Measurements of Hygroscopicity- and Size-Resolved Sea Spray Aerosol

NASA Astrophysics Data System (ADS)

Phillips, B.; Dawson, K. W.; Royalty, T. M.; Reed, R. E.; Petters, M.; Meskhidze, N.

2015-12-01

Atmospheric aerosols play a central role in many environmental processes by influencing the Earth's radiative balance, tropospheric chemistry, clouds, biogeochemical cycles, and visibility as well as adversely impacting human health. Based on their origin, atmospheric aerosols can be defined as anthropogenic or natural. Recent studies have shown that a large fraction of uncertainty in the radiative effects of anthropogenic aerosols is related to uncertainty in natural—background—aerosols. Marine aerosols are of particular interest due to the abundance of oceans covering the Earth's surface. Despite their importance, limited information is currently available for size- and composition-resolved marine aerosol emission fluxes. Our group has designed and built an instrument for measuring the size- and hygroscopicity-resolved sea spray aerosol fluxes. The instrument was first deployed during spring 2015 at the end of the 560 m pier of the US Army Corps of Engineers' Field Research Facility in Duck, NC. Measurements include 200 nm-sized diameter growth factor (hygroscopicity) distributions, sea spray particle flux measurements, and total sub-micron sized aerosol concentration. Ancillary ocean data includes salinity, pH, sea surface temperature, dissolved oxygen content, and relative fluorescence (proxy for [Chl-a]). Hygroscopicity distribution measurements show two broad peaks, one indicative of organics and sulfates and another suggestive of sea salt. The fraction of 200 nm-sized salt particles having hygroscopicity similar to that of sea-spray aerosol contributes up to ~24% of the distribution on days with high-speed onshore winds and up to ~3% on calm days with winds blowing from the continent. However, the total concentration of sea-spray-like particles originating from offshore versus onshore winds was relatively similar. Changes in the relative contribution of sea-salt to number concentration were caused by a concomitant changes in total aerosol concentration, indicating a local source.

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

Hand, Jenny L.; Day, Derek E.; McMeeking, Gavin M.

During the 2006 FLAME study (Fire Laboratory at Missoula Experiment), laboratory burns of biomass fuels were performed to investigate the physico-chemical, optical, and hygroscopic properties of fresh biomass smoke. As part of the experiment, two nephelometers simultaneously measured dry and humidified light scattering coefficients (bsp(dry) and bsp(RH), respectively) in order to explore the role of relative humidity (RH) on the optical properties of biomass smoke aerosols. Results from burns of several biomass fuels showed large variability in the humidification factor (f(RH) = bsp(RH)/bsp(dry)). Values of f(RH) at RH=85-90% ranged from 1.02 to 2.15 depending on fuel type. We incorporated measuredmore » chemical composition and size distribution data to model the smoke hygroscopic growth to investigate the role of inorganic and organic compounds on water uptake for these aerosols. By assuming only inorganic constituents were hygroscopic, we were able to model the water uptake within experimental uncertainty, suggesting that inorganic species were responsible for most of the hygroscopic growth. In addition, humidification factors at 85-90% RH increased for smoke with increasing inorganic salt to carbon ratios. Particle morphology as observed from scanning electron microscopy revealed that samples of hygroscopic particles contained soot chains either internally or externally mixed with inorganic potassium salts, while samples of weak to non-hygroscopic particles were dominated by soot and organic constituents. This study provides further understanding of the compounds responsible for water uptake by young biomass smoke, and is important for accurately assessing the role of smoke in climate change studies and visibility regulatory efforts.« less

Hygroscopic properties of potassium chloride and its internal mixtures with organic compounds relevant to biomass burning aerosol particles

PubMed Central

Jing, Bo; Peng, Chao; Wang, Yidan; Liu, Qifan; Tong, Shengrui; Zhang, Yunhong; Ge, Maofa

2017-01-01

While water uptake of aerosols exerts considerable impacts on climate, the effects of aerosol composition and potential interactions between species on hygroscopicity of atmospheric particles have not been fully characterized. The water uptake behaviors of potassium chloride and its internal mixtures with water soluble organic compounds (WSOCs) related to biomass burning aerosols including oxalic acid, levoglucosan and humic acid at different mass ratios were investigated using a hygroscopicity tandem differential mobility analyzer (HTDMA). Deliquescence points of KCl/organic mixtures were observed to occur at lower RH values and over a broader RH range eventually disappearing at high organic mass fractions. This leads to substantial under-prediction of water uptake at intermediate RH. Large discrepancies for water content between model predictions and measurements were observed for KCl aerosols with 75 wt% oxalic acid content, which is likely due to the formation of less hygroscopic potassium oxalate from interactions between KCl and oxalic acid without taken into account in the model methods. Our results also indicate strong influence of levoglucosan on hygroscopic behaviors of multicomponent mixed particles. These findings are important in further understanding the role of interactions between WSOCs and inorganic salt on hygroscopic behaviors and environmental effects of atmospheric particles. PMID:28240258

Hygroscopic properties of potassium chloride and its internal mixtures with organic compounds relevant to biomass burning aerosol particles.

PubMed

Jing, Bo; Peng, Chao; Wang, Yidan; Liu, Qifan; Tong, Shengrui; Zhang, Yunhong; Ge, Maofa

2017-02-27

While water uptake of aerosols exerts considerable impacts on climate, the effects of aerosol composition and potential interactions between species on hygroscopicity of atmospheric particles have not been fully characterized. The water uptake behaviors of potassium chloride and its internal mixtures with water soluble organic compounds (WSOCs) related to biomass burning aerosols including oxalic acid, levoglucosan and humic acid at different mass ratios were investigated using a hygroscopicity tandem differential mobility analyzer (HTDMA). Deliquescence points of KCl/organic mixtures were observed to occur at lower RH values and over a broader RH range eventually disappearing at high organic mass fractions. This leads to substantial under-prediction of water uptake at intermediate RH. Large discrepancies for water content between model predictions and measurements were observed for KCl aerosols with 75 wt% oxalic acid content, which is likely due to the formation of less hygroscopic potassium oxalate from interactions between KCl and oxalic acid without taken into account in the model methods. Our results also indicate strong influence of levoglucosan on hygroscopic behaviors of multicomponent mixed particles. These findings are important in further understanding the role of interactions between WSOCs and inorganic salt on hygroscopic behaviors and environmental effects of atmospheric particles.

Hygroscopic properties of potassium chloride and its internal mixtures with organic compounds relevant to biomass burning aerosol particles

NASA Astrophysics Data System (ADS)

Jing, Bo; Peng, Chao; Wang, Yidan; Liu, Qifan; Tong, Shengrui; Zhang, Yunhong; Ge, Maofa

2017-02-01

While water uptake of aerosols exerts considerable impacts on climate, the effects of aerosol composition and potential interactions between species on hygroscopicity of atmospheric particles have not been fully characterized. The water uptake behaviors of potassium chloride and its internal mixtures with water soluble organic compounds (WSOCs) related to biomass burning aerosols including oxalic acid, levoglucosan and humic acid at different mass ratios were investigated using a hygroscopicity tandem differential mobility analyzer (HTDMA). Deliquescence points of KCl/organic mixtures were observed to occur at lower RH values and over a broader RH range eventually disappearing at high organic mass fractions. This leads to substantial under-prediction of water uptake at intermediate RH. Large discrepancies for water content between model predictions and measurements were observed for KCl aerosols with 75 wt% oxalic acid content, which is likely due to the formation of less hygroscopic potassium oxalate from interactions between KCl and oxalic acid without taken into account in the model methods. Our results also indicate strong influence of levoglucosan on hygroscopic behaviors of multicomponent mixed particles. These findings are important in further understanding the role of interactions between WSOCs and inorganic salt on hygroscopic behaviors and environmental effects of atmospheric particles.

Internally mixed sea salt, soot, and sulfates at Macao, a coastal city in South China.

PubMed

Li, Weijun; Shao, Longyi; Shen, Rongrong; Yang, Shusheng; Wang, Zhishi; Tang, Uwa

2011-11-01

Direct observation of the mixing state of aerosol particles in a coastal urban city is critical to understand atmospheric processing and hygroscopic growth in humid air. Morphology, composition, and mixing state of individual aerosol particles from Macao, located south of the Pearl River Delta (PRD) and 100 km west of Hong Kong, were investigated using scanning electron microscopy (SEM) and transmission electron microscopy coupled with energy-dispersive X-ray spectrometry (TEM/EDX). SEM images show that soot and roughly spherical particles are prevalent in the samples. Based on the compositions of individual aerosol particles, aerosol particles with roughly spherical shape are classified into coarse Na-rich and fine S-rich particles. TEM/EDX indicates that each Na-rich particle consists of a Na-S core and NaNO3 shell. Even in the absence of heavy pollution, the marine sea salt particles were completely depleted in chloride, and Na-related sulfates and nitrates were enriched in Macao air. The reason could be that SO2 from the polluted PRD and ships in the South China Sea and NO2 from vehicles in the city sped up the chlorine depletion in sea salt through heterogeneous reactions. Fresh soot particles from vehicular emissions mainly occur near curbside. However, there are many aged soot particles in the sampling site surrounded by main roads 200 to 400 m away, suggesting that the fresh soot likely underwent a quick aging. Overall, secondary nitrates and sulfates internally mixed with soot and sea salt particles can totally change their surface hygroscopicity in coastal cities.

Control of binder viscosity and hygroscopicity on particle aggregation efficiency

NASA Astrophysics Data System (ADS)

Mueller, Sebastian B.; Kueppers, Ulrich; Ayris, Paul M.; Jacob, Michael; Delmelle, Pierre; Dingwell, Donald B.

2016-04-01

In the course of explosive volcanic eruptions, large amounts of ash are released into the atmosphere and may subsequently pose a threat to infrastructure, such as aviation industry. Ash plume forecasting is therefore a crucial tool for volcanic hazard mitigation but may be significantly affected by aggregation, altering the aerodynamic properties of particles. Models struggle with the implementation of aggregation since external conditions promoting aggregation have not been completely understood; in a previous study we have shown the rapid generation of ash aggregates through liquid bonding via the use of fluidization bed technology and further defined humidity and temperature ranges necessary to trigger aggregation. Salt (NaCl) was required for the recovery of stable aggregates, acting as a cementation agent and granting aggregate cohesion. A numerical model was used to explain the physics behind particle aggregation mechanisms and further predicted a dependency of aggregation efficiency on liquid binder viscosity. In this study we proof the effect of viscosity on particle aggregation. HCl and H2SO4 solutions were diluted to various concentrations resulting in viscosities between 1 and 2 mPas. Phonolitic and rhyolitic ash samples as well as soda-lime glass beads (serving as analogue material) were fluidized in the ProCell Lab® of Glatt Ingenieurtechnik GmbH and treated with the acids via a bottom-spray technique. Chemically driven interaction between acid liquids and surfaces of the three used materials led to crystal precipitation. Salt crystals (e.g. NaCl) have been confirmed through scanning electron microscopy (SEM) and leachate analysis. Both volcanic ash samples as well as the glass beads showed a clear dependency of aggregation efficiency on viscosity of the sprayed HCl solution. Spraying H2SO4 provoked a collapse of the fluidized bed and no aggregation has been observed. This is accounted by the high hygroscopicity of H2SO4. Dissolving CaCl2 (known to be a highly hygroscopic salt) in de-ionized water yielded comparable results without observable aggregation. In case of successful aggregation, concentration of salts has been found to be in the range of published values. We conclude that non-hygroscopic salt crystal precipitation from an aqueous liquid interacting with the glass phase in volcanic ash is a very efficient way to produce cohesive ash aggregates that can survive external forces acting during transport and sedimentation.

Does the long-range transport of African mineral dust across the Atlantic enhance their hygroscopicity?

NASA Astrophysics Data System (ADS)

Denjean, Cyrielle; Caquineau, Sandrine; Desboeufs, Karine; Laurent, Benoit; Quiñones Rosado, Mariana; Vallejo, Pamela; Mayol-Bracero, Olga; Formenti, Paola

2015-04-01

Influence of mineral dust on radiation balance is largely dependent on their ability to interact with water. While fresh mineral dusts are highly hydrophobic, various transformation processes (coagulation, heterogeneous chemical reaction) can modify the dust physical and chemical properties during long-range transport, which, in turn, can change the dust hygroscopic properties. The model predictions of the radiative effect by mineral dust still suffer of the lack of certainty of dust hygroscopic properties, and their temporal evolution during long-range transport. We present the first direct surface measurements of the hygroscopicity of Saharan dust after long-range transport over the Atlantic Ocean, their relationship with chemical composition, their influence on particle size and shape and implications for optical properties. Particles were collected during the DUST Aging and TransporT from Africa to the Caribbean (Dust-AttaCk) campaign at the Cape San Juan Puerto Rico station in June-July 2012. Environmental scanning electron microscopy (ESEM) was used to analyze the size, shape, chemical composition and hygroscopic properties of individual particles. At different levels of concentrations in summertime, the coarse mode of atmospheric aerosols in Puerto Rico is dominated by Saharan mineral dust. Most of aged dust particles survived atmospheric transport intact with no observed internal mixture with other species and did not show hygroscopic growth up to 94% relative humidity. This is certainly due to the fact that in summertime dust is mostly transported above the marine boundary layer. A minor portion of mineral dust (approximately 19-28% by number) were involved in atmospheric heterogeneous reactions with acidic gases (likely SO2 and HCl) and sea salt aggregation. While sulfate- and chloride-coated dust remained extremely hydrophobic, dust particles in internal mixing with NaCl underwent profound changes in their hygroscopicity, therefore in size and shape. We show that this change in particles size has important implications for their ability to scatter and absorb light. This behavior is also important for cloud properties since the increase of particles size reduces the supersaturating required for cloud droplet activation.

Observations and implications of liquid–liquid phase separation at high relative humidities in secondary organic material produced by α-pinene ozonolysis without inorganic salts

DOE PAGES

Renbaum-Wolff, Lindsay; Song, Mijung; Marcolli, Claudia; ...

2016-07-01

Particles consisting of secondary organic material (SOM) are abundant in the atmosphere. In order to predict the role of these particles in climate, visibility and atmospheric chemistry, information on particle phase state (i.e., single liquid, two liquids and solid) is needed. Our paper focuses on the phase state of SOM particles free of inorganic salts produced by the ozonolysis of α-pinene. Phase transitions were investigated in the laboratory using optical microscopy and theoretically using a thermodynamic model at 290 K and for relative humidities ranging from < 0.5 to 100%. In the laboratory studies, a single phase was observed frommore » 0 to 95% relative humidity (RH) while two liquid phases were observed above 95% RH. For increasing RH, the mechanism of liquid–liquid phase separation (LLPS) was spinodal decomposition. The RH range over which two liquid phases were observed did not depend on the direction of RH change. In the modeling studies, the SOM took up very little water and was a single organic-rich phase at low RH values. At high RH, the SOM underwent LLPS to form an organic-rich phase and a water-rich phase, consistent with the laboratory studies. The presence of LLPS at high RH values can have consequences for the cloud condensation nuclei (CCN) activity of SOM particles. In the simulated Köhler curves for SOM particles, two local maxima were observed. Depending on the composition of the SOM, the first or second maximum can determine the critical supersaturation for activation. Recently researchers have observed inconsistencies between measured CCN properties of SOM particles and hygroscopic growth measured below water saturation (i.e., hygroscopic parameters measured below water saturation were inconsistent with hygroscopic parameters measured above water saturation). Furthermore, the work presented here illustrates that such inconsistencies are expected for systems with LLPS when the water uptake at subsaturated conditions represents the hygroscopicity of an organic-rich phase while the barrier for CCN activation can be determined by the second maximum in the Köhler curve when the particles are water rich.« less

Quartz Crystal Microbalance: Aerosol Viscoelastic Measurement Calibration and Subsiquent H2O Uptake

NASA Astrophysics Data System (ADS)

Farland, D. R., Jr.; Gilles, M. K.; Harder, T.; Weis, J.; Mueller, S.

2015-12-01

Aerosol particles exposed to various atmospheric relative humidity (RH) levels exhibit hygroscopic properties which are not fully understood. Water adsorption or diffusion depends on particle viscosity in semi-solid to liquid states. This relationship between particle viscosity as a function of RH and the corresponding hygroscopic behavioral response is the purpose of this study. However, reliable techniques for viscosity quantification have been limited. A Quartz Crystal Microbalance with Dissipation (QCM-D) was used for viscosity measurements and to determine phase changes. Prior to studies on field samples, microscope immersion/viscosity standard oils, salt crystals, sugars and alpha-pinene secondary organic aerosol (SOA) surrogates are used for viscosity, RH calibrations, water uptake and phase change measurements. RH was controlled by flowing N2 gas saturated with H2O for RH's between 0-75% RH. For higher RH values, (75-100% RH range) saturated salt solutions were flowed over a gore membrane to protect the QCM sensor from direct contact with the solutions. The viscosity calibration constructed via QTools fitting software illustrates the limitations as well as the ranges of reliability of the QCM viscosity measurements. Deliquescing salt crystals of differing deliquescence relative humidity's (DRH), sugars and alpha-pinene SOA's provided insight into the detection of various phase change behaviors. Water uptake experiments performed on alpha-pinene SOA and sucrose sugar yielded significantly different frequency and dissipation responses than the deliquescing salts. Future work will apply these experimental methods and analysis on aerosol particles collected during the GoAmazon field campaign.

Hygroscopic growth and cloud droplet activation of xanthan gum as a proxy for marine hydrogels

NASA Astrophysics Data System (ADS)

Dawson, K. W.; Petters, M. D.; Meskhidze, N.; Petters, S. Suda; Kreidenweis, S. M.

2016-10-01

Knowledge of the physical characteristics and chemical composition of marine organic aerosols is needed for the quantification of their effects on cloud microphysical processes and solar radiative transfer. Here we use xanthan gum (XG)—a bacterial biopolymer—as a proxy for marine hydrogels. Measurements were performed for pure XG particles and mixtures of XG with sodium chloride, calcium nitrate, and calcium carbonate. The aerosol hygroscopicity parameter (κ) is derived from hygroscopic growth factor measurements (κgf) at variable water activity (aw) and from cloud condensation nuclei activation efficiency (κccn). The Zdanovskii, Stokes, and Robinson (ZSR) hygroscopicity parameter derived for multicomponent systems (κmix, sol) is used to compare measurements of κgf and κccn. Pure XG shows close agreement of κgf (at aw = 0.9) and κccn of 0.09 and 0.10, respectively. Adding salts to the system results in deviations of κgf (at aw = 0.9) from κccn. The measured κgf and ZSR-derived hygroscopicity parameter (κmix, sol) values for different solutions show close agreement at aw > 0.9, while κgf is lower in comparison to κmix, sol at aw < 0.9. The differences between predicted κmix, sol and measured κgf and κccn values are explained by the effects of hydration and presence of salt ions on the structure of the polymer networks. Results from this study imply that at supersaturations of 0.1 and 0.5%, the presence of 30% sea salt by mass can reduce the activation diameter of pure primary marine organic aerosols from 257 to 156 nm and from 87 to 53 nm, respectively.

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.

Seasonal variation of fractionated sea-salt particles on the Antarctic coast

NASA Astrophysics Data System (ADS)

Hara, K.; Osada, K.; Yabuki, M.; Yamanouchi, T.

2012-09-01

Aerosol sampling was conducted at Syowa Station, Antarctica (coastal station) in 2004-2006. SO42-depletion by mirabilite precipitation was identified from April through November. The fractionated sea-salt particles were distributed in ultrafine- coarse modes. Molar ratios of Mg2+/Na+ and K+/Na+ were higher than in bulk seawater ratio during winter-spring. The Mg2+/Na+ ratio in aerosols greatly exceeded the upper limit in the case only with mirabilite precipitation. The temperature dependence of Mg2+/Na+ ratio strongly suggested that higher ratios of Mg2+/Na+ and K+/Na+ were associated with sea-salt fractionation by precipitation of mirabilite at -9°C, hydrohalite at ca. -23°C and other salts such as ikaite at ca. -5°C and gypsum at ca. -22°C during winter-spring. Mg-salts with lower deliquescence relative humidity can be enriched gradually in the fractionated sea-salt particles. Results suggests that sea-salt fractionation can alter aerosol hygroscopicity and atmospheric chemistry in polar regions.

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.

Synthesis and properties of acetamidinium salts

PubMed Central

2011-01-01

Background Acetamidines are starting materials for synthesizing many chemical substances, such as imidazoles, pyrimidines and triazines, which are further used for biochemically active compounds as well as energetic materials. The aim of this study was to synthesise and characterise a range of acetamidinium salts in order to overcome the inconvenience connected with acetamidinium chloride, which is the only commercially available acetamidinium salt. Results Acetamidinium salts were synthesised and characterised by elemental analysis, mass spectrometry, NMR and - in the case of energetic salts - DTA. The structures of previously unknown acetamidinium salts were established by X-ray diffraction analysis. Hygroscopicities in 90% humidity of eight acetamidinium salts were evaluated. Conclusions The different values of hygroscopicity are corroborated by the structures determined by X-ray analysis. The acetamidinium salts with 2D layered structures (acetamidinium nitrate, formate, oxalate and dinitromethanide) show a lack of hygroscopicity, and the compounds with 3D type of structure (acetamidinium chloride, acetate, sulphate and perchlorate) and possessing rather large cavities are quite hygroscopic. PMID:22152129

Liquid–liquid phase separation in particles containing secondary organic material free of inorganic salts

DOE PAGES

Song, Mijung; Liu, Pengfei; Martin, Scot T.; ...

2017-09-25

Particles containing secondary organic material (SOM) are ubiquitous in the atmosphere and play a role in climate and air quality. Recently, research has shown that liquid–liquid phase separation (LLPS) occurs at high relative humidity (RH) (greater than ~95 %) in α-pinene-derived SOM particles free of inorganic salts, while LLPS does not occur in isoprene-derived SOM particles free of inorganic salts. We expand on these findings by investigating LLPS at 290 ± 1 K in SOM particles free of inorganic salts produced from ozonolysis of β-caryophyllene, ozonolysis of limonene, and photo-oxidation of toluene. LLPS was observed at greater than ~95 %more » RH in the biogenic SOM particles derived from β-caryophyllene and limonene while LLPS was not observed in the anthropogenic SOM particles derived from toluene. This work combined with the earlier work on LLPS in SOM particles free of inorganic salts suggests that the occurrence of LLPS in SOM particles free of inorganic salts is related to the oxygen-to-carbon elemental ratio (O : C) of the organic material. These results help explain the difference between the hygroscopic parameter κ of SOM particles measured above and below water saturation in the laboratory and field, and have implications for predicting the cloud condensation nucleation properties of SOM particles.« less

Liquid–liquid phase separation in particles containing secondary organic material free of inorganic salts

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

Song, Mijung; Liu, Pengfei; Martin, Scot T.

Particles containing secondary organic material (SOM) are ubiquitous in the atmosphere and play a role in climate and air quality. Recently, research has shown that liquid–liquid phase separation (LLPS) occurs at high relative humidity (RH) (greater than ~95 %) in α-pinene-derived SOM particles free of inorganic salts, while LLPS does not occur in isoprene-derived SOM particles free of inorganic salts. We expand on these findings by investigating LLPS at 290 ± 1 K in SOM particles free of inorganic salts produced from ozonolysis of β-caryophyllene, ozonolysis of limonene, and photo-oxidation of toluene. LLPS was observed at greater than ~95 %more » RH in the biogenic SOM particles derived from β-caryophyllene and limonene while LLPS was not observed in the anthropogenic SOM particles derived from toluene. This work combined with the earlier work on LLPS in SOM particles free of inorganic salts suggests that the occurrence of LLPS in SOM particles free of inorganic salts is related to the oxygen-to-carbon elemental ratio (O : C) of the organic material. These results help explain the difference between the hygroscopic parameter κ of SOM particles measured above and below water saturation in the laboratory and field, and have implications for predicting the cloud condensation nucleation properties of SOM particles.« less

Liquid-liquid phase separation in particles containing secondary organic material free of inorganic salts

NASA Astrophysics Data System (ADS)

Song, Mijung; Liu, Pengfei; Martin, Scot T.; Bertram, Allan K.

2017-09-01

Particles containing secondary organic material (SOM) are ubiquitous in the atmosphere and play a role in climate and air quality. Recently, research has shown that liquid-liquid phase separation (LLPS) occurs at high relative humidity (RH) (greater than ˜ 95 %) in α-pinene-derived SOM particles free of inorganic salts, while LLPS does not occur in isoprene-derived SOM particles free of inorganic salts. We expand on these findings by investigating LLPS at 290 ± 1 K in SOM particles free of inorganic salts produced from ozonolysis of β-caryophyllene, ozonolysis of limonene, and photo-oxidation of toluene. LLPS was observed at greater than ˜ 95 % RH in the biogenic SOM particles derived from β-caryophyllene and limonene while LLPS was not observed in the anthropogenic SOM particles derived from toluene. This work combined with the earlier work on LLPS in SOM particles free of inorganic salts suggests that the occurrence of LLPS in SOM particles free of inorganic salts is related to the oxygen-to-carbon elemental ratio (O : C) of the organic material. These results help explain the difference between the hygroscopic parameter κ of SOM particles measured above and below water saturation in the laboratory and field, and have implications for predicting the cloud condensation nucleation properties of SOM particles.

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

NASA Astrophysics Data System (ADS)

Sullivan, Ryan Christopher

Mineral dust particles are a major component of tropospheric aerosol mass and affect regional and global atmospheric chemistry and climate. Dust particles experience heterogeneous reactions with atmospheric gases that alter the gas and particle-phase chemistry. These in turn influence the warm and cold cloud nucleation ability and optical properties of the dust particles. This dissertation investigates the atmospheric chemistry of mineral dust particles and their role in warm cloud nucleation through a combination of synergistic field measurements, laboratory experiments, and theoretical modeling. In-situ measurements made with a single-particle mass spectrometer during the ACE-Asia field campaign in 2001 provide the motivation for this work. The observed mixing state of the individual ambient particles with secondary organic and inorganic components is described in Chapter 2. A large Asian dust storm occurred during the campaign and produced dramatic changes in the aerosol's composition and mixing state. The effect of particle size and mineralogy on the atmospheric processing of individual dust particles is explored in Chapters 3 & 4. Sulfate was found to accumulate preferentially in submicron iron and aluminosilicate-rich dust particles, while nitrate and chloride were enriched in supermicron calcite-rich dust. The mineral dust (and sea salt particles) were also enriched in oxalic acid, the dominant component of water soluble organic carbon. Chapter 5 explores the roles of gas-phase photochemistry and partitioning of the diacids to the alkaline particles in producing this unique behavior. The effect of the dust's mixing state with secondary organic and inorganic components on the dust particles' solubility, hygroscopicity, and thus warm cloud nucleation properties is explored experimentally and theoretically in Chapter 6. Cloud condensation nucleation (CCN) activation curves revealed that while calcium nitrate and calcium chloride particles were very hygroscopic and CCN-active, due to the high solubility of these compounds, calcium sulfate and calcium oxalate were not. Particles composed of these two sparingly soluble compounds had apparent hygroscopicities similar to pure calcium carbonate. This implies that the commonly made assumption that all dust particles become more hygroscopic after atmospheric processing must be revisited. Calcium sulfate and oxalate represent two forms of aged mineral dust particles that remain non-hygroscopic and thus have poor CCN nucleation ability. The particle generation method (dry versus wet) was found to significantly affect the chemistry and hygroscopicity of the aerosolized particles. Finally, in Chapter 7 the timescale for the atmospheric conversion of insoluble calcite particles to soluble, CCN-active calcium nitrate particles was derived from aerosol flow tube experiments. The reaction rate is rapid was used to estimate the conversion of calcite particles to very hygroscopic particles can occur in just a few hours of exposure to tropospheric levels of nitric acid. This process will therefore be controlled by the availability of nitric acid and its precursors, as opposed to the available atmospheric reaction time.

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.

Hygroscopic Growth and Activation of Particles containing Algea-Exudate

NASA Astrophysics Data System (ADS)

Wex, Heike; Fuentes, Elena; Tsagkogeorgas, Georgios; Voigtländer, Jens; Clauss, Tina; Kiselev, Alexei; Green, David; Coe, Hugh; McFiggans, Gordon; Stratmann, Frank

2010-05-01

A large amount of the Earth is covered by oceans, which provide a constant source of marine aerosol particles, produced due to bubble bursting processes that depend on wind speed (O'Dowd and de Leeuw, 2007). In general, marine particles can be assumed to play an important role for the Earth atmosphere on a global scale, due to their abundance and due to their effect on clouds. E.g. marine stratus and stratocumulus clouds contribute about 30% to 40% to the Earth's albedo (Randall et al., 1984). The activation of aerosol particles to cloud droplets depends on the hygroscopic properties of the particles, which, in turn, depend on their chemical composition. For marine particles, is has been and still is discussed what the effects of organic substances being present in the particles might be. These substances originate from marine biota where they enrich at the ocean surface. To mimic marine aerosol particles, algae-exudates of different algae species were mixed with artificial sea-water. These samples were used in the laboratory to produce particles via a bubble bursting process (Fuentes et al., 2009). The hygroscopic growth and activation of the (size selected) particles was measured, using LACIS (Leipzig Aerosol Cloud Interaction Simulator, Stratmann et al., 2004) and the DMT-CCNc (Cloud Condensation Nucleus counter from Droplet Measurement Technologies, Roberts and Nenes, 2005). The hygroscopic growth was measured twice, 3 and 10 seconds after humidification, and no difference in the grown size was detected, i.e. no kinetic effect was observed for the examined time range. From LACIS and CCNc measurements, the hygroscopicity was deduced through determination of the amount of ions being effective in the particle / droplet solution (Rho(ion), Wex et al., 2007). A concentration dependent non-ideal behaviour was found for particles produced from an artificial sea-water sample that contained only inorganic salts, as can be expected (see e.g. Niedermeier et al., 2008). For particles containing also algae-exudate, however, the concentration dependent non-ideal behaviour was quenched, resulting in a quasi ideal solution behavior. Such solutions could be described by a single-parameter representation for all water-vapour saturations at which measurements had been done (from 0.8 up to supersaturation). References: Fuentes, E., H. Coe, D. Green, G. De Leeuw, and G. McFiggans (2009), Laboratory-generated primary marine aerosol via bubble-bursting and atomization, Aerosol Meas. Tech. Discuss., 2, 2281-2320. O'Dowd, C. D., and G. de Leeuw (2007), Marine aerosol production: A review of the current knowledge, Phil. Trans. R. Soc. A, 365(1856), 1753-1774, doi:1710.1098/rsta.2007.2043. Niedermeier, D., H. Wex, J. Voigtländer, F. Stratmann, E. Brüggemann, A. Kiselev, H. Henk, and J. Heintzenberg (2008), LACIS-measurements and parameterization of sea-salt particle hygroscopic growth and activation, Atmos. Chem. Phys., 8, 579-590. Randall, D. A., Coakley, J. A., Fairall, C. W., Kropfli, R. A., and Lenschow, D. H. (1984) Outlook for research on subtropical marine stratiform clouds, Bull. Am. Meteor. Soc., 65, 1290-1301, 1984. Roberts, G., and A. Nenes (2005), A continuous-flow streamwise thermal-gradient CCN chamber for atmospheric measurements, Aerosol Sci. Technol., 39, 206-221. Stratmann, F., A. Kiselev, S. Wurzler, M. Wendisch, J. Heintzenberg, R. J. Charlson, K. Diehl, H. Wex, and S. Schmidt (2004), Laboratory studies and numerical simulations of cloud droplet formation under realistic super-saturation conditions, J. Atmos. Oceanic Technol., 21, 876-887. Wex, H., T. Hennig, I. Salma, R. Ocskay, A. Kiselev, S. Henning, A. Massling, A. Wiedensohler, and F. Stratmann (2007), Hygroscopic growth and measured and modeled critical super-saturations of an atmospheric HULIS sample, Geophys. Res. Lett., 34(L02818), doi:10.1029/2006GL028260.

Measuring Mass-Based Hygroscopicity of Atmospheric Particles through in situ Imaging

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

Piens, Dominique` Y.; Kelly, Stephen T.; Harder, Tristan

Quantifying how atmospheric particles interact with water vapor is critical for understanding the effects of aerosols on climate. We present a novel method to measure the mass-based hygroscopicity of particles while characterizing their elemental and carbon functional group compositions. Since mass-based hygroscopicity is insensitive to particle geometry, it is advantageous for probing the hygroscopic behavior of atmospheric particles, which can have irregular morphologies. Combining scanning electron microscopy with energy dispersive X-ray analysis (SEM/EDX), scanning transmission X-ray microscopy (STXM) analysis, and in situ STXM humidification experiments, this method was validated using laboratory-generated, atmospherically relevant particles. Then, the hygroscopicity and elemental compositionmore » of 15 complex atmospheric particles were analyzed by leveraging quantification of C, N, and O from STXM, and complementary elemental quantification from SEM/EDX. We found three types of hygroscopic responses, and correlated high hygroscopicity with Na and Cl content. The mixing state determined for 158 particles broadly agreed with those of the humidified particles, indicating the potential to infer the atmospheric hygroscopic behavior from a selected subset of particles. These methods offer unique quantitative capabilities to characterize and correlate the hygroscopicity and chemistry of individual submicron atmospheric particles.« less

Measuring mass-based hygroscopicity of atmospheric particles through in situ imaging

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

Piens, Dominique S.; Kelly, Stephen T.; Harder, Tristan H.

Quantifying how atmospheric particles interact with water vapor is critical for understanding the effects of aerosols on climate. We present a novel method to measure the mass-based hygroscopicity of particles while characterizing their elemental and carbon functional group compositions. Since mass-based hygroscopicity is insensitive to particle geometry, it is advantageous for probing the hygroscopic behavior of atmospheric particles, which can have irregular morphologies. Combining scanning electron microscopy with energy dispersive X-ray analysis (SEM/EDX), scanning transmission X-ray microscopy (STXM) analysis, and in situ STXM humidification experiments, this method was validated using laboratory-generated, atmospherically relevant particles. Then, the hygroscopicity and elemental compositionmore » of 15 complex atmospheric particles were analyzed by leveraging quantification of C, N, and O from STXM, and complementary elemental quantification from SEM/EDX. We found three types of hygroscopic responses, and correlated high hygroscopicity with Na and Cl content. The mixing state of 158 other particles from the sample broadly agreed with those of the humidified particles, indicating the potential to infer atmospheric hygroscopic behavior from a selected subset of particles. As a result, these methods offer unique quantitative capabilities to characterize and correlate the hygroscopicity and chemistry of individual submicrometer atmospheric particles.« less

Measuring mass-based hygroscopicity of atmospheric particles through in situ imaging

DOE PAGES

Piens, Dominique S.; Kelly, Stephen T.; Harder, Tristan H.; ...

2016-04-18

Quantifying how atmospheric particles interact with water vapor is critical for understanding the effects of aerosols on climate. We present a novel method to measure the mass-based hygroscopicity of particles while characterizing their elemental and carbon functional group compositions. Since mass-based hygroscopicity is insensitive to particle geometry, it is advantageous for probing the hygroscopic behavior of atmospheric particles, which can have irregular morphologies. Combining scanning electron microscopy with energy dispersive X-ray analysis (SEM/EDX), scanning transmission X-ray microscopy (STXM) analysis, and in situ STXM humidification experiments, this method was validated using laboratory-generated, atmospherically relevant particles. Then, the hygroscopicity and elemental compositionmore » of 15 complex atmospheric particles were analyzed by leveraging quantification of C, N, and O from STXM, and complementary elemental quantification from SEM/EDX. We found three types of hygroscopic responses, and correlated high hygroscopicity with Na and Cl content. The mixing state of 158 other particles from the sample broadly agreed with those of the humidified particles, indicating the potential to infer atmospheric hygroscopic behavior from a selected subset of particles. As a result, these methods offer unique quantitative capabilities to characterize and correlate the hygroscopicity and chemistry of individual submicrometer atmospheric particles.« less

Thermodynamics Of Common Atmospheric Particles On The Nanoscale

NASA Astrophysics Data System (ADS)

Onasch, T.; Han, J.; Oatis, S.; Brechtel, F.; Imre, D. G.

2002-12-01

A significant fraction of atmospheric particles are hygroscopic by nature and exhibit the properties of deliquescence and efflorescence. Recent field studies have observed large nucleation events of hygroscopic particles and note discrepancies between predicted and observed particle growth rates after nucleation. These growth rates are governed, in part, by the thermodynamic properties of particles only a few nanometers in diameter. However, little thermodynamic information is currently available for nanometer?sized particles. The Kelvin relation indicates that the surface tension of a particle less than 100nm in diameter can dramatically affect the thermodynamics, and surface states may begin to influence the bulk physical properties in these small particles with high surface to volume ratios. In this context, we are investigating the thermodynamic properties, including pre-deliquescence water adsorption, deliquescence, efflorescence, and supersaturated particle compositions of nanoparticles with mobility diameters in the range of 5 to 50 nm. We have developed a temperature and humidity-controlled laboratory-based Nano Differential Mobility Analyzer (NDMA) system to characterize the hygroscopic properties of the common atmospheric salt particles as a function of size. Two different aerosol generation systems have been used to cover the full size range. The first system (less than 20nm diameter) relies on an Atomizer (TSI 3076) to produce particles which are size?selected using an initial DMA. For particle sizes smaller than 20 nm, the Electrospray Aerosol Generator (EAG, TSI 3480) has been employed as a particle source. The EAG characteristically provides narrow size distributions, comparable to the monodisperse size distribution from a DMA, but with higher number concentrations. Once generated, the monodisperse aerosol flow is then conditioned with respect to humidity at a constant temperature and subsequently analyzed using a TSI Ultrafine CPC (Model 3010) modified for Pulse-Height Analysis. The dry particle sizes are also continually monitored by an external SMPS system (TSI 3936) to rectify errors in the calculated growth factor resulting from any drift in the dry particle size. The size changes of the humidified particles are directly correlated with the relative humidity and temperature. Our results of ammonium sulfate particles from 5 - 50 nm in diameter are consistent with those predicted from the Kelvin relation. The particle size affects both deliquescence and efflorescence of the homogeneous salt particles: the deliquescence relative humidity increases and the efflorescence decreases as particles become smaller. In addition, although the smaller the particle size the more significant water adsorption, the sharp deliquescence phase transition was obvious regardless of the particle sizes. The implications with respect to these observations will be further discussed at the presentation.

Rupturing of Biological Spores As a Source of Secondary Particles in Amazonia.

PubMed

China, Swarup; Wang, Bingbing; Weis, Johannes; Rizzo, Luciana; Brito, Joel; Cirino, Glauber G; Kovarik, Libor; Artaxo, Paulo; Gilles, Mary K; Laskin, Alexander

2016-11-15

Airborne biological particles, such as fungal spores and pollen, are ubiquitous in the Earth's atmosphere and may influence the atmospheric environment and climate, impacting air quality, cloud formation, and the Earth's radiation budget. The atmospheric transformations of airborne biological spores at elevated relative humidity remain poorly understood and their climatic role is uncertain. Using an environmental scanning electron microscope (ESEM), we observed rupturing of Amazonian fungal spores and subsequent release of submicrometer size fragments after exposure to high humidity. We find that fungal fragments contain elements of inorganic salts (e.g., Na and Cl). They are hygroscopic in nature with a growth factor up to 2.3 at 96% relative humidity, thus they may potentially influence cloud formation. Due to their hygroscopic growth, light scattering cross sections of the fragments are enhanced by up to a factor of 10. Furthermore, rupturing of fungal spores at high humidity may explain the bursting events of new particle formation in Amazonia.

Desiccation by Foliar Deposition of Hygroscopic Aerosols may link Air Pollution to Forest Decline and Tree Mortality associated with Global-Change-Type Drought

NASA Astrophysics Data System (ADS)

Burkhardt, J.; Grantz, D. A.; Hunsche, M.; Pariyar, S.; Sutton, M. A.; Zinsmeister, D.

2016-12-01

Leaf surfaces are a major sink for atmospheric aerosol deposition. Plants benefit from aerosol associated nutrients and are able to increase deposition by leaf surface micromorphology. Recent studies have shown that deposited hygroscopic aerosols can also influence plant water relations. This might be an important issue even for remote forest ecosystems, given the strong anthropogenic influence on aerosol production and efficient atmospheric transport. We study processes of aerosol deposition to plant surfaces and their impact on water relations and drought tolerance, both for experimental particle amendment and for aerosol exclusion in filtered air (FA). FA plants experience an environment with < 10% concentration of hygroscopic aerosols compared to ambient air (AA), but no difference in trace gases. Increasing particle concentration leads to decreasing water use efficiency and increasing minimum epidermal conductance (gmin; a measure of uncontrolled water loss inversely related to drought tolerance). After particle amendment, anisohydric beech seedlings increased transpiration and maintained photosynthesis, while isohydric pine seedlings maintained transpiration and tended to reduce photosynthesis. FA seedlings of pine, oak, and fir showed lower gmin than corresponding AA seedlings. The results support the concept of hydraulic activation of stomata (HAS) and an associated wick action caused by leaf surface particles. Concentrated salt solutions formed by hygroscopicity even in unsaturated air may create a thin liquid film that penetrates the stomatal pore, allowing evaporation of liquid water at the leaf surface. Increased gmin suggests the significance of this process under ambient conditions. The direct impact of air pollution on plant drought tolerance is poorly integrated in current scenarios of forest decline and tree mortality, but might represent an important component.

Measurements of cloud condensation nuclei activity and droplet activation kinetics of wet processed regional dust samples and minerals

NASA Astrophysics Data System (ADS)

Kumar, P.; Sokolik, I. N.; Nenes, A.

2011-04-01

This study reports laboratory measurements of particle size distributions, cloud condensation nuclei (CCN) activity, and droplet activation kinetics of wet generated aerosols from clays, calcite, quartz, and desert soil samples from Northern Africa, East Asia/China, and Northern America. The dependence of critical supersaturation, sc, on particle dry diameter, Ddry, is used to characterize particle-water interactions and assess the ability of Frenkel-Halsey-Hill adsorption activation theory (FHH-AT) and Köhler theory (KT) to describe the CCN activity of the considered samples. Regional dust samples produce unimodal size distributions with particle sizes as small as 40 nm, CCN activation consistent with KT, and exhibit hygroscopicity similar to inorganic salts. Clays and minerals produce a bimodal size distribution; the CCN activity of the smaller mode is consistent with KT, while the larger mode is less hydrophilic, follows activation by FHH-AT, and displays almost identical CCN activity to dry generated dust. Ion Chromatography (IC) analysis performed on regional dust samples indicates a soluble fraction that cannot explain the CCN activity of dry or wet generated dust. A mass balance and hygroscopicity closure suggests that the small amount of ions (of low solubility compounds like calcite) present in the dry dust dissolve in the aqueous suspension during the wet generation process and give rise to the observed small hygroscopic mode. Overall these results identify an artifact that may question the atmospheric relevance of dust CCN activity studies using the wet generation method. Based on a threshold droplet growth analysis, wet generated mineral aerosols display similar activation kinetics compared to ammonium sulfate calibration aerosol. Finally, a unified CCN activity framework that accounts for concurrent effects of solute and adsorption is developed to describe the CCN activity of aged or hygroscopic dusts.

Linking variations in sea spray aerosol particle hygroscopicity to composition during two microcosm experiments

NASA Astrophysics Data System (ADS)

Forestieri, Sara D.; Cornwell, Gavin C.; Helgestad, Taylor M.; Moore, Kathryn A.; Lee, Christopher; Novak, Gordon A.; Sultana, Camille M.; Wang, Xiaofei; Bertram, Timothy H.; Prather, Kimberly A.; Cappa, Christopher D.

2016-07-01

The extent to which water uptake influences the light scattering ability of marine sea spray aerosol (SSA) particles depends critically on SSA chemical composition. The organic fraction of SSA can increase during phytoplankton blooms, decreasing the salt content and therefore the hygroscopicity of the particles. In this study, subsaturated hygroscopic growth factors at 85 % relative humidity (GF(85 %)) of predominately submicron SSA particles were quantified during two induced phytoplankton blooms in marine aerosol reference tanks (MARTs). One MART was illuminated with fluorescent lights and the other was illuminated with sunlight, referred to as the "indoor" and "outdoor" MARTs, respectively. Optically weighted GF(85 %) values for SSA particles were derived from measurements of light scattering and particle size distributions. The mean optically weighted SSA diameters were 530 and 570 nm for the indoor and outdoor MARTs, respectively. The GF(85 %) measurements were made concurrently with online particle composition measurements, including bulk composition (using an Aerodyne high-resolution aerosol mass spectrometer) and single particle (using an aerosol time-of-flight mass spectrometer) measurement, and a variety of water-composition measurements. During both microcosm experiments, the observed optically weighted GF(85 %) values were depressed substantially relative to pure inorganic sea salt by 5 to 15 %. There was also a time lag between GF(85 %) depression and the peak chlorophyll a (Chl a) concentrations by either 1 (indoor MART) or 3-to-6 (outdoor MART) days. The fraction of organic matter in the SSA particles generally increased after the Chl a peaked, also with a time lag, and ranged from about 0.25 to 0.5 by volume. The observed depression in the GF(85 %) values (relative to pure sea salt) is consistent with the large observed volume fractions of non-refractory organic matter (NR-OM) comprising the SSA. The GF(85 %) values exhibited a reasonable negative correlation with the SSA NR-OM volume fractions after the peak of the blooms (i.e., Chl a maxima); i.e., the GF(85 %) values generally decreased when the NR-OM volume fractions increased. The GF(85 %) vs. NR-OM volume fraction relationship was interpreted using the Zdanovskii-Stokes-Robinson (ZSR) mixing rule and used to estimate the GF(85 %) of the organic matter in the nascent SSA. The estimated pure NR-OM GF(85 %) values were 1.16 ± 0.09 and 1.23 ± 0.10 for the indoor and outdoor MARTS, respectively. These measurements demonstrate a clear relationship between SSA particle composition and the sensitivity of light scattering to variations in relative humidity. The implications of these observations to the direct climate effects of SSA particles are discussed.

Cloud condensation nuclei in pristine tropical rainforest air of Amazonia: size-resolved measurements and modeling of atmospheric aerosol composition and CCN activity

NASA Astrophysics Data System (ADS)

Gunthe, S. S.; King, S. M.; Rose, D.; Chen, Q.; Roldin, P.; Farmer, D. K.; Jimenez, J. L.; Artaxo, P.; Andreae, M. O.; Martin, S. T.; Pöschl, U.

2009-10-01

Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. We have measured and characterized CCN at water vapor supersaturations in the range of S=0.10-0.82% in pristine tropical rainforest air during the AMAZE-08 campaign in central Amazonia. The effective hygroscopicity parameters describing the influence of chemical composition on the CCN activity of aerosol particles varied in the range of κ≍0.1-0.4 (0.16±0.06 arithmetic mean and standard deviation). The overall median value of κ≍0.15 was by a factor of two lower than the values typically observed for continental aerosols in other regions of the world. Aitken mode particles were less hygroscopic than accumulation mode particles (κ≍0.1 at D≍50 nm; κ≍0.2 at D≍200 nm), which is in agreement with earlier hygroscopicity tandem differential mobility analyzer (H-TDMA) studies. The CCN measurement results are consistent with aerosol mass spectrometry (AMS) data, showing that the organic mass fraction (forg) was on average as high as ~90% in the Aitken mode (D≤100 nm) and decreased with increasing particle diameter in the accumulation mode (~80% at D≍200 nm). The κ values exhibited a negative linear correlation with forg (R2=0.81), and extrapolation yielded the following effective hygroscopicity parameters for organic and inorganic particle components: κorg≍0.1 which can be regarded as the effective hygroscopicity of biogenic secondary organic aerosol (SOA) and κinorg≍0.6 which is characteristic for ammonium sulfate and related salts. Both the size dependence and the temporal variability of effective particle hygroscopicity could be parameterized as a function of AMS-based organic and inorganic mass fractions (κp=κorg×forg +κinorg×finorg). The CCN number concentrations predicted with κp were in fair agreement with the measurement results (~20% average deviation). The median CCN number concentrations at S=0.1-0.82% ranged from NCCN,0.10≍35 cm-3 to NCCN,0.82≍160 cm-3, the median concentration of aerosol particles larger than 30 nm was NCN,30≍200 cm-3, and the corresponding integral CCN efficiencies were in the range of NCCN,0.10/NCN,30≍0.1 to NCCN,0.82/NCN,30≍0.8. Although the number concentrations and hygroscopicity parameters were much lower in pristine rainforest air, the integral CCN efficiencies observed were similar to those in highly polluted megacity air. Moreover, model calculations of NCCN,S assuming an approximate global average value of κ≍0.3 for continental aerosols led to systematic overpredictions, but the average deviations exceeded ~50% only at low water vapor supersaturation (0.1%) and low particle number concentrations (≤100 cm-3). Model calculations assuming a constant aerosol size distribution led to higher average deviations at all investigated levels of supersaturation: ~60% for the campaign average distribution and ~1600% for a generic remote continental size distribution. These findings confirm earlier studies suggesting that aerosol particle number and size are the major predictors for the variability of the CCN concentration in continental boundary layer air, followed by particle composition and hygroscopicity as relatively minor modulators. Depending on the required and applicable level of detail, the information and parameterizations presented in this paper should enable efficient description of the CCN properties of pristine tropical rainforest aerosols of Amazonia in detailed process models as well as in large-scale atmospheric and climate models.

Application of Aerosol Hygroscopicity Measured at the Atmospheric Radiation Measurement Program's Southern Great Plains Site to Examine Composition and Evolution

NASA Technical Reports Server (NTRS)

Gasparini, Roberto; Runjun, Li; Collins, Don R.; Ferrare, Richard A.; Brackett, Vincent G.

2006-01-01

A Differential Mobility Analyzer/Tandem Differential Mobility Analyzer (DMA/TDMA) was used to measure submicron aerosol size distributions, hygroscopicity, and occasionally volatility during the May 2003 Aerosol Intensive Operational Period (IOP) at the Central Facility of the Atmospheric Radiation Measurement Program's Southern Great Plains (ARM SGP) site. Hygroscopic growth factor distributions for particles at eight dry diameters ranging from 0.012 micrometers to 0.600 micrometers were measured throughout the study. For a subset of particle sizes, more detailed measurements were occasionally made in which the relative humidity or temperature to which the aerosol was exposed was varied over a wide range. These measurements, in conjunction with backtrajectory clustering, were used to infer aerosol composition and to gain insight into the processes responsible for evolution. The hygroscopic growth of both the smallest and largest particles analyzed was typically less than that of particles with dry diameters of about 0.100 micrometers. It is speculated that condensation of secondary organic aerosol on nucleation mode particles is largely responsible for the minimal hygroscopic growth observed at the smallest sizes considered. Growth factor distributions of the largest particles characterized typically contained a nonhygroscopic mode believed to be composed primarily of dust. A model was developed to characterize the hygroscopic properties of particles within a size distribution mode through analysis of the fixed size hygroscopic growth measurements. The performance of this model was quantified through comparison of the measured fixed size hygroscopic growth factor distributions with those simulated through convolution of the size-resolved concentration contributed by each of the size modes and the mode-resolved hygroscopicity. This transformation from sizeresolved hygroscopicity to mode-resolved hygroscopicity facilitated examination of changes in the hygroscopic properties of particles within a size distribution mode that accompanied changes in the sizes of those particles. This model was used to examine three specific cases in which the sampled aerosol evolved slowly over a period of hours or days.

Deposition or not? The fate of volcanic ash after aggregation processes

NASA Astrophysics Data System (ADS)

Mueller, Sebastian B.; Kueppers, Ulrich; Wadsworth, Fabian B.; Ayris, Paul M.; Casas, Ana S.; Cimarelli, Corrado; Ametsbichler, Jonathan; Delmelle, Pierre; Taddeucci, Jacopo; Jacob, Michael; Dingwell, Donald B.

2017-04-01

In the course of explosive volcanic eruptions, large amounts of ash are released into the atmosphere and may subsequently pose a threat to infrastructure, such as aviation industry. Ash plume forecasting is therefore a crucial tool for volcanic hazard mitigation but may be significantly affected by aggregation, altering the aerodynamic properties of particles. Models struggle with the implementation of aggregation since external conditions promoting aggregation have not been completely understood; in a previous study we have shown the rapid generation of ash aggregates through liquid bonding via the use of fluidization bed technology and further defined humidity and temperature ranges necessary to trigger aggregation. Salt (NaCl) was required for the recovery of stable aggregates, acting as a cementation agent and granting aggregate cohesion. A numerical model was used to explain the physics behind particle aggregation mechanisms and further predicted a dependency of aggregation efficiency on liquid binder viscosity. In this study we proof the effect of viscosity on particle aggregation. HCl and H2SO4 solutions were diluted to various concentrations resulting in viscosities between 1 and 2 mPas. Phonolitic and rhyolitic ash samples as well as soda-lime glass beads (serving as analogue material) were fluidized in the ProCell Lab® of Glatt Ingenieurtechnik GmbH and treated with the acids via a bottom-spray technique. Chemically driven interaction between acid liquids and surfaces of the three used materials led to crystal precipitation. Salt crystals (e.g. NaCl) have been confirmed through scanning electron microscopy (SEM) and leachate analysis. Both volcanic ash samples as well as the glass beads showed a clear dependency of aggregation efficiency on viscosity of the sprayed HCl solution. Spraying H2SO4 provoked a collapse of the fluidized bed and no aggregation has been observed. This is accounted by the high hygroscopicity of H2SO4. Dissolving CaCl2 (known to be a highly hygroscopic salt) in de-ionized water yielded comparable results without observable aggregation. In case of successful aggregation, concentration of salts has been found to be in the range of published values. We conclude that non-hygroscopic salt crystal precipitation from an aqueous liquid interacting with the glass phase in volcanic ash is a very efficient way to produce cohesive ash aggregates that can survive external forces acting during transport and sedimentation. Our parameterization of ash aggregation processes shall now be implemented in ash plume dispersal modelling for improved and more accurate ash distribution forecasting in the event of explosive volcanic eruptions.

Combined use of optical and electron microscopic techniques for the measurement of hygroscopic property, chemical composition, and morphology of individual aerosol particles.

PubMed

Ahn, Kang-Ho; Kim, Sun-Man; Jung, Hae-Jin; Lee, Mi-Jung; Eom, Hyo-Jin; Maskey, Shila; Ro, Chul-Un

2010-10-01

In this work, an analytical method for the characterization of the hygroscopic property, chemical composition, and morphology of individual aerosol particles is introduced. The method, which is based on the combined use of optical and electron microscopic techniques, is simple and easy to apply. An optical microscopic technique was used to perform the visual observation of the phase transformation and hygroscopic growth of aerosol particles on a single particle level. A quantitative energy-dispersive electron probe X-ray microanalysis, named low-Z particle EPMA, was used to perform a quantitative chemical speciation of the same individual particles after the measurement of the hygroscopic property. To validate the analytical methodology, the hygroscopic properties of artificially generated NaCl, KCl, (NH(4))(2)SO(4), and Na(2)SO(4) aerosol particles of micrometer size were investigated. The practical applicability of the analytical method for studying the hygroscopic property, chemical composition, and morphology of ambient aerosol particles is demonstrated.

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

Renbaum-Wolff, Lindsay; Song, Mijung; Marcolli, Claudia

Particles consisting of secondary organic material (SOM) are abundant in the atmosphere. In order to predict the role of these particles in climate, visibility and atmospheric chemistry, information on particle phase state (i.e., single liquid, two liquids and solid) is needed. Our paper focuses on the phase state of SOM particles free of inorganic salts produced by the ozonolysis of α-pinene. Phase transitions were investigated in the laboratory using optical microscopy and theoretically using a thermodynamic model at 290 K and for relative humidities ranging from < 0.5 to 100%. In the laboratory studies, a single phase was observed frommore » 0 to 95% relative humidity (RH) while two liquid phases were observed above 95% RH. For increasing RH, the mechanism of liquid–liquid phase separation (LLPS) was spinodal decomposition. The RH range over which two liquid phases were observed did not depend on the direction of RH change. In the modeling studies, the SOM took up very little water and was a single organic-rich phase at low RH values. At high RH, the SOM underwent LLPS to form an organic-rich phase and a water-rich phase, consistent with the laboratory studies. The presence of LLPS at high RH values can have consequences for the cloud condensation nuclei (CCN) activity of SOM particles. In the simulated Köhler curves for SOM particles, two local maxima were observed. Depending on the composition of the SOM, the first or second maximum can determine the critical supersaturation for activation. Recently researchers have observed inconsistencies between measured CCN properties of SOM particles and hygroscopic growth measured below water saturation (i.e., hygroscopic parameters measured below water saturation were inconsistent with hygroscopic parameters measured above water saturation). Furthermore, the work presented here illustrates that such inconsistencies are expected for systems with LLPS when the water uptake at subsaturated conditions represents the hygroscopicity of an organic-rich phase while the barrier for CCN activation can be determined by the second maximum in the Köhler curve when the particles are water rich.« less

Towards closing the gap between hygroscopic growth and activation for secondary organic aerosol: Part 1 - Evidence from measurements

NASA Astrophysics Data System (ADS)

Wex, H.; Petters, M. D.; Carrico, C. M.; Hallbauer, E.; Massling, A.; McMeeking, G. R.; Poulain, L.; Wu, Z.; Kreidenweis, S. M.; Stratmann, F.

2009-01-01

Secondary Organic Aerosols (SOA) studied in laboratory experiments generally was found to show only slight hygroscopic growth, but a much better activity as a CCN (Cloud Condensation Nucleus) than indicated by the hygroscopic growth. This discrepancy was examined at LACIS (Leipzig Aerosol Cloud Interaction Simulator), using a portable generator that produced SOA particles from the ozonolysis of α-pinene, and adding butanol or butanol and water vapor during some of the experiments. The light scattering signal of dry SOA-particles was measured by the LACIS optical particle spectrometer and was used to derive a refractive index for SOA of 1.45. LACIS also measured the hygroscopic growth of SOA particles up to 99.6% relative humidity (RH), and a CCN counter was used to measure the particle activation. SOA-particles were CCN active with critical diameters of e.g. 100 and 55 nm at supersaturations of 0.4 and 1.1%, respectively. But only slight hygroscopic growth with hygroscopic growth factors ≤1.05 was observed at RH<98% RH. The hygroscopic growth increased slightly with the OH concentration present during the SOA-generation. At RH>98%, the hygroscopic growth increased stronger than would be expected if a constant hygroscopicity parameter for the particle/droplet solution was assumed. An increase of the hygroscopicity parameter by a factor of 4-6 was observed in the RH-range from below 90 to 99.6%, and this increase continued for increasingly diluted particle solutions for activating particles. This explains an observation already made in the past: that the relation between critical supersaturation and dry diameter for activation is steeper than what would be expected for a constant value of the hygroscopicity. The increase in the hygroscopicity parameter could be explained by either an increase in the number of ions/molecules in solution (e.g. due to the presence of slightly soluble particles with deliquescence RHs above 98%), or a change in the non-ideal behaviour (see companion paper Petters et al., 2008). Combining measurements of hygroscopic growth and activation, it was found that the surface tension that has to be assumed to interpret the measurements consistently is greater than 55 mN/m, possibly close to that of pure water, depending on the different SOA-types produced, and therefore only in part accounts for the discrepancy between hygroscopic growth and CCN activity observed for SOA particles in the past.

Spatial distribution of aerosol hygroscopicity and its effect on PM2.5 retrieval in East China

NASA Astrophysics Data System (ADS)

He, Qianshan; Zhou, Guangqiang; Geng, Fuhai; Gao, Wei; Yu, Wei

2016-03-01

The hygroscopic properties of aerosol particles have strong impact on climate as well as visibility in polluted areas. Understanding of the scattering enhancement due to water uptake is of great importance in linking dry aerosol measurements with relevant ambient measurements, especially for satellite retrievals. In this study, an observation-based algorithm combining meteorological data with the particulate matter (PM) measurement was introduced to estimate spatial distribution of indicators describing the integrated humidity effect in East China and the main factors impacting the hygroscopicity were explored. Investigation of 1 year data indicates that the larger mass extinction efficiency αext values (> 9.0 m2/g) located in middle and northern Jiangsu Province, which might be caused by particulate organic material (POM) and sulfate aerosol from industries and human activities. The high level of POM in Jiangsu Province might also be responsible for the lower growth coefficient γ value in this region. For the inland junction provinces of Jiangsu and Anhui, a considerable higher hygroscopic growth region in East China might be attributed to more hygroscopic particles mainly comprised of inorganic salts (e.g., sulfates and nitrates) from several large-scale industrial districts distributed in this region. Validation shows good agreement of calculated PM2.5 mass concentrations with in situ measurements in most stations with correlative coefficients of over 0.85, even if several defective stations induced by station location or seasonal variation of aerosol properties in this region. This algorithm can be used for more accurate surface level PM2.5 retrieval from satellite-based aerosol optical depth (AOD) with combination of the vertical correction for aerosol profile.

Hygroscopicity of mineral dust particles: Roles of chemical mixing state and hygroscopic conversion timescale

NASA Astrophysics Data System (ADS)

Sullivan, R. C.; Moore, M. J.; Petters, M. D.; Laskin, A.; Roberts, G. C.; Kreidenweis, S. M.; Prather, K. A.

2009-05-01

Our laboratory investigations of mineral dust particle hygroscopicity are motivated by field observations of the atmospheric processing of dust. During ACE-Asia we observed sulphate and nitrate to be strongly segregated from each other in individual aged Asian dust particles. CCN activation curves of pure calcium minerals as proxies for fresh (calcium carbonate) and aged (calcium sulphate, nitrate, chloride) dust indicate that this mixing state would cause a large fraction of aged dust particles to remain poor warm cloud nucleation potential, contrary to previous assumptions. The enrichment of oxalic acid in calcium-rich dust particles could have similar effects due to the formation of insoluble calcium oxalate. Soluble calcium nitrate and chloride reaction products are hygroscopic and will transform mineral dust into excellent CCN. Generating insoluble mineral particles wet by atomization produced particles with much higher hygroscopicity then when resuspended dry. The atomized particles are likely composed of dissolved residuals and do not properly reflect the chemistry of dry mineral powders. Aerosol flow tube experiments were employed to study the conversion of calcium carbonate into calcium nitrate via heterogeneous reaction with nitric acid, with simultaneous measurements of the reacted particles' chemistry and hygroscopicity. The timescale for this hygroscopic conversion was found to occur on the order of a few hours under tropospheric conditions. This implies that the conversion of non-hygroscopic calcite- containing dust into hygroscopic particles will be controlled by the availability of nitric acid, and not by the atmospheric residence time. Results from recent investigations of the effect of secondary coatings on the ice nucleation properties of dust particles will also be presented. The cloud formation potential of aged dust particles depends on both the quantity and form of the secondary species that have reacted or mixed with the dust. These results have important implications for the treatment of mineral dust particles in global chemistry and climate models.

Rupturing of Biological Spores As a Source of Secondary Particles in Amazonia

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

China, Swarup; Wang, Bingbing; Weis, Johannes

Airborne biological particles, such as fungal spores and pollen, are ubiquitous in the Earth’s atmosphere and play an important role in the atmospheric environment and climate, impacting air quality, cloud formation, and the Earth’s radiation budget. The atmospheric transformations of airborne biological spores at elevated relative humidity remain poorly understood and their climatic role is uncertain. Using an environmental scanning electron microscope (ESEM), we observed rupturing of Amazonian fungal spores and subsequent release of nanometer to submicron size fragments after exposure to high humidity. We find that fungal fragments contain elements of inorganic salts (e.g., Na and Cl). They aremore » hygroscopic in nature with a growth factor up to 2.3 at 96% relative humidity, thus they may potentially influence cloud formation. Due to their hygroscopic growth, light scattering cross sections of the fragments are enhanced by up to a factor of 10. Furthermore, rupturing of fungal spores at high humidity may explain the bursting events of nanoparticles and may provide insight into new particle formation in Amazonia.« less

Measurements of hygroscopicity and volatility of atmospheric ultrafine particles during ultrafine particle formation events at urban, industrial, and coastal sites.

PubMed

Park, Kihong; Kim, Jae-Seok; Park, Seung Ho

2009-09-01

The tandem differential mobility analyzer (TDMA) technique was applied to determine the hygroscopicity and volatility of atmospheric ultrafine particles in three sites of urban Gwangju, industrial Yeosu, and coastal Taean in South Korea. A database for the hygroscopicity and volatility of the known compositions and sizes of the laboratory-generated particles wasfirst constructed for comparison with the measured properties of atmospheric ultrafine particles. Distinct differences in hygroscopicity and volatility of atmospheric ultrafine particles werefound between a "photochemical event" and a "combustion event" as well as among different sites. At the Gwangju site, ultrafine particles in the "photochemical event" were determined to be more hygroscopic (growth factor (GF) = 1.05-1.33) than those in the "combustion event" (GF = 1.02-1.12), but their hygroscopicity was not as high as pure ammonium sulfate or sulfuric acid particles in the laboratory-generated database, suggesting they were internally mixed with less soluble species. Ultrafine particles in the "photochemical event" at the Yeosu site, having a variety of SO2, CO, and VOC emission sources, were more hygroscopic (GF = 1.34-1.60) and had a higher amount of volatile species (47-75%)than those observed at the Gwangju site. Ultrafine particle concentration at the Taean site increased during daylight hours with low tide, having a higher GF (1.34-1.80) than the Gwangju site and a lower amount of volatile species (17-34%) than the Yeosu site. Occasionally ultrafine particles were externally mixed according to their hygroscopicity and volatility, and TEM/EDS data showed that each type of particle had a distinct morphology and elemental composition.

Effect of Morphology and Composition on the Hygroscopicity of Soot Aerosols

NASA Astrophysics Data System (ADS)

Williams, L.; Slowik, J.; Davidovits, P.; Jayne, J.; Kolb, C.; Worsnop, D.; Rudich, Y.

2003-12-01

Freshly generated soot aerosols are initially hydrophobic and unlikely to act as cloud condensation nuclei (CCN). However, during combustion many low vapor pressure gas products are formed that may then condense on existing soot aerosols. Additionally, soot particles may acquire coatings as they age, such as acids, salts, and oxygenated organics. An understanding of this aging process and its effect on soot hygroscopicity is necessary to address the potential of soot to act as a CCN. The transformation of soot from hydrophobic to hydrophilic is the focus of this work. An aim here is to determine the minimum coating required for hygroscopic growth. Soot particles produced by combustion of mixtures of fuel and air are size selected by a Differential Mobility Analyzer (DMA) and entrained in a laminar flow passing through a flow tube. The size selected soot particles are mixed with a controlled amount of the gas phase precursors to produce the coatings to be studied. Initial studies are focused on coatings of H2SO4, NH4NO3, and selected organics. The number of particles per unit volume of air is counted by a Condensation Particle Counter (CPC) and the particles are isokinetically sampled into an Aerosol Mass Spectrometer (AMS). Two distinct types of soot aerosols have been observed depending on the type of fuel and air mixture. With soot produced by the combustion of propane and air, the AMS shows a polydisperse particle size distribution with aerodynamic diameters ranging from 100 nm to 400 nm. The aerodynamic diameter is linearly related to the DMA-determined mobility diameter with the product density x shape factor = 1.2. The organic molecules in this soot are mostly PAH compounds. However, when kerosene is added to the propane flame, the soot particle morphology and composition is strikingly altered. While the DMA shows an essentially unchanged mobility diameter distribution, in the range 100 nm to 400, aerodynamic particle diameter is constant at about 100 nm, independent of the mobility diameter. This type of constancy of the aerodynamic diameter has been observed for soot particles in diesel engine exhaust and has been interpreted in terms of a size-dependent effective density. The soot chemical composition is also altered. In this soot the organics are mainly linear hydrocarbons. The differences between these two types of soot with respect to hygroscopicity and effective area are being investigated.

Cloud condensation nuclei activity and droplet activation kinetics of wet processed regional dust samples and minerals

NASA Astrophysics Data System (ADS)

Kumar, P.; Sokolik, I. N.; Nenes, A.

2011-08-01

This study reports laboratory measurements of particle size distributions, cloud condensation nuclei (CCN) activity, and droplet activation kinetics of wet generated aerosols from clays, calcite, quartz, and desert soil samples from Northern Africa, East Asia/China, and Northern America. The dependence of critical supersaturation, sc, on particle dry diameter, Ddry, is used to characterize particle-water interactions and assess the ability of Frenkel-Halsey-Hill adsorption activation theory (FHH-AT) and Köhler theory (KT) to describe the CCN activity of the considered samples. Wet generated regional dust samples produce unimodal size distributions with particle sizes as small as 40 nm, CCN activation consistent with KT, and exhibit hygroscopicity similar to inorganic salts. Wet generated clays and minerals produce a bimodal size distribution; the CCN activity of the smaller mode is consistent with KT, while the larger mode is less hydrophilic, follows activation by FHH-AT, and displays almost identical CCN activity to dry generated dust. Ion Chromatography (IC) analysis performed on regional dust samples indicates a soluble fraction that cannot explain the CCN activity of dry or wet generated dust. A mass balance and hygroscopicity closure suggests that the small amount of ions (from low solubility compounds like calcite) present in the dry dust dissolve in the aqueous suspension during the wet generation process and give rise to the observed small hygroscopic mode. Overall these results identify an artifact that may question the atmospheric relevance of dust CCN activity studies using the wet generation method. Based on the method of threshold droplet growth analysis, wet generated mineral aerosols display similar activation kinetics compared to ammonium sulfate calibration aerosol. Finally, a unified CCN activity framework that accounts for concurrent effects of solute and adsorption is developed to describe the CCN activity of aged or hygroscopic dusts.

Cloud condensation nuclei in pristine tropical rainforest air of Amazonia: size-resolved measurements and modeling of atmospheric aerosol composition and CCN activity

NASA Astrophysics Data System (ADS)

Gunthe, S. S.; King, S. M.; Rose, D.; Chen, Q.; Roldin, P.; Farmer, D. K.; Jimenez, J. L.; Artaxo, P.; Andreae, M. O.; Martin, S. T.; Pöschl, U.

2009-02-01

Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. We have measured and characterized CCN at water vapor supersaturations in the range of S=0.10-0.82% in pristine tropical rainforest air during the AMAZE-08 campaign in central Amazonia. The effective hygroscopicity parameters describing the influence of chemical composition on the CCN activity of aerosol particles varied in the range of κ=0.05-0.45. The overall median value of κ≍0.15 was only half of the value typically observed for continental aerosols in other regions of the world. Aitken mode particles were less hygroscopic than accumulation mode particles (κ≍0.1 at D≍50 nm; κ≍0.2 at D≍200 nm). The CCN measurement results were fully consistent with aerosol mass spectrometry (AMS) data, which showed that the organic mass fraction (Xm,org) was on average as high as ~90% in the Aitken mode (D≤100 nm) and decreased with increasing particle diameter in the accumulation mode (~80% at D≍200 nm). The κ values exhibited a close linear correlation with Xm,org and extrapolation yielded the following effective hygroscopicity parameters for organic and inorganic particle components: κorg≍0.1 which is consistent with laboratory measurements of secondary organic aerosols and κinorg≍0.6 which is characteristic for ammonium sulfate and related salts. Both the size-dependence and the temporal variability of effective particle hygroscopicity could be parameterized as a function of AMS-based organic and inorganic mass fractions (κp=0.1 Xm,org+0.6 Xm,inorg), and the CCN number concentrations predicted with κp were in fair agreement with the measurement results. The median CCN number concentrations at S=0.1-0.82% ranged from NCCN,0.10≍30 cm-3 to NCCN,0.82≍150 cm-3, the median concentration of aerosol particles larger than 30 nm was NCN,30≍180 cm-3, and the corresponding integral CCN efficiencies were in the range of NCCN,0.10/NCN,30≍0.1 to NCCN,0.82/NCN,30≍0.8. Although the number concentrations and hygroscopicity parameters were much lower, the integral CCN efficiencies observed in pristine rainforest air were similar to those in highly polluted mega-city air. Moreover, model calculations of NCCN,S with a global average value of κ=0.3 led to systematic overpredictions, but the relative deviations exceeded ~50% only at low water vapor supersaturation (0.1%) and low particle number concentrations (≤100 cm-3). These findings confirm earlier studies suggesting that aerosol particle number and size are the major predictors for the variability of the CCN concentration in continental boundary layer air, followed by particle composition and hygroscopicity as relatively minor modulators. Depending on the required and applicable level of detail, the information and parameterizations presented in this paper should enable efficient description of the CCN properties of pristine tropical rainforest aerosols in detailed process models as well as in large-scale atmospheric and climate models.

Hygroscopic properties of ultrafine particles at an urban site in northern Japan during the summer of 2011

NASA Astrophysics Data System (ADS)

Jung, Jinsang; Kawamura, Kimitaka

2013-04-01

To investigate the hygroscopic property of ultrafine particles, hygroscopic growth factors [g(RH)] of size-segregated atmospheric particles were measured at an urban site in Sapporo, northern Japan, during the summer of 2011. Hygroscopic growth factors at 85% RH [g(85%)] of freshly formed nucleation mode particles ranged from 1.11 to 1.28 with an average of 1.16 ± 0.06. These values are similar to those of secondary organic aerosols, suggesting that low volatile organic vapors are important to the growth of nucleated clusters into quasi-stable aerosol particles larger than 3 nm. Higher g(85%) values (range: 1.21-1.31, AVG: 1.27 ± 0.04) were obtained for grown Aitken mode nucleated particles. This result may indicate that the growth of freshly formed nucleation mode particles to the Aitken mode particles at the urban site can be attributed to condensation not only of low volatility organic vapors but also of highly water-soluble inorganic compounds like sulfuric acid. Diel variations in the number concentrations of less-hygroscopic particles [g(85%) <1.05] were similar to those in NO concentrations, suggesting that less-hygroscopic particles are mainly produced by local anthropogenic emissions such as traffic. Higher g(85%) values (1.27 ± 0.05) were obtained at a dry particle diameter of 120 nm when the air masses originated from downwind areas of the Asian continent, whereas lower g(85%) values (1.19 ± 0.06) were obtained when clean marine air masses arrived in the urban site. These results indicate that the hygroscopic property of large Aitken and small accumulation mode particles (80-165 nm) are highly influenced by the long-range transport of atmospheric particles.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

The oceans cover the majority of the earth's surface, host nearly half the total global primary productivity and are a major source of atmospheric aerosol particles. However, effects of biological activity on sea spray generation and composition, and subsequent cloud formation are not well understood. Our goal is to elucidate these effects which will be particularly important over nutrient rich seas, where microorganisms can reach concentrations of 10^9 per mL and along with transparent exopolymer particles (TEP) can become aerosolized. Here we report the results of mesocosm experiments in which bubbles were generated by two methods, either recirculating impinging water jets or glass frits, in natural or artificial seawater containing bacteria and unialgal cultures of three representative phytoplankton species, Thalassiosira pseudonana, Emiliania huxleyi, and Nannochloris atomus. Over time we followed the size distribution of aerosolized particles as well as their hygroscopicity, heterogeneous ice nucleation potential, and individual physical-chemical characteristics. Numbers of cells and the mass of dissolved and particulate organic carbon (DOC, POC), TEP (which includes polysaccharide-containing microgels and nanogels >0.4 μm in diameter) were determined in the bulk water, the surface microlayer, and aerosolized material. Aerosolized particles were also impacted onto substrates for ice nucleation and water uptake experiments, elemental analysis using computer controlled scanning electron microscopy and energy dispersive analysis of X-rays (CCSEM/EDX), and determination of carbon bonding with scanning transmission X-ray microscopy and near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Regardless of bubble generation method, the overall concentration of aerosol particles, TEP, POC and DOC increased as concentrations of bacterial and phytoplankton cells increased, stabilized, and subsequently declined. Particles <100 nm generated by means of jets were enhanced with time compared with larger sizes. In contrast, all particle sizes were equally enhanced when frits were used. Aerosolized particles were hygroscopic, a finding with significance for warm cloud formation and potential liquid-to-ice phase transformations. Aqueous and dry aerosolized particles from biologically active mesocosm water were found to efficiently nucleate ice exposed to supersaturated water vapor. The majority of particles, including those nucleating ice, consisted of a sea salt core coated with organic material dominated by the carboxyl functional group, and corresponded to a particle type commonly found in marine air. Our results provide improved estimates of marine aerosol production, chemical composition, and hygroscopicity, as well as an accurate physical and chemical representation of ice nucleation by marine biogenic aerosol particles for use in cloud and climate models.

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

PubMed

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

2015-06-24

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

Hygroscopic Behavior of Multicomponent Aerosols Involving NaCl and Dicarboxylic Acids.

PubMed

Peng, Chao; Jing, Bo; Guo, Yu-Cong; Zhang, Yun-Hong; Ge, Mao-Fa

2016-02-25

Atmospheric aerosols are usually complex mixtures of inorganic and organic compounds. The hygroscopicity of mixed particles is closely related to their chemical composition and interactions between components, which is still poorly understood. In this study, the hygroscopic properties of submicron particles composed of NaCl and dicarboxylic acids including oxalic acid (OA), malonic acid (MA), and succinic acid (SA) with various mass ratios are investigated with a hygroscopicity tandem differential mobility analyzer (HTDMA) system. Both the Zdanovskii-Stokes-Robinson (ZSR) method and extended aerosol inorganics model (E-AIM) are applied to predict the water uptake behaviors of sodium chloride/dicarboxylic acid mixtures. For NaCl/OA mixed particles, the measured growth factors were significantly lower than predictions from the model methods, indicating a change in particle composition caused by chloride depletion. The hygroscopic growth of NaCl/MA particles was well described by E-AIM, and that of NaCl/SA particles was dependent upon mixing ratio. Compared with model predictions, it was determined that water uptake of the NaCl/OA mixture could be enhanced and could be closer to the predictions by addition of levoglucosan or malonic acid, which retained water even at low relative humidity (RH), leading to inhibition of HCl evaporation during dehydration. These results demonstrate that the coexisting hygroscopic species have a strong influence on the phase state of particles, thus affecting chemical interactions between inorganic and organic compounds as well as the overall hygroscopicity of mixed particles.

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.

Sea salt aerosols as a reactive surface for inorganic and organic acidic gases in the arctic troposphere

NASA Astrophysics Data System (ADS)

Chi, J. W.; Li, W. J.; Zhang, D. Z.; Zhang, J. C.; Lin, Y. T.; Shen, X. J.; Sun, J. Y.; Chen, J. M.; Zhang, X. Y.; Zhang, Y. M.; Wang, W. X.

2015-06-01

Sea salt aerosols (SSA) are dominant particles in the arctic atmosphere and determine the polar radiative balance. SSA react with acidic pollutants that lead to changes of physical and chemical properties of their surface, which in turn alter their hygroscopic and optical properties. Transmission electron microscopy with energy-dispersive X-ray spectrometry was used to analyze morphology, composition, size, and mixing state of individual SSA at Ny-Ålesund, Svalbard in summertime. Individual fresh SSA contained cubic NaCl coated by certain amounts of MgCl2 and CaSO4. Individual partially aged SSA contained irregular NaCl coated by a mixture of NaNO3, Na2SO4, Mg(NO3)2, and MgSO4. The comparison suggests the hydrophilic MgCl2 coating in fresh SSA likely intrigued the heterogeneous reactions at the beginning of SSA and acidic gases. Individual fully aged SSA normally had Na2SO4 cores and an amorphous coating of NaNO3. Elemental mappings of individual SSA particles revealed that as the particles ageing Cl gradually decreased but the C, N, O, and S content increased. 12C14N- mapping from nanoscale secondary ion mass spectrometry indicates that organic matter increased in the aged SSA compared with the fresh SSA. 12C14N- line scans further show that organic matter was mainly concentrated on the aged SSA surface. These new findings indicate that this mixture of organic matter and NaNO3 on particle surfaces determines their hygroscopic and optical properties. These abundant SSA, whose reactive surfaces absorb inorganic and organic acidic gases in the arctic troposphere, need to be incorporated into atmospheric chemical models.

Sea salt aerosols as a reactive surface for inorganic and organic acidic gases in the Arctic troposphere

NASA Astrophysics Data System (ADS)

Chi, J. W.; Li, W. J.; Zhang, D. Z.; Zhang, J. C.; Lin, Y. T.; Shen, X. J.; Sun, J. Y.; Chen, J. M.; Zhang, X. Y.; Zhang, Y. M.; Wang, W. X.

2015-10-01

Sea salt aerosols (SSA) are dominant particles in the Arctic atmosphere and determine the polar radiative balance. SSA react with acidic pollutants that lead to changes in physical and chemical properties of their surface, which in turn alter their hygroscopic and optical properties. Transmission electron microscopy with energy-dispersive X-ray spectrometry was used to analyze morphology, composition, size, and mixing state of individual SSA at Ny-Ålesund, Svalbard, in summertime. Individual fresh SSA contained cubic NaCl coated by certain amounts of MgCl2 and CaSO4. Individual partially aged SSA contained irregular NaCl coated by a mixture of NaNO3, Na2SO4, Mg(NO3)2, and MgSO4. The comparison suggests the hydrophilic MgCl2 coating in fresh SSA likely intrigued the heterogeneous reactions at the beginning of SSA and acidic gases. Individual fully aged SSA normally had Na2SO4 cores and an amorphous coating of NaNO3. Elemental mappings of individual SSA particles revealed that as the particles ageing Cl gradually decreased, the C, N, O, and S content increased. 12C- mapping from nanoscale secondary ion mass spectrometry indicates that organic matter increased in the aged SSA compared with the fresh SSA. 12C- line scan further shows that organic matter was mainly concentrated on the aged SSA surface. These new findings indicate that this mixture of organic matter and NaNO3 on particle surfaces likely determines their hygroscopic and optical properties. These abundant SSA as reactive surfaces adsorbing inorganic and organic acidic gases can shorten acidic gas lifetime and influence the possible gaseous reactions in the Arctic atmosphere, which need to be incorporated into atmospheric chemical models in the Arctic troposphere.

Sea salt aerosols as a reactive surface for inorganic and organic acidic gases in the arctic troposphere

NASA Astrophysics Data System (ADS)

Li, W.

2016-12-01

Sea salt aerosols (SSA) are dominant particles in the arctic atmosphere and determine the polar radiative balance. SSA react with acidic pollutants that lead to changes of physical and chemical properties of their surface, which in turn alter their hygroscopic and optical properties. Transmission electron microscopy with energy-dispersive X-ray spectrometry was used to analyze morphology, composition, size, and mixing state of individual SSA at Ny-Ålesund, Svalbard in summertime. Individual fresh SSA contained cubic NaCl coated by certain amounts of MgCl2 and CaSO4. Individual partially aged SSA contained irregular NaCl coated by a mixture of NaNO3, Na2SO4, Mg(NO3)2, and MgSO4. The comparison suggests the hydrophilic MgCl2 coating in fresh SSA likely intrigued the heterogeneous reactions at the beginning of SSA and acidic gases. Individual fully aged SSA normally had Na2SO4 cores and an amorphous coating of NaNO3. Elemental mappings of individual SSA particles revealed that as the particles ageing Cl gradually decreased but the C, N, O, and S content increased. 12C- mapping from nanoscale secondary ion mass spectrometry indicates that organic matter increased in the aged SSA compared with the fresh SSA. 12C- line scan further shows that organic matter was mainly concentrated on the aged SSA surface. These new findings indicate that this mixture of organic matter and NaNO3 on particle surfaces likely determines their hygroscopic and optical properties. These abundant SSA as reactive surfaces absorbing inorganic and organic acidic gases can shorten acidic gas lifetime and influence the possible gaseous reactions in the arctic atmosphere, which need to be incorporated into atmospheric chemical models in the arctic troposphere.

Impact of mixing state and hygroscopicity on CCN activity of biomass burning aerosol in Amazonia

NASA Astrophysics Data System (ADS)

Sánchez Gácita, Madeleine; Longo, Karla M.; Freire, Julliana L. M.; Freitas, Saulo R.; Martin, Scot T.

2017-02-01

Smoke aerosols prevail throughout Amazonia because of widespread biomass burning during the dry season, and external mixing, low variability in the particle size distribution and low particle hygroscopicity are typical. There can be profound effects on cloud properties. This study uses an adiabatic cloud model to simulate the activation of smoke particles as cloud condensation nuclei (CCN) for three hypothetical case studies, chosen as to resemble biomass burning aerosol observations in Amazonia. The relative importance of variability in hygroscopicity, mixing state, and activation kinetics for the activated fraction and maximum supersaturation is assessed. For a population with κp = 0.04, an overestimation of the cloud droplet number concentration Nd for the three selected case studies between 22.4 ± 1.4 and 54.3 ± 3.7 % was obtained when assuming a hygroscopicity parameter κp = 0.20. Assuming internal mixing of the aerosol population led to overestimations of up to 20 % of Nd when a group of particles with medium hygroscopicity was present in the externally mixed population cases. However, the overestimations were below 10 % for external mixtures between very low and low-hygroscopicity particles, as seems to be the case for Amazon smoke particles. Kinetic limitations were significant for medium- and high-hygroscopicity particles, and much lower for very low and low-hygroscopicity particles. When particles were assumed to be at equilibrium and to respond instantly to changes in the air parcel supersaturation, the overestimation of the droplet concentration was up to ˜ 100 % in internally mixed populations, and up to ˜ 250 % in externally mixed ones, being larger for the higher values of hygroscopicity. In addition, a perceptible delay between the times when maximum supersaturation and maximum aerosol activated fraction are reached was noticed and, for aerosol populations with effective hygroscopicity κpeff higher than a certain threshold value, the delay in particle activation was such that no particles were activated at the time of maximum supersaturation. Considering internally mixed populations, for an updraft velocity W = 0.5 m s-1 this threshold of no activation varied between κpeff = 0.35 and κpeff = 0.5 for the different case studies. However, for low hygroscopicity, kinetic limitations played a weaker role for CCN activation of particles, even when taking into account the large aerosol mass and number concentrations. For the very low range of hygroscopicities, the overestimation of the droplet concentration due to the equilibrium assumption was lowest and the delay between the times when maximum supersaturation and maximum activated fraction were reached was greatly reduced or no longer observed (depending on the case study). These findings on uncertainties and sensitivities provide guidance on appropriate simplifications that can be used for modeling of smoke aerosols within general circulation models. The use of medium values of hygroscopicity representative of smoke aerosols for other biomass burning regions on Earth can lead to significant errors compared to the use of low hygroscopicity for Amazonia (between 0.05 and 0.13, according to available observations). Also in this region, consideration of the biomass burning population as internally mixed will lead to small errors in the droplet concentration, while significantly increasing the computational burden. Regardless of the large smoke aerosol loads in the region during the dry season, kinetic limitations are expected to be low.

Deliquescence behavior of photo-irradiated single NaNO3 droplets

NASA Astrophysics Data System (ADS)

Seng, Samantha; Guo, Fangqin; Tobon, Yeny A.; Ishikawa, Tomoki; Moreau, Myriam; Ishizaka, Shoji; Sobanska, Sophie

2018-06-01

Nitrate-containing particles are ubiquitous in the troposphere because of their secondary production due to anthropogenic emissions of NOx from the combustion of fossil fuels. Nitrate ions are recognized as photoactive species that may contribute to the formation of oxidants in the atmosphere through heterogeneous photochemical reactions. The chemical transformation of aerosol particles in the atmosphere often leads to modification of the particles' hygroscopic properties. Although the photo-transformation of nitrate ions into nitrite within aerosol particles has been investigated, the influence of the photoproducts formation on the hygroscopic behavior of particles has not been reported. In this study, we examined the hygroscopic properties of single, ultraviolet-irradiated NaNO3 droplets using Raman microspectrometry. We are the first demonstrated that irradiating NaNO3 particles affects their hygroscopic behavior. For short-term exposures, regarding hygroscopic behavior, the irradiated particles exhibited two-stage transitions that were clearly reproduced in the experimental NaNO3-NaNO2 phase diagram. The production of NO2- decreased the deliquescence relative humidity values. For long irradiation times (>5 h), these values are even more affected by the additional production of peroxynitrite and carbonate ions in individual droplets. The NaNO3-NaNO2 deliquescence phase diagram cannot explain the hygroscopic behavior of long-term irradiated particles. Finally, we demonstrated the influence that CO2 has on the photo-transformation process in NaNO3 droplets.

Toward Quantifying the Mass-Based Hygroscopicity of Individual Submicron Atmospheric Aerosol Particles with STXM/NEXAFS and SEM/EDX

NASA Astrophysics Data System (ADS)

Yancey Piens, D.; Kelly, S. T.; OBrien, R. E.; Wang, B.; Petters, M. D.; Laskin, A.; Gilles, M. K.

2014-12-01

The hygroscopic behavior of atmospheric aerosols influences their optical and cloud-nucleation properties, and therefore affects climate. Although changes in particle size as a function of relative humidity have often been used to quantify the hygroscopic behavior of submicron aerosol particles, it has been noted that calculations of hygroscopicity based on size contain error due to particle porosity, non-ideal volume additivity and changes in surface tension. We will present a method to quantify the hygroscopic behavior of submicron aerosol particles based on changes in mass, rather than size, as a function of relative humidity. This method results from a novel experimental approach combining scanning transmission x-ray microscopy with near-edge x-ray absorption fine spectroscopy (STXM/NEXAFS), as well as scanning electron microscopy with energy dispersive x-ray spectroscopy (SEM/EDX) on the same individual particles. First, using STXM/NEXAFS, our methods are applied to aerosol particles of known composition ‒ for instance ammonium sulfate, sodium bromide and levoglucosan ‒ and validated by theory. Then, using STXM/NEXAFS and SEM/EDX, these methods are extended to mixed atmospheric aerosol particles collected in the field at the DOE Atmospheric Radiation Measurement (ARM) Climate Research Facility at the Southern Great Planes sampling site in Oklahoma, USA. We have observed and quantified a range of hygroscopic behaviors which are correlated to the composition and morphology of individual aerosol particles. These methods will have implications for parameterizing aerosol mixing state and cloud-nucleation activity in atmospheric models.

