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

Aqueous-Phase Mechanism for Secondary Organic Aerosol Formation from Isoprene: Application to the Southeast United States and Co-Benefit of SO2 Emission Controls

NASA Technical Reports Server (NTRS)

Marais, E. A.; Jacob, D. J.; Jimenez, J. L.; Campuzano-Jost, P.; Day, D. A.; Hu, W.; Krechmer, J.; Zhu, L.; Kim, P. S.; Miller, C. C.;

Effects of Precursor Concentration and Acidic Sulfate in Aqueous Glyoxal−OH Radical Oxidation and Implications for Secondary Organic Aerosol

PubMed Central

2009-01-01

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

Nighttime aqueous-phase secondary organic aerosols in Los Angeles and its implication for fine particulate matter composition and oxidative potential

NASA Astrophysics Data System (ADS)

Saffari, Arian; Hasheminassab, Sina; Shafer, Martin M.; Schauer, James J.; Chatila, Talal A.; Sioutas, Constantinos

2016-05-01

Recent investigations suggest that aqueous phase oxidation of hydrophilic organic compounds can be a significant source of secondary organic aerosols (SOA) in the atmosphere. Here we investigate the possibility of nighttime aqueous phase formation of SOA in Los Angeles during winter, through examination of trends in fine particulate matter (PM2.5) carbonaceous content during two contrasting seasons. Distinctive winter and summer trends were observed for the diurnal variation of organic carbon (OC) and secondary organic carbon (SOC), with elevated levels during the nighttime in winter, suggesting an enhanced formation of SOA during that period. The nighttime ratio of SOC to OC was positively associated with the relative humidity (RH) at high RH levels (above 70%), which is when the liquid water content of the ambient aerosol would be high and could facilitate dissolution of hydrophilic primary organic compounds into the aqueous phase. Time-integrated collection and analysis of wintertime particles at three time periods of the day (morning, 6:00 a.m.-9:00 a.m.; afternoon, 11:00 a.m.-3:00 p.m.; night, 8:00 p.m.-4:00 a.m.) revealed higher levels of water soluble organic carbon (WSOC) and organic acids during the night and afternoon periods compared to the morning period, indicating that the SOA formation in winter continues throughout the nighttime. Furthermore, diurnal trends in concentrations of semi-volatile organic compounds (SVOCs) from primary emissions showed that partitioning of SVOCs from the gas to the particle phase due to the decreased nighttime temperatures cannot explain the substantial OC and SOC increase at night. The oxidative potential of the collected particles (quantified using a biological macrophage-based reactive oxygen species assay, in addition to the dithiothreitol assay) was comparable during afternoon and nighttime periods, but higher (by at least ∼30%) compared to the morning period, suggesting that SOA formation processes possibly

Aqueous photooxidation of ambient Po Valley Italy air samples: Insights into secondary organic aerosol formation

NASA Astrophysics Data System (ADS)

Kirkland, J. R.; Lim, Y. B.; Sullivan, A. P.; Decesari, S.; Facchini, C.; Collett, J. L.; Keutsch, F. N.; Turpin, B. J.

2012-12-01

In this work, we conducted aqueous photooxidation experiments with ambient samples in order to develop insights concerning the formation of secondary organic aerosol through gas followed by aqueous chemistry (SOAaq). Water-soluble organics (e.g., glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone) are formed through gas phase oxidation of alkene and aromatic emissions of anthropogenic and biogenic origin. Their further oxidation in clouds, fogs and wet aerosols can form lower volatility products (e.g., oligomers, organic acids) that remain in the particle phase after water evaporation, thus producing SOA. The aqueous OH radical oxidation of several individual potentially important precursors has been studied in the laboratory. In this work, we used a mist-chamber apparatus to collect atmospheric mixtures of water-soluble gases from the ambient air at San Pietro Capofiume, Italy during the PEGASOS field campaign. We measured the concentration dynamics after addition of OH radicals, in order to develop new insights regarding formation of SOA through aqueous chemistry. Specifically, batch aqueous reactions were conducted with 33 ml mist-chamber samples (TOC ~ 50-100μM) and OH radicals (~10-12M) in a new low-volume aqueous reaction vessel. OH radicals were formed in-situ, continuously by H2O2 photolysis. Products were analyzed by ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS +/-), and ESI-MS with IC pre-separation (IC/ESI-MS-). Reproducible formation of pyruvate and oxalate were observed both by IC and ESI-MS. These compounds are known to form from aldehyde oxidation in the aqueous phase. New insights regarding the aqueous chemistry of these "more atmospherically-realistic" experiments will be discussed.

Ethylene glycol emissions from on-road vehicles: implications for aqueous phase secondary organic aerosol formation

NASA Astrophysics Data System (ADS)

Wood, E. C.; Knighton, W. B.; Fortner, E.; Herndon, S. C.; Onasch, T. B.; Franklin, J.; Harley, R. A.; Gentner, D. R.; Goldstein, A. H.

2012-12-01

Ethylene glycol (HOCH2CH2OH), used as an engine coolant for most on-road vehicles, is an intermediate volatility organic compound (IVOC) with a high Henry's Law Coefficient (kH > 10,000 M atm-1) . Oxidation of ethylene glycol, especially in the atmospheric aqueous phase (clouds, fog, wet aerosol), can lead to the formation of glycolaldehyde, oxalic acid, and ultimately secondary organic aerosol. We present measurements of unexpectedly high ethylene glycol emissions in the Caldecott Tunnel near San Francisco (Summer 2010) and the Washburn Tunnel near Houston (Spring 2009). Ethylene glycol was detected using a proton-transfer reaction mass spectrometer (PTR-MS) at m/z = 45, which is usually interpreted as acetaldehyde. Although not necessarily a tailpipe emission, effective fuel-based emission factors are calculated using the carbon balance method and range from 50 to 400 mg ethylene glycol per kg fuel. Total US and global emissions are estimated using these emission factors and fuel consumption rates and are compared to previous model estimates of ethylene glycol emissions (e.g., the Regional Atmospheric Chemistry Model). Compared to biogenically emitted isoprene, ethylene glycol is likely a minor source of glycolaldehyde globally, but may contribute significantly to glycolaldehyde, oxalate and SOA formation in areas dominated by urban emissions.

Photochemistry of aqueous pyruvic acid

PubMed Central

Griffith, Elizabeth C.; Carpenter, Barry K.; Shoemaker, Richard K.; Vaida, Veronica

2013-01-01

The study of organic chemistry in atmospheric aerosols and cloud formation is of interest in predictions of air quality and climate change. It is now known that aqueous phase chemistry is important in the formation of secondary organic aerosols. Here, the photoreactivity of pyruvic acid (PA; CH3COCOOH) is investigated in aqueous environments characteristic of atmospheric aerosols. PA is currently used as a proxy for α-dicarbonyls in atmospheric models and is abundant in both the gas phase and the aqueous phase (atmospheric aerosols, fog, and clouds) in the atmosphere. The photoreactivity of PA in these phases, however, is very different, thus prompting the need for a mechanistic understanding of its reactivity in different environments. Although the decarboxylation of aqueous phase PA through UV excitation has been studied for many years, its mechanism and products remain controversial. In this work, photolysis of aqueous PA is shown to produce acetoin (CH3CHOHCOCH3), lactic acid (CH3CHOHCOOH), acetic acid (CH3COOH), and oligomers, illustrating the progression from a three-carbon molecule to four-carbon and even six-carbon molecules through direct photolysis. These products are detected using vibrational and electronic spectroscopy, NMR, and MS, and a reaction mechanism is presented accounting for all products detected. The relevance of sunlight-initiated PA chemistry in aqueous environments is then discussed in the context of processes occurring on atmospheric aerosols. PMID:23821751

Formation of aqueous-phase secondary organic aerosols from glycolaldehyde and ammonium sulfate/amines: A kinetic and mechanistic study

NASA Astrophysics Data System (ADS)

Yi, Yayi; Cao, Zhaoyu; Zhou, Xuehua; Xue, Likun; Wang, Wenxing

2018-05-01

Atmospheric particles are largely represented by secondary organic aerosols (SOAs) produced by either aqueous- or gas-phase reactions. Recently, the contribution of the former to SOA formation has been shown to substantially increase and even reach that of the latter, which necessitates in-depth mechanistic investigations. For a deeper understanding of aqueous-phase SOA generation, we herein studied the production of these aerosols in the dark from glycolaldehyde (GAld) and ammonium sulfate (AS)/amines (methylamine (MAm) and glycine (Gly)). UV-vis spectroscopy showed that reaction mixtures featured two main absorption bands (at 209-230 and 280-330 nm) that were attributed to the π-π* transitions of Schiff bases and the n-π* transitions of oligomers produced in the above reactions, respectively. Further studies revealed that irrespective of reactant concentration and pH, all the investigated reactions were well fitted by first-order kinetics and were accelerated by increasing AS/MAm concentrations and solution pH under acidic conditions. The reaction rate constants (determined from changes of absorption at 300 nm) followed the order of Gly (kI = 2.39 × 10-6 s-1) > MAm (kI = 1.19 × 10-6 s-1) > AS (kI = 8.33 × 10-7 s-1) at identical low AS/amine concentrations and were in the order of MAm (kI = 2.5 × 10-6 s-1) > AS (kI = 1.39 × 10-6 s-1) at high AS/MAm concentrations. The main reaction pathways corresponded to the aldol self-condensation of GAld and the nucleophilic attack of AS/amines on GAld followed by dehydration, which afforded imines as the major products. The stronger light absorption of (GAld + Gly) mixtures than that of (glyoxal/methylglyoxal + Gly) mixtures was ascribed to the increased amount of imine- and carbonyl group-containing products produced in the former case.

Chemical characterization of the main products formed through aqueous-phase photonitration of guaiacol

NASA Astrophysics Data System (ADS)

Kitanovski, Z.; Čusak, A.; Grgić, I.; Claeys, M.

2014-08-01

Guaiacol (2-methoxyphenol) and its derivatives can be emitted into the atmosphere by thermal degradation (i.e., burning) of wood lignins. Due to its volatility, guaiacol is predominantly distributed atmospherically in the gaseous phase. Recent studies have shown the importance of aqueous-phase reactions in addition to the dominant gas-phase and heterogeneous reactions of guaiacol, in the formation of secondary organic aerosol (SOA) in the atmosphere. The main objectives of the present study were to chemically characterize the main products of the aqueous-phase photonitration of guaiacol and examine their possible presence in urban atmospheric aerosols. The aqueous-phase reactions were carried out under simulated sunlight and in the presence of hydrogen peroxide and nitrite. The formed guaiacol reaction products were concentrated by solid-phase extraction and then purified with semi-preparative high-performance liquid chromatography (HPLC). The fractionated individual compounds were isolated as pure solids and further analyzed with liquid-state proton, carbon-13 and two-dimensional nuclear magnetic resonance (NMR) spectroscopy, and direct infusion negative ion electrospray ionization tandem mass spectrometry ((-)ESI-MS/MS). The NMR and product ion (MS2) spectra were used for unambiguous product structure elucidation. The main products of guaiacol photonitration are 4-nitroguaiacol (4NG), 6-nitroguaiacol (6NG), and 4,6-dinitroguaiacol (4,6DNG). Using the isolated compounds as standards, 4NG and 4,6DNG were unambiguously identified in winter PM10 aerosols from the city of Ljubljana (Slovenia) by means of HPLC/(-)ESI-MS/MS. Owing to the strong absorption of ultraviolet and visible light, 4,6DNG could be an important constituent of atmospheric "brown" carbon, especially in regions affected by biomass burning.

Photo-oxidation of Nitrophenols in the Aqueous Phase: Reaction Kinetics, Mechanistic Insights, and Evolution of Light Absorption

NASA Astrophysics Data System (ADS)

Hems, R.; Abbatt, J.

2017-12-01

Nitrophenols are a class of water soluble, light absorbing compounds which can make up a significant fraction of biomass burning brown carbon. The atmospheric lifetime and aging of these compounds can have important implications for their impact on climate through the aerosol direct effect. Recent studies have shown that brown carbon aerosols can be bleached of their colour by direct photolysis and photo-oxidation reactions on the timescale of hours to days. However, during aqueous phase photo-oxidation of nitrophenol compounds light absorption is sustained or enhanced, even after the parent nitrophenol molecule has been depleted. In this work, we use online aerosol chemical ionization mass spectrometry (aerosol-CIMS) to investigate the aqueous phase photo-oxidation mechanism and determine the second order rate constants for the reaction of OH radicals with three commonly detected nitrophenol compounds: nitrocatechol, nitroguaiacol, and dinitrophenol. These nitrophenol compounds are found to have aqueous phase lifetimes with respect to oxidation by the OH radical ranging between 5 - 11 hours. Our results indicate that functionalization of the parent nitrophenol molecule by addition of hydroxyl groups leads to the observed absorption enhancement. Further photo-oxidation forms breakdown products that no longer absorb significantly in the visible light range.

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

Volatility of organic aerosol: evaporation of ammonium sulfate/succinic acid aqueous solution droplets.

PubMed

Yli-Juuti, Taina; Zardini, Alessandro A; Eriksson, Axel C; Hansen, Anne Maria K; Pagels, Joakim H; Swietlicki, Erik; Svenningsson, Birgitta; Glasius, Marianne; Worsnop, Douglas R; Riipinen, Ilona; Bilde, Merete

2013-01-01

Condensation and evaporation modify the properties and effects of atmospheric aerosol particles. We studied the evaporation of aqueous succinic acid and succinic acid/ammonium sulfate droplets to obtain insights on the effect of ammonium sulfate on the gas/particle partitioning of atmospheric organic acids. Droplet evaporation in a laminar flow tube was measured in a Tandem Differential Mobility Analyzer setup. A wide range of droplet compositions was investigated, and for some of the experiments the composition was tracked using an Aerosol Mass Spectrometer. The measured evaporation was compared to model predictions where the ammonium sulfate was assumed not to directly affect succinic acid evaporation. The model captured the evaporation rates for droplets with large organic content but overestimated the droplet size change when the molar concentration of succinic acid was similar to or lower than that of ammonium sulfate, suggesting that ammonium sulfate enhances the partitioning of dicarboxylic acids to aqueous particles more than currently expected from simple mixture thermodynamics. If extrapolated to the real atmosphere, these results imply enhanced partitioning of secondary organic compounds to particulate phase in environments dominated by inorganic aerosol.

Volatility of Organic Aerosol: Evaporation of Ammonium Sulfate/Succinic Acid Aqueous Solution Droplets

PubMed Central

2013-01-01

Condensation and evaporation modify the properties and effects of atmospheric aerosol particles. We studied the evaporation of aqueous succinic acid and succinic acid/ammonium sulfate droplets to obtain insights on the effect of ammonium sulfate on the gas/particle partitioning of atmospheric organic acids. Droplet evaporation in a laminar flow tube was measured in a Tandem Differential Mobility Analyzer setup. A wide range of droplet compositions was investigated, and for some of the experiments the composition was tracked using an Aerosol Mass Spectrometer. The measured evaporation was compared to model predictions where the ammonium sulfate was assumed not to directly affect succinic acid evaporation. The model captured the evaporation rates for droplets with large organic content but overestimated the droplet size change when the molar concentration of succinic acid was similar to or lower than that of ammonium sulfate, suggesting that ammonium sulfate enhances the partitioning of dicarboxylic acids to aqueous particles more than currently expected from simple mixture thermodynamics. If extrapolated to the real atmosphere, these results imply enhanced partitioning of secondary organic compounds to particulate phase in environments dominated by inorganic aerosol. PMID:24107221

Investigating hygroscopic behavior and phase separation of organic/inorganic mixed phase aerosol particles with FTIR spectroscopy

NASA Astrophysics Data System (ADS)

Zawadowicz, M. A.; Cziczo, D. J.

2013-12-01

Atmospheric aerosol particles can be composed of inorganic salts, such as ammonium sulfate and sodium chloride, and therefore exhibit hygroscopic properties. Many inorganic salts have very well-defined deliquescence and efflorescence points at which they take up and lose water, respectively. For example, the deliquescence relative humidity of pure ammonium sulfate is about 80% and its efflorescence point is about 35%. This behavior of ammonium sulfate is important to atmospheric chemistry because some reactions, such as the hydrolysis of nitrogen pentoxide, occur on aqueous but not crystalline surfaces. Deliquescence and efflorescence of simple inorganic salt particles have been investigated by a variety of methods, such as IR spectroscopy, tandem mobility analysis and electrodynamic balance. Field measurements have shown that atmospheric aerosol are not typically a single inorganic salt, instead they often contain organic as well as inorganic species. Mixed inorganic/organic aerosol particles, while abundant in the atmosphere, have not been studied as extensively. Many recent studies have focused on microscopy techniques that require deposition of the aerosol on a glass slide, possibly changing its surface properties. This project investigates the deliquescence and efflorescence points, phase separation and ability to exchange gas-phase components of mixed organic and inorganic aerosol using a flow tube coupled with FTIR spectroscopy. Ammonium sulfate aerosol mixed with organic polyols with different O:C ratios, including glycerol, 1,2,6-hexanetriol, 1,4-butanediol and 1,5-pentanediol have been investigated. This project aims to study gas-phase exchange in these aerosol systems to determine if exchange is impacted when phase separation occurs.

Variation in pH of Model Secondary Organic Aerosol during Liquid-Liquid Phase Separation.

PubMed

Dallemagne, Magda A; Huang, Xiau Ya; Eddingsaas, Nathan C

2016-05-12

The majority of atmospheric aerosols consist of both organic and inorganic components. At intermediate relative humidity (RH), atmospheric aerosol can undergo liquid-liquid phase separation (LLPS) in which the organic and inorganic fractions segregate from each other. We have extended the study of LLPS to the effect that phase separation has on the pH of the overall aerosols and the pH of the individual phases. Using confocal microscopy and pH sensitive dyes, the pH of internally mixed model aerosols consisting of polyethylene glycol 400 and ammonium sulfate as well as the pH of the organic fraction during LLPS have been directly measured. During LLPS, the pH of the organic fraction was observed to increase to 4.2 ± 0.2 from 3.8 ± 0.1 under high RH when the aerosol was internally mixed. In addition, the high spatial resolution of the confocal microscope allowed us to characterize the composition of each of the phases, and we have observed that during LLPS the organic shell still contains large quantities of water and should be characterized as an aqueous organic-rich phase rather than simply an organic phase.

Aqueous-phase story of isoprene - A mini-review and reaction with HONO

NASA Astrophysics Data System (ADS)

Rudziński, Krzysztof J.; Szmigielski, Rafał; Kuznietsova, Inna; Wach, Paulina; Staszek, Dorota

2016-04-01

Isoprene is a major biogenic hydrocarbon emitted to the atmosphere and a well-recognized player in atmospheric chemistry, formation of secondary organic aerosol and air quality. Most of the scientific work on isoprene has focused on the gas-phase and smog chamber processing while direct aqueous chemistry has escaped the major attention because physical solubility of isoprene in water is low. Therefore, this work recollects the results of genuine research carried on atmospherically relevant aqueous-phase transformations of isoprene. It clearly shows that isoprene dissolves in water and reacts in aqueous solutions with common atmospheric oxidants such as hydrogen peroxide, ozone, hydroxyl radicals, sulfate radicals and sulfite radicals. The reactions take place in the bulk of solutions or on the gas-liquid interfaces and often are acid-catalyzed and/or enhanced by light. The review is appended by an experimental study of the aqueous-phase reaction of isoprene with nitrous acid (HONO). The decay of isoprene and formation of new products are demonstrated. The tentative chemical mechanism of the reaction is suggested, which starts with slow decomposition of HONO to NO2 and NO. The aqueous chemistry of isoprene explains the formation of a few tropospheric components identified by scientists yet considered of unknown origin. The reaction of isoprene with sulfate radicals explains formation of the MW 182 organosulfate found in ambient aerosol and rainwater while the reaction of isoprene with HONO explains formation of the MW 129 and MW 229 nitroorganic compounds identified in rainwater. Thus, aqueous transformations of isoprene should not be neglected without evidence but rather considered and evaluated in modeling of atmospheric chemical processes even if alternative and apparently dominant heterogeneous pathways of isoprene transformation, dry or wet, are demonstrated.

Key Role of Nitrate in Phase Transitions of Urban Particles: Implications of Important Reactive Surfaces for Secondary Aerosol Formation

NASA Astrophysics Data System (ADS)

Sun, Jiaxing; Liu, Lei; Xu, Liang; Wang, Yuanyuan; Wu, Zhijun; Hu, Min; Shi, Zongbo; Li, Yongjie; Zhang, Xiaoye; Chen, Jianmin; Li, Weijun

2018-01-01

Ammonium sulfate (AS) and ammonium nitrate (AN) are key components of urban fine particles. Both field and model studies showed that heterogeneous reactions of SO2, NO2, and NH3 on wet aerosols accelerated the haze formation in northern China. However, little is known on phase transitions of AS-AN containing haze particles. Here hygroscopic properties of laboratory-generated AS-AN particles and individual particles collected during haze events in an urban site were investigated using an individual particle hygroscopicity system. AS-AN particles showed a two-stage deliquescence at mutual deliquescence relative humidity (MDRH) and full deliquescence relative humidity (DRH) and three physical states: solid before MDRH, solid-aqueous between MDRH and DRH, and aqueous after DRH. During hydration, urban haze particles displayed a solid core and aqueous shell at RH = 60-80% and aqueous phase at RH > 80%. Most particles were in aqueous phase at RH > 50% during dehydration. Our results show that AS content in individual particles determines their DRH and AN content determines their MDRH. AN content increase can reduce MDRH, which indicates occurrence of aqueous shell at lower RH. The humidity-dependent phase transitions of nitrate-abundant urban particles are important to provide reactive surfaces of secondary aerosol formation in the polluted air.

Simulating Aqueous-Phase Isoprene-Epoxydiol (IEPOX) ...

EPA Pesticide Factsheets

The lack of statistically robust relationships between IEPOX (isoprene epoxydiol)-derived SOA (IEPOX SOA) and aerosol liquid water and pH observed during the 2013 Southern Oxidant and Aerosol Study (SOAS) emphasizes the importance of modeling the whole system to understand the controlling factors governing IEPOX SOA formation. We present a mechanistic modeling investigation predicting IEPOX SOA based on Community Multiscale Air Quality (CMAQ) model algorithms and a recently introduced photochemical box model, simpleGAMMA. We aim to (1) simulate IEPOX SOA tracers from the SOAS Look Rock ground site, (2) compare the two model formulations, (3) determine the limiting factors in IEPOX SOA formation, and (4) test the impact of a hypothetical sulfate reduction scenario on IEPOX SOA. The estimated IEPOX SOA mass variability is in similar agreement (r2 ∼ 0.6) with measurements. Correlations of the estimated and measured IEPOX SOA tracers with observed aerosol surface area (r2 ∼ 0.5–0.7), rate of particle-phase reaction (r2 ∼ 0.4–0.7), and sulfate (r2 ∼ 0.4–0.5) suggest an important role of sulfate in tracer formation via both physical and chemical mechanisms. A hypothetical 25% reduction of sulfate results in ∼70% reduction of IEPOX SOA formation, reaffirming the importance of aqueous phase chemistry in IEPOX SOA production. The National Exposure Research Laboratory (NERL) Computational Exposure Division (CED) develops and evaluates data, decision-suppor

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.

Aerosol Particle Interfacial Thermodynamics and Phase Partitioning Measurements Using Biphasic Microfluidics

NASA Astrophysics Data System (ADS)

Dutcher, Cari; Metcalf, Andrew

2015-03-01

Secondary organic aerosol particles are nearly ubiquitous in the atmosphere and yet there remain large uncertainties in their formation processes and ambient properties. These particles are complex microenvironments, which can contain multiple interfaces due to internal aqueous-organic phase partitioning and to the external liquid-vapor surface. Interfacial properties affect the ambient aerosol morphology, or internal structure of the particle, which in turn can affect the way a particle interacts with an environment of condensable clusters and organic vapors. To improve our ability to accurately predict ambient aerosol morphology, we must improve our knowledge of aerosol interfaces and their interactions with the ambient environment. Unfortunately, many techniques employed to measure interfacial properties do so in bulk solutions or in the presence of a ternary (e.g. solid) phase. In this talk, a novel method using biphasic microscale flows will be introduced for generating, trapping, and perturbing complex interfaces at atmospherically relevant conditions. These microfluidic experiments utilize high-speed imaging to monitor interfacial phenomena at the microscale and are performed with phase contrast and fluorescence microscopy on a temperature-controlled inverted microscope stage. From these experiments, interfacial thermodynamic properties such as surface or interfacial tension, rheological properties such as interfacial moduli, and kinetic properties such as mass transfer coefficients can be measured or inferred.

Aqueous phase oligomerization of methyl vinyl ketone through photooxidation - Part 1: Aging processes of oligomers

NASA Astrophysics Data System (ADS)

Renard, P.; Siekmann, F.; Salque, G.; Smaani, A.; Demelas, C.; Coulomb, B.; Vassalo, L.; Ravier, S.; Temime-Roussel, B.; Voisin, D.; Monod, A.

2014-06-01

Secondary organic aerosol (SOA) represents a substantial part of organic aerosol, which affects climate and human health. It is now accepted that one of the important pathways of SOA formation occurs via aqueous phase chemistry in the atmosphere. Recently, we have shown in a previous study (Renard et al., 2013) the mechanism of oligomerization of MVK (methyl vinyl ketone), and suggested that unsaturated water soluble organic compounds (UWSOC) might efficiently form SOA in wet aerosol particles, even for weakly soluble ones like MVK. The atmospheric relevance of these processes is explored by means of process model studies (in a companion paper). In the present study we investigate the aging of these aqueous phase MVK-oligomers (Part 1). We compared aqueous phase composition and SOA composition after nebulization, mainly by means of UPLC-ESI-MS and AMS, respectively. Both instruments match and show similar trend of oligomer formation and aging. The SMPS analysis performed on the nebulized solutions allow to quantify these SOA and to measure their mass yields. We have highlighted in the current study that MVK •OH-oxidation undergoes kinetic competition between functionalization and oligomerization. The SOA composition and its evolution highly depend on the precursor initial concentration. We determined the threshold of MVK concentration, i.e. 2 mM, from which oligomerization prevails over functionalization. Hence, at these concentrations, •OH-oxidation of MVK forms oligomers that are SV-OOA, with low O / C and high f43. Oligomers are then fragmented, via unidentified intermediates that have the properties of LV-OOA which then end into succinic, malonic and oxalic diacids. For lower initial MVK concentrations, the oligomerization is not the major process, and functionalization dominates, resulting in small carbonyls, dicarbonyls and mainly monoacids. The aging of these oligomers could be an explanation for the presence of a part of the diacids observed in aerosol.

ON-LINE ANALYSIS OF AQUEOUS AEROSOLS BY LASER DESORPTION IONIZATION. (R823980)

EPA Science Inventory

In this work the effects of water on the laser desorption ionization mass spectra of single aerosol particles are explored. Aqueous aerosols are produced by passing dry particles through a humid environment so that they undergo deliquescent growth. Laser desorption ionization is ...

Insights into Aqueous-phase processing through Comparison of the Organic Chemical Composition of Atmospheric Particles and Cloud Water in the Southeast United States

NASA Astrophysics Data System (ADS)

Boone, E.; Laskin, J.; Laskin, A.; Wirth, C.; Shepson, P. B.; Stirm, B. H.; Pratt, K.

2014-12-01

Organic compounds comprise a significant mass fraction of submicron atmospheric particles with considerable contribution from secondary organic aerosol (SOA), a large fraction of which is formed from the oxidation of biogenic volatile organic compounds. Aqueous-phase reactions in particles and cloud droplets are suggested to increase SOA mass and change the chemical composition the particles following cloud evaporation. Aqueous-phase processing may also explain discrepancies between measurements and models. To gain a better understanding of these processes, cloud water and below-cloud atmospheric particles were collected onboard a research aircraft during the Southeast Oxidants and Aerosol Study (SOAS) over Alabama in June 2013. Nanospray desorption electrospray ionization (nano-DESI) and direct electrospray ionization (ESI) coupled with high resolution mass spectrometry were utilized to compare the organic molecular composition of the particle and cloud water samples, respectively. Several hundred unique compounds have been identified in the particle and cloud water samples, allowing possible aqueous-phase reactions to be examined. Hydrolysis of organosulfate compounds, aqueous-phase formation of nitrogen-containing compounds, and possible fragmentation of oligomeric compounds will be discussed, with comparisons to previous laboratory studies. This study provides insights into aqueous-phase reactions in ambient cloud droplets.

Partitioning phase preference for secondary organic aerosol in an urban atmosphere

NASA Astrophysics Data System (ADS)

Chang, Wayne Li-Wen

Secondary organic aerosol (SOA) comprises a significant portion of atmospheric particular matter (PM). The impact of PM on both human health and global climate has long been recognized. Despite its importance, there are still many unanswered questions regarding the formation and evolution of SOA in the atmosphere. This study uses a modeling approach to understand the preferred partitioning behavior of SOA species into aqueous or organic condensed phases. More specifically, this work uses statistical analyses of approximately 24,000 data values for each variable from a state-of-the-art 3-D airshed model. Spatial and temporal distributions of fractions of SOA residing in the aqueous phase (fAQ) in the South Coast Air Basin of California are presented. Typical values of fAQ within the basin near the surface range from 5 to 80%. Results show that the distribution of fAQ values is inversely proportional to the total SOA loading. Further analysis accounting for various meteorological parameters indicates that large fAQ values are the results of aqueous-phase SOA insensitivity to the ambient conditions; while organic-phase SOA concentrations are dramatically reduced under unfavorable SOA formation conditions, aqueous-phase SOA level remains relatively unchanged, thus increasing fAQ at low SOA loading. Diurnal variations of fAQ near the surface are also observed: it tends to be larger during daytime hours than nighttime hours. When examining the vertical gradient of fAQ, largest values are found at heights above the surface layer. In summary, one must consider SOA in both organic and aqueous phases for proper regional and global SOA budget estimation.

Aerosol partitioning in natural mixed-phase clouds

NASA Astrophysics Data System (ADS)

Henning, S.; Bojinski, S.; Diehl, K.; Ghan, S.; Nyeki, S.; Weingartner, E.; Wurzler, S.; Baltensperger, U.

2004-03-01

In situ aerosol and cloud drop microphysical measurements at a high-alpine site are used to investigate aerosol partitioning between cloud and interstitial phases in natural, mid-latitude, mixed-phase clouds. Measurements indicate a decrease in the activated aerosol fraction (FN) for particle diameters dP > 100 nm with cloud temperature from FN ~ 0.54 in summer liquid-phase clouds to FN ~ 0.08 in winter mixed-phase clouds. The latter may be attributed to the Bergeron-Findeisen mechanism whereby ice crystals grow at the expense of liquid water drops, releasing formerly activated aerosols back into the interstitial phase. This provides a means to distinguish the indirect effects of aerosols on drops and ice crystals.

Spectral changes induced by pH variation of aqueous extracts derived from biomass burning aerosols: Under dark and in presence of simulated sunlight irradiation

NASA Astrophysics Data System (ADS)

Cai, Jing; Zhi, Guorui; Yu, Zhiqiang; Nie, Peng; Gligorovski, Sasho; Zhang, Yuzhe; Zhu, Like; Guo, Xixiang; Li, Pei; He, Tan; He, Youjiang; Sun, Jianzhong; Zhang, Yang

2018-07-01

Water soluble organic carbon (WSOC) can significantly influence the aerosol optical properties and the aqueous phase chemistry in cloudwater, fogwater and aerosol liquid water. Here, we examine how the changing pH (in acidic range) affects the absorption spectra of aqueous extracts from field biomass burning aerosols, under dark conditions and in presence of simulated sunlight illumination. The observation under dark conditions indicates that pH variation from 2 to 5 induces significantly enhanced light absorbance in the wavelength ranges of 235-270 nm and 300-550 nm, whereas the light absorbance decreased in the range of 270-300 nm, which might be partially ascribed to the deprotonation of carboxylic acids and phenols. During the extract photolysis, light absorption exhibits photo-bleaching below 380 nm and photo-enhancement above 380 nm, indicating that at acidic levels (pH = 2-5), the particle extracts could undergo a significant composition evolution leading to a modification of absorptive properties. Meanwhile, after 12 h-photolysis, the acidity ([H+]) normalized by WSOC concentration in aqueous extracts ([WSOCae]) increased with a variation of Δ[H+]/[WSOCae]=(3.7 ± 0.7) × 10-7 mol mgC-1 (mean ± standard deviation), suggesting the formation of new acidic substances. Although these findings were acquired in aqueous solutions more relevant to cloud and fog water, the similar evolution likely occurs in wetted aerosols. This calls more attention to the effect of acidity on the wetted aerosols in order to better estimate the aerosol radiative forcing.

Partitioning phase preference for secondary organic aerosol in an urban atmosphere.

PubMed

Chang, Wayne L; Griffin, Robert J; Dabdub, Donald

2010-04-13

Secondary organic aerosol (SOA) comprises a significant portion of atmospheric particular matter. The impact of particular matter on both human health and global climate has long been recognized. Despite its importance, there are still many unanswered questions regarding the formation and evolution of SOA in the atmosphere. This study uses a modeling approach to understand the preferred partitioning behavior of SOA species into aqueous or organic condensed phases. More specifically, this work uses statistical analyses of approximately 24,000 data values for each variable from a state of the art 3D airshed model. Spatial and temporal distributions of fractions of SOA residing in the aqueous phase (fAQ) in the South Coast Air Basin of California are presented. Typical values of fAQ within the basin near the surface range from 5 to 80%. Results show that the likelihood of large fAQ values is inversely proportional to the total SOA loading. Analysis of various meteorological parameters indicates that large fAQ values are predicted because modeled aqueous-phase SOA formation is less sensitive than that of organic-phase SOA to atmospheric conditions that are not conducive to SOA formation. There is a diurnal variation of fAQ near the surface: It tends to be larger during daytime hours than during nighttime hours. Results also indicate that the largest fAQ values are simulated in layers above ground level at night. In summary, one must consider SOA in both organic and aqueous phases for proper regional and global SOA budget estimation.

Humidity influence on gas-particle phase partitioning of α-pinene + O3 secondary organic aerosol

NASA Astrophysics Data System (ADS)

Prisle, N. L.; Engelhart, G. J.; Bilde, M.; Donahue, N. M.

2010-01-01

Water vapor uptake to particles could potentially affect organic-aerosol mass in three ways: first, water in the organic phase could reduce organic (equilibrium) partial pressures according to Raoult's law; second, an aqueous phase could attract water soluble organics according to Henry's law; finally, deliquescence of inorganic particle cores could mix the organic and inorganic particle phases, significantly diluting the organics and again reducing organic partial pressures according to Raoult's law. We present experiments using initially dry α-pinene + ozone secondary organic aerosol (SOA) on ammonium sulfate (AS) seeds at atmospheric concentrations in a smog chamber. After SOA formation, the chamber relative humidity is increased steadily by addition of steam to near 100%. Little subsequent SOA mass growth is observed, suggesting that none of these potential effects play a strong role in this system.

Secondary Organic Aerosol and Brown Carbon Formation in the Sunlit Aqueous Phase: Aldehyde Photooxidation in the Presence of Ammonium Salts and Amines

NASA Astrophysics Data System (ADS)

De Haan, D. O.; Galloway, M. M.; Sharp, K. D.; Jiménez, N. G.

2014-12-01

The chemistry of water-soluble carbonyl compounds in clouds is now acknowledged as an important source of secondary organic aerosol. These reactive carbonyl compounds are oxidized to carboxylic acids and form oligomers by radical-radical reactions and by "dark reactions" with ammonium salts (AS) and/or amines. The latter class of reactions also produces light-absorbing brown carbon compounds, especially reactions involving methylglyoxal or glyoxal and amines. However, recent work has found that UV light fades the color of glyoxal + AS and methylgyloxal + AS reaction mixtures. We recently studied aldehyde-AS-amine reactions in sunlight and in control vessels at the same temperature to determine the effects of solar radiation on the aqueous-phase production of brown carbon. In sunlight, methylglyoxal reaction mixtures lost their initial color and failed to brown, indicating the photolytic loss of reactants and/or pre-brown intermediates. In many other reactions, brown products are lost to photolysis, reducing the overall browning of solutions exposed to sunlight. In other experiments, hydrogen peroxide was added to generate OH radicals by photolysis. In the presence of OH radicals, some carbonyl compound mixtures (e.g. those containing hydroxyacetone or glycolaldehyde) browned more rapidly when exposed to sunlight. This indicates the existence of uncharacterized photooxidative browning pathways involving aqueous-phase OH radicals, carbonyls, ammonium salts, and/or amine compounds.

Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

NASA Astrophysics Data System (ADS)

Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

2012-09-01

The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (<2%) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

NASA Astrophysics Data System (ADS)

Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

2013-01-01

The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (yield less than 2% on carbon atom basis) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

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

Aerosol Fragmentation Driven by Coupling of Acid-Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals.

PubMed

Liu, Matthew J; Wiegel, Aaron A; Wilson, Kevin R; Houle, Frances A

2017-08-10

A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps with physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low molecular

Aerosol Fragmentation Driven by Coupling of Acid–Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals

DOE PAGES

Liu, Matthew J.; Wiegel, Aaron A.; Wilson, Kevin R.; ...

2017-07-14

A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps withmore » physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low

Aerosol Fragmentation Driven by Coupling of Acid–Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals

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

Liu, Matthew J.; Wiegel, Aaron A.; Wilson, Kevin R.

A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps withmore » physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low

Surfactant Driven Post-Deposition Spreading of Aerosols on Complex Aqueous Subphases. 2: Low Deposition Flux Representative of Aerosol Delivery to Small Airways

PubMed Central

Sharma, Ramankur; Khanal, Amsul; Corcoran, Timothy E.; Przybycien, Todd M.; Tilton, Robert D.

2015-01-01

Abstract Background: Cystic fibrosis (CF) is associated with the accumulation of dehydrated mucus in the pulmonary airways. This alters ventilation and aerosol deposition patterns in ways that limit drug delivery to peripheral lung regions. We investigated the use of surfactant-based, self-dispersing aerosol carriers that produce surface tension gradients to drive two-dimensional transport of aerosolized medications via Marangoni flows after deposition on the airway surface liquid (ASL). We considered the post-deposition spreading of individual aerosol droplets and two-dimensional expansion of a field of aerosol droplets, when deposited at low fluxes that are representative of aerosol deposition in the small airways. Methods: We used physically entangled aqueous solutions of poly(acrylamide) or porcine gastric mucin as simple ASL mimics that adequately capture the full miscibility but slow penetration of entangled macromolecular chains of the ASL into the deposited drop. Surfactant formulations were prepared with aqueous solutions of nonionic tyloxapol or FS-3100 fluorosurfactant. Fluorescein dye served as a model “drug” tracer and to visualize the extent of post-deposition spreading. Results: The surfactants not only enhanced post-deposition spreading of individual aerosol droplets due to localized Marangoni stresses, as previously observed with macroscopic drops, but they also produced large-scale Marangoni stresses that caused the deposited aerosol fields to expand into initially unexposed regions of the subphase. We show that the latter is the main mechanism for spreading drug over large distances when aerosol is deposited at low fluxes representative of the small airways. The large scale convective expansion of the aerosol field drives the tracer (drug mimic) over areas that would cover an entire airway generation or more, in peripheral airways, where sub-monolayer droplet deposition is expected during aerosol inhalation. Conclusions: The results suggest

pH Variance in Aerosols Undergoing Liquid-Liquid Phase Separation

NASA Astrophysics Data System (ADS)

Eddingsaas, N. C.; Dallemagne, M.; Huang, X.

2014-12-01

The water content of aerosols is largely governed by relative humidity (RH). As the relative humidity decreases, and thus the water content of aerosols, a number of processes occur including the shrinking of aerosols, the increase in concentration of components, and potentially the formation of liquid liquid phase separation (llps) due to the salting out of inorganic salts. The most ubiquitous salt in atmospheric aerosols is ammonium sulfate which results in many aerosols to be at least mildly acidic. However, during llps, the pH of the different phases is not necessarily the same. Many reactions that take place within atmospheric aerosols are acid catalyzed so a better understanding of the pH of the individual phases as well as the interface between the phases is important to understanding aerosol processing and aging. Through the use of pH sensitive dyes and confocal microscopy we have directly measured the pH of micron sized model aerosols during high RH where the aerosols are in a single phase, at intermediate while the aerosols are in llps, and low RH where the aerosols consist of one liquid phase and one solid phase. We will discuss the variation in RH during these different phase states in the presence and absence of excess sulfuric acid. We will also discuss how this variation in pH affects aging of aerosols.

Comparison of Methods for Predicting the Compositional Dependence of the Density and Refractive Index of Organic-Aqueous Aerosols.

PubMed

Cai, Chen; Miles, Rachael E H; Cotterell, Michael I; Marsh, Aleksandra; Rovelli, Grazia; Rickards, Andrew M J; Zhang, Yun-Hong; Reid, Jonathan P

2016-08-25

Representing the physicochemical properties of aerosol particles of complex composition is of crucial importance for understanding and predicting aerosol thermodynamic, kinetic, and optical properties and processes and for interpreting and comparing analysis methods. Here, we consider the representations of the density and refractive index of aqueous-organic aerosol with a particular focus on the dependence of these properties on relative humidity and water content, including an examination of the properties of solution aerosol droplets existing at supersaturated solute concentrations. Using bulk phase measurements of density and refractive index for typical organic aerosol components, we provide robust approaches for the estimation of these properties for aerosol at any intermediate composition between pure water and pure solute. Approximately 70 compounds are considered, including mono-, di- and tricarboxylic acids, alcohols, diols, nitriles, sulfoxides, amides, ethers, sugars, amino acids, aminium sulfates, and polyols. We conclude that the molar refraction mixing rule should be used to predict the refractive index of the solution using a density treatment that assumes ideal mixing or, preferably, a polynomial dependence on the square root of the mass fraction of solute, depending on the solubility limit of the organic component. Although the uncertainties in the density and refractive index predictions depend on the range of subsaturated compositional data available for each compound, typical errors for estimating the solution density and refractive index are less than ±0.1% and ±0.05%, respectively. Owing to the direct connection between molar refraction and the molecular polarizability, along with the availability of group contribution models for predicting molecular polarizability for organic species, our rigorous testing of the molar refraction mixing rule provides a route to predicting refractive indices for aqueous solutions containing organic molecules

Brown carbon formation by aqueous-phase carbonyl compound reactions with amines and ammonium sulfate.

PubMed

Powelson, Michelle H; Espelien, Brenna M; Hawkins, Lelia N; Galloway, Melissa M; De Haan, David O

2014-01-21

Reactions between small water-soluble carbonyl compounds, ammonium sulfate (AS), and/or amines were evaluated for their ability to form light-absorbing species in aqueous aerosol. Aerosol chemistry was simulated with bulk phase reactions at pH 4, 275 K, initial concentrations of 0.05 to 0.25 M, and UV-vis and fluorescence spectroscopy monitoring. Glycolaldehyde-glycine mixtures produced the most intense absorbance. In carbonyl compound reactions with AS, methylamine, or AS/glycine mixtures, product absorbance followed the order methylglyoxal > glyoxal > glycolaldehyde > hydroxyacetone. Absorbance extended into the visible, with a wavelength dependence fit by absorption Ångstrom coefficients (Å(abs)) of 2 to 11, overlapping the Å(abs) range of atmospheric, water-soluble brown carbon. Many reaction products absorbing between 300 and 400 nm were strongly fluorescent. On a per mole basis, amines are much more effective than AS at producing brown carbon. In addition, methylglyoxal and glyoxal produced more light-absorbing products in reactions with a 5:1 AS-glycine mixture than with AS or glycine alone, illustrating the importance of both organic and inorganic nitrogen in brown carbon formation. Through comparison to biomass burning aerosol, we place an upper limit on the contribution of these aqueous carbonyl-AS-amine reactions of ≤ 10% of global light absorption by brown carbon.

Aerosol Delivery for Amendment Distribution in Contaminated Vadose Zones

NASA Astrophysics Data System (ADS)

Hall, R. J.; Murdoch, L.; Riha, B.; Looney, B.

2011-12-01

Remediation of contaminated vadose zones is often hindered by an inability to effectively distribute amendments. Many amendment-based approaches have been successful in saturated formations, however, have not been widely pursued when treating contaminated unsaturated materials due to amendment distribution limitations. Aerosol delivery is a promising new approach for distributing amendments in contaminated vadose zones. Amendments are aerosolized and injected through well screens. During injection the aerosol particles are transported with the gas and deposited on the surfaces of soil grains. Resulting distributions are radially and vertically broad, which could not be achieved by injecting pure liquid-phase solutions. The objectives of this work were A) to characterize transport and deposition behaviors of aerosols; and B) to develop capabilities for predicting results of aerosol injection scenarios. Aerosol transport and deposition processes were investigated by conducting lab-scale injection experiments. These experiments involved injection of aerosols through a 2m radius, sand-filled wedge. A particle analyzer was used to measure aerosol particle distributions with time, and sand samples were taken for amendment content analysis. Predictive capabilities were obtained by constructing a numerical model capable of simulating aerosol transport and deposition in porous media. Results from tests involving vegetable oil aerosol injection show that liquid contents appropriate for remedial applications could be readily achieved throughout the sand-filled wedge. Lab-scale tests conducted with aqueous aerosols show that liquid accumulation only occurs near the point of injection. Tests were also conducted using 200 g/L salt water as the aerosolized liquid. Liquid accumulations observed during salt water tests were minimal and similar to aqueous aerosol results. However, particles were measured, and salt deposited distal to the point of injection. Differences between

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.

FT-IR quantification of the carbonyl functional group in aqueous-phase secondary organic aerosol from phenols

NASA Astrophysics Data System (ADS)

George, Kathryn M.; Ruthenburg, Travis C.; Smith, Jeremy; Yu, Lu; Zhang, Qi; Anastasio, Cort; Dillner, Ann M.

2015-01-01

Recent findings suggest that secondary organic aerosols (SOA) formed from aqueous-phase reactions of some organic species, including phenols, contribute significantly to particulate mass in the atmosphere. In this study, we employ a Fourier transform infrared (FT-IR) spectroscopic technique to identify and quantify the functional group makeup of phenolic SOA. Solutions containing an oxidant (hydroxyl radical or 3,4-dimethoxybenzaldehyde) and either one phenol (phenol, guaiacol, or syringol) or a mixture of phenols mimicking softwood or hardwood emissions were illuminated to make SOA, atomized, and collected on a filter. We produced laboratory standards of relevant organic compounds in order to develop calibrations for four functional groups: carbonyls (Cdbnd O), saturated C-H, unsaturated C-H and O-H. We analyzed the SOA samples with transmission FT-IR to identify and determine the amounts of the four functional groups. The carbonyl functional group accounts for 3-12% of the SOA sample mass in single phenolic SOA samples and 9-14% of the SOA sample mass in mixture samples. No carbonyl functional groups are present in the initial reactants. Varying amounts of each of the other functional groups are observed. Comparing carbonyls measured by FT-IR (which could include aldehydes, ketones, esters, and carboxylic acids) with eight small carboxylic acids measured by ion chromatography indicates that the acids only account for an average of 20% of the total carbonyl reported by FT-IR.

Novel characterization of the aerosol and gas-phase composition of aerosolized jet fuel.

PubMed

Tremblay, Raphael T; Martin, Sheppard A; Fisher, Jeffrey W

2010-04-01

Few robust methods are available to characterize the composition of aerosolized complex hydrocarbon mixtures. The difficulty in separating the droplets from their surrounding vapors and preserving their content is challenging, more so with fuels, which contain hydrocarbons ranging from very low to very high volatility. Presented here is a novel method that uses commercially available absorbent tubes to measure a series of hydrocarbons in the vapor and droplets from aerosolized jet fuels. Aerosol composition and concentrations were calculated from the differential between measured total (aerosol and gas-phase) and measured gas-phase concentrations. Total samples were collected directly, whereas gas-phase only samples were collected behind a glass fiber filter to remove droplets. All samples were collected for 1 min at 400 ml min(-1) and quantified using thermal desorption-gas chromatography-mass spectrometry. This method was validated for the quantification of the vapor and droplet content from 4-h aerosolized jet fuel exposure to JP-8 and S-8 at total concentrations ranging from 200 to 1000 mg/m(3). Paired samples (gas-phase only and total) were collected every approximately 40 min. Calibrations were performed with neat fuel to calculate total concentration and also with a series of authentic standards to calculate specific compound concentrations. Accuracy was good when compared to an online GC-FID (gas chromatography-flame ionization detection) technique. Variability was 15% or less for total concentrations, the sum of all gas-phase compounds, and for most specific compound concentrations in both phases. Although validated for jet fuels, this method can be adapted to other hydrocarbon-based mixtures.

Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol.

PubMed

Smith, Jeremy D; Kinney, Haley; Anastasio, Cort

2015-04-21

Chemical processing in atmospheric aqueous phases, such as cloud and fog drops, can play a significant role in the production and evolution of secondary organic aerosol (SOA). In this work we examine aqueous SOA production via the oxidation of benzene-diols (dihydroxy-benzenes) by the triplet excited state of 3,4-dimethoxybenzaldehyde, (3)DMB*, and by hydroxyl radical, ˙OH. Reactions of the three benzene-diols (catechol (CAT), resorcinol (RES) and hydroquinone (HQ)) with (3)DMB* or ˙OH proceed rapidly, with rate constants near diffusion-controlled values. The two oxidants exhibit different behaviors with pH, with rate constants for (3)DMB* increasing as pH decreases from pH 5 to 2, while rate constants with ˙OH decrease in more acidic solutions. Mass yields of SOA were near 100% for all three benzene-diols with both oxidants. We also examined the reactivity of atmospherically relevant mixtures of phenols and benzene-diols in the presence of (3)DMB*. We find that the kinetics of phenol and benzene-diol loss, and the production of SOA mass, in mixtures are generally consistent with rate constants determined in experiments containing a single phenol or benzene-diol. Combining our aqueous kinetic and SOA mass yield data with previously published gas-phase data, we estimate a total SOA production rate from benzene-diol oxidation in a foggy area with significant wood combustion to be nearly 0.6 μg mair(-3) h(-1), with approximately half from the aqueous oxidation of resorcinol and hydroquinone, and half from the gas-phase oxidation of catechol.

Aerosol processing in mixed-phase clouds in ECHAM5-HAM: Model description and comparison to observations

NASA Astrophysics Data System (ADS)

Hoose, C.; Lohmann, U.; Stier, P.; Verheggen, B.; Weingartner, E.

2008-04-01

The global aerosol-climate model ECHAM5-HAM has been extended by an explicit treatment of cloud-borne particles. Two additional modes for in-droplet and in-crystal particles are introduced, which are coupled to the number of cloud droplet and ice crystal concentrations simulated by the ECHAM5 double-moment cloud microphysics scheme. Transfer, production, and removal of cloud-borne aerosol number and mass by cloud droplet activation, collision scavenging, aqueous-phase sulfate production, freezing, melting, evaporation, sublimation, and precipitation formation are taken into account. The model performance is demonstrated and validated with observations of the evolution of total and interstitial aerosol concentrations and size distributions during three different mixed-phase cloud events at the alpine high-altitude research station Jungfraujoch (Switzerland). Although the single-column simulations cannot be compared one-to-one with the observations, the governing processes in the evolution of the cloud and aerosol parameters are captured qualitatively well. High scavenged fractions are found during the presence of liquid water, while the release of particles during the Bergeron-Findeisen process results in low scavenged fractions after cloud glaciation. The observed coexistence of liquid and ice, which might be related to cloud heterogeneity at subgrid scales, can only be simulated in the model when assuming nonequilibrium conditions.

