The Chemistry-Aerosol Mediterranean Experiment (ChArMEx; http://charmex.lsce.ipsl.fr) is a collaborative research program federating international activities to investigate Mediterranean regional chemistry-climate interactions. A special observing period (SOP-1a) including intensive airborne measurements was performed in the framework of the Aerosol Direct Radiative Impact on the regional climate in the MEDiterranean region (ADRIMED) project during the Mediterranean dry season over the western and central Mediterranean basins, with a focus on aerosol-radiation measurements and their modeling. The SOP-1a took place from 11 June to 5 July 2013. Airborne measurements were made by both the ATR-42 and F-20 French research aircraft operated from Sardinia (Italy) and instrumented for in situ and remote-sensing measurements, respectively, and by sounding and drifting balloons, launched in Minorca. The experimental setup also involved several ground-based measurement sites on islands including two ground-based reference stations in Corsica and Lampedusa and secondary monitoring sites in Minorca and Sicily. Additional measurements including lidar profiling were also performed on alert during aircraft operations at EARLINET/ACTRIS stations at Granada and Barcelona in Spain, and in southern Italy. Remote-sensing aerosol products from satellites (MSG/SEVIRI, MODIS) and from the AERONET/PHOTONS network were also used. Dedicated meso-scale and regional modeling experiments were performed in relation to this observational effort. We provide here an overview of the different surface and aircraft observations deployed during the ChArMEx/ADRIMED period and of associated modeling studies together with an analysis of the synoptic conditions that determined the aerosol emission and transport. Meteorological conditions observed during this campaign (moderate temperatures and southern flows) were not favorable to producing high

Defining Tropospheric Chemistry As A Heterogeneous Ensemble Of Reactive Air Parcels

NASA Astrophysics Data System (ADS)

Prather, M. J.; Zhu, X.; Flynn, C.; Mao, J.; Strode, S. A.; Steenrod, S. D.; Strahan, S. E.; Lamarque, J. F.; Fiore, A. M.; Horowitz, L. W.; Shindell, D. T.; Murray, L. T.

2016-12-01

Two major challenges in model-measurement comparisons have been: Which measurements are the most important to match? At what level do models need to simulate the variegated fine structures observed in trace gases and aerosols? This talk presents a novel approach for evaluating high-resolution global chemistry models (1/2 to 1 deg) that is integral to NASA's Atmospheric Tomography (ATom) mission. The approach seeks to develop a chemical climatology for tropospheric regions rather than just event-based testing of specific observations. It enables chemistry-climate models to be readily compared and more severely tested with observations. It uses the reactivity of air parcels (e.g., loss of methane, production and loss of ozone) to weight each parcel in terms of its importance in controlling the two most important chemically reactive greenhouse gases. It looks at the entire statistical distribution of air parcels in terms of a chemical phase space for those species that control the reactivity (e.g., O3, H2O, CH4, CO, NOx, HNO3, HNO4, PAN, CH3NO3, HCHO, HOOH, CH3OOH, C2H6, C3H6O, and other VOCs when present in sufficiently large abundances). It builds statistics of chemically extreme air parcels such as pollution layers to determine if a model failure to match such cases affects the overall reactivity of the region. This approach was designed for the ATom in situ measurements using the DC-8 to slice through the middle of the Pacific and Atlantic Ocean basins each season. The ATom payload will measure the above key trace gases and many other gases and aerosols in every designated air parcel (i.e., 10-sec averages). The first ATom measurements will not be available until mid-2017 and this presentation shows how this climatology looks when sampled with different models. Six global chemistry models have simulated one day in August (no particular year), and we sample all six showing how the 2D probability density plots highlight different regions when weighted by chemical

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

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.

Simplified aerosol modeling for variational data assimilation

NASA Astrophysics Data System (ADS)

Huneeus, N.; Boucher, O.; Chevallier, F.

2009-11-01

We have developed a simplified aerosol model together with its tangent linear and adjoint versions for the ultimate aim of optimizing global aerosol and aerosol precursor emission using variational data assimilation. The model was derived from the general circulation model LMDz; it groups together the 24 aerosol species simulated in LMDz into 4 species, namely gaseous precursors, fine mode aerosols, coarse mode desert dust and coarse mode sea salt. The emissions have been kept as in the original model. Modifications, however, were introduced in the computation of aerosol optical depth and in the processes of sedimentation, dry and wet deposition and sulphur chemistry to ensure consistency with the new set of species and their composition. The simplified model successfully manages to reproduce the main features of the aerosol distribution in LMDz. The largest differences in aerosol load are observed for fine mode aerosols and gaseous precursors. Differences between the original and simplified models are mainly associated to the new deposition and sedimentation velocities consistent with the definition of species in the simplified model and the simplification of the sulphur chemistry. Furthermore, simulated aerosol optical depth remains within the variability of monthly AERONET observations for all aerosol types and all sites throughout most of the year. Largest differences are observed over sites with strong desert dust influence. In terms of the daily aerosol variability, the model is less able to reproduce the observed variability from the AERONET data with larger discrepancies in stations affected by industrial aerosols. The simplified model however, closely follows the daily simulation from LMDz. Sensitivity analyses with the tangent linear version show that the simplified sulphur chemistry is the dominant process responsible for the strong non-linearity of the model.

Volcanic aerosols: Chemistry, evolution, and effects

NASA Technical Reports Server (NTRS)

Turco, Richard

1991-01-01

Stratospheric aerosols have been the subject of scientific speculation since the 1880s, when the powerful eruption of Krakatoa attracted worldwide attention to the upper atmosphere through spectacular optical displays. The presence of a permanent tenuous dust layer in the lower stratosphere was postulated in the 1920s following studies of the twilight glow. Junge collected the first samples of these 'dust' particles and demonstrated that they were actually composed of sulfates, most likely concentrated sulfuric acid (Junge and Manson, 1961; Junge, 1963). Subsequent research has been spurred by the realization that stratospheric particles can influence the surface climate of earth through their effects on atmospheric radiation. Such aerosols can also influence, through chemical and physical effects, the trace composition of the atmosphere, ozone concentrations, and atmospheric electrical properties. The properties of stratospheric aerosols (both the background particles and those enhanced by volcanic eruptions) were measured in situ by balloon ascents and high altitude aircraft sorties. The aerosols were also observed remotely from the ground and from satellites using both active (lidar) and passive (solar occultation) techniques (remote sensing instruments were carried on aircraft and balloon platforms as well). In connection with the experimental work, models were developed to test theories of particle formation and evolution, to guide measurement strategies, to provide a means of connecting laboratory and field data, and to apply the knowledge gained to answer practical questions about global changes in climate, depletion of the ozone layer, and related environmental problems.

Response of an aerosol mass spectrometer to organonitrates and organosulfates and implications for atmospheric chemistry.

PubMed

Farmer, D K; Matsunaga, A; Docherty, K S; Surratt, J D; Seinfeld, J H; Ziemann, P J; Jimenez, J L

2010-04-13

Organonitrates (ON) are important products of gas-phase oxidation of volatile organic compounds in the troposphere; some models predict, and laboratory studies show, the formation of large, multifunctional ON with vapor pressures low enough to partition to the particle phase. Organosulfates (OS) have also been recently detected in secondary organic aerosol. Despite their potential importance, ON and OS remain a nearly unexplored aspect of atmospheric chemistry because few studies have quantified particulate ON or OS in ambient air. We report the response of a high-resolution time-of-flight aerosol mass spectrometer (AMS) to aerosol ON and OS standards and mixtures. We quantify the potentially substantial underestimation of organic aerosol O/C, commonly used as a metric for aging, and N/C. Most of the ON-nitrogen appears as NO(x)+ ions in the AMS, which are typically dominated by inorganic nitrate. Minor organonitrogen ions are observed although their identity and intensity vary between standards. We evaluate the potential for using NO(x)+ fragment ratios, organonitrogen ions, HNO(3)+ ions, the ammonium balance of the nominally inorganic ions, and comparison to ion-chromatography instruments to constrain the concentrations of ON for ambient datasets, and apply these techniques to a field study in Riverside, CA. OS manifests as separate organic and sulfate components in the AMS with minimal organosulfur fragments and little difference in fragmentation from inorganic sulfate. The low thermal stability of ON and OS likely causes similar detection difficulties for other aerosol mass spectrometers using vaporization and/or ionization techniques with similar or larger energy, which has likely led to an underappreciation of these species.

An overview of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx)

NASA Astrophysics Data System (ADS)

Dulac, François

2014-05-01

The Chemistry-Aerosol Mediterranean Experiment (ChArMEx, http://charmex.lsce.ipsl.fr) is a French initiative of the MISTRALS meta-programme (Mediterranean Integrated Studies at Regional And Locals Scales, http://www.mistrals-home.org). It federates a great number of national and international cooperative research actions aiming at a scientific assessment of the present and future state of the atmospheric environment in the Mediterranean Basin, and of its impacts on the regional climate, air quality, and marine biogeochemistry. The target is short-lived particulate and gaseous tropospheric trace species which are the cause of poor air quality events, have two-way interactions with climate, or impact the marine biogeochemistry, in a context of strong regional anthropogenic and climatic pressures. The six ChArMEx work packages include Emissions, Chemical processes and ageing, Transport processes and air quality, Aerosol-radiation-climate interactions, Deposition, and Present and future variability and trends. For several years, efforts have been deployed in several countries to develop (i) a network of relevant stations for atmospheric chemistry at background sites on islands and continental coasts around the basin and (ii) several intensive field campaigns including the operation of surface supersites and various instrumented mobile platforms (large and ultra-light aircraft, sounding and drifting balloons, ZeroCO2 sailboat). This presentation is an attempt to provide an overview of the various experimental, remote sensing and modelling efforts produced and to highlight major findings, by referencing more detailed ChArMEx presentations given in this conference and recently published or submitted papers. During the first phase of the project experimental efforts have been mainly concentrated on the western basin. Plans for the 2nd phase of ChArMEx, more dedicated towards the eastern basin, will also be given. In particular we plan to develop monitoring activities at

Effect of MERRA-2 initial and boundary conditions on WRF-Chem aerosol simulations over the Arabian Peninsula

NASA Astrophysics Data System (ADS)

Ukhov, Alexander; Stenchikov, Georgiy

2017-04-01

In this study, we test the sensitivity of the horizontal and vertical distributions of aerosols to the initial and boundary conditions (IC&BC) of the aerosol/chemistry. We use the WRF-Chem model configured over the Arabian Peninsula to study both dust and anthropogenic aerosols. Currently, in the WRF-Chem the aerosol/chemistry IC&BC are constructed using either default aerosol/chemistry profiles with no inflow of aerosols and chemicals through the lateral boundaries or using the aerosol/chemistry fields from MOZART, the model for ozone and related chemical tracers from the NCAR. Here, we construct aerosol/chemistry IC&BC using MERRA-2 output. MERRA-2 is a recently developed reanalysis that assimilates ground-based and satellite observations to provide the improved distributions of aerosols and chemical species. We ran WRF-Chem simulations for July-August 2015 using GOCART/AFWA dust emission and GOCART aerosol schemes. We used the EDGAR HTAP V4 dataset to calculate SO2 emissions. Comparison of three runs initiated using the same ERA-Interim reanalysis fields but different aerosol/chemistry IC&BC (default WRF-Chem, MOZART, and MERRA-2) with AERONET, Micropulse Lidar, Balloon, and satellite observations shows that the MERRA-2 IC&BC are superior.

Heterogeneity, pore pressure, and injectate chemistry: Control measures for geologic carbon storage

DOE PAGES

Dewers, Thomas; Eichhubl, Peter; Ganis, Ben; ...

2017-11-28

Desirable outcomes for geologic carbon storage include maximizing storage efficiency, preserving injectivity, and avoiding unwanted consequences such as caprock or wellbore leakage or induced seismicity during and post injection. Here, to achieve these outcomes, three control measures are evident including pore pressure, injectate chemistry, and knowledge and prudent use of geologic heterogeneity. Field, experimental, and modeling examples are presented that demonstrate controllable GCS via these three measures. Observed changes in reservoir response accompanying CO 2 injection at the Cranfield (Mississippi, USA) site, along with lab testing, show potential for use of injectate chemistry as a means to alter fracture permeabilitymore » (with concomitant improvements for sweep and storage efficiency). Further control of reservoir sweep attends brine extraction from reservoirs, with benefit for pressure control, mitigation of reservoir and wellbore damage, and water use. State-of-the-art validated models predict the extent of damage and deformation associated with pore pressure hazards in reservoirs, timing and location of networks of fractures, and development of localized leakage pathways. Experimentally validated geomechanics models show where wellbore failure is likely to occur during injection, and efficiency of repair methods. Use of heterogeneity as a control measure includes where best to inject, and where to avoid attempts at storage. Lastly, an example is use of waste zones or leaky seals to both reduce pore pressure hazards and enhance residual CO 2 trapping.« less

Heterogeneity, pore pressure, and injectate chemistry: Control measures for geologic carbon storage

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

Dewers, Thomas; Eichhubl, Peter; Ganis, Ben

Desirable outcomes for geologic carbon storage include maximizing storage efficiency, preserving injectivity, and avoiding unwanted consequences such as caprock or wellbore leakage or induced seismicity during and post injection. Here, to achieve these outcomes, three control measures are evident including pore pressure, injectate chemistry, and knowledge and prudent use of geologic heterogeneity. Field, experimental, and modeling examples are presented that demonstrate controllable GCS via these three measures. Observed changes in reservoir response accompanying CO 2 injection at the Cranfield (Mississippi, USA) site, along with lab testing, show potential for use of injectate chemistry as a means to alter fracture permeabilitymore » (with concomitant improvements for sweep and storage efficiency). Further control of reservoir sweep attends brine extraction from reservoirs, with benefit for pressure control, mitigation of reservoir and wellbore damage, and water use. State-of-the-art validated models predict the extent of damage and deformation associated with pore pressure hazards in reservoirs, timing and location of networks of fractures, and development of localized leakage pathways. Experimentally validated geomechanics models show where wellbore failure is likely to occur during injection, and efficiency of repair methods. Use of heterogeneity as a control measure includes where best to inject, and where to avoid attempts at storage. Lastly, an example is use of waste zones or leaky seals to both reduce pore pressure hazards and enhance residual CO 2 trapping.« less

Modeling Atmospheric Aerosols in WRF/Chem

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

Zhang, Yang; Hu, X.-M.; Howell, G.

2005-06-01

In this study, three aerosol modules are tested and compared. The first module is the Modal Aerosol Dynamics Model for Europe (MADE) with the secondary organic aerosol model (SORGAM) (referred to as MADE/SORGAM). The second module is the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC). The third module is the Model of Aerosol Dynamics, Reaction, Ionization and Dissolution (MADRID). The three modules differ in terms of size representation used, chemical species treated, assumptions and numerical algorithms used. Table 1 compares the major processes among the three aerosol modules.

Chemical characteristics of size-resolved atmospheric aerosols in Iasi, north-eastern Romania: nitrogen-containing inorganic compounds control aerosol chemistry in the area

NASA Astrophysics Data System (ADS)

Giorgiana Galon-Negru, Alina; Iulian Olariu, Romeo; Arsene, Cecilia

2018-04-01

This study assesses the effects of particle size and season on the content of the major inorganic and organic aerosol ionic components in the Iasi urban area, north-eastern Romania. Continuous measurements were carried out over 2016 using a cascade Dekati low-pressure impactor (DLPI) performing aerosol size classification in 13 specific fractions over the 0.0276-9.94 µm size range. Fine-particulate Cl-, NO3-, NH4+, and K+ exhibited clear minima during the warm season and clear maxima over the cold season, mainly due to trends in emission sources, changes in the mixing layer depth and specific meteorological conditions. Fine-particulate SO42- did not show much variation with respect to seasons. Particulate NH4+ and NO3- ions were identified as critical parameters controlling aerosol chemistry in the area, and their measured concentrations in fine-mode (PM2.5) aerosols were found to be in reasonable good agreement with modelled values for winter but not for summer. The likely reason is that NH4NO3 aerosols are lost due to volatility over the warm season. We found that NH4+ in PM2.5 is primarily associated with SO42- and NO3- but not with Cl-. Actually, indirect ISORROPIA-II estimations showed that the atmosphere in the Iasi area might be ammonia rich during both the cold and warm seasons, enabling enough NH3 to be present to neutralize H2SO4, HNO3, and HCl acidic components and to generate fine-particulate ammonium salts, in the form of (NH4)2SO4, NH4NO3, and NH4Cl. ISORROPIA-II runs allowed us to estimate that over the warm season ˜ 35 % of the total analysed samples had very strongly acidic pH (0-3), a fraction that rose to ˜ 43 % over the cold season. Moreover, while in the cold season the acidity is mainly accounted for by inorganic acids, in the warm ones there is an important contribution by other compounds, possibly organic. Indeed, changes in aerosol acidity would most likely impact the gas-particle partitioning of semi-volatile organic acids. Overall, we

Heterogeneous ice nucleation and phase transition of viscous α-pinene secondary organic aerosol

NASA Astrophysics Data System (ADS)

Ignatius, Karoliina; Kristensen, Thomas B.; Järvinen, Emma; Nichman, Leonid; Fuchs, Claudia; Gordon, Hamish; Herenz, Paul; Hoyle, Christopher R.; Duplissy, Jonathan; Baltensperger, Urs; Curtius, Joachim; Donahue, Neil M.; Gallagher, Martin W.; Kirkby, Jasper; Kulmala, Markku; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin; Virtanen, Annele; Stratmann, Frank

2016-04-01

There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate deposition ice nucleation and thus influence cirrus cloud properties. Global model simulations of monoterpene SOA particles suggest that viscous biogenic SOA are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle (INP) budget. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles at the CLOUD (Cosmics Leaving OUtdoor Droplets) experiment at CERN (Ignatius et al., 2015, Järvinen et al., 2015). In the CLOUD chamber, the SOA particles were produced from the ozone initiated oxidation of α-pinene at temperatures in the range from -38 to -10° C at 5-15 % relative humidity with respect to water (RHw) to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. We found that particles formed and grown in the chamber developed an asymmetric shape through coagulation. As the RHw was increased to between 35 % at -10° C and 80 % at -38° C, a transition to spherical shape was observed with a new in-situ optical method. This transition confirms previous modelling of the viscosity transition conditions. The ice nucleation ability of SOA particles was investigated with a new continuous flow diffusion chamber SPIN (Spectrometer for Ice Nuclei) for different SOA particle sizes. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA in the deposition mode for ice saturation ratios between 1.3 and 1.4, significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between -36.5 and -38.3° C ranged from 6 to 20 % and did not depend on the particle surface area. References Ignatius, K. et al., Heterogeneous ice

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

Identifying robust regional precipitation responses to regional aerosol emissions perturbations in three coupled chemistry-climate models

NASA Astrophysics Data System (ADS)

Westervelt, D. M.; Fiore, A. M.; Lamarque, J. F.; Previdi, M. J.; Conley, A. J.; Shindell, D. T.; Mascioli, N. R.; Correa, G. J. P.; Faluvegi, G.; Horowitz, L. W.

2017-12-01

Regional emissions of anthropogenic aerosols and their precursors will likely decrease for the remainder of the 21st century, due to emission reduction policies enacted to protect human health. Although there is some evidence that regional climate effects of aerosols can be significant, we currently lack a robust understanding of the magnitude, spatio-temporal pattern, statistical significance, and physical processes responsible for these influences, especially for precipitation. Here, we aim to quantify systematically the precipitation response to regional changes in aerosols and investigate underlying mechanisms using three fully coupled chemistry-climate models: NOAA Geophysical Fluid Dynamics Laboratory Coupled Model 3 (GFDL-CM3), NCAR Community Earth System Model (CESM), and NASA Goddard Institute for Space Studies ModelE2 (GISS-E2). The central approach we use is to contrast a long control experiment (400 years, run with perpetual year 2000 emissions) with 14 individual aerosol emissions perturbation experiments ( 200 years each). We perturb emissions of sulfur dioxide (SO2) and carbonaceous aerosol (BC and OM) within several world regions and assess which responses are significant relative to internal variability determined by the control run and robust across the three models. Initial results show significant changes in precipitation in several vulnerable regions including the Western Sahel and the Indian subcontinent. SO2 emissions reductions from Europe and the United States have the largest impact on precipitation among most of the selected response regions. The precipitation response to emissions changes from these regions projects onto known modes of variability, such as the North Atlantic Oscillation (NAO) and the El Niño Southern Oscillation (ENSO). Across all perturbation experiments, we find a strong linear relationship between the responses of Sahel precipitation and the interhemispheric temperature difference, suggesting a common mechanism of an

Heterogeneous kinetics of N2O5 reactive uptake and chlorine activation in authentic biomass burning aerosol

NASA Astrophysics Data System (ADS)

Sullivan, R. C.; Jahl, L.; Goldberger, L.; Ahern, A.; Thornton, J. A.

2017-12-01

Nitryl chloride (ClNO2) is a nighttime reservoir of NOx that is formed from the uptake of dinitrogen pentoxide (N2O5) into particles containing chloride. The formation of ClNO2 from heterogeneous reactions of N2O5(g) with authentic biomass burning aerosol has not previously been studied. We observed the rapid production of N2O5 and then ClNO2 during dark chemical transformations of biomass burning aerosol produced from a variety of fuels using both a smog chamber and an aerosol flow tube reactor. Iodide adduct chemical ionization mass spectrometry was used to measure gas phase ClNO2 and N2O5, and acetate chemical ionization mass spectrometry to measure gaseous HCl and other compounds, while a soot particle aerosol mass spectrometer measured changes in aerosol composition as chloride was displaced by nitrate. Upon the addition of ozone to the biomass burning smoke, N2O5 was always rapidly formed and ClNO2 was subsequently detected in the gas phase. During experiments at high relative humidity, we observed decreases in particulate chloride and increases in particulate nitrate which we believe are due to acid displacement of HCl(g) by HNO3 since no additional ClNO2 was produced in the gas phase. The reactive uptake probability of N2O5 on authentic biomass burning aerosol and the yield of ClNO2 were determined for the first time using chamber and flow tube experiments on smoke from biomass fuels including sawgrass, giant cutgrass, palmetto leaves, and ponderosa pine. These experiments confirm the formation of N2O5 and ClNO2 in biomass burning emissions and suggest that biomass burning is a likely source of continental ClNO2 and HCl.

Sensitivity of aerosol optical depth, single scattering albedo, and phase function calculations to assumptions on physical and chemical properties of aerosol

EPA Science Inventory

In coupled chemistry-meteorology simulations, the calculation of aerosol optical properties is an important task for the inclusion of the aerosol effects on the atmospheric radiative budget. However, the calculation of these properties from an aerosol profile is not uniquely defi...

The oxidation of SO2 by NO2(g) at the air-water interface of aquated aerosol: implications for the rapid onset of haze-aerosol events in China

NASA Astrophysics Data System (ADS)

Li, L.; Colussi, A. J.; Hoffmann, M. R.

2017-12-01

Aqueous phase chemistry plays a vital role in the global atmosphere. The importance of heterogeneous chemistry has been recently underscored by the severe haze-fog pollution episodes experienced in Chinese megacities. A key finding is that despite reduced photochemistry during the wintertime haze events, the oxidation of S(IV) into sulfate aerosol occurs rapidly in spite of the low levels of ozone and H2O2. Field observations suggest that NO2 could serve as a suitable oxidant of S(IV) during the events under neutral pH conditions. However, the haze aerosols are mostly acidic. Furthermore, the air-water interface is more acidic than bulk-phase aquated system according to our recent findings. This work investigates the chemistry taking place as NO2(g) collides with the surface of aqueous S(IV) microdroplets as a function of pH to closely simulate actual haze aerosol events under atmospheric conditions. The reaction between NO2(g) and HSO3- (aq) is studied in situ under ambient temperature and pressure via online electrospray ionization mass spectrometry. The aqueous aerosols containing HSO3- is generated using a microjet which is exposed to NO2(g) alternatively, while the composition of the 1 nm interfacial liquid layer of the aerosol is instantaneously measured. The ratio of HSO3- to HSO4- is observed to decrease with the concomitant appearance of a strong m/z 62 signal upon NO2(g) exposure. The appearance of m/z 62 indicates the formation of NO3- via the disproportionation of NO2 (2NO2(g) + H2O (l) ⇌ H++NO3-(aq) + HONO(aq)) and thus impacts the ion-ion interactions of NO3- on the ratio of HSO3- to HSO4- in the outermost interfacial layers. Parallel experiments with NO3-(aq) additions are conducted to quantify the impact of NO3- on the the ratio, in order to unravel the contribution of NO2 to the oxidation of S(IV). After accounting for the HNO3 effect, it is concluded: (1) most NO2(g) is converted into NO3- via anion-catalyzed hydrolytic disproportionation; (2

The Response of Ozone and Nitrogen Dioxide to the Eruption of Mount Pinatubo at Southern and Northern Midlatitudes

NASA Technical Reports Server (NTRS)

Aquila, Valentina; Oman, Luke D.; Stolarski, Richard S.; Douglass, Anne R.; Newman, Paul A.

2013-01-01

Observations have shown that the mass of nitrogen dioxide decreased at both southern and northern midlatitudes in the year following the eruption of Mt. Pinatubo, indicating that the volcanic aerosol had enhanced nitrogen dioxide depletion via heterogeneous chemistry. In contrast, the observed ozone response showed a northern midlatitude decrease and a small southern midlatitude increase. Previous simulations that included an enhancement of heterogeneous chemistry by the volcanic aerosol but no other effect of this aerosol produce ozone decreases in both hemispheres, contrary to observations. The authors simulations show that the heating due to the volcanic aerosol enhanced both the tropical upwelling and Southern Hemisphere extratropical downwelling. This enhanced extratropical downwelling, combined with the time of the eruption relative to the phase of the Brewer Dobson circulation, increased Southern Hemisphere ozone via advection, counteracting the ozone depletion due to heterogeneous chemistry on the Pinatubo aerosol.

Modeling Trends in Aerosol Direct Radiative Effects over the Northern Hemisphere using a Coupled Meteorology-Chemistry Model

NASA Astrophysics Data System (ADS)

Mathur, R.; Pleim, J.; Wong, D.; Hogrefe, C.; Xing, J.; Wei, C.; Gan, M.

2013-12-01

While aerosol radiative effects have been recognized as some of the largest sources of uncertainty among the forcers of climate change, the verification of the spatial and temporal variability of the magnitude and directionality of aerosol radiative forcing has remained challenging. A detailed investigation of the processes regulating aerosol distributions, their optical properties, and their radiative effects and verification of their simulated effects for past conditions relative to measurements is needed in order to build confidence in the estimates of the projected impacts arising from changes in both anthropogenic forcing and climate change. Anthropogenic emissions of primary aerosol and gaseous precursors have witnessed dramatic changes over the past two decades across the northern hemisphere. During the period 1990-2010, SO2 and NOx emissions across the US have reduced by about 66% and 50%, respectively, mainly due to Title IV of the U.S. Clean Air Act Amendments (CAA). In contrast, anthropogenic emissions have increased dramatically in many developing regions during this period. We conduct a systematic investigation of changes in anthropogenic emissions of primary aerosols and gaseous precursors over the past two decades, their impacts on trends and spatial heterogeneity in anthropogenic aerosol loading across the northern hemisphere troposphere, and subsequent impacts on regional radiation budgets. The coupled WRF-CMAQ model is applied for selected time periods spanning the period 1990-2010 over a domain covering the northern hemisphere and a nested finer resolution continental U.S. domain. The model includes detailed treatment of direct effects of aerosols on photolysis rates as well as on shortwave radiation. Additionally, treatment of aerosol indirect effects on clouds has also recently been implemented. A methodology is developed to consistently estimate U.S. emission inventories for the 20-year period accounting for air quality regulations as well as

Comparison of heterogeneous photolytic reduction of Hg(II) in the coal fly ashes and synthetic aerosols

NASA Astrophysics Data System (ADS)

Tong, Yindong; Eichhorst, Terry; Olson, Michael R.; Rutter, Andrew P.; Shafer, Martin M.; Wang, Xuejun; Schauer, James J.

2014-03-01

In this study, we examined the heterogeneous reduction of Hg(II) on the coal fly ash samples and synthetic aerosols under different light conditions in a controlled laboratory reactor. Three types of coal fly ashes were studied: a high carbon fly ash from a stoker boiler, a low carbon/low sulfate fly ash from a pulverized coal combustor burning low sulfur coal, and a high sulfate fly ash from a pulverized coal combustor burning high sulfur coal. The rate of Hg(II) reduction on the three diverse fly ash samples was found to be relatively fast with an average half-life of 1.6 h under clear sky atmospheric conditions (under the irradiance of 1000 W/m2). The reduction rate in the low sulfate/low carbon fly ash was approximately 1.5 times faster than with the other coal fly ash samples. Synthetic aerosols made of carbon black and levoglucosan produced Hg(II) reduction rates similar to coal fly ashes. However, aerosols composed of adipic acid resulted in reduction rates that were 3-5 times faster. The sensitivity of adipic acid reduction to light source wavelength was found to be greater than for the coal fly ash and other synthetic aerosols. Aerosols made from the water extracts of coal fly ash samples produced reduction rates equal to or slightly higher than with the native fly ash suggesting that the soluble components of fly ash play a significant role in the reduction mechanism. The measured reduction rates are likely important in the chemical processing of mercury in power plant plumes and potentially in the atmosphere and should be considered for incorporation in atmospheric transport models that are used to understand the fate of atmospheric mercury.

Dynamic viscosity mapping of the oxidation of squalene aerosol particles.

PubMed

Athanasiadis, Athanasios; Fitzgerald, Clare; Davidson, Nicholas M; Giorio, Chiara; Botchway, Stanley W; Ward, Andrew D; Kalberer, Markus; Pope, Francis D; Kuimova, Marina K

2016-11-09

Organic aerosols (OAs) play important roles in multiple atmospheric processes, including climate change, and can impact human health. The physico-chemical properties of OAs are important for all these processes and can evolve through reactions with various atmospheric components, including oxidants. The dynamic nature of these reactions makes it challenging to obtain a true representation of their composition and surface chemistry. Here we investigate the microscopic viscosity of the model OA composed of squalene, undergoing chemical aging. We employ Fluorescent Lifetime Imaging Microscopy (FLIM) in conjunction with viscosity sensitive probes termed molecular rotors, in order to image the changes in microviscosity in real time during oxidation with ozone and hydroxyl radicals, which are two key oxidising species in the troposphere. We also recorded the Raman spectra of the levitated particles to follow the reactivity during particle ozonolysis. The levitation of droplets was achieved via optical trapping that enabled simultaneous levitation and measurement via FLIM or Raman spectroscopy and allowed the true aerosol phase to be probed. Our data revealed a very significant increase in viscosity of the levitated squalene droplets upon ozonolysis, following their transformation from the liquid to solid phase that was not observable when the oxidation was carried out on coverslip mounted droplets. FLIM imaging with sub-micron spatial resolution also revealed spatial heterogeneity in the viscosity distribution of oxidised droplets. Overall, a combination of molecular rotors, FLIM and optical trapping is able to provide powerful insights into OA chemistry and the microscopic structure that enables the dynamic monitoring of microscopic viscosity in aerosol particles in their true phase.

Wintertime nitric acid chemistry - Implications from three-dimensional model calculations

NASA Technical Reports Server (NTRS)

Rood, Richard B.; Kaye, Jack A.; Douglass, Anne R.; Allen, Dale J.; Steenford, Stephen

1990-01-01

A three-dimensional simulation of the evolution of HNO3 has been run for the winter of 1979. Winds and temperatures are taken from a stratospheric data assimilation analysis, and the chemistry is based on Limb Infrared Monitor of the Stratosphere (LIMS) observations. The model is compared to LIMS observations to investigate the problem of 'missing' nitric acid chemistry in the winter hemisphere. Both the model and observations support the contention that a nitric acid source is needed outside of the polar vortex and north of the subtropics. Observations suggest that HNO3 is not dynamically controlled in middle latitudes. The model shows that given the time scales of conventional chemistry, dynamical control is expected. Therefore, an error exists in the conventional chemistry or additional processes are needed to bring the model and data into agreement. Since the polar vortex is dynamically isolated from the middle latitudes, and since the highest HNO3 values are observed in October and November, a source associated solely with polar stratospheric clouds cannot explain the deficiencies in the chemistry. The role of heterogeneous processes on background aerosols is reviewed in light of these results.

An evaluation of uncertainty in the aerosol optical properties as represented by satellites and an ensemble of chemistry-climate coupled models over Europe

NASA Astrophysics Data System (ADS)

Palacios-Peña, Laura; Baró, Rocío; Jiménez-Guerrero, Pedro

2016-04-01

The changes in Earth's climate are produced by forcing agents such as greenhouse gases, clouds and atmospheric aerosols. The latter modify the Earth's radiative budget due to their optical, microphysical and chemical properties, and are considered to be the most uncertain forcing agent. There are two main approaches to the study of aerosols: (1) ground-based and remote sensing observations and (2) atmospheric modelling. With the aim of characterizing the uncertainties associated with these approaches, and estimating the radiative forcing caused by aerosols, the main objective of this work is to assess the representation of aerosol optical properties by different remote sensing sensors and online-coupled chemistry-climate models and to determine whether the inclusion of aerosol radiative feedbacks in this type of models improves the modelling outputs over Europe. Two case studies have been selected under the framework of the EuMetChem COST Action ES1004, when important aerosol episodes during 2010 over Europe took place: a Russian wildfires episode and a Saharan desert dust outbreak covering most of Europe. Model data comes from an ensemble of regional air quality-climate simulations performed by the working group 2 of EuMetChem, that investigates the importance of different processes and feedbacks in on-line coupled chemistry-climate models. These simulations are run for three different configurations for each model, differing in the inclusion (or not) of aerosol-radiation and aerosol-cloud interactions. The remote sensing data comes from three different sensors, MODIS (Moderate Resolution Imaging Spectroradiometer), OMI (Ozone Monitoring Instrument) and SeaWIFS (Sea-viewing Wide Field-of-view Sensor). The evaluation has been performed by using classical statistical metrics, comparing modelled and remotely sensed data versus a ground-based instrument network (AERONET). The evaluated variables are aerosol optical depth (AOD) and the Angström exponent (AE) at

Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA)

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

Hu, Weiwei; Palm, Brett B.; Day, Douglas A.

Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigatedmore » with an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding ~100 µg m -3 of pure H 2SO 4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical ( k OH) was estimated as 4.0 ± 2.0 ×10 -13 cm 3 molec -1 s -1, which is equivalent to more than a 2-week lifetime. A similar k OH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (> 1 × 10 12 molec cm -3 s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients ( γ OH = 0.59±0.33 in SE US and γ OH = 0.68±0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of k OH and γ OH was observed, consistent with surface-area-limited OH uptake. No decrease of k OH was observed as OH concentrations increased. These observations of physicochemical properties of IEPOX-SOA can help to constrain OA impact on air quality and climate.« less

Forcing of stratospheric chemistry and dynamics during the Dalton Minimum

NASA Astrophysics Data System (ADS)

Anet, J. G.; Muthers, S.; Rozanov, E.; Raible, C. C.; Peter, T.; Stenke, A.; Shapiro, A. I.; Beer, J.; Steinhilber, F.; Brönnimann, S.; Arfeuille, F.; Brugnara, Y.; Schmutz, W.

2013-11-01

The response of atmospheric chemistry and dynamics to volcanic eruptions and to a decrease in solar activity during the Dalton Minimum is investigated with the fully coupled atmosphere-ocean chemistry general circulation model SOCOL-MPIOM (modeling tools for studies of SOlar Climate Ozone Links-Max Planck Institute Ocean Model) covering the time period 1780 to 1840 AD. We carried out several sensitivity ensemble experiments to separate the effects of (i) reduced solar ultra-violet (UV) irradiance, (ii) reduced solar visible and near infrared irradiance, (iii) enhanced galactic cosmic ray intensity as well as less intensive solar energetic proton events and auroral electron precipitation, and (iv) volcanic aerosols. The introduced changes of UV irradiance and volcanic aerosols significantly influence stratospheric dynamics in the early 19th century, whereas changes in the visible part of the spectrum and energetic particles have smaller effects. A reduction of UV irradiance by 15%, which represents the presently discussed highest estimate of UV irradiance change caused by solar activity changes, causes global ozone decrease below the stratopause reaching as much as 8% in the midlatitudes at 5 hPa and a significant stratospheric cooling of up to 2 °C in the mid-stratosphere and to 6 °C in the lower mesosphere. Changes in energetic particle precipitation lead only to minor changes in the yearly averaged temperature fields in the stratosphere. Volcanic aerosols heat the tropical lower stratosphere, allowing more water vapour to enter the tropical stratosphere, which, via HOx reactions, decreases upper stratospheric and mesospheric ozone by roughly 4%. Conversely, heterogeneous chemistry on aerosols reduces stratospheric NOx, leading to a 12% ozone increase in the tropics, whereas a decrease in ozone of up to 5% is found over Antarctica in boreal winter. The linear superposition of the different contributions is not equivalent to the response obtained in a simulation

Nighttime Chemistry in the Polluted Boundary Layer (Invited)

NASA Astrophysics Data System (ADS)

Stutz, J.; Wong, K.; Tsai, C.; Pikelnaya, O.

2009-12-01

Chemistry in the urban nocturnal boundary layer (NBL) has received surprisingly little attention in the past. Surface observations often see low ozone and high NO levels, which lead to low nocturnal radical levels and consequently slow chemistry near the ground. Above the surface, however, ozone and radical levels, for example of NO3, are considerably higher, and more efficient chemical pathways for the removal of gaseous pollutants such as nitrogen oxides, ozone, and hydrocarbons, are active. The influence of nocturnal chemistry on aerosol composition is also largest aloft. These processes are poorly understood due to a lack of observations in the altitude range from 20 - 500m. The strong influence of vertical mixing and transport on the composition of the NBL poses an additional challenge, requiring the measurement of vertical concentration profiles and the use of chemical transport models for their interpretation. In addition, heterogeneous processes on the ground and on aerosol surfaces play an important role in the nocturnal atmosphere. In this presentation we will review our current understanding of nocturnal chemistry in the lowest 300m of the polluted atmosphere, with a focus on nitrogen compounds. A number of field experiments in recent years have given insight into the vertical distribution of some of the most important nocturnal trace gases in urban areas, such as ozone, NO2, NO3, N2O5, and HONO. In particular, two 6-week long experiments in Houston, TX, in 2006 and 2009, have shown the strong and persistent impact of vertical mixing on the distribution of all trace gases, as well as the chemistry in the lowest 300m of the atmosphere. These observations were accompanied by detailed meteorological observations and in-situ measurements of chemical species at 70m above the ground. The observations in Houston were interpreted with a 1D chemical transport model that allows quantification of chemistry and transport at night. Our results identify gaps in our

Online and offline mass spectrometric study of the impact of oxidation and ageing on glyoxal chemistry and uptake onto ammonium sulfate aerosols.

PubMed

Hamilton, Jacqueline F; Baeza-Romero, M Teresa; Finessi, Emanuela; Rickard, Andrew R; Healy, Robert M; Peppe, Salvatore; Adams, Thomas J; Daniels, Mark J S; Ball, Stephen M; Goodall, Iain C A; Monks, Paul S; Borrás, Esther; Muñoz, Amalia

2013-01-01

Recent laboratory and modelling studies have shown that reactive uptake of low molecular weight alpha-dicarbonyls such as glyoxal (GLY) by aerosols is a potentially significant source of secondary organic aerosol (SOA). However, previous studies disagree in the magnitude of the uptake of GLY, the mechanism involved and the physicochemical factors affecting particle formation. In this study, the chemistry of GLY with ammonium sulfate (AS) in both bulk laboratory solutions and in aerosol particles is investigated. For the first time, Aerosol Time of Flight Mass Spectrometry (ATOFMS), a single particle technique, is used together with offline (ESI-MS and LC-MS2) mass spectrometric techniques to investigate the change in composition of bulk solutions of GLY and AS resulting from aqueous photooxidation by OH and from ageing of the solutions in the dark. The mass spectral ions obtained in these laboratory studies were used as tracers of GLY uptake and chemistry in AS seed particles in a series of experiments carried out under dark and natural irradiated conditions at the outdoor European Photo-reactor (EUPHORE). Glyoxal oligomers formed were not detected by the ATOFMS, perhaps due to inefficient absorption at the laser wavelength. However, the presence of organic nitrogen compounds, formed by reaction of GLY with ammonia was confirmed, resulting in an increase in the absorption efficiency of the aerosol, and this increased the number of particles successfully ionised by the ATOFMS. A number of light absorbing organic nitrogen species, including 1H-imidazole, 1H-imidazole-2-carboxaldehyde, 2,2'-bis-imidazole and a glyoxal substituted 2,2'-bisimidazole, previously identified in aqueous laboratory solutions, were also identified in chamber aerosol and formed on atmospherically relevant timescales. An additional compound, predicted to be 1,2,5-oxadiazole, had an enhanced formation rate when the chamber was open and is predicted to be formed via a light activated pathway

Insights into aerosols, chemistry, and clouds from NETCARE: Observations from the Canadian Arctic in summer 2014

NASA Astrophysics Data System (ADS)

Abbatt, J.

2015-12-01

The Canadian Network on Aerosols and Climate: Addressing Key Uncertainties in Remote Canadian Regions (or NETCARE) was established in 2013 to study the interactions between aerosols, chemistry, clouds and climate. The network brings together Canadian academic and government researchers, along with key international collaborators. Attention is being given to observations and modeling of Arctic aerosol, with the goal to understand underlying processes and so improve predictions of aerosol climate forcing. Motivation to understand the summer Arctic atmosphere comes from the retreat of summer sea ice and associated increase in marine influence. To address these goals, a suite of measurements was conducted from two platforms in summer 2014 in the Canadian Arctic, i.e. an aircraft-based campaign on the Alfred Wegener Institute POLAR 6 and an ocean-based campaign from the CGCS Amundsen icebreaker. NETCARE-POLAR was based out of Resolute Bay, Nunavut during an initial period of little transport and cloud-free conditions and a later period characterized by more transport with potentially biomass burning influence. Measurements included particle and cloud droplet numbers and size distributions, aerosol composition, cloud nuclei, and levels of gaseous tracers. Ultrafine particle events were more frequently observed in the marine boundary layer than above, with particle growth observed in some cases to cloud condensation nucleus sizes. The influence of biological processes on atmospheric constituents was also assessed from the ship during NETCARE-AMUNDSEN, as indicated by high measured levels of gaseous ammonia, DMS and oxygenated VOCs, as well as isolated particle formation and growth episodes. The cruise took place in Baffin Bay and through the Canadian archipelago. Interpretation of the observations from both campaigns is enhanced through the use of chemical transport and particle dispersion models. This talk will provide an overview of NETCARE Arctic observational and

A 2D Microphysical Analysis of Aerosol Nucleation in the Polar Winter Stratosphere: Implications for H2SO4 Photolysis and Nucleation Mechanisms

NASA Technical Reports Server (NTRS)

Mills, Michael J.; Toon, Owen B.; Mills, Michael J.; Solomon, Susan

1997-01-01

Each spring a layer of small particles forms between 20 and 30 km in the polar regions. Results are presented from a 2D microphysical model of sulfate aerosol, which provide the first self-consistent explanation of the observed "CN layer." Photochemical conversion of sulfuric acid to SO2 in the upper stratosphere and mesosphere is necessary for this layer to form. Recent laboratory measurements of H2SO4 and SO3 photolysis rates are consistent with such conversion, though an additional source of SO2 may be required. Nucleation throughout the polar winter extends the top of the aerosol layer to higher altitudes, despite strong downward transport of ambient air. This finding may be important to heterogeneous chemistry at the top of the aerosol layer in polar winter and spring.

Enviro-HIRLAM/ HARMONIE Studies in ECMWF HPC EnviroAerosols Project

NASA Astrophysics Data System (ADS)

Hansen Sass, Bent; Mahura, Alexander; Nuterman, Roman; Baklanov, Alexander; Palamarchuk, Julia; Ivanov, Serguei; Pagh Nielsen, Kristian; Penenko, Alexey; Edvardsson, Nellie; Stysiak, Aleksander Andrzej; Bostanbekov, Kairat; Amstrup, Bjarne; Yang, Xiaohua; Ruban, Igor; Bergen Jensen, Marina; Penenko, Vladimir; Nurseitov, Daniyar; Zakarin, Edige

2017-04-01

The EnviroAerosols on ECMWF HPC project (2015-2017) "Enviro-HIRLAM/ HARMONIE model research and development for online integrated meteorology-chemistry-aerosols feedbacks and interactions in weather and atmospheric composition forecasting" is aimed at analysis of importance of the meteorology-chemistry/aerosols interactions and to provide a way for development of efficient techniques for on-line coupling of numerical weather prediction and atmospheric chemical transport via process-oriented parameterizations and feedback algorithms, which will improve both the numerical weather prediction and atmospheric composition forecasts. Two main application areas of the on-line integrated modelling are considered: (i) improved numerical weather prediction with short-term feedbacks of aerosols and chemistry on formation and development of meteorological variables, and (ii) improved atmospheric composition forecasting with on-line integrated meteorological forecast and two-way feedbacks between aerosols/chemistry and meteorology. During 2015-2016 several research projects were realized. At first, the study on "On-line Meteorology-Chemistry/Aerosols Modelling and Integration for Risk Assessment: Case Studies" focused on assessment of scenarios with accidental and continuous emissions of sulphur dioxide for case studies for Atyrau (Kazakhstan) near the northern part of the Caspian Sea and metallurgical enterprises on the Kola Peninsula (Russia), with GIS integration of modelling results into the RANDOM (Risk Assessment of Nature Detriment due to Oil spill Migration) system. At second, the studies on "The sensitivity of precipitation simulations to the soot aerosol presence" & "The precipitation forecast sensitivity to data assimilation on a very high resolution domain" focused on sensitivity and changes in precipitation life-cycle under black carbon polluted conditions over Scandinavia. At third, studies on "Aerosol effects over China investigated with a high resolution

Chemistry of Titan's Aerosols : Correlation of The C/n &C/h Ratios To Pressure and Temperature

NASA Astrophysics Data System (ADS)

Bernard, J.-M.; Coll, P.; Raulin, F.

The gas present in Titan's atmosphere are forming organics aerosols under action of the solar radiations and of electrons from Saturn's magnetosphere. Many experimental simulations are been realised by irradiating N2/CH4 gas mixtures with different en- ergy sources in order to reproduce the chemistry of gas and particulate phases (Thomp- son et al, 1991; Mc Donald et al, 1994; de Vanssay et al, 1995; McKay, 1996; Coll et al, 1997, 1998a,b; and Refs. included). Until very recently, only one organics re- mains detected in Titan but not in laboratory simulation : C4N2. A full program of experimental research has been developed at LISA, which was able to provide a com- plete identification of a wide range of compounds, proposed to be present in Titan's atmosphere, including C4N2. The composition of aerosol on Titan is not known, due to its complexity. Especially its building molecules are difficult to identify. Only functional groups of analogues have been determined using spectroscopy and pyrolysis. However this chemical composi- tion is a key parameter for Cassini-Huygens experiments and atmospheric modeling : even the optical properties of aerosols are related to C/N and C/H ratios. We will present the results of the variation of C/N and C/H ratios according to the temperature and the pressure in Titan's atmosphere simulations. This data will allow to constraint photochemical models, in order for them to be more realistic. Then the comprehension of the mechanism of aerosols formation on Titan as function of altitude will be easier.

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.

Nano-sized metabolic precursors for heterogeneous tumor-targeting strategy using bioorthogonal click chemistry in vivo.

PubMed

Lee, Sangmin; Jung, Seulhee; Koo, Heebeom; Na, Jin Hee; Yoon, Hong Yeol; Shim, Man Kyu; Park, Jooho; Kim, Jong-Ho; Lee, Seulki; Pomper, Martin G; Kwon, Ick Chan; Ahn, Cheol-Hee; Kim, Kwangmeyung

2017-12-01

Herein, we developed nano-sized metabolic precursors (Nano-MPs) for new tumor-targeting strategy to overcome the intrinsic limitations of biological ligands such as the limited number of biological receptors and the heterogeneity in tumor tissues. We conjugated the azide group-containing metabolic precursors, triacetylated N-azidoacetyl-d-mannosamine to generation 4 poly(amidoamine) dendrimer backbone. The nano-sized dendrimer of Nano-MPs could generate azide groups on the surface of tumor cells homogeneously regardless of cell types via metabolic glycoengineering. Importantly, these exogenously generated 'artificial chemical receptors' containing azide groups could be used for bioorthogonal click chemistry, regardless of phenotypes of different tumor cells. Furthermore, in tumor-bearing mice models, Nano-MPs could be mainly localized at the target tumor tissues by the enhanced permeation and retention (EPR) effect, and they successfully generated azide groups on tumor cells in vivo after an intravenous injection. Finally, we showed that these azide groups on tumor tissues could be used as 'artificial chemical receptors' that were conjugated to bioorthogonal chemical group-containing liposomes via in vivo click chemistry in heterogeneous tumor-bearing mice. Therefore, overall results demonstrated that our nano-sized metabolic precursors could be extensively applied to new alternative tumor-targeting technique for molecular imaging and drug delivery system, regardless of the phenotype of heterogeneous tumor cells. Copyright © 2017 Elsevier Ltd. All rights reserved.

Impacts of heterogeneous reactions to atmospheric peroxides: Observations and budget analysis study

NASA Astrophysics Data System (ADS)

Qin, Mengru; Chen, Zhongming; Shen, Hengqing; Li, Huan; Wu, Huihui; Wang, Yin

2018-06-01

Atmospheric peroxides play important roles in atmospheric chemistry, acting as reactive oxidants and reservoirs of HOX and ROX radicals. Field measurements of atmospheric peroxides were conducted over urban Beijing from 2015 to 2016, including dust storm days, haze days and different seasons. We employed a box model based on RACM2 mechanism to conduct concentration simulation and budget analysis of hydrogen peroxide (H2O2) and peroxyacetic acid (PAA). In this study, heterogeneous reaction is found to be a significant sink for atmospheric H2O2 and PAA in urban Beijing. Here, we recommend a suitable uptake coefficient formula considering the water effect for model research of peroxides. It is found that H2O2 and PAA unexpectedly maintained considerable concentrations on haze days, even higher than that on non-haze days. This phenomenon is mainly ascribed to relatively high levels of volatile organic compounds and ozone on haze days. In addition, high levels of water vapor in pollution episode can promote not only the heterogeneous uptake to aerosol phase but also the production of H2O2. Atmospheric PAA formation is suggested to be sensitive to alkenes and NOX in urban Beijing. In particular, with the help of peroxides, sulfate formation rate from heterogeneous uptake could increase by ∼4 times on haze days, indicating the potential effect of peroxides on enhancement of aerosol oxidative property and secondary sulfate formation.

Balloon profiles of stratospheric NO2 and HNO3 for testing the heterogeneous hydrolysis of N2O5 on sulfate aerosols

NASA Technical Reports Server (NTRS)

Webster, C. R.; May, R. D.; Allen, M.; Jaegle, L.; Mccormick, M. P.

1994-01-01

Simultaneous in situ measurements of stratospheric NO2, HNO3, HCl, and CH4 from 34 to 24 km were made in August 1992 from Palestine, Texas, using the Balloon-borne Laser In-Situ Sensor (BLISS) tunable diode laser spectrometer. Although the measurements of NO2, HNO3, and NO2/HNO3 agree well with gas-phase model calculations near 34 km where Stratospheric Aerosol and Gas Experiment (SAGE) 2 data show little sulfate aerosol, this is not true at the lower altitudes where SAGE 2 shows high aerosol loadings. At 24 km the BLISS NO2 and HNO3 measurements are 70% lower and 50% higher, respectively, than the gas phase model predictions, with a measured NO2/HNO3 ratio 5 times smaller. When the heterogeneous hydrolysis of N2O5 and ClONO2 on sulfate aerosol of surface area densities matching the SAGE 2 measurements is added to the model, good agreement with the BLISS measurements is found over the whole altitude range.

Sensitivity of Tropospheric Chemical Composition to Halogen-Radical Chemistry Using a Fully Coupled Size-Resolved Multiphase Chemistry-Global Climate System: Halogen Distributions, Aerosol Composition, and Sensitivity of Climate-Relevant Gases

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

Long, M.; Keene, W. C.; Easter, Richard C.

Observations and model studies suggest a significant but highly non-linear role for halogens, primarily Cl and Br, in multiphase atmospheric processes relevant to tropospheric chemistry and composition, aerosol evolution, radiative transfer, weather, and climate. The sensitivity of global atmospheric chemistry to the production of marine aerosol and the associated activation and cycling of inorganic Cl and Br was tested using a size-resolved multiphase coupled chemistry/global climate model (National Center for Atmospheric Research’s Community Atmosphere Model (CAM); v3.6.33). Simulation results showed strong meridional and vertical gradients in Cl and Br species. The simulation reproduced most available observations with reasonable confidence permittingmore » the formulation of potential mechanisms for several previously unexplained halogen phenomena including the enrichment of Br- in submicron aerosol, and the presence of a BrO maximum in the polar free troposphere. However, simulated total volatile Br mixing ratios were generally high in the troposphere. Br in the stratosphere was lower than observed due to the lack of long-lived organobromine species in the simulation. Comparing simulations using chemical mechanisms with and without reactive Cl and Br species demonstrated a significant temporal and spatial sensitivity of primary atmospheric oxidants (O3, HOx, NOx), CH4, and non-methane hydrocarbons (NMHC’s) to halogen cycling. Simulated O3 and NOx were globally lower (65% and 35%, respectively, less in the planetary boundary layer based on median values) in simulations that included halogens. Globally, little impact was seen in SO2 and non-sea-salt SO42- processing due to halogens. Significant regional differences were evident: The lifetime of nss-SO42- was extended downwind of large sources of SO2. The burden and lifetime of DMS (and its oxidation products) were lower by a factor of 5 in simulations that included halogens, versus those without, leading

Insight into Chemistry on Cloud/Aerosol Water Surfaces.

PubMed

Zhong, Jie; Kumar, Manoj; Francisco, Joseph S; Zeng, Xiao Cheng

2018-05-15

Cloud/aerosol water surfaces exert significant influence over atmospheric chemical processes. Atmospheric processes at the water surface are observed to follow mechanisms that are quite different from those in the gas phase. This Account summarizes our recent findings of new reaction pathways on the water surface. We have studied these surface reactions using Born-Oppenheimer molecular dynamics simulations. These studies provide useful information on the reaction time scale, the underlying mechanism of surface reactions, and the dynamic behavior of the product formed on the aqueous surface. According to these studies, the aerosol water surfaces confine the atmospheric species into a specific orientation depending on the hydrophilicity of atmospheric species or the hydrogen-bonding interactions between atmospheric species and interfacial water. As a result, atmospheric species are activated toward a particular reaction on the aerosol water surface. For example, the simplest Criegee intermediate (CH 2 OO) exhibits high reactivity toward the interfacial water and hydrogen sulfide, with the reaction times being a few picoseconds, 2-3 orders of magnitude faster than that in the gas phase. The presence of interfacial water molecules induces proton-transfer-based stepwise pathways for these reactions, which are not possible in the gas phase. The strong hydrophobicity of methyl substituents in larger Criegee intermediates (>C1), such as CH 3 CHOO and (CH 3 ) 2 COO, blocks the formation of the necessary prereaction complexes for the Criegee-water reaction to occur at the water droplet surface, which lowers their proton-transfer ability and hampers the reaction. The aerosol water surface provides a solvent medium for acids (e.g., HNO 3 and HCOOH) to participate in reactions via mechanisms that are different from those in the gas and bulk aqueous phases. For example, the anti-CH 3 CHOO-HNO 3 reaction in the gas phase follows a direct reaction between anti-CH 3 CHOO and HNO 3

Implementation of aerosol-cloud interactions in the regional atmosphere-aerosol model COSMO-MUSCAT(5.0) and evaluation using satellite data

NASA Astrophysics Data System (ADS)

Dipu, Sudhakar; Quaas, Johannes; Wolke, Ralf; Stoll, Jens; Mühlbauer, Andreas; Sourdeval, Odran; Salzmann, Marc; Heinold, Bernd; Tegen, Ina

2017-06-01

The regional atmospheric model Consortium for Small-scale Modeling (COSMO) coupled to the Multi-Scale Chemistry Aerosol Transport model (MUSCAT) is extended in this work to represent aerosol-cloud interactions. Previously, only one-way interactions (scavenging of aerosol and in-cloud chemistry) and aerosol-radiation interactions were included in this model. The new version allows for a microphysical aerosol effect on clouds. For this, we use the optional two-moment cloud microphysical scheme in COSMO and the online-computed aerosol information for cloud condensation nuclei concentrations (Cccn), replacing the constant Cccn profile. In the radiation scheme, we have implemented a droplet-size-dependent cloud optical depth, allowing now for aerosol-cloud-radiation interactions. To evaluate the models with satellite data, the Cloud Feedback Model Intercomparison Project Observation Simulator Package (COSP) has been implemented. A case study has been carried out to understand the effects of the modifications, where the modified modeling system is applied over the European domain with a horizontal resolution of 0.25° × 0.25°. To reduce the complexity in aerosol-cloud interactions, only warm-phase clouds are considered. We found that the online-coupled aerosol introduces significant changes for some cloud microphysical properties. The cloud effective radius shows an increase of 9.5 %, and the cloud droplet number concentration is reduced by 21.5 %.

Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA)

DOE PAGES

Hu, Weiwei; Palm, Brett B.; Day, Douglas A.; ...

2016-09-19

Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated withmore » an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding  ∼  100 µg m −3 of pure H 2SO 4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical ( k OH) was estimated as 4.0 ± 2.0  ×  10 −13 cm 3 molec −1 s −1, which is equivalent to more than a 2-week lifetime. A similar k OH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (>  1  ×  10 12 molec cm −3 s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients ( γ OH =  0.59 ± 0.33 in SE US and γ OH =  0.68 ± 0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of k OH and γ OH was observed, consistent with surface-area-limited OH uptake. No decrease of k OH was observed as OH concentrations increased. These observations of

Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA)

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

Hu, Weiwei; Palm, Brett B.; Day, Douglas A.

Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated withmore » an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding  ∼  100 µg m −3 of pure H 2SO 4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical ( k OH) was estimated as 4.0 ± 2.0  ×  10 −13 cm 3 molec −1 s −1, which is equivalent to more than a 2-week lifetime. A similar k OH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (>  1  ×  10 12 molec cm −3 s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients ( γ OH =  0.59 ± 0.33 in SE US and γ OH =  0.68 ± 0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of k OH and γ OH was observed, consistent with surface-area-limited OH uptake. No decrease of k OH was observed as OH concentrations increased. These observations of

The impact of port emissions and marine biogenics on the single-particle chemistry of marine aerosol measured on board the R/V Atlantis during the CalNEX 2010 field campaign

NASA Astrophysics Data System (ADS)

Gaston, C. J.; Quinn, P.; Bates, T. S.; Prather, K. A.

2010-12-01

Marine environments are characterized by low particle concentrations and, as such, are sensitive to changes in particle number concentration and chemistry induced by biogenic and anthropogenic influences. Measurements of both gas phase and particle phase emissions on board the R/V Atlantis during the CalNEX 2010 field campaign provided an opportunity to examine the impact of anthropogenic and marine biogenic emissions on particle chemistry along the California coast. Real-time, single-particle measurements made using an aerosol time-of-flight mass spectrometer (ATOFMS) revealed the single-particle mixing state of the sampled marine aerosols. Submicron particles (0.2-1.0 um) containing organic carbon, elemental carbon mixed with organic carbon, and unique V-containing particles previously detected in port regions were prevalent throughout the Southern California coast; most of these particles were also associated with sulfate. Measurements made in the deep water channel near Sacramento, CA revealed dramatically different particle chemistry that was characterized by organic carbon and amines. Particles measured further away from the continent toward the open ocean were influenced by marine biological activity due to a phytoplankton bloom that was occurring off the California coast. During this sampling period, unique ocean-derived particles containing internal mixtures of Mg and organic carbon were detected in addition to unique particles containing elemental S ions, which were only detected at night. An aerosol generator used to bubble seawater in order to characterize primary emissions from the ocean confirmed that the Mg-organic carbon and S-containing particles were indeed emitted from the ocean. These measurements reveal the strong impact of both port emissions as well as marine biogenic emissions on aerosol chemistry along the California coast.

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

Ozone Depletion at Mid-Latitudes: Coupling of Volcanic Aerosols and Temperature Variability to Anthropogenic Chlorine

NASA Technical Reports Server (NTRS)

Solomon, S.; Portmann, R. W.; Garcia, R. R.; Randel, W.; Wu, F.; Nagatani, R.; Gleason, J.; Thomason, L.; Poole, L. R.; McCormick, M. P.

1998-01-01

Satellite observations of total ozone at 40-60 deg N are presented from a variety of instruments over the time period 1979-1997. These reveal record low values in 1992-3 (after Pinatubo) followed by partial but incomplete recovery. The largest post-Pinatubo reductions and longer-term trends occur in spring, providing a critical test for chemical theories of ozone depletion. The observations are shown to be consistent with current understanding of the chemistry of ozone depletion when changes in reactive chlorine and stratospheric aerosol abundances are considered along with estimates of wave-driven fluctuations in stratospheric temperatures derived from global temperature analyses. Temperature fluctuations are shown to make significant contributions to model calculated northern mid-latitude ozone depletion due to heterogeneous chlorine activation on liquid sulfate aerosols at temperatures near 200-210 K (depending upon water vapor pressure), particularly after major volcanic eruptions. Future mid-latitude ozone recovery will hence depend not only on chlorine recovery but also on temperature trends and/or variability, volcanic activity, and any trends in stratospheric sulfate aerosol.

Primary aerosol and secondary inorganic aerosol budget over the Mediterranean Basin during 2012 and 2013

NASA Astrophysics Data System (ADS)

Guth, Jonathan; Marécal, Virginie; Josse, Béatrice; Arteta, Joaquim; Hamer, Paul

2018-04-01

In the frame of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx), we analyse the budget of primary aerosols and secondary inorganic aerosols over the Mediterranean Basin during the years 2012 and 2013. To do this, we use two year-long numerical simulations with the chemistry-transport model MOCAGE validated against satellite- and ground-based measurements. The budget is presented on an annual and a monthly basis on a domain covering 29 to 47° N latitude and 10° W to 38° E longitude. The years 2012 and 2013 show similar seasonal variations. The desert dust is the main contributor to the annual aerosol burden in the Mediterranean region with a peak in spring, and sea salt being the second most important contributor. The secondary inorganic aerosols, taken as a whole, contribute a similar level to sea salt. The results show that all of the considered aerosol types, except for sea salt aerosols, experience net export out of our Mediterranean Basin model domain, and thus this area should be considered as a source region for aerosols globally. Our study showed that 11 % of the desert dust, 22.8 to 39.5 % of the carbonaceous aerosols, 35 % of the sulfate and 9 % of the ammonium emitted or produced into the study domain are exported. The main sources of variability for aerosols between 2012 and 2013 are weather-related variations, acting on emissions processes, and the episodic import of aerosols from North American fires. In order to assess the importance of the anthropogenic emissions of the marine and the coastal areas which are central for the economy of the Mediterranean Basin, we made a sensitivity test simulation. This simulation is similar to the reference simulation but with the removal of the international shipping emissions and the anthropogenic emissions over a 50 km wide band inland along the coast. We showed that around 30 % of the emissions of carbonaceous aerosols and 35 to 60 % of the exported carbonaceous aerosols originates from the marine and

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

NASA Astrophysics Data System (ADS)

Shiraiwa, Manabu; Pfrang, Christian; Pöschl, Ulrich

2010-05-01

Aerosols are ubiquitous in the atmosphere and have strong effects on climate and public health. Gas-particle interactions can significantly change the physical and chemical properties of aerosols such as toxicity, reactivity, hygroscopicity and radiative properties. Chemical reactions and mass transport lead to continuous transformation and changes in the composition of atmospheric aerosols ("chemical aging"). Resistor model formulations are widely used to describe and investigate heterogeneous reactions and multiphase processes in laboratory, field and model studies of atmospheric chemistry. The traditional resistor models, however, are usually based on simplifying assumptions such as steady state conditions, homogeneous mixing, and limited numbers of non-interacting species and processes. In order to overcome these limitations, Pöschl, Rudich and Ammann have developed a kinetic model framework (PRA framework) with a double-layer surface concept and universally applicable rate equations and parameters for mass transport and chemical reactions at the gas-particle interface of aerosols and clouds [1]. Based on the PRA framework, we present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB) [2]. The model includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and

An assessment of aerosol optical properties from remote-sensing observations and regional chemistry-climate coupled models over Europe

NASA Astrophysics Data System (ADS)

Palacios-Peña, Laura; Baró, Rocío; Baklanov, Alexander; Balzarini, Alessandra; Brunner, Dominik; Forkel, Renate; Hirtl, Marcus; Honzak, Luka; María López-Romero, José; Montávez, Juan Pedro; Pérez, Juan Luis; Pirovano, Guido; San José, Roberto; Schröder, Wolfram; Werhahn, Johannes; Wolke, Ralf; Žabkar, Rahela; Jiménez-Guerrero, Pedro

2018-04-01

Atmospheric aerosols modify the radiative budget of the Earth due to their optical, microphysical and chemical properties, and are considered one of the most uncertain climate forcing agents. In order to characterise the uncertainties associated with satellite and modelling approaches to represent aerosol optical properties, mainly aerosol optical depth (AOD) and Ångström exponent (AE), their representation by different remote-sensing sensors and regional online coupled chemistry-climate models over Europe are evaluated. This work also characterises whether the inclusion of aerosol-radiation (ARI) or/and aerosol-cloud interactions (ACI) help improve the skills of modelling outputs.Two case studies were selected within the EuMetChem COST Action ES1004 framework when important aerosol episodes in 2010 all over Europe took place: a Russian wildfire episode and a Saharan desert dust outbreak that covered most of the Mediterranean Sea. The model data came from different regional air-quality-climate simulations performed by working group 2 of EuMetChem, which differed according to whether ARI or ACI was included or not. The remote-sensing data came from three different sensors: MODIS, OMI and SeaWIFS. The evaluation used classical statistical metrics to first compare satellite data versus the ground-based instrument network (AERONET) and then to evaluate model versus the observational data (both satellite and ground-based data).Regarding the uncertainty in the satellite representation of AOD, MODIS presented the best agreement with the AERONET observations compared to other satellite AOD observations. The differences found between remote-sensing sensors highlighted the uncertainty in the observations, which have to be taken into account when evaluating models. When modelling results were considered, a common trend for underestimating high AOD levels was observed. For the AE, models tended to underestimate its variability, except when considering a sectional approach in

Balloon-Borne Measurements of CLO, NO and O3 in a Volcanic Cloud: An Analysis of Heterogeneous Chemistry between 20 and 30 KM

NASA Technical Reports Server (NTRS)

Dessler, A. E.; Stimpfle, R. M.; Daube, B. C.; Salawitch, R. J.; Weinstock, E. M.; Judah, D. M.; Burley, J. D.; Munger, J. W.; Wofsy, S. C.; Anderson, J. G.;

Photochemistry of Glyoxal in Wet Aerosols: Smog Chamber Study

NASA Astrophysics Data System (ADS)

Lim, Y. B.; Kim, H.; Turpin, B. J.