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

PubMed

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

2015-05-14

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

Individual Aerosol Particles from Biomass Burning in Southern Africa Compositions and Aging of Inorganic Particles. 2; Compositions and Aging of Inorganic Particles

NASA Technical Reports Server (NTRS)

Li, Jia; Posfai, Mihaly; Hobbs, Peter V.; Buseck, Peter R.

2003-01-01

Individual aerosol particles collected over southern Africa during the SAFARI 2000 field study were studied using transmission electron microscopy and field-emission scanning electron microscopy. The sizes, shapes, compositions, mixing states, surface coatings, and relative abundances of aerosol particles from biomass burning, in boundary layer hazes, and in the free troposphere were compared, with emphasis on aging and reactions of inorganic smoke particles. Potassium salts and organic particles were the predominant species in the smoke, and most were internally mixed. More KCl particles occur in young smoke, whereas more K2SO4 and KNO3 particles were present in aged smoke. This change indicates that with the aging of the smoke, KCl particles from the fires were converted to K2SO4 and KNO3 through reactions with sulfur- and nitrogen- bearing species from biomass burning as well as other sources. More soot was present in smoke from flaming grass fires than bush and wood fires, probably due to the predominance of flaming combustion in grass fires. The high abundance of organic particles and soluble salts can affect the hygroscopic properties of biomass-burning aerosols and therefore influence their role as cloud condensation nuclei. Particles from biomass burning were important constituents of the regional hazes.

A numerical study of the effects of aerosol hygroscopic properties to dry deposition on a broad-leaved forest

NASA Astrophysics Data System (ADS)

Katata, Genki; Kajino, Mizuo; Matsuda, Kazuhide; Takahashi, Akira; Nakaya, Ko

2014-11-01

To investigate the impact of hygroscopic growth on dry deposition onto forest canopies, numerical simulations of PM2.5 sulfate deposition using a multi-layer atmosphere-SOiL-VEGetation model (SOLVEG) ware performed. The scheme of particle dry deposition in SOLVEG was extended for application to a broad-leaved forest. An aerosol hygroscopic model based on the widely used κ-Köhler theory was incorporated into the model to calculate water uptake by the aerosols. The model accurately reproduced essential turbulent exchange fluxes (momentum, heat, and water vapor) over the canopies and the soil temperature and moisture for a deciduous broad-leaved forest in central Japan. Temporal variations in the measured PM2.5 sulfate deposition velocity were generally reproduced by the model. By considering an increase in particle diameter due to hygroscopic growth, the prediction accuracy of the modeled deposition velocity under humid conditions was improved. Numerical experiments for varying aerosol size distributions and hygroscopic properties showed that the geometric mean diameter and hygroscopicity of particles have a large influence on hygroscopic growth levels. The results also suggested that the deposition velocity of wet particles increased due to hygroscopic growth when the relative humidity (RH) was approximately 50%, and that the velocity reached five times greater than that under dry conditions when RH exceeded 95%.

Uncertainty in aerosol hygroscopicity resulting from semi-volatile organic compounds

NASA Astrophysics Data System (ADS)

Goulden, Olivia; Crooks, Matthew; Connolly, Paul

2018-01-01

We present a novel method of exploring the effect of uncertainties in aerosol properties on cloud droplet number using existing cloud droplet activation parameterisations. Aerosol properties of a single involatile particle mode are randomly sampled within an uncertainty range and resulting maximum supersaturations and critical diameters calculated using the cloud droplet activation scheme. Hygroscopicity parameters are subsequently derived and the values of the mean and uncertainty are found to be comparable to experimental observations. A recently proposed cloud droplet activation scheme that includes the effects of co-condensation of semi-volatile organic compounds (SVOCs) onto a single lognormal mode of involatile particles is also considered. In addition to the uncertainties associated with the involatile particles, concentrations, volatility distributions and chemical composition of the SVOCs are randomly sampled and hygroscopicity parameters are derived using the cloud droplet activation scheme. The inclusion of SVOCs is found to have a significant effect on the hygroscopicity and contributes a large uncertainty. For non-volatile particles that are effective cloud condensation nuclei, the co-condensation of SVOCs reduces their actual hygroscopicity by approximately 25 %. A new concept of an effective hygroscopicity parameter is introduced that can computationally efficiently simulate the effect of SVOCs on cloud droplet number concentration without direct modelling of the organic compounds. These effective hygroscopicities can be as much as a factor of 2 higher than those of the non-volatile particles onto which the volatile organic compounds condense.

Characterization of particle hygroscopicity by Raman lidar: Selected case studies from the convective and orographically-induced precipitation study

NASA Astrophysics Data System (ADS)

Stelitano, Dario; Di Girolamo, Paolo; Summa, Donato

2013-05-01

The characterization of particle hygroscopicity has primary importance for climate monitoring and prediction. Model studies have demonstrated that relative humidity (RH) has a critical influence on aerosol climate forcing. Hygroscopic properties of aerosols influence particle size distribution and refractive index and hence their radiative effects. Aerosol particles tend to grow at large relative humidity values as a result of their hygroscopicity. Raman lidars with aerosol, water vapor and temperature measurement capability are potentially attractive tools for studying aerosol hygroscopicity as in fact they can provide continuous altitude-resolved measurements of particle optical, size and microphysical properties, as well as relative humidity, without perturbing the aerosols or their environment. Specifically, the University of Basilicata Raman lidar system (BASIL) considered for the present study, has the capability to perform all-lidar measurements of relative humidity based on the application of both the rotational and the vibrational Raman lidar techniques in the UV. BASIL was operational in Achern (Black Forest, Lat: 48.64° N, Long: 8.06° E, Elev.: 140 m) between 25 May and 30 August 2007 in the framework of the Convective and Orographically-induced Precipitation Study (COPS). The present analysis is focused on selected case studies characterized by the presence of different aerosol types with different hygroscopic behavior. The observed behavior, dependent upon aerosol composition, may range from hygrophobic to strongly hygroscopic.

Hygroscopic aerosol deposition in the human upper respiratory tract under various thermo-humidity conditions.

PubMed

Xi, Jinxiang; Kim, Jongwon; Si, Xiuhua A; Zhou, Yue

2013-01-01

The deposition of hygroscopic aerosols is highly complex in nature, which results from a cumulative effect of dynamic particle growth and the real-time size-specific deposition mechanisms. The objective of this study is to evaluate hygroscopic effects on the particle growth, transport, and deposition of nasally inhaled aerosols across a range of 0.2-2.5 μm in an adult image-based nose-throat model. Temperature and relative humidity fields were simulated using the LRN k-ω turbulence model and species transport model under a spectrum of thermo-humidity conditions. Particle growth and transport were simulated using a well validated Lagrangian tracking model coupled with a user-defined hygroscopic growth module. Results of this study indicate that the saturation level and initial particle size are the two major factors that determine the particle growth rate (d/d0), while the effect of inhalation flow rate is found to be not significant. An empirical correlation of condensation growth of nasally inhaled hygroscopic aerosols in adults has been developed based on a variety of thermo-humidity inhalation conditions. Significant elevated nasal depositions of hygroscopic aerosols could be induced by condensation growth for both sub-micrometer and small micrometer particulates. In particular, the deposition of initially 2.5 μm hygroscopic aerosols was observed to be 5-8 times that of inert particles under warm to hot saturated conditions. Results of this study have important implications in exposure assessment in hot humid environments, where much higher risks may be expected compared to normal conditions.

Modeling aerosol water uptake in the arctic based on the κ-Kohler theory

NASA Astrophysics Data System (ADS)

Rastak, N.; Ekman, A.; Silvergren, S.; Zieger, P.; Wideqvist, U.; Ström, J.; Svenningsson, B.; Tunved, P.; Riipinen, I.

2013-05-01

Water uptake or hygroscopicity is one of the most fundamental properties of atmospheric aerosols. Aerosol particles containing soluble materials can grow in size by absorbing water in ambient atmosphere. This property is measured by a parameter known as growth factor (GF), which is defined as the ratio of the wet diameter to the dry diameter. Hygroscopicity controls the size of an aerosol particle and therefore its optical properties in the atmosphere. Hygroscopic growth depends on the dry size of the particle, its chemical composition and the relative humidity in the ambient air (Fitzgerald, 1975; Pilinis et al., 1995). One of the typical problems in aerosol studies is the lack of measurements of aerosol size distributions and optical properties in ambient conditions. The gap between dry measurements and the real humid atmosphere is filled in this study by utilizing a hygroscopic model which calculates the hygroscopic growth of aerosol particles at Mt Zeppelin station, Ny Ålesund, Svalbard during 2008.

A humidity-controlled fast integrated mobility spectrometer (HFIMS) for rapid measurements of particle hygroscopic growth

NASA Astrophysics Data System (ADS)

Pinterich, Tamara; Spielman, Steven R.; Wang, Yang; Hering, Susanne V.; Wang, Jian

2017-12-01

We present a humidity-controlled fast integrated mobility spectrometer (HFIMS) for rapid particle hygroscopicity measurements. The HFIMS consists of a differential mobility analyzer (DMA), a relative humidity (RH) control unit and a water-based FIMS (WFIMS) coupled in series. The WFIMS (Pinterich et al., 2017) combines the fast integrated mobility spectrometer (Kulkarni and Wang, 2006a, b) with laminar flow water condensation methodologies (Hering and Stolzenburg, 2005; Spielman et al., 2017). Inside the WFIMS, particles of different electrical mobilities are spatially separated in an electric field, condensationally enlarged and imaged to provide 1 Hz measurements of size distribution spanning a factor of ˜ 3 in particle diameter, which is sufficient to cover the entire range of growth factor (GF) for atmospheric aerosol particles at 90 % RH. By replacing the second DMA of a traditional hygroscopicity tandem DMA (HTDMA) system with the WFIMS, the HFIMS greatly increases the speed of particle growth factor measurement. The performance of the HFIMS was evaluated using NaCl particles with well-known hygroscopic growth behavior and further through measurements of ambient aerosols. Results show that the HFIMS can reproduce, within 2 %, the literature values for hygroscopic growth of NaCl particles. NaCl deliquescence was observed between 76 and 77 % RH in agreement with the theoretical value of 76.5 % (Ming and Russell, 2001), and efflorescence relative humidity (43 %) was found to lie within the RH range of 41 to 56 % reported in the literature. Ambient data indicate that the HFIMS can measure the hygroscopic growth of five standard dry particle sizes ranging from 35 to 165 nm within less than 3 min, which makes it about 1 order of magnitude faster than traditional HTDMA systems.

A Humidity-controlled Fast Integrated Mobility Spectrometer (HFIMS) for rapid measurements of particle hygroscopic growth

DOE PAGES

Pinterich, Tamara; Spielman, Steven R.; Hering, Susanne; ...

2017-06-26

We present a Humidity-controlled Fast Integrated Mobility Spectrometer (HFIMS) for rapid particle hygroscopicity measurements. The HFIMS consists of a differential mobility analyzer (DMA), a relative humidity (RH) control unit and a water-based FIMS (WFIMS) coupled in series. The WFIMS (Pinterich et al., 2017) combines the Fast Integrated Mobility Spectrometer (Kulkarni and Wang, 2006a, b) with laminar flow water condensation methodologies (Hering and Stolzenburg, 2005; Spielman et al., 2017). Inside the WFIMS, particles of different electrical mobilities are spatially separated in an electric field, condensationally enlarged and imaged to provide 1-Hz measurements of size distribution spanning a factor of ~ 3more » in particle diameter, sufficient to cover the entire range of growth factor for atmospheric aerosol particles at 90 % RH. By replacing the second DMA of a traditional hygroscopicity tandem DMA (HTDMA) system with the WFIMS, the HFIMS greatly increases the speed of particle growth factor measurement. The performance of the HFIMS was evaluated using NaCl particles with well-known hygroscopic growth behavior, and further through measurements of ambient aerosols. Results show that HFIMS can reproduce, within 2 % the literature values for hygroscopic growth of NaCl particles. NaCl deliquescence was observed between 76 % and 77 % RH in agreement with the theoretical value of 76.5 % (Ming and Russell, 2001), and efflorescence relative humidity (43 %) was found to lie within the RH range of 41 % to 56 % reported in the literature. Ambient data indicate that HFIMS can measure the hygroscopic growth of five standard dry particle sizes ranging from 35 to 165 nm within less than three minutes, which makes it about an order of magnitude faster than traditional HTDMA systems.« less

A Humidity-controlled Fast Integrated Mobility Spectrometer (HFIMS) for rapid measurements of particle hygroscopic growth

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

Pinterich, Tamara; Spielman, Steven R.; Hering, Susanne

We present a Humidity-controlled Fast Integrated Mobility Spectrometer (HFIMS) for rapid particle hygroscopicity measurements. The HFIMS consists of a differential mobility analyzer (DMA), a relative humidity (RH) control unit and a water-based FIMS (WFIMS) coupled in series. The WFIMS (Pinterich et al., 2017) combines the Fast Integrated Mobility Spectrometer (Kulkarni and Wang, 2006a, b) with laminar flow water condensation methodologies (Hering and Stolzenburg, 2005; Spielman et al., 2017). Inside the WFIMS, particles of different electrical mobilities are spatially separated in an electric field, condensationally enlarged and imaged to provide 1-Hz measurements of size distribution spanning a factor of ~ 3more » in particle diameter, sufficient to cover the entire range of growth factor for atmospheric aerosol particles at 90 % RH. By replacing the second DMA of a traditional hygroscopicity tandem DMA (HTDMA) system with the WFIMS, the HFIMS greatly increases the speed of particle growth factor measurement. The performance of the HFIMS was evaluated using NaCl particles with well-known hygroscopic growth behavior, and further through measurements of ambient aerosols. Results show that HFIMS can reproduce, within 2 % the literature values for hygroscopic growth of NaCl particles. NaCl deliquescence was observed between 76 % and 77 % RH in agreement with the theoretical value of 76.5 % (Ming and Russell, 2001), and efflorescence relative humidity (43 %) was found to lie within the RH range of 41 % to 56 % reported in the literature. Ambient data indicate that HFIMS can measure the hygroscopic growth of five standard dry particle sizes ranging from 35 to 165 nm within less than three minutes, which makes it about an order of magnitude faster than traditional HTDMA systems.« less

Water uptake of clay and desert dust aerosol particles at sub- and supersaturated water vapor conditions.

PubMed

Herich, Hanna; Tritscher, Torsten; Wiacek, Aldona; Gysel, Martin; Weingartner, Ernest; Lohmann, Ulrike; Baltensperger, Urs; Cziczo, Daniel J

2009-09-28

Airborne mineral dust particles serve as cloud condensation nuclei (CCN), thereby influencing the formation and properties of warm clouds. It is therefore of atmospheric interest how dust aerosols with different mineralogy behave when exposed to high relative humidity (RH) or supersaturation (SS) with respect to liquid water. In this study the subsaturated hygroscopic growth and the supersaturated cloud condensation nucleus activity of pure clays and real desert dust aerosols were determined using a hygroscopicity tandem differential mobility analyzer (HTDMA) and a cloud condensation nuclei counter (CCNC), respectively. Five different illite, montmorillonite and kaolinite clay samples as well as three desert dust samples (Saharan dust (SD), Chinese dust (CD) and Arizona test dust (ATD)) were investigated. Aerosols were generated both with a wet and a dry disperser. The water uptake was parameterized via the hygroscopicity parameter kappa. The hygroscopicity of dry generated dust aerosols was found to be negligible when compared to processed atmospheric aerosols, with CCNC derived kappa values between 0.00 and 0.02 (the latter corresponds to a particle consisting of 96.7% by volume insoluble material and approximately 3.3% ammonium sulfate). Pure clay aerosols were generally found to be less hygroscopic than natural desert dust particles. The illite and montmorillonite samples had kappa approximately 0.003. The kaolinite samples were less hygroscopic and had kappa=0.001. SD (kappa=0.023) was found to be the most hygroscopic dry-generated desert dust followed by CD (kappa=0.007) and ATD (kappa=0.003). Wet-generated dust showed an increased water uptake when compared to dry-generated samples. This is considered to be an artifact introduced by redistribution of soluble material between the particles. Thus, the generation method is critically important when presenting such data. These results indicate any atmospheric processing of a fresh mineral dust particle which leads to the addition of more than approximately 3% soluble material will significantly enhance its hygroscopicity and CCN activity.

Ternary nucleation as a mechanism for the production of diesel nanoparticles: experimental analysis of the volatile and hygroscopic properties of diesel exhaust using the volatilization and humidification tandem differential mobility analyzer.

PubMed

Meyer, N K; Ristovski, Z D

2007-11-01

The volatile and hygroscopic properties of diesel nanoparticles were simultaneously determined under a range of engine loads using the volatilization and humidification tandem differential mobility analyzer (VH-TDMA). Additionally, the VH-TDMA was used to measure changes in the hygroscopic behavior of the heterogeneously nucleated diesel nanoparticles as one or more semivolatile species were removed via thermal evaporation or decomposition. Particles produced at high loads exhibited high, dual-step volatility, while those particles produced at low loads were less volatile and exhibited continuous volatilization curves. The hygroscopic growth factor of the particles was shown to be load dependent with high-load particles exhibiting growth factors similar to that of ammonium sulfate. At 85% relative humidity, particles produced at moderate loads exhibited growth factors of approximately 1.1 while low-load particles were shown to be hydrophobic. Growth factors and volatilization temperatures measured for high-load particles clearly indicate that ternary nucleation is involved in particle formation.

Size distribution, chemical composition, and hygroscopicity of fine particles emitted from an oil-fired heating plant.

PubMed

Happonen, Matti; Mylläri, Fanni; Karjalainen, Panu; Frey, Anna; Saarikoski, Sanna; Carbone, Samara; Hillamo, Risto; Pirjola, Liisa; Häyrinen, Anna; Kytömäki, Jorma; Niemi, Jarkko V; Keskinen, Jorma; Rönkkö, Topi

2013-12-17

Heavy fuel oil (HFO) is a commonly used fuel in industrial heating and power generation and for large marine vessels. In this study, the fine particle emissions of a 47 MW oil-fired boiler were studied at 30 MW power and with three different fuels. The studied fuels were HFO, water emulsion of HFO, and water emulsion of HFO mixed with light fuel oil (LFO). With all the fuels, the boiler emitted considerable amounts of particles smaller than 200 nm in diameter. Further, these small particles were quite hygroscopic even as fresh and, in the case of HFO+LFO emulsion, the hygroscopic growth of the particles was dependent on particle size. The use of emulsions and the addition of LFO to the fuel had a reducing effect on the hygroscopic growth of particles. The use of emulsions lowered the sulfate content of the smallest particles but did not affect significantly the sulfate content of particles larger than 42 nm and, further, the addition of LFO considerably increased the black carbon content of particulate matter. The results indicate that even the fine particles emitted from HFO based combustion can have a significant effect on cloud formation, visibility, and air quality.

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

Statistical analysis and parameterization of the hygroscopic growth of the sub-micrometer urban background aerosol in Beijing

NASA Astrophysics Data System (ADS)

Wang, Yu; Wu, Zhijun; Ma, Nan; Wu, Yusheng; Zeng, Limin; Zhao, Chunsheng; Wiedensohler, Alfred

2018-02-01

The take-up of water of aerosol particles plays an important role in heavy haze formation over North China Plain, since it is related with particle mass concentration, visibility degradation, and particle chemistry. In the present study, we investigated the size-resolved hygroscopic growth factor (HGF) of sub-micrometer aerosol particles (smaller than 350 nm) on a basis of 9-month Hygroscopicity-Tandem Differential Mobility Analyzer measurement in the urban background atmosphere of Beijing. The mean hygroscopicity parameter (κ) values derived from averaging over the entire sampling period for particles of 50 nm, 75 nm, 100 nm, 150 nm, 250 nm, and 350 nm in diameters were 0.14 ± 0.07, 0.17 ± 0.05, 0.18 ± 0.06, 0.20 ± 0.07, 0.21 ± 0.09, and 0.23 ± 0.12, respectively, indicating the dominance of organics in the sub-micrometer urban aerosols. In the spring, summer, and autumn, the number fraction of hydrophilic particles increased with increasing particle size, resulting in an increasing trend of overall particle hygroscopicity with enhanced particle size. Differently, the overall mean κ values peaked in the range of 75-150 nm and decreased for particles larger than 150 nm in diameter during wintertime. Such size-dependency of κ in winter was related to the strong primary particle emissions from coal combustion during domestic heating period. The number fraction of hydrophobic particles such as freshly emitted soot decreased with increasing PM2.5 mass concentration, indicating aged and internal mixed particles were dominant in the severe particulate matter pollution. Parameterization schemes of the HGF as a function of relative humidity (RH) and particle size between 50 and 350 nm were determined for different seasons and pollution levels. The HGFs calculated from the parameterizations agree well with the measured HGFs at 20-90% RH. The parameterizations can be applied to determine the hygroscopic growth of aerosol particles at ambient conditions for the area of Beijing (ultrafine and fine particles) and the North China plain (fine particles).

Water uptake by fresh Indonesian peat burning particles is limited by water-soluble organic matter

NASA Astrophysics Data System (ADS)

Chen, Jing; Hapsari Budisulistiorini, Sri; Itoh, Masayuki; Lee, Wen-Chien; Miyakawa, Takuma; Komazaki, Yuichi; Qing Yang, Liu Dong; Kuwata, Mikinori

2017-09-01

The relationship between hygroscopic properties and chemical characteristics of Indonesian biomass burning (BB) particles, which are dominantly generated from peatland fires, was investigated using a humidified tandem differential mobility analyzer. In addition to peat, acacia (a popular species at plantation) and fern (a pioneering species after disturbance by fire) were used for experiments. Fresh Indonesian peat burning particles are almost non-hygroscopic (mean hygroscopicity parameter, κ < 0.06) due to predominant contribution of water-insoluble organics. The range of κ spans from 0.02 to 0.04 (dry diameter = 100 nm, hereinafter) for Riau peat burning particles, while that for Central Kalimantan ranges from 0.05 to 0.06. Fern combustion particles are more hygroscopic (κ = 0. 08), whereas the acacia burning particles have a mediate κ value (0.04). These results suggest that κ is significantly dependent on biomass types. This variance in κ is partially determined by fractions of water-soluble organic carbon (WSOC), as demonstrated by a correlation analysis (R = 0.65). κ of water-soluble organic matter is also quantified, incorporating the 1-octanol-water partitioning method. κ values for the water extracts are high, especially for peat burning particles (A0 (a whole part of the water-soluble fraction): κ = 0.18, A1 (highly water-soluble fraction): κ = 0.30). This result stresses the importance of both the WSOC fraction and κ of the water-soluble fraction in determining the hygroscopicity of organic aerosol particles. Values of κ correlate positively (R = 0.89) with the fraction of m/z 44 ion signal quantified using a mass spectrometric technique, demonstrating the importance of highly oxygenated organic compounds to the water uptake by Indonesian BB particles. These results provide an experimentally validated reference for hygroscopicity of organics-dominated particles, thus contributing to more accurate estimation of environmental and climatic impacts driven by Indonesian BB particles on both regional and global scales.

Biomass-burning impact on CCN number, hygroscopicity and cloud formation during summertime in the eastern Mediterranean

NASA Astrophysics Data System (ADS)

Bougiatioti, Aikaterini; Bezantakos, Spiros; Stavroulas, Iasonas; Kalivitis, Nikos; Kokkalis, Panagiotis; Biskos, George; Mihalopoulos, Nikolaos; Papayannis, Alexandros; Nenes, Athanasios

2016-06-01

This study investigates the concentration, cloud condensation nuclei (CCN) activity and hygroscopic properties of particles influenced by biomass burning in the eastern Mediterranean and their impacts on cloud droplet formation. Air masses sampled were subject to a range of atmospheric processing (several hours up to 3 days). Values of the hygroscopicity parameter, κ, were derived from CCN measurements and a Hygroscopic Tandem Differential Mobility Analyzer (HTDMA). An Aerosol Chemical Speciation Monitor (ACSM) was also used to determine the chemical composition and mass concentration of non-refractory components of the submicron aerosol fraction. During fire events, the increased organic content (and lower inorganic fraction) of the aerosol decreases the values of κ, for all particle sizes. Particle sizes smaller than 80 nm exhibited considerable chemical dispersion (where hygroscopicity varied up to 100 % for particles of same size); larger particles, however, exhibited considerably less dispersion owing to the effects of condensational growth and cloud processing. ACSM measurements indicate that the bulk composition reflects the hygroscopicity and chemical nature of the largest particles (having a diameter of ˜ 100 nm at dry conditions) sampled. Based on positive matrix factorization (PMF) analysis of the organic ACSM spectra, CCN concentrations follow a similar trend as the biomass-burning organic aerosol (BBOA) component, with the former being enhanced between 65 and 150 % (for supersaturations ranging between 0.2 and 0.7 %) with the arrival of the smoke plumes. Using multilinear regression of the PMF factors (BBOA, OOA-BB and OOA) and the observed hygroscopicity parameter, the inferred hygroscopicity of the oxygenated organic aerosol components is determined. We find that the transformation of freshly emitted biomass burning (BBOA) to more oxidized organic aerosol (OOA-BB) can result in a 2-fold increase of the inferred organic hygroscopicity; about 10 % of the total aerosol hygroscopicity is related to the two biomass-burning components (BBOA and OOA-BB), which in turn contribute almost 35 % to the fine-particle organic water of the aerosol. Observation-derived calculations of the cloud droplet concentrations that develop for typical boundary layer cloud conditions suggest that biomass burning increases droplet number, on average by 8.5 %. The strongly sublinear response of clouds to biomass-burning (BB) influences is a result of strong competition of CCN for water vapor, which results in very low maximum supersaturation (0.08 % on average). Attributing droplet number variations to the total aerosol number and the chemical composition variations shows that the importance of chemical composition increases with distance, contributing up to 25 % of the total droplet variability. Therefore, although BB may strongly elevate CCN numbers, the impact on droplet number is limited by water vapor availability and depends on the aerosol particle concentration levels associated with the background.

Raman lidar observations of particle hygroscopicity during COPS

NASA Astrophysics Data System (ADS)

Stelitano, D.; Di Girolamo, P.; Summa, D.

2012-04-01

The characterization of particle hygroscopicity has primary importance for climate monitoring and prediction. Model studies have demonstrated that relative humidity (RH) has a critical influence on aerosol climate forcing. The relationship between aerosol backscattering and relative humidity has been investigated in numerous studies (among others, Pahlow et al., 2006; Wulfmeyer and Feingold, 2000; Veselovskii et al., 2009). Hygroscopic properties of aerosols influence particle size distribution and refractive index and hence their radiative effects. Aerosol particles tend to grow at large relative humidity values as a result of their hygroscopicity. Raman lidars with aerosol, water vapour and temperature measurement capability are potentially attractive tools for studying aerosol hygroscopicity as in fact they can provide continuous altitude-resolved measurements of particle optical, size and microphysical properties, as well as relative humidity, without perturbing the aerosols or their environment. Specifically, the University of Basilicata Raman lidar system (BASIL) considered for the present study, has the capability to perform all-lidar measurements of relative humidity based on the application of both the rotational and the vibrational Raman lidar techniques in the UV. BASIL was operational in Achern (Black Forest, Lat: 48.64 ° N, Long: 8.06 ° E, Elev.: 140 m) between 25 May and 30 August 2007 in the framework of the Convective and Orographically-induced Precipitation Study (COPS). During COPS, BASIL collected more than 500 hours of measurements, distributed over 58 measurement days and 34 intensive observation periods (IOPs). The present analysis is focused on selected case studies characterized by the presence of different aerosol types with different hygroscopic behaviour. The observed behaviour, dependent upon aerosol composition, may range from hygrophobic to strongly hygroscopic. Results from the different case studies will be illustrated and discussed at the Conference.

Hygroscopic properties of atmospheric particles emitted during wintertime biomass burning episodes in Athens

NASA Astrophysics Data System (ADS)

Psichoudaki, Magda; Nenes, Athanasios; Florou, Kalliopi; Kaltsonoudis, Christos; Pandis, Spyros N.

2018-04-01

This study explores the Cloud Condensation Nuclei (CCN) activity of atmospheric particles during intense biomass burning periods in an urban environment. During a one-month campaign in the center of Athens, Greece, a CCN counter coupled with a Scanning Mobility Particle Sizer (SMPS) and a high resolution Aerosol Mass Spectrometer (HR-AMS) were used to measure the size-resolved CCN activity and composition of the atmospheric aerosols. During the day, the organic fraction of the particles was more than 50%, reaching almost 80% at night, when the fireplaces were used. Positive Matrix Factorization (PMF) analysis revealed 4 factors with biomass burning being the dominant source after 18:00 until the early morning. The CCN-based overall hygroscopicity parameter κ ranged from 0.15 to 0.25. During the night, when the biomass burning organic aerosol (bbOA) dominated, the hygroscopicity parameter for the mixed organic/inorganic particles was on average 0.16. The hygroscopicity of the biomass-burning organic particles was 0.09, while the corresponding average value for all organic particulate matter during the campaign was 0.12.

On the link between hygroscopicity, volatility, and oxidation state of ambient and water-soluble aerosol in the Southeastern United States

NASA Astrophysics Data System (ADS)

Cerully, K. M.; Bougiatioti, A.; Hite, J. R., Jr.; Guo, H.; Xu, L.; Ng, N. L.; Weber, R.; Nenes, A.

2014-12-01

The formation of secondary organic aerosol (SOA) combined with the partitioning of semi-volatile organic components can impact numerous aerosol properties including cloud condensation nuclei (CCN) activity, hygroscopicity and volatility. During the summer 2013 Southern Oxidant and Aerosol Study (SOAS) field campaign in a rural site in the Southeastern United States, a suite of instruments including a CCN counter, a thermodenuder (TD) and a high resolution time-of-flight aerosol mass spectrometer (AMS) were used to measure CCN activity, aerosol volatility, composition and oxidation state. Particles were either sampled directly from ambient or through a Particle Into Liquid Sampler (PILS), allowing the investigation of the water-soluble aerosol component. Ambient aerosol exhibited size-dependent composition with larger particles being more hygroscopic. The hygroscopicity of thermally-denuded aerosol was similar between ambient and PILS-generated aerosol and showed limited dependence on volatilization. Results of AMS 3-factor Positive Matrix Factorization (PMF) analysis for the PILS-generated aerosol showed that the most hygroscopic components are most likely the most and the least volatile features of the aerosol. No clear relationship was found between organic hygroscopicity and oxygen-to-carbon ratio; in fact, Isoprene organic aerosol (Isoprene-OA) was found to be the most hygroscopic factor, while at the same time being the least oxidized and likely most volatile of all PMF factors. Considering the diurnal variation of each PMF factor and its associated hygroscopicity, Isoprene-OA and More Oxidized - Oxidized Oxygenated Organic Aerosol (MO-OOA) are the prime contributors to hygroscopicity and covary with Less Oxidized - Oxidized Oxygenated Organic Aerosol (LO-OOA) in a way that induces the observed diurnal invariance in total organic hygroscopicity. Biomass Burning Organic Aerosol (BBOA) contributed little to aerosol hygroscopicity, which is expected since there was little biomass burning activity during the sampling period examined.

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.

Hygroscopicity of dicarbonyl-amine secondary organic aerosol products investigated with HTDMA

NASA Astrophysics Data System (ADS)

Hawkins, L. N.; de Haan, D. O.

2010-12-01

Recent studies have shown the importance of amine-dicarbonyl chemistry as a secondary organic aerosol (SOA) formation pathway, producing imines, imidazoles, and N-containing oligomers. Preliminary work in our group has suggested that some of these products may be surface active. Therefore, the presence of these products may result in important changes to submicron particle hygroscopicity that affect aerosol scattering and cloud condensation nuclei (CCN) activity, especially in regions with significant amine-containing particles. To investigate their hygroscopicity, we have designed a hygroscopicity tandem differential mobility analyzer (HTDMA) system around a 300 L Teflon chamber that allows for longer humidification times needed for some organic aerosol components that are only slightly hygroscopic. This modification provides a range of residence times from 2.5 minutes up to 1 hour, unlike previously published systems that vary from 2-30 seconds. Using the modified hygroscopicity tandem differential mobility analyzer (HTDMA), we have measured the hygroscopic growth factor (HGF) of SOA formed from reactions of glyoxal (and methylglyoxal) with methylamine, ammonium sulfate, and several amino acids. Changes to inorganic aerosol HGF in response to the presence of SOA products are also investigated.

Structural Change of Aerosol Particle Aggregates with Exposure to Elevated Relative Humidity.

PubMed

Montgomery, James F; Rogak, Steven N; Green, Sheldon I; You, Yuan; Bertram, Allan K

2015-10-20

Structural changes of aggregates composed of inorganic salts exposed to relative humidity (RH) between 0 and 80% after formation at selected RH between 0 and 60% were investigated using a tandem differential mobility analyzer (TDMA) and fluorescence microscopy. The TDMA was used to measure a shift in peak mobility diameter for 100-700 nm aggregates of hygroscopic aerosol particles composed of NaCl, Na2SO4, (NH4)2SO4, and nonhygroscopic Al2O3 as the RH was increased. Aggregates of hygroscopic particles were found to shrink when exposed to RH greater than that during the aggregation process. The degree of aggregate restructuring is greater for larger aggregates and greater increases in RH. Growth factors (GF) calculated from mobility diameter measurements as low as 0.77 were seen for NaCl before deliquescence. The GF subsequently increased to 1.23 at 80% RH, indicating growth after deliquescence. Exposure to RH lower than that experienced during aggregation did not result in structural changes. Fluorescent microscopy confirmed that aggregates formed on wire surfaces undergo an irreversible change in structure when exposed to elevated RH. Analysis of 2D movement of aggregates shows a displacement of 5-13% compared to projected length of initial aggregate from a wire surface. Surface tension due to water adsorption within the aggregate structure is a potential cause of the structural changes.

Hygroscopicity- and Size-Resolved Measurements of Submicron Aerosol on the East Coast of the United States

NASA Astrophysics Data System (ADS)

Phillips, B. N.; Royalty, T. M.; Dawson, K. W.; Reed, R.; Petters, M. D.; Meskhidze, N.

2018-02-01

Atmospheric measurements of aerosol size-resolved hygroscopicity at submicron sizes are carried out at the United States Army Corps of Engineers Field Research Facility in Duck, North Carolina. The scientific aim of the field deployment is to gain improved understanding of the springtime advection of aerosols from the East Coast of the United States over the Atlantic and help to constrain assessments of anthropogenic particle contributions to the marine boundary layer aerosol budget. Air mass back trajectories show that the aerosol sampled at the coast is largely of continental origin that either gets transported directly from the land or spends some time over the Atlantic Ocean. Aerosol size-resolved hygroscopicity measurements are consistent with air masses of both continental and marine background that are heavily influenced by the continental outflow. Aitken and accumulation mode mean diameters range from 49.1 ± 1.7 nm to 66.9 ± 0.8 nm and 142.8 ± 1.1 nm to 155.0 ± 2.8 nm, respectively. Hygroscopicity distributions for 96 nm, 188 nm, and 284 nm dry-sized particles show the mode hygroscopicity parameter range from 0.20 ± 0.01 to 0.54 ± 0.03, suggesting the presence of anthropogenic aerosols. We have used the method described by Royalty et al. (2017) to decompose the hygroscopicity distributions into three distinct classes based on the ambient aerosol hygroscopic properties relative to the hygroscopic properties of a reference compound. The method shows that continental outflow heavily influences aerosol chemical and physical properties at the East Coast, with hygroscopicities of submicron aerosols consistent with sulfate-containing species (62% to 83%), with small contributions from sodium- and carbon-containing particles (up to 9% and 37%, respectively).

Hygroscopic behavior and chemical composition evolution of internally mixed aerosols composed of oxalic acid and ammonium sulfate

NASA Astrophysics Data System (ADS)

Wang, Xiaowei; Jing, Bo; Tan, Fang; Ma, Jiabi; Zhang, Yunhong; Ge, Maofa

2017-10-01

Although water uptake of aerosol particles plays an important role in the atmospheric environment, the effects of interactions between components on chemical composition and hygroscopicity of particles are still not well constrained. The hygroscopic properties and phase transformation of oxalic acid (OA) and mixed particles composed of ammonium sulfate (AS) and OA with different organic to inorganic molar ratios (OIRs) have been investigated by using confocal Raman spectroscopy. It is found that OA droplets first crystallize to form OA dihydrate at 71 % relative humidity (RH), and further lose crystalline water to convert into anhydrous OA around 5 % RH during the dehydration process. The deliquescence and efflorescence point for AS is determined to be 80.1 ± 1.5 % RH and 44.3 ± 2.5 % RH, respectively. The observed efflorescence relative humidity (ERH) for mixed OA / AS droplets with OIRs of 1 : 3, 1 : 1 and 3 : 1 is 34.4 ± 2.0, 44.3 ± 2.5 and 64.4 ± 3.0 % RH, respectively, indicating the elevated OA content appears to favor the crystallization of mixed systems at higher RH. However, the deliquescence relative humidity (DRH) of AS in mixed OA / AS particles with OIRs of 1 : 3 and 1 : 1 is observed to occur at 81.1 ± 1.5 and 77 ± 1.0 % RH, respectively. The Raman spectra of mixed OA / AS droplets indicate the formation of ammonium hydrogen oxalate (NH4HC2O4) and ammonium hydrogen sulfate (NH4HSO4) from interactions between OA and AS in aerosols during the dehydration process on the time scale of hours, which considerably influence the subsequent deliquescence behavior of internally mixed particles with different OIRs. The mixed OA / AS particles with an OIR of 3 : 1 exhibit no deliquescence transition over the RH range studied due to the considerable transformation of (NH4)2SO4 into NH4HC2O4 with a high DRH. Although the hygroscopic growth of mixed OA / AS droplets is comparable to that of AS or OA at high RH during the dehydration process, Raman growth factors of mixed particles after deliquescence are substantially lower than those of mixed OA / AS droplets during the efflorescence process and further decrease with elevated OA content. The discrepancies for Raman growth factors of mixed OA / AS particles between the dehydration and hydration process at high RH can be attributed to the significant formation of NH4HC2O4 and residual OA, which remain solid at high RH and thus result in less water uptake of mixed particles. These findings improve the understanding of the role of reactions between dicarboxylic acid and inorganic salt in the chemical and physical properties of aerosol particles, and might have important implications for atmospheric chemistry.

Water uptake of clay and desert dust aerosol particles at sub- and supersaturated water vapor conditions

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

Herich, Hanna; Tritscher, Torsten; Wiacek, Aldona

2009-11-01

Airborne mineral dust particles serve as cloud condensation nuclei (CCN), thereby influencing the formation and properties of warm clouds. It is therefore of particular interest how dust aerosols with different mineralogy behave when exposed to high relative humidity (RH) or supersaturation with respect to liquid water similar to atmospheric conditions. In this study the sub-saturated hygroscopic growth and the supersaturated cloud condensation nucleus activity of pure clays and real desert dust aerosols was determined using a hygroscopicity tandem differential mobility analyzer (HTDMA) and a cloud condensation nuclei counter (CCNC), respectively. Five different illite, montmorillonite and kaolinite clay samples as wellmore » as three desert dust samples (Saharan dust (SD), Chinese dust (CD) and Arizona test dust (ATD)) were used. Aerosols were generated both with a wet and a dry disperser and the water uptake was parameterized via the hygroscopicity parameter, κ. The hygroscopicity of dry generated dust aerosols was found to be negligible when compared to processed atmospheric aerosols, with CCNC derived κ values between 0.00 and 0.02. The latter value can be idealized as a particle consisting of 96.7% (by volume) insoluble material and ~3.3% ammonium sulfate. Pure clay aerosols were found to be generally less hygroscopic than real desert dust particles. All illite and montmorillonite samples had κ~0.003, kaolinites were least hygroscopic and had κ=0.001. SD (κ=0.023) was found to be the most hygroscopic dry-generated desert dust followed by CD (κ=0.007) and ATD (κ=0.003). Wet-generated dust showed an increased water uptake when compared to dry-generated samples. This is considered to be an artifact introduced by redistribution of soluble material between the particles while immersed in an aqueous medium during atomization, thus indicating that specification of the generation method is critically important when presenting such data. Any atmospheric processing of fresh mineral dust which leads to the addition of more than ~3% soluble material is expected to significantly enhance hygroscopicity and CCN activity.« less

Hygroscopic and Chemical Properties of Aerosols collected near a Copper Smelter: Implications for Public and Environmental Health

PubMed Central

Sorooshian, Armin; Csavina, Janae; Shingler, Taylor; Dey, Stephen; Brechtel, Fred J.; Sáez, A. Eduardo; Betterton, Eric A.

2012-01-01

Particulate matter emissions near active copper smelters and mine tailings in the southwestern United States pose a potential threat to nearby environments owing to toxic species that can be inhaled and deposited in various regions of the body depending on the composition and size of the particles, which are linked by particle hygroscopic properties. This study reports the first simultaneous measurements of size-resolved chemical and hygroscopic properties of particles next to an active copper smelter and mine tailings by the towns of Hayden and Winkelman in southern Arizona. Size-resolved particulate matter samples collected near an active copper smelter were examined with inductively coupled plasma mass spectrometry, ion chromatography, and a humidified tandem differential mobility analyzer. Aerosol particles collected at the measurement site are enriched in metals and metalloids (e.g. arsenic, lead, and cadmium) and water-uptake measurements of aqueous extracts of collected samples indicate that the particle diameter range of particles most enriched with these species (0.18–0.55 µm) overlaps with the most hygroscopic mode at a relative humidity of 90% (0.10–0.32 µm). These measurements have implications for public health, microphysical effects of aerosols, and regional impacts owing to the transport and deposition of contaminated aerosol particles. PMID:22852879

Spray-dried chitosan/acid/NaCl microparticles enhance saltiness perception.

PubMed

Yi, Cheng; Tsai, Min-Lang; Liu, Tristan

2017-09-15

The composition, physicochemical properties and salinity of spray-dried chitosan/acid/NaCl microparticles were tested to ensure a low-sodium and high-salinity salty agent. The spray-dried chitosan/acid/NaCl microparticles were hollow and had a favourable hygroscopicity, and increased NaCl content and decreased organic acid content. Their size of the microparticles was 15.4-32.0μm and increased with NaCl concentration. The microparticles of acetic and lactic acid groups had a NaCl crystal size of 1-2 and 1-4μm, respectively. The NaCl crystals of acetic, lactic and citric acid group microparticles were distributed on the microparticle matrices, mostly on the microparticle surface and mainly on the inner walls of the microparticles walls, respectively. The acetic and lactic acid group microparticles were relatively smaller than general salt, with NaCl crystals distributed on the particle surfaces. Consequently, they were perceived as saltier than general salt and could potentially be regarded as a low-sodium salt for surface-salted foods. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Orozco, Daniel

The Earth's atmosphere is composed of a large number of different gases as well as tiny suspended particles, both in solid and liquid state. These tiny particles, called atmospheric aerosols, have an immense impact on our health and on our global climate. Atmospheric aerosols influence the Earth's radiation budget both directly and indirectly. In the direct effect, aerosols scatter and absorb sunlight changing the radiative balance of the Earth-atmosphere system. Aerosols indirectly influence the Earth's radiation budget by modifying the microphysical and radiative properties of clouds as well as their water content and lifetime. In ambient conditions, aerosol particles experience hygroscopic growth due to the influence of relative humidity (RH), scattering more light than when the particles are dry. The quantitative knowledge of the RH effect and its influence on the light scattering coefficient and, in particular, on the phase function and polarization of aerosol particles is of substantial importance when comparing ground based observations with other optical aerosol measurements techniques such satellite and sunphotometric retrievals of aerosol optical depth and their inversions. This dissertation presents the aerosol hygroscopicity experiment investigated using a novel dryer-humidifier system, coupled to a TSI-3563 nephelometer, to obtain the light scattering coefficient (sp) as a function of relative humidity (RH) in hydration and dehydration modes. The measurements were performed in Porterville, CA (Jan 10-Feb 6, 2013), Baltimore, MD (Jul 3-30, 2013), and Golden, CO (Jul 12-Aug 10, 2014). Observations in Porterville and Golden were part of the NASA-sponsored DISCOVER-AQ project. The measured sp under varying RH in the three sites was combined with ground aerosol extinction, PM2:5mass concentrations, particle composition measurements, and compared with airborne observations performed during campaigns. The enhancement factor, f(RH), defined as the ratio of sp(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 sampled in Baltimore, MD with the PI-Neph. This study was centered on specific case studies where different aerosol conditions were experienced such as clean, haze episode, and transported smoke event. The approach employed consisted of dry and humid observations of ambient aerosols to compare them with total column products by AERONET. A relatively low difference between the phase function and the degree of linear polarization was measured at high and low RH. The small difference found in the scattering elements and their retrievals is attributed to the general aerosol composition in the region. It was observed that a RH increase causes the particles to scatter more light uniformly over all the scattering angles, and also, that the water uptake did not change markedly the particle's polarization properties. The comparison between in-situ and total column derived observations were highly correlated for most of the cases. The size distribution retrievals from the in-situ measurements were very comparable to the size distributions reported by AERONET, but only for the fine modes.

Hygroscopic Properties and Respiratory System Deposition Behavior of Particulate Matter Emitted By Mining and Smelting Operations

PubMed Central

Youn, Jong-sang; Csavina, Janae; Rine, Kyle P.; Shingler, Taylor; Taylor, Mark Patrick; Sáez, A. Eduardo; Betterton, Eric A.; Sorooshian, Armin

2016-01-01

This study examines size-resolved physicochemical data for particles sampled near mining and smelting operations and a background urban site in Arizona with a focus on how hygroscopic growth impacts particle deposition behavior. Particles with aerodynamic diameters between 0.056 – 18 μm were collected at three sites: (i) an active smelter operation in Hayden, AZ, (ii) a legacy mining site with extensive mine tailings in Iron King, AZ, and (iii) an urban site, inner-city Tucson, AZ. Mass size distributions of As and Pb exhibit bimodal profiles with a dominant peak between 0.32-0.56 μm and a smaller mode in the coarse range (> 3 μm). The hygroscopicity profile did not exhibit the same peaks owing to dependence on other chemical constituents. Sub-micrometer particles were generally more hygroscopic than super-micrometer ones at all three sites with finite water-uptake ability at all sites and particle sizes examined. Model calculations at a relative humidity of 99.5% reveal significant respiratory system particle deposition enhancements at sizes with the largest concentrations of toxic contaminants. Between dry diameters of 0.32 and 0.56 μm, for instance, ICRP and MPPD models predict deposition fraction enhancements of 171%-261% and 33%-63%, respectively, at the three sites. PMID:27700056

Variations in organic aerosol optical and hygroscopic properties upon heterogeneous OH oxidation

NASA Astrophysics Data System (ADS)

Cappa, Christopher D.; Che, Daphne L.; Kessler, Sean H.; Kroll, Jesse H.; Wilson, Kevin R.

2011-08-01

Measurements of the evolution of organic aerosol extinction cross sections (σext) and subsaturated hygroscopicity upon heterogeneous OH oxidation are reported for two model compounds, squalane (a C30 saturated hydrocarbon) and azelaic acid (a C9 dicarboxylic acid). For both compounds, the σext values at 532 nm increase substantially as the particles undergo oxidation, exhibiting a logarithmic increase with OH exposure. The increase in σext correlates with both an increase in the particle oxygen to carbon (O:C) atomic ratio and density and a decrease in mean molecular weight. The measurements have been used to calculate the variation with oxidation of the mean polarizability, α, of the molecules comprising the particles. The absolute α values for the two systems are shown to be related through the variation in the particle chemical composition, specifically the relative abundances of C, O, and H atoms and the mean molecular weight. Unlike σext, it was found that the evolution of the particle hygroscopicity upon oxidation is quite different for the two model systems considered. Hygroscopicity was quantified by measuring γext, which is a single-parameter representation of hygroscopicity that describes the increase in extinction upon exposure of the particles to a high-relative humidity environment (here, 75% and 85% RH). For unoxidized squalane, γext was zero and only increased slowly as the particles were oxidized by OH radicals. In contrast, γext for azelaic acid increased rapidly upon exposure to OH, eventually reaching a plateau at high OH exposures. In general, γext appears to vary sigmoidally with O:C, reaching a plateau at high O:C.

Low hygroscopicity of ambient fresh carbonaceous aerosols from pyrotechnics smoke

DOE PAGES

Carrico, Christian M.; Gomez, Samantha Laray; Dubey, Manvendra Krishna; ...

2018-01-31

Pyrotechnics (fireworks) displays are common for many cultures worldwide, with Independence Day celebrations occurring annually on July 4th as the most notable in the U.S. Given an episodic nature, fireworks aerosol properties are poorly characterized. Here we report observations of optical properties of fresh smoke emissions from Independence Day fireworks smoke sampled at Los Alamos National Laboratory, New Mexico U.S.A. on 4–5 July 2016. Aerosol optical properties were measured with a photoacoustic extinctiometer (PAX, DMT, Inc., Model 870 nm) at low RH < 30% and a humidity controlled nephelometry system (Ecotech, Inc., 450 nm Aurora). ‘Dry’ light scattering coefficient (σsp)more » increased from background < 15 Mm –1 reaching 120 Mm –1 (450 nm) as a 2-min event peak, while the absorption coefficient increased from background of 0.5–4.4 Mm –1 (870 nm). The event peak occurred at 00:35 on 5 July 2016, ~3 h after local fireworks events, and decreased to background by 04:00 on 5 July 2016, showing well mixed aerosol properties. A notable result is that the aerosol hygroscopic response, as characterized by the ratio of wet to dry light scattering or f(RH = 85%), declined to 1.02 at the peak fireworks influence from a background ~1.7. Strong wavelength dependence of light scattering with Ångström exponent ~2.2 throughout the event showed a size distribution dominated by sub-micrometer particles. Likewise, single scattering albedo at 870 nm remained constant throughout the event with ω = 0.86 ± 0.03, indicating light absorbing carbon, though not dominant, was mixed with organic carbon. Subsequent laboratory testing with ground-level sparklers showed that pyrotechnics smoke can generate a strong hygroscopic response, however. As confirmed with chemical analysis, the chemistry of the fireworks was key to defining the hygroscopic response. As a result, sparkler smoke was dominated by salt species such as hygroscopic potassium chloride while it lacked the black powder explosives in aerial fireworks that contribute organic and elemental carbon to its non-hygroscopic smoke.« less

Low hygroscopicity of ambient fresh carbonaceous aerosols from pyrotechnics smoke

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

Carrico, Christian M.; Gomez, Samantha Laray; Dubey, Manvendra Krishna

Pyrotechnics (fireworks) displays are common for many cultures worldwide, with Independence Day celebrations occurring annually on July 4th as the most notable in the U.S. Given an episodic nature, fireworks aerosol properties are poorly characterized. Here we report observations of optical properties of fresh smoke emissions from Independence Day fireworks smoke sampled at Los Alamos National Laboratory, New Mexico U.S.A. on 4–5 July 2016. Aerosol optical properties were measured with a photoacoustic extinctiometer (PAX, DMT, Inc., Model 870 nm) at low RH < 30% and a humidity controlled nephelometry system (Ecotech, Inc., 450 nm Aurora). ‘Dry’ light scattering coefficient (σsp)more » increased from background < 15 Mm –1 reaching 120 Mm –1 (450 nm) as a 2-min event peak, while the absorption coefficient increased from background of 0.5–4.4 Mm –1 (870 nm). The event peak occurred at 00:35 on 5 July 2016, ~3 h after local fireworks events, and decreased to background by 04:00 on 5 July 2016, showing well mixed aerosol properties. A notable result is that the aerosol hygroscopic response, as characterized by the ratio of wet to dry light scattering or f(RH = 85%), declined to 1.02 at the peak fireworks influence from a background ~1.7. Strong wavelength dependence of light scattering with Ångström exponent ~2.2 throughout the event showed a size distribution dominated by sub-micrometer particles. Likewise, single scattering albedo at 870 nm remained constant throughout the event with ω = 0.86 ± 0.03, indicating light absorbing carbon, though not dominant, was mixed with organic carbon. Subsequent laboratory testing with ground-level sparklers showed that pyrotechnics smoke can generate a strong hygroscopic response, however. As confirmed with chemical analysis, the chemistry of the fireworks was key to defining the hygroscopic response. As a result, sparkler smoke was dominated by salt species such as hygroscopic potassium chloride while it lacked the black powder explosives in aerial fireworks that contribute organic and elemental carbon to its non-hygroscopic smoke.« less

Low hygroscopicity of ambient fresh carbonaceous aerosols from pyrotechnics smoke

NASA Astrophysics Data System (ADS)

Carrico, Christian M.; Gomez, Samantha L.; Dubey, Manvendra K.; Aiken, Allison C.

2018-04-01

Pyrotechnics (fireworks) displays are common for many cultures worldwide, with Independence Day celebrations occurring annually on July 4th as the most notable in the U.S. Given an episodic nature, fireworks aerosol properties are poorly characterized. Here we report observations of optical properties of fresh smoke emissions from Independence Day fireworks smoke sampled at Los Alamos National Laboratory, New Mexico U.S.A. on 4-5 July 2016. Aerosol optical properties were measured with a photoacoustic extinctiometer (PAX, DMT, Inc., Model 870 nm) at low RH < 30% and a humidity controlled nephelometry system (Ecotech, Inc., 450 nm Aurora). 'Dry' light scattering coefficient (σsp) increased from background < 15 Mm-1 reaching 120 Mm-1 (450 nm) as a 2-min event peak, while the absorption coefficient increased from background of 0.5-4.4 Mm-1 (870 nm). The event peak occurred at 00:35 on 5 July 2016, ∼3 h after local fireworks events, and decreased to background by 04:00 on 5 July 2016, showing well mixed aerosol properties. A notable result is that the aerosol hygroscopic response, as characterized by the ratio of wet to dry light scattering or f(RH = 85%), declined to 1.02 at the peak fireworks influence from a background ∼1.7. Strong wavelength dependence of light scattering with Ångström exponent ∼2.2 throughout the event showed a size distribution dominated by sub-micrometer particles. Likewise, single scattering albedo at 870 nm remained constant throughout the event with ω = 0.86 ± 0.03, indicating light absorbing carbon, though not dominant, was mixed with organic carbon. Subsequent laboratory testing with ground-level sparklers showed that pyrotechnics smoke can generate a strong hygroscopic response, however. As confirmed with chemical analysis, the chemistry of the fireworks was key to defining the hygroscopic response. Sparkler smoke was dominated by salt species such as hygroscopic potassium chloride while it lacked the black powder explosives in aerial fireworks that contribute organic and elemental carbon to its non-hygroscopic smoke.

What have we learned from HaChi (HAZE IN CHINA) project?

NASA Astrophysics Data System (ADS)

Zhao, Chunsheng; Wiedensohler, Alfred

2016-04-01

HaChi (Haze in China) project, a joint research between Chinese NSFC and German DFG, focuses on investigating the aerosol hygroscopic properties in the North China Plain and their relationships to aerosol optics, radiation, cloud physics and ozone photochemistry. As we know, Eastern China has suffered from severe pollution caused by large concentrations of aerosol particles resulting from emissions from fossil fuel and biomass burning, transportation and some other combustion sources. Low visibility events are frequently encountered and mainly accompanied with haze as a result of either high aerosol loading or the strong hygroscopic growth of the aerosol particles. Especially at relative humidities between 90 and 99%, the aerosol particles grow exponentially. The hygroscopic behaviors at relative humidities close to 100% are also strongly linked to the particles ability to grow into cloud droplets at supersaturation. In my talk, I will present an overview of the up to date results from a serial of intensive and comprehensive field campaigns conducted at the sites of Wuqing and Xianghe, China, between 2009 and 2014. The measurements of the ambient aerosol hygroscopic properties at high RH between 90 and 98.5% are reported first. These in situ field measurements of atmospheric aerosol are unique with respect to their high RH range and especially of importance to better understand the widespread anthropogenic haze over the North China Plain. Then I will introduce the methods for calculating of aerosol hygroscopicity and their parameterization schemes derived from size-segregated chemical composition and the light scattering enhancement factor measurements in the North China Plain. A new method was proposed to retrieve the ratio of the externally mixed light absorbing carbon mass to the total mass of light absorbing carbon. A new parameterization scheme of light extinction for low visibilities on hazy days is proposed based on visibility, relative humidity, aerosol hygroscopic growth factors and particle number size distributions measured. Cloud Condensation Nuclei (CCN) closure study is conducted with bulk CCN number concentration and calculated CCN number concentration based on the aerosol number size distribution and size-resolved activation properties. An evaluation of various methods for CCN parameterization is presented based on in situ measurements of aerosol activation properties within HaChi project. Hygroscopic growth of aerosol particles can significantly affect their single-scattering albedo, and consequently alters the aerosol effect on tropospheric photochemistry. At last, I will introduce the results on the relationship between aerosol hygroscopic properties and aerosol radiation including impacts of aerosol hygroscopic growth on the NO2 photolysis rate coefficient and the estimation of direct aerosol radiative effect in the North China Plan.

Gas-particle partitioning of alcohol vapors on organic aerosols.

PubMed

Chan, Lap P; Lee, Alex K Y; Chan, Chak K

2010-01-01

Single particle levitation using an electrodynamic balance (EDB) has been found to give accurate and direct hygroscopic measurements (gas-particle partitioning of water) for a number of inorganic and organic aerosol systems. In this paper, we extend the use of an EDB to examine the gas-particle partitioning of volatile to semivolatile alcohols, including methanol, n-butanol, n-octanol, and n-decanol, on levitated oleic acid particles. The measured K(p) agreed with Pankow's absorptive partitioning model. At high n-butanol vapor concentrations (10(3) ppm), the uptake of n-butanol reduced the average molecular-weight of the oleic acid particle appreciably and hence increased the K(p) according to Pankow's equation. Moreover, the hygroscopicity of mixed oleic acid/n-butanol particles was higher than the predictions given by the UNIFAC model (molecular group contribution method) and the ZSR equation (additive rule), presumably due to molecular interactions between the chemical species in the mixed particles. Despite the high vapor concentrations used, these findings warrant further research on the partitioning of atmospheric organic vapors (K(p)) near sources and how collectively they affect the hygroscopic properties of organic aerosols.

Measurements of submicron aerosols at the California-Mexico border during the Cal-Mex 2010 field campaign

NASA Astrophysics Data System (ADS)

Levy, Misti E.; Zhang, Renyi; Zheng, Jun; Tan, Haobo; Wang, Yuan; Molina, Luisa T.; Takahama, S.; Russell, L. M.; Li, Guohui

2014-05-01

We present measurements of submicron aerosols in Tijuana, Mexico during the Cal-Mex 2010 field campaign. A suite of aerosol instrumentations were deployed, including a hygroscopic-volatility tandem differential mobility analyzer (HV-TDMA), aerosol particle mass analyzer (APM), condensation particle counter (CPC), cavity ring-down spectrometer (CRDS), and nephelometer to measure the aerosol size distributions, effective density, hygroscopic growth factors (HGF), volatility growth factors (VGF), and optical properties. The average mass concentration of PM0.6 is 10.39 ± 7.61 μg m-3, and the derived average black carbon (BC) mass concentration is 2.87 ± 2.65 μg m-3. There is little new particle formation or particle growth during the day, and the mass loading is dominated by organic aerosols and BC, which on average are 37% and 27% of PM1.0, respectively. For four particle sizes of 46, 81, 151, and 240 nm, the measured particle effective density, HGFs, and VGFs exhibit distinct diurnal trends and size-dependence. For smaller particles (46 and 81 nm), the effective density distribution is unimodal during the day and night, signifying an internally mixed aerosol composition. In contrast, larger particles (151 and 240 nm) exhibit a bi-modal effective density distribution during the daytime, indicating an external mixture of fresh BC and organic aerosols, but a unimodal distribution during the night, corresponding to an internal mixture of BC and organic aerosols. The smaller particles show a noticeable diurnal trend in the effective density distribution, with the highest effective density (1.70 g cm-3) occurring shortly after midnight and the lowest value (0.90 g cm-3) occurring during the afternoon, corresponding most likely to primary organic aerosols and BC, respectively. Both HGFs and VGFs measured are strongly size-dependent. HGFs increase with increasing particle size, indicating that the largest particles are more hygroscopic. VGFs decrease with increasing particle size, indicating that larger particles are more volatile. The hygroscopicity distributions of smaller particles (46 and 81 nm) are unimodal, with a HGF value close to unity. Large particles typically exhibit a bi-modal distribution, with a non-hygroscopic mode and a hygroscopic mode. For all particle sizes, the VGF distributions are bimodal, with a primary non-volatile mode and a secondary volatile mode. The average extinction, scattering, and absorption coefficients are 86.04, 63.07, and 22.97 Mm-1, respectively, and the average SSA is 0.75. Our results reveal that gasoline and diesel vehicles produce a significant amount of black carbon particles in this US-Mexico border region, which impacts the regional environment and climate.

Hygroscopic salts and the potential for life on Mars.

PubMed

Davila, Alfonso F; Duport, Luis Gago; Melchiorri, Riccardo; Jänchen, Jochen; Valea, Sergio; de Los Rios, Asunción; Fairén, Alberto G; Möhlmann, Diedrich; McKay, Christopher P; Ascaso, Carmen; Wierzchos, Jacek

2010-01-01

Hygroscopic salts have been detected in soils in the northern latitudes of Mars, and widespread chloride-bearing evaporitic deposits have been detected in the southern highlands. The deliquescence of hygroscopic minerals such as chloride salts could provide a local and transient source of liquid water that would be available for microorganisms on the surface. This is known to occur in the Atacama Desert, where massive halite evaporites have become a habitat for photosynthetic and heterotrophic microorganisms that take advantage of the deliquescence of the salt at certain relative humidity (RH) levels. We modeled the climate conditions (RH and temperature) in a region on Mars with chloride-bearing evaporites, and modeled the evolution of the water activity (a(w)) of the deliquescence solutions of three possible chloride salts (sodium chloride, calcium chloride, and magnesium chloride) as a function of temperature. We also studied the water absorption properties of the same salts as a function of RH. Our climate model results show that the RH in the region with chloride-bearing deposits on Mars often reaches the deliquescence points of all three salts, and the temperature reaches levels above their eutectic points seasonally, in the course of a martian year. The a(w) of the deliquescence solutions increases with decreasing temperature due mainly to the precipitation of unstable phases, which removes ions from the solution. The deliquescence of sodium chloride results in transient solutions with a(w) compatible with growth of terrestrial microorganisms down to 252 K, whereas for calcium chloride and magnesium chloride it results in solutions with a(w) below the known limits for growth at all temperatures. However, taking the limits of a(w) used to define special regions on Mars, the deliquescence of calcium chloride deposits would allow for the propagation of terrestrial microorganisms at temperatures between 265 and 253 K, and for metabolic activity (no growth) at temperatures between 253 and 233 K.

Direct measurements of the optical cross sections and refractive indices of individual volatile and hygroscopic aerosol particles.

PubMed

Mason, B J; Cotterell, M I; Preston, T C; Orr-Ewing, A J; Reid, J P

2015-06-04

We present measurements of the evolving extinction cross sections of individual aerosol particles (spanning 700-2500 nm in radius) during the evaporation of volatile components or hygroscopic growth using a combination of a single particle trap formed from a Bessel light beam and cavity ring-down spectroscopy. For single component organic aerosol droplets of 1,2,6-hexanetriol, polyethylene glycol 400, and glycerol, the slow evaporation of the organic component (over time scales of 1000 to 10,000 s) leads to a time-varying size and extinction cross section that can be used to estimate the refractive index of the droplet. Measurements on binary aqueous-inorganic aerosol droplets containing one of the inorganic solutes ammonium bisulfate, ammonium sulfate, sodium nitrate, or sodium chloride (over time scales of 1000 to 15,000 s) under conditions of changing relative humidity show that extinction cross-section measurements are consistent with expectations from accepted models for the variation in droplet refractive index with hygroscopic growth. In addition, we use these systems to establish an experimental protocol for future single particle extinction measurements. The advantages of mapping out the evolving light extinction cross-section of an individual particle over extended time frames accompanied by hygroscopic cycling or component evaporation are discussed.

Contributions to the Understanding of Aerosol Microphysics Towards Improving the Assessment of Climate Radiative Forcing

NASA Astrophysics Data System (ADS)

Dawson, Kyle William

The study of climate and the associated impacts imposed by human activity has garnered the attention of scientists and policy makers since the 1950s. Research into the various atmospheric constituents that interact with solar radiation thus modulating Earth's radiative budget has been largely focused on the contributions from greenhouse gases and later focused on the role of atmospheric aerosol. The role of atmospheric aerosol, i.e. a solid or aqueous phase particulate, is complex and presents an opportunity for bettering the assessments of climate radiative forcing (i.e. the fraction of climate change due to anthropogenic, rather than natural, activities) in several ways. First, motivated to better understand the radiative effects of the Earth's background aerosol state to improve the assessment of anthropogenic effects, an experimental study on the water uptake ability of xanthan gum as a proxy for marine hydrogel, a component of natural primary emitted seaspray aerosol, is presented. Marine hydrogel comprises an organic component of the ocean surface microlayer that is released to the atmosphere via the bursting of bubbles generated by entrainment of air through crashing waves. This study investigates the water uptake ability (i.e. hygroscopicity) of these particles when exposed to a range of relative humidity (RH). The hydration characteristics of aerosolized pure xanthan gum as well as xanthan gum/salt mixtures were studied using a hygroscopic tandem differential mobility analyzer (HTDMA) and cloud condensation nuclei counter (CCNc). The hygroscopicity of the various solutions were compared to theoretical thermodynamic calculations accounting for the component volume fractions as a function of relative humidity. The data show that pure xanthan gum aerosol hygroscopicity behaves as other organic polysaccharides and, when combined with salts, is reasonably approximated by the volume fraction mixing rules above 90% RH. Deviations occur below 90% RH as well as for CCNc measured hygroscopicity and HTDMA measured hygroscopicity at 90% RH, and are discussed in terms of hydration regimes associated with structural changes imposed by polymer/salt crosslinks. Second, motivated by a necessity to provide better constraints for climate model assessments of radiative forcing, a computational study for developing a link between climate models and observations from remote sensing techniques is presented. The Creating Aerosol Types from CHemistry (CATCH) algorithm has been developed for providing atmospheric models with estimated aerosol types, analogous to those that are retrieved by remote sensing methods. To date, the link between models and remote sensing retrievals is crude and is based on the total column attenuation of radiation by aerosol called the aerosol optical depth (AOD). In this study, through multivariate clustering techniques, this link is expanded to produce model-calculated aerosol types of dusty mix, maritime, urban, smoke, and fresh smoke, that are analogous to those retrieved by remote sensing. The CATCH algorithm shows that vertically-resolved aerosol types compare well to those measured by aircraft-mounted High Spectral Resolution Lidar - version 1 (HSRL-1) during the Ship-Aircraft Bio-Optical Research (SABOR) field campaign during July/August of 2014. Flight-by-flight comparisons of the type-apportioned AOD and vertically-resolved aerosol extinction also compare well. The CATCH algorithm is then applied to a high-resolution nested grid domain over North America and found to produce encouraging results of spatially relevant aerosol types such as dusty mix aerosol over the Caribbean, maritime aerosol over oceans, urban aerosol over large cities, smoke aerosol over weak forest fires, and fresh smoke aerosol over strong forest fires.

Reduction in biomass burning aerosol light absorption upon humidification: roles of inorganically-induced hygroscopicity, particle collapse, and photoacoustic heat and mass transfer

NASA Astrophysics Data System (ADS)

Lewis, K. A.; Arnott, W. P.; Moosmüller, H.; Chakrabarty, R. K.; Carrico, C. M.; Kreidenweis, S. M.; Day, D. E.; Malm, W. C.; Laskin, A.; Jimenez, J. L.; Ulbrich, I. M.; Huffman, J. A.; Onasch, T. B.; Trimborn, A.; Liu, L.; Mishchenko, M. I.

2009-07-01

Smoke particle emissions from the combustion of biomass fuels typical for the western and southeastern United States were studied and compared under high humidity and ambient conditions in the laboratory. The fuels used are Montana ponderosa pine (Pinus ponderosa), southern California chamise (Adenostoma fasciculatum), and Florida saw palmetto (Serenoa repens). Information on the non-refractory chemical composition of biomass burning aerosol from each fuel was obtained with an aerosol mass spectrometer and through estimation of the black carbon concentration from light absorption measurements at 870 nm. Changes in the optical and physical particle properties under high humidity conditions were observed for hygroscopic smoke particles containing substantial inorganic mass fractions that were emitted from combustion of chamise and palmetto fuels. Light scattering cross sections increased under high humidity for these particles, consistent with the hygroscopic growth measured for 100 nm particles in HTDMA measurements. Photoacoustic measurements of aerosol light absorption coefficients reveal a 20% reduction with increasing relative humidity, contrary to the expectation of light absorption enhancement by the liquid coating taken up by hygroscopic particles. This reduction is hypothesized to arise from two mechanisms: 1. Shielding of inner monomers after particle consolidation or collapse with water uptake; 2. The contribution of mass transfer through evaporation and condensation at high relative humidity to the usual heat transfer pathway for energy release by laser-heated particles in the photoacoustic measurement of aerosol light absorption. The mass transfer contribution is used to evaluate the fraction of aerosol surface covered with liquid water solution as a function of RH.

High-temperature XAFS measurement of molten salt systems

NASA Astrophysics Data System (ADS)

Okamoto, Y.; Akabori, M.; Motohashi, H.; Itoh, A.; Ogawa, T.

2002-07-01

A measurement system for high temperature XAFS was developed for investigating the local structure of hygroscopic molten salts like rare earth halides. A solid sample was enclosed in the upper tank of a quartz cell having a sandglass shape under reduced pressure to avoid oxygen and moisture. The measurement was carried out in an electric furnace capable of a highest temperature of 1273 K. After melting, the sample runs down through the melt path with 0.1 mm (or 0.2 mm) thickness to the lower tank. The measurable energy was limited to be above 10 keV due to the absorption of the quartz cell. We confirmed that the measurement of the expensive hygroscopic sample is possible with this system.

Chemical composition, microstructure, and hygroscopic properties of aerosol particles at the Zotino Tall Tower Observatory (ZOTTO), Siberia, during a summer campaign

DOE PAGES

Mikhailov, E. F.; Mironov, G. N.; Pöhlker, C.; ...

2015-03-16

In this study we describe the hygroscopic properties of accumulation- and coarse-mode aerosol particles sampled at the Zotino Tall Tower Observatory (ZOTTO) in Central Siberia (61° N; 89° E) from 16 to 21 June 2013. The hygroscopic growth measurements were supplemented with chemical analyses of the samples, including inorganic ions and organic/elemental carbon. In addition, the microstructure and chemical composition of aerosol particles were analyzed by X-ray micro-spectroscopy (STXM-NEXAFS) and transmission electron microscopy (TEM). A mass closure analysis indicates that organic carbon accounted for 61 and 38% of PM in the accumulation mode and coarse mode, respectively. The water solublemore » fraction of organic matter was estimated to be 52 and 8% of PM in these modes. Sulfate, predominantly in the form of ammoniated sulfate, was the dominant inorganic component in both size modes: ~ 34% in the accumulation vs. ~ 47% in the coarse mode. The hygroscopic growth measurements were conducted with a filter-based differential hygroscopicity analyzer (FDHA) over the range of 5–99.4% RH in the hydration and dehydration operation modes. The FDHA study indicates that both accumulation and coarse modes exhibit pronounced water uptake approximately at the same RH, starting at ~ 70%, while efflorescence occurred at different humidities, i.e., at ~ 35% RH for submicron particles vs. ~ 50% RH for supermicron particles. This ~ 15% RH difference was attributed to higher content of organic material in the submicron particles, which suppresses water release in the dehydration experiments. The kappa mass interaction model (KIM) was applied to characterize and parameterize non-ideal solution behavior and concentration-dependent water uptake by atmospheric aerosol samples in the 5–99.4% RH range. Based on KIM, the volume-based hygroscopicity parameter, κ v, was calculated. The κ v, ws value related to the water soluble (ws) fraction was estimated to be ~ 0.15 for the accumulation mode and ~ 0.36 for the coarse mode, respectively. The obtained κ v, ws for the accumulation mode is in good agreement with earlier data reported for remote sites in the Amazon rain forest (κ v ≈ 0.15) and a Colorado boreal forest (κ v ≈ 0.16). We used the Zdanovskii–Stokes–Robinson (ZSR) mixing rule to predict the chemical composition dependent hygroscopicity, κ v, p. The obtained κ v, p values overestimate the experimental FDHA-KIM-derived κ v, ws by factors of 1.8 and 1.5 for the accumulation and coarse modes, respectively. This divergence can be partly explained by incomplete dissolution of the hygroscopic inorganic compounds resulting from kinetic limitations due to a sparingly soluble organic coating. The TEM and STXM-NEXAFS results indicate that aged submicron (>300 nm) and supermicron aerosol particles possess core-shell structures with an inorganic core, and are enriched in organic carbon at the mixed particle surface. The direct FDHA kinetic studies provide a bulk diffusion coefficient of water of ~ 10 −12 cm 2 s −1 indicating a semi-solid state of the organic-rich phase leading to kinetic limitations of water uptake and release during hydration and dehydration cycles. Overall the present ZOTTO data set, obtained in the growing season, has revealed a strong influence of organic carbon on the hygroscopic properties of the ambient aerosols. The sparingly soluble organic coating controls hygroscopic growth, phase transitions, and microstructural rearrangement processes. The observed kinetic limitations can strongly influence the outcome of experiments performed on multi-second time scales, such as the commonly applied HTDMA (Hygroscopicity Tandem Differential Mobility Analyzer) and CCNC (Cloud Condensation Nuclei Counter) measurements.« less

Chemical composition, microstructure, and hygroscopic properties of aerosol particles at the Zotino Tall Tower Observatory (ZOTTO), Siberia, during a summer campaign

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

Mikhailov, E. F.; Mironov, G. N.; Pöhlker, C.

In this study we describe the hygroscopic properties of accumulation- and coarse-mode aerosol particles sampled at the Zotino Tall Tower Observatory (ZOTTO) in Central Siberia (61° N; 89° E) from 16 to 21 June 2013. The hygroscopic growth measurements were supplemented with chemical analyses of the samples, including inorganic ions and organic/elemental carbon. In addition, the microstructure and chemical composition of aerosol particles were analyzed by X-ray micro-spectroscopy (STXM-NEXAFS) and transmission electron microscopy (TEM). A mass closure analysis indicates that organic carbon accounted for 61 and 38% of PM in the accumulation mode and coarse mode, respectively. The water solublemore » fraction of organic matter was estimated to be 52 and 8% of PM in these modes. Sulfate, predominantly in the form of ammoniated sulfate, was the dominant inorganic component in both size modes: ~ 34% in the accumulation vs. ~ 47% in the coarse mode. The hygroscopic growth measurements were conducted with a filter-based differential hygroscopicity analyzer (FDHA) over the range of 5–99.4% RH in the hydration and dehydration operation modes. The FDHA study indicates that both accumulation and coarse modes exhibit pronounced water uptake approximately at the same RH, starting at ~ 70%, while efflorescence occurred at different humidities, i.e., at ~ 35% RH for submicron particles vs. ~ 50% RH for supermicron particles. This ~ 15% RH difference was attributed to higher content of organic material in the submicron particles, which suppresses water release in the dehydration experiments. The kappa mass interaction model (KIM) was applied to characterize and parameterize non-ideal solution behavior and concentration-dependent water uptake by atmospheric aerosol samples in the 5–99.4% RH range. Based on KIM, the volume-based hygroscopicity parameter, κ v, was calculated. The κ v, ws value related to the water soluble (ws) fraction was estimated to be ~ 0.15 for the accumulation mode and ~ 0.36 for the coarse mode, respectively. The obtained κ v, ws for the accumulation mode is in good agreement with earlier data reported for remote sites in the Amazon rain forest (κ v ≈ 0.15) and a Colorado boreal forest (κ v ≈ 0.16). We used the Zdanovskii–Stokes–Robinson (ZSR) mixing rule to predict the chemical composition dependent hygroscopicity, κ v, p. The obtained κ v, p values overestimate the experimental FDHA-KIM-derived κ v, ws by factors of 1.8 and 1.5 for the accumulation and coarse modes, respectively. This divergence can be partly explained by incomplete dissolution of the hygroscopic inorganic compounds resulting from kinetic limitations due to a sparingly soluble organic coating. The TEM and STXM-NEXAFS results indicate that aged submicron (>300 nm) and supermicron aerosol particles possess core-shell structures with an inorganic core, and are enriched in organic carbon at the mixed particle surface. The direct FDHA kinetic studies provide a bulk diffusion coefficient of water of ~ 10 −12 cm 2 s −1 indicating a semi-solid state of the organic-rich phase leading to kinetic limitations of water uptake and release during hydration and dehydration cycles. Overall the present ZOTTO data set, obtained in the growing season, has revealed a strong influence of organic carbon on the hygroscopic properties of the ambient aerosols. The sparingly soluble organic coating controls hygroscopic growth, phase transitions, and microstructural rearrangement processes. The observed kinetic limitations can strongly influence the outcome of experiments performed on multi-second time scales, such as the commonly applied HTDMA (Hygroscopicity Tandem Differential Mobility Analyzer) and CCNC (Cloud Condensation Nuclei Counter) measurements.« less

Chemical composition, microstructure, and hygroscopic properties of aerosol particles at the Zotino Tall Tower Observatory (ZOTTO), Siberia, during a summer campaign

NASA Astrophysics Data System (ADS)

Mikhailov, E. F.; Mironov, G. N.; Pöhlker, C.; Chi, X.; Krüger, M. L.; Shiraiwa, M.; Förster, J.-D.; Pöschl, U.; Vlasenko, S. S.; Ryshkevich, T. I.; Weigand, M.; Kilcoyne, A. L. D.; Andreae, M. O.

2015-03-01

In this study we describe the hygroscopic properties of accumulation- and coarse-mode aerosol particles sampled at the Zotino Tall Tower Observatory (ZOTTO) in Central Siberia (61° N; 89° E) from 16 to 21 June 2013. The hygroscopic growth measurements were supplemented with chemical analyses of the samples, including inorganic ions and organic/elemental carbon. In addition, the microstructure and chemical composition of aerosol particles were analyzed by X-ray micro-spectroscopy (STXM-NEXAFS) and transmission electron microscopy (TEM). A mass closure analysis indicates that organic carbon accounted for 61 and 38% of PM in the accumulation mode and coarse mode, respectively. The water soluble fraction of organic matter was estimated to be 52 and 8% of PM in these modes. Sulfate, predominantly in the form of ammoniated sulfate, was the dominant inorganic component in both size modes: ∼34% in the accumulation vs. ∼47% in the coarse mode. The hygroscopic growth measurements were conducted with a filter-based differential hygroscopicity analyzer (FDHA) over the range of 5-99.4% RH in the hydration and dehydration operation modes. The FDHA study indicates that both accumulation and coarse modes exhibit pronounced water uptake approximately at the same RH, starting at ∼70%, while efflorescence occurred at different humidities, i.e., at ∼35% RH for submicron particles vs. ∼50% RH for supermicron particles. This ∼15% RH difference was attributed to higher content of organic material in the submicron particles, which suppresses water release in the dehydration experiments. The kappa mass interaction model (KIM) was applied to characterize and parameterize non-ideal solution behavior and concentration-dependent water uptake by atmospheric aerosol samples in the 5-99.4% RH range. Based on KIM, the volume-based hygroscopicity parameter, κv, was calculated. The κv, ws value related to the water soluble (ws) fraction was estimated to be ∼0.15 for the accumulation mode and ∼0.36 for the coarse mode, respectively. The obtained κv, ws for the accumulation mode is in good agreement with earlier data reported for remote sites in the Amazon rain forest (κv ≈ 0.15) and a Colorado boreal forest (κv ≈ 0.16). We used the Zdanovskii-Stokes-Robinson (ZSR) mixing rule to predict the chemical composition dependent hygroscopicity, κv, p. The obtained κv, p values overestimate the experimental FDHA-KIM-derived κv, ws by factors of 1.8 and 1.5 for the accumulation and coarse modes, respectively. This divergence can be partly explained by incomplete dissolution of the hygroscopic inorganic compounds resulting from kinetic limitations due to a sparingly soluble organic coating. The TEM and STXM-NEXAFS results indicate that aged submicron (>300 nm) and supermicron aerosol particles possess core-shell structures with an inorganic core, and are enriched in organic carbon at the mixed particle surface. The direct FDHA kinetic studies provide a bulk diffusion coefficient of water of ∼10-12 cm2 s-1 indicating a semi-solid state of the organic-rich phase leading to kinetic limitations of water uptake and release during hydration and dehydration cycles. Overall the present ZOTTO data set, obtained in the growing season, has revealed a strong influence of organic carbon on the hygroscopic properties of the ambient aerosols. The sparingly soluble organic coating controls hygroscopic growth, phase transitions, and microstructural rearrangement processes. The observed kinetic limitations can strongly influence the outcome of experiments performed on multi-second time scales, such as the commonly applied HTDMA (Hygroscopicity Tandem Differential Mobility Analyzer) and CCNC (Cloud Condensation Nuclei Counter) measurements.

Chemical composition, microstructure, and hygroscopic properties of aerosol particles at the Zotino Tall Tower Observatory (ZOTTO), Siberia, during a summer campaign

NASA Astrophysics Data System (ADS)

Mikhailov, E. F.; Mironov, G. N.; Pöhlker, C.; Chi, X.; Krüger, M. L.; Shiraiwa, M.; Förster, J.-D.; Pöschl, U.; Vlasenko, S. S.; Ryshkevich, T. I.; Weigand, M.; Kilcoyne, A. L. D.; Andreae, M. O.

2015-08-01

In this study we describe the hygroscopic properties of accumulation- and coarse-mode aerosol particles sampled at the Zotino Tall Tower Observatory (ZOTTO) in central Siberia (61° N, 89° E) from 16 to 21 June 2013. The hygroscopic growth measurements were supplemented with chemical analyses of the samples, including inorganic ions and organic/elemental carbon. In addition, the microstructure and chemical compositions of aerosol particles were analyzed by x-ray micro-spectroscopy (STXM-NEXAFS) and transmission electron microscopy (TEM). A mass closure analysis indicates that organic carbon accounted for 61 and 38 % of particulate matter (PM) in the accumulation mode and coarse mode, respectively. The water-soluble fraction of organic matter was estimated to be 52 and 8 % of PM in these modes. Sulfate, predominantly in the form of ammoniated sulfate, was the dominant inorganic component in both size modes: ~ 34 % in the accumulation mode vs. ~ 47 % in the coarse mode. The hygroscopic growth measurements were conducted with a filter-based differential hygroscopicity analyzer (FDHA) over the range of 5-99.4 % RH in the hydration and dehydration operation modes. The FDHA study indicates that both accumulation and coarse modes exhibit pronounced water uptake approximately at the same relative humidity (RH), starting at ~ 70 %, while efflorescence occurred at different humidities, i.e., at ~ 35 % RH for submicron particles vs. ~ 50 % RH for supermicron particles. This ~ 15 % RH difference was attributed to higher content of organic material in the submicron particles, which suppresses water release in the dehydration experiments. The kappa mass interaction model (KIM) was applied to characterize and parameterize non-ideal solution behavior and concentration-dependent water uptake by atmospheric aerosol samples in the 5-99.4 % RH range. Based on KIM, the volume-based hygroscopicity parameter, κv, was calculated. The κv,ws value related to the water-soluble (ws) fraction was estimated to be ~ 0.15 for the accumulation mode and ~ 0.36 for the coarse mode, respectively. The obtained κv,ws for the accumulation mode is in good agreement with earlier data reported for remote sites in the Amazon rain forest (κv ≈ 0.15) and a Colorado mountain forest (κv ≈ 0.16 ). We used the Zdanovskii-Stokes-Robinson (ZSR) mixing rule to predict the chemical composition dependent hygroscopicity, κv,p. The obtained κv,p values overestimate the experimental FDHA-KIM-derived κv,ws by factors of 1.8 and 1.5 for the accumulation and coarse modes, respectively. This divergence can be explained by incomplete dissolution of the hygroscopic inorganic compounds resulting from kinetic limitations due to a sparingly soluble organic coating. The TEM and STXM-NEXAFS results indicate that aged submicron (> 300 nm) and supermicron aerosol particles possess core-shell structures with an inorganic core, and are enriched in organic carbon at the mixed particle surface. The direct FDHA kinetic studies provide a bulk diffusion coefficient of water of ~ 10-12 cm2 s-1 indicating a semi-solid state of the organic-rich phase leading to kinetic limitations of water uptake and release during hydration and dehydration cycles. Overall, the present ZOTTO data set, obtained in the growing season, has revealed a strong influence of organic carbon on the hygroscopic properties of the ambient aerosols. The sparingly soluble organic coating controls hygroscopic growth, phase transitions, and microstructural rearrangement processes. The observed kinetic limitations can strongly influence the outcome of experiments performed on multi-second timescales, such as the commonly applied HTDMA (Hygroscopicity Tandem Differential Mobility Analyzer) and CCNC (Cloud Condensation Nuclei Counter) measurements.

Measurements of the hygroscopic and deliquescence properties of organic compounds of different solubilities in water and their relationship with cloud condensation nuclei activities.

PubMed

Chan, Man Nin; Kreidenweis, Sonia M; Chan, Chak K

2008-05-15

The initial phase (solid or aqueous droplet) of aerosol particles prior to activation is among the critical factors in determining their cloud condensation nuclei (CCN) activity. Single-particle levitation in an electrodynamic balance (EDB)was used to measure the phase transitions and hygroscopic properties of aerosol particles of 11 organic compounds with different solubilities (10(-1) to 102 g solute/100 g water). We use these data and other literature data to relate the CCN activity and hygroscopicity of organic compounds with different solubilities. The EDB data show that glyoxylic acid, 4-methylphthalic acid, monosaccharides (fructose and mannose), and disaccharides (maltose and lactose) did not crystallize and existed as metastable droplets at low relative humidity (RH). Hygroscopic data from this work and in the literature support earlier studies showing that the CCN activities of compounds with solubilities down to the order of 10(-1) g solute/100 g water can be predicted by standard Köhler theory with the assumption of complete dissolution of the solute at activation. We also demonstrate the use of evaporation data (or efflorescence data), which provides information on the water contents of metastable solutions below the compound deliquescence RH that can be extrapolated to higher dilutions, to predict the CCN activity of organic particles, particularly for sparingly soluble organic compounds that do not deliquesce at RH achievable in the EDB and in the hygroscopic tandem differential mobility analyzer.

Long-term observations of the background aerosol at Cabauw, The Netherlands.

PubMed

Mamali, D; Mikkilä, J; Henzing, B; Spoor, R; Ehn, M; Petäjä, T; Russchenberg, H; Biskos, G

2018-06-01

Long-term measurements of PM 2.5 mass concentrations and aerosol particle size distributions from 2008 to 2015, as well as hygroscopicity measurements conducted over one year (2008-2009) at Cabauw, The Netherlands, are compiled here in order to provide a comprehensive dataset for understanding the trends and annual variabilities of the atmospheric aerosol in the region. PM 2.5 concentrations have a mean value of 14.4μgm -3 with standard deviation 2.1μgm -3 , and exhibit an overall decreasing trend of -0.74μgm -3 year -1 . The highest values are observed in winter and spring and are associated with a shallower boundary layer and lower precipitation, respectively, compared to the rest of the seasons. Number concentrations of particles smaller than 500nm have a mean of 9.2×10 3 particles cm -3 and standard deviation 4.9×10 3 particles cm -3 , exhibiting an increasing trend between 2008 and 2011 and a decreasing trend from 2013 to 2015. The particle number concentrations exhibit highest values in spring and summer (despite the increased precipitation) due to the high occurrence of nucleation-mode particles, which most likely are formed elsewhere and are transported to the observation station. Particle hygroscopicity measurements show that, independently of the air mass origin, the particles are mostly externally mixed with the more hydrophobic mode having a mean hygroscopic parameter κ of 0.1 while for the more hydrophilic mode κ is 0.35. The hygroscopicity of the smaller particles investigated in this work (i.e., particles having diameters of 35nm) appears to increase during the course of the nucleation events, reflecting a change in the chemical composition of the particles. Copyright © 2017 Elsevier B.V. All rights reserved.

Enhanced hydrophobicity and volatility of submicron aerosols under severe emission control conditions in Beijing

NASA Astrophysics Data System (ADS)

Wang, Yuying; Zhang, Fang; Li, Zhanqing; Tan, Haobo; Xu, Hanbing; Ren, Jingye; Zhao, Jian; Du, Wei; Sun, Yele

2017-04-01

A series of strict emission control measures was implemented in Beijing and the surrounding seven provinces to ensure good air quality during the 2015 China Victory Day parade, rendering a unique opportunity to investigate the anthropogenic impact of aerosol properties. Submicron aerosol hygroscopicity and volatility were measured during and after the control period using a hygroscopic and volatile tandem differential mobility analyzer (H/V-TDMA) system. Three periods, namely the control clean period (Clean1), the non-control clean period (Clean2), and the non-control pollution period (Pollution), were selected to study the effect of the emission control measures on aerosol hygroscopicity and volatility. Aerosol particles became more hydrophobic and volatile due to the emission control measures. The hygroscopicity parameter (κ) of 40-200 nm particles decreased by 32.0-8.5 % during the Clean1 period relative to the Clean2 period, while the volatile shrink factor (SF) of 40-300 nm particles decreased by 7.5-10.5 %. The emission controls also changed the diurnal variation patterns of both the probability density function of κ (κ-PDF) and the probability density function of SF (SF-PDF). During Clean1 the κ-PDF showed one nearly hydrophobic (NH) mode for particles in the nucleation mode, which was likely due to the dramatic reduction in industrial emissions of inorganic trace gases. Compared to the Pollution period, particles observed during the Clean1 and Clean2 periods exhibited a more significant nonvolatile (NV) mode throughout the day, suggesting a more externally mixed state particularly for the 150 nm particles. Aerosol hygroscopicities increased as particle sizes increased, with the greatest increases seen during the Pollution period. Accordingly, the aerosol volatility became weaker (i.e., SF increased) as particle sizes increased during the Clean1 and Clean2 periods, but no apparent trend was observed during the Pollution period. Based on a correlation analysis of the number fractions of NH and NV particles, we found that a higher number fraction of hydrophobic and volatile particles during the emission control period.