Aerosol Processing in Mixed-Phase Clouds in ECHAM5-HAM: Comparison of Single-Column Model Simulations to Observations

NASA Astrophysics Data System (ADS)

Hoose, C.; Lohmann, U.; Stier, P.; Verheggen, B.; Weingartner, E.; Herich, H.

2007-12-01

The global aerosol-climate model ECHAM5-HAM (Stier et al., 2005) has been extended by an explicit treatment of cloud-borne particles. Two additional modes for in-droplet and in-crystal particles are introduced, which are coupled to the number of cloud droplet and ice crystal concentrations simulated by the ECHAM5 double-moment cloud microphysics scheme (Lohmann et al., 2007). Transfer, production and removal of cloud-borne aerosol number and mass by cloud droplet activation, collision scavenging, aqueous-phase sulfate production, freezing, melting, evaporation, sublimation and precipitation formation are taken into account. The model performance is demonstrated and validated with observations of the evolution of total and interstitial aerosol concentrations and size distributions during three different mixed-phase cloud events at the alpine high-altitude research station Jungfraujoch (Switzerland) (Verheggen et al, 2007). Although the single-column simulations can not be compared one-to-one with the observations, the governing processes in the evolution of the cloud and aerosol parameters are captured qualitatively well. High scavenged fractions are found during the presence of liquid water, while the release of particles during the Bergeron-Findeisen process results in low scavenged fractions after cloud glaciation. The observed coexistence of liquid and ice, which might be related to cloud heterogeneity at subgrid scales, can only be simulated in the model when forcing non-equilibrium conditions. References: U. Lohmann et al., Cloud microphysics and aerosol indirect effects in the global climate model ECHAM5-HAM, Atmos. Chem. Phys. 7, 3425-3446 (2007) P. Stier et al., The aerosol-climate model ECHAM5-HAM, Atmos. Chem. Phys. 5, 1125-1156 (2005) B. Verheggen et al., Aerosol partitioning between the interstitial and the condensed phase in mixed-phase clouds, Accepted for publication in J. Geophys. Res. (2007)

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

Oxidation of Organic Compoundsin the Atmospheric Aqueous Phase: Development of a New Explicit Oxidation Mechanism

NASA Astrophysics Data System (ADS)

Mouchel-Vallon, C.; Bregonzio-Rozier, L.; Monod, A.; Leriche, M.; Doussin, J. F.; Chaumerliac, N. M.; Deguillaume, L.

2014-12-01

Current 3D models tend to underestimate the production of secondary organic aerosol (SOA) in the atmosphere (Volkamer et al., 2006). Recent studies argue that aqueous chemistry in clouds could be responsible for a significant production of SOA (Ervens et al., 2011; Carlton and Turpin, 2013) through oxidative and non-oxidative processes. Aqueous phase reactivity of organic compounds needs to be thoroughly described in models to identify organic molecules available to contribute to SOA mass. Recently, new empirical methods have been developed to allow the estimate of HO·reaction rates in the aqueous phase (Doussin and Monod, 2013, Minakata et al., 2009). These methods provide global rate constants together with branching ratios for HO·abstraction and addition on organic compounds of atmospheric interests. Current cloud chemistry mechanisms do not take the different possible pathways into account. Based on these structure-activity relationships, a new detailed aqueous phase mechanism describing the oxidation of hydrosoluble organic compounds resulting from isoprene oxidation is proposed. This new aqueous phase mechanism is coupled with the detailed gas phase mechanism MCM v3.2 (Jenkin et al., 1997; Saunders et al., 2003) through a kinetic of mass transfer parameterization for the exchange between gas phase and aqueous phase. The GROMHE SAR (Raventos-Duran et al., 2010) allows the evaluation of Henry's law constants for organic compounds. Variable photolysis in both phases using the TUV 4.5 radiative transfer model (Madronich and Flocke, 1997) is also calculated. The resulting multiphase mechanism has been implemented in a cloud chemistry model. Focusing on oxygenated compounds produced from the isoprene oxidation, sensitivity tests and comparisons with multiphase experiments performed in the framework of the CUMULUS project in the CESAM atmospheric simulation chamber (Wang et al., 2011) will be presented. Volkamer et al., GRL, 33, L17811, 2006. Carlton and Turpin

Aqueous aerosol may build up large upper tropospheric ice supersaturation

NASA Astrophysics Data System (ADS)

Bogdan, Anatoli; Molina, Mario J.

2010-05-01

Keywords: ice supersaturation, upper tropospheric cirrus clouds, freezing of aqueous aerosol. Observations often reveal enhanced and persistent upper tropospheric (UT) ice supersaturation, Si up to 100%, independently of whether cirrus ice clouds are present or not (Krämer et al., 2009; Lawson et al., 2008). However, a water activity criterion (WAC) (Koop et al., 2000) does not allow the formation of Si > ~67% by the homogeneous freezing of aqueous droplets even at the lowest atmospheric temperature of ~185 K. For aqueous aerosol the WAC predicts the existence of a so called homogeneous ice nucleation threshold which, being expressed as Si, is between ~52 and 67% in the temperature range of ~220 - 185 K. The nature of the formation of large Si remains unclear. Since water vapor is the dominant greenhouse gas it is important to know the nature of the accumulation and persistence of water vapor in the UT. We studied the freezing behavior of micrometer-scaled 3-, 4-, and 5-component droplets, which contain different weight fractions of H2O, H2SO4, HNO3, (NH4)2SO4, (NH4)HSO4, NH4NO3, and (NH4)3H(SO4)2. The study was performed between 133 and 278 K at cooling rates of 3, 0.1, and 0.05 K/min using differential scanning calorimetry (DSC) (Bogdan and Molina, 2010). The cooling rates of 0.1 and 0.05 K/min (6 and 3 K/h) are similar to the smallest reported synoptic temperature change of ~2 K/h (Carslaw et al., 1998). Using the measured freezing temperature of ice, Ti, and the thermodynamic E-AIM model of the system of H+ - NH4+ - SO42-- NO3-- H2O (Clegg et al., 1998), we calculated the corresponding clear-sky Si which would be built up immediately prior to the formation of ice cirrus clouds by the homogeneous freezing of aqueous aerosol of similar composition. We found that our calculated values of Si are both larger and smaller than the homogeneous ice nucleation threshold. For example, for the droplets of compositions of 15/10 and 20/10 wt % (NH4)3H(SO4)2/H2SO4, which

Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

DOE PAGES

Yu, L.; Smith, J.; Laskin, A.; ...

2014-08-19

Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl ( 3C*) and hydroxyl radical (·OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules aremore » identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than ·OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

DOE PAGES

Yu, L.; Smith, J.; Laskin, A.; ...

2014-12-23

Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C 6H 5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants – the triplet excited states of an aromatic carbonyl ( 3C *) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). Amore » large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C * are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV–visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

Temperature- and pH-dependent aqueous-phase kinetics of the reactions of glyoxal and methylglyoxal with atmospheric amines and ammonium sulfate

NASA Astrophysics Data System (ADS)

Sedehi, Nahzaneen; Takano, Hiromi; Blasic, Vanessa A.; Sullivan, Kristin A.; De Haan, David O.

2013-10-01

Reactions of glyoxal (Glx) and methylglyoxal (MG) with primary amines and ammonium salts may produce brown carbon and N-containing oligomers in aqueous aerosol. 1H NMR monitoring of reactant losses and product appearance in bulk aqueous reactions were used to derive rate constants and quantify competing reaction pathways as a function of pH and temperature. Glx + ammonium sulfate (AS) and amine reactions generate products containing C-N bonds, with rates depending directly on pH: rate = (70 ± 60) M-1 s-1fAld [Glx]totfAm [Am]tot, where fAld is the fraction of aldehyde with a dehydrated aldehyde functional group, and fAm is the fraction of amine or ammonia that is deprotonated at a given pH. MG + amine reactions generate mostly aldol condensation products and exhibit less pH dependence: rate = 10[(0.36 ± 0.06) × pH - (3.6 ± 0.3)] M-1 s-1fAld [MG]tot [Am]tot. Aldehyde + AS reactions are less temperature-dependent (Ea = 18 ± 8 kJ mol-1) than corresponding amine reactions (Ea = 50 ± 11 kJ mol-1). Using aerosol concentrations of [OH] = 10-12 M, [amine]tot = [AS] = 0.1 M, fGlx = 0.046 and fMG = 0.09, we estimate that OH radical reactions are normally the major aerosol-phase sink for both dicarbonyl compounds. However, reactions with AS and amines together can account for up to 12 and 45% of daytime aerosol-phase glyoxal and methylglyoxal reactivity, respectively, in marine aerosol at pH 5.5. Reactions with AS and amines become less important in acidic or non-marine aerosol, but may still be significant atmospheric sources of brown carbon, imidazoles, and nitrogen-containing oligomers.

Aerosol-cloud interactions in mixed-phase convective clouds - Part 1: Aerosol perturbations

NASA Astrophysics Data System (ADS)

Miltenberger, Annette K.; Field, Paul R.; Hill, Adrian A.; Rosenberg, Phil; Shipway, Ben J.; Wilkinson, Jonathan M.; Scovell, Robert; Blyth, Alan M.

2018-03-01

Changes induced by perturbed aerosol conditions in moderately deep mixed-phase convective clouds (cloud top height ˜ 5 km) developing along sea-breeze convergence lines are investigated with high-resolution numerical model simulations. The simulations utilise the newly developed Cloud-AeroSol Interacting Microphysics (CASIM) module for the Unified Model (UM), which allows for the representation of the two-way interaction between cloud and aerosol fields. Simulations are evaluated against observations collected during the COnvective Precipitation Experiment (COPE) field campaign over the southwestern peninsula of the UK in 2013. The simulations compare favourably with observed thermodynamic profiles, cloud base cloud droplet number concentrations (CDNC), cloud depth, and radar reflectivity statistics. Including the modification of aerosol fields by cloud microphysical processes improves the correspondence with observed CDNC values and spatial variability, but reduces the agreement with observations for average cloud size and cloud top height. Accumulated precipitation is suppressed for higher-aerosol conditions before clouds become organised along the sea-breeze convergence lines. Changes in precipitation are smaller in simulations with aerosol processing. The precipitation suppression is due to less efficient precipitation production by warm-phase microphysics, consistent with parcel model predictions. In contrast, after convective cells organise along the sea-breeze convergence zone, accumulated precipitation increases with aerosol concentrations. Condensate production increases with the aerosol concentrations due to higher vertical velocities in the convective cores and higher cloud top heights. However, for the highest-aerosol scenarios, no further increase in the condensate production occurs, as clouds grow into an upper-level stable layer. In these cases, the reduced precipitation efficiency (PE) dominates the precipitation response and no further

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.

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.

Measurement of phase function of aerosol at different altitudes by CCD Lidar

NASA Astrophysics Data System (ADS)

Sun, Peiyu; Yuan, Ke'e.; Yang, Jie; Hu, Shunxing

2018-02-01

The aerosols near the ground are closely related to human health and climate change, the study on which has important significance. As we all know, the aerosol is inhomogeneous at different altitudes, of which the phase function is also different. In order to simplify the retrieval algorithm, it is usually assumed that the aerosol is uniform at different altitudes, which will bring measurement error. In this work, an experimental approach is demonstrated to measure the scattering phase function of atmospheric aerosol particles at different heights by CCD lidar system, which could solve the problem of the traditional CCD lidar system in assumption of phase function. The phase functions obtained by the new experimental approach are used to retrieve the aerosol extinction coefficient profiles. By comparison of the aerosol extinction coefficient retrieved by Mie-scattering aerosol lidar and CCD lidar at night, the reliability of new experimental approach is verified.

Simultaneous Separation of Manganese, Cobalt, and Nickel by the Organic-Aqueous-Aqueous Three-Phase Solvent Extraction

NASA Astrophysics Data System (ADS)

Shirayama, Sakae; Uda, Tetsuya

2016-04-01

This research outlines an organic-aqueous-aqueous three-phase solvent extraction method and proposes its use in a new metal separation process for the recycling of manganese (Mn), cobalt (Co), and nickel (Ni) from used lithium ion batteries (LIBs). The three-phase system was formed by mixing xylene organic solution, 50 pct polyethylene glycol (PEG) aqueous solution, and 1 mol L-1 sodium sulfate (Na2SO4) aqueous solution. The xylene organic solution contained 2-ethylhexylphosphonic acid (D2EHPA) as an extractant for Mn ion, and the Na2SO4 aqueous solution contained 1 mol L-1 potassium thiocyanate (KSCN) as an extractant for Co ion. Concentrations of the metal ions were varied by dissolving metal sulfates in the Na2SO4 aqueous solution. As a result of the experiments, Mn, Co, and Ni ions were distributed in the xylene organic phase, PEG-rich aqueous phase, and Na2SO4-rich aqueous phase, respectively. The separation was effective when the pH value was around 4. Numerical simulation was also conducted in order to predict the distribution of metal ions after the multi-stage counter-current extractions.

Quantitative analysis of aqueous phase composition of model dentin adhesives experiencing phase separation

PubMed Central

Ye, Qiang; Park, Jonggu; Parthasarathy, Ranganathan; Pamatmat, Francis; Misra, Anil; Laurence, Jennifer S.; Marangos, Orestes; Spencer, Paulette

2013-01-01

There have been reports of the sensitivity of our current dentin adhesives to excess moisture, for example, water-blisters in adhesives placed on over-wet surfaces, and phase separation with concomitant limited infiltration of the critical dimethacrylate component into the demineralized dentin matrix. To determine quantitatively the hydrophobic/hydrophilic components in the aqueous phase when exposed to over-wet environments, model adhesives were mixed with 16, 33, and 50 wt % water to yield well-separated phases. Based upon high-performance liquid chromatography coupled with photodiode array detection, it was found that the amounts of hydrophobic BisGMA and hydrophobic initiators are less than 0.1 wt % in the aqueous phase. The amount of these compounds decreased with an increase in the initial water content. The major components of the aqueous phase were hydroxyethyl methacrylate (HEMA) and water, and the HEMA content ranged from 18.3 to 14.7 wt %. Different BisGMA homologues and the relative content of these homologues in the aqueous phase have been identified; however, the amount of crosslinkable BisGMA was minimal and, thus, could not help in the formation of a crosslinked polymer network in the aqueous phase. Without the protection afforded by a strong crosslinked network, the poorly photoreactive compounds of this aqueous phase could be leached easily. These results suggest that adhesive formulations should be designed to include hydrophilic multimethacrylate monomers and water compatible initiators. PMID:22331596

Aqueous-Phase Acetic Acid Ketonization over Monoclinic Zirconia

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

Cai, Qiuxia; Lopez-Ruiz, Juan A.; Cooper, Alan R.

The effect of aqueous phase on the acetic acid ketonization over monoclinic zirconia has been investigated using first-principles based density functional theory (DFT) calculations. To capture the aqueous phase chemistry over the solid zirconia catalyst surface, the aqueous phase is represented by 111 explicit water molecules with a liquid water density of 0.93 g/cm3 and the monoclinic zirconia is modeled by the most stable surface structure . The dynamic nature of aqueous phase/ interface was studied using ab initio molecular dynamics simulation, indicating that nearly half of the surface Zr sites are occupied by either adsorbed water molecules or hydroxylmore » groups at 550 K. DFT calculations show that the adsorption process of acetic acid from the liquid water phase to the surface is nearly thermodynamically neutral with a Gibbs free energy of -2.3 kJ/mol although the adsorption strength of acetic acid on the surface in aqueous phase is much stronger than in vapor phase. Therefore it is expected that the adsorption of acetic acid will dramatically affects aqueous phase ketonization reactivity over the monoclinic zirconia catalyst. Using the same ketonization mechanism via the β-keto acid intermediate, we have compared acetic acid ketonization to acetone in both vapor and aqueous phases. Our DFT calculation results show although the rate-determining step of the β-keto acid formation via the C-C coupling is not pronouncedly affected, the presence of liquid water molecules will dramatically affect dehydrogenation and hydrogenation steps via proton transfer mechanism. This work was financially supported by the United States Department of Energy (DOE)’s Bioenergy Technologies Office (BETO) and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle Memorial Institute. Computing time and advanced catalyst characterization use was granted by a user proposal at the William R. Wiley

Aerosol partitioning between the interstitial and the condensed phase in mixed-phase clouds

NASA Astrophysics Data System (ADS)

Verheggen, Bart; Cozic, Julie; Weingartner, Ernest; Bower, Keith; Mertes, Stephan; Connolly, Paul; Gallagher, Martin; Flynn, Michael; Choularton, Tom; Baltensperger, Urs

2007-12-01

The partitioning of aerosol particles between the cloud and the interstitial phase (i.e., unactivated aerosol) has been investigated during several Cloud and Aerosol Characterization Experiments (CLACE-3, CLACE-3? and CLACE-4) conducted in winter and summer 2004 and winter 2005 at the high alpine research station Jungfraujoch (3580 m altitude, Switzerland). Ambient air was sampled using different inlets in order to determine the activated fraction of aerosol particles, FN, defined as the fraction of the total aerosol number concentration (with particle diameter dp > 100 nm) that has been incorporated into cloud particles. The liquid and ice water content of mixed-phase clouds were characterized by analyzing multiple cloud probes. The dependence of the activated fraction on several environmental factors is discussed on the basis of more than 900 h of in-cloud observations and parameterizations for key variables are given. FN is found to increase with increasing liquid water content and to decrease with increasing particle number concentration in liquid clouds. FN also decreases with increasing cloud ice mass fraction and with decreasing temperature from 0 to -25°C. The Wegener-Bergeron-Findeisen process probably contributed to this trend, since the presence of ice crystals causes liquid droplets to evaporate, thus releasing the formerly activated particles back into the interstitial phase. Ice nucleation could also have prevented additional cloud condensation nuclei from activating. The observed activation behavior has significant implications for our understanding of the indirect effect of aerosols on climate.

Simulating Aqueous-Phase Isoprene-Epoxydiol (IEPOX) Secondary Organic Aerosol Production During the 2013 Southern Oxidant and Aerosol Study (SOAS)

EPA Science Inventory

The lack of statistically robust relationships between IEPOX (isoprene epoxydiol)-derived SOA (IEPOX SOA) and aerosol liquid water and pH observed during the 2013 Southern Oxidant and Aerosol Study (SOAS) emphasizes the importance of modeling the whole system to understand the co...

Ice crystallization in ultrafine water-salt aerosols: nucleation, ice-solution equilibrium, and internal structure.

PubMed

Hudait, Arpa; Molinero, Valeria

2014-06-04

Atmospheric aerosols have a strong influence on Earth's climate. Elucidating the physical state and internal structure of atmospheric aqueous aerosols is essential to predict their gas and water uptake, and the locus and rate of atmospherically important heterogeneous reactions. Ultrafine aerosols with sizes between 3 and 15 nm have been detected in large numbers in the troposphere and tropopause. Nanoscopic aerosols arising from bubble bursting of natural and artificial seawater have been identified in laboratory and field experiments. The internal structure and phase state of these aerosols, however, cannot yet be determined in experiments. Here we use molecular simulations to investigate the phase behavior and internal structure of liquid, vitrified, and crystallized water-salt ultrafine aerosols with radii from 2.5 to 9.5 nm and with up to 10% moles of ions. We find that both ice crystallization and vitrification of the nanodroplets lead to demixing of pure water from the solutions. Vitrification of aqueous nanodroplets yields nanodomains of pure low-density amorphous ice in coexistence with vitrified solute rich aqueous glass. The melting temperature of ice in the aerosols decreases monotonically with an increase of solute fraction and decrease of radius. The simulations reveal that nucleation of ice occurs homogeneously at the subsurface of the water-salt nanoparticles. Subsequent ice growth yields phase-segregated, internally mixed, aerosols with two phases in equilibrium: a concentrated water-salt amorphous mixture and a spherical cap-like ice nanophase. The surface of the crystallized aerosols is heterogeneous, with ice and solution exposed to the vapor. Free energy calculations indicate that as the concentration of salt in the particles, the advance of the crystallization, or the size of the particles increase, the stability of the spherical cap structure increases with respect to the alternative structure in which a core of ice is fully surrounded by

Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

2010-05-01

Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of the phase diagram. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system simulation

Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: Competition among oligomerization, functionalization, and fragmentation

DOE PAGES

Yu, Lu; Smith, Jeremy; Laskin, Alexander; ...

2016-04-13

Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants – the triplet excited state of an aromatic carbonyl ( 3C *) and hydroxyl radical ( • OH). Changes in themore » molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OS C) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ~2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OS C values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers ( n C) below 6. The average n C of phenolic aqSOA decreases while average OS C increases over the course of photochemical aging. In addition, the saturation vapor pressures ( C *) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C * values is

Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: Competition among oligomerization, functionalization, and fragmentation

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

Yu, Lu; Smith, Jeremy; Laskin, Alexander

Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants – the triplet excited state of an aromatic carbonyl ( 3C *) and hydroxyl radical ( • OH). Changes in themore » molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OS C) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ~2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OS C values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers ( n C) below 6. The average n C of phenolic aqSOA decreases while average OS C increases over the course of photochemical aging. In addition, the saturation vapor pressures ( C *) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C * values is

Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation

NASA Astrophysics Data System (ADS)

Yu, L.; Smith, J.; Laskin, A.; George, K. M.; Anastasio, C.; Laskin, J.; Dillner, A. M.; Zhang, Q.

2015-10-01

Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants - the triplet excited state of an aromatic carbonyl (3C*) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ∼ 2 h irradiation under midday, winter solstice sunlight in northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated open-ring molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures C*) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C* values is observed

Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation

NASA Astrophysics Data System (ADS)

Yu, Lu; Smith, Jeremy; Laskin, Alexander; George, Katheryn M.; Anastasio, Cort; Laskin, Julia; Dillner, Ann M.; Zhang, Qi

2016-04-01

Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants - the triplet excited state of an aromatic carbonyl (3C∗) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ˜ 2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures (C∗) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C∗ values is observed

Photochemical organonitrate formation in wet aerosols

NASA Astrophysics Data System (ADS)

Lim, Yong Bin; Kim, Hwajin; Kim, Jin Young; Turpin, Barbara J.

2016-10-01

Water is the most abundant component of atmospheric fine aerosol. However, despite rapid progress, multiphase chemistry involving wet aerosols is still poorly understood. In this work, we report results from smog chamber photooxidation of glyoxal- and OH-containing ammonium sulfate or sulfuric acid particles in the presence of NOx and O3 at high and low relative humidity. Particles were analyzed using ultra-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS). During the 3 h irradiation, OH oxidation products of glyoxal that are also produced in dilute aqueous solutions (e.g., oxalic acids and tartaric acids) were formed in both ammonium sulfate (AS) aerosols and sulfuric acid (SA) aerosols. However, the major products were organonitrogens (CHNO), organosulfates (CHOS), and organonitrogen sulfates (CHNOS). These were also the dominant products formed in the dark chamber, indicating non-radical formation. In the humid chamber (> 70 % relative humidity, RH), two main products for both AS and SA aerosols were organonitrates, which appeared at m / z- 147 and 226. They were formed in the aqueous phase via non-radical reactions of glyoxal and nitric acid, and their formation was enhanced by photochemistry because of the photochemical formation of nitric acid via reactions of peroxy radicals, NOx and OH during the irradiation.

Sensitivity studies of different aerosol indirect effects in mixed-phase clouds

NASA Astrophysics Data System (ADS)

Lohmann, U.; Hoose, C.

2009-11-01

Aerosols affect the climate system by changing cloud characteristics. Using the global climate model ECHAM5-HAM, we investigate different aerosol effects on mixed-phase clouds: The glaciation effect, which refers to a more frequent glaciation due to anthropogenic aerosols, versus the de-activation effect, which suggests that ice nuclei become less effective because of an anthropogenic sulfate coating. The glaciation effect can partly offset the indirect aerosol effect on warm clouds and thus causes the total anthropogenic aerosol effect to be smaller. It is investigated by varying the parameterization for the Bergeron-Findeisen process and the threshold coating thickness of sulfate (SO4-crit), which is required to convert an externally mixed aerosol particle into an internally mixed particle. Differences in the net radiation at the top-of-the-atmosphere due to anthropogenic aerosols between the different sensitivity studies amount up to 0.5 W m-2. This suggests that the investigated mixed-phase processes have a major effect on the total anthropogenic aerosol effect.

Sensitivity studies of different aerosol indirect effects in mixed-phase clouds

NASA Astrophysics Data System (ADS)

Lohmann, U.; Hoose, C.

2009-07-01

Aerosols affect the climate system by changing cloud characteristics. Using the global climate model ECHAM5-HAM, we investigate different aerosol effects on mixed-phase clouds: The glaciation effect, which refers to a more frequent glaciation due to anthropogenic aerosols, versus the de-activation effect, which suggests that ice nuclei become less effective because of an anthropogenic sulfate coating. The glaciation effect can partly offset the indirect aerosol effect on warm clouds and thus causes the total anthropogenic aerosol effect to be smaller. It is investigated by varying the parameterization for the Bergeron-Findeisen process and the threshold coating thickness of sulfate (SO4-crit), which is required to convert an externally mixed aerosol particle into an internally mixed particle. Differences in the net radiation at the top-of-the-atmosphere due to anthropogenic aerosols between the different sensitivity studies amount up to 0.5 W m-2. This suggests that the investigated mixed-phase processes have a major effect on the total anthropogenic aerosol effect.

Secondary organic aerosol formation through cloud processing of aromatic VOCs

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

2010-08-01

Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of multicomponent systems. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system

Studies on aerosols. I. Reduction of dust deposition in lungs of rabbits by aqueous aerosols

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

Dautrebande, L.; Highman, B.; Alford, W.C.

1948-01-01

Rabbits were exposed to air containing 0.01 to 0.04 mg/liter zinc silicate dust with a mean diameter of 0.9 ..mu..m. Irregular breathing with some cyanosis after 2 hr was observed. Pulmonary changes after 4.5 to 5 hr included bronchitis, patchy atelectasis, emphysema, interstitial pneumonitis (thickening of septa, moderate congestion, infiltration of mononuclear cells and polymorphonuclear leukocytes). After 1, 7, or 14 days recovery there were no or only slight pulmonary problems. There was localization of particles at surfaces facing, deflecting or slowing air currents, particularly near pleura and hilus and less in central portion of lobes. Rabbits exposed to abovemore » dust plus aqueous wetting agent aerosol averaging 0.5 ..mu..m in diameter showed no cyanosis or marked respiratory difficulty. Rabbits showed less of above pulmonary changes and lesser amount of dust in lungs, particularly in alveoli and alveolar ducts. Most particles were cleared in 1 day in both groups, especially aerosol group, and essentially were all gone after 7 days. Differences were primarily due to coating of particles with liquid (increased size) and aggregation.« less

Secondary organic aerosol formation from semi- and intermediate-volatility organic compounds and glyoxal: Relevance of O/C as a tracer for aqueous multiphase chemistry

NASA Astrophysics Data System (ADS)

Waxman, Eleanor M.; Dzepina, Katja; Ervens, Barbara; Lee-Taylor, Julia; Aumont, Bernard; Jimenez, Jose L.; Madronich, Sasha; Volkamer, Rainer

2013-03-01

The role of aqueous multiphase chemistry in the formation of secondary organic aerosol (SOA) remains difficult to quantify. We investigate it here by testing the rapid formation of moderate oxygen-to-carbon (O/C) SOA during a case study in Mexico City. A novel laboratory-based glyoxal-SOA mechanism is applied to the field data, and explains why less gas-phase glyoxal mass is observed than predicted. Furthermore, we compare an explicit gas-phase chemical mechanism for SOA formation from semi- and intermediate-volatility organic compounds (S/IVOCs) with empirical parameterizations of S/IVOC aging. The mechanism representing our current understanding of chemical kinetics of S/IVOC oxidation combined with traditional SOA sources and mixing of background SOA underestimates the observed O/C by a factor of two at noon. Inclusion of glyoxal-SOA with O/C of 1.5 brings O/C predictions within measurement uncertainty, suggesting that field observations can be reconciled on reasonable time scales using laboratory-based empirical relationships for aqueous chemistry.

Effect of high concentrations of inorganic seed aerosols on secondary organic aerosol formation in the m-xylene/NO x photooxidation system

NASA Astrophysics Data System (ADS)

Lu, Zifeng; Hao, Jiming; Takekawa, Hideto; Hu, Lanhua; Li, Junhua

High concentrations (>15 μm 3 cm -3) of CaSO 4, Ca(NO 3) 2 and (NH 4) 2SO 4 were selected as surrogates of dry neutral, aqueous neutral and dry acidic inorganic seed aerosols, respectively, to study the effects of inorganic seeds on secondary organic aerosol (SOA) formation in irradiated m-xylene/NO x photooxidation systems. The results indicate that neither ozone formation nor SOA formation is significantly affected by the presence of neutral aerosols (both dry CaSO 4 and aqueous Ca(NO 3) 2), even at elevated concentrations. The presence of high concentrations of (NH 4) 2SO 4 aerosols (dry acidic) has no obvious effect on ozone formation, but it does enhance SOA generation and increase SOA yields. In addition, the effect of dry (NH 4) 2SO 4 on SOA yield is found to be positively correlated with the (NH 4) 2SO 4 surface concentration, and the effect is pronounced only when the surface concentration reaches a threshold value. Further, it is proposed that the SOA generation enhancement is achieved by particle-phase heterogeneous reactions induced and catalyzed by the acidity of dry (NH 4) 2SO 4 seed aerosols.

Reversible, on-demand generation of aqueous two-phase microdroplets

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

Collier, Charles Patrick; Retterer, Scott Thomas; Boreyko, Jonathan Barton

The present invention provides methods of on-demand, reversible generation of aqueous two-phase microdroplets core-shell microbeads, microparticle preparations comprising the core-shell microbeads, and drug delivery formulation comprising the microparticle preparations. Because these aqueous microdroplets have volumes comparable to those of cells, they provide an approach to mimicking the dynamic microcompartmentation of biomaterial that naturally occurs within the cytoplasm of cells. Hence, the present methods generate femtoliter aqueous two-phase droplets within a microfluidic oil channel using gated pressure pulses to generate individual, stationary two-phase microdroplets with a well-defined time zero for carrying out controlled and sequential phase transformations over time. Reversible phasemore » transitions between single-phase, two-phase, and core-shell microbead states are obtained via evaporation-induced dehydration and water rehydration.« less

Quantifying the equilibrium partitioning of substituted polycyclic aromatic hydrocarbons in aerosols and clouds using COSMOtherm.

PubMed

Awonaike, Boluwatife; Wang, Chen; Goss, Kai-Uwe; Wania, Frank

2017-03-22

Functional groups attached to polycyclic aromatic hydrocarbons (PAHs) can significantly modify the environmental fate of the parent compound. Equilibrium partition coefficients, which are essential for describing the environmental phase distribution of a compound, are largely unavailable for substituted PAHs (SPAHs). Here, COSMOtherm, a software based on quantum-chemical calculations is used to estimate the atmospherically relevant partition coefficients between the gas phase, the aqueous bulk phase, the water surface and the water insoluble organic matter phase, as well as the salting-out coefficients, for naphthalene, anthracene, phenanthrene, benz(a)anthracene, benzo(a)pyrene and dibenz(a,h)anthracene and 62 of their substituted counterparts. They serve as input parameters for the calculation of equilibrium phase distribution of these compounds in aerosols and clouds. Our results, which were compared with available experimental data, show that the effect of salts, the adsorption to the water surface and the dissolution in a bulk aqueous phase can be safely neglected when estimating the gas-particle partitioning of SPAHs in aerosols. However, for small PAHs with more than one polar functional group the aqueous phase can be the dominant reservoir in a cloud.

A new method for multicomponent activity coefficients of electrolytes in aqueous atmospheric aerosols

NASA Astrophysics Data System (ADS)

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

2005-01-01

Three-dimensional models of atmospheric inorganic aerosols need accurate and computationally efficient parameterizations of activity coefficients of various electrolytes in multicomponent aqueous solutions. In this paper, we extend the Taylor's series expansion mixing rule used by C. Wagner in 1952 for estimating activity coefficients in dilute alloy solutions to aqueous electrolyte solutions at any concentration. The resulting method, called the multicomponent Taylor expansion method (MTEM), estimates the mean activity coefficient of an electrolyte in a multicomponent solution on the basis of its values in binary solutions of all the electrolytes present in the mixture at the solution water activity aw, assuming aw is equal to the ambient relative humidity. MTEM is applied here for atmospheric aerosol systems containing H+, NH4+, Na+, Ca2+, SO42-, HSO4-, NO3-, and Cl- ions. The aerosol water content is calculated using the Zdanovskii-Stokes-Robinson (ZSR) method. For self-consistency, most of the MTEM and ZSR parameters are derived using the comprehensive Pitzer-Simonson-Clegg model at 298.15 K and are valid for an aw range of 0.2-0.97. Because CaSO4 is sparingly soluble, it is treated as a solid in the model over the entire aw range. MTEM is evaluated for several multicomponent systems representing various continental and marine aerosols and is contrasted against the mixing rule of C. L. Kusik and H. P. Meissner and of L. A. Bromley and the newer approach of S. Metzger and colleagues. Predictions of MTEM are found to be generally within a factor of 0.8-1.25 of the comprehensive Pitzer-Simonson-Clegg model and are shown to be significantly more accurate than predictions of the other three methods. MTEM also yields a noniterative solution of the bisulfate ion dissociation in sulfate-rich systems: a major computational advantage over other ionic-strength-based methods that require an iterative solution. CPU time requirements of MTEM relative to other methods for

Metal-Catalyzed Aqueous Oxidation Processes in Merged Microdroplets

NASA Astrophysics Data System (ADS)

Davis, R. D.; Wilson, K. R.

2017-12-01

Iron-catalyzed production of reactive oxygen species (ROS) from hydrogen peroxide (Fenton's reaction) is a fundamental process throughout nature, from groundwater to cloud droplets. In recent years, Fenton's chemistry has gained further interest in atmospheric science as a potentially important process in the oxidation of aqueous secondary organic aerosol (e.g., Chu et al., Sci. Rep., 2017), with some observations indicating that Fenton's reaction proceeds at a higher rate at aerosol interfaces compared to in the bulk (Enami et al., PNAS, 2014). However, a fundamental-level mechanistic understanding of this process remains elusive and the relative importance of interfacial versus bulk chemistry for aqueous organic processing via Fenton's has yet to be fully established. Here, we present a microreactor experimental approach to studying aqueous-phase Fenton's chemistry in microdroplets by rapidly mixing droplets of different composition. Utilizing two on-demand droplet generators, a stream of microdroplets containing aqueous iron chloride were merged with a separate stream of microdroplets containing aqueous hydrogen peroxide and a range of aromatic organic compounds, initiating ROS production and subsequent aqueous-phase oxidation reactions. Upon merging, mixing of the microdroplets occurred in submillisecond timescales, thus allowing the reaction progress to be monitored with high spatial and temporal resolution. For relatively large microreactor (droplet) sizes (50 µm diameter post-merging), the Fenton-initiated aqueous oxidation of aromatic organic compounds in merged microdroplets was consistent with bulk predictions with hydroxyl radicals as the ROS. The microdroplet-size dependence of this observation, along with the role of other ROS species produced from Fenton and Fenton-like processes, will be discussed in the context of relative importance to aqueous organic processing of atmospheric particles.

Aqueous Oxidation of Green Leaf Volatiles as a Source of Secondary Organic Aerosol

NASA Astrophysics Data System (ADS)

Richards-Henderson, N. K.; Hansel, A.; Pham, A. T.; Vempati, H. S.; Valsaraj, K. T.; Anastasio, C.

2013-12-01

Vegetation emits volatile oxygenated hydrocarbons - the green leaf volatiles (GLVs) - which are formed from the biochemical conversion of linoleic and linolenic acids within plant cells. Stress or damage to vegetation can significantly elevate emission fluxes of these compounds, some of which are fairly water soluble. Aqueous-phase reactions of the GLVs with photochemically generated oxidants - such as hydroxyl radical (OH), singlet oxygen (1O2) and excited triplet states of organic compounds (3C*) _ might then form low-volatility products that can act as secondary organic aerosol (SOA). In order to determine if GLVs can be a significant source of secondary organic carbon in fogwater, studies of GLVs in laboratory solutions are needed to elucidate the oxidation kinetics and the corresponding SOA mass yields. In this study we are determining the second-order rate constants, and SOA mass yields, for five GLVs (cis-3-hexen-1-ol, cis-3-hexenylacetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol) reacting with OH,1O2 and 3C*. Experiments are performed at relevant fog water pHs, temperatures, and oxidant concentrations. Rate constants are determined using a relative rate approach in which the decay of GLVs and reference compounds are monitored as function of time by HPLC. The capacity of GLVs to form aqueous SOA was determined by following the formation of their decomposition products with HPLC-UV/DAD and HPLC-ESI/MS. SOA mass yields are measured gravimetrically from laboratory solutions containing atmospherically relevant concentrations of photooxidants and GLVs, and irradiated with simulated sunlight. We will use our results to assess the potential contribution of aqueous GLV reactions as a source of SOA in cloudy or foggy atmospheres.

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

NASA Astrophysics Data System (ADS)

Khan, M. H.; Holzinger, R.

2013-12-01

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

Ship track observations of a reduced shortwave aerosol indirect effect in mixed-phase clouds

NASA Astrophysics Data System (ADS)

Christensen, M. W.; Suzuki, K.; Zambri, B.; Stephens, G. L.

2014-10-01

Aerosol influences on clouds are a major source of uncertainty to our understanding of forced climate change. Increased aerosol can enhance solar reflection from clouds countering greenhouse gas warming. Recently, this indirect effect has been extended from water droplet clouds to other types including mixed-phase clouds. Aerosol effects on mixed-phase clouds are important because of their fundamental role on sea ice loss and polar climate change, but very little is known about aerosol effects on these clouds. Here we provide the first analysis of the effects of aerosol emitted from ship stacks into mixed-phase clouds. Satellite observations of solar reflection in numerous ship tracks reveal that cloud albedo increases 5 times more in liquid clouds when polluted and persist 2 h longer than in mixed-phase clouds. These results suggest that seeding mixed-phase clouds via shipping aerosol is unlikely to provide any significant counterbalancing solar radiative cooling effects in warming polar regions.

Small molecules as tracers in atmospheric secondary organic aerosol

NASA Astrophysics Data System (ADS)

Yu, Ge

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

Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

NASA Astrophysics Data System (ADS)

Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

2015-01-01

To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic aerosols (BA), for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2) and malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment, except for ω-oxooctanoic acid (ωC8) that showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids dominates their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

NASA Astrophysics Data System (ADS)

Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

2015-07-01

To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic (BA) aerosols, for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2), malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols, whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment except for ω-oxooctanoic acid (ωC8), which showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids controls their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

Discontinuous hygroscopic growth of an aqueous surfactant/salt aerosol particle levitated in an electrodynamic balance

NASA Astrophysics Data System (ADS)

Soonsin, V.; Krieger, U. K.; Peter, T.

2010-12-01

Organic compounds are a major fraction of tropospheric aerosol. The organic fraction is usually internally mixed with inorganic salts. Surface-active organic matter or surfactants, enriched in the oceanic surface layer and transferred to the atmosphere by bubble-bursting processes, are the most likely candidates to contribute the observed organic fraction in sea salt aerosol [1, 2]. If the organic substance is a surfactant, it will lower the surface tension. In addition aggregates of the organic monomers, called micelles, will form if the concentration of the organic exceeds a certain limit (critical micelle concentration). These aggregates do have different morphology (spheres or globular or rod like micelles, or spherical bilayer vesicles etc.) and size, depending on the nature of the organic molecule, its concentration and the concentration of inorganic salts [3]. These aggregate may promote solubilisation of organic compounds in aqueous atmospheric aerosol. We performed measurements of ternary aqueous solution particles consisting of tetraethylene glycol monooctyl ether (C8E4) as organic surfactant and sodium chloride (NaCl) as inorganic salt and water (H2O) using single levitated aerosol particles in an electrodynamic balance. The particles can be stored contact-free in a temperature and humidity controlled chamber and optical resonance spectroscopy is used to monitor radius change [4]. Mie resonance spectra of ternary droplets show discontinuous growth with increasing relative humidity (RH) and also discontinuous shrinkage with decreasing relative humidity. We observe this behavior at temperatures and RHs at which the salt is completely deliquesced and the concentration of the organic surfactant is larger than the critical micelle concentration. Independent measurements of particle mass show also discontinuous water uptake. We speculate that this discontinuous, step-like, growth is caused by disaggregation of a micelle needed to conserve the monolayer of

Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid and methylglyoxal

NASA Astrophysics Data System (ADS)

Tan, Y.; Lim, Y. B.; Altieri, K. E.; Seitzinger, S. P.; Turpin, B. J.

2012-01-01

Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA). Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 μM-10 mM) was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

Rapid Formation of Molecular Bromine from Deliquesced NaBr Aerosol in the Presence of Ozone and UV Light

EPA Science Inventory

The formation of gas-phase bromine from aqueous sodium bromide aerosols is investigated through a combination of chamber experiments and chemical kinetics modeling. Experiments show that Br2(g) is produced rapidly from deliquesced NaBr aerosols in the presence of OH radicals prod...

Formation of aqueous-phase sulfate during the haze period in China: Kinetics and atmospheric implications

NASA Astrophysics Data System (ADS)

Zhang, Haijie; Chen, Shilu; Zhong, Jie; Zhang, Shaowen; Zhang, Yunhong; Zhang, Xiuhui; Li, Zesheng; Zeng, Xiao Cheng

2018-03-01

Sulfate is one of the most important components in the aerosol due to its key role in air pollution and global climate change. Recent work has suggested that reactive nitrogen chemistry in aqueous water can explain the missing source of sulfate in the aqueous water. Herein, we have mapped out the energy profile of the oxidization process of SO2 leading from NO2 and two feasible three-step mechanisms have been proposed. For the oxidation of HOSO2- and HSO3- by the dissolved NO2 in weakly acidic and neutral aerosol (pH ≤ 7), the main contribution to the missing sulfate production comes from the oxidation of HOSO2-. The whole process is a self-sustaining process. For the oxidation of SO32- in alkaline aerosol (pH > 7), the third step - decomposition step of H2O or hydrolysis of SO3 step which are two parallel processes are the rate-limiting steps. The present results are of avail to better understand the missing source of sulfate in the aerosol and hence may lead to better science-based solutions for resolving the severe haze problems in China.

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.

Aqueous oxidation of green leaf volatiles by hydroxyl radical as a source of SOA: Kinetics and SOA yields

NASA Astrophysics Data System (ADS)

Richards-Henderson, Nicole K.; Hansel, Amie K.; Valsaraj, Kalliat T.; Anastasio, Cort

2014-10-01

Green leaf volatiles (GLVs) are a class of oxygenated hydrocarbons released from vegetation, especially during mechanical stress or damage. The potential for GLVs to form secondary organic aerosol (SOA) via aqueous-phase reactions is not known. Fog events over vegetation will lead to the uptake of GLVs into water droplets, followed by aqueous-phase reactions with photooxidants such as the hydroxyl radical (OH). In order to determine if the aqueous oxidation of GLVs by OH can be a significant source of secondary organic aerosol, we studied the partitioning and reaction of five GLVs: cis-3-hexen-1-ol, cis-3-hexenyl acetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol. For each GLV we measured the kinetics of aqueous oxidation by OH, and the corresponding SOA mass yield. The second-order rate constants for GLVs with OH were all near diffusion controlled, (5.4-8.6) × 109 M-1 s-1 at 298 K, and showed a small temperature dependence, with an average activation energy of 9.3 kJ mol-1 Aqueous-phase SOA mass yields ranged from 10 to 88%, although some of the smaller values were not statistically different from zero. Methyl jasmonate was the most effective aqueous-phase SOA precursor due to its larger Henry's law constant and high SOA mass yield (68 ± 8%). While we calculate that the aqueous-phase SOA formation from the five GLVs is a minor source of aqueous-phase SOA, the availability of other GLVs, other oxidants, and interfacial reactions suggest that GLVs overall might be a significant source of SOA via aqueous reactions.

Properties of aerosols and formation mechanisms over southern China during the monsoon season

NASA Astrophysics Data System (ADS)

Chen, Weihua; Wang, Xuemei; Blake Cohen, Jason; Zhou, Shengzhen; Zhang, Zhisheng; Chang, Ming; Chan, Chuen-Yu

2016-10-01

Measurements of size-resolved aerosols from 0.25 to 18 µm were conducted at three sites (urban, suburban and background sites) and used in tandem with an atmospheric transport model to study the size distribution and formation of atmospheric aerosols in southern China during the monsoon season (May-June) in 2010. The mass distribution showed the majority of chemical components were found in the smaller size bins (< 2.5 µm). Sulfate was found to be strongly correlated with aerosol water and anticorrelated with atmospheric SO2, hinting at aqueous-phase reactions being the main formation pathway. Nitrate was the only major species that showed a bimodal distribution at the urban site and was dominated by the coarse mode in the other two sites, suggesting that an important component of nitrate formation is chloride depletion of sea salt transported from the South China Sea. In addition to these aqueous-phase reactions and interactions with sea salt aerosols, new particle formation, chemical aging, and long-range transport from upwind urban or biomass burning regions was also found to be important in at least some of the sites on some of the days. This work therefore summarizes the different mechanisms that significantly impact the aerosol chemical composition during the monsoon over southern China.

Vapour pressure of ammonium chloride aerosol: Effect of temperature and humidity

NASA Astrophysics Data System (ADS)

Pio, Casimiro A.; Harrison, Roy M.

The effect of relative humidity (RH) on the constant for dissociation of ammonium chloride into gaseous HCl and NH 3 has been estimated for different temperatures, using thermodynamic data. At RH over 75-85% the ammonium chloride aerosol exists in the liquid phase, with the dissociation constant two orders of magnitude lower at 98% RH than for solid aerosol at the same temperature. It is predicted that ammonium chloride aqueous aerosol forms predominantly in fogwater and cloud droplets, and in regions where local emissions of NH 3 are important.

A single-step aerosol process for in-situ surface modification of nanoparticles: Preparation of stable aqueous nanoparticle suspensions.

PubMed

Sapra, Mahak; Pawar, Amol Ashok; Venkataraman, Chandra

2016-02-15

Surface modification of nanoparticles during aerosol or gas-phase synthesis, followed by direct transfer into liquid media can be used to produce stable water-dispersed nanoparticle suspensions. This work investigates a single-step, aerosol process for in-situ surface-modification of nanoparticles. Previous studies have used a two-step sublimation-condensation mechanism following droplet drying, for surface modification, while the present process uses a liquid precursor containing two solutes, a matrix lipid and a surface modifying agent. A precursor solution in chloroform, of stearic acid lipid, with 4 %w/w of surface-active, physiological molecules [1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol)-sodium salt (DPPG) or 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy (polyethylene glycol) 2000]-ammonium salt (DPPE-PEG)] was processed in an aerosol reactor at a low gas temperatures. The surface modified nanoparticles were characterized for morphology, surface composition and suspension properties. Spherical, surface-modified lipid nanoparticles with median mobility diameters in the range of 105-150nm and unimodal size distributions were obtained. Fourier transform infra-red spectroscopy (FTIR) measurements confirmed the presence of surface-active molecules on external surfaces of modified lipid nanoparticles. Surface modified nanoparticles exhibited improved suspension stability, compared to that of pure lipid nanoparticles for a period of 30days. Lowest aggregation was observed in DPPE-PEG modified nanoparticles from combined electrostatic and steric effects. The study provides a single-step aerosol method for in-situ surface modification of nanoparticles, using minimal amounts of surface active agents, to make stable, aqueous nanoparticle suspensions. Copyright © 2015 Elsevier Inc. All rights reserved.

Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid

NASA Astrophysics Data System (ADS)

Tan, Y.; Lim, Y. B.; Altieri, K. E.; Seitzinger, S. P.; Turpin, B. J.

2011-06-01

Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA). Acetic acid is an important intermediate in aqueous methylglyoxal oxidation and a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. Altieri et al. (2008) proposed that acetic acid was the precursor of oligoesters observed in methylglyoxal oxidation. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid at concentrations relevant to atmospheric waters (20 μM-10 mM) was oxidized by OH radical. Products were analyzed by ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS), and IC-ESI-MS. The formation of glyoxylic, glycolic, and oxalic acids were observed. In contrast to methylglyoxal oxidation, succinic acid and oligomers were not detected. Using results from these and methylglyoxal + OH radical experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

The frequency-dependent response of single aerosol particles to vapour phase oscillations and its application in measuring diffusion coefficients

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

Preston, Thomas C.; Davies, James F.; Wilson, Kevin R.

A new method for measuring diffusion in the condensed phase of single aerosol particles is proposed and demonstrated. The technique is based on the frequency-dependent response of a binary particle to oscillations in the vapour phase of one of its chemical components. Here, we discuss how this physical situation allows for what would typically be a non-linear boundary value problem to be approximately reduced to a linear boundary value problem. For the case of aqueous aerosol particles, we investigate the accuracy of the closed-form analytical solution to this linear problem through a comparison with the numerical solution of the fullmore » problem. Then, using experimentally measured whispering gallery modes to track the frequency-dependent response of aqueous particles to relative humidity oscillations, we determine diffusion coefficients as a function of water activity. The measured diffusion coefficients are compared to previously reported values found using the two common experiments: (i) the analysis of the sorption/desorption of water from a particle after a step-wise change to the surrounding relative humidity and (ii) the isotopic exchange of water between a particle and the vapour phase. The technique presented here has two main strengths: first, when compared to the sorption/desorption experiment, it does not require the numerical evaluation of a boundary value problem during the fitting process as a closed-form expression is available. Second, when compared to the isotope exchange experiment, it does not require the use of labeled molecules. Therefore, the frequency-dependent experiment retains the advantages of these two commonly used methods but does not suffer from their drawbacks.« less

The frequency-dependent response of single aerosol particles to vapour phase oscillations and its application in measuring diffusion coefficients

DOE PAGES

Preston, Thomas C.; Davies, James F.; Wilson, Kevin R.

2017-01-13

A new method for measuring diffusion in the condensed phase of single aerosol particles is proposed and demonstrated. The technique is based on the frequency-dependent response of a binary particle to oscillations in the vapour phase of one of its chemical components. Here, we discuss how this physical situation allows for what would typically be a non-linear boundary value problem to be approximately reduced to a linear boundary value problem. For the case of aqueous aerosol particles, we investigate the accuracy of the closed-form analytical solution to this linear problem through a comparison with the numerical solution of the fullmore » problem. Then, using experimentally measured whispering gallery modes to track the frequency-dependent response of aqueous particles to relative humidity oscillations, we determine diffusion coefficients as a function of water activity. The measured diffusion coefficients are compared to previously reported values found using the two common experiments: (i) the analysis of the sorption/desorption of water from a particle after a step-wise change to the surrounding relative humidity and (ii) the isotopic exchange of water between a particle and the vapour phase. The technique presented here has two main strengths: first, when compared to the sorption/desorption experiment, it does not require the numerical evaluation of a boundary value problem during the fitting process as a closed-form expression is available. Second, when compared to the isotope exchange experiment, it does not require the use of labeled molecules. Therefore, the frequency-dependent experiment retains the advantages of these two commonly used methods but does not suffer from their drawbacks.« less

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

PubMed Central

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

2013-01-01

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

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

PubMed

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

2013-07-16

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

To Which Extent can Aerosols Affect Alpine Mixed-Phase Clouds?