2015-12-01

Aqueous chemistry is an important pathway for the formation of secondary organic aerosol (SOA). Reaction vessel studies provide evidence that in the aqueous phase photooxidation of water soluble organic compounds (e.g., glyoxal, methylglyoxal) form multifunctional organic products and oligomers. In this work, we extend this bulk-phase chemistry to the condensed-phase chemistry that occurs in/on aerosols by conducting smog chamber experiments — photooxidation of ammonium sulfate and sulfuric acid aerosols containing glyoxal and hydrogen peroxide in the presence of NOx under dry/humid conditions. Particles were analyzed using ultra performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS). In the irradiated chamber, photooxidation products of glyoxal as seen in reaction vessel experiments (e.g., oxalic acids and tartaric acids) were also formed in both ammonium sulfate aerosols and sulfuric acid aerosols at humid and even dry conditions. However, the major products were organosulfurs (CHOS), organonitrogens (CHON), and nitrooxy-organosulfates (CHONS), which were also dominantly formed in the dark chamber. These products were formed via non-radical reactions, which depend on acidity and humidity. However, the real-time profiles in the dark chamber and the irradiated chamber were very different, suggesting photochemistry substantially affects non-radical formation in the condensed phase.

Aerosol in the Upper Troposphere Lower Stratosphere, decadal Simulations of Radiative Forcing using the Chemistry Circulation Model EMAC and MIPAS, GOMOS, IASI and other Satellite Data

NASA Astrophysics Data System (ADS)

Bruehl, C.; Schallock, J.; Lelieveld, J.; Bingen, C.; Robert, C. E.; Hoepfner, M.; Clarisse, L.

2017-12-01

The atmospheric chemistry - general circulation model EMAC with a modal interactive aerosol module is used to estimate radiative effects of UTLS aerosol for the ENVISAT period 2002 to 2012 in the framework of SPARC/SSIRC. Volcanic SO2 injections by about 230 explosive volcano eruptions are estimated mostly from MIPAS limb observations. For periods of data gaps, injected SO2 is estimated indirectly from extinctions observed by GOMOS. GOMOS extinctions in the UTLS and the seasonal component of radiative forcing can be only reproduced by the model if a comprehensive treatment of desert dust and organic and black carbon is included. Upward transport of particles and gases by the Asian Monsoon appears to contribute importantly. The time series of simulated stratospheric aerosol optical depth and radiative forcing agree with the corresponding quantities derived from different satellite data sets. Comparisons of total aerosol optical depth with IASI show that tropospheric and stratospheric aerosol in the model are consistently and realistically represented.

Radiative and Chemical Response to Interactive Stratospheric Sulfate Aerosols in Fully Coupled CESM1(WACCM): Stratospheric Aerosols in CESM1(WACCM)

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

Mills, Michael J.; Richter, Jadwiga H.; Tilmes, Simone

We present a new version of the Community Earth System Model, version 1 (CESM1) with the Whole Atmosphere Community Climate Model (WACCM) featuring numerous improvements that are unique among earth system models. Improved horizontal resolution, dynamics, and chemistry now provide the development of an internally generated quasi-biennial oscillation, and significant improvements to temperatures and ozone throughout the stratosphere. The prognostic treatment of stratospheric sulfate aerosols is shown to represent well the evolution of stratospheric aerosol optical depth and perturbations to solar and longwave radiation following volcanic eruptions. We identify the inclusion of interactive OH chemistry as crucial to the studymore » of aerosol formation following large inputs of SO2 to the stratosphere. We show that depletion of OH levels within the dense SO2 cloud in the first weeks following the June 1991 eruption of Mt. Pinatubo significantly prolonged the e-folding decay time for SO2 oxidation to 47 days. Previous observational and model studies showing a 30-day decay time have not accounted for the large initial losses of SO2 on ash and ice in the first 7-9 days following the eruption, and have not correctly accounted for OH depletion. The completeness of the chemistry, dynamics, and aerosol microphysics in WACCM uniquely qualify it for studies of stratospheric sulfate aerosol geoengineering.« less

Stratospheric Aerosol--Observations, Processes, and Impact on Climate

NASA Technical Reports Server (NTRS)

Kresmer, Stefanie; Thomason, Larry W.; von Hobe, Marc; Hermann, Markus; Deshler, Terry; Timmreck, Claudia; Toohey, Matthew; Stenke, Andrea; Schwarz, Joshua P.; Weigel, Ralf;

Using the OMI Aerosol Index and Absorption Aerosol Optical Depth to evaluate the NASA MERRA Aerosol Reanalysis

NASA Astrophysics Data System (ADS)

Buchard, V.; da Silva, A. M.; Colarco, P. R.; Darmenov, A.; Randles, C. A.; Govindaraju, R.; Torres, O.; Campbell, J.; Spurr, R.

2014-12-01

A radiative transfer interface has been developed to simulate the UV Aerosol Index (AI) from the NASA Goddard Earth Observing System version 5 (GEOS-5) aerosol assimilated fields. The purpose of this work is to use the AI and Aerosol Absorption Optical Depth (AAOD) derived from the Ozone Monitoring Instrument (OMI) measurements as independent validation for the Modern Era Retrospective analysis for Research and Applications Aerosol Reanalysis (MERRAero). MERRAero is based on a version of the GEOS-5 model that is radiatively coupled to the Goddard Chemistry, Aerosol, Radiation, and Transport (GOCART) aerosol module and includes assimilation of Aerosol Optical Depth (AOD) from the Moderate Resolution Imaging Spectroradiometer (MODIS) sensor. Since AI is dependent on aerosol concentration, optical properties and altitude of the aerosol layer, we make use of complementary observations to fully diagnose the model, including AOD from the Multi-angle Imaging SpectroRadiometer (MISR), aerosol retrievals from the Aerosol Robotic Network (AERONET) and attenuated backscatter coefficients from the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) mission to ascertain potential misplacement of plume height by the model. By sampling dust, biomass burning and pollution events in 2007 we have compared model produced AI and AAOD with the corresponding OMI products, identifying regions where the model representation of absorbing aerosols was deficient. As a result of this study over the Saharan dust region, we have obtained a new set of dust aerosol optical properties that retains consistency with the MODIS AOD data that were assimilated, while resulting in better agreement with aerosol absorption measurements from OMI. The analysis conducted over the South African and South American biomass burning regions indicates that revising the spectrally-dependent aerosol absorption properties in the near-UV region improves the modeled-observed AI comparisons

Using the OMI aerosol index and absorption aerosol optical depth to evaluate the NASA MERRA Aerosol Reanalysis

NASA Astrophysics Data System (ADS)

Buchard, V.; da Silva, A. M.; Colarco, P. R.; Darmenov, A.; Randles, C. A.; Govindaraju, R.; Torres, O.; Campbell, J.; Spurr, R.

2015-05-01

A radiative transfer interface has been developed to simulate the UV aerosol index (AI) from the NASA Goddard Earth Observing System version 5 (GEOS-5) aerosol assimilated fields. The purpose of this work is to use the AI and aerosol absorption optical depth (AAOD) derived from the Ozone Monitoring Instrument (OMI) measurements as independent validation for the Modern Era Retrospective analysis for Research and Applications Aerosol Reanalysis (MERRAero). MERRAero is based on a version of the GEOS-5 model that is radiatively coupled to the Goddard Chemistry, Aerosol, Radiation, and Transport (GOCART) aerosol module and includes assimilation of aerosol optical depth (AOD) from the Moderate Resolution Imaging Spectroradiometer (MODIS) sensor. Since AI is dependent on aerosol concentration, optical properties and altitude of the aerosol layer, we make use of complementary observations to fully diagnose the model, including AOD from the Multi-angle Imaging SpectroRadiometer (MISR), aerosol retrievals from the AErosol RObotic NETwork (AERONET) and attenuated backscatter coefficients from the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) mission to ascertain potential misplacement of plume height by the model. By sampling dust, biomass burning and pollution events in 2007 we have compared model-produced AI and AAOD with the corresponding OMI products, identifying regions where the model representation of absorbing aerosols was deficient. As a result of this study over the Saharan dust region, we have obtained a new set of dust aerosol optical properties that retains consistency with the MODIS AOD data that were assimilated, while resulting in better agreement with aerosol absorption measurements from OMI. The analysis conducted over the southern African and South American biomass burning regions indicates that revising the spectrally dependent aerosol absorption properties in the near-UV region improves the modeled-observed AI comparisons

Aqueous organic chemistry in the atmosphere: sources and chemical processing of organic aerosols.

PubMed

McNeill, V Faye

2015-02-03

Over the past decade, it has become clear that aqueous chemical processes occurring in cloud droplets and wet atmospheric particles are an important source of organic atmospheric particulate matter. Reactions of water-soluble volatile (or semivolatile) organic gases (VOCs or SVOCs) in these aqueous media lead to the formation of highly oxidized organic particulate matter (secondary organic aerosol; SOA) and key tracer species, such as organosulfates. These processes are often driven by a combination of anthropogenic and biogenic emissions, and therefore their accurate representation in models is important for effective air quality management. Despite considerable progress, mechanistic understanding of some key aqueous processes is still lacking, and these pathways are incompletely represented in 3D atmospheric chemistry and air quality models. In this article, the concepts, historical context, and current state of the science of aqueous pathways of SOA formation are discussed.

Ozone response to enhanced heterogeneous processing after the eruption of Mt. Pinatubo

NASA Technical Reports Server (NTRS)

Rodriguez, Jose M.; Ko, M. K. W.; Sze, N. D.; Heisey, C. W.; Yue, G. K.; Mccormick, M. P.

1994-01-01

Increases in aerosol loading after the Pinatubo eruption are expected to cause additional ozone depletion. Even though aerosol loadings were highest in the winter of 1991-1992, recent analyses of satellite and ground-based ozone measurements indicate that ozone levels in the winter of 1992-1993 are the lowest recorded in recent years, raising the question of the mechanisms responsible for such behavior. We have incorporated aerosol surface areas derived from the Stratospheric Aerosol and Gas Experiment II (SAGE-II) measurements into our two-dimensional model. Inclusion of heterogeneous chemsitry on these enhanced aerosol surfaces yields maximum ozone reductions during the winter of 1992-1993 in the Northern Hemisphere, consistent with those derived from observations. This delayed behavior is due to the combination of the non-linear nature of the impact of heterogeneous reactions as a function of aerosol surface area, and the long time constants for ozone in the lower stratosphere. If heterogeneous mechanisms are primarily responsible for the low 1992-1993 ozone levels, we expect ozone concentrations to start recovering in 1994.

Influences of emission sources and meteorology on aerosol chemistry in a polluted urban environment: results from DISCOVER-AQ California

NASA Astrophysics Data System (ADS)

Young, D. E.; Kim, H.; Parworth, C.; Zhou, S.; Zhang, X.; Cappa, C. D.; Seco, R.; Kim, S.; Zhang, Q.

2015-12-01

-volatile oxygenated OA (SV-OOA; 16 % of total OA; O / C = 0.63) and low volatility oxygenated OA (LV-OOA; 24 % of total OA; O / C = 0.90) formed via chemical reactions in the atmosphere. Large differences in aerosol chemistry at Fresno were observed between the current campaign (winter 2013) and a~previous wintertime campaign (winter 2010), most notably that PM1 concentrations were nearly three times higher in 2013 than in 2010. These variations were attributed to differences in the meteorological conditions, which influenced primary emissions and secondary aerosol formation. In particular, COA and BBOA concentrations were greater in 2013 than 2010, where colder temperatures in 2013 likely resulted in increased biomass burning activities. The influence from a nighttime formed residual layer that mixed down in the morning was found to be much more intense in 2013 than 2010, leading to sharp increases in ground-level concentrations of secondary aerosol species including nitrate, sulfate, and OOA, in the morning between 08:00 to 12:00 PST. This is an indication that nighttime chemistry might also be higher in 2013. As solar radiation was stronger in 2013 the higher nitrate and OOA concentrations in 2013 could also be partly due to greater photochemical production of secondary aerosol species. The greater solar radiation and larger range in temperature in 2013 also likely led to both SV-OOA and LV-OOA being observed in 2013 whereas only a single OOA factor was identified in 2010.

Formation of high-molecular-weight compounds via the heterogeneous reactions of gaseous C8-C10 n-aldehydes in the presence of atmospheric aerosol components

NASA Astrophysics Data System (ADS)

Han, Yuemei; Kawamura, Kimitaka; Chen, Qingcai; Mochida, Michihiro

2016-02-01

A laboratory study on the heterogeneous reactions of straight-chain aldehydes was performed by exposing n-octanal, nonanal, and decanal vapors to ambient aerosol particles. The aerosol and blank filters were extracted using methanol. The extracts were nebulized and the resulting compositions were examined using a high-resolution time-of-flight aerosol mass spectrometer. The mass spectral analysis showed that the exposures of the aldehydes to aerosol samples increased the peak intensities in the high mass range. The peaks in the mass spectra of the aerosol samples after exposure to different aldehydes were characterized by a homologous series of peak shifts due to the addition of multiple CH2 units. This result is explained by the formation of high-molecular-weight (HMW) compounds that contain single or multiple aldehyde moieties. The HMW fragment peaks for the blank filters exposed to n-aldehydes were relatively weak, indicating an important contribution from the ambient aerosol components to the formation of the HMW compounds. Among the factors affecting the overall interaction of aldehydes with atmospheric aerosol components, gas phase diffusion possibly limited the reactions under the studied conditions; therefore, their occurrence to a similar degree in the atmosphere is not ruled out, at least for the reactions involving n-nonanal and decanal. The major formation pathways for the observed HMW products may be the self-reactions of n-aldehydes mediated by atmospheric aerosol components and the reactions of n-aldehydes with organic aerosol components. The observed formation of HMW compounds encourages further investigations into their effects on the aerosol properties as well as the organic aerosol mass in the atmosphere.

Aerosol Retrievals Using Channel 1 and 2 AVHRR Data

NASA Technical Reports Server (NTRS)

Mishchenko, Michael I.; Geogdzhayev, Igor V.; Cairns, Brian; Rossow, William B.

1999-01-01

The effect of tropospheric aerosols on global climate via the direct and indirect radiative forcings is one of the largest remaining uncertainties in climate change studies. Current assessments of the direct aerosol radiative effect mainly focus on sulfate aerosols. It has become clear, however, that other aerosol types like soil dust and smoke from biomass burning are also likely to be important climate forcing factors. The magnitude and even the sign of the climate forcing caused by these aerosol types is still unknown. General circulation models (GCMs) can be used to estimate the climatic effect of the direct radiative forcing by tropospheric and stratospheric aerosols. Aerosol optical properties are already parameterized in the Goddard Institute for Space Studies GCM. Once the global distribution of aerosol properties (optical thickness, size distribution, and chemical composition) is available, the calculation of the direct aerosol forcing is rather straighfforward. However, estimates of the indirect aerosol effect require additional knowledge of the physics and chemistry of aerosol-cloud interactions which are still poorly understood. One of the main objectives of the Global Aerosol Climatology Project, established in 1998 as a joint initiative of NASA's Radiation Science Program and GEWEX, is to infer the global distribution of aerosols, their properties, and their seasonal and interannual variations for the full period of available satellite data. This will be accomplished primarily through a systematic application of multichannel aerosol retrieval algorithms to existing satellite data and advanced 3-dimensional aerosol chemistry/transport models. In this paper we outline the methodology of analyzing channel 1 and 2 AVHRR radiance data over the oceans and describe preliminary retrieval results.

Sources and Variability of Aerosols and Aerosol-Cloud Interactions in the Arctic

NASA Astrophysics Data System (ADS)

Liu, H.; Zhang, B.; Taylor, P. C.; Moore, R.; Barahona, D.; Fairlie, T. D.; Chen, G.; Ham, S. H.; Kato, S.

2017-12-01

Arctic sea ice in recent decades has significantly declined. This requires understanding of the Arctic surface energy balance, of which clouds are a major driver. However, the mechanisms for the formation and evolution of clouds in the Arctic and the roles of aerosols therein are highly uncertain. Here we conduct data analysis and global model simulations to examine the sources and variability of aerosols and aerosol-cloud interactions in the Arctic. We use the MERRA-2 reanalysis data (2006-present) from the NASA Global Modeling and Assimilation Office (GMAO) to (1) quantify contributions of different aerosol types to the aerosol budget and aerosol optical depths in the Arctic, (2) ­examine aerosol distributions and variability and diagnose the major pathways for mid-latitude pollution transport to the Arctic, including their seasonal and interannual variability, and (3) characterize the distribution and variability of clouds (cloud optical depth, cloud fraction, cloud liquid and ice water path, cloud top height) in the Arctic. We compare MERRA-2 aerosol and cloud properties with those from C3M, a 3-D aerosol and cloud data product developed at NASA Langley Research Center and merged from multiple A-Train satellite (CERES, CloudSat, CALIPSO, and MODIS) observations. We also conduct perturbation experiments using the NASA GEOS-5 chemistry-climate model (with GOCART aerosol module coupled with two-moment cloud microphysics), and discuss the roles of various types of aerosols in the formation and evolution of clouds in the Arctic.

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

MAESTRO Measurements of Atmospheric Aerosol

NASA Astrophysics Data System (ADS)

McElroy, Tom; Drummond, James; Zou, Jason

2014-05-01

MAESTRO (Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) is now in its 11th year on orbit as part of the Atmospheric Chemistry Experiment on the Canadian Space Agency's SCISAT satellite. MAESTRO data analysis has been dogged by a deficiency in accurate timing between the measurements made by the partner instrument, the ACE-FTS (Atmospheric Chemistry Experiment, Fourier Transform Spectrometer), that provides the atmospheric pressure-temperature profile and observation tangent altitudes used in the MAESTRO data analysis. Attempts have been made to use apparent air column density and oxygen A-band absorption as a mechanism to line up the tangent heights, but to no avail. A new product is now being produced, based on matching the modeled ozone slant columns from the ACE-FTS retrievals with the MAESTRO slant column measurements. The approach is very promising and indicates that a valuable product from the MAESTRO wavelength-dependent aerosol extinction likely result. The usefulness of the profile matching technique will be demonstrated and some aerosol absorption profiles will be presented in comparison with measurements made by the ACE Imager aerosol profile results. While the process optimizes the comparison between ACE-FTS ozone profile data and that from MAESTRO, it does not detract from the higher vertical resolution information provided by MAESTRO.

Innovative Sol-Gel Routes for the Bottom-up Preparation of Heterogeneous Catalysts.

PubMed

Debecker, Damien P

2017-12-11

Heterogeneous catalysts can be prepared by different methods offering various levels of control on the final properties of the solid. In this account, we exemplify bottom-up preparation routes that are based on the sol-gel chemistry and allow to tailor some decisive properties of solid catalysts. First, an emulsion templating strategy is shown to lead to macrocellular self-standing monoliths with a macroscopic 3D structure. The latter can be used as catalyst or catalyst supports in flow chemistry, without requiring any subsequent shaping step. Second, the aerosol-assisted sol-gel process allows for the one-step and continuous production of porous mixed oxides. Tailored textural properties can be obtained together with an excellent control on composition and homogeneity. Third, the application of non-hydrolytic sol-gel routes, in the absence of water, leads to mixed oxides with outstanding textural properties and with peculiar surface chemistry. In all cases, the resulting catalytic performance can be correlated with the specificities of the preparation routes presented. This is exemplified in catalytic reactions in the fields of biomass conversion, petro chemistry, enantioselective organic synthesis, and air pollution mitigation. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Organic Coatings, Humidity and Aerosol Acidity on Multiphase Chemistry of Isoprene Epoxydiols

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

Riva, Matthieu; Bell, David M.; Hansen, Anne-Maria Kaldal

2016-06-07

Multiphase chemistry of isomeric isoprene epoxydiols (IEPOX) has been shown to be the dominant source of isoprene-derived secondary organic aerosol (SOA). Recent studies have reported particles composed of ammonium bisulfate (ABS) mixed with model organics exhibit slower rates of IEPOX uptake. In the present study, we investigate the effect of atmospherically-relevant organic coatings of α-pinene (AP) SOA on the reactive uptake of trans-β-IEPOX onto ABS particles under different conditions and coating thicknesses. Single particle mass spectrometry was used to characterize in real-time particle size, shape, density, and quantitative composition before and after reaction with IEPOX. We find that IEPOX uptakemore » by pure sulfate particles is a volume-controlled process, which results in particles with uniform concentration of IEPOX-derived SOA across a wide range of sizes. Aerosol acidity was shown to enhance IEPOX-derived SOA formation, consistent with recent studies. The presence of water has a weaker impact on IEPOX-derived SOA yield, but significantly enhanced formation of 2-methyltetrols, consistent with offline filter analysis. In contrast, IEPOX uptake by ABS particles coated by AP-derived SOA is strongly dependent on particle size and composition. IEPOX uptake occurred only when weight fraction of AP-derived SOA dropped below 50 %, effectively limiting IEPOX uptake to larger particles.« less

Aerosol typing - key information from aerosol studies

NASA Astrophysics Data System (ADS)

Mona, Lucia; Kahn, Ralph; Papagiannopoulos, Nikolaos; Holzer-Popp, Thomas; Pappalardo, Gelsomina

2016-04-01

Aerosol typing is a key source of aerosol information from ground-based and satellite-borne instruments. Depending on the specific measurement technique, aerosol typing can be used as input for retrievals or represents an output for other applications. Typically aerosol retrievals require some a priori or external aerosol type information. The accuracy of the derived aerosol products strongly depends on the reliability of these assumptions. Different sensors can make use of different aerosol type inputs. A critical review and harmonization of these procedures could significantly reduce related uncertainties. On the other hand, satellite measurements in recent years are providing valuable information about the global distribution of aerosol types, showing for example the main source regions and typical transport paths. Climatological studies of aerosol load at global and regional scales often rely on inferred aerosol type. There is still a high degree of inhomogeneity among satellite aerosol typing schemes, which makes the use different sensor datasets in a consistent way difficult. Knowledge of the 4d aerosol type distribution at these scales is essential for understanding the impact of different aerosol sources on climate, precipitation and air quality. All this information is needed for planning upcoming aerosol emissions policies. The exchange of expertise and the communication among satellite and ground-based measurement communities is fundamental for improving long-term dataset consistency, and for reducing aerosol type distribution uncertainties. Aerosol typing has been recognized as one of its high-priority activities of the AEROSAT (International Satellite Aerosol Science Network, http://aero-sat.org/) initiative. In the AEROSAT framework, a first critical review of aerosol typing procedures has been carried out. The review underlines the high heterogeneity in many aspects: approach, nomenclature, assumed number of components and parameters used for the

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

Multi-Decadal Variation of Aerosols: Sources, Transport, and Climate Effects

NASA Technical Reports Server (NTRS)

Chin, Mian; Diehl, Thomas; Bian, Huisheng; Streets, David

2008-01-01

We present a global model study of multi-decadal changes of atmospheric aerosols and their climate effects using a global chemistry transport model along with the near-term to longterm data records. We focus on a 27-year time period of satellite era from 1980 to 2006, during which a suite of aerosol data from satellite observations, ground-based measurements, and intensive field experiments have become available. We will use the Goddard Chemistry Aerosol Radiation and Transport (GOCART) model, which involves a time-varying, comprehensive global emission dataset that we put together in our previous investigations and will be improved/extended in this project. This global emission dataset includes emissions of aerosols and their precursors from fuel combustion, biomass burning, volcanic eruptions, and other sources from 1980 to the present. Using the model and satellite data, we will analyze (1) the long-term global and regional aerosol trends and their relationship to the changes of aerosol and precursor emissions from anthropogenic and natural sources, (2) the intercontinental source-receptor relationships controlled by emission, transport pathway, and climate variability.

Chemical Characterization and Source Apportionment of Size Fractionated Atmospheric Aerosols, and, Evaluating Student Attitudes and Learning in Large Lecture General Chemistry Classes

NASA Astrophysics Data System (ADS)

Allen, Gregory Harold

between the OOA2 and WBOA factors and smoke levels indicates that these factors can be used to identify the influence of biomass burning on ambient aerosols. The effectiveness of using the ChemWiki instead of a traditional textbook was investigated during the spring quarter of 2014. Student performance was measured using common midterms, a final, and a pre/post content exams. We also employed surveys, the Colorado Learning Attitudes about Science Survey (CLASS) for Chemistry, and a weekly time-on-task survey to quantify students' attitudes and study habits. The effectiveness of the ChemWiki compared to a traditional textbook was examined using multiple linear regression analysis with a standard non-inferiority testing framework. Results show that the performance of students in the section who were assigned readings from the ChemWiki was non-inferior to the performance of students in the section who were assigned readings from the traditional textbook, indicating that the ChemWiki does not substantially differ from the standard textbook in terms of student learning outcomes. The results from the surveys also suggest that the two classes were similar in their beliefs about chemistry and overall average time spent studying. These results indicate that the ChemWiki is a viable cost-saving alternative to traditional textbooks. The impact of using active learning techniques in a large lecture general chemistry class was investigated by assessing student performance and attitudes during the fall 2014 and winter 2015 quarters. One instructor applied active learning strategies while the remaining instructors employed more traditional lecture styles. Student performance, learning, learning environments, and attitudes were measured using a standardized pre/post exams, common final exams, classroom observations, and the CLASS chemistry instrument in large lecture general chemistry courses. Classroom observation data showed that the active learning class was the most student centered

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

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.

A new chemistry option in WRF-Chem v. 3.4 for the simulation of direct and indirect aerosol effects using VBS: evaluation against IMPACT-EUCAARI data

NASA Astrophysics Data System (ADS)

Tuccella, P.; Curci, G.; Grell, G. A.; Visconti, G.; Crumeyrolle, S.; Schwarzenboeck, A.; Mensah, A. A.

2015-09-01

A parameterization for secondary organic aerosol (SOA) production based on the volatility basis set (VBS) approach has been coupled with microphysics and radiative schemes in the Weather Research and Forecasting model with Chemistry (WRF-Chem) model. The new chemistry option called "RACM-MADE-VBS-AQCHEM" was evaluated on a cloud resolving scale against ground-based and aircraft measurements collected during the IMPACT-EUCAARI (Intensive Cloud Aerosol Measurement Campaign - European Integrated project on Aerosol Cloud Climate and Air quality interaction) campaign, and complemented with satellite data from MODIS. The day-to-day variability and the diurnal cycle of ozone (O3) and nitrogen oxides (NOx) at the surface are captured by the model. Surface aerosol mass concentrations of sulfate (SO4), nitrate (NO3), ammonium (NH4), and organic matter (OM) are simulated with correlations larger than 0.55. WRF-Chem captures the vertical profile of the aerosol mass concentration in both the planetary boundary layer (PBL) and free troposphere (FT) as a function of the synoptic condition, but the model does not capture the full range of the measured concentrations. Predicted OM concentration is at the lower end of the observed mass concentrations. The bias may be attributable to the missing aqueous chemistry processes of organic compounds and to uncertainties in meteorological fields. A key role could be played by assumptions on the VBS approach such as the SOA formation pathways, oxidation rate, and dry deposition velocity of organic condensable vapours. Another source of error in simulating SOA is the uncertainties in the anthropogenic emissions of primary organic carbon. Aerosol particle number concentration (condensation nuclei, CN) is overestimated by a factor of 1.4 and 1.7 within the PBL and FT, respectively. Model bias is most likely attributable to the uncertainties of primary particle emissions (mostly in the PBL) and to the nucleation rate. Simulated cloud

Chlorine Chemistry of the Lower Stratosphere: Aircraft (ALIAS, ER-2) and Balloon (BLISSs) In-Situ Measurements of HC1,NO(sub 2), andN(sub 2)O for Testing Heterogeneous Chemistry

NASA Technical Reports Server (NTRS)

Webster, C.; May, R.; Jaegle, L.; Hu, H.; Scott, D.; Stimpfle, R.; Salawitch, R.; Fahey, D.; Woodbridge, E.; Proffitt, M.;

Impact of aerosol size representation on modeling aerosol-cloud interactions

DOE PAGES

Zhang, Y.; Easter, R. C.; Ghan, S. J.; ...

2002-11-07

In this study, we use a 1-D version of a climate-aerosol-chemistry model with both modal and sectional aerosol size representations to evaluate the impact of aerosol size representation on modeling aerosol-cloud interactions in shallow stratiform clouds observed during the 2nd Aerosol Characterization Experiment. Both the modal (with prognostic aerosol number and mass or prognostic aerosol number, surface area and mass, referred to as the Modal-NM and Modal-NSM) and the sectional approaches (with 12 and 36 sections) predict total number and mass for interstitial and activated particles that are generally within several percent of references from a high resolution 108-section approach.more » The modal approach with prognostic aerosol mass but diagnostic number (referred to as the Modal-M) cannot accurately predict the total particle number and surface areas, with deviations from the references ranging from 7-161%. The particle size distributions are sensitive to size representations, with normalized absolute differences of up to 12% and 37% for the 36- and 12-section approaches, and 30%, 39%, and 179% for the Modal-NSM, Modal-NM, and Modal-M, respectively. For the Modal-NSM and Modal-NM, differences from the references are primarily due to the inherent assumptions and limitations of the modal approach. In particular, they cannot resolve the abrupt size transition between the interstitial and activated aerosol fractions. For the 12- and 36-section approaches, differences are largely due to limitations of the parameterized activation for non-log-normal size distributions, plus the coarse resolution for the 12-section case. Differences are larger both with higher aerosol (i.e., less complete activation) and higher SO2 concentrations (i.e., greater modification of the initial aerosol distribution).« less

Atmospheric chemistry in volcanic plumes.

PubMed

von Glasow, Roland

2010-04-13

Recent field observations have shown that the atmospheric plumes of quiescently degassing volcanoes are chemically very active, pointing to the role of chemical cycles involving halogen species and heterogeneous reactions on aerosol particles that have previously been unexplored for this type of volcanic plumes. Key features of these measurements can be reproduced by numerical models such as the one employed in this study. The model shows sustained high levels of reactive bromine in the plume, leading to extensive ozone destruction, that, depending on plume dispersal, can be maintained for several days. The very high concentrations of sulfur dioxide in the volcanic plume reduces the lifetime of the OH radical drastically, so that it is virtually absent in the volcanic plume. This would imply an increased lifetime of methane in volcanic plumes, unless reactive chlorine chemistry in the plume is strong enough to offset the lack of OH chemistry. A further effect of bromine chemistry in addition to ozone destruction shown by the model studies presented here, is the oxidation of mercury. This relates to mercury that has been coemitted with bromine from the volcano but also to background atmospheric mercury. The rapid oxidation of mercury implies a drastically reduced atmospheric lifetime of mercury so that the contribution of volcanic mercury to the atmospheric background might be less than previously thought. However, the implications, especially health and environmental effects due to deposition, might be substantial and warrant further studies, especially field measurements to test this hypothesis.

The Response of Ozone and Nitrogen Dioxide to the Eruption of Mount Pinatubo

NASA Technical Reports Server (NTRS)

Aquila. Valentina; Oman, Luke D.; Stolarsk, Richard S.; Douglass, Anne R.; Newman, Paul A.

2012-01-01

Observations have shown that the global mass of nitrogen dioxide decreased in both hemispheres in the year following the eruption of Mt. Pinatubo, indicating an enhanced heterogeneous chemistry. In contrast, the observed ozone response was largely asymmetrical with respect to the equator, with a decrease in the northern hemisphere and little change in the southern hemisphere. Simulations including enhanced heterogeneous chemistry due to the presence of the volcanic aerosol reproduce a decrease of ozone in the northern hemisphere, but also produce a comparable ozone decrease in the southern hemisphere, contrary to observations. Our simulations show that the heating due to the volcanic aerosol enhanced both the tropical upwelling and the extratropical downwelling. The enhanced extratropical downwelling, combined with the time of the eruption relative to the phase of the Brewer-Dobson circulation, increased the ozone in the southern hemisphere and counteracted the ozone depletion due to heterogeneous chemistry on volcanic aerosol.

Aerosol and precipitation chemistry measurements in a remote site in Central Amazonia: the role of biogenic contribution

NASA Astrophysics Data System (ADS)

Pauliquevis, T.; Lara, L. L.; Antunes, M. L.; Artaxo, P.