Measurements of the evaporation and hygroscopic response of single fine-mode aerosol particles using a Bessel beam optical trap.

PubMed

Cotterell, Michael I; Mason, Bernard J; Carruthers, Antonia E; Walker, Jim S; Orr-Ewing, Andrew J; Reid, Jonathan P

2014-02-07

A single horizontally-propagating zeroth order Bessel laser beam with a counter-propagating gas flow was used to confine single fine-mode aerosol particles over extended periods of time, during which process measurements were performed. Particle sizes were measured by the analysis of the angular variation of light scattered at 532 nm by a particle in the Bessel beam, using either a probe beam at 405 nm or 633 nm. The vapour pressures of glycerol and 1,2,6-hexanetriol particles were determined to be 7.5 ± 2.6 mPa and 0.20 ± 0.02 mPa respectively. The lower volatility of hexanetriol allowed better definition of the trapping environment relative humidity profile over the measurement time period, thus higher precision measurements were obtained compared to those for glycerol. The size evolution of a hexanetriol particle, as well as its refractive index at wavelengths 532 nm and 405 nm, were determined by modelling its position along the Bessel beam propagation length while collecting phase functions with the 405 nm probe beam. Measurements of the hygroscopic growth of sodium chloride and ammonium sulfate have been performed on particles as small as 350 nm in radius, with growth curves well described by widely used equilibrium state models. These are the smallest particles for which single-particle hygroscopicity has been measured and represent the first measurements of hygroscopicity on fine mode and near-accumulation mode aerosols, the size regimes bearing the most atmospheric relevance in terms of loading, light extinction and scattering. Finally, the technique is contrasted with other single particle and ensemble methods, and limitations are assessed.

Enrichment of Mineral Dust Storm Particles with Sea Salt Elements - Using bulk and Single Particle Analyses

NASA Astrophysics Data System (ADS)

Mamane, Y.; Perrino, C.; Yossef, O.

2009-12-01

Mineral aerosol emitted from African and Asian deserts plays an important role in the atmosphere. During their long-range transport, the physical and chemical properties of mineral dust particles change due to heterogeneous reactions with trace gases, coagulation with other particles, and in-cloud processing. These processes affect the optical and hygroscopic properties of dust particles, and in general influencing the physics and chemistry of the atmosphere. Four African and Arabian dust storm episodes affecting the East Mediterranean Coast in the spring of 2006 have been characterized, to determine if atmospheric natural dust particles are enriched with sea salt and anthropogenic pollution. Particle samplers included PM10 and manual dichotomous sampler that collected fine and coarse particles. Three sets of filters were used: Teflon filters for gravimetric, elemental and ionic analyses; Pre-fired Quartz-fiber filters for elemental and organic carbon; and Nuclepore filters for scanning electron microscopy analysis. Computer-controlled scanning electron microscopy (Philips XL 30 ESEM) was used to analyze single particle, for morphology, size and chemistry of selected filter samples. A detailed chemical and microscopical characterization has been performed for the particles collected during dust event days and during clear days. The Saharan and Arabian air masses increased significantly the daily mass concentrations of the coarse and the fine particle fractions. Carbonates, mostly as soil calcites mixed with dolomites, and silicates are the major components of the coarse fraction, followed by sea salt particles. In addition, the levels of anthropogenic heavy metals and sea salt elements registered during the dust episode were considerably higher than levels recorded during clear days. Sea salt elements contain Na and Cl, and smaller amounts of Mg, K, S and Br. Cl ranges from 300 to 5500 ng/m3 and Na from 100 to almost 2400 ng/m3. The Cl to Na ratio on dusty days in the coarse fraction is 2.94 versus 1.88 on clear days, quite different from the value of 1.8 found in sea water. It is rather clear that dust events are enriched with Cl. Those findings are to be investigated. The computer controlled SEM-EDX observations of the coarse fraction of PM10 confirmed the results obtained by XRF. The majority of the African dust particles are made up of mixed minerals, mostly carbonates and alumino - silicates. The EDX analysis coupled to CCSEM showed that minerals are mixed often with sea salt particles. Although some of it may be artifact (a sea salt particle is pile up on a mineral particle), it is believed that the results present reality: sea salt particles were often found on the surfaces of the aggregate minerals. Pollen and spores of diameters were not identified. Those results may have implication on the atmospheric chemistry. High concentrations of sulfates were also observed in the coarse fraction of dust episodes, and were not correlated with sea salt particles. They could be part of the soil matrix and may also form by the reaction of sulfur oxides with the natural aerosols. These reactions may be affected by the high concentration of coarse mineral particles during the Saharan and Arabian episodes.

Hygroscopicity Behavior, Activation Properties and Chemical Composition of Atmospheric Aerosol at a Background Site in the Megacity Region of Peking

NASA Astrophysics Data System (ADS)

Henning, Silvia; Nowak, Andreas; Mildenberger, Katrin; Göbel, Tina; Nekat, Bettina; van Pinxteren, Dominik; Herrmann, Hartmut; Zhao, Chunsheng; Wiedensohler, Alfred; Stratmann, Frank

2010-05-01

Large areas of China suffer from heavy air pollution (both gaseous and particulate) caused by strong economic growth in the last two decades. However, knowledge concerning the physical and chemical properties of the resulting aerosol particles populations, and their effects on the optical properties of the atmosphere, is still sparse. In the framework of the investigations presented here, comprehensive measurements concerning aerosol particle hygroscopicity, CCN ability, composition, and optical properties were performed. The investigations are part of the DFG-funded project HaChi (Haze in China) and are conducted in collaboration with the Peking University. A conclusive parameterization of aerosol hygroscopicity and activation data is aimed for, which will then be implemented in a meso-scale model to investigate aerosol-cloud-radiation and precipitation interactions. During two intensive measurements campaigns (March 2009 and July/ August 2009), in-situ aerosol measurements have been performed in an air-conditioned mobile laboratory next to the Wuqing Meteorological Station (39°23'8.53"N, 117°1'25.88"E), which is located between Bejing and Tijanjin and is thereby an ideal background site in a megacity region. The particle number size distribution (TDMPS), the particle optical properties (MAAP and nephelometer) and their hygroscopic properties at high RH (HH-TDMA, LACIS-mobile) were characterized as well as their cloud nucleating properties above supersaturation (DMT-CCNC). 24 h PM1 particle samples were continuously collected over the two campaigns in winter and summer using a DIGITEL high volume sampler (DHA-80). Additionally two 6h size-resolved samples (daytime and night-time) were collected each day applying an 11-stage Berner impactor. The size-selection of HH-TDMA, LACIS and the CCNC was synchronized with the Berner stages. Opening analysis of the winter campaign data showed that the HH-TDMA usually detected a hydrophobic and a hygroscopic mode, i.e., the particles were externally mixed. On average the growth factor in the hydrophobic mode was about 1.1 (200nm @ 98.5%). 12% of the particles were of hydrophobic nature for 200 nm and 15% over all sizes. LACIS-mobile focused on the hygroscopic mode, as this mode is mainly responsible for the optical properties of the atmosphere at high RHs. During the whole campaign very high growth factors (GFmedian = 3.56, 200 nm @ 99.2%) were observed, close to those of ammonium sulfate, with only slight dependence on the air mass. The analysis of the DIGITEL samples showed that the main components of PM1 are inorganic ions like the secondary formed ammonium nitrate und ammonium sulphate, as well as carbonaceous material. The organic carbon fraction is mostly dominated by water soluble organic carbon (80% in average) and was more analyzed in more detail for dicarboxylic acids, fatty acids, sugars and sugar related compounds. High concentrations of tracers like the anhydrosugar levoglucosan suggest biomass burning emissions as a dominant source of organic particles in the area. Closure between hygroscopic growth, CCN activation and chemical composition is aimed for with two different approaches: a) one single-parameter Köhler model applying the hygroscopicity parameter kappa following [Petters and Kreidenweis, 2007] and b) a standard Köhler model using as input parameter 4 major chemical components as analyzed from the DIGITEL samples. First tests for 200 nm particles showed very good agreement for the kappa-approach between measured and predicted critical activation. In the second approach the mass of 4 major components, namely ammonium sulfate, ammonium nitrate, sodium chloride and soluble organic mater were used as input parameter of a standard Köhler model including an insoluble core. Here the hygroscopic growth factor was underestimated, but the activation point was predicted well. Petters, M. D., and S. M. Kreidenweis (2007), A single parameter representation of hygroscopic growth and cloud condensation nucleus activity, Atmospheric Chemistry and Physics, 7, 1961-1971.

Enhanced hydrophobicity and volatility of submicron aerosols under severe emission control conditions in Beijing

NASA Astrophysics Data System (ADS)

Wang, Yuying; Zhang, Fang; Li, Zhanqing

2017-04-01

A series of strict emission control measures were implemented in Beijing and the surrounding seven provinces to ensure good air quality during the 2015 China Victory Day parade, rendering a unique opportunity to investigate anthropogenic impact of aerosol properties. Submicron aerosol hygroscopicity and volatility were measured during and after the control period using a hygroscopic and volatile tandem differential mobility analyzer (H/V-TDMA) system. Three periods, namely, the control clean period (Clean1), the non-control clean period (Clean2), and the non-control pollution period (Pollution), were selected to study the effect of the emission control measures on aerosol hygroscopicity and volatility. Aerosol particles became more hydrophobic and volatile due to the emission control measures. The hygroscopicity parameter (κ) of 40-200 nm particles decreased by 32.0%-8.5% during the Clean1 period relative to the Clean2 period, while the volatile shrink factor (SF) of 40-300 nm particles decreased by 7.5%-10.5%. The emission controls also changed the diurnal variation patterns of both the probability density function of κ (κ-PDF) and the probability density function of SF (SF-PDF). During Clean1 the κ-PDF showed one nearly-hydrophobic (NH) mode for particles in the nucleation mode, which was likely due to the dramatic reduction in industrial emissions of inorganic trace gases. Compared to the Pollution period, particles observed during the Clean1 and Clean2 periods exhibited a more significant non-volatile (NV) mode throughout the day, suggesting a more externally-mixed state particularly for the 150 nm particles. Aerosol hygroscopicities increased as particle sizes increased, with the greatest increases seen during the Pollution period. Accordingly, the aerosol volatility became weaker (i.e., SF increased) during the Clean1 and Clean2 periods, but no apparent trend was observed during the Pollution period. Based on a correlation analysis of the number fractions of NH and NV particles, we found that a higher number fraction of hydrophobic and volatile particles during the emission control period.

Aerosol Properties Observed in the Subtropical North Pacific Boundary Layer

NASA Astrophysics Data System (ADS)

Royalty, T. M.; Phillips, B. N.; Dawson, K. W.; Reed, R.; Meskhidze, N.; Petters, M. D.

2017-09-01

The impact of anthropogenic aerosol on climate forcing remains uncertain largely due to inadequate representation of natural aerosols in climate models. The marine boundary layer (MBL) might serve as a model location to study natural aerosol processes. Yet source and sink mechanisms controlling the MBL aerosol number, size distribution, chemical composition, and hygroscopic properties remain poorly constrained. Here aerosol size distribution and water uptake measurements were made aboard the R/V Hi'ialakai from 27 June to 3 July 2016 in the subtropical North Pacific Ocean. Size distributions were predominantly bimodal with an average integrated number concentration of 197 ± 98 cm-3. Hygroscopic growth factors were measured using the tandem differential mobility analyzer technique for dry 48, 96, and 144 nm particles. Mode kappa values for these were 0.57 ± 0.12, 0.51 ± 0.09, and 0.52 ± 0.08, respectively. To better understand remote MBL aerosol sources, a new algorithm was developed which decomposes hygroscopicity distributions into three classes: carbon-containing particles, sulfate-like particles, and sodium-containing particles. Results from this algorithm showed low and steady sodium-containing particle concentrations while the sulfate-like and carbon-containing particle concentrations varied during the cruise. According to the classification scheme, carbon-containing particles contributed at least 3-7%, sulfate-like particles contributed at most 77-88% and sodium-containing particles at least contributed 9-16% to the total aerosol number concentration. Size distribution and hygroscopicity data, in conjunction with air mass back trajectory analysis, suggested that the aerosol budget in the subtropical North Pacific MBL may be controlled by aerosol entrainment from the free troposphere.

Reduction in biomass burning aerosol light absorption upon humidification: roles of inorganically-induced hygroscopicity, particle collapse, and photoacoustic heat and mass transfer

NASA Astrophysics Data System (ADS)

Lewis, K. A.; Arnott, W. P.; Moosmüller, H.; Chakrabarty, R. K.; Carrico, C. M.; Kreidenweis, S. M.; Day, D. E.; Malm, W. C.; Laskin, A.; Jimenez, J. L.; Ulbrich, I. M.; Huffman, J. A.; Onasch, T. B.; Trimborn, A.; Liu, L.; Mishchenko, M. I.

2009-11-01

Smoke particle emissions from the combustion of biomass fuels typical for the western and southeastern United States were studied and compared under high humidity and ambient conditions in the laboratory. The fuels used were Montana ponderosa pine (Pinus ponderosa), southern California chamise (Adenostoma fasciculatum), and Florida saw palmetto (Serenoa repens). Information on the non-refractory chemical composition of biomass burning aerosol from each fuel was obtained with an aerosol mass spectrometer and through estimation of the black carbon concentration from light absorption measurements at 870 nm. Changes in the optical and physical particle properties under high humidity conditions were observed for hygroscopic smoke particles containing substantial inorganic mass fractions that were emitted from combustion of chamise and palmetto fuels. Light scattering cross sections increased under high humidity for these particles, consistent with the hygroscopic growth measured for 100 nm particles in HTDMA measurements. Photoacoustic measurements of aerosol light absorption coefficients revealed a 20% reduction with increasing relative humidity, contrary to the expectation of light absorption enhancement by the liquid coating taken up by hygroscopic particles. This reduction is hypothesized to arise from two mechanisms: (1) shielding of inner monomers after particle consolidation or collapse with water uptake; (2) the lower case contribution of mass transfer through evaporation and condensation at high relative humidity (RH) to the usual heat transfer pathway for energy release by laser-heated particles in the photoacoustic measurement of aerosol light absorption. The mass transfer contribution is used to evaluate the fraction of aerosol surface covered with liquid water solution as a function of RH.

Evaluation and Comparison of Three Types of Spray Dried Coprocessed Excipient Avicel® for Direct Compression

PubMed Central

Solný, Tomaš

2018-01-01

As coprocessed excipients (CPE) gain a lot of focus recently, this article compares three commercially available CPE of Avicel brand, namely, CE 15, DG, and HFE 102. Comparison is based on measured physical properties of coprocessed mixtures, respectively, flow properties, pycnometric density, mean particle size, specific surface area, moisture content, hygroscopicity, solubility, pH leaching, electrostatic charge, SEM images, and DSC. Tablets were made employing three pressure sets. Viscoelastic properties and ejection force were assessed during compression, as well as pycnometric density, mass uniformity, height, tensile strength, friability, disintegration, and wetting times. Avicel CE 15 is of mid-range flow properties, contains mid-size and nonspherical particles, and has high hygroscopicity, growing negative charge, best lubricity, lowest tensile strength, and mid-long disintegration times. Avicel DG possesses the worst flow properties, small asymmetrical particles, lowest hygroscopicity, stable charge, intermediate lubricity, and tensile strength and exhibits fast disintegration of tablets. Finally, Avicel HFE 102 has the best flow properties, large symmetrical particles, and middle hygroscopicity and its charge fluctuates throughout blending. It also exhibits inferior lubricity, the highest tensile strength, and slow disintegration of tablets. Generally, it is impossible to select the best CPE, as their different properties fit versatile needs of countless manufacturers and final products. PMID:29850496

Investigation of Biomass Burning Aerosol Hygroscopicity Using a New Tandem Differential Mobility Analyzer and New Inversion Routine.

NASA Astrophysics Data System (ADS)

Oxford, C. R.; Williams, B. J.

2017-12-01

Biomass burning aerosol (BBA) constitutes a significant fraction of atmospheric aerosol and impacts health, visibility, and radiative forcing. The nature and scale of these impacts are influenced by the size distribution of the aerosol. Hygroscopicity governs the water content of an aerosol at elevated relative humidity, and thus determines the size distribution of the hydrated aerosol. Characterization of BBA during the second Fire Lab At Missoula Experiment (FLAME-II) determined that BBA with high inorganic concentrations did not have a single hygroscopicity, but exhibited a bimodal nature. Mechanisms contributing to this bimodality could include condensation of hygrophilic inorganics, release of hygrophobic soot aerosol, presence of non-spherical morphologies, and condensation of volatile organic compounds with low hygroscopicity. Conclusions from FLAME-II attribute the bimodality to externally mixed BBA at a given diameter. Other authors, using different fuels, attribute differences in BBA hygroscopicity to non-spherical morphologies. We measured the hygroscopicity of BBA emitted from the burning of grasses obtained from western Montana in a laboratory burn chamber. The investigation used a newly built Tandem Differential Mobility Analyzer (TDMA) and a Scanning Mobility Particle Sizer together with a new TDMA inversion routine specifically designed for the analysis of multi-charged phenomena. Additionally, we used Transmission Electron Microscopy (TEM) to assess particle morphology. Outputs from the inversion routine along with images from TEM were used to evaluate reasons for hygroscopicity dependence on mobility diameter.

Hygroscopicity of organic surrogate compounds from biomass burning and their effect on the efflorescence of ammonium sulfate in mixed aerosol particles

NASA Astrophysics Data System (ADS)

Lei, Ting; Zuend, Andreas; Cheng, Yafang; Su, Hang; Wang, Weigang; Ge, Maofa

2018-01-01

Hygroscopic growth factors of organic surrogate compounds representing biomass burning and mixed organic-inorganic aerosol particles exhibit variability during dehydration experiments depending on their chemical composition, which we observed using a hygroscopicity tandem differential mobility analyzer (HTDMA). We observed that levoglucosan and humic acid aerosol particles release water upon dehumidification in the range from 90 to 5 % relative humidity (RH). However, 4-Hydroxybenzoic acid aerosol particles remain in the solid state upon dehumidification and exhibit a small shrinking in size at higher RH compared to the dry size. For example, the measured growth factor of 4-hyroxybenzoic acid aerosol particles is ˜ 0.96 at 90 % RH. The measurements were accompanied by RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model and Extended Aerosol Inorganics Model (E-AIM), the Zdanovskii-Stokes-Robinson (ZSR) relation, and a fitted hygroscopicity expression. We observed several effects of organic components on the hygroscopicity behavior of mixtures containing ammonium sulfate (AS) in relation to the different mass fractions of organic compounds: (1) a shift of efflorescence relative humidity (ERH) of ammonium sulfate to higher RH due to the presence of 25 wt % levoglucosan in the mixture. (2) There is a distinct efflorescence transition at 25 % RH for mixtures consisting of 25 wt % of 4-hydroxybenzoic acid compared to the ERH at 35 % for organic-free AS particles. (3) There is indication for a liquid-to-solid phase transition of 4-hydroxybenzoic acid in the mixed particles during dehydration. (4) A humic acid component shows no significant effect on the efflorescence of AS in mixed aerosol particles. In addition, consideration of a composition-dependent degree of dissolution of crystallization AS (solid-liquid equilibrium) in the AIOMFAC and E-AIM models leads to a relatively good agreement between models and observed growth factors, as well as ERH of AS in the mixed system. The use of the ZSR relation leads to good agreement with measured diameter growth factors of aerosol particles containing humic acid and ammonium sulfate. Lastly, two distinct mixtures of organic surrogate compounds, including levoglucosan, 4-hydroxybenzoic acid, and humic acid, were used to represent the average water-soluble organic carbon (WSOC) fractions observed during the wet and dry seasons in the central Amazon Basin. A comparison of the organic fraction's hygroscopicity parameter for the simple mixtures, e.g., κ ≈ 0.12 to 0.15 for the wet-season mixture in the 90 to 40 % RH range, shows good agreement with field data for the wet season in the Amazon Basin (WSOC κ ≈ 0.14±0.06 at 90 % RH). This suggests that laboratory-generated mixtures containing organic surrogate compounds and ammonium sulfate can be used to mimic, in a simplified manner, the chemical composition of ambient aerosols from the Amazon Basin for the purpose of RH-dependent hygroscopicity studies.

Use of Li.sub.2[B.sub.12H.sub.12] salt to absorb water into polymers

DOEpatents

Eastwood, Eric A.; Bowen, III, Daniel E.

2016-08-30

Methods of adjusting the properties of a composition are provided. The compositions comprise a polymer-containing matrix and a filler comprising a hygroscopic salt. Preferred such salts comprise a cage compound selected from the group consisting of borane cage compounds, carborane cage compounds, metal complexes thereof, residues thereof, mixtures thereof, and/or agglomerations thereof, where the cage compound is not covalently bound to the matrix polymer.

Secondary aerosol formation promotes water uptake by organic-rich wildfire haze particles in equatorial Asia

NASA Astrophysics Data System (ADS)

Chen, Jing; Hapsari Budisulistiorini, Sri; Miyakawa, Takuma; Komazaki, Yuichi; Kuwata, Mikinori

2018-06-01

The diameter growth factor (GF) of 100 nm haze particles at 85 % relative humidity (RH) and their chemical characteristics were simultaneously monitored at Singapore in October 2015 during a pervasive wildfire haze episode that was caused by peatland burning in Indonesia. Non-refractory submicron particles (NR-PM1) were dominated by organics (OA; approximating 77.1 % in total mass), whereas sulfate was the most abundant inorganic constituent (11.7 % on average). A statistical analysis of the organic mass spectra showed that most organics (36.0 % of NR-PM1 mass) were highly oxygenated. Diurnal variations of GF, number fractions of more hygroscopic mode particles, mass fractions of sulfate, and mass fractions of oxygenated organics (OOA) synchronized well, peaking during the day. The mean hygroscopicity parameter (κ) of the haze particles was 0.189 ± 0.087, and the mean κ values of organics were 0.157 ± 0.108 (κorg, bulk organics) and 0.266 ± 0.184 (κOOA, OOA), demonstrating the important roles of both sulfate and highly oxygenated organics in the hygroscopic growth of organics-dominated wildfire haze particles. κorg correlated with the water-soluble organic fraction insignificantly, but it positively correlated with f44 (fraction of the ion fragment at m/z 44 in total organics) (R = 0.70), implying the oxygenation degree of organics could be more critical for the water uptake of organic compounds. These results further suggest the importance of sulfate and secondary organic aerosol formation in promoting the hygroscopic growth of wildfire haze particles. Further detailed size-resolved as well as molecular-level chemical information about organics is necessary for the profound exploration of water uptake by wildfire haze particles in equatorial Asia.

Shipborne measurements of aerosol number size distribution and hygroscopicity over the North Pacific Ocean

NASA Astrophysics Data System (ADS)

Royalty, T. M.; Phillips, B.; Dawson, K. W.; Reed, R. E.; Meskhidze, N.

2016-12-01

We report aerosol number size distribution and hygroscopicity data collected over the Pacific Ocean near the Hawaii Ocean Timeseries (HOT) Station ALOHA (centered near 22°N, 158°W). From June 25 to July 3, 2016 our hygroscopicity tandem differential mobility analyzer (HTDMA)/scanning mobility particle sizer (SMPS) system was deployed onboard of NOAA Ship Hi'ialakai that participated in mooring operations associated with the Woods Hole Oceanographic Institution WHOTS project. The ambient aerosol data was collected during the ship's planned operations. The inlet was located at the bow of the ship and the air samples were drawn (using 3/8 inch stainless steel tubing) inside a dry, air-conditioned lab. The region north of Oahu was very clean, with total particle number approximately 200 cm-3, occasionally dropping below 100 cm-3. We compare our particle number size distribution and hygroscopicity data with previously reported estimates. Our measurements contribute to process-level understanding of the role of sea spray aerosol in marine boundary layer cloud condensation nuclei (CCN) budget and provide crucial information to the community interested in studying and projecting climate change using Earth System Models.

On the Link Between Ocean Biota Emissions, Aerosol, and Maritime Clouds: Airborne, Ground, and Satellite Measurements Off the Coast of California

DTIC Science & Technology

2009-10-14

sulfate. DEA is likely produced via the reaction of the gaseous amine and acidic sulfates. Subsaturated aerosol hygroscopicity data indicate 14 that the...D., and A. Wiedensohler (1998). NaCl aerosol particle hygroscopicity dependence on mixing with organic compounds, J. Atmos. Chem., 31, 321–346...M. N., and C. K. Chan (2001). The hygroscopic properties of dicarboxylic and multifunctional acids : measurements and UNIFAC

Distinct high molecular weight organic compound (HMW-OC) types in aerosol particles collected at a coastal urban site

NASA Astrophysics Data System (ADS)

Dall'Osto, M.; Healy, R. M.; Wenger, J. C.; O'Dowd, C.; Ovadnevaite, J.; Ceburnis, D.; Harrison, Roy M.; Beddows, D. C. S.

2017-12-01

Organic oligomers were discovered in laboratory-generated atmospheric aerosol over a decade ago. However, evidence for the presence of oligomers in ambient aerosols is scarce and mechanisms for their formation have yet to be fully elucidated. In this work, three unique aerosol particle types internally mixed with High molecular weight organic compounds (HMW-OC) species - likely oligomers - were detected in ambient air using single particle Aerosol Time-Of-Flight Mass Spectrometry (ATOFMS) in Cork (Ireland) during winter 2009. These particle types can be described as follows: (1) HMW-OCs rich in organic nitrogen - possibly containing nitrocatechols and nitroguaiacols - originating from primary emissions of biomass burning particles during evening times; (2) HMW-OCs internally mixed with nitric acid, occurring in stagnant conditions during night time; and (3) HMW-OCs internally mixed with sea salt, likely formed via photochemical reactions during day time. The study exemplifies the power of methodologies capable of monitoring the simultaneous formation of organic and inorganic particle-phase reaction products. Primary emissions and atmospheric aging of different types of HMW-OC contributes to aerosol with a range of acidity, hygroscopic and optical properties, which can have different impacts on climate and health.

[Study on process and principle of lactose grinding modification to decrease hygroscopic of Rhodiolae Crenulatae Radix et Rhizoma extract].

PubMed

Zhang, Ding-Kun; Zhang, Fang; Lin, Jun-Zhi; Han, Li; Wu, Zhen-Feng; Yang, Ying-Guang; Yang, Ming

2014-04-01

In this paper, Rhodiolae Crenulatae Radix et Rhizoma extract,with high hygroscopic,was selected as research model, while lactose was selected as modifiers to study the effect of the grinding modification method on the hygroscopic. Subsequently, particle size distribution, scannin electron microscopy, infrared spectroscopy and surface properties were adopted for a phase analysis. The results showed that the modified extract, prepared by Rhodiolae Crenulatae Radix et Rhizoma extract grinding 5 min with the same amount of lactose UP2, which hygroscopic initial velocity, acceleration, and critical relative humidity moisture were less than that of Rhodiolae Crenulatae Radix et Rhizoma extract and the mixture dramatically. In addition, compared with the mixture, the size distribution of modified extract was much less, the microstructure was also difference, while the infrared spectroscopy and surface properties were similar with that of lactose. It is the main principle that lactose particle adhered to the surface of Rhodiolae Crenulatae Radix et Rhizoma extract after grinding mofication to decress the moisture obviously.

On the Effect of Dust Particles on Global Cloud Condensation Nuclei and Cloud Droplet Number

NASA Technical Reports Server (NTRS)

Karydis, V. A.; Kumar, P.; Barahona, D.; Sokolik, I. N.; Nenes, A.

2011-01-01

Aerosol-cloud interaction studies to date consider aerosol with a substantial fraction of soluble material as the sole source of cloud condensation nuclei (CCN). Emerging evidence suggests that mineral dust can act as good CCN through water adsorption onto the surface of particles. This study provides a first assessment of the contribution of insoluble dust to global CCN and cloud droplet number concentration (CDNC). Simulations are carried out with the NASA Global Modeling Initiative chemical transport model with an online aerosol simulation, considering emissions from fossil fuel, biomass burning, marine, and dust sources. CDNC is calculated online and explicitly considers the competition of soluble and insoluble CCN for water vapor. The predicted annual average contribution of insoluble mineral dust to CCN and CDNC in cloud-forming areas is up to 40 and 23.8%, respectively. Sensitivity tests suggest that uncertainties in dust size distribution and water adsorption parameters modulate the contribution of mineral dust to CDNC by 23 and 56%, respectively. Coating of dust by hygroscopic salts during the atmospheric aging causes a twofold enhancement of the dust contribution to CCN; the aged dust, however, can substantially deplete in-cloud supersaturation during the initial stages of cloud formation and can eventually reduce CDNC. Considering the hydrophilicity from adsorption and hygroscopicity from solute is required to comprehensively capture the dust-warm cloud interactions. The framework presented here addresses this need and can be easily integrated in atmospheric models.

Hygroscopicity of internally mixed particles composed of (NH4)2SO4 and citric acid under pulsed RH change.

PubMed

Shi, Xiao-Min; Wu, Feng-Min; Jing, Bo; Wang, Na; Xu, Lin-Lin; Pang, Shu-Feng; Zhang, Yun-Hong

2017-12-01

In this research, we applied a pulsed RH controlling system and a rapid scan vacuum FTIR spectrometer (PRHCS-RSVFTIR) to investigate hygroscopicity of internally mixed (NH 4 ) 2 SO 4 (AS)/citric acid (CA) particles. The water content and efflorescence ratio of AS in the particles and ambient relative humidity (RH) as a function of time were obtained with a subsecond time resolution. The hygroscopic behavior of AS aerosols in two different RH control processes (equilibrium and RH pulsed processes) showed that AS droplets crystallize with RH ranging from 42% to 26.5%. It was found that the half-life time ratio between the water content in the CA particles and the gas phase under RH pulsed change was greater than one under low RH conditions (<40% RH), indicating the significant water transfer limitation due to the high viscosity of CA aerosols at low RH, especially at RH<20%. In addition, water diffusion constants between 10 -12  m 2  s -1 and 10 -13  m 2  s -1 in micron size CA aerosols were obtained in a sub-second and second timescale. The addition of AS enhanced the water transfer limitation in the mixed aerosols. The efflorescence relative humidity (ERH) of the mixed particles with AS/CA by molar ratio 3:1 was found between 22.7% and 5.9%, which was much lower than AS particles. No efflorescence process was observed for the 1:1 mixed particles, indicating that CA greatly suppressed nucleation of AS. Our results have shown that the PRHCS-RSVFTIR is effective to simulate hygroscopicity and water transport of aerosols under fast variations in RH in atmosphere. Copyright © 2017 Elsevier Ltd. All rights reserved.

Hygroscopic properties of oxalic acid and atmospherically relevant oxalates

NASA Astrophysics Data System (ADS)

Ma, Qingxin; He, Hong; Liu, Chang

2013-04-01

Oxalic acid and oxalates represent an important fraction of atmospheric organic aerosols, however, little knowledge about the hygroscopic behavior of these particles is known. In this study, the hygroscopic behavior of oxalic acid and atmospherically relevant oxalates (H2C2O4, (NH4)2C2O4, CaC2O4, and FeC2O4) were studied by Raman spectrometry and vapor sorption analyzer. Under ambient relative humidity (RH) of 10-90%, oxalic acid and these oxalates hardly deliquesce and exhibit low hygroscopicity, however, transformation between anhydrous and hydrated particles was observed during the humidifying and dehumidifying processes. During the water adsorption process, conversion of anhydrous H2C2O4, (NH4)2C2O4, CaC2O4, and FeC2O4 to their hydrated particles (i.e., H2C2O4·2H2O, (NH4)2C2O4·H2O, CaC2O4·H2O, and FeC2O4·2H2O) occurred at about 20% RH, 55% RH, 10% RH, and 75% RH, respectively. Uptake of water on hydrated Ca-oxalate and Fe-oxalate particles can be described by a multilayer adsorption isotherm. During the dehumidifying process, dehydration of H2C2O4·2H2O and (NH4)2C2O4·H2O occurred at 5% RH while CaC2O4·H2O and FeC2O4·2H2O did not undergo dehydration. These results implied that hydrated particles represent the most stable state of oxalic acid and oxalates in the atmosphere. In addition, the assignments of Raman shift bands in the range of 1610-1650 cm-1 were discussed according to the hygroscopic behavior measurement results.

Contact efflorescence as a pathway for crystallization of atmospherically relevant particles

PubMed Central

Davis, Ryan D.; Lance, Sara; Gordon, Joshua A.; Ushijima, Shuichi B.; Tolbert, Margaret A.

2015-01-01

Inadequate knowledge of the phase state of atmospheric particles represents a source of uncertainty in global climate and air quality models. Hygroscopic aqueous inorganic particles are often assumed to remain liquid throughout their atmospheric lifetime or only (re)crystallize at low relative humidity (RH) due to the kinetic limitations of efflorescence (salt crystal nucleation and growth from an aqueous solution). Here we present experimental observations of a previously unexplored heterogeneous nucleation pathway that we have termed “contact efflorescence,” which describes efflorescence initiated by an externally located solid particle coming into contact with the surface of a metastable aqueous microdroplet. This study demonstrates that upon a single collision, contact efflorescence is a pathway for crystallization of atmospherically relevant aqueous particles at high ambient RH (≤80%). Soluble inorganic crystalline particles were used as contact nuclei to induce efflorescence of aqueous ammonium sulfate [(NH4)2SO4], sodium chloride (NaCl), and ammonium nitrate (NH4NO3), with efflorescence being observed in several cases close to their deliquescence RH values (80%, 75%, and 62%, respectively). To our knowledge, these observations represent the highest reported efflorescence RH values for microdroplets of these salts. These results are particularly important for considering the phase state of NH4NO3, where the contact efflorescence RH (∼20–60%) is in stark contrast to the observation that NH4NO3 microdroplets do not homogeneously effloresce, even when exposed to extremely arid conditions (<1% RH). Considering the occurrence of particle collisions in the atmosphere (i.e., coagulation), these observations of contact efflorescence challenge many assumptions made about the phase state of inorganic aerosol. PMID:26668396

Contact efflorescence as a pathway for crystallization of atmospherically relevant particles.

PubMed

Davis, Ryan D; Lance, Sara; Gordon, Joshua A; Ushijima, Shuichi B; Tolbert, Margaret A

2015-12-29

Inadequate knowledge of the phase state of atmospheric particles represents a source of uncertainty in global climate and air quality models. Hygroscopic aqueous inorganic particles are often assumed to remain liquid throughout their atmospheric lifetime or only (re)crystallize at low relative humidity (RH) due to the kinetic limitations of efflorescence (salt crystal nucleation and growth from an aqueous solution). Here we present experimental observations of a previously unexplored heterogeneous nucleation pathway that we have termed "contact efflorescence," which describes efflorescence initiated by an externally located solid particle coming into contact with the surface of a metastable aqueous microdroplet. This study demonstrates that upon a single collision, contact efflorescence is a pathway for crystallization of atmospherically relevant aqueous particles at high ambient RH (≤80%). Soluble inorganic crystalline particles were used as contact nuclei to induce efflorescence of aqueous ammonium sulfate [(NH4)2SO4], sodium chloride (NaCl), and ammonium nitrate (NH4NO3), with efflorescence being observed in several cases close to their deliquescence RH values (80%, 75%, and 62%, respectively). To our knowledge, these observations represent the highest reported efflorescence RH values for microdroplets of these salts. These results are particularly important for considering the phase state of NH4NO3, where the contact efflorescence RH (∼20-60%) is in stark contrast to the observation that NH4NO3 microdroplets do not homogeneously effloresce, even when exposed to extremely arid conditions (<1% RH). Considering the occurrence of particle collisions in the atmosphere (i.e., coagulation), these observations of contact efflorescence challenge many assumptions made about the phase state of inorganic aerosol.

Internally mixed soot, sulfates, and organic matter in aerosol particles from Mexico City

NASA Astrophysics Data System (ADS)

Adachi, K.; Buseck, P. R.

2008-05-01

Soot particles are major aerosol constituents that result from emissions of burning of fossil fuel and biomass. Because they both absorb sunlight and contribute to cloud formation, they are an influence on climate on local, regional, and global scales. It is therefore important to evaluate their optical and hygroscopic properties and those effects on the radiation budget. Those properties commonly change through reaction with other particles or gases, resulting in complex internal mixtures. Using transmission electron microscopy, we measured ~8000 particles (25 samples) with aerodynamic diameters from 0.05 to 0.3 μm that were collected in March 2006 from aircraft over Mexico City (MC) and adjacent areas. More than 50% of the particles consist of internally mixed soot, organic matter, and sulfate. Imaging combined with chemical analysis of individual particles show that many are coated, consist of aggregates, or both. Coatings on soot particles can amplify their light absorption, and coagulation with sulfates changes their hygroscopic properties, resulting in shorter lifetime. Our results suggest that a mixture of materials from multiple sources such as vehicles, power plants, and biomass burning occurs in individual particles, thereby increasing their complexity. Through changes in their optical and hygroscopic properties, internally mixed soot particles have a greater effect on the regional climate than uncoated soot particles. Moreover, soot occurs in more than 60% of all particles in the MC plumes, suggesting its important role in the formation of secondary aerosol particles.

Hygroscopic growth study in the framework of EARLINET during the SLOPE I campaign: synergy of remote sensing and in situ instrumentation

NASA Astrophysics Data System (ADS)

Esteban Bedoya-Velásquez, Andrés; Navas-Guzmán, Francisco; José Granados-Muñoz, María; Titos, Gloria; Román, Roberto; Andrés Casquero-Vera, Juan; Ortiz-Amezcua, Pablo; Benavent-Oltra, Jose Antonio; de Arruda Moreira, Gregori; Montilla-Rosero, Elena; Hoyos, Carlos David; Artiñano, Begoña; Coz, Esther; José Olmo-Reyes, Francisco; Alados-Arboledas, Lucas; Guerrero-Rascado, Juan Luis

2018-05-01

This study focuses on the analysis of aerosol hygroscopic growth during the Sierra Nevada Lidar AerOsol Profiling Experiment (SLOPE I) campaign by using the synergy of active and passive remote sensors at the ACTRIS Granada station and in situ instrumentation at a mountain station (Sierra Nevada, SNS). To this end, a methodology based on simultaneous measurements of aerosol profiles from an EARLINET multi-wavelength Raman lidar (RL) and relative humidity (RH) profiles obtained from a multi-instrumental approach is used. This approach is based on the combination of calibrated water vapor mixing ratio (r) profiles from RL and continuous temperature profiles from a microwave radiometer (MWR) for obtaining RH profiles with a reasonable vertical and temporal resolution. This methodology is validated against the traditional one that uses RH from co-located radiosounding (RS) measurements, obtaining differences in the hygroscopic growth parameter (γ) lower than 5 % between the methodology based on RS and the one presented here. Additionally, during the SLOPE I campaign the remote sensing methodology used for aerosol hygroscopic growth studies has been checked against Mie calculations of aerosol hygroscopic growth using in situ measurements of particle number size distribution and submicron chemical composition measured at SNS. The hygroscopic case observed during SLOPE I showed an increase in the particle backscatter coefficient at 355 and 532 nm with relative humidity (RH ranged between 78 and 98 %), but also a decrease in the backscatter-related Ångström exponent (AE) and particle linear depolarization ratio (PLDR), indicating that the particles became larger and more spherical due to hygroscopic processes. Vertical and horizontal wind analysis is performed by means of a co-located Doppler lidar system, in order to evaluate the horizontal and vertical dynamics of the air masses. Finally, the Hänel parameterization is applied to experimental data for both stations, and we found good agreement on γ measured with remote sensing (γ532 = 0.48 ± 0.01 and γ355 = 0.40 ± 0.01) with respect to the values calculated using Mie theory (γ532 = 0.53 ± 0.02 and γ355 = 0.45 ± 0.02), with relative differences between measurements and simulations lower than 9 % at 532 nm and 11 % at 355 nm.

Comparison of experimental and modeled absorption enhancement by black carbon (BC) cored polydisperse aerosols under hygroscopic conditions.

PubMed

Shamjad, P M; Tripathi, S N; Aggarwal, S G; Mishra, S K; Joshi, Manish; Khan, Arshad; Sapra, B K; Ram, Kirpa

2012-08-07

The quantification of the radiative impacts of light absorbing ambient black carbon (BC) particles strongly depends on accurate measurements of BC mass concentration and absorption coefficient (β(abs)). In this study, an experiment has been conducted to quantify the influence of hygroscopic growth of ambient particles on light absorption. Using the hygroscopic growth factor (i.e., Zdanovskii-Stokes-Robinson (ZSR) approach), a model has been developed to predict the chemical composition of particles based on measurements, and the absorption and scattering coefficients are derived using a core-shell assumption with light extinction estimates based on Mie theory. The estimated optical properties agree within 7% for absorption coefficient and 30% for scattering coefficient with that of measured values. The enhancement of absorption is found to vary according to the thickness of the shell and BC mass, with a maximum of 2.3 for a shell thickness of 18 nm for the particles. The findings of this study underline the importance of considering aerosol-mixing states while calculating their radiative forcing.

Condensational Growth of Combination Drug-Excipient Submicrometer Particles for Targeted High Efficiency Pulmonary Delivery: Comparison of CFD Predictions with Experimental Results

PubMed Central

Hindle, Michael

2011-01-01

Purpose The objective of this study was to investigate the hygroscopic growth of combination drug and excipient submicrometer aerosols for respiratory drug delivery using in vitro experiments and a newly developed computational fluid dynamics (CFD) model. Methods Submicrometer combination drug and excipient particles were generated experimentally using both the capillary aerosol generator and the Respimat inhaler. Aerosol hygroscopic growth was evaluated in vitro and with CFD in a coiled tube geometry designed to provide residence times and thermodynamic conditions consistent with the airways. Results The in vitro results and CFD predictions both indicated that the initially submicrometer particles increased in mean size to a range of 1.6–2.5 µm for the 50:50 combination of a non-hygroscopic drug (budesonide) and different hygroscopic excipients. CFD results matched the in vitro predictions to within 10% and highlighted gradual and steady size increase of the droplets, which will be effective for minimizing extrathoracic deposition and producing deposition deep within the respiratory tract. Conclusions Enhanced excipient growth (EEG) appears to provide an effective technique to increase pharmaceutical aerosol size, and the developed CFD model will provide a powerful design tool for optimizing this technique to produce high efficiency pulmonary delivery. PMID:21948458

Hygroscopicity and volatility of semi-volatile organic components in optical levitated single organic/inorganic aqueous aerosol droplet

NASA Astrophysics Data System (ADS)

Cai, C.; Zhao, C.

2017-12-01

Quantifying the gas/particle partitioning of organic compounds is of great significance to the understanding of atmospheric aerosol indirect effect. Accurate determination of the hygroscopicities and vapor pressures of semi-volatile organic compounds (SVOC) is of crucial importance in studying their partitioning behavior into atmospheric aerosol, as current published vapor pressures results of compounds of interest (usually with vapor pressures smaller than 0.01 Pa) vary by several orders of magnitude. On the other hand, influences on SVOCs evaporation from participation of inorganic species remains ambiguous. In this study we present quantitative investigation of hygroscopicities and volatilities of single aerosol droplets in an aerosol optical tweezers. The trapped droplet (3-7 µm radii) in the aerosol optical tweezers acts as a micro cavity, which stimulates the cavity enhanced Raman spectroscopy (CERS) signal. Size and composition of the particle are calculated from Mie fit to the positions of the "whispering gallery modes" in the CERS fingerprint. Hygroscopic behaviors and SVOC pure component vapor pressure can then be extracted from the correlation between the changing droplet radius and solute concentration (derived from experimentally determined RI real part). We will further present the influences between mass transfer on the gas-particle interface and within the droplet.

Condensational growth of combination drug-excipient submicrometer particles for targeted high efficiency pulmonary delivery: comparison of CFD predictions with experimental results.

PubMed

Longest, P Worth; Hindle, Michael

2012-03-01

The objective of this study was to investigate the hygroscopic growth of combination drug and excipient submicrometer aerosols for respiratory drug delivery using in vitro experiments and a newly developed computational fluid dynamics (CFD) model. Submicrometer combination drug and excipient particles were generated experimentally using both the capillary aerosol generator and the Respimat inhaler. Aerosol hygroscopic growth was evaluated in vitro and with CFD in a coiled tube geometry designed to provide residence times and thermodynamic conditions consistent with the airways. The in vitro results and CFD predictions both indicated that the initially submicrometer particles increased in mean size to a range of 1.6-2.5 μm for the 50:50 combination of a non-hygroscopic drug (budesonide) and different hygroscopic excipients. CFD results matched the in vitro predictions to within 10% and highlighted gradual and steady size increase of the droplets, which will be effective for minimizing extrathoracic deposition and producing deposition deep within the respiratory tract. Enhanced excipient growth (EEG) appears to provide an effective technique to increase pharmaceutical aerosol size, and the developed CFD model will provide a powerful design tool for optimizing this technique to produce high efficiency pulmonary delivery.

Relating hygroscopicity and optical properties to chemical composition and structure of secondary organic aerosol particles generated from the ozonolysis of α-pinene

NASA Astrophysics Data System (ADS)

Denjean, C.; Formenti, P.; Picquet-Varrault, B.; Pangui, E.; Zapf, P.; Katrib, Y.; Giorio, C.; Tapparo, A.; Monod, A.; Temime-Roussel, B.; Decorse, P.; Mangeney, C.; Doussin, J. F.

2014-04-01

Secondary Organic Aerosol (SOA) were generated from the ozonolysis of α-pinene in the CESAM simulation chamber. The formation and ageing of the SOA were studied by following their optical, hygroscopic and chemical properties. The optical properties investigated by determining the particle Complex Refractive Index (CRI). The hygroscopicity was quantified by measuring the effect of RH on particle size (Growth Factor, GF) and scattering coefficient (f(RH)). The oxygen to carbon (O : C) atomic ratio of the particle surface and bulk were used as a sensitive parameter to correlate the changes in hygroscopic and optical properties of the SOA composition in CESAM. The real CRI at 525 nm wavelength decreased from 1.43-1.60 (±0.02) to 1.32-1.38 (±0.02) during the SOA formation. The decrease in real CRI correlates with a decrease in the O : C ratio of SOA from 0.68 (±0.20) to 0.55 (±0.16). In contrast, the GF stayed roughly constant over the reaction time, with values of 1.02-1.07 (±0.02) at 90% (±4.2) RH. Simultaneous measurements of O : C ratio of the particle surface revealed that the SOA was not composed of a homogeneous mixture, but with less oxidised species at the surface which would limit the water adsorption onto particle. In addition, an apparent change of both mobility diameter and scattering coefficient with increasing RH from 0 to 30% was observed for SOA after 16 h reaction. We postulate that this change could be due to a change in the viscosity of the SOA from a predominantly glassy state to a predominantly liquid state.

Hygroscopicity of organic compounds as a function of carbon chain length, carboxyl, hydroperoxy, and carbonyl functional groups

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

Petters, Sarah Suda; Pagonis, Demetrios; Claflin, Megan Suzanne

The albedo and microphysical properties of clouds are controlled in part by the hygroscopicity of particles serving as cloud condensation nuclei (CCN). Hygroscopicity of complex organic mixtures in the atmosphere varies widely and remains challenging to predict. Here we present new measurements characterizing the CCN activity of pure compounds in which carbon chain length and the number of hydroperoxy, carboxyl, and carbonyl functional groups were systematically varied to establish the contributions of these groups to organic aerosol apparent hygroscopicity. Apparent hygroscopicity decreased with carbon chain length and increased with polar functional groups in the order carboxyl > hydroperoxy > carbonyl.more » Activation diameters at different supersaturations deviated from the -3/2 slope in log-log space predicted by Köhler theory, suggesting that water solubility limits CCN activity of particles composed of weakly functionalized organic compounds. Results are compared to a functional group contribution model that predicts CCN activity of organic compounds. The model performed well for most compounds but under-predicted the CCN activity of hydroperoxy groups. New best-fit hydroperoxy group/water interaction parameters were derived from the available CCN data. Lastly, these results may help improve estimates of the CCN activity of ambient organic aerosols from composition data.« less

Hygroscopicity of organic compounds as a function of carbon chain length, carboxyl, hydroperoxy, and carbonyl functional groups

DOE PAGES

Petters, Sarah Suda; Pagonis, Demetrios; Claflin, Megan Suzanne; ...

2017-06-16

The albedo and microphysical properties of clouds are controlled in part by the hygroscopicity of particles serving as cloud condensation nuclei (CCN). Hygroscopicity of complex organic mixtures in the atmosphere varies widely and remains challenging to predict. Here we present new measurements characterizing the CCN activity of pure compounds in which carbon chain length and the number of hydroperoxy, carboxyl, and carbonyl functional groups were systematically varied to establish the contributions of these groups to organic aerosol apparent hygroscopicity. Apparent hygroscopicity decreased with carbon chain length and increased with polar functional groups in the order carboxyl > hydroperoxy > carbonyl.more » Activation diameters at different supersaturations deviated from the -3/2 slope in log-log space predicted by Köhler theory, suggesting that water solubility limits CCN activity of particles composed of weakly functionalized organic compounds. Results are compared to a functional group contribution model that predicts CCN activity of organic compounds. The model performed well for most compounds but under-predicted the CCN activity of hydroperoxy groups. New best-fit hydroperoxy group/water interaction parameters were derived from the available CCN data. Lastly, these results may help improve estimates of the CCN activity of ambient organic aerosols from composition data.« less

Aging of Diesel and Wood Burning Emissions in Smogchamber Experiments

NASA Astrophysics Data System (ADS)

Prevot, Andre S. H.

2010-05-01

Photochemical aging experiments were performed for emissions of a diesel passenger car and logwood-burner at the smogchamber at the Paul Scherrer Institute in Switzerland. The measurements include black carbon measurements (with Aethalometer, Multi-Angle Absorption Photometer, Single Particle Soot Photometer (SP-2), and Photoacoustic Spectrometer), organic mass measurements with the Aerodyne high-resolution Aerosol mass spectrometer and off-line GC-MS measurements. Single particle composition was measured with the TSI-Aerosol time-of-flight mass spectrometer. The size distribution is characterized with a scanning mobility particle sizer, and the hygroscopicity with a hygroscopicity tandem differential mobility analyzer. The given overview of the results of experiments during the last 1.5 years will focus on the formation secondary organic aerosol and include the oxidation of primary organic aerosols and the change of optical and hygroscopic properties. A considerable variability of most results is found for different after treatment systems of diesel cars and for different burning conditions of the log-wood burner which will be discussed in detail.

Oxalate metal complexes in aerosol particles: implications for the hygroscopicity of oxalate-containing particles

NASA Astrophysics Data System (ADS)

Furukawa, T.; Takahashi, Y.

2011-05-01

Atmospheric aerosols have both a direct and an indirect cooling effect that influences the radiative balance at the Earth's surface. It has been estimated that the degree of cooling is large enough to weaken the warming effect of carbon dioxide. Among the cooling factors, secondary organic aerosols (SOA) play an important role in the solar radiation balance in the troposphere as SOA can act as cloud condensation nuclei (CCN) and extend the lifespan of clouds because of their high hygroscopic and water soluble nature. Oxalic acid is an important component of SOA, and is produced via several formation pathways in the atmosphere. However, it is not certain whether oxalic acid exists as free oxalic acid or as metal oxalate complexes in aerosols, although there is a marked difference in their solubility in water and their hygroscopicity. We employed X-ray absorption fine structure spectroscopy to characterize the calcium (Ca) and zinc (Zn) in aerosols collected at Tsukuba in Japan. Size-fractionated aerosol samples were collected for this purpose using an impactor aerosol sampler. It was shown that 10-60% and 20-100% of the total Ca and Zn in the finer particles (<2.1 μm) were present as Ca and Zn oxalate complexes, respectively. Oxalic acid is hygroscopic and can thus increase the CCN activity of aerosol particles, while complexes with various polyvalent metal ions such as Ca and Zn are not hygroscopic, which cannot contribute to the increase of the CCN activity of aerosols. Based on the concentrations of noncomplexed and metal-complexed oxalate species, we found that most of the oxalic acid is present as metal oxalate complexes in the aerosols, suggesting that oxalic acid does not always increase the hygroscopicity of aerosols in the atmosphere. Similar results are expected for other dicarboxylic acids, such as malonic and succinic acids. Thus, it is advisable that the cooling effect of organic aerosols should be estimated by including the information on metal oxalate complexes and metal complexes with other dicarboxylic acids in aerosols.

Droplet activation, separation, and compositional analysis: laboratory studies and atmospheric measurements

NASA Astrophysics Data System (ADS)

Hiranuma, N.; Kohn, M.; Pekour, M. S.; Nelson, D. A.; Shilling, J. E.; Cziczo, D. J.

2011-10-01

Droplets produced in a cloud condensation nuclei chamber (CCNC) as a function of supersaturation have been separated from unactivated aerosol particles using counterflow virtual impaction. Residual material after droplets were evaporated was chemically analyzed with an Aerodyne Aerosol Mass Spectrometer (AMS) and the Particle Analysis by Laser Mass Spectrometry (PALMS) instrument. Experiments were initially conducted to verify activation conditions for monodisperse ammonium sulfate particles and to determine the resulting droplet size distribution as a function of supersaturation. Based on the observed droplet size, the counterflow virtual impactor cut-size was set to differentiate droplets from unactivated interstitial particles. Validation experiments were then performed to verify that only droplets with sufficient size passed through the counterflow virtual impactor for subsequent analysis. A two-component external mixture of monodisperse particles was also exposed to a supersaturation which would activate one of the types (hygroscopic salts) but not the other (polystyrene latex spheres or adipic acid). The mass spectrum observed after separation indicated only the former, validating separation of droplets from unactivated particles. Results from ambient measurements using this technique and AMS analysis were inconclusive, showing little chemical differentiation between ambient aerosol and activated droplet residuals, largely due to low signal levels. When employing as single particle mass spectrometer for compositional analysis, however, we observed enhancement of sulfate in droplet residuals.

Hygroscopic behavior of water-soluble matter in marine aerosols over the East China Sea.

PubMed

Yan, Yu; Fu, Pingqing; Jing, Bo; Peng, Chao; Boreddy, S K R; Yang, Fan; Wei, Lianfang; Sun, Yele; Wang, Zifa; Ge, Maofa

2017-02-01

In this study, we investigated hygroscopic properties of water-soluble matter (WSM) in marine aerosols over the East China Sea, which were collected during a Natural Science Foundation of China (NSFC) sharing cruise in 2014. Hygroscopic growth factors (g) of WSM were measured by a hygroscopicity tandem differential mobility analyzer (H-TDMA) with an initial dry particle mobility diameter of 100nm. The observed g at 90% relative humidity (RH), g(90%) WSM , defined as the ratio of the particle diameter at 90% RH to that at RH<5% (initial dry diameter), ranged from 1.67 to 2.41 (mean±std: 1.99±0.23). The g values were lower than that of seawater (2.1) but comparable with those reported for marine aerosols (1.79-2.08). The H-TDMA retrieved hygroscopicity parameter of WSM, κ WSM , ranged from 0.46 to 1.56 (0.88±0.35). The observed g(90%) WSM during the daytime ranged from 1.67 to 2.40 (1.95±0.21) versus 1.71 to 2.41 (2.03±0.26) during the nighttime. κ WSM was 0.81±0.32 in the daytime and 0.95±0.40 in the nighttime. The day/night differences of g(90%) WSM and κ WSM indicated that nighttime marine aerosols were more hygroscopic than those in daytime, which was likely related to enhanced heterogeneous reaction of ammonium nitrate in nighttime and the higher Cl - /Na + molar ratios obtained (0.80) in nighttime than those (0.47) in daytime. Inorganic ions accounted for 72-99% of WSM with SO 4 2- being the dominant species, contributing to 47% of the total inorganic ion mass. The declined g(90%) comparing with sea water was likely due to the transport of anthropogenic aerosols, chemical aging of dust particles, the contribution of biomass burning products, and the aerosol hygroscopic growth inhibition of organics. Copyright © 2016 Elsevier B.V. All rights reserved.

CCN activity and organic hygroscopicity of aerosols downwind of an urban region in central Amazonia: seasonal and diel variations and impact of anthropogenic emissions

NASA Astrophysics Data System (ADS)

Thalman, Ryan; de Sá, Suzane S.; Palm, Brett B.; Barbosa, Henrique M. J.; Pöhlker, Mira L.; Lizabeth Alexander, M.; Brito, Joel; Carbone, Samara; Castillo, Paulo; Day, Douglas A.; Kuang, Chongai; Manzi, Antonio; Ng, Nga Lee; Sedlacek, Arthur J., III; Souza, Rodrigo; Springston, Stephen; Watson, Thomas; Pöhlker, Christopher; Pöschl, Ulrich; Andreae, Meinrat O.; Artaxo, Paulo; Jimenez, Jose L.; Martin, Scot T.; Wang, Jian

2017-10-01

During the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign, size-resolved cloud condensation nuclei (CCN) spectra were characterized at a research site (T3) 60 km downwind of the city of Manaus, Brazil, in central Amazonia for 1 year (12 March 2014 to 3 March 2015). Particle hygroscopicity (κCCN) and mixing state were derived from the size-resolved CCN spectra, and the hygroscopicity of the organic component of the aerosol (κorg) was then calculated from κCCN and concurrent chemical composition measurements. The annual average κCCN increased from 0.13 at 75 nm to 0.17 at 171 nm, and the increase was largely due to an increase in sulfate volume fraction. During both wet and dry seasons, κCCN, κorg, and particle composition under background conditions exhibited essentially no diel variations. The constant κorg of ˜ 0. 15 is consistent with the largely uniform and high O : C value (˜ 0. 8), indicating that the aerosols under background conditions are dominated by the aged regional aerosol particles consisting of highly oxygenated organic compounds. For air masses strongly influenced by urban pollution and/or local biomass burning, lower values of κorg and organic O : C atomic ratio were observed during night, due to accumulation of freshly emitted particles, dominated by primary organic aerosol (POA) with low hygroscopicity, within a shallow nocturnal boundary layer. The O : C, κorg, and κCCN increased from the early morning hours and peaked around noon, driven by the formation and aging of secondary organic aerosol (SOA) and dilution of POA emissions into a deeper boundary layer, while the development of the boundary layer, which leads to mixing with aged particles from the residual layer aloft, likely also contributed to the increases. The hygroscopicities associated with individual organic factors, derived from PMF (positive matrix factorization) analysis of AMS (aerosol mass spectrometry) spectra, were estimated through multivariable linear regression. For the SOA factors, the variation of the κ value with O : C agrees well with the linear relationship reported from earlier laboratory studies of SOA hygroscopicity. On the other hand, the variation in O : C of ambient aerosol organics is largely driven by the variation in the volume fractions of POA and SOA factors, which have very different O : C values. As POA factors have hygroscopicity values well below the linear relationship between SOA hygroscopicity and O : C, mixtures with different POA and SOA fractions exhibit a steeper slope for the increase in κorg with O : C, as observed during this and earlier field studies. This finding helps better understand and reconcile the differences in the relationships between κorg and O : C observed in laboratory and field studies, therefore providing a basis for improved parameterization in global models, especially in a tropical context.

CCN activity and organic hygroscopicity of aerosols downwind of an urban region in central Amazonia: Seasonal and diel variations and impact of anthropogenic emissions

DOE PAGES

Thalman, Ryan; de Sá, Suzane S.; Palm, Brett B.; ...

2017-10-05

During the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign, size-resolved cloud condensation nuclei (CCN) spectra were characterized at a research site (T3) 60km downwind of the city of Manaus, Brazil, in central Amazonia for one year (12 March 2014 to 3 March 2015). Particle hygroscopicity (κCCN) and mixing state were derived from the size-resolved CCN spectra, and the hygroscopicity of the organic component of the aerosol (κorg) was then calculated from κCCN and concurrent chemical composition measurements. The annual average κCCN increased from 0.13 at 75 nm to 0.17 at 171 nm, and the increase was largely duemore » to an increase in sulfate volume fraction. Also, during both wet and dry seasons, κCCN, κorg, and particle composition under background conditions exhibited essentially no diel variations. The constant κorg of ~0.15 is consistent with the largely uniform and high O:C value (~0.8), indicating that the aerosols under background conditions are dominated by the aged regional aerosol particles consisting of highly oxygenated organic compounds. For air masses strongly influenced by urban pollution and/or local biomass burning, lower values of κorg and organic O:C atomic ratio were observed during night, due to accumulation of freshly emitted particles, dominated by primary organic aerosol (POA) with low hygroscopicity, within a shallow nocturnal boundary layer. The O:C, κorg, and κCCN increased from the early morning hours and peaked around noon, driven by the formation and aging of secondary organic aerosol (SOA) and dilution of POA emissions into a deeper boundary layer, while the development of the boundary layer, which leads to mixing with aged particles from the residual layer aloft, likely also contributed to the increases. The hygroscopicities associated with individual organic factors, derived from PMF analysis of AMS spectra, were estimated through multi-variable linear regression. For the SOA factors, the variation of the κ value with O:C agrees well with the linear relationship reported from earlier laboratory studies of SOA hygroscopicity. On the other hand, the variation in O:C of ambient aerosol organics is largely driven by the variation in the volume fractions of POA and SOA factors, which have very different O:C values. As POA factors have hygroscopicity values well below the linear relationship between SOA hygroscopicity and O:C, mixtures with different POA and SOA fractions exhibit a steeper slope for the increase of κorg with O:C, as observed during this and earlier field studies. Our finding helps better understand and reconcile the differences in the relationships between κorg and O:C observed in laboratory and field studies, therefore providing a basis for improved parameterization in global models, especially in a tropical context.« less

CCN activity and organic hygroscopicity of aerosols downwind of an urban region in central Amazonia: Seasonal and diel variations and impact of anthropogenic emissions

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

Thalman, Ryan; de Sá, Suzane S.; Palm, Brett B.

During the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign, size-resolved cloud condensation nuclei (CCN) spectra were characterized at a research site (T3) 60km downwind of the city of Manaus, Brazil, in central Amazonia for one year (12 March 2014 to 3 March 2015). Particle hygroscopicity (κCCN) and mixing state were derived from the size-resolved CCN spectra, and the hygroscopicity of the organic component of the aerosol (κorg) was then calculated from κCCN and concurrent chemical composition measurements. The annual average κCCN increased from 0.13 at 75 nm to 0.17 at 171 nm, and the increase was largely duemore » to an increase in sulfate volume fraction. Also, during both wet and dry seasons, κCCN, κorg, and particle composition under background conditions exhibited essentially no diel variations. The constant κorg of ~0.15 is consistent with the largely uniform and high O:C value (~0.8), indicating that the aerosols under background conditions are dominated by the aged regional aerosol particles consisting of highly oxygenated organic compounds. For air masses strongly influenced by urban pollution and/or local biomass burning, lower values of κorg and organic O:C atomic ratio were observed during night, due to accumulation of freshly emitted particles, dominated by primary organic aerosol (POA) with low hygroscopicity, within a shallow nocturnal boundary layer. The O:C, κorg, and κCCN increased from the early morning hours and peaked around noon, driven by the formation and aging of secondary organic aerosol (SOA) and dilution of POA emissions into a deeper boundary layer, while the development of the boundary layer, which leads to mixing with aged particles from the residual layer aloft, likely also contributed to the increases. The hygroscopicities associated with individual organic factors, derived from PMF analysis of AMS spectra, were estimated through multi-variable linear regression. For the SOA factors, the variation of the κ value with O:C agrees well with the linear relationship reported from earlier laboratory studies of SOA hygroscopicity. On the other hand, the variation in O:C of ambient aerosol organics is largely driven by the variation in the volume fractions of POA and SOA factors, which have very different O:C values. As POA factors have hygroscopicity values well below the linear relationship between SOA hygroscopicity and O:C, mixtures with different POA and SOA fractions exhibit a steeper slope for the increase of κorg with O:C, as observed during this and earlier field studies. Our finding helps better understand and reconcile the differences in the relationships between κorg and O:C observed in laboratory and field studies, therefore providing a basis for improved parameterization in global models, especially in a tropical context.« less

Formation of semisolid, oligomerized aqueous SOA: lab simulations of cloud processing.

PubMed

Hawkins, Lelia N; Baril, Molly J; Sedehi, Nahzaneen; Galloway, Melissa M; De Haan, David O; Schill, Gregory P; Tolbert, Margaret A

2014-02-18

Glyoxal, methylglyoxal, glycolaldehyde, and hydroxyacetone form N-containing and oligomeric compounds during simulated cloud processing with small amines. Using a novel hygroscopicity tandem differential mobility analysis (HTDMA) system that allows varied humidification times, the hygroscopic growth (HG) of each of the resulting products of simulated cloud processing was measured. Continuous water uptake (gradual deliquescence) was observed beginning at ∼ 40% RH for all aldehyde-methylamine products. Particles containing ionic reaction products of either glyoxal or glycine were most hygroscopic, with HG between 1.16 and 1.20 at 80% RH. Longer humidification times (up to 20 min) produced an increase in growth factors for glyoxal-methylamine (19% by vol) and methylglyoxal-methylamine (8% by vol) aerosol, indicating that unusually long equilibration times can be required for HTDMA measurements of such particles. Glyoxal- and methylglyoxal-methylamine aerosol particles shattered in Raman microscopy impact-flow experiments, revealing that the particles were semisolid. Similar experiments on glycolaldehyde- and hydroxyacetone-methylamine aerosol found that the aerosol particles were liquid when dried for <1 h, but semisolid when dried for 20 h under ambient conditions. The RH required for flow (liquification) during humidification experiments followed the order methylglyoxal > glyoxal > glycolaldehyde = hydroxyacetone, likely caused by the speed of oligomer formation in each system.

Characterizing the Hygroscopicity of Nascent Sea Spray Aerosol from Synthetic Blooms

NASA Astrophysics Data System (ADS)

Forestieri, S.; Cappa, C. D.; Sultana, C. M.; Lee, C.; Wang, X.; Helgestad, T.; Moore, K.; Prather, K. A.; Cornwell, G.; Novak, G.; Bertram, T. H.

2015-12-01

Marine sea spray aerosol (SSA) particles make up a significant portion of natural aerosols and are therefore important in establishing the baseline for anthropogenic aerosol climate impacts. Scattering of solar radiation by aerosols affects Earth's radiative budget and the degree of scattering is size-dependent. Thus, aerosols scatter more light at elevated relative humidities when they grow larger via water uptake. This growth depends critically on chemical composition. SSA can become enriched in organics during phytoplankton blooms, becoming less salty and therefore less hygroscopic. Subsaturated hygroscopic growth factors at 85% relative humidity (GF(85%)) of SSA particles were quantified during two mesocosm experiments in enclosed marine aerosol reference tanks (MARTs). The two experiments were conducted with filtered seawater collected at separate times from the Scripps Institute of Oceanography Pier in La Jolla, CA. Phytoplankton blooms in each tank were induced via the addition of nutrients and photosynthetically active radiation. The "indoor" MART was illuminated with fluorescent light and the other "outdoor" MART was illuminated with sunlight. The peak chlorophyll-a concentrations were 59 micrograms/L and 341 micrograms /L for the indoor and outdoor MARTs, respectively. GF(85%) values for SSA particles were quantified using a humidified cavity ringdown spectrometer and particle size distributions. Particle composition was monitored with a single particle aerosol mass spectrometer (ATOFMS) and an Aerodyne aerosol mass spectrometer (AMS). Relationships between the observed particle GFs and the particle composition markers will be discussed.

Hygroscopic properties and cloud condensation nuclei activation of limonene-derived organosulfates and their mixtures with ammonium sulfate

NASA Astrophysics Data System (ADS)

Hansen, A. M. K.; Hong, J.; Raatikainen, T.; Kristensen, K.; Ylisirniö, A.; Virtanen, A.; Petäjä, T.; Glasius, M.; Prisle, N. L.

2015-12-01

Organosulfates have been observed as constituents of atmospheric aerosols in a wide range of environments; however their hygroscopic properties remain uncharacterised. Here, limonene-derived organosulfates with a molecular weight of 250 Da (L-OS 250) were synthesised and used for simultaneous measurements with a hygroscopicity tandem differential mobility analyser (H-TDMA) and a cloud condensation nuclei counter (CCNC) to determine the hygroscopicity parameter, κ, for pure L-OS 250 and mixtures of L-OS 250 with ammonium sulfate (AS) over a wide range of humidity conditions. The κ values derived from measurements with H-TDMA decreased with increasing particle dry diameter for all chemical compositions investigated, indicating that κH-TDMA depends on particle diameter and/or surface effects; however, it is not clear if this trend is statistically significant. For pure L-OS 250, κ was found to increase with increasing relative humidity, indicating dilution/solubility effects to be significant. Discrepancies in κ between the sub- and supersaturated measurements were observed for L-OS 250, whereas κ of AS and mixed L-OS 250/AS were similar. This discrepancy was primarily ascribed to limited dissolution of L-OS 250 at subsaturated conditions. In general, hygroscopic growth factor, critical particle diameter and κ for the mixed L-OS 250/AS particles converged towards the values of pure AS for mixtures with ≥ 20 % w / w AS. Surface tension measurements of bulk aqueous L-OS 250/AS solutions showed that L-OS 250 was indeed surface active, as expected from its molecular structure, decreasing the surface tension of solutions with 24 % from the pure water value at a L-OS 250 concentration of 0.0025 mol L-1. Based on these surface tension measurements, we present the first concentration-dependent parametrisation of surface tension for aqueous L-OS 250, which was implemented to different process-level models of L-OS 250 hygroscopicity and CCN activation. The values of κ obtained from the measurements were compared with κ calculated applying the volume additive Zdanovskii-Stokes-Robinson mixing rule, as well as κ modelled from equilibrium Köhler theory with different assumptions regarding L-OS 250 bulk-to-surface partitioning and aqueous droplet surface tension. This study is to our knowledge the first to investigate the hygroscopic properties and surface activity of L-OS 250; hence it is an important first step towards understanding the atmospheric impact of organosulfates.

The Effect of Organic Compounds on the Hygroscopic Properties of Inorganic Aerosol

NASA Astrophysics Data System (ADS)

Krieger, U. K.; Zardini, A. A.; Marcolli, C.

2006-12-01

The hygroscopicity of the aerosols plays a major role for the direct and indirect effect on the climate. It is known that aerosols are often a mixture of inorganic and organic matter. A significant fraction of the organic matter is water soluble (WSOC) and affects light scattering, water uptake and phase transitions of multicomponent aerosols. Additionally, organic matter can act as a surfactant around an inorganic particle, affecting the evaporation-condensation time scale. This research project benefits from the combined measurements performed by two different instrumentations: the electrodynamic trap at IACETH, Zürich, Switzerland, and a Tandem Differential Mobility Analizer (TDMA) at the Paul Scherrer Institute, Switzerland. The Electrodynamic Trap consists of a chamber in which a levitated particle can experience all the atmospherically relevant conditions of temperature, pressure, and humidity. All these parameters can be continuously varied so that the hygroscopic curve of the aerosol particle can be measured. Additional tools help to better characterize the aerosol particle: 90 degrees angular scattering of lasers (for radius measurements) and intensity fluctuation of the scattered light with time (for phase changes detection). In this poster the results obtained through the electrodynamic balance technique will be shown and compared with the TDMA. In particular, bicomponent ammonium sulphate with adipic acid bicomponent particles are studied, with different mixing ratios. Particular emphasis is put on assessing the water uptake and the phase changes of the particles.

Ambient observations of hygroscopic growth factor and f(RH) below 1: Case studies from surface and airborne measurements

NASA Astrophysics Data System (ADS)

Shingler, Taylor; Sorooshian, Armin; Ortega, Amber; Crosbie, Ewan; Wonaschütz, Anna; Perring, Anne E.; Beyersdorf, Andreas; Ziemba, Luke; Jimenez, Jose L.; Campuzano-Jost, Pedro; Mikoviny, Tomas; Wisthaler, Armin; Russell, Lynn M.

2016-11-01

This study reports a detailed set of ambient observations of optical/physical shrinking of particles from exposure to water vapor with consistency across different instruments and regions. Data have been utilized from (i) a shipboard humidified tandem differential mobility analyzer during the Eastern Pacific Emitted Aerosol Cloud Experiment in 2011, (ii) multiple instruments on the NASA DC-8 research aircraft during the Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys in 2013, and (iii) the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe during ambient measurements in Tucson, Arizona, during summer 2014 and winter 2015. Hygroscopic growth factor (ratio of humidified-to-dry diameter, GF = Dp,wet/Dp,dry) and f(RH) (ratio of humidified-to-dry scattering coefficients) values below 1 were observed across the range of relative humidity (RH) investigated (75-95%). A commonality of observations of GF and f(RH) below 1 in these experiments was the presence of particles enriched with carbonaceous matter, especially from biomass burning. Evidence of externally mixed aerosol, and thus multiple GFs with at least one GF < 1, was observed concurrently with f(RH) < 1 during smoke periods. Possible mechanisms responsible for observed shrinkage are discussed and include particle restructuring, volatilization effects, and refractive index modifications due to aqueous processing resulting in optical size modification. To further investigate ambient observations of GFs and f(RH) values less than 1, it is recommended to add an optional prehumidification bypass module to hygroscopicity instruments, to preemptively collapse particles prior to controlled RH measurements.

Properties of jet engine combustion particles during the PartEmis experiment: Microphysics and Chemistry

NASA Astrophysics Data System (ADS)

Petzold, A.; Stein, C.; Nyeki, S.; Gysel, M.; Weingartner, E.; Baltensperger, U.; Giebl, H.; Hitzenberger, R.; Döpelheuer, A.; Vrchoticky, S.; Puxbaum, H.; Johnson, M.; Hurley, C. D.; Marsh, R.; Wilson, C. W.

2003-07-01

The particles emitted from an aircraft engine combustor were investigated in the European project PartEmis. Measured aerosol properties were mass and number concentration, size distribution, mixing state, thermal stability of internally mixed particles, hygroscopicity, and cloud condensation nuclei (CCN) activation potential. The combustor operation conditions corresponded to modern and older engine gas path temperatures at cruise altitude, with fuel sulphur contents (FSC) of 50, 410, and 1270 μg g-1. Operation conditions and FSC showed only a weak influence on the microphysical aerosol properties, except for hygroscopic and CCN properties. Particles of size D >= 30 nm were almost entirely internally mixed. Particles of sizes D < 20 nm showed a considerable volume fraction of compounds that volatilise at 390 K (10-15%) and 573 K (4-10%), while respective fractions decreased to <5% for particles of size D >= 50 nm.

Molecular Diversity of Sea Spray Aerosol Particles: Impact of Ocean Biology on Particle Composition and Hygroscopicity

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

Cochran, Richard E.; Laskina, Olga; Trueblood, Jonathan V.

The impact of sea spray aerosol (SSA) on climate depends on the size and chemical composition of individual particles that make-up the total SSA ensemble. While the organic fraction of SSA has been characterized from a bulk perspective, there remains a lack of understanding as to the composition of individual particles within the SSA ensemble. To better understand the molecular components within SSA particles and how SSA composition changes with ocean biology, simultaneous measurements of seawater and SSA were made during a month-long mesocosm experiment performed in an ocean-atmosphere facility. Herein, we deconvolute the composition of freshly emitted SSA devoidmore » of anthropogenic and terrestrial influences by characterizing classes of organic compounds as well as specific molecules within individual SSA particles. Analysis of SSA particles show that the diversity of molecules within the organic fraction varies between two size fractions (submicron and supermicron) with contributions from fatty acids, monosaccharides, polysaccharides and siliceous material. Significant changes in the distribution of these compounds within individual particles are observed to coincide with the rise and fall of phytoplankton and bacterial populations within the seawater. Furthermore, water uptake is impacted as shown by hygroscopicity measurements of model systems composed of representative organic compounds. Thus, the how changes in the hygroscopic growth of SSA evolves with composition can be elucidated. Overall, this study provides an important connection between biological processes that control the composition of seawater and changes in single particle composition which will enhances our ability to predict the impact of SSA on climate.« less

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

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

Mei, Fan; Setyan, Ari; Zhang, Qi

2013-12-17

During the Carbonaceous Aerosols and Radiative Effects Study (CARES), activation fraction of size-resolved aerosol particles and aerosol chemical composition were characterized at the T1 site (~60 km downwind of Sacramento, California) from 10 June to 28 June 2010. The hygroscopicity of CCN-active particles (K CCN) with diameter from 100 to 170 nm, derived from the size-resolved activated fraction, varied from 0.10 to 0.21, with an average of 0.15, which was substantially lower than that proposed for continental sites in earlier studies. The low K CCN value was due to the high organic volume fraction, averaged over 80% at the T1more » site. The derived K CCN exhibited little diurnal variation, consistent with the relatively constant organic volume fraction observed. At any time, over 90% of the size selected particles with diameter between 100 and 171nm were CCN active, suggesting most particles within this size range were aged background particles. Due to the large organic volume fraction, organic hygroscopicity (K org) strongly impacted particle hygroscopicity and therefore calculated CCN concentration. For vast majority of the cases, an increase of K org from 0.03 to 0.18, which are within the typical range, doubled the calculated CCN concentration. Organic hygroscopicity was derived from K CCN and aerosol chemical composition, and its variations with the fraction of total organic mass spectral signal at m/z 44 (f 44) and O:C were compared to results from previous studies. Overall, the relationships between K org and f 44 are quite consistent for organic aerosol (OA) observed during field studies and those formed in smog chamber. Compared to the relationship between K org and f 44, the relationship between K org and O:C exhibits more significant differences among different studies, suggesting korg may be better parameterized using f 44. A least squares fit yielded K org = 2.10 (±0.07) × f 44 -0.11 (±0.01) with the Pearson R 2 value of 0.71. One possible explanation for the stronger correlation between K org and f 44 is that the m/z 44 signal (mostly contributed by the CO 2 + ion) is more closely related to organic acids, which may dominate the overall korg due to their relatively high water solubility and hygroscopicity.« less

Poly-m-aramid nanofiber mats: Production for application as structural modifiers in CFRP laminates

NASA Astrophysics Data System (ADS)

Mazzocchetti, Laura; D'Angelo, Emanuele; Benelli, Tiziana; Belcari, Juri; Brugo, Tommaso Maria; Zucchelli, Andrea; Giorgini, Loris

2016-05-01

Poly(m-phenylene isophtalamide) electrospun nanofibrous membranes were produced to be used as structural reinforcements for carbon fiber reinforced composites production. In order for the polymer to be electrospun, it needs however to be fully solubilized, so the addition of some salts is required to help disrupt the tight macromolecular packing based on intra- and inter-molecular hydrogen bonding. Such salts may also contribute to the electrospinnability of the overall solution, since the provide it with a higher conductivity, whatever the solvent might be. The salt haobwever stays in the final nanofibrous mat. The membranes containing the salt are also observed to be highly hygroscopic, with a water content up to 26%, in the presence of 20%wt LiCl in the nanofibrous mat. When those membranes were interleaved among prepregs to produce a laminates, the obtained composite displayed thermal properties comparable to those of a reference nanofiber-free composite, though the former showed also easier delamination. Hence the removal of the hygroscopic salt was performed, that lead to thinner membranes, whose water content matched that of the pristine polymer. The washing step induced a thinning of the layers and of the fibers diameters, though no fiber shrinking nor membrane macroscopic damages were observed. These preliminary encouraging results thus pave the way to a deeper study of the optimized condition for producing convenient poly(m-phenylene isophtalamide) electrospun nanofibrous membranes to be used for carbon fiber reinforced composites structural modification.

Contrasting aerosol refractive index and hygroscopicity in the inflow and outflow of deep convective storms: Analysis of airborne data from DC3

NASA Astrophysics Data System (ADS)

Sorooshian, Armin; Shingler, T.; Crosbie, E.; Barth, M. C.; Homeyer, C. R.; Campuzano-Jost, P.; Day, D. A.; Jimenez, J. L.; Thornhill, K. L.; Ziemba, L. D.; Blake, D. R.; Fried, A.

2017-04-01

We examine three case studies during the Deep Convective Clouds and Chemistry (DC3) field experiment when storm inflow and outflow air were sampled for aerosol subsaturated hygroscopicity and the real part of refractive index (n) with a Differential Aerosol Sizing and Hygroscopicity Probe (DASH-SP) on the NASA DC-8. Relative to inflow aerosol particles, outflow particles were more hygroscopic (by 0.03 based on the estimated κ parameter) in one of the three storms examined. Two of three "control" flights with no storm convection reveal higher κ values, albeit by only 0.02, at high altitude (> 8 km) versus < 4 km. Entrainment modeling shows that measured κ values in the outflow of the three storm flights are higher than predicted values (by 0.03-0.11) based on knowledge of κ values from the inflow and clear air adjacent to the storms. This suggests that other process(es) contributed to hygroscopicity enhancements such as secondary aerosol formation via aqueous-phase chemistry. Values of n were higher in the outflow of two of the three storm flights, reaching as high as 1.54. More statistically significant differences were observed in control flights (no storms) where n decreased from 1.50-1.52 (< 4 km) to 1.49-1.50 (> 8 km). Chemical data show that enhanced hygroscopicity was coincident with lower organic mass fractions, higher sulfate mass fractions, and higher O:C ratios of organic aerosol. Refractive index did not correlate as well with available chemical data. Deep convection is shown to alter aerosol radiative properties, which has implications for aerosol effects on climate.

Insight into winter haze formation mechanisms based on aerosol hygroscopicity and effective density measurements

NASA Astrophysics Data System (ADS)

Xie, Yuanyuan; Ye, Xingnan; Ma, Zhen; Tao, Ye; Wang, Ruyu; Zhang, Ci; Yang, Xin; Chen, Jianmin; Chen, Hong

2017-06-01

We characterize a representative particulate matter (PM) episode that occurred in Shanghai during winter 2014. Particle size distribution, hygroscopicity, effective density, and single particle mass spectrometry were determined online, along with offline analysis of water-soluble inorganic ions. The mass ratio of SNA / PM1. 0 (sulfate, nitrate, and ammonium) fluctuated slightly around 0.28, suggesting that both secondary inorganic compounds and carbonaceous aerosols contributed substantially to the haze formation, regardless of pollution level. Nitrate was the most abundant ionic species during hazy periods, indicating that NOx contributed more to haze formation in Shanghai than did SO2. During the representative PM episode, the calculated PM was always consistent with the measured PM1. 0, indicating that the enhanced pollution level was attributable to the elevated number of larger particles. The number fraction of the near-hydrophobic group increased as the PM episode developed, indicating the accumulation of local emissions. Three banana-shaped particle evolutions were consistent with the rapid increase of PM1. 0 mass loading, indicating that the rapid size growth by the condensation of condensable materials was responsible for the severe haze formation. Both hygroscopicity and effective density of the particles increased considerably with growing particle size during the banana-shaped evolutions, indicating that the secondary transformation of NOx and SO2 was one of the most important contributors to the particle growth. Our results suggest that the accumulation of gas-phase and particulate pollutants under stagnant meteorological conditions and subsequent rapid particle growth by secondary processes were primarily responsible for the haze pollution in Shanghai during wintertime.

Mechanisms for Improved Hygroscopicity of L-Arginine Valproate Revealed by X-Ray Single Crystal Structure Analysis.

PubMed

Ito, Masataka; Nambu, Kaori; Sakon, Aya; Uekusa, Hidehiro; Yonemochi, Etsuo; Noguchi, Shuji; Terada, Katsuhide

2017-03-01

Valproic acid is widely used as an antiepileptic agent. Valproic acid is in liquid phase while sodium valproate is in solid phase at room temperature. Sodium valproate is hard to manufacture because of its hygroscopic and deliquescent properties. To improve these, cocrystal and salt screening for valproic acid was employed in this study. Two solid salt forms, l-arginine valproate and l-lysine valproate, were obtained and characterized. By using dynamic vapor sorption method, the critical relative humidity of sodium valproate, l-arginine valproate, and l-lysine valproate were measured. Critical relative humidity of sodium valproate was 40%, of l-lysine valproate was 60%, and of l-arginine valproate was 70%. Single-crystal X-ray structure determination of l-arginine valproate was employed. l-Lysine valproate was of low diffraction quality, and l-arginine valproate formed a 1:1 salt. Crystal l-arginine valproate has a disorder in the methylene carbon chain that creates 2 conformations. The carboxylate group of valproic acid is connected to the amino group of l-arginine. Crystalline morphologies were calculated from its crystal structure. Adsorption of water molecules to crystal facets was simulated by Material Studio. When comparing adsorption energy per site of these salts, sodium valproate is more capable of adsorption of water molecule than l-arginine valproate. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Vertically resolved concentration and liquid water content of atmospheric nanoparticles at the US DOE Southern Great Plains site

NASA Astrophysics Data System (ADS)

Chen, Haihan; Hodshire, Anna L.; Ortega, John; Greenberg, James; McMurry, Peter H.; Carlton, Annmarie G.; Pierce, Jeffrey R.; Hanson, Dave R.; Smith, James N.

2018-01-01

Most prior field studies of new particle formation (NPF) have been performed at or near ground level, leaving many unanswered questions regarding the vertical extent of NPF. To address this, we measured concentrations of 11-16 nm diameter particles from ground level to 1000 m during the 2013 New Particle Formation Study at the Atmospheric Radiation Measurement Southern Great Plains site in Lamont, Oklahoma. The measurements were performed using a tethered balloon carrying two condensation particle counters that were configured for two different particle cut-off diameters. These observations were compared to data from three scanning mobility particle sizers at the ground level. We observed that 11-16 nm diameter particles were generated at the top region of the boundary layer, and were then rapidly mixed throughout the boundary layer. We also estimate liquid water content of nanoparticles using ground-based measurements of particle hygroscopicity obtained with a Humidified Tandem Differential Mobility Analyzer and vertically resolved relative humidity (RH) and temperature measured with a Raman lidar. Our analyses of these observations lead to the following conclusions regarding nanoparticles formed during NPF events at this site: (1) ground-based observations may not always accurately represent the timing, distribution, and meteorological conditions associated with the onset of NPF; (2) nanoparticles are highly hygroscopic and typically contain up to 50 % water by volume, and during conditions of high RH combined with high particle hygroscopicity, particles can be up to 95 % water by volume; (3) increased liquid water content of nanoparticles at high RH greatly enhances the partitioning of water-soluble species like organic acids into ambient nanoparticles.

Condensation Kinetics of Water on Amorphous Aerosol Particles.

PubMed

Rothfuss, Nicholas E; Marsh, Aleksandra; Rovelli, Grazia; Petters, Markus D; Reid, Jonathan P

2018-06-25

Responding to changes in the surrounding environment, aerosol particles can grow by water condensation changing rapidly in composition and changing dramatically in viscosity. The timescale for growth is important to establish for particles undergoing hydration processes in the atmosphere or during inhalation. Using an electrodynamic balance, we report direct measurements at -7.5, 0, and 20 °C of timescales for hygroscopic condensational growth on a range of model hygroscopic aerosol systems. These extend from viscous aerosol particles containing a single saccharide solute (sucrose, glucose, raffinose, or trehalose) and a starting viscosity equivalent to a glass of ∼10 12 Pa·s, to nonviscous (∼10 -2 Pa·s) tetraethylene glycol particles. The condensation timescales observed in this work indicate that water condensation occurs rapidly at all temperatures examined (<10 s) and for particles of all initial viscosities spanning 10 -2 to 10 12 Pa·s. Only a marginal delay (<1 order of magnitude) is observed for particles starting as a glass.

Variability in morphology, hygroscopicity, and optical properties of soot aerosols during atmospheric processing

PubMed Central

Zhang, Renyi; Khalizov, Alexei F.; Pagels, Joakim; Zhang, Dan; Xue, Huaxin; McMurry, Peter H.

2008-01-01

The atmospheric effects of soot aerosols include interference with radiative transfer, visibility impairment, and alteration of cloud formation and are highly sensitive to the manner by which soot is internally mixed with other aerosol constituents. We present experimental studies to show that soot particles acquire a large mass fraction of sulfuric acid during atmospheric aging, considerably altering their properties. Soot particles exposed to subsaturated sulfuric acid vapor exhibit a marked change in morphology, characterized by a decreased mobility-based diameter but an increased fractal dimension and effective density. These particles experience large hygroscopic size and mass growth at subsaturated conditions (<90% relative humidity) and act efficiently as cloud-condensation nuclei. Coating with sulfuric acid and subsequent hygroscopic growth enhance the optical properties of soot aerosols, increasing scattering by ≈10-fold and absorption by nearly 2-fold at 80% relative humidity relative to fresh particles. In addition, condensation of sulfuric acid is shown to occur at a similar rate on ambient aerosols of various types of a given mobility size, regardless of their chemical compositions and microphysical structures. Representing an important mechanism of atmospheric aging, internal mixing of soot with sulfuric acid has profound implications on visibility, human health, and direct and indirect climate forcing. PMID:18645179

Investigations of the hygroscopic properties of ammonium sulfate and mixed ammonium sulfate and glutaric acid micro droplets by means of optical levitation and Raman spectroscopy.

PubMed

Jordanov, N; Zellner, R

2006-06-21

In the presented work an optical levitation technique performed by means of a focused laser beam, Mie and Raman spectroscopy have been utilized for measuring hygroscopic growth curves and composition of laboratory generated single ammonium sulfate (AS) and internally mixed ammonium sulfate-glutaric acid (GA) droplets in the micrometer range. The generated particles have been found to immediately supersaturate (above 45wt% for AS) at 297 K after capturing in the laser beam. Further increase of the relative humidity (RH) up to 85% does not dilute the droplets under the saturation point. A spontaneous hygroscopic growth takes place at 73.5-78% RH for pure AS. The particle grows with an average factor of 1.62 at the deliquescence relative humidity (DRH). Efflorescence of AS occurs at 43% RH with a corresponding concentration of more than 85wt%. Independent of the mixing ratios in ranges 25/75, 50/50, 75/25% AS/GA mixed particles don't exist as a metastable supersaturated solution droplets in the 35-85% RH range. Instead of growing with increasing relative humidity internally mixed particles build up a solid crystalline layer on the surface. This crystalline phase is not further influenced by ambient relative humidities.