NASA Astrophysics Data System (ADS)

Henneberg, O.; Lohmann, U.

2017-12-01

Aerosol-cloud interactions constitute a high uncertainty in regional climate and changing weather patterns. Such uncertainties are due to the multiple processes that can be triggered by aerosol especially in mixed-phase clouds. Mixed-phase clouds most likely result in precipitation due to the formation of ice crystals, which can grow to precipitation size. Ice nucleating particles (INPs) determine how fast these clouds glaciate and form precipitation. The potential for INP to transfer supercooled liquid clouds to precipitating clouds depends on the available humidity and supercooled liquid. Those conditions are determined by dynamics. Moderately high updraft velocities result in persistent mixed-phase clouds in the Swiss Alps [1], which provide an ideal testbed to investigate the effect of aerosol on precipitation in mixed-phase clouds. To address the effect of aerosols in orographic winter clouds under different dynamic conditions, we run a number of real case ensembles with the regional climate model COSMO on a horizontal resolution of 1.1 km. Simulations with different INP concentrations within the range observed at the GAW research station Jungfraujoch in the Swiss Alps are conducted and repeated within the ensemble. Microphysical processes are described with a two-moment scheme. Enhanced INP concentrations enhance the precipitation rate of a single precipitation event up to 20%. Other precipitation events of similar strength are less affected by the INP concentration. The effect of CCNs is negligible for precipitation from orographic winter clouds in our case study. There is evidence for INP to change precipitation rate and location more effectively in stronger dynamic regimes due to the enhanced potential to transfer supercooled liquid to ice. The classification of the ensemble members according to their dynamics will quantify the interaction of aerosol effects and dynamics. Reference [1] Lohmann et al, 2016: Persistence of orographic mixed-phase clouds, GRL

Size distribution and scattering phase function of aerosol particles retrieved from sky brightness measurements

NASA Technical Reports Server (NTRS)

Kaufman, Y. J.; Gitelson, A.; Karnieli, A.; Ganor, E. (Editor); Fraser, R. S.; Nakajima, T.; Mattoo, S.; Holben, B. N.

1994-01-01

Ground-based measurements of the solar transmission and sky radiance in a horizontal plane through the Sun are taken in several geographical regions and aerosol types: dust in a desert transition zone in Israel, sulfate particles in Eastern and Western Europe, tropical aerosol in Brazil, and mixed continental/maritime aerosol in California. Stratospheric aerosol was introduced after the eruption of Mount Pinatubo in June 1991. Therefore measurements taken before the eruption are used to analyze the properties of tropospheric aerosol; measurements from 1992 are also used to detect the particle size and concentration of stratospheric aerosol. The measurements are used to retrieve the size distribution and the scattering phase function at large scattering angles of the undisturbed aerosol particles. The retrieved properties represent an average on the entire atmospheric column. A comparison between the retrieved phase function for a scattering angle of 120 deg, with phase function predicted from the retrieved size distribution, is used to test the assumption of particle homogeneity and sphericity in radiative transfer models (Mie theory). The effect was found to be small (20% +/- 15%). For the stratospheric aerosol (sulfates), as expected, the phase function was very well predicted using the Mie theory. A model with a power law distribution, based on the spectral dependence of the optical thickness, alpha, cannot estimate accurately the phase function (up to 50% error for lambda = 0.87 microns). Before the Pinatubo eruption the ratio between the volumes of sulfate and coarse particles was very well correlated with alpha. The Pinatubo stratospheric aerosol destroyed this correlation. The aerosol optical properties are compared with analysis of the size, shape, and composition of the individual particles by electron microscopy of in situ samples. The measured volume size distribution before the injection of stratospheric aerosol consistently show two modes, sulfate

Reactive Heterogeneous Chemistry on Organic Aerosols: Two Case Studies

NASA Astrophysics Data System (ADS)

Abbatt, J.; Braban, C.; Broekhuizen, K.; Thornberry, T.; Thornton, J.

2003-12-01

Two sets of laboratory studies will be discussed to illustrate the impact that heterogeneous chemistry involving tropospheric organic aerosols may have on both the gas-phase composition of the atmosphere and the chemical nature of the particles themselves. In the first case, the reactive uptake coefficient for the hydrolysis of dinitrogen pentoxide (N2O5) on organic aerosols has been measured in an entrained aerosol flow tube coupled to a Chemical-Ionization Mass Spectrometer (CIMS). The general observation is that the reaction on aqueous malonic acid aerosols behaves in an analogous manner to that on aqueous inorganic salts, i.e. the uptake coefficient shows a linear dependence on the particle water content up to 50% relative humidity (RH), at which point the effect saturates. In addition, there is evidence for the kinetics being dependent on both the size of the particles and the levels of dissolved nitrate. By contrast, the N2O5 hydrolysis kinetics on solid azelaic acid particles are too slow to be atmospherically significant, even at 85% RH. In the second case, the kinetics and product yields from the oxidation of liquid oleic acid by ozone have been studied in considerable detail, with emphasis on the quantification of gas-phase products (nonanal) by CIMS and water-soluble species by HPLC/Electrospray-Ionization Mass Spectrometry (azelaic acid, nonanoic acid). The atmospheric importance of these results will be discussed, in particular with respect to the role of organic aerosol oxidation as a source of cloud condensation nuclei.

Aerosol-Phase Production of Nitrogen-Containing Oligomers After Uptake of Methylglyoxal and Cloud Processing

NASA Astrophysics Data System (ADS)

De Haan, D. O.; Riva, M.; Surratt, J. D.; Cazaunau, M.; Doussin, J. F.

2016-12-01

Minimal organic aerosol forms when aerosol particles are exposed to gas-phase methylglyoxal, but condensed phase laboratory studies of aerosol chemistry have suggested that methylglyoxal is a significant source of oligomerized aerosol material. In this study, various types of seed particles were exposed to gaseous methylglyoxal and then cloud-processed in the CESAM chamber. The gas phase was continuously probed by high-resolution PTR-MS during the experiments, and the particle phase WSOC was chemically characterized by high-resolution UPLC/ESI-DAD-QTOFMS. Uptake of methylglyoxal to dry particles caused optical rather than size changes, along with the release of imine products to the gas phase. High RH and cloud processing released some particle-bound methylglyoxal back to the gas phase but triggered an uptake of imine products. Analysis of the particle phase identified N-containing aldol condensation products derived from methylglyoxal, imine (produced from methylglyoxal and amine reactions), acetaldehyde (produced by methylglyoxal photolysis) and hydroxyacetone (produced by methylglyoxal disproportionation) monomers.

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.

Photochemical aging of light-absorbing secondary organic aerosol material.

PubMed

Sareen, Neha; Moussa, Samar G; McNeill, V Faye

2013-04-11

Dark reactions of methylglyoxal with NH4(+) in aqueous aerosols yield light-absorbing and surface-active products that can influence the physical properties of the particles. Little is known about how the product mixture and its optical properties will change due to photolysis as well as oxidative aging by O3 and OH in the atmosphere. Here, we report the results of kinetics and product studies of the photochemical aging of aerosols formed by atomizing aqueous solutions of methylglyoxal and ammonium sulfate. Experiments were performed using aerosol flow tube reactors coupled with an aerosol chemical ionization mass spectrometer (Aerosol-CIMS) for monitoring gas- and particle-phase compositions. Particles were also impacted onto quartz windows in order to assess changes in their UV-visible absorption upon oxidation. Photooxidation of the aerosols leads to the formation of small, volatile organic acids including formic acid, acetic acid, and glyoxylic acid. The atmospheric lifetime of these species during the daytime is predicted to be on the order of minutes, with photolysis being an important mechanism of degradation. The lifetime with respect to O3 oxidation was observed to be on the order of hours. O3 oxidation also leads to a net increase in light absorption by the particles due to the formation of additional carbonyl compounds. Our results are consistent with field observations of high brown carbon absorption in the early morning.

The Secondary Organic Aerosol Processor (SOAP v1.0) model: a unified model with different ranges of complexity based on the molecular surrogate approach

NASA Astrophysics Data System (ADS)

Couvidat, F.; Sartelet, K.

2014-01-01

The Secondary Organic Aerosol Processor (SOAP v1.0) model is presented. This model is designed to be modular with different user options depending on the computing time and the complexity required by the user. This model is based on the molecular surrogate approach, in which each surrogate compound is associated with a molecular structure to estimate some properties and parameters (hygroscopicity, absorption on the aqueous phase of particles, activity coefficients, phase separation). Each surrogate can be hydrophilic (condenses only on the aqueous phase of particles), hydrophobic (condenses only on the organic phase of particles) or both (condenses on both the aqueous and the organic phases of particles). Activity coefficients are computed with the UNIFAC thermodynamic model for short-range interactions and with the AIOMFAC parameterization for medium and long-range interactions between electrolytes and organic compounds. Phase separation is determined by Gibbs energy minimization. The user can choose between an equilibrium and a dynamic representation of the organic aerosol. In the equilibrium representation, compounds in the particle phase are assumed to be at equilibrium with the gas phase. However, recent studies show that the organic aerosol (OA) is not at equilibrium with the gas phase because the organic phase could be semi-solid (very viscous liquid phase). The condensation or evaporation of organic compounds could then be limited by the diffusion in the organic phase due to the high viscosity. A dynamic representation of secondary organic aerosols (SOA) is used with OA divided into layers, the first layer at the center of the particle (slowly reaches equilibrium) and the final layer near the interface with the gas phase (quickly reaches equilibrium).

Development of Recombinant Human Growth Hormone (rhGH) sustained-release microspheres by a low temperature aqueous phase/aqueous phase emulsion method.

PubMed

Kang, Jian; Wu, Fei; Cai, Yunpeng; Xu, Mingxin; He, Mu; Yuan, Weien

2014-10-01

A novel method has been developed to protect Recombinant Human Growth Hormone (rhGH) in poly (lactic-co-glycolic acid) (PLGA) microspheres using an aqueous phase/aqueous phase emulsion and S/O/W multi-emulsion method. This method develops a novel rhGH sustained-release system, which is based on the combination of rhGH-loaded dextran microparticles and PLGA microspheres. The process to fabricate rhGH-loaded dextran microparticles involves an aqueous phase/aqueous phase emulsion system formed at the reduced temperature. RhGH was first dissolved in water together with dextran and polyethylene glycol, followed by stirring at the speed of 2000 rpm for 20-30s at 0°C, and then a freezing process could enable the dextran phase to separate from the continuous PEG phase and rhGH could preferentially be loaded with dextran. The sample after freezing and phase separation was then lyophilized to powder and washed with dichloromethane to remove the PEG. Once loaded in the dextran microparticles (1-4 μm in diameter), rhGH gained resistance to interface tensions and was encapsulated into PLGA microspheres without aggregation thereafter. RhGH released from PLGA microspheres was in a sustained manner with minimal burst and maximally reduced incomplete release in vitro. Single subcutaneous injection of rhGH-loaded PLGA microspheres to rats resulted in a stable plasma concentration for 30 days avoiding the drug concentration fluctuations after multiple injections of protein solutions. In a hypophysectomized rat model, the IGF-1 and bodyweight results showed that there were higher than the levels obtained for the sustained release formulation by W/O/W for 40 days. These results suggest that the microsphere delivery system had the potential to be an injectable depot for sustained-release of the biocompatible protein of rhGH. Copyright © 2014 Elsevier B.V. All rights reserved.

Development of tropine-salt aqueous two-phase systems and removal of hydrophilic ionic liquids from aqueous solution.

PubMed

Wu, Haoran; Yao, Shun; Qian, Guofei; Song, Hang

2016-08-26

A novel aqueous two-phase systems (ATPS) composed of a small molecule organic compound tropine and an organic or inorganic salt aqueous solution has been developed for the first time. The phase behavior of tropine-salt ATPS was systemically investigated and the phase equilibrium data were measured in different temperatures and concentrations and correlated by the Merchuk equation with satisfactory results. The detection of the conductivity and particle size proved the formation of micelle in the process of forming tropine-salt ATPS. The separation application of the ATPS was assessed with the removal of hydrophilic benzothiazolium-based ionic liquids (ILs) from aqueous solution. The result showed that ILs were effectively extracted into the top tropine-rich phase. Finally, ILs in the top tropine-rich phase were further separated by the means of adsorption-desorption with DM301 macroporous resin and ethanol. The method of novel tropine-salt ATPS combined with adsorption-desorption is demonstrated a promising alternative thought and approach for the removal or recovery of hydrophilic compounds from aqueous media and also could provide a potential application for bio-separation. Copyright © 2016. Published by Elsevier B.V.

Chemical reactions at aqueous interfaces

NASA Astrophysics Data System (ADS)

Vecitis, Chad David

2009-12-01

Interfaces or phase boundaries are a unique chemical environment relative to individual gas, liquid, or solid phases. Interfacial reaction mechanisms and kinetics are often at variance with homogeneous chemistry due to mass transfer, molecular orientation, and catalytic effects. Aqueous interfaces are a common subject of environmental science and engineering research, and three environmentally relevant aqueous interfaces are investigated in this thesis: 1) fluorochemical sonochemistry (bubble-water), 2) aqueous aerosol ozonation (gas-water droplet), and 3) electrolytic hydrogen production and simultaneous organic oxidation (water-metal/semiconductor). Direct interfacial analysis under environmentally relevant conditions is difficult, since most surface-specific techniques require relatively `extreme' conditions. Thus, the experimental investigations here focus on the development of chemical reactors and analytical techniques for the completion of time/concentration-dependent measurements of reactants and their products. Kinetic modeling, estimations, and/or correlations were used to extract information on interfacially relevant processes. We found that interfacial chemistry was determined to be the rate-limiting step to a subsequent series of relatively fast homogeneous reactions, for example: 1) Pyrolytic cleavage of the ionic headgroup of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorbed to cavitating bubble-water interfaces during sonolysis was the rate-determining step in transformation to their inorganic constituents carbon monoxide, carbon dioxide, and fluoride; 2) ozone oxidation of aqueous iodide to hypoiodous acid at the aerosol-gas interface is the rate-determining step in the oxidation of bromide and chloride to dihalogens; 3) Electrolytic oxidation of anodic titanol surface groups is rate-limiting for the overall oxidation of organics by the dichloride radical. We also found chemistry unique to the interface, for example: 1

Intercomparison of aerosol-cloud-precipitation interactions in stratiform orographic mixed-phase clouds

NASA Astrophysics Data System (ADS)

Muhlbauer, A.; Hashino, T.; Xue, L.; Teller, A.; Lohmann, U.; Rasmussen, R. M.; Geresdi, I.; Pan, Z.

2010-09-01

Anthropogenic aerosols serve as a source of both cloud condensation nuclei (CCN) and ice nuclei (IN) and affect microphysical properties of clouds. Increasing aerosol number concentrations is hypothesized to retard the cloud droplet coalescence and the riming in mixed-phase clouds, thereby decreasing orographic precipitation. This study presents results from a model intercomparison of 2-D simulations of aerosol-cloud-precipitation interactions in stratiform orographic mixed-phase clouds. The sensitivity of orographic precipitation to changes in the aerosol number concentrations is analysed and compared for various dynamical and thermodynamical situations. Furthermore, the sensitivities of microphysical processes such as coalescence, aggregation, riming and diffusional growth to changes in the aerosol number concentrations are evaluated and compared. The participating numerical models are the model from the Consortium for Small-Scale Modeling (COSMO) with bulk microphysics, the Weather Research and Forecasting (WRF) model with bin microphysics and the University of Wisconsin modeling system (UWNMS) with a spectral ice habit prediction microphysics scheme. All models are operated on a cloud-resolving scale with 2 km horizontal grid spacing. The results of the model intercomparison suggest that the sensitivity of orographic precipitation to aerosol modifications varies greatly from case to case and from model to model. Neither a precipitation decrease nor a precipitation increase is found robustly in all simulations. Qualitative robust results can only be found for a subset of the simulations but even then quantitative agreement is scarce. Estimates of the aerosol effect on orographic precipitation are found to range from -19% to 0% depending on the simulated case and the model. Similarly, riming is shown to decrease in some cases and models whereas it increases in others, which implies that a decrease in riming with increasing aerosol load is not a robust result

Aqueous-phase source of formic acid in clouds

NASA Technical Reports Server (NTRS)

Chameides, W. L.; Davis, D. D.

1983-01-01

The coupled gas- and aqueous-phase cloud chemistry of HCOOH were examined for controlling factors in the acidity of cloud and rainwater. Attention was given to the aqueous OH/HO2 system that yields an OH species that is highly reactive with other species, notably SO2 and the formaldehyde/formic acid complex. A numerical model was developed to simulate the cloud chemistry in the remote troposphere, with considerations given to CH4-CO-NO(x)-O3-H(x)O(y) system. It was determined that aqueous phase OH radicals can produce and destroy formic acid droplets in daylight conditions, as well as control formic acid levels in rainwater. It is sugested that the same types of reactions may be involved in the control of acetic acid and other organic acids.

Understanding the Nature of Marine Aerosols and Their Effects in the Coupled Ocean-Atmosphere System

DTIC Science & Technology

2013-09-30

into aqueous- phase mechanistic relationships leading up to oxalate production. Monocarboxylic and dicarboxylic acids exhibited contrasting spatial...ocean surface. Three case flights show that oxalate (and no other organic acid ) concentrations drop by nearly an order of magnitude relative to...aerosol- cloud interactions. REFERENCES Crahan, K. K., D. Hegg, D. S. Covert, and H. Jonsson (2004), An exploration of aqueous oxalic acid

On the implications of aerosol liquid water and phase ...

EPA Pesticide Factsheets

Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to organic carbon (OM ∕ OC) ratios are high such that separation relative humidities (SRH) are below the ambient relative humidity (RH). As OM ∕ OC ratios in the SE US are often between 1.8 and 2.2, organic aerosol experiences both mixing with inorganic water and separation from it. Regional chemical transport model simulations including inorganic water (but excluding water uptake by organic compounds) in the partitioning medium for secondary organic aerosol (SOA) when RH  >  SRH led to increased SOA concentrations, particularly at night. Water uptake to the organic phase resulted in even greater SOA concentrations as a result of a positive feedback in which water uptake increased SOA, which further increased aerosol water and organic aerosol. Aerosol properties, such as the OM ∕ OC and hygroscopicity parameter (κorg), were captured well by the model compared with measurements during the Southern Oxidant and Aerosol Study (SOAS) 2013. Organic nitrates from monoterpene oxidation were predicted to be the least water-soluble semivolatile species in the model, but most biogenically derived semivolatile species in the Community Multiscale Air Quality (CMAQ) model were hig

Morphology and Optical Properties of Mixed Aerosol Particles

NASA Astrophysics Data System (ADS)

Fard, Mehrnoush M.; Krieger, Ulrich; Rudich, Yinon; Marcolli, Claudia; Peter, Thomas

2015-04-01

Experiments and modeling studies have shown that deliquesced aerosols can be present not only as one-phase system containing organics, inorganic salts and water, but often as two-phase systems consisting of a predominantly organic and a predominantly inorganic aqueous phase 1,2. Recent laboratory studies conducted with model mixtures representing tropospheric aerosols1,2,3, secondary organic aerosol (SOA) from smog chamber experiments4, and field measurements5 suggest that liquid- liquid phase separations (LLPS) is indeed a common phenomenon in mixed organic/ ammonium sulfate (AS) particles. During LLPS, particles may adopt different morphologies mainly core- shell and partially engulfed. A core- shell configuration will have consequences for heterogeneous chemistry and hygroscopicity and as a result will alter the optical properties of the particles since the aqueous inorganic-rich phase will be totally enclosed by a probably highly viscous organic coating with low diffusivity for reactants and water. The primary objective of this project is to establish a method for investigating the morphology of mixed inorganic and absorbing organic compounds of atmospheric relevance and study their radiative properties before, during, and after phase transitions mainly during LLPS. This will be the first study looking into the radiative effect of LLPS in detail. In this first experiment, the behavior of single droplets of carminic acid (CA)/ AS/ H2O mixture was monitored during relative humidity (RH) cycles using optical microscopy. The same mixture particle was levitated in an electrodynamic balance (EDB) and the change in its absorption properties was measured at varying RH. We also intend to determine the occurrence of LLPS in accumulation- sized particles and the change in their absorption using a cavity ring down aerosol spectrometer. If LLPS alters the absorptive properties of the suggested model aerosols significantly, absorption measurements of accumulation mode

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

Cloud Processing of Secondary Organic Aerosol from Isoprene and Methacrolein Photooxidation.

PubMed

Giorio, Chiara; Monod, Anne; Brégonzio-Rozier, Lola; DeWitt, Helen Langley; Cazaunau, Mathieu; Temime-Roussel, Brice; Gratien, Aline; Michoud, Vincent; Pangui, Edouard; Ravier, Sylvain; Zielinski, Arthur T; Tapparo, Andrea; Vermeylen, Reinhilde; Claeys, Magda; Voisin, Didier; Kalberer, Markus; Doussin, Jean-François

2017-10-12

Aerosol-cloud interaction contributes to the largest uncertainties in the estimation and interpretation of the Earth's changing energy budget. The present study explores experimentally the impacts of water condensation-evaporation events, mimicking processes occurring in atmospheric clouds, on the molecular composition of secondary organic aerosol (SOA) from the photooxidation of methacrolein. A range of on- and off-line mass spectrometry techniques were used to obtain a detailed chemical characterization of SOA formed in control experiments in dry conditions, in triphasic experiments simulating gas-particle-cloud droplet interactions (starting from dry conditions and from 60% relative humidity (RH)), and in bulk aqueous-phase experiments. We observed that cloud events trigger fast SOA formation accompanied by evaporative losses. These evaporative losses decreased SOA concentration in the simulation chamber by 25-32% upon RH increase, while aqueous SOA was found to be metastable and slowly evaporated after cloud dissipation. In the simulation chamber, SOA composition measured with a high-resolution time-of-flight aerosol mass spectrometer, did not change during cloud events compared with high RH conditions (RH > 80%). In all experiments, off-line mass spectrometry techniques emphasize the critical role of 2-methylglyceric acid as a major product of isoprene chemistry, as an important contributor to the total SOA mass (15-20%) and as a key building block of oligomers found in the particulate phase. Interestingly, the comparison between the series of oligomers obtained from experiments performed under different conditions show a markedly different reactivity. In particular, long reaction times at high RH seem to create the conditions for aqueous-phase processing to occur in a more efficient manner than during two relatively short cloud events.

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

NASA Astrophysics Data System (ADS)

Hutchings, James W., III

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

Inhomogeneities in particle composition of single, levitated aerosol particles observed by Mie resonance spectroscopy

NASA Astrophysics Data System (ADS)

Krieger, Ulrich; Lienhard, Daniel; Bastelberger, Sandra; Steimer, Sarah

2014-05-01

Recent observations have indicated that organic aerosol particles in the atmosphere may exist in an amorphous semi-solid or even solid (i.e. glassy) state, e.g. [1]. The influence of highly viscous and glassy states on the timescale of aerosol particle equilibration with respect to water vapor have been investigated for some model systems of atmospheric aerosol, e.g. [2,3]. In particular, it has been shown that the kinetics of the water absorption/desorption process is controlled entirely by liquid-phase diffusion of water molecules for a highly viscous aerosol particle. A liquid phase diffusion model based on numerically solving the non-linear diffusion equation predicts strong internal gradients in water concentration when condensed phase diffusion impedes the water uptake from the gas phase [2]. Here we observe and quantify the internal concentration gradients in single, levitated, micron size aerosol particles of aqueous shikimic acid using elastic Mie resonance spectroscopy. A single, aqueous particle is levitated in an electro-dynamic balance (for details see [2]), dried for several days at room temperature, cooled to the target temperature and exposed to a rapid change in relative humidity. In addition to measuring the elastically backscattered light of a "white light" LED source and recording the full spectrum with a spectrograph as in [2], we use a tunable diode laser (TDL) to scan high resolution TE- and TM spectra. This combination allows observing various Mie resonance mode orders simultaneously. Since we perform the experiment at low temperatures and low humidities the changes in the Mie-spectra due to water uptake are sufficiently slow to resolve the kinetics. Experimental Mie resonance spectra are inverted to concentration profiles of water within the particle by applying the numerical diffusion model [2] in conjunction with Mie calculations of multilayered spheres [4]. [1] A. Virtanen et al. (2010): An amorphous solid state of biogenic secondary

Morphologies of aerosol particles consisting of two liquid phases

NASA Astrophysics Data System (ADS)

Song, Mijung; Marcolli, Claudia; Krieger, Ulrich; Peter, Thomas

2013-04-01

Recent studies have shown that liquid-liquid phase separation (LLPS) might be a common feature in mixed organic/ammonium sulfate (AS)/H2O particles. Song et al. (2012) observed that in atmospheric relevant organic/AS/H2O mixtures LLPS always occurred for organic aerosol compositions with O:C < 0.56, depended on the specific functional groups of organics in the range of 0.56 < O:C < 0.80 and never appeared for O:C > 0.80. The composition of the organic fraction and the mixing state of aerosol particles may influence deliquescence relative humidity (DRH) and efflorescence relative humidity (ERH) of inorganic salts during RH cycles and also aerosol morphology. In order to determine how the deliquescence and efflorescence of AS in mixed organic/AS/H2O particles is influenced by LLPS and to identify the corresponding morphologies of the particles, we subjected organic/AS/H2O particles deposited on a hydrophobically coated substrate to RH cycles and observed the phase transitions using optical microscopy and Raman spectroscopy. In this study, we report results from 21 organic/AS/H2O systems with O:C ranging from 0.55 - 0.85 covering aliphatic and aromatic oxidized compounds. Eight systems did not show LLPS for all investigated organic-to-inorganic ratios, nine showed core-shell morphology when present in a two-liquid-phases state and four showed both, core-shell or partially engulfed configurations depending on the organic-to-inorganic ratio. While AS in aerosol particles with complete LLPS showed almost constant values of ERH = 44 ± 4 % and DRH = 77 ± 2 %, a strong reduction or complete inhibition of efflorescence occurred for mixtures that did not exhibit LLPS. To confirm these findings, we performed supplementary experiments on levitated particles in an electrodynamic balance and compared surface and interfacial tensions of the investigated mixtures. Reference Song, M., C. Marcolli, U. K. Krieger, A. Zuend, and T. Peter (2012), Liquid-liquid phase separation in

Intercomparison of aerosol-cloud-precipitation interactions in stratiform orographic mixed-phase clouds

NASA Astrophysics Data System (ADS)

Muhlbauer, A.; Hashino, T.; Xue, L.; Teller, A.; Lohmann, U.; Rasmussen, R. M.; Geresdi, I.; Pan, Z.

2010-04-01

Anthropogenic aerosols serve as a source of both cloud condensation nuclei (CCN) and ice nuclei (IN) and affect microphysical properties of clouds. Increasing aerosol number concentrations is hypothesized to retard the cloud droplet collision/coalescence and the riming in mixed-phase clouds, thereby decreasing orographic precipitation. This study presents results from a model intercomparison of 2-D simulations of aerosol-cloud-precipitation interactions in stratiform orographic mixed-phase clouds. The sensitivity of orographic precipitation to changes in the aerosol number concentrations is analyzed and compared for various dynamical and thermodynamical situations. Furthermore, the sensitivities of microphysical processes such as collision/coalescence, aggregation and riming to changes in the aerosol number concentrations are evaluated and compared. The participating models are the Consortium for Small-Scale Modeling's (COSMO) model with bulk-microphysics, the Weather Research and Forecasting (WRF) model with bin-microphysics and the University of Wisconsin modeling system (UWNMS) with a spectral ice-habit prediction microphysics scheme. All models are operated on a cloud-resolving scale with 2 km horizontal grid spacing. The results of the model intercomparison suggest that the sensitivity of orographic precipitation to aerosol modifications varies greatly from case to case and from model to model. Neither a precipitation decrease nor a precipitation increase is found robustly in all simulations. Qualitative robust results can only be found for a subset of the simulations but even then quantitative agreement is scarce. Estimates of the second indirect aerosol effect on orographic precipitation are found to range from -19% to 0% depending on the simulated case and the model. Similarly, riming is shown to decrease in some cases and models whereas it increases in others which implies that a decrease in riming with increasing aerosol load is not a robust result

Vacuum FTIR observation on hygroscopic properties and phase transition of malonic acid aerosols

NASA Astrophysics Data System (ADS)

Shao, Xu; Zhang, Yun; Pang, Shu-Feng; Zhang, Yun-Hong

2017-02-01

A novel approach based on a combination of a pulse relative humidity (RH) controlling system and a rapid scan vacuum FTIR spectrometer was utilized to investigate the hygroscopic property and phase transition of malonic acid (MA) aerosols. By using this approach, both water vapor amount around the aerosols and water content within aerosols with sub-second time resolution were obtained. Based on the features of FTIR absorbing bands, it can be known that the evolution of hydrogen-bonding structures of malonic acid aerosols took place from (H2O)n-MA to MA-MA accompanying with phase transition in the dehumidifying process. And in present paper, the stepwise efflorescence of MA aerosols and nucleation rates at different RHs are first reported. Our observation has shown that the efflorescence of MA started at ∼17% RH and the nucleation rates increased with decreasing RH.

Modelling non-equilibrium secondary organic aerosol formation and evaporation with the aerosol dynamics, gas- and particle-phase chemistry kinetic multilayer model ADCHAM

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

Roldin, P.; Eriksson, A. C.; Nordin, E. Z.

2014-08-11

We have developed the novel Aerosol Dynamics, gas- and particle- phase chemistry model for laboratory CHAMber studies (ADCHAM). The model combines the detailed gas phase Master Chemical Mechanism version 3.2, an aerosol dynamics and particle phase chemistry module (which considers acid catalysed oligomerization, heterogeneous oxidation reactions in the particle phase and non-ideal interactions between organic compounds, water and inorganic ions) and a kinetic multilayer module for diffusion limited transport of compounds between the gas phase, particle surface and particle bulk phase. In this article we describe and use ADCHAM to study: 1) the mass transfer limited uptake of ammonia (NH3)more » and formation of organic salts between ammonium (NH4+) and carboxylic acids (RCOOH), 2) the slow and almost particle size independent evaporation of α-pinene secondary organic aerosol (SOA) particles, and 3) the influence of chamber wall effects on the observed SOA formation in smog chambers.« less

Thermodynamic Modeling of Organic-Inorganic Aerosols with the Group-Contribution Model AIOMFAC

NASA Astrophysics Data System (ADS)

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

2009-04-01

Liquid aerosol particles are - from a physicochemical viewpoint - mixtures of inorganic salts, acids, water and a large variety of organic compounds (Rogge et al., 1993; Zhang et al., 2007). Molecular interactions between these aerosol components lead to deviations from ideal thermodynamic behavior. Strong non-ideality between organics and dissolved ions may influence the aerosol phases at equilibrium by means of liquid-liquid phase separations into a mainly polar (aqueous) and a less polar (organic) phase. A number of activity models exists to successfully describe the thermodynamic equilibrium of aqueous electrolyte solutions. However, the large number of different, often multi-functional, organic compounds in mixed organic-inorganic particles is a challenging problem for the development of thermodynamic models. The group-contribution concept as introduced in the UNIFAC model by Fredenslund et al. (1975), is a practical method to handle this difficulty and to add a certain predictability for unknown organic substances. We present the group-contribution model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients), which explicitly accounts for molecular interactions between solution constituents, both organic and inorganic, to calculate activities, chemical potentials and the total Gibbs energy of mixed systems (Zuend et al., 2008). This model enables the computation of vapor-liquid (VLE), liquid-liquid (LLE) and solid-liquid (SLE) equilibria within one framework. Focusing on atmospheric applications we considered eight different cations, five anions and a wide range of alcohols/polyols as organic compounds. With AIOMFAC, the activities of the components within an aqueous electrolyte solution are very well represented up to high ionic strength. We show that the semi-empirical middle-range parametrization of direct organic-inorganic interactions in alcohol-water-salt solutions enables accurate computations of vapor-liquid and liquid

Regional Air Quality Model Application of the Aqueous-Phase ...

EPA Pesticide Factsheets

In most ecosystems, atmospheric deposition is the primary input of mercury. The total wet deposition of mercury in atmospheric chemistry models is sensitive to parameterization of the aqueous-phase reduction of divalent oxidized mercury (Hg2+). However, most atmospheric chemistry models use a parameterization of the aqueous-phase reduction of Hg2+ that has been shown to be unlikely under normal ambient conditions or use a non mechanistic value derived to optimize wet deposition results. Recent laboratory experiments have shown that Hg2+ can be photochemically reduced to elemental mercury (Hg) in the aqueous-phase by dissolved organic matter and a mechanism and the rate for Hg2+ photochemical reduction by dicarboxylic acids (DCA) has been proposed. For the first time in a regional scale model, the DCA mechanism has been applied. The HO2-Hg2+ reduction mechanism, the proposed DCA reduction mechanism, and no aqueous-phase reduction (NAR) of Hg2+ are evaluated against weekly wet deposition totals, concentrations and precipitation observations from the Mercury Deposition Network (MDN) using the Community Multiscale Air Quality (CMAQ) model version 4.7.1. Regional scale simulations of mercury wet deposition using a DCA reduction mechanism evaluated well against observations, and reduced the bias in model evaluation by at least 13% over the other schemes evaluated, although summertime deposition estimates were still biased by −31.4% against observations. The use of t

Secondary organic aerosol formation through fog processing of VOCs

NASA Astrophysics Data System (ADS)

Herckes, P.; Hutchings, J. W.

2010-07-01

Volatile Organic Compounds (VOCs) including benzene, toluene, ethylbenzene and xylenes (BTEX) have been determined in highly concentrated amounts (>1 ug/L) in intercepted clouds in northern Arizona (USA). These VOCs are found in concentrations much higher than predicted by partitioning alone. The reactivity of BTEX in the fog/cloud aqueous phase was investigated through laboratory studies. BTEX species showed fast degradation in the aqueous phase in the presence of peroxides and light. Observed half-lives ranged from three and six hours, substantially shorter than the respective gas phase half-lives (several days). The observed reaction rates were on the order of 1 ppb/min but decreased substantially with increasing concentrations of organic matter (TOC). The products of BTEX oxidation reactions were analyzed using HPLC-UV and LCMS. The first generation of products identified included phenol and cresols which correspond to the hydroxyl-addition reaction to benzene and toluene. Upon investigating of multi-generational products, smaller, less volatile species are predominant although a large variety of products is found. Most reaction products have substantially lower vapor pressure and will remain in the particle phase upon droplet evaporation. The SOA generation potential of cloud and fog processing of BTEX was evaluated using simple calculations and showed that in ideal situations these reactions could add up to 9% of the ambient aerosol mass. In more conservative scenarios, the contribution of the processing of BTEX was around 1% of ambient aerosol concentrations. Overall, cloud processing of VOC has the potential to contribute to the atmospheric aerosol mass. However, the contribution will depend upon many factors such as the irradiation, organic matter content in the droplets and droplet lifetime.

Aqueous-phase oxidation of green leaf volatiles by hydroxyl radical as a source of SOA: Product identification from methyl jasmonate and methyl salicylate oxidation

NASA Astrophysics Data System (ADS)

Hansel, Amie K.; Ehrenhauser, Franz S.; Richards-Henderson, Nicole K.; Anastasio, Cort; Valsaraj, Kalliat T.

2015-02-01

Green leaf volatiles (GLVs) are a group of biogenic volatile organic compounds (BVOCs) released into the atmosphere by vegetation. BVOCs produce secondary organic aerosol (SOA) via gas-phase reactions, but little is known of their aqueous-phase oxidation as a source of SOA. GLVs can partition into atmospheric water phases, e.g., fog, mist, dew or rain, and be oxidized by hydroxyl radicals (˙OH). These reactions in the liquid phase also lead to products that have higher molecular weights, increased polarity, and lower vapor pressures, ultimately forming SOA after evaporation of the droplet. To examine this process, we investigated the aqueous, ˙OH-mediated oxidation of methyl jasmonate (MeJa) and methyl salicylate (MeSa), two GLVs that produce aqueous-phase SOA. High performance liquid chromatography/electrospray ionization mass spectrometry (HPLC-ESI-MS) was used to monitor product formation. The oxidation products identified exhibit higher molecular mass than their parent GLV due to either dimerization or the addition of oxygen and hydroxyl functional groups. The proposed structures of potential products are based on mechanistic considerations combined with the HPLC/ESI-MS data. Based on the structures, the vapor pressure and the Henry's law constant were estimated with multiple methods (SPARC, SIMPOL, MPBPVP, Bond and Group Estimations). The estimated vapor pressures of the products identified are significantly (up to 7 orders of magnitude) lower than those of the associated parent compounds, and therefore, the GLV oxidation products may remain as SOA after evaporation of the water droplet. The contribution of the identified oxidation products to SOA formation is estimated based on measured HPLC-ESI/MS responses relative to previous aqueous SOA mass yield measurements.

“Towards building better linkages between aqueous phase ...

EPA Pesticide Factsheets

Currently, CMAQ’s aqueous phase chemistry routine (AQCHEM-base) assumes Henry’s Law equilibrium and employs a forward Euler method to solve a small set of oxidation equations, considering the additional processes of aitken scavenging and wet deposition in series and employing a bisection method to calculate H+ concentrations. With potentially hundreds of reactions that may be important in cloud water and only seven reactions in the current model, expansion of the existing mechanism is an important area of investigation. However, with the current mechanism hardwired into the solver code, the module is difficult to expand with additional chemistry. It also ignores the impacts of mass transfer limitations on cloud chemistry which may be significant. Here, the Kinetic PreProcessor has been applied to generate a Rosenbrock solver for the CMAQ v5.0.1 aqueous phase chemistry mechanism. The module has been updated to simultaneously solve kinetic mass transfer between the phases, dissociation/association, chemical kinetics, Aitken scavenging, and wet deposition. This will allow for easier expansion of the chemical mechanism in the future and a better link between aqueous phase chemistry and droplet microphysics. The National Exposure Research Laboratory (NERL) Atmospheric Modeling and Analysis Division (AMAD) conducts research in support of EPA mission to protect human health and the environment. AMAD research program is engaged in developing and evaluating pre

Comparing the mechanism of water condensation and evaporation in glassy aerosol.

PubMed

Bones, David L; Reid, Jonathan P; Lienhard, Daniel M; Krieger, Ulrich K

2012-07-17

Atmospheric models generally assume that aerosol particles are in equilibrium with the surrounding gas phase. However, recent observations that secondary organic aerosols can exist in a glassy state have highlighted the need to more fully understand the kinetic limitations that may control water partitioning in ambient particles. Here, we explore the influence of slow water diffusion in the condensed aerosol phase on the rates of both condensation and evaporation, demonstrating that significant inhibition in mass transfer occurs for ultraviscous aerosol, not just for glassy aerosol. Using coarse mode (3-4 um radius) ternary sucrose/sodium chloride/aqueous droplets as a proxy for multicomponent ambient aerosol, we demonstrate that the timescale for particle equilibration correlates with bulk viscosity and can be ≫10(3) s. Extrapolation of these timescales to particle sizes in the accumulation mode (e.g., approximately 100 nm) by applying the Stokes-Einstein equation suggests that the kinetic limitations imposed on mass transfer of water by slow bulk phase diffusion must be more fully investigated for atmospheric aerosol. Measurements have been made on particles covering a range in dynamic viscosity from < 0.1 to > 10(13) Pa s. We also retrieve the radial inhomogeneities apparent in particle composition during condensation and evaporation and contrast the dynamics of slow dissolution of a viscous core into a labile shell during condensation with the slow percolation of water during evaporation through a more homogeneous viscous particle bulk.

On the Implications of aerosol liquid water and phase separation for modeled organic aerosol mass

EPA Science Inventory

Current chemical transport models assume that organic aerosol (OA)-forming compounds partition mostly to a water-poor, organic-rich phase in accordance with their vapor pressures. However, in the southeast United States, a significant fraction of ambient organic compounds are wat...

The Secondary Organic Aerosol Processor (SOAP v1.0) model: a unified model with different ranges of complexity based on the molecular surrogate approach

NASA Astrophysics Data System (ADS)

Couvidat, F.; Sartelet, K.

2015-04-01

In this paper the Secondary Organic Aerosol Processor (SOAP v1.0) model is presented. This model determines the partitioning of organic compounds between the gas and particle phases. It is designed to be modular with different user options depending on the computation time and the complexity required by the user. This model is based on the molecular surrogate approach, in which each surrogate compound is associated with a molecular structure to estimate some properties and parameters (hygroscopicity, absorption into the aqueous phase of particles, activity coefficients and phase separation). Each surrogate can be hydrophilic (condenses only into the aqueous phase of particles), hydrophobic (condenses only into the organic phases of particles) or both (condenses into both the aqueous and the organic phases of particles). Activity coefficients are computed with the UNIFAC (UNIversal Functional group Activity Coefficient; Fredenslund et al., 1975) thermodynamic model for short-range interactions and with the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) parameterization for medium- and long-range interactions between electrolytes and organic compounds. Phase separation is determined by Gibbs energy minimization. The user can choose between an equilibrium representation and a dynamic representation of organic aerosols (OAs). In the equilibrium representation, compounds in the particle phase are assumed to be at equilibrium with the gas phase. However, recent studies show that the organic aerosol is not at equilibrium with the gas phase because the organic phases could be semi-solid (very viscous liquid phase). The condensation-evaporation of organic compounds could then be limited by the diffusion in the organic phases due to the high viscosity. An implicit dynamic representation of secondary organic aerosols (SOAs) is available in SOAP with OAs divided into layers, the first layer being at the center of the particle (slowly

Relative Contributions of Regional and Sector Emissions to the Radiative Forcing of Aerosol-Radiation and Aerosol-Cloud Interactions Based on the AeroCOM Phase III/HTAP2 Experiment

NASA Astrophysics Data System (ADS)

Takemura, T.; Chin, M.

2014-12-01

It is important to understand relative contributions of each regional and sector emission of aerosols and their precursor gases to the regional and global mean radiative forcing of aerosol-radiation and aerosol-cloud interactions. This is because it is useful for international cooperation on controls of air pollution and anthropogenic climate change along most suitable reduction path of their emissions from each region and sector. The Task Force on Hemispheric Transport of Air Pollution (TF HTAP) under the United Nations researches the intercontinental transport of air pollutants including aerosols with strong support of the Aerosol Comparisons between Observations and Models (AeroCOM). The ongoing AeroCOM Phase III/HTAP2 experiment assesses relative contributions of regional and sector sources of aerosols and their precursor gases to the air quality using global aerosol transport models with latest emission inventories. In this study, the extended analyses on the relative contributions of each regional and sector emission to the radiative forcing of aerosol-radiation and aerosol-cloud interactions are done from the AeroCOM Phase III/HTAP2 experiment. Simulated results from MIROC-SPRINTARS and other some global aerosol models participating in the the AeroCOM Phase III/HTAP2 experiment are assessed. Acknowledgements: This study is based on the AeroCOM Phase III/HTAP2 experiment and partly supported by the Environment Research and Technology Development Fund (S-12-3) of the Ministry of the Environment, Japan.

Modeling the Transition From Predominantly Gas- to Predominantly Aerosol-Phase Products From OH Reactions With the Homologous Series of C10 to C15 n- Alkanes

NASA Astrophysics Data System (ADS)

Jordan, C. E.; Ziemann, P. J.; Griffin, R. J.; Lim, Y. B.; Atkinson, R.; Arey, J.

2006-12-01

Recent laboratory studies have shown significant formation of secondary organic aerosol (SOA) from OH reactions with a homologous series of n-alkanes. SOA mass yields of 56% were observed for pentadecane (C15), while only 0.5% yield was observed from octane (C8, the smallest alkane in the series). A rapid transition in SOA yield is observed from C10 to C13, with SOA yields increasing from 4% to 49%. In standard gas-aerosol partitioning theory, the vapor pressure controls the amount of material that can condense into the particle phase. However, the rapid transition observed here suggests there may also be a shift in the predominant reaction pathways for longer chain alkanes, leading to greater production of lower vapor pressure products. Here we present an investigation of the role of vapor pressure versus the role of shifting branching ratios to test the influence of each of these on SOA mass yields. We have added each of the alkanes in this series to the Caltech Atmospheric Chemistry Mechanism (CACM). This mechanism was developed in part to predict explicitly concentrations of secondary and tertiary semivolatile oxidation products that potentially form SOA. Although it is has been developed to lump similar compounds together for computational efficiency, it is nonetheless easily adapted and ideally suited for a detailed zero-dimensional modeling study of this kind. This gas-phase mechanism is linked to the aerosol partitioning module MPMPO (Model to Predict the Multi- phase Partitioning of Organics). MPMPO is a fully coupled module that allows the simultaneous partitioning of semi-volatile species to both an aqueous and an organic aerosol phase.

CLEPS 1.0: A new protocol for cloud aqueous phase oxidation of VOC mechanisms

NASA Astrophysics Data System (ADS)

Mouchel-Vallon, Camille; Deguillaume, Laurent; Monod, Anne; Perroux, Hélène; Rose, Clémence; Ghigo, Giovanni; Long, Yoann; Leriche, Maud; Aumont, Bernard; Patryl, Luc; Armand, Patrick; Chaumerliac, Nadine

2017-03-01

A new detailed aqueous phase mechanism named the Cloud Explicit Physico-chemical Scheme (CLEPS 1.0) is proposed to describe the oxidation of water soluble organic compounds resulting from isoprene oxidation. It is based on structure activity relationships (SARs) which provide global rate constants together with branching ratios for HOṡ abstraction and addition on atmospheric organic compounds. The GROMHE SAR allows the evaluation of Henry's law constants for undocumented organic compounds. This new aqueous phase mechanism is coupled with the MCM v3.3.1 gas phase mechanism through a mass transfer scheme between gas phase and aqueous phase. The resulting multiphase mechanism has then been implemented in a model based on the Dynamically Simple Model for Atmospheric Chemical Complexity (DSMACC) using the Kinetic PreProcessor (KPP) that can serve to analyze data from cloud chamber experiments and field campaigns. The simulation of permanent cloud under low-NOx conditions describes the formation of oxidized monoacids and diacids in the aqueous phase as well as a significant influence on the gas phase chemistry and composition and shows that the aqueous phase reactivity leads to an efficient fragmentation and functionalization of organic compounds.

Hydroxyhydroperoxide (HHP) Formation From H2O2 Addition to Carbonyls in the Aqueous Phase and Its Environmental Implications

NASA Astrophysics Data System (ADS)

Zhao, R.; Soong, R.; Simpson, A. J.; Abbatt, J.

2012-12-01

Organic peroxides are major components of secondary organic aerosol (SOA), affecting the toxicity of SOA and its oxidative capacity. Hydroxyhydroperoxide (HHP) is a class of organic peroxide observed in ambient air, rain water, and cloud water. However, the formation pathway of HHPs remains under debate, with one potential path via reaction of water with Criegee Intermediates. The current study focuses on a formation mechanism involving reversible nucleophilic addition of H2O2 to aldehydes. This formation pathway of HHPs has been known for decades, but has long been considered as a minor reaction. This is because HHPs were observed to decompose rapidly into H2O2 and the corresponding aldehydes in dilute aqueous solutions. In the current study, proton transfer reaction mass spectrometry (PTR-MS) and proton nuclear magnetic resonance (1H NMR) spectrometry were employed to determine the equilibrium constants (Keq) of H2O2 addition to a variety of atmospherically relevant carbonyls in the aqueous phase. HHP formation was insignificant from ketones and methacrolein, but was significant from formaldehyde, acetaldehyde and propionaldehyde. The Keq values ranged from 80 to 150 M-1 at 25 °C. Based on these values, the environmental implications of HHP formation via this pathway suggest that HHP formation is unlikely to be significant in cloud water. However, in aerosol liquid water, where the concentrations of aldehydes and H2O2 can be at the mM level, this pathway may be significant.

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.

Chemical evolution of multicomponent aerosol particles during evaporation

NASA Astrophysics Data System (ADS)

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

2010-05-01

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

Impact of Aerosol Processing on Orographic Clouds

NASA Astrophysics Data System (ADS)

Pousse-Nottelmann, Sara; Zubler, Elias M.; Lohmann, Ulrike

2010-05-01

Aerosol particles undergo significant modifications during their residence time in the atmosphere. Physical processes like coagulation, coating and water uptake, and aqueous surface chemistry alter the aerosol size distribution and composition. At this, clouds play a primary role as physical and chemical processing inside cloud droplets contributes considerably to the changes in aerosol particles. A previous study estimates that on global average atmospheric particles are cycled three times through a cloud before being removed from the atmosphere [1]. An explicit and detailed treatment of cloud-borne particles has been implemented in the regional weather forecast and climate model COSMO-CLM. The employed model version includes a two-moment cloud microphysical scheme [2] that has been coupled to the aerosol microphysical scheme M7 [3] as described by Muhlbauer and Lohmann, 2008 [4]. So far, the formation, transfer and removal of cloud-borne aerosol number and mass were not considered in the model. Following the parameterization for cloud-borne particles developed by Hoose et al., 2008 [5], distinction between in-droplet and in-crystal particles is made to more physically account for processes in mixed-phase clouds, such as the Wegener-Bergeron-Findeisen process and contact and immersion freezing. In our model, this approach has been extended to allow for aerosol particles in five different hydrometeors: cloud droplets, rain drops, ice crystals, snow flakes and graupel. We account for nucleation scavenging, freezing and melting processes, autoconversion, accretion, aggregation, riming and selfcollection, collisions between interstitial aerosol particles and hydrometeors, ice multiplication, sedimentation, evaporation and sublimation. The new scheme allows an evaluation of the cloud cycling of aerosol particles by tracking the particles even when scavenged into hydrometeors. Global simulations of aerosol processing in clouds have recently been conducted by Hoose et al

Multiphase OH oxidation kinetics of organic aerosol: The role of particle phase state and relative humidity

NASA Astrophysics Data System (ADS)

Slade, Jonathan H.; Knopf, Daniel A.

2014-07-01

Organic aerosol can exhibit different phase states in response to changes in relative humidity (RH), thereby influencing heterogeneous reaction rates with trace gas species. OH radical uptake by laboratory-generated levoglucosan and methyl-nitrocatechol particles, serving as surrogates for biomass burning aerosol, is determined as a function of RH. Increasing RH lowers the viscosity of amorphous levoglucosan aerosol particles enabling enhanced OH uptake. Conversely, OH uptake by methyl-nitrocatechol aerosol particles is suppressed at higher RH as a result of competitive coadsorption of H2O that occupies reactive sites. This is shown to have substantial impacts on organic aerosol lifetimes with respect to OH oxidation. The results emphasize the importance of organic aerosol phase state to accurately describe the multiphase chemical kinetics and thus chemical aging process in atmospheric models to better represent the evolution of organic aerosol and its role in air quality and climate.

Phase-separable aqueous amide solutions as a thermal history indicator.

PubMed

Kitsunai, Makoto; Miyajima, Kentaro; Mikami, Yuzuru; Kim, Shokaku; Hirasawa, Akira; Chiba, Kazuhiro

2008-12-01

Aqueous solutions of several new amide compounds for use as simple thermal history indicators in the low-temperature transport of food and other products were synthesized. The phase transition temperatures of the aqueous solutions can be freely adjusted by changing the amide-water ratio in solution, the sodium chloride concentration of the water, and the type of amide compound. It is expected that these aqueous solutions can be applied as new thermal history indicators.

Understanding hygroscopic growth and phase transformation of aerosols using single particle Raman spectroscopy in an electrodynamic balance.