2012-06-01

In this analysis a 3.5 years data set of aerosol and precipitation chemistry, obtained in a remote site in Central Amazonia (Balbina, (1°55' S, 59°29' W, 174 m a.s.l.), about 200 km north of Manaus) is discussed. Aerosols were sampled using stacked filter units (SFU), which separate fine (d < 2.5 μm) and coarse mode (2.5 μm < d < 10.0 μm) aerosol particles. Filters were analyzed for particulate mass (PM), Equivalent Black Carbon (BCE) and elemental composition by Particle Induced X-Ray Emission (PIXE). Rainwater samples were collected using a wet-only sampler and samples were analyzed for pH and ionic composition, which was determined using ionic chromatography (IC). Natural sources dominated the aerosol mass during the wet season, when it was predominantly of natural biogenic origin mostly in the coarse mode, which comprised up to 81% of PM10. Biogenic aerosol from both primary emissions and secondary organic aerosol dominates the fine mode in the wet season, with very low concentrations (average 2.2 μg m-3). Soil dust was responsible for a minor fraction of the aerosol mass (less than 17%). Sudden increases in the concentration of elements as Al, Ti and Fe were also observed, both in fine and coarse mode (mostly during the April-may months), which we attribute to episodes of Saharan dust transport. During the dry periods, a significant contribution to the fine aerosols loading was observed, due to the large-scale transport of smoke from biomass burning in other portions of the Amazon basin. This contribution is associated with the enhancement of the concentration of S, K, Zn and BCE. Chlorine, which is commonly associated to sea salt and also to biomass burning emissions, presented higher concentration not only during the dry season but also for the April-June months, due to the establishment of more favorable meteorological conditions to the transport of Atlantic air masses to Central Amazonia. The chemical composition of rainwater was similar to those

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

On the Feasibility of Studying Shortwave Aerosol Radiative Forcing of Climate Using Dual-Wavelength Aerosol Backscatter Lidar

NASA Technical Reports Server (NTRS)

Redemann, Jens; Russell, Philip B.; Winker, David M.; McCormick, M. Patrick; Hipskind, R. Stephen (Technical Monitor)

2000-01-01

The current low confidence in the estimates of aerosol-induced perturbations of Earth's radiation balance is caused by the highly non-uniform compositional, spatial and temporal distributions of tropospheric aerosols on a global scale owing to their heterogeneous sources and short lifetimes. Nevertheless, recent studies have shown that the inclusion of aerosol effects in climate model calculations can improve agreement with observed spatial and temporal temperature distributions. In light of the short lifetimes of aerosols, determination of their global distribution with space-borne sensors seems to be a necessary approach. Until recently, satellite measurements of tropospheric aerosols have been approximate and did not provide the full set of information required to determine their radiative effects. With the advent of active aerosol remote sensing from space (e.g., PICASSO-CENA), the applicability fo lidar-derived aerosol 180 deg -backscatter data to radiative flux calculations and hence studies of aerosol effects on climate needs to be investigated.

Aerosols in the Atmosphere: Sources, Transport, and Multi-decadal Trends

NASA Technical Reports Server (NTRS)

Chin, M.; Diehl, T.; Bian, H.; Kucsera, T.

2016-01-01

We present our recent studies with global modeling and analysis of atmospheric aerosols. We have used the Goddard Chemistry Aerosol Radiation and Transport (GOCART) model and satellite and in situ data to investigate (1) long-term variations of aerosols over polluted and dust source regions and downwind ocean areas in the past three decades and the cause of the changes and (2) anthropogenic and volcanic contributions to the sulfate aerosol in the upper tropospherelower stratosphere.

Novel insight on photochemistry at interfaces: potential impact on Seconday Aerosol Formation?

NASA Astrophysics Data System (ADS)

Rossignol, S.; George, C.; Aregahegn, K.

2014-12-01

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 cannot 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), Differential Mobility Analyzer (DMA) and Condensation Particle Sizer (CPC), we identified that traces in the aerosol phase of glyoxal chemistry products, namely imidazole-2-carboxaldehyde (IC) are strong photo-sensitizers when irradiated with near-UV. In the presence of volatile organic compounds such as terpenes, this chemistry leads to a fast aerosol growth. Given the potential importance of this new photosensitized growth pathway for ambient OA, the related reaction mechanism was investigated at a molecular level. Bulk and flow tube experiments were performed to identify major products of the reaction of limonene with the triplet state of IC by direct (+/-)ESI-HRMS and UPLC/(+/-)HESI-HRMS analysis. Detection of recombination products of IC with limonene or with itself, in bulk and flow tube experiment ts, showed that IC is able to initiate a radical chemistry in the aerosol phase under realistic irradiation conditions. Furthermore, highly oxygenated limonene reaction products were detected, clearly explaining the observed OA growth. The chemistry of peroxy radicals derived from limonene upon addition of oxygen explains the formation of such low-volatile compounds without any traditional gas phase oxidant

Estimating Marine Aerosol Particle Volume and Number from Maritime Aerosol Network Data

NASA Technical Reports Server (NTRS)

Sayer, A. M.; Smirnov, A.; Hsu, N. C.; Munchak, L. A.; Holben, B. N.

2012-01-01

As well as spectral aerosol optical depth (AOD), aerosol composition and concentration (number, volume, or mass) are of interest for a variety of applications. However, remote sensing of these quantities is more difficult than for AOD, as it is more sensitive to assumptions relating to aerosol composition. This study uses spectral AOD measured on Maritime Aerosol Network (MAN) cruises, with the additional constraint of a microphysical model for unpolluted maritime aerosol based on analysis of Aerosol Robotic Network (AERONET) inversions, to estimate these quantities over open ocean. When the MAN data are subset to those likely to be comprised of maritime aerosol, number and volume concentrations obtained are physically reasonable. Attempts to estimate surface concentration from columnar abundance, however, are shown to be limited by uncertainties in vertical distribution. Columnar AOD at 550 nm and aerosol number for unpolluted maritime cases are also compared with Moderate Resolution Imaging Spectroradiometer (MODIS) data, for both the present Collection 5.1 and forthcoming Collection 6. MODIS provides a best-fitting retrieval solution, as well as the average for several different solutions, with different aerosol microphysical models. The average solution MODIS dataset agrees more closely with MAN than the best solution dataset. Terra tends to retrieve lower aerosol number than MAN, and Aqua higher, linked with differences in the aerosol models commonly chosen. Collection 6 AOD is likely to agree more closely with MAN over open ocean than Collection 5.1. In situations where spectral AOD is measured accurately, and aerosol microphysical properties are reasonably well-constrained, estimates of aerosol number and volume using MAN or similar data would provide for a greater variety of potential comparisons with aerosol properties derived from satellite or chemistry transport model data.

Photochemical Formation of Sulfur-Containing Aerosols

NASA Astrophysics Data System (ADS)

Kroll, Jay A.; Vaida, Veronica

2017-06-01

In order to understand planetary climate systems, modeling the properties of atmospheric aerosols is vital. Aerosol formation plays an important role in planetary climates and is tied to feedback loops that can either warm or cool a planet. Sulfur compounds are known to play an important role in new particle aerosol formation and have been observed in a number of planetary atmospheres throughout our solar system. Our current understanding of sulfur chemistry explains much of what we observe in Earth's atmosphere; however, several discrepancies arise when comparing observations of the Venusian atmosphere with model predictions. This suggests that there are still problems in our fundamental understanding of sulfur chemistry. This is concerning given recent renewed interest in sulfate injections in the stratosphere for solar radiation management geo-engineering schemes. We investigate the role of sunlight as a potential driver of the formation of sulfur-containing aerosols. I will present recent work investigating the generation of large quantities of aerosol from the irradiation of mixtures of SO_2 with water and organic species, using a solar simulator that mimics the light that is available in the Earth's troposphere and the Venusian middle atmosphere. I will present on recent work done in our lab suggesting the formation of sulfurous acid, H_2SO_3, and describe experimental work that supports this proposed mechanism. Additionally I will present on new work showing the highly reactive nature of electronically excited SO_2 with saturated alkane species. The implications of this photochemically induced sulfur aerosol formation in the atmosphere of Earth and other planetary atmospheres will be discussed.

A study on the relationship between mass concentrations, chemistry and number size distribution of urban fine aerosols in Milan, Barcelona and London

NASA Astrophysics Data System (ADS)

Rodríguez, S.; van Dingenen, R.; Putaud, J.-P.; Dell'Acqua, A.; Pey, J.; Querol, X.; Alastuey, A.; Chenery, S.; Ho, K.-F.; Harrison, R.; Tardivo, R.; Scarnato, B.; Gemelli, V.

2007-05-01

A physicochemical characterization, including aerosol number size distribution, chemical composition and mass concentrations, of the urban fine aerosol captured in MILAN, BARCELONA and LONDON is presented in this article. The objective is to obtain a comprehensive picture of the microphysical processes involved in aerosol dynamics during the: 1) regular evolution of the urban aerosol (daily, weekly and seasonal basis) and in the day-to-day variations (from clean-air to pollution-events), and 2) the link between "aerosol chemistry and mass concentrations" with the "number size distribution". The mass concentrations of the fine PM2.5 aerosol exhibit a high correlation with the number concentration of >100 nm particles N>100 (nm) ("accumulation mode particles") which only account for <20% of the total number concentration N of fine aerosols; but do not correlate with the number of <100 nm particles ("ultrafine particles"), which accounts for >80% of fine particles number concentration. Organic matter and black-carbon are the only aerosol components showing a significant correlation with the ultrafine particles, attributed to vehicles exhausts emissions; whereas ammonium-nitrate, ammonium-sulphate and also organic matter and black-carbon correlate with N>100 (nm) and attributed to condensation mechanisms, other particle growth processes and some primary emissions. Time series of the aerosol DpN diameter (dN/dlogD mode), mass PM2.5 concentrations and number N>100 (nm) concentrations exhibit correlated day-to-day variations, which point to a significant involvement of condensation of semi-volatile compounds during urban pollution events. This agrees with the observation that ammonium-nitrate is the component exhibiting the highest increases from mid-to-high pollution episodes, when the highest DpN increases are observed. The results indicates that "fine PM2.5 particles urban pollution events" tend to occur when condensation processes have made particles grow large enough

Regional aerosol chemistry of the Amazon Basin during the dry season

NASA Technical Reports Server (NTRS)

Talbot, R. W.; Harriss, R. C.; Andreae, M. O.; Andreae, T. W.

1988-01-01

The distribution and chemical composition of the atmospheric aerosol over the Amazon Basin forest were determined during the 1985 July-August dry season, using data on the aerosol chemical constituent concentration collected during the NASA Global Tropospheric Experiment Amazon Boundary Layer Experiment 2A mission. The results of the analyses suggest that there is a remarkable compositional and spatial homogeneity of the atmospheric aerosol on an extensive regional scale. Particulate organic carbon is the dominant component of the atmospheric aerosol, exhibiting an average concentration of about 740 nmol/cu m in the mixed layer and about 220 nmol/cu m in free tropospheric air. Oxalate and SO4(2-) exhibited the greatest enrichment in the mixed layer, while Cl(-) showed essentially no enrichment. The aerosol in the Amazonian atmosphere is essentially acid-base neutral, primarily as a result of incorporation of NH(+), which is presumably derived from NH3 released by the forest ecosystem.

Impact of resolution on aerosol radiative feedbacks with in online-coupled chemistry/climate simulations (WRF-Chem) for EURO-CORDEX compliant domains

NASA Astrophysics Data System (ADS)

López-Romero, Jose Maria; Baró, Rocío; Palacios-Peña, Laura; Jerez, Sonia; Jiménez-Guerrero, Pedro; Montávez, Juan Pedro

2016-04-01

Several studies have shown that a high spatial resolution in atmospheric model runs improves the simulation of some meteorological variables, such as precipitation, particularly extreme events and in regions with complex orography [1]. However, increasing model spatial resolution makes the computational time rise exponentially. Hence, very high resolution experiments on large domains can hamper the execution of climatic runs. This problem shoots up when using online-coupled chemistry climate models, making a careful evaluation of improvements versus costs mandatory. Under this umbrella, the objective of this work is to investigate the sensitivity of aerosol radiative feedbacks from online-coupled chemistry regional model simulations to the spatial resolution. For that, the WRF-Chem [2] model is used for a case study to simulate the episode occurring between July 25th and August 15th of 2010. It is characterized by a high loading of atmospheric aerosol particles coming mainly from wildfires over large European regions (Russia, Iberian Peninsula). Three spatial resolutions are used defined for Euro-Cordex compliant domains [3]: 0.44°, 0.22° and 0.11°. Anthropogenic emissions come from TNO databases [4]. The analysis focuses on air quality variables (mainly PM10, PM2.5), meteorological variables (temperature, radiation) and other aerosol optical properties (aerosol optical depth). The CPU time ratio for the different domains is 1 (0.44°), 4(0.22°) and 28(0.11°) (normalized times). Comparison among simulations and observations are analyzed. Preliminary results show the difficulty to justify the much larger computational cost of high-resolution experiments when comparing with observations from a meteorological point of view, despite the finer spatio-temporal detail of the obtained pollutant fields. [1] Prein, A. F. (2014, December). Precipitation in the EURO-CORDEX 0.11° and 0.44° simulations: high resolution, high benefits?. In AGU Fall Meeting Abstracts (Vol

Novel pathway of SO2 oxidation in the atmosphere: reactions with monoterpene ozonolysis intermediates and secondary organic aerosol

NASA Astrophysics Data System (ADS)

Ye, Jianhuai; Abbatt, Jonathan P. D.; Chan, Arthur W. H.

2018-04-01

Ozonolysis of monoterpenes is an important source of atmospheric biogenic secondary organic aerosol (BSOA). While enhanced BSOA formation has been associated with sulfate-rich conditions, the underlying mechanisms remain poorly understood. In this work, the interactions between SO2 and reactive intermediates from monoterpene ozonolysis were investigated under different humidity conditions (10 % vs. 50 %). Chamber experiments were conducted with ozonolysis of α-pinene or limonene in the presence of SO2. Limonene SOA formation was enhanced in the presence of SO2, while no significant changes in SOA yields were observed during α-pinene ozonolysis. Under dry conditions, SO2 primarily reacted with stabilized Criegee intermediates (sCIs) produced from ozonolysis, but at 50 % RH heterogeneous uptake of SO2 onto organic aerosol was found to be the dominant sink of SO2, likely owing to reactions between SO2 and organic peroxides. This SO2 loss mechanism to organic peroxides in SOA has not previously been identified in experimental chamber studies. Organosulfates were detected and identified using an electrospray ionization-ion mobility spectrometry-high-resolution time-of-flight mass spectrometer (ESI-IMS-TOF) when SO2 was present in the experiments. Our results demonstrate the synergistic effects between BSOA formation and SO2 oxidation through sCI chemistry and SO2 uptake onto organic aerosol and illustrate the importance of considering the chemistry of organic and sulfur-containing compounds holistically to properly account for their reactive sinks.

Modelling the optical properties of aerosols in a chemical transport model

NASA Astrophysics Data System (ADS)

Andersson, E.; Kahnert, M.

2015-12-01

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

Modeling Trends in Tropospheric Aerosol Burden & Its Radiative Effects

EPA Science Inventory

Large changes in emissions of aerosol precursors have occurred across the southeast U.S., North America, as well as the northern hemisphere. The spatial heterogeneity and contrasting trends in the aerosol burden is resulting in differing effects on regional radiative balance. Mul...

Imaging aerosol viscosity

NASA Astrophysics Data System (ADS)

Pope, Francis; Athanasiadis, Thanos; Botchway, Stan; Davdison, Nicholas; Fitzgerald, Clare; Gallimore, Peter; Hosny, Neveen; Kalberer, Markus; Kuimova, Marina; Vysniauskas, Aurimas; Ward, Andy

2017-04-01

Organic aerosol particles play major roles in atmospheric chemistry, climate, and public health. Aerosol particle viscosity is important since it can determine the ability of chemical species such as oxidants, organics or water to diffuse into the particle bulk. Recent measurements indicate that OA may be present in highly viscous states; however, diffusion rates of small molecules such as water appear not to be limited by these high viscosities. We have developed a technique for measuring viscosity that allows for the imaging of aerosol viscosity in micron sized aerosols through use of fluorescence lifetime imaging of viscosity sensitive dyes which are also known as 'molecular rotors'. These rotors can be introduced into laboratory generated aerosol by adding minute quantities of the rotor to aerosol precursor prior to aerosolization. Real world aerosols can also be studied by doping them in situ with the rotors. The doping is achieved through generation of ultrafine aerosol particles that contain the rotors; the ultrafine aerosol particles deliver the rotors to the aerosol of interest via impaction and coagulation. This work has been conducted both on aerosols deposited on microscope coverslips and on particles that are levitated in their true aerosol phase through the use of a bespoke optical trap developed at the Central Laser Facility. The technique allows for the direct observation of kinetic barriers caused by high viscosity and low diffusivity in aerosol particles. The technique is non-destructive thereby allowing for multiple experiments to be carried out on the same sample. It can dynamically quantify and track viscosity changes during atmospherically relevant processes such oxidation and hygroscopic growth (1). This presentation will focus on the oxidation of aerosol particles composed of unsaturated and saturated organic species. It will discuss how the type of oxidant, oxidation rate and the composition of the oxidized products affect the time

Chemistry and Composition of Atmospheric Aerosol Particles

NASA Astrophysics Data System (ADS)

Kolb, Charles E.; Worsnop, Douglas R.

2012-05-01

For more than two decades a cadre of physical chemists has focused on understanding the formation processes, chemical composition, and chemical kinetics of atmospheric aerosol particles and droplets with diameters ranging from a few nanometers to ˜10,000 nm. They have adapted or invented a range of fundamental experimental and theoretical tools to investigate the thermochemistry, mass transport, and chemical kinetics of processes occurring at nanoscale gas-liquid and gas-solid interfaces for a wide range of nonideal, real-world substances. State-of-the-art laboratory methods devised to study molecular spectroscopy, chemical kinetics, and molecular dynamics also have been incorporated into field measurement instruments that are deployed routinely on research aircraft, ships, and mobile laboratories as well as at field sites from megacities to the most remote jungle, desert, and polar locations. These instruments can now provide real-time, size-resolved aerosol particle physical property and chemical composition data anywhere in Earth's troposphere and lower stratosphere.

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

carbon (BC ~ 0.2 μg m-3). Particle-phase sulfate is fairly correlated (r2 ~ 0.3) with both methacrylic acid epoxide (MAE)/hydroxymethyl-methyl-α-lactone (HMML)- (henceforth called methacrolein (MACR)-derived SOA tracers) and IEPOX-derived SOA tracers, and more strongly correlated (r2 ~ 0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the MACR-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NOy; r2 = 0.38) and nitrate (r2 = 0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy (r2 ~ 0.5 and ~ 0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC as well as aerosol viscosity and morphology becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.

A sensitivity analysis of volcanic aerosol dispersion in the stratosphere. [Mt. Fuego, Guatemala eruptions

NASA Technical Reports Server (NTRS)

Butler, C. F.

1979-01-01

A computer sensitivity analysis was performed to determine the uncertainties involved in the calculation of volcanic aerosol dispersion in the stratosphere using a 2 dimensional model. The Fuego volcanic event of 1974 was used. Aerosol dispersion processes that were included are: transport, sedimentation, gas phase sulfur chemistry, and aerosol growth. Calculated uncertainties are established from variations in the stratospheric aerosol layer decay times at 37 latitude for each dispersion process. Model profiles are also compared with lidar measurements. Results of the computer study are quite sensitive (factor of 2) to the assumed volcanic aerosol source function and the large variations in the parameterized transport between 15 and 20 km at subtropical latitudes. Sedimentation effects are uncertain by up to a factor of 1.5 because of the lack of aerosol size distribution data. The aerosol chemistry and growth, assuming that the stated mechanisms are correct, are essentially complete in several months after the eruption and cannot explain the differences between measured and modeled results.

Prebiotic-like chemistry on Titan.

PubMed

Raulin, François; Brassé, Coralie; Poch, Olivier; Coll, Patrice

2012-08-21

Titan, the largest satellite of Saturn, is the only one in the solar system with a dense atmosphere. Mainly composed of dinitrogen with several % of methane, this atmosphere experiences complex organic processes, both in the gas and aerosol phases, which are of prebiotic interest and within an environment of astrobiological interest. This tutorial review presents the different approaches which can be followed to study such an exotic place and its chemistry: observation, theoretical modeling and experimental simulation. It describes the Cassini-Huygens mission, as an example of observational tools, and gives the new astrobiologically oriented vision of Titan which is now available by coupling the three approaches. This includes the many analogies between Titan and the Earth, in spite of the much lower temperature in the Saturn system, the complex organic chemistry in the atmosphere, from the gas to the aerosol phases, but also the potential organic chemistry on Titan's surface, and in its possible internal water ocean.

Heterogeneous Atmospheric Chemistry of Lead Oxide Particles with Nitrogen Dioxide Increases Lead Solubility: Environmental and Health Implications

PubMed Central

Baltrusaitis, Jonas; Chen, Haihan; Rubasinghege, Gayan

2012-01-01

Heterogeneous chemistry of nitrogen dioxide with lead-containing particles is investigated to better understand lead metal mobilization in the environment. In particular, PbO particles, a model lead-containing compound due to its wide spread presence as a component of lead paint and as naturally occurring minerals, massicot and litharge, are exposed to nitrogen dioxide at different relative humidity. X-ray photoelectron spectroscopy (XPS) shows that upon exposure to nitrogen dioxide the surface of PbO particles react to form adsorbed nitrates and lead nitrate thin films with the extent of formation of nitrate relative humidity dependent. Surface adsorbed nitrate increases the amount of dissolved lead. These reacted particles are found to have an increase in the amount of lead that dissolves in aqueous suspensions at circumneutral pH compared to unreacted particles. These results point to the potential importance and impact that heterogeneous chemistry with trace atmospheric gases can have on increasing solubility and therefore the mobilization of heavy metals, such as lead, in the environment. This study also show that surface intermediates, such as adsorbed nitrates, that form can yield higher concentrations of lead in water systems. In the environment, these water systems can include drinking water, ground water, estuaries and lakes. PMID:23057678

Aqueous Chemistry in the Clouds of Venus: A Possible Source for the UV Absorber

NASA Astrophysics Data System (ADS)

Baines, Kevin H.; Delitsky, M. L.

2013-10-01

The identity and cause of the UV absorber near the Venusian cloudtops 62-70 km altitude) has been an enduring mystery. Given the role of sulfur in Venus’s atmosphere, where, somewhat analogous to water on Earth, it cycles through gas, liquid, and (possibly) solid phases in the atmosphere, it has been a prime suspect as at least a key component, perhaps as long-lived solid poly-sulfur aerosols, Sn, where n > 4. However, the narrow range of altitudes inhabited by the UV absorber (thought to form and reside primarily above 62 km altitude) seems incompatible with Sn, which should vertically disperse after formation. Here, we point to another process that could lead to somewhat more exotic chemistries that favor formation and sequestration at high altitudes: Aqueous chemistry within H2SO4-nH2O cloud particles. Due to (1) the decrease of temperature and (2) the increase in the fraction of water (“n” in the previous formula) of each cloud droplet with altitude, high-altitude particles near the cloudtops are - via the “heterogeneous uptake” process - significantly more capable of capturing and concentrating trace gases, in particular HCl. For example, the heterogeneous uptake of HCl in H2SO4 droplets near the 65-km cloudtops is at least three times greater than that found in the middle of the clouds near 55 km altitude. Other factors such as local mixing ratios and the concentration of other solvents in the droplet also modify the uptake. Within the cloud droplets, solution chemistry between HCl and H2SO4 may lead to the formation of chlorosulfonic acid, ClSO3H, which is a weak acid that readily breaks down into other species, such as SO2Cl2 (sulfuryl chloride) and SOCl2 (thionyl chloride). Together, these three materials have UV-blue absorptions at 0.21, 0.29, 0.39 and 0.47 micron. Thus, H2SO4 aerosols at high altitudes may take on lasting UV absorption characteristics, dependent on temperature (altitude) and other conditions, Balloons floating at benign Earth

Explicit Cloud Nucleation from Arbitrary Mixtures of Aerosol Types and Sizes Using an Ultra-Efficient In-Line Aerosol Bin Model in High-Resolution Simulations of Hurricanes

NASA Astrophysics Data System (ADS)

Walko, R. L.; Ashby, T.; Cotton, W. R.

2017-12-01

The fundamental role of atmospheric aerosols in the process of cloud droplet nucleation is well known, and there is ample evidence that the concentration, size, and chemistry of aerosols can strongly influence microphysical, thermodynamic, and ultimately dynamic properties and evolution of clouds and convective systems. With the increasing availability of observation- and model-based environmental representations of different types of anthropogenic and natural aerosols, there is increasing need for models to be able to represent which aerosols nucleate and which do not in supersaturated conditions. However, this is a very complex process that involves competition for water vapor between multiple aerosol species (chemistries) and different aerosol sizes within each species. Attempts have been made to parameterize the nucleation properties of mixtures of different aerosol species, but it is very difficult or impossible to represent all possible mixtures that may occur in practice. As part of a modeling study of the impact of anthropogenic and natural aerosols on hurricanes, we developed an ultra-efficient aerosol bin model to represent nucleation in a high-resolution atmospheric model that explicitly represents cloud- and subcloud-scale vertical motion. The bin model is activated at any time and location in a simulation where supersaturation occurs and is potentially capable of activating new cloud droplets. The bins are populated from the aerosol species that are present at the given time and location and by multiple sizes from each aerosol species according to a characteristic size distribution, and the chemistry of each species is represented by its absorption or adsorption characteristics. The bin model is integrated in time increments that are smaller than that of the atmospheric model in order to temporally resolve the peak supersaturation, which determines the total nucleated number. Even though on the order of 100 bins are typically utilized, this leads only

Coupling spectral-bin cloud microphysics with the MOSAIC aerosol model in WRF-Chem: Methodology and results for marine stratocumulus clouds

NASA Astrophysics Data System (ADS)

Gao, Wenhua; Fan, Jiwen; Easter, R. C.; Yang, Qing; Zhao, Chun; Ghan, Steven J.

2016-09-01

Aerosol-cloud interaction processes can be represented more physically with bin cloud microphysics relative to bulk microphysical parameterizations. However, due to computational power limitations in the past, bin cloud microphysics was often run with very simple aerosol treatments. The purpose of this study is to represent better aerosol-cloud interaction processes in the Chemistry version of Weather Research and Forecast model (WRF-Chem) at convection-permitting scales by coupling spectral-bin cloud microphysics (SBM) with the MOSAIC sectional aerosol model. A flexible interface is built that exchanges cloud and aerosol information between them. The interface contains a new bin aerosol activation approach, which replaces the treatments in the original SBM. It also includes the modified aerosol resuspension and in-cloud wet removal processes with the droplet loss tendencies and precipitation fluxes from SBM. The newly coupled system is evaluated for two marine stratocumulus cases over the Southeast Pacific Ocean with either a simplified aerosol setup or full-chemistry. We compare the aerosol activation process in the newly coupled SBM-MOSAIC against the SBM simulation without chemistry using a simplified aerosol setup, and the results show consistent activation rates. A longer time simulation reinforces that aerosol resuspension through cloud drop evaporation plays an important role in replenishing aerosols and impacts cloud and precipitation in marine stratocumulus clouds. Evaluation of the coupled SBM-MOSAIC with full-chemistry using aircraft measurements suggests that the new model works realistically for the marine stratocumulus clouds, and improves the simulation of cloud microphysical properties compared to a simulation using MOSAIC coupled with the Morrison two-moment microphysics.

An overview of geoengineering of climate using stratospheric sulphate aerosols

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

Rasch, Philip J.; Tilmes, S.; Turco, Richard P.

2010-01-01

We provide an overview of geoengineering by stratospheric sulphate aerosols. The state of understanding about this topic as of early 2008 is reviewed, summarizing the past 30 years of work in the area, highlighting some very recent studies using climate models, and discussing methods used to deliver sulphur species to the stratosphere. The studies reviewed here suggest that sulphate aerosols can counteract the globally averaged temperature increase associated with increasing greenhouse gases, and reduce changes to some other components of the Earth system. There are likely to be remaining regional climate changes after geoengineering, with some regions experiencing significant changesmore » in temperature or precipitation. The aerosols also serve as surfaces for heterogeneous chemistry resulting in increased ozone depletion. The delivery of sulphur species to the stratosphere in a way that will produce particles of the right size is shown to be a complex and potentially very difficult task. Two simple delivery scenarios are explored, but similar exercises will be needed for other suggested delivery mechanisms. While the introduction of the geoengineering source of sulphate aerosol will perturb the sulphur cycle of the stratosphere signicantly, it is a small perturbation to the total (stratosphere and troposphere) sulphur cycle. The geoengineering source would thus be a small contributor to the total global source of ‘acid rain’ that could be compensated for through improved pollution control of anthropogenic tropospheric sources. Some areas of research remain unexplored. Although ozone may be depleted, with a consequent increase to solar ultraviolet-B (UVB) energy reaching the surface and a potential impact on health and biological populations, the aerosols will also scatter and attenuate this part of the energy spectrum, and this may compensate the UVB enhancement associated with ozone depletion. The aerosol will also change the ratio of diffuse to direct

An overview of geoengineering of climate using stratospheric sulphate aerosols.

PubMed

Rasch, Philip J; Tilmes, Simone; Turco, Richard P; Robock, Alan; Oman, Luke; Chen, Chih-Chieh; Stenchikov, Georgiy L; Garcia, Rolando R

2008-11-13

We provide an overview of geoengineering by stratospheric sulphate aerosols. The state of understanding about this topic as of early 2008 is reviewed, summarizing the past 30 years of work in the area, highlighting some very recent studies using climate models, and discussing methods used to deliver sulphur species to the stratosphere. The studies reviewed here suggest that sulphate aerosols can counteract the globally averaged temperature increase associated with increasing greenhouse gases, and reduce changes to some other components of the Earth system. There are likely to be remaining regional climate changes after geoengineering, with some regions experiencing significant changes in temperature or precipitation. The aerosols also serve as surfaces for heterogeneous chemistry resulting in increased ozone depletion. The delivery of sulphur species to the stratosphere in a way that will produce particles of the right size is shown to be a complex and potentially very difficult task. Two simple delivery scenarios are explored, but similar exercises will be needed for other suggested delivery mechanisms. While the introduction of the geoengineering source of sulphate aerosol will perturb the sulphur cycle of the stratosphere signicantly, it is a small perturbation to the total (stratosphere and troposphere) sulphur cycle. The geoengineering source would thus be a small contributor to the total global source of 'acid rain' that could be compensated for through improved pollution control of anthropogenic tropospheric sources. Some areas of research remain unexplored. Although ozone may be depleted, with a consequent increase to solar ultraviolet-B (UVB) energy reaching the surface and a potential impact on health and biological populations, the aerosols will also scatter and attenuate this part of the energy spectrum, and this may compensate the UVB enhancement associated with ozone depletion. The aerosol will also change the ratio of diffuse to direct energy

Explicit modeling of organic chemistry and secondary organic aerosol partitioning for Mexico City and its outflow plume

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

Lee-Taylor, J.; Madronich, Sasha; Aumont, B.

2011-12-21

The evolution of organic aerosols (OA) in Mexico City and its outflow is investigated with the nearly explicit gas phase photochemistry model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere), wherein precursor hydrocarbons are oxidized to numerous intermediate species for which vapor pressures are computed and used to determine gas/particle partitioning in a chemical box model. Precursor emissions included observed C3-10 alkanes, alkenes, and light aromatics, as well as larger n-alkanes (up to C25) not directly observed but estimated by scaling to particulate emissions according to their volatility. Conditions were selected for comparison with observations mademore » in March 2006 (MILAGRO). The model successfully reproduces the magnitude and diurnal shape for both primary (POA) and secondary (SOA) organic aerosols, with POA peaking in the early morning at 15-20 ug m-3, and SOA peaking at 10-15 μg m-3 during mid-day. The majority (> 75%) of the model SOA stems from the large n-alkanes, with the remainder mostly from the light aromatics. Simulated OA elemental composition reproduces observed H/C and O/C ratios reasonably well, although modeled ratios develop more slowly than observations suggest. SOA chemical composition is initially dominated by *- hydroxy ketones and nitrates from the large alkanes, with contributions from peroxy acyl nitrates and, at later times when NOx is lower, organic hydroperoxides. The simulated plume-integrated OA mass continues to increase for several days downwind despite dilution-induced particle evaporation, since oxidation chemistry leading to SOA formation remains strong. In this model, the plume SOA burden several days downwind exceeds that leaving the city by a factor of >3. These results suggest significant regional radiative impacts of SOA.« less

Nitrogen Incorporation in CH4-N2 Photochemical Aerosol Produced by Far UV Irradiation

NASA Technical Reports Server (NTRS)

Trainer, Melissa G.; Jimenez, Jose L.; Yung, Yuk L.; Toon, Owen B.; Tolbert, Margaret A.

2012-01-01

Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (lambda < 120 nm) or magnetospheric electrons in the outer reaches of the atmosphere. Far UV radiation (120 - 200 nm), which is transmitted down to the stratosphere of Titan, is expected to affect hydrocarbon chemistry only and not initiate the formation of nitrogenated species. We have examined the chemical properties of photochemical aerosol produced at far UV wavelengths using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS), which allows for elemental analysis of particle-phase products. Our results show that aerosol formed from CH4/N2 photochemistry contains a surprising amount of nitrogen, up to 16% by mass, a result of photolysis in the far UV. The proportion of nitrogenated organics to hydrocarbon species is shown to be correlated with that of N2 in the irradiated gas. The aerosol mass greatly decreases when N2 is removed, indicating that N2 plays a major role in aerosol production. Because direct dissociation of N2 is highly improbable given the immeasurably low cross-section at the wavelengths studied, the chemical activation of N2 must occur via another pathway. Any chemical activation of N2 at wavelengths > 120 nm is presently unaccounted for in atmospheric photochemical models. We suggest that reaction with CH radicals produced from CH4 photolysis may provide a mechanism for incorporating N into the molecular structure of the aerosol. Further work is needed to understand the chemistry involved, as these processes may have significant implications for prebiotic chemistry on the early Earth and similar planets.