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 surfactant molecules on the aqueous aerosol particle surface upon growing. The number of molecules of the disaggregating micelle can be deduced from the known polar surface area of the C8E4 molecule and the surface area increase of the aerosol particle calculated from the step increase in radius. Our measurements yield a broad distribution of aggregation numbers with a peak aggregation number of 105 molecules. This number agrees reasonably well with aggregate sizes directly observed with Cryo-TEM in a related system [5]. References: [1] Oppo, C., Bellandi, S., Degli Innocenti, N., Stortini, A.M., Loglio, G., Schiavuta, E., & Cini, R., Marine Chemistry, 63, 235-253, 1999. [2] O'Dowd, C.D., Facchini, M.C., Cavalli, F., Ceburnis, D., Mircea, M., Decesari, S., Fuzzi, S., Yoon, Y.J., & Putaud, J.P., Nature, 431, 676-680, 2004. [3] Israelachvili, J.N., Intermolecular and surface forces, Academic press London, 1991. [4] Zardini, A.A., Krieger, U.K., & Marcolli, C., Optics Express, 14, 6951-6962, 2006. [5] Bernheim-Groswasser, A., Wachtel E., & Talmon, Y., Langmuir, 16, 4131-4140, 2000.

Impact of Wildfire Emissions on Chloride and Bromide Depletion in Marine Aerosol Particles.

PubMed

Braun, Rachel A; Dadashazar, Hossein; MacDonald, Alexander B; Aldhaif, Abdulamonam M; Maudlin, Lindsay C; Crosbie, Ewan; Aghdam, Mojtaba Azadi; Hossein Mardi, Ali; Sorooshian, Armin

2017-08-15

This work examines particulate chloride (Cl - ) and bromide (Br - ) depletion in marine aerosol particles influenced by wildfires at a coastal California site in the summers of 2013 and 2016. Chloride exhibited a dominant coarse mode due to sea salt influence, with substantially diminished concentrations during fire periods as compared to nonfire periods. Bromide exhibited a peak in the submicrometer range during fire and nonfire periods, with an additional supermicrometer peak in the latter periods. Chloride and Br - depletions were enhanced during fire periods as compared to nonfire periods. The highest observed %Cl - depletion occurred in the submicrometer range, with maximum values of 98.9% (0.32-0.56 μm) and 85.6% (0.56-1 μm) during fire and nonfire periods, respectively. The highest %Br - depletion occurred in the supermicrometer range during fire and nonfire periods with peak depletion between 1.8-3.2 μm (78.8% and 58.6%, respectively). When accounting for the neutralization of sulfate by ammonium, organic acid particles showed the greatest influence on Cl - depletion in the submicrometer range. These results have implications for aerosol hygroscopicity and radiative forcing in areas with wildfire influence owing to depletion effects on composition.

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

Organic component vapor pressures and hygroscopicities of aqueous aerosol measured by optical tweezers.

PubMed

Cai, Chen; Stewart, David J; Reid, Jonathan P; Zhang, Yun-hong; Ohm, Peter; Dutcher, Cari S; Clegg, Simon L

2015-01-29

Measurements of the hygroscopic response of aerosol and the particle-to-gas partitioning of semivolatile organic compounds are crucial for providing more accurate descriptions of the compositional and size distributions of atmospheric aerosol. Concurrent measurements of particle size and composition (inferred from refractive index) are reported here using optical tweezers to isolate and probe individual aerosol droplets over extended timeframes. The measurements are shown to allow accurate retrievals of component vapor pressures and hygroscopic response through examining correlated variations in size and composition for binary droplets containing water and a single organic component. Measurements are reported for a homologous series of dicarboxylic acids, maleic acid, citric acid, glycerol, or 1,2,6-hexanetriol. An assessment of the inherent uncertainties in such measurements when measuring only particle size is provided to confirm the value of such a correlational approach. We also show that the method of molar refraction provides an accurate characterization of the compositional dependence of the refractive index of the solutions. In this method, the density of the pure liquid solute is the largest uncertainty and must be either known or inferred from subsaturated measurements with an error of <±2.5% to discriminate between different thermodynamic treatments.

Hygroscopic Measurements of Aerosol Particles in Colorado during the Discover AQ Campaign 2014

NASA Astrophysics Data System (ADS)

Orozco, D.; Delgado, R.; Espinosa, R.; Martins, J. V.; Hoff, R. M.

2014-12-01

In ambient conditions, aerosol particles experience hygroscopic growth due to the influence of relative humidity (RH), scattering more light than when the particles are dry. The quantitative knowledge of the RH effect and its influence on the light scattering and, in particular, on the phase function and polarization of aerosol particles is of substantial importance when comparing ground observations with other optical aerosol measurements such satellite and sunphotometric retrievals of aerosol optical depth and their inversions. In the summer of 2014, the DISCOVER-AQ campaign was held in Colorado, where systematic and concurrent observations of column- integrated surface, and vertically-resolved distributions of aerosols and trace gases relevant to air quality and their evolution during the day were observed. Aerosol optical properties were measured in the UMBC trailer at the city of Golden using a TSI-3563 nephelometer and an in-situ Polarized Imaging Nephelometer (PI-NEPH) designed and built by the LACO group at UMBC. The PI-NEPH measures aerosol phase matrix components in high angular range between 2 and 178 degrees scattering angle at three wavelengths (λ=473, 532 and 671nm). The two measured elements of the phase matrix, intensity (P11) and linear polarization (P12) provide extensive characterization of the scattering properties of the studied aerosol. The scattering coefficient, P11 and P12 were measured under different humidity conditions to obtain the enhancement factor f(RH) and the dependence of P11 and P12 to RH using a humidifier dryer system covering a RH range from 20 to 90%. The ratio between scattering coefficients at high and low humidity in Golden Colorado showed relatively low hygroscopic growth in the aerosol particles f(RH=80%) was 1.27±0.19 for the first three weeks of sampling. According to speciated measurements performed at the UMBC trailer, the predominance of dust and organic aerosols over more hygroscopic nitrate and sulfate in the region are responsible for the low hygroscopicity. In addition, transported smoke remnants from wildfires in the Pacific Northwest were detected as the elemental and organic carbon concentrations increased. The P11 and P12 elements from smoke and local sources are discussed as well as the vertical distribution by airborne and ground comparisons.

Implications of abundant hygroscopic minerals in the Martian regolith

NASA Technical Reports Server (NTRS)

Clark, B. C.

1978-01-01

Converging lines of evidence suggest that a significant portion of the Martian surface fines may consist of salts and smectite clays. Salts can form stoichiometric hydrates as well as eutectic solutions with depressed freezing points; clays contain bound water of constitution and adsorb significant quantities of water from the vapor phase. The formation of ice may be suppressed by these minerals in some regions on Mars, and their presence in abundance would imply important consequences for atmospheric and geologic processes and the prospects for exobiology.

Beyond the Alphabet Soup: Molecular Properties of Aerosol Components Influence Optics. (Invited)

NASA Astrophysics Data System (ADS)

Thompson, J. E.

2013-12-01

Components within atmospheric aerosols exhibit almost every imaginable model of chemical bonding and physical diversity. The materials run the spectrum from crystalline to amorphous, covalent to ionic, and have varying viscosities, phase, and hygroscopicity. This seminar will focus on the molecular properties of materials that influence the optical behavior of aerosols. Special focus will be placed on the polarizability of materials, hygroscopic growth, and particle phase.

Relating hygroscopicity and optical properties to chemical composition and structure of secondary organic aerosol particles generated from the ozonolysis of α-pinene

NASA Astrophysics Data System (ADS)

Denjean, C.; Formenti, P.; Picquet-Varrault, B.; Pangui, E.; Zapf, P.; Katrib, Y.; Giorio, C.; Tapparo, A.; Monod, A.; Temime-Roussel, B.; Decorse, P.; Mangeney, C.; Doussin, J. F.

2015-03-01

Secondary organic aerosol (SOA) were generated from the ozonolysis of α-pinene in the CESAM (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber) simulation chamber. The SOA formation and aging were studied by following their optical, hygroscopic and chemical properties. The optical properties were investigated by determining the particle complex refractive index (CRI). The hygroscopicity was quantified by measuring the effect of relative humidity (RH) on the particle size (size growth factor, GF) and on the scattering coefficient (scattering growth factor, f(RH)). The oxygen to carbon atomic ratios (O : C) of the particle surface and bulk were used as a sensitive parameter to correlate the changes in hygroscopic and optical properties of the SOA composition during their formation and aging in CESAM. The real CRI at 525 nm wavelength decreased from 1.43-1.60 (±0.02) to 1.32-1.38 (±0.02) during the SOA formation. The decrease in the real CRI correlated to the O : C decrease from 0.68 (±0.20) to 0.55 (±0.16). In contrast, the GF remained roughly constant over the reaction time, with values of 1.02-1.07 (±0.02) at 90% (±4.2%) RH. Simultaneous measurements of O : C of the particle surface revealed that the SOA was not composed of a homogeneous mixture, but contained less oxidised species at the surface which may limit water absorption. In addition, an apparent change in both mobility diameter and scattering coefficient with increasing RH from 0 to 30% was observed for SOA after 14 h of reaction. We postulate that this change could be due to a change in the viscosity of the SOA from a predominantly glassy state to a predominantly liquid state.

Long-term observations of cloud condensation nuclei in the Amazon rain forest – Part 1: Aerosol size distribution, hygroscopicity, and new model parametrizations for CCN prediction

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

Pöhlker, Mira L.; Pöhlker, Christopher; Ditas, Florian

Size-resolved long-term measurements of atmospheric aerosol and cloud condensation nuclei (CCN) concentrations and hygroscopicity were conducted at the remote Amazon Tall Tower Observatory (ATTO) in the central Amazon Basin over a 1-year period and full seasonal cycle (March 2014–February 2015). Our measurements provide a climatology of CCN properties characteristic of a remote central Amazonian rain forest site.The CCN measurements were continuously cycled through 10 levels of supersaturation ( S=0.11 to 1.10 %) and span the aerosol particle size range from 20 to 245 nm. The mean critical diameters of CCN activation range from 43 nm at S = 1.10 % to 172more » nm at S = 0.11 %. Furthermore, the particle hygroscopicity exhibits a pronounced size dependence with lower values for the Aitken mode ( κ Ait = 0.14 ± 0.03), higher values for the accumulation mode ( κ Acc = 0.22 ± 0.05), and an overall mean value of κ mean = 0.17 ± 0.06, consistent with high fractions of organic aerosol.The hygroscopicity parameter, κ, exhibits remarkably little temporal variability: no pronounced diurnal cycles, only weak seasonal trends, and few short-term variations during long-range transport events. In contrast, the CCN number concentrations exhibit a pronounced seasonal cycle, tracking the pollution-related seasonality in total aerosol concentration. Here, we find that the variability in the CCN concentrations in the central Amazon is mostly driven by aerosol particle number concentration and size distribution, while variations in aerosol hygroscopicity and chemical composition matter only during a few episodes.For modeling purposes, we compare different approaches of predicting CCN number concentration and present a novel parametrization, which allows accurate CCN predictions based on a small set of input data.« less

Long-term observations of cloud condensation nuclei in the Amazon rain forest – Part 1: Aerosol size distribution, hygroscopicity, and new model parametrizations for CCN prediction

DOE PAGES

Pöhlker, Mira L.; Pöhlker, Christopher; Ditas, Florian; ...

2016-12-20

Size-resolved long-term measurements of atmospheric aerosol and cloud condensation nuclei (CCN) concentrations and hygroscopicity were conducted at the remote Amazon Tall Tower Observatory (ATTO) in the central Amazon Basin over a 1-year period and full seasonal cycle (March 2014–February 2015). Our measurements provide a climatology of CCN properties characteristic of a remote central Amazonian rain forest site.The CCN measurements were continuously cycled through 10 levels of supersaturation ( S=0.11 to 1.10 %) and span the aerosol particle size range from 20 to 245 nm. The mean critical diameters of CCN activation range from 43 nm at S = 1.10 % to 172more » nm at S = 0.11 %. Furthermore, the particle hygroscopicity exhibits a pronounced size dependence with lower values for the Aitken mode ( κ Ait = 0.14 ± 0.03), higher values for the accumulation mode ( κ Acc = 0.22 ± 0.05), and an overall mean value of κ mean = 0.17 ± 0.06, consistent with high fractions of organic aerosol.The hygroscopicity parameter, κ, exhibits remarkably little temporal variability: no pronounced diurnal cycles, only weak seasonal trends, and few short-term variations during long-range transport events. In contrast, the CCN number concentrations exhibit a pronounced seasonal cycle, tracking the pollution-related seasonality in total aerosol concentration. Here, we find that the variability in the CCN concentrations in the central Amazon is mostly driven by aerosol particle number concentration and size distribution, while variations in aerosol hygroscopicity and chemical composition matter only during a few episodes.For modeling purposes, we compare different approaches of predicting CCN number concentration and present a novel parametrization, which allows accurate CCN predictions based on a small set of input data.« less

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

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

Thalman, R.; Thalman, R.; Wang, J.

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

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

DOE PAGES

Thalman, R.; Thalman, R.; Wang, J.; ...

2015-03-06

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

Uncertainty in Predicting CCN Activity of Aged and Primary Aerosols

NASA Astrophysics Data System (ADS)

Zhang, Fang; Wang, Yuying; Peng, Jianfei; Ren, Jingye; Collins, Don; Zhang, Renyi; Sun, Yele; Yang, Xin; Li, Zhanqing

2017-11-01

Understanding particle CCN activity in diverse atmospheres is crucial when evaluating aerosol indirect effects. Here aerosols measured at three sites in China were categorized as different types for attributing uncertainties in CCN prediction in terms of a comprehensive data set including size-resolved CCN activity, size-resolved hygroscopic growth factor, and chemical composition. We show that CCN activity for aged aerosols is unexpectedly underestimated 22% at a supersaturation (S) of 0.2% when using κ-Kohler theory with an assumption of an internal mixture with measured bulk composition that has typically resulted in an overestimate of the CCN activity in previous studies. We conclude that the underestimation stems from neglect of the effect of aging/coating on particle hygroscopicity, which is not considered properly in most current models. This effect enhanced the hygroscopicity parameter (κ) by between 11% (polluted conditions) and 30% (clean days), as indicated in diurnal cycles of κ based on measurements by different instruments. In the urban Beijing atmosphere heavily influenced by fresh emissions, the CCN activity was overestimated by 45% at S = 0.2%, likely because of inaccurate assumptions of particle mixing state and because of variability of chemical composition over the particle size range. For both fresh and aged aerosols, CCN prediction exhibits very limited sensitivity to κSOA, implying a critical role of other factors like mixing of aerosol components within and between particles in regulating CCN activity. Our findings could help improving CCN parameterization in climate models.

Individual aerosol particles in ambient and updraft conditions below convective cloud bases in the Oman mountain region

NASA Astrophysics Data System (ADS)

Semeniuk, T. A.; Bruintjes, R. T.; Salazar, V.; Breed, D. W.; Jensen, T. L.; Buseck, P. R.

2014-03-01

An airborne study of cloud microphysics provided an opportunity to collect aerosol particles in ambient and updraft conditions of natural convection systems for transmission electron microscopy (TEM). Particles were collected simultaneously on lacey carbon and calcium-coated carbon (Ca-C) TEM grids, providing information on particle morphology and chemistry and a unique record of the particle's physical state on impact. In total, 22 particle categories were identified, including single, coated, aggregate, and droplet types. The fine fraction comprised up to 90% mixed cation sulfate (MCS) droplets, while the coarse fraction comprised up to 80% mineral-containing aggregates. Insoluble (dry), partially soluble (wet), and fully soluble particles (droplets) were recorded on Ca-C grids. Dry particles were typically silicate grains; wet particles were mineral aggregates with chloride, nitrate, or sulfate components; and droplets were mainly aqueous NaCl and MCS. Higher numbers of droplets were present in updrafts (80% relative humidity (RH)) compared with ambient conditions (60% RH), and almost all particles activated at cloud base (100% RH). Greatest changes in size and shape were observed in NaCl-containing aggregates (>0.3 µm diameter) along updraft trajectories. Their abundance was associated with high numbers of cloud condensation nuclei (CCN) and cloud droplets, as well as large droplet sizes in updrafts. Thus, compositional dependence was observed in activation behavior recorded for coarse and fine fractions. Soluble salts from local pollution and natural sources clearly affected aerosol-cloud interactions, enhancing the spectrum of particles forming CCN and by forming giant CCN from aggregates, thus, making cloud seeding with hygroscopic flares ineffective in this region.

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

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

Slade, J. H.; Thalman, R.; Wang, J.

Multiphase OH and O 3 oxidation reactions with atmospheric organic aerosol (OA) can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low-soluble single-component OA by OH and O 3 can increase their water solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN) and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA) surrogate particlesmore » exposed to OH and O 3 is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type, mixing state, and OH and O 3 exposure applying a CCN counter (CCNc) coupled to an aerosol flow reactor (AFR). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O 3 exposure. Following exposure to OH, κ of MNC was enhanced by an order of magnitude, from 0.009 to ~ 0.1, indicating that chemically aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in κ was observed for pure LEV particles following OH exposure. κ of the internally mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH-exposed MNC-coated KS particles is similar to the OH unexposed atomized 1 : 1 by mass MNC : KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC) or inorganic ions, chemical aging has no significant impact on OA hygroscopicity. The organic compounds exhibiting low solubility behave as if they are infinitely soluble when mixed with a sufficient number of water-soluble compounds. At and beyond this point, the particles' CCN activity is governed entirely by the water-soluble fraction and is not influenced by the oxidized organic fraction. Our results have important implications for heterogeneous oxidation and its impact on cloud formation given that atmospheric aerosol is a complex mixture of organic and inorganic compounds exhibiting a wide range of solubilities.« less

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

DOE PAGES

Slade, J. H.; Thalman, R.; Wang, J.; ...

2015-09-14

Multiphase OH and O 3 oxidation reactions with atmospheric organic aerosol (OA) can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low-soluble single-component OA by OH and O 3 can increase their water solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN) and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA) surrogate particlesmore » exposed to OH and O 3 is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type, mixing state, and OH and O 3 exposure applying a CCN counter (CCNc) coupled to an aerosol flow reactor (AFR). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O 3 exposure. Following exposure to OH, κ of MNC was enhanced by an order of magnitude, from 0.009 to ~ 0.1, indicating that chemically aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in κ was observed for pure LEV particles following OH exposure. κ of the internally mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH-exposed MNC-coated KS particles is similar to the OH unexposed atomized 1 : 1 by mass MNC : KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC) or inorganic ions, chemical aging has no significant impact on OA hygroscopicity. The organic compounds exhibiting low solubility behave as if they are infinitely soluble when mixed with a sufficient number of water-soluble compounds. At and beyond this point, the particles' CCN activity is governed entirely by the water-soluble fraction and is not influenced by the oxidized organic fraction. Our results have important implications for heterogeneous oxidation and its impact on cloud formation given that atmospheric aerosol is a complex mixture of organic and inorganic compounds exhibiting a wide range of solubilities.« less

Plume-exit modeling to determine cloud condensation nuclei activity of aerosols from residential biofuel combustion

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

Mena, Francisco; Bond, Tami C.; Riemer, Nicole

Residential biofuel combustion is an important source of aerosols and gases in the atmosphere. The change in cloud characteristics due to biofuel burning aerosols is uncertain, in part, due to the uncertainty in the added number of cloud condensation nuclei (CCN) from biofuel burning. We provide estimates of the CCN activity of biofuel burning aerosols by explicitly modeling plume dynamics (coagulation, condensation, chemical reactions, and dilution) in a young biofuel burning plume from emission until plume exit, defined here as the condition when the plume reaches ambient temperature and specific humidity through entrainment. We found that aerosol-scale dynamics affect CCNmore » activity only during the first few seconds of evolution, after which the CCN efficiency reaches a constant value. Homogenizing factors in a plume are co-emission of semi-volatile organic compounds (SVOCs) or emission at small particle sizes; SVOC co-emission can be the main factor determining plume-exit CCN for hydrophobic or small particles. Coagulation limits emission of CCN to about 10 16 per kilogram of fuel. Depending on emission factor, particle size, and composition, some of these particles may not activate at low supersaturation ( s sat). Hygroscopic Aitken-mode particles can contribute to CCN through self-coagulation but have a small effect on the CCN activity of accumulation-mode particles, regardless of composition differences. Simple models (monodisperse coagulation and average hygroscopicity) can be used to estimate plume-exit CCN within about 20 % if particles are unimodal and have homogeneous composition, or when particles are emitted in the Aitken mode even if they are not homogeneous. On the other hand, if externally mixed particles are emitted in the accumulation mode without SVOCs, an average hygroscopicity overestimates emitted CCN by up to a factor of 2. This work has identified conditions under which particle populations become more homogeneous during plume processes. This homogenizing effect requires the components to be truly co-emitted, rather than sequentially emitted.« less

Plume-exit modeling to determine cloud condensation nuclei activity of aerosols from residential biofuel combustion

NASA Astrophysics Data System (ADS)

Mena, Francisco; Bond, Tami C.; Riemer, Nicole

2017-08-01

Residential biofuel combustion is an important source of aerosols and gases in the atmosphere. The change in cloud characteristics due to biofuel burning aerosols is uncertain, in part, due to the uncertainty in the added number of cloud condensation nuclei (CCN) from biofuel burning. We provide estimates of the CCN activity of biofuel burning aerosols by explicitly modeling plume dynamics (coagulation, condensation, chemical reactions, and dilution) in a young biofuel burning plume from emission until plume exit, defined here as the condition when the plume reaches ambient temperature and specific humidity through entrainment. We found that aerosol-scale dynamics affect CCN activity only during the first few seconds of evolution, after which the CCN efficiency reaches a constant value. Homogenizing factors in a plume are co-emission of semi-volatile organic compounds (SVOCs) or emission at small particle sizes; SVOC co-emission can be the main factor determining plume-exit CCN for hydrophobic or small particles. Coagulation limits emission of CCN to about 1016 per kilogram of fuel. Depending on emission factor, particle size, and composition, some of these particles may not activate at low supersaturation (ssat). Hygroscopic Aitken-mode particles can contribute to CCN through self-coagulation but have a small effect on the CCN activity of accumulation-mode particles, regardless of composition differences. Simple models (monodisperse coagulation and average hygroscopicity) can be used to estimate plume-exit CCN within about 20 % if particles are unimodal and have homogeneous composition, or when particles are emitted in the Aitken mode even if they are not homogeneous. On the other hand, if externally mixed particles are emitted in the accumulation mode without SVOCs, an average hygroscopicity overestimates emitted CCN by up to a factor of 2. This work has identified conditions under which particle populations become more homogeneous during plume processes. This homogenizing effect requires the components to be truly co-emitted, rather than sequentially emitted.

Plume-exit modeling to determine cloud condensation nuclei activity of aerosols from residential biofuel combustion

DOE PAGES

Mena, Francisco; Bond, Tami C.; Riemer, Nicole

2017-08-07

Residential biofuel combustion is an important source of aerosols and gases in the atmosphere. The change in cloud characteristics due to biofuel burning aerosols is uncertain, in part, due to the uncertainty in the added number of cloud condensation nuclei (CCN) from biofuel burning. We provide estimates of the CCN activity of biofuel burning aerosols by explicitly modeling plume dynamics (coagulation, condensation, chemical reactions, and dilution) in a young biofuel burning plume from emission until plume exit, defined here as the condition when the plume reaches ambient temperature and specific humidity through entrainment. We found that aerosol-scale dynamics affect CCNmore » activity only during the first few seconds of evolution, after which the CCN efficiency reaches a constant value. Homogenizing factors in a plume are co-emission of semi-volatile organic compounds (SVOCs) or emission at small particle sizes; SVOC co-emission can be the main factor determining plume-exit CCN for hydrophobic or small particles. Coagulation limits emission of CCN to about 10 16 per kilogram of fuel. Depending on emission factor, particle size, and composition, some of these particles may not activate at low supersaturation ( s sat). Hygroscopic Aitken-mode particles can contribute to CCN through self-coagulation but have a small effect on the CCN activity of accumulation-mode particles, regardless of composition differences. Simple models (monodisperse coagulation and average hygroscopicity) can be used to estimate plume-exit CCN within about 20 % if particles are unimodal and have homogeneous composition, or when particles are emitted in the Aitken mode even if they are not homogeneous. On the other hand, if externally mixed particles are emitted in the accumulation mode without SVOCs, an average hygroscopicity overestimates emitted CCN by up to a factor of 2. This work has identified conditions under which particle populations become more homogeneous during plume processes. This homogenizing effect requires the components to be truly co-emitted, rather than sequentially emitted.« less

Formation of liquid water at low temperatures via the deliquescence of calcium chloride: Implications for Antarctica and Mars

NASA Astrophysics Data System (ADS)

Gough, R. V.; Chevrier, V. F.; Tolbert, M. A.

2016-10-01

There is significant interest in the potential existence of even small amounts of liquid brine on current Mars. It has been proposed that aqueous solutions could form on Mars via the deliquescence of hygroscopic salts in contact with atmospheric water vapor, and these hygroscopic salts have recently been detected in recurring slope linae (RSL). While past work has largely focused on perchlorate species, another Mars-relevant salt that has a low eutectic temperature and may be deliquescent is calcium chloride, CaCl2. This salt may be linked to RSL formation on Mars, and deliquescence of CaCl2 is also known to be responsible for the only terrestrial RSL analog features known thus far: water tracks in the McMurdo Dry Valleys. Here we use Raman microscopy to monitor the low-temperature (223-273 K) deliquescence (solid to aqueous phase transition) and efflorescence (aqueous to solid phase transition) of two hydration states of CaCl2, the dihydrate and the hexahydrate. We find the deliquescence relative humidity (DRH) decreases with decreasing hydration state and with increasing temperature. Average DRH values over the temperature range studied are 15.8±3.5% RH for the dihydrate and 63.3±12.5% RH for the hexahydrate, making this salt at least as deliquescent as many perchlorate salts. A remarkable property of CaCl2 is its ability to persist as metastable, supersaturated brine. Once an aqueous solution was formed, efflorescence (recrystallization) of the liquid did not occur until single-digit RH values were reached (3.9±2.4% RH on average). We show that temperature and relative humidity conditions in the martian subsurface are sufficient to allow deliquescence of CaCl2, and the resulting brines may persist for over half of a martian sol. Therefore, this salt could play a role in RSL formation, the martian water cycle, and have implications for the potential habitability of Mars.

Ex vivo assessment and validation of water exchange performance of 23 heat and moisture exchangers for laryngectomized patients.

PubMed

van den Boer, Cindy; Muller, Sara H; Vincent, Andrew D; van den Brekel, Michiel W M; Hilgers, Frans J M

2014-08-01

Breathing through a tracheostoma results in insufficient warming and humidification of the inspired air. This loss of air conditioning, especially humidification, can be partially restored with the application of a heat and moisture exchanger (HME) over the tracheostoma. For medical professionals, it is not easy to judge differences in water exchange performance of various HMEs owing to the lack of universal outcome measures. This study has three aims: assessment of the water exchange performance of commercially available HMEs for laryngectomized patients, validation of these results with absolute humidity outcomes, and assessment of the role of hygroscopic salt present in some of the tested HMEs. Measurements of weight and absolute humidity at end inspiration and end expiration at different breathing volumes of a healthy volunteer were performed using a microbalance and humidity sensor. Twenty-three HMEs from 6 different manufacturers were tested. Associations were determined between core weight, weight change, breathing volume, and absolute humidity, using both linear and nonlinear mixed effects models. Water exchange of the 23 HMEs at a breathing volume of 0.5 L varies between 0.5 and 3.6 mg. Both water exchange and wet core weight correlate strongly with the end-inspiratory absolute humidity values (r2 =0.89/0.87). Hygroscopic salt increases core weight. The 23 tested HMEs for laryngectomized patients show wide variation in water exchange performance. Water exchange correlates well with the end-inspiratory absolute humidity outcome, which validates the ex vivo weight change method. Wet core weight is a predictor of HME performance. Hygroscopic salt increases the weight of the core material. The results of this study can help medical professionals to obtain a more founded opinion about the performance of available HMEs for pulmonary rehabilitation in laryngectomized patients, and allow them to make an informed decision about which HME type to use.

Hygroscopic growth of size-resolved, emission-source classified, aerosol particles sampled across the United States

NASA Astrophysics Data System (ADS)

Shingler, T.; Crosbie, E. C.; Ziemba, L. D.; Anderson, B. E.; Campuzano Jost, P.; Jimenez, J. L.; Mikoviny, T.; Wisthaler, A.; Sorooshian, A.

2014-12-01

The hygroscopic growth of atmospheric aerosol particles is a key air quality parameter, impacting the radiation budget, visibility, and cloud formation. During the DC3 and SEAC4RS field campaigns (>300 total flight hours), measurements were made over 32 US states, Canada, the Pacific Ocean, and the Gulf of Mexico, between the surface and 41,000 feet ASL. The aircraft research payloads included a suite of in-situ aerosol and gas phase instruments. The Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe (DASH-SP) and the Langley Aerosol Research Group Experiment (LARGE) humidified nephelometer instrument applied different techniques to measure water uptake by aerosol particles at prescribed relative humidity values. Size-resolved growth factor (GF ≡ Dp,wet/Dp,dry) measurements by the DASH-SP are compared to bulk scattering measurements (f(RH) ≡ σscat,wet/σscat,dry) by the LARGE instrument. Spatial location and volatile organic compound tracers such as isoprene and acetonitrile are used to classify the origin of distinct air masses, including: forest fires, biogenic-emitting forests, agricultural use lands, marine boundary layer, urban, and rural background. Analyses of GF results by air mass origin are reported and results are compared with f(RH) measurements. A parameterization between the f(RH) and GF measurements and its potential uses are discussed.

Will Aerosol Hygroscopicity Change with Biodiesel, Renewable Diesel Fuels and Emission Control Technologies?

PubMed

Vu, Diep; Short, Daniel; Karavalakis, Georgios; Durbin, Thomas D; Asa-Awuku, Akua

2017-02-07

The use of biodiesel and renewable diesel fuels in compression ignition engines and aftertreatment technologies may affect vehicle exhaust emissions. In this study two 2012 light-duty vehicles equipped with direct injection diesel engines, diesel oxidation catalyst (DOC), diesel particulate filter (DPF), and selective catalytic reduction (SCR) were tested on a chassis dynamometer. One vehicle was tested over the Federal Test Procedure (FTP) cycle on seven biodiesel and renewable diesel fuel blends. Both vehicles were exercised over double Environmental Protection Agency (EPA) Highway fuel economy test (HWFET) cycles on ultralow sulfur diesel (ULSD) and a soy-based biodiesel blend to investigate the aerosol hygroscopicity during the regeneration of the DPF. Overall, the apparent hygroscopicity of emissions during nonregeneration events is consistently low (κ < 0.1) for all fuels over the FTP cycle. Aerosol emitted during filter regeneration is significantly more CCN active and hygroscopic; average κ values range from 0.242 to 0.439 and are as high as 0.843. Regardless of fuel, the current classification of "fresh" tailpipe emissions as nonhygroscopic remains true during nonregeneration operation. However, aftertreatment technologies such as DPF, will produce significantly more hygroscopic particles during regeneration. To our knowledge, this is the first study to show a significant enhancement of hygroscopic materials emitted during DPF regeneration of on-road diesel vehicles. As such, the contribution of regeneration emissions from a growing fleet of diesel vehicles will be important.

Nascent Marine Aerosol Acting as Ultra-Efficient Cloud Nuclei

NASA Astrophysics Data System (ADS)

Ovadnevaite, J.; Zuend, A.; Laaksonen, A.; Sanchez, K.; Roberts, G.; Ceburnis, D.; Decesari, S.; Rinaldi, M.; Hodas, N.; Facchini, C.; Seinfeld, J.; O'Dowd, C. D. D.

2017-12-01

Marine aerosol is an important part of the natural aerosol and often dominates the total burden in remote locations. Moreover, it contributes significantly to the global radiative budget through the formation of haze and cloud layers. Even if these layers are optically-thin at times, they can have a profound impact on the radiative budget as they overly a dark and extensive ocean surface. Since the postulation of marine aerosol global importance several decades ago1, understanding has progressed from evaluation of the nss-sulphate and sea salt effects to the acknowledgement of a significant role of organic aerosol2. Dependence of organic matter (OM) fraction enrichment in sea spray on phytoplankton biomass has been shown3 as well as an apparent dichotomous OM behaviour in terms of water uptake4. Hygroscopicity of organic aerosol in sub-saturated humidity fields is typically less than most common salts found in the atmospheric aerosol; however, the ability of organic aerosol to activate cloud droplets is predicted to be greatly increased in supersaturated air due a lowering of the droplets surface tension5. While this phenomenon has been acknowledged for some time, it has yet to be demonstrated in the real atmosphere. Here, we present evidence that recently-formed secondary organic aerosol particles, in marine air, lead to enhanced cloud droplet activation resulting from surface tension reduction. Whilst the surface tension lowering is expected to be negated by a concomitant reduction in the Raoult effect, driven by the displacement of solute ions by surfactant molecules at the droplet-vapour interface, we present new observational and theoretical evidence illustrating that, in ambient air, the former can prevail over the latter. Consideration of liquid-liquid phase-separation, leading to complete or partial engulfing of a hygroscopic particle core by a hydrophobic organic-rich phase, explains the lack of suppression of the Raoult effect, while maintaining substantial surface tension lowering and resulting in a tenfold increase in predicted CCN number concentration. 1Charlson R. J. et al. Nature 326, 655-661, 1987; 2O'Dowd C. D. et al. Nature 431, 676-680, 2004; 3O'Dowd C. et al. Scientific Reports 5, 2015; 4Ovadnevaite J. et al. Geophys Res Lett 38, 2011; 5Facchini M. C. et al. Atmos Environ 34, 4853-4857, 2000.

Aging of black carbon particles under polluted urban environments: timescale, hygroscopicity and enhanced absorption and direct radiative forcing

NASA Astrophysics Data System (ADS)

Peng, J.; Hu, M.; Guo, S.; Du, Z.; Zheng, J.; Shang, D.; Levy Zamora, M.; Shao, M.; Wu, Y.; Zheng, J.; Wang, Y.; Zeng, L.; Collins, D. R.; Molina, M.; Zhang, R.

2017-12-01

Black carbon (BC) exerts profound impacts on air quality and climate because of its high absorption cross-section over a broad range of electromagnetic spectra, but the current results on absorption enhancement of BC particles during atmospheric aging remain conflicting. Here, we quantified the aging and variation in the hygroscopic and optical properties of BC particles under ambient conditions in Beijing, China, and Houston, United States, using an outdoor environmental chamber approach. BC aging exhibits two distinct stages, i.e., initial transformation from a fractal to spherical morphology with little absorption variation and subsequent growth of fully compact particles with a large absorption enhancement. The timescales to achieve complete morphology modification and an absorption amplification factor of 2.4 for BC particles are estimated to be 2.3 h and 4.6 h, respectively, in Beijing, compared with 9 h and 18 h, respectively, in Houston. The κ (kappa) values of coating materials are calculated as 0.04 at both subsaturation and supersaturation conditions, respectively, indicating that the initial photochemical aging of BC particles does not appreciably alter the BC hygroscopicity. Our findings suggest that BC aging under polluted urban environments could play an essential role in pollution development and contribute importantly to large positive radiative forcing. The variation in direct radiative forcing is dependent on the rate and timescale of BC aging, with a clear distinction between urban cities in developed and developing countries, i.e., a higher climatic impact in more polluted environments. We suggest that mediation in BC emissions achieves a cobenefit in simultaneously controlling air pollution and protecting climate, especially for developing countries.

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.

Clouds and aerosols in Puerto Rico - a new evaluation

NASA Astrophysics Data System (ADS)

Allan, J. D.; Baumgardner, D.; Raga, G. B.; Mayol-Bracero, O. L.; Morales-García, F.; García-García, F.; Montero-Martínez, G.; Borrmann, S.; Schneider, J.; Mertes, S.; Walter, S.; Gysel, M.; Dusek, U.; Frank, G. P.; Krämer, M.

2008-03-01

The influence of aerosols, both natural and anthropogenic, remains a major area of uncertainty when predicting the properties and behaviour of clouds and their influence on climate. In an attempt to better understand warm cloud formation in a tropical marine environment, a period of intensive measurements took place in December 2004 in Puerto Rico, using some of the latest developments in online instrumentation such as aerosol mass spectrometers, cloud condensation nuclei counters and a hygroscopicity tandem differential mobility analyser. Simultaneous online measurements of aerosol size distributions, composition, hygroscopicity and optical properties were made near the lighthouse of Cape San Juan in the north-eastern corner of the island and at the top of East Peak mountain (1040 m a.s.l.), the two sites separated by 17 km. Additional measurements of the cloud droplet residual and interstitial aerosol properties were made at the mountain site, accompanied by measurements of cloud droplet size distributions, liquid water content and the chemical composition of cloud and rain water samples. Both aerosol composition and cloud properties were found to be sensitive to wind sector. Air from the east-northeast (ENE) was mostly free of anthropogenic influences, the submicron fraction being mainly composed of non-sea salt sulphate, while that from the east-southeast (ESE) was found to be moderately influenced by populated islands upwind, adding smaller (<100 nm), externally mixed, carbonaceous particles to the aerosol that increased the number concentrations by over a factor of 3. This change in composition was also accompanied with a reduction in the measured hygroscopicity and fractional cloud activation potential of the aerosol. At the mountain site, the average cloud droplet concentrations increased from 193 to 519 cm-3, median volume diameter decreased from 20 to 14 μm and the liquid water content increased from 0.24 to 0.31 g m-3 when the winds shifted from the ENE to ESE. Larger numbers of interstitial particles were recorded, most notably at sizes greater than 100 nm, which were absent during clean conditions. The average size of the residual particles and concentrations of cloudwater nitrate, sulphate and insoluble material increased during polluted conditions. Previous studies in Puerto Rico had reported the presence of a significant non-anthropogenic organic fraction in the aerosols measured and concluded that this was a factor controlling the in situ cloud properties. However, this was not observed in our case. In contrast to the 1.00±0.14 μg m-3 of organic carbon measured in 1992 and 1995, the organic matter measured in the current study of 0.17±0.35 μg m-3 is many times lower, most of which can be attributed to anthropogenic sources. During clean conditions, the submicron aerosol was observed to be almost entirely inorganic, an observation supported by the hygroscopicity measurements. This suggests that organic aerosols from marine sources may not be completely ubiquitous (either spatially or temporally) in this environment and requires further investigation to quantify their true extent and implications, with more extensive, longer-term sampling in conjunction with wind field analyses.

A novel method for deriving the aerosol hygroscopicity parameter based only on measurements from a humidified nephelometer system

NASA Astrophysics Data System (ADS)

Kuang, Ye; Zhao, Chunsheng; Tao, Jiangchuan; Bian, Yuxuan; Ma, Nan; Zhao, Gang

2017-06-01

Aerosol hygroscopicity is crucial for understanding roles of aerosol particles in atmospheric chemistry and aerosol climate effects. Light-scattering enhancement factor f(RH, λ) is one of the parameters describing aerosol hygroscopicity, which is defined as f(RH, λ) = σsp(RH, λ)/σsp(dry, λ), where σsp(RH, λ) or σsp(dry, λ) represents σsp at wavelength λ under certain relative humidity (RH) or dry conditions. Traditionally, an overall hygroscopicity parameter κ can be retrieved from measured f(RH, λ), hereinafter referred to as κf(RH), by combining concurrently measured particle number size distribution (PNSD) and mass concentration of black carbon. In this paper, a new method is proposed to directly derive κf(RH) based only on measurements from a three-wavelength humidified nephelometer system. The advantage of this newly proposed approach is that κf(RH) can be estimated without any additional information about PNSD and black carbon. This method is verified with measurements from two different field campaigns. Values of κf(RH) estimated from this new method agree very well with those retrieved by using the traditional method: all points lie near the 1 : 1 line and the square of correlation coefficient between them is 0.99. The verification results demonstrate that this newly proposed method of deriving κf(RH) is applicable at different sites and in seasons of the North China Plain and might also be applicable in other regions around the world.

The Hygroscopicity Parameter of Marine Organics in Sea Spray Aerosols

NASA Astrophysics Data System (ADS)

Boyer, M.; Chang, R. Y. W.

2015-12-01

The effects of aerosols on climate are poorly understood, specifically with respect to their influence on cloud properties. Since oceans cover >70% of Earth's surface, sea spray aerosols (SSA), which act efficiently as cloud condensation nuclei (CCN), may have important implications on Earth's radiation budget. Surface active organic species readily accumulate in the sea surface microlayer (SML), located at the ocean-atmosphere interface, and transfer onto nascent SSA. While it is understood that SSA are commonly enriched with organics, the resulting effect of the organic content on CCN activation remains unresolved. The hygroscopicity parameter, kappa (k), allows for the cloud nucleating properties of individual components to be predicted in particles of mixed composition; however, most studies typically infer k from ambient measurements without assessing the contribution of the individual components to the overall k. In this study, a method for quantifying the cloud nucleating properties of the organic species in surface seawater using k-Kohler theory is proposed. Ambient SML and bulk water samples will be collected and atomized to generate particles such that the overall k can be inferred from CCN measurements. The inorganic and organic components will be quantified, and the organic component will be separated so that the hygroscopicity of only the organic constituents can be determined. By comparing the inferred k values for the samples before and after removal of the inorganic component, the hygroscopicity of the organic constituents alone can be calculated, providing insight on the effect of organic species on CCN activation in SSA.

Particle deposition in human respiratory system: deposition of concentrated hygroscopic aerosols.

PubMed

Varghese, Suresh K; Gangamma, S

2009-06-01

In the nearly saturated human respiratory tract, the presence of water-soluble substances in the inhaled aerosols can cause change in the size distribution of the particles. This consequently alters the lung deposition profiles of the inhaled airborne particles. Similarly, the presence of high concentration of hygroscopic aerosols also affects the water vapor and temperature profiles in the respiratory tract. A model is presented to analyze these effects in human respiratory system. The model solves simultaneously the heat and mass transfer equations to determine the size evolution of respirable particles and gas-phase properties within human respiratory tract. First, the model predictions for nonhygroscopic aerosols are compared with experimental results. The model results are compared with experimental results of sodium chloride particles. The model reproduces the major features of the experimental data. The water vapor profile is significantly modified only when a high concentration of particles is present. The model is used to study the effect of equilibrium assumptions on particle deposition. Simulations show that an infinite dilution solution assumption to calculate the saturation equilibrium over droplet could induce errors in estimating particle growth. This error is significant in the case of particles of size greater than 1 mum and at number concentrations higher than 10(5)/cm(3).

Continuous flow hygroscopicity-resolved relaxed eddy accumulation (Hy-Res REA) method of measuring size-resolved sodium chloride particle fluxes

EPA Science Inventory

The accurate representation of aerosols in climate models requires direct ambient measurement of the size- and composition-dependent particle production fluxes. Here, we present the design, testing, and analysis of data collected through the first instrument capable of measuring ...

Chemical and physical properties of biomass burning aerosols and their CCN activity: A case study in Beijing, China.

PubMed

Wu, Zhijun; Zheng, Jing; Wang, Yu; Shang, Dongjie; Du, Zhoufei; Zhang, Yuanhang; Hu, Min

2017-02-01

Biomass burning emits large amounts of both trace gases and particles into the atmosphere. It plays a profound role in regional air quality and climate change. In the present study, an intensive campaign was carried out at an urban site in Beijing, China, in June 2014, which covered the winter wheat harvest season over the North China Plain (NCP). Meanwhile, two evident biomass-burning events were observed. A clear burst in ultrafine particles (below 100nm in diameter, PM 1 ) and subsequent particle growth took place during the events. With the growth of the ultrafine particles, the organic fraction of PM 1 increased significantly. The ratio of oxygen to carbon (O:C), which had an average value of 0.23±0.04, did not show an obvious enhancement, indicating that a significant chemical aging process of the biomass-burning aerosols was not observed during the course of events. This finding might have been due to the fact that the biomass-burning events occurred in the late afternoon and grew during the nighttime, which is associated with a low atmospheric oxidation capacity. On average, organics and black carbon (BC) were dominant in the biomass-burning aerosols, accounting for 60±10% and 18±3% of PM 1 . The high organic and BC fractions led to a significant suppression of particle hygroscopicity. Comparisons among hygroscopicity tandem differential mobility analyzer (HTDMA)-derived, cloud condensation nuclei counter (CCNc)-derived, and aerosol mass spectrometer-based hygroscopicity parameter (κ) values were consistent. The mean κ values of biomass-burning aerosols derived from both HTDMA and CCNc measurements were approximately 0.1, regardless of the particle size, indicating that the biomass-burning aerosols were less active. The burst in particle count during the biomass-burning events resulted in an increased number of cloud condensation nuclei (CCN) at supersaturation (SS)=0.2-0.8%. Copyright © 2016 Elsevier B.V. All rights reserved.

[Improvement of powder flowability and hygroscopicity of traditional Chinese medicine extract by surface coating modification technology].

PubMed

Zeng, Rong-Gui; Jiang, Qie-Ying; Liao, Zheng-Gen; Zhao, Guo-Wei; Luo, Yun; Luo, Juan; Lv, Dan

2016-06-01

To study the improvement of powder flowability and hygroscopicity of traditional Chinese medicine extract by surface coating modification technology. The 1% hydrophobic silica nanoparticles were used as surface modifier, and andrographis extract powder was taken as a model drug. Three different techniques were used for coating model drugs, with angle of repose, compressibility, flat angle and cohesion as the comprehensive evaluation indexes for the powder flowability. The powder particle size and the size distribution were measured by Mastersizer 2000. FEI scanning electron microscope was used to observe the surface morphology and structure of the powder. The percentage of Si element on the powder surface was measured by energy dispersive spectrometer. The hygroscopicity of powder was determined by Chinese pharmacopoeia method. All of the three techniques can improve the flowability of powder extract. In particular, hygroscopicity of extract powder can also be improved by dispersion and then high-speed mixing, which can produce a higher percentage of Si element on the powder surface. The improvement principle may be correlated with a modifier adhered to the powder surface. Copyright© by the Chinese Pharmaceutical Association.

Investigating water adsorption onto natural mineral dust particles: Linking DRIFTS experiments and BET theory

NASA Astrophysics Data System (ADS)

Joshi, Nitesh; Romanias, Manolis N.; Riffault, Veronique; Thevenet, Frederic

2017-08-01

The adsorption of water molecules on natural mineral dusts was investigated employing in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). The natural dust samples originated from North and West Africa, Saudi Arabia and Gobi desert regions. Furthermore, the hygroscopicity of commercially available Arizona Test Dusts (ATDs) and Icelandic volcanic ash were examined. N2 sorption measurements, X-ray fluorescence and diffraction (XRF and XRD), as well as Inductively Coupled Plasma Mass Spectrometry (ICP-MS) analyses were performed to determine the physicochemical properties of the particles. The water adsorption experiments were conducted in an optical cell, at room temperature under the relative humidity (RH) range of 1.9-95%. Results were simulated using a modified three-parameter Brunauer-Emmett-Teller (BET) equation. Water monolayer (ML) was formed in the RH range of 15-25%, while additional water layers were formed at higher RH. Besides, the standard adsorption enthalpies of water onto natural mineral dust samples were determined. A thorough comparison of two commercially available ATD samples indicated that size distribution and/or porosity should play a key role in particle hygroscopicity. Regarding the natural mineral particles, Ca/Si ratios, and to a lesser extent Al/Si, Na/Si, Mg/Si ratios, were found to impact the minimum RH level required for water monolayer formation. These results suggest that the hygroscopic properties of investigated African dusts are quite similar over the whole investigated RH range. Furthermore, one of the major conclusions is that under most atmospheric relative humidity conditions, natural mineral samples are always covered with at least one layer of adsorbed water.

Effect of phytoplackton-derived organic matter on the behavior of marine aerosols

NASA Astrophysics Data System (ADS)

Fuentes, E.; Coe, H.; McFiggans, G.; Green, D.

2009-04-01

The presence of significant concentrations of organic material in marine aerosols has been appreciated for several decades; however, only recently has significant progress been made towards demonstrating that this organic content is biogenically formed. Biogenic organics of placktonic life origin are incorporated in marine aerosol composition as a result of bubble bursting/breaking waves mechanisms that occur at the ocean surface. The presence of organic surfactants in the marine aerosol composition might have a significant impact on the properties of the generated aerosols by affecting the particles surface tension and solution balance properties. Nevertheless, it remains uncertain the role of such organics on the physical-chemical behavior of marine aerosols. In this work an experimental study was performed in order to determine the influence of biogenic marine organic compounds on the size distribution, hygroscopicity and cloud-nucleating properties of marine aerosols. For the experimental study a laboratory water recirculation system (bubble tank), designed for the simulation of bubble-burst aerosol formation, was used as marine aerosol generator. The bubble spectra produced by such system was characterized by means of an optical bubble measuring device (BMS) and it was found to be consistent with oceanic bubble spectra properties. Seawater proxy solutions were prepared from laboratory biologically-synthesized exudates produced by oceanic representative algal species and introduced in the tank for the generation of marine aerosol by bubble bursting. Two experimental methods were employed for seawater proxies preparation: the formation of surface monolayers from the biogenic surfactants extracted by a solid phase extraction technique (monolayer method) and the mixing of the exudates in the sea salt water bulk (bulk mixing method). Particle size distribution, hygroscopicity and cloud condensation nuclei experiments for different monolayers, and exudate mixtures were performed. This contribution provides an overview of the experimental study conducted and the most relevant results found in this research work.

Optical Extinction and Aerosol Hygroscopicity in the Southeastern United States

NASA Astrophysics Data System (ADS)

Brock, C. A.; Gordon, T.; Wagner, N.; Lack, D. A.; Richardson, M.; Middlebrook, A. M.; Liao, J.; Murphy, D. M.; Attwood, A. R.; Washenfelder, R. A.; Campuzano Jost, P.; Day, D. A.; Jimenez, J. L.; Carlton, A. M. G.

2015-12-01

Most aerosol particles take up water and grow as relative humidity increases, leading to increased optical extinction, reduced visibility, greater aerosol optical depths (AODs), and altered radiative forcing, even while dry particulate mass remains constant. Relative humidity varies greatly temporally, horizontally, and especially vertically. Thus hygroscopicity is a confounding factor when attempting to link satellite-based observations of AOD to surface measurements of particulate mass or to model predictions of aerosol mass concentrations. Airborne observations of aerosol optical, chemical, and microphysical properties were made in the southeastern United States in the daytime in summer 2013 during the NOAA SENEX and NASA SEAC4RS projects. Applying κ-Köhler theory for hygroscopic growth to these data, the inferred hygroscopicity parameter κ for the organic fraction of the aerosol was <0.11. This κ for organics is toward the lower end of values found from laboratory studies of the aerosol formed from oxidation of biogenic precursors and from several field studies in rural environments. The gamma (γ) parameterization is commonly used to describe the change in aerosol extinction as a function of relative humidity. Because this formulation did not fit the airborne data well, a new parameterization was developed that better describes the observations. This new single-parameter κext formulation is physically based and relies upon the well-known approximately linear relationship between particle volume and optical extinction. The fitted parameter, κext, is nonlinearly related to the chemically derived κ parameter used in κ-Köhler theory. The values of κext determined from the airborne measurements are consistent with independent observations at a nearby ground site.

Long-term observations of cloud condensation nuclei in the Amazon rain forest

NASA Astrophysics Data System (ADS)

Pöhlker, Mira L.; Pöhlker, Christopher; Ditas, Florian; Klimach, Thomas; Hrabe de Angelis, Isabella; Brito, Joel; Carbone, Samara; Cheng, Yafang; Martin, Scot T.; Moran-Zuloaga, Daniel; Rose, Diana; Saturno, Jorge; Su, Hang; Thalman, Ryan; Walter, David; Wang, Jian; Barbosa, Henrique; Artaxo, Paulo; Andreae, Meinrat O.; Pöschl, Ulrich

2017-04-01

Size-resolved long-term measurements of atmospheric aerosol and cloud condensation nuclei (CCN) concentrations and hygroscopicity were conducted at the remote Amazon Tall Tower Observatory (ATTO) in the central Amazon Basin over a full seasonal cycle (Mar 2014 - Feb 2015). The measurements provide a climatology of CCN properties characteristic of a remote central Amazonian rain forest site [1,2]. The CCN measurements were continuously cycled through 10 levels of supersaturation (S = 0.11 to 1.10 %) and span the aerosol particle size range from 20 to 245 nm. The particle hygroscopicity exhibits a pronounced size dependence with lower values for the Aitken mode (κAit = 0.14 ± 0.03), higher values for the accumulation mode (κAcc = 0.22 ± 0.05), and an overall mean value of κmean = 0.17 ± 0.06, consistent with high fractions of organic aerosol. The hygroscopicity parameter, κ, exhibits remarkably little temporal variability: no pronounced diurnal cycles, only weak seasonal trends, and few short-term variations during long-range transport events. In contrast, the CCN number concentrations exhibit a pronounced seasonal cycle, tracking the pollution-related seasonality in total aerosol concentration. We find that the variability in the CCN concentrations in the central Amazon is mostly driven by aerosol particle number concentration and size distribution, while variations in aerosol hygroscopicity and chemical composition matter only during a few episodes. For modelling purposes, we compare different approaches of predicting CCN number concentration and present a novel parameterization, which allows accurate CCN predictions based on a small set of input data. In addition, we analyzed the CCN short-term variability in relation to air mass changes as well as aerosol emission and transformation processes. The CCN short term variability is presented for selected case studies, which analyze particularly interesting and characteristic events/conditions in the Amazon region. References: [1] Andreae, M. O., et al. (2015), Atmos. Chem. Phys., 15, 10723-10776. [2] Pöhlker, M. L.., et al. (2016), Atmos. Chem. Phys., 16, 15709-15740.

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

PubMed Central

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

2016-01-01

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

Hygroscopic properties and cloud condensation nuclei activation of limonene-derived organosulfates and their mixtures with ammonium sulfate

NASA Astrophysics Data System (ADS)

Hansen, A. M. K.; Hong, J.; Raatikainen, T.; Kristensen, K.; Ylisirniö, A.; Virtanen, A.; Petäjä, T.; Glasius, M.; Prisle, N. L.

2015-06-01

Even though organosulfates have been observed as constituents of atmospheric aerosols in a wide range of environments spanning from the subtropics to the high Arctic, their hygroscopic properties have not been investigated prior to this study. Here, limonene-derived organosulfates with a molecular weight of 250 Da (L-OS 250) were synthesized and used for simultaneous measurements with a Hygroscopicity Tandem Differential Mobility Analyzer (H-TDMA) and a Cloud Condensation Nuclei Counter (CCNC) to determine the hygroscopicity parameter, κ, for pure L-OS 250 and mixtures of L-OS 250 with ammonium sulfate (AS) over a wide range of humidity conditions. The κ values derived from measurements with H-TDMA decreased with increasing particle dry size for all chemical compositions investigated, indicating size dependency and/or surface effects. For pure L-OS 250, κ was found to increase with increasing relative humidity, indicating dilution/solubility effects to be significant. Discrepancies in κ between the sub- and supersaturated measurements were observed for L-OS 250, whereas κ of AS and mixed L-OS 250/AS were similar. This discrepancy was primarily ascribed to limited dissolution of L-OS 250 at subsaturated conditions. In general, hygroscopic growth factor, critical activation diameter and κ for the mixed L-OS 250/AS particles converged towards the values of pure AS for mixtures with ≥ 20 % w/w AS. Surface tension measurements of bulk aqueous L-OS 250/AS solutions showed that L-OS 250 was indeed surface active, as expected from its molecular structure, decreasing the surface tension of solutions with 24 % from the pure water-value at a L-OS 250 concentration of 0.0025 mol L-1. Based on these surface tension measurements, we present the first concentration-dependent parametrisation of surface tension for aqueous L-OS 250, which was implemented to different process-level models of L-OS 250 hygroscopicity and CCN activation. The values of κ obtained from the measurements were compared with κ calculated applying the volume additive Zdanovskii-Stokes-Robinson mixing rule, as well as κ modelled from equilibrium Köhler theory with different assumptions regarding L-OS 250 bulk-to-surface partitioning and aqueous droplet surface tension. This study is to our knowledge the first to investigate the hygroscopic properties and surface activity of L-OS 250; hence it is an important first step towards understanding the atmospheric impact of organosulfates.

Hygroscopic Characteristics of Organic Laden Ambient Aerosols in Yosemite National Park

NASA Astrophysics Data System (ADS)

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

2003-12-01

Water absorption by inorganic compounds can be modeled with some degree of certainty; however, water uptake by ambient organic aerosols remains speculative. To improve the understanding of organic hygroscopicity, an aerosol characterization study was conducted at Yosemite National Park, California, starting in July and ending in the first week of September 2002. High time resolution measurement (15-minute time increments) of PM2.5 ionic species (Cl-, SO42-, NO3-, Na+, NH4+, K+, Mg2+, and Ca2+) were measured using PILS (Particle-Into-Liquid-System)/IC (Ion Chromatography). Commercially available annular denuders and a PM2.5 cyclone (URG) were used upstream of the PILS/IC to remove particles greater than 2.5 μm and acidic and basic gases. A dual wavelength aethalometer and an R&P particulate carbon monitor were used to measure carbon on a semi-continuous basis while a DRUM sampler allowed for semi-continuous estimates of concentrations of elements associated with crustal material. Standard IMPROVE type samplers were used to measure 24-hr integrated samples of these same aerosols. Two nephelometers operated in tandem, one dry and the other with a controlled humidity environment, were used to measure f(RH) = bscat(RH)/bscat,dry, where bscat(RH) is the scattering coefficient measured at some relative humidity and bscat,dry is the scattering coefficient measured at RH <10%. The aerosol composition was highly variable in time, with a strong diurnal cycle. Organic carbon mass was observed to be, on the average, 70% of the fine mass with days where its contribution was well over 95% of the mass. Measurements of carbon isotopes revealed the fraction of carbon from biogenic sources to range from approximately 73 to 95%. Water soluble potassium was highly correlated with carbon mass, suggesting the influence of wood smoke. The ionic fraction of the aerosol consisted primarily of ammonium sulfate and in most cases nitrate was in the form of sodium nitrate. Fine soil mass was less than 1% of PM2.5 mass. The ambient aerosol was observed to deliquesce on days when the inorganic and organic aerosol were approximately equal in concentration; however, on days when the organic component was dominant, only smooth f(RH) curves were observed. Equilibrium models, exercised in combination with Mie scattering theory, were used to predict atmospheric aerosol water content and associated increases in aerosol scattering coefficient. The analyses suggest that in most cases the hygroscopic growth of inorganic salts alone could account for the observed increase in scattering as a function of relative humidity.

Eddy Covariance Measurements of the Sea-Spray Aerosol Flu

NASA Astrophysics Data System (ADS)

Brooks, I. M.; Norris, S. J.; Yelland, M. J.; Pascal, R. W.; Prytherch, J.

2015-12-01

Historically, almost all estimates of the sea-spray aerosol source flux have been inferred through various indirect methods. Direct estimates via eddy covariance have been attempted by only a handful of studies, most of which measured only the total number flux, or achieved rather coarse size segregation. Applying eddy covariance to the measurement of sea-spray fluxes is challenging: most instrumentation must be located in a laboratory space requiring long sample lines to an inlet collocated with a sonic anemometer; however, larger particles are easily lost to the walls of the sample line. Marine particle concentrations are generally low, requiring a high sample volume to achieve adequate statistics. The highly hygroscopic nature of sea salt means particles change size rapidly with fluctuations in relative humidity; this introduces an apparent bias in flux measurements if particles are sized at ambient humidity. The Compact Lightweight Aerosol Spectrometer Probe (CLASP) was developed specifically to make high rate measurements of aerosol size distributions for use in eddy covariance measurements, and the instrument and data processing and analysis techniques have been refined over the course of several projects. Here we will review some of the issues and limitations related to making eddy covariance measurements of the sea spray source flux over the open ocean, summarise some key results from the last decade, and present new results from a 3-year long ship-based measurement campaign as part of the WAGES project. Finally we will consider requirements for future progress.

Effect of sea breeze circulation on aerosol mixing state and radiative properties in a desert setting

NASA Astrophysics Data System (ADS)

Derimian, Yevgeny; Choël, Marie; Rudich, Yinon; Deboudt, Karine; Dubovik, Oleg; Laskin, Alexander; Legrand, Michel; Damiri, Bahaiddin; Koren, Ilan; Unga, Florin; Moreau, Myriam; Andreae, Meinrat O.; Karnieli, Arnon

2017-09-01

Chemical composition, microphysical, and optical properties of atmospheric aerosol deep inland in the Negev Desert of Israel are found to be influenced by daily occurrences of sea breeze flow from the Mediterranean Sea. Abrupt increases in aerosol volume concentration and shifts of size distributions towards larger sizes, which are associated with increase in wind speed and atmospheric water content, were systematically recorded during the summertime at a distance of at least 80 km from the coast. Chemical imaging of aerosol samples showed an increased contribution of highly hygroscopic particles during the intrusion of the sea breeze. Besides a significant fraction of marine aerosols, the amount of internally mixed marine and mineral dust particles was also increased during the sea breeze period. The number fraction of marine and internally mixed particles during the sea breeze reached up to 88 % in the PM1-2. 5 and up to 62 % in the PM2. 5-10 size range. Additionally, numerous particles with residuals of liquid coating were observed by SEM/EDX analysis. Ca-rich dust particles that had reacted with anthropogenic nitrates were evidenced by Raman microspectroscopy. The resulting hygroscopic particles can deliquesce at very low relative humidity. Our observations suggest that aerosol hygroscopic growth in the Negev Desert is induced by the daily sea breeze arrival. The varying aerosol microphysical and optical characteristics perturb the solar and thermal infrared radiations. The changes in aerosol properties induced by the sea breeze, relative to the background situation, doubled the shortwave radiative cooling at the surface (from -10 to -20.5 W m-2) and increased by almost 3 times the warming of the atmosphere (from 5 to 14 W m-2), as evaluated for a case study. Given the important value of observed liquid coating of particles, we also examined the possible influence of the particle homogeneity assumption on the retrieval of aerosol microphysical characteristics. The tests suggest that sensitivity to the coating appears if backward scattering and polarimetric measurements are available for the inversion algorithm. This may have an important implication for retrievals of aerosol microphysical properties in remote sensing applications.

Redefining the importance of nitrate during haze pollution to help optimize an emission control strategy

NASA Astrophysics Data System (ADS)

Pan, Yuepeng; Wang, Yuesi; Zhang, Junke; Liu, Zirui; Wang, Lili; Tian, Shili; Tang, Guiqian; Gao, Wenkang; Ji, Dongsheng; Song, Tao; Wang, Yonghong

2016-09-01

Nitrate salts represent a major component of fine mode aerosols, which play an important role in air pollution worldwide. Based on on-line and off-line aerosol measurements in urban Beijing for both clean and haze conditions, we demonstrate that the absolute and relative concentrations of nitrate increased with visibility degradation (relative humidity), whereas the variations of organics tracked the patterns of mixing-layer height and temperature. We propose that the increase in the relative contribution of nitrate to PM1 observed during the early stages of haze pollution was due to new particle formation, whereas the nitrate formed in PM1-2.5 during the latter stages was due to heterogeneous formation and hygroscopic growth. The increasing trend of nitrate (and also sulfate and ammonium) but decreasing trends of organics during haze development, together with the increase of the NO2/SO2 molar ratio with increasing proximity to downtown Beijing and with visibility degradation, provide further evidence that controlling NOx emissions should be a priority for improving air quality in mega cities. Additional large-scale investigation is required to adequately characterize the regional features of NOx-induced haze pollution in China. Such studies may provide insight into the formation of critical nuclei or the subsequent growth of freshly nucleated particles and advance our understanding of the role of nitrate in new particle formation.

The Aerosol Models in MODTRAN: Incorporating Selected Measurements From Northern Australia

DTIC Science & Technology

2005-12-01

biomass burning smoke aerosol is modelled assuming the particles are spherical and Mie scattering theory is used to calculate the extinction and...and therefore internally mixed aerosol particles are hygroscopic . Shettle and Fenn model the growth in the size of aerosol particles and changes in...by Sutherland and Khanna [21] was to obtain measurements of the optical properties of organic -based aerosols produced by burning vegetation.

Individual Aerosol Particle Types Produced by Savanna Burning

NASA Astrophysics Data System (ADS)

Posfai, M.; Simonics, R.; Li, J.; Hobbs, P. V.; Buseck, P. R.; Buseck, P. R.

2001-12-01

We used analytical transmission electron microscopy (TEM) to study individual aerosol particles that were collected on the University of Washington Convair-580 research aircraft over southern Africa during the Safari2000 Dry Season Experiment. Our goals were to study the compositions, morphologies, and mixing states of carbonaceous particles, in order to better understand the physical and chemical properties of biomass smoke on the individual-particle level. The compositions of single particles were determined using energy-dispersive x-ray spectrometry (EDS) and electron energy-loss spectroscopy (EELS). Energy-loss maps obtained with the TEM are useful for studying the spatial distribution of light elements such as carbon within the particles; thus, they provide a detailed picture of complex particles. Carbonaceous particles were assigned into three main groups on the basis of morphology and composition: "organic particles with inorganic inclusions," "tar balls," and "soot." Soot is recognized by its characteristic morphology and microstructure. The distinction between "organic particles with inorganic inclusions" and "tar balls" is somewhat arbitrary, since the two criteria that are used for their distinction (composition and aspect ratio) change continually. The relative concentrations of the three major particle types vary with the type of fire and distance from fire. In the plume of a smoldering fire west of Beria (August 31) the relative concentration of tar balls increased with aging of the plume. Tar balls have a fairly narrow size distribution with a maximum between 100 and 200 nm (diameter). The inorganic K-salt inclusions (KCl, K2SO4, KNO3) within "organic particles" should make these particles hygroscopic, regardless of the properties of the organic compounds. Aging causes the conversion of KCl into K2SO4, KNO3. Aerosol production from flaming and smoldering fires was compared over Kruger National Park on August 17; more soot and more Cl-rich inclusions in organic particles were produced by the flaming fire than by the smoldering fire. Further sets of samples from other flights of Safari2000 are being studied.

Laboratory Studies of Water Uptake by Biomass Burning Smoke: Role of Fuel Inorganic Content, Combustion Phase and Aging

NASA Astrophysics Data System (ADS)

Dubey, M. K.; Bixler, S. L.; Romonosky, D.; Lam, J.; Carrico, C.; Aiken, A. C.

2017-12-01

Biomass burning aerosol emissions have substantially increased with observed warming and drying in the southwestern US. While wildfires are projected to intensify missing knowledge on the aerosols hampers assessments. Observations demonstrate that enhanced light absorption by coated black carbon and brown carbon can offset the cooling effects of organic aerosols in wildfires. However, if mixing processes that enhance this absorption reduce the aerosol lifetime it would lower their atmospheric burden. In order to elucidate mechanisms regulating this tradeoff we performed laboratory studies of smoke from biomass burning. We focus on aerosol optical properties and their hygroscopic response. Fresh emissions from burning 30 fuels under flaming and smoldering conditions were investigated. We measured aerosol absorption, scattering and extinction at multiple wavelengths, water uptake at 85% relative humidity (fRH85%) with a humidity controlled dual nephelometer, and black carbon mass with a SP2. Trace gases and the ionic content of the fuel and smoke were also measured We find that whereas the optical properties of smoke were strongly dictated by the flaming versus smoldering nature of the burn, the observed hygroscopicity was intimately linked to the chemical composition of the fuel. The mean hygroscopicity ranged from nearly hydrophobic (fRH85% = 1) to very hydrophilic (fRH85% = 2.1) values typical of pure deliquescent salts. The k values varied from 0.004 to 0.18 and correlated well with inorganic content. Inorganic fuel content was the key driver of hygroscopicity with combustion phase playing a secondary but important role ( 20%). Flaming combustion promoted hygroscopicity by generating refractory black carbon and ions. Smoldering combustion suppressed hygroscopicity by producing hydrogenated organic species. Wildfire smoke was hydrophobic since the evergreen species with low inorganic content dominated in these fires. We also quantify the mass absorption cross-sections at 780nm and 430nm to evaluate the absorbing species. We plan to extend our studies to aged biomass burning smoke with a potential aerosol mass reactor and monitor the ionic content of black carbon with a SP-AMS. Our analysis will develop a mechanistic framework of water uptake and optical properties of biomass burning aerosols.

The Influence of Chemical Composition and Relative Humidity on the Optical Properties of Aerosols During the Southern Oxidant and Aerosol Study (SOAS)

NASA Astrophysics Data System (ADS)

Attwood, A. R.; Washenfelder, R. A.; Brock, C. A.; Brown, S. S.; Hu, W.; Campuzano Jost, P.; Day, D. A.; Palm, B. B.; Simoes de Sa, S.; Jimenez, J. L.

2013-12-01

Atmospheric particles are produced from a wide variety of both anthropogenic and natural sources and play an important role in the Earth's radiative budget by direct scattering and absorption of radiation. To address this impact, in situ measurements of aerosol optical, chemical and hygroscopic properties were performed during the Southern Oxidant and Aerosol Study (SOAS), which took place in the summer of 2013. Ground based measurements of sub-micron aerosol in the southeastern United States were made to investigate the influence of chemical composition and hygroscopicity on aerosol optical properties. We report the wavelength dependence of aerosol extinction cross sections measured with a novel broadband cavity enhanced spectrometer covering a wavelength range of 360-420 nm using two light emitting diodes (LED) and a separate cavity ring down (CRDS) channel. The sensitivity of the relative humidity dependence of extinction based on the type of aerosol present is examined and we show that the optical properties and hygroscopicity of aerosols are greatly influenced by the fraction of sulfate and organics within the particles. Additional data analysis from the SOAS campaign will be presented. The results, thus far, illustrate that the variability in aerosol chemical composition can impact visibility and climate forcing in this region.

Selected physical and chemical properties of Feverfew (Tanacetum parthenium) extracts important for formulated product quality and performance.

PubMed

Jin, Ping; Madieh, Shadi; Augsburger, Larry L

2008-01-01

The objectives of this research are: (1) to assess selected formulation-relevant physical properties of several commercial Feverfew extracts, including flowability, hygroscopicity, compressibility and compactibility (2) to develop and validate a suitable extraction method and HPLC assay, and (3) to determine the parthenolide content of several commercial Feverfew extracts. Carr's index, minimum orifice diameter and particle-particle interaction were used to evaluate powder flowability. Hygroscopicity was evaluated by determining the equilibrium moisture content (EMC) after storage at various % relative humidities. Heckle analysis and compression pressure-radial tensile strength relationship were used to represent compression and compaction properties of feverfew extracts. An adapted analytical method was developed based on literature methods and then validated for the determination of parthenolide in feverfew. The commercial extracts tested exhibited poor to very poor flowability. The comparatively low mean yield pressure suggested that feverfew extracts deformed mainly plastically. Hygroscopicity and compactibility varied greatly with source. No commercial feverfew extracts tested contained the label claimed parthenolide. Even different batches from the same manufacturer showed significantly different parthenolide content. Therefore, extract manufactures should commit to proper quality control procedures that ensure accurate label claims, and supplement manufacturers should take into account possible differences in physico-chemical properties when using extracts from multiple suppliers.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

Hygroscopicity is an important property of aerosols which describes their propensity to absorb water vapor. The hygroscopicity of organic aerosol (OA) can change during its atmospheric aging affecting the total aerosol hygroscopicity. A more hygroscopic particle will grow more rapidly under humid conditions, scatter incident sunlight more efficiently; and it will more likely form cloud droplets. Both phenomena strongly influence the radiative forcing of climate through the direct and indirect effects of aerosols. Therefore, taking into account the hygrscopicity changes of OA during its atmospheric aging is of prime importance to accurately estimate the aerosol climatic impact. Here, we use a computationally efficient module for the description of OA composition and evolution in the atmosphere (ORACLE) (Tsimpidi et al., 2014) in the frame of the global chemistry climate model EMAC to simulate the global distribution of the OA oxidation state and hygroscopicity. To track the evolution of the OA oxidation state during its atmospheric aging, ORACLE is modified to include the description of the OA oxygen content change when mass from any OA surrogate species reacts with the OH radical. Subsequently, it is assumed that the cloud condensation nuclei (CCN) activity of OA, expressed in the form of the hygroscopicity parameter κ, will increase with increasing oxygen content (expressed by the oxygen per carbon ratio, O:C) and will range from κ = 0 (for O:C ≤ 0.2) to κ = 0.35 (for O:C = 1). The exact relationship between O:C and κ is determined based on aerosol mass spectrometer (AMS) and continuous flow CCN (CCNC) measurements of SOA (Lambe et al., 2011). Following a straightforward mixing rule, the hygroscopicity and oxygen content of total OA is calculated based on the hygroscopicities of the individual OA compounds and their degree of oxidation. A global dataset of O:C measurements is used to validate the model results. ReferencesLambe, A. T., et al. : Laboratory studies of the chemical composition and cloud condensation nuclei (CCN) activity of secondary organic aerosol (SOA) and oxidized primary organic aerosol (OPOA), Atmos. Chem. Phys., 11, 8913-8928, 2011. Tsimpidi, A. P., et al. : ORACLE (v1.0): module to simulate the organic aerosol composition and evolution in the atmosphere, Geo. Mod. Devel., 7, 3153-3172, 2014.

Investigation of cloud condensation nuclei properties and droplet growth kinetics of the water-soluble aerosol fraction in Mexico City

NASA Astrophysics Data System (ADS)

Padró, Luz T.; Tkacik, Daniel; Lathem, Terry; Hennigan, Chris J.; Sullivan, Amy P.; Weber, Rodney J.; Huey, L. Greg; Nenes, Athanasios

2010-05-01

We present hygroscopic and cloud condensation nuclei (CCN) relevant properties of the water-soluble fraction of Mexico City aerosol collected upon filters during the 2006 Megacity Initiative: Local and Global Research Observations (MILAGRO) campaign. Application of κ-Köhler theory to the observed CCN activity gave a fairly constant hygroscopicity parameter (κ = 0.28 ± 0.06) regardless of location and organic fraction. Köhler theory analysis was used to understand this invariance by separating the molar volume and surfactant contributions to the CCN activity. Organics were found to depress surface tension (10-15%) from that of pure water. Daytime samples exhibited lower molar mass (˜200 amu) and surface tension depression than nighttime samples (˜400 amu); this is consistent with fresh hygroscopic secondary organic aerosol (SOA) condensing onto particles during peak photochemical hours, subsequently aging during nighttime periods of high relative humidity. Changes in surface tension partially compensate for shifts in average molar volume to give the constant hygroscopicity observed, which implies the amount (volume fraction) of soluble material in the parent aerosol is the key composition parameter required for CCN predictions. This finding, if applicable elsewhere, may explain why CCN predictions are often found to be insensitive to assumptions of chemical composition and provides a very simple way to parameterize organic hygroscopicity in atmospheric models (i.e., κorg = 0.28ɛWSOC). Special care should be given, however, to surface tension depression from organic surfactants, as its nonlinear dependence with organic fraction may introduce biases in observed (and predicted) hygroscopicity. Finally, threshold droplet growth analysis suggests the water-soluble organics do not affect activation kinetics.

Laboratory Studies of the Cloud Droplet Activation Properties and Corresponding Chemistry of Saline Playa Dust

NASA Astrophysics Data System (ADS)

Gaston, C.; Pratt, K.; Suski, K. J.; May, N.; Gill, T. E.; Prather, K. A.

2016-12-01

Saline playas (dried lake beds) emit large quantities of dust that can facilitate the activation of cloud droplets. Despite the potential importance of playa dust for cloud formation, several models assume that dust is non-hygroscopic highlighting the need for measurements to clarify the role of dust from multiple sources in aerosol-cloud-climate interactions. Here we present water uptake measurements onto playa dust represented by the hygroscopicity parameter κ, which ranged from 0.002 ± 0.001 to 0.818 ± 0.094. Single-particle measurements made using an aircraft-aerosol time-of-flight mass spectrometer (A-ATOFMS) revealed the presence of halite, sodium sulfates, and sodium carbonates that were strongly correlated with κ underscoring the role that dust composition plays in water uptake. Predictions of κ made using bulk chemical techniques generally showed good agreement with measured values; however, several samples were poorly predicted using bulk particle composition. The lack of measurements/model agreement using this method and the strong correlations between κ and single-particle data are suggestive of chemical heterogeneities as a function of particle size and/or chemically distinct particle surfaces that dictate the water uptake properties of playa dust particles. Overall, our results highlight the ability of playa dust particles to act as cloud condensation nuclei that should be accounted for in models.

Environmental conditions regulate the impact of plants on cloud formation

PubMed Central

Zhao, D. F.; Buchholz, A.; Tillmann, R.; Kleist, E.; Wu, C.; Rubach, F.; Kiendler-Scharr, A.; Rudich, Y.; Wildt, J.; Mentel, Th. F.

2017-01-01

The terrestrial vegetation emits large amounts of volatile organic compounds (VOC) into the atmosphere, which on oxidation produce secondary organic aerosol (SOA). By acting as cloud condensation nuclei (CCN), SOA influences cloud formation and climate. In a warming climate, changes in environmental factors can cause stresses to plants, inducing changes of the emitted VOC. These can modify particle size and composition. Here we report how induced emissions eventually affect CCN activity of SOA, a key parameter in cloud formation. For boreal forest tree species, insect infestation by aphids causes additional VOC emissions which modifies SOA composition thus hygroscopicity and CCN activity. Moderate heat increases the total amount of constitutive VOC, which has a minor effect on hygroscopicity, but affects CCN activity by increasing the particles' size. The coupling of plant stresses, VOC composition and CCN activity points to an important impact of induced plant emissions on cloud formation and climate. PMID:28218253

Environmental conditions regulate the impact of plants on cloud formation.

PubMed

Zhao, D F; Buchholz, A; Tillmann, R; Kleist, E; Wu, C; Rubach, F; Kiendler-Scharr, A; Rudich, Y; Wildt, J; Mentel, Th F

2017-02-20

The terrestrial vegetation emits large amounts of volatile organic compounds (VOC) into the atmosphere, which on oxidation produce secondary organic aerosol (SOA). By acting as cloud condensation nuclei (CCN), SOA influences cloud formation and climate. In a warming climate, changes in environmental factors can cause stresses to plants, inducing changes of the emitted VOC. These can modify particle size and composition. Here we report how induced emissions eventually affect CCN activity of SOA, a key parameter in cloud formation. For boreal forest tree species, insect infestation by aphids causes additional VOC emissions which modifies SOA composition thus hygroscopicity and CCN activity. Moderate heat increases the total amount of constitutive VOC, which has a minor effect on hygroscopicity, but affects CCN activity by increasing the particles' size. The coupling of plant stresses, VOC composition and CCN activity points to an important impact of induced plant emissions on cloud formation and climate.

Glass formation and unusual hygroscopic growth of iodic acid solution droplets with relevance for iodine mediated particle formation in the marine boundary layer

NASA Astrophysics Data System (ADS)

Murray, B. J.; Haddrell, A. E.; Peppe, S.; Davies, J. F.; Reid, J. P.; O'Sullivan, D.; Price, H. C.; Kumar, R.; Saunders, R. W.; Plane, J. M. C.; Umo, N. S.; Wilson, T. W.

2012-09-01

Iodine oxide particles are known to nucleate in the marine boundary layer where gas phase molecular iodine and organoiodine species are produced by macroalgae. These ultra-fine particles may then grow through the condensation of other materials to sizes where they may serve as cloud condensation nuclei. There has been some debate over the chemical identity of the initially nucleated particles. In laboratory simulations, hygroscopic measurements have been used to infer that they are composed of insoluble I2O4, while elemental analysis of laboratory generated particles suggests soluble I2O5 or its hydrated form iodic acid, HIO3 (I2O5·H2O). In this paper we explore the response of super-micron sized aqueous iodic acid solution droplets to varying humidity using both Raman microscopy and single particle electrodynamic traps. These measurements reveal that the propensity of an iodic acid solution droplet to crystallise is negligible on drying to ~0% relative humidity (RH). On applying mechanical pressure to these droplets they shatter in a manner consistent with an ultra-viscous liquid or a brittle glass. Water retention in amorphous material at low RH is important for understanding the hygroscopic growth of aerosol particles and uptake of other condensable material. Subsequent water uptake between 10 and 20% RH causes their viscosity to reduce sufficiently that the cracked droplets flow and merge. The persistence of iodic acid solution in an amorphous state, rather than a crystalline state, suggests they will more readily accommodate other condensable material and are therefore more likely to grow to sizes where they may serve as cloud condensation nuclei. On increasing the humidity to ~90% the mass of the droplets only increases by ~20% with a corresponding increase in radius of only 6%, which is remarkably small for a highly soluble material. We suggest that the small growth factor of aqueous iodic acid solution droplets is consistent with the small aerosol growth factors observed in previous experiments.

L-Leucine as an excipient against moisture on in vitro aerosolization performances of highly hygroscopic spray-dried powders.

PubMed

Li, Liang; Sun, Siping; Parumasivam, Thaigarajan; Denman, John A; Gengenbach, Thomas; Tang, Patricia; Mao, Shirui; Chan, Hak-Kim

2016-05-01

L-Leucine (LL) has been widely used to enhance the dispersion performance of powders for inhalation. LL can also protect powders against moisture, but this effect is much less studied. The aim of this study was to investigate whether LL could prevent moisture-induced deterioration in in vitro aerosolization performances of highly hygroscopic spray-dried powders. Disodium cromoglycate (DSCG) was chosen as a model drug and different amounts of LL (2-40% w/w) were added to the formulation, with the aim to explore the relationship between powder dispersion, moisture protection and physicochemical properties of the powders. The powder formulations were prepared by spray drying of aqueous solutions containing known concentrations of DSCG and LL. The particle sizes were measured by laser diffraction. The physicochemical properties of fine particles were characterized by X-ray powder diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic vapor sorption (DVS). The surface morphology and chemistry of fine particles were analyzed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). In vitro aerosolization performances were evaluated by a next generation impactor (NGI) after the powders were stored at 60% or 75% relative humidity (RH), and 25°C for 24h. Spray-dried (SD) DSCG powders were amorphous and absorbed 30-45% (w/w) water at 70-80% RH, resulting in deterioration in the aerosolization performance of the powders. LL did not decrease the water uptake of DSCG powders, but it could significantly reduce the effect of moisture on aerosolization performances. This is due to enrichment of crystalline LL on the surface of the composite particles. The effect was directly related to the percentage of LL coverage on the surface of particles. Formulations having 61-73% (molar percent) of LL on the particle surface (which correspond to 10-20% (w/w) of LL in the bulk powders) could minimize moisture-induced deterioration in the aerosol performance. In conclusion, particle surface coverage of LL can offer short-term protection against moisture on dispersion of hygroscopic powders. Copyright © 2016 Elsevier B.V. All rights reserved.

Experimental Characterization and Hygroscopicity Determination of Secondary Aerosol from D5 Cyclic Siloxane Oxidation

NASA Astrophysics Data System (ADS)

Stanier, C. O.; Janechek, N. J.; Bryngelson, N.; Marek, R. F.; Lersch, T.; Bunker, K.; Casuccio, G.; Brune, W. H.; Hornbuckle, K. C.

2017-12-01

Cyclic volatile methyl siloxanes are anthropogenic chemicals present in personal care products such as antiperspirants and lotions. These are volatile chemicals that are readily released into the atmosphere by product use. Due to their emission and relatively slow kinetics of their major transformation pathway, reaction with hydroxyl radicals (OH), these compounds are present in high concentrations in indoor environments and widespread in outdoor environments. Cyclic siloxane reaction with OH can lead to secondary organic aerosols, and due to the widespread prevalence of the parent compounds, may be an important source of ambient aerosols. Atmospheric aerosols have important influences to the climate by affecting the radiative balance and by serving as cloud condensation nuclei (CCN) which influence clouds. While the parent compounds have been well-studied, the oxidation products have received much less attention, with almost no ambient measurements or experimental physical property data. We report physical properties of aerosols generated by reacting the cyclic siloxane D5 with OH using a Potential Aerosol Mass (PAM) photochemical chamber. The particles were characterized by SMPS, imaging and elemental analysis using both Transmission Electron Microscopy and Scanning Transmission Electron Microscopy equipped with Energy Dispersive X-ray Spectroscopy systems (TEM-EDS and STEM-EDS), volatility measurements using Volatility Tandem Differential Mobility Analyzer (V-TDMA), and hygroscopicity measurements to determine CCN potential using a Droplet Measurement Technologies Cloud Condensation Nuclei Counter (DMT-CCN). Aerosol yield sensitivity to D5 and OH concentrations, residence time, and seed aerosols were analyzed. TEM-EDS and STEM-EDS analysis show spherical particle morphology with elemental composition consistent with aerosols derived from cyclic siloxane sources. Measured aerosol yields were 20-50% with typical aerosol concentrations 300,000 particles cm-3, up to 200 μg m-3, and diameters of 30-90 nm. Particles experienced little diameter change after heating up to 200°C suggesting low volatility, while particle activation was shifted to higher supersaturations compared to ammonium sulfate suggesting moderate hygroscopicity in line with other secondary organics.

Component-specific, cigarette particle deposition modeling in the human respiratory tract

PubMed Central

Price, Owen T.; Yurteri, Caner U.; Dickens, Colin; McAughey, John

2014-01-01

Inhalation of cigarette smoke particles (CSP) leads to adverse health effects in smokers. Determination of the localized dose to the lung of the inhaled smoke aids in determining vulnerable sites, and identifying components of the smoke that may be responsible for the adverse effects; thus providing a roadmap for harm reduction of cigarette smoking. A particle deposition model specific to CSP was developed for the oral cavity and the lung by accounting for cigarette particle size growth by hygroscopicity, phase change and coagulation. In addition, since the cigarette puff enters the respiratory tract as a dense cloud, the cloud effect on particle drag and deposition was accounted for in the deposition model. Models of particle losses in the oral cavities were developed during puff drawing and subsequent mouth-hold. Cigarette particles were found to grow by hygroscopicity and coagulation, but to shrink as a result of nicotine evaporation. The particle size reached a plateau beyond which any disturbances in the environmental conditions caused the various mechanisms to balance each other out and the particle size remain stable. Predicted particle deposition considering the cloud effects was greater than when treated as a collection of non-interacting particles (i.e. no cloud effects). Accounting for cloud movement provided the necessary physical mechanism to explain the greater than expected, experimentally observed and particle deposition. The deposition model for CSP can provide the necessary input to determine the fate of inhaled CSP in the lung. The knowledge of deposition will be helpful for health assessment and identification and reduction of harmful components of CSP. PMID:24354791

The chemical composition of fine ambient aerosol particles in the Beijing area

NASA Astrophysics Data System (ADS)

Nekat, Bettina; van Pinxteren, Dominik; Iinuma, Yoshiteru; Gnauk, Thomas; Müller, Konrad; Herrmann, Hartmut

2010-05-01

The strong economical growth in China during the last few decades led to heavy air pollution caused by significantly increased particle emissions. The aerosol particles affect not only the regional air quality and visibility, but can also influence cloud formation processes and the radiative balance of the atmosphere by their optical and microphysical properties. The ability to act as Cloud Condensation Nuclei (CCN) is related to microphysical properties like the hygroscopic growth or the cloud droplet activation. The chemical composition of CCN plays an important role on these properties and varies strongly with the particle size and the time of day. Hygroscopic or surface active substances can increase the hygroscopicity and lower the surface tension of the particle liquid phase, respectively. The presence of such compounds may result in faster cloud droplet activation by faster water uptake. The DFG project HaChi (Haze in China) aimed at studying physical and chemical parameters of urban aerosol particles in the Beijing area in order to associate the chemical composition of aerosol particles with their ability to act as CCN. To this end, two measurement campaigns were performed at the Wuqing National Ordinary Meteorological Observing Station, which is a background site near Beijing. The winter campaign was realized in March 2009 and the summer campaign took place from mid July 2009 to mid August 2009. Fine particles with an aerodynamic diameter smaller than or equal 1 μm were continuously sampled for 24h over the two campaigns using a DIGITEL high volume sampler (DHA-80). The present contribution presents and discusses the results of the chemical characterization of the DIGITEL filters samples. The filters were analyzed for the mass concentration, inorganic ions and carbon sum parameters like elemental (EC), organic (OC) and water soluble organic carbon (WSOC). The WSOC fraction was further characterized for hygroscopic substances like low molecular dicarboxylic acids as well as sugars and sugar related compounds. Additionally fatty acids were analyzed to investigate surface active substances. Usually, the highest PM1 concentrations were observed during periods with prevailing wind directions from southern areas, while northern wind directions led to significantly lower concentrations. The main components of the fine particles are inorganic ions like the secondary formed ammonium nitrate und ammonium sulphate, as well as carbonaceous material. The organic carbon fraction is mostly dominated by water soluble organic carbon (80% in average). High concentrations of tracers like the anhydrosugar levoglucosan (Iinuma et al., 2007) suggest biomass burning emissions as a dominant source of organic particles in the area. A significant fraction of PM1 remains unidentified and most likely consists of crust material like dust as well as water. Iinuma, Y., E. Brüggemann, T. Gnauk, K. Müller, M. O. Andreae, G. Helas, R. Parmar, and H. Herrmann (2007), Source characterization of biomass burning particles: The combustion of selected European conifers, African hardwood, savanna grass, and German and Indonesian peat, J. Geophys. Res. [Atmos.], 112(D8), Doi 10.1029/2006jd007120.

Cloud condensation nuclei activity and hygroscopicity of fresh and aged cooking organic aerosol

NASA Astrophysics Data System (ADS)

Li, Yanwei; Tasoglou, Antonios; Liangou, Aikaterini; Cain, Kerrigan P.; Jahn, Leif; Gu, Peishi; Kostenidou, Evangelia; Pandis, Spyros N.