PubMed

Lee, Alex K Y; Ling, T Y; Chan, Chak K

2008-01-01

Hygroscopic growth is one of the most fundamental properties of atmospheric aerosols. By absorbing or evaporating water, an aerosol particle changes its size, morphology, phase, chemical composition and reactivity and other parameters such as its refractive index. These changes affect the fate and the environmental impacts of atmospheric aerosols, including global climate change. The ElectroDynamic Balance (EDB) has been widely accepted as a unique tool for measuring hygroscopic properties and for investigating phase transformation of aerosols via single particle levitation. Coupled with Raman spectroscopy, an EDB/Raman system is a powerful tool that can be used to investigate both physical and chemical changes associated with the hygroscopic properties of individually levitated particles under controlled environments. In this paper, we report the use of an EDB/Raman system to investigate (1) contact ion pairs formation in supersaturated magnesium sulfate solutions; (2) phase transformation in ammonium nitrate/ammonium sulfate mixed particles; (3) hygroscopicity of organically coated inorganic aerosols; and (4) heterogeneous reactions altering the hygroscopicity of organic aerosols.

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

NASA Technical Reports Server (NTRS)

Liao, Hong; Seinfeld, John H.

2005-01-01

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

Exploring the ionic strength effects on the photochemical degradation of pyruvic acid in atmospheric deliquescent aerosol particles

NASA Astrophysics Data System (ADS)

Mekic, Majda; Brigante, Marcello; Vione, Davide; Gligorovski, Sasho

2018-07-01

There is increasing evidence that aqueous-phase atmospheric chemistry is an important source of secondary organic aerosols (SOA), but the related processes are currently not adequately represented in atmospheric chemistry models. Here we show that the absorption spectrum of pyruvic acid (PA) exhibits both an increase of the absorption intensity and a red shift of 13 nm while going from a dilute aqueous phase to a solution containing the inert salt sodium perchlorate (5M NaClO4). If this phenomenon turns out to be more general, many compounds that do not absorb actinic light in clouds and fog could become light absorbers at elevated salt concentrations in aerosol deliquescent particles. Compared to the direct photolysis of PA in dilute aqueous solution, the photolysis rate is increased by three times at high ionic strength (5M NaClO4). Such a considerable enhancement can be rationalized in the framework of the Debye-McAulay approach for reactions of ionic + neutral (or neutral + neutral) species, considering that the PA direct photolysis likely involves interaction between the photogenerated triplet state and water. This is, to our knowledge, the first report of a significant effect of the ionic strength on the rate of an atmospheric photochemical reaction. The phenomenon has important implications for the fate of PA and, potentially, of other organic compounds in atmospheric aerosol deliquescent particles.

Novel Measurements of Aerosol Particle Interfaces Using Biphasic Microfluidics

NASA Astrophysics Data System (ADS)

Metcalf, A. R.; Dutcher, C. S.

2014-12-01

Secondary organic aerosol (SOA) particles are nearly ubiquitous in the atmosphere and yet there remains large uncertainties in their formation processes and ambient properties. These particles are complex microenvironments, which can contain multiple interfaces due to internal aqueous-organic phase partitioning and to the external liquid-vapor surface. These aerosol interfaces can profoundly affect the fate of condensable organic compounds emitted into the atmosphere by altering the way in which organic vapors interact with the ambient aerosol. Aerosol interfaces affect particle internal structure, species uptake, equilibrium partitioning, activation to cloud condensation or ice nuclei, and optical properties. For example, organic thin films can shield the core of the aerosol from the ambient environment, which may disrupt equilibrium partitioning and mass transfer. To improve our ability to accurately predict the fate of SOA in the atmosphere, we must improve our knowledge of aerosol interfaces and their interactions with the ambient environment. Few technologies exist to accurately probe aerosol interfaces at atmospherically-relevant conditions. In this talk, a novel method using biphasic microscale flows will be introduced for generating, trapping, and perturbing complex interfaces at atmospherically relevant conditions. These microfluidic experiments utilize high-speed imaging to monitor interfacial phenomena at the microscale and are performed with phase contrast and fluorescence microscopy on a temperature-controlled inverted microscope stage. From these experiments, interfacial thermodynamic properties such as surface tension, rheological properties such as interfacial moduli, and kinetic properties such as mass transfer coefficients can be measured or inferred. Chemical compositions of the liquid phases studied here span a range of viscosities and include electrolyte and water soluble organic acid species often observed in the atmosphere, such as mixtures

Heterogeneous Production of Sulfate Aerosol over China.

NASA Astrophysics Data System (ADS)

Shao, J.; Alexander, B.; Chen, Q.; Zhang, L.; Wang, Y.; Xie, Z.; He, P.

2017-12-01

Sulfate is thought to be the main contributor to the growth of PM2.5 during the severe haze pollution over China, but most studies have shown that traditional gas- and aqueous-phase chemistry cannot explain the rapid sulfate production during haze events, suggesting a missing heterogeneous oxidation mechanism. In this work, we implement heterogeneous sulfate formation into a 3-D global chemical transport model (GEOS-Chem) to evaluate the different pathways for global and regional sulfate production, including SO2 oxidation by NO2, O3, H2O2, and TMI+O2. Heterogeneous sulfate production rates and the dominant heterogeneous sulfate formation mechanism depends on calculations of aerosol pH, which is in turn is dependent upon thermodynamic state assumptions. We evaluate the influence of aerosol pH and potential impacts of aerosol ionic strength on sulfate production rates and mechanisms in the model, and its implications for PM2.5 in Chinese haze events.

Photochemical Cycling of Humic-Like Substances in Atmospheric Aerosols

NASA Astrophysics Data System (ADS)

Rincon, A. G.; Guzman, M. I.; Hoffmann, M. R.; Colussi, A. J.

2007-12-01

Colored, humic-like substances (HULIS) arising from the biodegradation of organic detritus are widespread in natural surface waters, where they ultimately undergo solar photolysis into small alpha-dicarbonylic species, such as glyoxal, glyoxylic and pyruvic acids. Diversely generated and chemically dissimilar HULIS are also found in the atmospheric aerosol. How are significant levels of colored HULIS produced and sustained in the concentrated aerosol phase under intense solar irradiation? Here, this issue is tackled by investigating the solar photolysis of aqueous pyruvic acid (PA) solutions at concentrations representative of the atmospheric aerosol using UV-absorption, high resolution electrospray mass, and nuclear magnetic resonance spectrometries. Under such conditions, PA is not photodegraded but yields polyfunctional polymers, whose mass and UV-absorption spectra remain unaffected after 3, 8 and 22 h photolysis. Unless diluted, these polymers undergo condensation/polymerization in the post-photolysis period into mass < 700 Da species that absorb in the visible, and are bleached upon resuming irradiation. The re- photolyzed solutions recover the mass and UV-absorption spectra of first photolyzed solutions. Whereas initial pH has no effect on the mechanism of reaction, ammonium bisulfate, a major component of the aerosol, markedly influences these processes. These findings suggest that the chemical identity and concentration levels of complex organic substances in the aerosol are the result of dynamic photochemical processing in the condensed phase.

Primary and secondary aerosols in Beijing in winter: sources, variations and processes

NASA Astrophysics Data System (ADS)

Sun, Yele; Du, Wei; Fu, Pingqing; Wang, Qingqing; Li, Jie; Ge, Xinlei; Zhang, Qi; Zhu, Chunmao; Ren, Lujie; Xu, Weiqi; Zhao, Jian; Han, Tingting; Worsnop, Douglas R.; Wang, Zifa

2016-07-01

Winter has the worst air pollution of the year in the megacity of Beijing. Despite extensive winter studies in recent years, our knowledge of the sources, formation mechanisms and evolution of aerosol particles is not complete. Here we have a comprehensive characterization of the sources, variations and processes of submicron aerosols that were measured by an Aerodyne high-resolution aerosol mass spectrometer from 17 December 2013 to 17 January 2014 along with offline filter analysis by gas chromatography/mass spectrometry. Our results suggest that submicron aerosols composition was generally similar across the winter of different years and was mainly composed of organics (60 %), sulfate (15 %) and nitrate (11 %). Positive matrix factorization of high- and unit-mass resolution spectra identified four primary organic aerosol (POA) factors from traffic, cooking, biomass burning (BBOA) and coal combustion (CCOA) emissions as well as two secondary OA (SOA) factors. POA dominated OA, on average accounting for 56 %, with CCOA being the largest contributor (20 %). Both CCOA and BBOA showed distinct polycyclic aromatic hydrocarbons (PAHs) spectral signatures, indicating that PAHs in winter were mainly from coal combustion (66 %) and biomass burning emissions (18 %). BBOA was highly correlated with levoglucosan, a tracer compound for biomass burning (r2 = 0.93), and made a considerable contribution to OA in winter (9 %). An aqueous-phase-processed SOA (aq-OOA) that was strongly correlated with particle liquid water content, sulfate and S-containing ions (e.g. CH2SO2+) was identified. On average aq-OOA contributed 12 % to the total OA and played a dominant role in increasing oxidation degrees of OA at high RH levels (> 50 %). Our results illustrate that aqueous-phase processing can enhance SOA production and oxidation states of OA as well in winter. Further episode analyses highlighted the significant impacts of meteorological parameters on aerosol composition, size

Radial inhomogeneities in particle composition of single, levitated aerosol particles observed by Mie resonance spectroscopy (Invited)

NASA Astrophysics Data System (ADS)

Krieger, U. K.; Steimer, S.; Lienhard, D.; Bastelberger, S.

2013-12-01

Recent observations have indicated that organic aerosol particles in the atmosphere may exist in an amorphous semi-solid or even solid (i.e. glassy) state, e.g. [1]. The influence of highly viscous and glassy states on the timescale of aerosol particle equilibration with respect to water vapor have been investigated for some model systems of atmospheric aerosol, e.g. [2,3]. In particular, it has been shown that the kinetics of the water absorption/desorption process is controlled entirely by liquid-phase diffusion of water molecules for a highly viscous aerosol particle. A liquid phase diffusion model based on numerically solving the non-linear diffusion equation predicts strong internal gradients in water concentration when condensed phase diffusion impedes the water uptake from the gas phase [2]. Here we observe and quantify the internal concentration gradients in single, levitated, micron size aerosol particles of aqueous MBTCA (3-methyl-1,2,3-Butanetricarboxylic acid) and shikimic acid using elastic Mie resonance spectroscopy. A single, aqueous particle is levitated in an electro-dynamic balance (for details see [2]), dried for several days at room temperature, cooled to the target temperature and exposed to a rapid change in relative humidity. In addition to measuring the elastically backscattered light of a 'white light ' LED source and recording the full spectrum with a spectrograph as in [2], we use a tunable diode laser (TDL) to scan high resolution TE- and TM spectra. This combination allows observing various Mie resonance mode orders simultaneously. Since we perform the experiment at low temperatures and low humidities the changes in the Mie-spectra due to water uptake are sufficiently slow to resolve the kinetics. Experimental Mie resonance spectra are inverted to concentration profiles of water within the particle by applying the numerical diffusion model [2] in conjunction with Mie calculations of multilayered spheres [4]. Potential implications for

Aqueous SOA formation from radical oligomerization of methyl vinyl ketone (MVK) and methacrolein (MACR)

NASA Astrophysics Data System (ADS)

Renard, P.; Siekmann, F.; Ravier, S.; Temime-Roussel, B.; Clément, J.; Ervens, B.; Monod, A.

2013-12-01

It is now accepted that one of the important pathways of secondary organic aerosol (SOA) formation occurs through aqueous phase chemistry in the atmosphere. However, the chemical mechanisms leading to macromolecules are still not well understood. It was recently shown that oligomer production by OH radical oxidation in the aerosol aqueous phase from α-dicarbonyl precursors, such as methylglyoxal and glyoxal, is irreversible and fast. We have investigated the aqueous phase photooxidation of MACR and MVK, which are biogenic organic compounds derived from isoprene. Aqueous phase photooxidation of MVK and MACR was investigated in a photoreactor using photolysis of H2O2 as OH radical source. Electrospray high resolution mass spectrometry analysis of the solutions brought clear evidence for the formation of oligomer systems having a mass range of up to 1800 Da within less than 15 minutes of reaction. Highest oligomer formation rates were obtained under conditions of low dissolved oxygen, highest temperature (T = 298 K) and highest precursor initial concentrations ([MVK]0 = 20 mM). A radical mechanism of oligomerization is proposed to explain the formation of the high molecular weight products. Furthermore, we quantified the total amount of carbon present in oligomers. Kinetic parameters of the proposed oligomerization mechanism are constrained by means of a box model that is able to reproduce the temporal evolution of intermediates and products as observed in the laboratory experiments. Additional model simulations for atmospherically-relevant conditions will be presented that show the extent to which these radical processes contribute to SOA formation in the atmospheric multiphase system as compared to other aqueous phase as well as traditional SOA sources. MVK time profile (as measured by UV Spectroscopy) and mass spectra (obtained using UPLC-ESI-MS for the retention time range 0-5 min in the positive mode) at 5, 10 and 50 min of reaction (MVK 20 mM, 25° C, under

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

Secondary Organic Aerosol Formation from Glyoxal: photochemical versus dark uptake and reversible versus irreversible SOA formation

NASA Astrophysics Data System (ADS)

Waxman, E.; Slowik, J. G.; Kampf, C. J.; Timkovsky, J.; Noziere, B.; Praplan, A. P.; Pfaffenberger, L.; Holzinger, R.; Hoffmann, T.; Dommen, J.; Prevot, A. S.; Baltensperger, U.; Volkamer, R.

2011-12-01

Glyoxal forms secondary organic aerosol (SOA) by partitioning to the aerosol aqueous phase according to Henry's law. The subsequent processing by heterogeneous and multiphase reactions shifts the partitioning towards aerosols. Currently it is not well understood whether these reactions result in reversible or irreversible SOA formation, and what parameters influence the rate limiting step of multiphase processing. We conducted a series of simulation chamber experiments at PSI in April and May 2011 to investigate processing under dark conditions, UV and/or visible light irradiated conditions, and in the presence and absence of OH radicals. Experiments used ammonium sulfate or ammonium sulfate/fulvic acid mixtures as seed aerosols, and were conducted between 50% and 85% relative humidity at approximately constant RH over the course of any given experiment. Glyoxal was produced photochemically from acetylene, using HONO photolysis as the OH radical source. Gas-phase glyoxal was measured by the CU LED-Cavity Enhanced-DOAS. The Thermal-Desorption Proton-Transfer-Reaction Mass Spectrometer (TD-PTR-MS) and Ion Chromatography Mass Spectrometer (IC-MS) monitored both gas and aerosol-phase organic reaction products. Particle composition was monitored by High-Resolution Time-of-Flight Aerosol Mass Spectrometry (HR-ToF-AMS), and HPLC-ESI MS/MS and LC-MS analysis of filter samples.

Secondary Organic Aerosol Formation from Glyoxal: photochemical versus dark uptake and reversible versus irreversible SOA formation

NASA Astrophysics Data System (ADS)

Waxman, E.; Slowik, J.; Kampf, C.; Timkovsky, J.; Noziere, B.; Praplan, A.; Pffafenberger, L.; Holzinger, R.; Hoffmann, T.; Dommen, J.; Prevot, A.; Baltensperger, U.; Volkamer, R.

2012-04-01

Glyoxal forms secondary organic aerosol (SOA) by partitioning to the aerosol aqueous phase according to Henry's law. The subsequent processing by heterogeneous and multiphase reactions shifts the partitioning towards aerosols. Currently it is not well understood whether these reactions result in reversible or irreversible SOA formation, and what parameters influence the rate limiting step of multiphase processing. We conducted a series of simulation chamber experiments at PSI in April and May 2011 to investigate processing under dark conditions, UV and/or visible light irradiated conditions, and in the presence and absence of OH radicals. Experiments used ammonium sulfate or ammonium sulfate/fulvic acid mixtures as seed aerosols, and were conducted between 50% and 85% relative humidity at approximately constant RH over the course of any given experiment. Glyoxal was produced photochemically from acetylene, using HONO photolysis as the OH radical source. Gas-phase glyoxal was measured by the CU LED-Cavity Enhanced-DOAS. The Thermal-Desorption Proton-Transfer-Reaction Mass Spectrometer (TD-PTR-MS) and Ion Chromatography Mass Spectrometer (IC-MS) monitored both gas and aerosol-phase organic reaction products. Particle composition was monitored by High-Resolution Time-of-Flight Aerosol Mass Spectrometry (HR-ToF-AMS), and HPLC-ESI MS/MS and LC-MS analysis of filter samples.

Cell separations and the demixing of aqueous two phase polymer solutions in microgravity

NASA Technical Reports Server (NTRS)

Brooks, Donald E.; Bamberger, Stephan; Harris, J. M.; Van Alstine, James M.

1991-01-01

Partition in phase separated aqueous polymer solutions is a cell separation procedure thought to be adversely influenced by gravity. In preparation for performing cell partitioning experiments in space, and to provide general information concerning the demixing of immiscible liquids in low gravity, a series of phase separated aqueous polymer solutions have been flown on two shuttle flights. Fluorocarbon oil and water emulsions were also flown on the second flight. The aqueous polymer emulsions, which in one g demix largely by sedimentation and convection due to the density differences between the phases, demixed more slowly than on the ground and the final disposition of the phases was determined by the wetting of the container wall by the phases. The demixing behavior and kinetics were influenced by the phase volume ratio, physical properties of the systems and chamber wall interaction. The average domain size increased linearly with time as the systems demixed.

How Is the Oxidative Capacity of the Cloud Aqueous Phase Modified By Bacteria?

NASA Astrophysics Data System (ADS)

Deguillaume, L.; Mouchel-Vallon, C.; Passananti, M.; Wirgot, N.; Joly, M.; Sancelme, M.; Bianco, A.; Cartier, N.; Brigante, M.; Mailhot, G.; Delort, A. M.; Chaumerliac, N. M.

2014-12-01

The aqueous phase photochemical reactions of constituents present in atmospheric water like H2O2, NO3-, NO2- and Fe(III) aqua-complexes or organic complexes can form radicals such as the hydroxyl radical HO within the water drop. However, the literature lacks of data precising the rate of HO formation and the relative contribution of the photochemical sources of HO. The production of radicals in cloud aqueous phase drives the oxidative capacity of the cloud medium and the efficiency of organic matter oxidation. The oxidation of organic compounds is suspected to lead to oxygenated species that could contribute to secondary organic aerosol (SOA) mass (Ervens et al., 2011). In current cloud chemistry models, HO concentrations strongly depend on the organic and iron amount. For high concentrations of organic compounds, this radical is efficiently consumed during the day due to the oxidation process. When iron concentrations are typical from continental cloud, the photolysis of Fe(III) complexes and the Fenton reaction drive the HO concentrations in the cloud models. The concept of biocatalysed reactions contributing to atmospheric chemistry as an alternative route to photochemistry is quite new (Vaïtilingom et al., 2013); it emerged from the recent discovery of metabolically active microorganisms in clouds. Microorganisms are well-known to degrade organic matter but they could also interact with oxidant species such as H2O2 (or their precursors) thanks to their oxidative and nitrosative stress metabolism that will act directly on these species and on their interactions with iron (metalloproteins and siderophores). For the moment, biological impact on radical chemistry within cloud has not been yet considered in cloud chemistry models. Bacterial activity will be introduced as catalysts in a multiphase cloud chemistry model using degradation rates measured in the laboratory. For example, biodegradation rates of the oxidants H2O2 by model bacteria will be tested in the

Aqueous-Phase Photochemical Production of Oxidants in Atmospheric Waters.

NASA Astrophysics Data System (ADS)

Allen, John Morrison

1992-01-01

The photochemical formation and subsequent reactions of oxidants plays an important role in the overall chemistry of the atmosphere. Much of the interest in atmospheric oxidation reactions has been fueled by the environmental consequences of the oxidation of sulfur dioxide (SO _2) forming sulfuric acid (H_2 SO_4). Oxidation reactions also play a crucial role in other atmospheric chemical transformations such as: (1) the destruction of tropospheric ozone, (2) redox cycling of transition metals, and (3) oxidation of organic compounds. Much of the research pertaining to atmospheric oxidant formation and the reactions that these oxidants undergo has centered upon gas-phase photochemical oxidant formation and: (1) subsequent reactions in the gas phase, or (2) partitioning of oxidants into cloud and fog drops and subsequent reactions in the aqueous phase. Only a very limited amount of data is available concerning aqueous -phase photochemical sources of oxidants in cloud and fog drops. The focus of one aspect of the work presented in this dissertation is upon the aqueous-phase sunlight photochemical formation of oxidants in authentic cloud and fog water samples from across the United States and Canada. It will be demonstrated that atmospheric waters typically absorb solar ultraviolet radiation at wavelengths ranging from 290 to 340 nm. This absorption is due to the presence of chemical constituents in the cloud and fog waters that contain chromophoric functional groups that give rise to the formation of: (1) singlet molecular oxygen O_2(^1Delta_ {rm g}), (2) peroxyl radicals (HO _2cdot and RO_2 cdot), (3) peroxides (HOOH, ROOH, and ROOR '), and (4) hydroxyl radical ( cdotOH). This work will demonstrate that aqueous-phase photochemical reactions are a significant and in some cases dominant source of these oxidants in cloud and fog drops. The transition metal catalyzed oxidation of SO _2 to H_2SO _4 by molecular oxygen has been extensively studied. This reaction is thought

Tube Radial Distribution Flow Separation in a Microchannel Using an Ionic Liquid Aqueous Two-Phase System Based on Phase Separation Multi-Phase Flow.

PubMed

Nagatani, Kosuke; Shihata, Yoshinori; Matsushita, Takahiro; Tsukagoshi, Kazuhiko

2016-01-01

Ionic liquid aqueous two-phase systems were delivered into a capillary tube to achieve tube radial distribution flow (TRDF) or annular flow in a microspace. The phase diagram, viscosity of the phases, and TRDF image of the 1-butyl-3-methylimidazolium chloride and NaOH system were examined. The TRDF was formed with inner ionic liquid-rich and outer ionic liquid-poor phases in the capillary tube. The phase configuration was explained using the viscous dissipation principle. We also examined the distribution of rhodamine B in a three-branched microchannel on a microchip with ionic liquid aqueous two-phase systems for the first time.

Radiative forcing of the direct aerosol effect from AeroCom Phase II simulations

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

Myhre, G.; Samset, B. H.; Schulz, M.

2013-01-01

We report on the AeroCom Phase II direct aerosol effect (DAE) experiment where 16 detailed global aerosol models have been used to simulate the changes in the aerosol distribution over the industrial era. All 16 models have estimated the radiative forcing (RF) of the anthropogenic DAE, and have taken into account anthropogenic sulphate, black carbon (BC) and organic aerosols (OA) from fossil fuel, biofuel, and biomass burning emissions. In addition several models have simulated the DAE of anthropogenic nitrate and anthropogenic influenced secondary organic aerosols (SOA). The model simulated all-sky RF of the DAE from total anthropogenic aerosols has amore » range from -0.58 to -0.02 Wm -2, with a mean of -0.27 Wm -2 for the 16 models. Several models did not include nitrate or SOA and modifying the estimate by accounting for this with information from the other AeroCom models reduces the range and slightly strengthens the mean. Modifying the model estimates for missing aerosol components and for the time period 1750 to 2010 results in a mean RF for the DAE of -0.35 Wm -2. Compared to AeroCom Phase I (Schulz et al., 2006) we find very similar spreads in both total DAE and aerosol component RF. However, the RF of the total DAE is stronger negative and RF from BC from fossil fuel and biofuel emissions are stronger positive in the present study than in the previous AeroCom study. We find a tendency for models having a strong (positive) BC RF to also have strong (negative) sulphate or OA RF. This relationship leads to smaller uncertainty in the total RF of the DAE compared to the RF of the sum of the individual aerosol components. The spread in results for the individual aerosol components is substantial, and can be divided into diversities in burden, mass extinction coefficient (MEC), and normalized RF with respect to AOD. We find that these three factors give similar contributions to the spread in results.« less

Radiative Forcing of the Direct Aerosol Effect from AeroCom Phase II Simulations

NASA Technical Reports Server (NTRS)

Myhre, G.; Samset, B. H.; Schulz, M.; Balkanski, Y.; Bauer, S.; Berntsen, T. K.; Bian, H.; Bellouin, N.; Chin, M.; Diehl, T.;

Radiative forcing of the direct aerosol effect from AeroCom Phase II simulations

NASA Astrophysics Data System (ADS)

Myhre, G.; Samset, B. H.; Schulz, M.; Balkanski, Y.; Bauer, S.; Berntsen, T. K.; Bian, H.; Bellouin, N.; Chin, M.; Diehl, T.; Easter, R. C.; Feichter, J.; Ghan, S. J.; Hauglustaine, D.; Iversen, T.; Kinne, S.; Kirkevåg, A.; Lamarque, J.-F.; Lin, G.; Liu, X.; Lund, M. T.; Luo, G.; Ma, X.; van Noije, T.; Penner, J. E.; Rasch, P. J.; Ruiz, A.; Seland, Ø.; Skeie, R. B.; Stier, P.; Takemura, T.; Tsigaridis, K.; Wang, P.; Wang, Z.; Xu, L.; Yu, H.; Yu, F.; Yoon, J.-H.; Zhang, K.; Zhang, H.; Zhou, C.

2013-02-01

We report on the AeroCom Phase II direct aerosol effect (DAE) experiment where 16 detailed global aerosol models have been used to simulate the changes in the aerosol distribution over the industrial era. All 16 models have estimated the radiative forcing (RF) of the anthropogenic DAE, and have taken into account anthropogenic sulphate, black carbon (BC) and organic aerosols (OA) from fossil fuel, biofuel, and biomass burning emissions. In addition several models have simulated the DAE of anthropogenic nitrate and anthropogenic influenced secondary organic aerosols (SOA). The model simulated all-sky RF of the DAE from total anthropogenic aerosols has a range from -0.58 to -0.02 Wm-2, with a mean of -0.27 Wm-2 for the 16 models. Several models did not include nitrate or SOA and modifying the estimate by accounting for this with information from the other AeroCom models reduces the range and slightly strengthens the mean. Modifying the model estimates for missing aerosol components and for the time period 1750 to 2010 results in a mean RF for the DAE of -0.35 Wm-2. Compared to AeroCom Phase I (Schulz et al., 2006) we find very similar spreads in both total DAE and aerosol component RF. However, the RF of the total DAE is stronger negative and RF from BC from fossil fuel and biofuel emissions are stronger positive in the present study than in the previous AeroCom study. We find a tendency for models having a strong (positive) BC RF to also have strong (negative) sulphate or OA RF. This relationship leads to smaller uncertainty in the total RF of the DAE compared to the RF of the sum of the individual aerosol components. The spread in results for the individual aerosol components is substantial, and can be divided into diversities in burden, mass extinction coefficient (MEC), and normalized RF with respect to AOD. We find that these three factors give similar contributions to the spread in results.

Radiative forcing of the direct aerosol effect from AeroCom Phase II simulations

NASA Astrophysics Data System (ADS)

Myhre, G.; Samset, B. H.; Schulz, M.; Balkanski, Y.; Bauer, S.; Berntsen, T. K.; Bian, H.; Bellouin, N.; Chin, M.; Diehl, T.; Easter, R. C.; Feichter, J.; Ghan, S. J.; Hauglustaine, D.; Iversen, T.; Kinne, S.; Kirkevåg, A.; Lamarque, J.-F.; Lin, G.; Liu, X.; Luo, G.; Ma, X.; Penner, J. E.; Rasch, P. J.; Seland, Ø.; Skeie, R. B.; Stier, P.; Takemura, T.; Tsigaridis, K.; Wang, Z.; Xu, L.; Yu, H.; Yu, F.; Yoon, J.-H.; Zhang, K.; Zhang, H.; Zhou, C.

2012-08-01

We report on the AeroCom Phase II direct aerosol effect (DAE) experiment where 15 detailed global aerosol models have been used to simulate the changes in the aerosol distribution over the industrial era. All 15 models have estimated the radiative forcing (RF) of the anthropogenic DAE, and have taken into account anthropogenic sulphate, black carbon (BC) and organic aerosols (OA) from fossil fuel, biofuel, and biomass burning emissions. In addition several models have simulated the DAE of anthropogenic nitrate and anthropogenic influenced secondary organic aerosols (SOA). The model simulated all-sky RF of the DAE from total anthropogenic aerosols has a range from -0.58 to -0.02 W m-2, with a mean of -0.30 W m-2 for the 15 models. Several models did not include nitrate or SOA and modifying the estimate by accounting for this with information from the other AeroCom models reduces the range and slightly strengthens the mean. Modifying the model estimates for missing aerosol components and for the time period 1750 to 2010 results in a mean RF for the DAE of -0.39 W m-2. Compared to AeroCom Phase I (Schulz et al., 2006) we find very similar spreads in both total DAE and aerosol component RF. However, the RF of the total DAE is stronger negative and RF from BC from fossil fuel and biofuel emissions are stronger positive in the present study than in the previous AeroCom study. We find a tendency for models having a strong (positive) BC RF to also have strong (negative) sulphate or OA RF. This relationship leads to smaller uncertainty in the total RF of the DAE compared to the RF of the sum of the individual aerosol components. The spread in results for the individual aerosol components is substantial, and can be divided into diversities in burden, mass extinction coefficient (MEC), and normalized RF with respect to AOD. We find that these three factors give similar contributions to the spread in results.

Monodisperse aerosol generator

DOEpatents

Ortiz, Lawrence W.; Soderholm, Sidney C.

1990-01-01

An aerosol generator is described which is capable of producing a monodisperse aerosol within narrow limits utilizing an aqueous solution capable of providing a high population of seed nuclei and an organic solution having a low vapor pressure. The two solutions are cold nebulized, mixed, vaporized, and cooled. During cooling, particles of the organic vapor condense onto the excess seed nuclei, and grow to a uniform particle size.

Unexpected high yields of carbonyl and peroxide products of aqueous isoprene ozonolysis and implications

NASA Astrophysics Data System (ADS)

Wang, H. L.; Huang, D.; Zhang, X.; Zhao, Y.; Chen, Z. M.

2012-03-01

The aqueous phase reaction of volatile organic compounds (VOCs) has not been considered in most analyses of atmospheric chemical processes. However, some experimental evidence has shown that, compared to the corresponding gas phase reaction, the aqueous chemical processes of VOCs in the bulk solutions and surfaces of ambient wet particles (cloud, fog, and wet aerosols) may potentially contribute to the products and formation of secondary organic aerosol (SOA). In the present study, we performed a laboratory experiment of the aqueous ozonolysis of isoprene at different pHs (3-7) and temperatures (4-25 °C). We detected three important kinds of products, including carbonyl compounds, peroxide compounds, and organic acids. Our results showed that the molar yields of these products were nearly independent of the investigated pHs and temperatures. These products included (1) carbonyls: 56.7 ± 6.7% formaldehyde, 42.8 ± 2.5% methacrolein (MAC), and 57.7 ± 3.4% methyl vinyl ketone (MVK); (2) peroxides: 53.4 ± 4.1% hydrogen peroxide (H2O2) and 15.1 ± 3.1% hydroxylmethyl hydroperoxide (HMHP); and (3) organic acids: undetectable (< 1% estimated by the detection limit). Based on the amounts of products formed and the isoprene consumed, the total carbon yield was estimated to be 95 ± 4%. This implied that most of the products in the reaction system were detected. Of note, the combined yields of both MAC + MVK and H2O2 + HMHP in the aqueous isoprene ozonolysis were much higher than those observed in the corresponding gas phase reaction. We suggested that these unexpected high yields of carbonyls and peroxides were related to the greater capability of condensed water, compared to water vapor, to stabilize energy-rich Criegee radicals. This aqueous ozonolysis of isoprene (and possibly other biogenic VOCs) could potentially occur on the surfaces of ambient wet particles and plants. Moreover, the high-yield carbonyl and peroxide products might provide a considerable source of

Aerosols, light, and water: Measurements of aerosol optical properties at different relative humidities

NASA Astrophysics Data System (ADS)

Orozco, Daniel

(RH) at a certain RH divided by sp at a dry value, was used to evaluate the aerosol hygroscopicity. Different empirical fits were evaluated using the f(RH) data. The widely used gamma model was found inappropriate, as it overestimates f(RH) for RH<75%. Abetter empirical fit with two power-law curve-fitting parameters c and k was found to replicate f(RH) accurately from the three sites. The relationship between the organic carbon mass (OMC) and the species that are affected by RH and f(RH) was also studied and categorized between the sites. A second experiment is reported where the first two elements of the scattering matrix of laboratory generated particles were studied under different humidity conditions. The non-spherical particles generated were ammonium sulfate, sodium chloride, and ammonium nitrate. The optical measurements were performed with a polarized imaging nephelometer (PI-Neph) installed in series with the humidifier dryer apparatus. The inorganic salts experienced low (80%) RH levels so that the observations could contrast the differences when the salts were crystallized (low RH) and when the particles turned to aqueous solutions after deliquesence (high RH). The measurements with the PI-Neph produce the aerosol phase function and the polarized phase function in a range of angles that go from 3 to 177. The results showed significant changes in the phase function and polarized phase function due to the hygroscopic growth. Although the inorganic salts used inthe experiments were non-spherical, the dry measurements were successfully reproduced with the Mie theory using literature values for the dry index of refraction. Moreover, the changes in the particle size distribution and index of refraction were evaluated through classic thermodynamic equilibrium theory producing comparable results with the simulations performed with Mie formalism. The final experiment consisted in the measurements of phase function and degree of linear polarization of ambient aerosols

Aircraft Measurements of Aerosol Phase Matrix Elements by the Polarized Imaging Nephelometer (Invited)

NASA Astrophysics Data System (ADS)

Dolgos, G.; Martins, J.; Espinosa, R.; Dubovik, O.; Beyersdorf, A. J.; Ziemba, L. D.; Hair, J. W.

2013-12-01

Aerosols have a significant impact on the radiative balance and water cycle of our planet through influencing atmospheric radiation. Remote sensing of aerosols relies on scattering phase matrix information to retrieve aerosol properties with frequent global coverage, the assumed phase matrices must be validated by measurements. At the Laboratory for Aerosols, Clouds and Optics (LACO) at the University of Maryland, Baltimore County (UMBC) we developed a new technique to directly measure the aerosol phase function (P11), the degree of linear polarization of the scattered light (-P12/P11), and the volume scattering coefficient (SCAT). We designed and built a portable instrument called the Polarized Imaging Nephelometer (PI-Neph), shown in Figure 1 (a). The PI-Neph successfully participated in dozens of flights of the NASA Development and Evaluation of satellite ValidatiOn Tools by Experimenters (DEVOTE) project and the Deep Convective Clouds and Chemistry (DC3) project and the January and February deployment of the Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (Discover-AQ) mission. The ambient aerosol enters the PI-Neph through an inlet and the sample is illuminated by laser light (wavelength of 532 nm); the scattered light is imaged by a stationary wide field of view camera in the scattering angle range of 2° to 178° (in some cases stray light limited the scattering angle range to 3° to 176°). Data for P11, P12, and SCAT were taken every 12 seconds, example datasets from DEVOTE of P11 times SCAT are shown on Figure 1 (b). The talk will highlight results from the three field deployments and will show microphysical retrievals from the scattering data. The size distribution and the average complex refractive index of the ambient aerosol ensemble can be retrieved from the data by an algorithm similar to that of AERONET, as illustrated in Figure 1 (c). Particle sphericity can potentially be

High-Resolution Mass Spectrometry and Molecular Characterization of Aqueous Photochemistry Products of Common Types of Secondary Organic Aerosols

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

Romonosky, Dian E.; Laskin, Alexander; Laskin, Julia

2015-03-19

A significant fraction of atmospheric organic compounds is predominantly found in condensed phases, such as aerosol particles and cloud droplets. Many of these compounds are photolabile and can degrade through direct photolysis or indirect photooxidation processes on time scales that are comparable to the typical lifetimes of aqueous droplets (hours) and particles (days). This paper presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d- limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate amore » remote atmosphere) or by OH in the presence of NOx (to simulate an urban atmosphere). Chamber- and flow tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3-8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features, and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NOx generated SOA had more unique visual appearance, and indicated a lower extent of products overlap. Furthermore, the fraction of nitrogen containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NOx oxidation conditions compared to the ozone driven oxidation. Comparison of the SOA

What Controls the Vertical Distribution of Aerosol? Relationships Between Process Sensitivity in HadGEM3-UKCA and Inter-Model Variation from AeroCom Phase II

NASA Technical Reports Server (NTRS)

Kipling, Zak; Stier, Philip; Johnson, Colin E.; Mann, Graham W.; Bellouin, Nicolas; Bauer, Susanne E.; Bergman, Tommi; Chin, Mian; Diehl, Thomas; Ghan, Steven J.;

Cloud droplet activation through oxidation of organic aerosol influenced by temperature and particle phase state: CLOUD ACTIVATION BY AGED ORGANIC AEROSOL

DOE PAGES

Slade, Jonathan H.; Shiraiwa, Manabu; Arangio, Andrea; ...

2017-02-04

Chemical aging of organic aerosol (OA) through multiphase oxidation reactions can alter their cloud condensation nuclei (CCN) activity and hygroscopicity. However, the oxidation kinetics and OA reactivity depend strongly on the particle phase state, potentially influencing the hydrophobic-to-hydrophilic conversion rate of carbonaceous aerosol. Here, amorphous Suwannee River fulvic acid (SRFA) aerosol particles, a surrogate humic-like substance (HULIS) that contributes substantially to global OA mass, are oxidized by OH radicals at different temperatures and phase states. When oxidized at low temperature in a glassy solid state, the hygroscopicity of SRFA particles increased by almost a factor of two, whereas oxidation ofmore » liquid-like SRFA particles at higher temperatures did not affect CCN activity. Low-temperature oxidation appears to promote the formation of highly-oxygenated particle-bound fragmentation products with lower molar mass and greater CCN activity, underscoring the importance of chemical aging in the free troposphere and its influence on the CCN activity of OA.« less

Treatment of aqueous phase of bio-oil by granular activated carbon and evaluation of biogas production.

PubMed

Shanmugam, Saravanan R; Adhikari, Sushil; Wang, Zhouhang; Shakya, Rajdeep

2017-01-01

Hydrothermal liquefaction of wet biomass such as algae is a promising thermochemical process for the production of bio-oil. Bio-oil aqueous phase generated during liquefaction process is rich in complex organics and can be utilized for biogas production following its pre-treatment with granular activated carbon. In our study, use of 30% activated carbon resulted in higher chemical oxygen demand (COD) reduction (53±0.3%) from aqueous phase. Higher CH 4 production (84±12mL/gCOD) was also observed in 30% carbon-treated aqueous phase fed cultures, whereas only 32±6mLCH 4 /gCOD was observed in control (non-carbon treated) cultures. The results from this study indicate that almost 67±0.3% initial COD of aqueous phase can be reduced using a combination of both carbon treatment and biogas production. This study shows that aqueous phase can be utilized for CH 4 production. Copyright © 2016 Elsevier Ltd. All rights reserved.

A hybrid formalism of aerosol gas phase interaction for 3-D global models

NASA Astrophysics Data System (ADS)

Benduhn, F.

2009-04-01

Aerosol chemical composition is a relevant factor to the global climate system with respect to both atmospheric chemistry and the aerosol direct and indirect effects. Aerosol chemical composition determines the capacity of aerosol particles to act as cloud condensation nuclei both explicitly via particle size and implicitly via the aerosol hygroscopic property. Due to the primary role of clouds in the climate system and the sensitivity of cloud formation and radiative properties to the cloud droplet number it is necessary to determine with accuracy the chemical composition of the aerosol. Dissolution, although a formally fairly well known process, may be subject to numerically prohibitive properties that result from the chemical interaction of the species engaged. So-far approaches to model the dissolution of inorganics into the aerosol liquid phase in the framework of a 3-D global model were based on an equilibrium, transient or hybrid equilibrium-transient approach. All of these methods present the disadvantage of a priori assumptions with respect to the mechanism and/or are numerically not manageable in the context of a global climate system model. In this paper a new hybrid formalism to aerosol gas phase interaction is presented within the framework of the H2SO4/HNO3/HCl/NH3 system and a modal approach of aerosol size discretisation. The formalism is distinct from prior hybrid approaches in as much as no a priori assumption on the nature of the regime a particular aerosol mode is in is made. Whether a particular mode is set to be in the equilibrium or the transitory regime is continuously determined during each time increment against relevant criteria considering the estimated equilibration time interval and the interdependence of the aerosol modes relative to the partitioning of the dissolving species. Doing this the aerosol composition range of numerical stiffness due to species interaction during transient dissolution is effectively eluded, and the numerical

Preparative crystallization of a single chain antibody using an aqueous two-phase system.

PubMed

Huettmann, Hauke; Berkemeyer, Matthias; Buchinger, Wolfgang; Jungbauer, Alois

2014-11-01

A simultaneous crystallization and aqueous two-phase extraction of a single chain antibody was developed, demonstrating process integration. The process conditions were designed to form an aqueous two-phase system, and to favor crystallization, using sodium sulfate and PEG-2000. At sufficiently high concentrations of PEG, a second phase was generated in which the protein crystallization occurred simultaneously. The single chain antibody crystals were partitioned to the top, polyethylene glycol-rich phase. The crystal nucleation took place in the sodium sulfate-rich phase and at the phase boundary, whereas crystal growth was progressing mainly in the polyethylene glycol-rich phase. The crystals in the polyethylene glycol-rich phase grew to a size of >50 µm. Additionally, polyethylene glycol acted as an anti-solvent, thus, it influenced the crystallization yield. A phase diagram with an undersaturation zone, crystallization area, and amorphous precipitation zone was established. Only small differences in polyethylene glycol concentration caused significant shifts of the crystallization yield. An increase of the polyethylene glycol content from 2% (w/v) to 4% (w/v) increased the yield from approximately 63-87%, respectively. Our results show that crystallization in aqueous two-phase systems is an opportunity to foster process integration. © 2014 Wiley Periodicals, Inc.

Simulating the SOA formation of isoprene from partitioning and aerosol phase reactions in the presence of inorganics

NASA Astrophysics Data System (ADS)

Beardsley, Ross L.; Jang, Myoseon

2016-05-01

The secondary organic aerosol (SOA) produced by the photooxidation of isoprene with and without inorganic seed is simulated using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model. Recent work has found the SOA formation of isoprene to be sensitive to both aerosol acidity ([H+], mol L-1) and aerosol liquid water content (LWC) with the presence of either leading to significant aerosol phase organic mass generation and large growth in SOA yields (YSOA). Classical partitioning models alone are insufficient to predict isoprene SOA formation due to the high volatility of photooxidation products and sensitivity of their mass yields to variations in inorganic aerosol composition. UNIPAR utilizes the chemical structures provided by a near-explicit chemical mechanism to estimate the thermodynamic properties of the gas phase products, which are lumped based on their calculated vapor pressure (eight groups) and aerosol phase reactivity (six groups). UNIPAR then determines the SOA formation of each lumping group from both partitioning and aerosol phase reactions (oligomerization, acid-catalyzed reactions and organosulfate formation) assuming a single homogeneously mixed organic-inorganic phase as a function of inorganic composition and VOC / NOx (VOC - volatile organic compound). The model is validated using isoprene photooxidation experiments performed in the dual, outdoor University of Florida Atmospheric PHotochemical Outdoor Reactor (UF APHOR) chambers. UNIPAR is able to predict the experimental SOA formation of isoprene without seed, with H2SO4 seed gradually titrated by ammonia, and with the acidic seed generated by SO2 oxidation. Oligomeric mass is predicted to account for more than 65 % of the total organic mass formed in all cases and over 85 % in the presence of strongly acidic seed. The model is run to determine the sensitivity of YSOA to [H+], LWC and VOC / NOx, and it is determined that the SOA formation of isoprene is most strongly related to [H

Kinetic modeling of secondary organic aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

NASA Astrophysics Data System (ADS)

Chan, A. W. H.; Kroll, J. H.; Ng, N. L.; Seinfeld, J. H.

2007-08-01

The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

Kinetic modeling of Secondary Organic Aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

NASA Astrophysics Data System (ADS)

Chan, A. W. H.; Kroll, J. H.; Ng, N. L.; Seinfeld, J. H.

2007-05-01

The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

Gas-particle partitioning of atmospheric aerosols: interplay of physical state, non-ideal mixing and morphology.

PubMed

Shiraiwa, Manabu; Zuend, Andreas; Bertram, Allan K; Seinfeld, John H

2013-07-21

Atmospheric aerosols, comprising organic compounds and inorganic salts, play a key role in air quality and climate. Mounting evidence exists that these particles frequently exhibit phase separation into predominantly organic and aqueous electrolyte-rich phases. As well, the presence of amorphous semi-solid or glassy particle phases has been established. Using the canonical system of ammonium sulfate mixed with organics from the ozone oxidation of α-pinene, we illustrate theoretically the interplay of physical state, non-ideality, and particle morphology affecting aerosol mass concentration and the characteristic timescale of gas-particle mass transfer. Phase separation can significantly affect overall particle mass and chemical composition. Semi-solid or glassy phases can kinetically inhibit the partitioning of semivolatile components and hygroscopic growth, in contrast to the traditional assumption that organic compounds exist in quasi-instantaneous gas-particle equilibrium. These effects have significant implications for the interpretation of laboratory data and the development of improved atmospheric air quality and climate models.

Nasal deposition of ciclesonide nasal aerosol and mometasone aqueous nasal spray in allergic rhinitis patients.

PubMed

Emanuel, Ivor A; Blaiss, Michael S; Meltzer, Eli O; Evans, Philip; Connor, Alyson

2014-01-01

Sensory attributes of intranasal corticosteroids, such as rundown to the back of the throat, may influence patient treatment preferences. This study compares the nasal deposition and nasal retention of a radiolabeled solution of ciclesonide nasal aerosol (CIC-hydrofluoroalkane [HFA]) with a radiolabeled suspension of mometasone furoate monohydrate aqueous nasal spray (MFNS) in subjects with either perennial allergic rhinitis (AR) or seasonal AR. In this open-label, single-dose, randomized, crossover scintigraphy study, 14 subjects with symptomatic AR received a single dose of radiolabeled 74-μg CIC-HFA (37 μg/spray, 1 spray/each nostril) via a nasal metered-dose inhaler or a single dose of radiolabeled 200-μg MFNS (50 μg/spray, 2 sprays/each nostril), with a minimum 5-day washout period between treatments. Initial deposition (2 minutes postdose) of radiolabeled CIC-HFA and MFNS in the nasal cavity, nasopharynx, and on nasal wipes, and retention of radioactivity in the nasal cavity and nasal run-out on nasal wipes at 2, 4, 6, 8, and 10 minutes postdose were quantified with scintigraphy. At 2 and 10 minutes postdose, deposition of radiolabeled CIC-HFA was significantly higher in the nasal cavity versus radiolabeled MFNS (99.42% versus 86.50% at 2 minutes, p = 0.0046; and 81.10% versus 54.31% at 10 minutes, p < 0.0001, respectively; p values unadjusted for multiplicity). Deposition of radioactivity on nasal wipes was significantly higher with MFNS versus CIC-HFA at all five time points, and posterior losses of radiolabeled formulation were significantly higher with MFNS at 6, 8, and 10 minutes postdose. In this scintigraphic study, significantly higher nasal deposition and retention of radiolabeled aerosol CIC-HFA were observed versus radiolabeled aqueous MFNS in subjects with AR.

Non-conventional solvents in liquid phase microextraction and aqueous biphasic systems.

PubMed

An, Jiwoo; Trujillo-Rodríguez, María J; Pino, Verónica; Anderson, Jared L

2017-06-02

The development of rapid, convenient, and high throughput sample preparation approaches such as liquid phase microextraction techniques have been continuously developed over the last decade. More recently, significant attention has been given to the replacement of conventional organic solvents used in liquid phase microextraction techniques in order to reduce toxic waste and to improve selectivity and/or extraction efficiency. With these objectives, non-conventional solvents have been explored in liquid phase microextraction and aqueous biphasic systems. The utilized non-conventional solvents include ionic liquids, magnetic ionic liquids, and deep eutectic solvents. They have been widely used as extraction solvents or additives in various liquid phase microextraction modes including dispersive liquid-liquid microextraction, single-drop microextraction, hollow fiber-liquid phase microextraction, as well as in aqueous biphasic systems. This review provides an overview into the use of non-conventional solvents in these microextraction techniques in the past 5 years (2012-2016). Analytical applications of the techniques are also discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Global distribution of particle phase state in atmospheric secondary organic aerosols

NASA Astrophysics Data System (ADS)

Shiraiwa, Manabu; Li, Ying; Tsimpidi, Alexandra P.; Karydis, Vlassis A.; Berkemeier, Thomas; Pandis, Spyros N.; Lelieveld, Jos; Koop, Thomas; Pöschl, Ulrich

2017-04-01

Secondary organic aerosols (SOA) are a large source of uncertainty in our current understanding of climate change and air pollution. The phase state of SOA is important for quantifying their effects on climate and air quality, but its global distribution is poorly characterized. We developed a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, and we used the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the phase state of atmospheric SOA. For the planetary boundary layer, global simulations indicate that SOA are 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 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 in SOA.

Global distribution of particle phase state in atmospheric secondary organic aerosols.

PubMed

Shiraiwa, Manabu; Li, Ying; Tsimpidi, Alexandra P; Karydis, Vlassis A; Berkemeier, Thomas; Pandis, Spyros N; Lelieveld, Jos; Koop, Thomas; Pöschl, Ulrich

2017-04-21

Secondary organic aerosols (SOA) are a large source of uncertainty in our current understanding of climate change and air pollution. The phase state of SOA is important for quantifying their effects on climate and air quality, but its global distribution is poorly characterized. We developed a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, and we used the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the phase state of atmospheric SOA. For the planetary boundary layer, global simulations indicate that SOA are 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 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 in SOA.

Global distribution of particle phase state in atmospheric secondary organic aerosols

PubMed Central

Shiraiwa, Manabu; Li, Ying; Tsimpidi, Alexandra P.; Karydis, Vlassis A.; Berkemeier, Thomas; Pandis, Spyros N.; Lelieveld, Jos; Koop, Thomas; Pöschl, Ulrich

2017-01-01

Secondary organic aerosols (SOA) are a large source of uncertainty in our current understanding of climate change and air pollution. The phase state of SOA is important for quantifying their effects on climate and air quality, but its global distribution is poorly characterized. We developed a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, and we used the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the phase state of atmospheric SOA. For the planetary boundary layer, global simulations indicate that SOA are 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 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 in SOA. PMID:28429776

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

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

Retrieval of Aerosol Phase Function and Polarized Phase Function from Polarization of Skylight for Different Observation Geometries

NASA Astrophysics Data System (ADS)

Li, L.; Qie, L. L.; Xu, H.; Li, Z. Q.

2018-04-01

The phase function and polarized phase function are important optical parameters, which describe scattering properties of atmospheric aerosol particles. Polarization of skylight induced by the scattering processes is sensitive to the scattering properties of aerosols. The Stokes parameters I, Q, U and the polarized radiance Lp of skylight measured by the CIMEL dual-polar sun-sky radiometer CE318- DP can be use to retrieve the phase function and polarized phase function, respectively. Two different observation geometries (i.e., the principal plane and almucantar) are preformed by the CE318-DP to detect skylight polarization. Polarization of skylight depends on the illumination and observation geometries. For the same solar zenith angle, retrievals of the phase function and the polarized phase function are still affected by the observation geometry. The performance of the retrieval algorithm for the principal plane and almucantar observation geometries was assessed by the numerical experiments at two typical high and low sun's positions (i.e. solar zenith angles are equal to 45° and 65°). Comparing the results for the principal plane and almucantar geometries, it is recommended to utilize the principal plane observations to retrieve the phase function when the solar zenith angle is small. The Stokes parameter U and the polarized radiance Lp from the almucantar observations are suggested to retrieve the polarized phase function, especially for short wavelength channels (e.g., 440 and 500 nm).