Chemistry on the mesoscale: Modeling and measurement issues

NASA Technical Reports Server (NTRS)

Thompson, Anne; Pleim, John; Walcek, Christopher; Ching, Jason; Binkowski, Frank; Tao, Wei-Kuo; Dickerson, Russell; Pickering, Kenneth

1993-01-01

The topics covered include the following: Regional Acid Deposition Model (RADM) -- a coupled chemistry/mesoscale model; convection in RADM; unresolved issues for mesoscale modeling with chemistry -- nonprecipitating clouds; unresolved issues for mesoscale modeling with chemistry -- aerosols; tracer studies with Goddard Cumulus Ensemble Model (GCEM); field observations of trace gas transport in convection; and photochemical consequences of convection.

Element composition of insoluble fraction of aerosols in snow in the vicinity of oil chemistry refinery (Pavlodar City, Kazakhstan) and petrochemical plant (Tomsk City, Russia)

NASA Astrophysics Data System (ADS)

Talovskaya, Anna V.; Filimonenko, Ekaterina A.; Yazikov, Egor G.; Shakhova, Tatyana S.; Parygina, Irina A.

2015-11-01

Tomsk petrochemical plant (Russia) and Pavlodar oil chemistry refinery (Kazakhstan) are the sources of air contamination in Tomsk and Pavlodar respectively. Therefore, it is very important to study the level of air contamination with particulate matter as well as ultimate composition of these particles. Disposable solid particles fall out to the snow cover, so snow is an accumulator of the particles. The article deals with the study results of dust load and concentrations of Br, Sb, La, Ce, Sm and Nd in insoluble fraction of aerosols in snow in the vicinity of Pavlodar oil chemistry refinery and Tomsk petrochemical plant. The instrumental neutron activation analysis was used for the ultimate composition detection. Results were shown that the dust load in the vicinity of Tomsk petrochemical plant is higher than in Pavlodar. We have detected high concentrations of La, Br and Sm in insoluble fraction of aerosols in snow in the vicinity of Pavlodar refinery and high concentrations of Sb and Ce in Tomsk. Moreover, we have detected high Br concentration in insoluble fraction of aerosols in snow of the vicinity of both plants. Gas burning on the flares of these enterprises is likely a potential source of Br. La to light lanthanoids ratio have shown La is of anthropogenic origin. In addition, enrichment factor estimation reflects an anthropogenic origin of La, Sm, Br, Ce and Sb as well. These elements might be emitted from different production facilities of the plants.

The Sectional Stratospheric Sulfate Aerosol module (S3A-v1) within the LMDZ general circulation model: description and evaluation against stratospheric aerosol observations

NASA Astrophysics Data System (ADS)

Kleinschmitt, Christoph; Boucher, Olivier; Bekki, Slimane; Lott, François; Platt, Ulrich

2017-09-01

Stratospheric aerosols play an important role in the climate system by affecting the Earth's radiative budget as well as atmospheric chemistry, and the capabilities to simulate them interactively within global models are continuously improving. It is important to represent accurately both aerosol microphysical and atmospheric dynamical processes because together they affect the size distribution and the residence time of the aerosol particles in the stratosphere. The newly developed LMDZ-S3A model presented in this article uses a sectional approach for sulfate particles in the stratosphere and includes the relevant microphysical processes. It allows full interaction between aerosol radiative effects (e.g. radiative heating) and atmospheric dynamics, including e.g. an internally generated quasi-biennial oscillation (QBO) in the stratosphere. Sulfur chemistry is semi-prescribed via climatological lifetimes. LMDZ-S3A reasonably reproduces aerosol observations in periods of low (background) and high (volcanic) stratospheric sulfate loading, but tends to overestimate the number of small particles and to underestimate the number of large particles. Thus, it may serve as a tool to study the climate impacts of volcanic eruptions, as well as the deliberate anthropogenic injection of aerosols into the stratosphere, which has been proposed as a method of geoengineering to abate global warming.

Impact of volcanic aerosols on stratospheric ozone recovery

NASA Astrophysics Data System (ADS)

Naik, Vaishali; Horowitz, Larry W.; Daniel Schwarzkopf, M.; Lin, Meiyun

2017-09-01

We use transient GFDL-CM3 chemistry-climate model simulations over the 2006-2100 period to show how the influence of volcanic aerosols on the extent and timing of ozone recovery varies with (a) future greenhouse gas scenarios (Representative Concentration Pathway (RCP)4.5 and RCP8.5) and (b) halogen loading. Current understanding is that elevated volcanic aerosols reduce ozone under high halogen loading but increase ozone under low halogen loading when the chemistry is more NOx dominated. With extremely low aerosol loadings (designated here as "background"), global stratospheric ozone burden is simulated to return to 1980 levels around 2050 in the RCP8.5 scenario but remains below 1980 levels throughout the 21st century in the RCP4.5 scenario. In contrast, with elevated volcanic aerosols, ozone column recovers more quickly to 1980 levels, with recovery dates ranging from the mid-2040s in RCP8.5 to the mid-2050s to early 2070s in RCP4.5. The ozone response in both future emission scenarios increases with enhanced volcanic aerosols. By 2100, the 1980 baseline-adjusted global stratospheric ozone column is projected to be 20-40% greater in RCP8.5 and 110-200% greater in RCP4.5 with elevated volcanic aerosols compared to simulations with the extremely low background aerosols. The weaker ozone enhancement at 2100 in RCP8.5 than in RCP4.5 in response to elevated volcanic aerosols is due to a factor of 2.5 greater methane in RCP8.5 compared with RCP4.5. Our results demonstrate the substantial uncertainties in stratospheric ozone projections and expected recovery dates induced by volcanic aerosol perturbations that need to be considered in future model ozone projections.

The impact of temperature dependent CO2 cross section measurements: A role for heterogeneous chemistry in the atmosphere of Mars?

NASA Technical Reports Server (NTRS)

Anbar, A. D.; Allen, M.; Nair, H.; Leu, M-T.; Yung, Y. L.

1992-01-01

Carbon dioxide comprises over 95 percent of the Mars atmosphere, despite continuous photolysis of CO2 by solar ultraviolet (UV) radiation. Since the direct recombination of CO and O is spinforbidden, the chemical stability of CO2 in the Martian atmosphere is thought to be the result of a HO(x)-catalyzed recombination scheme. Thus the rate of CO oxidation is sensitive to the abundance and altitude distribution of OH, H, and HO2. Most Martian atmospheric models assume that HO(x) abundances are governed purely by gas phase chemistry. However, it is well established that reactive HO(x) radical are adsorbed by a wide variety of surfaces. The authors have combined laboratory studies of H, OH, and HO2 adsorption on inorganic surfaces, observational data of aerosol distributions, and an updated photochemical model to demonstrate that adsorption on either dust or ice aerosols is capable of reducing HO(x) abundances significantly, thereby retarding the rate of CO oxidation.

A 3-D Model Study of Aerosol Composition and Radiative Forcing in the Asian-Pacific Region

NASA Technical Reports Server (NTRS)

Chin, Mian; Ginoux, Paul; Torres, Omar; Zhao, Xuepeng; Einaudi, Franco (Technical Monitor)

2000-01-01

The Georgia Tech/Goddard Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) model will be used in analyzing the aerosol data in the ACE-Asia program. Our objectives are (1) to understand the physical, chemical, and optical properties of aerosol and the processes that control these properties over the Asian-Pacific region, (2) to determine the aerosol radiative forcing over the Asian-Pacific region, and (3) to investigate the interaction between aerosol and tropospheric chemistry. We will present the GOCART aerosol simulations of sulfate, dust, carbonaceous, and sea salt concentrations, their optical thicknesses, and their radiative effects. We will also show the comparisons of model results with data taken from previous field campaigns, ground-based sun photometer measurements, and satellite observations. Finally, we will present our plan for the ACE-Asia study.

Description and evaluation of tropospheric chemistry and aerosols in the Community Earth System Model (CESM1.2)

DOE PAGES

Tilmes, S.; Lamarque, J. -F.; Emmons, L. K.; ...

2015-01-01

The Community Atmosphere Model (CAM), version 5, is now coupled to extensive tropospheric and stratospheric chemistry, called CAM5-chem, and is available in addition to CAM4-chem in the Community Earth System Model (CESM) version 1.2. The main focus of this paper is to compare the performance of configurations with internally derived "free running" (FR) meteorology and "specified dynamics" (SD) against observations from surface, aircraft, and satellite, as well as understand the origin of the identified differences. We focus on the representation of aerosols and chemistry. All model configurations reproduce tropospheric ozone for most regions based on in situ and satellite observations.more » However, shortcomings exist in the representation of ozone precursors and aerosols. Tropospheric ozone in all model configurations agrees for the most part with ozonesondes and satellite observations in the tropics and the Northern Hemisphere within the variability of the observations. Southern hemispheric tropospheric ozone is consistently underestimated by up to 25%. Differences in convection and stratosphere to troposphere exchange processes are mostly responsible for differences in ozone in the different model configurations. Carbon monoxide (CO) and other volatile organic compounds are largely underestimated in Northern Hemisphere mid-latitudes based on satellite and aircraft observations. Nitrogen oxides (NO x) are biased low in the free tropical troposphere, whereas peroxyacetyl nitrate (PAN) is overestimated in particular in high northern latitudes. The present-day methane lifetime estimates are compared among the different model configurations. These range between 7.8 years in the SD configuration of CAM5-chem and 8.8 years in the FR configuration of CAM4-chem and are therefore underestimated compared to observational estimations. We find that differences in tropospheric aerosol surface area between CAM4 and CAM5 play an important role in controlling the burden of

Description and evaluation of tropospheric chemistry and aerosols in the Community Earth System Model (CESM1.2)

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

Tilmes, S.; Lamarque, J. -F.; Emmons, L. K.

The Community Atmosphere Model (CAM), version 5, is now coupled to extensive tropospheric and stratospheric chemistry, called CAM5-chem, and is available in addition to CAM4-chem in the Community Earth System Model (CESM) version 1.2. The main focus of this paper is to compare the performance of configurations with internally derived "free running" (FR) meteorology and "specified dynamics" (SD) against observations from surface, aircraft, and satellite, as well as understand the origin of the identified differences. We focus on the representation of aerosols and chemistry. All model configurations reproduce tropospheric ozone for most regions based on in situ and satellite observations.more » However, shortcomings exist in the representation of ozone precursors and aerosols. Tropospheric ozone in all model configurations agrees for the most part with ozonesondes and satellite observations in the tropics and the Northern Hemisphere within the variability of the observations. Southern hemispheric tropospheric ozone is consistently underestimated by up to 25%. Differences in convection and stratosphere to troposphere exchange processes are mostly responsible for differences in ozone in the different model configurations. Carbon monoxide (CO) and other volatile organic compounds are largely underestimated in Northern Hemisphere mid-latitudes based on satellite and aircraft observations. Nitrogen oxides (NO x) are biased low in the free tropical troposphere, whereas peroxyacetyl nitrate (PAN) is overestimated in particular in high northern latitudes. The present-day methane lifetime estimates are compared among the different model configurations. These range between 7.8 years in the SD configuration of CAM5-chem and 8.8 years in the FR configuration of CAM4-chem and are therefore underestimated compared to observational estimations. We find that differences in tropospheric aerosol surface area between CAM4 and CAM5 play an important role in controlling the burden of

A study on the relationship between mass concentrations, chemistry and number size distribution of urban fine aerosols in Milan, Barcelona and London

NASA Astrophysics Data System (ADS)

Rodríguez, S.; van Dingenen, R.; Putaud, J.-P.; Dell'Acqua, A.; Pey, J.; Querol, X.; Alastuey, A.; Chenery, S.; Ho, K.-F.; Harrison, R. M.; Tardivo, R.; Scarnato, B.; Gianelle, V.

2007-01-01

A physicochemical characterization of the urban fine aerosol (aerosol number size distribution, chemical composition and mass concentrations) in Milan, Barcelona and London is presented in this article. The objective is to obtain a comprehensive picture on the involvement of the microphysical processes of the aerosol dynamic in the: 1) regular evolution of the urban aerosol (daily, weekly and seasonal basis) and in the day-to-day variations (from clean-air to pollution-events), and 2) link between "aerosol chemistry and mass concentrations" with the "number size distribution". The mass concentrations of the fine PM2.5 aerosol exhibit a high correlation with the number concentration of particles >100 nm (which only accounts for <20% of the total number concentration N of fine aerosols) and do not correlate with the number of particles <100 nm ("ultrafine particles", which accounts for >80% of fine particles). Organic matter (OM) and black-carbon (BC) are the only aerosol components showing a significant correlation with ultrafine particles (attributed to vehicles emissions), whereas ammonium-nitrate, ammonium-sulphate and also OM and BC correlate with N>100(nm) (attributed to gas-to-particle transformation mechanisms and some primary emissions). Time series of the aerosol DpN diameter (dN/dlogD mode), mass PM2.5 concentrations and number N>100(nm) concentrations, exhibit correlated day-to-day variations which point to a significant involvement of condensation of semi-volatile compounds during urban pollution events. This agrees with the fact that ammonium-nitrate is the component exhibiting the highest increases from mid-to-high pollution episodes, when the highest DpN increases are observed. The results indicates that "fine PM2.5 particles urban pollution events" tend to occur when condensation processes have made particles grow enough to produce significant concentrations of N>100(nm). In contrast, because the low contribution of ultrafine particles to the fine

A perspective on SOA generated in aerosol water from glyoxal and methylglyoxal and its impacts on climate-relevant aerosol properties

NASA Astrophysics Data System (ADS)

Sareen, N.; McNeill, V. F.

2011-12-01

In recent years, glyoxal and methylglyoxal have emerged to be potentially important SOA precursors with significant implications for climate-related aerosol properties. Here we will discuss how the chemistry of these and similar organic compounds in aerosol water can affect the aerosol optical and cloud formation properties. Aqueous-phase SOA production from glyoxal and methylglyoxal is a potential source of strongly light-absorbing organics, or "brown carbon". We characterized the kinetics of brown carbon formation from these precursors in mixtures of ammonium sulfate and water using UV-Vis spectrophotometry. This mechanism has been incorporated into a photochemical box model with coupled gas phase-aqueous aerosol chemistry. Methylglyoxal and related compounds also may impact an aerosol's ability to act as a cloud condensation nucleus. We recently showed via pendant drop tensiometry and aerosol chamber studies that uptake of methylglyoxal from the gas phase driven by aqueous-phase oligomerization chemistry is a potentially significant, previously unidentified source of surface-active organic material in aerosols. Results from pendant drop tensiometry showed significantly depressed surface tension in methylglyoxal-ammonium sulfate solutions. We further found that ammonium sulfate particles exposed to gas-phase methylglyoxal in a 3.5 m3 aerosol reaction chamber activate into cloud droplets at sizes up to 15% lower at a given supersaturation than do pure ammonium sulfate particles. The observed enhancement exceeds that predicted based on Henry's Law and our measurements of surface tension depression in bulk solutions, suggesting that surface adsorption of methylglyoxal plays a role in determining CCN activity. Methylglyoxal and similar gas-phase surfactants may be an important and overlooked source of enhanced CCN activity in the atmosphere. To characterize the SOA products formed in these solutions, an Aerosol Chemical Ionization Mass Spectrometer (CIMS) was used

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

.2 μg m-3). Particle-phase sulfate is fairly correlated (r2~0.3) with both MAE- and IEPOX-derived SOA tracers, and more strongly correlated (r2~0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the methacrylic acid epoxide (MAE)-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NOy; r2=0.38) and nitrate (r2=0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a~clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy (r2~0.5 and ~0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.

The Impact of Aerosol Particle Mixing State on the Hygroscopicity of Sea Spray Aerosol.

PubMed

Schill, Steven R; Collins, Douglas B; Lee, Christopher; Morris, Holly S; Novak, Gordon A; Prather, Kimberly A; Quinn, Patricia K; Sultana, Camille M; Tivanski, Alexei V; Zimmermann, Kathryn; Cappa, Christopher D; Bertram, Timothy H

2015-06-24

Aerosol particles influence global climate by determining cloud droplet number concentrations, brightness, and lifetime. Primary aerosol particles, such as those produced from breaking waves in the ocean, display large particle-particle variability in chemical composition, morphology, and physical phase state, all of which affect the ability of individual particles to accommodate water and grow into cloud droplets. Despite such diversity in molecular composition, there is a paucity of methods available to assess how particle-particle variability in chemistry translates to corresponding differences in aerosol hygroscopicity. Here, an approach has been developed that allows for characterization of the distribution of aerosol hygroscopicity within a chemically complex population of atmospheric particles. This methodology, when applied to the interpretation of nascent sea spray aerosol, provides a quantitative framework for connecting results obtained using molecular mimics generated in the laboratory with chemically complex ambient aerosol. We show that nascent sea spray aerosol, generated in situ in the Atlantic Ocean, displays a broad distribution of particle hygroscopicities, indicative of a correspondingly broad distribution of particle chemical compositions. Molecular mimics of sea spray aerosol organic material were used in the laboratory to assess the volume fractions and molecular functionality required to suppress sea spray aerosol hygroscopicity to the extent indicated by field observations. We show that proper accounting for the distribution and diversity in particle hygroscopicity and composition are important to the assessment of particle impacts on clouds and global climate.

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.

Decadal simulation and comprehensive evaluation of CESM/CAM5.1 with advanced chemistry, aerosol microphysics, and aerosol-cloud interactions

NASA Astrophysics Data System (ADS)

He, Jian; Zhang, Yang; Glotfelty, Tim; He, Ruoying; Bennartz, Ralf; Rausch, John; Sartelet, Karine

2015-03-01

Earth system models have been used for climate predictions in recent years due to their capabilities to include biogeochemical cycles, human impacts, as well as coupled and interactive representations of Earth system components (e.g., atmosphere, ocean, land, and sea ice). In this work, the Community Earth System Model (CESM) with advanced chemistry and aerosol treatments, referred to as CESM-NCSU, is applied for decadal (2001-2010) global climate predictions. A comprehensive evaluation is performed focusing on the atmospheric component—the Community Atmosphere Model version 5.1 (CAM5.1) by comparing simulation results with observations/reanalysis data and CESM ensemble simulations from the Coupled Model Intercomparison Project phase 5 (CMIP5). The improved model can predict most meteorological and radiative variables relatively well with normalized mean biases (NMBs) of -14.1 to -9.7% and 0.7-10.8%, respectively, although temperature at 2 m (T2) is slightly underpredicted. Cloud variables such as cloud fraction (CF) and precipitating water vapor (PWV) are well predicted, with NMBs of -10.5 to 0.4%, whereas cloud condensation nuclei (CCN), cloud liquid water path (LWP), and cloud optical thickness (COT) are moderately-to-largely underpredicted, with NMBs of -82.2 to -31.2%, and cloud droplet number concentration (CDNC) is overpredictd by 26.7%. These biases indicate the limitations and uncertainties associated with cloud microphysics (e.g., resolved clouds and subgrid-scale cumulus clouds). Chemical concentrations over the continental U.S. (CONUS) (e.g., SO42-, Cl-, OC, and PM2.5) are reasonably well predicted with NMBs of -12.8 to -1.18%. Concentrations of SO2, SO42-, and PM10 are also reasonably well predicted over Europe with NMBs of -20.8 to -5.2%, so are predictions of SO2 concentrations over the East Asia with an NMB of -18.2%, and the tropospheric ozone residual (TOR) over the globe with an NMB of -3.5%. Most meteorological and radiative variables

Understanding the impact of saharan dust aerosols on tropical cyclones

NASA Astrophysics Data System (ADS)

Naeger, Aaron

Genesis of Tropical Cyclones (TCs) in the main development region for Atlantic hurricanes is tied to convection initiated by African easterly waves (AEWs) during Northern hemisphere summer and fall seasons. The main development region is also impacted by dust aerosols transported from the Sahara. It has been hypothesized that dust aerosols can modulate the development of TCs through aerosol-radiation and aerosol-cloud interaction processes. In this study, we investigate the impact of dust aerosols on TC development using the Weather Research and Forecasting model coupled with chemistry (WRF-Chem). We first develop a technique to constrain the WRF-Chem model with a realistic three-dimensional spatial distribution of dust aerosols. The horizontal distribution of dust is specified using the Moderate Resolution Imaging Spectroradiometer (MODIS) derived aerosol products and output from the Goddard Chemistry Aerosol Radiation and Transport (GOCART) model. The vertical distribution of dust is constrained using the Cloud Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO). We validate our technique through in situ aircraft measurements where both showed aerosol number concentrations from 20-30 cm-3 in the atmosphere for Saharan dust moving over the eastern Atlantic Ocean. Then, we use the satellite data constraint technique to nudge the WRF-Chem aerosol fields throughout the simulation of TC Florence developing over the eastern Atlantic Ocean during September 2006. Three different experiments are conducted where the aerosol-radiation and aerosol-cloud interaction processes are either activated or deactivated in the model while all other model options are identical between the experiments. By comparing the model experiment results, the impact of the aerosol interaction processes on TC development can be understood. The results indicate that dust aerosols can delay or prevent the development of a TC as the minimum sea level pressure of TC Florence was 13 h

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.

Coupling Spectral-bin Cloud Microphysics with the MOSAIC Aerosol Model in WRF-Chem: Methodology and Results for Marine Stratocumulus Clouds

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

Gao, Wenhua; Fan, Jiwen; Easter, Richard C.

Aerosol-cloud interaction processes can be represented more physically with bin cloud microphysics relative to bulk microphysical parameterizations. However, due to computational power limitations in the past, bin cloud microphysics was often run with very simple aerosol treatments. The purpose of this study is to represent better aerosol-cloud interaction processes in the Chemistry version of Weather Research and Forecast model (WRF-Chem) at convection-permitting scales by coupling spectral-bin cloud microphysics (SBM) with the MOSAIC sectional aerosol model. A flexible interface is built that exchanges cloud and aerosol information between them. The interface contains a new bin aerosol activation approach, which replaces themore » treatments in the original SBM. It also includes the modified aerosol resuspension and in-cloud wet removal processes with the droplet loss tendencies and precipitation fluxes from SBM. The newly coupled system is evaluated for two marine stratocumulus cases over the Southeast Pacific Ocean with either a simplified aerosol setup or full-chemistry. We compare the aerosol activation process in the newly-coupled SBM-MOSAIC against the SBM simulation without chemistry using a simplified aerosol setup, and the results show consistent activation rates. A longer time simulation reinforces that aerosol resuspension through cloud drop evaporation plays an important role in replenishing aerosols and impacts cloud and precipitation in marine stratocumulus clouds. Evaluation of the coupled SBM-MOSAIC with full-chemistry using aircraft measurements suggests that the new model works realistically for the marine stratocumulus clouds, and improves the simulation of cloud microphysical properties compared to a simulation using MOSAIC coupled with the Morrison two-moment microphysics.« less

Ozone response to a CO2 doubling - Results from a stratospheric circulation model with heterogeneous chemistry

NASA Technical Reports Server (NTRS)

Pitari, G.; Palermi, S.; Visconti, G.; Prinn, R. G.

1992-01-01

A spectral 3D model of the stratosphere has been used to study the sensitivity of polar ozone with respect to a carbon dioxide increase. The lower stratospheric cooling associated with an imposed CO2 doubling may increase the probability of polar stratospheric cloud (PSC) formation and this affect ozone. The ozone perturbation obtained with the inclusion of a simple parameterization for heterogeneous chemistry on PSCs is compared to that relative to a pure homogeneous chemistry. In both cases the temperature perturbation is determined by a CO2 doubling, while the total chlorine content is kept at the present level. It is shown that the lower temperature may increase the depth and the extension of the ozone hole by extending the area amenable to PSC formation. It may be argued that this effect, coupled with an increasing amount of chlorine, may produce a positive feedback on the ozone destruction.

Evaluation of a new microphysical aerosol module in the ECMWF Integrated Forecasting System

NASA Astrophysics Data System (ADS)

Woodhouse, Matthew; Mann, Graham; Carslaw, Ken; Morcrette, Jean-Jacques; Schulz, Michael; Kinne, Stefan; Boucher, Olivier

2013-04-01

The Monitoring Atmospheric Composition and Climate II (MACC-II) project will provide a system for monitoring and predicting atmospheric composition. As part of the first phase of MACC, the GLOMAP-mode microphysical aerosol scheme (Mann et al., 2010, GMD) was incorporated within the ECMWF Integrated Forecasting System (IFS). The two-moment modal GLOMAP-mode scheme includes new particle formation, condensation, coagulation, cloud-processing, and wet and dry deposition. GLOMAP-mode is already incorporated as a module within the TOMCAT chemistry transport model and within the UK Met Office HadGEM3 general circulation model. The microphysical, process-based GLOMAP-mode scheme allows an improved representation of aerosol size and composition and can simulate aerosol evolution in the troposphere and stratosphere. The new aerosol forecasting and re-analysis system (known as IFS-GLOMAP) will also provide improved boundary conditions for regional air quality forecasts, and will benefit from assimilation of observed aerosol optical depths in near real time. Presented here is an evaluation of the performance of the IFS-GLOMAP system in comparison to in situ aerosol mass and number measurements, and remotely-sensed aerosol optical depth measurements. Future development will provide a fully-coupled chemistry-aerosol scheme, and the capability to resolve nitrate aerosol.

Modelled and observed changes in aerosols and surface solar radiation over Europe between 1960 and 2009

NASA Astrophysics Data System (ADS)

Turnock, S. T.; Spracklen, D. V.; Carslaw, K. S.; Mann, G. W.; Woodhouse, M. T.; Forster, P. M.; Haywood, J.; Johnson, C. E.; Dalvi, M.; Bellouin, N.; Sanchez-Lorenzo, A.

2015-08-01

Substantial changes in anthropogenic aerosols and precursor gas emissions have occurred over recent decades due to the implementation of air pollution control legislation and economic growth. The response of atmospheric aerosols to these changes and the impact on climate are poorly constrained, particularly in studies using detailed aerosol chemistry-climate models. Here we compare the HadGEM3-UKCA (Hadley Centre Global Environment Model-United Kingdom Chemistry and Aerosols) coupled chemistry-climate model for the period 1960-2009 against extensive ground-based observations of sulfate aerosol mass (1978-2009), total suspended particle matter (SPM, 1978-1998), PM10 (1997-2009), aerosol optical depth (AOD, 2000-2009), aerosol size distributions (2008-2009) and surface solar radiation (SSR, 1960-2009) over Europe. The model underestimates observed sulfate aerosol mass (normalised mean bias factor (NMBF) = -0.4), SPM (NMBF = -0.9), PM10 (NMBF = -0.2), aerosol number concentrations (N30 NMBF = -0.85; N50 NMBF = -0.65; and N100 NMBF = -0.96) and AOD (NMBF = -0.01) but slightly overpredicts SSR (NMBF = 0.02). Trends in aerosol over the observational period are well simulated by the model, with observed (simulated) changes in sulfate of -68 % (-78 %), SPM of -42 % (-20 %), PM10 of -9 % (-8 %) and AOD of -11 % (-14 %). Discrepancies in the magnitude of simulated aerosol mass do not affect the ability of the model to reproduce the observed SSR trends. The positive change in observed European SSR (5 %) during 1990-2009 ("brightening") is better reproduced by the model when aerosol radiative effects (ARE) are included (3 %), compared to simulations where ARE are excluded (0.2 %). The simulated top-of-the-atmosphere aerosol radiative forcing over Europe under all-sky conditions increased by > 3.0 W m-2 during the period 1970-2009 in response to changes in anthropogenic emissions and aerosol concentrations.

Aerosol Indirect Effects on Cirrus Clouds in Global Aerosol-Climate Models

NASA Astrophysics Data System (ADS)

Liu, X.; Zhang, K.; Wang, Y.; Neubauer, D.; Lohmann, U.; Ferrachat, S.; Zhou, C.; Penner, J.; Barahona, D.; Shi, X.

2015-12-01

Cirrus clouds play an important role in regulating the Earth's radiative budget and water vapor distribution in the upper troposphere. Aerosols can act as solution droplets or ice nuclei that promote ice nucleation in cirrus clouds. Anthropogenic emissions from fossil fuel and biomass burning activities have substantially perturbed and enhanced concentrations of aerosol particles in the atmosphere. Global aerosol-climate models (GCMs) have now been used to quantify the radiative forcing and effects of aerosols on cirrus clouds (IPCC AR5). However, the estimate uncertainty is very large due to the different representation of ice cloud formation and evolution processes in GCMs. In addition, large discrepancies have been found between model simulations in terms of the spatial distribution of ice-nucleating aerosols, relative humidity, and temperature fluctuations, which contribute to different estimates of the aerosol indirect effect through cirrus clouds. In this presentation, four GCMs with the start-of-the art representations of cloud microphysics and aerosol-cloud interactions are used to estimate the aerosol indirect effects on cirrus clouds and to identify the causes of the discrepancies. The estimated global and annual mean anthropogenic aerosol indirect effect through cirrus clouds ranges from 0.1 W m-2 to 0.3 W m-2 in terms of the top-of-the-atmosphere (TOA) net radiation flux, and 0.5-0.6 W m-2 for the TOA longwave flux. Despite the good agreement on global mean, large discrepancies are found at the regional scale. The physics behind the aerosol indirect effect is dramatically different. Our analysis suggests that burden of ice-nucleating aerosols in the upper troposphere, ice nucleation frequency, and relative role of ice formation processes (i.e., homogeneous versus heterogeneous nucleation) play key roles in determining the characteristics of the simulated aerosol indirect effects. In addition to the indirect effect estimate, we also use field campaign

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

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

Glyoxal contribution to aerosols over Los Angeles

NASA Astrophysics Data System (ADS)

Balcerak, Ernie

2012-01-01

Laboratory and field studies have indicated that glyoxal (chemical formula OCHCHO), an atmospheric oxidation product of isoprene and aromatic compounds, may contribute to secondary organic aerosols in the atmosphere, which can block sunlight and affect atmospheric chemistry. Some aerosols are primary aerosols, emitted directly into the atmosphere, while others are secondary, formed through chemical reactions in the atmosphere. Washenfelder et al. describe in situ glyoxal measurements from Pasadena, Calif., near Los Angeles, made during summer 2010. They used three different methods to calculate the contribution of glyoxal to secondary atmospheric aerosol and found that it is responsible for 0-0.2 microgram per cubic meter, or 0-4%, of the secondary organic aerosol mass. The researchers also compared their results to those of a previous study that calculated the glyoxal contribution to aerosol for Mexico City. Mexico City had higher levels of organic aerosol mass from glyoxal. They suggest that the lower contribution of glyoxal to aerosol concentrations for Los Angeles may be due to differences in the composition or water content of the aerosols above the two cities. (Journal of Geophysical Research-Atmospheres, doi:10.1029/2011JD016314, 2011)

Trends in aerosol abundances and distributions

NASA Technical Reports Server (NTRS)

Turco, R. P.; Mccormick, M. P.; Clancy, R. T.; Curran, R.; Deluisi, J.; Hamill, P.; Kent, G.; Rosen, J. M.; Toon, O. B.; Yue, G.

1989-01-01

The properties of aerosols that reside in the upper atmosphere are described. Special emphasis is given to the influence these aerosols have on ozone observation systems, mainly through radiative effects, and on ambient ozone concentrations, mainly through chemical effects. It has long been appreciated that stratospheric particles can interfere with the remote sensing of ozone distribution. The mechanism and magnitude of this interference are evaluated. Separate sections deal with the optical properties of upper atmospheric aerosols, long-term trends in stratospheric aerosols, perturbations of the stratospheric aerosol layer by volcanic eruptions, and estimates of the impacts that such particles have on remotely measured ozone concentrations. Another section is devoted to a discussion of the polar stratospheric clouds (PSC's). These unique clouds, recently discovered by satellite observation, are now thought to be intimately connected with the Antarctic ozone hole. Accordingly, interest in PSC's has grown considerably in recent years. This chapter describes what we know about the morphology, physical chemistry, and microphysics of PSC's.

New Photosensitized Processes at Aerosol and Ocean Surfaces

NASA Astrophysics Data System (ADS)

Rossignol, S.; Aregahegn, K. Z.; Ciuraru, R.; Bernard, F.; Tinel, L.; Fine, L.; George, C.

2014-12-01

From a few years now, there is a growing body of evidence that photoinduced processes could be of great importance for the tropospheric chemistry. Here, we would like to present two additional outcomes of this new area of research, firstly the photosensitized direct VOC uptake by aerosols and, secondly, the photoinduced chemical formation of unsaturated VOC from marine microlayer proxy. It was recently shown that the chemistry of glyoxal toward ammonium ions into droplets and wet aerosols leads to the formation of light-absorbing compounds. Among them, we found that imidazole-2-carboxaldehyde (IC) acts as a photosensitizer and is able to initiate the growth of organic aerosols via the uptake of VOC, such as limonene. Given its potential importance, the mechanism of this photoinduced uptake was investigated thanks to aerosol flow tube experiments and UPLC-ESI-HRMS analysis. Results reveal hydrogen abstraction on the VOC molecule by the triplet state of IC leading to the VOC oxidation without any traditional oxidant. As well as aerosol, the sea-surface microlayer, known to be enriched in light-absorbing organics, is largely impacted by photochemical processes. Recent studies have pointed out for example the role of photosentitized processes in the loss of NO2 and ozone at water surfaces containing photoactive compounds such as chlorophyll. In order to go further, we worked from sea-surface microlayer proxy containing humic acids as photoactive material and organic acids as surfactants. Beside oxidation processes, we monitored by high resolution PTR-MS the release in the gas phase of unsaturated compounds, including C5 dienes (isoprene ?). A strong correlation between the measured surface tension and the C5 diene concentration in the gas phase was evidenced, clearly pointing toward an interfacial process. This contribution will highlight the similarities between both systems and will attempt to present a general chemical scheme for photosensitized chemistry at

Investigation of Heterogeneous N2O5 Uptake and ClNO2 Yield at a Rural and a Mountain-top Site in Northern China

NASA Astrophysics Data System (ADS)

Wang, Z.; Tham, Y. J.; Wang, W.; LI, Q.; Yun, H.; Wang, X.; Xue, L.; Wang, T.