2018-03-01

Cooking organic aerosol (COA) is potentially a significant fraction of organic particulate matter in urban areas. COA chemical aging experiments, using aerosol produced by grilling hamburgers, took place in a smog chamber in the presence of UV light or excess ozone. The water solubility distributions, cloud condensation nuclei (CCN) activity, and corresponding hygroscopicity of fresh and aged COA were measured. The average mobility equivalent activation diameter of the fresh particles at 0.4% supersaturation ranged from 87 to 126 nm and decreased for aged particles, ranging from 65 to 88 nm. Most of the fresh COA had water solubility less than 0.1 g L-1, even though the corresponding particles were quite CCN active. After aging, the COA fraction with water solubility greater than 0.1 g L-1 increased more than 2 times. Using the extended Köhler theory for multiple partially soluble components in order to predict the measured activation diameters, the COA solubility distribution alone could not explain the CCN activity. Surface tensions less than 30 dyn cm-1 were required to explain the measured activation diameters. In addition, COA particles appear to not be spherical, which can introduce uncertainties into the corresponding calculations.

Microencapsulation of grape (Vitis labrusca var. Bordo) skin phenolic extract using gum Arabic, polydextrose, and partially hydrolyzed guar gum as encapsulating agents.

PubMed

Kuck, Luiza Siede; Noreña, Caciano Pelayo Zapata

2016-03-01

Bordo grape skin extract was microencapsulated by spray-drying and freeze-drying, using gum arabic (GA), partially hydrolyzed guar gum (PHGG), and polydextrose (PD) as encapsulating agents. Total phenolics and total monomeric anthocyanin, antioxidant activity, color, moisture, water activity (aw), solubility, hygroscopicity, glass transition temperature (Tg), particle size, and microstructure of the powders were evaluated. The retention of phenolics and anthocyanins ranged from 81.4% to 95.3%, and 80.8% to 99.6%, respectively, while the retention of antioxidant activity ranged from 45.4% to 83.7%. Treatments subjected to spray-drying had lower moisture, aw, and particle size, and greater solubility, while the freeze-dried samples were less hygroscopic. Tg values ranged from 10.1 to 52.2°C, and the highest values corresponded to the spray-dried microparticles. The spray-dried particles had spherical shape, while the freeze-dried powders showed irregular structures. The spray drying technique and the use of 5% PHGG and 5% PD has proven to be the best treatment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Aerosol and CCN in southwest Saudi Arabia

NASA Astrophysics Data System (ADS)

Collins, Don; Li, Runjun; Axisa, Duncan; Kucera, Paul; Burger, Roelof

2010-05-01

As part of an ongoing study of the microphysical and dynamical controls on precipitation in southwest Saudi Arabia, a number of surface and aircraft-based instruments were used in summer / fall 2009 to measure the size distribution, hygroscopic properties, and cloud droplet nucleation efficiency of the local aerosol. Submicron size distributions were measured using differential mobility analyzers both on the ground and on board the aircraft, while an aerodynamic particle sizer and a forward scattering spectrometer probe were used to measure the supermicron size distributions on the ground and from on board the aircraft, respectively. Identical continuous flow cloud condensation nuclei counters were used to measure CCN spectra at the surface and aloft and a humidified tandem differential mobility analyzer was operated on the ground to measure size-resolved hygroscopicity. The aerosol in this arid environment is characterized by a persistent accumulation mode having hygroscopic and CCN efficiency properties consistent with a sulfate-rich aged aerosol. The particles in that background aerosol are generally sufficiently large and hygroscopic to activate at those supersaturations expected in the convective clouds responsible for most of the regional precipitation, which consequently acts as a lower bound on the resulting cloud droplet concentrations. Though the concentration, size distribution, and properties of the submicron aerosol generally changed very slowly over periods of several hours, abrupt ~doubling in concentration almost always accompanied the arrival of the sea breeze front that began along the Red Sea. Interestingly, the hygroscopicity and the shape of the size distribution differed little in the pre- and post-sea breeze air masses. The dust-dominated coarse mode typically contributed significantly more to the aerosol mass concentration than did the submicron mode and likely controlled the ice nuclei concentration, though no direct measurements were made to confirm this. Results of routine flight patterns designed to examine the spatial, vertical, and day-to-day variability of the aerosol will be presented and the link between the aerosol at the surface and aloft will be quantified. This presentation will emphasize the regional character of the aerosol and will assess its influence on cloud microphysics.

Core/Shell Microstructure Induced Synergistic Effect for Efficient Water-Droplet Formation and Cloud-Seeding Application.

PubMed

Tai, Yanlong; Liang, Haoran; Zaki, Abdelali; El Hadri, Nabil; Abshaev, Ali M; Huchunaev, Buzgigit M; Griffiths, Steve; Jouiad, Mustapha; Zou, Linda

2017-12-26

Cloud-seeding materials as a promising water-augmentation technology have drawn more attention recently. We designed and synthesized a type of core/shell NaCl/TiO 2 (CSNT) particle with controlled particle size, which successfully adsorbed more water vapor (∼295 times at low relative humidity, 20% RH) than that of pure NaCl, deliquesced at a lower environmental RH of 62-66% than the hygroscopic point (h g.p ., 75% RH) of NaCl, and formed larger water droplets ∼6-10 times its original measured size area, whereas the pure NaCl still remained as a crystal at the same conditions. The enhanced performance was attributed to the synergistic effect of the hydrophilic TiO 2 shell and hygroscopic NaCl core microstructure, which attracted a large amount of water vapor and turned it into a liquid faster. Moreover, the critical particle size of the CSNT particles (0.4-10 μm) as cloud-seeding materials was predicted via the classical Kelvin equation based on their surface hydrophilicity. Finally, the benefits of CSNT particles for cloud-seeding applications were determined visually through in situ observation under an environmental scanning electron microscope on the microscale and cloud chamber experiments on the macroscale, respectively. These excellent and consistent performances positively confirmed that CSNT particles could be promising cloud-seeding materials.

Cloud forming potential of oligomers relevant to secondary organic aerosols

NASA Astrophysics Data System (ADS)

Xu, Wen; Guo, Song; Gomez-Hernandez, Mario; Zamora, Misti L.; Secrest, Jeremiah; Marrero-Ortiz, Wilmarie; Zhang, Annie L.; Collins, Don R.; Zhang, Renyi

2014-09-01

The hygroscopic growth factor (HGF) and cloud condensation nuclei (CCN) activity are measured for surrogates that mimic atmospherically relevant oligomers, including glyoxal trimer dihydrate, methyl glyoxal trimer dihydrate, sucrose, methyl glyoxal mixtures with sulfuric acid and glycolic acid, and 2,4-hexandienal mixtures with sulfuric acid and glycolic acid. For the single-component aerosols, the measured HGF ranges from 1.3 to 1.4 at a relative humidity of 90%, and the hygroscopicity parameter (κ) is in the range of 0.06 to 0.19 on the basis of the measured CCN activity and 0.13 to 0.22 on the basis of the measured HGF, compared to the calculated values of 0.08 to 0.16. Large differences exist in the κ values derived using the measured HGF and CCN data for the multi-component aerosols. Our results reveal that, in contrast to the oxidation process, oligomerization decreases particle hygroscopicity and CCN activity and provides guidance for analyzing the organic species in ambient aerosols.

A Microbial Oasis in the Hypersaline Atacama Subsurface Discovered by a Life Detector Chip: Implications for the Search for Life on Mars

PubMed Central

de Diego-Castilla, Graciela; Moreno-Paz, Mercedes; Blanco, Yolanda; Cruz-Gil, Patricia; Rodríguez-Manfredi, José A.; Fernández-Remolar, David; Gómez, Felipe; Gómez, Manuel J.; Rivas, Luis A.; Demergasso, Cecilia; Echeverría, Alex; Urtuvia, Viviana N.; Ruiz-Bermejo, Marta; García-Villadangos, Miriam; Postigo, Marina; Sánchez-Román, Mónica; Chong-Díaz, Guillermo; Gómez-Elvira, Javier

2011-01-01

Abstract The Atacama Desert has long been considered a good Mars analogue for testing instrumentation for planetary exploration, but very few data (if any) have been reported about the geomicrobiology of its salt-rich subsurface. We performed a Mars analogue drilling campaign next to the Salar Grande (Atacama, Chile) in July 2009, and several cores and powder samples from up to 5 m deep were analyzed in situ with LDChip300 (a Life Detector Chip containing 300 antibodies). Here, we show the discovery of a hypersaline subsurface microbial habitat associated with halite-, nitrate-, and perchlorate-containing salts at 2 m deep. LDChip300 detected bacteria, archaea, and other biological material (DNA, exopolysaccharides, some peptides) from the analysis of less than 0.5 g of ground core sample. The results were supported by oligonucleotide microarray hybridization in the field and finally confirmed by molecular phylogenetic analysis and direct visualization of microbial cells bound to halite crystals in the laboratory. Geochemical analyses revealed a habitat with abundant hygroscopic salts like halite (up to 260 g kg−1) and perchlorate (41.13 μg g−1 maximum), which allow deliquescence events at low relative humidity. Thin liquid water films would permit microbes to proliferate by using detected organic acids like acetate (19.14 μg g−1) or formate (76.06 μg g−1) as electron donors, and sulfate (15875 μg g−1), nitrate (13490 μg g−1), or perchlorate as acceptors. Our results correlate with the discovery of similar hygroscopic salts and possible deliquescence processes on Mars, and open new search strategies for subsurface martian biota. The performance demonstrated by our LDChip300 validates this technology for planetary exploration, particularly for the search for life on Mars. Key Words: Atacama Desert—Life detection—Biosensor—Biopolymers—In situ measurement. Astrobiology 11, 969–996. PMID:22149750

A microbial oasis in the hypersaline Atacama subsurface discovered by a life detector chip: implications for the search for life on Mars.

PubMed

Parro, Victor; de Diego-Castilla, Graciela; Moreno-Paz, Mercedes; Blanco, Yolanda; Cruz-Gil, Patricia; Rodríguez-Manfredi, José A; Fernández-Remolar, David; Gómez, Felipe; Gómez, Manuel J; Rivas, Luis A; Demergasso, Cecilia; Echeverría, Alex; Urtuvia, Viviana N; Ruiz-Bermejo, Marta; García-Villadangos, Miriam; Postigo, Marina; Sánchez-Román, Mónica; Chong-Díaz, Guillermo; Gómez-Elvira, Javier

2011-12-01

The Atacama Desert has long been considered a good Mars analogue for testing instrumentation for planetary exploration, but very few data (if any) have been reported about the geomicrobiology of its salt-rich subsurface. We performed a Mars analogue drilling campaign next to the Salar Grande (Atacama, Chile) in July 2009, and several cores and powder samples from up to 5 m deep were analyzed in situ with LDChip300 (a Life Detector Chip containing 300 antibodies). Here, we show the discovery of a hypersaline subsurface microbial habitat associated with halite-, nitrate-, and perchlorate-containing salts at 2 m deep. LDChip300 detected bacteria, archaea, and other biological material (DNA, exopolysaccharides, some peptides) from the analysis of less than 0.5 g of ground core sample. The results were supported by oligonucleotide microarray hybridization in the field and finally confirmed by molecular phylogenetic analysis and direct visualization of microbial cells bound to halite crystals in the laboratory. Geochemical analyses revealed a habitat with abundant hygroscopic salts like halite (up to 260 g kg(-1)) and perchlorate (41.13 μg g(-1) maximum), which allow deliquescence events at low relative humidity. Thin liquid water films would permit microbes to proliferate by using detected organic acids like acetate (19.14 μg g(-1)) or formate (76.06 μg g(-1)) as electron donors, and sulfate (15875 μg g(-1)), nitrate (13490 μg g(-1)), or perchlorate as acceptors. Our results correlate with the discovery of similar hygroscopic salts and possible deliquescence processes on Mars, and open new search strategies for subsurface martian biota. The performance demonstrated by our LDChip300 validates this technology for planetary exploration, particularly for the search for life on Mars.

Microscopic composition measurements of organic individual particles collected in the Southern Great Plains

NASA Astrophysics Data System (ADS)

Bonanno, D.; China, S.; Fraund, M. W.; Pham, D.; Kulkarni, G.; Laskin, A.; Gilles, M. K.; Moffet, R.

2016-12-01

The Holistic Interactions of Shallow Clouds, Aerosols, and Land-Ecosystems (HI-SCALE) Campaign was carried out to gain a better understanding of the lifecycle of shallow clouds. The HISCALE experiment was designed to contrast two seasons, wet and dry, and determine their effect on atmospheric cloud and aerosol processes. The spring component to HISCALE was selected to characterize mixing state for particles collected onto substrates. Sampling was performed before and after rain events to obtain airborne soil organic particles (ASOP), which are ejected after rain events. The unique composition of the ASOP may affect optical properties and/or hygroscopic properties. The collection of particles took place at the Atmospheric Radiation Measurement Southern Great Plains (ARM SGP) field site. The Scanning Transmission X-Ray Microscope (STXM) was used to image the samples collected during the first HI-SCALE Campaign to determine the carbonaceous mixing state. Scanning Electron Microscopy Energy-dispersive X-ray (SEM/EDX) analysis is more sensitive to the inorganic makeup of particles, while STXM renders a more comprehensive analysis of the organics. Measurements such as nephelometry, Particle Soot Absorption Photometry (PSAP), and Aerosol Mass Spectrometry (AMS) from the ARM archive will be correlated with microscopy measurements. The primary focus is the relation between composition and morphology of ASOP with hygroscopicity and optical properties. Further investigation of these organic particles will be performed to provide a mixing state parameterization and aid in the advancement of current climate models.

Numerical investigation of the coagulation mixing between dust and hygroscopic aerosol particles and its impacts

NASA Astrophysics Data System (ADS)

Tsai, I.-Chun; Chen, Jen-Ping; Lin, Yi-Chiu; Chung-Kuang Chou, Charles; Chen, Wei-Nai

2015-05-01

A statistical-numerical aerosol parameterization was incorporated into the Community Multiscale Air Quality modeling system to study the coagulation mixing process focusing on a dust storm event that occurred over East Asia. Simulation results show that the coagulation mixing process tends to decrease aerosol mass, surface area, and number concentrations over the dust source areas. Over the downwind oceanic areas, aerosol concentrations generally increased due to enhanced sedimentation as particles became larger upon coagulation. The mixture process can reduce the overall single-scattering albedo by up to 10% as a result of enhanced core with shell absorption by dust and reduction in the number of scattering particles. The enhanced dry deposition speed also altered the vertical distribution. In addition, the ability of aerosol particles to serve as cloud condensation nuclei (CCN) increased from around 107 m-3 to above 109 m-3 over downwind areas because a large amount of mineral dust particles became effective CCN with solute coating, except over the highly polluted areas where multiple collections of hygroscopic particles by dust in effect reduced CCN number. This CCN effect is much stronger for coagulation mixing than by the uptake of sulfuric acid gas on dust, although the nitric acid gas uptake was not investigated. The ability of dust particles to serve as ice nuclei may decrease or increase at low or high subzero temperatures, respectively, due to the switching from deposition nucleation to immersion freezing or haze freezing.

Vacuum FTIR study on the hygroscopicity of magnesium acetate aerosols

NASA Astrophysics Data System (ADS)

Wang, Na; Cai, Chen; He, Xiang; Pang, Shu-Feng; Zhang, Yun-Hong

2018-03-01

Hygroscopicity and volatility of secondary organic aerosol (SOA) are two important properties, which determine the composition, concentration, size, phase state of SOA and thus chemical and optical properties for SOA. In this work, magnesium acetate (Mg(Ac)2) aerosol was used as a simple SOA model in order to reveal relationship between hygroscopicity and volatility. A novel approach was set up based on a combination of a vacuum FTIR spectrometer and a home-made relative humidity (RH) controlling system. The striking advantage of this approach was that the RH and the compositions of aerosols could be obtained from a same IR spectrum, which guaranteed the synchronism between RH and spectral features on a sub-second scale. At the constant RH of 90% and 80% for 3000 s, the water content within Mg(Ac)2 aerosol particles decreased about 19.0% and 9.4% while there were 13.4% and 6.0% of acetate loss. This was attributed to a cooperation between volatile of acetic acid and Mg2 + hydrolysis in Mg(Ac)2 aerosols, which greatly suppressed the hygroscopicity of Mg(Ac)2 aerosols. When the RH changed with pulsed mode between 70% and 90%, hygroscopicity relaxation was observed for Mg(Ac)2 aerosols. Diffuse coefficient of water in the relaxation process was estimated to be 5 × 10- 12 m2·s- 1 for the Mg(Ac)2 aerosols. Combining the IR spectra analysis, the decrease in the diffuse coefficient of water was due to the formation of magnesium hydroxide accompanying acetic acid evaporation in the aerosols.

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

NASA Astrophysics Data System (ADS)

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

2017-02-01

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

Bacterial growth tolerance to concentrations of chlorate and perchlorate salts relevant to Mars

NASA Astrophysics Data System (ADS)

Al Soudi, Amer F.; Farhat, Omar; Chen, Fei; Clark, Benton C.; Schneegurt, Mark A.

2017-07-01

The Phoenix lander at Mars polar cap found appreciable levels of (per)chlorate salts, a mixture of perchlorate and chlorate salts of Ca, Fe, Mg and Na at levels of ~0.6% in regolith. These salts are highly hygroscopic and can form saturated brines through deliquescence, likely producing aqueous solutions with very low freezing points on Mars. To support planetary protection efforts, we have measured bacterial growth tolerance to (per)chlorate salts. Existing bacterial isolates from the Great Salt Plains of Oklahoma (NaCl-rich) and Hot Lake in Washington (MgSO4-rich) were tested in high concentrations of Mg, K and Na salts of chlorate and perchlorate. Strong growth was observed with nearly all of these salinotolerant isolates at 1% (~0.1 M) (per)chlorate salts, similar to concentrations observed in bulk soils on Mars. Growth in perchlorate salts was observed at concentrations of at least 10% (~1.0 M). Greater tolerance was observed for chlorate salts, where growth was observed to 2.75 M (>25%). Tolerance to K salts was greatest, followed by Mg salts and then Na salts. Tolerances varied among isolates, even among those within the same phylogenetic clade. Tolerant bacteria included genera that also are found in spacecraft assembly facilities. Substantial microbial tolerance to (per)chlorate salts is a concern for planetary protection since tolerant microbes contaminating spacecraft would have a greater chance for survival and proliferation, despite the harsh chemical conditions found near the surface of Mars.

Scattering properties of soot-containing particles and their impact by humidity in 1.6 μm

NASA Astrophysics Data System (ADS)

Fan, M.; Chen, L.; Xiong, X.; Li, S.; Tao, J.; Su, L.; Zou, M.; Zhang, Y.

2014-02-01

Short-wave infrared (SWIR) band in wavelength near 1.6 μm is one of the key bands used for satellite observation of Carbon Dioxide (CO2). However, one major uncertainty to use this band for the CO2 retrieval is the scattering by cloud and aerosol particles. To better understand the scattering properties of soot-containing particles in this band, this paper studied the scattering properties for three typical types of soot-containing particles in China: (I) internal mixture, (II) pure soot aggregate, and (III) semi-external mixture. Assumed as single non-spherical particle for type I, its scattering property is computed using the T-matrix method combined with the Maxwell-Garnett effective medium theory and the hygroscopic growth theory. For types II and III, a particle-cluster aggregation algorithm is employed to generate fractal-like aggregates, and their scattering properties are computed using the Core-Mantle Generalized Multi-sphere Mie-solution method combined with the hygroscopic growth theory of both monomers and aggregated particles. The simulated results demonstrate that their scattering properties are quite different and strongly impacted by the levels of relative humidity (RH). For type I, the RH plays a much more important role than the morphology in impacting the scattering properties, and the scattering phase functions among different shaped particles have a larger difference for larger particles and higher RH. For type II, both the RH and morphology significantly affect its scattering properties. The single scattering albedo (ω) can be underestimated up to ~50% without considering the effects of RH and morphological changes. For type III, its scattering properties mainly depend on the RH and the size of the large water-soluble particle. Although the enlarged soot aggregate, which is attached to a water-soluble particle, almost does not change the light direction, it can result in a significant reduction in ω (~0.15) at low RH for small particles. By comparing the scattering parameters of wet particles at a certain RH level with the dry ones, the impact by the heterogeneity of aerosols generally becomes larger with the increase of RH, but becomes smaller with the increase of particle size. These results suggest that, although the water vapor absorption itself is small in 1.6 μm CO2 band, it can significantly impact the scattering properties of these particles through its effect on the hygroscopic growth of the non-spherical and heterogeneous aerosols. This impact should be taken into account in the retrieval of CO2 using 1.6 μm as well as other related remote sensing applications.

In situ measurements of cloud microphysics and aerosol over coastal Antarctica during the MAC campaign

NASA Astrophysics Data System (ADS)

O'Shea, Sebastian J.; Choularton, Thomas W.; Flynn, Michael; Bower, Keith N.; Gallagher, Martin; Crosier, Jonathan; Williams, Paul; Crawford, Ian; Fleming, Zoë L.; Listowski, Constantino; Kirchgaessner, Amélie; Ladkin, Russell S.; Lachlan-Cope, Thomas

2017-11-01

During austral summer 2015, the Microphysics of Antarctic Clouds (MAC) field campaign collected unique and detailed airborne and ground-based in situ measurements of cloud and aerosol properties over coastal Antarctica and the Weddell Sea. This paper presents the first results from the experiment and discusses the key processes important in this region, which is critical to predicting future climate change. The sampling was predominantly of stratus clouds, at temperatures between -20 and 0 °C. These clouds were dominated by supercooled liquid water droplets, which had a median concentration of 113 cm-3 and an interquartile range of 86 cm-3. Both cloud liquid water content and effective radius increased closer to cloud top. The cloud droplet effective radius increased from 4 ± 2 µm near cloud base to 8 ± 3 µm near cloud top. Cloud ice particle concentrations were highly variable with the ice tending to occur in small, isolated patches. Below approximately 1000 m, glaciated cloud regions were more common at higher temperatures; however, the clouds were still predominantly liquid throughout. When ice was present at temperatures higher than -10 °C, secondary ice production most likely through the Hallett-Mossop mechanism led to ice concentrations 1 to 3 orders of magnitude higher than the number predicted by commonly used primary ice nucleation parameterisations. The drivers of the ice crystal variability are investigated. No clear dependence on the droplet size distribution was found. The source of first ice in the clouds remains uncertain but may include contributions from biogenic particles, blowing snow or other surface ice production mechanisms. The concentration of large aerosols (diameters 0.5 to 1.6 µm) decreased with altitude and were depleted in air masses that originated over the Antarctic continent compared to those more heavily influenced by the Southern Ocean and sea ice regions. The dominant aerosol in the region was hygroscopic in nature, with the hygroscopicity parameter κ having a median value for the campaign of 0.66 (interquartile range of 0.38). This is consistent with other remote marine locations that are dominated by sea salt/sulfate.

Potential climatic impact of organic haze on early Earth.

PubMed

Hasenkopf, Christa A; Freedman, Miriam A; Beaver, Melinda R; Toon, Owen B; Tolbert, Margaret A

2011-03-01

We have explored the direct and indirect radiative effects on climate of organic particles likely to have been present on early Earth by measuring their hygroscopicity and cloud nucleating ability. The early Earth analog aerosol particles were generated via ultraviolet photolysis of an early Earth analog gas mixture, which was designed to mimic possible atmospheric conditions before the rise of oxygen. An analog aerosol for the present-day atmosphere of Saturn's moon Titan was tested for comparison. We exposed the early Earth aerosol to a range of relative humidities (RHs). Water uptake onto the aerosol was observed to occur over the entire RH range tested (RH=80-87%). To translate our measurements of hygroscopicity over a specific range of RHs into their water uptake ability at any RH < 100% and into their ability to act as cloud condensation nuclei (CCN) at RH > 100%, we relied on the hygroscopicity parameter κ, developed by Petters and Kreidenweis. We retrieved κ=0.22 ±0.12 for the early Earth aerosol, which indicates that the humidified aerosol (RH < 100 %) could have contributed to a larger antigreenhouse effect on the early Earth atmosphere than previously modeled with dry aerosol. Such effects would have been of significance in regions where the humidity was larger than 50%, because such high humidities are needed for significant amounts of water to be on the aerosol. Additionally, Earth organic aerosol particles could have activated into CCN at reasonable-and even low-water-vapor supersaturations (RH > 100%). In regions where the haze was dominant, it is expected that low particle concentrations, once activated into cloud droplets, would have created short-lived, optically thin clouds. Such clouds, if predominant on early Earth, would have had a lower albedo than clouds today, thereby warming the planet relative to current-day clouds. © Mary Ann Liebert, Inc.

Hygroscopic Measurements of Aerosol Particles in the San Joaquin Valley California during the DRAGON and Discover AQ Campaign 2013

NASA Astrophysics Data System (ADS)

Orozco, D.; Delgado, R.; Hoff, R. M.

2013-12-01

In the ambient atmosphere, aerosol particles experience hygroscopic growth due to the influence of relative humidity (RH). Wet aerosols particles are larger than their dry equivalents, therefore they scatter more light. Quantitative knowledge of the RH effect and its influence on the light scattering coefficient on aerosol particles is of substantial importance when comparing ground based observations with other optical aerosol measurements techniques such satellite and sunphotometric retrievals of aerosol optical depth. The DISCOVER-AQ campaign is focused in improving the interpretation and relation between satellite observations and surface conditions related to air quality. In the winter of 2013, this campaign was held in the San Joaquin Valley, California, where systematic and concurrent observations of column integrated surface, and vertically resolved distributions of aerosols and trace gases relevant to air quality and their evolution during the day were observed. Different instruments such as particulate samplers, lidars, meteorological stations and airborne passive and active monitoring were coordinated to measure the aerosol structure of the San Joaquin Valley in a simultaneous fashion. A novel humidifier-dryer system for a TSI 3563 Nephelometer was implemented in the Penn State University NATIVE trailer located in Porterville California in order to measure the scattering coefficient σsp(λ) at three different wavelengths (λ=440, 550 and 700nm) in a RH range from 30 to 95%. The system was assembled by combining Nafion tubes to humidify and dry the aerosols and stepping motor valves to control the flow and the amount of humidity entering to the Nephelometer. Measurements in Porterville California reached dry scattering coefficient readings greater than 300Mm-1 at 550nm indicating the presence of a large amount of particles in the region. However, the ratio between scattering coefficients at high and low humidity, called the enhancement factor f(RH), showed relatively low hygroscopic growth in the aerosol particles, especially in comparison to a similar experiment conducted in 2012 in the Baltimore-Washington area. In average, during January and early February, the f(RH=85%) was 1.57×0.16 in the sampling site, which leads to the conclusion that the particle loading was dominated by black carbon and remnants of biomass burning. We refer to concurrent speciation measurements by Zhang et al. (private communication) in Fresno, during the study. The implications for sunphotometer measurements in DRAGON are discussed.

Relationships Between Molecular Structure and Chemical Reactivity in Hypergolic Ionic Liquids: Progress Toward Designing Green Fuels for Bipropellant Applications

DTIC Science & Technology

2012-05-01

molten salts can be employed over a wide range of applications, which include solvents, 7 electrolytes , 8 pharmaceuticals and therapeutics,9 and...waxy, hygroscopic solid at room temperature, where the additional products in the HP series exist as liquids at room 9 temperature. In general...compressed aluminum pans. Melting and decomposition points for solids were measured by DSC from 40 to 400 oC at a scan rate of 5 ºC/min. IR spectra

Physiochemical properties of alkylaminium sulfates: hygroscopicity, thermostability, and density.

PubMed

Qiu, Chong; Zhang, Renyi

2012-04-17

Although heterogeneous interaction of amines has been recently shown to play an important role in the formation and growth of atmospheric aerosols, little information is available on the physicochemical properties of aminium sulfates. In this study, the hygroscopicity, thermostability, and density of alkylaminium sulfates (AASs) have been measured by an integrated aerosol analytical system including a tandem differential mobility analyzer and an aerosol particle mass analyzer. AAS aerosols exhibit monotonic size growth at increasing RH without a well-defined deliquescence point. Mixing of ammonium sulfate (AS) with AASs lowers the deliquescence point corresponding to AS. Particles with AASs show comparable or higher thermostability than that of AS. The density of AASs is determined to be 1.2-1.5 g cm(-3), and an empirical model is developed to predict the density of AASs on the basis of the mole ratio of alkyl carbons to total sulfate. Our results reveal that the heterogeneous uptake of amines on sulfate particles may considerably alter the aerosol properties. In particular, the displacement reaction of alkylamines with ammonium sulfate aerosols leads to a transition from the crystalline to an amorphorous phase and an improved water uptake, considerably enhancing their direct and indirect climate forcing.

Hygroscopicity of Early Earth and Titan Laboratory Aerosol Analogs

NASA Astrophysics Data System (ADS)

Hasenkopf, C. A.; Beaver, M. R.; Freedman, M. A.; Toon, O. B.; Tolbert, M. A.

2009-12-01

We have explored the ability of organic hazes, known to exist in the atmosphere of Titan and postulated to have existed in the Archean Earth atmosphere, to act as cloud condensation nuclei (CCN). These laboratory aerosol analogs are generated via UV-photolysis of early Earth and Titan analog gas mixtures and are designed to mimic the present day atmospheric conditions on Titan and the early Earth atmosphere before the rise of oxygen. Water uptake is observed to occur on the early Earth and Titan aerosol analogs at relative humidities of 80% - 90% via optical growth measurements using cavity ring-down aerosol extinction spectroscopy. We find the optical growth of these aerosols is similar to known slightly-soluble organic acids, such as phthalic and pyromellitic acids. On average, the optical growth of the early Earth analog is slightly larger than the Titan analog. In order to translate our measurements obtained in a subsaturated regime into the CCN ability of these particles, we rely on the hygroscopicity parameter κ, developed by Petters & Kreidenweis (2007). We retrieve κ = 0.17±0.03 and 0.06±0.01 for the early Earth and Titan analogs, respectively. This early Earth analog hygroscopicity value indicates that the aerosol could activate at reasonable water vapor supersaturations. We use previous aerosol mass spectrometry results to correlate the chemical structure of the two types of analog with their hygroscopicity. The hygroscopicity of the early Earth aerosol analog, coupled with the apparent lack of other good CCN during the Archean, helps explain the role of the organic haze in the indirect effect of clouds on the early Earth and indicates that it may have had a significant impact on the hydrological cycle.

Cloud condensation nuclei in Western Colorado: Observations and model predictions

NASA Astrophysics Data System (ADS)

Ward, Daniel Stewart

Variations in the warm cloud-active portion of atmospheric aerosols, or cloud condensation nuclei (CCN), have been shown to impact cloud droplet number concentration and subsequently cloud and precipitation processes. This issue carries special significance in western Colorado where a significant portion of the region's water resources is supplied by precipitation from winter season, orographic clouds, which are particularly sensitive to variations in CCN. Temporal and spatial variations in CCN in western Colorado were investigated using a combination of observations and a new method for modeling CCN. As part of the Inhibition of Snowfall by Pollution Aerosols (ISPA-III) field campaign, total particle and CCN number concentration were measured for a 24-day period in Mesa Verde National Park, climatologically upwind of the San Juan Mountains. These data were combined with CCN observations from Storm Peak Lab (SPL) in northwestern Colorado and from the King Air platform, flying north to south along the Western Slope. Altogether, the sampled aerosols were characteristic of a rural continental environment and the cloud-active portion varied slowly in time, and little in space. Estimates of the is hygroscopicity parameter indicated consistently low aerosol hygroscopicity typical of organic aerosol species. The modeling approach included the addition of prognostic CCN to the Regional Atmospheric Modeling System (RAMS). The RAMS droplet activation scheme was altered using parcel model simulations to include variations in aerosol hygroscopicity, represented by K. Analysis of the parcel model output and a supplemental sensitivity study showed that model CCN will be sensitive to changes in aerosol hygroscopicity, but only for conditions of low supersaturation or small particle sizes. Aerosol number, size distribution median radius, and hygroscopicity (represented by the K parameter) in RAMS were constrained by nudging to forecasts of these quantities from the Weather Research and Forecasting with Chemistry (WRF/Chem) model. The new system was validated against observations from SPL and research flights along the Colorado Front Range, and used to test the sensitivity of CCN in western Colorado to various anthropogenic emissions of aerosols and aerosol precursor gases. Results showed complex interactions between gas and aerosol species that could lead to an increase in CCN even when some emissions are eliminated. Both observations and modeling suggest that, although several large anthropogenic aerosol sources are located within the study region, these sources have a minor impact on the local CCN population.

Cloud condensation nuclei and ice nucleation activity of hydrophobic and hydrophilic soot particles.

PubMed

Koehler, Kirsten A; DeMott, Paul J; Kreidenweis, Sonia M; Popovicheva, Olga B; Petters, Markus D; Carrico, Christian M; Kireeva, Elena D; Khokhlova, Tatiana D; Shonija, Natalia K

2009-09-28

Cloud condensation nuclei (CCN) activity and ice nucleation behavior (for temperatures

Clouds and aerosols in Puerto Rico - a new evaluation

NASA Astrophysics Data System (ADS)

Allan, J. D.; Baumgardner, D.; Raga, G. B.; Mayol-Bracero, O. L.; Morales-García, F.; García-García, F.; Montero-Martínez, G.; Borrmann, S.; Schneider, J.; Mertes, S.; Walter, S.; Gysel, M.; Dusek, U.; Frank, G. P.; Krämer, M.

2007-08-01

The influence of aerosols, both natural and anthropogenic, remains a major area of uncertainty when predicting the properties and behaviour of clouds and their influence on climate. In an attempt to better understand warm cloud formation in a tropical marine environment, a period of intensive measurements using some of the latest developments in online instrumentation took place in December 2004 in Puerto Rico. Simultaneous online measurements of aerosol size distributions, composition, hygroscopicity and optical properties were made near the lighthouse of Cape San Juan in the north-eastern corner of the island and at the top of East Peak mountain (1040 m a.s.l.), the two sites separated by 17 km. Additional measurements of the cloud droplet residual and interstitial aerosol properties were made at the mountain site, accompanied by measurements of cloud droplet size distributions, liquid water content and the chemical composition of cloud and rain water samples. Both aerosol composition and cloud properties were found to be sensitive to wind sector. Air from the east-northeast (ENE) was mostly free of anthropogenic influences, the submircron fraction being mainly composed of non-sea salt sulphate, while that from the east-southeast (ESE) was found to be moderately influenced by populated islands upwind, adding smaller (<100 nm), externally mixed, carbonaceous particles to the aerosol that increased the number concentrations by over a factor of 3. This change in composition was also accompanied with a reduction in the measured hygroscopicity and fractional cloud activation potential of the aerosol. At the mountain site, the average cloud droplet concentrations increased from 193 to 519 cm-3, median volume diameter decreased from 20 to 14 μm and the liquid water content increased from 0.24 to 0.31 g m-3 when the winds shifted from the ENE to ESE. Larger numbers of interstitial particles were recorded, most notably at sizes greater than 100 nm, which were absent during clean conditions. The average size of the residual particles and concentrations of cloudwater nitrate, sulphate and insoluble material increased during polluted conditions. Previous studies in Puerto Rico had reported the presence of a significant non-anthropogenic organic fraction in the aerosols measured and concluded that this was a factor controlling the in situ cloud properties. However, this was not observed in our case. In contrast to the 1.00±0.14 μg m-3 of organic carbon measured in 1992 and 1995, the organic matter measured in the current study of 0.17±0.35 μg m-3 is many times lower, most of which can be attributed to anthropogenic sources. During clean conditions, the submicron aerosol was observed to be almost entirely inorganic, an observation supported by the hygroscopicity measurements. This suggests that organic aerosols from marine sources may not be completely ubiquitous (either spatially or temporally) in this environment and requires further investigation to quantify their true extent and implications, with more extensive, longer-term sampling in conjunction with back trajectory analyses.

Collaborative Project: Understanding the Chemical Processes tat Affect Growth rates of Freshly Nucleated Particles

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

McMurry, Peter; Smuth, James

This final technical report describes our research activities that have, as the ultimate goal, the development of a model that explains growth rates of freshly nucleated particles. The research activities, which combine field observations with laboratory experiments, explore the relationship between concentrations of gas-phase species that contribute to growth and the rates at which those species are taken up. We also describe measurements of the chemical composition of freshly nucleated particles in a variety of locales, as well as properties (especially hygroscopicity) that influence their effects on climate.

Nucleation and growth of crystals under cirrus and polar stratospheric cloud conditions

NASA Technical Reports Server (NTRS)

Hallett, John; Queen, Brian; Teets, Edward; Fahey, James

1995-01-01

Laboratory studies examine phase changes of hygroscopic substances which occur as aerosol in stratosphere and troposphere (sodium chloride, ammonium sulfate, ammonium bisulfate, nitric acid, sulfuric acid), under controlled conditions, in samples volume 1 to 10(exp -4) ml. Crystallization of salts from supersaturated solutions is examined by slowly evaporating a solution drop on a substrate, under controlled relative humidity, until self nucleation occurs; controlled nucleation of ice in a mm capillary U-tube gives a measured ice crystallization velocity at known supercooling. Two states of crystallization occur for regions where hydrates exist. It is inferred that all of the materials readily exist as supersaturated/supercooled solutions; the degree of metastability appears to be slightly enhanced by inclusion of aircraft produced soot. The crystallization velocity is taken as a measure of viscosity. Results suggest an approach to a glass transition at high molality, supersaturation and/or supercooling within the range of atmospheric interest. It is hypothesized that surface reactions occur more readily on solidified particles - either crystalline or glass, whereas volume reactions are more important on droplets with sufficiently low viscosity and volume diffusivity. Implications are examined for optical properties of such particles in the atmosphere. In a separate experiment, crystal growth was examined in a modified thermal vapor diffusion chamber over the range of cirrus temperature (-30 to -70 C) and under controlled supersaturation and air pressure. The crystals grew at a velocity of 1-2 microns/s, thickness 60-70 micron, in the form of thin column crystals. Design criteria are given for a system to investigate particle growth down to -100 C, (PSC temperatures) where nitric acid particles can be grown under similar control and in the form of hydrate crystals.

The effects of snow and salt on ice table stability in University Valley, Antarctica

USGS Publications Warehouse

Williams, Kaj; Heldmann, Jennifer L.; McKay, Christopher P.; Mellon, Michael T.

2018-01-01

The Antarctic Dry Valleys represent a unique environment where it is possible to study dry permafrost overlaying an ice-rich permafrost. In this paper, two opposing mechanisms for ice table stability in University Valley are addressed: i) diffusive recharge via thin seasonal snow deposits and ii) desiccation via salt deposits in the upper soil column. A high-resolution time-marching soil and snow model was constructed and applied to University Valley, driven by meteorological station atmospheric measurements. It was found that periodic thin surficial snow deposits (observed in University Valley) are capable of drastically slowing (if not completely eliminating) the underlying ice table ablation. The effects of NaCl, CaCl2 and perchlorate deposits were then modelled. Unlike the snow cover, however, the presence of salt in the soil surface (but no periodic snow) results in a slight increase in the ice table recession rate, due to the hygroscopic effects of salt sequestering vapour from the ice table below. Near-surface pore ice frequently forms when large amounts of salt are present in the soil due to the suppression of the saturation vapour pressure. Implications for Mars high latitudes are discussed.

Experimental and computational study of the effect of breath-actuated mechanism built in the NEXThaler® dry powder inhaler.

PubMed

Farkas, Árpád; Lewis, David; Church, Tanya; Tweedie, Alan; Mason, Francesca; Haddrell, Allen E; Reid, Jonathan P; Horváth, Alpár; Balásházy, Imre

2017-11-25

The breath-actuated mechanism (BAM) is a mechanical unit included in NEXThaler ® with the role of delaying the emission of the drug until the inhalation flow rate of the patient is sufficiently high to detach the drug particles from their carriers. The main objective of this work was to analyse the effect of the presence of BAM on the size distribution of the emitted drug and its airway deposition efficiency and distribution. Study of the hygroscopic growth of the emitted drug particles and its effect on the deposition was another goal of this study. Size distributions of Foster ® NEXThaler ® drug particles emitted by dry powder inhalers with and without BAM have been measured by a Next Generation Impactor. Three characteristic inhalation profiles of asthmatic patients (low, moderate and high flow rates) were used for both experimental and modelling purposes. Particle hygroscopic growth was determined by a new method, where experimental measurements are combined with simulations. Upper airway and lung deposition fractions were computed assuming 5s and 10s breath-hold times. By the inclusion of BAM the fine particle fraction of the steroid component increased from 24 to 30% to 47-51%, while that of bronchodilator from 25-34% to 52-55%. The predicted upper airway steroid and bronchodilator doses decreased from about 60% to 35-40% due to BAM. At the same time, predicted lung doses increased from about 20%-35% (steroid) and from 22% to 38% (bronchodilator) for the moderate flow profile and from about 25% to 40% (steroid) and from 29% to 47% (bronchodilator) for the high inhalation flow profile. Although BDP and FF upper airway doses decreased by a factor of about two when BAM was present, lung doses of both components were about the same in the BAM and no-BAM configurations at the weakest flow profile. However, lung dose increased by 2-3% even for this profile when hygroscopic growth was taken into account. In conclusion, the NEXThaler ® BAM mechanism is a unique feature enabling high emitted fine particle fraction and enhanced drug delivery to the lungs. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Processing of aerosol particles within the Habshan pollution plume

NASA Astrophysics Data System (ADS)

Semeniuk, T. A.; Bruintjes, R.; Salazar, V.; Breed, D.; Jensen, T.; Buseck, P. R.

2015-03-01

The Habshan industrial site in the United Arab Emirates produces a regional-scale pollution plume associated with oil and gas processing, discharging high loadings of sulfates and chlorides into the atmosphere, which interact with the ambient aerosol population. Aerosol particles and trace gas chemistry at this site were studied on two flights in the summer of 2002. Measurements were collected along vertical plume profiles to show changes associated with atmospheric processing of particle and gas components. Close to the outlet stack, particle concentrations were over 10,000 cm-3, dropping to <2000 cm-3 in more dilute plume around 1500 m above the stack. Particles collected close to the stack and within the dilute plume were individually measured for size, morphology, composition, and mixing state using transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy. Close to the stack, most coarse particles consisted of mineral dust and NaCl crystals from burning oil brines, while sulfate droplets dominated the fine mode. In more dilute plume, at least 1500 m above the stack, the particle spectrum was more diverse, with a significant increase in internally mixed particle types. Dilute plume samples consisted of coarse NaCl/silicate aggregates or NaCl-rich droplets, often with a sulfate component, while fine-fraction particles were of mixed cation sulfates, also internally mixed with nanospherical soot or silicates. Thus, both chloride and sulfate components of the pollution plume rapidly reacted with ambient mineral dust to form coated and aggregate particles, enhancing particle size, hygroscopicity, and reactivity of the coarse mode. The fine-fraction sulfate-bearing particles formed in the plume contribute to regional transport of sulfates, while coarse sulfate-bearing fractions locally reduced the SO2 loading through sedimentation. The chloride- and sulfate-bearing internally mixed particles formed in the plume markedly changed the reflectivity and scattering properties of the ambient aerosol population, as well as its hygroscopic and ice nucleation properties.

A new method for calculating number concentrations of cloud condensation nuclei based on measurements of a three-wavelength humidified nephelometer system

NASA Astrophysics Data System (ADS)

Tao, Jiangchuan; Zhao, Chunsheng; Kuang, Ye; Zhao, Gang; Shen, Chuanyang; Yu, Yingli; Bian, Yuxuan; Xu, Wanyun

2018-02-01

The number concentration of cloud condensation nuclei (CCN) plays a fundamental role in cloud physics. Instrumentations of direct measurements of CCN number concentration (NCCN) based on chamber technology are complex and costly; thus a simple way for measuring NCCN is needed. In this study, a new method for NCCN calculation based on measurements of a three-wavelength humidified nephelometer system is proposed. A three-wavelength humidified nephelometer system can measure the aerosol light-scattering coefficient (σsp) at three wavelengths and the light-scattering enhancement factor (fRH). The Ångström exponent (Å) inferred from σsp at three wavelengths provides information on mean predominate aerosol size, and hygroscopicity parameter (κ) can be calculated from the combination of fRH and Å. Given this, a lookup table that includes σsp, κ and Å is established to predict NCCN. Due to the precondition for the application, this new method is not suitable for externally mixed particles, large particles (e.g., dust and sea salt) or fresh aerosol particles. This method is validated with direct measurements of NCCN using a CCN counter on the North China Plain. Results show that relative deviations between calculated NCCN and measured NCCN are within 30 % and confirm the robustness of this method. This method enables simplerNCCN measurements because the humidified nephelometer system is easily operated and stable. Compared with the method using a CCN counter, another advantage of this newly proposed method is that it can obtain NCCN at lower supersaturations in the ambient atmosphere.

How much surface coating of hydrophobic azithromycin is sufficient to prevent moisture-induced decrease in aerosolisation of hygroscopic colistin powder?

PubMed Central

Zhou, Qi (Tony); Loh, Zhi Hui; Yu, Jiaqi; Sun, Si-ping; Gengenbach, Thomas; Denman, John A.; Li, Jian; Chan, Hak-Kim

2017-01-01

Aerosolisation performance of hygroscopic particles of colistin could be compromised at elevated humidity due to increased capillary forces. Co-spray drying colistin with a hydrophobic drug is known to provide a protective coating on the composite particle surfaces against moisture-induced reduction in aerosolisation performance; however, the effects of component ratio on surface coating quality and powder aerosolisation at elevated relative humidities are unknown. In this study, we have systematically examined the effects of mass ratio of hydrophobic azithromycin on surface coating quality and aerosolisation performance of the co-spray dried composite particles. Four combination formulations with varying drug ratios were prepared by co-spray drying drug solutions. Both of the drugs in each combination formulation had similar in vitro deposition profiles, suggesting that each composite particle comprise two drugs in the designed mass ratio, which is supported by XPS and ToF-SIMS data. XPS and ToF-SIMS measurements also revealed that 50 % by weight (or 35 % by molecular fraction) of azithromycin in the formulation provided a near-complete coating of 96.5 % (molar fraction) on the composite particle surface, which is sufficient to prevent moisture-induced reduction in FPFrecovered and FPFemitted. Higher azithromycin content did not increase coating coverage, while contents of azithromycin lower than 20 %w/w did not totally prevent the negative effects of humidity on aerosolisation performance. This study has highlighted that a critical amount of azithromycin is required to sufficiently coat the colistin particles for short-term protection against moisture. PMID:27255350

Increased resistance of hygroscopic condenser humidifiers when using a closed circuit suction system.

PubMed

Martinez, F J; Pietchel, S; Wise, C; Walek, J; Beamis, J F

1994-10-01

To examine a hygroscopic condenser after clinical use and to describe the interaction of a hygroscopic condenser and a closed circuit suction system used simultaneously. Prospective evaluation of hygroscopic condensers used clinically, and laboratory investigation of a hygroscopic condenser used with a closed circuit suction system. Tertiary referral centers. The hygroscopic condenser used during mechanical ventilation was removed and peak inflation pressure was measured by delivering a standard tidal volume and inspiratory flow across the isolated hygroscopic condenser while recording the peak inflation pressure. In the laboratory, four 10-mL aliquots of saline were instilled via closed circuit suction system into a test lung with fresh hygroscopic condensers (n = 15) inline. At baseline and after each instillation, the hygroscopic condenser was weighed and the peak inflation pressure was measured while in five condensers, peak expiratory flow rate was also measured. In these five devices, hygroscopic condenser resistance was measured with 100 L/min of constant gas flow while measuring the pressure drop across the hygroscopic condenser. In 11 hygroscopic condensers used for 27.5 +/- 11.9 hrs with no closed circuit suction system, the peak inflation pressure was 3.74 +/- 0.58 cm H2O. In the laboratory, instillation of saline via closed circuit suction system was associated with an increase in hygroscopic condenser weight. Peak inflation pressure increased in a quadratic fashion with the increase in hygroscopic condenser weight, while peak expiratory flow rate decreased in a linear fashion. After four saline instillations, hygroscopic condenser resistance increased from 5.66 +/- 0.31 to 13.9 +/- 2.42 cm H2O/L/sec. Clinical use of a hygroscopic condenser alone is not associated with a significant increase in peak inflation pressure. We caution the use of a hygroscopic condenser and a closed circuit suction system simultaneously, as an increase in hygroscopic condenser resistance may develop and may be poorly tolerated in patients with marginal ventilatory reserve.

Salt Efflorescence Effects on Soil Surface Erodibility and Dust Emissions

NASA Astrophysics Data System (ADS)

Van Pelt, R. S.; Zhang, G.

2017-12-01

Soluble salts resulting from weathering of geological materials often form surface crusts or efflorescences in areas with shallow saline groundwater. In many cases, the affected areas are susceptible to wind erosion due to their lack of protective vegetation and their flat topography. Fugitive dusts containing soluble salts affect the biogeochemistry of deposition regions and may result in respiratory irritation during transport. We created efflorescent crusts on soil trays by surface evaporation of single salt solutions and bombarded the resultant efflorescences with quartz abrader sand in a laboratory wind tunnel. Four replicate trays containing a Torrifluvent soil affected by one of nine salts commonly found in arid and semiarid streams were tested and the emissions were captured by an aspirated multi-stage deposition and filtering system. We found that in most cases the efflorescent crust reduced the soil surface erodibility but also resulted in the emission of salt rich dust. Two of the salts, sodium thiosulfate and calcium chloride, resulted in increased soil volume and erodibility. However, one of the calcium chloride replicates was tested after an outbreak of humid air caused hygroscopic wetting of the soil and it became indurated upon drying greatly decreasing the erodibility. Although saline affected soils are not used for agricultural production and degradation is not a great concern, the release of salt rich dust is an area of environmental concern and steps to control the dust emissions from affected soils should be developed. Future testing will utilize suites of salts found in streams of arid and semiarid regions.

The Influence of Aerosol Hygroscopicity on Retrieving the Aerosol Extincting Coefficient from MPL Data

NASA Astrophysics Data System (ADS)

Zhao, G.; Zhao, C.

2016-12-01

Micro-pulse Lidar (MPL) measurements have been widely used to profile the ambient aerosol extincting coefficient(). Lidar Ratio (LR) ,which highly depends on the particle number size distribution (PNSD) and aerosol hygroscopicity, is the most important factor to retrieve the profile. A constant AOD constrained LR is usually used in current algorithms, which would lead to large bias when the relative humidity (RH) in the mixed layer is high. In this research, the influences of PNSD, aerosol hygroscopicity and RH profiles on the vertical variation of LR were investigated based on the datasets from field measurements in the North China Plain (NCP). Results show that LR can have an enhancement factor of more than 120% when the RH reaches to 92%. A new algorithm of retrieving the profile is proposed based on the variation of LR due to aerosol hygroscopicity. The magnitude and vertical structures of retrieved using this method can be significantly different to that of the fiexed LR method. The relative difference can reach up to 40% when the RH in the mixed layer is higher than 90% . Sensitivity studies show that RH profile and PNSD affect most on the retrieved by fiexed LR method. In view of this, a scheme of LR enhancement factor by RH is proposed in the NCP. The relative differnce of the calculated between using this scheme and the new algorithm with the variable LR can be less than 10%.

Airborne cloud condensation nuclei measurements during the 2006 Texas Air Quality Study

NASA Astrophysics Data System (ADS)

Asa-Awuku, Akua; Moore, Richard H.; Nenes, Athanasios; Bahreini, Roya; Holloway, John S.; Brock, Charles A.; Middlebrook, Ann M.; Ryerson, Thomas B.; Jimenez, Jose L.; Decarlo, Peter F.; Hecobian, Arsineh; Weber, Rodney J.; Stickel, Robert; Tanner, Dave J.; Huey, Lewis G.

2011-06-01

Airborne measurements of aerosol and cloud condensation nuclei (CCN) were conducted aboard the National Oceanic and Atmospheric Administration WP-3D platform during the 2006 Texas Air Quality Study/Gulf of Mexico Atmospheric Composition and Climate Study (TexAQS/GoMACCS). The measurements were conducted in regions influenced by industrial and urban sources. Observations show significant local variability of CCN activity (CCN/CN from 0.1 to 0.5 at s = 0.43%), while variability is less significant across regional scales (˜100 km × 100 km; CCN/CN is ˜0.1 at s = 0.43%). CCN activity can increase with increasing plume age and oxygenated organic fraction. CCN measurements are compared to predictions for a number of mixing state and composition assumptions. Mixing state assumptions that assumed internally mixed aerosol predict CCN concentrations well. Assuming organics are as hygroscopic as ammonium sulfate consistently overpredicted CCN concentrations. On average, the water-soluble organic carbon (WSOC) fraction is 60 ± 14% of the organic aerosol. We show that CCN closure can be significantly improved by incorporating knowledge of the WSOC fraction with a prescribed organic hygroscopicity parameter (κ = 0.16 or effective κ ˜ 0.3). This implies that the hygroscopicity of organic mass is primarily a function of the WSOC fraction. The overall aerosol hygroscopicity parameter varies between 0.08 and 0.88. Furthermore, droplet activation kinetics are variable and 60% of particles are smaller than the size characteristic of rapid droplet growth.

Methanol Steam Reforming Promoted by Molten Salt-Modified Platinum on Alumina Catalysts

PubMed Central

Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

2014-01-01

We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the “solid catalyst with ionic liquid layer” (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass %. PMID:25124120

Efflorescence of Magnesium Perchlorate by Contact with Mineral Dust Particles

NASA Astrophysics Data System (ADS)

Ushijima, S.; Tolbert, M. A.; Gough, R. V.

2017-12-01

Liquid water was not uncommon on early Mars and it shaped geologic features on the surface that are still seen today. Due to the extremely cold and dry conditions of Mars currently, only water ice and water vapor have been observed and or detected. However, it has been suggested that liquid may form seasonally based on the observations of recurring slope lineae (RSL). The liquid may be a brine composed of hygroscopic salts such as perchlorates whose hydrated form has recently been detected in an RSL by the Mars Reconnaissance Orbiter. Through a process called deliquescence, the salts can absorb water from the surrounding environment and become a brine above a specific relative humidity (RH) known as the deliquescence relative humidity (DRH). The reverse process, recrystallization or efflorescence, often occurs at a much lower RH called the efflorescence relative humidity (ERH). The hysteresis effect caused by the distinctly different RH values allows for liquid brines to be metastable even under dry conditions. However, there is evidence that ERH can be raised when a mineral particle encounters the surface of the brine or it is immersed inside, effectively diminishing the metastability potential of liquid brines. If the brines are responsible for RSL formation, the brine will inevitably mix with the Martian soil. Thus, it is important to understand the effects that mineral particles can have on efflorescence. Here we use optical trapping to examine efflorescence of magnesium perchlorate in the presence of montmorillonite and halite. Studies on the efflorescence and deliquescence of magnesium perchlorate has shown that its brine could be stable in the subsurface of Mars during certain periods of time. Both montmorillonite and halite have been suggested to be a part of or similar to components of the Martian soil. Results at ambient conditions have shown that efflorescence of magnesium perchlorate is unaffected by the presence of either minerals. Whether the droplet of magnesium perchlorate was pure or exposed to halite or montmorillonite the ERH was near 13% RH at room temperature. Although not under Mars conditions, the results suggest that the stability of magnesium perchlorate brine could be unaffected by the surrounding mineral and could still possibly contribute to RSL formation.

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

NASA Astrophysics Data System (ADS)

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

2010-06-01

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

Study of the hygroscopic properties of selected pharmaceutical aerosols using single particle levitation.

PubMed

Peng, C; Chow, A H; Chan, C K

2000-09-01

To use a single particle levitation technique to investigate the equilibrium water sorption characteristics in both the evaporation and growth of four respiratory drugs at 37 degrees C: atropine sulfate (AS), isoproterenol hydrochloride (IPHC) and isoproterenol hemisulfate (IPHS) and disodium cromoglycate (DSCG). The equilibrium water content was measured as a function of relative humidity (RH) by a single particle levitation technique using an electrodynamic balance (EDB). The change of water content was determined by the voltage required to balance the weight of the levitated particle electrostatically. The water activities of bulk samples were also measured. Growth ratios were determined and compared with values in the literature. Crystallization or deliquescence was not observed for AS, IPHC and IPHS. The hysteresis in the water cycle was not observed for any of the drugs. At RH approximately 0%, AS particles still contain about 5% water but IPHC and IPHS particles do not contain any residual water. The aerodynamic growth ratio from RH 0% to 99.5% is 2.60, 2.86, 2.42 and 1.26 for AS, IPHC, IPHS and DSCG, respectively. Supersaturated droplets of IPHC and IPHS are expected to exist in the ambient conditions. DSCG is in a solid state in the RH range of 10-90%. It is expected that some aerosolized drugs of low solubility may experience supersaturation before they enter the human body and this could exert a significant influence both on particle loss before inhalation and on the deposition of the drugs in the lungs. The EDB is a convenient and reliable tool for studying the hygroscopic properties of pharmaceutical aerosols, especially for supersaturated solutions.

How Much Surface Coating of Hydrophobic Azithromycin Is Sufficient to Prevent Moisture-Induced Decrease in Aerosolisation of Hygroscopic Amorphous Colistin Powder?

PubMed

Zhou, Qi Tony; Loh, Zhi Hui; Yu, Jiaqi; Sun, Si-Ping; Gengenbach, Thomas; Denman, John A; Li, Jian; Chan, Hak-Kim

2016-09-01

Aerosolisation performance of hygroscopic particles of colistin could be compromised at elevated humidity due to increased capillary forces. Co-spray drying colistin with a hydrophobic drug is known to provide a protective coating on the composite particle surfaces against moisture-induced reduction in aerosolisation performance; however, the effects of component ratio on surface coating quality and powder aerosolisation at elevated relative humidities are unknown. In this study, we have systematically examined the effects of mass ratio of hydrophobic azithromycin on surface coating quality and aerosolisation performance of the co-spray dried composite particles. Four combination formulations with varying drug ratios were prepared by co-spray drying drug solutions. Both of the drugs in each combination formulation had similar in vitro deposition profiles, suggesting that each composite particle comprises two drugs in the designed mass ratio, which is supported by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) data. XPS and ToF-SIMS measurements also revealed that 50% by weight (or 35% by molecular fraction) of azithromycin in the formulation provided a near complete coating of 96.5% (molar fraction) on the composite particle surface, which is sufficient to prevent moisture-induced reduction in fine particle fraction (FPF)recovered and FPFemitted. Higher azithromycin content did not increase coating coverage, while contents of azithromycin lower than 20% w/w did not totally prevent the negative effects of humidity on aerosolisation performance. This study has highlighted that a critical amount of azithromycin is required to sufficiently coat the colistin particles for short-term protection against moisture.

Observation of nitrate coatings on atmospheric mineral dust particles

NASA Astrophysics Data System (ADS)

Li, W. J.; Shao, L. Y.

2009-03-01

Nitrate compounds have received much attention because of their ability to alter the hygroscopic properties and cloud condensation nuclei (CCN) activity of mineral dust particles in the atmosphere. However, very little is known about specific characteristics of ambient nitrate-coated mineral particles on an individual particle scale. In this study, sample collection was conducted during brown haze and dust episodes between 24 May and 21 June 2007 in Beijing, northern China. Sizes, morphologies, and compositions of 332 mineral dust particles together with their coatings were analyzed using transmission electron microscopy (TEM) coupled with energy-dispersive X-ray (EDX) microanalyses. Structures of some mineral particles were verified using selected-area electron diffraction (SAED). TEM observation indicates that approximately 90% of the collected mineral particles are covered by visible coatings in haze samples whereas only 5% are coated in the dust sample. 92% of the analyzed mineral particles are covered with Ca-, Mg-, and Na-rich coatings, and 8% are associated with K- and S-rich coatings. The majority of coatings contain Ca, Mg, O, and N with minor amounts of S and Cl, suggesting that they are possibly nitrates mixed with small amounts of sulfates and chlorides. These nitrate coatings are strongly correlated with the presence of alkaline mineral components (e.g., calcite and dolomite). CaSO4 particles with diameters from 10 to 500 nm were also detected in the coatings including Ca(NO3)2 and Mg(NO3)2. Our results indicate that mineral particles in brown haze episodes were involved in atmospheric heterogeneous reactions with two or more acidic gases (e.g., SO2, NO2, HCl, and HNO3). Mineral particles that acquire hygroscopic nitrate coatings tend to be more spherical and larger, enhancing their light scattering and CCN activity, both of which have cooling effects on the climate.

Characterization of Ambient Black Carbon Aerosols

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Demonstration of Aerosol Property Profiling by Multi-wavelength Lidar Under Varying Relative Humidity Conditions

NASA Technical Reports Server (NTRS)

Whiteman, D.N.; Veselovskii, I.; Kolgotin, A.; Korenskii, M.; Andrews, E.

2008-01-01

The feasibility of using a multi-wavelength Mie-Raman lidar based on a tripled Nd:YAG laser for profiling aerosol physical parameters in the planetary boundary layer (PBL) under varying conditions of relative humidity (RH) is studied. The lidar quantifies three aerosol backscattering and two extinction coefficients and from these optical data the particle parameters such as concentration, size and complex refractive index are retrieved through inversion with regularization. The column-integrated, lidar-derived parameters are compared with results from the AERONET sun photometer. The lidar and sun photometer agree well in the characterization of the fine mode parameters, however the lidar shows less sensitivity to coarse mode. The lidar results reveal a strong dependence of particle properties on RH. The height regions with enhanced RH are characterized by an increase of backscattering and extinction coefficient and a decrease in the Angstrom exponent coinciding with an increase in the particle size. We present data selection techniques useful for selecting cases that can support the calculation of hygroscopic growth parameters using lidar. Hygroscopic growth factors calculated using these techniques agree with expectations despite the lack of co-located radiosonde data. Despite this limitation, the results demonstrate the potential of multi-wavelength Raman lidar technique for study of aerosol humidification process.

Process for making silver metal filaments

DOEpatents

Bamberger, Carlos E.

1997-01-01

A process for making silver metal particles from silver salt particles having the same morphology. Precursor silver salt particles selected from the group consisting of silver acetate and silver sulfide having a selected morphology are contained in a reactor vessel having means for supporting the particles in an air suspension to prevent the agglomeration of the particles. Air is flowed through the reactor vessel at a flow rate sufficient to suspend the particles in the reactor vessel. The suspended precursor silver salt particles are heated to a processing temperature and at a heating rate below which the physical deterioration of the suspended precursor silver salt particles takes place. The suspended precursor silver salt particles are maintained at the processing temperature for a period of time sufficient to convert the particles into silver metal particles having the same morphology as the precursor silver salt particles.

Visibility in the Netherlands during New Year's fireworks: The role of soot and salty aerosol products

NASA Astrophysics Data System (ADS)

ten Brink, Harry; Henzing, Bas; Otjes, René; Weijers, Ernie

2018-01-01

The visibility on New Year's nights in the Netherlands is low during stagnant weather. This is due to the scattering and absorption of light by the aerosol-smoke from the fireworks. We made an assessment of the responsible aerosol-species. The investigation took place during the New Year's night of 2009. Measurements were made at a regional site in the centre of the country away from specific local sources. An Integrating Nephelometer measured the light-scattering by the inherent compounds after removal of water from the aerosol by drying the air. The actual light-scattering was determined in an open-air scatterometer; it was a factor of five higher than the ;dry; value. The difference in actual and ;dry; light-scattering can only be explained by water-uptake of the salty hygroscopic components of the aerosol. This hypothesis is substantiated by measurements of the composition of the aerosol. The size-dependent concentrations of the salty ionic species were determined on-line with a MARGA-;sizer;. These components were for a large part in particles in the size range that most effectively scatter light. The ;dry; light-scattering was exerted by the inorganic salt components and the sooty carbonaceous material alike. However, the salty products from the fireworks are hygroscopic and take up water at the high relative humidities occurring that night. This explains the fivefold larger light-scattering by the wet ambient aerosol as compared to that by the dry aerosol in the integrating nephelometer. The visibility, which is the inverse of the open-air scattering, is thus indirectly governed by the salty products of the fireworks due to their uptake of water. Under stagnant weather conditions during New Year's nights in the Netherlands both the aerosol concentrations and the relative humidity are high; this implies that the ionic species govern the low visibilities in general, be it via their uptake of water.

Chemical composition and characteristics of ambient aerosols and rainwater residues during Indian summer monsoon: Insight from aerosol mass spectrometry

NASA Astrophysics Data System (ADS)

Chakraborty, Abhishek; Gupta, Tarun; Tripathi, Sachchida N.

2016-07-01

Real time composition of non-refractory submicron aerosol (NR-PM1) is measured via Aerosol mass spectrometer (AMS) for the first time during Indian summer monsoon at Kanpur, a polluted urban location located at the heart of Indo Gangetic Plain (IGP). Submicron aerosols are found to be dominated by organics followed by nitrate. Source apportionment of organic aerosols (OA) via positive matrix factorization (PMF) revealed several types of secondary/oxidized and primary organic aerosols. On average, OA are completely dominated by oxidized OA with a very little contribution from biomass burning OA. During rain events, PM1 concentration is decreased almost by 60%, but its composition remains nearly the same. Oxidized OA showed slightly more decrease than primary OAs, probably due to their higher hygroscopicity. The presence of organo nitrates (ON) is also detected in ambient aerosols. Apart from real-time sampling, collected fog and rainwater samples were also analyzed via AMS in offline mode and in the ICP-OES (Inductively coupled plasma - Optical emission spectrometry) for elements. The presence of sea salt, organo nitrates and sulfates has been observed. Rainwater residues are also dominated by organics but their O/C ratios are 15-20% lower than the observed values for ambient OA. Alkali metals such as Ca, Na, K are found to be most abundant in the rainwater followed by Zn. Rainwater residues are also found to be much less oxidized than the aerosols present inside the fog water, indicating presence of less oxidized organics. These findings indicate that rain can act as an effective scavenger of different types of pollutants even for submicron particle range. Rainwater residues also contain organo sulfates which indicate that some portion of the dissolved aerosols has undergone aqueous processing, possibly inside the cloud. Highly oxidized and possibly hygroscopic OA during monsoon period compared to other seasons (winter, post monsoon), indicates that they can act more efficiently as cloud condensation nuclei.

Impact of organic coating on growth of ammonium sulfate particles: light extinction measurements relevant for the direct effect

NASA Astrophysics Data System (ADS)

Robinson, C. B.; Zarzana, K. J.; Hasenkopf, C. A.; Tolbert, M. A.

2012-12-01

Light extinction by particles is strongly dependent on chemical composition, particle size, and water uptake. Relative humidity affects extinction by causing changes in refractive index and particle size due to hygroscopic growth. The ability of particles to take up water depends on their composition and structure. In both laboratory and field studies, inorganic salts completely covered by an organic coating have been observed. The impact of this coating on water uptake is uncertain, and a systematic study that examines water uptake as a function of relative humidity is highly desirable. These data are critical to evaluate the aerosol direct effect on climate, which is one of the most uncertain aspects of future climate change. In this study, we probe the connection between aerosol composition, size and light extinction directly by measuring fRHext, the ratio of the extinction coefficient for humidified particles to the extinction coefficient for dry particles. Particles were composed of 1,2,6-hexanetriol and ammonium sulfate, a system that forms organic coatings around the inorganic core. A cavity ring-down aerosol extinction spectrometer at 532 nm is used to measure the optical growth factor as a function of relative humidity. The fRHext values for a range of %RH for pure ammonium sulfate, pure 1,2,6-hexanetriol, and ammonium sulfate particles with 1,2,6-hexanetriol coatings were measured. The coated particles are created using a method of liquid-liquid separation, where the particles are exposed to water vapor creating a RH% above their deliquescence RH%. The particles are then dried with a Nafion dryer to a RH% that is below the point where liquid-liquid phase separation is observed, but above the efflorescence RH%. Pure 1,2,6-hexanetriol takes up little water over the observed RH range of 45-65%, and therefore fRHext ~ 1. With pure ammonium sulfate for the same RH% range, the fRHext varied from 1.5 - 2, depending on the RH% and the particle size. For the coated particles, at each RH%, the fRHext values fall between those for pure ammonium sulfate and pure 1,2,6-hexanetriol values. This suggests that the organic coating does not prevent water uptake by the ammonium sulfate cores.

The Influence of Aerosol Hygroscopicity on Precipitation Intensity During a Mesoscale Convective Event

NASA Astrophysics Data System (ADS)

Kawecki, Stacey; Steiner, Allison L.

2018-01-01

We examine how aerosol composition affects precipitation intensity using the Weather and Research Forecasting Model with Chemistry (version 3.6). By changing the prescribed default hygroscopicity values to updated values from laboratory studies, we test model assumptions about individual component hygroscopicity values of ammonium, sulfate, nitrate, and organic species. We compare a baseline simulation (BASE, using default hygroscopicity values) with four sensitivity simulations (SULF, increasing the sulfate hygroscopicity; ORG, decreasing organic hygroscopicity; SWITCH, using a concentration-dependent hygroscopicity value for ammonium; and ALL, including all three changes) to understand the role of aerosol composition on precipitation during a mesoscale convective system (MCS). Overall, the hygroscopicity changes influence the spatial patterns of precipitation and the intensity. Focusing on the maximum precipitation in the model domain downwind of an urban area, we find that changing the individual component hygroscopicities leads to bulk hygroscopicity changes, especially in the ORG simulation. Reducing bulk hygroscopicity (e.g., ORG simulation) initially causes fewer activated drops, weakened updrafts in the midtroposphere, and increased precipitation from larger hydrometeors. Increasing bulk hygroscopicity (e.g., SULF simulation) simulates more numerous and smaller cloud drops and increases precipitation. In the ALL simulation, a stronger cold pool and downdrafts lead to precipitation suppression later in the MCS evolution. In this downwind region, the combined changes in hygroscopicity (ALL) reduces the overprediction of intense events (>70 mm d-1) and better captures the range of moderate intensity (30-60 mm d-1) events. The results of this single MCS analysis suggest that aerosol composition can play an important role in simulating high-intensity precipitation events.

The Influence of topography on formation characteristics of hygroscopic and condensate water in Shapotou

NASA Astrophysics Data System (ADS)

Pan, Yanxia; Li, Xinrong; Hui, Rong; Zhao, Yang

2016-04-01

The formation characteristics of hygroscopic and condensate water for different topographic positions were observed using the PVC pipes manual weighing and CPM method in the typical mobile dunes fixed by straw checkerboard barriers in Shapotou. The results indicated that the formation amounts and duration of hygroscopic and condensate water show moderate spatial heterogeneity at the influence of topography. The formation amounts of hygroscopic and condensate water at different aspects conform to the classical convection model, in which the hygroscopic and condensate water amounts are highest at hollow, and windward aspect gets more water than leeward aspect, the hygroscopic and condensate water amounts at different aspects are expressed as: hollow>Western-faced aspect>Northern-faced aspect>hilltop>Southern-faced aspect>Eastern-faced aspect. The hygroscopic and condensate water amounts at different slope positions for every aspect are as follows: the foot of slope>middle slope>hilltop. A negatively linear correlation is got between slope angles and hygroscopic and condensate water amounts, hygroscopic and condensate water amounts decrease gradually along with the increase of slope angles, the amounts of hygroscopic and condensate water at the vertical aspect are only half of horizontal aspect, which indicated topography were important influence factors for the formation of the hygroscopic and condensate water in arid area.

Microplastic Pollution in Table Salts from China.

PubMed

Yang, Dongqi; Shi, Huahong; Li, Lan; Li, Jiana; Jabeen, Khalida; Kolandhasamy, Prabhu

2015-11-17

Microplastics have been found in seas all over the world. We hypothesize that sea salts might contain microplastics, because they are directly supplied by seawater. To test our hypothesis, we collected 15 brands of sea salts, lake salts, and rock/well salts from supermarkets throughout China. The microplastics content was 550-681 particles/kg in sea salts, 43-364 particles/kg in lake salts, and 7-204 particles/kg in rock/well salts. In sea salts, fragments and fibers were the prevalent types of particles compared with pellets and sheets. Microplastics measuring less than 200 μm represented the majority of the particles, accounting for 55% of the total microplastics, and the most common microplastics were polyethylene terephthalate, followed by polyethylene and cellophane in sea salts. The abundance of microplastics in sea salts was significantly higher than that in lake salts and rock/well salts. This result indicates that sea products, such as sea salts, are contaminated by microplastics. To the best of our knowledge, this is the first report on microplastic pollution in abiotic sea products.

Aerosol properties associated with air masses arriving into the North East Atlantic during the 2008 Mace Head EUCAARI intensive observing period: an overview

NASA Astrophysics Data System (ADS)

Dall'Osto, M.; Ceburnis, D.; Martucci, G.; Bialek, J.; Dupuy, R.; Jennings, S. G.; Berresheim, H.; Wenger, J. C.; Sodeau, J. R.; Healy, R. M.; Facchini, M. C.; Rinaldi, M.; Giulianelli, L.; Finessi, E.; Worsnop, D.; O'Dowd, C. D.

2009-12-01

As part of the EUCAARI Intensive Observing Period, a 4-week campaign to measure aerosol physical, chemical and optical properties, atmospheric structure, and cloud microphysics was conducted from mid-May to mid-June 2008 at the Mace Head Atmospheric Research Station, located at the interface of Western Europe and the NE Atlantic and centered on the west Irish coastline. During the campaign, continental air masses comprising both young and aged continental plumes were encountered, along with polar, Arctic and tropical air masses. Polluted-continental aerosol concentrations were of the order of 3000 cm-3, while background marine air aerosol concentrations were between 400-600 cm-3. The highest marine air concentrations occurred in polar air masses in which a 15 nm nucleation mode, with concentration of 1100 cm-3, was observed and attributed to open ocean particle formation. Black carbon concentrations in polluted air were between 300-400 ng m-3, and in clean marine air were less than 50 ng m-3. Continental air submicron chemical composition (excluding refractory sea salt) was dominated by organic matter, closely followed by sulphate mass. Although the concentrations and size distribution spectral shape were almost identical for the young and aged continental cases, hygroscopic growth factors (GF) and cloud condensation nuclei (CCN) to total condensation nuclei (CN) concentration ratios were significantly less in the younger pollution plume, indicating a more oxidized organic component to the aged continental plume. The difference in chemical composition and hygroscopic growth factor appear to result in a 40-50% impact on aerosol scattering coefficients and Aerosol Optical Depth, despite almost identical aerosol microphysical properties in both cases, with the higher values been recorded for the more aged case. For the CCN/CN ratio, the highest ratios were seen in the more age plume. In marine air, sulphate mass dominated the sub-micron component, followed by water soluble organic carbon, which, in turn, was dominated by methanesulphonic acid (MSA). Sulphate concentrations were highest in marine tropical air - even higher than in continental air. MSA was present at twice the concentrations of previously-reported concentrations at the same location and the same season. Both continental and marine air exhibited aerosol GFs significantly less than ammonium sulphate and even less in terms of sea salt aerosol pointing to a significant organic contribution to all air mass aerosol properties.

Novel perchlorate and phosphate salts of vinpocetine: Characterization, relative solid-state stability evaluation and Hirshfeld surface analysis

NASA Astrophysics Data System (ADS)

Ma, Yu-heng; Ge, Shu-wang; Wang, Wei; Zheng, Qiang; Zuo, Yun-wei; Zhong, Chang-jiang; Sun, Bai-wang

2016-02-01

Salt formation is a very common and effective method of improving a drug's physicochemical properties such as hygroscopicity and physical stability at different humidity conditions. Aqueous solubility is another important parameter that can be improved by salt formation; however this strategy has not yet been evaluated for the important alkaloid drug, Vinpocetine. A poorly water-soluble basic drug (water solubility value≈ 5 μg/ml and pKa value of 7.31), vinpocetine was converted into two novel salts in this work, with perchloric acid and phosphoric acid in a 1: 1 M ratio. However, an unexpected phase transformation occurred in one of the salts after the stability test, which is a major concern in studies on dosage form. The conversion of the salt to free base could be related to the temperature-humidity profile of the type II salt (formed by vinpocetine and phosphoric acid). When the temperature was more than 70 °C under high humidity conditions of more than 80%, the phase transformation occurred immediately. To gain further understanding of this phenomenon, single crystals of the two novel salts were prepared and characterized by single crystal X-ray diffraction, Powder-XRD, infrared spectroscopy, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Constituents of the crystalline phase were also investigated in terms of Hirshfeld surface. The structures were found to be stabilized by H⋯H, C-H⋯O, O-H⋯N and C-H⋯π intermolecular interactions. Our stability studies showed that both these two novel salts could improve the stability of vinpocetine, however the type I salt (formed by vinpocetine and perchloric acid) offers more advantages. This finding will provide valuable information for vinpocetine dosage form development.

Synthesis of palm-based polyurethane-LiClO{sub 4} via prepolymerization

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

Sien, Jason Wong Chee; School of Biosciences, Taylor’s University, Subang Jaya; Badri, Khairiah Haji

2015-09-25

Palm-based polyurethane (pPU) with varying lithium salt (LiClO{sub 4}) content was synthesized. Higher loading percentage of LiClO{sub 4} in the pPU led to the inhibition of prepolymerization process from taking place. Hydrogen bonded C=O was detected in the FTIR spectrum indicating the hydrogen bonding between the urethane bonds. Ordered complexed C=O was observed in the FTIR spectrum confirming the complex formation between urethane bond and Li{sup +} ion. DSC thermogram showed the increase in the LiClO{sub 4} content could increase the glass transition temperature. SEM micrographs exhibited that more bubbles were formed when the LiClO{sub 4} increased from 10 tomore » 30wt% indicating the reaction between free isocyanate groups with moisture presence in the salt due to the hygroscopic properties of LiClO{sub 4}.« less

Hydrophobic Organic Hole Transporters for Improved Moisture Resistance in Metal Halide Perovskite Solar Cells.

PubMed

Leijtens, Tomas; Giovenzana, Tommaso; Habisreutinger, Severin N; Tinkham, Jonathan S; Noel, Nakita K; Kamino, Brett A; Sadoughi, Golnaz; Sellinger, Alan; Snaith, Henry J

2016-03-09

Solar cells based on organic-inorganic perovskite semiconductor materials have recently made rapid improvements in performance, with the best cells performing at over 20% efficiency. With such rapid progress, questions such as cost and solar cell stability are becoming increasingly important to address if this new technology is to reach commercial deployment. The moisture sensitivity of commonly used organic-inorganic metal halide perovskites has especially raised concerns. Here, we demonstrate that the hygroscopic lithium salt commonly used as a dopant for the hole transport material in perovskite solar cells makes the top layer of the devices hydrophilic and causes the solar cells to rapidly degrade in the presence of moisture. By using novel, low cost, and hydrophobic hole transporters in conjunction with a doping method incorporating a preoxidized salt of the respective hole transporters, we are able to prepare efficient perovskite solar cells with greatly enhanced water resistance.

Methanol steam reforming promoted by molten salt-modified platinum on alumina catalysts.

PubMed

Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

2014-09-01

We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the "solid catalyst with ionic liquid layer" (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laboratory-generated mixtures of mineral dust particles with biological substances: characterization of the particle mixing state and immersion freezing behavior

NASA Astrophysics Data System (ADS)

Augustin-Bauditz, Stefanie; Wex, Heike; Denjean, Cyrielle; Hartmann, Susan; Schneider, Johannes; Schmidt, Susann; Ebert, Martin; Stratmann, Frank

2016-05-01

Biological particles such as bacteria, fungal spores or pollen are known to be efficient ice nucleating particles. Their ability to nucleate ice is due to ice nucleation active macromolecules (INMs). It has been suggested that these INMs maintain their nucleating ability even when they are separated from their original carriers. This opens the possibility of an accumulation of such INMs in soils, resulting in an internal mixture of mineral dust and INMs. If particles from such soils which contain biological INMs are then dispersed into the atmosphere due to wind erosion or agricultural processes, they could induce ice nucleation at temperatures typical for biological substances, i.e., above -20 up to almost 0 °C, while they might be characterized as mineral dust particles due to a possibly low content of biological material. We conducted a study within the research unit INUIT (Ice Nucleation research UnIT), where we investigated the ice nucleation behavior of mineral dust particles internally mixed with INM. Specifically, we mixed a pure mineral dust sample (illite-NX) with ice active biological material (birch pollen washing water) and quantified the immersion freezing behavior of the resulting particles utilizing the Leipzig Aerosol Cloud Interaction Simulator (LACIS). A very important topic concerning the investigations presented here as well as for atmospheric application is the characterization of the mixing state of aerosol particles. In the present study we used different methods like single-particle aerosol mass spectrometry, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray analysis (EDX), and a Volatility-Hygroscopicity Tandem Differential Mobility Analyser (VH-TDMA) to investigate the mixing state of our generated aerosol. Not all applied methods performed similarly well in detecting small amounts of biological material on the mineral dust particles. Measuring the hygroscopicity/volatility of the mixed particles with the VH-TDMA was the most sensitive method. We found that internally mixed particles, containing ice active biological material, follow the ice nucleation behavior observed for the pure biological particles. We verified this by modeling the freezing behavior of the mixed particles with the Soccerball model (SBM). It can be concluded that a single INM located on a mineral dust particle determines the freezing behavior of that particle with the result that freezing occurs at temperatures at which pure mineral dust particles are not yet ice active.

Glass formation and unusual hygroscopic growth of iodic acid solution droplets with relevance for iodine oxide particles in the coastal marine boundary layer

NASA Astrophysics Data System (ADS)

Murray, B. J.; Haddrell, A. E.; Peppe, S.; Davies, J. F.; Reid, J. P.; O'Sullivan, D.; Price, H. C.; Kumar, R.; Saunders, R. W.; Plane, J. M. C.; Umo, N. S.; Wilson, T. W.

2012-03-01

Iodine oxide particles are known to nucleate in the marine boundary layer where gas phase molecular iodine and organoiodine species are produced by macroalgae. There has been some debate over the chemical identity of these particles. Hygroscopic measurements have been used to infer that they are composed of insoluble I2O4, while elemental analysis of laboratory generated particles suggests soluble I2O5 or its hydrated form iodic acid, HIO3 (I2O5 · H2O). In this paper we explore the response of super-micron sized aqueous iodic acid solution droplets to varying humidity using both Raman microscopy and single particle electrodynamic traps. These measurements reveal that the propensity of an iodic acid solution droplet to crystallise is negligible on drying to ~0% relative humidity (RH). On applying mechanical pressure to these droplets they shatter in a manner consistent with an ultra-viscous liquid or a brittle glass, but subsequent water uptake between 10 and 20% RH causes their viscosity to reduce sufficiently that the cracked droplets flow and merge. The persistence of iodic acid solution in an amorphous state, rather than a crystalline state, suggests they will more readily accommodate other condensable material and are therefore more likely to grow to sizes where they may serve as cloud condensation nuclei. On increasing the humidity to ~90% the mass of the droplets only increases by ~20% with a corresponding increase in radius of only ~6 %, which is remarkably small for a highly soluble material. We suggest that the small growth factor of aqueous iodic acid solution droplets is consistent with the small aerosol growth factors observed in field experiments.

Cloud Formation Potential of Biomass Burning Aerosol Surrogate-Particles Chemically Aged by OH

NASA Astrophysics Data System (ADS)

Slade, J. H.; Thalman, R. M.; Wang, J.; Li, Z. Q.; Knopf, D. A.

2014-12-01

Heterogeneous or multiphase reactions between trace gases such as OH and atmospheric aerosol can influence physicochemical properties of the particles including composition, morphology and lifetime. In this work, the cloud condensation nuclei (CCN) activity of laboratory-generated biomass burning aerosol (BBA) exposed to OH radicals is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type and OH exposure ([OH]×time) using a CCN counter coupled to a custom-built aerosol flow reactor (AFR). The composition of particles collected by a micro-orifice uniform deposit impactor (MOUDI) first subjected to different OH exposures is analyzed by Raman and scanning transmission X-ray microscopy coupled with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative compounds found in BBA that have different hygroscopicity, chemical functionalities, and reactivity with OH radicals. BBA surrogate-particles are generated following atomization of aqueous solutions with mass ratios LEV:MNC:KS of 1:0:0, 0:1:0, 0:0:1, 1:1:0, 0:1:1, 1:0:1, 1:1:1, and 1:0.03:0.3. OH radicals are generated in the AFR following photolysis of O3 in the presence of H2O using a variable intensity ultra-violet (UV) lamp, which allows equivalent atmospheric OH exposures from days to weeks. In addition, we investigate how κ changes i) in response to varying [O3] with and without OH, and ii) at a fixed OH exposure while varying RH. The impact of OH exposure on the CCN activity of BBA will be presented and its atmospheric implications will be discussed.

Nano spray-dried sodium chloride and its effects on the microbiological and sensory characteristics of surface-salted cheese crackers.

PubMed

Moncada, Marvin; Astete, Carlos; Sabliov, Cristina; Olson, Douglas; Boeneke, Charles; Aryana, Kayanush J

2015-09-01

Reducing particle size of salt to approximately 1.5 µm would increase its surface area, leading to increased dissolution rate in saliva and more efficient transfer of ions to taste buds, and hence, perhaps, a saltier perception of foods. This has a potential for reducing the salt level in surface-salted foods. Our objective was to develop a salt using a nano spray-drying method, to use the developed nano spray-dried salt in surface-salted cheese cracker manufacture, and to evaluate the microbiological and sensory characteristics of cheese crackers. Sodium chloride solution (3% wt/wt) was sprayed through a nano spray dryer. Particle sizes were determined by dynamic light scattering, and particle shapes were observed by scanning electron microscopy. Approximately 80% of the salt particles produced by the nano spray dryer, when drying a 3% (wt/wt) salt solution, were between 500 and 1,900 nm. Cheese cracker treatments consisted of 3 different salt sizes: regular salt with an average particle size of 1,500 µm; a commercially available Microsized 95 Extra Fine Salt (Cargill Salt, Minneapolis, MN) with an average particle size of 15 µm; and nano spray-dried salt with an average particle size of 1.5 µm, manufactured in our laboratory and 3 different salt concentrations (1, 1.5, and 2% wt/wt). A balanced incomplete block design was used to conduct consumer analysis of cheese crackers with nano spray-dried salt (1, 1.5, and 2%), Microsized salt (1, 1.5, and 2%) and regular 2% (control, as used by industry) using 476 participants at 1wk and 4mo. At 4mo, nano spray-dried salt treatments (1, 1.5, and 2%) had significantly higher preferred saltiness scores than the control (regular 2%). Also, at 4mo, nano spray-dried salt (1.5 and 2%) had significantly more just-about-right saltiness scores than control (regular 2%). Consumers' purchase intent increased by 25% for the nano spray-dried salt at 1.5% after they were notified about the 25% reduction in sodium content of the cheese cracker. We detected significantly lower yeast counts for nano spray-dried salt treatments (1, 1.5, and 2%) at 4mo compared with control (regular) salt (1, 1.5 and 2%). We detected no mold growth in any of the treatments at any time. At 4mo, we found no significant differences in sensory color, aroma, crunchiness, overall liking, or acceptability scores of cheese crackers using 1.5 and 1% nano spray-dried salt compared with control. Therefore, 25 to 50% less salt would be suitable for cheese crackers if the particle size of regular salt was reduced 3 log to form nano spray-dried salt. A 3-log reduction in sodium chloride particle size from regular salt to nano spray-dried salt increased saltiness, but a 1-log reduction in salt size from Microsized salt to nano spray-dried salt did not increase saltiness of surface-salted cheese crackers. The use of salt with reduced particle size by nano spray drying is recommended for use in surface-salted cheese crackers to reduce sodium intake. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Bio-inspired colorimetric film based on hygroscopic coloration of longhorn beetles (Tmesisternus isabellae)

PubMed Central

Seo, Han-bok; Lee, Seung-Yop

2017-01-01

Structure-dependent colour is caused by the interaction of light with photonic crystal structures rather than pigments. The elytra of longhorn beetles Tmesisternus isabellae appear to be iridescent green in a dry state and turn to red when exposed to humidity. Based on the hygroscopic colouration of the longhorn beetle, we have developed centimeter-scale colorimetric opal films using a novel self-assembly method. The micro-channel assisted assembly technique adopts both natural evaporation and rotational forced drying, enhancing the surface binding of silica particles and the packing density by reducing the lattice constant and structural defects. The fabricated large-scale photonic film changes its structural colour from green to red when exposed to water vapour, similarly to the colorimetric feature of the longhorn beetle. The humidity-dependent colour change of the opal film is shown to be reversible and durable over five-hundred cycles of wetting and drying. PMID:28322307

Bio-inspired colorimetric film based on hygroscopic coloration of longhorn beetles (Tmesisternus isabellae)

NASA Astrophysics Data System (ADS)

Seo, Han-Bok; Lee, Seung-Yop

2017-03-01

Structure-dependent colour is caused by the interaction of light with photonic crystal structures rather than pigments. The elytra of longhorn beetles Tmesisternus isabellae appear to be iridescent green in a dry state and turn to red when exposed to humidity. Based on the hygroscopic colouration of the longhorn beetle, we have developed centimeter-scale colorimetric opal films using a novel self-assembly method. The micro-channel assisted assembly technique adopts both natural evaporation and rotational forced drying, enhancing the surface binding of silica particles and the packing density by reducing the lattice constant and structural defects. The fabricated large-scale photonic film changes its structural colour from green to red when exposed to water vapour, similarly to the colorimetric feature of the longhorn beetle. The humidity-dependent colour change of the opal film is shown to be reversible and durable over five-hundred cycles of wetting and drying.

[Study on transformation mechanism of SOA from biogenic VOC under UV-B condition].