Aerosols at the Poles: An Aerocom Phase II Multi-Model Evaluation

NASA Technical Reports Server (NTRS)

Sand, Maria; Bauer, Susanne E.; Samset, Bjorn H.; Balkanski, Yves; Bellouin, Nicolas; Berntsen, Terje K.; Bian, Huisheng; Chin, Mian; Diehl, Thomas; Easter, Richard;

Cell Partition in Two Polymer Aqueous Phases

NASA Technical Reports Server (NTRS)

Harris, J. M.

1985-01-01

Partition of biological cells in two phase aqueous polymer systems is recognized as a powerful separation technique which is limited by gravity. The synthesis of new, selective polymer ligand conjugates to be used in affinity partition separations is of interest. The two most commonly used polymers in two phase partitioning are dextran and polyethylene glycol. A thorough review of the chemistry of these polymers was begun, particularly in the area of protein attachment. Preliminary studies indicate the importance in affinity partitioning of minimizing gravity induced randomizing forces in the phase separation process. The PEG-protein conjugates that were prepared appear to be ideally suited for achieving high quality purifications in a microgravity environment. An interesting spin-off of this synthetic work was the observation of catalytic activity for certain of our polymer derivatives.

Phase Partitioning of Soluble Trace Gases with Size-Resolved Aerosols during the Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT) Campaign

NASA Astrophysics Data System (ADS)

Young, A.; Keene, W. C.; Pszenny, A.; Sander, R.; Maben, J. R.; Warrick-Wriston, C.; Bearekman, R.

2011-12-01

During February and March 2011, size-resolved and bulk aerosol were sampled at 22 m above the surface over nominal 12-hour (daytime and nighttime) intervals from the Boulder Atmospheric Observatory tower (40.05 N, 105.01 W, 1584-m elevation). Samples were analyzed for major organic and inorganic ionic constituents by high performance ion chromatography (IC). Soluble trace gases (HCl, HNO3, NH3, HCOOH, and CH3COOH) were sampled in parallel over 2-hour intervals with tandem mist chambers and analyzed on site by IC. NH4+, NO3-, and SO42- were the major ionic components of aerosols (median values of 57.7, 34.5, and 7.3 nmol m-3 at STP, respectively, N = 45) with 86%, 82%, and 82%, respectively, associated with sub-μm size fractions. Cl- and Na+ were present at significant concentrations (median values of 6.8 and 6.6 nmol m-3, respectively) but were associated primarily with super-μm size fractions (75% and 78%, respectively). Median values (and ranges) for HCl, HNO3, and NH3 were 21 (<20-1257), 120 (<45-1638), and 5259 (<1432-48,583) pptv, respectively. Liquid water contents of size-resolved aerosols and activity coefficients for major ionic constituents were calculated with the Extended Aerosol Inorganic Model II and IV (E-AIM) based on the measured aerosol composition, RH, temperature, and pressure. Size-resolved aerosol pHs were inferred from the measured phase partitioning of HCl, HNO3, and NH3. Major controls of phase partitioning and associated chemical dynamics will be presented.

Influence of metal-mediated aerosol-phase oxidation on secondary organic aerosol formation from the ozonolysis and OH-oxidation of α-pinene

PubMed Central

Chu, Biwu; Liggio, John; Liu, Yongchun; He, Hong; Takekawa, Hideto; Li, Shao-Meng; Hao, Jiming

2017-01-01

The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9 m3 smog chamber. The presence of FeSO4 or Fe2(SO4)3 seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of α-pinene compared to that in the presence of ZnSO4 or (NH4)2SO4. These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO4 or Fe2(SO4)3 seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation. PMID:28059151

Influence of metal-mediated aerosol-phase oxidation on secondary organic aerosol formation from the ozonolysis and OH-oxidation of α-pinene.

PubMed

Chu, Biwu; Liggio, John; Liu, Yongchun; He, Hong; Takekawa, Hideto; Li, Shao-Meng; Hao, Jiming

2017-01-06

The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9 m 3 smog chamber. The presence of FeSO 4 or Fe 2 (SO 4 ) 3 seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of α-pinene compared to that in the presence of ZnSO 4 or (NH 4 ) 2 SO 4 . These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO 4 or Fe 2 (SO 4 ) 3 seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation.

Arsenic interactions with a fullerene-like BN cage in the vacuum and aqueous phase.

PubMed

Beheshtian, Javad; Peyghan, Ali Ahmadi; Bagheri, Zargham

2013-02-01

Adsorption of arsenic ions, As (III and V), on the surface of fullerene-like B(12)N(12) cage has been explored in vacuum and aqueous phase using density functional theory in terms of Gibbs free energies, enthalpies, geometry, and density of state analysis. It was found that these ions can be strongly chemisorbed on the surface of the cluster in both vacuum and aqueous phase, resulting in significant changes in its electronic properties so that the cluster transforms from a semi-insulator to a semiconductor. The solvent significantly affects the geometry parameters and electronic properties of the As/B(12)N(12) complexes and the interaction between components is considerably weaker in the aqueous phase than that in the vacuum.

Ammonium fluoride as a mobile phase additive in aqueous normal phase chromatography.

PubMed

Pesek, Joseph J; Matyska, Maria T

2015-07-03

The use of ammonium fluoride as a mobile phase additive in aqueous normal phase chromatography with silica hydride-based stationary phases and mass spectrometry detection is evaluated. Retention times, peak shape, efficiency and peak intensity are compared to the more standard additives formic acid and ammonium formate. The test solutes were NAD, 3-hydroxyglutaric acid, α-ketoglutaric acid, p-aminohippuric acid, AMP, ATP, aconitic acid, threonine, N-acetyl carnitine, and 3-methyladipic acid. The column parameters are assessed in both the positive and negative ion detection modes. Ammonium fluoride is potentially an aggressive mobile phase additive that could have detrimental effects on column lifetime. Column reproducibility is measured and the effects of switching between different additives are also tested. Copyright © 2015 Elsevier B.V. All rights reserved.

A Chain of Modeling Tools For Gas and Aqueous Phase Chemstry

NASA Astrophysics Data System (ADS)

Audiffren, N.; Djouad, R.; Sportisse, B.

Atmospheric chemistry is characterized by the use of large set of chemical species and reactions. Handling with the set of data required for the definition of the model is a quite difficult task. We prsent in this short article a preprocessor for diphasic models (gas phase and aqueous phase in cloud droplets) named SPACK. The main interest of SPACK is the automatic generation of lumped species related to fast equilibria. We also developped a linear tangent model using the automatic differentiation tool named ODYSSEE in order to perform a sensitivity analysis of an atmospheric multi- phase mechanism based on RADM2 kinetic scheme.Local sensitivity coefficients are computed for two different scenarii. We focus in this study on the sensitivity of the ozone,NOx,HOx, system with respect to some aqueous phase reactions and we inves- tigate the influence of the reduction in the photolysis rates in the area below the cloud region.

HCl in rocket exhaust clouds - Atmospheric dispersion, acid aerosol characteristics, and acid rain deposition

NASA Technical Reports Server (NTRS)

Pellett, G. L.; Sebacher, D. I.; Bendura, R. J.; Wornom, D. E.

1983-01-01

Both measurements and model calculations of the temporal dispersion of peak HCl (g + aq) concentration in Titan III exhaust clouds are found to be well characterized by one-term power-law decay expressions. The respective coefficients and decay exponents, however, are found to vary widely with meteorology. The HCl (g), HCl (g + aq), dewpoint, and temperature-pressure-altitude data for Titan III exhaust clouds are consistent with accurately calculated HCl/H2O vapor-liquid compositions for a model quasi-equilibrated flat surface aqueous aerosol. Some cloud evolution characteristics are also defined. Rapid and extensive condensation of aqueous acid clearly occurs during the first three min of cloud rise. Condensation is found to be intensified by the initial entrainment of relatively moist ambient air from lower levels, that is, from levels below eventual cloud stabilization. It is pointed out that if subsequent dilution air at stabilization altitude is significantly drier, a state of maximum condensation soon occurs, followed by an aerosol evaporation phase.

Aerosol partitioning in mixed-phase clouds at the Jungfraujoch (3580 m asl)

NASA Astrophysics Data System (ADS)

Henning, S.; Bojinski, S.; Diehl, K.; Ghan, S.; Nyeki, S.; Weingartner, E.; Wurzler, S.; Baltensperger, U.

2003-04-01

Field measurements on the partitioning between the interstitial and the liquid/ice phase in natural clouds were performed at the high-alpine research station Jungfraujoch (3580 m asl, Switzerland) during a summer and a winter campaign. The size distributions of the total and the interstitial aerosol were determined by means of a scanning mobility particle sizer (SMPS). From these, size resolved scavenging ratios were calculated. Simultaneously, cloud water content (CWC) and cloud particle size distributions along with meteorological data were obtained. In cold mixed phase clouds (existing of liquid droplets and ice crystals), strong differences were found in comparison to the warm summer clouds. In the warm cloud types all particles above a certain diameter were activated and thereby the scavenging ratio (number of activated particles divided by the total number concentration) above a certain threshold diameter approached 1. In the winter clouds, the scavenging ratio never reached the value of 1 and could be as low as 0. These observations are explained by the Bergeron-Findeisen process: Here, particles are also activated to droplets in the first step, but after the formation of the ice phase droplets evaporate while the ice crystals grow, due to difference in the saturation vapor pressure over water and ice. This release of aerosol particles to the interstitial aerosol has significant implications for the climate forcing: It can be expected that the number of CCN is of less importance as soon as ice crystals are formed.

Distribution of Dechlorinating Bacteria between the Aqueous and Solid Phases

NASA Astrophysics Data System (ADS)

Cápiro, N. L.; Hatt, J. K.; Wang, Y.; Loeffler, F. E.; Pennell, K. D.

2010-12-01

Microbial monitoring of aquifers relies on nucleic acid biomarker analysis, which is typically performed with biomass recovered from groundwater samples; however, it is unclear what fraction of the target population(s) is associated with groundwater (i.e., planktonic cells) or is attached to solid phases (i.e., biofilms). Understanding how the titer of target organism(s) in groundwater correlates with the true cell titers of the target organism in the aquifer (i.e., planktonic plus attached cells) is critical for a meaningful interpretation of the data, the prediction of bioremediation performance, and the implementation of site management strategies. To evaluate the distribution of active cells between resident solid phase and the aqueous phase, one-dimensional columns were packed under water-saturated conditions with Bio-Dechlor INOCULUM, a PCE-to ethene-dechlorinating bacterial consortium containing both multiple Dehalococcoides (Dhc) strains and Geobacter lovleyi strain SZ (GeoSZ). The columns were packed with two distinct solid matrices: a low organic content sandy Federal Fine Ottawa soil or Appling soil with higher organic matter content. Influent reduced mineral salts medium supplied at a groundwater pore-water velocity of 0.3 m/day contained both 10 mM lactate as electron donor and 0.33 mM PCE as electron acceptor. Routine collection of biomass from column side ports and effluent samples measured the titers of target cells in the aqueous phase and determined when steady state conditions had been reached. A second set of column experiments evaluated delivery and filtration effects by the solid matrix (i.e., Federal Fine Ottawa sand versus Appling soil) under the same conditions except that electron donor or acceptor were omitted (no growth conditions). Quantitative real-time PCR (qPCR) analysis using Dhc and GeoSZ 16S rRNA gene-targeted primer and probe sets determined the planktonic cell counts, and destructive sampling of the columns allowed measurement

Perspective: Aerosol microphysics: From molecules to the chemical physics of aerosols

NASA Astrophysics Data System (ADS)

Bzdek, Bryan R.; Reid, Jonathan P.

2017-12-01

Aerosols are found in a wide diversity of contexts and applications, including the atmosphere, pharmaceutics, and industry. Aerosols are dispersions of particles in a gas, and the coupling of the two phases results in highly dynamic systems where chemical and physical properties like size, composition, phase, and refractive index change rapidly in response to environmental perturbations. Aerosol particles span a wide range of sizes from 1 nm to tens of micrometres or from small molecular clusters that may more closely resemble gas phase molecules to large particles that can have similar qualities to bulk materials. However, even large particles with finite volumes exhibit distinct properties from the bulk condensed phase, due in part to their higher surface-to-volume ratio and their ability to easily access supersaturated solute states inaccessible in the bulk. Aerosols represent a major challenge for study because of the facile coupling between the particle and gas, the small amounts of sample available for analysis, and the sheer breadth of operative processes. Time scales of aerosol processes can be as short as nanoseconds or as long as years. Despite their very different impacts and applications, fundamental chemical physics processes serve as a common theme that underpins our understanding of aerosols. This perspective article discusses challenges in the study of aerosols and highlights recent chemical physics advancements that have enabled improved understanding of these complex systems.

Continuous-flow ultrasound assisted oxidative desulfurization (UAOD) process: An efficient diesel treatment by injection of the aqueous phase.

PubMed

Rahimi, Masoud; Shahhosseini, Shahrokh; Movahedirad, Salman

2017-11-01

A new continuous-flow ultrasound assisted oxidative desulfurization (UAOD) process was developed in order to decrease energy and aqueous phase consumption. In this process the aqueous phase is injected below the horn tip leading to enhanced mixing of the phases. Diesel fuel as the oil phase with sulfur content of 1550ppmw and an appropriate mixture of hydrogen peroxide and formic acid as the aqueous phase were used. At the first step, the optimized condition for the sulfur removal has been obtained in the batch mode operation. Hence, the effect of more important oxidation parameters; oxidant-to-sulfur molar ratio, acid-to-sulfur molar ratio and sonication time were investigated. Then the optimized conditions were obtained using Response Surface Methodology (RSM) technique. Afterwards, some experiments corresponding to the best batch condition and also with objective of minimizing the residence time and aqueous phase to fuel volume ratio have been conducted in a newly designed double-compartment reactor with injection of the aqueous phase to evaluate the process in a continuous flow operation. In addition, the effect of nozzle diameter has been examined. Significant improvement on the sulfur removal was observed specially in lower sonication time in the case of dispersion method in comparison with the conventional contact between two phases. Ultimately, the flow pattern induced by ultrasonic device, and also injection of the aqueous phase were analyzed quantitatively and qualitatively by capturing the sequential images. Copyright © 2017 Elsevier B.V. All rights reserved.

Method for producing monodisperse aerosols

DOEpatents

Ortiz, Lawrence W.; Soderholm, Sidney C.

1990-01-01

An aerosol generator is described which is capable of producing a monodisperse aerosol within narrow limits utilizing an aqueous solution capable of providing a high population of seed nuclei and an organic solution having a low vapor pressure. The two solutions are cold nebulized, mixed, vaporized, and cooled. During cooling, particles of the organic vapor condense onto the excess seed nuclei, and grow to a uniform particle size.

A novel ultrasonic aerosol generator.

PubMed

Davies, A; Hudson, N; Pirie, L

1995-07-01

An ultrasonic aerosol generator constructed from a domestic humidifier is described which has been used to produce liquid aerosols for physiological investigations. The instrument was constructed from a Pifco domestic humidifier modified to include an energy guide to direct the oscillations of the transducer through the coupling water, which would normally be aerosolized, onto a small membrane based sample chamber containing the liquid to be aerosolized. The size distribution of the aerosol produced was found to be between 2 and 6 mm, optimum for diffuse intrapulmonary deposition. Up to 4 ml/min of aqueous liquid was used; however the sample chamber could be made small enough to contain economic amounts of expensive material to administer by inhalation. The instrument has proved to be reliable over a period of three years.

Solubility of HOBr in Acidic Solution and Implications for Liberation of Halogens Via Aerosol Processing

NASA Technical Reports Server (NTRS)

Iraci, Laura T.; Michelsen, R. R.; Rammer, T. A.; Ashbourn, S. F. M.

2004-01-01

Halogen species are known to catalytically destroy ozone in several regions of the atmosphere. In addition to direct catalytic losses, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr) is a key species in the linkage of BrOx to ClOx and HOx. The aqueous- phase coupling reaction HOBr + HCI (right arrow) BrCl + H2O may provide a pathway for chlorine activation on sulfate aerosols at temperatures warmer than those required for polar stratospheric cloud formation. We have measured t h e solubility of HOBr in 45 - 70 wt% sulfuric acid solutions. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, H* = 10(exp 4) - 10(exp 7) mol dm(exp -3) atm(exp -1). The expected inverse dependence of H* on temperature was observed, but only a weak dependence on acidity was found. The solubility of HOBr is comparable to that of HBr, indicating that equilibrium concentrations of HOBr could equal or exceed those of HBr in upper tropospheric and lower stratospheric aerosols. Despite the high solubility of HOBr, aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Our measurements of HOBr uptake in aqueous sulfuric acid in the presence of other brominated gases show the evolution of gaseous products including Br2O and Br2.

Measurement of Biologically Available Naphthalene in Gas and Aqueous Phases by Use of a Pseudomonas putida Biosensor

PubMed Central

Werlen, Christoph; Jaspers, Marco C. M.; van der Meer, Jan Roelof

2004-01-01

Genetically constructed microbial biosensors for measuring organic pollutants are mostly applied in aqueous samples. Unfortunately, the detection limit of most biosensors is insufficient to detect pollutants at low but environmentally relevant concentrations. However, organic pollutants with low levels of water solubility often have significant gas-water partitioning coefficients, which in principle makes it possible to measure such compounds in the gas rather than the aqueous phase. Here we describe the first use of a microbial biosensor for measuring organic pollutants directly in the gas phase. For this purpose, we reconstructed a bioluminescent Pseudomonas putida naphthalene biosensor strain to carry the NAH7 plasmid and a chromosomally inserted gene fusion between the sal promoter and the luxAB genes. Specific calibration studies were performed with suspended and filter-immobilized biosensor cells, in aqueous solution and in the gas phase. Gas phase measurements with filter-immobilized biosensor cells in closed flasks, with a naphthalene-contaminated aqueous phase, showed that the biosensor cells can measure naphthalene effectively. The biosensor cells on the filter responded with increasing light output proportional to the naphthalene concentration added to the water phase, even though only a small proportion of the naphthalene was present in the gas phase. In fact, the biosensor cells could concentrate a larger proportion of naphthalene through the gas phase than in the aqueous suspension, probably due to faster transport of naphthalene to the cells in the gas phase. This led to a 10-fold lower detectable aqueous naphthalene concentration (50 nM instead of 0.5 μM). Thus, the use of bacterial biosensors for measuring organic pollutants in the gas phase is a valid method for increasing the sensitivity of these valuable biological devices. PMID:14711624

Aerosol Correction for Remotely Sensed Sea Surface Temperatures From the NOAA AVHRR: Phase II

NASA Astrophysics Data System (ADS)

Nalli, N. R.; Ignatov, A.

2002-05-01

For over two decades, the National Oceanic and Atmospheric Administration (NOAA) has produced global retrievals of sea surface temperature (SST) using infrared (IR) data from the Advanced Very High Resolution Radiometer (AVHRR). The standard multichannel retrieval algorithms are derived from regression analyses of AVHRR window channel brightness temperatures against in situ buoy measurements under non-cloudy conditions thus providing a correction for IR attenuation due to molecular water vapor absorption. However, for atmospheric conditions with elevated aerosol levels (e.g., arising from dust, biomass burning and volcanic eruptions), such algorithms lead to significant negative biases in SST because of IR attenuation arising from aerosol absorption and scattering. This research presents the development of a 2nd-phase aerosol correction algorithm for daytime AVHRR SST. To accomplish this, a long-term (1990-1998), global AVHRR-buoy matchup database was created by merging the Pathfinder Atmospheres (PATMOS) and Oceans (PFMDB) data sets. The merged data are unique in that they include multi-year, global daytime estimates of aerosol optical depth (AOD) derived from AVHRR channels 1 and 2 (0.63 and 0.83 μ m, respectively), along with an effective Angstrom exponent derived from the AOD retrievals (Ignatov and Nalli, 2002). Recent enhancements in the aerosol data constitute an improvement over the Phase I algorithm (Nalli and Stowe, 2002) which relied only on channel 1 AOD and the ratio of normalized reflectance from channels 1 and 2. The Angstrom exponent and channel 2 AOD provide important statistical information about the particle size distribution of the aerosol. The SST bias can be parametrically expressed as a function of observed AVHRR channels 1 and 2 slant-path AOD, normalized reflectance ratio and the Angstrom exponent. Based upon these empirical relationships, aerosol correction equations are then derived for the daytime multichannel and nonlinear SST (MCSST

What controls the vertical distribution of aerosol? Relationships between process sensitivity in HadGEM3–UKCA and inter-model variation from AeroCom Phase II

DOE PAGES

Kipling, Zak; Stier, Philip; Johnson, Colin E.; ...

2016-02-26

The vertical profile of aerosol is important for its radiative effects, but weakly constrained by observations on the global scale, and highly variable among different models. To investigate the controlling factors in one particular model, we investigate the effects of individual processes in HadGEM3–UKCA and compare the resulting diversity of aerosol vertical profiles with the inter-model diversity from the AeroCom Phase II control experiment. In this way we show that (in this model at least) the vertical profile is controlled by a relatively small number of processes, although these vary among aerosol components and particle sizes. We also show that sufficientlymore » coarse variations in these processes can produce a similar diversity to that among different models in terms of the global-mean profile and, to a lesser extent, the zonal-mean vertical position. However, there are features of certain models' profiles that cannot be reproduced, suggesting the influence of further structural differences between models. In HadGEM3–UKCA, convective transport is found to be very important in controlling the vertical profile of all aerosol components by mass. In-cloud scavenging is very important for all except mineral dust. Growth by condensation is important for sulfate and carbonaceous aerosol (along with aqueous oxidation for the former and ageing by soluble material for the latter). The vertical extent of biomass-burning emissions into the free troposphere is also important for the profile of carbonaceous aerosol. Boundary-layer mixing plays a dominant role for sea salt and mineral dust, which are emitted only from the surface. Dry deposition and below-cloud scavenging are important for the profile of mineral dust only. In this model, the microphysical processes of nucleation, condensation and coagulation dominate the vertical profile of the smallest particles by number (e.g. total CN > 3 nm), while the profiles of larger particles (e.g. CN > 100 nm) are

A new description of Titan's aerosol optical properties from the analysis of VIMS Emission Phase Function observations

NASA Astrophysics Data System (ADS)

Maltagliati, Luca; Rodriguez, Sebastien; Sotin, Christophe; Rannou, Pascal; Bezard, Bruno; Cornet, Thomas

2016-06-01

The Huygens probe gave unprecedented information on the properties of Titan's aerosols (vertical distribution, opacity as a function of wavelength, phase function, single scattering albedo) by in-situ measurements (Tomasko et al. 2008). Being the only existing in-situ atmospheric probing for Titan, this aerosol model currently is the reference for many Titan studies (e.g. by being applied as physical input in radiative transfer models of the atmosphere). Recently a reanalysis of the DISR dataset, corroborated by data from the Downward-Looking Visible Spectrometer (DLVS), was carried out by the same group (Doose et al. 2016), leading to significant changes to the indications given by Tomasko et al. (2008). Here we present the analysis of the Emission Phase Function observation (EPF) performed by VIMS during the Cassini flyby T88 (November 2012). An EPF observes the same spot on the surface (and thus the same atmosphere) with the same emergence angle but with different incidence angles. In this way, our EPF allows, for the first time, to have direct information on the phase function of Titan's aerosols, as well as on other important physical parameters of the aerosols as the behavior of their extinction as a function of wavelength and the single scattering albedo (also as a function of wavelength) for the whole VIMS range (0.8-5.2 µm). The T88 EPF is composed of 25 VIMS datacubes spanning a scattering angle range approximately from 0°to 70°. We used the radiative transfer model described in Hirtzig et al. (2013) as baseline, updated with improved methane (+ related isotopes) spectroscopy. By changing the aerosol description in the model, we found the combination of aerosol optical parameters that fits best a constant aerosol column density over the whole set of the VIMS datacubes. We confirmed that the new results from Doose et al. (2016) do improve the fit for what concerns the vertical profile and the extinction as a function of wavelength. However, a different

A new description of Titan's aerosol optical properties from the analysis of VIMS Emission Phase Function observations

NASA Astrophysics Data System (ADS)

Rodriguez, Sebastien; Maltagliati, Luca; Sotin, Christophe; Rannou, Pascal; Bézard, Bruno; Cornet, Thomas

2016-10-01

The Huygens probe gave unprecedented information on the properties of Titan's aerosols (vertical distribution, opacity as a function of wavelength, phase function, single scattering albedo) by in-situ measurements (Tomasko et al. 2008). Being the only existing in-situ atmospheric probing for Titan, this aerosol model currently is the reference for many Titan studies (e.g. by being applied as physical input in radiative transfer models of the atmosphere). Recently a reanalysis of the DISR dataset, corroborated by data from the Downward-Looking Visible Spectrometer (DLVS), was carried out by the same group (Doose et al. 2016), leading to significant changes to the indications given by Tomasko et al. (2008).Here we present the analysis of the Emission Phase Function observation (EPF) performed by VIMS during the Cassini flyby T88 (November 2012). An EPF observes the same spot on the surface (and thus the same atmosphere) with the same emergence angle but with different incidence angles. In this way, our EPF allows, for the first time, to have direct information on the phase function of Titan's aerosols, as well as on other important physical parameters of the aerosols as the behavior of their extinction as a function of wavelength and the single scattering albedo (also as a function of wavelength) for the whole VIMS range (0.8-5.2 μm). The T88 EPF is composed of 25 VIMS datacubes spanning a scattering angle range approximately from 0°to 70°.We used the radiative transfer model described in Hirtzig et al. (2013) as baseline, updated with improved methane (+ related isotopes) spectroscopy. By changing the aerosol description in the model, we found the combination of aerosol optical parameters that fits best a constant aerosol column density over the whole set of the VIMS datacubes. We confirmed that the new results from Doose et al. (2016) do improve the fit for what concerns the vertical profile and the extinction as a function of wavelength. However, a different

Aerosols at the poles: an AeroCom Phase II multi-model evaluation

DOE PAGES

Sand, Maria; Samset, Bjorn H.; Balkanski, Yves; ...

2017-10-13

Atmospheric aerosols from anthropogenic and natural sources reach the polar regions through long-range transport and affect the local radiation balance. Such transport is, however, poorly constrained in present-day global climate models, and few multi-model evaluations of polar anthropogenic aerosol radiative forcing exist. Here we compare the aerosol optical depth (AOD) at 550 nm from simulations with 16 global aerosol models from the AeroCom Phase II model intercomparison project with available observations at both poles. We show that the annual mean multi-model median is representative of the observations in Arctic, but that the intermodel spread is large. We also document themore » geographical distribution and seasonal cycle of the AOD for the individual aerosol species: black carbon (BC) from fossil fuel and biomass burning, sulfate, organic aerosols (OAs), dust, and sea-salt. For a subset of models that represent nitrate and secondary organic aerosols (SOAs), we document the role of these aerosols at high latitudes. The seasonal dependence of natural and anthropogenic aerosols differs with natural aerosols peaking in winter (sea-salt) and spring (dust), whereas AOD from anthropogenic aerosols peaks in late spring and summer. The models produce a median annual mean AOD of 0.07 in the Arctic (defined here as north of 60° N). The models also predict a noteworthy aerosol transport to the Antarctic (south of 70° S) with a resulting AOD varying between 0.01 and 0.02. The models have estimated the shortwave anthropogenic radiative forcing contributions to the direct aerosol effect (DAE) associated with BC and OA from fossil fuel and biofuel (FF), sulfate, SOAs, nitrate, and biomass burning from BC and OA emissions combined. The Arctic modelled annual mean DAE is slightly negative (-0.12 W m -2), dominated by a positive BC FF DAE in spring and a negative sulfate DAE in summer. The Antarctic DAE is governed by BC FF. We perform sensitivity experiments with one of

Aerosols at the poles: an AeroCom Phase II multi-model evaluation

NASA Astrophysics Data System (ADS)

Sand, Maria; Samset, Bjørn H.; Balkanski, Yves; Bauer, Susanne; Bellouin, Nicolas; Berntsen, Terje K.; Bian, Huisheng; Chin, Mian; Diehl, Thomas; Easter, Richard; Ghan, Steven J.; Iversen, Trond; Kirkevåg, Alf; Lamarque, Jean-François; Lin, Guangxing; Liu, Xiaohong; Luo, Gan; Myhre, Gunnar; van Noije, Twan; Penner, Joyce E.; Schulz, Michael; Seland, Øyvind; Skeie, Ragnhild B.; Stier, Philip; Takemura, Toshihiko; Tsigaridis, Kostas; Yu, Fangqun; Zhang, Kai; Zhang, Hua

2017-10-01

Atmospheric aerosols from anthropogenic and natural sources reach the polar regions through long-range transport and affect the local radiation balance. Such transport is, however, poorly constrained in present-day global climate models, and few multi-model evaluations of polar anthropogenic aerosol radiative forcing exist. Here we compare the aerosol optical depth (AOD) at 550 nm from simulations with 16 global aerosol models from the AeroCom Phase II model intercomparison project with available observations at both poles. We show that the annual mean multi-model median is representative of the observations in Arctic, but that the intermodel spread is large. We also document the geographical distribution and seasonal cycle of the AOD for the individual aerosol species: black carbon (BC) from fossil fuel and biomass burning, sulfate, organic aerosols (OAs), dust, and sea-salt. For a subset of models that represent nitrate and secondary organic aerosols (SOAs), we document the role of these aerosols at high latitudes.The seasonal dependence of natural and anthropogenic aerosols differs with natural aerosols peaking in winter (sea-salt) and spring (dust), whereas AOD from anthropogenic aerosols peaks in late spring and summer. The models produce a median annual mean AOD of 0.07 in the Arctic (defined here as north of 60° N). The models also predict a noteworthy aerosol transport to the Antarctic (south of 70° S) with a resulting AOD varying between 0.01 and 0.02. The models have estimated the shortwave anthropogenic radiative forcing contributions to the direct aerosol effect (DAE) associated with BC and OA from fossil fuel and biofuel (FF), sulfate, SOAs, nitrate, and biomass burning from BC and OA emissions combined. The Arctic modelled annual mean DAE is slightly negative (-0.12 W m-2), dominated by a positive BC FF DAE in spring and a negative sulfate DAE in summer. The Antarctic DAE is governed by BC FF. We perform sensitivity experiments with one of the Aero

Aerosols at the poles: an AeroCom Phase II multi-model evaluation

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

Sand, Maria; Samset, Bjorn H.; Balkanski, Yves

Atmospheric aerosols from anthropogenic and natural sources reach the polar regions through long-range transport and affect the local radiation balance. Such transport is, however, poorly constrained in present-day global climate models, and few multi-model evaluations of polar anthropogenic aerosol radiative forcing exist. Here we compare the aerosol optical depth (AOD) at 550 nm from simulations with 16 global aerosol models from the AeroCom Phase II model intercomparison project with available observations at both poles. We show that the annual mean multi-model median is representative of the observations in Arctic, but that the intermodel spread is large. We also document themore » geographical distribution and seasonal cycle of the AOD for the individual aerosol species: black carbon (BC) from fossil fuel and biomass burning, sulfate, organic aerosols (OAs), dust, and sea-salt. For a subset of models that represent nitrate and secondary organic aerosols (SOAs), we document the role of these aerosols at high latitudes. The seasonal dependence of natural and anthropogenic aerosols differs with natural aerosols peaking in winter (sea-salt) and spring (dust), whereas AOD from anthropogenic aerosols peaks in late spring and summer. The models produce a median annual mean AOD of 0.07 in the Arctic (defined here as north of 60° N). The models also predict a noteworthy aerosol transport to the Antarctic (south of 70° S) with a resulting AOD varying between 0.01 and 0.02. The models have estimated the shortwave anthropogenic radiative forcing contributions to the direct aerosol effect (DAE) associated with BC and OA from fossil fuel and biofuel (FF), sulfate, SOAs, nitrate, and biomass burning from BC and OA emissions combined. The Arctic modelled annual mean DAE is slightly negative (-0.12 W m -2), dominated by a positive BC FF DAE in spring and a negative sulfate DAE in summer. The Antarctic DAE is governed by BC FF. We perform sensitivity experiments with one of

Monodisperse hydrogel microspheres by forced droplet formation in aqueous two-phase systems.

PubMed

Ziemecka, Iwona; van Steijn, Volkert; Koper, Ger J M; Rosso, Michel; Brizard, Aurelie M; van Esch, Jan H; Kreutzer, Michiel T

2011-02-21

This paper presents a method to form micron-sized droplets in an aqueous two-phase system (ATPS) and to subsequently polymerize the droplets to produce hydrogel beads. Owing to the low interfacial tension in ATPS, droplets do not easily form spontaneously. We enforce the formation of drops by perturbing an otherwise stable jet that forms at the junction where the two aqueous streams meet. This is done by actuating a piezo-electric bending disc integrated in our device. The influence of forcing amplitude and frequency on jet breakup is described and related to the size of monodisperse droplets with a diameter in the range between 30 and 60 μm. Rapid on-chip polymerization of derivatized dextran inside the droplets created monodisperse hydrogel particles. This work shows how droplet-based microfluidics can be used in all-aqueous, surfactant-free, organic-solvent-free biocompatible two-phase environment.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Development of linear free energy relationships for aqueous phase radical-involved chemical reactions.

PubMed

Minakata, Daisuke; Mezyk, Stephen P; Jones, Jace W; Daws, Brittany R; Crittenden, John C

2014-12-02

Aqueous phase advanced oxidation processes (AOPs) produce hydroxyl radicals (HO•) which can completely oxidize electron rich organic compounds. The proper design and operation of AOPs require that we predict the formation and fate of the byproducts and their associated toxicity. Accordingly, there is a need to develop a first-principles kinetic model that can predict the dominant reaction pathways that potentially produce toxic byproducts. We have published some of our efforts on predicting the elementary reaction pathways and the HO• rate constants. Here we develop linear free energy relationships (LFERs) that predict the rate constants for aqueous phase radical reactions. The LFERs relate experimentally obtained kinetic rate constants to quantum mechanically calculated aqueous phase free energies of activation. The LFERs have been applied to 101 reactions, including (1) HO• addition to 15 aromatic compounds; (2) addition of molecular oxygen to 65 carbon-centered aliphatic and cyclohexadienyl radicals; (3) disproportionation of 10 peroxyl radicals, and (4) unimolecular decay of nine peroxyl radicals. The LFERs correlations predict the rate constants within a factor of 2 from the experimental values for HO• reactions and molecular oxygen addition, and a factor of 5 for peroxyl radical reactions. The LFERs and the elementary reaction pathways will enable us to predict the formation and initial fate of the byproducts in AOPs. Furthermore, our methodology can be applied to other environmental processes in which aqueous phase radical-involved reactions occur.

AN INVESTIGATION OF THE RELATIONSHIP BETWEEN GAS-PHASE AND AEROSOL-BORNE HYDROPEROXIDES IN URBAN AIR. (R827352)

EPA Science Inventory

Simultaneous measurements of hydroperoxides in both the gas- and the aerosol-phase have been made for the first time. In addition, hydroperoxide levels in the ‘coarse’ (>PM₂) and ‘fine’ (PM₂) aerosol modes have been characteriz...

Phase state of ambient aerosol linked with water uptake and chemical aging in the southeastern US

DOE PAGES

Pajunoja, Aki; Hu, Weiwei; Leong, Yu J.; ...

2016-09-09

During the summer 2013 Southern Aerosol and Oxidant Study (SOAS) field campaign in a rural site in the southeastern United States, the effect of hygroscopicity and composition on the phase state of atmospheric aerosol particles dominated by the organic fraction was studied. The analysis is based on hygroscopicity measurements by a Hygroscopic Tandem Differential Mobility Analyzer (HTDMA), physical phase state investigations by an Aerosol Bounce Instrument (ABI) and composition measurements using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). To study the effect of atmospheric aging on these properties, an OH-radical oxidation flow reactor (OFR) was used to simulate longer atmosphericmore » aging times of up to 3 weeks. Hygroscopicity and bounce behavior of the particles had a clear relationship showing higher bounce at elevated relative humidity (RH) values for less hygroscopic particles, which agrees well with earlier laboratory studies. Additional OH oxidation of the aerosol particles in the OFR increased the O:C and the hygroscopicity resulting in liquefying of the particles at lower RH values. At the highest OH exposures, the inorganic fraction starts to dominate the bounce process due to production of inorganics and concurrent loss of organics in the OFR. Our results indicate that at typical ambient RH and temperature, organic-dominated particles stay mostly liquid in the atmospheric conditions in the southeastern US, but they often turn semisolid when dried below ~50 % RH in the sampling inlets. Furthermore, while the liquid phase state suggests solution behavior and equilibrium partitioning for the SOA particles in ambient air, the possible phase change in the drying process highlights the importance of thoroughly considered sampling techniques of SOA particles.« less

Phase state of ambient aerosol linked with water uptake and chemical aging in the southeastern US

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

Pajunoja, Aki; Hu, Weiwei; Leong, Yu J.

During the summer 2013 Southern Aerosol and Oxidant Study (SOAS) field campaign in a rural site in the southeastern United States, the effect of hygroscopicity and composition on the phase state of atmospheric aerosol particles dominated by the organic fraction was studied. The analysis is based on hygroscopicity measurements by a Hygroscopic Tandem Differential Mobility Analyzer (HTDMA), physical phase state investigations by an Aerosol Bounce Instrument (ABI) and composition measurements using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). To study the effect of atmospheric aging on these properties, an OH-radical oxidation flow reactor (OFR) was used to simulate longer atmosphericmore » aging times of up to 3 weeks. Hygroscopicity and bounce behavior of the particles had a clear relationship showing higher bounce at elevated relative humidity (RH) values for less hygroscopic particles, which agrees well with earlier laboratory studies. Additional OH oxidation of the aerosol particles in the OFR increased the O:C and the hygroscopicity resulting in liquefying of the particles at lower RH values. At the highest OH exposures, the inorganic fraction starts to dominate the bounce process due to production of inorganics and concurrent loss of organics in the OFR. Our results indicate that at typical ambient RH and temperature, organic-dominated particles stay mostly liquid in the atmospheric conditions in the southeastern US, but they often turn semisolid when dried below ~50 % RH in the sampling inlets. Furthermore, while the liquid phase state suggests solution behavior and equilibrium partitioning for the SOA particles in ambient air, the possible phase change in the drying process highlights the importance of thoroughly considered sampling techniques of SOA particles.« less

Aqueous two-phase assisted by ultrasound for the extraction of anthocyanins from Lycium ruthenicum Murr.

PubMed

Qin, Benlin; Liu, Xuecong; Cui, Haiming; Ma, Yue; Wang, Zimin; Han, Jing

2017-10-21

In this study, an efficient ultrasound-assisted aqueous two-phase extraction method was used for the extraction of anthocyanins from Lycium ruthenicum Murr. An ethanol/ammonium sulfate system was chosen for the aqueous two-phase system due to its fine partitioning and recycling behaviors. Single-factor experiments were conducted to determine the optimized composition of the system, and the response surface methodology was used for the further optimization of the ultrasound-assisted aqueous two-phase extraction. The optimal conditions were as follows: a salt concentration of 20%, an ethanol concentration of 25%, an extraction time of 33.7 min, an extraction temperature of 25°C, a liquid/solid ratio of 50:1 w/w, pH value of 3.98, and an ultrasound power of 600 W. Under the above conditions, the yields of anthocyanins reached 4.71 mg/g dry sample. For the further purification, D-101 resin was used, and the purity of anthocyanins reached 25.3%. In conclusion, ultrasound-assisted aqueous two-phase extraction was an efficient, ecofriendly, and economical method, and it may be a promising technique for extracting bioactive components from plants.

Investigating Aerosol Morphology Using Scattering Phase Functions Measured with a Laser Imaging Nephelometer

NASA Astrophysics Data System (ADS)

Manfred, K.; Adler, G. A.; Erdesz, F.; Franchin, A.; Lamb, K. D.; Schwarz, J. P.; Wagner, N.; Washenfelder, R. A.; Womack, C.; Murphy, D. M.

2017-12-01

Particle morphology has important implications for light scattering and radiative transfer, but can be difficult to measure. Biomass burning and other important aerosol sources can generate a mixture of both spherical and non-spherical particle morphologies, and it is necessary to represent these populations correctly in models. We describe a laser imaging nephelometer that measures the unpolarized scattering phase function of bulk aerosol at 375 and 405 nm using a wide-angle lens and CCD. We deployed this instrument to the Missoula Fire Sciences Laboratory to measure biomass burning aerosol morphology from controlled fires during the recent FIREX intensive laboratory study. Total integrated scattering signal agreed with that determined by a cavity ring-down photoacoustic spectrometer system and a traditional integrating nephelometer within instrument uncertainties. We compared measured scattering phase functions at 405 nm to theoretical models for spherical (Mie) and fractal (Rayleigh-Debye-Gans) particle morphologies based on the size distribution reported by an optical particle counter. We show that particle morphology can vary dramatically for different fuel types, and present results for two representative fires (pine tree vs arid shrub). We find that Mie theory is inadequate to describe the actual behavior of realistic aerosols from biomass burning in some situations. This study demonstrates the capabilities of the laser imaging nephelometer instrument to provide real-time, in situ information about dominant particle morphology that is vital for accurate radiative transfer calculations.

Transfer Kinetics at the Aqueous/Non-Aqueous Phase Liquid Interface. A Statistical Mechanic Approach

NASA Astrophysics Data System (ADS)

Doss, S. K.; Ezzedine, S.; Ezzedine, S.; Ziagos, J. P.; Hoffman, F.; Gelinas, R. J.

2001-05-01

Many modeling efforts in the literature use a first-order, linear-driving-force model to represent the chemical dissolution process at the non-aqueous/aqueous phase liquid (NAPL/APL) interface. In other words, NAPL to APL phase flux is assumed to be equal to the difference between the solubility limit and the "bulk aqueous solution" concentrations times a mass transfer coefficient. Under such assumptions, a few questions are raised: where, in relation to a region of pure NAPL, does the "bulk aqueous solution" regime begin and how does it behave? The answers are assumed to be associated with an arbitrary, predetermined boundary layer, which separates the NAPL from the surrounding solution. The mass transfer rate is considered to be, primarily, limited by diffusion of the component through the boundary layer. In fact, compositional models of interphase mass transfer usually assume that a local equilibrium is reached between phases. Representing mass flux as a rate-limiting process is equivalent to assuming diffusion through a stationary boundary layer with an instantaneous local equilibrium and linear concentration profile. Some environmental researchers have enjoyed success explaining their data using chemical engineering-based correlations. Correlations are strongly dependent on the experimental conditions employed. A universally applicable theory for NAPL dissolution in natural systems does not exist. These correlations are usually expressed in terms of the modified Sherwood number as a function of Reynolds, Peclet, and Schmidt numbers. The Sherwood number may be interpreted as the ratio between the grain size and the thickness of the Nernst stagnant film. In the present study, we show that transfer kinetics at the NAPL/APL interface under equilibrium conditions disagree with approaches based on the Nernst stagnant film concept. It is unclear whether local equilibrium assumptions used in current models are suitable for all situations.A statistical mechanic

Separation of chemical groups from bio-oil aqueous phase via sequential organic solvent extraction

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

Ren, Shoujie; Ye, Philip; Borole, Abhijeet P

Bio-oil aqueous phase contains a considerable amount of furans, alcohols, ketones, aldehydes and phenolics besides the major components of organic acids and anhydrosugars. The complexity of bio-oil aqueous phase limits its efficient utilization. To improve the efficiency of bio-oil biorefinery, this study focused on the separation of chemical groups from bio-oil aqueous phase via sequential organic solvent extractions. Due to their high recoverability and low solubility in water, four solvents (hexane, petroleum ether, chloroform, and ethyl acetate) with different polarities were evaluated, and the optimum process conditions for chemical extraction were determined. Chloroform had high extraction efficiency for furans, phenolics,more » and ketones. In addition to these chemical groups, ethyl acetate had high extraction efficiency for organic acids. The sequential extraction by using chloroform followed by ethyl acetate rendered that 62.2 wt.% of original furans, ketones, alcohols, and phenolics were extracted to chloroform, over 62 wt.% acetic acid was extracted to ethyl acetate, resulting in a high concentration of levoglucosan (~53.0 wt.%) in the final aqueous phase. Chemicals separated via the sequential extraction could be used as feedstocks in biorefinery using processes such as catalytic upgrading of furans and phenolics to hydrocarbons, fermentation of levoglucosan to produce alcohols and diols, and hydrogen production from organic acids via microbial electrolysis.« less

Separation of chemical groups from bio-oil aqueous phase via sequential organic solvent extraction

DOE PAGES

Ren, Shoujie; Ye, Philip; Borole, Abhijeet P

2017-01-05

Bio-oil aqueous phase contains a considerable amount of furans, alcohols, ketones, aldehydes and phenolics besides the major components of organic acids and anhydrosugars. The complexity of bio-oil aqueous phase limits its efficient utilization. To improve the efficiency of bio-oil biorefinery, this study focused on the separation of chemical groups from bio-oil aqueous phase via sequential organic solvent extractions. Due to their high recoverability and low solubility in water, four solvents (hexane, petroleum ether, chloroform, and ethyl acetate) with different polarities were evaluated, and the optimum process conditions for chemical extraction were determined. Chloroform had high extraction efficiency for furans, phenolics,more » and ketones. In addition to these chemical groups, ethyl acetate had high extraction efficiency for organic acids. The sequential extraction by using chloroform followed by ethyl acetate rendered that 62.2 wt.% of original furans, ketones, alcohols, and phenolics were extracted to chloroform, over 62 wt.% acetic acid was extracted to ethyl acetate, resulting in a high concentration of levoglucosan (~53.0 wt.%) in the final aqueous phase. Chemicals separated via the sequential extraction could be used as feedstocks in biorefinery using processes such as catalytic upgrading of furans and phenolics to hydrocarbons, fermentation of levoglucosan to produce alcohols and diols, and hydrogen production from organic acids via microbial electrolysis.« less

Is there a role for aerosol nasal sprays in the treatment of allergic rhinitis: a white paper.

PubMed

Luskin, Allan T; Blaiss, Michael S; Farrar, Judith R; Settipane, Russell; Hayden, Mary Lou; Stoloff, Stuart; Chadwick, Stephen J; Derebery, M Jennifer; Ettari, Mary P; Luskin, Susan; Naclerio, Robert

2011-01-01

This White Paper presents the Consensus Statements derived from a Special Issues Board (SIB) held in Chicago, IL, in October 2010. The SIB was convened to address the question of whether there is a need for both aerosol and aqueous intranasal steroids (INSs) in the treatment of allergic rhinitis (AR). The faculty reviewed the published record of efficacy and safety of aerosol and aqueous INSs, as well as patient and physician satisfaction and preferences for currently available INSs, and burden of disease. Agreement on unmet needs also included the practice experience of the faculty and their colleagues. The body of evidence indicates that INSs are equally effective and well tolerated for most patients. However, differences exist among current aqueous formulations as well as between these products and their aerosol antecedents, based on the properties of the nasal spray. Aerosol formulations, although no longer available, may be preferred for some patients with specific pathophysiology and may be preferred by some patients based on sensory perception. There are good reasons to expand the currently available options of INSs by having both aerosol and aqueous formulations.

Compact and highly stable quantum dots through optimized aqueous phase transfer

NASA Astrophysics Data System (ADS)

Tamang, Sudarsan; Beaune, Grégory; Poillot, Cathy; De Waard, Michel; Texier-Nogues, Isabelle; Reiss, Peter

2011-03-01

A large number of different approaches for the aqueous phase transfer of quantum dots have been proposed. Surface ligand exchange with small hydrophilic thiols, such as L-cysteine, yields the lowest particle hydrodynamic diameter. However, cysteine is prone to dimer formation, which limits colloidal stability. We demonstrate that precise pH control during aqueous phase transfer dramatically increases the colloidal stability of InP/ZnS quantum dots. Various bifunctional thiols have been applied. The formation of disulfides, strongly diminishing the fluorescence QY has been prevented through addition of appropriate reducing agents. Bright InP/ZnS quantum dots with a hydrodynamic diameter <10 nm and long-term stability have been obtained. Finally we present in vitro studies of the quantum dots functionalized with the cell-penetrating peptide maurocalcine.

Observed Aerosol Influence on Ice Water Content of Arctic Mixed-Phase Clouds

NASA Astrophysics Data System (ADS)

Norgren, M.; de Boer, G.; Shupe, M.

2016-12-01

The response of ice water content (IWC) in Arctic mixed-phase stratocumulus to atmospheric aerosols is observed. IWC retrievals from ground based radars operated by the Atmospheric Radiation Measurement (ARM) program in Barrow, Alaska are used to construct composite profiles of cloud IWC from a 9-year radar record starting in January of 2000. The IWC profiles for high (polluted) and low (clean) aerosol loadings are compared. Generally, we find that clean clouds exhibit statistically significant higher levels of IWC than do polluted clouds by a factor of 2-4 at cloud base. For springtime clouds, with a maximum relative humidity with respect to ice (RHI) above 110% in the cloud layer, the IWC at cloud base was a factor of 3.25 times higher in clean clouds than it was in polluted clouds. We infer that the aerosol loading of the cloud environment alters the liquid drop size distribution within the cloud, with larger drops being more frequent in clean clouds. Larger cloud drops promote riming within the cloud layer, which is one explanation for the higher IWC levels in clean clouds. The drop size distribution may also be a significant control of ice nucleation events within mixed-phase clouds. Whether the high IWC levels in clean clouds are due to increased riming or nucleation events is unclear at this time.

Adsorption of water from aqueous acetonitrile on silica-based stationary phases in aqueous normal-phase liquid chromatography.

PubMed

Soukup, Jan; Jandera, Pavel

2014-12-29

Excess adsorption of water from aqueous acetonitrile mobile phases was investigated on 16 stationary phases using the frontal analysis method and coulometric Karl-Fischer titration. The stationary phases include silica gel and silica-bonded phases with different polarities, octadecyl and cholesterol, phenyl, nitrile, pentafluorophenylpropyl, diol and zwitterionic sulfobetaine and phosphorylcholine ligands bonded on silica, hybrid organic-silica and hydrosilated matrices. Both fully porous and core-shell column types were included. Preferential uptake of water by the columns can be described by Langmuir isotherms. Even though a diffuse rather than a compact adsorbed discrete layer of water on the adsorbent surface can be formed because of the unlimited miscibility of water with acetonitrile, for convenience, the preferentially adsorbed water was expressed in terms of a hypothetical monomolecular water layer equivalent in the inner pores. The uptake of water strongly depends on the polarity and type of the column. Less than one monomolecular water layer equivalent was adsorbed on moderate polar silica hydride-based stationary phases, Ascentis Express F5 and Ascentis Express CN column at the saturation capacity, while on more polar stationary phases, several water layer equivalents were up-taken from the mobile phase. The strongest affinity to water was observed on the ZIC cHILIC stationary phases, where more than nine water layer equivalents were adsorbed onto its surface at its saturation capacity. Columns with bonded hydroxyl and diol ligands show stronger water adsorption in comparison to bare silica. Columns based on hydrosilated silica generally show significantly decreased water uptake in comparison to stationary phases bonded on ordinary silica. Significant correlations were found between the water uptake and the separation selectivity for compounds with strong polarity differences. Copyright © 2014 Elsevier B.V. All rights reserved.