2017-12-01

Dinitrogen pentoxide (N2O5) is a reactive intermediate in the atmospheric oxidation of nitrogen oxides (NOx), and its heterogeneous reaction plays key roles in the chemical transformation and removal of NOx, as well as the production of nitrate and nitryl chloride (ClNO2) that affects the radical budget and photochemical ozone formation. Ambient measurements at a rural site and a mountain top site in northern China in the summer of 2014 revealed significant ClNO2 mixing ratios (up to 2.1 ppbv) produced by fast heterogeneous N2O5 uptake on atmospheric aerosols. Frequently intercepted ClNO2-laden plumes at the mountain site indicate significant ClNO2 production occurred in the nocturnal residual layer, and could help explain the sustained ClNO2 peaks after sunrise observed in the ground site in the region. The meteorological and chemical analysis suggested that elevated ClNO2 plumes were mostly associated with nocturnal buoyant emission from point combustion sources, such as power and industry plants. The uptake coefficients (γ) of N2O5 and yields (ϕ) of ClNO2 were then derived for different plumes observed at the ground and mountain sites, and the factors affecting the variability of γ and ϕ under different conditions were also investigated. The uptake coefficients and yields obtained in this study in northern China will be compared with other observations in the world, and also compared to the existing parameterizations based on aerosol compositions. The contribution of fast N2O5 heterogeneous reaction to the nocturnal NOx processing and nitrate aerosol formation will be further examined, to better understand the impacts of heterogeneous reactive nitrogen chemistry on air quality in northern China.

Enhanced PM2.5 pollution in China due to aerosol-cloud interactions.

PubMed

Zhao, Bin; Liou, Kuo-Nan; Gu, Yu; Li, Qinbin; Jiang, Jonathan H; Su, Hui; He, Cenlin; Tseng, Hsien-Liang R; Wang, Shuxiao; Liu, Run; Qi, Ling; Lee, Wei-Liang; Hao, Jiming

2017-06-30

Aerosol-cloud interactions (aerosol indirect effects) play an important role in regional meteorological variations, which could further induce feedback on regional air quality. While the impact of aerosol-cloud interactions on meteorology and climate has been extensively studied, their feedback on air quality remains unclear. Using a fully coupled meteorology-chemistry model, we find that increased aerosol loading due to anthropogenic activities in China substantially increases column cloud droplet number concentration and liquid water path (LWP), which further leads to a reduction in the downward shortwave radiation at surface, surface air temperature and planetary boundary layer (PBL) height. The shallower PBL and accelerated cloud chemistry due to larger LWP in turn enhance the concentrations of particulate matter with diameter less than 2.5 μm (PM 2.5 ) by up to 33.2 μg m -3 (25.1%) and 11.0 μg m -3 (12.5%) in January and July, respectively. Such a positive feedback amplifies the changes in PM 2.5 concentrations, indicating an additional air quality benefit under effective pollution control policies but a penalty for a region with a deterioration in PM 2.5 pollution. Additionally, we show that the cloud processing of aerosols, including wet scavenging and cloud chemistry, could also have substantial effects on PM 2.5 concentrations.

Aerosol composition, chemistry, and source characterization during the 2008 VOCALS Experiment

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

Lee, Y.; Springston, S.; Jayne, J.

2010-03-15

Chemical composition of fine aerosol particles over the northern Chilean coastal waters was determined onboard the U.S. DOE G-1 aircraft during the VOCALS (VAMOS Ocean-Cloud-Atmosphere-Land Study) field campaign between October 16 and November 15, 2008. SO42-, NO3-, NH4+, and total organics (Org) were determined using an Aerodyne Aerosol Mass Spectrometer, and SO42-, NO3-, NH4+, Na+, Cl-, CH3SO3-, Mg2+, Ca2+, and K+ were determined using a particle-into-liquid sampler-ion chromatography technique. The results show the marine boundary layer (MBL) aerosol mass was dominated by non- sea-salt SO42- followed by Na+, Cl-, Org, NO3-, and NH4+, in decreasing importance; CH3SO3-, Ca2+, and K+more » rarely exceeded their respective limits of detection. The SO42- aerosols were strongly acidic as the equivalent NH4+ to SO42- ratio was only {approx}0.25 on average. NaCl particles, presumably of sea-salt origin, showed chloride deficits but retained Cl- typically more than half the equivalency of Na+, and are externally mixed with the acidic sulfate aerosols. Nitrate was observed only on sea-salt particles, consistent with adsorption of HNO3 on sea-salt aerosols, responsible for the Cl- deficit. Dust particles appeared to play a minor role, judging from the small volume differences between that derived from the observed mass concentrations and that calculated based on particle size distributions. Because SO42- concentrations were substantial ({approx}0.5 - {approx}3 {micro}g/m3) with a strong gradient (highest near the shore), and the ocean-emitted dimethylsulfide and its unique oxidation product, CH3SO3-, were very low (i.e., {le} 40 parts per trillion and <0.05 {micro}g/m3, respectively), the observed SO42- aerosols are believed to be primarily of terrestrial origin. Back trajectory calculations indicate sulfur emissions from smelters and power plants along coastal regions of Peru and Chile are the main sources of these SO4- aerosols. However, compared to observations, model

SOA formation from partitioning and heterogeneous reactions: model study in the presence of inorganic species.

PubMed

Jang, Myoseon; Czoschke, Nadine M; Northcross, Amanda L; Cao, Gang; Shaof, David

2006-05-01

A predictive model for secondary organic aerosol (SOA) formation by both partitioning and heterogeneous reactions was developed for SOA created from ozonolysis of alpha-pinene in the presence of preexisting inorganic seed aerosols. SOA was created in a 2 m3 polytetrafluoroethylene film indoor chamber under darkness. Extensive sets of SOA experiments were conducted varying humidity, inorganic seed compositions comprising of ammonium sulfate and sulfuric acid, and amounts of inorganic seed mass. SOA mass was decoupled into partitioning (OM(P)) and heterogeneous aerosol production (OM(H)). The reaction rate constant for OM(H) production was subdivided into three categories (fast, medium, and slow) to consider different reactivity of organic products for the particle phase heterogeneous reactions. The influence of particle acidity on reaction rates was treated in a previous semiempirical model. Model OM(H) was developed with medium and strong acidic seed aerosols, and then extrapolated to OM(H) in weak acidic conditions, which are more relevant to atmospheric aerosols. To demonstrate the effects of preexisting glyoxal derivatives (e.g., glyoxal hydrate and dimer) on OM(H), SOA was created with a seed mixture comprising of aqueous glyoxal and inorganic species. Our results show that heterogeneous SOA formation was also influenced by preexisting reactive glyoxal derivatives.

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.

Crystal nucleation initiated by transient ion-surface interactions at aerosol interfaces.

PubMed

Davis, Ryan D; Tolbert, Margaret A

2017-07-01

Particle collisions are a common occurrence in the atmosphere, but no empirical observations exist to fully predict the potential effects of these collisions on air quality and climate projections. The current consensus of heterogeneous crystal nucleation pathways relevant to the atmosphere dictates that collisions with amorphous particles have no effect on the crystallization relative humidity (RH) of aqueous inorganic aerosols because there is no stabilizing ion-surface interaction to facilitate the formation of crystal nuclei. In contrast to this view of heterogeneous nucleation, we report laboratory observations demonstrating that collisions with hydrophobic amorphous organic aerosols induced crystallization of aqueous inorganic microdroplets at high RH, the effect of which was correlated with destabilizing water-mediated ion-specific surface interactions. These same organic aerosols did not induce crystallization once internally mixed in the droplet, pointing toward a previously unconsidered transient ion-specific crystal nucleation pathway that can promote aerosol crystallization via particle collisions.

Stratospheric Aerosol and Gas Experiment (SAGE) II and III Aerosol Extinction Measurements in the Arctic Middle and Upper Troposphere

NASA Technical Reports Server (NTRS)

Treffeisen, R. E.; Thomason, L. W.; Strom, J.; Herber, A. B.; Burton, S. P.; Yamanouchi, T.

2006-01-01

In recent years, substantial effort has been expended toward understanding the impact of tropospheric aerosols on Arctic climate and chemistry. A significant part of this effort has been the collection and documentation of extensive aerosol physical and optical property data sets. However, the data sets present significant interpretive challenges because of the diverse nature of these measurements. Among the longest continuous records is that by the spaceborne Stratospheric Aerosol and Gas Experiment (SAGE) II. Although SAGE tropospheric measurements are restricted to the middle and upper troposphere, they may be able to provide significant insight into the nature and variability of tropospheric aerosol, particularly when combined with ground and airborne observations. This paper demonstrates the capacity of aerosol products from SAGE II and its follow-on experiment SAGE III to describe the temporal and vertical variations of Arctic aerosol characteristics. We find that the measurements from both instruments are consistent enough to be combined. Using this combined data set, we detect a clear annual cycle in the aerosol extinction for the middle and upper Arctic troposphere.

Radiative Effects of Aerosols

NASA Technical Reports Server (NTRS)

Valero, Francisco P. J.

1996-01-01

During the Atlantic Stratocumulus Transition Experiment (ASTEX) in June 1992, two descents in cloud-free regions allowed comparison of the change in aerosol optical depth as determined by an onboard total-direct-diffuse radiometer (TDDR) to the change calculated from measured size-resolved aerosol microphysics and chemistry. Both profiles included a pollution haze from Europe but the second also included the effect of a Saharan dust layer above the haze. The separate contributions of supermicrometer (coarse) and submicrometer (fine) aerosol were determined and thermal analysis of the pollution haze indicated that the fine aerosol was composed primarily of a sulfate/water mixture with a refractory soot-like core. The soot core increased the calculated extinction by about 10% in the most polluted drier layer relative to a pure sulfate aerosol but had significantly less effect at higher humidities. A 3 km descent through a boundary layer air mass dominated by pollutant aerosol with relative humidities (RH) 10-77% yielded a close agreement between the measured and calculated aerosol optical depths (550 nm) of 0.160 (+/- 0.07) and 0. 157 (+/- 0.034) respectively. During descent the aerosol mass scattering coefficient per unit sulfate mass varied from about 5 to 16 m(exp 2)/g and primarily dependent upon ambient RH. However, the total scattering coefficient per total fine mass was far less variable at about 4+/- 0.7 m(exp 2)/g. A subsequent descent through a Saharan dust layer located above the pollution aerosol layer revealed that both layers contributed similarly to aerosol optical depth. The scattering per unit mass of the coarse aged dust was estimated at 1.1 +/- 0.2 m(exp 2)/g. The large difference (50%) in measured and calculated optical depth for the dust layer exceeded measurements.

Quantifying the response of the ORAC aerosol optical depth retrieval for MSG SEVIRI to aerosol model assumptions

NASA Astrophysics Data System (ADS)

Bulgin, Claire E.; Palmer, Paul I.; Merchant, Christopher J.; Siddans, Richard; Gonzi, Siegfried; Poulsen, Caroline A.; Thomas, Gareth E.; Sayer, Andrew M.; Carboni, Elisa; Grainger, Roy G.; Highwood, Eleanor J.; Ryder, Claire L.

2011-03-01

We test the response of the Oxford-RAL Aerosol and Cloud (ORAC) retrieval algorithm for Meteosat Second Generation Spinning Enhanced Visible and InfraRed Imager (MSG SEVIRI) to changes in the aerosol properties used in the dust aerosol model, using data from the Dust Outflow and Deposition to the Ocean (DODO) flight campaign in August 2006. We find that using the observed DODO free tropospheric aerosol size distribution and refractive index increases simulated top of the atmosphere radiance at 0.55 μm assuming a fixed aerosol optical depth of 0.5 by 10-15%, reaching a maximum difference at low solar zenith angles. We test the sensitivity of the retrieval to the vertical distribution of the aerosol and find that this is unimportant in determining simulated radiance at 0.55 μm. We also test the ability of the ORAC retrieval when used to produce the GlobAerosol data set to correctly identify continental aerosol outflow from the African continent, and we find that it poorly constrains aerosol speciation. We develop spatially and temporally resolved prior distributions of aerosols to inform the retrieval which incorporates five aerosol models: desert dust, maritime, biomass burning, urban, and continental. We use a Saharan Dust Index and the GEOS-Chem chemistry transport model to describe dust and biomass burning aerosol outflow and compare AOD using our speciation against the GlobAerosol retrieval during January and July 2006. We find AOD discrepancies of 0.2-1 over regions of intense biomass burning outflow, where AOD from our aerosol speciation and GlobAerosol speciation can differ by as much as 50-70%.

Heterogeneous Catalysis.

ERIC Educational Resources Information Center

Miranda, R.

1989-01-01

Described is a heterogeneous catalysis course which has elements of materials processing embedded in the classical format of catalytic mechanisms and surface chemistry. A course outline and list of examples of recent review papers written by students are provided. (MVL)

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

Coupled Aerosol-Chemistry-Climate Twentieth-Century Transient Model Investigation: Trends in Short-Lived Species and Climate Responses

NASA Technical Reports Server (NTRS)

Koch, Dorothy; Bauer, Susanne E.; Del Genio, Anthony; Faluvegi, Greg; McConnell, Joseph R.; Menon, Surabi; Miller, Ronald L.; Rind, David; Ruedy, Reto; Schmidt, Gavin A.;

Maritime Aerosol Network as a Component of AERONET - a Useful Tool for Evaluation of the Global Sea-Salt Aerosol Distribution

NASA Astrophysics Data System (ADS)

Smirnov, A.; Holben, B. N.; Kinne, S.; Nelson, N. B.; Stenchikov, G. L.; Broccardo, S. P.; Sowers, D.; Lobecker, E.; Ondrusek, M.; Zielinski, T. P.; Gray, L. M.; Frouin, R.; Radionov, V. F.; Smyth, T. J.; Zibordi, G.; Heller, M. I.; Slabakova, V.; Krüger, K.; Reid, E. A.; Istomina, L.; Vandermeulen, R. A.; O'Neill, N. T.; Levy, G.; Giles, D. M.; Slutsker, I.; Sorokin, M. G.; Eck, T. F.

2016-02-01

Sea-salt aerosol plays an important role in radiation balance and chemistry of marine atmosphere. Sea-salt production depends on various factors. There is a significant uncertainty in the parametrization of the sea-salt production and budget. Ship-based aerosol optical depth (AOD) measurements can be used as an important validation tool for various global models and in-situ measurements. The paper presents the current status of the Maritime Aerosol Network (MAN) which is a component of Aerosol Robotic Network. Since 2006 over 300 cruises were completed and data archive of more than 5500 measurement days is accessible at http://aeronet.gsfc.nasa.gov/new_web/maritime_aerosol_network.html . AOD measurements from ships of opportunity complemented island-based AERONET measurements and provided important reference points for satellite retrieved and modelled AOD climatology over the oceans. The program exemplifies mutually beneficial international, multi-agency effort in atmospheric aerosol optical studies over the oceans.

Probing chemical transformation in picolitre volume aerosol droplets

NASA Astrophysics Data System (ADS)

Miloserdov, Anatolij; Day, Calum P. F.; Rosario, Gabriela L.; Horrocks, Benjamin R.; Carruthers, Antonia E.

2017-08-01

We have demonstrated chemical transformation in single microscopic-sized aerosol droplets localised in optical tweezers. Droplets in situ are measured during chemical transformation processes of solvent exchange and solute transformation through an ion exchange reaction. Solvent exchange between deionised water and heavy water in aerosol droplets is monitored through observation of the OH and OD Raman stretches. A change in solute chemistry of aerosol is achieved through droplet coalescence events between calcium chloride and sodium carbonate to promote ion exchange. The transformation forming meta-stable and stable states of CaCO3 is observed and analysed using Gaussian peak decomposition to reveal polymorphs.

Radiative and Chemical Response to Interactive Stratospheric Sulfate Aerosols in Fully Coupled CESM1(WACCM)

NASA Astrophysics Data System (ADS)

Mills, Michael J.; Richter, Jadwiga H.; Tilmes, Simone; Kravitz, Ben; MacMartin, Douglas G.; Glanville, Anne A.; Tribbia, Joseph J.; Lamarque, Jean-François; Vitt, Francis; Schmidt, Anja; Gettelman, Andrew; Hannay, Cecile; Bacmeister, Julio T.; Kinnison, Douglas E.

2017-12-01

We present new insights into the evolution and interactions of stratospheric aerosol using an updated version of the Whole Atmosphere Community Climate Model (WACCM). Improved horizontal resolution, dynamics, and chemistry now produce an internally generated quasi-biennial oscillation and significant improvements to stratospheric temperatures and ozone compared to observations. We present a validation of WACCM column ozone and climate calculations against observations. The prognostic treatment of stratospheric sulfate aerosols accurately represents the evolution of stratospheric aerosol optical depth and perturbations to solar and longwave radiation following the June 1991 eruption of Mount Pinatubo. We confirm the inclusion of interactive OH chemistry as an important factor in the formation and initial distribution of aerosol following large inputs of sulfur dioxide (SO2) to the stratosphere. We calculate that depletion of OH levels within the dense SO2 cloud in the first weeks following the Pinatubo eruption significantly prolonged the average initial e-folding decay time for SO2 oxidation to 47 days. Previous observational and model studies showing a 30 day decay time have not accounted for the large (30-55%) losses of SO2 on ash and ice within 7-9 days posteruption and have not correctly accounted for OH depletion. We examine the variability of aerosol evolution in free-running climate simulations due to meteorology, with comparison to simulations nudged with specified dynamics. We assess calculated impacts of volcanic aerosols on ozone loss with comparisons to observations. The completeness of the chemistry, dynamics, and aerosol microphysics in WACCM qualify it for studies of stratospheric sulfate aerosol geoengineering.

GCM Simulations of the Aerosol Indirect Effect: Sensitivity to Cloud Parameterization and Aerosol Burden

NASA Technical Reports Server (NTRS)

Menon, Surabi; DelGenio, Anthony D.; Koch, Dorothy; Tselioudis, George; Hansen, James E. (Technical Monitor)

2001-01-01

We describe the coupling of the Goddard Institute for Space Studies (GISS) general circulation model (GCM) to an online sulfur chemistry model and source models for organic matter and sea-salt that is used to estimate the aerosol indirect effect. The cloud droplet number concentration is diagnosed empirically from field experiment datasets over land and ocean that observe droplet number and all three aerosol types simultaneously; corrections are made for implied variations in cloud turbulence levels. The resulting cloud droplet number is used to calculate variations in droplet effective radius, which in turn allows us to predict aerosol effects on cloud optical thickness and microphysical process rates. We calculate the aerosol indirect effect by differencing the top-of-the-atmosphere net cloud radiative forcing for simulations with present-day vs. pre-industrial emissions. Both the first (radiative) and second (microphysical) indirect effects are explored. We test the sensitivity of our results to cloud parameterization assumptions that control the vertical distribution of cloud occurrence, the autoconversion rate, and the aerosol scavenging rate, each of which feeds back significantly on the model aerosol burden. The global mean aerosol indirect effect for all three aerosol types ranges from -1.55 to -4.36 W m(exp -2) in our simulations. The results are quite sensitive to the pre-industrial background aerosol burden, with low pre-industrial burdens giving strong indirect effects, and to a lesser extent to the anthropogenic aerosol burden, with large burdens giving somewhat larger indirect effects. Because of this dependence on the background aerosol, model diagnostics such as albedo-particle size correlations and column cloud susceptibility, for which satellite validation products are available, are not good predictors of the resulting indirect effect.

GCM Simulations of the Aerosol Indirect Effect: Sensitivity to Cloud Parameterization and Aerosol Burden

NASA Technical Reports Server (NTRS)

Menon, Surabi; DelGenio, Anthony D.; Koch, Dorothy; Tselioudis, George; Hansen, James E. (Technical Monitor)

2001-01-01

We describe the coupling of the Goddard Institute for Space Studies (GISS) general circulation model (GCM) to an online sulfur chemistry model and source models for organic matter and sea-salt that is used to estimate the aerosol indirect effect. The cloud droplet number concentration is diagnosed empirically from field experiment datasets over land and ocean that observe droplet number and all three aerosol types simultaneously; corrections are made for implied variations in cloud turbulence levels. The resulting cloud droplet number is used to calculate variations in droplet effective radius, which in turn allows us to predict aerosol effects on cloud optical thickness and microphysical process rates. We calculate the aerosol indirect effect by differencing the top-of-the-atmosphere net cloud radiative forcing for simulations with present-day vs. pre-industrial emissions. Both the first (radiative) and second (microphysical) indirect effects are explored. We test the sensitivity of our results to cloud parameterization assumptions that control the vertical distribution of cloud occurrence, the autoconversion rate, and the aerosol scavenging rate, each of which feeds back significantly on the model aerosol burden. The global mean aerosol indirect effect for all three aerosol types ranges from -1.55 to -4.36 W/sq m in our simulations. The results are quite sensitive to the pre-industrial background aerosol burden, with low pre-industrial burdens giving strong indirect effects, and to a lesser extent to the anthropogenic aerosol burden, with large burdens giving somewhat larger indirect effects. Because of this dependence on the background aerosol, model diagnostics such as albedo-particle size correlations and column cloud susceptibility, for which satellite validation products are available, are not good predictors of the resulting indirect effect.

Indirect effect of changing aerosol concentrations on methane and ozone radiative forcing

NASA Astrophysics Data System (ADS)

Rowlinson, Matthew; Rap, Alexandru; Arnold, Steve; Forster, Piers; Chipperfield, Martyn

2017-04-01

Atmospheric aerosols interact with climate in number of complex ways and quantifying the overall effect remains the dominant uncertainty in estimating anthropogenic climate forcing (IPCC, 2013). The radiative forcing (RF) caused by the direct effect of aerosol interacting with radiation is estimated at -0.35 (-0.85 to +0.15) Wm-2, while cloud-aerosol interactions are estimated at -0.45 (-1.2 to 0.0) Wm-2 (IPCC, 2013). The net impact is a cooling with an effective radiative forcing (ERF) of 0.9 (-1.9 to -0.1) Wm-2 (IPCC, 2013). One effect of aerosols which has not been well evaluated is their effect on atmospheric chemistry. Atmospheric aerosols provide a surface for homogeneous reactions to occur, altering reactions rates and the availability of oxidants, thereby influencing the removal/production of radiatively important species such as methane (CH4) and tropospheric ozone (O3). Oxidants such as the hydroxyl radical (OH) determine the atmospheric lifetime and hence burden of CH4, therefore changes to atmospheric aerosols which impact oxidation chemistry will also influence RF due to CH4. This effect could enhance or offset the negative RF of aerosols, depending on how the individual aerosol changes availability of oxidants. Quantifying the importance of this mechanism for RF is necessary to provide accurate estimates of the effect of aerosols, and assess relative effectiveness of measures to decrease aerosol emissions and precursors. Using a sophisticated aerosol micro-physics model (GLOMAP) coupled to the TOMCAT three-dimensional chemical transport model, we separately simulate changes in atmospheric composition resulting from a 50% decline in anthropogenic emissions of black carbon aerosol (BC), volatile organic compounds (VOCs) and anthropogenic precursors of sulphate and nitrate. The impact of changes to each aerosol on lifetime of CH4 is then calculated to establish the resulting impact on CH4 burden and RF. Cutting global anthropogenic SO2 emissions by 50

The DACCIWA Project: Dynamics-Aerosol-Chemistry-Cloud interactions in West Africa

NASA Astrophysics Data System (ADS)

Knippertz, Peter

2014-05-01

Massive economic and population growth and urbanisation are expected to lead to a tripling of anthropogenic emissions from southern West Africa (SWA) between 2000 and 2030, the impacts of which on human health, ecosystems, food security and the regional climate are largely unknown. An assessment of these impacts is complicated by (a) a superposition with effects of global climate change, (b) the strong dependence of SWA on the sensitive West African monsoon, (c) incomplete scientific understanding of interactions between emissions, clouds, radiation, precipitation and regional circulations and (d) by a lack of observations to advance our understanding and improve predictions. The purpose of this contribution is to introduce the research consortium DACCIWA (Dynamics-Aerosol-Chemistry-Cloud interactions in West Africa), which comprises 16 partners in six European and West African countries. The interdisciplinary DACCIWA team will build on the scientific and logistical foundations established by the African Monsoon Multidisciplinary Analysis (AMMA) project and collaborate closely with operational centres. DACCIWA will receive funding of about M8.75€ from the European Commission as part of Framework Programme 7 from 2015 until 2018. The DACCIWA project will conduct extensive fieldwork in SWA to collect high-quality observations, spanning the entire process chain from surface-based natural and anthropogenic emissions to impacts on health, ecosystems and climate. This will include a major field campaign in summer 2015 with three research aircrafts and two ground-based supersites. Combining the resulting benchmark dataset with a wide range of modelling activities will allow us: (a) to assess all relevant physical and chemical processes, (b) to improve the monitoring of climate and compositional parameters from space, (c) to determine health impacts from air pollution, and (d) to develop the next generation of weather and climate models capable of representing coupled

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

Crystal nucleation initiated by transient ion-surface interactions at aerosol interfaces

PubMed Central

Davis, Ryan D.; Tolbert, Margaret A.

2017-01-01

Particle collisions are a common occurrence in the atmosphere, but no empirical observations exist to fully predict the potential effects of these collisions on air quality and climate projections. The current consensus of heterogeneous crystal nucleation pathways relevant to the atmosphere dictates that collisions with amorphous particles have no effect on the crystallization relative humidity (RH) of aqueous inorganic aerosols because there is no stabilizing ion-surface interaction to facilitate the formation of crystal nuclei. In contrast to this view of heterogeneous nucleation, we report laboratory observations demonstrating that collisions with hydrophobic amorphous organic aerosols induced crystallization of aqueous inorganic microdroplets at high RH, the effect of which was correlated with destabilizing water-mediated ion-specific surface interactions. These same organic aerosols did not induce crystallization once internally mixed in the droplet, pointing toward a previously unconsidered transient ion-specific crystal nucleation pathway that can promote aerosol crystallization via particle collisions. PMID:28776032

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.

Synchronised Aerosol Mass Spectrometer Measurements across Europe

NASA Astrophysics Data System (ADS)

Nemitz, Eiko

2010-05-01

sites concentrations of inorganic precursor gases (e.g. NH3, HNO3, SO2) were measured simultaneously, mainly with a denuder based wet chemistry technique. The database provides a powerful dataset against which to compare the performance of European scale Chemistry and Transport Models (CTMs) in reproducing transport patterns, thermodynamics (e.g. daytime vs. night-time concentrations and gas/aerosol partitioning) and organic aerosol partitioning (e.g. primary versus oxidised aerosol). Future analysis will include a detailed analysis of the organic aerosol composition, through statistical factor analysis and based on the high mass resolution data provided by a subset of the AMS instruments.

Aerosol-associated changes in tropical stratospheric ozone following the eruption of Mount Pinatubo

NASA Technical Reports Server (NTRS)

Grant, William B.; Browell, Edward V.; Fishman, Jack; Brackett, Vincent G.; Veiga, Robert E.; Nganga, Dominique; Minga, A.; Cros, Bernard; Butler, Carolyn F.; Fenn, Marta A.

1994-01-01

The large amount of sulfuric acid aerosol formed in the stratosphere by conversion of sulfur dioxide emitted by the eruption of Mount Pinatubo (15.14 deg N, 120.35 deg E) in the Philippines around June 15, 1991, has had a pronounced effect on lower stratospheric ozone in the tropics. Measurements of stratospheric ozone in the tropics using electrochemical concentration cell (ECC) sondes before and after the eruption and the airborne UV differential absorption lidar (DIAL) system after the eruption are compared with Stratospheric Aerosol and Gas Experiment II (SAGE II) measurements from several years before the eruption and ECC sonde measurements from the year prior to the eruption to determine the resulting changes. Ozone decreases of up to 33 % compared with SAGE II climatological values were found to be directly correlated with altitude regions of enhanced aerosol loading in the 16- to 28-km range. A maximum partial-column decrease of 29 +/- Dobson units (DU) was found over the 16- to 28-km range in September 1991 along with small increases (to 5.9 +/- 2 DU) from 28 to 31.5 km. A large decrease of ozone was also found at 4 deg to 8 deg S from May to August 1992, with a maximum decrease of 33 +/- 7 DU found above Brazzaville in July. Aerosol data form the visible channel of the advanced very high resolution radiometer (AVHRR) and the visible wavelength of the UV DIAL system were used to examine the relationship between aerosol (surface area) densities and ozone changes. The tropical stratospheric ozone changes we observed in 1991 and 1992 are likely be explained by a combination of dynamical (vertical transport) perturbations, radiative perturbations on ozone photochemistry, and heterogeneous chemistry.

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.

Aerosolization and Atmospheric Transformation of Engineered Nanoparticles

NASA Astrophysics Data System (ADS)

Tiwari, Andrea J.

While research on the environmental impacts of engineered nanoparticles (ENPs) is growing, the potential for them to be chemically transformed in the atmosphere has been largely ignored. The overall objective of this work was to assess the atmospheric transformation of carbonaceous nanoparticles (CNPs). The research focuses on C60 fullerene because it is an important member of the carbonaceous nanoparticle (CNP) family and is used in a wide variety of applications. The first specific objective was to review the potential of atmospheric transformations to alter the environmental impacts of CNPs. We described atmospheric processes that were likely to physically or chemically alter aerosolized CNPs and demonstrated their relevance to CNP behavior and toxicity in the aqueous and terrestrial environment. In order to investigate the transformations of CNP aerosols under controlled conditions, we developed an aerosolization technique that produces nano-scale aerosols without using solvents, which can alter the surface chemistry of the aerosols. We demonstrated the technique with carbonaceous (C60) and metal oxide (TiO2, CeO2) nanoparticle powders. All resulting aerosols exhibited unimodal size distributions and mode particle diameters below 100 nm. We used the new aerosolization technique to investigate the reaction between aerosolized C60 and atmospherically realistic levels of ozone (O3) in terms of reaction products, reaction rate, and oxidative stress potential. We identified C60O, C60O2, and C60O3 as products of the C60-O3 reaction. We demonstrated that the oxidative stress potential of C 60 may be enhanced by exposure to O3. We found the pseudo-first order reaction rate to be 9 x 10-6 to 2 x 10 -5 s-1, which is several orders of magnitude lower than the rate for several PAH species under comparable conditions. This research has demonstrated that a thorough understanding of atmospheric chemistry of ENPs is critical for accurate prediction of their environmental

Production of N2O5 and ClNO2 through Nocturnal Processing of Biomass-Burning Aerosol.

PubMed

Ahern, Adam T; Goldberger, Lexie; Jahl, Lydia; Thornton, Joel; Sullivan, Ryan C

2018-01-16

Biomass burning is a source of both particulate chloride and nitrogen oxides, two important precursors for the formation of nitryl chloride (ClNO 2 ), a source of atmospheric oxidants that is poorly prescribed in atmospheric models. We investigated the ability of biomass burning to produce N 2 O 5 (g) and ClNO 2 (g) through nocturnal chemistry using authentic biomass-burning emissions in a smog chamber. There was a positive relationship between the amount of ClNO 2 formed and the total amount of particulate chloride emitted and with the chloride fraction of nonrefractory particle mass. In every fuel tested, dinitrogen pentoxide (N 2 O 5 ) formed quickly, following the addition of ozone to the smoke aerosol, and ClNO 2 (g) production promptly followed. At atmospherically relevant relative humidities, the particulate chloride in the biomass-burning aerosol was rapidly but incompletely displaced, likely by the nitric acid produced largely by the heterogeneous uptake of N 2 O 5 (g). Despite this chloride acid displacement, the biomass-burning aerosol still converted on the order of 10% of reacted N 2 O 5 (g) into ClNO 2 (g). These experiments directly confirm that biomass burning is a potentially significant source of atmospheric N 2 O 5 and ClNO 2 to the atmosphere.

Review of sulfur dioxide to sulfate aerosol chemistry at Kīlauea Volcano, Hawai'i

NASA Astrophysics Data System (ADS)

Pattantyus, Andre K.; Businger, Steven; Howell, Steven G.

2018-07-01

Sulfur dioxide emissions from the Kīlauea Volcano on the island of Hawai'i and the subsequent formation of sulfate aerosols have caused a public health hazard across the state of Hawai'i since the volcano began erupting continuously in 1983. The University of Hawai'i at Mānoa began to forecast the trajectory and dispersion of emissions in 2010 to help mitigate the hazards to public health. In this paper a comprehensive review of potential conversion reactions is presented with the goal of more accurately representing the sulfur dioxide chemistry in the dispersion model. Atmospheric sulfur dioxide chemistry and major process responsible for sulfate formation are well documented in urban and industrial settings. The atmosphere in the vicinity of Kīlauea Volcano on the island of Hawai'i differs from that in previous investigations by virtue of being far removed from both urban and industrial settings in a remote, tropical marine atmosphere. Additionally, the combination of the high rate of sulfur dioxide emissions and trace gases and metals from Kīlauea Volcano creates a unique circumstance that requires a new look at potential conversion pathways to determine the dominant reactions. The theoretical analysis suggests that the dominant reaction in clear air will be between sulfur dioxide and the hydroxyl radical (0.01-5% h-1) and the dominant reaction in cloudy air involves hydrogen peroxide (3-50% s-1). Moreover, given the high SO2 emissions from the Halema'uma'u Crater vent, the oxidation of sulfur dioxide by these reactants is limited by their rate of production.