PubMed

Li, Ying-Ying; Li, Xiang; Chen, Jian-Min

2011-12-01

A laboratory study was carried out to investigate the biogenic volatile organic compounds (BVOC) in a lab-made glass chamber. The secondary organic aerosol (SOA) products can be detected under the UV photooxidation of BVOC. Pelargonium x Citrenella was chosen as the target plant in this research because it can release a large amount of BVOCs. The predominant 7 alkene and ketol compounds were detected by using solid phase microextraction (SPME) sampling and gas chromatography/mass spectrometry (GC/MS) analysis. The photochemical experiment indicated that these BVOC can be rapidly oxidized into SOA under UV-B irradiation. A tandem differential mobility analyzer (TDMA) was used to measure the size distribution and the hygroscopicity of the SOA. The particle diameter was in the range of 50 nm to 320 nm. The high hygroscopicity of SOA was also obtained and the size increased from 1.05 to 1.11 during the wet experiment.

Aerosol optical properties along the northeast coast of North America during the New England Air Quality Study-Intercontinental Transport and Chemical Transformation 2004 campaign and the influence of aerosol composition

NASA Astrophysics Data System (ADS)

Wang, Wei; Rood, Mark J.; Carrico, Christian M.; Covert, David S.; Quinn, Patricia K.; Bates, Timothy S.

2007-05-01

Optical and hygroscopic properties of submicrometer diameter aerosol particles were measured on board the NOAA R/V Ronald H. Brown as part of the NEAQS-ITCT field campaign. The campaign occurred along the northeast coast of North America during the summer of 2004. A scanning relative humidity (RH) nephelometry system (humidograph) measured total light scattering and backscattering coefficients (σsp and σbsp, respectively) at three wavelengths (λs) and RH = 26% and while RH was scanned between 40% and 85%. These measurements were combined with aerosol light absorption and composition measurements to describe σsp, σbsp, single scattering albedo (ω), Ångström exponent (å), and hemispheric backscatter fraction (b) at a low reference RH of 26 ± 4% and the aerosol's hygroscopic properties based on its optical response up to 85% RH. Humidogram curve structure was dominated by hygroscopic growth without hysteresis (76% frequency). Dependence of the aerosol's σsp values with changes in RH, fσsp(RH, 26), was observed to decrease with increasing mass fraction of particulate organic matter (POM, FO). Statistical analyses indicated that increasing FO resulted in a less hygroscopic aerosol, while increasing molar equivalence ratio (ER) resulted in lower hysteresis factors based on the aerosols' optical responses at a 0.95 confidence level. ω showed little RH dependence while å and b decreased with increasing RH values. Values for å(λ1, λ2), b, and fσsp(82, 26) increased with increasing λ values. Sensitivities of top of the atmosphere aerosol radiative forcing to changes in ω, b, and σsp with RH were also estimated.

Black carbon's contribution to aerosol absorption optical depth over S. Korea

NASA Astrophysics Data System (ADS)

Lamb, K.; Perring, A. E.; Beyersdorf, A. J.; Anderson, B. E.; Segal-Rosenhaimer, M.; Redemann, J.; Holben, B. N.; Schwarz, J. P.

2017-12-01

Aerosol absorption optical depth (AAOD) monitored by ground-based sites (AERONET, SKYNET, etc.) is used to constrain climate radiative forcing from black carbon (BC) and other absorbing aerosols in global models, but few validation studies between in situ aerosol measurements and ground-based AAOD exist. AAOD is affected by aerosol size distributions, composition, mixing state, and morphology. Megacities provide appealing test cases for this type of study due to their association with very high concentrations of anthropogenic aerosols. During the KORUS-AQ campaign in S. Korea, which took place in late spring and early summer of 2016, in situ aircraft measurements over the Seoul Metropolitan Area and Taehwa Research Forest (downwind of Seoul) were repeated three times per flight over a 6 week period, providing significant temporal coverage of vertically resolved aerosol properties influenced by different meteorological conditions and sources. Measurements aboard the NASA DC-8 by the NOAA Humidified Dual Single Particle Soot Photometers (HD-SP2) quantified BC mass, size distributions, mixing state, and the hygroscopicity of BC containing aerosols. The in situ BC mass vertical profiles are combined with estimated absorption enhancement calculated from observed optical size and hygroscopicity using Mie theory, and then integrated over the depth of the profile to calculate BC's contribution to AAOD. Along with bulk aerosol size distributions and hygroscopicity, bulk absorbing aerosol optical properties, and on-board sky radiance measurements, these measurements are compared with ground-based AERONET site measurements of AAOD to evaluate closure between in situ vertical profiles of BC and AAOD measurements. This study will provide constraints on the relative importance of BC (including lensing and hygroscopicity effects) and non-BC components to AAOD over S. Korea.

Coating Methods for Surface Modification of Ammonium Nitrate: A Mini-Review

PubMed Central

Elzaki, Baha I.; Zhang, Yue Jun

2016-01-01

Using ammonium nitrate (AN) as a propellant oxidizer is limited due to its hygroscopicity. This review consolidated the available information of various issues pertaining to the coating methods of the surface modification of ammonium nitrate for reducing its hygroscopicity. Moreover this review summarizes the recent advances and issues involved in ammonium nitrate surface modification by physical, chemical and encapsulation coating methods to reduce the hygroscopicity. Furthermore, coating materials, process conditions, and the hygroscopicity test conditions are extensively discussed along, with summaries of the advantages and disadvantages of each coating method. Our findings indicated that the investigation and development of anti-hygroscopicity of AN, and the mechanisms of surface modification by coating urgently require further research in order to further reduce the hygroscopicity. Therefore, this review is useful to researchers concerned with the improvement of ammonium salts’ anti-hygroscopicity. PMID:28773625

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.

Cloud condensation nuclei closure study on summer arctic aerosol

NASA Astrophysics Data System (ADS)

Martin, M.; Chang, R. Y.-W.; Sierau, B.; Sjogren, S.; Swietlicki, E.; Abbatt, J. P. D.; Leck, C.; Lohmann, U.

2011-11-01

We present an aerosol - cloud condensation nuclei (CCN) closure study on summer high Arctic aerosol based on measurements that were carried out in 2008 during the Arctic Summer Cloud Ocean Study (ASCOS) on board the Swedish ice breaker Oden. The data presented here were collected during a three-week time period in the pack ice (>85° N) when the icebreaker Oden was moored to an ice floe and drifted passively during the most biological active period into autumn freeze up conditions. CCN number concentrations were obtained using two CCN counters measuring at different supersaturations. The directly measured CCN number concentration was then compared with a CCN number concentration calculated using both bulk aerosol mass composition data from an aerosol mass spectrometer (AMS) and aerosol number size distributions obtained from a differential mobility particle sizer, assuming κ-Köhler theory, surface tension of water and an internally mixed aerosol. The last assumption was supported by measurements made with a hygroscopic tandem differential mobility analyzer (HTDMA) for particles >70 nm. For the two highest measured supersaturations, 0.73 and 0.41%, closure could not be achieved with the investigated settings concerning hygroscopicity and density. The calculated CCN number concentration was always higher than the measured one for those two supersaturations. This might be caused by a relative larger insoluble organic mass fraction of the smaller particles that activate at these supersaturations, which are thus less good CCN than the larger particles. On average, 36% of the mass measured with the AMS was organic mass. At 0.20, 0.15 and 0.10% supersaturation, closure could be achieved with different combinations of hygroscopic parameters and densities within the uncertainty range of the fit. The best agreement of the calculated CCN number concentration with the observed one was achieved when the organic fraction of the aerosol was treated as nearly water insoluble (κorg=0.02), leading to a mean total κ, κtot, of 0.33 ± 0.13. However, several settings led to closure and κorg=0.2 is found to be an upper limit at 0.1% supersaturation. κorg≤0.2 leads to a κtot range of 0.33 ± 013 to 0.50 ± 0.11. Thus, the organic material ranges from being sparingly soluble to effectively insoluble. These results suggest that an increase in organic mass fraction in particles of a certain size would lead to a suppression of the Arctic CCN activity.

The global impact of mineral dust on cloud droplet number concentration

NASA Astrophysics Data System (ADS)

Karydis, V.; Tsimpidi, A.; Bacer, S.; Pozzer, A.; Nenes, A.; Lelieveld, J.

2016-12-01

This study assesses the importance of mineral dust for cloud droplet formation by taking into account i) the adsorption of water on the surface of insoluble dust particles, ii) the coating of soluble material on the surface of mineral particles which augments their cloud condensation nuclei activity, and iii) the effect of dust on the inorganic aerosol concentrations through thermodynamic interactions with mineral cations. Simulations are carried out with the EMAC chemistry climate model that calculates the global atmospheric aerosol composition using the ISORROPIA-II thermodynamic equilibrium model and considers the gas phase interactions with K+-Ca2+-Mg2+-NH4+-Na+-SO42-NO3-Cl-H2O particle components. Emissions of the inert mineral dust and the reactive dust aerosol components are calculated online by taking into account the soil particle size distribution and chemical composition of different deserts worldwide (Karydis et al., 2016). We have implemented the "unified dust activation parameterization" (Kumar et al., 2011; Karydis et al., 2011) to calculate the droplet number concentration by taking into account the inherent hydrophilicity from adsorption and the acquired hygroscopicity from soluble salts by dust particles. Our simulations suggest that mineral dust significantly increases the cloud droplet number concentration (CDNC) over the main deserts and the adjacent oceans. However, over polluted areas the CDNC decreases significantly in the presence of dust. Furthermore, we investigate the role of adsorption activation of insoluble aerosols and the mineral dust thermodynamic interactions with inorganic anions on the cloud droplet formation. The CDNC sensitivity to the emission load, chemical composition, and inherent hydrophilicity of mineral dust is also tested. ReferencesKarydis, et al. (2011). "On the effect of dust particles on global cloud condensation nuclei and cloud droplet number." J. Geophys. Res. Atmos. 116. Karydis, et al. (2016). "Effects of mineral dust on global atmospheric nitrate concentrations." Atmos. Chem. Phys. 16(3): 1491-1509. Kumar, et al. (2011). "Measurements of cloud condensation nuclei activity and droplet activation kinetics of wet processed regional dust samples and minerals." Atmos. Chem. Phys. Discuss. 11(4): 12561-12605.

Biogenic cloud nuclei in the central Amazon during the transition from wet to dry season

NASA Astrophysics Data System (ADS)

Whitehead, James D.; Darbyshire, Eoghan; Brito, Joel; Barbosa, Henrique M. J.; Crawford, Ian; Stern, Rafael; Gallagher, Martin W.; Kaye, Paul H.; Allan, James D.; Coe, Hugh; Artaxo, Paulo; McFiggans, Gordon

2016-08-01

The Amazon basin is a vast continental area in which atmospheric composition is relatively unaffected by anthropogenic aerosol particles. Understanding the properties of the natural biogenic aerosol particles over the Amazon rainforest is key to understanding their influence on regional and global climate. While there have been a number of studies during the wet season, and of biomass burning particles in the dry season, there has been relatively little work on the transition period - the start of the dry season in the absence of biomass burning. As part of the Brazil-UK Network for Investigation of Amazonian Atmospheric Composition and Impacts on Climate (BUNIAACIC) project, aerosol measurements, focussing on unpolluted biogenic air masses, were conducted at a remote rainforest site in the central Amazon during the transition from wet to dry season in July 2013. This period marks the start of the dry season but before significant biomass burning occurs in the region. Median particle number concentrations were 266 cm-3, with size distributions dominated by an accumulation mode of 130-150 nm. During periods of low particle counts, a smaller Aitken mode could also be seen around 80 nm. While the concentrations were similar in magnitude to those seen during the wet season, the size distributions suggest an enhancement in the accumulation mode compared to the wet season, but not yet to the extent seen later in the dry season, when significant biomass burning takes place. Submicron nonrefractory aerosol composition, as measured by an aerosol chemical speciation monitor (ACSM), was dominated by organic material (around 81 %). Aerosol hygroscopicity was probed using measurements from a hygroscopicity tandem differential mobility analyser (HTDMA), and a quasi-monodisperse cloud condensation nuclei counter (CCNc). The hygroscopicity parameter, κ, was found to be low, ranging from 0.12 for Aitken-mode particles to 0.18 for accumulation-mode particles. This was consistent with previous studies in the region, but lower than similar measurements conducted in Borneo, where κ ranged 0.17-0.37. A wide issue bioaerosol sensor (WIBS-3M) was deployed at ground level to probe the coarse mode, detecting primary biological aerosol by fluorescence (fluorescent biological aerosol particles, or FBAPs). The mean FBAP number concentration was 400 ± 242 L-1; however, this ranged from around 200 L-1 during the day to as much as 1200 L-1 at night. FBAPs dominated the coarse-mode particles, comprising between 55 and 75 % of particles during the day to more than 90 % at night. Non-FBAPs did not show a strong diurnal pattern. Comparison with previous FBAP measurements above canopy at the same location suggests there is a strong vertical gradient in FBAP concentrations through the canopy. Cluster analysis of the data suggests that FBAPs were dominated (around 70 %) by fungal spores. Further, long-term measurements will be required in order to fully examine the seasonal variability and distribution of primary biological aerosol particles through the canopy. This is the first time that such a suite of measurements has been deployed at this site to investigate the chemical composition and properties of the biogenic contributions to Amazonian aerosol during the transition period from the wet to the dry season, and thus provides a unique comparison to the aerosol properties observed during the wet season in previous similar campaigns. This was also the first deployment of a WIBS in the Amazon rainforest to study coarse-mode particles, particularly primary biological aerosol particles, which are likely to play an important role as ice nuclei in the region.

Laboratory Studies of the Cloud Droplet Activation Properties and Corresponding Chemistry of Saline Playa Dust.

PubMed

Gaston, Cassandra J; Pratt, Kerri A; Suski, Kaitlyn J; May, Nathaniel W; Gill, Thomas E; Prather, Kimberly A

2017-02-07

Playas emit large quantities of dust that can facilitate the activation of cloud droplets. Despite the potential importance of playa dusts for cloud formation, most climate models assume that all dust is nonhygroscopic; however, measurements are needed to clarify the role of dusts in aerosol-cloud interactions. Here, we report measurements of CCN activation from playa dusts and parameterize these results in terms of both κ-Köhler theory and adsorption activation theory for inclusion in atmospheric models. κ ranged from 0.002 ± 0.001 to 0.818 ± 0.094, whereas Frankel-Halsey-Hill (FHH) adsorption parameters of A FHH = 2.20 ± 0.60 and B FHH = 1.24 ± 0.14 described the water uptake properties of the dusts. Measurements made using aerosol time-of-flight mass spectrometry (ATOFMS) revealed the presence of halite, sodium sulfates, and sodium carbonates that were strongly correlated with κ underscoring the role that mineralogy, including salts, plays in water uptake by dust. Predictions of κ made using bulk chemical techniques generally showed good agreement with measured values. However, several samples were poorly predicted suggesting that chemical heterogeneities as a function of size or chemically distinct particle surfaces can determine the hygroscopicity of playa dusts. Our results further demonstrate the importance of dust in aerosol-cloud interactions.

CCN activation and efficiency of nucleation and impaction removal process of biomass burning aerosols in Brazil: preliminary results.

NASA Astrophysics Data System (ADS)

Sánchez Gácita, Madeleine; Longo, Karla M.; Freitas, Saulo R.; Martin, Scot T.

2015-04-01

The biomass burning activity constitutes an important source of aerosols and trace gases to the atmosphere globally. In South America, during the dry season, aerosols prevenient from biomass burning are typically transported to long distances from its sources before being removed though contributing significantly to the aerosol budget on a continental scale. The uncertainties in the magnitude of the impacts on the hydrological cycle, the radiation budget and the biogeochemical cycles on a continental scale are still noteworthy. The still unknowns on the efficiency of biomass burning aerosol to act as cloud condensation nuclei (CCN) and the effectiveness of the nucleation and impaction scavenging mechanisms in removing them from the atmosphere contribute to such uncertainties. In the present work, the explicit modelling of the early stages of cloud development using a parcel model for the typical conditions of the dry season and dry-to-wet transition periods in Amazonia allowed an estimation of the efficiency of nucleation scavenging process and the ability of South American biomass burning aerosol to act as CCN. Additionally, the impaction scavenging was simulated for the same aerosol population following a method based on the widely used concept of the efficiency of collision between a raindrop and an aerosol particle. DMPS and H-TDMA data available in the literature for biomass burning aerosol population in the region indicated the presence of a nearly hydrophobic fraction (on average, with specific hygroscopic parameter κ=0.04, and relative abundance of 73 %) and nearly hygroscopic fraction (κ=0.13, 27 %), externally mixed. The hygroscopic parameters and relative abundances of each hygroscopic group, as well as the weighted average specific hygroscopic parameter for the entire population κ=0.06, were used in calculations of aerosol activation and population mass and number concentration scavenged by nucleation. Results from both groups of simulations are presented and discussed. This work provides an insight on the importance of the inclusion of these processes in regional/global models. The authors thank the Sao Paulo Research Foundation FAPESP for supporting this work through the projects DR 2012/09934-3 and BEPE-DR 2013/02101-9.

Method for making fine and ultrafine spherical particles of zirconium titanate and other mixed metal oxide systems

DOEpatents

Hu, Michael Z.

2006-05-23

Disclosed is a method for making amorphous spherical particles of zirconium titanate and crystalline spherical particles of zirconium titanate comprising the steps of mixing an aqueous solution of zirconium salt and an aqueous solution of titanium salt into a mixed solution having equal moles of zirconium and titanium and having a total salt concentration in the range from 0.01 M to about 0.5 M. A stearic dispersant and an organic solvent is added to the mixed salt solution, subjecting the zirconium salt and the titanium salt in the mixed solution to a coprecipitation reaction forming a solution containing amorphous spherical particles of zirconium titanate wherein the volume ratio of the organic solvent to aqueous part is in the range from 1 to 5. The solution of amorphous spherical particles is incubated in an oven at a temperature .ltoreq.100.degree. C. for a period of time .ltoreq.24 hours converting the amorphous particles to fine or ultrafine crystalline spherical particles of zirconium titanate.

Additive impacts on particle emissions from heating low emitting cooking oils

NASA Astrophysics Data System (ADS)

Amouei Torkmahalleh, M.; Zhao, Y.; Hopke, P. K.; Rossner, A.; Ferro, A. R.

2013-08-01

The effect of five additives, including table salt, sea salt, black pepper, garlic powder, and turmeric, on the emission of PM2.5 and ultrafine particles (UFP) from heated cooking oil (200 °C) were studied. One hundred milligrams of the additives were added individually to either canola or soybean oil without stirring. Black pepper, table salt, and sea salt reduced the PM2.5 emission of canola oil by 86% (p < 0.001), 88% (p < 0.001), and 91% (p < 0.001), respectively. Black pepper, table salt, and sea salt also decreased the total particle number emissions of canola oil by 45% (p = 0.003), 52% (p = 0.001), and 53% (p < 0.001), respectively. Turmeric and garlic powder showed no changes in the PM2.5 and total number emissions of canola oil. Table salt and sea salt, decreased the level of PM2.5 emissions from soybean oil by 47% (p < 0.001) and 77% (p < 0.001), respectively. No differences in the PM2.5 emissions were observed when other additives were added to soybean oil. Black pepper, sea salt, and table salt reduced the total particle number emissions from the soybean oil by 51%, 61% and 68% (p < 0.001), respectively. Turmeric and garlic powder had no effect on soybean oil with respect to total particle number emissions. Our results indicate that table salt, sea salt, and black pepper can be used to reduce the particle total number and PM2.5 emissions when cooking with oil.

Salting-out and salting-in: competitive effects of salt on the aggregation behavior of soy protein particles and their emulsifying properties.

PubMed

Xu, Hua-Neng; Liu, Yang; Zhang, Lianfu

2015-08-07

Emulsions stabilized by protein particles have gained increasing research attention due to their combined advantages of biocompatibility and superior stability. In this study, colloidal particles consisting of soy protein isolates (SPIs) prepared through a heat-treatment procedure are used to make oil-in-water emulsions at a protein concentration of 10 g L(-1) and a pH of 5.91. We investigate parallelly the effects of NaCl on the stability and rheological properties of the particle suspensions and their stabilized emulsions at salt concentrations of 0, 100 and 400 mM. The aggregation behavior of the particles is strongly dependent on the NaCl concentration, showing signs of sedimentation at low NaCl concentration (100 mM) but redispersion again at high NaCl concentration (400 mM). The extensive particle aggregation is beneficial to the formation of a continuous interfacial film for the emulsions, and hence results in a remarkable increase of creaming stability and interfacial viscoelastic moduli. The results can be explained in terms of two competitive effects of NaCl: salting-out and salting-in, which are attributed to complex electrostatic interactions between the particles as a function of NaCl concentration. The delicate balance between salting-out and salting-in provides an interesting insight into the nature of underlying protein particle interactions in aqueous suspensions and a possible mechanism for tailoring their emulsifying properties via salt effects.

Components of Particle Emissions from Light-Duty Spark-Ignition Vehicles with Varying Aromatic Content and Octane Rating in Gasoline.

PubMed

Short, Daniel Z; Vu, Diep; Durbin, Thomas D; Karavalakis, Georgios; Asa-Awuku, Akua

2015-09-01

Typical gasoline consists of varying concentrations of aromatic hydrocarbons and octane ratings. However, their impacts on particulate matter (PM) such as black carbon (BC) and water-soluble and insoluble particle compositions are not well-defined. This study tests seven 2012 model year vehicles, which include one port fuel injection (PFI) configured hybrid vehicle, one PFI vehicle, and six gasoline direct injection (GDI) vehicles. Each vehicle was driven on the Unified transient testing cycle (UC) using four different fuels. Three fuels had a constant octane rating of 87 with varied aromatic concentrations at 15%, 25%, and 35%. A fourth fuel with higher octane rating, 91, contained 35% aromatics. BC, PM mass, surface tension, and water-soluble organic mass (WSOM) fractions were measured. The water-insoluble mass (WIM) fraction of the vehicle emissions was estimated. Increasing fuel aromatic content increases BC emission factors (EFs) of transient cycles. BC concentrations were higher for the GDI vehicles than the PFI and hybrid vehicles, suggesting a potential climate impact for increased GDI vehicle production. Vehicle steady-state testing showed that the hygroscopicity of PM emissions at high speeds (70 mph; κ > 1) are much larger than emissions at low speeds (30 mph; κ < 0.1). Iso-paraffin content in the fuels was correlated to the decrease in WSOM emissions. Both aromatic content and vehicle speed increase the amount of hygroscopic material found in particle emissions.

Influences of aerosol physiochemical properties and new particle formation on CCN activity from observation at a suburban site of China

NASA Astrophysics Data System (ADS)

Li, Yanan; Zhang, Fang; Li, Zhanqing; Sun, Li; Wang, Zhenzhu; Li, Ping; Sun, Yele; Ren, Jingye; Wang, Yuying; Cribb, Maureen; Yuan, Cheng

2017-05-01

With the aim of understanding the impact of aerosol particle size and chemical composition on CCN activity, the size-resolved cloud condensation nuclei (CCN) number concentration (NCCN), particle number size distribution (PSD) (10-600 nm), and bulk chemical composition of particles with a diameter < 1.0 μm (PM1) were measured simultaneously at Xinzhou, a suburban site in northern China, from 22 July to 26 August 2014. The NCCN was measured at five different supersaturations (SS) ranging from 0.075%-0.76%. Diurnal variations in the aerosol number concentration (NCN), NCCN, the bulk aerosol activation ratio (AR), the hygroscopicity parameter (κchem), and the ratio of 44 mass to charge ration (m/z 44) to total organic signal in the component spectrum (f44), and the PSD were examined integrally to study the influence of particle size and chemical composition on CCN activation. We found that particle size was more related to the CCN activation ratios in the morning, whereas in the afternoon ( 1400 LST), κchem and f44 were more closely associated with the bulk AR. Assuming the internal mixing of aerosol particles, NCCN was estimated using the bulk chemical composition and real-time PSD. We found that the predicted CCN number concentrations were underestimated by 20-30% at SS < 0.2% probably due to the measurement uncertainties. Estimates were more accurate at higher SS levels, suggesting that the hygroscopicity parameter based on bulk chemical composition information can provide a good estimate of CCN number concentrations. We studied the impacts of new particle formation (NPF) events on size-resolved CCN activity at the ;growth; stage and ;leveling-off; stage during a typical NPF event by comparing with the case during non-NPF event. It has been found that CCN activation was restrained at the ;growth; stage during which larger particle diameters were needed to reach an activation diameter(Da), and the bulk AR decreased as well. However, during the ;leveling-off; stage, a lower Da was observed and CCN activation was greatly enhanced.

Frost flowers and sea-salt aerosols over seasonal sea-ice areas in northwestern Greenland during winter-spring

NASA Astrophysics Data System (ADS)

Hara, Keiichiro; Matoba, Sumito; Hirabayashi, Motohiro; Yamasaki, Tetsuhide

2017-07-01

Sea salts and halogens in aerosols, frost flowers, and brine play an important role in atmospheric chemistry in polar regions. Simultaneous sampling and observations of frost flowers, brine, and aerosol particles were conducted around Siorapaluk in northwestern Greenland during December 2013 to March 2014. Results show that water-soluble frost flower and brine components are sea-salt components (e.g., Na+, Cl-, Mg2+, K+, Ca2+, Br-, and iodine). Concentration factors of sea-salt components of frost flowers and brine relative to seawater were 1.14-3.67. Sea-salt enrichment of Mg2+, K+, Ca2+, and halogens (Cl-, Br-, and iodine) in frost flowers is associated with sea-salt fractionation by precipitation of mirabilite and hydrohalite. High aerosol number concentrations correspond to the occurrence of higher abundance of sea-salt particles in both coarse and fine modes, and blowing snow and strong winds. Aerosol number concentrations, particularly in coarse mode, are increased considerably by release from the sea-ice surface under strong wind conditions. Sulfate depletion by sea-salt fractionation was found to be limited in sea-salt aerosols because of the presence of non-sea-salt (NSS) SO42-. However, coarse and fine sea-salt particles were found to be rich in Mg. Strong Mg enrichment might be more likely to proceed in fine sea-salt particles. Magnesium-rich sea-salt particles might be released from the surface of snow and slush layer (brine) on sea ice and frost flowers. Mirabilite-like and ikaite-like particles were identified only in aerosol samples collected near new sea-ice areas. From the field evidence and results from earlier studies, we propose and describe sea-salt cycles in seasonal sea-ice areas.

Salt formation improved the properties of a candidate drug during early formulation development.

PubMed

Sigfridsson, Kalle; Ahlqvist, Matti; Lindsjö, Martin; Paulsson, Stefan

2018-07-30

The purpose of this study was to investigate if AZD5329, a dual neurokinin NK1/2 receptor antagonist, is a suitable candidate for further development as an oral immediate release (IR) solid dosage form as a final product. The neutral form of AZD5329 has only been isolated as amorphous material. In order to search for a solid material with improved physical and chemical stability and more suitable solid-state properties, a salt screen was performed. Crystalline material of a maleic acid salt and a fumaric acid salt of AZD5329 were obtained. X-ray powder diffractiometry, thermogravimetric analysis, differential scanning calorimetry and dynamic vapor sorption were used to investigate the physicochemical characteristics of the two salts. The fumarate salt of AZD5329 is anhydrous, the crystallization is reproducible and the hygroscopicity is acceptable. Early polymorphism assessment work using slurry technique did not reveal any better crystal modification or crystallinity for the fumarate salt. For the maleate salt, the form isolated originally was found to be a solvate, but an anhydrous form was found in later experiments; by suspension in water or acetone, by drying of the solvate to 100-120 °C or by subjecting the solvate form to conditions of 40 °C/75%RH for 3 months. The dissolution behavior and the chemical stability (in aqueous solutions, formulations and solid-state) of both salts were also studied and found to be satisfactory. The compound displays sensitivity to low pH, and the salt of the maleic acid, which is the stronger acid, shows more degradation during stability studies, in line with this observation. The presented data indicate that the substance fulfils basic requirements for further development of an IR dosage form, based on the characterization on crystalline salts of AZD5329. Copyright © 2018 Elsevier B.V. All rights reserved.

The impact of marine surface organic enrichment on the measured hygroscopicity parameter of laboratory generated sea-spray aerosols

NASA Astrophysics Data System (ADS)

Schill, S.; Novak, G.; Zimmermann, K.; Bertram, T. H.

2014-12-01

The ocean serves as a major source for atmospheric aerosol particles, yet the chemicophysical properties of sea spray aerosol to date are not well characterized. Understanding the transfer of organic compounds, present in the sea surface microlayer (SSML), to sea-spray particles and their resulting impact on cloud formation is important for predicting aerosol impact on climate in remote marine environments. Here, we present a series of laboratory experiments designed to probe the fractionation of select organic molecules during wave breaking. We use a representative set of organic mimics (e.g. sterols, sugars, lipids, proteins, fatty acids) to test a recent physically based model of organic enrichment in sea-spray aerosol [Burrows et al., 2014] that is based on Langmuir absorption equilibria. Experiments were conducted in the UCSD Marine Aerosol Reference Tank (MART) permitting accurate representation of wave breaking processes in the laboratory. We report kappa values for the resulting sea-spray aerosols and compare them to a predictions made using Kappa-Köhler Theory driven by a linear combination of the pure component kappa values. Hygroscopicity determinations made using the model systems are discussed within the context of measurements of CCN activity made using natural, coastal water.

Aerosol optical properties in the southeastern United States in summer - Part 1: Hygroscopic growth

NASA Astrophysics Data System (ADS)

Brock, C. A.; Wagner, N. L.; Anderson, B. E.; Attwood, A. R.; Beyersdorf, A.; Campuzano-Jost, P.; Carlton, A. G.; Day, D. A.; Diskin, G. S.; Gordon, T. D.; Jimenez, J. L.; Lack, D. A.; Liao, J.; Markovic, M. Z.; Middlebrook, A. M.; Ng, N. L.; Perring, A. E.; Richardson, M. S.; Schwarz, J. P.; Washenfelder, R. A.; Welti, A.; Xu, L.; Ziemba, L. D.; Murphy, D. M.

2015-09-01

Aircraft observations of meteorological, trace gas, and aerosol properties were made during May-September 2013 in the southeastern United States (US) under fair-weather, afternoon conditions with well-defined planetary boundary layer structure. Optical extinction at 532 nm was directly measured at three relative humidities and compared with extinction calculated from measurements of aerosol composition and size distribution using the κ-Köhler approximation for hygroscopic growth. Using this approach, the hygroscopicity parameter κ for the organic fraction of the aerosol must have been < 0.10 to be consistent with 75 % of the observations within uncertainties. This subsaturated κ value for the organic aerosol in the southeastern US is consistent with several field studies in rural environments. We present a new parameterization of the change in aerosol extinction as a function of relative humidity that better describes the observations than does the widely used power-law (gamma, γ) parameterization. This new single-parameter κext formulation is based upon κ-Köhler and Mie theories and relies upon the well-known approximately linear relationship between particle volume (or mass) and optical extinction (Charlson et al., 1967). The fitted parameter, κext, is nonlinearly related to the chemically derived κ parameter used in κ-Köhler theory. The values of κext we determined from airborne measurements are consistent with independent observations at a nearby ground site.

Limited production of sulfate and nitrate on front-associated dust storm particles moving from desert to distant populated areas in northwestern China

NASA Astrophysics Data System (ADS)

Wu, Feng; Zhang, Daizhou; Cao, Junji; Guo, Xiao; Xia, Yao; Zhang, Ting; Lu, Hui; Cheng, Yan

2017-12-01

Sulfate and nitrate compounds can greatly increase the hygroscopicity of mineral particles in the atmosphere and consequently alter the particles' physical and chemical properties. Their uptake on long-distance-transported Asian dust particles within mainland China has been reported to be substantial in previous studies, but the production was very inefficient in other studies. We compared these two salts in particles collected from a synoptic-scale, mid-latitude, cyclone-induced dust storm plume at the Tengger Desert (38.79° N, 105.38° E) and in particles collected in a postfrontal dust plume at an urban site in Xi'an (34.22° N, 108.87° E) when a front-associated dust storm from the Tengger Desert arrived there approximately 700 km downwind. The results showed that the sulfate concentration was not considerably different at the two sites, while the nitrate concentration was slightly larger at the urban site than that at the desert site. The estimated nitrate production rate was 4-5 ng µg-1 of mineral dust per day, which was much less than that in polluted urban air. The adiabatic process of the dust-loading air was suggested to be the reason for the absence of sulfate formation, and the uptake of background HNO3 was suggested to be the reason for the small nitrate production. According to our investigation of the published literature, the significant sulfate and nitrate in dust-storm-associated samples within the continental atmosphere reported in previous studies cannot be confirmed as actually produced on desert dust particles; the contribution from locally emitted and urban mineral particles or from soil-derived sulfate was likely substantial because the weather conditions in those studies indicated that the collection of the samples was started before dust arrival, or the air from which the samples were collected was a mixture of desert dust and locally emitted mineral particles. These results suggest that the production of nitrate and sulfate on dust particles following cold fronts is likely limited when the particles move from the desert to populated areas within the continent. For an accurate quantification of sulfate and nitrate formed on long-distance-transported desert dust particles at downwind populated areas in eastern China, dust collection efforts are indispensable to minimize any possible influence by locally emitted particles or at least to ensure that the samples are collected after dust arrival.

Food-grade submicrometer particles from salts prepared using ethanol-in-oil mixtures.

PubMed

Paques, Jerome P; van der Linden, Erik; Sagis, Leonard M C; van Rijn, Cees J M

2012-08-29

A simple method for preparing food-grade particles in the submicrometer range of ethanol soluble salts using ethanol-in-oil (E/O) mixtures is described. Salts CaCl2·2H2O and MgCl2·6H2O were dissolved in ethanol that subsequently was mixed with a medium-chain triglyceride oil phase. It was found that type and concentration of salt have a significant influence on the miscibility of ethanol and oil phase and on the stability of E/O mixtures. The ethanol phase was evaporated from the mixture at elevated temperatures, and salt particles with dimensions in the submicrometer range (6-400 nm) remained suspended in the oil phase. It was found that the concentration of salt and volume fraction of ethanol in MCT oil have a significant influence on the size distribution of salt particles. The size of CaCl2 and MgCl2 submicrometer particles was ascertained by scanning electron microscopy and dynamic light scattering.

Cloud condensation nuclei closure study on summer arctic aerosol

NASA Astrophysics Data System (ADS)

Martin, M.; Chang, R. Y.-W.; Sierau, B.; Sjogren, S.; Swietlicki, E.; Abbatt, J. P. D.; Leck, C.; Lohmann, U.

2011-03-01

We present an aerosol - cloud condensation nuclei CCN) closure study on summer high Arctic aerosol based on measurements that were carried out in summer 2008 during the Arctic Summer Cloud Ocean Study (ASCOS) on board the Swedish ice breaker Oden. The data presented here were collected during a three-week time period in the pack ice (>85° N) when the icebreaker Oden was moored to an ice floe and drifted passively during the most biological active period into autumn freeze up conditions. CCN number concentrations were obtained using two CCN counters measuring at different supersaturations. The directly measured CCN number concentration is then compared with a CCN number concentration calculated using both bulk aerosol mass composition data from an aerosol mass spectrometer and aerosol number size distributions obtained from a differential mobility particle sizer, assuming κ-Köhler theory and an internally mixed aerosol. For the two highest measured supersaturations, 0.73 and 0.41%, closure could not be achieved with the investigated settings concerning hygroscopicity and density. The calculated CCN number concentration was always higher than the measured one. One possible explanation is that the smaller particles that activate at these supersaturations have a relative larger insoluble organic mass fraction and thus are less good CCN than the larger particles. At 0.20, 0.15 and 0.10% supersaturation, the measured CCN number can be represented with different parameters for the hygroscopicity and density of the particles. For the best agreement of the calculated CCNnumber concentration with the measured one the organic fraction of the aerosol needs to be nearly insoluble (қorg=0.02). However, this is not unambigious and қorg=0.2 is found as an upper limit at 0.1% supersaturation.

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 particles of the same composition would allow proving that LLPS indeed occurs in particles of atmospheric relevant size ranges. Up to now this prove is missing. References: 1. Bertram, et al. Atmos. Chem & Phys, 11(21), 10995-11006, 2011. 2. Krieger, et al. Chemical Society Reviews, 41(19), 6631-6662, 2012 3. Song, M. et al. Geophys Res Lett, 39(19), 2012b 4. Smith et al. Atmos Chem & Phys, 12(20), 9613- 9628, 2012. 5. You, Y. et al. Proceedings of the National Academy of Sciences, 109(33), 13188-13193, 2012.

Characteristics of Submicron Aerosols in 2013 summer of Beijing

NASA Astrophysics Data System (ADS)

Guo, Song; Hu, Min; Shang, Dongjie; Zheng, Jing; Du, Zhuofei; Wu, Yusheng; Lu, Sihua; Zeng, Limin; Zhang, Renyi

2016-04-01

To characterize the air pollution of North China Plain of China, CAREBEIJING-2013 field campaign (Campaigns of Air quality REsearch in BEIJING and surrounding region) was conducted in summer of 2013. Submicron aerosols were measured at an urban site PKU (Peking University, 39° 59'21"N, 116° 18'25"E) from July 28th to September 31st 2013. A suite of integrated instruments was used to measure the size distribution, effective density and hygroscopicity of ambient particles. The chemical composition of submicron particles were measured by using an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) (Billerica, MA, USA). The average PM2.5 concentration was 73.0±70.7 μg m-3 during the measurement. The particulate pollution showed distinct 4-7 days cycles controlled by the meteorological conditions. Each cycle started with low PM2.5 mass concentrations (<20 μg m-3), since the air mass was from relatively clean mountainous area. The particle number concentrations were high, but and the sizes were small (<30 nm) at this stage, which can be explained by the new particle formation. In the succeeding days, both the particle mass and size continuously increased. The PM2.5concentration increased rapidly by >60 μg day-1, and the particle mean diameter grew to >100 nm. It is interesting to note that the mean diameters showed similar trend to PM2.5 mass concentrations, indicating the particle pollution attributed to the growth of the newly formed small particles. During the measurement, the average particle densities are between 1.3-1.5 g cm-3, indicating organics and sulfate were dominant in the particles. The densities of smaller particles, i.e. 46 nm, 81nm, showed single peak at 1.3-1.5 g cm-3, indicating the particles are internal mixed sulfate and organics. While the 150nm and 240 nm particle densities exhibited bimodal distribution with an additional small peak at ˜1.1 g cm-3, which is considered as external mixed organic particles or aged soot particles. The particle hygroscopic growth factor for all the measured sizes at RH of 90% showed bimodal distribution, attributing to external mixed organics (or aged soot) and internal mixed organics and sulfate. Both the density and HGF were higher than Tijuana, but similar to Houston. PMF (Positive Matrix Factorization) model was deployed to quantify the contributions of different mixing state particles. Internal mixed organics and sulfate were dominant in the ambient particles in Beijing.

Single-particle characterization of summertime Antarctic aerosols collected at King George Island using quantitative energy-dispersive electron probe X-ray microanalysis and attenuated total reflection Fourier transform-infrared imaging techniques.

PubMed

Maskey, Shila; Geng, Hong; Song, Young-Chul; Hwang, Heejin; Yoon, Young-Jun; Ahn, Kang-Ho; Ro, Chul-Un

2011-08-01

Single-particle characterization of Antarctic aerosols was performed to investigate the impact of marine biogenic sulfur species on the chemical compositions of sea-salt aerosols in the polar atmosphere. Quantitative energy-dispersive electron probe X-ray microanalysis was used to characterize 2900 individual particles in 10 sets of aerosol samples collected between March 12 and 16, 2009 at King Sejong Station, a Korean scientific research station located at King George Island in the Antarctic. Two size modes of particles, i.e., PM(2.5-10) and PM(1.0-2.5), were analyzed, and four types of particles were identified, with sulfur-containing sea-salt particles being the most abundant, followed by genuine sea-salt particles without sulfur species, iron-containing particles, and other species including CaCO(3)/CaMg(CO(3))(2), organic carbon, and aluminosilicates. When a sulfur-containing sea-salt particle showed an atomic concentration ratio of sulfur to sodium of >0.083 (seawater ratio), it is regarded as containing nonsea-salt sulfate (nss-SO(4)(2-)) and/or methanesulfonate (CH(3)SO(3)(-)), which was supported by attenuated total reflection Fourier transform-infrared imaging measurements. These internal mixture particles of sea-salt/CH(3)SO(3)(-)/SO(4)(2-) were very frequently encountered. As nitrate-containing particles were not encountered, and the air-masses for all of the samples originated from the Pacific Ocean (based on 5-day backward trajectories), the oxidation of dimethylsulfide (DMS) emitted from phytoplanktons in the ocean is most likely to be responsible for the formation of the mixed sea-salt/CH(3)SO(3)(-)/SO(4)(2-) particles.

Individual aerosol particles in and below clouds along a Mt. Fuji slope: Modification of sea-salt-containing particles by in-cloud processing

NASA Astrophysics Data System (ADS)

Ueda, S.; Hirose, Y.; Miura, K.; Okochi, H.

2014-02-01

Sizes and compositions of atmospheric aerosol particles can be altered by in-cloud processing by absorption/adsorption of gaseous and particulate materials and drying of aerosol particles that were formerly activated as cloud condensation nuclei. To elucidate differences of aerosol particles before and after in-cloud processing, aerosols were observed along a slope of Mt. Fuji, Japan (3776 m a.s.l.) during the summer in 2011 and 2012 using a portable laser particle counter (LPC) and an aerosol sampler. Aerosol samples for analyses of elemental compositions were obtained using a cascade impactor at top-of-cloud, in-cloud, and below-cloud altitudes. To investigate composition changes via in-cloud processing, individual particles (0.5-2 μm diameter) of samples from five cases (days) collected at different altitudes under similar backward air mass trajectory conditions were analyzed using a transmission electron microscope (TEM) equipped with an energy dispersive X-ray analyzer. For most cases (four cases), most particles at all altitudes mainly comprised sea salts: mainly Na with some S and/or Cl. Of those, in two cases, sea-salt-containing particles with Cl were found in below-cloud samples, although sea-salt-containing particles in top-of-cloud samples did not contain Cl. This result suggests that Cl in the sea salt was displaced by other cloud components. In the other two cases, sea-salt-containing particles on samples at all altitudes were without Cl. However, molar ratios of S to Na (S/Na) of the sea-salt-containing particles of top-of-cloud samples were higher than those of below-cloud samples, suggesting that sulfuric acid or sulfate was added to sea-salt-containing particles after complete displacement of Cl by absorption of SO2 or coagulation with sulfate. The additional volume of sulfuric acid in clouds for the two cases was estimated using the observed S/Na values of sea-salt-containing particles. The estimation revealed that size changes by in-cloud processing from below-cloud to top-of-cloud altitudes were less than 6% for sizes of 0.5-2 μm diameter. The obtained results will be useful to evaluate the aging effect and transition of aerosol particles through in-cloud processing.

Black Carbon Particle Number Distribution Measurements during the ATHENS-2013 Winter Campaign

NASA Astrophysics Data System (ADS)

Gkatzelis, Georgios; Papanastasiou, Dimitris; Florou, Kalliopi; Kaltsonoudis, Christos; Louvaris, Eyaggelos; Bezentakos, Spiridon; Biskos, Georgios; Pandis, Spuros

2014-05-01

Black Carbon (BC) particles emitted by anthropogenic sources play an important role both in climate change and in air quality degradation. Open burning in forests and savannas, combustion of diesel and solid fuels for cooking and heating in homes represent the majority of BC emissions. Earlier work has focused on the BC atmospheric direct radiative forcing that is mostly related to its mass concentration and optical properties of the corresponding particles. A variety of measurement techniques are used to measure the mass concentration of BC by taking advantage of its optical or physical properties. Moreover, the carbonaceous particles containing BC are also important for the indirect forcing of climate. This effect is mostly related to the number concentration of BC particles. The number distribution of BC particles especially below 100 nm is quite uncertain due to limitations of the existing measurement techniques. In this work we employed a thermodenuder-based method as an approach for the measurement of the BC number distribution. More specifically, we combined a thermodenuder (TD) operating at temperatures up to 300 ° C, with a Scanning Mobility Particle Sizer (SMPS) and a High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF AMS). Aerosol size and composition measurements were carried out both at ambient and at elevated TD temperatures in Athens field campaign during January and February of 2013. In parallel, a Multi-Angle Absorption Photometer (MAAP) provided information about the BC mass concentration while a Hygroscopic Tandem Differential Mobility Analyzer (HTDMA) measured the mixing state and the hygroscopicity of the particles as a function of their size. These measurements were then combined to estimate the number concentration of BC particles. Our analysis focused on different periods during the study. During some of them one source dominated the carbonaceous aerosol concentration. Such periods included rush hour traffic, nighttime wood burning, clean air transported from other areas, mixed sources, etc. The number fraction remaining after heating at 300 ° C for approximately 15 s during wood burning events was 80-90%, suggesting that practically all particles contained nonvolatile material. Combining the SMPS, MAAP, AMS, and HTDMA measurements we show that most of the sampled material was BC. On the contrary, during rush hour traffic the number fraction remaining was only 50-60% suggesting that more than half of the particles did not contain BC.

Spiders Tune Glue Viscosity to Maximize Adhesion.

PubMed

Amarpuri, Gaurav; Zhang, Ci; Diaz, Candido; Opell, Brent D; Blackledge, Todd A; Dhinojwala, Ali

2015-11-24

Adhesion in humid conditions is a fundamental challenge to both natural and synthetic adhesives. Yet, glue from most spider species becomes stickier as humidity increases. We find the adhesion of spider glue, from five diverse spider species, maximizes at very different humidities that matches their foraging habitats. By using high-speed imaging and spreading power law, we find that the glue viscosity varies over 5 orders of magnitude with humidity for each species, yet the viscosity at maximal adhesion for each species is nearly identical, 10(5)-10(6) cP. Many natural systems take advantage of viscosity to improve functional response, but spider glue's humidity responsiveness is a novel adaptation that makes the glue stickiest in each species' preferred habitat. This tuning is achieved by a combination of proteins and hygroscopic organic salts that determines water uptake in the glue. We therefore anticipate that manipulation of polymer-salts interaction to control viscosity can provide a simple mechanism to design humidity responsive smart adhesives.

Properties of jet engine combustion particles during the PartEmis experiment. Hygroscopic growth at supersaturated conditions

NASA Astrophysics Data System (ADS)

Hitzenberger, R.; Giebl, H.; Petzold, A.; Gysel, M.; Nyeki, S.; Weingartner, E.; Baltensperger, U.; Wilson, C. W.

2003-07-01

During the EU Project PartEmis, the microphysical properties of aircraft combustion aerosol were investigated. This study is focused on the ability of exhaust aerosols to act as cloud condensation nuclei (CCN). The combustor was operated at two different conditions representing old and modern aircraft engine technology. CCN concentrations were measured with the University of Vienna CCN counter [ Giebl et al., 2002] at supersaturations around 0.7%. The activation ratio (fraction of CCN in total aerosol) depended on the fuel sulphur content (FSC) and also on the operation conditions. CCN/CN ratios increased from 0.93 through 1.43 to 5.15 . 10-3 (old cruise conditions) and 0.67 through 3.04 to 7.94 . 10-3 (modern cruise conditions) when FSC increased from 50 through 410 to1270 μg/g. The activation behaviour was modelled using classical theories and with a semi-empirical model [ Gysel et al., 2003] based on measured hygroscopicity of the aerosol under subsaturated conditions, which gave the best agreement.

A technique for the measurement of organic aerosol hygroscopicity, oxidation level, and volatility distributions

NASA Astrophysics Data System (ADS)

Cain, Kerrigan P.; Pandis, Spyros N.

2017-12-01

Hygroscopicity, oxidation level, and volatility are three crucial properties of organic pollutants. This study assesses the feasibility of a novel measurement and analysis technique to determine these properties and establish their relationship. The proposed experimental setup utilizes a cloud condensation nuclei (CCN) counter to quantify hygroscopic activity, an aerosol mass spectrometer to measure the oxidation level, and a thermodenuder to evaluate the volatility. The setup was first tested with secondary organic aerosol (SOA) formed from the ozonolysis of α-pinene. The results of the first experiments indicated that, for this system, the less volatile SOA contained species that had on average lower O : C ratios and hygroscopicities. In this SOA system, both low- and high-volatility components can have comparable oxidation levels and hygroscopicities. The method developed here can be used to provide valuable insights about the relationships among organic aerosol hygroscopicity, oxidation level, and volatility.

Chemical composition of atmospheric aerosols resolved via positive matrix factorization

NASA Astrophysics Data System (ADS)

Äijälä, Mikko; Junninen, Heikki; Heikkinen, Liine; Petäjä, Tuukka; Kulmala, Markku; Worsnop, Douglas; Ehn, Mikael

2017-04-01

Atmospheric particulate matter is a complex mixture of various chemical species such as organic compounds, sulfates, nitrates, ammonia, chlorides, black carbon and sea salt. As aerosol chemical composition strongly influences aerosol climate effects (via cloud condensation nucleus activation, hygroscopic properties, aerosol optics, volatility and condensation) as well as health effects (toxicity, carcinogenicity, particle morphology), detailed understanding of atmospheric fine particle composition is widely beneficial for understanding these interactions. Unfortunately the comprehensive, detailed measurement of aerosol chemistry remains difficult due to the wide range of compounds present in the atmosphere as well as for the miniscule mass of the particles themselves compared to their carrier gas. Aerosol mass spectrometer (AMS; Canagaratna et al., 2007) is an instrument often used for characterization of non-refractive aerosol types: the near-universal vaporization and ionisation technique allows for measurement of most atmospheric-relevant compounds (with the notable exception of refractory matter such as sea salt, black carbon, metals and crustal matter). The downside of the hard ionisation applied is extensive fragmentation of sample molecules. However, the apparent loss of information in fragmentation can be partly offset by applying advanced statistical methods to extract information from the fragmentation patterns. In aerosol mass spectrometry statistical analysis methods, such as positive matrix factorization (PMF; Paatero, 1999) are usually applied for aerosol organic component only, to keep the number of factors to be resolved manageable, to retain the inorganic components for solution validation via correlation analysis, and to avoid inorganic species dominating the factor model. However, this practice smears out the interactions between organic and inorganic chemical components, and hinders the understanding of the connections between primary and secondary aerosols via atmospheric physicochemical processes (e.g. condensation and evaporation of gases) and on the other hand the potential non-linear summation (Spracklen et al., 2011 2011) of anthropogenic and biogenic aerosol emissions. From the perspective of statistical analysis there is no definite reason why inorganics could not be included, as long as their uncertainties are estimated correctly and their influence is properly weighted in the factor model. For result validation, external, additional information available from most measurement sites, such as correlations with trace gas concentrations or size distribution derived, mode-specific mass loadings can be used instead of AMS inorganics. In recent analyses, nitrate compounds have already been added to PMF analyses and shown to interact with organic semi-volatile compounds (Hao et al., 2014). In this study we tested including all the default AMS chemical species, i.e. organics, sulfates, nitrates, ammonia and chlorides, in a PMF analysis, and present potential interpretations of the results with regard to aerosol sources and the chemical processes shaping the aerosol types. In addition to resolving organic-dominated aerosol classes, the results shed light on inorganic salt formation and may imply formation of organics salts. Canagaratna, M. et al. (2007). Mass Spectrom Rev., 26:185-222. Hao, L. et al. (2014). Atmos. Chem. Phys., 14, 13483-13495. Paatero, P. (1999). J Comput Graph Stat, 8: 854-888. Spracklen, D. et al (2011) Atmos. Chem. Phys., 11, 12109-12136.

The Role of Biogenic and Anthropogenic Hydrocarbons in Aging of Atmospheric Soot

NASA Astrophysics Data System (ADS)

Khalizov, A. F.; Qiu, C.; Lin, Y.; Ma, Y.; Wang, L.; Zhang, R.

2012-12-01

Atmospheric soot is often found to be internally mixed with other aerosol constituents, yet the processes responsible for the soot aging are not well understood. We have conducted a systematic study on the role of several representative biogenic and anthropogenic volatile organic compounds (VOCs), including monoterpenes and aromatics, in atmospheric aging of combustion soot. Aging experiments were conducted in a fluoropolymer chamber on size-classified soot aerosols in the presence of a VOC and an oxidant, either ozone or photolytically generated hydroxyl radical (OH). The evolution in the aging state of soot was monitored from measurements of the particle mobility size and mass, which were used to derive information about particle effective density, dynamic shape factor, and coating thickness. When exposed to VOC and oxidant, soot particles promptly gain mass due to condensation of low-volatility and partitioning of semi-volatile VOC oxidation products. Depending on the VOC, the increase in the particle mass is accompanied by an increase or a decrease in the particle mobility diameter. In either case, the effective density of coated soot particles increases during aging because the condensed material fills in the voids of fractal soot aggregates, forcing their restructuring. The latter is confirmed by thermal denuding experiments, which show an increase in the effective density for soot that was first aged and then heated to remove the coating from the soot core. Hygroscopic and optical properties of soot are significantly altered by aging. Upon humidification, the coating absorbs water, increasing in volume and causing an additional restructuring of soot aggregates. Coated particles are sufficiently hygroscopic to activate to cloud droplets at atmospherically relevant water supersaturations. Aged soot shows stronger light absorption and scattering, with an enhancement magnitude depending on the coating thickness and nature of the coating precursor. The rate of aging and corresponding changes in the properties of soot are enhanced in the presence of nitrogen oxides (NOx = NO + NO2), a common combustion co-pollutant of soot. On the basis of our experimental results we conclude that biogenic and anthropogenic VOCs play a significant role in the atmospheric aging of combustion soot, shortening its atmospheric lifetime while enhancing impacts on air quality and climate.

Fabrication of SiC-Particles-Shielded Al Spheres upon Recycling Al/SiC Composites

NASA Astrophysics Data System (ADS)

Madarasz, D.; Budai, I.; Kaptay, G.

2011-06-01

Wettability of liquid A359 alloy on SiC particles under molten salt NaCl-KCl-NaF is found at 180 deg, meaning that SiC particles prefer the molten salt phase against the Al phase or the Al/molten salt interface. Thus, this molten salt can be used for recycling, i.e., to separate the phases in the SiC reinforced Al matrix composites. If the separation process is interrupted, Al droplets (submillimeter solidified powder) can be produced, stabilized/surrounded by a monolayer of shielding SiC particles.

Self-assembly of marine exudate particles and their impact on the CCN properties of nascent marine aerosol

NASA Astrophysics Data System (ADS)

Schill, S.; Zimmermann, K.; Ryder, O. S.; Campbell, N.; Collins, D. B.; Gianneschi, N.; Bertram, T. H.

2013-12-01

Spontaneous self-assembly of marine exudate particles has previously been observed in filtered seawater samples. The chemicophysical properties of these particles may alter the chemical composition and CCN properties of nascent marine aerosol, yet to date simultaneous measurement of seawater exudate particle formation rates and number distributions, with aerosol particle formation rates and CCN activity are lacking. Here, we use a novel Marine Aerosol Reference Tank (MART) system to experimentally mimic a phytoplankton bloom via sequential addition of biological surrogates, including sterol, galactose, lipopolysaccharide, BSA protein, and dipalmitoylphosphatidylcholine. Nascent sea-spray aerosol are generated in the MART system via a continuous plunging waterfall. Exudate particle assembly in the water is monitored via dynamic light scattering (DLS) and transmission electron microscopy (TEM) to obtain both the assembly kinetics of the particles as well as particle number distributions Simultaneous characterization of both particle production rates and super-saturated particle hygroscopicity are also discussed. This study permits analysis of the controlling role of the molecular composition of dissolved organic carbon in setting the production rates of colloidal material in the surface oceans.

Open-path, closed-path and reconstructed aerosol extinction at a rural site.

PubMed

Gordon, Timothy D; Prenni, Anthony J; Renfro, James R; McClure, Ethan; Hicks, Bill; Onasch, Timothy B; Freedman, Andrew; McMeeking, Gavin R; Chen, Ping

2018-04-09

The Handix Scientific Open-Path Cavity Ringdown Spectrometer (OPCRDS) was deployed during summer 2016 in Great Smoky Mountains National Park (GRSM). Extinction coefficients from the relatively new OPCRDS and from a more well-established extinction instrument agreed to within 7%. Aerosol hygroscopic growth (f(RH)) was calculated from the ratio of ambient extinction measured by the OPCRDS to dry extinction measured by a closed-path extinction monitor (Aerodyne's Cavity Attenuated Phase Shift Particulate Matter Extinction Monitor, CAPS PMex). Derived hygroscopicity (RH < 95%) from this campaign agreed with data from 1995 at the same site and time of year, which is noteworthy given the decreasing trend for organics and sulfate in the eastern U.S. However, maximum f(RH) values in 1995 were less than half as large as those recorded in 2016-possibly due to nephelometer truncation losses in 1995. Two hygroscopicity parameterizations were investigated using high time resolution OPCRDS+CAPS PMex data, and the K ext model was more accurate than the γ model. Data from the two ambient optical instruments, the OPCRDS and the open-path nephelometer, generally agreed; however, significant discrepancies between ambient scattering and extinction were observed, apparently driven by a combination of hygroscopic growth effects, which tend to increase nephelometer truncation losses and decrease sensitivity to the wavelength difference between the two instruments as a function of particle size. There was not a statistically significant difference in the mean reconstructed extinction values obtained from the original and the revised IMPROVE (Interagency Monitoring of Protected Visual Environments) equations. On average IMPROVE reconstructed extinction was ~25% lower than extinction measured by the OPCRDS, which suggests that the IMPROVE equations and 24-hr aerosol data are moderately successful in estimating current haze levels at GRSM. However, this conclusion is limited by the coarse temporal resolution and the low dynamic range of the IMPROVE reconstructed extinction.

How salt lakes affect atmospheric new particle formation: A case study in Western Australia.

PubMed

Kamilli, K A; Ofner, J; Krause, T; Sattler, T; Schmitt-Kopplin, P; Eitenberger, E; Friedbacher, G; Lendl, B; Lohninger, H; Schöler, H F; Held, A

2016-12-15

New particle formation was studied above salt lakes in-situ using a mobile aerosol chamber set up above the salt crust and organic-enriched layers of seven different salt lakes in Western Australia. This unique setup made it possible to explore the influence of salt lake emissions on atmospheric new particle formation, and to identify interactions of aqueous-phase and gas-phase chemistry. New particle formation was typically observed at enhanced air temperatures and enhanced solar irradiance. Volatile organic compounds were released from the salt lake surfaces, probably from a soil layer enriched in organic compounds from decomposed leaf litter, and accumulated in the chamber air. After oxidation of these organic precursor gases, the reaction products contributed to new particle formation with observed growth rates from 2.7 to 25.4nmh -1 . The presence of ferrous and ferric iron and a drop of pH values in the salt lake water just before new particle formation events indicated that organic compounds were also oxidized in the aqueous phase, affecting the new particle formation process in the atmosphere. The contribution of aqueous-phase chemistry to new particle formation is assumed, as a mixture of hundreds of oxidized organic compounds was characterized with several analytical techniques. This chemically diverse composition of the organic aerosol fraction contained sulfur- and nitrogen-containing organic compounds, and halogenated organic compounds. Coarse mode particles were analyzed using electron microscopy, energy dispersive X-ray spectroscopy and Raman spectroscopy. Ultra-high resolution mass spectrometry was applied to analyze filter samples. A targeted mass spectral analysis revealed the formation of organosulfates from monoterpene precursors and two known tracers for secondary organic aerosol formation from atmospheric oxidation of 1,8-cineole, which indicates that a complex interplay of aqueous-phase and gas-phase oxidation of monoterpenes contributes to new particle formation in the investigated salt lake environment. Copyright © 2016. Published by Elsevier B.V.

Numerical Investigation of the Ability of Salt Tracers to Represent the Residence Time Distribution of Fluidized Catalytic Cracking Particles

DOE PAGES

Lu, Liqiang; Gao, Xi; Li, Tingwen; ...

2017-11-02

For a long time, salt tracers have been used to measure the residence time distribution (RTD) of fluidized catalytic cracking (FCC) particles. However, due to limitations in experimental measurements and simulation methods, the ability of salt tracers to faithfully represent RTDs has never been directly investigated. Our current simulation results using coarse-grained computational fluid dynamic coupled with discrete element method (CFD-DEM) with filtered drag models show that the residence time of salt tracers with the same terminal velocity as FCC particles is slightly larger than that of FCC particles. This research also demonstrates the ability of filtered drag models tomore » predict the correct RTD curve for FCC particles while the homogeneous drag model may only be used in the dilute riser flow of Geldart type B particles. The RTD of large-scale reactors can then be efficiently investigated with our proposed numerical method as well as by using the old-fashioned salt tracer technology.« less

From hygroscopic aerosols to cloud droplets: The HygrA-CD campaign in the Athens basin - An overview.

PubMed

Papayannis, A; Argyrouli, A; Bougiatioti, A; Remoundaki, E; Vratolis, S; Nenes, A; Solomos, S; Komppula, M; Giannakaki, E; Kalogiros, J; Banks, R; Eleftheriadis, K; Mantas, E; Diapouli, E; Tzanis, C G; Kazadzis, S; Binietoglou, I; Labzovskii, L; Vande Hey, J; Zerefos, C S

2017-01-01

The international experimental campaign Hygroscopic Aerosols to Cloud Droplets (HygrA-CD), organized in the Greater Athens Area (GAA), Greece from 15 May to 22 June 2014, aimed to study the physico-chemical properties of aerosols and their impact on the formation of clouds in the convective Planetary Boundary Layer (PBL). We found that under continental (W-NW-N) and Etesian (NE) synoptic wind flow and with a deep moist PBL (~2-2.5km height), mixed hygroscopic (anthropogenic, biomass burning and marine) particles arrive over the GAA, and contribute to the formation of convective non-precipitating PBL clouds (of ~16-20μm mean diameter) with vertical extent up to 500m. Under these conditions, high updraft velocities (1-2ms -1 ) and cloud condensation nuclei (CCN) concentrations (~2000cm -3 at 1% supersaturation), generated clouds with an estimated cloud droplet number of ~600cm -3 . Under Saharan wind flow conditions (S-SW) a shallow PBL (<1-1.2km height) develops, leading to much higher CCN concentrations (~3500-5000cm -3 at 1% supersaturation) near the ground; updraft velocities, however, were significantly lower, with an estimated maximum cloud droplet number of ~200cm -3 and without observed significant PBL cloud formation. The largest contribution to cloud droplet number variance is attributed to the updraft velocity variability, followed by variances in aerosol number concentration. Copyright © 2016 Elsevier B.V. All rights reserved.

Diffusiophoresis of charged colloidal particles in the limit of very high salinity.

PubMed

Prieve, Dennis C; Malone, Stephanie M; Khair, Aditya S; Stout, Robert F; Kanj, Mazen Y

2018-06-13

Diffusiophoresis is the migration of a colloidal particle through a viscous fluid, caused by a gradient in concentration of some molecular solute; a long-range physical interaction between the particle and solute molecules is required. In the case of a charged particle and an ionic solute (e.g., table salt, NaCl), previous studies have predicted and experimentally verified the speed for very low salt concentrations at which the salt solution behaves ideally. The current study presents a study of diffusiophoresis at much higher salt concentrations (approaching the solubility limit). At such large salt concentrations, electrostatic interactions are almost completely screened, thus eliminating the long-range interaction required for diffusiophoresis; moreover, the high volume fraction occupied by ions makes the solution highly nonideal. Diffusiophoretic speeds were found to be measurable, albeit much smaller than for the same gradient at low salt concentrations.

Atmospheric Tar Balls: Particles from Biomass and Biofuel Burning

NASA Technical Reports Server (NTRS)

Posfai, Mihaly; Gelencser, Andras; Simonics, Renata; Arato, Krisztina; Li, Jia; Hobbs, Peter V.; Buseck, Peter R.

2004-01-01

Tar balls are amorphous, carbonaceous spherules that occur in the tropospheric aerosol as a result of biomass and biofuel burning. They form a distinct group of particles with diameters typically between 30 and 500 nm and readily identifiable with electron microscopy. Their lack of a turbostratic microstructure distinguishes them from soot, and their morphology and composition (approximately 90 mol% carbon) renders them distinct from other carbonaceous particles. Tar balls are particularly abundant in slightly aged (minutes to hours old) biomass smoke, indicating that they likely form by gas-to-particle conversion within smoke plumes. The material of tar balls is initially hygroscopic; however, the particles become largely insoluble as a result of free radical polymerization of their organic molecules. Consequently, tar balls are primarily externally mixed with other particle types, and they do not appreciably increase in size during aging. When tar balls coagulate with water-bearing particles, their material may partly dissolve and no longer be recognizable as distinct particles. Tar balls may contain organic compounds that absorb sunlight. They are an important, previously unrecognized type of carbonaceous (organic) atmospheric particle.

"Breath figures" on leaf surfaces-formation and effects of microscopic leaf wetness.

PubMed

Burkhardt, Juergen; Hunsche, Mauricio

2013-01-01

"Microscopic leaf wetness" means minute amounts of persistent liquid water on leaf surfaces which are invisible to the naked eye. The water is mainly maintained by transpired water vapor condensing onto the leaf surface and to attached leaf surface particles. With an estimated average thickness of less than 1 μm, microscopic leaf wetness is about two orders of magnitude thinner than morning dewfall. The most important physical processes which reduce the saturation vapor pressure and promote condensation are cuticular absorption and the deliquescence of hygroscopic leaf surface particles. Deliquescent salts form highly concentrated solutions. Depending on the type and concentration of the dissolved ions, the physicochemical properties of microscopic leaf wetness can be considerably different from those of pure water. Microscopic leaf wetness can form continuous thin layers on hydrophobic leaf surfaces and in specific cases can act similar to surfactants, enabling a strong potential influence on the foliar exchange of ions. Microscopic leaf wetness can also enhance the dissolution, the emission, and the reaction of specific atmospheric trace gases e.g., ammonia, SO2, or ozone, leading to a strong potential role for microscopic leaf wetness in plant/atmosphere interaction. Due to its difficult detection, there is little knowledge about the occurrence and the properties of microscopic leaf wetness. However, based on the existing evidence and on physicochemical reasoning it can be hypothesized that microscopic leaf wetness occurs on almost any plant worldwide and often permanently, and that it significantly influences the exchange processes of the leaf surface with its neighboring compartments, i.e., the plant interior and the atmosphere. The omission of microscopic water in general leaf wetness concepts has caused far-reaching, misleading conclusions in the past.

Real-time observational evidence of changing Asian dust morphology with the mixing of heavy anthropogenic pollution

NASA Astrophysics Data System (ADS)

Pan, X.; Uno, I.; Wang, Z.; Nishizawa, T.; Sugimoto, N.; Yamamoto, S.; Kobayashi, H.; Sun, Y.; Fu, P.; Tang, X.; Wang, Z.

2017-12-01

Natural mineral dust and heavy anthropogenic pollution and its complex interactions cause significant environmental problems in East Asia. Due to restrictions of observing technique, real-time morphological change in Asian dust particles owing to coating process of anthropogenic pollutants is still statistically unclear. Here, we first used a newly developed, single-particle polarization detector and quantitatively investigate the evolution of the polarization property of backscattering light reflected from dust particle as they were mixing with anthropogenic pollutants in North China. The decrease in observed depolarization ratio is mainly attributed to the decrease of aspect ratio of the dust particles as a result of continuous coating processes. Hygroscopic growth of Calcium nitrate (Ca(NO3)2) on the surface of the dust particles played a vital role, particularly when they are stagnant in the polluted region with high RH conditions. Reliable statistics highlight the significant importance of internally mixed, `quasi-spherical' Asian dust particles, which markedly act as cloud condensation nuclei and exert regional climate change.

Real-time observational evidence of changing Asian dust morphology with the mixing of heavy anthropogenic pollution.

PubMed

Pan, Xiaole; Uno, Itsushi; Wang, Zhe; Nishizawa, Tomoaki; Sugimoto, Nobuo; Yamamoto, Shigekazu; Kobayashi, Hiroshi; Sun, Yele; Fu, Pingqing; Tang, Xiao; Wang, Zifa

2017-03-23

Natural mineral dust and heavy anthropogenic pollution and its complex interactions cause significant environmental problems in East Asia. Due to restrictions of observing technique, real-time morphological change in Asian dust particles owing to coating process of anthropogenic pollutants is still statistically unclear. Here, we first used a newly developed, single-particle polarization detector and quantitatively investigate the evolution of the polarization property of backscattering light reflected from dust particle as they were mixing with anthropogenic pollutants in North China. The decrease in observed depolarization ratio is mainly attributed to the decrease of aspect ratio of the dust particles as a result of continuous coating processes. Hygroscopic growth of Calcium nitrate (Ca(NO 3 ) 2 ) on the surface of the dust particles played a vital role, particularly when they are stagnant in the polluted region with high RH conditions. Reliable statistics highlight the significant importance of internally mixed, 'quasi-spherical' Asian dust particles, which markedly act as cloud condensation nuclei and exert regional climate change.

Influence of air mass origin on aerosol properties at a remote Michigan forest site

NASA Astrophysics Data System (ADS)

VanReken, T. M.; Mwaniki, G. R.; Wallace, H. W.; Pressley, S. N.; Erickson, M. H.; Jobson, B. T.; Lamb, B. K.

2015-04-01

The northern Great Lakes region of North America is a large, relatively pristine area. To date, there has only been limited study of the atmospheric aerosol in this region. During summer 2009, a detailed characterization of the atmospheric aerosol was conducted at the University of Michigan Biological Station (UMBS) as part of the Community Atmosphere-Biosphere Interactions Experiment (CABINEX). Measurements included particle size distribution, water-soluble composition, and CCN activity. Aerosol properties were strongly dependent on the origin of the air masses reaching the site. For ∼60% of the study period, air was transported from sparsely populated regions to the northwest. During these times aerosol loadings were low, with mean number and volume concentrations of 1630 cm-3 and 1.91 μm3 cm-3, respectively. The aerosol during clean periods was dominated by organics, and exhibited low hygroscopicities (mean κ = 0.18 at s = 0.3%). When air was from more populated regions to the east and south (∼29% of the time), aerosol properties reflected a stronger anthropogenic influence, with 85% greater particle number concentrations, 2.5 times greater aerosol volume, six times more sulfate mass, and increased hygroscopicity (mean к = 0.24 at s = 0.3%). These trends are have the potential to influence forest-atmosphere interactions and should be targeted for future study.

Influence of air mass origin on aerosol properties at a remote Michigan forest site

DOE PAGES

VanReken, T. M.; Mwaniki, G. R.; Wallace, H. W.; ...

2015-02-10

The northern Great Lakes region of North America is a large, relatively pristine area. To date, there has only been limited study of the atmospheric aerosol in this region. During summer 2009, a detailed characterization of the atmospheric aerosol was conducted at the University of Michigan Biological Station (UMBS) as part of the Community Atmosphere–Biosphere Interactions Experiment (CABINEX). Measurements included particle size distribution, water-soluble composition, and CCN activity. Aerosol properties were strongly dependent on the origin of the air masses reaching the site. For ~60% of the study period, air was transported from sparsely populated regions to the northwest. Duringmore » these times aerosol loadings were low, with mean number and volume concentrations of 1630 cm -3 and 1.91 μm 3 cm -3, respectively. The aerosol during clean periods was dominated by organics, and exhibited low hygroscopicities (mean κ = 0.18 at s = 0.3%). When air was from more populated regions to the east and south (~29% of the time), aerosol properties reflected a stronger anthropogenic influence, with 85% greater particle number concentrations, 2.5 times greater aerosol volume, six times more sulfate mass, and increased hygroscopicity (mean к = 0.24 at s = 0.3%). Furthermore, these trends are have the potential to influence forest–atmosphere interactions and should be targeted for future study.« less

Anthropogenic contamination of tap water, beer, and sea salt

PubMed Central

2018-01-01

Plastic pollution has been well documented in natural environments, including the open waters and sediments within lakes and rivers, the open ocean and even the air, but less attention has been paid to synthetic polymers in human consumables. Since multiple toxicity studies indicate risks to human health when plastic particles are ingested, more needs to be known about the presence and abundance of anthropogenic particles in human foods and beverages. This study investigates the presence of anthropogenic particles in 159 samples of globally sourced tap water, 12 brands of Laurentian Great Lakes beer, and 12 brands of commercial sea salt. Of the tap water samples analyzed, 81% were found to contain anthropogenic particles. The majority of these particles were fibers (98.3%) between 0.1–5 mm in length. The range was 0 to 61 particles/L, with an overall mean of 5.45 particles/L. Anthropogenic debris was found in each brand of beer and salt. Of the extracted particles, over 99% were fibers. After adjusting for particles found in lab blanks for both salt and beer, the average number of particles found in beer was 4.05 particles/L with a range of 0 to 14.3 particles/L and the average number of particles found in each brand of salt was 212 particles/kg with a range of 46.7 to 806 particles/kg. Based on consumer guidelines, our results indicate the average person ingests over 5,800 particles of synthetic debris from these three sources annually, with the largest contribution coming from tap water (88%). PMID:29641556

Direct observation of nitrate and sulfate formations from mineral dust and sea-salts using low- Z particle electron probe X-ray microanalysis

NASA Astrophysics Data System (ADS)

Hwang, HeeJin; Ro, Chul-Un

In the present work, it is demonstrated that a single particle analytical technique, named low- Z particle electron probe X-ray microanalysis, is a practically useful tool for the study of heterogeneous reactions of mineral dust and sea-salts when this analytical technique was applied to a sample collected during an Asian Dust storm event. The technique does not require a special treatment of sample to identify particles reacted in the air. Also, quantitative chemical speciation of reacted particles can provide concrete information on what chemical reaction, if any, occurred for individual particles. Among overall 178 analyzed particles, the number of reacted particles is 81 and heterogeneous chemical reactions mostly occurred on CaCO 3 mineral dust (54 particles) and sea-salts (26 particles). Several observations made for the Asian Dust sample in the present work are: (1) CaCO 3 species almost completely reacted to produce mostly Ca(NO 3) 2 species, and CaSO 4 to a much lesser extent. (2) When reacted particles contain CaSO 4, almost all of them are internally mixed with nitrate. (3) Reacted CaCO 3 particles seem to contain moisture when they were collected. (4) Some reacted CaCO 3 particles have unreacted mineral species, such as aluminosilicates, iron oxide, SiO 2, etc., in the core region. (5) All sea-salt particles are observed to have reacted in the air. Some of them were recrystallized in the air before being collected and they are observed as crystalline NaNO 3 particles. (6) Many sea-salts were collected as water drops, and some of them were fractionally recrystallized on Ag collecting substrate. When sea-salts were not recrystallized on the substrate, they are found as particles internally mixed with NaNO 3 and Mg(NO 3) 2, and in some cases SO 4 and Cl species as additional anions.

Improved oral absorption of cilostazol via sulfonate salt formation with mesylate and besylate

PubMed Central

Seo, Jae Hong; Park, Jung Bae; Choi, Woong-Kee; Park, Sunhwa; Sung, Yun Jin; Oh, Euichaul; Bae, Soo Kyung

2015-01-01

Objective Cilostazol is a Biopharmaceutical Classification System class II drug with low solubility and high permeability, so its oral absorption is variable and incomplete. The aim of this study was to prepare two sulfonate salts of cilostazol to increase the dissolution and hence the oral bioavailability of cilostazol. Methods Cilostazol mesylate and cilostazol besylate were synthesized from cilostazol by acid addition reaction with methane sulfonic acid and benzene sulfonic acid, respectively. The salt preparations were characterized by nuclear magnetic resonance spectroscopy. The water contents, hygroscopicity, stress stability, and photostability of the two cilostazol salts were also determined. The dissolution profiles in various pH conditions and pharmacokinetic studies in rats were compared with those of cilostazol-free base. Results The two cilostazol salts exhibited good physicochemical properties, such as nonhygroscopicity, stress stability, and photostability, which make it suitable for the preparation of pharmaceutical formulations. Both cilostazol mesylate and cilostazol besylate showed significantly improved dissolution rate and extent of drug release in the pH range 1.2–6.8 compared to the cilostazol-free base. In addition, after oral administration to rats, cilostazol mesylate and cilostazol besylate showed increases in Cmax and AUCt of approximately 3.65- and 2.87-fold and 3.88- and 2.94-fold, respectively, compared to cilostazol-free base. Conclusion This study showed that two novel salts of cilostazol, such as cilostazol mesylate and cilostazol besylate, could be used to enhance its oral absorption. The findings warrant further preclinical and clinical studies on cilostazol mesylate and cilostazol besylate at doses lower than the usually recommended dosage, so that it can be established as an alternative to the marketed cilostazol tablet. PMID:26251575

Cryochemical method for forming spherical metal oxide particles from metal salt solutions

DOEpatents

Tinkle, M.C.

1973-12-01

A method is described of preparing small metal oxide spheres cryochemically utilizing metal salts (e.g., nitrates) that cannot readily be dried and calcined without loss of sphericity of the particles. Such metal salts are cryochemically formed into small spheres, partially or completely converted to an insoluble salt, and dried and calcined. (Official Gazette)

Laboratory Investigations on the Survival of Bacillus subtilis Spores in Deliquescent Salt Mars Analog Environments.

PubMed

Nuding, Danielle L; Gough, Raina V; Venkateswaran, Kasthuri J; Spry, James A; Tolbert, Margaret A

2017-10-01

Observed features such as recurring slope lineae suggest that liquid water may exist on the surface and near-subsurface of Mars today. The presence of this liquid water, likely in the form of a brine, has important implications for the present-day water cycle, habitability, and planetary protection policies. It is possible that this water is formed, at least partially, by deliquescence of salts, a process during which hygroscopic salts absorb water vapor from the atmosphere and form a saturated liquid brine. We performed laboratory experiments to examine the ability of Bacillus subtilis (B-168) spores, alone or mixed with calcium perchlorate salt (Ca(ClO 4 ) 2 ), to form liquid water via deliquescence under Mars-relevant conditions. Spore survival after exposure to these conditions was examined. An environmental chamber was used to expose the samples to temperature and relative humidity (RH) values similar to those found on Mars, and Raman microscopy was used to identify the phases of water and salt that were present and to confirm the presence of spores. We found that B-168 spores did not condense any detectable water vapor on their own during the diurnal cycle, even at 100% RH. However, when spores were mixed with perchlorate salt, the entire sample deliquesced at low RH values, immersing the spores in a brine solution during the majority of the simulated martian temperature and humidity cycle. After exposure to the simulated diurnal cycles and, in some cases, perchlorate brine, the impact of each environmental scenario on spore survival was estimated by standard plate assay. We found that, if there are deliquescent salts in contact with spores, there is a mechanism for the spores to acquire liquid water starting with only atmospheric water vapor as the H 2 O source. Also, neither crystalline nor liquid Ca(ClO 4 ) 2 is sporicidal despite the low water activity. Key Words: Raman microscopy-Mars-Planetary protection-Salts-Water activity. Astrobiology 17, 997-1008.

60 years of UK visibility measurements: impact of meteorology and atmospheric pollutants on visibility

NASA Astrophysics Data System (ADS)

Singh, Ajit; Bloss, William J.; Pope, Francis D.

2017-02-01

Reduced visibility is an indicator of poor air quality. Moreover, degradation in visibility can be hazardous to human safety; for example, low visibility can lead to road, rail, sea and air accidents. In this paper, we explore the combined influence of atmospheric aerosol particle and gas characteristics, and meteorology, on long-term visibility. We use visibility data from eight meteorological stations, situated in the UK, which have been running since the 1950s. The site locations include urban, rural and marine environments. Most stations show a long-term trend of increasing visibility, which is indicative of reductions in air pollution, especially in urban areas. Additionally, the visibility at all sites shows a very clear dependence on relative humidity, indicating the importance of aerosol hygroscopicity on the ability of aerosol particles to scatter radiation. The dependence of visibility on other meteorological parameters, such as wind speed and wind direction, is also investigated. Most stations show long-term increases in temperature which can be ascribed to climate change, land-use changes (e.g. urban heat island effects) or a combination of both; the observed effect is greatest in urban areas. The impact of this temperature change upon local relative humidity is discussed. To explain the long-term visibility trends and their dependence on meteorological conditions, the measured data were fitted to a newly developed light-extinction model to generate predictions of historic aerosol and gas scattering and absorbing properties. In general, an excellent fit was achieved between measured and modelled visibility for all eight sites. The model incorporates parameterizations of aerosol hygroscopicity, particle concentration, particle scattering, and particle and gas absorption. This new model should be applicable and is easily transferrable to other data sets worldwide. Hence, historical visibility data can be used to assess trends in aerosol particle properties. This approach may help constrain global model simulations which attempt to generate aerosol fields for time periods when observational data are scarce or non-existent. Both the measured visibility and the modelled aerosol properties reported in this paper highlight the success of the UK's Clean Air Act, which was passed in 1956, in cleaning the atmosphere of visibility-reducing pollutants.

Ash aggregation enhanced by deposition and redistribution of salt on the surface of volcanic ash in eruption plumes.

PubMed

Mueller, Sebastian B; Ayris, Paul M; Wadsworth, Fabian B; Kueppers, Ulrich; Casas, Ana S; Delmelle, Pierre; Taddeucci, Jacopo; Jacob, Michael; Dingwell, Donald B

2017-03-31

Interactions with volcanic gases in eruption plumes produce soluble salt deposits on the surface of volcanic ash. While it has been postulated that saturation-driven precipitation of salts following the dissolution of ash surfaces by condensed acidic liquids is a primary mechanism of salt formation during an eruption, it is only recently that this mechanism has been subjected to detailed study. Here we spray water and HCl droplets into a suspension of salt-doped synthetic glass or volcanic ash particles, and produce aggregates. Deposition of acidic liquid droplets on ash particles promotes dissolution of existing salts and leaches cations from the underlying material surface. The flow of liquid, due to capillary forces, will be directed to particle-particle contact points where subsequent precipitation of salts will cement the aggregate. Our data suggest that volcanically-relevant loads of surface salts can be produced by acid condensation in eruptive settings. Several minor and trace elements mobilised by surface dissolution are biologically relevant; geographic areas with aggregation-mediated ash fallout could be "hotspots" for the post-deposition release of these elements. The role of liquids in re-distributing surface salts and cementing ash aggregates also offers further insight into the mechanisms which preserve well-structured aggregates in some ash deposits.

Ash aggregation enhanced by deposition and redistribution of salt on the surface of volcanic ash in eruption plumes

PubMed Central

Mueller, Sebastian B.; Ayris, Paul M.; Wadsworth, Fabian B.; Kueppers, Ulrich; Casas, Ana S.; Delmelle, Pierre; Taddeucci, Jacopo; Jacob, Michael; Dingwell, Donald B.

2017-01-01

Interactions with volcanic gases in eruption plumes produce soluble salt deposits on the surface of volcanic ash. While it has been postulated that saturation-driven precipitation of salts following the dissolution of ash surfaces by condensed acidic liquids is a primary mechanism of salt formation during an eruption, it is only recently that this mechanism has been subjected to detailed study. Here we spray water and HCl droplets into a suspension of salt-doped synthetic glass or volcanic ash particles, and produce aggregates. Deposition of acidic liquid droplets on ash particles promotes dissolution of existing salts and leaches cations from the underlying material surface. The flow of liquid, due to capillary forces, will be directed to particle-particle contact points where subsequent precipitation of salts will cement the aggregate. Our data suggest that volcanically-relevant loads of surface salts can be produced by acid condensation in eruptive settings. Several minor and trace elements mobilised by surface dissolution are biologically relevant; geographic areas with aggregation-mediated ash fallout could be “hotspots” for the post-deposition release of these elements. The role of liquids in re-distributing surface salts and cementing ash aggregates also offers further insight into the mechanisms which preserve well-structured aggregates in some ash deposits. PMID:28361966

The presence of microplastics in commercial salts from different countries

NASA Astrophysics Data System (ADS)

Karami, Ali; Golieskardi, Abolfazl; Keong Choo, Cheng; Larat, Vincent; Galloway, Tamara S.; Salamatinia, Babak

2017-04-01

The occurrence of microplastics (MPs) in saltwater bodies is relatively well studied, but nothing is known about their presence in most of the commercial salts that are widely consumed by humans across the globe. Here, we extracted MP-like particles larger than 149 μm from 17 salt brands originating from 8 different countries followed by the identification of their polymer composition using micro-Raman spectroscopy. Microplastics were absent in one brand while others contained between 1 to 10 MPs/Kg of salt. Out of the 72 extracted particles, 41.6% were plastic polymers, 23.6% were pigments, 5.50% were amorphous carbon, and 29.1% remained unidentified. The particle size (mean ± SD) was 515 ± 171 μm. The most common plastic polymers were polypropylene (40.0%) and polyethylene (33.3%). Fragments were the primary form of MPs (63.8%) followed by filaments (25.6%) and films (10.6%). According to our results, the low level of anthropogenic particles intake from the salts (maximum 37 particles per individual per annum) warrants negligible health impacts. However, to better understand the health risks associated with salt consumption, further development in extraction protocols are needed to isolate anthropogenic particles smaller than 149 μm.

The presence of microplastics in commercial salts from different countries

PubMed Central

Karami, Ali; Golieskardi, Abolfazl; Keong Choo, Cheng; Larat, Vincent; Galloway, Tamara S.; Salamatinia, Babak

2017-01-01

The occurrence of microplastics (MPs) in saltwater bodies is relatively well studied, but nothing is known about their presence in most of the commercial salts that are widely consumed by humans across the globe. Here, we extracted MP-like particles larger than 149 μm from 17 salt brands originating from 8 different countries followed by the identification of their polymer composition using micro-Raman spectroscopy. Microplastics were absent in one brand while others contained between 1 to 10 MPs/Kg of salt. Out of the 72 extracted particles, 41.6% were plastic polymers, 23.6% were pigments, 5.50% were amorphous carbon, and 29.1% remained unidentified. The particle size (mean ± SD) was 515 ± 171 μm. The most common plastic polymers were polypropylene (40.0%) and polyethylene (33.3%). Fragments were the primary form of MPs (63.8%) followed by filaments (25.6%) and films (10.6%). According to our results, the low level of anthropogenic particles intake from the salts (maximum 37 particles per individual per annum) warrants negligible health impacts. However, to better understand the health risks associated with salt consumption, further development in extraction protocols are needed to isolate anthropogenic particles smaller than 149 μm. PMID:28383020

A preliminary evaluation of immune stimulation following exposure to metal particles and ions using the mouse popliteal lymph node assay

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

Tvermoes, Brooke E., E-mail: brooke.tvermoes@cardn

The objective of this preliminary study was to evaluate the threshold for immune stimulation in mice following local exposure to metal particles and ions representative of normal-functioning cobalt-chromium (CoCr) metal-on-metal (MoM) hip implants. The popliteal lymph node assay (PLNA) was used in this study to assess immune responses in BALB/c mice following treatment with chromium-oxide (Cr{sub 2}O{sub 3}) particles, metal salts (CoCl{sub 2}, CrCl{sub 3} and NiCl{sub 2}), or Cr{sub 2}O{sub 3} particles together with metal salts using single-dose exposures representing approximately 10 days (0.000114 mg), 19 years (0.0800 mg), and 40 years (0.171 mg) of normal implant wear. Themore » immune response elicited following treatment with Cr{sub 2}O{sub 3} particles together with metal salts was also assessed at four additional doses equivalent to approximately 1.5 months (0.0005 mg), 0.6 years (0.0025 mg), 2.3 years (0.01 mg), and 9.3 years (0.04 mg) of normal implant wear. Mice were injected subcutaneously (50 μL) into the right hind foot with the test article, or with the relevant vehicle control. The proliferative response of the draining lymph node cells (LNC) was measured four days after treatment, and stimulation indices (SI) were derived relative to vehicle controls. The PLNA was negative (SI < 3) for all Cr{sub 2}O{sub 3} particle doses, and was also negative at the lowest dose of the metal salt mixture, and the lowest four doses of the Cr{sub 2}O{sub 3} particles with metal salt mixture. The PLNA was positive (SI > 3) at the highest two doses of the metal salt mixture and the highest three doses of the Cr{sub 2}O{sub 3} particles with the metal salt mixture. The provisional NOAEL and LOAEL values identified in this study for immune activation corresponds to Co and Cr concentrations in the synovial fluid approximately 500 and 2000 times higher than that reported for normal-functioning MoM hip implants, respectively. Overall, these results indicate that normal wear conditions are unlikely to result in immune stimulation in individuals not previously sensitized to metals. - Highlights: • Immune responses in mice were assessed following treatment with Cr2O3 particles with metal salts. • The PLNA was negative (SI < 3) for all Cr2O3 particle doses. • A LOAEL for immune activation was identified at 0.04 mg of metal particles with metal salts. • A NOAEL for immune activation was identified at 0.01 mg of metal particles with metal salts.« less

Aerosol hygroscopic growth parameterization based on a solute specific coefficient

NASA Astrophysics Data System (ADS)

Metzger, S.; Steil, B.; Xu, L.; Penner, J. E.; Lelieveld, J.

2011-09-01

Water is a main component of atmospheric aerosols and its amount depends on the particle chemical composition. We introduce a new parameterization for the aerosol hygroscopic growth factor (HGF), based on an empirical relation between water activity (aw) and solute molality (μs) through a single solute specific coefficient νi. Three main advantages are: (1) wide applicability, (2) simplicity and (3) analytical nature. (1) Our approach considers the Kelvin effect and covers ideal solutions at large relative humidity (RH), including CCN activation, as well as concentrated solutions with high ionic strength at low RH such as the relative humidity of deliquescence (RHD). (2) A single νi coefficient suffices to parameterize the HGF for a wide range of particle sizes, from nanometer nucleation mode to micrometer coarse mode particles. (3) In contrast to previous methods, our analytical aw parameterization depends not only on a linear correction factor for the solute molality, instead νi also appears in the exponent in form x · ax. According to our findings, νi can be assumed constant for the entire aw range (0-1). Thus, the νi based method is computationally efficient. In this work we focus on single solute solutions, where νi is pre-determined with the bisection method from our analytical equations using RHD measurements and the saturation molality μssat. The computed aerosol HGF and supersaturation (Köhler-theory) compare well with the results of the thermodynamic reference model E-AIM for the key compounds NaCl and (NH4)2SO4 relevant for CCN modeling and calibration studies. The equations introduced here provide the basis of our revised gas-liquid-solid partitioning model, i.e. version 4 of the EQuilibrium Simplified Aerosol Model (EQSAM4), described in a companion paper.