Wintertime water-soluble aerosol composition and particle water content in Fresno, California

NASA Astrophysics Data System (ADS)

Parworth, Caroline L.; Young, Dominique E.; Kim, Hwajin; Zhang, Xiaolu; Cappa, Christopher D.; Collier, Sonya; Zhang, Qi

2017-03-01

The composition and concentrations of water-soluble gases and ionic aerosol components were measured from January to February 2013 in Fresno, CA, with a particle-into-liquid sampler with ion chromatography and annular denuders. The average (±1σ) ionic aerosol mass concentration was 15.0 (±9.4) µg m-3, and dominated by nitrate (61%), followed by ammonium, sulfate, chloride, potassium, nitrite, and sodium. Aerosol-phase organic acids, including formate and glycolate, and amines including methylaminium, triethanolaminium, ethanolaminium, dimethylaminium, and ethylaminium were also detected. Although the dominant species all came from secondary aerosol formation, there were primary sources of ionic aerosols as well, including biomass burning for potassium and glycolate, sea spray for sodium, chloride, and dimethylamine, and vehicles for formate. Particulate methanesulfonic acid was also detected and mainly associated with terrestrial sources. On average, the molar concentration of ammonia was 49 times greater than nitric acid, indicating that ammonium nitrate formation was limited by nitric acid availability. Particle water was calculated based on the Extended Aerosol Inorganics Model (E-AIM) thermodynamic prediction of inorganic particle water and κ-Köhler theory approximation of organic particle water. The average (±1σ) particle water concentration was 19.2 (±18.6) µg m-3, of which 90% was attributed to inorganic species. The fractional contribution of particle water to total fine particle mass averaged at 36% during this study and was greatest during early morning and night and least during the day. Based on aqueous-phase concentrations of ions calculated by using E-AIM, the average (±1σ) pH of particles in Fresno during the winter was estimated to be 4.2 (±0.2).

Heterogeneous oxidation of pesticides on aerosol condensed phase

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

Simulation of semi-explicit mechanisms of SOA formation from glyoxal in aerosol in a 3-D model

NASA Astrophysics Data System (ADS)

Knote, C.; Hodzic, A.; Jimenez, J. L.; Volkamer, R.; Orlando, J. J.; Baidar, S.; Brioude, J.; Fast, J.; Gentner, D. R.; Goldstein, A. H.; Hayes, P. L.; Knighton, W. B.; Oetjen, H.; Setyan, A.; Stark, H.; Thalman, R.; Tyndall, G.; Washenfelder, R.; Waxman, E.; Zhang, Q.

2014-06-01

New pathways to form secondary organic aerosol (SOA) have been postulated recently. Glyoxal, the smallest dicarbonyl, is one of the proposed precursors. It has both anthropogenic and biogenic sources, and readily partitions into the aqueous phase of cloud droplets and deliquesced particles where it undergoes both reversible and irreversible chemistry. In this work we extend the regional scale chemistry transport model WRF-Chem to include detailed gas-phase chemistry of glyoxal formation as well as a state-of-the-science module describing its partitioning and reactions in the aerosol aqueous-phase. A comparison of several proposed mechanisms is performed to quantify the relative importance of different formation pathways and their regional variability. The CARES/CalNex campaigns over California in summer 2010 are used as case studies to evaluate the model against observations. A month-long simulation over the continental United States (US) enables us to extend our results to the continental scale. In all simulations over California, the Los Angeles (LA) basin was found to be the hot spot for SOA formation from glyoxal, which contributes between 1% and 15% of the model SOA depending on the mechanism used. Our results indicate that a mechanism based only on a reactive (surface limited) uptake coefficient leads to higher SOA yields from glyoxal compared to a more detailed description that considers aerosol phase state and chemical composition. In the more detailed simulations, surface uptake is found to give the highest SOA mass yields compared to a volume process and reversible formation. We find that the yields of the latter are limited by the availability of glyoxal in aerosol water, which is in turn controlled by an increase in the Henry's law constant depending on salt concentrations ("salting-in"). A time dependence in this increase prevents substantial partitioning of glyoxal into aerosol water at high salt concentrations. If this limitation is removed, volume

First-principles Study of Phenol Hydrogenation on Pt and Ni Catalysts in Aqueous Phase

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

Yoon, Yeohoon; Rousseau, Roger J.; Weber, Robert S.

2014-07-23

The effects of aqueous phase on the reactivity of phenol hydrogenation over Pt and Ni catalysts were investigated using density functional theory based ab initio molecular dynamics (AIMD) calculations. The adsorption of phenol and the first hydrogenation steps via three carbon positions (ortho, meta and para) with respect to the phenolic OH group were studied in both vacuum and liquid phase conditions. To gain insight into how the aqueous phase affects the metal catalyst surface, increasing water environments including singly adsorbed water molecule, mono- (9 water molecules), double layers (24 water molecules), and the bulk liquid water which (52 watermore » molecules) on the Pt(111) and the Ni(111) surfaces were modeled. Compared to the vacuum/metal interfaces, AIMD simulation results suggest that the aqueous Pt(111) and Ni(111) interfaces have a lower metal work function in the order of 0.8 - 0.9 eV, thus, making the metals in aqueous phase stronger reducing agents and poorer oxidizing agents. Phenol adsorption from the aqueous phase is found to be slightly weaker that from the vapor phase. The first hydrogenation step of phenol at the ortho position of the phenolic ring is slightly favored over the other two positions. The polarization induced by the surrounding water molecules and the solvation effect play important roles in stabilizing the transition states associated with phenol hydrogenation by lowering the barriers of 0.1 - 0.4 eV. The detailed discussion on the basis of the interfacial electrostatics from the current study is very useful to understand the nature of a broader class of metal catalyzed reactions in liquid solution phase. This work was supported by the US Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences and Office of Energy Efficiency and Renewable Energy. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle

Reforming Biomass Derived Pyrolysis Bio-oil Aqueous Phase to Fuels

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

Mukarakate, Calvin; Evans, Robert J.; Deutch, Steve

Fast pyrolysis and catalytic fast pyrolysis (CFP) of biomass produce a liquid product stream comprised of various classes of organic compounds having different molecule size and polarity. This liquid, either spontaneously in the case of catalytic fast pyrolysis or by water addition for the non-catalytic process separates into a non-polar organic-rich fraction and a highly polar water-rich fraction. The organic fraction can be used as a blendstock or feedstock for further processing in a refinery while, in the CFP process design, the aqueous phase is currently sent to wastewater treatment, which results in a loss of residual biogenic carbon presentmore » in this stream. Our work focuses on the catalytic conversion of the biogenic carbon in pyrolysis aqueous phase streams to produce hydrocarbons using a vertical micro-reactor coupled to a molecular beam mass spectrometer (MBMS). Furthermore, the MBMS provides real-time analysis of products while also tracking catalyst deactivation. The catalyst used in this work was HZSM-5, which upgraded the oxygenated organics in the aqueous fraction to fuels comprising small olefins and aromatic hydrocarbons. During processing the aqueous bio-oil fraction the HZSM-5 catalyst exhibited higher activity and coke resistance than those observed in similar experiments using biomass or whole bio-oils. Reduced coking is likely due to ejection of coke precursors from the catalyst pores that was enhanced by excess process water available for steam stripping. The water reacted with coke precursors to form phenol, methylated phenols, naphthol, and methylated naphthols. Conversion data shows that up to 40 wt% of the carbon in the feed stream is recovered as hydrocarbons.« less

Reforming Biomass Derived Pyrolysis Bio-oil Aqueous Phase to Fuels

DOE PAGES

Mukarakate, Calvin; Evans, Robert J.; Deutch, Steve; ...

2017-01-07

Fast pyrolysis and catalytic fast pyrolysis (CFP) of biomass produce a liquid product stream comprised of various classes of organic compounds having different molecule size and polarity. This liquid, either spontaneously in the case of catalytic fast pyrolysis or by water addition for the non-catalytic process separates into a non-polar organic-rich fraction and a highly polar water-rich fraction. The organic fraction can be used as a blendstock or feedstock for further processing in a refinery while, in the CFP process design, the aqueous phase is currently sent to wastewater treatment, which results in a loss of residual biogenic carbon presentmore » in this stream. Our work focuses on the catalytic conversion of the biogenic carbon in pyrolysis aqueous phase streams to produce hydrocarbons using a vertical micro-reactor coupled to a molecular beam mass spectrometer (MBMS). Furthermore, the MBMS provides real-time analysis of products while also tracking catalyst deactivation. The catalyst used in this work was HZSM-5, which upgraded the oxygenated organics in the aqueous fraction to fuels comprising small olefins and aromatic hydrocarbons. During processing the aqueous bio-oil fraction the HZSM-5 catalyst exhibited higher activity and coke resistance than those observed in similar experiments using biomass or whole bio-oils. Reduced coking is likely due to ejection of coke precursors from the catalyst pores that was enhanced by excess process water available for steam stripping. The water reacted with coke precursors to form phenol, methylated phenols, naphthol, and methylated naphthols. Conversion data shows that up to 40 wt% of the carbon in the feed stream is recovered as hydrocarbons.« less

Liquid-liquid phase separation in aerosol particles: Imaging at the Nanometer Scale

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

O'Brien, Rachel; Wang, Bingbing; Kelly, Stephen T.

2015-04-21

Atmospheric aerosols can undergo phase transitions including liquid-liquid phase separation (LLPS) while responding to changes in the ambient relative humidity (RH). Here, we report results of chemical imaging experiments using environmental scanning electron microscopy (ESEM) and scanning transmission x-ray microscopy (STXM) to investigate the LLPS of micron sized particles undergoing a full hydration-dehydration cycle. Internally mixed particles composed of ammonium sulfate (AS) and either: limonene secondary organic carbon (LSOC), a, 4-dihydroxy-3-methoxybenzeneaceticacid (HMMA), or polyethylene glycol (PEG-400) were studied. Events of LLPS with apparent core-shell particle morphology were observed for all samples with both techniques. Chemical imaging with STXM showed thatmore » both LSOC/AS and HMMA/AS particles were never homogeneously mixed for all measured RH’s above the deliquescence point and that the majority of the organic component was located in the shell. The shell composition was estimated as 65:35 organic: inorganic in LSOC/AS and as 50:50 organic: inorganic for HMMA/AS. PEG-400/AS particles showed fully homogeneous mixtures at high RH and phase separated below 89-92% RH with an estimated 50:50% organic to inorganic mix in the shell. These two chemical imaging techniques are well suited for in-situ analysis of the hygroscopic behavior, phase separation, and surface composition of collected ambient aerosol particles.« less

Morphology and Optical Properties of Mixed Aerosol Particles

NASA Astrophysics Data System (ADS)

Fard, Mehrnoush M.; Krieger, Ulrich; Rudich, Yinon; Marcolli, Claudia; Peter, Thomas

2016-04-01

Experiments and modeling studies have shown that deliquesced aerosols can exist not only as one-phase system containing organics, inorganic salts and water, but often as two-phase systems consisting of a predominantly organic and a predominantly inorganic aqueous phase (1,2). Recent laboratory studies conducted with model mixtures representing tropospheric aerosols (1,2,3), secondary organic aerosol (SOA) from smog chamber experiments (4), and field measurements (5) suggest that liquid-liquid phase separations (LLPS) is indeed a common phenomenon in mixed organic/ inorganic particles. During LLPS, particles may adopt different morphologies mainly core-shell and partially engulfed. A core-shell configuration will have consequences for heterogeneous chemistry and hygroscopicity and as a result will alter the optical properties of the particles in particular for organic phases containing absorbing molecules, e.g. brown carbon. The primary objective of this project is to establish a method for investigating the morphology of mixed inorganic and absorbing organic compounds of atmospheric relevance and study their radiative properties before, during, and after phase transitions mainly during LLPS. This will be the first study looking into the radiative effect of LLPS in detail. Our ternary model system consist of ammonium sulfate (AS)/ Polyethylene Glycol (PEG)/ and water (H2O). Carminic acid (CA) was added as a proxy for an absorbing organic compound to the system. The behavior of single droplets of above ternary mixture was monitored during relative humidity (RH) cycles using optical microscopy. The same ternary mixture particle was levitated in an electrodynamic balance (EDB) and the change in its absorption properties was measured at varying RH. In addition, Mie-code modeling is used to predict the absorption efficiency of the same ternary system and the result will be compared with the data obtained from EDB experiment. We also intend to determine the occurrence of

A New Parameterization of H2SO4/H2O Aerosol Composition: Atmospheric Implications

NASA Technical Reports Server (NTRS)

Tabazadeh, Azadeh; Toon, Owen B.; Clegg, Simon L.; Hamill, Patrick

1997-01-01

Recent results from a thermodynamic model of aqueous sulfuric acid are used to derive a new parameterization for the variation of sulfuric acid aerosol composition with temperature and relative humidity. This formulation is valid for relative humidities above 1 % in the temperature range of 185 to 260 K. An expression for calculating the vapor pressure of supercooled liquid water, consistent with the sulfuric acid model, is also presented. We show that the Steele and Hamill [1981] formulation underestimates the water partial pressure over aqueous H2SOI solutions by up to 12% at low temperatures. This difference results in a corresponding underestimate of the H2SO4 concentration in the aerosol by about 6 % of the weight percent at approximately 190 K. In addition, the relation commonly used for estimating the vapor pressure of H2O over supercooled liquid water differs by up to 10 % from our derived expression. The combined error can result in a 20 % underestimation of water activity over a H2SO4 solution droplet in the stratosphere, which has implications for the parameterization of heterogeneous reaction rates in stratospheric sulfuric acid aerosols. The influence of aerosol composition on the rate of homogeneous ice nucleation from a H2SO4 solution droplet is also discussed. This parameterization can also be used for homogeneous gas phase nucleation calculations of H2SO4 solution droplets under various environmental conditions such as in aircraft exhaust or in volcanic plumes.

Different Diversity and Distribution of Archaeal Community in the Aqueous and Oil Phases of Production Fluid From High-Temperature Petroleum Reservoirs.

PubMed

Liang, Bo; Zhang, Kai; Wang, Li-Ying; Liu, Jin-Feng; Yang, Shi-Zhong; Gu, Ji-Dong; Mu, Bo-Zhong

2018-01-01

To get a better knowledge on how archaeal communities differ between the oil and aqueous phases and whether environmental factors promote substantial differences on microbial distributions among production wells, we analyzed archaeal communities in oil and aqueous phases from four high-temperature petroleum reservoirs (55-65°C) by using 16S rRNA gene based 454 pyrosequencing. Obvious dissimilarity of the archaeal composition between aqueous and oil phases in each independent production wells was observed, especially in production wells with higher water cut, and diversity in the oil phase was much higher than that in the corresponding aqueous phase. Statistical analysis further showed that archaeal communities in oil phases from different petroleum reservoirs tended to be more similar, but those in aqueous phases were the opposite. In the high-temperature ecosystems, temperature as an environmental factor could have significantly affected archaeal distribution, and archaeal diversity raised with the increase of temperature ( p < 0.05). Our results suggest that to get a comprehensive understanding of petroleum reservoirs microbial information both in aqueous and oil phases should be taken into consideration. The microscopic habitats of oil phase, technically the dispersed minuscule water droplets in the oil could be a better habitat that containing the indigenous microorganisms.

The Two-Column Aerosol Project: Phase I - Overview and Impact of Elevated Aerosol Layers on Aerosol Optical Depth

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

Berg, Larry K.; Fast, Jerome D.; Barnard, James C.

2016-01-08

The Two-Column Aerosol Project (TCAP), which was conducted from June 2012 through June 2013, was a unique field study that was designed to provide a comprehensive data set that can be used to investigate a number of important climate science questions, including those related to aerosol mixing state and aerosol radiative forcing. The study was designed to sample the atmosphere at a number of altitudes, from near the surface to as high as 8 km, within two atmospheric columns; one located near the coast of North America (over Cape Cod, MA) and a second over the Atlantic Ocean several hundredmore » kilometers from the coast. TCAP included the yearlong deployment of the U.S. Department of Energy’s (DOE) Atmospheric Radiation Measurement (ARM) Mobile Facility (AMF) that was located at the base of the Cape Cod column, as well as summer and winter aircraft intensive observation periods of the ARM Aerial Facility. One important finding from TCAP is the relatively common occurrence (on four of six nearly cloud-free flights) of elevated aerosol layers in both the Cape Cod and maritime columns that were detected using the nadir pointing second-generation NASA high-spectral resolution lidar (HSRL-2). These layers contributed up to 60% of the total aerosol optical depth (AOD) observed in the column. Many of these layers were also intercepted by the aircraft configured for in situ sampling, and the aerosol in the layers was found to have increased amounts of biomass burning aerosol and nitrate compared to the aerosol found near the surface.« less

The Two-Column Aerosol Project: Phase I-Overview and impact of elevated aerosol layers on aerosol optical depth

DOE PAGES

Berg, Larry K.; Fast, Jerome D.; Barnard, James C.; ...

2016-01-08

The Two-Column Aerosol Project (TCAP), conducted from June 2012 through June 2013, was a unique study designed to provide a comprehensive data set that can be used to investigate a number of important climate science questions, including those related to aerosol mixing state and aerosol radiative forcing. The study was designed to sample the atmosphere between and within two atmospheric columns; one fixed near the coast of North America (over Cape Cod, MA) and a second moveable column over the Atlantic Ocean several hundred kilometers from the coast. The U.S. Department of Energy's (DOE) Atmospheric Radiation Measurement (ARM) Mobile Facilitymore » (AMF) was deployed at the base of the Cape Cod column, and the ARM Aerial Facility was utilized for the summer and winter intensive observation periods. One important finding from TCAP is that four of six nearly cloud-free flight days had aerosol layers aloft in both the Cape Cod and maritime columns that were detected using the nadir pointing second-generation NASA high-spectral resolution lidar (HSRL-2). In addition, these layers contributed up to 60% of the total observed aerosol optical depth (AOD). Many of these layers were also intercepted by the aircraft configured for in situ sampling, and the aerosol in the layers was found to have increased amounts of biomass burning material and nitrate compared to aerosol found near the surface. Lastly, while there was a great deal of spatial and day-to-day variability in the aerosol chemical composition and optical properties, no systematic differences between the two columns were observed.« less

The Two-Column Aerosol Project: Phase I - Overview and Impact of Elevated Aerosol Layers on Aerosol Optical Depth

NASA Technical Reports Server (NTRS)

Berg, Larry K.; Fast, Jerome D.; Barnard, James C.; Burton, Sharon P.; Cairns, Brian; Chand, Duli; Comstock, Jennifer M.; Dunagan, Stephen; Ferrare, Richard A.; Flynn, Connor J.;

The Two-Column Aerosol Project: Phase I—Overview and impact of elevated aerosol layers on aerosol optical depth

NASA Astrophysics Data System (ADS)

Berg, Larry K.; Fast, Jerome D.; Barnard, James C.; Burton, Sharon P.; Cairns, Brian; Chand, Duli; Comstock, Jennifer M.; Dunagan, Stephen; Ferrare, Richard A.; Flynn, Connor J.; Hair, Johnathan W.; Hostetler, Chris A.; Hubbe, John; Jefferson, Anne; Johnson, Roy; Kassianov, Evgueni I.; Kluzek, Celine D.; Kollias, Pavlos; Lamer, Katia; Lantz, Kathleen; Mei, Fan; Miller, Mark A.; Michalsky, Joseph; Ortega, Ivan; Pekour, Mikhail; Rogers, Ray R.; Russell, Philip B.; Redemann, Jens; Sedlacek, Arthur J.; Segal-Rosenheimer, Michal; Schmid, Beat; Shilling, John E.; Shinozuka, Yohei; Springston, Stephen R.; Tomlinson, Jason M.; Tyrrell, Megan; Wilson, Jacqueline M.; Volkamer, Rainer; Zelenyuk, Alla; Berkowitz, Carl M.

2016-01-01

The Two-Column Aerosol Project (TCAP), conducted from June 2012 through June 2013, was a unique study designed to provide a comprehensive data set that can be used to investigate a number of important climate science questions, including those related to aerosol mixing state and aerosol radiative forcing. The study was designed to sample the atmosphere between and within two atmospheric columns; one fixed near the coast of North America (over Cape Cod, MA) and a second moveable column over the Atlantic Ocean several hundred kilometers from the coast. The U.S. Department of Energy's (DOE) Atmospheric Radiation Measurement (ARM) Mobile Facility (AMF) was deployed at the base of the Cape Cod column, and the ARM Aerial Facility was utilized for the summer and winter intensive observation periods. One important finding from TCAP is that four of six nearly cloud-free flight days had aerosol layers aloft in both the Cape Cod and maritime columns that were detected using the nadir pointing second-generation NASA high-spectral resolution lidar (HSRL-2). These layers contributed up to 60% of the total observed aerosol optical depth (AOD). Many of these layers were also intercepted by the aircraft configured for in situ sampling, and the aerosol in the layers was found to have increased amounts of biomass burning material and nitrate compared to aerosol found near the surface. In addition, while there was a great deal of spatial and day-to-day variability in the aerosol chemical composition and optical properties, no systematic differences between the two columns were observed.

403 nm cavity ring-down measurements of brown carbon aerosol

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Hygroscopic and phase separation properties of ammonium sulfate/organic/water ternary solutions

NASA Astrophysics Data System (ADS)

Zawadowicz, M. A.; Proud, S. R.; Seppalainen, S. S.; Cziczo, D. J.

2015-03-01

Atmospheric aerosol particles are often partially or completely composed of inorganic salts, such as ammonium sulfate and sodium chloride, and therefore exhibit hygroscopic properties. Many inorganic salts have well-defined deliquescence and efflorescence points at which they take up and lose water, respectively. Deliquescence and efflorescence of simple inorganic salt particles have been investigated by a variety of methods, such as IR spectroscopy, tandem mobility analysis and electrodynamic balance. Field measurements have shown that atmospheric aerosols are not typically pure inorganic salt, instead they often also contain organic species. There is ample evidence from laboratory studies that suggests that mixed particles exist in a phase-separated state, with an aqueous inorganic core and organic shell. Although phase separation has not been measured in situ, there is no reason it would not also take place in the atmosphere. Many recent studies have focused on microscopy techniques that require deposition of the aerosol on a glass slide, possibly changing its surface properties. Here, we investigate the deliquescence and efflorescence points, phase separation and ability to exchange gas-phase components of mixed organic and inorganic aerosol using a flow tube coupled with FTIR spectroscopy. Ammonium sulfate aerosol mixed with organic polyols with different O : C ratios, including 1,4-butanediol, glycerol, 1,2,6-hexanetriol, 1,2-hexanediol, and 1,5-pentanediol have been investigated. Those constituents correspond to materials found in the atmosphere in great abundance, and therefore, particles prepared in this study should mimic atmospheric mixed phase aerosol particles. The results of this study tend to be in agreement with previous microscopy experiments, with several key differences, which possibly reveal a size-dependent effect on phase separation in organic/inorganic aerosol particles.

On The Cloud Processing of Aerosol Particles: An Entraining Air Parcel Model With Two-dimensional Spectral Cloud Microphysics and A New Formulation of The Collection Kernel

NASA Astrophysics Data System (ADS)

Bott, Andreas; Kerkweg, Astrid; Wurzler, Sabine

A study has been made of the modification of aerosol spectra due to cloud pro- cesses and the impact of the modified aerosols on the microphysical structure of future clouds. For this purpose an entraining air parcel model with two-dimensional spectral cloud microphysics has been used. In order to treat collision/coalescence processes in the two-dimensional microphysical module, a new realistic and continuous formu- lation of the collection kernel has been developed. Based on experimental data, the kernel covers the entire investigated size range of aerosols, cloud and rain drops, that is the kernel combines all important coalescence processes such as the collision of cloud drops as well as the impaction scavenging of small aerosols by big raindrops. Since chemical reactions in the gas phase and in cloud drops have an important impact on the physico-chemical properties of aerosol particles, the parcel model has been extended by a chemical module describing gas phase and aqueous phase chemical reactions. However, it will be shown that in the numerical case studies presented in this paper the modification of aerosols by chemical reactions has a minor influence on the microphysical structure of future clouds. The major process yielding in a second cloud event an enhanced formation of rain is the production of large aerosol particles by collision/coalescence processes in the first cloud.

THE EFFECT OF METASTABLE EQUILIBRIUM STATES ON THE PARTITIONING OF NITRATE BETWEEN THE GAS AND AEROSOL PHASES. (R824793)

EPA Science Inventory

With the aid of three atmospheric aerosol equilibrium models, we quantify the effect of metastable equilibrium states (efflorescence branch) in comparison to stable (deliquescence branch) on the partitioning of total nitrate between the gas and aerosol phases. On average, efflore...

Optical constants of concentrated aqueous ammonium sulfate.

NASA Technical Reports Server (NTRS)

Remsberg, E. E.

1973-01-01

Using experimental data obtained from applying spectroscopy to a 39-wt-% aqueous ammonium sulfate solution, it is shown that, even though specific aerosol optical constants appear quite accurate, spectral variations may exist as functions of material composition or concentration or both. Prudent users of optical constant data must then include liberal data error estimates when performing calculations or in interpreting spectroscopic surveys of collected aerosol material.

Non-aqueous phase cold vapor generation and determination of trace cadmium by atomic fluorescence spectrometry.

PubMed

Lei, Zirong; Chen, Luqiong; Hu, Kan; Yang, Shengchun; Wen, Xiaodong

2018-06-05

Cold vapor generation (CVG) of cadmium was firstly accomplished in non-aqueous media by using solid reductant of potassium borohydride (KBH 4 ) as a derivation reagent. The mixture of surfactant Triton X-114 micelle and octanol was innovatively used as the non-aqueous media for the CVG and atomic fluorescence spectrometry (AFS) was used for the elemental determination. The analyte ions were firstly extracted into the non-aqueous media from the bulk aqueous phase of analyte/sample solution via a novelly established ultrasound-assisted rapidly synergistic cloud point extraction (UARS-CPE) process and then directly mixed with the solid redcutant KBH 4 to generate volatile elemental state cadmium in a specially designed reactor, which was then rapidly transported to a commercial atomic fluorescence spectrometer for detection. Under the optimal conditions, the limit of detection (LOD) for cadmium was 0.004 μg L -1 . Compared to conventional hydride generation (HG)-AFS, the efficiency of non-aqueous phase CVG and the analytical performance of the developed system was considerably improved. Copyright © 2018 Elsevier B.V. All rights reserved.

In-situ measurements of scattering phase functions of stratospheric aerosol particles in Alaska during July 1979

NASA Technical Reports Server (NTRS)

Grams, G. W.

1981-01-01

A laser nephelometer developed for airborne measurements of polar scattering diagrams of atmospheric aerosols was flown on the NCAR Sabreliner aircraft to obtain data on light-scattering parameters for stratospheric aerosol particles over Alaska during July 1979. Observed values of the angular variation of scattered-light intensity were compared with those calculated for different values of the asymmetry parameter g in the Henyey-Greenstein phase function. The observations indicate that, for the time and location of the experiments, the Henyey-Greenstein phase function could be used to calculate polar scattering diagrams to within experimental errors for an asymmetry parameter value of 0.49 plus or minus 0.07.

Constraining Aerosol-Cloud-Precipitation Interactions of Orographic Mixed-Phase Clouds with Trajectory Budgets

NASA Astrophysics Data System (ADS)

Glassmeier, F.; Lohmann, U.

2016-12-01

Orographic precipitation is prone to strong aerosol-cloud-precipitation interactions because the time for precipitation development is limited to the ascending section of mountain flow. At the same time, cloud microphysical development is constraint by the strong dynamical forcing of the orography. In this contribution, we discuss how changes in the amount and composition of droplet- and ice-forming aerosols influence precipitation in idealized simulations of stratiform orographic mixed-phase clouds. We find that aerosol perturbations trigger compensating responses of different precipitation formation pathways. The effect of aerosols is thus buffered. We explain this buffering by the requirement to fulfill aerosol-independent dynamical constraints. For our simulations, we use the regional atmospheric model COSMO-ART-M7 in a 2D setup with a bell-shaped mountain. The model is coupled to a 2-moment warm and cold cloud microphysics scheme. Activation and freezing rates are parameterized based on prescribed aerosol fields that are varied in number, size and composition. Our analysis is based on the budget of droplet water along trajectories of cloud parcels. The budget equates condensation as source term with precipitation formation from autoconversion, accretion, riming and the Wegener-Bergeron-Findeisen process as sink terms. Condensation, and consequently precipitation formation, is determined by dynamics and largely independent of the aerosol conditions. An aerosol-induced change in the number of droplets or crystals perturbs the droplet budget by affecting precipitation formation processes. We observe that this perturbation triggers adjustments in liquid and ice water content that re-equilibrate the budget. As an example, an increase in crystal number triggers a stronger glaciation of the cloud and redistributes precipitation formation from collision-coalescence to riming and from riming to vapor deposition. We theoretically confirm the dominant effect of water

NMR Studies on the Aqueous Phase Photochemical Degradation of TNT

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

Thorn, Kevin A.; Cox, Larry G.

2008-04-06

Aqueous phase photochemical degradation of 2,4,6-trinitrotoluene (TNT) is an important pathway in several environments, including washout lagoon soils, impact craters from partially detonated munitions that fill with rain or groundwater, and shallow marine environments containing unexploded munitions that have corroded. Knowledge of the degradation products is necessary for compliance issues on military firing ranges and formerly used defense sites. Previous laboratory studies have indicated that UV irradiation of aqueous TNT solutions results in a multicomponent product mixture, including polymerization compounds, that has been only partially resolved by mass spectrometric analyses. This study illustrates how a combination of solid and liquidmore » state 1H, 13C, and 15N NMR spectroscopy, including two dimensional analyses, provides complementary information on the total product mixture from aqueous photolysis of TNT, and the effect of reaction conditions. Among the degradation products detected were amine, amide, azoxy, azo, and carboxylic acid compounds.« less

MATRIX-VBS Condensing Organic Aerosols in an Aerosol Microphysics Model

NASA Technical Reports Server (NTRS)

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

2015-01-01

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

Characterization of the temperature and humidity-dependent phase diagram of amorphous nanoscale organic aerosols.

PubMed

Rothfuss, Nicholas E; Petters, Markus D

2017-03-01

Atmospheric aerosols can exist in amorphous semi-solid or glassy phase states. These states are determined by the temperature (T) and relative humidity (RH). New measurements of viscosity for amorphous semi-solid nanometer size sucrose particles as a function of T and RH are reported. Viscosity is measured by inducing coagulation between two particles and probing the thermodynamic states that induce the particle to relax into a sphere. It is shown that the glass transition temperature can be obtained by extrapolation to 10 12 Pa s from the measured temperature-dependent viscosity in the 10 6 to 10 7 Pa s range. The experimental methodology was refined to allow isothermal probing of RH dependence and to increase the range of temperatures over which the dry temperature dependence can be studied. Several experiments where one monomer was sodium dodecyl sulfate (SDS), which remains solid at high RH, are also reported. These sucrose-SDS dimers were observed to relax into a sphere at T and RH similar to those observed in sucrose-sucrose dimers, suggesting that amorphous sucrose will flow over an insoluble particle at a viscosity similar to that characteristic of coalescence between two sucrose particles. Possible physical and analytical implications of this observation are considered. The data reported here suggest that semi-solid viscosity between 10 4 and 10 12 Pa s can be modelled over a wide range of T and RH using an adapted Vogel-Fulcher-Tammann equation and the Gordon-Taylor mixing rule. Sensitivity of modelled viscosity to variations in dry glass transition temperature, Gordon-Taylor constant, and aerosol hygroscopicity are explored, along with implications for atmospheric processes such as ice nucleation of glassy organic aerosols in the upper free troposphere. The reported measurement and modelling framework provides a template for characterizing the phase diagram of other amorphous aerosol systems, including secondary organic aerosols.

Hierarchical drug release of pH-sensitive liposomes encapsulating aqueous two phase system.

PubMed

Zhang, Xunan; Zong, Wei; Bi, Hongmei; Zhao, Kunming; Fuhs, Thomas; Hu, Ying; Cheng, Wenlong; Han, Xiaojun

2018-06-01

As promising drug delivery vehicles, previous investigations of liposomes as carriers are primarily focused on insertion and modification of lipid membrane interfaces. The utility of the inner core seems to be overlooked. Herein, we developed pH-sensitive liposomes (PSLs) containing an aqueous two phase system (ATPS), and intriguingly discovered their hierarchical release under acidic stimuli. ATPS containing two polymers (poly(ethylene glycol) (PEG) and dextran) is homogeneous above phase transition temperature when producing ATPS-liposomes, and separated into PEG-rich phase and dextran-rich phase after cooling down to room temperature. The overall release time of ATPS-liposomes is divided into two stages and prolonged compared to simple aqueous liposomes. The unique release profile is due to the disproportional distribution of drugs in two phases. Doxorubicin (DOX) is loaded in the ATPS-liposomes, and their half maximum inhibition concentration on HeLa cells is 0.018 μmol L -1 , which means 27.5 fold increase in inhibition efficiency over free DOX. Copyright © 2018 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Isotropic-nematic phase transition in aqueous sepiolite suspensions.

PubMed

Woolston, Phillip; van Duijneveldt, Jeroen S

2015-01-01

Aqueous suspensions of sepiolite clay rods in water tend to form gels on increase of concentration. Here it is shown how addition of a small amount (0.1% of the clay mass) of a common stabiliser for clay suspensions, sodium polyacrylate, can allow the observation of an isotropic-nematic liquid crystal phase transition. This transition was found to move to higher clay concentrations upon adding NaCl, with samples containing 10(-3) M salt or above only displaying a gel phase. Even samples that initially formed liquid crystals had a tendency to form gels after several weeks, possibly due to Mg(2+) ions leaching from the clay mineral. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.

Rapid aqueous phase SO2 oxidation in winter fog in the Indo-Gangetic Plain

NASA Astrophysics Data System (ADS)

Sachan, Himanshu; Sarkar, Chinmoy; Sinha, Baerbel

2013-04-01

Sulphate and sulphur dioxide play an important role in environmental chemistry and climate. The majority of anthropogenic sulphur is released directly as SO2, and a significant fraction of biogenic and natural sulphur emissions are also either directly released as SO2 or oxidised to SO2 in the atmosphere (e.g. H2S, OCS, DMS). Around 50% of global atmospheric sulphur dioxide is then oxidised to sulphate, while the rest is lost through dry and wet deposition. The pathway by which SO2 is oxidised to sulphate is critical in determining the climate forcing and environmental effects of sulphate. Gas-phase oxidation of SO2 by OH radicals or criegee intermediates produces H2SO4 (g), which plays an important role in controlling new particle formation in the troposphere and also modifies the surface properties of hydrophobic particles such as soot and mineral dust. Heterogeneous oxidation of SO2 is considered to occur primarily in cloud droplets, although oxidation on sea salt aerosols and mineral dust surfaces are considered to be regionally important. Heterogeneous oxidation leads to the formation of fewer and larger particles with shorter atmospheric lifetime. The major oxidation pathways which are considered to contribute to sulphate formation in the aqueous phase are oxidation by H2O2 and oxidation by O3 and the lifetime of SO2 with respect to all known loss processes combined is considered to be 1-2 days. Here we report measurements of SO2 measurements from IISER Mohali - Ambient Air Quality Station (30.67°N, 76.73°E), a station located at a suburban site in the Indo Gangetic Basin (IGB) during wintertime (10th Dec. 2011 to 29th Feb. 2012). We use a strong point source of SO2 with known SO2/CO emission ratio (brick kiln) located 6.5 km east of our measurement site to estimate the loss rate of SO2 in wintertime fog in the IGB. We consider the transport from the source to the receptor site to be Lagrangian and use the measured CO concentration at the receptors site to

Crystallization pathways of sulfate-nitrate-ammonium aerosol particles.

PubMed

Schlenker, Julie C; Martin, Scot T

2005-11-10

Crystallization experiments are conducted for aerosol particles composed of aqueous mixtures of (NH(4))(2)SO(4)(aq) and NH(4)NO(3)(aq), (NH(4))(2)SO(4)(aq) and NH(4)HSO(4)(aq), and NH(4)NO(3)(aq) and NH(4)HSO(4)(aq). Depending on the aqueous composition, crystals of (NH(4))(2)SO(4)(s), (NH(4))(3)H(SO(4))(2)(s), NH(4)HSO(4)(s), NH(4)NO(3)(s), 2NH(4)NO(3) x (NH(4))(2)SO(4)(s), and 3NH(4)NO(3) x (NH(4))(2)SO(4)(s) are formed. Although particles of NH(4)NO(3)(aq) and NH(4)HSO(4)(aq) do not crystallize even at 1% relative humidity, additions of 0.05 mol fraction SO(4)(2-)(aq) or NO(3)(-)(aq) ions promote crystallization, respectively. 2NH(4)NO(3) x (NH(4))(2)SO(4)(s) and (NH(4))(3)H(SO(4))(2)(s) appear to serve as good heterogeneous nuclei for NH(4)NO(3)(s) and NH(4)HSO(4)(s), respectively. 2NH(4)NO(3) x (NH(4))(2)SO(4)(s) crystallizes over a greater range of aqueous compositions than 3NH(4)NO(3) x (NH(4))(2)SO(4)(s). An infrared aerosol spectrum is provided for each solid based upon a linear decomposition analysis of the recorded spectra. Small nonzero residuals occur in the analysis because aerosol spectra depend on particle morphology, which changes slightly across the range of compositions studied. In addition, several of the mixed compositions crystallize with residual aqueous water of up to 5% particle mass. We attribute this water content to enclosed water pockets. The results provide further insights into the nonlinear crystallization pathways of sulfate-nitrate-ammonium aerosol particles.

Hygroscopic and phase separation properties of ammonium sulfate/organics/water ternary solutions

NASA Astrophysics Data System (ADS)

Zawadowicz, M. A.; Proud, S. R.; Seppalainen, S. S.; Cziczo, D. J.

2015-08-01

Atmospheric aerosol particles are often partially or completely composed of inorganic salts, such as ammonium sulfate and sodium chloride, and therefore exhibit hygroscopic properties. Many inorganic salts have well-defined deliquescence and efflorescence points at which they take up and lose water, respectively. Field measurements have shown that atmospheric aerosols are not typically pure inorganic salt, instead, they often also contain organic species. There is ample evidence from laboratory studies that suggests that mixed particles exist in a phase-separated state, with an aqueous inorganic core and organic shell. Although phase separation has not been measured in situ, there is no reason it would not also take place in the atmosphere. Here, we investigate the deliquescence and efflorescence points, phase separation and ability to exchange gas-phase components of mixed organic and inorganic aerosol using a flow tube coupled with FTIR (Fourier transform infrared) spectroscopy. Ammonium sulfate aerosol mixed with organic polyols with different O : C ratios, including 1,4-butanediol, glycerol, 1,2,6-hexanetriol, 1,2-hexanediol, and 1,5-pentanediol have been investigated. Those constituents correspond to materials found in the atmosphere in great abundance and, therefore, particles prepared in this study should mimic atmospheric mixed-phase aerosol particles. Some results of this study tend to be in agreement with previous microscopy experiments, but others, such as phase separation properties of 1,2,6-hexanetriol, do not agree with previous work. Because the particles studied in this experiment are of a smaller size than those used in microscopy studies, the discrepancies found could be a size-related effect.

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.

Theoretical Investigation of the Structural Stabilities of Ceria Surfaces and Supported Metal Nanocluster in Vapor and Aqueous Phases

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

Ren, Zhibo; Liu, Ning; Chen, Biaohua

Understanding the structural stability and dynamics at the interface between the solid metal oxide and aqueous phase is significant in a variety of industrial applications including heterogeneous catalysis and environmental remediation. In the present work, the stabilities of three low-index ceria (CeO2) surfaces, i.e., (111), (110) and (100) in vapor and aqueous phases were studied using ab initio molecular dynamics simulations and density functional theory (DFT) calculations. Gibbs surface free energies as a function of temperature, water partial pressure, and water coverages were calculated using DFT based atomistic thermodynamic approach. On the basis of surface free energies, the morphology andmore » exposed surface structures of the CeO2 nanoparticle were predicted using Wulff construction principle. It is found that the partially hydroxylated (111) and (100) are two major surface structures of CeO2 nanoparticles in vapor phase at ambient temperature (300 K). As the temperature increases, the fully dehydrated (111) surface gradually becomes the most dominant surface structure. While in aqueous phase, the exposed surface of the CeO2 nanoparticle is dominated by the hydroxylated (110) structure at 393 K. Finally, the morphology and stability of a cuboctahedron Pt13 nanocluster supported on CeO2 surfaces in both gas and aqueous phases were investigated. In gas phase, the supported Pt13 nanocluster has the tendency to wetting the CeO2 surface due to the strong metal-support interaction. The calculated interaction energies suggest the CeO2(110) surface provides the best stability for the Pt13 nanocluster. The CeO2 supported Pt13 nanoclusters are oxidized. Compared to the gas phase, the morphology of the CeO2 supported Pt13 nanocluster is less distorted due to the solvation effect provided by surrounding water molecules in aqueous phase. More electrons are transferred from the Pt13 nanocluster to the CeO2 support, implying the supported Pt13 nanocluster is

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Characteristics of aerosol pollution during heavy haze events in Suzhou, China

NASA Astrophysics Data System (ADS)

Tian, M.; Wang, H. B.; Chen, Y.; Yang, F. M.; Zhang, X. H.; Zou, Q.; Zhang, R. Q.; Ma, Y. L.; He, K. B.

2015-11-01

A comprehensive measurement was carried out to analyze the heavy haze events in Suzhou in January 2013 when extremely severe haze pollution occurred in many cities in China especially in the East. Hourly concentrations of PM2.5, chemical composition (including water-soluble inorganic ions, OC, and EC), and gas-phase precursors were obtained via on-line monitoring system. Based on these data, detailed aerosol composition, light extinction and gas-phase precursors were analyzed to understand the characteristics of the haze events, moreover, the formation mechanism of nitrate and sulfate in PM2.5 and the regional sources deduced from trajectory and PSCF were discussed to explore the origin of the heavy aerosol pollution. The results showed that frequent haze events were occurred on January 2013 and the concentrations of PM2.5 often exceeded 150 μg m-3 during the haze occurrence, with a maximum concentration of 324 μg m-3 on 14 January 2013. Unfavorable weather conditions (high RH, and low rainfall, wind speed and atmospheric pressure), high concentration of secondary aerosol species (including SO42-, NO3-, NH4+, and SOC) and precursors were observed during the haze events. Additionally, OM, (NH4)2SO4, NH4NO3 were demonstrated to be the major contributors to the visibility impairment but the share differed from haze events. This study also found that the high concentration of sulfate might be explained by the heterogeneous reactions in the aqueous surface layer of pre-existing particles or in cloud processes while nitrate might be mainly formed through homogeneous gas-phase reactions. The results of trajectory clustering and the PSCF method manifested that aerosol pollutions in the studied areas were mainly affected by local activities and surrounding sources transported from nearby cities.

A resolution approach of racemic phenylalanine with aqueous two-phase systems of chiral tropine ionic liquids.

PubMed

Wu, Haoran; Yao, Shun; Qian, Guofei; Yao, Tian; Song, Hang

2015-10-30

Aqueous two-phase systems (ATPS) based on tropine type chiral ionic liquids and inorganic salt solution were designed and prepared for the enantiomeric separation of racemic phenylalanine. The phase behavior of IL-based ATPS was comprehensive investigated, and phase equilibrium data were correlated by Merchuk equation. Various factors were also systematically investigated for their influence on separation efficiency. Under the appropriate conditions (0.13g/g [C8Tropine]pro, 35mg/g Cu(Ac)2, 20mg/g d,l-phenylalanine, 0.51g/g H2O and 0.30g/g K2HPO4), the enantiomeric excess value of phenylalanine in solid phase (mainly containing l-enantiomer) was 65%. Finally, the interaction mechanism was studied via 1D and 2D NMR. The results indicate that d-enantiomer of phenylalanine interacts more strongly with chiral ILs and Cu(2+) based on the chiral ion-pairs space coordination mechanism, which makes it tend to remain in the top IL-rich phase. By contrast, l-enantiomer is transferred into the solid phase. Above chiral ionic liquids aqueous two-phase systems have demonstrated obvious resolution to racemic phenylalanine and could be promising alterative resolution approach for racemic amino acids in aqueous circumstance. Copyright © 2015. Published by Elsevier B.V.

Effects of NO(y) aging on the dehydration dynamics of model sea spray aerosol.

PubMed

Woods, Ephraim; Heylman, Kevin D; Gibson, Amanda K; Ashwell, Adam P; Rossi, Sean R

2013-05-23

The reactions of NO(y) species in the atmosphere with sea spray aerosol replace halogen anions with nitrate. These experiments show the effect of increasing the nitrate content of model sea spray aerosol particles on the morphology changes and the phase transitions driven by changes in relative humidity (RH). The components of the model particles include H2O, Na+, Mg2+, Cl-, NO3-, and SO4(2-). Tandem differential mobility analyzer (TDMA) measurements yield the water content and efflorescence relative humidity (ERH) of these particles, and probe molecule spectroscopic measurements reveal subsequent phase transitions and partially characterize the salt composition on the surface of dry particles. The results show three effects of increasing the nitrate composition: decreasing the EFH (46 to 29%), production of a metastable aqueous layer on the surface of effloresced particles, and decreasing the sulfate content near the surface of dry particles. For the mixtures studied here, the initial crystallization event forms a core of NaCl. For particles that contain a substantial metastable aqueous layer following efflorescence, probe molecule spectroscopy shows a second crystallization at a lower RH. This subsequent phase transition is likely the formation of Na2SO4. Homogeneous nucleation theory (HNT) using a semiempirical formulation predicts the ERH of all mixtures within 2.0% RH, with a mean absolute deviation of 1.0%. The calculations suggest that structures associated with highly concentrated or supersaturated magnesium ions strongly affect the interfacial tension between the NaCl crystal nucleus and the droplet from which it forms.

Hydrothermal upgrading of algae paste: Inorganics and recycling potential in the aqueous phase.

PubMed

Patel, Bhavish; Guo, Miao; Chong, Chinglih; Sarudin, Syazwani Hj Mat; Hellgardt, Klaus

2016-10-15

Hydrothermal Liquefaction (HTL) for algal biomass conversion is a promising technology capable of producing high yields of biocrude as well as partitioning even higher quantity of nutrients in the aqueous phase. To assess the feasibility of utilizing the aqueous phase, HTL of Nannochloropsis sp. was carried out in the temperature range of 275 to 350°C and Residence Times (RT) ranging between 5 and 60min The effect of reaction conditions on the NO3(-),PO4(3-),SO4(2-),Cl(-),Na(+),andK(+) ions as well as Chemical Oxygen Demand (COD) and pH was investigated with view of recycling the aqueous phase for either cultivation or energy generation via Anaerobic Digestion (AD), quantified via Lifecycle Assessment (LCA). It addition to substantial nutrient partitioning at short RT, an increase in alkalinity to almost pH10 and decrease in COD at longer RT was observed. The LCA investigation found reaction conditions of 275°C/30min and 350°C/10min to be most suitable for nutrient and energy recovery but both processing routes offer environmental benefit at all reaction conditions, however recycling for cultivation has marginally better environmental credentials compared to AD. Copyright © 2016 Elsevier B.V. All rights reserved.

Homogeneous Bacterial Aerosols Produced with a Spinning-Disc Generator

PubMed Central

Harstad, J. Bruce; Filler, Melvin E.; Hushen, William T.; Decker, Herbert M.

1970-01-01

Aerosols composed of viable particles of a uniform size were produced with a commercial spinning-disc generator from aqueous suspensions of Bacillus subtilis var. niger spores containing various amounts of an inert material, dextran, to regulate aerosol particle size. Aerosols composed of single naked spores having an equivalent spherical diameter of 0.87 μm were produced from spore suspensions without dextran, whereas aerosols produced from suspensions containing 0.001, 0.01, 0.1, and 1% dextran had median diameters of 0.90, 1.04, 1.80, and 3.62 μm, respectively. Such aerosols, both homogeneous and viable, would be useful for calibrating air sampling devices, evaluating air filter systems, or for employment wherever aerosol behavior may be size-dependent. Images PMID:4989672

Demixing of aqueous polymer two-phase systems in low gravity

NASA Technical Reports Server (NTRS)

Bamberger, S.; Harris, J. M.; Baird, J. K.; Boyce, J.; Vanalstine, J. M.; Snyder, R. S.; Brooks, D. E.

1986-01-01

When polymers such as dextran and poly(ethylene glycol) are mixed in aqueous solution biphasic systems often form. On Earth the emulsion formed by mixing the phases rapidly demixes because of phase density differences. Biological materials can be purified by selective partitioning between the phases. In the case of cells and other particulates the efficiency of these separations appears to be somewhat compromised by the demixing process. To modify this process and to evaluate the potential of two-phase partitioning in space, experiments on the effects of gravity on phase emulsion demixing were undertaken. The behavior of phase systems with essentially identical phase densities was studied at one-g and during low-g parabolic aircraft maneuvers. The results indicate the demixing can occur rather rapidly in space, although more slowly than on Earth. The demixing process was examined from a theoretical standpoint by applying the theory of Ostwald ripening. This theory predicts demizing rates many orders of magnitude lower than observed. Other possible demixing mechanisms are considered.

Cloud Point and Liquid-Liquid Equilibrium Behavior of Thermosensitive Polymer L61 and Salt Aqueous Two-Phase System.

PubMed

Rao, Wenwei; Wang, Yun; Han, Juan; Wang, Lei; Chen, Tong; Liu, Yan; Ni, Liang

2015-06-25

The cloud point of thermosensitive triblock polymer L61, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO), was determined in the presence of various electrolytes (K2HPO4, (NH4)3C6H5O7, and K3C6H5O7). The cloud point of L61 was lowered by the addition of electrolytes, and the cloud point of L61 decreased linearly with increasing electrolyte concentration. The efficacy of electrolytes on reducing cloud point followed the order: K3C6H5O7 > (NH4)3C6H5O7 > K2HPO4. With the increase in salt concentration, aqueous two-phase systems exhibited a phase inversion. In addition, increasing the temperature reduced the concentration of salt needed that could promote phase inversion. The phase diagrams and liquid-liquid equilibrium data of the L61-K2HPO4/(NH4)3C6H5O7/K3C6H5O7 aqueous two-phase systems (before the phase inversion but also after phase inversion) were determined at T = (25, 30, and 35) °C. Phase diagrams of aqueous two-phase systems were fitted to a four-parameter empirical nonlinear expression. Moreover, the slopes of the tie-lines and the area of two-phase region in the diagram have a tendency to rise with increasing temperature. The capacity of different salts to induce aqueous two-phase system formation was the same order as the ability of salts to reduce the cloud point.

Atmospheric reactions of ortho cresol: Gas phase and aerosol products

NASA Astrophysics Data System (ADS)

Grosjean, Daniel

Photo-oxidation of ortho-cresol (0.5-1.1 ppm) and oxides of nitrogen (0.12-0.66 ppm) in air yielded the following gas-phase products: pyruvic acid, acetaldehyde, formaldehyde, peroxyacetylnitrate, nitrocresol and trace levels of nitric acid and methyl nitrate. particulate phase products included 2-hydroxy3-nitro toluene, 2-hydroxy-5-nitro toluene, 2-hydroxy-3,5-dinitrotoluene and, tentatively, several hydroxynitrocresol isomers. Yields of gas-phase products (0.8 % for pyruvic acid, 5-11 % for the sum of the aromatic ring fragmentation products) and of aerosol products (5-19% on a carbon basis, with particulate carbon formation rates of 30-80 μ g m -3 h -1) are discussed in terms of photochemical reaction pathways. From 60 to 89 % of the initial NO x was consumed in these reactions and a significant fraction of the reacted NO x could be accounted for as particulate nitro-aromatic products.