Evaluating Aerosol Process Modules within the Framework of the Aerosol Modeling Testbed

NASA Astrophysics Data System (ADS)

Fast, J. D.; Velu, V.; Gustafson, W. I.; Chapman, E.; Easter, R. C.; Shrivastava, M.; Singh, B.

2012-12-01

Factors that influence predictions of aerosol direct and indirect forcing, such as aerosol mass, composition, size distribution, hygroscopicity, and optical properties, still contain large uncertainties in both regional and global models. New aerosol treatments are usually implemented into a 3-D atmospheric model and evaluated using a limited number of measurements from a specific case study. Under this modeling paradigm, the performance and computational efficiency of several treatments for a specific aerosol process cannot be adequately quantified because many other processes among various modeling studies (e.g. grid configuration, meteorology, emission rates) are different as well. The scientific community needs to know the advantages and disadvantages of specific aerosol treatments when the meteorology, chemistry, and other aerosol processes are identical in order to reduce the uncertainties associated with aerosols predictions. To address these issues, an Aerosol Modeling Testbed (AMT) has been developed that systematically and objectively evaluates new aerosol treatments for use in regional and global models. The AMT consists of the modular Weather Research and Forecasting (WRF) model, a series testbed cases for which extensive in situ and remote sensing measurements of meteorological, trace gas, and aerosol properties are available, and a suite of tools to evaluate the performance of meteorological, chemical, aerosol process modules. WRF contains various parameterizations of meteorological, chemical, and aerosol processes and includes interactive aerosol-cloud-radiation treatments similar to those employed by climate models. In addition, the physics suite from the Community Atmosphere Model version 5 (CAM5) have also been ported to WRF so that they can be tested at various spatial scales and compared directly with field campaign data and other parameterizations commonly used by the mesoscale modeling community. Data from several campaigns, including the 2006

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).

Climatological simulations of ozone and atmospheric aerosols in the Greater Cairo region

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

Steiner, A. L.; Tawfik, A. B.; Shalaby, A.

An integrated chemistry-climate model (RegCM4-CHEM) simulates present-day climate, ozone and tropospheric aerosols over Egypt with a focus on Greater Cairo (GC) region. The densley populated GC region is known for its severe air quality issues driven by high levels of anthropogenic pollution in conjuction with natural sources such as dust and agricultural burning events. We find that current global emission inventories underestimate key pollutants such as nitrogen oxides and anthropogenic aerosol species. In the GC region, average-ground-based NO2 observations of 40-60 ppb are substantially higher than modeled estimates (5-10 ppb), likely due to model grid resolution, improper boundary layer representation,more » and poor emissions inventories. Observed ozone concentrations range from 35 ppb (winter) to 80 ppb (summer). The model reproduces the seasonal cycle fairly well, but modeled summer ozone is understimated by approximately 15 ppb and exhibits little interannual variability. For aerosols, springtime dust events dominate the seasonal aerosol cycle. The chemistry-climate model captures the springtime peak aerosol optical depth (AOD) of 0.7-1 but is slightly greater than satellite-derived AOD. Observed AOD decreases in the summer and increases again in the fall due to agricultural burning events in the Nile Delta, yet the model underestimates this fall observed AOD peak, as standard emissions inventories underestimate this burning and the resulting aerosol emissions. Our comparison of modeled gas and particulate phase atmospheric chemistry in the GC region indicates that improved emissions inventories of mobile sources and other anthropogenic activities are needed to improve air quality simulations in this region.« less

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

PubMed Central

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

2013-01-01

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

Speciation of iron in ambient aerosol and cloudwater

NASA Astrophysics Data System (ADS)

Siefert, Ronald Lyn

1997-03-01

Atmospheric iron (Fe) is thought to play an important role in cloudwater chemistry (e.g., S(IV) oxidation, oxidant production, etc.), and is also an important source of Fe to certain regions of the world's oceans where Fe is believed to be a rate-limiting nutrient for primary productivity. This thesis focuses on understanding the chemistry, speciation and abundance of Fe in cloudwater and aerosol in the troposphere, through observations of Fe speciation in the cloudwater and aerosol samples collected over the continental United States and the Arabian Sea. Different chemical species of atmospheric Fe were measured in aerosol and cloudwater samples to help assess the role of Fe in cloudwater chemistry. Chapter 2 presents a set of experiments which used ambient aerosol samples suspended in aqueous solution and then irradiated with uv-light to simulate cloudwater conditions. These experiments found Fe to be a critical component for the production of H2O2. Chapter 3 discusses the development and application of a novel photochemical extraction method for the determination of photochemically-available Fe in ambient aerosol samples. Photochemically-available Fe ranged from <4 ng m-3 to 308 ng m-3, and accounted for 2.8% to 100% of the total Fe in aerosol samples collected in California and New York. Calculations based on the results of these experiments predicted that redox reactions of Fe in cloudwater could be an important in situ source of oxidants (ċOH, HO2ċ/O2/cdot/sb- ). Chapter 4 presents results of several field studies which measured the redox states of Fe and other transition metals (Mn, Cu and Cr) in cloudwater. These measurements were then used in thermodynamic models which predicted Fe(III) to be either as Fe(III)-hydroxy species or Fe(III)-oxalate species. However, an unidentified strong chelating ligand with Fe(III) was also suggested by the thermodynamic model results. Chapter 5 presents results of a field study conducted on the Arabian Sea. Total

Microphysical processes affecting stratospheric aerosol particles

NASA Technical Reports Server (NTRS)

Hamill, P.; Toon, O. B.; Kiang, C. S.

1977-01-01

Physical processes which affect stratospheric aerosol particles include nucleation, condensation, evaporation, coagulation and sedimentation. Quantitative studies of these mechanisms to determine if they can account for some of the observed properties of the aerosol are carried out. It is shown that the altitude range in which nucleation of sulfuric acid-water solution droplets can take place corresponds to that region of the stratosphere where the aerosol is generally found. Since heterogeneous nucleation is the dominant nucleation mechanism, the stratospheric solution droplets are mainly formed on particles which have been mixed up from the troposphere or injected into the stratosphere by volcanoes or meteorites. Particle growth by heteromolecular condensation can account for the observed increase in mixing ratio of large particles in the stratosphere. Coagulation is important in reducing the number of particles smaller than 0.05 micron radius. Growth by condensation, applied to the mixed nature of the particles, shows that available information is consistent with ammonium sulfate being formed by liquid phase chemical reactions in the aerosol particles. The upper altitude limit of the aerosol layer is probably due to the evaporation of sulfuric acid aerosol particles, while the lower limit is due to mixing across the tropopause.

Aerosols from fires: an examination of the effects on ozone photochemistry in the Western United States.

PubMed

Jiang, Xiaoyan; Wiedinmyer, Christine; Carlton, Annmarie G

2012-11-06

This study presents a first attempt to investigate the roles of fire aerosols in ozone (O(3)) photochemistry using an online coupled meteorology-chemistry model, the Weather Research and Foresting model with Chemistry (WRF-Chem). Four 1-month WRF-Chem simulations for August 2007, with and without fire emissions, were carried out to assess the sensitivity of O(3) predictions to the emissions and subsequent radiative feedbacks associated with large-scale fires in the Western United States (U.S.). Results show that decreases in planetary boundary layer height (PBLH) resulting from the radiative effects of fire aerosols and increases in emissions of nitrogen oxides (NO(x)) and volatile organic compounds (VOCs) from the fires tend to increase modeled O(3) concentrations near the source. Reductions in downward shortwave radiation reaching the surface and surface temperature due to fire aerosols cause decreases in biogenic isoprene emissions and J(NO(2)) photolysis rates, resulting in reductions in O(3) concentrations by as much as 15%. Thus, the results presented in this study imply that considering the radiative effects of fire aerosols may reduce O(3) overestimation by traditional photochemical models that do not consider fire-induced changes in meteorology; implementation of coupled meteorology-chemistry models are required to simulate the atmospheric chemistry impacted by large-scale fires.

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

Investigation of the relative fine and coarse mode aerosol loadings and properties in the Southern Arabian Gulf region

NASA Astrophysics Data System (ADS)

Kaku, Kathleen C.; Reid, Jeffrey S.; Reid, Elizabeth A.; Ross-Langerman, Kristy; Piketh, Stuart; Cliff, Steven; Al Mandoos, Abdulla; Broccardo, Stephen; Zhao, Yongjing; Zhang, Jianglong; Perry, Kevin D.

2016-03-01

The aerosol chemistry environment of the Arabian Gulf region is extraordinarily complex, with high concentrations of dust aerosols from surrounding deserts mixed with anthropogenic aerosols originating from a large petrochemical industry and pockets of highly urbanized areas. Despite the high levels of aerosols experienced by this region, little research has been done to explore the chemical composition of both the anthropogenic and mineral dust portion of the aerosol burden. The intensive portion of the United Arab Emirates Unified Aerosol Experiment (UAE2), conducted during August and September 2004 was designed in part to resolve the aerosol chemistry through the use of multiple size-segregated aerosol samplers. The coarse mode mass (derived by subtracting the PM2.5 aerosol mass from the PM10 mass) is largely dust at 76% ± 7% of the total coarse mode mass, but is significantly impacted by anthropogenic pollution, primarily sulfate and nitrate. The PM2.5 aerosol mass also contains a large dust burden, at 38% ± 26%, but the anthropogenic component dominates. The total aerosol burden has significant impact not only on the atmosphere, but also the local population, as the air quality levels for both the PM10 and PM2.5 aerosol masses reached unhealthy levels for 24% of the days sampled.

Spatiotemporal variability and contribution of different aerosol types to the Aerosol Optical Depth over the Eastern Mediterranean.

PubMed

Georgoulias, Aristeidis K; Alexandri, Georgia; Kourtidis, Konstantinos A; Lelieveld, Jos; Zanis, Prodromos; Pöschl, Ulrich; Levy, Robert; Amiridis, Vassilis; Marinou, Eleni; Tsikerdekis, Athanasios

2016-01-01

This study characterizes the spatiotemporal variability and relative contribution of different types of aerosols to the Aerosol Optical Depth (AOD) over the Eastern Mediterranean as derived from MODIS Terra (3/2000-12/2012) and Aqua (7/2002-12/2012) satellite instruments. For this purpose, a 0.1° × 0.1° gridded MODIS dataset was compiled and validated against sunphotometric observations from the AErosol RObotic NETwork (AERONET). The high spatial resolution and long temporal coverage of the dataset allows for the determination of local hot spots like megacities, medium sized cities, industrial zones, and power plant complexes, seasonal variabilities, and decadal averages. The average AOD at 550 nm (AOD 550 ) for the entire region is ~ 0.22 ± 0.19 with maximum values in summer and seasonal variabilities that can be attributed to precipitation, photochemical production of secondary organic aerosols, transport of pollution and smoke from biomass burning in Central and Eastern Europe, and transport of dust from the Sahara Desert and the Middle East. The MODIS data were analyzed together with data from other satellite sensors, reanalysis projects and a chemistry-aerosol-transport model using an optimized algorithm tailored for the region and capable of estimating the contribution of different aerosol types to the total AOD 550 . The spatial and temporal variability of anthropogenic, dust and fine mode natural aerosols over land and anthropogenic, dust and marine aerosols over the sea is examined. The relative contribution of the different aerosol types to the total AOD 550 exhibits a low/high seasonal variability over land/sea areas, respectively. Overall, anthropogenic aerosols, dust and fine mode natural aerosols account for ~ 51 %, ~ 34 % and ~ 15 % of the total AOD 550 over land, while, anthropogenic aerosols, dust and marine aerosols account ~ 40 %, ~ 34 % and ~ 26 % of the total AOD 550 over the sea, based on MODIS Terra and Aqua observations.

The Influence of Particle Charge on Heterogeneous Reaction Rate Coefficients

NASA Technical Reports Server (NTRS)

Aikin, A. C.; Pesnell, W. D.

2000-01-01

The effects of particle charge on heterogeneous reaction rates are presented. Many atmospheric particles, whether liquid or solid are charged. This surface charge causes a redistribution of charge within a liquid particle and as a consequence a perturbation in the gaseous uptake coefficient. The amount of perturbation is proportional to the external potential and the square of the ratio of debye length in the liquid to the particle radius. Previous modeling has shown how surface charge affects the uptake coefficient of charged aerosols. This effect is now included in the heterogeneous reaction rate of an aerosol ensemble. Extension of this analysis to ice particles will be discussed and examples presented.

Response of heterogeneous vegetation to aerosol radiative forcing over a northeast Indian station.

PubMed

Latha, R; Vinayak, B; Murthy, B S

2018-01-15

Importance of atmospheric aerosols through direct and indirect effects on hydrological cycle is highlighted through multiple studies. This study tries to find how much the aerosols can affect evapo-transpiration (ET), a key component of the hydrological cycle over high NDVI (normalized difference vegetation index)/dense canopy, over Dibrugarh, known for vast tea plantation. The radiative effects of aerosols are calculated using satellite (Terra-MODIS) and reanalysis data on daily and monthly scales. Aerosol optical depth (AOD) obtained from satellite and ground observations compares well. Aerosol radiative forcing (ARF), calculated using MERRA data sets of 'clean-clear radiation' and 'clear-radiation' at the surface, shows a lower forcing efficiency, 35 Wm -zs , that is about half of that of ground observations. As vegetation controls ET over high NDVI area to the maximum and that gets modified through ARF, a regression equation is fitted between ET, AOD and NDVI for this station as ET = 0.25 + (-84.27) × AOD + (131.51) × NDVI that explains 82% of 'daily' ET variation using easily available satellite data. ET is found to follow net radiation closely and the direct relation between soil moisture and ET is weak on daily scale over this station as it may be acting through NDVI. Copyright © 2017 Elsevier Ltd. All rights reserved.

Gas uptake and chemical aging of semisolid organic aerosol particles

PubMed Central

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

2011-01-01

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

Heavy Ion Formation in Titan's Ionosphere: Magnetospheric Introduction of Free Oxygen and Source of Titan's Aerosols?

NASA Technical Reports Server (NTRS)

Sittler, E. C., Jr.; Hartle, R. E.; Cooper, J. F.; Johnson, R. E.; Coates, A.; dePater, imke; Strom, Daphne; Simoes, F.; Steele, A.; Robb, F.

2007-01-01

With the recent discovery of heavy ions, positive and negative, by the Cassini Plasma Spectrometer (CAPS) instrument in Titan's ionosphere, it reveals new possibilities for aerosol formation at Titan and the introduction of free oxygen to the aerosol chemistry from Saturn's magnetosphere with Enceladus as the primary oxygen source. One can estimate whether the heavy ions in the ionosphere are of sufficient number to account for all the aerosols, under what conditions are favorable for heavy ion formation and how they are introduced as seed particles deeper in Titan's atmosphere where the aerosols form and eventually find themselves on Titan's surface where unknown chemical processes can take place. Finally, what are the possibilities with regard to their chemistry on the surface with some free oxygen present in their seed particles?

The ion chemistry, seasonal cycle, and sources of PM 2.5 and TSP aerosol in Shanghai

NASA Astrophysics Data System (ADS)

Wang, Ying; Zhuang, Guoshun; Zhang, Xingying; Huang, Kan; Xu, Chang; Tang, Aohan; Chen, Jianmin; An, Zhisheng

Daily total suspended particulate (TSP), particle size smaller than 100 μm and particle size smaller than 2.5 μm (PM 2.5) aerosol samples were collected at two sites in Shanghai in four seasons from September 2003 to January 2005. Concentrations of the water-soluble ions (SO 42-, NO 3-, Cl -, F -, PO 43-, HCOO -, CH 3COO -, NO 2-, MSA, C 2O 42-, NH 4+, Ca 2+, Na +, K +, Mg 2+) were measured for a total of 202 samples. Daily TSP and PM 2.5 mass concentrations ranged from 66.1 to 666.8 μg m -3 and 17.8 to 217.9 μg m -3, with annual average concentrations of 230.5 and 94.6 μg m -3, respectively. The sum of ions contributed an average of 26% and 32% of TSP and PM 2.5 mass concentrations, respectively. In PM 2.5, the concentration of the major ions followed the order of SO 42->NO 3->NH 4+>Cl ->Ca 2+>K +, while in TSP was SO 42->NO 3->Cl ->Ca 2+>NH 4+>Na +. These major ions were mainly in the form of (NH 4) 2SO 4, Ca(NO 3) 2, CaCl 2, and CaSO 4 in aerosol particles. The aerosol was slightly acidic in the fine particle size range, and alkaline in the coarse mode. Seasonal variation of ion concentrations was significant, with the highest concentrations observed in winter and spring and the lowest in summer and autumn. Three types of air masses, i.e. marine, mixing, and continental, were frequently observed, and their distribution in four seasons might result in the clear seasonal variation. It is Shanghai that has the highest NO 3-/SO 42- value among all of those cities in China, indicating that as the biggest city in China the mobile source of the air pollution becomes more and more predominant. However, stationary emissions were still the dominant source in Shanghai indicated by the NO 3-/SO 42- ratio of lower than 1. The formation of NO 3- was largely from the gas-phase photochemical reaction in the cold season, and from the heterogeneous reaction in the warm season, while the formation of SO 42- might be from the heterogeneous reaction in the entire year round. NH

Modelling heterogeneous ice nucleation on mineral dust and soot with parameterizations based on laboratory experiments

NASA Astrophysics Data System (ADS)

Hoose, C.; Hande, L. B.; Mohler, O.; Niemand, M.; Paukert, M.; Reichardt, I.; Ullrich, R.

2016-12-01

Between 0 and -37°C, ice formation in clouds is triggered by aerosol particles acting as heterogeneous ice nuclei. At lower temperatures, heterogeneous ice nucleation on aerosols can occur at lower supersaturations than homogeneous freezing of solutes. In laboratory experiments, the ability of different aerosol species (e.g. desert dusts, soot, biological particles) has been studied in detail and quantified via various theoretical or empirical parameterization approaches. For experiments in the AIDA cloud chamber, we have quantified the ice nucleation efficiency via a temperature- and supersaturation dependent ice nucleation active site density. Here we present a new empirical parameterization scheme for immersion and deposition ice nucleation on desert dust and soot based on these experimental data. The application of this parameterization to the simulation of cirrus clouds, deep convective clouds and orographic clouds will be shown, including the extension of the scheme to the treatment of freezing of rain drops. The results are compared to other heterogeneous ice nucleation schemes. Furthermore, an aerosol-dependent parameterization of contact ice nucleation is presented.

Effect of Dust and Anthropogenic Aerosols on Columnar Aerosol Optical Properties over Darjeeling (2200 m asl), Eastern Himalayas, India

PubMed Central

Chatterjee, Abhijit; Ghosh, Sanjay K.; Adak, Anandamay; Singh, Ajay K.; Devara, Panuganti C. S.; Raha, Sibaji

2012-01-01

Background The loading of atmospheric particulate matter (aerosol) in the eastern Himalaya is mainly regulated by the locally generated anthropogenic aerosols from the biomass burning and by the aerosols transported from the distance sources. These different types of aerosol loading not only affect the aerosol chemistry but also produce consequent signature on the radiative properties of aerosol. Methodology/Principal Findings An extensive study has been made to study the seasonal variations in aerosol components of fine and coarse mode aerosols and black carbon along with the simultaneous measurements of aerosol optical depth on clear sky days over Darjeeling, a high altitude station (2200 masl) at eastern Himalayas during the year 2008. We observed a heavy loading of fine mode dust component (Ca2+) during pre-monsoon (Apr – May) which was higher by 162% than its annual mean whereas during winter (Dec – Feb), the loading of anthropogenic aerosol components mainly from biomass burning (fine mode SO4 2− and black carbon) were higher (76% for black carbon and 96% for fine mode SO4 2−) from their annual means. These high increases in dust aerosols during pre-monsoon and anthropogenic aerosols during winter enhanced the aerosol optical depth by 25 and 40%, respectively. We observed that for every 1% increase in anthropogenic aerosols, AOD increased by 0.55% during winter whereas for every 1% increase in dust aerosols, AOD increased by 0.46% during pre-monsoon. Conclusion/Significance The natural dust transport process (during pre-monsoon) plays as important a role in the radiation effects as the anthropogenic biomass burning (during winter) and their differential effects (rate of increase of the AOD with that of the aerosol concentration) are also very similar. This should be taken into account in proper modeling of the atmospheric environment over eastern Himalayas. PMID:22792264

Effect of dust and anthropogenic aerosols on columnar aerosol optical properties over Darjeeling (2200 m asl), eastern Himalayas, India.

PubMed

Chatterjee, Abhijit; Ghosh, Sanjay K; Adak, Anandamay; Singh, Ajay K; Devara, Panuganti C S; Raha, Sibaji

2012-01-01

The loading of atmospheric particulate matter (aerosol) in the eastern Himalaya is mainly regulated by the locally generated anthropogenic aerosols from the biomass burning and by the aerosols transported from the distance sources. These different types of aerosol loading not only affect the aerosol chemistry but also produce consequent signature on the radiative properties of aerosol. An extensive study has been made to study the seasonal variations in aerosol components of fine and coarse mode aerosols and black carbon along with the simultaneous measurements of aerosol optical depth on clear sky days over Darjeeling, a high altitude station (2200 masl) at eastern Himalayas during the year 2008. We observed a heavy loading of fine mode dust component (Ca(2+)) during pre-monsoon (Apr-May) which was higher by 162% than its annual mean whereas during winter (Dec-Feb), the loading of anthropogenic aerosol components mainly from biomass burning (fine mode SO(4)(2-) and black carbon) were higher (76% for black carbon and 96% for fine mode SO(4)(2-)) from their annual means. These high increases in dust aerosols during pre-monsoon and anthropogenic aerosols during winter enhanced the aerosol optical depth by 25 and 40%, respectively. We observed that for every 1% increase in anthropogenic aerosols, AOD increased by 0.55% during winter whereas for every 1% increase in dust aerosols, AOD increased by 0.46% during pre-monsoon. The natural dust transport process (during pre-monsoon) plays as important a role in the radiation effects as the anthropogenic biomass burning (during winter) and their differential effects (rate of increase of the AOD with that of the aerosol concentration) are also very similar. This should be taken into account in proper modeling of the atmospheric environment over eastern Himalayas.

The physico-chemical evolution of atmospheric aerosols and the gas-particle partitioning of inorganic aerosol during KORUS-AQ

NASA Astrophysics Data System (ADS)

Lee, T.; Park, T.; Lee, J. B.; Lim, Y. J.; Ahn, J.; Park, J. S.; Soo, C. J.; Desyaterik, Y.; Collett, J. L., Jr.

2017-12-01

Aerosols influence climate change directly by scattering and absorption and indirectly by acting as cloud condensation nuclei and some of the effects of aerosols are reduction in visibility, deterioration of human health, and deposition of pollutants to ecosystems. Urban area is large source of aerosols and aerosol precursors. Aerosol sources are both local and from long-range transport. Long-range transport processed aerosol are often dominant sources of aerosol pollution in Korea. To improve our knowledge of aerosol chemistry, Korea and U.S-Air Quality (KORUS-AQ) of Aircraft-based aerosol measurement took place in and around Seoul, Korea during May and June 2016. KORUS-AQ campaigns were conducted to study the chemical characterization and processes of pollutants in the Seoul Metropolitan area to regional scales of Korean peninsula. Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed on aircraft platforms on-board DC-8 (NASA) aircraft. We characterized aerosol chemical properties and mass concentrations of sulfate, nitrate, ammonium and organics in polluted air plumes and investigate the spatial and vertical distribution of the species. The results of studies show that organics is predominant in Aerosol and a significant fraction of the organics is oxygenated organic aerosol (OOA) at the high altitude. Both Nitrate and sulfate can partition between the gas and particle phases. The ratios for HNO3/(N(V) (=gaseous HNO3 + particulate Nitrate) and SO2/(SO2+Sulfate) were found to exhibit quite different distributions between the particles and gas phase for the locations during KORUS-AQ campaign, representing potential for formation of additional particulate nitrate and sulfate. The results of those studies can provide highly resolved temporal and spatial air pollutant, which are valuable for air quality model input parameters for aerosol behaviour.

Aerosol data assimilation in the chemical transport model MOCAGE during the TRAQA/ChArMEx campaign: aerosol optical depth

NASA Astrophysics Data System (ADS)

Sič, Bojan; El Amraoui, Laaziz; Piacentini, Andrea; Marécal, Virginie; Emili, Emanuele; Cariolle, Daniel; Prather, Michael; Attié, Jean-Luc

2016-11-01

In this study, we describe the development of the aerosol optical depth (AOD) assimilation module in the chemistry transport model (CTM) MOCAGE (Modèle de Chimie Atmosphérique à Grande Echelle). Our goal is to assimilate the spatially averaged 2-D column AOD data from the National Aeronautics and Space Administration (NASA) Moderate-resolution Imaging Spectroradiometer (MODIS) instrument, and to estimate improvements in a 3-D CTM assimilation run compared to a direct model run. Our assimilation system uses 3-D-FGAT (first guess at appropriate time) as an assimilation method and the total 3-D aerosol concentration as a control variable. In order to have an extensive validation dataset, we carried out our experiment in the northern summer of 2012 when the pre-ChArMEx (CHemistry and AeRosol MEditerranean EXperiment) field campaign TRAQA (TRAnsport à longue distance et Qualité de l'Air dans le bassin méditerranéen) took place in the western Mediterranean basin. The assimilated model run is evaluated independently against a range of aerosol properties (2-D and 3-D) measured by in situ instruments (the TRAQA size-resolved balloon and aircraft measurements), the satellite Spinning Enhanced Visible and InfraRed Imager (SEVIRI) instrument and ground-based instruments from the Aerosol Robotic Network (AERONET) network. The evaluation demonstrates that the AOD assimilation greatly improves aerosol representation in the model. For example, the comparison of the direct and the assimilated model run with AERONET data shows that the assimilation increased the correlation (from 0.74 to 0.88), and reduced the bias (from 0.050 to 0.006) and the root mean square error in the AOD (from 0.12 to 0.07). When compared to the 3-D concentration data obtained by the in situ aircraft and balloon measurements, the assimilation consistently improves the model output. The best results as expected occur when the shape of the vertical profile is correctly simulated by the direct model. We

Tropospheric Aerosols

NASA Astrophysics Data System (ADS)

Buseck, P. R.; Schwartz, S. E.

2003-12-01

within the atmosphere. Therefore, the few existing approaches to chemical transformation and aerosol evolution rest heavily on assumptions, for example, that particles are adequately represented as spheres and are homogeneous in composition as a function of particle size, although both assumptions are known to be inaccurate (e.g., Buseck and Pósfai, 1999; Buseck et al., 2002).This chapter provides an overview of the loading, geographical distribution, and chemical and physical properties of both natural and anthropogenic atmospheric aerosols and of the processes controlling their production, reaction, transport, and ultimate removal - the "life cycle" of tropospheric aerosols. More detailed treatment may be found in texts by Junge (1963), Friedlander (1977), Twomey (1977), Hinds (1982, 1999), Seinfeld and Pandis (1998), and Jacob (1999). We highlight here the effects of aerosols on climate. The effects of aerosols on health, visibility, heterogeneous chemistry, and ozone are examined by Heintzenberg et al. (2003), Jacob (2000), Kreidenweis (1995), Anastasio and Martin (2001), Pósfai and Molnár (2000), and Prospero et al. (2002). A detailed overview of tropospheric aerosols and their environmental effects is given by EPA (2002). Kaufman et al. (2002) provide an overview of satellite measurement of aerosols pertinent to climate change.

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

Spatial and temporal variations of aerosols around Beijing in summer 2006: 2. Local and column aerosol optical properties

NASA Astrophysics Data System (ADS)

Matsui, H.; Koike, M.; Kondo, Y.; Takegawa, N.; Fast, J. D.; PöSchl, U.; Garland, R. M.; Andreae, M. O.; Wiedensohler, A.; Sugimoto, N.; Zhu, T.

2010-11-01

Model calculations were conducted using the Weather Research and Forecasting model coupled with chemistry (WRF-chem) for the region around Beijing, China, in the summer of 2006, when the CAREBeijing-2006 intensive campaign was conducted. In this paper, we interpret aerosol optical properties in terms of aerosol mass concentrations and their chemical compositions by linking model calculations with measurements. The model calculations generally captured the observed variability of various surface and column aerosol optical parameters in and around Beijing. At the surface, the spatial and temporal variations of aerosol absorption and scattering coefficients corresponded well to those of elemental carbon and sulfate mass concentrations, respectively, and were controlled by local-scale (<100 km and <24 hours) and regional-scale (<500 km and <3 days) emissions, respectively. The contribution of secondary aerosols and their water uptake increased with altitude within the planetary boundary layer. This variation led to a considerable increase in column aerosol optical depth and was responsible for the differences in regional and temporal variations between surface and column aerosol optical properties around Beijing. These processes are expected to be common in other megacity regions as well. Model calculations, however, underestimated or overestimated the absolute levels of aerosol optical properties in and around Beijing by up to 60%. Sensitivity studies showed that these discrepancies were mostly due to the uncertainties in aerosol mixing state and aerosol density (affecting mass extinction efficiency) in the model calculations. Good agreement with measurements is achieved when these aerosol properties are accurately predicted or assumed; however, significant bias can result when these properties are inadequately treated, even if total aerosol mass concentrations are reproduced well in the model calculations.

Increasing aeolian dust deposition to snowpacks in the Rocky Mountains inferred from snowpack, wet deposition, and aerosol chemistry

USGS Publications Warehouse

Clow, David W.; Williams, Mark W.; Schuster, Paul F.

2016-01-01

Mountain snowpacks are a vital natural resource for ∼1.5 billion people in the northern Hemisphere, helping to meet human and ecological demand for water in excess of that provided by summer rain. Springtime warming and aeolian dust deposition accelerate snowmelt, increasing the risk of water shortages during late summer, when demand is greatest. While climate networks provide data that can be used to evaluate the effect of warming on snowpack resources, there are no established regional networks for monitoring aeolian dust deposition to snow. In this study, we test the hypothesis that chemistry of snow, wet deposition, and aerosols can be used as a surrogate for dust deposition to snow. We then analyze spatial patterns and temporal trends in inferred springtime dust deposition to snow across the Rocky Mountains, USA, for 1993–2014. Geochemical evidence, including strong correlations (r2 ≥ 0.94) between Ca2+, alkalinity, and dust concentrations in snow deposited during dust events, indicate that carbonate minerals in dust impart a strong chemical signature that can be used to track dust deposition to snow. Spatial patterns in chemistry of snow, wet deposition, and aerosols indicate that dust deposition increases from north to south in the Rocky Mountains, and temporal trends indicate that winter/spring dust deposition increased by 81% in the southern Rockies during 1993–2014. Using a multivariate modeling approach, we determined that increases in dust deposition and decreases in springtime snowfall combined to accelerate snowmelt timing in the southern Rockies by approximately 7–18 days between 1993 and 2014. Previous studies have shown that aeolian dust emissions may have doubled globally during the 20th century, possibly due to drought and land-use change. Climate projections for increased aridity in the southwestern U.S., northern Africa, and other mid-latitude regions of the northern Hemisphere suggest that aeolian dust emissions may continue to

Investigating expanded chemistry in CMAQ clouds

EPA Science Inventory

Clouds and fogs significantly impact the amount, composition, and spatial distribution of gas and particulate atmospheric species, not least of which through the chemistry that occurs in cloud droplets.ﾠ Atmospheric sulfate is an important component of fine aerosol mass an...

A new chemistry option in WRF/Chem v. 3.4 for the simulation of direct and indirect aerosol effects using VBS: evaluation against IMPACT-EUCAARI data

NASA Astrophysics Data System (ADS)

Tuccella, P.; Curci, G.; Grell, G. A.; Visconti, G.; Crumeroylle, S.; Schwarzenboeck, A.; Mensah, A. A.

2015-02-01

A parameterization for secondary organic aerosol (SOA) production based on the volatility basis set (VBS) approach has been coupled with microphysics and radiative scheme in WRF/Chem model. The new chemistry option called "RACM/MADE/VBS" was evaluated on a cloud resolving scale against ground-based and aircraft measurements collected during the IMPACT-EUCAARI campaign, and complemented with satellite data from MODIS. The day-to-day variability and the diurnal cycle of ozone (O3) and nitrogen oxides (NOx) at the surface is captured by the model. Surface aerosol mass of sulphate (SO4), nitrate (NO3), ammonium (NH4), and organic matter (OM) is simulated with a correlation larger than 0.55. WRF/Chem captures the vertical profile of the aerosol mass in both the planetary boundary layer (PBL) and free troposphere (FT) as a function of the synoptic condition, but the model does not capture the full range of the measured concentrations. Predicted OM concentration is at the lower end of the observed mass. The bias may be attributable to the missing aqueous chemistry processes of organic compounds, the uncertainties in meteorological fields, the assumption on the deposition velocity of condensable organic vapours, and the uncertainties in the anthropogenic emissions of primary organic carbon. Aerosol particle number concentration (condensation nuclei, CN) is overestimated by a factor 1.4 and 1.7 within PBL and FT, respectively. Model bias is most likely attributable to the uncertainties of primary particle emissions (mostly in the PBL) and to the nucleation rate. The overestimation of simulated cloud condensation nuclei (CCN) is more contained with respect to that of CN. The CCN efficiency, which is a measure of the ability of aerosol particles to nucleate cloud droplets, is underestimated by a factor of 1.5 and 3.8 in the PBL and FT, respectively. The comparison with MODIS data shows that the model overestimates the aerosol optical thickness (AOT). The domain averages (for

Untangling the Chemical Evolution of Titan's Atmosphere and Surface -- From Homogeneous to Heterogeneous Chemistry

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

Kaiser, Ralf I.; Maksyutenko, Pavlo; Ennis, Courtney

The arrival of the Cassini-Huygens probe at Saturn's moon Titan - the only Solar System body besides Earth and Venus with a solid surface and a thick atmosphere with a pressure of 1.4 atm at surface level - in 2004 opened up a new chapter in the history of Solar System exploration. The mission revealed Titan as a world with striking Earth-like landscapes involving hydrocarbon lakes and seas as well as sand dunes and lava-like features interspersed with craters and icy mountains of hitherto unknown chemical composition. The discovery of a dynamic atmosphere and active weather system illustrates further themore » similarities between Titan and Earth. The aerosol-based haze layers, which give Titan its orange-brownish color, are not only Titan's most prominent optically visible features, but also play a crucial role in determining Titan's thermal structure and chemistry. These smog-like haze layers are thought to be very similar to those that were present in Earth's atmosphere before life developed more than 3.8 billion years ago, absorbing the destructive ultraviolet radiation from the Sun, thus acting as 'prebiotic ozone' to preserve astrobiologically important molecules on Titan. Compared to Earth, Titan's low surface temperature of 94 K and the absence of liquid water preclude the evolution of biological chemistry as we know it. Exactly because of these low temperatures, Titan provides us with a unique prebiotic 'atmospheric laboratory' yielding vital clues - at the frozen stage - on the likely chemical composition of the atmosphere of the primitive Earth. However, the underlying chemical processes, which initiate the haze formation from simple molecules, have been not understood well to date.« less

Radiative and Chemical Response to Interactive Stratospheric Sulfate Aerosols in Fully Coupled CESM1(WACCM)

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

Mills, Mike; Richter, Jadwiga; Tilmes, S.