North Atlantic Aerosol Radiative Impacts Based on Satellite Measurements and Aerosol Intensive Properties from TARFOX and ACE-2

NASA Technical Reports Server (NTRS)

Russell, P. B.; Bergstrom, Robert W.; Schmid, B.; Livingston, J. M.

2000-01-01

We estimate the impact of North Atlantic aerosols on the net short-wave flux at the tropopause by combining satellite-derived aerosol optical depth (AOD) maps with model aerosol properties determined via closure analyses in TARFOX and ACE 2. We exclude African dust, primarily by restricting latitudes to 25-60 N. The analyses use in situ aerosol composition measurements and air- and ship-borne sun-photometer measurements of AOD spectra. The aerosol model yields computed flux sensitivities (dFlux/dAOD) that agree with measurements by airborne flux radiometers in TARFOX. Its midvisible single-scattering albedo is 0.9. which is in the range obtained from in situ measurements of scattering and absorption in both TARFOX and ACE 2. Combining satellite-derived AOD maps with the aerosol model yields maps of 24-hour average net radiative flux changes. For simultaneous AVHRR, radiance measurements exceeded the sunphotometer AODs by about 0.04. However. shipboard sunphotometer and AVHRR AODs agreed Within 0.02 for data acquired during satellite overflights on two other days. We discuss attempts to demonstrate column closure within the MBL by comparing shipboard sunphotometer AODs and values calculated from simultaneous shipboard in-situ aerosol size distribution measurements. These comparisons were mostly unsuccessful, but they illustrate the difficulties inherent in this type of closure analysis. Specifically, AODs derived from near-surface in-situ size distribution measurements are extremely sensitive to the assumed hygroscopic growth model that itself requires an assumption of particle composition as a function of height and size, to the radiosonde-measured relative humidity, and to the vertical profile of particle number. We investigate further the effects of hygroscopic particle growth within the MBL by using shipboard lidar aerosol backscatter profiles together with the sunphotometer AOD.

Final Report: "Collaborative Project. Understanding the Chemical Processes That Affect Growth Rates of Freshly Nucleated Particles"

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

Smith, James N.; McMurry, Peter H.

This final technical report describes our research activities that have, as the ultimate goal, the development of a model that explains growth rates of freshly nucleated particles. The research activities, which combine field observations with laboratory experiments, explore the relationship between concentrations of gas-phase species that contribute to growth and the rates at which those species are taken up. We also describe measurements of the chemical composition of freshly nucleated particles in a variety of locales, as well as properties (especially hygroscopicity) that influence their effects on climate. Our measurements include a self-organized, DOE-ARM funded project at the Southern Greatmore » Plains site, the New Particle Formation Study (NPFS), which took place during spring 2013. NPFS data are available to the research community on the ARM data archive, providing a unique suite observations of trace gas and aerosols that are associated with the formation and growth of atmospheric aerosol particles.« less

Biogenic Potassium Salt Particles as Seeds for Secondary Organic Aerosol in the Amazon

NASA Astrophysics Data System (ADS)

Pöhlker, Christopher; Wiedemann, Kenia T.; Sinha, Bärbel; Shiraiwa, Manabu; Gunthe, Sachin S.; Smith, Mackenzie; Su, Hang; Artaxo, Paulo; Chen, Qi; Cheng, Yafang; Elbert, Wolfgang; Gilles, Mary K.; Kilcoyne, Arthur L. D.; Moffet, Ryan C.; Weigand, Markus; Martin, Scot T.; Pöschl, Ulrich; Andreae, Meinrat O.

2012-08-01

The fine particles serving as cloud condensation nuclei in pristine Amazonian rainforest air consist mostly of secondary organic aerosol. Their origin is enigmatic, however, because new particle formation in the atmosphere is not observed. Here, we show that the growth of organic aerosol particles can be initiated by potassium-salt-rich particles emitted by biota in the rainforest. These particles act as seeds for the condensation of low- or semi-volatile organic compounds from the atmospheric gas phase or multiphase oxidation of isoprene and terpenes. Our findings suggest that the primary emission of biogenic salt particles directly influences the number concentration of cloud condensation nuclei and affects the microphysics of cloud formation and precipitation over the rainforest.

Fabrication of transparent ceramics using nanoparticles

DOEpatents

Cherepy, Nerine J; Tillotson, Thomas M; Kuntz, Joshua D; Payne, Stephen A

2012-09-18

A method of fabrication of a transparent ceramic using nanoparticles synthesized via organic acid complexation-combustion includes providing metal salts, dissolving said metal salts to produce an aqueous salt solution, adding an organic chelating agent to produce a complexed-metal sol, heating said complexed-metal sol to produce a gel, drying said gel to produce a powder, combusting said powder to produce nano-particles, calcining said nano-particles to produce oxide nano-particles, forming said oxide nano-particles into a green body, and sintering said green body to produce the transparent ceramic.

Optical and physical requirements for fluid particles marking trailing vortices from aircraft

NASA Technical Reports Server (NTRS)

Back, L. H.

1976-01-01

A theoretical study of the optical and physical requirements of marking trailing vortices that emanate from aircraft wings was carried out by considering particulate light-scattering properties, ability of particles to follow trailing vortices, and survival time of particles to vortex dissipation. Liquid droplets undergoing evaporation and molecular dispersion were investigated. Droplets should have lifetimes of about 300 sec. Droplet size should be about 1 micron to maximize light scattering with the minimum mass of liquid required. Droplets of this small size would spiral outward very slowly and essentially remain in the vortex cores. Nontoxic hygroscopic liquids, having an affinity for moisture in the air, have been identified. These liquids have relatively low vapor pressures of order 10 to the -5 mm Hg that would insure droplet persistence long enough to mark trailing vortices.

Design of a solar energy assisted air conditioning system

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

Varlet, J.L.P.; Johnson, B.R.; Vora, J.N.

1976-03-24

Energy consumption in air conditioning systems can be reduced by reducing the water content of air before cooling. This reduction in humidity can be accomplished by contacting the humid air with a hygroscopic solution in a spray tower. The hydroscopic solution, diluted by water from the air, can be reconcentrated in a solar evaporator. A solar evaporator for this purpose was evaluated by formulating simultaneous energy and mass balances for forced air convection through the evaporator. Temperatures in the evaporator were calculated by numerical integration of the mathematical model. The calculations indicated that the salt solution cannot be reconcentrated inmore » a forced convection evaporator because of the large energy losses associated with the air stream passing through the evaporator.« less

On the edge of habitability and the extremes of liquidity

NASA Astrophysics Data System (ADS)

Hansen-Goos, Hendrik; Thomson, Erik S.; Wettlaufer, J. S.

2014-08-01

The physical and biological mechanisms that extend the equilibrium domain of liquid water into the ice region of the bulk phase diagram are examined in view of their importance for the enhancement of planetary habitability. The physical phenomena studied are the premelting of ice, which allows for films of liquid water at temperatures well below freezing, and the wetting of hygroscopic salts with the persistence of briny films even for thermodynamic conditions remote from those of bulk liquid water. Organisms are known to produce a variety of frost-suppressing substances, one of which, the anti-freeze protein, is described here. In this article, we provide a synthesis of theoretical and experimental studies whilst extending ideas into new territory as we address the question of habitability.

Low hygroscopic spray-dried powders with trans-glycosylated food additives enhance the solubility and oral bioavailability of ipriflavone.

PubMed

Fujimori, Miki; Kadota, Kazunori; Kato, Kouki; Seto, Yoshiki; Onoue, Satomi; Sato, Hideyuki; Ueda, Hiroshi; Tozuka, Yuichi

2016-01-01

The improvement in the solubility and dissolution rate may promote a superior absorption property towards the human body. The spray-dried powders (SDPs) of ipriflavone, which was used as a model hydrophobic flavone, with trans-glycosylated rutin (Rutin-G) showed the highest solubilizing effect of ipriflavone among three types of trans-glycosylated food additives. The SDPs of ipriflavone with Rutin-G have both a significant higher dissolution rate and solubility enhancement of ipriflavone. This spray-dried formulation of ipriflavone with Rutin-G exhibited a low hygroscopicity as a critical factor in product preservation. In addition, an improvement in the oral absorption of ipriflavone was achieved by means of preparing composite particles of ipriflavone/Rutin-G via spray drying, indicating a 4.3-fold increase in the area under the plasma concentration-time curve compared with that of untreated ipriflavone. These phenomena could be applicable to food ingredients involving hydrophobic flavones for producing healthy food with a high quality. Copyright © 2015 Elsevier Ltd. All rights reserved.

A new method of nanocrystalline nickel powder formation by magnetron sputtering on the water-soluble substrates

NASA Astrophysics Data System (ADS)

Tučkutė, S.; Urbonavičius, M.; Lelis, M.; Maiorov, M.; Díaz Ordaz, J. R.; Milčius, D.

2018-01-01

Due to the accurate and relatively easy control magnetron sputtering is an attractive technique for the synthesis of metallic particles. This work describes a new method of nickel powder production by depositing nickel on the surface of sodium chloride particles which were used as the template and are soluble in water. Ni powder with flake-like structure was obtained after washing Ni coated salt particles in ultrasonic cleaner. Salt particles and nickel powder were characterized using scanning electron microscope (SEM), energy-dispersive x-ray spectrometer, XRD and X-ray photoelectron spectroscopy (XPS) techniques. SEM images showed that thickness of the received Ni particles varied in the nanoscale and depended on the magnetron deposition time but did not depend on the size of salt particles. On the other hand initial size of the salt particles was successfully employed a measure to control lateral dimensions of Ni powder. XRD and XPS analysis results revealed that Ni particles had metallic core and oxidized shell which was a cause of the slightly deteriorated magnetic properties.

Hygrosopicity measurements of aerosol particles in the San Joaquin Valley, CA, Baltimore, MD, and Golden, CO

NASA Astrophysics Data System (ADS)

Orozco, Daniel; Beyersdorf, A. J.; Ziemba, L. D.; Berkoff, T.; Zhang, Q.; Delgado, R.; Hennigan, C. J.; Thornhill, K. L.; Young, D. E.; Parworth, C.; Kim, H.; Hoff, R. M.

2016-06-01

Aerosol hygroscopicity was investigated using a novel dryer-humidifier system, coupled to a TSI-3563 nephelometer, to obtain the light scattering coefficient (σscat) as a function of relative humidity (RH) in hydration and dehydration modes. The measurements were performed in Porterville, CA (10 January to 6 February 2013), Baltimore, MD (3-30 July 2013), and Golden, CO (12 July to 10 August 2014). Observations in Porterville and Golden were part of the NASA-sponsored Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality project. The measured σscat under varying RH in the three sites was combined with ground aerosol extinction, PM2.5 mass concentrations, and particle composition measurements and compared with airborne observations performed during campaigns. The enhancement factor, f(RH), defined as the ratio of σscat(RH) at a certain RH divided by σscat at a dry value, was used to evaluate the aerosol hygroscopicity. Particles in Porterville showed low average f(RH = 80%) (1.42) which was attributed to the high carbonaceous loading in the region where residential biomass burning and traffic emissions contribute heavily to air pollution. In Baltimore, the high average f(RH = 80%) (2.06) was attributed to the large contribution of SO42- in the region. The lowest water uptake was observed in Golden, with an average f(RH = 80%) = 1.24 where organic carbon dominated the particle loading. Different empirical fits were evaluated using the f(RH) data. The widely used Kasten (gamma) model was found least satisfactory, as it overestimates f(RH) for RH < 75%. A better 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 and the species that are affected by RH and f(RH) was also studied and categorized.

Impact of organic coating on optical growth of ammonium sulfate particles.

PubMed

Robinson, Carly B; Schill, Gregory P; Zarzana, Kyle J; Tolbert, Margaret A

2013-01-01

Light extinction by particles in Earth's atmosphere is strongly dependent on particle size, chemical composition, hygroscopic growth properties, and particle mixing state. Here, the influence of an organic coating on particle optical growth was studied. The particle optical growth factor, fRHext, was measured using cavity ring-down aerosol extinction spectroscopy at 532 nm. The particles were composed of ammonium sulfate (AS), 1,2,6-hexanetriol, and mixed particles containing a wet or dry ammonium sulfate core and a 1,2,6-hexanetriol coating. Dry, coated particles were generated by atomization followed by drying. Wet, coated particles were formed via liquid-liquid phase separation (LLPS). LLPS was achieved by deliquescing and then drying the particles to a relative humidity (RH) between the phase separation RH and the efflorescence RH. For the LLPS particles, the fRHext at each RH was between the fRHext of ammonium sulfate and that of 1,2,6-hexanetriol. In contrast, for the mixed dry, coated particles, the fRHext was the same as 1,2,6-hexanetriol particles. At room temperature, the water uptake properties of AS coated with 1,2,6-hexanetriol are largely dictated by the phase of the AS. Thus, the total water uptake depends on the RH history of the particle and the resulting phase of AS.

Study of constraints in using household NaCl salt for retrospective dosimetry

NASA Astrophysics Data System (ADS)

Elashmawy, M.

2018-05-01

Thermoluminescence (TL) characteristics of 5 different household NaCl salts and one analytical salt were determined to investigate the possible factors that affect the reliability of using household salt for retrospective dosimetry. Salts' TL sensitivities were found to be particle-size dependent and approached saturation at the largest size, whereas for salts that have the same particle size, the TL sensitivity depended on their origin. TL dependence on the particle size interprets significant variations in TL response reported in the literature for the same salt patch. The first TL readout indicated that all salts have similar glow curves with one distinctive peak. Typical second TL readout at two different doses showed a dramatic decrease in TL sensitivity associated with a significant change in the glow curve structure possessing two prominent peaks. Glow curve deconvolution (GCD) of the first TL readout for all salts yielded 6 individual glow peaks of first-order kinetics, whereas in GCD of second TL readouts, 5 individual glow peaks of second-order kinetics were obtained. Similarities in the glow curve structures of the first and second TL readouts suggest that additives such as KIO3 and MgCO3 have no effect on the TL process. Fading effect was evaluated for the salt of highest TL sensitivity, and it was found that the integral TL intensity decreased gradually and lost 40% of its initial value over 2 weeks, after which it remained constant. Results conclude that a household salt cannot be used for retrospective dosimetry without considering certain constraints such as the salt's origin and particle size. Furthermore, preparedness for radiological accidents and accurate dose reconstructions require that most of the commonly distributed household salt brands should be calibrated in advance and stored in a repository to be recalled in case of accidents.

Selective catalysts and their preparation for catalytic hydrocarbon synthesis

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

Iglesia, E.; Vroman, H.; Soled, S.

1991-07-30

This patent describes a method for preparing a supported cobalt catalyst particle. It comprises contacting a support particle with a molten cobalt salt, for a period sufficient to impregnate substantially all of the molten cobalt salt on the support to a depth of less than about 200 {mu}m; drying the supported cobalt salt obtained; reducing the cobalt of the supported cobalt salt to metallic cobalt by heating the salt in the presence of H{sub 2}, wherein the heating is conducted at a rate of less than about 1{degrees} C./min. up to a maximum temperature ranging from about 100{degrees} C. tomore » about 500{degrees} C., to produce a supported cobalt catalyst particle.« less

Laboratory Investigations on the Survival of Bacillus subtilis Spores in Deliquescent Salt Mars Analog Environments

NASA Astrophysics Data System (ADS)

Nuding, Danielle L.; Gough, Raina V.; Venkateswaran, Kasthuri J.; Spry, James A.; Tolbert, Margaret A.

2017-10-01

Observed features such as recurring slope lineae suggest that liquid water may exist on the surface and near-subsurface of Mars today. The presence of this liquid water, likely in the form of a brine, has important implications for the present-day water cycle, habitability, and planetary protection policies. It is possible that this water is formed, at least partially, by deliquescence of salts, a process during which hygroscopic salts absorb water vapor from the atmosphere and form a saturated liquid brine. We performed laboratory experiments to examine the ability of Bacillus subtilis (B-168) spores, alone or mixed with calcium perchlorate salt (Ca(ClO4)2), to form liquid water via deliquescence under Mars-relevant conditions. Spore survival after exposure to these conditions was examined. An environmental chamber was used to expose the samples to temperature and relative humidity (RH) values similar to those found on Mars, and Raman microscopy was used to identify the phases of water and salt that were present and to confirm the presence of spores. We found that B-168 spores did not condense any detectable water vapor on their own during the diurnal cycle, even at 100% RH. However, when spores were mixed with perchlorate salt, the entire sample deliquesced at low RH values, immersing the spores in a brine solution during the majority of the simulated martian temperature and humidity cycle. After exposure to the simulated diurnal cycles and, in some cases, perchlorate brine, the impact of each environmental scenario on spore survival was estimated by standard plate assay. We found that, if there are deliquescent salts in contact with spores, there is a mechanism for the spores to acquire liquid water starting with only atmospheric water vapor as the H2O source. Also, neither crystalline nor liquid Ca(ClO4)2 is sporicidal despite the low water activity.

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

Lu, Liqiang; Gao, Xi; Li, Tingwen

For a long time, salt tracers have been used to measure the residence time distribution (RTD) of fluidized catalytic cracking (FCC) particles. However, due to limitations in experimental measurements and simulation methods, the ability of salt tracers to faithfully represent RTDs has never been directly investigated. Our current simulation results using coarse-grained computational fluid dynamic coupled with discrete element method (CFD-DEM) with filtered drag models show that the residence time of salt tracers with the same terminal velocity as FCC particles is slightly larger than that of FCC particles. This research also demonstrates the ability of filtered drag models tomore » predict the correct RTD curve for FCC particles while the homogeneous drag model may only be used in the dilute riser flow of Geldart type B particles. The RTD of large-scale reactors can then be efficiently investigated with our proposed numerical method as well as by using the old-fashioned salt tracer technology.« less

Understanding water uptake in bioaerosols using laboratory measurements, field tests, and modeling

NASA Astrophysics Data System (ADS)

Chaudhry, Zahra; Ratnesar-Shumate, Shanna A.; Buckley, Thomas J.; Kalter, Jeffrey M.; Gilberry, Jerome U.; Eshbaugh, Jonathan P.; Corson, Elizabeth C.; Santarpia, Joshua L.; Carter, Christopher C.

2013-05-01

Uptake of water by biological aerosols can impact their physical and chemical characteristics. The water content in a bioaerosol can affect the backscatter cross-section as measured by LIDAR systems. Better understanding of the water content in controlled-release clouds of bioaerosols can aid in the development of improved standoff detection systems. This study includes three methods to improve understanding of how bioaerosols take up water. The laboratory method measures hygroscopic growth of biological material after it is aerosolized and dried. Hygroscopicity curves are created as the humidity is increased in small increments to observe the deliquescence point, then the humidity is decreased to observe the efflorescence point. The field component of the study measures particle size distributions of biological material disseminated into a large humidified chamber. Measurements are made with a Twin-Aerodynamic Particle Sizer (APS, TSI, Inc), -Relative Humidity apparatus where two APS units measure the same aerosol cloud side-by-side. The first operated under dry conditions by sampling downstream of desiccant dryers, the second operated under ambient conditions. Relative humidity was measured within the sampling systems to determine the difference in the aerosol water content between the two sampling trains. The water content of the bioaerosols was calculated from the twin APS units following Khlystov et al. 2005 [1]. Biological material is measured dried and wet and compared to laboratory curves of the same material. Lastly, theoretical curves are constructed from literature values for components of the bioaerosol material.

A study of the sea-salt chemistry using size-segregated aerosol measurements at coastal Antarctic station Neumayer

NASA Astrophysics Data System (ADS)

Teinilä, K.; Frey, A.; Hillamo, R.; Tülp, H. C.; Weller, R.

2014-10-01

Aerosol chemical and physical properties were measured in 2010 at Neumayer research station, Antarctica. Samples for chemical analysis (ion chromatography) were collected using a Teflon/Nylon filter combination (TNy) sampler, and with a multi stage low pressure impactor (SDI). Particle number concentration was measured continuously with a Grimm OPC optical particle counter. Total particle number concentration varied largely throughout the year, and the highest number concentrations for particles larger than 0.3 μm were observed simultaneously with the highest sea salt concentrations. About 50% of the sea salt aerosol mass was found in the submicron size range. Below 0.2 μm of particle aerodynamic diameter the contribution of sea salt aerosols was negligible. Further analysis showed that sea salt aerosols had undergone physico-chemical processes, either during the transportation, or during their formation. High degree of chloride depletion was observed during austral summer, when the presence of acidic gases exhibit their characteristic seasonal maximum. Apart from chloride depletion, excess chloride relating to sodium was also detected in one SDI sample, indicating actually a sodium depletion by mirabilite formation on freshly formed sea ice areas. Analysis of selected episodes showed that the concentration of sea salt particles, their modal structure, and their chemical composition is connected with their source areas, their formation mechanisms, and local transport history.

How does the VPD response of isohydric and anisohydric plants depend on leaf surface particles?

PubMed

Burkhardt, J; Pariyar, S

2016-01-01

Atmospheric vapour pressure deficit (VPD) is the driving force for plant transpiration. Plants have different strategies to respond to this 'atmospheric drought'. Deposited aerosols on leaf surfaces can interact with plant water relations and may influence VPD response. We studied transpiration and water use efficiency of pine, beech and sunflower by measuring sap flow, gas exchange and carbon isotopes, thereby addressing different time scales of plant/atmosphere interaction. Plants were grown (i) outdoors under rainfall exclusion (OD) and in ventilated greenhouses with (ii) ambient air (AA) or (iii) filtered air (FA), the latter containing <1% ambient aerosol concentrations. In addition, some AA plants were sprayed once with 25 mM salt solution of (NH4 )2 SO4 or NaNO3 . Carbon isotope values (δ(13) C) became more negative in the presence of more particles; more negative for AA compared to FA sunflower and more negative for OD Scots pine compared to other growth environments. FA beech had less negative δ(13) C than AA, OD and NaNO3 -treated beech. Anisohydric beech showed linearly increasing sap flow with increasing VPD. The slopes doubled for (NH4 )2 SO4 - and tripled for NaNO3 -sprayed beech compared to control seedlings, indicating decreased ability to resist atmospheric demand. In contrast, isohydric pine showed constant transpiration rates with increasing VPD, independent of growth environment and spray, likely caused by decreasing gs with increasing VPD. Generally, NaNO3 spray had stronger effects on water relations than (NH4 )2 SO4 spray. The results strongly support the role of leaf surface particles as an environmental factor affecting plant water use. Hygroscopic and chaotropic properties of leaf surface particles determine their ability to form wicks across stomata. Such wicks enhance unproductive water loss of anisohydric plant species and decrease CO2 uptake of isohydric plants. They become more relevant with increasing number of fine particles and increasing VPD and are thus related to air pollution and climate change. Wicks cause a deviation from the analogy between CO2 and water pathways through stomata, bringing some principal assumptions of gas exchange theory into question. © 2015 German Botanical Society and The Royal Botanical Society of the Netherlands.

Global impact of mineral dust on cloud droplet number concentration

NASA Astrophysics Data System (ADS)

Karydis, Vlassis A.; Tsimpidi, Alexandra P.; Bacer, Sara; Pozzer, Andrea; Nenes, Athanasios; Lelieveld, Jos

2017-05-01

The importance of wind-blown mineral dust for cloud droplet formation is studied by considering (i) the adsorption of water on the surface of insoluble particles, (ii) particle coating by soluble material (atmospheric aging) which augments cloud condensation nuclei (CCN) activity, and (iii) the effect of dust on inorganic aerosol concentrations through thermodynamic interactions with mineral cations. The ECHAM5/MESSy Atmospheric Chemistry (EMAC) model is used to simulate the composition of global atmospheric aerosol, while the ISORROPIA-II thermodynamic equilibrium model treats the interactions of K+-Ca2+-Mg2+-NH4+-Na+-SO42--NO3--Cl--H2O aerosol with gas-phase inorganic constituents. Dust is considered a mixture of inert material with reactive minerals and its emissions are calculated online by taking into account the soil particle size distribution and chemical composition of different deserts worldwide. The impact of dust on droplet formation is treated through the unified dust activation parameterization that considers the inherent hydrophilicity from adsorption and acquired hygroscopicity from soluble salts during aging. Our simulations suggest that the presence of dust increases cloud droplet number concentration (CDNC) over major deserts (e.g., up to 20 % over the Sahara and the Taklimakan desert) and decreases CDNC over polluted areas (e.g., up to 10 % over southern Europe and 20 % over northeastern Asia). This leads to a global net decrease in CDNC by 11 %. The adsorption activation of insoluble aerosols and the mineral dust chemistry are shown to be equally important for the cloud droplet formation over the main deserts; for example, these effects increase CDNC by 20 % over the Sahara. Remote from deserts the application of adsorption theory is critically important since the increased water uptake by the large aged dust particles (i.e., due to the added hydrophilicity by the soluble coating) reduce the maximum supersaturation and thus cloud droplet formation from the relatively smaller anthropogenic particles (e.g., CDNC decreases by 10 % over southern Europe and 20 % over northeastern Asia by applying adsorption theory). The global average CDNC decreases by 10 % by considering adsorption activation, while changes are negligible when accounting for the mineral dust chemistry. Sensitivity simulations indicate that CDNC is also sensitive to the mineral dust mass and inherent hydrophilicity, and not to the chemical composition of the emitted dust.

Aerosol properties associated with air masses arriving into the North East Atlantic during the 2008 Mace Head EUCAARI intensive observing period: an overview

NASA Astrophysics Data System (ADS)

Dall'Osto, M.; Ceburnis, D.; Martucci, G.; Bialek, J.; Dupuy, R.; Jennings, S. G.; Berresheim, H.; Wenger, J.; Healy, R.; Facchini, M. C.; Rinaldi, M.; Giulianelli, L.; Finessi, E.; Worsnop, D.; Ehn, M.; Mikkilä, J.; Kulmala, M.; O'Dowd, C. D.

2010-09-01

As part of the EUCAARI Intensive Observing Period, a 4-week campaign to measure aerosol physical, chemical and optical properties, atmospheric structure, and cloud microphysics was conducted from mid-May to mid-June, 2008 at the Mace Head Atmospheric Research Station, located at the interface of Western Europe and the N. E. Atlantic and centered on the west Irish coastline. During the campaign, continental air masses comprising both young and aged continental plumes were encountered, along with polar, Arctic and tropical air masses. Polluted-continental aerosol concentrations were of the order of 3000 cm-3, while background marine air aerosol concentrations were between 400-600 cm-3. The highest marine air concentrations occurred in polar air masses in which a 15 nm nucleation mode, with concentration of 1100 cm-3, was observed and attributed to open ocean particle formation. Continental air submicron chemical composition (excluding refractory sea salt) was dominated by organic matter, closely followed by sulphate mass. Although the concentrations and size distribution spectral shape were almost identical for the young and aged continental cases, hygroscopic growth factors (GF) and cloud condensation nuclei (CCN) to total condensation nuclei (CN) concentration ratios were significantly less in the younger pollution plume, indicating a more oxidized organic component to the aged continental plume. The difference in chemical composition and hygroscopic growth factor appear to result in a 40-50% impact on aerosol scattering coefficients and Aerosol Optical Depth, despite almost identical aerosol microphysical properties in both cases, with the higher values been recorded for the more aged case. For the CCN/CN ratio, the highest ratios were seen in the more age plume. In marine air, sulphate mass dominated the sub-micron component, followed by water soluble organic carbon, which, in turn, was dominated by methanesulphonic acid (MSA). Sulphate concentrations were highest in marine tropical air - even higher than in continental air. MSA was present at twice the concentrations of previously-reported concentrations at the same location and the same season. Both continental and marine air exhibited aerosol GFs significantly less than ammonium sulphate aerosol pointing to a significant organic contribution to all air mass aerosol properties.

Method of forming a relatively stable slip of silicon metal particles and yttrium containing particles

DOEpatents

Dickie, Ray A.; Mangels, John A.

1984-01-01

The method concerns forming a relatively stable slip of silicon metal particles and yttrium containing particles. In one embodiment, a casting slip of silicon metal particles is formed in water. Particles of a yttrium containing sintering aid are added to the casting slip. The yttrium containing sintering aid is a compound which has at least some solubility in water to form Y.sup.+3 ions which have a high potential for totally flocculating the silicon metal particles into a semiporous solid. A small amount of a fluoride salt is added to the casting slip which contains the yttrium containing sintering aid. The fluoride salt is one which will produce fluoride anions when dissolved in water. The small amount of the fluoride anions produced are effective to suppress the flocculation of the silicon metal particles by the Y.sup.+3 ions so that all particles remain in suspension in the casting slip and the casting slip has both an increased shelf life and can be used to cast articles having a relatively thick cross-section. The pH of the casting slip is maintained in a range from 7.5 to 9. Preferably, the fluoride salt used is one which is based on a monovalent cation such as sodium or ammonia. The steps of adding the yttrium containing sintering aid and the fluoride salt may be interchanged if desired, and the salt may be added to a solution containing the sintering aid prior to addition of the silicon metal particles.

Electroosmotic velocity in an array of parallel soft cylinders in a salt-free medium.

PubMed

Ohshima, Hiroyuki

2004-11-15

A theory of electroosmosis in an array of parallel soft cylinders (i.e. polyelectrolyte-coated cylinders) in a salt-free medium is presented. It is shown that there is a certain critical value of the particle charge and that if the particle charge is greater than the critical value, then the electroosmotic velocity becomes constant independent of the particle charge due to the counterion condensation effects, as in the case of other electrokinetic phenomena in salt-free media.

Simulating Emission and Chemical Evolution of Coarse Sea-Salt Particles in the Community Multiscale Air Quality (CMAQ) Model

EPA Science Inventory

Chemical processing of sea-salt particles in coastal environments significantly impacts concentrations of particle components and gas-phase species and has implications for human exposure to particulate matter and nitrogen deposition to sensitive ecosystems. Emission of sea-sal...

The Hygroscopic Condenser Humidifier. A new device for general use in anaesthesia and intensive care.

PubMed

Gedeon, A; Mebius, C

1979-01-01

The design and performance of the Hygroscopic Condenser Humidifier (HCH) are described. In principle the HCH consists of two parts, a conventional Heat-Moisture-Exchanger (HME) and a hygroscopic unit. The hygroscopic action is shown to improve the water retention efficiency of the device by about a factor of two as compared with optimal HME designs. As a result, humidification levels corresponding to around 80% relative humidity at 37 degrees C are obtained in the trachea and this is also achieved when completely dry gases are delivered to the patient. The unit can therefore be used for all procedures in anaesthesia and in intensive care.

Organic Condensation and Particle Growth to CCN Sizes in the Summertime Marine Arctic Is Driven by Materials More Semivolatile Than at Continental Sites

NASA Astrophysics Data System (ADS)

Burkart, Julia; Hodshire, Anna L.; Mungall, Emma L.; Pierce, Jeffrey R.; Collins, Douglas B.; Ladino, Luis A.; Lee, Alex K. Y.; Irish, Victoria; Wentzell, Jeremy J. B.; Liggio, John; Papakyriakou, Tim; Murphy, Jennifer; Abbatt, Jonathan

2017-10-01

Ship-based aerosol measurements in the summertime Arctic indicate elevated concentrations of ultrafine particles with occasional growth to cloud condensation nuclei (CCN) sizes. Focusing on one episode with two continuously growing modes, growth occurs faster for a large, preexisting mode (dp ≈ 90 nm) than for a smaller nucleation mode (dp ≈ 20 nm). We use microphysical modeling to show that growth is largely via organic condensation. Unlike results for midlatitude forested regions, most of these condensing species behave as semivolatile organics, as lower volatility organics would lead to faster growth of the smaller mode. The magnitude of the CCN hygroscopicity parameter for the growing particles, 0.1, is also consistent with organic species constituting a large fraction of the particle composition. Mixing ratios of common aerosol growth precursors, such as isoprene and sulfur dioxide, are not elevated during the episode, indicating that an unidentified aerosol growth precursor is present in this high-latitude marine environment.

Molten salt synthesis of La0.8Sr0.2MnO3 powders for SOFC cathode electrode

NASA Astrophysics Data System (ADS)

Gu, Sin-il; Shin, Hyo-soon; Hong, Youn-woo; Yeo, Dong-hun; Kim, Jong-hee; Nahm, Sahn; Yoon, Sang-ok

2012-08-01

For La0.8Sr0.2MnO3 (LSM) perovskite, used as the cathode material for solid oxide fuel cells (SOFC), it is known that the formation of a triple-phase-boundary is restrained due to the formation of a second phase at the YSZ/electrode interface at high temperature. To decrease the 2nd phase, lowering the sintering temperature has been used. LSM powder was synthesized by molten salt synthesis method to control its particle size, shape, and agglomeration. We have characterized the phase formation, particle size, shape, and sintering behavior of LSM in the synthesis using the variation of KCl, LiCl, KF and its mixed salts as raw materials. In the case of KCl and KCl-KF salts, the particle size and shape of the LSM was well controlled and synthesized. However, in the case of LiCl and KCl-LiCl salts, LiMnOx as 2nd phase and LSM were synthesized simultaneously. In the case of the mixed salt of KCl-KF, the growth mechanism of the LSM particle was changed from `diffusion-controlled' to `reaction-controlled' according to the amount of mixed salt. The sintering temperature can be decreased below 1000 °C by using the synthesized LSM powder.

The hygroscopicity of moisture barrier film coatings.

PubMed

Mwesigwa, Enosh; Buckton, Graham; Basit, Abdul W

2005-12-01

The hygroscopicity of three commercial moisture-barrier film coatings, namely, Eudragit L30 D-55 (methacrylic acid-ethyl acrylate copolymer), Opadry AMB (polyvinyl alcohol based system), and Sepifilm LP 014 (hypromellose, microcrystalline cellulose, and stearic acid based formulation), was investigated using a dynamic vapor sorption apparatus. Moisture uptake by cast films and uncoated and coated tablet cores, which were designed to be hygroscopic, low hygroscopic, and waxy, was measured following exposure to repeat relative humidity (RH) cycles of 0-50-0-50-0%, 0-75-0-75-0%, and 0-90-0-90-0% RH at 25 degrees C. Eudragit cast film exhibited the fastest equilibration but was also the least hygroscopic. Sepifilm had the fastest sorption and took up the greatest mass of water. The rate of uptake for Opadry film was similar to Sepifilm. However, this film continued to sorb moisture for a longer period. When returned to 0% RH it retained moisture in the film showing that it had a high affinity for moisture within the film. The data for the different cores indicated that there was very little benefit in using a moisture barrier film on cores with low hygroscopicity, the mass gain being a sum of that which would be expected to sorb to the film and that which sorbs to the uncoated core. There was, however, some advantage for hygroscopic cores where, even though the barrier coatings allowed substantial water sorption into the core, the extent of this was less and the rate of uptake lower than for the uncoated sample.

Highly Effective Pt-Based Water-Gas Shift Catalysts by Surface Modification with Alkali Hydroxide Salts

DOE PAGES

Kusche, Matthias; Bustillo, Karen; Agel, Friederike; ...

2015-01-29

Here, we describe an economical and convenient method to improve the performance of Pt/alumina catalysts for the water–gas shift reaction through surface modification of the catalysts with alkali hydroxides according to the solid catalyst with ionic liquid layer approach. The results are in agreement with our findings reported earlier for methanol steam reforming. This report indicates that alkali doping of the catalyst plays an important role in the observed catalyst activation. In addition, the basic and hygroscopic nature of the salt coating contributes to a significant improvement in the performance of the catalyst. During the reaction, a partly liquid filmmore » of alkali hydroxide forms on the alumina surface, which increases the availability of H 2O at the catalytically active sites. Kinetic studies reveal a negligible effect of the KOH coating on the rate dependence of CO and H 2O partial pressures. In conclusion, TEM studies indicate an agglomeration of the active Pt clusters during catalyst preparation; restructuring of Pt nanoparticles occurs under reaction conditions, which leads to a highly active and stable system over 240h time on stream. Excessive pore fillings with KOH introduce a mass transfer barrier as indicated in a volcano-shaped curve of activity versus salt loading. The optimum KOH loading was found to be 7.5wt%.« less

Assessment of oral bioavailability enhancing approaches for SB-247083 using flow-through cell dissolution testing as one of the screens.

PubMed

Perng, Cherng-Yih; Kearney, Albert S; Palepu, Nagesh R; Smith, Brian R; Azzarano, Leonard M

2003-01-02

SB-247083 is a potent, nonpeptidic, orally active, ETA-selective, endothelin receptor antagonist. The diacid form and three salts (monoarginine, diarginine and disodium) of SB-247083 were evaluated during the pre-clinical phase of development. The developability attributes (i.e. hygroscopicity, thermal behavior, aqueous solubility, and drug-excipient compatibility) of these compounds were evaluated. In addition to these attributes, the flow-through cell (FTC) dissolution testing (using USP Apparatus 4) was used as a screening technique to evaluate several SB-247083 formulations of the diacid and its salts. FTC dissolution testing offers two distinct advantages over the more traditional static-condition dissolution testing: (1) maintenance of sink conditions; and (2) the ability to change the dissolution medium during a dissolution run. The former advantage is especially important for poorly aqueous soluble drugs having associated dissolution-rate-limitations, and the latter advantage allows one to more closely simulate the pH gradient associated with transit through the GI tract. Based on the comparative dissolution data, three formulations were chosen for oral dosing in dogs. The reasonable correlation found between the FTC dissolution results and the oral bioavailability data demonstrate that FTC dissolution testing can be a valuable tool for aiding in salt (solid-state form) and formulation selection in the early stages of development of drug candidates.

Direct comparison of the hygroscopic properties of ammonium sulfate and sodium chloride aerosol at relative humidities approaching saturation.

PubMed

Walker, Jim S; Wills, Jon B; Reid, Jonathan P; Wang, Liangyu; Topping, David O; Butler, Jason R; Zhang, Yun-Hong

2010-12-09

Holographic optical tweezers are used to make comparative measurements of the hygroscopic properties of single component aqueous aerosol containing sodium chloride and ammonium sulfate over a range of relative humidity from 84% to 96%. The change in RH over the course of the experiment is monitored precisely using a sodium chloride probe droplet with accuracy better than ±0.09%. The measurements are used to assess the accuracy of thermodynamic treatments of the relationship between water activity and solute mass fraction with particular attention focused on the dilute solute limit approaching saturation vapor pressure. The consistency of the frequently used Clegg-Brimblecombe-Wexler (CBW) treatment for predicting the hygroscopic properties of sodium chloride and ammonium sulfate aerosol is confirmed. Measurements of the equilibrium size of ammonium sulfate aerosol are found to agree with predictions to within an uncertainty of ±0.2%. Given the accuracy of treating equilibrium composition, the inconsistencies highlighted in recent calibration measurements of critical supersaturations of sodium chloride and ammonium sulfate aerosol cannot be attributed to uncertainties associated with the thermodynamic predictions and must have an alternative origin. It is concluded that the CBW treatment can allow the critical supersaturation to be estimated for sodium chloride and ammonium sulfate aerosol with an accuracy of better than ±0.002% in RH. This corresponds to an uncertainty of ≤1% in the critical supersaturation for typical supersaturations of 0.2% and above. This supports the view that these systems can be used to accurately calibrate instruments that measure cloud condensation nuclei concentrations at selected supersaturations. These measurements represent the first study in which the equilibrium properties of two particles of chemically distinct composition have been compared simultaneously and directly alongside each other in the same environment.

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 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 particles of the same composition would allow proving that LLPS indeed occurs in particles of accumulation mode size. Up to now LLPS has not been studied for particles in this size range. References: 1. Bertram, et al. Atmos. Chem & Phys, 11(21), 10995-11006, 2011.
 2. Krieger, et al. Chemical Society Reviews, 41(19), 6631-6662, 2012 
3. Song, M. et al. Geophys Res Lett, 39(19), 2012b 4. Smith et al. Atmos Chem & Phys, 12(20), 9613- 9628, 2012.
 5. You, Y. et al. Proceedings of the National Academy of Sciences, 109(33), 13188-13193, 2012.

Controlling chitosan-based encapsulation for protein and vaccine delivery

PubMed Central

Koppolu, Bhanu prasanth; Smith, Sean G.; Ravindranathan, Sruthi; Jayanthi, Srinivas; Kumar, Thallapuranam K.S.; Zaharoff, David A.

2014-01-01

Chitosan-based nano/microencapsulation is under increasing investigation for the delivery of drugs, biologics and vaccines. Despite widespread interest, the literature lacks a defined methodology to control chitosan particle size and drug/protein release kinetics. In this study, the effects of precipitation-coacervation formulation parameters on chitosan particle size, protein encapsulation efficiency and protein release were investigated. Chitosan particle sizes, which ranged from 300 nm to 3 μm, were influenced by chitosan concentration, chitosan molecular weight and addition rate of precipitant salt. The composition of precipitant salt played a significant role in particle formation with upper Hofmeister series salts containing strongly hydrated anions yielding particles with a low polydispersity index (PDI) while weaker anions resulted in aggregated particles with high PDIs. Sonication power had minimal effect on mean particle size, however, it significantly reduced polydispersity. Protein loading efficiencies in chitosan nano/microparticles, which ranged from 14.3% to 99.2%, was inversely related to the hydration strength of precipitant salts, protein molecular weight and directly related to the concentration and molecular weight of chitosan. Protein release rates increased with particle size and were generally inversely related to protein molecular weight. This study demonstrates that chitosan nano/microparticles with high protein loading efficiencies can be engineered with well-defined sizes and controllable release kinetics through manipulation of specific formulation parameters. PMID:24560459

Optical Modeling of Sea Salt Aerosols: The Effects of Nonsphericity and Inhomogeneity

NASA Astrophysics Data System (ADS)

Bi, Lei; Lin, Wushao; Wang, Zheng; Tang, Xiaoyun; Zhang, Xiaoyu; Yi, Bingqi

2018-01-01

The nonsphericity and inhomogeneity of marine aerosols (sea salts) have not been addressed in pertinent radiative transfer calculations and remote sensing studies. This study investigates the optical properties of nonspherical and inhomogeneous sea salts using invariant imbedding T-matrix simulations. Dry sea salt aerosols are modeled based on superellipsoidal geometries with a prescribed aspect ratio and roundness parameter. Wet sea salt particles are modeled as coated superellipsoids, as spherical particles with a superellipsoidal core, and as homogeneous spheres depending on the level of relative humidity. Aspect ratio and roundness parameters are found to be critical to interpreting the linear depolarization ratios (LDRs) of NaCl crystals from laboratory measurements. The optimal morphology parameters of NaCl necessary to reproduce the measurements are found to be consistent with data gleaned from an electron micrograph. The LDRs of wet sea salts are computed based on inhomogeneous models and compared with the measured data from ground-based LiDAR. The dependence of the LDR on relative humidity is explicitly considered. The increase in the LDR with relative humidity at the initial phase of deliquescence is attributed to both the size increase and the inhomogeneity effect. For large humidity values, the LDR substantially decreases because the overall particle shape becomes more spherical and the inhomogeneity effect in a particle on the LDR is suppressed for submicron sea salts. However, the effect of inhomogeneity on optical properties is pronounced for coarse-mode sea salts. These findings have important implications for atmospheric radiative transfer and remote sensing involving sea salt aerosols.

Kinetic study of heterogeneous reaction of deliquesced NaCl particles with gaseous HNO3 using particle-on-substrate stagnation flow reactor approach.

PubMed

Liu, Y; Cain, J P; Wang, H; Laskin, A

2007-10-11

Heterogeneous reaction kinetics of gaseous nitric acid with deliquesced sodium chloride particles NaCl(aq) + HNO3(g) --> NaNO3(aq) + HCl(g) were investigated with a novel particle-on-substrate stagnation flow reactor (PS-SFR) approach under conditions, including particle size, relative humidity, and reaction time, directly relevant to the atmospheric chemistry of sea salt particles. Particles deposited onto an electron microscopy grid substrate were exposed to the reacting gas at atmospheric pressure and room temperature by impingement via a stagnation flow inside the reactor. The reactor design and choice of flow parameters were guided by computational fluid dynamics to ensure uniformity of the diffusion flux to all particles undergoing reaction. The reaction kinetics was followed by observing chloride depletion in the particles by computer-controlled scanning electron microscopy with energy-dispersive X-ray analysis (CCSEM/EDX). The validity of the current approach was examined first by conducting experiments with median dry particle diameter D(p) = 0.82 microm, 80% relative humidity, particle loading densities 4 x 10(4)

Magnetic particles

NASA Technical Reports Server (NTRS)

Chang, Manchium (Inventor); Colvin, Michael S. (Inventor)

1989-01-01

Magnetic polymer particles are formed by swelling porous, polymer particles and impregnating the particles with an aqueous solution of precursor magnetic metal salt such as an equimolar mixture of ferrous chloride and ferric chloride. On addition of a basic reagent such as dilute sodium hydroxide, the metal salts are converted to crystals of magnetite which are uniformly contained througout the pores of the polymer particle. The magnetite content can be increased and neutral buoyancy achieved by repetition of the impregnaton and neutralization steps to adjust the magnetite content to a desired level.

4D Imaging of Salt Precipitation during Evaporation from Saline Porous Media Influenced by the Particle Size Distribution

NASA Astrophysics Data System (ADS)

Norouzi Rad, M.; Shokri, N.

2014-12-01

Understanding the physics of water evaporation from saline porous media is important in many processes such as evaporation from porous media, vegetation, plant growth, biodiversity in soil, and durability of building materials. To investigate the effect of particle size distribution on the dynamics of salt precipitation in saline porous media during evaporation, we applied X-ray micro-tomography technique. Six samples of quartz sand with different grain size distributions were used in the present study enabling us to constrain the effects of particle and pore sizes on salt precipitation patterns and dynamics. The pore size distributions were computed using the pore-scale X-ray images. The packed beds were saturated with NaCl solution of 3 Molal and the X-ray imaging was continued for one day with temporal resolution of 30 min resulting in pore scale information about the evaporation and precipitation dynamics. Our results show more precipitation at the early stage of the evaporation in the case of sand with the larger particle size due to the presence of fewer evaporation sites at the surface. The presence of more preferential evaporation sites at the surface of finer sands significantly modified the patterns and thickness of the salt crust deposited on the surface such that a thinner salt crust was formed in the case of sand with smaller particle size covering larger area at the surface as opposed to the thicker patchy crusts in samples with larger particle sizes. Our results provide new insights regarding the physics of salt precipitation in porous media during evaporation.

Hygroscopic Swelling Determination of Cellulose Nanocrystal (CNC) Films by Polarized Light Microscopy Digital Image Correlation.

PubMed

Shrestha, Shikha; Diaz, Jairo A; Ghanbari, Siavash; Youngblood, Jeffrey P

2017-05-08

The coefficient of hygroscopic swelling (CHS) of self-organized and shear-oriented cellulose nanocrystal (CNC) films was determined by capturing hygroscopic strains produced as result of isothermal water vapor intake in equilibrium. Contrast enhanced microscopy digital image correlation enabled the characterization of dimensional changes induced by the hygroscopic swelling of the films. The distinct microstructure and birefringence of CNC films served in exploring the in-plane hygroscopic swelling at relative humidity values ranging from 0% to 97%. Water vapor intake in CNC films was measured using dynamic vapor sorption (DVS) at constant temperature. The obtained experimental moisture sorption and kinetic profiles were analyzed by fitting with Guggenheim, Anderson, and deBoer (GAB) and Parallel Exponential Kinetics (PEK) models, respectively. Self-organized CNC films showed isotropic swelling, CHS ∼0.040 %strain/%C. By contrast, shear-oriented CNC films exhibited an anisotropic swelling, resulting in CHS ∼0.02 and ∼0.30 %strain/%C, parallel and perpendicular to CNC alignment, respectively. Finite element analysis (FEA) further predicted moisture diffusion as the predominant mechanism for swelling of CNC films.

Observations and projections of visibility and aerosol optical thickness (1956-2100) in the Netherlands: impacts of time-varying aerosol composition and hygroscopicity

NASA Astrophysics Data System (ADS)

Boers, R.; van Weele, M.; van Meijgaard, E.; Savenije, M.; Siebesma, A. P.; Bosveld, F.; Stammes, P.

2015-01-01

Time series of visibility and aerosol optical thickness for the Netherlands have been constructed for 1956-2100 based on observations and aerosol mass scenarios. Aerosol optical thickness from 1956 to 2013 has been reconstructed by converting time series of visibility to visible extinction which in turn are converted to aerosol optical thickness using an appropriate scaling depth. The reconstruction compares closely with remote sensing observations of aerosol optical thickness between 1960 and 2013. It appears that aerosol optical thickness was relatively constant over the Netherlands in the years 1955-1985. After 1985, visibility has improved, while at the same time aerosol optical thickness has decreased. Based on aerosol emission scenarios for the Netherlands three aerosol types have been identified: (1) a constant background consisting of sea salt and mineral dust, (2) a hydrophilic anthropogenic inorganic mixture, and (3) a partly hydrophobic mixture of black carbon (BC) and organic aerosols (OAs). A reduction in overall aerosol concentration turns out to be the most influential factor in the reduction in aerosol optical thickness. But during 1956-1985, an upward trend in hydrophilic aerosols and associated upward trend in optical extinction has partly compensated the overall reduction in optical extinction due to the reduction in less hydrophilic BC and OAs. A constant optical thickness ensues. This feature highlights the influence of aerosol hygroscopicity on time-varying signatures of atmospheric optical properties. Within the hydrophilic inorganic aerosol mixture there is a gradual shift from sulfur-based (1956-1985) to a nitrogen-based water aerosol chemistry (1990 onwards) but always modulated by the continual input of sodium from sea salt. From 2013 to 2100, visibility is expected to continue its increase, while at the same time optical thickness is foreseen to continue to decrease. The contribution of the hydrophilic mixture to the aerosol optical thickness will increase from 30% to 35% in 1956 to more than 70% in 2100. At the same time the contribution of black and organic aerosols will decrease by more than 80%.

Long-term cloud condensation nuclei number concentration, particle number size distribution and chemical composition measurements at regionally representative observatories

NASA Astrophysics Data System (ADS)

Schmale, Julia; Henning, Silvia; Decesari, Stefano; Henzing, Bas; Keskinen, Helmi; Sellegri, Karine; Ovadnevaite, Jurgita; Pöhlker, Mira L.; Brito, Joel; Bougiatioti, Aikaterini; Kristensson, Adam; Kalivitis, Nikos; Stavroulas, Iasonas; Carbone, Samara; Jefferson, Anne; Park, Minsu; Schlag, Patrick; Iwamoto, Yoko; Aalto, Pasi; Äijälä, Mikko; Bukowiecki, Nicolas; Ehn, Mikael; Frank, Göran; Fröhlich, Roman; Frumau, Arnoud; Herrmann, Erik; Herrmann, Hartmut; Holzinger, Rupert; Kos, Gerard; Kulmala, Markku; Mihalopoulos, Nikolaos; Nenes, Athanasios; O'Dowd, Colin; Petäjä, Tuukka; Picard, David; Pöhlker, Christopher; Pöschl, Ulrich; Poulain, Laurent; Prévôt, André Stephan Henry; Swietlicki, Erik; Andreae, Meinrat O.; Artaxo, Paulo; Wiedensohler, Alfred; Ogren, John; Matsuki, Atsushi; Yum, Seong Soo; Stratmann, Frank; Baltensperger, Urs; Gysel, Martin

2018-02-01

Aerosol-cloud interactions (ACI) constitute the single largest uncertainty in anthropogenic radiative forcing. To reduce the uncertainties and gain more confidence in the simulation of ACI, models need to be evaluated against observations, in particular against measurements of cloud condensation nuclei (CCN). Here we present a data set - ready to be used for model validation - of long-term observations of CCN number concentrations, particle number size distributions and chemical composition from 12 sites on 3 continents. Studied environments include coastal background, rural background, alpine sites, remote forests and an urban surrounding. Expectedly, CCN characteristics are highly variable across site categories. However, they also vary within them, most strongly in the coastal background group, where CCN number concentrations can vary by up to a factor of 30 within one season. In terms of particle activation behaviour, most continental stations exhibit very similar activation ratios (relative to particles > 20 nm) across the range of 0.1 to 1.0 % supersaturation. At the coastal sites the transition from particles being CCN inactive to becoming CCN active occurs over a wider range of the supersaturation spectrum. Several stations show strong seasonal cycles of CCN number concentrations and particle number size distributions, e.g. at Barrow (Arctic haze in spring), at the alpine stations (stronger influence of polluted boundary layer air masses in summer), the rain forest (wet and dry season) or Finokalia (wildfire influence in autumn). The rural background and urban sites exhibit relatively little variability throughout the year, while short-term variability can be high especially at the urban site. The average hygroscopicity parameter, κ, calculated from the chemical composition of submicron particles was highest at the coastal site of Mace Head (0.6) and lowest at the rain forest station ATTO (0.2-0.3). We performed closure studies based on κ-Köhler theory to predict CCN number concentrations. The ratio of predicted to measured CCN concentrations is between 0.87 and 1.4 for five different types of κ. The temporal variability is also well captured, with Pearson correlation coefficients exceeding 0.87. Information on CCN number concentrations at many locations is important to better characterise ACI and their radiative forcing. But long-term comprehensive aerosol particle characterisations are labour intensive and costly. Hence, we recommend operating migrating-CCNCs to conduct collocated CCN number concentration and particle number size distribution measurements at individual locations throughout one year at least to derive a seasonally resolved hygroscopicity parameter. This way, CCN number concentrations can only be calculated based on continued particle number size distribution information and greater spatial coverage of long-term measurements can be achieved.

Porous metal oxide particles and their methods of synthesis

DOEpatents

Chen, Fanglin; Liu, Qiang

2013-03-12

Methods are generally disclosed for synthesis of porous particles from a solution formed from a leaving agent, a surfactant, and a soluble metal salt in a solvent. The surfactant congregates to form a nanoparticle core such that the metal salt forms about the nanoparticle core to form a plurality of nanoparticles. The solution is heated such that the leaving agent forms gas bubbles in the solution, and the plurality of nanoparticles congregate about the gas bubbles to form a porous particle. The porous particles are also generally disclosed and can include a particle shell formed about a core to define an average diameter from about 0.5 .mu.m to about 50 .mu.m. The particle shell can be formed from a plurality of nanoparticles having an average diameter of from about 1 nm to about 50 nm and defined by a metal salt formed about a surfactant core.

Particle formation above natural and simulated salt lakes

NASA Astrophysics Data System (ADS)

Kamilli, Katharina A.; Ofner, Johannes; Sattler, Tobias; Krause, Torsten; Held, Andreas

2014-05-01

Originally, Western Australia was covered with Eucalyptus trees. Large scale deforestation for agricultural purposes led to rising ground water levels and brought dissolved salts and minerals to the surface. Nowadays, Western Australia is known for a great plenty of salt lakes with pH levels reaching from 2.5 to 7.1. The land is mainly used for wheat farming and livestock and becomes drier due to the lack of rain periods. One possible reason could be the formation of ultrafine particles from salt lakes, which increases the number of cloud condensation nuclei, and thus potentially suppresses precipitation. Several field campaigns have been conducted between 2006 and 2011 with car-based and airborne measurements, where new particle formation has been observed and has been related to the Western Australian salt lakes (Junkermann et al., 2009). To identify particle formation directly above the salt lakes, a 2.35 m³ PTFE chamber was set up above several lakes in 2012 and 2013. Inside the chamber, photochemistry may take place whereas mixing through wind or advection of already existing particles is prevented. Salt lakes with a low pH level led to strongly increased aerosol formation. Also, the dependence on meteorological conditions has been examined. To obtain chemical information of the newly formed particles, during the chamber experiments also aerosol filter samples have been taken. The analysis of the anions by ion chromatography in 2012 showed an 8 to 17 times higher concentration of Cl- than SO42-, which led to the assumption that particle formation may have been influenced by halogens. As reference experiments, laboratory based aerosol smog-chamber runs were performed to examine halogen induced aerosol formation under atmospheric conditions using simulated sunlight and the simplified chemical composition of a salt lake. The mixture included FeSO4, NaCl and Na2SO4. After adding α-pinene to the simulated salt lake, a strong nucleation event began comparable to the observed events in Western Australia. Also, IR spectroscopy of filter samples of a simulated salt lake showed an aerosol with C=O/C=C vibrations and a significant C-Cl vibration, which underlined this assumption. In contrast, the filter analysis with FTIR microscopy of the aerosol collected in 2013 in Western Australia showed vibrations of organic and sulfate species. Further analyses are ongoing, which will allow a detailed analysis of the atmospheric aerosol based on high-resolution chemical imaging. The resulting elemental composition and vibrational information will help elucidating which compounds initiate the particle formation and which condense on already existing matter. Reference: Junkermann, W., Hacker, J., Lyons, T., and Nair, U.: Land use change suppresses precipitation, Atmos. Chem. Phys., 9, 6531-6539, 2009.

Use of Encapsulated Zinc Particles in a Eutectic Chloride Salt to Enhance Thermal Energy Storage Capacity for Concentrated Solar Power

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

Cingarapu, Sreeram; Singh, Dileep; Timofeeva, Elena V.

2015-08-01

Concentrated Solar Power (CSP) is considered as a viable large-scale renewable energy source to produce electricity. However, current costs to produce electricity from CSP are not cost competitive as compared to the traditional energy generation technologies based on fossil fuels and nuclear. It is envisioned that development of high efficiency and high heat capacity thermal storage fluids will increase system efficiency, reduce structural storage volume, and hence, contribute to reducing costs. Particularly, with respect to CSP, current high temperature energy storage fluids, such as molten salts, are relatively limited in terms of their thermal energy storage capacity and thermal conductivity.more » The current work explores possibility of boosting the thermal storage capacity of molten salts through latent heat of added phase change materials. We studied the advantage Of adding coated Zn micron-sized particles to alkali chloride salt eutectic for enhanced thermal energy storage. Zinc particles (0.6 mu m and 5 mu m) obtained from commercial source were coated with an organo-phosphorus shell to improve chemical stability and to prevent individual particles from coalescing with one another during melt/freeze cycles. Thermal cycling tests (200 melt/freeze cycles) showed that coated Zn particles have good thermal stability and are chemically inert to alkali chloride salt eutectic in both N-2 and in air atmospheres. Elemental mapping of the cross-sectional view of coated Zn particles from the composite after thermal cycles showed no signs of oxidation, agglomeration or other type of particle degradation. The measured enhancement in volumetric thermal storage capacity of the composite with just similar to 10 vol% of coated Zn particles over the base chloride salt eutectic varies from 15% to 34% depending on cycling temperature range (Delta T = 50 degrees C -100 degrees C. (C) 2015 Elsevier Ltd. All rights reserved.« less

Weathering and weathering rates of natural stone

NASA Astrophysics Data System (ADS)

Winkler, Erhard M.

1987-06-01

Physical and chemical weathering were studied as separate processes in the past. Recent research, however, shows that most processes are physicochemical in nature. The rates at which calcite and silica weather by dissolution are dependent on the regional and local climatic environment. The weathering of silicate rocks leaves discolored margins and rinds, a function of the rocks' permeability and of the climatic parameters. Salt action, the greatest disruptive factor, is complex and not yet fully understood in all its phases, but some of the causes of disruption are crystallization pressure, hydration pressure, and hygroscopic attraction of excess moisture. The decay of marble is complex, an interaction between disolution, crack-corrosion, and expansion-contraction cycies triggered by the release of residual stresses. Thin spalls of granites commonly found near the street level of buildings are generally caused by a combination of stress relief and salt action. To study and determine weathering rates of a variety of commercial stones, the National Bureau of Standards erected a Stone Exposure Test Wall in 1948. Of the many types of stone represented, only a few fossiliferous limestones permit a valid measurement of surface reduction in a polluted urban environment.

Method for the preparation of metal colloids in inverse micelles and product preferred by the method

DOEpatents

Wilcoxon, Jess P.

1992-01-01

A method is provided for preparing catalytic elemental metal colloidal particles (e.g. gold, palladium, silver, rhodium, iridium, nickel, iron, platinum, molybdenum) or colloidal alloy particles (silver/iridium or platinum/gold). A homogeneous inverse micelle solution of a metal salt is first formed in a metal-salt solvent comprised of a surfactant (e.g. a nonionic or cationic surfactant) and an organic solvent. The size and number of inverse micelles is controlled by the proportions of the surfactant and the solvent. Then, the metal salt is reduced (by chemical reduction or by a pulsed or continuous wave UV laser) to colloidal particles of elemental metal. After their formation, the colloidal metal particles can be stabilized by reaction with materials that permanently add surface stabilizing groups to the surface of the colloidal metal particles. The sizes of the colloidal elemental metal particles and their size distribution is determined by the size and number of the inverse micelles. A second salt can be added with further reduction to form the colloidal alloy particles. After the colloidal elemental metal particles are formed, the homogeneous solution distributes to two phases, one phase rich in colloidal elemental metal particles and the other phase rich in surfactant. The colloidal elemental metal particles from one phase can be dried to form a powder useful as a catalyst. Surfactant can be recovered and recycled from the phase rich in surfactant.

Synthesis of silver nanoparticles by silver salt reduction and its characterization

NASA Astrophysics Data System (ADS)

Muzamil, Muhammad; Khalid, Naveed; Danish Aziz, M.; Aun Abbas, S.

2014-06-01

The wet chemical method route by metal salt reduction has been used to synthesize nanoparticles, using silver nitrate as an inorganic salt, aldehyde as a reducing agent and amino acid as a catalyst. During the reaction aldehyde oxidizes to carboxylic acid and encapsulates the silver nanoparticles to prevent agglomeration and provide barrier in the growth of particle. The existing work produces particles using lab grade chemical, here the presented work is by using industrial grade chemicals to make the process more cost & time effective. The nano silver powder has been studied for their formation, particle size, shape & compositional analysis using Scanning Electron Microscope (SEM) equipped with EDS. The particles size distributions were analyzed by Laser Particle Analyzer (LPA), structure & morphological analysis using x-ray diffraction (XRD) and Fourier-transform-infrared Spectroscopy (FTIR) confirmed the stabilization of particles by coating of carboxylic group. These studies infer that the particles are mostly spherical in shape and have an average size between 70 to 350 nm.

Deposition and clearance of inhaled particles.

PubMed Central

Stuart, B O

1984-01-01

Theoretical models of respiratory tract deposition of inhaled particles are compared to experimental studies of deposition patterns in humans and animals, as governed principally by particle size, density, respiratory rate and flow parameters. Various models of inhaled particle deposition make use of approximations of the respiratory tract to predict fractional deposition caused by fundamental physical processes of particle impaction, sedimentation, and diffusion. These models for both total deposition and regional (nasopharyngeal, tracheobronchial, and pulmonary) deposition are compared with early and recent experimental studies. Reasonable correlation has been obtained between theoretical and experimental studies, but the behavior in the respiratory tract of very fine (less than 0.1 micron) particles requires further investigation. Properties of particle shape, charge and hygroscopicity as well as the degree of respiratory tract pathology also influence deposition patterns; definitive experimental work is needed in these areas. The influence upon deposition patterns of dynamic alterations in inspiratory flow profiles caused by a variety of breathing patterns also requires further study, and the use of differing ventilation techniques with selected inhaled particle sizes holds promise in diagnosis of respiratory tract diseases. Mechanisms of conducting airway and alveolar clearance processes involving the pulmonary macrophage, mucociliary clearance, dissolution, transport to systemic circulation, and translocation via regional lymphatic vessels are discussed. PMID:6376108

Cytoplasmic membrane changes during adaptation of the fresh water cyanobacterium Synechococcus 6311 to salinity

NASA Technical Reports Server (NTRS)

Lefort-Tran, M.; Pouphile, M.; Spath, S.; Packer, L.

1988-01-01

In this investigation, changes were characterized in cell structure and cytoplasmic membrane organization that occur when the freshwater cyanobacterium Synechococcus 6311 is transferred from 'low salt' (0.03 molar NaCl) to 'high salt' (0.5 molar NaCl) media (i.e. sea water concentration). Cells were examined at several time points after the imposition of the salt stress and compared to control cells, in thin sections and freeze fracture electron microscopy, and by flow cytometry. One minute after exposure to high salt, i.e. 'salt shock', virtually all intracellular granules disappeared, the density of the cytoplasm decreased, and the appearance of DNA material was changed. Glycogen and other granules, however, reappeared by 4 hours after salt exposure. The organization of the cytoplasmic membrane undergoes major reorganization following salt shock. Freeze-fracture electron microscopy showed that small intramembrane particles (diameter 7.5 and 8.5 nanometers) are reduced in number by two- to fivefold, whereas large particles, (diameters 14.5 and 17.5 nanometers) increase two- to fourfold in frequency, compared to control cells grown in low salt medium. The changes in particle size distribution suggest synthesis of new membrane proteins, in agreement with the known increases in respiration, cytochrome oxidase, and sodium proton exchange activity of the cytoplasmic membrane.

Variation of the radiative properties during black carbon aging: theoretical and experimental intercomparison

DOE PAGES

He, C.; Liou, K.-N.; Takano, Y.; ...

2015-10-28

A theoretical black carbon (BC) aging model is developed to account for three typical evolution stages, namely, freshly emitted aggregates, BC coated by soluble material, and BC particles undergoing further hygroscopic growth. The geometric-optics surface-wave (GOS) approach is employed to compute the BC single-scattering properties at each aging stage, which are subsequently compared with laboratory measurements. Theoretical calculations are consistent with measurements in extinction and absorption cross sections for fresh BC aggregates with different BC sizes (i.e., mobility diameters of 155, 245, and 320 nm), with differences of ≤ 25 %. The measured optical cross sections for BC coated bymore » sulfuric acid and for that undergoing further hygroscopic growth are generally captured (differences < 30 %) by theoretical calculations using a concentric core-shell structure, with an overestimate in extinction and absorption of the smallest BC size and an underestimate in scattering of the largest BC size. We find that the absorption and scattering cross sections of fresh BC aggregates vary by 20–40 and 50–65 %, respectively, due to the use of upper (1.95–0.79 i) and lower (1.75–0.63 i) bounds of BC refractive index, while the variations are < 20 % in absorption and < 50 % in scattering in the case of coated BC particles. Sensitivity analyses of the BC morphology show that the optical properties of fresh BC aggregates are more sensitive to fractal dimension than primary spherule size. The absorption and scattering cross sections of coated BC particles vary by more than a factor of 2 due to different coating structures. We find an increase of 20–250 % in absorption and a factor of 3–15 in scattering during aging, significantly depending on coating morphology and aging stages. This study suggests that an accurate estimate of BC radiative effects requires the incorporation of a dynamic BC aging process that accounts for realistic coating structures in climate models.« less

Variation of the radiative properties during black carbon aging: theoretical and experimental intercomparison

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

He, C.; Liou, K.-N.; Takano, Y.

A theoretical black carbon (BC) aging model is developed to account for three typical evolution stages, namely, freshly emitted aggregates, BC coated by soluble material, and BC particles undergoing further hygroscopic growth. The geometric-optics surface-wave (GOS) approach is employed to compute the BC single-scattering properties at each aging stage, which are subsequently compared with laboratory measurements. Theoretical calculations are consistent with measurements in extinction and absorption cross sections for fresh BC aggregates with different BC sizes (i.e., mobility diameters of 155, 245, and 320 nm), with differences of ≤ 25 %. The measured optical cross sections for BC coated bymore » sulfuric acid and for that undergoing further hygroscopic growth are generally captured (differences < 30 %) by theoretical calculations using a concentric core-shell structure, with an overestimate in extinction and absorption of the smallest BC size and an underestimate in scattering of the largest BC size. We find that the absorption and scattering cross sections of fresh BC aggregates vary by 20–40 and 50–65 %, respectively, due to the use of upper (1.95–0.79 i) and lower (1.75–0.63 i) bounds of BC refractive index, while the variations are < 20 % in absorption and < 50 % in scattering in the case of coated BC particles. Sensitivity analyses of the BC morphology show that the optical properties of fresh BC aggregates are more sensitive to fractal dimension than primary spherule size. The absorption and scattering cross sections of coated BC particles vary by more than a factor of 2 due to different coating structures. We find an increase of 20–250 % in absorption and a factor of 3–15 in scattering during aging, significantly depending on coating morphology and aging stages. This study suggests that an accurate estimate of BC radiative effects requires the incorporation of a dynamic BC aging process that accounts for realistic coating structures in climate models.« less

Shipboard Sunphotometer Measurements of Aerosol Optical Depth Spectra and Columnar Water Vapor During ACE-2 and Comparison with Selected Land, Ship, Aircraft, and Satellite Measurements

NASA Technical Reports Server (NTRS)

Livingston, John M.; Kapustin, Vladimir N.; Schmid, Beat; Russell, Philip B.; Quinn, Patricia K.; Bates, Timothy S.; Durkee, Philip A.; Smith, Peter J.; Freudenthaler, Volker; Wiegner, Matthias;

Potential sea salt aerosol sources from frost flowers in the pan-Arctic region

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

Xu, Li; Russell, Lynn M.; Burrows, Susannah M.

In order to better represent observed wintertime aerosol concentrations at Barrow, Alaska, we implemented an observationally-based parameterization for estimating sea salt production from frost flowers in the Community Earth System Model (CESM). In this work, we evaluate the potential influence of this sea salt source on the pan-Arctic (60ºN-90ºN) climate. Results show that frost flower salt emissions substantially increase the modeled surface sea salt aerosol concentration in the winter months when new sea ice and frost flowers are present. The parameterization reproduces both the magnitude and seasonal variation of the observed submicron sea salt aerosol concentration at surface in Barrowmore » during winter much better than the standard CESM simulation without a frost-flower salt particle source. Adding these frost flower salt particle emissions increases aerosol optical depth by 10% and results in a small cooling at surface. The increase in salt particle mass concentrations of a factor of 8 provides nearly two times the cloud condensation nuclei concentration, as well as 10% increases in cloud droplet number and 40% increases in liquid water content near coastal regions adjacent to continents. These cloud changes reduce longwave cloud forcing by 3% and cause a small surface warming, increasing the downward longwave flux at the surface by 2 W m-2 in the pan-Arctic under the present-day climate.« less

THE INFLUENCE OF THE CHEMICAL NATURE OF SOLID PARTICLES ON THEIR CATAPHORETIC P.D. IN AQUEOUS SOLUTIONS

PubMed Central

Loeb, Jacques

1923-01-01

1. The effect of eight salts, NaCl, Na2SO4, Na4Fe(CN)6, CaCl2, LaCl3, ThCl4, and basic and acid fuchsin on the cataphoretic P.D. between solid particles and aqueous solutions was measured near the point of neutrality of water (pH 5.8). It was found that without the addition of electrolyte the cataphoretic P.D. between particles and water is very minute near the point of neutrality (pH 5.8), often less than 10 millivolts, if care is taken that the solutions are free from impurities. Particles which in the absence of salts have a positive charge in water near the point of neutrality (pH 5.8) are termed positive colloids and particles which have a negative charge under these conditions are termed negative colloids. 2. If care is taken that the addition of the salt does not change the hydrogen ion concentration of the solution (which in these experiments was generally pH 5.8) it can be said in general, that as long as the concentration of salts is not too high, the anions of the salt have the tendency to make the particles more negative (or less positive) and that cations have the opposite effect; and that both effects increase with the increasing valency of the ions. As soon as a maximal P.D. is reached, which varies for each salt and for each type of particles, a further addition of salt depresses the P.D. again. Aside from this general tendency the effects of salts on the P.D. are typically different for positive and negative colloids. 3. Negative colloids (collodion, mastic, Acheson's graphite, gold, and metal proteinates) are rendered more negative by low concentrations of salts with monovalent cation (e.g. Na) the higher the valency of the anion, though the difference in the maximal P.D. is slight for the monovalent Cl and the tetravalent Fe(CN)6 ions. Low concentrations of CaCl2 also make negative colloids more negative but the maximal P.D. is less than for NaCl; even LaCl3 increases the P.D. of negative particles slightly in low concentrations. ThCl4 and basic fuchsin, however, seem to make the negative particles positive even in very low concentrations. 4. Positive colloids (ferric hydroxide, calcium oxalate, casein chloride—the latter at pH 4.0) are practically not affected by NaCl, are rendered slightly negative by high concentrations of Na2SO4, and are rendered more negative by Na4Fe(CN)6 and acid dyes. Low concentrations of CaCl2 and LaCl3 increase the positive charge of the particles until a maximum is reached after which the addition of more salt depresses the P.D. again. 5. It is shown that alkalies (NaOH) act on the cataphoretic P.D. of both negative and positive particles as Na4Fe(CN)6 does at the point of neutrality. 6. Low concentrations of HCl raise the cataphoretic P.D. of particles of collodion, mastic, graphite, and gold until a maximum is reached, after which the P.D. is depressed by a further increase in the concentration of the acid. No reversal in the sign of charge of the particle occurs in the case of collodion, while if a reversal occurs in the case of mastic, gold, and graphite, the P.D. is never more than a few millivolts. When HCl changes the chemical nature of the colloid, e.g. when HCl is added to particles of amphoteric electrolytes like sodium gelatinate, a marked reversal will occur, on account of the transformation of the metal proteinate into a protein-acid salt. 7. A real reversal in the sign of charge of positive particles occurs, however, at neutrality if Na4Fe(CN)6 or an acid dye is added; and in the case of negative colloids when low concentrations of basic dyes or minute traces of ThCl4 are added. 8. Flocculation of the suspensions by salts occurs when the cataphoretic P.D. reaches a critical value which is about 14 millivolts for particles of graphite, gold, or mastic or denatured egg albumin; while for collodion particles it was about 16 millivolts. A critical P.D. of about 15 millivolts was also observed by Northrop and De Kruif for the flocculation of certain bacteria. PMID:19872064

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

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

Lance, Sara; Raatikainen, T.; Onasch, Timothy B.

2013-05-15

Observations of aerosol hygroscopic growth and CCN activation spectra for submicron particles are reported for the T1 ground site outside of Mexico City during the MIRAGE 2006 campaign. K¨ohler theory is used to evaluate the characteristic water uptake coefficient, k*, for the CCN active aerosol population using both size-resolved HTMDA and size-resolved CCNc measurements. Organic mass fractions, (forg), are evaluated from size-resolved aerosol mass spectrometer (AMS) measurements, from which kAMS is inferred and compared against k*. Strong diurnal profiles of aerosol water uptake parameters and aerosol composition are observed. We find that new particle formation (NPF) events are correlated withmore » an increased k* and CCN-active fraction during the daytime, with greater impact on smaller particles. During NPF events, the number concentration of 40 nm particles acting as CCN can surpass by more than a factor of two the concentrations of 100 nm particles acting as CCN, at supersaturations of 0.51% +/- 0.06%. We also find that at 0600-0800 in the morning throughout the campaign, fresh traffic emissions result in substantial changes to the chemical distribution of the aerosol, with on average 65% externally-mixed fraction for 40 nm particles and 30% externally-mixed fraction for 100 nm particles, whereas at midday nearly all particles of both sizes can be described as “internally-mixed”. Average activation spectra and growth factor distributions are analyzed for different time periods characterizing the daytime (with and without NPF events), the early morning “rush hour”, and the entire campaign. We show that k* derived from CCNc measurements decreases as a function of size during all time periods, while the CCN-active fraction increases as a function of size. Size-resolved AMS measurements do not predict the observed trend for k* versus particle size, which can be attributed to unresolved mixing-state and the presence of refractory material not measured by the AMS. Measured k* typically ranges from 0.2 to 0.35, and organics typically make up 60-85% of the aerosol mass in the size range studied. Despite some disagreement between kAMS and kCCNc, we show that kAMS is able to describe CCN concentrations reasonably well, especially at the highest CCN concentrations. This is consistent with other CCN studies carried out in urban environments, and is partly due to the fact that the highest CCN concentrations occur during the daytime when the aerosol is internally-mixed and the organic fraction is relatively low. During the early morning rush hour, however, failing to account for the aerosol mixing state results in systematic overestimation of CCN concentrations by 50-100%.« less

Measurements of dispersion forces between colloidal latex particles with the atomic force microscope and comparison with Lifshitz theory

NASA Astrophysics Data System (ADS)

Elzbieciak-Wodka, Magdalena; Popescu, Mihail N.; Ruiz-Cabello, F. Javier Montes; Trefalt, Gregor; Maroni, Plinio; Borkovec, Michal

2014-03-01

Interaction forces between carboxylate colloidal latex particles of about 2 μm in diameter immersed in aqueous solutions of monovalent salts were measured with the colloidal probe technique, which is based on the atomic force microscope. We have systematically varied the ionic strength, the type of salt, and also the surface charge densities of the particles through changes in the solution pH. Based on these measurements, we have accurately measured the dispersion forces acting between the particles and estimated the apparent Hamaker constant to be (2.0 ± 0.5) × 10-21 J at a separation distance of about 10 nm. This value is basically independent of the salt concentration and the type of salt. Good agreement with Lifshitz theory is found when roughness effects are taken into account. The combination of retardation and roughness effects reduces the value of the apparent Hamaker constant and its ionic strength dependence with respect to the case of ideally smooth surfaces.

Measurements of dispersion forces between colloidal latex particles with the atomic force microscope and comparison with Lifshitz theory.

PubMed

Elzbieciak-Wodka, Magdalena; Popescu, Mihail N; Montes Ruiz-Cabello, F Javier; Trefalt, Gregor; Maroni, Plinio; Borkovec, Michal

2014-03-14

Interaction forces between carboxylate colloidal latex particles of about 2 μm in diameter immersed in aqueous solutions of monovalent salts were measured with the colloidal probe technique, which is based on the atomic force microscope. We have systematically varied the ionic strength, the type of salt, and also the surface charge densities of the particles through changes in the solution pH. Based on these measurements, we have accurately measured the dispersion forces acting between the particles and estimated the apparent Hamaker constant to be (2.0 ± 0.5) × 10(-21) J at a separation distance of about 10 nm. This value is basically independent of the salt concentration and the type of salt. Good agreement with Lifshitz theory is found when roughness effects are taken into account. The combination of retardation and roughness effects reduces the value of the apparent Hamaker constant and its ionic strength dependence with respect to the case of ideally smooth surfaces.

The promotion effect of coexisting hygroscopic composition on the reaction between oxalic acid and calcite during humidifying process

NASA Astrophysics Data System (ADS)

Ma, Q.; He, H.

2012-12-01

Internally mixed oxalic acid with mineral dust has been frequently detected in field measurements (Sullivan and Prather, 2007; Wang et al., 2012; Yang et al., 2009). Meanwhile, Furukawa and Takahashi (Furukawa and Takahashi, 2011) found that most of the oxalic acid in mineral mixture is present as metal oxalate complexes in the aerosols, however, the formation mechanism of these complexes is not well known. It was reported that cloud process of H2C2O4/CaCO3 mixture could lead to the formation of calcium oxalate (Gierlus et al., 2012). Recently, we used Raman spectroscopy to investigate the hygroscopic behavior of H2C2O4/CaCO3 mixture below saturation condition as well as the effect of coexisting hygroscopic compositions, e.g. Ca(NO3)2, NaCl, NH4NO3, and (NH4)2SO4. It was found that there was no interaction between H2C2O4 and calcite without third component during humidifying process under ambient condition. In contrast, the presence of coexisting Ca(NO)3, NaCl, or NH4NO3 could promote the reaction between H2C2O4 and calcite by providing an aqueous circumstance after deliquescence, resulting in the formation of calcium oxalate hydrates. Moreover, substitution of strong acid (HNO3) by medium acid (H2C2O4) occurred when water vapor was absorbed in Ca(NO3)2/H2C2O4 mixture (Ma and He, 2012). As for (NH4)2SO4, there existed a competition effect between (NH4)2SO4 and H2C2O4 for the reaction with CaCO3. CaCO3 was preferentially reacted with (NH4)2SO4 to form gypsum in the solution, while the residual NH4+ and C2O42- ions were bonded to (NH4)2C2O4 after efflorescence. These results implies a potential formation pathway of metal oxalate complexes in the atmosphere and also suggests that synergistic effect between different constituents in humidifying process of mixed particles should be considered in future hygroscopic behavior studies.

Rapid Measurements of Aerosol Size Distribution and Hygroscopic Growth via Image Processing with a Fast Integrated Mobility Spectrometer (FIMS)

NASA Astrophysics Data System (ADS)

Wang, Y.; Pinterich, T.; Spielman, S. R.; Hering, S. V.; Wang, J.

2017-12-01

Aerosol size distribution and hygroscopicity are among key parameters in determining the impact of atmospheric aerosols on global radiation and climate change. In situ submicron aerosol size distribution measurements commonly involve a scanning mobility particle sizer (SMPS). The SMPS scanning time is in the scale of minutes, which is often too slow to capture the variation of aerosol size distribution, such as for aerosols formed via nucleation processes or measurements onboard research aircraft. To solve this problem, a Fast Integrated Mobility Spectrometer (FIMS) based on image processing was developed for rapid measurements of aerosol size distributions from 10 to 500 nm. The FIMS consists of a parallel plate classifier, a condenser, and a CCD detector array. Inside the classifier an electric field separates charged aerosols based on electrical mobilities. Upon exiting the classifier, the aerosols pass through a three stage growth channel (Pinterich et al. 2017; Spielman et al. 2017), where aerosols as small as 7 nm are enlarged to above 1 μm through water or heptanol condensation. Finally, the grown aerosols are illuminated by a laser sheet and imaged onto a CCD array. The images provide both aerosol concentration and position, which directly relate to the aerosol size distribution. By this simultaneous measurement of aerosols with different sizes, the FIMS provides aerosol size spectra nearly 100 times faster than the SMPS. Recent deployment onboard research aircraft demonstrated that the FIMS is capable of measuring aerosol size distributions in 1s (Figure), thereby offering a great advantage in applications requiring high time resolution (Wang et al. 2016). In addition, the coupling of the FIMS with other conventional aerosol instruments provides orders of magnitude more rapid characterization of aerosol optical and microphysical properties. For example, the combination of a differential mobility analyzer, a relative humidity control unit, and a FIMS was used to measure aerosol hygroscopic growth. Such a system reduced the time of measuring the hygroscopic properties of submicron aerosols (six sizes) to less than three minutes in total, with an error within 1%. Pinterich et al. (2017) Aerosol Sci. Technol. accepted Spielman et al. (2017) Aerosol Sci. Technol. accepted Wang et al. (2016) Nature 539:416-419

Size Distribution of Sea-Salt Emissions as a Function of Relative Humidity

NASA Astrophysics Data System (ADS)

Zhang, K. M.; Knipping, E. M.; Wexler, A. S.; Bhave, P. V.; Tonnesen, G. S.

2004-12-01

Here we introduced a simple method for correcting sea-salt particle-size distributions as a function of relative humidity. Distinct from previous approaches, our derivation uses particle size at formation as the reference state rather than dry particle size. The correction factors, corresponding to the size at formation and the size at 80% RH, are given as polynomial functions of local relative humidity which are straightforward to implement. Without major compromises, the correction factors are thermodynamically accurate and can be applied between 0.45 and 0.99 RH. Since the thermodynamic properties of sea-salt electrolytes are weakly dependent on ambient temperature, these factors can be regarded as temperature independent. The correction factor w.r.t. to the size at 80% RH is in excellent agreement with those from Fitzgerald's and Gerber's growth equations; while the correction factor w.r.t. the size at formation has the advantage of being independent of dry size and relative humidity at formation. The resultant sea-salt emissions can be used directly in atmospheric model simulations at urban, regional and global scales without further correction. Application of this method to several common open-ocean and surf-zone sea-salt-particle source functions is described.

Protection of hydrophobic amino acids against moisture-induced deterioration in the aerosolization performance of highly hygroscopic spray-dried powders.

PubMed

Yu, Jiaqi; Chan, Hak-Kim; Gengenbach, Thomas; Denman, John A

2017-10-01

Inhalable particles containing amorphous form of drugs or excipients may absorb atmospheric moisture, causing powder aggregation and recrystallization, adversely affecting powder dispersion and lung deposition. The present study aims to explore hydrophobic amino acids for protection against moisture in spray-dried amorphous powders, using disodium cromoglycate (DSCG) as a model drug. DSCG powders were produced by co-spray drying with isoleucine (Ile), valine (Val) and methionine (Met) in various concentrations (10, 20 and 40%w/w). Particle size distribution and morphology were measured by laser diffraction and scanning electron microscopy (SEM). Physiochemical properties of the powders were characterized by X-ray powder diffraction (XRPD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamic vapor sorption (DVS). Particle surface chemistry was analyzed by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). In vitro aerosolization performance was evaluated by a next generation impactor (NGI) after the powders were stored at 60% or 75% relative humidity (RH) for one month and three months. Ile, Val and Met significantly reduced the deleterious effect of moisture on aerosol performance, depending on the amount of amino acids in the formulation. Formulations containing 10% or 20% of Ile, Val and Met showed notable deterioration in aerosol performance, with fine particle fraction (FPF) reduced by 6-15% after one-month storage at both 60% and 75% RH. However, 40% Ile was able to maintain the aerosol performance of DSCG stored at 75% RH for one month, while the FPF dropped by 7.5% after three months of storage. In contrast, 40% Val or Met were able to maintain the aerosol performance at 60% RH storage but not at 75% RH. At 40%w/w ratio, these formulations had particle surface coverage of 94.5% (molar percent) of Ile, 87.1% of Val and 84.6% of Met, respectively, which may explain their moisture protection effects. Ile, Val and Met showed promising moisture protection effect on aerosol performance. The results broaden the understanding on the use of hydrophobic amino acids as an excipient for long-term storage of inhalation powders formulations that are hygroscopic. Copyright © 2017 Elsevier B.V. All rights reserved.

The Effect of Mars-relevant Minerals on the Water Uptake of Magnesium Perchlorate and Implications for the Near-surface of Mars

NASA Astrophysics Data System (ADS)

Primm, Katherine; Gough, Raina; Rivera-Valentin, Edgard G.; Tolbert, Margaret

2017-10-01

The water uptake and release by hygroscopic salts such as perchlorate has been well studied in the decade since they were first discovered on the surface of Mars. However, there have been few studies on the effect of the insoluble regolith minerals on this well documented interaction of perchlorate and water vapor. In this work, we investigate the effect that two insoluble Mars-relevant minerals, montmorillonite and Mojave Mars Simulant (MMS), have on the water uptake (deliquescence), ice formation, and recrystallization (efflorescence) of pure magnesium perchlorate. We studied mixtures of equal parts (by mass) magnesium perchlorate hexahydrate and either montmorillonite or MMS. Although montmorillonite and MMS are insoluble minerals that may serve as nuclei for either ice nucleation or salt efflorescence, we find that these minerals did not affect any of the phase transitions of magnesium perchlorate. The salt-mineral mixture behaved like pure magnesium perchlorate in all cases, with stable deliquescence as well as metastable brine supersaturation and supercooling observed. Experiments were performed in both N2 and CO2 atmospheres, with no detectable difference. We use data from the Rover Environmental Monitoring Station instrument on MSL and from the Thermal and Electrical Conductivity Probe instrument on Phoenix, as well as modeling of the shallow subsurface near the rover and lander, to determine the likelihood of liquid water and water ice at Gale Crater and the Phoenix landing site.

Correlation of plume opacity with particles and sulfates from boilers

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

Lou, J.C.; Lee, M.; Chen, K.S.

1997-07-01

The effects of emission concentrations of particulate matters and sulfates on plume opacity are investigated by in situ measurements. The studies are conducted for three processes of two coal-fired plants and one oil-fired that are all equipped with electrostatic precipitators. Flue-gas sampling and analysis include the concentrations of particles and total water soluble sulfates, particle size distribution, and flue-gas composition; while in-stack and out-of-stack opacities are determined by a transmissometer and certified smoke inspectors, respectively. Experimental results show that plume opacity outside the stack linearly correlates well with the in-stack opacity. The mixing of hot flue gas with cold ambientmore » air would result in the condensation of hygroscopic sulfuric acid aerosols and an increase about 1.6% out of typical 15--25% measured opacity. An empirical equation similar to the Beer-Lambert-Bouger form is derived for predicting the plume opacity in terms of the stack diameter and the concentrations of particles and total water soluble sulfates. Good comparisons are achieved between predictions by the empirical equation and other available field data.« less

Mesoporous inorganic salts with crystal defects: unusual catalysts and catalyst supports† †Electronic supplementary information (ESI) available: Scheme S1 contains reaction equation, Fig. S1–S7 contain solubility test, XRD, SEM, TEM, micropore size distribution and reaction conversion. See DOI: 10.1039/c4sc03736g Click here for additional data file.

PubMed Central

Kang, Xinchen; Shang, Wenting; Zhu, Qinggong; Zhang, Jianling; Wu, Zhonghua; Li, Zhihong; Xing, Xueqing

2015-01-01

We proposed a strategy to synthesize mesoporous inorganic salt particles using the special properties of ionic liquid (IL) mixtures, and hollow mesoporous LaF3, NdF3, and YF3 particles were synthesized and characterized using different techniques. The size of the mesopores in the salt particles was about 4 nm, and the materials were full of crystal defects. The LaF3, NdF3 and YF3 particles were used as the catalysts for the cyanosilylation reaction of benzaldehyde using trimethylsilyl cyanide, and Ru/LaF3 and Ru/NdF3, in which Ru nanocatalysts were supported on the LaF3 and NdF3 particles with mesopores, were used to catalyze hydrogenations of benzene to cyclohexane and levulinic acid (LA) to γ-valerolactone (GVL). It was discovered that the activities of these catalysts were unprecedentedly high for these reactions. Detailed study showed that both the crystal defects and the mesopores in the salt particles played crucial roles for the extremely high catalytic activity. PMID:29308132

Mixing state of regionally transported soot particles and the coating effect on their size and shape at a mountain site in Japan

NASA Astrophysics Data System (ADS)

Adachi, Kouji; Zaizen, Yuji; Kajino, Mizuo; Igarashi, Yasuhito

2014-05-01

Soot particles influence the global climate through interactions with sunlight. A coating on soot particles increases their light absorption by increasing their absorption cross section and cloud condensation nuclei activity when mixed with other hygroscopic aerosol components. Therefore, it is important to understand how soot internally mixes with other materials to accurately simulate its effects in climate models. In this study, we used a transmission electron microscope (TEM) with an auto particle analysis system, which enables more particles to be analyzed than a conventional TEM. Using the TEM, soot particle size and shape (shape factor) were determined with and without coating from samples collected at a remote mountain site in Japan. The results indicate that ~10% of aerosol particles between 60 and 350 nm in aerodynamic diameters contain or consist of soot particles and ~75% of soot particles were internally mixed with nonvolatile ammonium sulfate or other materials. In contrast to an assumption that coatings change soot shape, both internally and externally mixed soot particles had similar shape and size distributions. Larger aerosol particles had higher soot mixing ratios, i.e., more than 40% of aerosol particles with diameters >1 µm had soot inclusions, whereas <20% of aerosol particles with diameters <1 µm included soot. Our results suggest that climate models may use the same size distributions and shapes for both internally and externally mixed soot; however, changing the soot mixing ratios in the different aerosol size bins is necessary.