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

NASA Technical Reports Server (NTRS)

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

2017-01-01

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

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

Evaluation of the aerosol vertical distribution in global aerosol models through comparison against CALIOP measurements: AeroCom phase II results: AEROSOL PROFILES IN AEROCOM II GCM

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

Koffi, Brigitte; Schulz, Michael; Bréon, François-Marie

2016-06-27

The ability of eleven models in simulating the aerosol vertical distribution from regional to global scales, as part of the second phase of the AeroCom model inter-comparison initiative (AeroCom II) is assessed and compared to results of the first phase. The evaluation is performed using a global monthly gridded dataset of aerosol extinction profiles built on purpose from the CALIOP (Cloud-Aerosol Lidar with Orthogonal Polarization) Layer Product 3.01. Results over 12 sub-continental regions show that five models improved whereas three degraded in reproducing the Zα 0-6 km mean extinction height diagnostic, which is computed over the 0-6 km altitude rangemore » for each studied region and season. While the models’ performance remains highly variable, it has generally improved in terms of inter-regional diversity and seasonality. The biases in Zα 0-6 km have notably decreased in the U.S. and European industrial and downwind maritime regions, whereas the timing of the Zα 0-6 km peak season has improved for all but two models. However, most of the models now show a Zα 0-6 km underestimation over land, notably in the dust and biomass burning regions in Asia and Africa. At global scale, the AeroCom II models better reproduce the Zα 0-6 km latitudinal variability over ocean than over land. Hypotheses for the (changes in the) the performance of the individual models and for the inter-model diversity are discussed. We also provide an analysis of the CALIOP limitations and uncertainties that can contribute to the differences between the simulations and observations.« less

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

Aerosol Modeling for the Global Model Initiative

NASA Technical Reports Server (NTRS)

Weisenstein, Debra K.; Ko, Malcolm K. W.

2001-01-01

The goal of this project is to develop an aerosol module to be used within the framework of the Global Modeling Initiative (GMI). The model development work will be preformed jointly by the University of Michigan and AER, using existing aerosol models at the two institutions as starting points. The GMI aerosol model will be tested, evaluated against observations, and then applied to assessment of the effects of aircraft sulfur emissions as needed by the NASA Subsonic Assessment in 2001. The work includes the following tasks: 1. Implementation of the sulfur cycle within GMI, including sources, sinks, and aqueous conversion of sulfur. Aerosol modules will be added as they are developed and the GMI schedule permits. 2. Addition of aerosol types other than sulfate particles, including dust, soot, organic carbon, and black carbon. 3. Development of new and more efficient parameterizations for treating sulfate aerosol nucleation, condensation, and coagulation among different particle sizes and types.

Microphysical processing of aerosol particles in orographic clouds

NASA Astrophysics Data System (ADS)

Pousse-Nottelmann, S.; Zubler, E. M.; Lohmann, U.

2015-01-01

An explicit and detailed treatment of cloud-borne particles allowing for the consideration of aerosol cycling in clouds has been implemented in the regional weather forecast and climate model COSMO. The effects of aerosol scavenging, cloud microphysical processing and regeneration upon cloud evaporation on the aerosol population and on subsequent cloud formation are investigated. For this, two-dimensional idealized simulations of moist flow over two bell-shaped mountains were carried out varying the treatment of aerosol scavenging and regeneration processes for a warm-phase and a mixed-phase orographic cloud. The results allowed to identify different aerosol cycling mechanisms. In the simulated non-precipitating warm-phase cloud, aerosol mass is incorporated into cloud droplets by activation scavenging and released back to the atmosphere upon cloud droplet evaporation. In the mixed-phase cloud, a first cycle comprises cloud droplet activation and evaporation via the Wegener-Bergeron-Findeisen process. A second cycle includes below-cloud scavenging by precipitating snow particles and snow sublimation and is connected to the first cycle via the riming process which transfers aerosol mass from cloud droplets to snow flakes. In the simulated mixed-phase cloud, only a negligible part of the total aerosol mass is incorporated into ice crystals. Sedimenting snow flakes reaching the surface remove aerosol mass from the atmosphere. The results show that aerosol processing and regeneration lead to a vertical redistribution of aerosol mass and number. However, the processes not only impact the total aerosol number and mass, but also the shape of the aerosol size distributions by enhancing the internally mixed/soluble accumulation mode and generating coarse mode particles. Concerning subsequent cloud formation at the second mountain, accounting for aerosol processing and regeneration increases the cloud droplet number concentration with possible implications for the ice

Microphysical processing of aerosol particles in orographic clouds

NASA Astrophysics Data System (ADS)

Pousse-Nottelmann, S.; Zubler, E. M.; Lohmann, U.

2015-08-01

An explicit and detailed treatment of cloud-borne particles allowing for the consideration of aerosol cycling in clouds has been implemented into COSMO-Model, the regional weather forecast and climate model of the Consortium for Small-scale Modeling (COSMO). The effects of aerosol scavenging, cloud microphysical processing and regeneration upon cloud evaporation on the aerosol population and on subsequent cloud formation are investigated. For this, two-dimensional idealized simulations of moist flow over two bell-shaped mountains were carried out varying the treatment of aerosol scavenging and regeneration processes for a warm-phase and a mixed-phase orographic cloud. The results allowed us to identify different aerosol cycling mechanisms. In the simulated non-precipitating warm-phase cloud, aerosol mass is incorporated into cloud droplets by activation scavenging and released back to the atmosphere upon cloud droplet evaporation. In the mixed-phase cloud, a first cycle comprises cloud droplet activation and evaporation via the Wegener-Bergeron-Findeisen (WBF) process. A second cycle includes below-cloud scavenging by precipitating snow particles and snow sublimation and is connected to the first cycle via the riming process which transfers aerosol mass from cloud droplets to snowflakes. In the simulated mixed-phase cloud, only a negligible part of the total aerosol mass is incorporated into ice crystals. Sedimenting snowflakes reaching the surface remove aerosol mass from the atmosphere. The results show that aerosol processing and regeneration lead to a vertical redistribution of aerosol mass and number. Thereby, the processes impact the total aerosol number and mass and additionally alter the shape of the aerosol size distributions by enhancing the internally mixed/soluble Aitken and accumulation mode and generating coarse-mode particles. Concerning subsequent cloud formation at the second mountain, accounting for aerosol processing and regeneration increases

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

Direct Aqueous Photochemistry of Isoprene High-NOx Secondary Organic Aerosol

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

Nguyen, Tran B.; Laskin, Alexander; Laskin, Julia

2012-05-17

Secondary organic aerosol (SOA) generated from the high-NOx photooxidation of isoprene was dissolved in water and irradiated with {lambda} > 290 nm light to simulate direct photolytic processing of organics in atmospheric water droplets. High-resolution mass spectrometry was used to characterize the composition at four time intervals (0, 1, 2, and 4 h). Photolysis resulted in the decomposition of high molecular weight (MW) oligomers, reducing the average length of organics by 2 carbon units. Approximately 65% by count of SOA molecules decomposed during photolysis, accompanied by the formation of new products. An average of 30 % of the organic massmore » was modified after 4 h of direct photolysis. In contrast, only a small fraction of the mass (<2 %), belonging primarily to organic nitrates, decomposed in the absence of irradiation by hydrolysis. We observed a statistically-significant increase in average O/C, decrease in H/C, and increase in N/C ratios resulting from photolysis. Furthermore, the concentration of aromatic compounds increased significantly during photolysis. Approximately 10 % of photodegraded compounds and 50 % of the photoproducts contain nitrogen. Organic nitrates and multifunctional oligomers were identified as compounds degraded by photolysis. Low-MW 0N (compounds with 0 nitrogen atoms in their structure) and 2N compounds were the dominant photoproducts. Fragmentation experiments using tandem mass spectrometry (MSn, n = 2-3) indicate that the 2N products are likely heterocyclic/aromatic and are tentatively identified as furoxans. Although the exact mechanism is unclear, these 2N heterocyclic compounds are produced by reactions between photochemically-formed aqueous NOx species and SOA organics.« less

Products and Mechanism of Aerosol Formation from the Reaction of β-Pinene with NO3 Radicals: Role of Oligomer Formation

NASA Astrophysics Data System (ADS)

Claflin, M. S.; Ziemann, P. J.

2017-12-01

) particle-phase reactions and (3) formation of separate organic and aqueous phases within aerosol.

The Mpi-M Aerosol Climatology (MAC)

NASA Astrophysics Data System (ADS)

Kinne, S.

2014-12-01

Monthly gridded global data-sets for aerosol optical properties (AOD, SSA and g) and for aerosol microphysical properties (CCN and IN) offer a (less complex) alternate path to include aerosol radiative effects and aerosol impacts on cloud-microphysics in global simulations. Based on merging AERONET sun-/sky-photometer data onto background maps provided by AeroCom phase 1 modeling output and AERONET sun-/the MPI-M Aerosol Climatology (MAC) version 1 was developed and applied in IPCC simulations with ECHAM and as ancillary data-set in satellite-based global data-sets. An updated version 2 of this climatology will be presented now applying central values from the more recent AeroCom phase 2 modeling and utilizing the better global coverage of trusted sun-photometer data - including statistics from the Marine Aerosol network (MAN). Applications include spatial distributions of estimates for aerosol direct and aerosol indirect radiative effects.

Aerosol Liquid Water Driven by Anthropogenic inorganic salts: Playing a key role in the winter haze formation over North China Plain

NASA Astrophysics Data System (ADS)

Wu, Z.; Liu, Y.; Tan, T.; Wang, Y.; Shang, D.; Xiao, Y.; Li, M.; Zeng, L.; Hu, M.

2017-12-01

Aerosol liquid water influences ambient particulate matter mass concentrations and aerosol optical properties, and can serve as a reactor for multiphase reactions that perturb local photochemistry1. Our observations revealed that ambient relative humidity, inorganic fraction (sulfate, ammonium, nitrate), and PM2.5 mass concentration generally simultaneously elevated during haze episodes, resulting in the abundant anthropogenic aerosol water in the atmosphere of Beijing. The enrichment of aerosol liquid water may significantly affect the particle phase, which plays a key role in determining the reactive uptake, gas-particle partitioning, and heterogeneous chemical reactivity2. A newly-built three-arm impactor was used to detect the particle rebound fraction. The observations showed the increased RH and inorganic-rich particulate matter led to an increased aerosol liquid water content, and thus a liquid phase state during haze episode during wintertime. Here, we proposed that the transition to a liquid phase state marked the beginning of the haze episode and kicked off a positive feedback loop, wherein the liquid particles readily uptake pollutants that could react to form inorganics which could then uptake more water. The strict controlling strategy of sulfur emissions in China might lead to a decreased sulfate fraction and increased nitrate fraction in PM1. As a result, due to the lower deliquescence RH of nitrate, the feedback loop proposed could start at an even lower RH in the future. Reference1 Herrmann, H., T. Schaefer, A. Tilgner, S. A. Styler, C. Weller, M. Teich, and T. Otto (2015), Tropospheric Aqueous-Phase Chemistry: Kinetics, Mechanisms, and Its Coupling to a Changing Gas Phase, Chemical Reviews, 115(10), 4259-4334.2 M. Kuwata, S. T. Martin (2012), Phase of atmospheric secondary organic material affects its reactivity, Proceedings of the National Academy of Sciences of the United States of America, 109(43):17354-17359

Interactions of aerosols (ammonium sulfate, ammonium nitrate and ammonium chloride) and of gases (HCl, HNO 3) with fogwater

NASA Astrophysics Data System (ADS)

Ruprecht, Heidi; Sigg, Laura

The concentrations of aerosols (NH 4NO 3, (NH 4) 2SO 4 and NH 4Cl) and of gases (HCl (g), HNO 3(g), NH 3(g) were determined by denuder methods under different conditions (in the absence of fog, before, during and after fog events). At this site situated in an urban region, high concentrations of the gaseous strong acids HCl (g) and HNO 3(g) are observed. NH 4Cl and NH 4NO 3 aerosols represent a major fraction of the Cl - and NO 3- aerosols (<2.4 μm)collected by denuders. During a fog event, very high concentrations of SO 42- were found in small aerosols, which are attributed to the aqueous phase oxidation of SO 2 under the influence of high pH due to the presence of NH 3. Differences in SO 42- concentrations measured in aerosols (<2.4 μm) and in fog droplets were probably due to mass-transport limitations of the SO 2 oxidation. Ammonium sulfate aerosols represent in some cases a significant fraction of the total S present (SO 2(g) + SO 42-. Soluble aerosols and gases contribute to the composition of fogwater and are released again after fog dissipation.

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.

Adsorptive removal of phthalate ester (Di-ethyl phthalate) from aqueous phase by activated carbon: a kinetic study.

PubMed

Venkata Mohan, S; Shailaja, S; Rama Krishna, M; Sarma, P N

2007-07-19

Adsorptive studies were carried out on Di-ethyl phthalate (DEP) removal from aqueous phase onto activated carbon. Batch sorption studies were performed and the results revealed that activated carbon demonstrated ability to adsorb DEP. Influence of varying experimental conditions such as DEP concentration, pH of aqueous solution, and dosage of adsorbent were investigated on the adsorption process. Sorption interaction of DEP onto activated carbon obeyed the pseudo second order rate equation. Experimental data showed good fit with both the Langmuir and Freundlich adsorption isotherm models. DEP sorption was found to be dependent on the aqueous phase pH and the uptake was observed to be greater at acidic pH.

Validation of MODIS Dust Aerosol Retrieval and Development Ambient Dust Phase Function using PRIDE Data

NASA Technical Reports Server (NTRS)

Remer, Lorraine A.; Lau, William (Technical Monitor)

2002-01-01

The PRIDE data set of MODIS aerosol retrievals co-located with sunphotometer measurements provides the basis of MODIS validation in a dust environment. The sunphotometer measurements include AERONET automatic instruments, land-based Microtops instruments, ship-board Microtops instruments and the AATS-6 aboard the Navajo aircraft. Analysis of these data indicate that the MODIS retrieval is within pre-launch estimates of uncertainty within the spectral range of 600-900 nm. However, the MODIS algorithm consistently retrieves smaller particles than reality thus leading to incorrect spectral response outside of the 600-900 nm range and improper size information. Further analysis of MODIS retrievals in other dust environments shows the inconsistencies are due to nonspherical effects in the phase function. These data are used to develop an ambient phase function for dust aerosol to be used for remote sensing purposes.

Aqueous two-phase partition applied to the isolation of plasma membranes and Golgi apparatus from cultured mammalian cells.

PubMed

Morré, D M; Morre, D J

2000-06-23

Partitioning in dextran-poly(ethylene)glycol (PEG) aqueous-aqueous phase systems represents a mature technology with many applications to separations of cells and to the preparation of membranes from mammalian cells. Most applications to membrane isolation and purification have focused on plasma membranes, plasma membrane domains and separation of right side-out and inside-out plasma membrane vesicles. The method exploits a combination of membrane properties, including charge and hydrophobicity. Purification is based upon differential distributions of the constituents in a sample between the two principal compartments of the two phases (upper and lower) and at the interface. The order of affinity of animal cell membranes for the upper phase is: endoplasmic reticulum aqueous two-phase partition with other procedures to obtain a more highly purified preparation. A procedure is described for preparation of Golgi apparatus from transformed mammalian cells that combines aqueous two-phase partition and centrifugation. Also described is a periodic NADH oxidase, a new enzyme marker for right side-out plasma membrane vesicles not requiring detergent disruptions for measurement of activity.

Aqueous two-phase partition applied to the isolation of plasma membranes and Golgi apparatus from cultured mammalian cells

NASA Technical Reports Server (NTRS)

Morre, D. M.; Morre, D. J.

2000-01-01

Partitioning in dextran-poly(ethylene)glycol (PEG) aqueous-aqueous phase systems represents a mature technology with many applications to separations of cells and to the preparation of membranes from mammalian cells. Most applications to membrane isolation and purification have focused on plasma membranes, plasma membrane domains and separation of right side-out and inside-out plasma membrane vesicles. The method exploits a combination of membrane properties, including charge and hydrophobicity. Purification is based upon differential distributions of the constituents in a sample between the two principal compartments of the two phases (upper and lower) and at the interface. The order of affinity of animal cell membranes for the upper phase is: endoplasmic reticulum aqueous two-phase partition with other procedures to obtain a more highly purified preparation. A procedure is described for preparation of Golgi apparatus from transformed mammalian cells that combines aqueous two-phase partition and centrifugation. Also described is a periodic NADH oxidase, a new enzyme marker for right side-out plasma membrane vesicles not requiring detergent disruptions for measurement of activity.

THE EFFECT OF METASTABLE EQUILIBRIUM STATES ON THE PARTITIONING OF NITRATE BETWEEN THE GAS AND AEROSOL PHASES. (R826371C005)

EPA Science Inventory

With the aid of three atmospheric aerosol equilibrium models, we quantify the effect of metastable equilibrium states (efflorescence branch) in comparison to stable (deliquescence branch) on the partitioning of total nitrate between the gas and aerosol phases. On average, effl...

Drowning-out crystallisation of sodium sulphate using aqueous two-phase systems.

PubMed

Taboada, M E; Graber, T A; Asenjo, J A; Andrews, B A

2000-06-23

A novel method to obtain crystals of pure, anhydrous salt, using aqueous two-phase systems was studied. A concentrated salt solution is mixed with polyethylene glycol (PEG), upon which three phases are formed: salt crystals, a PEG-rich liquid and a salt-rich liquid. After removal of the solid salt, a two-phase system is obtained. Both liquid phases are recycled, allowing the design of a continuous process, which could be exploited industrially. The phase diagram of the system water-Na2SO4-PEG 3350 at 28 degrees C was used. Several process alternatives are proposed and their economic potential is discussed. The process steps needed to produce sodium sulphate crystals include mixing, crystallisation, settling and, optionally, evaporation of water. The yield of sodium sulphate increases dramatically if an evaporation step is used.

Global direct radiative forcing by process-parameterized aerosol optical properties

NASA Astrophysics Data System (ADS)

KirkevâG, Alf; Iversen, Trond

2002-10-01

A parameterization of aerosol optical parameters is developed and implemented in an extended version of the community climate model version 3.2 (CCM3) of the U.S. National Center for Atmospheric Research. Direct radiative forcing (DRF) by monthly averaged calculated concentrations of non-sea-salt sulfate and black carbon (BC) is estimated. Inputs are production-specific BC and sulfate from [2002] and background aerosol size distribution and composition. The scheme interpolates between tabulated values to obtain the aerosol single scattering albedo, asymmetry factor, extinction coefficient, and specific extinction coefficient. The tables are constructed by full calculations of optical properties for an array of aerosol input values, for which size-distributed aerosol properties are estimated from theory for condensation and Brownian coagulation, assumed distribution of cloud-droplet residuals from aqueous phase oxidation, and prescribed properties of the background aerosols. Humidity swelling is estimated from the Köhler equation, and Mie calculations finally yield spectrally resolved aerosol optical parameters for 13 solar bands. The scheme is shown to give excellent agreement with nonparameterized DRF calculations for a wide range of situations. Using IPCC emission scenarios for the years 2000 and 2100, calculations with an atmospheric global cliamte model (AFCM) yield a global net anthropogenic DRF of -0.11 and 0.11 W m-2, respectively, when 90% of BC from biomass burning is assumed anthropogenic. In the 2000 scenario, the individual DRF due to sulfate and BC has separately been estimated to -0.29 and 0.19 W m-2, respectively. Our estimates of DRF by BC per BC mass burden are lower than earlier published estimates. Some sensitivity tests are included to investigate to what extent uncertain assumptions may influence these results.

Violent flows in aqueous foams III: physical multi-phase model comparison with aqueous foam shock tube experiments

NASA Astrophysics Data System (ADS)

Redford, J. A.; Ghidaglia, J.-M.; Faure, S.

2018-06-01

Mitigation of blast waves in aqueous foams is a problem that has a strong dependence on multi-phase effects. Here, a simplified model is developed from the previous articles treating violent flows (D'Alesio et al. in Eur J Mech B Fluids 54:105-124, 2015; Faure and Ghidaglia in Eur J Mech B Fluids 30:341-359, 2011) to capture the essential phenomena. The key is to have two fluids with separate velocities to represent the liquid and gas phases. This allows for the interaction between the two phases, which may include terms for drag, heat transfer, mass transfer due to phase change, added mass effects, to be included explicitly in the model. A good test for the proposed model is provided by two experimental data sets that use a specially designed shock tube. The first experiment has a test section filled with spray droplets, and the second has a range of aqueous foams in the test section. A substantial attenuation of the shock wave is seen in both cases, but a large difference is observed in the sound speeds. The droplets cause no observable change from the air sound speed, while the foams have a reduced sound speed of approximately 50-75 m/s . In the model given here, an added mass term is introduced in the governing equations to capture the low sound speed. The match between simulation and experiment is found to be satisfactory for both droplets and the foam. This is especially good when considering the complexity of the physics and the effects that are unaccounted for, such as three-dimensionality and droplet atomisation. The resulting statistics illuminate the processes occurring in such flows.

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

Comparative study of alkylthiols and alkylamines for the phase transfer of gold nanoparticles from an aqueous phase to n-hexane.

PubMed

Li, Lingxiangyu; Leopold, Kerstin; Schuster, Michael

2013-05-01

An efficient ligand-assisted phase transfer method has been developed to transfer gold nanoparticles (Au-NPs, d: 5-25 nm) from an aqueous solution to n-hexane. Four different ligands, namely 1-dodecanethiol (DDT), 1-octadecanethiol (ODT), dodecylamine (DDA), and octadecylamine (ODA) were investigated, and DDT was found to be the most efficient ligand. It appears that the molar ratio of DDT to Au-NPs is a critical factor affecting the transfer efficiency, and 270-310 is found to be the optimum range, under which the transfer efficiency is >96%. Moreover, the DDT-assisted phase transfer can preserve the shape and size of the Au-NPs, which was confirmed by UV-vis spectra and transmission electron microscopy (TEM). Additionally, the transferred Au-NPs still can be well dispersed in the n-hexane phase and remain stable for at least 2 weeks. On the other hand, the ODT-, DDA-, and ODA-assisted phase transfer is fraught with problems either related to transfer efficiency or NPs aggregation. Overall, the DDT-assisted phase transfer of Au-NPs provides a rapid and efficient method to recover Au-NPs from an aqueous solution to n-hexane. Copyright © 2013 Elsevier Inc. All rights reserved.

Particle phase photosensitized radical production and aerosol aging.

PubMed

Corral-Arroyo, Pablo; Bartels-Rausch, Thorsten; Alpert, Peter Aaron; Dumas, Stephane; Perrier, Sebastien; George, Christian; Ammann, Markus

2018-06-13

Atmospheric aerosol particles may contain light absorbing (brown carbon, BrC), triplet forming organic compounds that can sustain catalytic radical reactions and thus contribute to oxidative aerosol aging. We quantify UVA induced radical production initiated by imidazole-2-carboxaldehyde (IC), benzophenone (BPh) and 4-Benzoylbenzoic acid (BBA) in the presence of the non-absorbing organics citric acid (CA), shikimic acid (SA) and syringol (Syr) at varying mixing ratios. We observed a maximum HO 2 release of 10 13 molecules min -1 cm -2 at a mole ratio Χ BPh <0.02 for BPh in CA. Mixtures of either IC or BBA with CA resulted in 10 11 -10 12 molecules min -1 cm -2 of HO 2 at mole ratios (Χ IC and Χ BBA ) between 0.01 and 0.15. HO 2 release was affected by relative humidity (RH) and film thickness suggesting coupled photochemical reaction and diffusion processes. Quantum yields of HO 2 formed per absorbed photon for IC, BBA and BPh were between 10 -7 and 5∙10 -5 . The non-photoactive organics, Syr and SA, increased HO 2 production due to the reaction with the triplet excited species ensuing ketyl radical production. Rate coefficients of the triplet of IC with Syr and SA measured by laser flash photolysis experiments were k Syr =9.4±0.3∙10 8 M -1 s -1 and k SA =2.7±0.5∙10 7 M -1 s -1 . A simple kinetic model was used to assess total HO 2 and organic radical production in the condensed phase and to upscale to ambient aerosol, indicating that BrC induced radical production may amount to an upper limit of 20 and 200 M day -1 of HO 2 and organic radical respectively, which is greater or in the same order of magnitude as the internal radical production from other processes, previously estimated to be around 15 M per day.

Simulation of the effects of aerosol on mixed-phase orographic clouds using the WRF model with a detailed bin microphysics scheme

NASA Astrophysics Data System (ADS)

Xiao, Hui; Yin, Yan; Jin, Lianji; Chen, Qian; Chen, Jinghua

2015-08-01

The Weather Research Forecast (WRF) mesoscale model coupled with a detailed bin microphysics scheme is used to investigate the impact of aerosol particles serving as cloud condensation nuclei and ice nuclei on orographic clouds and precipitation. A mixed-phase orographic cloud developed under two scenarios of aerosol (a typical continental background and a relatively polluted urban condition) and ice nuclei over an idealized mountain is simulated. The results show that, when the initial aerosol condition is changed from the relatively clean case to the polluted scenario, more droplets are activated, leading to a delay in precipitation, but the precipitation amount over the terrain is increased by about 10%. A detailed analysis of the microphysical processes indicates that ice-phase particles play an important role in cloud development, and their contribution to precipitation becomes more important with increasing aerosol particle concentrations. The growth of ice-phase particles through riming and Wegener-Bergeron-Findeisen regime is more effective under more polluted conditions, mainly due to the increased number of droplets with a diameter of 10-30 µm. Sensitivity tests also show that a tenfold increase in the concentration of ice crystals formed from ice nucleation leads to about 7% increase in precipitation, and the sensitivity of the precipitation to changes in the concentration and size distribution of aerosol particles is becoming less pronounced when the concentration of ice crystals is also increased.

Purification of Active Myrosinase from Plants by Aqueous Two-Phase Counter-Current Chromatography

PubMed Central

Wade, Kristina L.; Ito, Yoichiro; Ramarathnam, Aarthi; Holtzclaw, W. David; Fahey, Jed W.

2014-01-01

Introduction Myrosinase (thioglucoside glucohydrolase; E.C. 3.2.1.147), is a plant enzyme of increasing interest and importance to the biomedical community. Myrosinase catalyses the formation of isothiocyanates such as sulforaphane (frombroccoli) and 4-(α-l-rhamnopyranosyloxy)benzyl isothiocyanate (from moringa), which are potent inducers of the cytoprotective phase-2 response in humans, by hydrolysis of their abundant glucosinolate (β-thioglucoside N-hydroxysulphate) precursors. Objective To develop an aqueous two-phase counter-current chromatography (CCC) system for the rapid, three-step purification of catalytically active myrosinase. Methods A high-concentration potassium phosphate and polyethylene glycol biphasic aqueous two-phase system (ATPS) is used with a newly developed CCC configuration that utilises spiral-wound, flat-twisted tubing (with an ovoid cross-section). Results Making the initial crude plant extract directly in the ATPS and injecting only the lower phase permitted highly selective partitioning of the myrosinase complex before a short chromatography on a spiral disk CCC. Optimum phase retention and separation of myrosinase from other plant proteins afforded a 60-fold purification. Conclusion Catalytically active myrosinase is purified from 3-day broccoli sprouts, 7-day daikon sprouts, mustard seeds and the leaves of field-grown moringa trees, in a CCC system that is predictably scalable. PMID:25130502

Purification of active myrosinase from plants by aqueous two-phase counter-current chromatography.

PubMed

Wade, Kristina L; Ito, Yoichiro; Ramarathnam, Aarthi; Holtzclaw, W David; Fahey, Jed W

2015-01-01

Myrosinase (thioglucoside glucohydrolase; E.C. 3.2.1.147), is a plant enzyme of increasing interest and importance to the biomedical community. Myrosinase catalyses the formation of isothiocyanates such as sulforaphane (from broccoli) and 4-(α-l-rhamnopyranosyloxy)benzyl isothiocyanate (from moringa), which are potent inducers of the cytoprotective phase-2 response in humans, by hydrolysis of their abundant glucosinolate (β-thioglucoside N-hydroxysulphate) precursors. To develop an aqueous two-phase counter-current chromatography (CCC) system for the rapid, three-step purification of catalytically active myrosinase. A high-concentration potassium phosphate and polyethylene glycol biphasic aqueous two-phase system (ATPS) is used with a newly developed CCC configuration that utilises spiral-wound, flat-twisted tubing (with an ovoid cross-section). Making the initial crude plant extract directly in the ATPS and injecting only the lower phase permitted highly selective partitioning of the myrosinase complex before a short chromatography on a spiral disk CCC. Optimum phase retention and separation of myrosinase from other plant proteins afforded a 60-fold purification. Catalytically active myrosinase is purified from 3-day broccoli sprouts, 7-day daikon sprouts, mustard seeds and the leaves of field-grown moringa trees, in a CCC system that is predictably scalable. Copyright © 2014 John Wiley & Sons, Ltd.

Analysis of organic sulfur compounds in atmospheric aerosols at the HKUST supersite in Hong Kong using HR-ToF-AMS.

PubMed

Huang, Dan Dan; Li, Yong Jie; Lee, Berto P; Chan, Chak K

2015-03-17

Organic sulfur compounds have been identified in ambient secondary organic aerosols, but their contribution to organic mass is not well quantified. In this study, using a high-resolution time-of-flight aerosol mass spectrometer (AMS), concentrations of organic sulfur compounds were estimated based on the high-resolution fragmentation patterns of methanesulfonic acid (MSA), and organosulfates (OS), including alkyl, phenyl, and cycloalkyl sulfates, obtained in laboratory experiments. Mass concentrations of MSA and minimum mass concentrations of OS were determined in a field campaign conducted at a coastal site of Hong Kong in September 2011. MSA and OS together accounted for at least 5% of AMS detected organics. MSA is of marine origin with its formation dominated by local photochemical activities and enhanced by aqueous phase processing. OS concentrations are better correlated with particle liquid water content (LWC) than with particle acidity. High-molecular-weight OS were detected in the continental influenced period probably because they had grown into larger molecules during long-range transport or they were formed from large anthropogenic precursors. This study highlights the importance of both aqueous-phase processing and regional influence, i.e., different air mass origins, on organic sulfur compound formation in coastal cities like Hong Kong.

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

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

EPA Science Inventory

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

Converting sugars to sugar alcohols by aqueous phase catalytic hydrogenation

DOEpatents

Elliott, Douglas C [Richland, WA; Werpy, Todd A [West Richland, WA; Wang, Yong [Richland, WA; Frye, Jr., John G.

2003-05-27

The present invention provides a method of converting sugars to their corresponding sugar alcohols by catalytic hydrogenation in the aqueous phase. It has been found that surprisingly superior results can be obtained by utilizing a relatively low temperature (less than 120.degree. C.), selected hydrogenation conditions, and a hydrothermally stable catalyst. These results include excellent sugar conversion to the desired sugar alcohol, in combination with long life under hydrothermal conditions.

Recovery of Picloram and 2,4-Dichlorophenoxyacetic Acid from Aqueous Samples by Reversed-Phase Solid-Phase Extraction

Treesearch

Martha J.M. Wells; Jerry L. Michael

1987-01-01

Extensive preparation of samples before chromatographic analysis is usually the most time-consuming process in the determination of many organic compounds in environmental matrices. In the past, removal of some organic from aqueous solution was commonly done by liquid/liquid extraction. However, the introduction of stable, covalently bonded reversed-phase sorbents now...

Biochar enables anaerobic digestion of aqueous phase from intermediate pyrolysis of biomass.

PubMed

Torri, Cristian; Fabbri, Daniele

2014-11-01

Intermediate pyrolysis produces a two-phase liquid whose aqueous phase is characterized by low heating value and high water content (aqueous pyrolysis liquid, APL). Anaerobic digestion can be the straightest way to produce a fuel (methane) from this material. Batch tests showed poor performance in anaerobic digestion of APL, which underlined the inhibition of biological process. Nutrient supplementation was ineffective, whereas biochar addition increased yield of methane (60±15% of theoretical) with respect to pure APL (34±6% of theoretical) and improved the reaction rate. On the basis of batch results, a semi-continuous biomethanation test was set up, by adding an increasingly amount of APL in a 30ml reactor preloaded with biochar (0.8gml(-1)). With a daily input of 5gd(-1)l(-1) of APL (corresponding to overall amount of 0.1kgl(-1) added before the end of the study) the yield of methane was 65±5% of the theoretical. Copyright © 2014 Elsevier Ltd. All rights reserved.

Impact of fog processing on water soluble organic aerosols.

NASA Astrophysics Data System (ADS)

Tripathi, S. N.; Chakraborty, A.; Gupta, T.

2017-12-01

Fog is a natural meteorological phenomenon that occurs all around the world, and contains a substantial quantity of liquid water. Fog is generally seen as a natural cleansing agent but can also form secondary organic aerosols (SOA) via aqueous processing of ambient organics. Few field studies have reported elevated O/C ratio and SOA mass during or after fog events. However, mechanism behind aqueous SOA formation and its contribution to total organic aerosols (OA) still remains unclear. In this study we have tried to explore the impact of fog/aqueous processing on the characteristics of water soluble organic aerosols (WSOC), which to our knowledge has not been studied before. To assess this, both online (using HR-ToF-AMS) and offline (using a medium volume PM2.5 sampler and quartz filter) aerosol sampling were carried out at Kanpur, India from 15 December 2014 - 10 February 2015. Further, offline analysis of the aqueous extracts of the collected filters were carried out by AMS to characterize the water soluble OA (WSOA). Several (17) fog events occurred during the campaign and high concentrations of OA (151 ± 68 µg/m3) and WSOA (47 ± 19 µg/m3) were observed. WSOA/OA ratios were similar during fog (0.36 ± 0.14) and nofog (0.34 ± 0.15) periods. WSOA concentrations were also similar (slightly higher) during foggy (49 ± 18 µg/m3) and non-foggy periods (46 ± 20 µg/m3), in spite of fog scavenging. However, WSOA was more oxidized during foggy period (average O/C = 0.81) than non foggy periods (average O/C = 0.70). Like WSOA, OA was also more oxidized during foggy periods (average O/C = 0.64) than non foggy periods (average O/C = 0.53). During fog, WSOA to WIOA (water insoluble OA) ratios were higher (0.65 ± 0.16) compared to non foggy periods (0.56 ± 0.15). These observations clearly showed that WSOA become more dominant and processed during fog events, possibly due to the presence of fog droplets. This study highlights that fog processing of soluble organics

Aerosolized antimicrobial agents based on degradable dextran nanoparticles loaded with silver carbene complexes.

PubMed

Ornelas-Megiatto, Cátia; Shah, Parth N; Wich, Peter R; Cohen, Jessica L; Tagaev, Jasur A; Smolen, Justin A; Wright, Brian D; Panzner, Matthew J; Youngs, Wiley J; Fréchet, Jean M J; Cannon, Carolyn L

2012-11-05

Degradable acetalated dextran (Ac-DEX) nanoparticles were prepared and loaded with a hydrophobic silver carbene complex (SCC) by a single-emulsion process. The resulting particles were characterized for morphology and size distribution using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and dynamic light scattering (DLS). The average particle size and particle size distribution were found to be a function of the ratio of the organic phase to the surfactant containing aqueous phase with a 1:5 volume ratio of Ac-DEX CH(2)Cl(2) (organic):PBS (aqueous) being optimal for the formulation of nanoparticles with an average size of 100 ± 40 nm and a low polydispersity. The SCC loading was found to increase with an increase in the SCC quantity in the initial feed used during particle formulation up to 30% (w/w); however, the encapsulation efficiency was observed to be the best at a feed ratio of 20% (w/w). In vitro efficacy testing of the SCC loaded Ac-DEX nanoparticles demonstrated their activity against both Gram-negative and Gram-positive bacteria; the nanoparticles inhibited the growth of every bacterial species tested. As expected, a higher concentration of drug was required to inhibit bacterial growth when the drug was encapsulated within the nanoparticle formulations compared with the free drug illustrating the desired depot release. Compared with free drug, the Ac-DEX nanoparticles were much more readily suspended in an aqueous phase and subsequently aerosolized, thus providing an effective method of pulmonary drug delivery.

Predicting the Fluid-Phase Behavior of Aqueous Solutions of ELP (VPGVG) Sequences Using SAFT-VR.

PubMed

Zhao, Binwu; Lindeboom, Tom; Benner, Steven; Jackson, George; Galindo, Amparo; Hall, Carol K

2017-10-24

The statistical associating fluid theory for potentials of variable range (SAFT-VR) is used to predict the fluid phase behavior of elastin-like polypeptide (ELP) sequences in aqueous solution with special focus on the loci of lower critical solution temperatures (LCSTs). A SAFT-VR model for these solutions is developed following a coarse-graining approach combining information from atomistic simulations and from previous SAFT models for previously reported relevant systems. Constant-pressure temperature-composition phase diagrams are determined for solutions of (VPGVG) n sequences + water with n = 1 to 300. The SAFT-VR equation of state lends itself to the straightforward calculation of phase boundaries so that complete fluid-phase equilibria can be calculated efficiently. A broad range of thermodynamic conditions of temperature and pressure are considered, and regions of vapor-liquid and liquid-liquid coexistence, including LCSTs, are found. The calculated phase boundaries at low concentrations match those measured experimentally. The temperature-composition phase diagrams of the aqueous ELP solutions at low pressure (0.1 MPa) are similar to those of types V and VI phase behavior in the classification of Scott and van Konynenburg. An analysis of the high-pressure phase behavior confirms, however, that a closed-loop liquid-liquid immiscibility region, separate from the gas-liquid envelope, is present for aqueous solutions of (VPGVG) 30 ; such a phase diagram is typical of type VI phase behavior. ELPs with shorter lengths exhibit both liquid-liquid and gas-liquid regions, both of which become less extensive as the chain length of the ELP is decreased. The strength of the hydrogen-bonding interaction is also found to affect the phase diagram of the (VPGVG) 30 system in that the liquid-liquid and gas-liquid regions expand as the hydrogen-bonding strength is decreased and shrink as it is increased. The LCSTs of the mixtures are seen to decrease as the ELP chain length

A Novel Aqueous Two Phase System Composed of Surfactant and Xylitol for the Purification of Lipase from Pumpkin (Cucurbita moschata) Seeds and Recycling of Phase Components.

PubMed

Amid, Mehrnoush; Manap, Mohd Yazid; Hussin, Muhaini; Mustafa, Shuhaimi

2015-06-17

Lipase is one of the more important enzymes used in various industries such as the food, detergent, pharmaceutical, textile, and pulp and paper sectors. A novel aqueous two-phase system composed of surfactant and xylitol was employed for the first time to purify lipase from Cucurbita moschata. The influence of different parameters such as type and concentration of surfactants, and the composition of the surfactant/xylitol mixtures on the partitioning behavior and recovery of lipase was investigated. Moreover, the effect of system pH and crude load on the degree of purification and yield of the purified lipase were studied. The results indicated that the lipase was partitioned into the top surfactant rich phase while the impurities partitioned into the bottom xylitol-rich phase using an aqueous two phase system composed of 24% (w/w) Triton X-100 and 20% (w/w) xylitol, at 56.2% of tie line length (TLL), (TTL is one of the important parameters in this study and it is determined from a bimodal curve in which the tie-line connects two nodes on the bimodal, that represent concentration of phase components in the top and bottom phases) and a crude load of 25% (w/w) at pH 8.0. Recovery and recycling of components was also measured in each successive step process. The enzyme was successfully recovered by the proposed method with a high purification factor of 16.4 and yield of 97.4% while over 97% of the phase components were also recovered and recycled. This study demonstrated that the proposed novel aqueous two phase system method is more efficient and economical than the traditional aqueous two phase system method for the purification and recovery of the valuable enzyme lipase.

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

NASA Astrophysics Data System (ADS)

Miyazaki, Yuzo; Kawamura, Kimitaka; Sawano, Maki

2010-12-01

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

Decomposition of Atmospheric Aerosol Phase Function by Particle Size and Morphology via Single Particle Scattering Measurements

NASA Astrophysics Data System (ADS)

Aptowicz, K. B.; Pan, Y.; Martin, S.; Fernandez, E.; Chang, R.; Pinnick, R. G.

2013-12-01

We report upon an experimental approach that provides insight into how particle size and shape affect the scattering phase function of atmospheric aerosol particles. Central to our approach is the design of an apparatus that measures the forward and backward scattering hemispheres (scattering patterns) of individual atmospheric aerosol particles in the coarse mode range. The size and shape of each particle is discerned from the corresponding scattering pattern. In particular, autocorrelation analysis is used to differentiate between spherical and non-spherical particles, the calculated asphericity factor is used to characterize the morphology of non-spherical particles, and the integrated irradiance is used for particle sizing. We found the fraction of spherical particles decays exponentially with particle size, decreasing from 11% for particles on the order of 1 micrometer to less than 1% for particles over 5 micrometer. The average phase functions of subpopulations of particles, grouped by size and morphology, are determined by averaging their corresponding scattering patterns. The phase functions of spherical and non-spherical atmospheric particles are shown to diverge with increasing size. In addition, the phase function of non-spherical particles is found to vary little as a function of the asphericity factor.

Uncertainties of aerosol retrieval from neglecting non-sphericity of dust aerosols

NASA Astrophysics Data System (ADS)

Li, Chi; Xue, Yong; Yang, Leiku; Guang, Jie

2013-04-01

The Mie theory is conventionally applied to calculate aerosol optical properties in satellite remote sensing applications, while dust aerosols cannot be well modeled by the Mie calculation for their non-sphericity. It has been cited in Mishchenko et al. (1995; 1997) that neglecting non-sphericity can severely influence aerosol optical depth (AOD, ?) retrieval in case of dust aerosols because of large difference of phase functions under spherical and non-spherical assumptions, whereas this uncertainty has not been thoroughly studied. This paper aims at a better understanding of uncertainties on AOD retrieval caused by aerosol non-sphericity. A dust aerosol model with known refractive index and size distribution is generated from long-term AERONET observations since 1999 over China. Then aerosol optical properties, such as the extinction, phase function, single scattering albedo (SSA) are calculated respectively in the assumption of spherical and non-spherical aerosols. Mie calculation is carried out for spherical assumption, meanwhile for non-spherical aerosol modeling, we adopt the pre-calculated scattering kernels and software package presented by Dubovik et al. (2002; 2006), which describes dust as a shape mixture of randomly oriented polydisperse spheroids. Consequently we generate two lookup tables (LUTspheric and LUTspheroid) from simulated satellite received reflectance at top of atmosphere (TOA) under varieties of observing conditions and aerosol loadings using Second Simulation of a Satellite Signal in the Solar Spectrum - Vector (6SV) code. All the simulations are made at 550 nm, and for simplicity the Lambertian surface is assumed. Using the obtained LUTs we examine the differences of TOA reflectance (Δ?TOA = ?spheric - ?spheroid) under different surface reflectance and aerosol loadings. Afterwards AOD is retrieved using LUTspheric from the simulated TOA reflectance by LUTspheroid in order to detect the retrieval errors (Δ? = ?retreived -?input) induced

Aqueous phase oligomerization of α,β-unsaturated carbonyls and acids investigated using ion mobility spectrometry coupled to mass spectrometry (IMS-MS)

NASA Astrophysics Data System (ADS)

Renard, Pascal; Tlili, Sabrine; Ravier, Sylvain; Quivet, Etienne; Monod, Anne

2016-04-01

One of the current essential issues to unravel our ability to forecast future climate change and air quality, implies a better understanding of natural processes leading to secondary organic aerosol (SOA) formation, and in particular the formation and fate of oligomers. The difficulty in characterizing macromolecules is to discern between large oxygenated molecules from series of oligomers containing repeated small monomers of diverse structures. In the present study, taking advantage from previously established radical vinyl oligomerization of methyl vinylketone (MVK) in the aqueous phase, where relatively simple oligomers containing up to 14 monomers were observed, we have investigated the same reactivity on several other unsaturated water soluble organic compounds (UWSOCs) and on a few mixtures of these precursor compounds. The technique used to characterize the formed oligomers was a traveling wave ion mobility spectrometry coupled to a hybrid quadrupole - time of flight mass spectrometer (IMS-MS) fitted with an electrospray source and ultra-high performance liquid chromatography (UPLC). The technique allows for an additional separation, especially for large ions, containing long carbon chains. We have shown the efficiency of the IMS-mass spectrometry technique to detect oligomers derived from MVK photooxidation in the aqueous phase. The results were then compared to other oligomers, derived from ten other individual biogenic UWSOCs. The technique allowed distinguishing between different oligomers arising from different precursors. It also clearly showed that compounds bearing a non-conjugated unsaturation did not provide oligomerization. Finally, it was shown that the IMS-mass spectrometry technique, applied to mixtures of unsaturated conjugated precursors, exhibited the ability of these precursors to co-oligomerize, i.e. forming only one complex oligomer system bearing monomers of different structures. The results are discussed in terms of atmospheric

Global and Regional Impacts of HONO on the Chemical Composition of Clouds and Aerosols

NASA Technical Reports Server (NTRS)

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

2014-01-01

Recently, realistic simulation of nitrous acid (HONO) based on the HONO / NOx ratio of 0.02 was found to have a significant impact on the global budgets of HOx (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and corroborate the central role of cloud chemical processing in S(IV) formation

Chemical composition, sources and secondary processes of aerosols in Baoji city of northwest China

NASA Astrophysics Data System (ADS)

Wang, Y. C.; Huang, R.-J.; Ni, H. Y.; Chen, Y.; Wang, Q. Y.; Li, G. H.; Tie, X. X.; Shen, Z. X.; Huang, Y.; Liu, S. X.; Dong, W. M.; Xue, P.; Fröhlich, R.; Canonaco, F.; Elser, M.; Daellenbach, K. R.; Bozzetti, C.; El Haddad, I.; Prévôt, A. S. H.; Canagaratna, M. R.; Worsnop, D. R.; Cao, J. J.

2017-06-01

Particulate air pollution is a severe environmental problem in China, affecting visibility, air quality, climate and human health. However, previous studies focus mainly on large cities such as Beijing, Shanghai, and Guangzhou. In this study, an Aerodyne Aerosol Chemical Speciation Monitor was deployed in Baoji, a middle size inland city in northwest China from 26 February to 27 March 2014. The non-refractory submicron aerosol (NR-PM1) was dominated by organics (55%), followed by sulfate (16%), nitrate (15%), ammonium (11%) and chloride (3%). A source apportionment of the organic aerosol (OA) was performed with the Sofi (Source Finder) interface of ME-2 (Multilinear Engine), and six main sources/factors were identified and classified as hydrocarbon-like OA (HOA), cooking OA (COA), biomass burning OA (BBOA), coal combustion OA (CCOA), less oxidized oxygenated OA (LO-OOA) and more oxidized oxygenated OA (MO-OOA), which contributed 20%, 14%, 13%, 9%, 23% and 21% of total OA, respectively. The contribution of secondary components shows increasing trends from clean days to polluted days, indicating the importance of secondary aerosol formation processes in driving particulate air pollution. The formation of LO-OOA and MO-OOA is mainly driven by photochemical reactions, but significantly influenced by aqueous-phase chemistry during periods of low atmospheric oxidative capacity.

“Towards building better linkages between aqueous phase chemistry and microphysics in CMAQ”

EPA Science Inventory

Currently, CMAQ’s aqueous phase chemistry routine (AQCHEM-base) assumes Henry’s Law equilibrium and employs a forward Euler method to solve a small set of oxidation equations, considering the additional processes of aitken scavenging and wet deposition in series and e...

Reactive oxygen species formed in aqueous mixtures of secondary organic aerosols and mineral dust influencing cloud chemistry and public health in the Anthropocene.

PubMed

Tong, Haijie; Lakey, Pascale S J; Arangio, Andrea M; Socorro, Joanna; Kampf, Christopher J; Berkemeier, Thomas; Brune, William H; Pöschl, Ulrich; Shiraiwa, Manabu

2017-08-24

Mineral dust and secondary organic aerosols (SOA) account for a major fraction of atmospheric particulate matter, affecting climate, air quality and public health. How mineral dust interacts with SOA to influence cloud chemistry and public health, however, is not well understood. Here, we investigated the formation of reactive oxygen species (ROS), which are key species of atmospheric and physiological chemistry, in aqueous mixtures of SOA and mineral dust by applying electron paramagnetic resonance (EPR) spectrometry in combination with a spin-trapping technique, liquid chromatography-tandem mass spectrometry (LC-MS/MS), and a kinetic model. We found that substantial amounts of ROS including OH, superoxide as well as carbon- and oxygen-centred organic radicals can be formed in aqueous mixtures of isoprene, α-pinene, naphthalene SOA and various kinds of mineral dust (ripidolite, montmorillonite, kaolinite, palygorskite, and Saharan dust). The molar yields of total radicals were ∼0.02-0.5% at 295 K, which showed higher values at 310 K, upon 254 nm UV exposure, and under low pH (<3) conditions. ROS formation can be explained by the decomposition of organic hydroperoxides, which are a prominent fraction of SOA, through interactions with water and Fenton-like reactions with dissolved transition metal ions. Our findings imply that the chemical reactivity and aging of SOA particles can be enhanced upon interaction with mineral dust in deliquesced particles or cloud/fog droplets. SOA decomposition could be comparably important to the classical Fenton reaction of H 2 O 2 with Fe 2+ and that SOA can be the main source of OH radicals in aqueous droplets at low concentrations of H 2 O 2 and Fe 2+ . In the human respiratory tract, the inhalation and deposition of SOA and mineral dust can also lead to the release of ROS, which may contribute to oxidative stress and play an important role in the adverse health effects of atmospheric aerosols in the Anthropocene.

Extraction and separation of tungsten (VI) from aqueous media with Triton X-100-ammonium sulfate-water aqueous two-phase system without any extractant.

PubMed

Yongqiang Zhang; Tichang Sun; Tieqiang Lu; Chunhuan Yan

2016-11-25

An aqueous two-phase system composed of Triton X-100-(NH 4 ) 2 SO 4 -H 2 O was proposed for extraction and separation of tungsten(VI) from aqueous solution without using any extractant. The effects of aqueous pH, concentration of ammonium sulfate, Triton X-100 and tungsten, extracting temperature on the extraction of tungsten were investigated. The extraction of tungsten has remarkable relationship with aqueous pH and are to above 90% at pH=1.0-3.0 under studied pH range (pH=1.0-7.0) and increases gradually with increasing Triton X-100 concentration, but decreases slightly with increasing ammonium sulfate concentration. The extraction percentage of tungsten is hardly relevant to temperature but its distribution coefficient linearly increases with increasing temperature within 303.15-343.15K. The distribution coefficient of tungsten increases with the increase of initial tungsten concentration (0.1-3%) and temperature (303.15 K-333.15K). The solubilization capacity of tungsten in Triton X-100 micellar phase is independent of temperature. FT-IR analysis reveals that there is no evident interaction between polytungstate anion and ether oxygen unit in Triton X-100, and DLS analysis indicates that zeta potential of Triton X-100 micellar phase have a little change from positive to negative after extracting tungsten. Based on the above-mentioned results, it can be deduced that polytungstate anions are solubilized in hydrophilic outer shell of Triton X-100 micelles by electrostatic attraction depending on its relatively high hydrophobic nature. The stripping of tungsten is mainly influenced by temperature and can be easily achieved to 95% in single stage stripping. The tungsten (VI) is separated out from solution containing Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Al(III), Cr(III) and Mn(II) under the suitable conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Cloud-Resolving Model Simulations of Aerosol-Cloud Interactions Triggered by Strong Aerosol Emissions in the Arctic

NASA Astrophysics Data System (ADS)

Wang, H.; Kravitz, B.; Rasch, P. J.; Morrison, H.; Solomon, A.