2017-11-06

We present a new version of the Community Earth System Model, version 1 (CESM1) with the Whole Atmosphere Community Climate Model (WACCM) featuring numerous improvements that are unique among earth system models. Improved horizontal resolution, dynamics, and chemistry now provide the development of an internally generated quasi-biennial oscillation, and significant improvements to temperatures and ozone throughout the stratosphere. The prognostic treatment of stratospheric sulfate aerosols is shown to represent well the evolution of stratospheric aerosol optical depth and perturbations to solar and longwave radiation following volcanic eruptions. We identify the inclusion of interactive OH chemistry as crucial to the studymore » of aerosol formation following large inputs of SO2 to the stratosphere. We show that depletion of OH levels within the dense SO2 cloud in the first weeks following the June 1991 eruption of Mt. Pinatubo significantly prolonged the e-folding decay time for SO2 oxidation to 47 days. Previous observational and model studies showing a 30-day decay time have not accounted for the large initial losses of SO2 on ash and ice in the first 7-9 days following the eruption, and have not correctly accounted for OH depletion. The completeness of the chemistry, dynamics, and aerosol microphysics in WACCM uniquely qualify it for studies of stratospheric sulfate aerosol geoengineering.« less

Isotopic constraints on heterogeneous sulfate production in Beijing haze

NASA Astrophysics Data System (ADS)

He, Pengzhen; Alexander, Becky; Geng, Lei; Chi, Xiyuan; Fan, Shidong; Zhan, Haicong; Kang, Hui; Zheng, Guangjie; Cheng, Yafang; Su, Hang; Liu, Cheng; Xie, Zhouqing

2018-04-01

Discerning mechanisms of sulfate formation during fine-particle pollution (referred to as haze hereafter) in Beijing is important for understanding the rapid evolution of haze and for developing cost-effective air pollution mitigation strategies. Here we present observations of the oxygen-17 excess of PM2.5 sulfate (Δ17O(SO42-)) collected in Beijing haze from October 2014 to January 2015 to constrain possible sulfate formation pathways. Throughout the sampling campaign, the 12-hourly averaged PM2.5 concentrations ranged from 16 to 323 µg m-3 with a mean of (141 ± 88 (1σ)) µg m-3, with SO42- representing 8-25 % of PM2.5 mass. The observed Δ17O(SO42-) varied from 0.1 to 1.6 ‰ with a mean of (0.9 ± 0.3) ‰. Δ17O(SO42-) increased with PM2.5 levels in October 2014 while the opposite trend was observed from November 2014 to January 2015. Our estimate suggested that in-cloud reactions dominated sulfate production on polluted days (PDs, PM2.5 ≥ 75 µg m-3) of Case II in October 2014 due to the relatively high cloud liquid water content, with a fractional contribution of up to 68 %. During PDs of Cases I and III-V, heterogeneous sulfate production (Phet) was estimated to contribute 41-54 % to total sulfate formation with a mean of (48 ± 5) %. For the specific mechanisms of heterogeneous oxidation of SO2, chemical reaction kinetics calculations suggested S(IV) ( = SO2 ⚫ H2O + HSO3- + SO32-) oxidation by H2O2 in aerosol water accounted for 5-13 % of Phet. The relative importance of heterogeneous sulfate production by other mechanisms was constrained by our observed Δ17O(SO42-). Heterogeneous sulfate production via S(IV) oxidation by O3 was estimated to contribute 21-22 % of Phet on average. Heterogeneous sulfate production pathways that result in zero-Δ17O(SO42-), such as S(IV) oxidation by NO2 in aerosol water and/or by O2 via a radical chain mechanism, contributed the remaining 66-73 % of Phet. The assumption about the thermodynamic state of aerosols

Modeling the global distribution of the oxygen isotopic composition of sulfate aerosols: Importance of transition metal catalyzed S(IV) oxidation chemistry

NASA Astrophysics Data System (ADS)

Alexander, B.; Park, R. J.

2006-12-01

The oxygen isotopic composition of sulfate aerosols (Δ17O ~ δ&&17O 0.5*δ18O) reflects the relative importance of different photochemical oxidation pathways in the atmosphere. Simulated isotopic variability in a global chemical transport model (GEOS-Chem) shows good agreement with observations in oceanic [Alexander et al., 2005] and some continental sites. However, a large discrepancy exists between modeled and measured isotopic composition in the high northern latitudes, reflecting an incomplete understanding of the sulfur budget in this region. Recent oxygen isotope measurements of sulfate aerosols collected at Alert, Canada suggest that transition metal catalyzed oxidation of SO2 by O2 in the aqueous-phase is significant during winter [Mc Cabe et al.,2006]. Global chemistry models ignore this oxidation pathway because it is believed to be important only regionally, and because of the large uncertainties in atmospheric metal concentrations and oxidation states. We have incorporated Fe(III) and Mn(II) catalyzed oxidation of S(IV) (S(IV) = SO2·H2O + HSO3- + SO32-) by O2 into the GEOS-Chem model using the McCabe et al. [2006] isotope measurements as a constraint. We will examine the importance of this oxidation pathway for the sulfur budget in the Arctic, and on the global scale. Preliminary results suggest that, during winter, up to 75% of aerosol sulfate at Alert forms via the metal catalysis pathway. The addition of this chemical pathway decreases the SO2 burden in the Arctic (north of 60°N) by 40% due to an increase in the oxidation rate. The comparison of large-scale sulfate aerosol models study (COSAM) showed that on average, models over-predict SO2 mixing ratios by factors of 2 or more [Barrie et al., 2001]. This "missing" S(IV) oxidation pathway can partially explain this discrepancy.

Lessons Learned About Organic Aerosol Formation in the Southeast U.S. Using Observations and Modeling

EPA Science Inventory

Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA). In this work, modeling of isoprene SOA via heterogeneous uptake is explored and compared to observations from the Southern Oxidant and Aerosol Study (SOAS).

Design and implementation of a prototype data system for earth radiation budget, cloud, aerosol, and chemistry data

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

Baum, B.A.; Barkstrom, B.R.

1993-04-01

The Earth Observing System (EOS) will collect data from a large number of satellite-borne instruments, beginning later in this decade, to make data accessible to the scientific community, NASA will build an EOS Data and Information System (EOSDIS). As an initial effort to accelerate the development of EOSDIS and to gain experience with such an information system, NASA and other agencies are working on a prototype system called Version O (VO). This effort will provide improved access to pre-EOS earth science data throughout the early EOSDIS period. Based on recommendations from the EOSDIS Science Advisory Panel, EOSDIS will have severalmore » distributed active archive centers (DAACs). Each DAAC will specialize in particular data sets. This paper describes work at the NASA Langley Research Center's (LaRC) DAAC. The Version 0 Langley DAAC began archiving and distributing existing data sets pertaining to the earth's radiation budget, clouds, aerosols, and tropospheric chemistry in late 1992. The primary goals of the LaRC VO effort are the following: (1) Enhance scientific use of existing data; (2) Develop institutional expertise in maintaining and distributing data; (3) Use institutional capability for processing data from previous missions such as the Earth Radiation Budget Experiment and the Stratospheric Aerosol and Gas Experiment to prepare for processing future EOS satellite data; (4) Encourage cooperative interagency and international involvement with data sets and research; and (5) Incorporate technological hardware and software advances quickly.« less

Assessing the Performance of Computationally Simple and Complex Representations of Aerosol Processes using a Testbed Methodology

NASA Astrophysics Data System (ADS)

Fast, J. D.; Ma, P.; Easter, R. C.; Liu, X.; Zaveri, R. A.; Rasch, P.

2012-12-01

Predictions of aerosol radiative forcing in climate models still contain large uncertainties, resulting from a poor understanding of certain aerosol processes, the level of complexity of aerosol processes represented in models, and the ability of models to account for sub-grid scale variability of aerosols and processes affecting them. In addition, comparing the performance and computational efficiency of new aerosol process modules used in various studies is problematic because different studies often employ different grid configurations, meteorology, trace gas chemistry, and emissions that affect the temporal and spatial evolution of aerosols. To address this issue, we have developed an Aerosol Modeling Testbed (AMT) to systematically and objectively evaluate aerosol process modules. The AMT consists of the modular Weather Research and Forecasting (WRF) model, a series of testbed cases for which extensive in situ and remote sensing measurements of meteorological, trace gas, and aerosol properties are available, and a suite of tools to evaluate the performance of meteorological, chemical, aerosol process modules. WRF contains various parameterizations of meteorological, chemical, and aerosol processes and includes interactive aerosol-cloud-radiation treatments similar to those employed by climate models. In addition, the physics suite from a global climate model, Community Atmosphere Model version 5 (CAM5), has also been ported to WRF so that these parameterizations can be tested at various spatial scales and compared directly with field campaign data and other parameterizations commonly used by the mesoscale modeling community. In this study, we evaluate simple and complex treatments of the aerosol size distribution and secondary organic aerosols using the AMT and measurements collected during three field campaigns: the Megacities Initiative Local and Global Observations (MILAGRO) campaign conducted in the vicinity of Mexico City during March 2006, the

The composition and variability of atmospheric aerosol over Southeast Asia during 2008

NASA Astrophysics Data System (ADS)

Trivitayanurak, W.; Palmer, P. I.; Barkley, M. P.; Robinson, N. H.; Coe, H.; Oram, D. E.

2012-01-01

We use a nested version of the GEOS-Chem global 3-D chemistry transport model to better understand the composition and variation of aerosol over Borneo and the broader Southeast Asian region in conjunction with aircraft and satellite observations. Our focus on Southeast Asia reflects the importance of this region as a source of reactive organic gases and aerosols from natural forests, biomass burning, and food and fuel crops. We particularly focus on July 2008 when the UK BAe-146 research aircraft was deployed over northern Malaysian Borneo as part of the ACES/OP3 measurement campaign. During July 2008 we find using the model that Borneo (defined as Borneo Island and the surrounding Indonesian islands) was a net exporter of primary organic aerosol (42 kT) and black carbon aerosol (11 kT). We find only 13% of volatile organic compound oxidation products partition to secondary organic aerosol (SOA), with Borneo being a net exporter of SOA (15 kT). SOA represents approximately 19% of the total organic aerosol over the region. Sulphate is mainly from aqueous-phase oxidation (68%), with smaller contributions from gas-phase oxidation (15%) and advection into the regions (14%). We find that there is a large source of sea salt, as expected, but this largely deposits within the region; we find that dust aerosol plays only a relatively small role in the aerosol burden. In contrast to coincident surface measurements over Northern Borneo that find a pristine environment with evidence for substantial biogenic SOA formation we find that the free troposphere is influenced by biomass burning aerosol transported from the northwest of the Island and further afield. We find several transport events during July 2008 over Borneo associated with elevated aerosol concentrations, none of which coincide with the aircraft flights. We use MODIS aerosol optical depths (AOD) data and the model to put the July campaign into a longer temporal perspective. We find that Borneo is where the model

Role of sucrose in the heterogeneous uptake of dimethylamine by ammonium sulfate aerosol particles

NASA Astrophysics Data System (ADS)

Chu, Y.; Chan, C. K.

2016-12-01

Alkyl amines are important alkaline gases besides ammonia in the atmosphere and widely detected in both gas and particle phases. Heterogeneous uptake by pre-existing particles containing acids as well as ammonium salts is one of the major pathways of alkyl amines partitioning into aerosols. Recently, phase state of ammonium salt particles has been revealed to largely affect the degree of alkyl amines uptake. Using an electrodynamic balance coupled with Raman spectroscopy, we extend the study by investigating the alkyl amine uptake by ammonium sulfate (AS) - sucrose mixed particles, since ambient aerosols usually consist of a mixed phase of organics and inorganics. Sucrose is a surrogate of hydrophilic viscous organics that can alter the phase of AS at low relative humidity (RH) and dimethylamine (DMA) is selected for its abundance amongst alkyl amine compounds. DMA uptake occurred effectively at not only 70% RH but also RH as low as 10%, significantly below the AS crystallization point. The net uptake coefficient decreased as RH decreased for fixed initial AS - sucrose particle compositions. Interestingly, it followed a first increasing then decreasing trend as sucrose molar fraction increased from 0 to 0.5, at RH below 30%. Sucrose, albeit inert to DMA vapor, indirectly affected the interaction between DMA and AS - sucrose particles. On one hand, it absorbed water at low RH and delayed the efflorescence of AS to promote DMA uptake. On the other hand, the particle became more viscous with higher sucrose concentration and exhibited an effective mass transport barrier. Hence, the uptake of alkyl amines may occur slowly once ammonium salts are mixed with viscous organics, such as those secondary organic materials formed via the oxidation of biogenic volatile organic compounds, in the particle phase. Acknowledgment This work is supported by Research Grants Council (RGC) of Hong Kong Special Administrative Region, China (GRF 16300214). The grant from Hong Kong RGC Ph

Balloon profiles of stratospheric NO[sub 2] and HNO[sub 3] for testing the heterogeneous hydrolysis of N[sub 2]O[sub 5] on sulfate aerosols

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

Webster, C.R.; May, R.D.; Allen, M.

1994-01-01

Simultaneous in situ measurements of stratospheric NO[sub 2], HNO[sub 3], HCl, and CH[sub 4] from 34 to 24 km were made in August 1992 from Palestine, Texas, using the Balloon-borne Laser In-Situ Sensor (BLISS) tunable diode laser spectrometer. Although the measurements of NO[sub 2], HNO[sub 3], and NO[sub 2]/HNO[sub 3] agree well with gas-phase model calculations near 34 km where SAGE II data show little sulfate aerosol, this is not true at the lower altitudes where SAGE II shows high aerosol loadings. At 24 km the BLISS NO[sub 2] and HNO[sub 3] measurements are 70% lower, and 50% higher, respectively,more » than the gas phase model predictions, with a measured NO[sub 2]/HNO[sub 3] ratio 5 times smaller. When the heterogeneous hydrolysis of N[sub 2]O[sub 5] and ClONO[sub 2] on sulfate aerosol of surface area densities matching the SAGE II measurements is added to the model, good agreement with the BLISS measurements is found over the whole altitude range. 24 refs., 4 figs., 1 tab.« less

Influences of emission sources and meteorology on aerosol chemistry in a polluted urban environment: Results from DISCOVER-AQ California

DOE PAGES

Young, Dominique E.; Kim, Hwajin; Parworth, Caroline; ...

2016-05-02

associated with residential space heating from wood combustion, and semivolatile oxygenated OA (SV-OOA; 16 % of total OA, O / C  =  0.63) and low-volatility oxygenated OA (LV-OOA; 24 % of total OA, O / C  =  0.90) formed via chemical reactions in the atmosphere. Large differences in aerosol chemistry at Fresno were observed between the current campaign (winter 2013) and a previous campaign in winter 2010, most notably that PM 1 concentrations were nearly 3 times higher in 2013 than in 2010. These variations were attributed to differences in the meteorological conditions, which influenced primary emissions and secondary aerosol formation. In particular, COA and BBOA concentrations were greater in 2013 than 2010, where colder temperatures in 2013 likely resulted in increased biomass burning activities. The influence from a nighttime formed residual layer that mixed down in the morning was found to be much more intense in 2013 than 2010, leading to sharp increases in ground-level concentrations of secondary aerosol species including nitrate, sulfate, and OOA, in the morning between 08:00 and 12:00 PST. This is an indication that nighttime chemical reactions may have played a more important role in 2013. As solar radiation was stronger in 2013 the higher nitrate and OOA concentrations in 2013 could also be partly due to greater photochemical production of secondary aerosol species. The greater solar radiation and larger range in temperature in 2013 also likely led to both SV-OOA and LV-OOA being observed in 2013 whereas only a single OOA factor was identified in 2010.« less

Influences of emission sources and meteorology on aerosol chemistry in a polluted urban environment: results from DISCOVER-AQ California

NASA Astrophysics Data System (ADS)

Young, Dominique E.; Kim, Hwajin; Parworth, Caroline; Zhou, Shan; Zhang, Xiaolu; Cappa, Christopher D.; Seco, Roger; Kim, Saewung; Zhang, Qi

2016-05-01

-OOA; 16 % of total OA, O / C = 0.63) and low-volatility oxygenated OA (LV-OOA; 24 % of total OA, O / C = 0.90) formed via chemical reactions in the atmosphere. Large differences in aerosol chemistry at Fresno were observed between the current campaign (winter 2013) and a previous campaign in winter 2010, most notably that PM1 concentrations were nearly 3 times higher in 2013 than in 2010. These variations were attributed to differences in the meteorological conditions, which influenced primary emissions and secondary aerosol formation. In particular, COA and BBOA concentrations were greater in 2013 than 2010, where colder temperatures in 2013 likely resulted in increased biomass burning activities. The influence from a nighttime formed residual layer that mixed down in the morning was found to be much more intense in 2013 than 2010, leading to sharp increases in ground-level concentrations of secondary aerosol species including nitrate, sulfate, and OOA, in the morning between 08:00 and 12:00 PST. This is an indication that nighttime chemical reactions may have played a more important role in 2013. As solar radiation was stronger in 2013 the higher nitrate and OOA concentrations in 2013 could also be partly due to greater photochemical production of secondary aerosol species. The greater solar radiation and larger range in temperature in 2013 also likely led to both SV-OOA and LV-OOA being observed in 2013 whereas only a single OOA factor was identified in 2010.

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.

Global volcanic aerosol properties derived from emissions, 1990-2014, using CESM1(WACCM): VOLCANIC AEROSOLS DERIVED FROM EMISSIONS

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

Mills, Michael J.; Schmidt, Anja; Easter, Richard

Accurate representation of global stratospheric aerosol properties from volcanic and non-volcanic sulfur emissions is key to understanding the cooling effects and ozone-loss enhancements of recent volcanic activity. Attribution of climate and ozone variability to volcanic activity is of particular interest in relation to the post-2000 slowing in the apparent rate of global average temperature increases, and variable recovery of the Antarctic ozone hole. We have developed a climatology of global aerosol properties from 1990 to 2014 calculated based on volcanic and non-volcanic emissions of sulfur sources. We have complied a database of volcanic SO2 emissions and plume altitudes for eruptionsmore » between 1990 and 2014, and a new prognostic capability for simulating stratospheric sulfate aerosols in version 5 of the Whole Atmosphere Community Climate Model, a component of the Community Earth System Model. Our climatology shows remarkable agreement with ground-based lidar observations of stratospheric aerosol optical depth (SAOD), and with in situ measurements of aerosol surface area density (SAD). These properties are key parameters in calculating the radiative and chemical effects of stratospheric aerosols. Our SAOD climatology represents a significant improvement over satellite-based analyses, which ignore aerosol extinction below 15 km, a region that can contain the vast majority of stratospheric aerosol extinction at mid- and high-latitudes. Our SAD climatology significantly improves on that provided for the Chemistry-Climate Model Initiative, which misses 60% of the SAD measured in situ. Our climatology of aerosol properties is publicly available on the Earth System Grid.« less

Size resolved fog water chemistry and its atmospheric implications

NASA Astrophysics Data System (ADS)

Chakraborty, Abhishek; Gupta, Tarun; Tripathi, Sachchida; Ervens, Barbara; Bhattu, Deepika

2015-04-01

Fog is a natural meteorological phenomenon that occurs throughout the world. It usually contains substantial quantity of liquid water and results in severe visibility reduction leading to disruption of normal life. Fog is generally seen as a natural cleansing agent but it also has the potential to form Secondary Organic Aerosol (SOA) via aqueous processing of ambient aerosols. Size- resolved fog water chemistry for inorganics were reported in previous studies but processing of organics inside the fog water and quantification of aqSOA remained a challenge. To assess the organics processing via fog aqueous processing, size resolved fog water samples were collected in two consecutive winter seasons (2012-13, 2013-14) at Kanpur, a heavily polluted urban area of India. Caltech 3 stage fog collector was used to collect the fog droplets in 3 size fraction; coarse (droplet diameter > 22 µm), medium (22> droplet diameter >16 µm) and fine (16> droplet diameter >4 µm). Collected samples were atomized into various instruments such as Aerosol Mass Spectrometer (AMS), Cloud Condensation Nucleus Counter (CCNc), Total Organic Carbon (TOC) and a thermo denuder (TD) for the physico-chemical characterization of soluble constituents. Fine droplets are found to be more enriched with different aerosol species and interestingly contain more aged and less volatile organics compared to other coarser sizes. Organics inside fine droplets have an average O/C = 0.87 compared to O/C of 0.67 and 0.74 of coarse and medium droplets. Metal chemistry and higher residence time of fine droplets are seemed to be the two most likely reasons for this outcome from as the results of a comprehensive modeling carried out on the observed data indicate. CCN activities of the aerosols from fine droplets are also much higher than that of coarse or medium droplets. Fine droplets also contain light absorbing material as was obvious from their 'yellowish' solution. Source apportionment of fog water organics via

Type of Aerosols Determination Over Malaysia by AERONET Data

NASA Astrophysics Data System (ADS)

Lim, H.; Tan, F.; Abdullah, K.; Holben, B. N.

2013-12-01

Aerosols are one of the most interesting studies by the researchers due to the complicated of their characteristic and are not yet well quantified. Besides that there still have huge uncertainties associated with changes in Earth's radiation budget. The previous study by other researchers shown a lot of difficulties and challenges in quantifying aerosol influences arise. As well as the heterogeneity from the aerosol loading and properties: spatial, temporal, size, and composition. In this study, we were investigated the aerosol characteristics over two regions with different environmental conditions and aerosol sources contributed. The study sites are Penang and Kuching, Malaysia where ground-based AErosol RObotic NETwork (AERONET) sun-photometer was deployed. The types of the aerosols for both study sites were identified by analyzing aerosol optical depth, angstrom parameter and spectral de-convolution algorithm product from sun-photometer. The analysis was carried out associated with the in-situ meteorological data of relative humidity, visibility and air pollution index. The major aerosol type over Penang found in this study was hydrophobic aerosols. Whereas the hydrophilic type of the aerosols was highly distributed in Kuching. The major aerosol size distributions for both regions were identified in this study. The result also shows that the aerosol optical properties were affected by the types and characteristic of aerosols. Therefore, in this study we generated an algorithm to determine the aerosols in Malaysia by considered the environmental factors. From this study we found that the source of aerosols should always being consider in to retrieve the accurate information of aerosol for air quality study.

Vertical structure of aerosol distribution and radiative properties over Svalbard - observations and modelling

NASA Astrophysics Data System (ADS)

Kaminski, Jacek W.; Struzewska, Joanna; Markowicz, Krzysztof; Jefimow, Maciej

2015-04-01

In the scope of the iAREA projects (Impact of absorbing aerosols on radiative forcing in the European Arctic - http://www.igf.fuw.edu.pl/iAREA) a field campaign was undertaken in March and April 2014 on Spitzbergen. Analysis of measurements was supported by the GEM-AQ model simulations. The GEM-AQ model is a chemical weather model. The core of the model is based on a weather prediction model with environmental processes (chemistry and aerosols) implanted on-line and are interactive (i.e. providing feedback of chemistry on radiation and dynamics). Numerical experiments were performed with the computational grid resolution of ˜15 km. The emission inventory developed by NILU in the ECLIPSE project was used. Preliminary analysis revealed small but systematic overestimation of modelled AOD and background BC levels. We will present the analysis of the vertical distribution of different aerosol species and its contribution to AOD for two stations on Svalbard. Also, changes of modelled chemical composition of aerosols with altitude will be analyzed.

Radiative effects of absorbing aerosols over northeastern India: Observations and model simulations

NASA Astrophysics Data System (ADS)

Gogoi, Mukunda M.; Babu, S. Suresh; Moorthy, K. Krishna; Bhuyan, Pradip Kumar; Pathak, Binita; Subba, Tamanna; Chutia, Lakhima; Kundu, Shyam Sundar; Bharali, Chandrakala; Borgohain, Arup; Guha, Anirban; De, Barin Kumar; Singh, Brajamani; Chin, Mian

2017-01-01

Multiyear measurements of spectral properties of aerosol absorption are examined over four geographically distinct locations of northeastern India. Results indicated significant spatiotemporal variation in aerosol absorption coefficients (σabs) with highest values in winter and lowest in monsoon. The western parts of the region, close to the outflow of Indo-Gangetic Plains, showed higher values of σabs and black carbon (BC) concentration—mostly associated with fossil fuel combustion. But, the eastern parts showed higher contributions from biomass-burning aerosols, as much as 20-25% to the total aerosol absorption, conspicuously during premonsoon season. This is attributed to a large number of burning activities over the Southeast Asian region, as depicted from Moderate Resolution Imaging Spectroradiometer fire count maps, whose spatial extent and magnitude peaks during March/April. The nearly consistent high values of aerosol index (AI) and layer height from Ozone Monitoring Instrument indicate the presence of absorbing aerosols in the upper atmosphere. The observed seasonality has been captured fairly well by Goddard Chemistry Aerosol Radiation and Transport (GOCART) as well as Weather Research and Forecasting-Chemistry (WRF-Chem) model simulations. The ratio of column-integrated optical depths due to particulate organic matter and BC from GOCART showed good coincidence with satellite-based observations, indicating the increased vertical dispersion of absorbing aerosols, probably by the additional local convection due to higher fire radiative power caused by the intense biomass-burning activities. In the WRF-Chem though underperformed by different magnitude in winter, the values are closer or overestimated near the burnt areas. Atmospheric forcing due to BC was highest ( 30 Wm-2) over the western part associated with the fossil fuel combustion.

Direct Observations of Isoprene Secondary Organic Aerosol Formation in Ambient Cloud Droplets

NASA Astrophysics Data System (ADS)

Zelenyuk, A.; Bell, D.; Thornton, J. A.; Fast, J. D.; Shrivastava, M. B.; Berg, L. K.; Imre, D. G.; Mei, F.; Shilling, J.; Suski, K. J.; Liu, J.; Tomlinson, J. M.; Wang, J.

2017-12-01

Multiphase chemistry of isoprene photooxidation products has been shown to be one of the major sources of secondary organic aerosol (SOA) in the atmosphere. A number of recent studies indicate that aqueous aerosol phase provides a medium for reactive uptake of isoprene photooxidation products, and in particular, isomeric isoprene epoxydiols (IEPOX), with reaction rates and yields being dependent on aerosol acidity, water content, sulfate concentration, and organic coatings. However, very few studies focused on chemistry occurring within actual cloud droplets. We will present data acquired during recent Holistic Interactions of Shallow Clouds, Aerosols, and Land Ecosystems (HI-SCALE) Campaign, which provide direct evidence for IEPOX-SOA formation in cloud droplets. Single particle mass spectrometer, miniSPLAT, and a high-resolution, time-of-flight aerosol mass spectrometer were used to characterize the composition of aerosol particles and cloud droplet residuals, while a high-resolution, time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) was used to characterize gas-phase compounds. We find that the composition of cloud droplet residuals was markedly different than that of aerosol particles sampled outside the cloud. Cloud droplet residuals were comprised of individual particles with high relative fractions of sulfate and nitrate and significant fraction of particles with mass spectra that are nearly identical to those of laboratory-generated IEPOX-SOA particles. The observed cloud-induced formation of IEPOX-SOA was accompanied by simultaneous decrease in measured concentrations of IEPOX and other gas-phase isoprene photooxidation products. Ultimately, the combined cloud, aerosol, and gas-phase measurements conducted during HI-SCALE will be used to develop and evaluate model treatments of aqueous-phase isoprene SOA formation.

Spatiotemporal variability and contribution of different aerosol types to the Aerosol Optical Depth over the Eastern Mediterranean

PubMed Central

Georgoulias, Aristeidis K.; Alexandri, Georgia; Kourtidis, Konstantinos A.; Lelieveld, Jos; Zanis, Prodromos; Pöschl, Ulrich; Levy, Robert; Amiridis, Vassilis; Marinou, Eleni; Tsikerdekis, Athanasios

2018-01-01

This study characterizes the spatiotemporal variability and relative contribution of different types of aerosols to the Aerosol Optical Depth (AOD) over the Eastern Mediterranean as derived from MODIS Terra (3/2000–12/2012) and Aqua (7/2002–12/2012) satellite instruments. For this purpose, a 0.1° × 0.1° gridded MODIS dataset was compiled and validated against sunphotometric observations from the AErosol RObotic NETwork (AERONET). The high spatial resolution and long temporal coverage of the dataset allows for the determination of local hot spots like megacities, medium sized cities, industrial zones, and power plant complexes, seasonal variabilities, and decadal averages. The average AOD at 550 nm (AOD550) for the entire region is ~ 0.22 ± 0.19 with maximum values in summer and seasonal variabilities that can be attributed to precipitation, photochemical production of secondary organic aerosols, transport of pollution and smoke from biomass burning in Central and Eastern Europe, and transport of dust from the Sahara Desert and the Middle East. The MODIS data were analyzed together with data from other satellite sensors, reanalysis projects and a chemistry-aerosol-transport model using an optimized algorithm tailored for the region and capable of estimating the contribution of different aerosol types to the total AOD550. The spatial and temporal variability of anthropogenic, dust and fine mode natural aerosols over land and anthropogenic, dust and marine aerosols over the sea is examined. The relative contribution of the different aerosol types to the total AOD550 exhibits a low/high seasonal variability over land/sea areas, respectively. Overall, anthropogenic aerosols, dust and fine mode natural aerosols account for ~ 51 %, ~ 34 % and ~ 15 % of the total AOD550 over land, while, anthropogenic aerosols, dust and marine aerosols account ~ 40 %, ~ 34 % and ~ 26 % of the total AOD550 over the sea, based on MODIS Terra and Aqua observations. PMID:29755508

Spatiotemporal variability and contribution of different aerosol types to the aerosol optical depth over the Eastern Mediterranean

NASA Astrophysics Data System (ADS)

Georgoulias, Aristeidis K.; Alexandri, Georgia; Kourtidis, Konstantinos A.; Lelieveld, Jos; Zanis, Prodromos; Pöschl, Ulrich; Levy, Robert; Amiridis, Vassilis; Marinou, Eleni; Tsikerdekis, Athanasios

2016-11-01

This study characterizes the spatiotemporal variability and relative contribution of different types of aerosols to the aerosol optical depth (AOD) over the Eastern Mediterranean as derived from MODIS (Moderate Resolution Imaging Spectroradiometer) Terra (March 2000-December 2012) and Aqua (July 2002-December 2012) satellite instruments. For this purpose, a 0.1° × 0.1° gridded MODIS dataset was compiled and validated against sun photometric observations from the AErosol RObotic NETwork (AERONET). The high spatial resolution and long temporal coverage of the dataset allows for the determination of local hot spots like megacities, medium-sized cities, industrial zones and power plant complexes, seasonal variabilities and decadal averages. The average AOD at 550 nm (AOD550) for the entire region is ˜ 0.22 ± 0.19, with maximum values in summer and seasonal variabilities that can be attributed to precipitation, photochemical production of secondary organic aerosols, transport of pollution and smoke from biomass burning in central and eastern Europe and transport of dust from the Sahara and the Middle East. The MODIS data were analyzed together with data from other satellite sensors, reanalysis projects and a chemistry-aerosol-transport model using an optimized algorithm tailored for the region and capable of estimating the contribution of different aerosol types to the total AOD550. The spatial and temporal variability of anthropogenic, dust and fine-mode natural aerosols over land and anthropogenic, dust and marine aerosols over the sea is examined. The relative contribution of the different aerosol types to the total AOD550 exhibits a low/high seasonal variability over land/sea areas, respectively. Overall, anthropogenic aerosols, dust and fine-mode natural aerosols account for ˜ 51, ˜ 34 and ˜ 15 % of the total AOD550 over land, while, anthropogenic aerosols, dust and marine aerosols account ˜ 40, ˜ 34 and ˜ 26 % of the total AOD550 over the sea, based on

Spatiotemporal Variability and Contribution of Different Aerosol Types to the Aerosol Optical Depth over the Eastern Mediterranean

NASA Technical Reports Server (NTRS)