2014-12-01

Previous process-oriented modeling studies have highlighted the dependence of effectiveness of cloud brightening by aerosols on cloud regimes in warm marine boundary layer. Cloud microphysical processes in clouds that contain ice, and hence the mechanisms that drive aerosol-cloud interactions, are more complicated than in warm clouds. Interactions between ice particles and liquid drops add additional levels of complexity to aerosol effects. A cloud-resolving model is used to study aerosol-cloud interactions in the Arctic triggered by strong aerosol emissions, through either geoengineering injection or concentrated sources such as shipping and fires. An updated cloud microphysical scheme with prognostic aerosol and cloud particle numbers is employed. Model simulations are performed in pure super-cooled liquid and mixed-phase clouds, separately, with or without an injection of aerosols into either a clean or a more polluted Arctic boundary layer. Vertical mixing and cloud scavenging of particles injected from the surface is still quite efficient in the less turbulent cold environment. Overall, the injection of aerosols into the Arctic boundary layer can delay the collapse of the boundary layer and increase low-cloud albedo. The pure liquid clouds are more susceptible to the increase in aerosol number concentration than the mixed-phase clouds. Rain production processes are more effectively suppressed by aerosol injection, whereas ice precipitation (snow) is affected less; thus the effectiveness of brightening mixed-phase clouds is lower than for liquid-only clouds. Aerosol injection into a clean boundary layer results in a greater cloud albedo increase than injection into a polluted one, consistent with current knowledge about aerosol-cloud interactions. Unlike previous studies investigating warm clouds, the impact of dynamical feedback due to precipitation changes is small. According to these results, which are dependent upon the representation of ice nucleation

Modeling the partitioning of organic chemical species in cloud phases with CLEPS (1.1)

NASA Astrophysics Data System (ADS)

Rose, Clémence; Chaumerliac, Nadine; Deguillaume, Laurent; Perroux, Hélène; Mouchel-Vallon, Camille; Leriche, Maud; Patryl, Luc; Armand, Patrick

2018-02-01

The new detailed aqueous-phase mechanism Cloud Explicit Physico-chemical Scheme (CLEPS 1.0), which describes the oxidation of isoprene-derived water-soluble organic compounds, is coupled with a warm microphysical module simulating the activation of aerosol particles into cloud droplets. CLEPS 1.0 was then extended to CLEPS 1.1 to include the chemistry of the newly added dicarboxylic acids dissolved from the particulate phase. The resulting coupled model allows the prediction of the aqueous-phase concentrations of chemical compounds originating from particle scavenging, mass transfer from the gas-phase and in-cloud aqueous chemical reactivity. The aim of the present study was more particularly to investigate the effect of particle scavenging on cloud chemistry. Several simulations were performed to assess the influence of various parameters on model predictions and to interpret long-term measurements conducted at the top of Puy de Dôme (PUY, France) in marine air masses. Specific attention was paid to carboxylic acids, whose predicted concentrations are on average in the lower range of the observations, with the exception of formic acid, which is rather overestimated in the model. The different sensitivity runs highlight the fact that formic and acetic acids mainly originate from the gas phase and have highly variable aqueous-phase reactivity depending on the cloud acidity, whereas C3-C4 carboxylic acids mainly originate from the particulate phase and are supersaturated in the cloud.

[Phase transfer catalyzed bioconversion of penicillin G to 6-APA by immobilized penicillin acylase in recyclable aqueous two-phase systems with light/pH sensitive copolymers].

PubMed

Jin, Ke-ming; Cao, Xue-jun; Su, Jin; Ma, Li; Zhuang, Ying-ping; Chu, Ju; Zhang, Si-liang

2008-03-01

Immobilized penicillin acylase was used for bioconversion of penicillin PG into 6-APA in aqueous two-phase systems consisting of a light-sensitive polymer PNBC and a pH-sensitive polymer PADB. Partition coefficients of 6-APA was found to be about 5.78 in the presence of 1% NaCl. Enzyme kinetics showed that the reaction reached equilibrium at roughly 7 h. The 6-APA mole yields were 85.3% (pH 7.8, 20 degrees C), with about 20% increment as compared with the reaction of single aqueous phase buffer. The partition coefficient of PG (Na) varied scarcely, while that of the product, 6-APA and phenylacetic acid (PA) significantly varied due to Donnan effect of the phase systems and hydrophobicity of the products. The variation of the partition coefficients of the products also affected the bioconversion yield of the products. In the aqueous two-phase systems, the substrate, PG, the products of 6-APA and PA were biased in the top phase, while immobilized penicillin acylase at completely partitioned at the bottom. The substrate and PG entered the bottom phase, where it was catalyzed into 6-APA and PA and entered the top phase. Inhibition of the substrate and products was removed to result in improvement of the product yield, and the immobilized enzyme showed higher efficiency than the immobilized cells and occupied smaller volume. Compared with the free enzyme, immobilized enzyme had greater stability, longer life-time, and was completely partitioned in the bottom phase and recycle. Bioconversion in two-phase systems using immobilized penicillin acylase showed outstanding advantage. The light-sensitive copolymer forming aqueous two-phase systems could be recovered by laser radiation at 488 nm or filtered 450 nm light, while pH-sensitive polymer PADB could be recovered at the isoelectric point (pH 4.1). The recovery of the two copolymers was between 95% and 99%.

Analysis of the WRF-Chem simulations contributing to the AQMEII-Phase II exercise with respect to aerosol impact on precipitation

NASA Astrophysics Data System (ADS)

Werhahn, Johannes; Balzarini, Allessandra; Baró, Roccio; Curci, Gabriele; Forkel, Renate; Hirtl, Marcus; Honzak, Luka; Jiménez-Guerrero, Pedro; Langer, Matthias; Lorenz, Christof; Pérez, Juan L.; Pirovano, Guido; San José, Roberto; Tuccella, Paolo; Žabkar, Rahela

2014-05-01

Simulated feedback effects between aerosol concentrations and meteorological variables and on pollutant distributions are expected to depend on model configuration and the meteorological situation. In order to quantity these effects the second phase of the AQMEII (Air Quality Model Evaluation International Initiative; http://aqmeii.jrc.ec.europa.eu/) model inter-comparison exercise focused on online coupled meteorology-chemistry models. Among others, seven of the participating groups contributed simulations with WRF-Chem (Grell et al., 2005) for Europe. According to the common simulation strategy for AQMEII phase 2, the entire year 2010 was simulated as a sequence of 2-day time slices. For better comparability, the seven groups using WRF-Chem applied the same grid spacing of 23 km and shared common processing of initial and boundary conditions as well as anthropogenic and fire emissions. The simulations differ by the chosen chemistry option, aerosol module, cloud microphysics, and by the degree of aerosol-meteorology feedback that was considered. Results from this small ensemble are analyzed with respect to the effect of the different degrees of aerosol-meteorology feedback, i.e. no aerosol feedback, direct aerosol effect, and direct plus indirect aerosol effect, on large scale precipitation. Simulated precipitation fields were compared against daily precipitation observations as given by E-OBS 25 km resolution gridded dataset from the EU-FP6 project ENSEMBLES (http://ensembles-eu.metoffice.com) and the data providers in the ECA&D project (http://www.ecad.eu). As expected, a first analysis confirms that the average impact of aerosol feedback is only very small on the considered spatial and temporal scale, i.e. due to the fact that initial meteorological conditions were taken every 3rd day from a one day non-feedback spin-up run. However, the analysis of the correlations between simulation and observations for the first and the second day indicates for some

Chelate-Modified Fenton Reaction for the Degradation of Trichloroethylene in Aqueous and Two-Phase Systems

PubMed Central

Lewis, Scott; Lynch, Andrew; Bachas, Leonidas; Hampson, Steve; Ormsbee, Lindell; Bhattacharyya, Dibakar

2009-01-01

Abstract The primary objective of this research was to model and understand the chelate-modified Fenton reaction for the destruction of trichloroethylene (TCE) present in both the aqueous and organic (in the form of droplets) phases. The addition of a nontoxic chelate (L), such as citrate or gluconic acid, allows for operation at near-neutral pH and controlled release of Fe(II)/Fe(III). For the standard Fenton reaction at low pH in two-phase systems, an optimum H2O2:Fe(II) molar ratio was found to be between 1:1 and 2:1. Experimentation proved the chelate-modified Fenton reaction effectively dechlorinated TCE in both the aqueous and organic phases at pH 6–7 using low H2O2:Fe(II) molar ratios (4:1 to 8:1). Increasing the L:Fe ratio was found to decrease the rate of H2O2 degradation in both Fe(II) and Fe(III) systems at near-neutral pH. Generalized models were developed to predict the concentration of TCE in the aqueous phase and TCE droplet radius as a function of time using literature-reported hydroxyl radical reaction kinetics and mass transfer relationships. Additional aspects of this work include the reusability of the Fe–citrate complex under repeated H2O2 injections in real water systems as well as packed column studies for simulated groundwater injection. PMID:20418966

Development and validation of reversed phase high performance liquid chromatography method for determination of dexpanthenol in pharmaceutical formulations.

PubMed

Kulikov, A U; Zinchenko, A A

2007-02-19

This paper describes the validation of an isocratic HPLC method for the assay of dexpanthenol in aerosol and gel. The method employs the Vydac Proteins C4 column with a mobile phase of aqueous solution of trifluoroacetic acid and UV detection at 206 nm. A linear response (r>0.9999) was observed in the range of 13.0-130 microg mL(-1). The method shows good recoveries and intra and inter-day relative standard deviations were less than 1.0%. Validation parameters as specificity, accuracy and robustness were also determined. The method can be used for dexpanthenol assay of panthenol aerosol and gel with dexpanthenol as the method separates dexpanthenol from aerosol or gel excipients.

Design of Phosphonium-Type Zwitterion as an Additive to Improve Saturated Water Content of Phase-Separated Ionic Liquid from Aqueous Phase toward Reversible Extraction of Proteins

PubMed Central

Ito, Yoritsugu; Kohno, Yuki; Nakamura, Nobuhumi; Ohno, Hiroyuki

2013-01-01

We designed phosphonium-type zwitterion (ZI) to control the saturated water content of separated ionic liquid (IL) phase in the hydrophobic IL/water biphasic systems. The saturated water content of separated IL phase, 1-butyl-3-methyimidazolium bis(trifluoromethanesulfonyl)imide, was considerably improved from 0.4 wt% to 62.8 wt% by adding N,N,N-tripentyl-4-sulfonyl-1-butanephosphonium-type ZI (P555C4S). In addition, the maximum water content decreased from 62.8 wt% to 34.1 wt% by increasing KH2PO4/K2HPO4 salt content in upper aqueous phosphate buffer phase. Horse heart cytochrome c (cyt.c) was dissolved selectively in IL phase by improving the water content of IL phase, and spectroscopic analysis revealed that the dissolved cyt.c retained its higher ordered structure. Furthermore, cyt. c dissolved in IL phase was re-extracted again from IL phase to aqueous phase by increasing the concentration of inorganic salts of the buffer solution. PMID:24013379

Constraining Aerosol Properties with the Spectrally-Resolved Phase Function of Pluto's Hazes

NASA Astrophysics Data System (ADS)

Parker, A. H.; Howett, C.; Olkin, C.; Protopapa, S.; Grundy, W. M.; Gladstone, R.; Young, L. A.; Horst, S. M.; Weaver, H. A., Jr.; Moore, J. M.; Ennico Smith, K.; Stern, A.

2017-12-01

The Multi-spectral Visible Imaging Camera (MVIC) and Lisa Hardaway Infrared Mapping Spectrometer (LEISA) aboard New Horizons imaged Pluto at high phase throughout departure from the system in July of 2015. The repeated MVIC color scans captured the phase behavior of Pluto's atmospheric hazes through phase angles of 165.0 to 169.5 degrees in four bandpasses in the visible and NIR. A spatially-resolved departure LEISA scan delivered moderate SNR NIR spectra of the hazes over wavelengths from 1.25 - 2.5 microns. Here we present our analysis of the departure MVIC and LEISA data, extracting high precision color phase curves of the hazes using the most up-to-date radiometric calibration and NIR gain drift corrections. We interpret these phase curves and spectra using Mie theory to constrain the size and composition of haze particles, with results indicating broad similarity to Titan aerosol analogues ("tholins"). Finally, we will explore the implications of the nature of these haze particles for the evolution of Pluto's surface as they settle out onto it over time.

Surface-Sensitive and Bulk Studies on the Complexation and Photosensitized Degradation of Catechol by Iron(III) as a Model for Multicomponent Aerosol Systems

NASA Astrophysics Data System (ADS)

Al-abadleh, H. A.; Tofan-Lazar, J.; Situm, A.; Ruffolo, J.; Slikboer, S.

2013-12-01

Surface water plays a crucial role in facilitating or inhibiting surface reactions in atmospheric aerosols. Little is known about the role of surface water in the complexation of organic molecules to transition metals in multicomponent aerosol systems. We will show results from real time diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments for the in situ complexation of catechol to Fe(III) and its photosensitized degradation under dry and humid conditions. Catechol was chosen as a simple model for humic-like substances (HULIS) in aerosols and aged polyaromatic hydrocarbons (PAH). It has also been detected in secondary organic aerosols (SOA) formed from the reaction of hydroxyl radicals with benzene. Given the importance of the iron content in aerosols and its biogeochemistry, our studies were conducted using FeCl3. For comparison, these surface-sensitive studies were complemented with bulk aqueous ATR-FTIR, UV-vis, and HPLC measurements for structural, quantitative and qualitative information about complexes in the bulk, and potential degradation products. The implications of our studies on understanding interfacial and condensed phase chemistry relevant to multicomponent aerosols, water thin islands on buildings, and ocean surfaces containing transition metals will be discussed.

Molecular characterization of free tropospheric aerosol collected at the Pico Mountain Observatory: a case study with a long-range transported biomass burning plume

NASA Astrophysics Data System (ADS)

Dzepina, K.; Mazzoleni, C.; Fialho, P.; China, S.; Zhang, B.; Owen, R. C.; Helmig, D.; Hueber, J.; Kumar, S.; Perlinger, J. A.; Kramer, L. J.; Dziobak, M. P.; Ampadu, M. T.; Olsen, S.; Wuebbles, D. J.; Mazzoleni, L. R.

2015-05-01

Free tropospheric aerosol was sampled at the Pico Mountain Observatory located at 2225 m above mean sea level on Pico Island of the Azores archipelago in the North Atlantic. The observatory is located ~ 3900 km east and downwind of North America, which enables studies of free tropospheric air transported over long distances. Aerosol samples collected on filters from June to October 2012 were analyzed to characterize organic carbon, elemental carbon, and inorganic ions. The average ambient concentration of aerosol was 0.9 ± 0.7 μg m-3. On average, organic aerosol components represent the largest mass fraction of the total measured aerosol (60 ± 51%), followed by sulfate (23 ± 28%), nitrate (13 ± 10%), chloride (2 ± 3%), and elemental carbon (2 ± 2%). Water-soluble organic matter (WSOM) extracted from two aerosol samples (9/24 and 9/25) collected consecutively during a pollution event were analyzed using ultrahigh-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Approximately 4000 molecular formulas were assigned to each of the mass spectra in the range of m/z 100-1000. The majority of the assigned molecular formulas had unsaturated structures with CHO and CHNO elemental compositions. FLEXPART retroplume analyses showed the sampled air masses were very aged (average plume age > 12 days). These aged aerosol WSOM compounds had an average O/C ratio of ~ 0.45, which is relatively low compared to O/C ratios of other aged aerosol. The increase in aerosol loading during the measurement period of 9/24 was linked to biomass burning emissions from North America by FLEXPART retroplume analysis and Moderate Resolution Imaging Spectroradiometer (MODIS) fire counts. This was confirmed with biomass burning markers detected in the WSOM and with the morphology and mixing state of particles as determined by scanning electron microscopy. The presence of markers characteristic of aqueous-phase reactions of phenolic species suggests

Comparative thermodynamic studies of aqueous glutaric acid, ammonium sulfate and sodium chloride aerosol at high humidity.

PubMed

Hanford, Kate L; Mitchem, Laura; Reid, Jonathan P; Clegg, Simon L; Topping, David O; McFiggans, Gordon B

2008-10-02

Aerosol optical tweezers are used to simultaneously characterize and compare the hygroscopic properties of two aerosol droplets, one containing inorganic and organic solutes and the second, referred to as the control droplet, containing a single inorganic salt. The inorganic solute is either sodium chloride or ammonium sulfate and the organic component is glutaric acid. The time variation in the size of each droplet (3-7 microm in radius) is recorded with 1 s time resolution and with nanometre accuracy. The size of the control droplet is used to estimate the relative humidity with an accuracy of better than +/-0.09%. Thus, the Kohler curve of the multicomponent inorganic/organic droplet, which characterizes the variation in equilibrium droplet size with relative humidity, can be determined directly. The measurements presented here focus on high relative humidities, above 97%, in the limit of dilute solutes. The experimental data are compared with theoretical treatments that, while ignoring the interactions between the inorganic and organic components, are based upon accurate representations of the activity-concentration relationships of aqueous solutions of the individual salts. The organic component is treated by a parametrized fit to experimental data or by the UNIFAC model and the water activity of the equilibrium solution droplet is calculated using the approach suggested by Clegg, Seinfeld and Brimblecombe or the Zdanovskii-Stokes-Robinson approximation. It is shown that such an experimental strategy, comparing directly droplets of different composition, enables highly accurate measurements of the hygroscopic properties, allowing the theoretical treatments to be rigorously tested. Typical deviations of the experimental measurements from theoretical predictions are shown to be around 1% in equilibrium size, comparable to the variation between the theoretical frameworks considered.

Control and measurement of the phase behavior of aqueous solutions using microfluidics

PubMed Central

Shim, Jung-uk; Cristobal, Galder; Link, Darren R.; Thorsen, Todd; Jia, Yanwei; Piattelli, Katie; Fraden, Seth

2008-01-01

A microfluidic device denoted the Phase Chip has been designed to measure and manipulate the phase diagram of multi-component fluid mixtures. The Phase Chip exploits the permeation of water through poly(dimethylsiloxane) (PDMS) in order to controllably vary the concentration of solutes in aqueous nanoliter volume microdrops stored in wells. The permeation of water in the Phase Chip is modeled using the diffusion equation and good agreement between experiment and theory is obtained. The Phase Chip operates by first creating drops of the water/solute mixture whose composition varies sequentially. Next, drops are transported down channels and guided into storage wells using surface tension forces. Finally, the solute concentration of each stored drop is simultaneously varied and measured. Two applications of the Phase Chip are presented. First, the phase diagram of a polymer/salt mixture is measured on-chip and validated off-chip and second, protein crystallization rates are enhanced through the manipulation of the kinetics of nucleation and growth. PMID:17580868

Rapid RNA Exchange in Aqueous Two-Phase System and Coacervate Droplets

NASA Astrophysics Data System (ADS)

Jia, Tony Z.; Hentrich, Christian; Szostak, Jack W.

2014-02-01

Compartmentalization in a prebiotic setting is an important aspect of early cell formation and is crucial for the development of an artificial protocell system that effectively couples genotype and phenotype. Aqueous two-phase systems (ATPSs) and complex coacervates are phase separation phenomena that lead to the selective partitioning of biomolecules and have recently been proposed as membrane-free protocell models. We show in this study through fluorescence recovery after photobleaching (FRAP) microscopy that despite the ability of such systems to effectively concentrate RNA, there is a high rate of RNA exchange between phases in dextran/polyethylene glycol ATPS and ATP/poly-L-lysine coacervate droplets. In contrast to fatty acid vesicles, these systems would not allow effective segregation and consequent evolution of RNA, thus rendering these systems ineffective as model protocells.

Characteristics and composition of atmospheric aerosols in Phimai, central Thailand during BASE-ASIA

NASA Astrophysics Data System (ADS)

Li, Can; Tsay, Si-Chee; Hsu, N. Christina; Kim, Jin Young; Howell, Steven G.; Huebert, Barry J.; Ji, Qiang; Jeong, Myeong-Jae; Wang, Sheng-Hsiang; Hansell, Richard A.; Bell, Shaun W.

2013-10-01

Comprehensive measurements of atmospheric aerosols were made in Phimai, central Thailand (15.183°N, 102.565°E, elevation: 206 m) during the BASE-ASIA field experiment from late February to early May in 2006. The observed aerosol loading was sizable for this rural site (mean aerosol scattering: 108 ± 64 Mm-1; absorption: 15 ± 8 Mm-1; PM10 concentration: 33 ± 17 μg m-3), and dominated by submicron particles. Major aerosol compounds included carbonaceous (OC: 9.5 ± 3.6 μg m-3; EC: 2.0 ± 2.3 μg m-3) and secondary species (SO42-: 6.4 ± 3.7 μg m-3, NH4+: 2.2 ± 1.3 μg m-3). While the site was seldom under the direct influence of large forest fires to its north, agricultural fires were ubiquitous during the experiment, as suggested by the substantial concentration of K+ (0.56 ± 0.33 μg m-3). Besides biomass burning, aerosols in Phimai during the experiment were also strongly influenced by industrial and vehicular emissions from the Bangkok metropolitan region and long-range transport from southern China. High humidity played an important role in determining the aerosol composition and properties in the region. Sulfate was primarily formed via aqueous phase reactions, and hygroscopic growth could enhance the aerosol light scattering by up to 60%, at the typical morning RH level of 85%. The aerosol single scattering albedo demonstrated distinct diurnal variation, ranging from 0.86 ± 0.04 in the evening to 0.92 ± 0.02 in the morning. This experiment marks the first time such comprehensive characterization of aerosols was made for rural central Thailand. Our results indicate that aerosol pollution has developed into a regional problem for northern Indochina, and may become more severe as the region's population and economy continue to grow.

Aerosolized Antimicrobial Agents Based on Degradable Dextran Nanoparticles Loaded with Silver Carbene Complexes

PubMed Central

Ornelas-Megiatto, Cátia; Shah, Parth N.; Wich, Peter R.; Cohen, Jessica L.; Tagaev, Jasur A.; Smolen, Justin A.; Wright, Brian D.; Panzner, Matthew J.; Youngs, Wiley J.; Fréchet, Jean M. J.; Cannon, Carolyn L.

2012-01-01

Degradable acetalated dextran (Ac-DEX) nanoparticles were prepared and loaded with a hydrophobic silver carbene complex (SCC) by a single-emulsion process. The resulting particles were characterized for morphology and size distribution using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and dynamic light scattering (DLS). The average particle size and particle size distribution were found to be a function of the ratio of the organic phase to the surfactant containing aqueous phase with a 1:5 volume ratio of Ac-DEX CH2Cl2 (organic): PBS (aqueous) being optimal for the formulation of nanoparticles with an average size of 100 ± 40 nm and a low polydispersity. The SCC loading was found to increase with an increase in the SCC quantity in the initial feed used during particle formulation up to 30% (w/w); however, the encapsulation efficiency was observed to be the best at a feed ratio of 20% (w/w). In vitro efficacy testing of the SCC loaded Ac-DEX nanoparticles demonstrated their activity against both Gram-negative and Gram-positive bacteria; the nanoparticles inhibited the growth of every bacterial species tested. As expected, a higher concentration of drug was required to inhibit bacterial growth when the drug was encapsulated within the nanoparticle formulations compared with the free drug illustrating the desired depot release. Compared with free drug, the Ac-DEX nanoparticles were much more readily suspended in an aqueous phase and subsequently aerosolized, thus providing an effective method of pulmonary drug delivery. PMID:23025592

Aqueous two-phase printing of cell-containing contractile collagen microgels.

PubMed

Moraes, Christopher; Simon, Arlyne B; Putnam, Andrew J; Takayama, Shuichi

2013-12-01

This work describes the use of aqueous two-phase systems to print cell-containing contractile collagen microdroplets. The fully aqueous conditions enable convenient formation of sub-microliter 'microgels' that are much smaller than otherwise possible to fabricate while maintaining high cell viability. The produced microgels contract over several days, mimicking the behavior of macroscale contraction assays, which have been valued as an important biological readout for over three decades. Use of microgels not only reduces reagent consumption and increases throughput of the assay, but also improves transport of molecules into and out of the collagen matrix, thereby enabling efficient and more precise studies of timed stimulation profiles. Utility of the technology is demonstrated by analyzing the effects of TGF-β1 on gel contraction, and we demonstrate that brief 'burst' stimulation profiles in microgels prompt contraction of the matrix, a feature not observed in the conventional macroscale assay. The fully aqueous process also enables the integration of contractile collagen microgels within existing cell culture systems, and we demonstrate proof-of-principle experiments in which a contractile collagen droplet is fabricated in situ on an existing epithelial monolayer. The simplicity, versatility and ability to robustly produce collagen microgels should allow effective translation of this microengineering technology into a variety of research environments. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

The surface tension of aqueous solutions of some atmospheric water-soluble organic compounds

NASA Astrophysics Data System (ADS)

Tuckermann, Rudolf; Cammenga, Heiko K.

The surface tensions of aqueous solutions of levoglucosan, 3-hydroxybutanoic acid, 3-hydroxybenzoic acid, azelaic acid, pinonic acid, and humic acid have been measured. These compounds are suggested as model substances for the water-soluble organic compounds (WSOC) in atmospheric aerosols and droplets which may play an important role in the aerosol cycle because of their surface-active potentials. The reductions in surface tension induced by single and mixed WSOC in aqueous solution of pure water is remarkable. However, the results of this investigation cannot explain the strong reduction in surface tension in real cloud and fog water samples at concentrations of WSOC below 1 mg/mL.

Diffusion-based process for carbon dioxide uptake and isoprene emission in gaseous/aqueous two-phase photobioreactors by photosynthetic microorganisms.

PubMed

Bentley, Fiona K; Melis, Anastasios

2012-01-01

Photosynthesis for the generation of fuels and chemicals from cyanobacteria and microalgae offers the promise of a single host organism acting both as photocatalyst and processor, performing sunlight absorption and utilization, as well as CO(2) assimilation and conversion into product. However, there is a need to develop methods for generating, sequestering, and trapping such bio-products in an efficient and cost-effective manner that is suitable for industrial scale-up and exploitation. A sealed gaseous/aqueous two-phase photobioreactor was designed and applied for the photosynthetic generation of volatile isoprene (C(5)H(8)) hydrocarbons, which operates on the principle of spontaneous diffusion of CO(2) from the gaseous headspace into the microalgal or cyanobacterial-containing aqueous phase, followed by photosynthetic CO(2) assimilation and isoprene production by the transgenic microorganisms. Volatile isoprene hydrocarbons were emitted from the aqueous phase and were sequestered into the gaseous headspace. Periodic replacement (flushing) of the isoprene (C(5)H(8)) and oxygen (O(2)) content of the gaseous headspace with CO(2) allowed for the simultaneous harvesting of the photoproducts and replenishment of the CO(2) supply in the gaseous headspace. Reduction in practice of the gaseous/aqueous two-phase photobioreactor is offered in this work with a fed-batch and a semi-continuous culturing system using Synechocystis sp. PCC 6803 heterologously expressing the Pueraria montana (kudzu) isoprene synthase (IspS) gene. Constitutive isoprene production was observed over 192 h of experimentation, coupled with cyanobacterial biomass accumulation. The diffusion-based process in gaseous/aqueous two-phase photobioreactors has the potential to be applied to other high-value photosynthetically derived volatile molecules, emanating from a variety of photosynthetic microorganisms. Copyright © 2011 Wiley Periodicals, Inc.

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

EPA Science Inventory

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

Hydrolysis of glyoxal in water-restricted environments: formation of organic aerosol precursors through formic acid catalysis.

PubMed

Hazra, Montu K; Francisco, Joseph S; Sinha, Amitabha

2014-06-12

The hydrolysis of glyoxal involving one to three water molecules and also in the presence of a water molecule and formic acid has been investigated. Our results show that glyoxal-diol is the major product of the hydrolysis and that formic acid, through its ability to facilitate intermolecular hydrogen atom transfer, is considerably more efficient than water as a catalyst in the hydrolysis process. Additionally, once the glyoxal-diol is formed, the barrier for further hydrolysis to form the glyoxal-tetrol is effectively reduced to zero in the presence of a single water and formic acid molecule. There are two important implications arising from these findings. First, the results suggest that under the catalytic influence of formic acid, glyoxal hydrolysis can impact the growth of atmospheric aerosols. As a result of enhanced hydrogen bonding, mediated through their polar OH functional groups, the diol and tetrol products are expected to have significantly lower vapor pressure than the parent glyoxal molecule; hence they can more readily partition into the particle phase and contribute to the growth of secondary organic aerosols. In addition, our findings provide insight into how glyoxal-diol and glyoxal-tetrol might be formed under atmospheric conditions associated with water-restricted environments and strongly suggest that the formation of these precursors for secondary organic aerosol growth is not likely restricted solely to the bulk aqueous phase as is currently assumed.

Global and Regional Impacts of HONO on the Chemical Composition of Clouds and Aerosols

NASA Technical Reports Server (NTRS)

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

2014-01-01

Recently, realistic simulation of nitrous acid (HONO) based on the HONO/NO(sub x) ratio of 0.02 was found to have a significant impact on the global budgets of HO(sub x) (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and corroborate the central role of cloud chemical processing in S(IV) formation.

Gas phase emissions from cooking processes and their secondary aerosol production potential

NASA Astrophysics Data System (ADS)

Klein, Felix; Platt, Stephen; Bruns, Emily; Termime-roussel, Brice; Detournay, Anais; Mohr, Claudia; Crippa, Monica; Slowik, Jay; Marchand, Nicolas; Baltensperger, Urs; Prevot, Andre; El Haddad, Imad

2014-05-01

-ToF-MS) were used to quantify OA and VOC emissions, respectively. SOA production potential of the different emissions was quantified by introducing them into the PSI mobile smog chamber and a potential aerosol chamber (PAM) where they were photochemically aged. The measurements of primary emissions suggest that the COA factor identified in ambient atmospheric aerosols is mostly related to fat release from frying with vegetable oils or grilling fatty-meats. In contrast, vegetable cooking (boiling and frying) was associated with significant VOC emissions. The VOC emissions from frying consist mainly of aldehydes which are formed through breaking of fatty acids. Gas phase composition, emission factors and SAPP from all these processes will be presented. This work was supported by the Swiss National Science Foundation as well as the Swiss Federal Office for the Environment. The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under grant agreement n.° 290605 (COFUND: PSI-FELLOW). J. Allan et al, Atmos. Chem. Phys. 10, 647-668 (2010) X.-F. Huang et al, Atmos. Chem. Phys. 10, 8933-8945 (2010) Y.-L. Sun et al, Atmos. Chem. Phys. 11, 1581-1602 (2011)

[Raman spectroscopic analysis of dissolution and phase transformation of chloropinnoite in the boric acid aqueous solution].

PubMed

Li, Xiao-Ping; Gao, Shi-Yang; Liu, Zhi-Hong; Hu, Man-Cheng; Xia, Shu-Ping

2005-01-01

Raman spectroscopy of dissolution and transformation of chloropinnoite in 4.5% (w.t.%) boric acid aqueous solution at 30 degrees C has been recorded. The Raman spectra of kinetics process have been obtained. The phase transformation product is kurnakovite (2MgO x 3B2O3 x 15H2O). The main polyborate anions and their interaction in aqueous solution have been proposed according to the Raman spectrum. Some assignments were tentatively given and the relations between the existing forms of polyborate anions and the crystallizing solid phases have been gained. A mechanisms of dissolution and crystallization reactions and the formation condition of kurnakovite in Qinghai-Tibet plateau were proposed and discussed.

Aerosol-phase activity of iodine captured from a triiodide resin filter on fine particles containing an infectious virus.

PubMed

Heimbuch, B K; Harnish, D A; Balzli, C; Lumley, A; Kinney, K; Wander, J D

2015-06-01

To avoid interference by water-iodine disinfection chemistry and measure directly the effect of iodine, captured from a triiodide complex bound to a filter medium, on viability of penetrating viral particles. Aerosols of MS2 coli phage were passed through control P100 or iodinated High-Efficiency Particulate Air media, collected in plastic bags, incubated for 0-10 min, collected in an impinger containing thiosulphate to consume all unreacted iodine, plated and enumerated. Comparison of viable counts demonstrated antimicrobial activity with an apparent half-life for devitalization in tens of seconds; rate of kill decreased at low humidity and free iodine was captured by the bags. The results support the mechanism of near-contact capture earlier proposed; however, the disinfection chemistry in the aerosol phase is very slow on the time scale of inhalation. This study shows that disinfection by filter-bound iodine in the aerosol phase is too slow to be clinically significant in individual respiratory protection, but that it might be of benefit to limit airborne transmission of infections in enclosed areas. Published 2015. This article is a U.S. Government work and is in the public domain in the USA.

INTEGRATED PROTECTIVE FABRIC SYSTEM (IPFS) PHASE III PROGRAM: AEROSOL PROTECTION REPORT

DTIC Science & Technology

2017-08-16

one layer control. It was observed that aerosol swatch measurements showed no correlation to aerosol system test performance for the materials and...the BRHA model employed. It was observed that aerosol swatch measurements showed no correlation to aerosol system test performance for the...Testing” (McVeety et al., 2015). This report includes a description of the materials and material controls, a description of the IPFS configurations

Mid-infrared laser-absorption diagnostic for vapor-phase measurements in an evaporating n-decane aerosol

NASA Astrophysics Data System (ADS)

Porter, J. M.; Jeffries, J. B.; Hanson, R. K.

2009-09-01

A novel three-wavelength mid-infrared laser-based absorption/extinction diagnostic has been developed for simultaneous measurement of temperature and vapor-phase mole fraction in an evaporating hydrocarbon fuel aerosol (vapor and liquid droplets). The measurement technique was demonstrated for an n-decane aerosol with D 50˜3 μ m in steady and shock-heated flows with a measurement bandwidth of 125 kHz. Laser wavelengths were selected from FTIR measurements of the C-H stretching band of vapor and liquid n-decane near 3.4 μm (3000 cm -1), and from modeled light scattering from droplets. Measurements were made for vapor mole fractions below 2.3 percent with errors less than 10 percent, and simultaneous temperature measurements over the range 300 K< T<900 K were made with errors less than 3 percent. The measurement technique is designed to provide accurate values of temperature and vapor mole fraction in evaporating polydispersed aerosols with small mean diameters ( D 50<10 μ m), where near-infrared laser-based scattering corrections are prone to error.

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

Improving the treatment of non-aqueous phase TCE in low permeability zones with permanganate.

PubMed

Chokejaroenrat, Chanat; Comfort, Steve; Sakulthaew, Chainarong; Dvorak, Bruce

2014-03-15

Treating dense non-aqueous phase liquids (DNAPLs) embedded in low permeability zones (LPZs) is a particularly challenging issue for injection-based remedial treatments. Our objective was to improve the sweeping efficiency of permanganate (MnO4(-)) into LPZs to treat high concentrations of TCE. This was accomplished by conducting transport experiments that quantified the penetration of various permanganate flooding solutions into a LPZ that was spiked with non-aqueous phase (14)C-TCE. The treatments we evaluated included permanganate paired with: (i) a shear-thinning polymer (xanthan); (ii) stabilization aids that minimized MnO2 rind formation and (iii) a phase-transfer catalyst. In addition, we quantified the ability of these flooding solutions to improve TCE destruction under batch conditions by developing miniature LPZ cylinders that were spiked with (14)C-TCE. Transport experiments showed that MnO4(-) alone was inefficient in penetrating the LPZ and reacting with non-aqueous phase TCE, due to a distinct and large MnO2 rind that inhibited the TCE from further oxidant contact. By including xanthan with MnO4(-), the sweeping efficiency increased (90%) but rind formation was still evident. By including the stabilization aid, sodium hexametaphosphate (SHMP) with xanthan, permanganate penetrated 100% of the LPZ, no rind was observed, and the percentage of TCE oxidized increased. Batch experiments using LPZ cylinders allowed longer contact times between the flooding solutions and the DNAPL and results showed that SHMP+MnO4(-) improved TCE destruction by ∼16% over MnO4(-) alone (56.5% vs. 40.1%). These results support combining permanganate with SHMP or SHMP and xanthan as a means of treating high concentrations of TCE in low permeable zones. Copyright © 2014 Elsevier B.V. All rights reserved.

Lignin solubilization and aqueous phase reforming for the production of aromatic chemicals and hydrogen.

PubMed

Zakzeski, Joseph; Weckhuysen, Bert M

2011-03-21

The solubilization and aqueous phase reforming of lignin, including kraft, soda, and alcell lignin along with sugarcane bagasse, at low temperatures (T≤498 K) and pressures (P≤29 bar) is reported for the first time for the production of aromatic chemicals and hydrogen. Analysis of lignin model compounds and the distribution of products obtained during the lignin aqueous phase reforming revealed that lignin was depolymerized through disruption of the abundant β-O-4 linkages and, to a lesser extent, the 5-5' carbon-carbon linkages to form monomeric aromatic compounds. The alkyl chains contained on these monomeric compounds were readily reformed to produce hydrogen and simple aromatic platform chemicals, particularly guaiacol and syringol, with the distribution of each depending on the lignin source. The methoxy groups present on the aromatic rings were subject to hydrolysis to form methanol, which was also readily reformed to produce hydrogen and carbon dioxide. The composition of the isolated yields of monomeric aromatic compounds and overall lignin conversion based on these isolated yields varied from 10-15% depending on the lignin sample, with the balance consisting of gaseous products and residual solid material. Furthermore, we introduce the use of a high-pressure autoclave with optical windows and an autoclave with ATR-IR sentinel for on-line in situ spectroscopic monitoring of biomass conversion processes, which provides direct insight into, for example, the solubilization process and aqueous phase reforming reaction of lignin. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Equivalent Aqueous Phase Modulation of Domain Segregation in Myelin Monolayers and Bilayer Vesicles

PubMed Central

Oliveira, Rafael G.; Schneck, Emanuel; Funari, Sergio S.; Tanaka, Motomu; Maggio, Bruno

2010-01-01

Purified myelin can be spread as monomolecular films at the air/aqueous interface. These films were visualized by fluorescence and Brewster angle microscopy, showing phase coexistence at low and medium surface pressures (<20–30 mN/m). Beyond this threshold, the film becomes homogeneous or not, depending on the aqueous subphase composition. Pure water as well as sucrose, glycerol, dimethylsulfoxide, and dimethylformamide solutions (20% in water) produced monolayers that become homogeneous at high surface pressures; on the other hand, the presence of salts (NaCl, CaCl2) in Ringer's and physiological solution leads to phase domain microheterogeneity over the whole compression isotherm. These results show that surface heterogeneity is favored by the ionic milieu. The modulation of the phase-mixing behavior in monolayers is paralleled by the behavior of multilamellar vesicles as determined by small-angle and wide-angle x-ray scattering. The correspondence of the behavior of monolayers and multilayers is achieved only at high surface pressures near the equilibrium adsorption surface pressure; at lower surface pressures, the correspondence breaks down. The equilibrium surface tension on all subphases corresponds to that of the air/alkane interface (27 mN/m), independently on the surface tension of the clean subphase. PMID:20816062

Characterization of carbonaceous aerosol by the stepwise-extraction thermal-optical-transmittance (SE-TOT) method

NASA Astrophysics Data System (ADS)

Cheng, Yuan; He, Ke-bin; Duan, Feng-kui; Du, Zhen-yu; Zheng, Mei; Ma, Yong-liang

2012-11-01

Carbonaceous aerosol collected in Beijing, China was characterized by a stepwise-extraction thermal-optical-transmittance (SE-TOT) method which allows for a quantitative separation of organic aerosol into distinct fractions. About 55% of the total organic carbon (OC) could be extracted by a mixture of hexane, methylene chloride and acetone. The extractable OC was further isolated into non-polar, low-polar and high-polar OC which constituted 10%, 23% and 22% of the total OC, respectively. The sum of low-polar and high-polar OC was found to coincide well with the secondary OC predicted by the elemental carbon tracer method, indicating that the low-polar and high-polar OC are strongly associated with secondary organic aerosol. Moreover, it was suggested that high relative humidity could enhance the production of high-polar OC through aqueous-phase reactions, because high-polar OC correlated strongly with oxalate and the ratio of high-polar OC to low-polar OC was significantly higher during the sampling events with high relative humidity (1.23 ± 0.35) comparing with results from the low relative humidity days (0.79 ± 0.23). In addition, the extractable OC was shown to be light-absorbing. The results of this study suggest that the SE-TOT method could provide new insights into the characterization of carbonaceous aerosol.

Interactions Between Atmospheric Aerosols and Marine Boundary Layer Clouds on Regional and Global Scales

NASA Astrophysics Data System (ADS)

Wang, Zhen

Airborne aerosols are crucial atmospheric constituents that are involved in global climate change and human life qualities. Understanding the nature and magnitude of aerosol-cloud-precipitation interactions is critical in model predictions for atmospheric radiation budget and the water cycle. The interactions depend on a variety of factors including aerosol physicochemical complexity, cloud types, meteorological and thermodynamic regimes and data processing techniques. This PhD work is an effort to quantify the relationships among aerosol, clouds, and precipitation on both global and regional scales by using satellite retrievals and aircraft measurements. The first study examines spatial distributions of conversion rate of cloud water to rainwater in warm maritime clouds over the globe by using NASA A-Train satellite data. This study compares the time scale of the onset of precipitation with different aerosol categories defined by values of aerosol optical depth, fine mode fraction, and Angstrom Exponent. The results indicate that conversion time scales are actually quite sensitive to lower tropospheric static stability (LTSS) and cloud liquid water path (LWP), in addition to aerosol type. Analysis shows that tropical Pacific Ocean is dominated by the highest average conversion rate while subtropical warm cloud regions (far northeastern Pacific Ocean, far southeastern Pacific Ocean, Western Africa coastal area) exhibit the opposite result. Conversion times are mostly shorter for lower LTSS regimes. When LTSS condition is fixed, higher conversion rates coincide with higher LWP and lower aerosol index categories. After a general global view of physical property quantifications, the rest of the presented PhD studies is focused on regional airborne observations, especially bulk cloud water chemistry and aerosol aqueous-phase reactions during the summertime off the California coast. Local air mass origins are categorized into three distinct types (ocean, ships, and land

Small GSH-Capped CuInS2 Quantum Dots: MPA-Assisted Aqueous Phase Transfer and Bioimaging Applications.

PubMed

Zhao, Chuanzhen; Bai, Zelong; Liu, Xiangyou; Zhang, Yijia; Zou, Bingsuo; Zhong, Haizheng

2015-08-19

An efficient ligand exchange strategy for aqueous phase transfer of hydrophobic CuInS2/ZnS quantum dots was developed by employing glutathione (GSH) and mercaptopropionic acid (MPA) as the ligands. The whole process takes less than 20 min and can be scaled up to gram amount. The material characterizations show that the final aqueous soluble samples are solely capped with GSH on the surface. Importantly, these GSH-capped CuInS2/ZnS quantum dots have small size (hydrodynamic diameter <10 nm), moderate fluorescent properties (up to 34%) as well as high stability in aqueous solutions (stable for more than three months in 4 °C without any significant fluorescence quenching). Moreover, this ligand exchange strategy is also versatile for the aqueous phase transfer of other hydrophobic quantum dots, for instance, CuInSe2 and CdSe/ZnS quantum dots. We further demonstrated that GSH-capped quantum dots could be suitable fluorescence markers to penetrate cell membrane and image the cells. In addition, the GSH-capped CuInS2 quantum dots also have potential use in other fields such as photocatalysis and quantum dots sensitized solar cells.

Marine Aerosols and Clouds.

PubMed

Brooks, Sarah D; Thornton, Daniel C O

2018-01-03

The role of marine bioaerosols in cloud formation and climate is currently so uncertain that even the sign of the climate forcing is unclear. Marine aerosols form through direct emissions and through the conversion of gas-phase emissions to aerosols in the atmosphere. The composition and size of aerosols determine how effective they are in catalyzing the formation of water droplets and ice crystals in clouds by acting as cloud condensation nuclei and ice nucleating particles, respectively. Marine organic aerosols may be sourced both from recent regional phytoplankton blooms that add labile organic matter to the surface ocean and from long-term global processes, such as the upwelling of old refractory dissolved organic matter from the deep ocean. Understanding the formation of marine aerosols and their propensity to catalyze cloud formation processes are challenges that must be addressed given the major uncertainties associated with aerosols in climate models.

Bubble bursting as an aerosol generation mechanism during an oil spill in the deep-sea environment: laboratory experimental demonstration of the transport pathway.

PubMed

Ehrenhauser, Franz S; Avij, Paria; Shu, Xin; Dugas, Victoria; Woodson, Isaiah; Liyana-Arachchi, Thilanga; Zhang, Zenghui; Hung, Francisco R; Valsaraj, Kalliat T

2014-01-01

Oil spills in the deep-sea environment such as the 2010 Deep Water Horizon oil spill in the Gulf of Mexico release vast quantities of crude oil into the sea-surface environment. Various investigators have discussed the marine transport and fate of the oil into different environmental compartments (air, water, sediment, and biota). The transport of the oil into the atmosphere in these previous investigations has been limited to only evaporation, a volatility dependent pathway. In this work, we studied the aerosolization of oil spill matter via bursting bubbles as they occur during whitecaps in a laboratory aerosolization reactor. By evaluating the alkane content in oil mousse, crude oil, the gas phase, and particulate matter we clearly demonstrate that aerosolization via bursting bubbles is a solubility and volatility independent transport pathway for alkanes. The signature of alkane fractions in the native oil and aerosolized matter matched well especially for the less volatile alkanes (C20-C29). Scanning electron microscope interfaced with energy dispersive X-ray images identified the carbon fractions associated with salt particles of aerosols. Theoretical molecular dynamics simulations in the accompanying paper lend support to the observed propensity for alkanes at air-salt water interfaces of breaking bubbles and the produced droplets. The presence of a dispersant in the aqueous phase increased the oil ejection rate at the surface especially for the C20-C29 alkanes. The information presented here emphasizes the need to further study sea-spray aerosols as a possible transport vector for spilled oil in the sea surface environment.

Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

NASA Astrophysics Data System (ADS)

Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

2015-08-01

= 4 × 10-4 JNO2. Modeling results indicate that this photolytic loss rate would decrease SOA mass by 40-60 % for most species after 10 days of equivalent atmospheric aging at mid-latitudes in the summer. It should be noted that in our simulations we do not consider in-particle or aqueous-phase reactions which could modify the chemical composition of the particle and thus the quantity of photolabile species. The atmospheric implications of our results are significant for both the SOA global distribution and lifetime. GEOS-Chem global model results suggest that particle-phase photolytic reactions could be an important loss process for SOA in the atmosphere, removing aerosols from the troposphere on timescales of less than 7 days that are comparable to wet deposition.

Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

DOE PAGES

Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; ...

2015-08-20

photolysis rate of J SOA = 4 × 10 −4 J NO2. Modeling results indicate that this photolytic loss rate would decrease SOA mass by 40–60 % for most species after 10 days of equivalent atmospheric aging at mid-latitudes in the summer. It should be noted that in our simulations we do not consider in-particle or aqueous-phase reactions which could modify the chemical composition of the particle and thus the quantity of photolabile species. The atmospheric implications of our results are significant for both the SOA global distribution and lifetime. GEOS-Chem global model results suggest that particle-phase photolytic reactions could be an important loss process for SOA in the atmosphere, removing aerosols from the troposphere on timescales of less than 7 days that are comparable to wet deposition.« less

Aqueous Two Phase System Assisted Self-Assembled PLGA Microparticles

NASA Astrophysics Data System (ADS)

Yeredla, Nitish; Kojima, Taisuke; Yang, Yi; Takayama, Shuichi; Kanapathipillai, Mathumai

2016-06-01

Here, we produce poly(lactide-co-glycolide) (PLGA) based microparticles with varying morphologies, and temperature responsive properties utilizing a Pluronic F127/dextran aqueous two-phase system (ATPS) assisted self-assembly. The PLGA polymer, when emulsified in Pluronic F127/dextran ATPS, forms unique microparticle structures due to ATPS guided-self assembly. Depending on the PLGA concentration, the particles either formed a core-shell or a composite microparticle structure. The microparticles facilitate the simultaneous incorporation of both hydrophobic and hydrophilic molecules, due to their amphiphilic macromolecule composition. Further, due to the lower critical solution temperature (LCST) properties of Pluronic F127, the particles exhibit temperature responsiveness. The ATPS based microparticle formation demonstrated in this study, serves as a novel platform for PLGA/polymer based tunable micro/nano particle and polymersome development. The unique properties may be useful in applications such as theranostics, synthesis of complex structure particles, bioreaction/mineralization at the two-phase interface, and bioseparations.

Pathways of sulfate enhancement by natural and anthropogenic mineral aerosols in China

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

Huang, Xin; Song, Yu; Zhao, Chun

2014-12-27

China, the world’s largest consumer of coal, emits approximately 30 million tons of sulfur dioxide (SO₂) per year. SO₂ is subsequently oxidized to sulfate in the atmosphere. However, large gaps exist between model-predicted and measured sulfate levels in China. Long-term field observations and numerical simulations were integrated to investigate the effect of mineral aerosols on sulfate formation. We found that mineral aerosols contributed a nationwide average of approximately 22% to sulfate production in 2006. The increased sulfate concentration was approximately 2 μg m⁻³ in the entire China. In East China and the Sichuan Basin, the increments reached 6.3 μg m⁻³more » and 7.3 μg m⁻³, respectively. Mineral aerosols led to faster SO₂ oxidation through three pathways. First, more SO₂ was dissolved as cloud water alkalinity increased due to water-soluble mineral cations. Sulfate production was then enhanced through the aqueous-phase oxidation of S(IV) (dissolved sulfur in oxidation state +4). The contribution to the national sulfate production was 5%. Second, sulfate was enhanced through S(IV) catalyzed oxidation by transition metals. The contribution to the annual sulfate production was 8%, with 19% during the winter that decreased to 2% during the summer. Third, SO₂ reacts on the surface of mineral aerosols to produce sulfate. The contribution to the national average sulfate concentration was 9% with 16% during the winter and a negligible effect during the summer. The inclusion of mineral aerosols does resolve model discrepancies with sulfate observations in China, especially during the winter. These three pathways, which are not fully considered in most current chemistry-climate models, will significantly impact assessments regarding the effects of aerosol on climate change in China.« less

Ruthenium on rutile catalyst, catalytic system, and method for aqueous phase hydrogenations

DOEpatents

Elliot, Douglas C.; Werpy, Todd A.; Wang, Yong; Frye, Jr., John G.

2001-01-01

An essentially nickel- and rhenium-free catalyst is described comprising ruthenium on a titania support where the titania is greater than 75% rutile. A catalytic system containing a nickel-free catalyst comprising ruthenium on a titania support where the titania is greater than 75% rutile, and a method using this catalyst in the hydrogenation of an organic compound in the aqueous phase is also described.

Separation of four flavonol glycosides from Solanum rostratum Dunal using aqueous two-phase flotation followed by preparative high-performance liquid chromatography.

PubMed