Estimating degradation-related settlement in two landfill-reclaimed soils by sand-salt analogues.

PubMed

McDougall, J R; Fleming, I R; Thiel, R; Dewaele, P; Parker, D; Kelly, D

2018-04-25

Landfill reclaimed soil here refers to largely degraded materials excavated from old landfill sites, which after processing can be reinstated as more competent fill, thereby restoring the former landfill space. The success of the process depends on the presence of remaining degradable particles and their influence on settlement. Tests on salt-sand mixtures, from which the salt is removed, have been used to quantify the impact of particle loss on settlement. Where the amount of particle loss is small, say 10% by mass or less, settlements are small and apparently independent of lost particle size. A conceptual model is presented to explain this behaviour in terms of nestling particles and strong force chains. At higher percentages of lost particles, greater rates of settlement together with some sensitivity to particle size were observed. The conceptual model was then applied to two landfill reclaimed soils, the long-term settlements of which were found to be consistent with the conceptual model suggesting that knowledge of particle content and relative size are sufficient to estimate the influence of degradable particles in landfill reclaimed soils. Copyright © 2018 Elsevier Ltd. All rights reserved.

Ion size effects on the electrokinetics of spherical particles in salt-free concentrated suspensions

NASA Astrophysics Data System (ADS)

Roa, Rafael; Carrique, Felix; Ruiz-Reina, Emilio

2012-02-01

In this work we study the influence of the counterion size on the electrophoretic mobility and on the dynamic mobility of a suspended spherical particle in a salt-free concentrated colloidal suspension. Salt-free suspensions contain charged particles and the added counterions that counterbalance their surface charge. A spherical cell model approach is used to take into account particle-particle electro-hydrodynamic interactions in concentrated suspensions. The finite size of the counterions is considered including an entropic contribution, related with the excluded volume of the ions, in the free energy of the suspension, giving rise to a modified counterion concentration profile. We are interested in studying the linear response of the system to an electric field, thus we solve the different electrokinetic equations by using a linear perturbation scheme. We find that the ionic size effect is quite important for moderate to high particles charges at a given particle volume fraction. In addition for such particle surface charges, both the electrophoretic mobility and the dynamic mobility suffer more important changes the larger the particle volume fraction for each ion size. The latter effects are more relevant the larger the ionic size.

Microbes at Surface-Air Interfaces: The Metabolic Harnessing of Relative Humidity, Surface Hygroscopicity, and Oligotrophy for Resilience

PubMed Central

Stone, Wendy; Kroukamp, Otini; Korber, Darren R.; McKelvie, Jennifer; Wolfaardt, Gideon M.

2016-01-01

The human environment is predominantly not aqueous, and microbes are ubiquitous at the surface-air interfaces with which we interact. Yet microbial studies at surface-air interfaces are largely survival-oriented, whilst microbial metabolism has overwhelmingly been investigated from the perspective of liquid saturation. This study explored microbial survival and metabolism under desiccation, particularly the influence of relative humidity (RH), surface hygroscopicity, and nutrient availability on the interchange between these two phenomena. The combination of a hygroscopic matrix (i.e., clay or 4,000 MW polyethylene glycol) and high RH resulted in persistent measurable microbial metabolism during desiccation. In contrast, no microbial metabolism was detected at (a) hygroscopic interfaces at low RH, and (b) less hygroscopic interfaces (i.e., sand and plastic/glass) at high or low RH. Cell survival was conversely inhibited at high RH and promoted at low RH, irrespective of surface hygroscopicity. Based on this demonstration of metabolic persistence and survival inhibition at high RH, it was proposed that biofilm metabolic rates might inversely influence whole-biofilm resilience, with ‘resilience’ defined in this study as a biofilm’s capacity to recover from desiccation. The concept of whole-biofilm resilience being promoted by oligotrophy was supported in desiccation-tolerant Arthrobacter spp. biofilms, but not in desiccation-sensitive Pseudomonas aeruginosa biofilms. The ability of microbes to interact with surfaces to harness water vapor during desiccation was demonstrated, and potentially to harness oligotrophy (the most ubiquitous natural condition facing microbes) for adaptation to desiccation. PMID:27746774

Salts affect the interaction of ZnO or CuO nanoparticles with wheat.

PubMed

Stewart, Jacob; Hansen, Trevor; McLean, Joan E; McManus, Paul; Das, Siddhartha; Britt, David W; Anderson, Anne J; Dimkpa, Christian O

2015-09-01

Exposure to nanoparticles (NPs) that release metals with potential phytotoxicity could pose problems in agriculture. The authors of the present study used growth in a model growth matrix, sand, to examine the influence of 5 mmol/kg of Na, K, or Ca (added as Cl salts) and root exudates on transformation and changes to the bioactivity of copper(II) oxide (CuO) and zinc oxide (ZnO) NPs on wheat. These salt levels are found in saline agricultural soils. After 14 d of seedling growth, particles with crystallinity typical of CuO or ZnO remained in the aqueous fraction from the sand; particles had negative surface charges that differed with NP type and salt, but salt did not alter particle agglomeration. Reduction in shoot and root elongation and lateral root induction by ZnO NPs were mitigated by all salts. However, whereas Na and K promoted Zn loading into shoots, Ca reduced loading, suggesting that competition with Zn ions for uptake occurred. With CuO NPs, plant growth and loading was modified equally by all salts, consistent with major interaction with the plant with CuO rather than Cu ions. Thus, for both NPs, loading into plant tissues was not solely dependent on ion solubility. These findings indicated that salts in agricultural soils could modify the phytotoxicity of NPs. © 2015 SETAC.

A three-dimensional sectional representation of aerosol mixing state for simulating optical properties and cloud condensation nuclei

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

Ching, Ping Pui; Zaveri, Rahul A.; Easter, Richard C.

2016-05-27

Light absorption by black carbon (BC) particles emitted from fossil fuel combustion depends on the how thickly they are coated with non-refractory species such as ammonium, sulfate, nitrate, organics, and water. The cloud condensation nuclei (CCN) activation property of a particle depends on its dry size and the hygroscopicities of all the individual species mixed together. It is therefore necessary to represent both size and mixing state of aerosols to reliably predict their climate-relevant properties in atmospheric models. Here we describe and evaluate a novel sectional framework in the Model for Simulating Aerosol Interactions and Chemistry, referred to as MOSAIC-mix,more » that represents the mixing state by resolving aerosol dry size (Ddry), BC dry mass fraction (wBC), and hygroscopicity (κ). Using ten idealized urban plume scenarios in which different types of aerosols evolve over 24 hours under a range of atmospherically relevant environmental conditions, we examine errors in CCN concentrations and optical properties with respect to a more explicit aerosol mixing state representation. We find that only a small number of wBC and κ bins are needed to achieve significant reductions in the errors, and propose a configuration consisting of 24 Ddry bins, 2 wBC bins, and 2 κ bins that gives 24-hour average errors of about 5% or less in CCN concentrations and optical properties, 3-4 times lower than those from size-only-resolved simulations. These results show that MOSAIC-mix is suitable for use in regional and global models to examine the effects of evolving aerosol mixing states on aerosol-radiation-cloud feedbacks.« less

Aerosol-Cloud Interactions During Puijo Cloud Experiments - The effects of weather and local sources

NASA Astrophysics Data System (ADS)

Komppula, Mika; Portin, Harri; Leskinen, Ari; Romakkaniemi, Sami; Brus, David; Neitola, Kimmo; Hyvärinen, Antti-Pekka; Kortelainen, Aki; Hao, Liqing; Miettinen, Pasi; Jaatinen, Antti; Ahmad, Irshad; Lihavainen, Heikki; Laaksonen, Ari; Lehtinen, Kari E. J.

2013-04-01

The Puijo measurement station has provided continuous data on aerosol-cloud interactions since 2006. The station is located on top of the Puijo observation tower (306 m a.s.l, 224 m above the surrounding lake level) in Kuopio, Finland. The top of the tower is covered by cloud about 15 % of the time, offering perfect conditions for studying aerosol-cloud interactions. With a twin-inlet setup (total and interstitial inlets) we are able to separate the activated particles from the interstitial (non-activated) particles. The continuous twin-inlet measurements include aerosol size distribution, scattering and absorption. In addition cloud droplet number and size distribution are measured continuously with weather parameters. During the campaigns the twin-inlet system was additionally equipped with aerosol mass spectrometer (AMS) and Single Particle Soot Photometer (SP-2). This way we were able to define the differences in chemical composition of the activated and non-activated particles. Potential cloud condensation nuclei (CCN) in different supersaturations were measured with two CCN counters (CCNC). The other CCNC was operated with a Differential Mobility Analyzer (DMA) to obtain size selected CCN spectra. Other additional measurements included Hygroscopic Tandem Differential Mobility Analyzer (HTDMA) for particle hygroscopicity. Additionally the valuable vertical wind profiles (updraft velocities) are available from Halo Doppler lidar during the 2011 campaign. Cloud properties (droplet number and effective radius) from MODIS instrument onboard Terra and Aqua satellites were retrieved and compared with the measured values. This work summarizes the two latest intensive campaigns, Puijo Cloud Experiments (PuCE) 2010 & 2011. We study especially the effect of the local sources on the cloud activation behaviour of the aerosol particles. The main local sources include a paper mill, a heating plant, traffic and residential areas. The sources can be categorized and identified by wind direction. Clear changes can be seen in the aerosol and cloud properties when being under the influence of a local pollutant source. Also differences in the chemical composition of aerosol activated to cloud droplet and those staying interstitial has been observed. For example, the light absorption by cloud interstitial particles is higher when the wind blows from the local pollutant sources compared to a cleaner sector. This may be due to the fact that the absorptive material, e.g. fresh soot, is generally hydrophobic and therefore inhibits activation. Another point of interest is the occasional freezing conditions during the campaign (temperature below zero), which also affects the activation behaviour. The full usage of this special data set will provide new information on the properties and differences of activating and non-activating aerosol particles, as well as on the variables affecting the activation.

Polymerization shrinkage and hygroscopic expansion of contemporary posterior resin-based filling materials--a comparative study.

PubMed

Rüttermann, Stefan; Krüger, Sören; Raab, Wolfgang H-M; Janda, Ralf

2007-10-01

To investigate the polymerization shrinkage and hygroscopic expansion of contemporary posterior resin-based filling materials. The densities of SureFil (SU), CeramXMono (CM), Clearfil AP-X (CF), Solitaire 2 (SO), TetricEvoCeram (TE), and Filtek P60 (FT) were measured using the Archimedes' principle prior to and 15min after curing for 20, 40 and 60s and after 1h, 24h, 7 d, and 30 d storage at 37 degrees C in water. Volumetric changes (DeltaV) in percent after polymerization and after each storage period in water were calculated from the changes of densities. Water sorption and solubility were determined after 30 d for all specimens and their curing times. Two-way ANOVA was calculated for shrinkage and repeated measures ANOVA was calculated for hygroscopic expansion (p<0.05). DeltaV depended on filler load but not on curing time (SU approximately -2.0%, CM approximately -2.6%, CF approximately -2.1%, SO approximately -3.3%, TE approximately -1.7%, FT approximately -1.8%). Hygroscopic expansion depended on water sorption and solubility. Except for SU, all materials showed DeltaV approximately +1% after water storage. Polymerization shrinkage depended on the type of resin-based filling material but not on curing time. Shrinkage was not compensated by hygroscopic expansion.

Triple-wavelength lidar observations of the linear depolarization ratio of dried marine particles

NASA Astrophysics Data System (ADS)

Haarig, Moritz; Ansmann, Albert; Baars, Holger; Engelmann, Ronny; Althausen, Dietrich; Bohlmann, Stephanie; Gasteiger, Josef; Farrell, David

2018-04-01

For aerosol typing with lidar, sea salt particles are usually assumed to be spherical with a consequently low depolarization ratio. Evidence of dried marine particles at the top of the humid marine aerosol layer with a depolarization ratio up to 0.1 has been found at predominately maritime locations on Barbados and in the Southern Atlantic. The depolarization ratio for these probably cubic sea salt particles has been measured at three wavelengths (355, 532 and 1064 nm) simultaneously for the first time and compared to model simulations.

A novel approach to a fine particle coating using porous spherical silica as core particles.

PubMed

Ishida, Makoto; Uchiyama, Jumpei; Isaji, Keiko; Suzuki, Yuta; Ikematsu, Yasuyuki; Aoki, Shigeru

2014-08-01

Abstract The applicability of porous spherical silica (PSS) was evaluated as core particles for pharmaceutical products by comparing it with commercial core particles such as mannitol (NP-108), sucrose and microcrystalline cellulose spheres. We investigated the physical properties of core particles, such as particle size distribution, flow properties, crushing strength, plastic limit, drying rate, hygroscopic property and aggregation degree. It was found that PSS was a core particle of small particle size, low friability, high water adsorption capacity, rapid drying rate and lower occurrence of particle aggregation, although wettability is a factor to be carefully considered. The aggregation and taste-masking ability using PSS and NP-108 as core particles were evaluated at a fluidized-bed coating process. The functional coating under the excess spray rate shows different aggregation trends and dissolution profiles between PSS and NP-108; thereby, exhibiting the formation of uniform coating under the excess spray rate in the case of PSS. This expands the range of the acceptable spray feed rates to coat fine particles, and indicates the possibility of decreasing the coating time. The results obtained in this study suggested that the core particle, which has a property like that of PSS, was useful in overcoming such disadvantages as large particle size, which feels gritty in oral cavity; particle aggregation; and the long coating time of the particle coating process. These results will enable the practical fine particle coating method by increasing the range of optimum coating conditions and decreasing the coating time in fluidized bed technology.

Measurements of dispersion forces between colloidal latex particles with the atomic force microscope and comparison with Lifshitz theory

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

Elzbieciak-Wodka, Magdalena; Ruiz-Cabello, F. Javier Montes; Trefalt, Gregor

2014-03-14

Interaction forces between carboxylate colloidal latex particles of about 2 μm in diameter immersed in aqueous solutions of monovalent salts were measured with the colloidal probe technique, which is based on the atomic force microscope. We have systematically varied the ionic strength, the type of salt, and also the surface charge densities of the particles through changes in the solution pH. Based on these measurements, we have accurately measured the dispersion forces acting between the particles and estimated the apparent Hamaker constant to be (2.0 ± 0.5) × 10{sup −21} J at a separation distance of about 10 nm. Thismore » value is basically independent of the salt concentration and the type of salt. Good agreement with Lifshitz theory is found when roughness effects are taken into account. The combination of retardation and roughness effects reduces the value of the apparent Hamaker constant and its ionic strength dependence with respect to the case of ideally smooth surfaces.« less

The effects of salt, particle and pore size on the process of carbon dioxide hydrate formation: A critical review

NASA Astrophysics Data System (ADS)

Ghaedi, Hosein; Ayoub, Muhammad; Bhat, A. H.; Mahmood, Syed Mohammad; Akbari, Saeed; Murshid, Ghulam

2016-11-01

Hydration is an alternative method for CO2 capture. In doing so, some researchers use porous media on an experimental scale. This paper tries to gather the researches on the formation of CO2 hydrate in different types of porous media such as silica sand, quartz sand, Toyoura, pumice, and fire hardened red clay. This review has attempted to examine the effects of salt and particle sizes as two major factors on the induction time, water to hydrate conversion, gas uptake (or gas consumption), and the rate of CO2 hydrate formation. By performing a critical assessment of previous research works, it was observed that the figure for the gas uptake (or gas consumption) and water to hydrate conversion in porous media was decreased by increasing the particle size provided that the pore size was constant. Although, salt can play a role in hydrate formation as the thermodynamic inhibitor, the results show that salt can be regarded as the kinetic growth inhibitor and kinetic promoter. Because of the fact that the gas uptake in seawater is lower than pure water at the end of experiment, the salt can act as a kinetic growth inhibitor. However, since gas uptake (after the nucleation period and for a short period) and the initial rate of hydrate formation in saline water were more than that of pure water, salt can play a promoter role in the kinetic reaction, too. Besides these, in the case of pure water and within a certain particle size, the amount of the hydrate formation rate has been seen to be greater in smaller particles (provided that the pore size is constant), however this has not been observed for seawater.

Adsorbent for metal ions and method of making and using

DOEpatents

White, Lloyd R.; Lundquist, Susan H.

1999-01-01

A method comprises the step of spray-drying a solution or slurry comprising (alkali metal or ammonium) (metal) hexacyanoferrate particles in a liquid, to provide monodisperse, substantially spherical particles in a yield of at least 70 percent of theoretical yield and having a particle size in the range of 1 to 500 micrometers, said particles being active towards Cs ions. The particles, which can be of a single salt or a combination of salts, can be used free flowing, in columns or beds, or entrapped in a nonwoven, fibrous web or matrix or a cast porous membrane, to selectively remove Cs ions from aqueous solutions.

Adsorbent for metal ions and method of making and using

DOEpatents

White, L.R.; Lundquist, S.H.

1999-08-10

A method comprises the step of spray-drying a solution or slurry comprising (alkali metal or ammonium) (metal) hexacyanoferrate particles in a liquid, to provide monodisperse, substantially spherical particles in a yield of at least 70 percent of theoretical yield and having a particle size in the range of 1 to 500 micrometers, said particles being active towards Cs ions. The particles, which can be of a single salt or a combination of salts, can be used free flowing, in columns or beds, or entrapped in a nonwoven, fibrous web or matrix or a cast porous membrane, to selectively remove Cs ions from aqueous solutions. 2 figs.

Adsorbent for metal ions and method of making and using

DOEpatents

White, Lloyd R.; Lundquist, Susan H.

2000-01-01

A method comprises the step of spray-drying a solution or slurry comprising (alkali metal or ammonium) (metal) hexacyanoferrate particles in a liquid, to provide monodisperse, substantially spherical particles in a yield of at least 70 percent of theoretical yield and having a particle size in the range of 1 to 500 micrometers, said particles being active towards Cs ions. The particles, which can be of a single salt or a combination of salts, can be used free flowing, in columns or beds, or entrapped in a nonwoven, fibrous web or matrix or a cast porous membrane, to selectively remove Cs ions from aqueous solutions.

Methods for producing monodispersed particles of barium titanate

DOEpatents

Hu, Zhong-Cheng

2001-01-01

The present invention is a low-temperature controlled method for producing high-quality, ultrafine monodispersed nanocrystalline microsphere powders of barium titanate and other pure or composite oxide materials having particles ranging from nanosized to micronsized particles. The method of the subject invention comprises a two-stage process. The first stage produces high quality monodispersed hydrous titania microsphere particles prepared by homogeneous precipitation via dielectric tuning in alcohol-water mixed solutions of inorganic salts. Titanium tetrachloride is used as an inorganic salt precursor material. The second stage converts the pure hydrous titania microsphere particles into crystalline barium titanate microsphere powders via low-temperature, hydrothermal reactions.

High quality interlayer dielectric for 4H SiC DMOSFETs

NASA Astrophysics Data System (ADS)

Okayama, T.; Arthur, S. D.; Waldrab, P.; Rao, Mulpuri V.

2007-11-01

In this work useful weight percentages of boron and phosphorus in boro-phospho-silicate-glass (BPSG) interlayer dielectric (ILD) films to getter mobile ions effectively in 4H-SiC DMOSFET structures are developed, considering the limitations, such as the required low glass flow temperature, and the possible hygroscopic nature of the films and formation of crystalline BPO4 particles, which may occur for high B and P weight percentages. The B and P weight percentage viscous flow temperature contours and empirical inequalities representing the above-mentioned limitations are developed and discussed. Results of this work are useful for both silicon and compound semiconductor device technologies.

Chain stiffness, salt valency, and concentration influences on titration curves of polyelectrolytes: Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Carnal, Fabrice; Stoll, Serge

2011-01-01

Monte Carlo simulations have been used to study two different models of a weak linear polyelectrolyte surrounded by explicit counterions and salt particles: (i) a rigid rod and (ii) a flexible chain. We focused on the influence of the pH, chain stiffness, salt concentration, and valency on the polyelectrolyte titration process and conformational properties. It is shown that chain acid-base properties and conformational properties are strongly modified when multivalent salt concentration variation ranges below the charge equivalence. Increasing chain stiffness allows to minimize intramolecular electrostatic monomer interactions hence improving the deprotonation process. The presence of di and trivalent salt cations clearly promotes the chain degree of ionization but has only a limited effect at very low salt concentration ranges. Moreover, folded structures of fully charged chains are only observed when multivalent salt at a concentration equal or above charge equivalence is considered. Long-range electrostatic potential is found to influence the distribution of charges along and around the polyelectrolyte backbones hence resulting in a higher degree of ionization and a lower attraction of counterions and salt particles at the chain extremities.

Chain stiffness, salt valency, and concentration influences on titration curves of polyelectrolytes: Monte Carlo simulations.

PubMed

Carnal, Fabrice; Stoll, Serge

2011-01-28

Monte Carlo simulations have been used to study two different models of a weak linear polyelectrolyte surrounded by explicit counterions and salt particles: (i) a rigid rod and (ii) a flexible chain. We focused on the influence of the pH, chain stiffness, salt concentration, and valency on the polyelectrolyte titration process and conformational properties. It is shown that chain acid-base properties and conformational properties are strongly modified when multivalent salt concentration variation ranges below the charge equivalence. Increasing chain stiffness allows to minimize intramolecular electrostatic monomer interactions hence improving the deprotonation process. The presence of di and trivalent salt cations clearly promotes the chain degree of ionization but has only a limited effect at very low salt concentration ranges. Moreover, folded structures of fully charged chains are only observed when multivalent salt at a concentration equal or above charge equivalence is considered. Long-range electrostatic potential is found to influence the distribution of charges along and around the polyelectrolyte backbones hence resulting in a higher degree of ionization and a lower attraction of counterions and salt particles at the chain extremities.

A randomized clinical trial comparing an extended-use hygroscopic condenser humidifier with heated-water humidification in mechanically ventilated patients.

PubMed

Kollef, M H; Shapiro, S D; Boyd, V; Silver, P; Von Harz, B; Trovillion, E; Prentice, D

1998-03-01

To determine the safety and cost-effectiveness of mechanical ventilation with an extended-use hygroscopic condenser humidifier (Duration; Nellcor Puritan-Bennett; Eden Prairie, Minn) compared with mechanical ventilation with heated-water humidification. Prospective randomized clinical trial. Medical and surgical ICUs of Barnes-Jewish Hospital, St. Louis, a university-affiliated teaching hospital. Three hundred ten consecutive qualified patients undergoing mechanical ventilation. Patients requiring mechanical ventilation were randomly assigned to receive humidification with either an extended-use hygroscopic condenser humidifier (for up to the first 7 days of mechanical ventilation) or heated-water humidification. Occurrence of ventilator-associated pneumonia, endotracheal tube occlusion, duration of mechanical ventilation, lengths of intensive care and hospitalization, acquired multiorgan dysfunction, and hospital mortality. One hundred sixty-three patients were randomly assigned to receive humidification with an extended-use hygroscopic condenser humidifier, and 147 patients were randomly assigned to receive heated-water humidification. The two groups were similar at the time of randomization with regard to demographic characteristics, ICU admission diagnoses, and severity of illness. Risk factors for the development of ventilator-associated pneumonia were also similar during the study period for both treatment groups. Ventilator-associated pneumonia was seen in 15 (9.2%) patients receiving humidification with an extended-use hygroscopic condenser humidifier and in 15 (10.2%) patients receiving heated-water humidification (relative risk, 0.90; 95% confidence interval=0.46 to 1.78; p=0.766). No statistically significant differences for hospital mortality, duration of mechanical ventilation, lengths of stay in the hospital ICU, or acquired organ system derangements were found between the two treatment groups. No episode of endotracheal tube occlusion occurred during the study period in either treatment group. The total cost of providing humidification was $2,605 for patients receiving a hygroscopic condenser humidifier compared with $5,625 for patients receiving heated-water humidification. Our findings suggest that the initial application of an extended-use hygroscopic condenser humidifier is a safe and more cost-effective method of providing humidification to patients requiring mechanical ventilation compared with heated-water humidification.

Sintering and Microstructure of BaTiO3 Nano Particles Synthesized by Molten Salt Method.

PubMed

Lee, Chang-Hyun; Shin, Hyo-Soon; Yeo, Dong-Hun; Ha, Gook-Hyun; Nahm, Sahn

2016-05-01

In order to establish thinner dielectric layers in thick film electronic components such as MLCC (Multilayer ceramic capacitor), BaTiO3 nanoparticles have been utilized. However, studies on the synthesis of nanoparticles smaller than 20 nm, the characteristics of the BaTiO3 powder, and the powder's sintering are lacking. Therefore, this paper aims to synthesize BaTiO3 particles smaller than 20 nm by using the molten salt method and evaluate the microstructure and dielectric properties by varying the sintering temperature from 750 degrees C to 1200 degrees C. Through the molten salt method and by using KOH-KCl mixed salt, 20 nm BaTiO3 powder was synthesized at a low temperature of 150 degrees C. Sintering the pellets formed from the synthesized 20 nm BaTiO3 nano powder led to the observation of an unusual phenomenon where the particles grew to approximate sizes below 850 degrees C where densification progressed. At sintering temperatures above 950 degrees C, particles that expanded into rod shapes were observed and these particles were identified to be unreacted TiO2 based on the results of the EDX (Energy Dispersive X-ray Spectroscopy) analysis and phase analysis results.

Particle formation above natural and simulated salt lakes

NASA Astrophysics Data System (ADS)

Kamilli, Katharina; Ofner, Johannes; Sattler, Tobias; Krause, Torsten; Zetzsch, Cornelius; Held, Andreas

2013-04-01

Western Australia was originally covered by natural eucalyptus forests, but land-use has changed considerably after large scale deforestation from 1950 to 1970. Thus, the ground-water level rose and brought dissolved salts and minerals to the surface. Nowadays, Western Australia is known for a great plenty of salt lakes with pH levels reaching from 2.5 to 7.1. The land is mainly used for wheat farming and livestock and becomes drier due to the lack of rain periods. One possible reason could be the formation of ultrafine particles from salt lakes, which increases the number of cloud condensation nuclei and thus potentially suppresses precipitation. Several field campaigns have been conducted between 2006 and 2011 with car-based and airborne measurements, where new particle formation has been observed and has been related to the Western Australian salt lakes (Junkermann et al., 2009). To identify particle formation directly above the salt lakes, a 1.5 m³ Teflon chamber was set up above several lakes in 2012. Inside the chamber, photochemistry may take place whereas mixing through wind or advection of already existing particles is prevented. Salt lakes with a low pH level lead to strongly increased aerosol formation. As salt lakes have been identified as a source for reactive halogen species (RHS; Buxmann et al., 2012) and RHS seem to interact with precursors of secondary organic aerosol (SOA), they could be producers of halogen induced secondary organic aerosol (XOA) (Ofner et al., 2012). As reference experiments, laboratory based aerosol smog-chamber runs were performed to examine XOA formation under atmospheric conditions using simulated sunlight and the chemical composition of a chosen salt lake. After adding α-pinene to the simulated salt lake, a strong nucleation event began in the absence of ozone comparable to the observed events in Western Australia. First results from the laboratory based aerosol smog-chamber experiments indicate a halogen-induced aerosol formation above Australian salt lakes. This work was funded by German Research Foundation (DFG) under grants HE 5214/5-1 and ZE792/5-2. References: Buxmann, J., Balzer, N., Bleicher, S., Platt, U., and Zetzsch, C.: Observations of bromine explosions in smog chamber experiments above a model salt pan, Int. J. Chem. Kinet., 44, 312-326, 2012. Junkermann, W., Hacker, J., Lyons, T., and Nair, U.: Land use change suppresses precipitation, Atmos. Chem. Phys., 9, 6531-6539, 2009. Ofner, J., Balzer, N., Buxmann, J., Grothe, H., Schmitt-Kopplin, Ph., Platt, U., and Zetzsch, C.: Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms, Atmos. Chem. Phys., 12, 5787-5806, 2012.

Parametric Study of Solder Flux Hygroscopicity: Impact of Weak Organic Acids on Water Layer Formation and Corrosion of Electronics

NASA Astrophysics Data System (ADS)

Piotrowska, Kamila; Ud Din, Rameez; Grumsen, Flemming Bjerg; Jellesen, Morten Stendahl; Ambat, Rajan

2018-07-01

The presence of solder flux residues on the printed circuit board assembly surface is an important factor contributing to humidity-related reliability issues that affect device lifetime. This investigation focuses on understanding the hygroscopic nature of typical wave solder flux activators—weak organic acids—under varied temperature conditions. In situ x-ray diffraction measurements assessed the effect of high temperature on the crystal structure of organic activators. The hygroscopicity studies were carried out under relative humidity (RH) levels varying from 30% to ˜ 99% and at temperatures 25°C, 40°C, and 60°C. Water absorption levels were determined using the gravimetric method, and the influence on reliability was assessed using electrochemical impedance and leak current measurements performed on the surface insulation resistance comb patterns. The corrosion studies were correlated with the hygroscopicity results and solubility data. Corrosion morphology was analysed using the optical microscopy and scanning electron microscopy. The results show that the hygroscopic nature of typical solder flux residue depends on its chemical structure and temperature. An increase of temperature shifts the critical RH level for water vapour absorption towards lower RH range, accelerating the formation of a conductive electrolyte and the occurrence of ion transport-induced electrochemical migration. The overall ranking of flux activators with the increasing order of aggressivity is: palmitic < suberic < adipic < succinic < glutaric < dl-malic acid.

Parametric Study of Solder Flux Hygroscopicity: Impact of Weak Organic Acids on Water Layer Formation and Corrosion of Electronics

NASA Astrophysics Data System (ADS)

Piotrowska, Kamila; Ud Din, Rameez; Grumsen, Flemming Bjerg; Jellesen, Morten Stendahl; Ambat, Rajan

2018-04-01

The presence of solder flux residues on the printed circuit board assembly surface is an important factor contributing to humidity-related reliability issues that affect device lifetime. This investigation focuses on understanding the hygroscopic nature of typical wave solder flux activators—weak organic acids—under varied temperature conditions. In situ x-ray diffraction measurements assessed the effect of high temperature on the crystal structure of organic activators. The hygroscopicity studies were carried out under relative humidity (RH) levels varying from 30% to ˜ 99% and at temperatures 25°C, 40°C, and 60°C. Water absorption levels were determined using the gravimetric method, and the influence on reliability was assessed using electrochemical impedance and leak current measurements performed on the surface insulation resistance comb patterns. The corrosion studies were correlated with the hygroscopicity results and solubility data. Corrosion morphology was analysed using the optical microscopy and scanning electron microscopy. The results show that the hygroscopic nature of typical solder flux residue depends on its chemical structure and temperature. An increase of temperature shifts the critical RH level for water vapour absorption towards lower RH range, accelerating the formation of a conductive electrolyte and the occurrence of ion transport-induced electrochemical migration. The overall ranking of flux activators with the increasing order of aggressivity is: palmitic < suberic < adipic < succinic < glutaric < uc(dl)-malic acid.

Formation of an Anti-Core–Shell Structure in Layered Oxide Cathodes for Li-Ion Batteries

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

Zhang, Hanlei; Omenya, Fredrick; Whittingham, M. Stanley

The layered → rock-salt phase transformation in the layered dioxide cathodes for Li-ion batteries is believed to result in a “core-shell” structure of the primary particles, in which the core region maintains as the layered phase while the surface region undergoes the phase transformation to the rock-salt phase. Using transmission electron microscopy, here we demonstrate the formation of an “anti-core-shell” structure in cycled primary particles with a formula of LiNi0.80Co0.15Al0.05O2, in which the surface and subsurface regions remain as the layered structure while the rock-salt phase forms as domains in the bulk with a thin layer of the spinel phasemore » between the rock-salt core and the skin of the layered phase. Formation of this anti-core-shell structure is attributed to the oxygen loss at the surface that drives the migration of oxygen from the bulk to the surface, thereby resulting in localized areas of significantly reduced oxygen levels in the bulk of the particle, which subsequently undergoes the phase transformation to the rock-salt domains. The formation of the anti-core-shell rock-salt domains is responsible for the reduced capacity, discharge voltage and ionic conductivity in cycled cathode.« 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

Low temperature oxidation using support molten salt catalysts

DOEpatents

Weimer, Alan W.; Czerpak, Peter J.; Hilbert, Patrick M.

2003-05-20

Molten salt reactions are performed by supporting the molten salt on a particulate support and forming a fluidized bed of the supported salt particles. The method is particularly suitable for combusting hydrocarbon fuels at reduced temperatures, so that the formation NO.sub.x species is reduced. When certain preferred salts are used, such as alkali metal carbonates, sulfur and halide species can be captured by the molten salt, thereby reducing SO.sub.x and HCl emissions.

A Continuous Flow Diffusion Chamber Study of Sea Salt Particles Acting as Cloud Seeds: Deliquescence, Ice Nucleation and Sublimation

NASA Astrophysics Data System (ADS)

Kong, X.; Wolf, M. J.; Garimella, S.; Roesch, M.; Cziczo, D. J.

2016-12-01

Sea Salt Aerosols (SSA) are abundant in the atmosphere, and important to the Earth's chemistry and energy budget. However, the roles of sea salts in the context of cloud formation are still poorly understood, which is partially due to the complexity of the water-salt phase diagram. At ambient temperatures, even well below 0°C, SSA deliquesces at sub-water saturated conditions. Since the ratio of the partial pressure over ice versus super-cooled water continuously declines with decreasing temperatures, it is interesting to consider if SSA continues to deliquesce under a super-saturated condition of ice, or if particles act as depositional ice nuclei when a critical supersaturation is reached. Some recent studies suggest hydrated NaCl and simulated sea salt might deliquesce between -35°C to -44°C, and below that deposition freezing becomes possible. Deliquesced droplets can subsequently freeze via the immersion or homogenous freezing mode, depending on if the deliquescence processes is complete. After the droplets or ice particles are formed, it is also interesting to consider how the different processes influence physical properties after evaporation or sublimation. This data is important for climate modeling that includes bromine burst observed in Antarctica, which is hypothesized to be relevant to the sublimation of blowing snow particles. In this study we use a SPectrometer for Ice Nuclei (SPIN; DMT, Inc., Boulder, CO) to perform experiments over a wide range of temperature and RH conditions to quantify deliquescence, droplet formation and ice nucleation. The formation of droplets and ice particles is detected by an advanced Optical Particle Counter (OPC) and the liquid/solid phases are distinguished by a machine learning method based on laser scattering and polarization data. Using an atomizer, four different sea salt samples are generated: pure NaCl and MgCl2 solutions, synthetic seawater, and natural seawater. Downstream of the SPIN chamber, a Pumped Counterflow Virtual Impactor (PCVI) is connected to separate the activated ice particles/large droplets to allow them undergo complete evaporation and sublimation. The particle size distributions are measured and compared to those upstream of SPIN to determine the effects of the ice/droplet nucleation process on the aerosol physical parameters.

Controlling silk fibroin particle features for drug delivery

PubMed Central

Lammel, Andreas; Hu, Xiao; Park, Sang-Hyug; Kaplan, David L.; Scheibel, Thomas

2010-01-01

Silk proteins are a promising material for drug delivery due to their aqueous processability, biocompatibility, and biodegradability. A simple aqueous preparation method for silk fibroin particles with controllable size, secondary structure and zeta potential is reported. The particles were produced by salting out a silk fibroin solution with potassium phosphate. The effect of ionic strength and pH of potassium phosphate solution on the yield and morphology of the particles was determined. Secondary structure and zeta potential of the silk particles could be controlled by pH. Particles produced by salting out with 1.25 M potassium phosphate pH 6 showed a dominating silk II (crystalline) structure whereas particles produced at pH 9 were mainly composed of silk I (less crystalline). The results show that silk I rich particles possess chemical and physical stability and secondary structure which remained unchanged during post treatments even upon exposure to 100% ethanol or methanol. A model is presented to explain the process of particle formation based on intra- and intermolecular interactions of the silk domains, influenced by pH and kosmotrope salts. The reported silk fibroin particles can be loaded with small molecule model drugs, such as alcian blue, rhodamine B, and crystal violet, by simple absorption based on electrostatic interactions. In vitro release of these compounds from the silk particles depends on charge – charge interactions between the compounds and the silk. With crystal violet we demonstrated that the release kinetics are dependent on the secondary structure of the particles. PMID:20219241

Imidazolium-Based Polymeric Materials as Alkaline Anion-Exchange Fuel Cell Membranes

NASA Technical Reports Server (NTRS)

Narayan, Sri R.; Yen, Shiao-Ping S.; Reddy, Prakash V.; Nair, Nanditha

2012-01-01

Polymer electrolyte membranes that conduct hydroxide ions have potential use in fuel cells. A variety of polystyrene-based quaternary ammonium hydroxides have been reported as anion exchange fuel cell membranes. However, the hydrolytic stability and conductivity of the commercially available membranes are not adequate to meet the requirements of fuel cell applications. When compared with commercially available membranes, polystyrene-imidazolium alkaline membrane electrolytes are more stable and more highly conducting. At the time of this reporting, this has been the first such usage for imidazolium-based polymeric materials for fuel cells. Imidazolium salts are known to be electrochemically stable over wide potential ranges. By controlling the relative ratio of imidazolium groups in polystyrene-imidazolium salts, their physiochemical properties could be modulated. Alkaline anion exchange membranes based on polystyrene-imidazolium hydroxide materials have been developed. The first step was to synthesize the poly(styrene-co-(1-((4-vinyl)methyl)-3- methylimidazolium) chloride through a free-radical polymerization. Casting of this material followed by in situ treatment of the membranes with sodium hydroxide solutions provided the corresponding hydroxide salts. Various ratios of the monomers 4-chloromoethylvinylbenzine (CMVB) and vinylbenzine (VB) provided various compositions of the polymer. The preferred material, due to the relative ease of casting the film, and its relatively low hygroscopic nature, was a 2:1 ratio of CMVB to VB. Testing confirmed that at room temperature, the new membranes outperformed commercially available membranes by a large margin. With fuel cells now in use at NASA and in transportation, and with defense potential, any improvement to fuel cell efficiency is a significant development.

21 CFR 884.4260 - Hygroscopic Laminaria cervical dilator.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Hygroscopic Laminaria cervical dilator. 884.4260 Section 884.4260 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES... conical and expansible material made from the root of a seaweed (Laminaria digitata or Laminaria japonica...

Influence of Humidity on the Aerosol Scattering Coefficient and Its Effect on the Upwelling Radiance During ACE-2

NASA Technical Reports Server (NTRS)

Gasso, B. S.; Hegg, D. A.; Covert, D. S.; Collins, D.; Noone, K.; Oestroem, E.; Schmid, B.; Russell, P. B.; Livingston, J. M.; Durkee, P. A.;

Wear forms of heterogeneous electro-rheological fluids working in a hydraulic clutch system

NASA Astrophysics Data System (ADS)

Ziabska, E.; Duchowski, J.; Olszak, A.; Osowski, K.; Kesy, A.; Kesy, Z.; Choi, S. B.

2017-09-01

The paper presents experimental results concerning the wear of heterogeneous electro-rheological (ER) fluids operating as working fluids in a complex clutch system consisting of a hydrodynamic clutch and a cylinder viscous clutch. The change of electric field intensity in the clutches results in change of sheer stress values in working fluids what causes the change of transmitted torque. This work shows that the most important factors affecting the wear of the ER fluid are the electric field of high intensity, the accompanying electrical breakdown, and the high temperature of the silicone oil. In addition, the water from the humid air absorbed mainly by hygroscopic particles influences a significant impact on the wear of the working fluid. Various forms of wear particles of the fluid depending on the prevailing conditions such as working mode are observed from the microscopic aspects. It is observed that the particles are flattened, rolled out or smashed into smaller fragments, partially melted, wrinkled and glued or caked. In addition, it is identified that the partial destruction of silicone oil is occurred due to the damage of the hydrocarbon chains, as evidenced by the decrease in its viscosity and the presence of the particle matter newly containing silicon.

Rice Starch Particle Interactions at Air/Aqueous Interfaces—Effect of Particle Hydrophobicity and Solution Ionic Strength

PubMed Central

McNamee, Cathy E.; Sato, Yu; Wiege, Berthold; Furikado, Ippei; Marefati, Ali; Nylander, Tommy; Kappl, Michael; Rayner, Marilyn

2018-01-01

Starch particles modified by esterification with dicarboxylic acids to give octenyl succinic anhydride (OSA) starch is an approved food additive that can be used to stabilize oil in water emulsions used in foods and drinks. However, the effects of the OSA modification of the starch particle on the interfacial interactions are not fully understood. Here, we directly measured the packing of films of rice starch granules, i.e., the natural particle found inside the plant, at air/aqueous interfaces, and the interaction forces in that system as a function of the particle hydrophobicity and ionic strength, in order to gain insight on how starch particles can stabilize emulsions. This was achieved by using a combined Langmuir trough and optical microscope system, and the Monolayer Interaction Particle Apparatus. Native rice starch particles were seen to form large aggregates at air/water interfaces, causing films with large voids to be formed at the interface. The OSA modification of the rice starches particles decreased this aggregation. Increasing the degree of modification improved the particle packing within the film of particles at the air/water interface, due to the introduction of inter-particle electrostatic interactions within the film. The introduction of salt to the water phase caused the particles to aggregate and form holes within the film, due to the screening of the charged groups on the starch particles by the salt. The presence of these holes in the film decreased the stiffness of the films. The effect of the OSA modification was concluded to decrease the aggregation of the particles at an air/water interface. The presence of salts, however, caused the particles to aggregate, thereby reducing the strength of the interfacial film. PMID:29868551

Rice Starch Particle Interactions at Air/Aqueous Interfaces-Effect of Particle Hydrophobicity and Solution Ionic Strength.

PubMed

McNamee, Cathy E; Sato, Yu; Wiege, Berthold; Furikado, Ippei; Marefati, Ali; Nylander, Tommy; Kappl, Michael; Rayner, Marilyn

2018-01-01

Starch particles modified by esterification with dicarboxylic acids to give octenyl succinic anhydride (OSA) starch is an approved food additive that can be used to stabilize oil in water emulsions used in foods and drinks. However, the effects of the OSA modification of the starch particle on the interfacial interactions are not fully understood. Here, we directly measured the packing of films of rice starch granules, i.e., the natural particle found inside the plant, at air/aqueous interfaces, and the interaction forces in that system as a function of the particle hydrophobicity and ionic strength, in order to gain insight on how starch particles can stabilize emulsions. This was achieved by using a combined Langmuir trough and optical microscope system, and the Monolayer Interaction Particle Apparatus. Native rice starch particles were seen to form large aggregates at air/water interfaces, causing films with large voids to be formed at the interface. The OSA modification of the rice starches particles decreased this aggregation. Increasing the degree of modification improved the particle packing within the film of particles at the air/water interface, due to the introduction of inter-particle electrostatic interactions within the film. The introduction of salt to the water phase caused the particles to aggregate and form holes within the film, due to the screening of the charged groups on the starch particles by the salt. The presence of these holes in the film decreased the stiffness of the films. The effect of the OSA modification was concluded to decrease the aggregation of the particles at an air/water interface. The presence of salts, however, caused the particles to aggregate, thereby reducing the strength of the interfacial film.

Rice starch particle interactions at air/aqueous interfaces– effect of particle hydrophobicity and solution ionic strength

NASA Astrophysics Data System (ADS)

McNamee, Cathy E.; Sato, Yu; Wiege, Berthold; Furikado, Ippei; Marefati, Ali; Nylander, Tommy; Kappl, Michael; Rayner, Marilyn

2018-05-01

Starch particles modified by esterification with dicarboxylic acids to give octenyl succinic anhydride (OSA) starch is an approved food additive that can be used to stabilize oil in water emulsions used in foods and drinks. However, the effects of the OSA modification of the starch particle on the interfacial interactions are not fully understood. Here, we directly measured the packing of films of rice starch granules, i.e. the natural particle found inside the plant, at air/aqueous interfaces and the interaction forces in that system as a function of the particle hydrophobicity and ionic strength, in order to gain insight on how starch particles can stabilize emulsions. This was achieved by using a combined Langmuir trough and optical microscope system, and the Monolayer Interaction Particle Apparatus. Native rice starch particles were seen to form large aggregates at air/water interfaces, causing films with large voids to be formed at the interface. The OSA modification of the rice starches particles decreased this aggregation. Increasing the degree of modification improved the particle packing within the film of particles at the air/water interface, due to the introduction of inter-particle electrostatic interactions within the film. The introduction of salt to the water phase caused the particles to aggregate and form holes within the film, due to the screening of the charged groups on the starch particles by the salt. The presence of these holes in the film decreased the stiffness of the films. The effect of the OSA modification was concluded to decrease the aggregation of the particles at an air/water interface. The presence of salts, however, caused the particles to aggregate, thereby reducing the strength of the interfacial film.

Removal of nanoaerosol during the bubbling of the salt melt of beryllium and lithium fluorides for the preparation of reactor radioisotopes

NASA Astrophysics Data System (ADS)

Zagnit'ko, A. V.; Chuvilin, D. Yu.

2010-06-01

The parameters of aerosol particles formed in the course of the spontaneous thermal condensation of vapors and bubbling a 66LiF-34BeF2 (mol %) eutectic salt mixture with helium have been studied. For this purpose, a vertical bubbling mode at T ≈ 900 K and an ampule device for obtaining reactor radioisotopes for medical applications were used. The rate of the bulk removal and the chemical composition of aerosols were measured. The size distribution of the aerosol particles was bimodal, and the mass concentration of the particles exceeded by far the maximum permissible concentration (MPC). The characteristics of regenerated nickel multilayer nanofilters for ultrahigh filtration of aerosols from the salt liquid melt were analyzed.

A Closure Study of Total Scattering Using Airborne In Situ Measurements from the Winter Phase of TCAP

DOE PAGES

Kassianov, Evgueni; Berg, Larry; Pekour, Mikhail; ...

2018-06-12

We examine the performance of our approach for calculating the total scattering coefficient of both non-absorbing and absorbing aerosol at ambient conditions from aircraft data. Our extended examination involves airborne in situ data collected by the U.S. Department of Energy’s (DOE) Gulf Stream 1 aircraft during winter over Cape Cod and the western North Atlantic Ocean as part of the Two-Column Aerosol Project (TCAP). The particle population represented by the winter dataset, in contrast with its summer counterpart, contains more hygroscopic particles and particles with an enhanced ability to absorb sunlight due to the larger fraction of black carbon. Moreover,more » the winter observations are characterized by more frequent clouds and a larger fraction of super-micron particles. We calculate model total scattering coefficient at ambient conditions using size spectra measured by optical particle counters (OPCs) and ambient complex refractive index (RI) estimated from measured chemical composition and relative humidity (RH). We demonstrate that reasonable agreement (~20% on average) between the observed and calculated scattering can be obtained under subsaturated ambient conditions (RH < 80%) by applying both screening for clouds and chemical composition data for the RI-based correction of the OPC-derived size spectra.« less

A Closure Study of Total Scattering Using Airborne In Situ Measurements from the Winter Phase of TCAP

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

Kassianov, Evgueni; Berg, Larry; Pekour, Mikhail

We examine the performance of our approach for calculating the total scattering coefficient of both non-absorbing and absorbing aerosol at ambient conditions from aircraft data. Our extended examination involves airborne in situ data collected by the U.S. Department of Energy’s (DOE) Gulf Stream 1 aircraft during winter over Cape Cod and the western North Atlantic Ocean as part of the Two-Column Aerosol Project (TCAP). The particle population represented by the winter dataset, in contrast with its summer counterpart, contains more hygroscopic particles and particles with an enhanced ability to absorb sunlight due to the larger fraction of black carbon. Moreover,more » the winter observations are characterized by more frequent clouds and a larger fraction of super-micron particles. We calculate model total scattering coefficient at ambient conditions using size spectra measured by optical particle counters (OPCs) and ambient complex refractive index (RI) estimated from measured chemical composition and relative humidity (RH). We demonstrate that reasonable agreement (~20% on average) between the observed and calculated scattering can be obtained under subsaturated ambient conditions (RH < 80%) by applying both screening for clouds and chemical composition data for the RI-based correction of the OPC-derived size spectra.« less

Shipboard Sunphotometer Measurements of Aerosol Optical Depth Spectra and Columnar Water Vapor During ACE-2, and Comparison with Selected Land, Ship, Aircraft, and Satellite Measurements

NASA Technical Reports Server (NTRS)

Livingston, John M.; Kapustin, Vladimir N.; Schmid, Beat; Russell, Philip B.; Quinn, Patricia K.; Bates, Timothy S.; Durkee, Philip A.; Smith, Peter J.; Freudenthaler, Volker; Wiegner, Matthias

2000-01-01

Analyses of aerosol optical depth (AOD) and columnar water vapor (CWV) measurements acquired with NASA Ames Research Center's six-channel Airborne Tracking Sunphotometer (AATS-6) operated aboard the R/V (research vehicle) Professor Vodyanitskiy during the second Aerosol Characterization Experiment (ACE-2) are discussed. Data are compared with various in situ and remote measurements for selected cases. The focus is on 10 July, when the Pelican airplane flew within 70 km of the ship near the time of a NOAA (National Oceanographic and Atmospheric Administration)-14/AVHRR (Advanced Very High Resolution Radiometer) satellite overpass and AOD measurements with the 14-channel Ames Airborne Tracking Sunphotometer (AATS-14) above the marine boundary layer (MBL) permitted calculation of AOD within the MBL from the AATS-6 measurements. A detailed column closure test is performed for MBL AOD on 10 July by comparing the AATS-6 MBL AODs with corresponding values calculated by combining shipboard particle size distribution measurements with models of hygroscopic growth and radiosonde humidity profiles (plus assumptions on the vertical profile of the dry particle size distribution and composition). Large differences (30-80% in the mid-visible) between measured and reconstructed AODs are obtained, in large part because of the high sensitivity of the closure methodology to hygroscopic growth models, which vary considerably and have not been validated over the necessary range of particle size/composition distributions. The wavelength dependence of AATS-6 AODs is compared with the corresponding dependence of aerosol extinction calculated from shipboard measurements of aerosol size distribution and of total scattering measured by a shipboard integrating nephelometer for several days. Results are highly variable, illustrating further the great difficulty of deriving column values from point measurements. AATS-6 CWV values are shown to agree well with corresponding values derived from radiosonde measurements during eight soundings on seven days and also with values calculated from measurements taken on 10 July with the AATS-14 and the University of Washington Passive Humidigraph aboard the Pelican.

TWO-PHASE FORMATION IN SOLUTIONS OF TOBACCO MOSAIC VIRUS AND THE PROBLEM OF LONG-RANGE FORCES

PubMed Central

Oster, Gerald

1950-01-01

In a nearly salt-free medium, a dilute tobacco mosaic virus solution of rod-shaped virus particles of uniform length forms two phases; the bottom optically anisotropic phase has a greater virus concentration than has the top optically isotropic phase. For a sample containing particles of various lengths, the bottom phase contains longer particles than does the top and the concentrations top and bottom are nearly equal. The longer the particles the less the minimum concentration necessary for two-phase formation. Increasing the salt concentration increases the minimum concentration. The formation of two phases is explained in terms of geometrical considerations without recourse to the concept of long-range attractive forces. The minimum concentration for two-phase formation is that concentration at which correlation in orientation between the rod-shaped particles begins to take place. This concentration is determined by the thermodynamically effective size and shape of the particles as obtained from the concentration dependence of the osmotic pressure of the solutions measured by light scattering. The effective volume of the particles is introduced into the theory of Onsager for correlation of orientation of uniform size rods and good agreement with experiment is obtained. The theory is extended to a mixture of non-uniform size rods and to the case in which the salt concentration is varied, and agreement with experiment is obtained. The thermodynamically effective volume of the particles and its dependence on salt concentration are explained in terms of the shape of the particles and the electrostatic repulsion between them. Current theories of the hydration of proteins and of long-range forces are critically discussed. The bottom layer of freshly purified tobacco mosaic virus samples shows Bragg diffraction of visible light. The diffraction data indicate that the virus particles in solution form three-dimensional crystals approximately the size of crystalline inclusion bodies found in the cells of plants suffering from the disease. PMID:15422102

Gas-phase hydrolysis of triplet SO2: A possible direct route to atmospheric acid formation

NASA Astrophysics Data System (ADS)

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

2016-07-01

Sulfur chemistry is of great interest to the atmospheric chemistry of several planets. In the presence of water, oxidized sulfur can lead to new particle formation, influencing climate in significant ways. Observations of sulfur compounds in planetary atmospheres when compared with model results suggest that there are missing chemical mechanisms. Here we propose a novel mechanism for the formation of sulfurous acid, which may act as a seed for new particle formation. In this proposed mechanism, the lowest triplet state of SO2 (3B1), which may be accessed by near-UV solar excitation of SO2 to its excited 1B1 state followed by rapid intersystem crossing, reacts directly with water to form H2SO3 in the gas phase. For ground state SO2, this reaction is endothermic and has a very high activation barrier; our quantum chemical calculations point to a facile reaction being possible in the triplet state of SO2. This hygroscopic H2SO3 molecule may act as a condensation nucleus for water, giving rise to facile new particle formation (NPF).

Method for forming thin composite solid electrolyte film for lithium batteries

NASA Technical Reports Server (NTRS)

Attia, Alan I. (Inventor); Nagasubramanian, Ganesan (Inventor)

1997-01-01

A composite solid electrolyte film is formed by dissolving a lithium salt such as lithium iodide in a mixture of a first solvent which is a cosolvent for the lithium salt and a binder polymer such as polyethylene oxide and a second solvent which is a solvent for the binder polymer and has poor solubility for the lithium salt. Reinforcing filler such as alumina particles are then added to form a suspension followed by the slow addition of binder polymer. The binder polymer does not agglomerate the alumina particles. The suspension is cast into a uniform film.

Method for forming thin composite solid electrolyte film for lithium batteries

NASA Technical Reports Server (NTRS)

Nagasubramanian, Ganesan (Inventor); Attia, Alan I. (Inventor)

1994-01-01

A composite solid electrolyte film is formed by dissolving a lithium salt such as lithium iodide in a mixture of a first solvent which is a co-solvent for the lithium salt and a binder polymer such as polyethylene oxide and a second solvent which is a solvent for the binder polymer and has poor solubility for the lithium salt. Reinforcing filler such as alumina particles are then added to form a suspension followed by the slow addition of binder polymer. The binder polymer does not agglomerate the alumina particles. The suspension is cast into a uniform film.

Rock-Salt Growth-Induced (003) Cracking in a Layered Positive Electrode for Li-Ion Batteries

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

Zhang, Hanlei; Omenya, Fredrick; Yan, Pengfei

For the first time, the (003) cracking is observed and determined to be the major cracking mechanism for the primary particles of Ni-rich layered dioxides as the positive electrode for Li-ion batteries. Using transmission electron microscopy techniques, here we show that the propagation and fracturing of platelet-like rock-salt phase along the (003) plane of the layered oxide are the leading cause for the cracking of primary particles. The fracturing of the rock-salt platelet is induced by the stress discontinuity between the parent layered oxide and the rock-salt phase. The high nickel content is considered to be the key factor formore » the formation of the rock-salt platelet and thus the (003) cracking. The (003)-type cracking can be a major factor for the structural degradation and associated capacity fade of the layered positive electrode.« less

Low-temperature synthesis of nanocrystalline ZrC coatings on flake graphite by molten salts

NASA Astrophysics Data System (ADS)

Ding, Jun; Guo, Ding; Deng, Chengji; Zhu, Hongxi; Yu, Chao

2017-06-01

A novel molten salt synthetic route has been developed to prepare nanocrystalline zirconium carbide (ZrC) coatings on flake graphite at 900 °C, using Zr powder and flake graphite as the source materials in a static argon atmosphere, along with molten salts as the media. The effects of different molten salt media, the sintered temperature, and the heat preservation time on the phase and microstructure of the synthetic materials were investigated. The ZrC coatings formed on the flake graphite were uniform and composed of nanosized particles (30-50 nm). With an increase in the reaction temperature, the ZrC nanosized particles were more denser, and the heat preservation time and thickness of the ZrC coating also increased accordingly. Electron microscopy was used to observe the ZrC coatings on the flake graphite, indicating that a "template mechanism" played an important role during the molten salt synthesis.

Effect of hygroscopic treatments and load applications on engineering properties of flakeboards

Treesearch

M.C. Yeh; R.C. Tang; C.Y. Hse

1991-01-01

The study of mechanical properties of hardwood structural flakeboards (white oak, red oak, and sweetgum) as affected by hygroscopic treatments and load applications, individually or collectively, is reported. The shear moduli and moduli of elasticty determined by stress waves (Esw) are drastically reduced by cycle conditions of 65/95/65 percent...

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

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

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

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

Seven years of aerosol scattering hygroscopic growth measurements from SGP: Factors influencing water uptake: Aerosol Scattering Hygroscopic Growth

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

Jefferson, A.; Hageman, D.; Morrow, H.

Long-term measurements of changes in the aerosol scattering coefficient hygroscopic growth at the U.S. Department of Energy Southern Great Plains site provide information on the seasonal as well as size and chemical dependence of aerosol hygroscopic growth. Annual average sub 10 um fRH values (the ratio of aerosol scattering at 85%/40% RH) were 1.75 and 1.87 for the gamma and kappa fit algorithms, respectively. The study found higher growth rates in the winter and spring seasons that correlated with high aerosol nitrate mass fraction. FRH, exhibited strong, but differing correlations with the scattering Ångström exponent and backscatter fraction, two opticalmore » size-dependent parameters. The aerosol organic fraction had a strong influence, with fRH decreasing with increases in the organic mass fraction and absorption Ångström exponent and increasing with the aerosol single scatter albedo. Uncertainty analysis if the fit algorithms revealed high uncertainty at low scattering coefficients and slight increases in uncertainty at high RH and fit parameters values.« less

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

DOE PAGES

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

2015-07-24

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

Hygroscopic properties of magnetic recording tape

NASA Technical Reports Server (NTRS)

Cuddihy, E. F.

1976-01-01

Relative humidity has been recognized as an important environmental factor in many head-tape interface phenomena such as headwear, friction, staining, and tape shed. Accordingly, the relative humidity is usually specified in many applications of tape use, especially when tape recorders are enclosed in hermetically sealed cases. Normally, the relative humidity is believed regulated by humidification of the fill gas to the specification relative humidity. This study demonstrates that the internal relative humidity in a sealed case is completely controlled by the time-dpendence of the hygroscopic properties of the pack of magnetic recording tape. Differences are found in the hygroscopic properties of the same brand of tape, which apparently result from aging, and which may have an effect on the long-term humidity-regulating behavior in a sealed case, and on the occurrence of head-tape interface phenomena from the long-term use of the tape. Results are presented on the basic hygroscopic properties of magnetic tape, its humidity-regulating behavior in a sealed case, and a theoretical commentary on the relative humidity dependence of head-wear by tape, is included.

Vacuum FTIR Observation on the Dynamic Hygroscopicity of Aerosols under Pulsed Relative Humidity.

PubMed

Leng, Chun-Bo; Pang, Shu-Feng; Zhang, Yun; Cai, Chen; Liu, Yong; Zhang, Yun-Hong

2015-08-04

A novel approach based on a combination of a pulse RH controlling system and a rapid scan vacuum FTIR spectrometer (PRHCS-RSVFTIR) was utilized to investigate dynamic hygroscopicity of two atmospheric aerosols: ammonium sulfate ((NH4)2SO4) and magnesium sulfate (MgSO4). In this approach, rapid-scan infrared spectra of water vapor and aerosols were obtained to determine relative humidity (RH) in sample cell and hygroscopic property of aerosols with a subsecond time resolution. Heterogeneous nucleation rates of (NH4)2SO4 were, for the first time, measured under low RH conditions (<35% RH). In addition, studies of MgSO4 aerosols revealed that water mass transport may be limited by different processes depending on RH values (surface limited at 40% < RH < 52% and bulk phase limited at RH < 40%). Furthermore, we are also the first to report water diffusion constants in micron size MgSO4 aerosols at very low RH values. Our results have shown that the PRHCS-RSVFTIR is well-suited for determination of hygroscopicity of atmospheric aerosols and water transport and nucleation kinetics of liquid aerosols.

Long term measurements of optical properties and their hygroscopic enhancement

NASA Astrophysics Data System (ADS)

Hervo, M.; Sellegri, K.; Pichon, J. M.; Roger, J. C.; Laj, P.

2014-11-01

Optical properties of aerosols were measured from the GAW Puy de Dôme station (1465 m) over a seven year period (2006-2012). The impact of hygroscopicity on aerosol optical properties was calculated over a two year period (2010-2011). The analysis of the spatial and temporal variability of the optical properties showed that while no long term trend was found, a clear seasonal and diurnal variation was observed on the extensive parameters (scattering, absorption). Scattering and absorption coefficients were highest during the warm season and daytime, in concordance with the seasonality and diurnal variation of the PBL height reaching the site. Intensive parameters (single scattering albedo, asymmetry factor, refractive index) did not show such a strong diurnal variability, but still indicated different values depending on the season. Both extensive and intensive optical parameters were sensitive to the air mass origin. A strong impact of hygroscopicity on aerosol optical properties was calculated, mainly on aerosol scattering, with a dependence on the aerosol type. At 90% humidity, the scattering factor enhancement (fσsca) was more than 4.4 for oceanic aerosol that have mixed with a pollution plume. Consequently, the aerosol radiative forcing was estimated to be 2.8 times higher at RH = 90% and 1.75 times higher at ambient RH when hygroscopic growth of the aerosol was considered. The hygroscopicity enhancement factor of the scattering coefficient was parameterized as a function of humidity and air mass type.

Hygroscopic Metamorphic 4D Pleats

NASA Astrophysics Data System (ADS)

Yang, Shu

There have been significant interests in morphing 2D sheets into 3D structures via programmed out-of-plane distortion, including bending, tilting, rotating, and folding as seen in recent origami and kirigami strategies. Hydrogel is one of the unique soft materials that can swell and shrink, thereby enabling real-time 4D motions in response to external stimuli, such as pH, temperature, and moisture. To achieve reliable folding behaviors, it often requires a large amount of water molecules or ions diffusing in and out of the hydrogel sheet, thus the entire sheet is immersed in an aqueous solution. Here, we demonstrate the design and folding of hierarchical pleats patterned from a combination of hydrophobic and hygroscopic materials, allowing us to spatially and locally control the water condensation induced by environmental humidity. In turn, we show out-of-plane deformation of the 2D sheets only in the patterned hygroscopic regions, much like the folding behaviors of many plants. By designing the dimension, geometry, and density of hygroscopic microstructures (as pixels) in the hydrophobic materials, we can display the enhanced water condensation together with the spatial guidance of obtained droplets as unified water-harvesting systems. When the water droplets become large enough, they roll off from the hierarchical sheet along the inclined plane that is programmed by the hygroscopic motion of hydrogel, and eventually wrapped by the folded sheet to keep them from evaporation. We acknowledge support from NSF/EFRI-ODISSEI, EFRI 13-31583.

Specific heat capacity of molten salt-based alumina nanofluid.

PubMed

Lu, Ming-Chang; Huang, Chien-Hsun

2013-06-21

There is no consensus on the effect of nanoparticle (NP) addition on the specific heat capacity (SHC) of fluids. In addition, the predictions from the existing model have a large discrepancy from the measured SHCs in nanofluids. We show that the SHC of the molten salt-based alumina nanofluid decreases with reducing particle size and increasing particle concentration. The NP size-dependent SHC is resulted from an augmentation of the nanolayer effect as particle size reduces. A model considering the nanolayer effect which supports the experimental results was proposed.

Specific heat capacity of molten salt-based alumina nanofluid

PubMed Central

2013-01-01

There is no consensus on the effect of nanoparticle (NP) addition on the specific heat capacity (SHC) of fluids. In addition, the predictions from the existing model have a large discrepancy from the measured SHCs in nanofluids. We show that the SHC of the molten salt-based alumina nanofluid decreases with reducing particle size and increasing particle concentration. The NP size-dependent SHC is resulted from an augmentation of the nanolayer effect as particle size reduces. A model considering the nanolayer effect which supports the experimental results was proposed. PMID:23800321

The mechanisms of fine particle generation and electrification during Mount St. Helens volcanic eruption

NASA Technical Reports Server (NTRS)

Cheng, R. J.

1982-01-01

Microscopical investigation of volcanic ash collected from ground stations during Mount St. Helens eruptions reveal a distinctive bimodel size distribution with high concentrations of particle ranges at (1) 200-100 microns and (2) 20-0.1 microns. Close examination of individual particles shows that most larger ones are solidified magma particles of porous pumice with numerous gas bubbles in the interior and the smaller ones are all glassy fragments without any detectable gas bubbles. Elemental analysis demonstrates that the fine fragments all have a composition similar to that of the larger pumice particles. Laboratory experiments suggest that the formation of the fine fragments is by bursting of glassy bubbles from a partially solidified surface of a crystallizing molten magma particle. The production of gas bubbles is due to the release of absorbed gases in molten magma particles when solubility decreases during phase transition. Diffusion cloud chamber experiments strongly indicate that sub-micron volcanic fragments are highly hygroscopic and extremely active as cloud condensation nuclei. Ice crystals also are evidently formed on those fragments in a supercooled (-20 C) cloud chamber. It has been reported that charge generation from ocean volcanic eruptions is due to contact of molten lava with sea water. This seems to be insufficient to explain the observed rapid and intense lightning activities over Mount St. Helens eruptions. Therefore, a hypothesis is presented here that highly electrically charged fine solid fragments are ejected by bursting of gas bubbles from the surface of a crystallizing molten magma particles.

Alterations in nanoparticle protein corona by biological surfactants: impact of bile salts on β-lactoglobulin-coated gold nanoparticles.

PubMed

Winuprasith, Thunnalin; Chantarak, Sirinya; Suphantharika, Manop; He, Lili; McClements, David Julian

2014-07-15

The impact of biological surfactants (bile salts) on the protein (β-lactoglobulin) corona surrounding gold nanoparticles (200 nm) was studied using a variety of analytical techniques at pH 7: dynamic light scattering (DLS); particle electrophoresis (ζ-potential); UV-visible (UV) spectroscopy; transmission electron microscopy (TEM); and surface-enhanced Raman scattering (SERS). The bile salts adsorbed to the protein-coated nanoparticle surfaces and altered their interfacial composition, charge, and structure. SERS spectra of protein-coated nanoparticles after bile salt addition contained bands from both protein and bile salts, indicating that the protein was not fully displaced by the bile salts. UV, DLS and TEM techniques also indicated that the protein coating was not fully displaced from the nanoparticle surfaces. The impact of bile salts could be described by an orogenic mechanism: mixed interfaces were formed that consisted of islands of aggregated proteins surrounded by a sea of bile salts. This knowledge is useful for understanding the interactions of bile salts with protein-coated colloidal particles, which may be important for controlling the fate of colloidal delivery systems in the human gastrointestinal tract, or the gastrointestinal fate of ingested inorganic nanoparticles. Copyright © 2014 Elsevier Inc. All rights reserved.

A Bottle-around-a-Ship Method To Generate Hollow Thin-Shelled Particles Containing Encapsulated Iron Species with Application to the Environmental Decontamination of Chlorinated Compounds.

PubMed

Su, Yang; Wang, Yingqing; Owoseni, Olasehinde; Zhang, Yueheng; Gamliel, David Pierce; Valla, Julia A; McPherson, Gary L; John, Vijay T

2018-04-25

Thin-shelled hollow silica particles are synthesized using an aerosol-based process where the concentration of a silica precursor tetraethyl orthosilicate (TEOS) determines the shell thickness. The synthesis involves a novel concept of the salt bridging of an iron salt, FeCl 3 , to a cationic surfactant, cetyltrimethylammonium bromide (CTAB), which modulates the templating effect of the surfactant on silica porosity. The salt bridging leads to a sequestration of the surfactant in the interior of the droplet with the formation of a dense silica shell around the organic material. Subsequent calcination consistently results in hollow particles with encapsulated iron oxides. Control of the TEOS levels leads to the generation of ultrathin-shelled (∼10 nm) particles which become susceptible to rupture upon exposure to ultrasound. The dense silica shell that is formed is impervious to entry of chemical species. Mesoporosity is restored to the shell through desilication and reassembly, again using CTAB as a template. The mesoporous-shelled hollow particles show good reactivity toward the reductive dichlorination of trichloroethylene (TCE), indicating access of TCE to the particle interior. The ordered mesoporous thin-shelled particles containing active iron species are viable systems for chemical reaction and catalysis.

Sedimentation field-flow fractionation for characterization of citric acid-modified Hβ zeolite particles: Effect of particle dispersion and carrier composition.

PubMed

Dou, Haiyang; Bai, Guoyi; Ding, Liang; Li, Yueqiu; Lee, Seungho

2015-11-27

In this study, sedimentation field-flow fractionation (SdFFF) was, for the first time, applied for determination of size distribution of Hβ zeolite particles modified by citric acid (CA-Hβ). Effects of the particle dispersion and the carrier liquid composition (type of dispersing reagent (surfactant) and salt added in the carrier liquid, ionic strength, and pH) on SdFFF elution behavior of CA-Hβ zeolite particles were systematically investigated. Also the SdFFF separation efficiency of the particles was discussed in terms of the forces such as van der Waals, hydrophobic, and induced-dipole interactions. Results reveal that the type of salt and pH of the carrier liquid significantly affect the SdFFF separation efficiency of the zeolite particles. It was found that addition of a salt (NaN3) into the carrier liquid affects the characteristic of the SdFFF channel surface. It was found that the use of an acidic medium (pH 3.2) leads to a particle-channel interaction, while the use of a basic medium (pH 10.6) promotes an inter-particle hydrophobic interaction. Result from SdFFF was compared with those from scanning electron microscopy (SEM) and dynamic light scattering (DLS). It seems that, once the experimental conditions are optimized, SdFFF becomes a valuable tool for size characterization of the zeolite particles. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of smoking parameters on the particle size distribution and predicted airway deposition of mainstream cigarette smoke.

PubMed

Kane, David B; Asgharian, Bahman; Price, Owen T; Rostami, Ali; Oldham, Michael J

2010-02-01

It is known that puffing conditions such as puff volume, duration, and frequency vary substantially among individual smokers. This study investigates how these parameters affect the particle size distribution and concentration of fresh mainstream cigarette smoke (MCS) and how these changes affect the predicted deposition of MCS particles in a model human respiratory tract. Measurements of the particle size distribution made with an electrical low pressure impactor for a variety of puffing conditions are presented. The average flow rate of the puff is found to be the major factor effecting the measured particle size distribution of the MCS. The results of these measurements were then used as input to a deterministic dosimetry model (MPPD) to estimate the changes in the respiratory tract deposition fraction of smoke particles. The MPPD dosimetry model was modified by incorporating mechanisms involved in respiratory tract deposition of MCS: hygroscopic growth, coagulation, evaporation of semivolatiles, and mixing of the smoke with inhaled dilution air. The addition of these mechanisms to MPPD resulted in reasonable agreement between predicted airway deposition and human smoke retention measurements. The modified MPPD model predicts a modest 10% drop in the total deposition efficiency in a model human respiratory tract as the puff flow rate is increased from 1050 to 3100 ml/min, for a 2-s puff.

Long-range-transported Saharan dust in the Caribbean - an electron microscopy perspective of aerosol composition and modification

NASA Astrophysics Data System (ADS)

Kandler, Konrad; Hartmann, Markus; Ebert, Martin; Weinbruch, Stephan; Weinzierl, Bernadett; Walser, Adrian; Sauer, Daniel; Wadinga Fomba, Khanneh

2015-04-01

From June to July in 2013, the Saharan Aerosol Long-range Transport and Aerosol-Cloud-Interaction Experiment (SALTRACE) was performed in the Caribbean. Airborne aerosol sampling was performed onboard the DLR Falcon aircraft in altitudes between 300 m and 5500 m. Ground-based samples were collected at Ragged Point (Barbados, 13.165 °N, 59.432 °W) and at the Cape Verde Atmospheric Observatory (Sao Vicente, 16.864 °N, 24.868 °W). Different types of impactors and sedimentation samplers were used to collect particles between 0.1 µm and 4 µm (airborne) and between 0.1 µm and 100 µm (ground-based). Particles were analyzed by scanning electron microscopy with attached energy-dispersive X-ray analysis, yielding information on particle size, particle shape and chemical composition for elements heavier than nitrogen. A particle size correction was applied to the chemical data to yield better quantification. A total of approximately 100,000 particles were analyzed. For particles larger than 0.7 µm, the aerosol in the Caribbean during the campaign was a mixture of mineral dust, sea-salt at different aging states, and sulfate. Inside the Saharan dust plume - outside the marine boundary layer (MBL) - the aerosol is absolutely dominated by mineral dust. Inside the upper MBL, sea-salt exists as minor component in the aerosol for particles smaller than 2 µm in diameter, larger ones are practically dust only. When crossing the Soufriere Hills volcano plume with the aircraft, an extremely high abundance of small sulfate particles could be observed. At Ragged Point, in contrast to the airborne measurements, aerosol is frequently dominated by sea-salt particles. Dust relative abundance at Ragged Point has a maximum between 5 µm and 10 µm particles diameter; at larger sizes, sea-salt again prevails due to the sea-spray influence. A significant number of dust particles larger than 20 µm was encountered. The dust component in the Caribbean - airborne as well as ground-based - is composed of mainly silicates and minor amounts of Ca-rich and Fe-/Fe-Ti-rich particles (less than 10 % of dust fraction). The composition of the silicates indicates a major contribution of kaolinite (Al/Si atomic ratio between 0.6 and 1) and a minor contribution of quartz and feldspar particles. The inter-sample variation of the dust composition is generally low, pointing to a very thorough mixing from differently-composed Saharan sources. The temporal evolution of aerosol composition at Ragged Point shows a variation in dust abundance, but strong isolated events could not be identified. An airmass change induced by the passing by of a hurricane, however, is visible in sulfate abundance and their composition. Strong internally mixed particles of dust and sulfate or dust and sea-salt are very rare (up to 1 % of particles in the airborne samples), but a slight increasing tendency with decreasing altitude was found. In the lower MBL at Ragged point, dust/sea-salt mixtures are more frequent (in the same abundance range as pure dust particles). A first conclusion from the data set is that dust aging with respect to internal mixtures does not happen during the long-range transport across the Atlantic Ocean, but rather at the end during the down-mixing of mineral dust into the Caribbean MBL.

Risk of high blood pressure in salt workers working near salt milling plants: A cross-sectional and interventional study

PubMed Central

Haldiya, Kripa Ram; Mathur, Murli Lal; Sachdev, Raman; Saiyed, Habibulla N

2005-01-01

Background Workers working close to salt milling plants may inhale salt particles floating in the air, leading to a rise in plasma sodium, which, in turn, may increase the blood pressure and the risk of hypertension. Methods To test the above hypothesis, occupational health check-up camps were organized near salt manufacturing units and all workers were invited for a free health examination. The workers who worked with dry salt in the vicinity of salt milling plants were defined as "non-brine workers," while those working in brine pans located far away from milling plants were defined as "brine workers." Blood pressure (BP) was measured during each clinical examination. In all, 474 non-brine workers and 284 brine workers were studied. Results Mean systolic blood pressure of non-brine workers (122.1 ± 13.3 mm Hg) was significantly higher than that of brine workers (118.8 ± 12.8 mm Hg, p < 0.01). Mean diastolic blood pressure of non-brine workers (71.5 ± 10.4 mm Hg) was significantly higher than that of brine workers (69.7 ± 9.4 mm Hg, p = 0.02). The prevalence of hypertension was significantly higher in non-brine workers (12.2%) than in brine workers (7.0%, p = 0.02). Nineteen salt workers were monitored while they used face masks and spectacles, for six days. Systolic, as well as diastolic, blood pressure of these workers began declining on the third day and continued to decline on the fourth day, but remained stationary up to the sixth day. The concentration of salt particles in the breathing zone of these workers was 376 mg/m3 air. Conclusion Inhalation of salt particles in non-brine workers may be an occupational cause of increased blood pressure. PMID:16042798

Sensitivity of estuarine turbidity maximum to settling velocity, tidal mixing, and sediment supply

USGS Publications Warehouse

Warner, J.C.; Sherwood, C.R.; Geyer, W.R.; ,

2007-01-01

Estuarine turbidity maximum, numerical modeling, settling velocity, stratification The spatial and temporal distribution of suspended material in an Estuarine Turbidity Maxima (ETM) is primarily controlled by particle settling velocity, tidal mixing, shear-stress thresholds for resuspension, and sediment supply. We vary these parameters in numerical experiments of an idealized two-dimensional (x-z) estuary to demonstrate their affects on the development and retention of particles in an ETM. Parameters varied are the settling velocity (0.01, 0.1, and 0.5 mm/s), tidal amplitude (0.4 m 12 hour tide and 0.3 to 0.6 m 14 day spring neap cycle), and sediment availability (spatial supply limited or unlimited; and temporal supply as a riverine pulse during spring vs. neap tide). Results identify that particles with a low settling velocity are advected out of the estuary and particles with a high settling velocity provide little material transport to an ETM. Particles with an intermediate settling velocity develop an ETM with the greatest amount of material retained. For an unlimited supply of sediment the ETM and limit of salt intrusion co-vary during the spring neap cycle. The ETM migrates landward of the salt intrusion during spring tides and seaward during neap tides. For limited sediment supply the ETM does not respond as an erodible pool of sediment that advects landward and seaward with the salt front. The ETM is maintained seaward of the salt intrusion and controlled by the locus of sediment convergence in the bed. For temporal variability of sediment supplied from a riverine pulse, the ETM traps more sediment if the pulse encounters the salt intrusion at neap tides than during spring tides. ?? 2007 Elsevier B.V. All rights reserved.

The analogy in the formation of hardness salts and gallstones according to the EPR study

NASA Astrophysics Data System (ADS)

Pichugina, Alina; Tsyro, Larisa; Unger, Felix

2017-11-01

The article shows that the hardness salts contain the same crystalline phases as the bile stone pigment. The identity of EPR spectra of hardness salts and pigment of gallstones containing calcium carbonate was established. An analogy between the processes of formation of hardness salts and gallstones is played, in which particles with open spin-orbitals (fermions) play a decisive role.

Carbon nanotubes grown on bulk materials and methods for fabrication

DOEpatents

Menchhofer, Paul A [Clinton, TN; Montgomery, Frederick C [Oak Ridge, TN; Baker, Frederick S [Oak Ridge, TN

2011-11-08

Disclosed are structures formed as bulk support media having carbon nanotubes formed therewith. The bulk support media may comprise fibers or particles and the fibers or particles may be formed from such materials as quartz, carbon, or activated carbon. Metal catalyst species are formed adjacent the surfaces of the bulk support material, and carbon nanotubes are grown adjacent the surfaces of the metal catalyst species. Methods employ metal salt solutions that may comprise iron salts such as iron chloride, aluminum salts such as aluminum chloride, or nickel salts such as nickel chloride. Carbon nanotubes may be separated from the carbon-based bulk support media and the metal catalyst species by using concentrated acids to oxidize the carbon-based bulk support media and the metal catalyst species.

Measurement Comparisons Towards Improving the Understanding of Aerosol-Cloud Processing

NASA Astrophysics Data System (ADS)

Noble, Stephen R.

Cloud processing of aerosol is an aerosol-cloud interaction that is not heavily researched but could have implications on climate. The three types of cloud processing are chemical processing, collision and coalescence processing, and Brownian capture of interstitial particles. All types improve cloud condensation nuclei (CCN) in size or hygroscopicity (kappa). These improved CCN affect subsequent clouds. This dissertation focuses on measurement comparisons to improve our observations and understanding of aerosol-cloud processing. Particle size distributions measured at the continental Southern Great Plains (SGP) site were compared with ground based measurements of cloud fraction (CF) and cloud base altitude (CBA). Particle size distributions were described by a new objective shape parameter to define bimodality rather than an old subjective one. Cloudy conditions at SGP were found to be correlated with lagged shape parameter. Horizontal wind speed and regional CF explained 42%+ of this lag time. Many of these surface particle size distributions were influenced by aerosol-cloud processing. Thus, cloud processing may be more widespread with more implications than previously thought. Particle size distributions measured during two aircraft field campaigns (MArine Stratus/stratocumulus Experiment; MASE; and Ice in Cloud Experiment-Tropical; ICE-T) were compared to CCN distributions. Tuning particle size to critical supersaturation revealed hygroscopicity expressed as ? when the distributions were overlain. Distributions near cumulus clouds (ICE-T) had a higher frequency of the same ?s (48% in ICE-T to 42% in MASE) between the accumulation (processed) and Aitken (unprocessed) modes. This suggested physical processing domination in ICE-T. More MASE (stratus cloud) kappa differences between modes pointed to chemical cloud processing. Chemistry measurements made in MASE showed increases in sulfates and nitrates with distributions that were more processed. This supported chemical cloud processing in MASE. This new method to determine kappa provides the needed information without interrupting ambient measurements. MODIS derived cloud optical thickness (COT), cloud liquid water path (LWP), and cloud effective radius (re) were compared to the same in situ derived variables from cloud probe measurements of two stratus/stratocumulus cloud campaigns (MASE and Physics Of Stratocumulus Tops; POST). In situ data were from complete vertical cloud penetrations, while MODIS data were from pixels along the aircraft penetration path. Comparisons were well correlated except that MODIS LWP (14-36%) and re (20-30%) were biased high. The LWP bias was from re bias and was not improved by using the vertically stratified assumption. MODIS re bias was almost removed when compared to cloud top maximum in situ re, but, that does not describe re for the full depth of the cloud. COT is validated by in situ COT. High correlations suggest that MODIS variables are useful in self-comparisons such as gradient changes in stratus cloud re during aerosol-cloud processing.

Hygroscopic condenser humidifier as a solution to nasal dryness due to nasal CPAP treatment for obstructive sleep apnea syndrome.

PubMed

Parra, O; Klamburg, J; Xirgu, J; Abad, J; Sala, H; Tomasa, A; Morera, J

1991-04-01

We report an apparent solution to nasal dryness for patients with obstructive sleep apnea syndrome treated with nasal continuous positive airway pressure (CPAP) when a hygroscopic condenser humidifier is introduced into the CPAP circuit. Six patients underwent a 5-h test period of nasal CPAP therapy with a mask containing a hygroscopic humidifier. The water vapor showed a statistically significant increase in both inspired and expired gases. The relative humidity of the inspired gases increased significantly. The levels of O2 and CO2 in the respired gases did not change. When patients were asked about nasal dryness at the end of the test, all of them reported marked improvement.

Composition and Morphology of Major Particle Types from Airborne Measurements during ICE-T and PRADACS Field Studies

NASA Astrophysics Data System (ADS)

Venero, I. M.; Mayol-Bracero, O. L.; Anderson, J. R.

2012-12-01

As part of the Puerto Rican African Dust and Cloud Study (PRADACS) and the Ice in Clouds Experiment - Tropical (ICE-T), we sampled giant airborne particles to study their elemental composition, morphology, and size distributions. Samples were collected in July 2011 during field measurements performed by NCAR's C-130 aircraft based on St Croix, U.S Virgin Island. The results presented here correspond to the measurements done during research flight #8 (RF8). Aerosol particles with Dp > 1 um were sampled with the Giant Nuclei Impactor and particles with Dp < 1 um were collected with the Wyoming Inlet. Collected particles were later analyzed using an automated scanning electron microscope (SEM) and manual observation by field emission SEM. We identified the chemical composition and morphology of major particle types in filter samples collected at different altitudes (e.g., 300 ft, 1000 ft, and 4500ft). Results from the flight upwind of Puerto Rico show that particles in the giant nuclei size range are dominated by sea salt. Samples collected at altitudes 300 ft and 1000 ft showed the highest number of sea salt particles and the samples collected at higher altitudes (> 4000 ft) showed the highest concentrations of clay material. HYSPLIT back trajectories for all samples showed that the low altitude samples initiated in the free troposphere in the Atlantic Ocean, which may account for the high sea salt content and that the source of the high altitude samples was closer to the Saharan - Sahel desert region and, therefore, these samples possibly had the influence of African dust. Size distribution results for quartz and unreacted sea-salt aerosols collected on the Giant Nuclei Impactor showed that sample RF08 - 12:05 UTM (300 ft) had the largest size value (mean = 2.936 μm) than all the other samples. Additional information was also obtained from the Wyoming Inlet present at the C - 130 aircraft which showed that size distribution results for all particles were smaller in size. The different mineral components of the dust have different size distributions so that a fractionation process could occur during transport. Also, the presence of supermicron sea salt at altitude is important for cloud processes.

Fabrication, characterization and simulation of 4H-SiC Schottky diode alpha particle detectors for pyroprocessing actinide monitoring

NASA Astrophysics Data System (ADS)

Garcia, Timothy Richard

Pyroprocessing is a method of using high-temperature molten salts and electric fields to separate and collect fuel isotopes of used nuclear fuel. It has been has been tested in the U.S. at Idaho National Laboratory as a key step in closing the nuclear fuel cycle. One technical problem with the pyroprocessing method is a lack of knowledge regarding the actinide concentrations in the salt bath during operation, since on-line techniques for measuring these concentrations are not presently available. 4H-SiC Schottky diode detectors can potentially fulfill this need. Such detectors would operate in contact with the molten salt, and measure concentrations via alpha-particle spectroscopy. This work seeks to fabricate and characterize 4H-SiC Schottky diode detectors at high temperature, model the alpha particle spectrum expected in a molten salt, and model the operation of the detectors to confirm the physics of operation is as expected. In this work, 4H-SiC Schottky diode detectors were fabricated at OSU Nanotech West. After fabrication, these detectors were characterized using both I-V curves and Am-241 alpha-particle energy spectra. All measurements were made as a function of temperature, from room temperature up to 500°C. The average energy required to create an electron-hole pair was observed to decrease with an increase of temperature, due to a decrease of both the 4H-SiC bandgap and non-linear energy loss terms. Furthermore, the FWHM of the spectra was observed to be dependent on the leakage current at a certain temperature, and not dependent on the temperature itself. Secondly, the alpha particle energy spectrum in the pyroprocessing environment was modeled using SRIM. The molten salt was modeled in 3 different geometries, with or without a protective cover material on top of the detector. Due to the loss of alpha-particle energy in the molten salt itself, a high-energy alpha emitter may completely cover the spectrum from a lower-energy alpha emitter. Each of the geometries simulated showed a different sensitivity to the lower-energy alpha emitter. Regardless of which geometry was modeled, it was observed that it is possible to measure both the emission energy of the alpha particles, as well as the concentration of the alpha emitter in the liquid. Lastly, Sentaurus TCAD was used to simulate the detection of alpha-particle charge collection in situations that are relevant to the molten salt alpha particle energy spectra. The effect of electric field negation was investigated, as well as velocity saturation. Finally, the dependence of charge recombination on temperature, alpha particle energy, and angle of incidence was investigated. These simulations captured the measurements performed at room temperature. With changed angle of incidence, the change in the amount of charge collected was less than 1 percent, indicating a weak dependence. Also, the amount of charge lost to Auger recombination was seen to increase with temperature. This disagrees with observations from experiment, indicating that the temperature dependence of one or more parameters of the model may not be accurate.

Experimental study of fouling and cleaning of sintered stainless steel membrane in electro-microfiltration of calcium salt particles.

PubMed

Qin, Frank G F; Mawson, John; Zeng, Xin An

2011-05-30

Sintered stainless steel (SSS) microfiltration membranes, which served as electrode directly, were used for the experiment of separating Alamin, a calcium salt and protein containing particles, found in dairy processing. Fouling and cleaning of the SSS membranes under the application of an external electric field were studied. The imposed electric field was found, diverging the pH of permeate and retentate. This in turn altered the solubility of the calcium salt and impacted the performance of electro microfiltration membrane. Using electric field as an enhanced cleaning-in-place (CIP) method in back flushing SSS membrane was also studied.

Experimental Study of Fouling and Cleaning of Sintered Stainless Steel Membrane in Electro-Microfiltration of Calcium Salt Particles

PubMed Central

Qin, Frank G. F.; Mawson, John; Zeng, Xin An

2011-01-01

Sintered stainless steel (SSS) microfiltration membranes, which served as electrode directly, were used for the experiment of separating Alamin, a calcium salt and protein containing particles, found in dairy processing. Fouling and cleaning of the SSS membranes under the application of an external electric field were studied. The imposed electric field was found, diverging the pH of permeate and retentate. This in turn altered the solubility of the calcium salt and impacted the performance of electro microfiltration membrane. Using electric field as an enhanced cleaning-in-place (CIP) method in back flushing SSS membrane was also studied. PMID:24957615

Delivery system for molten salt oxidation of solid waste

DOEpatents

Brummond, William A.; Squire, Dwight V.; Robinson, Jeffrey A.; House, Palmer A.

2002-01-01

The present invention is a delivery system for safety injecting solid waste particles, including mixed wastes, into a molten salt bath for destruction by the process of molten salt oxidation. The delivery system includes a feeder system and an injector that allow the solid waste stream to be accurately metered, evenly dispersed in the oxidant gas, and maintained at a temperature below incineration temperature while entering the molten salt reactor.

Evaluation of resistance in 8 different heat-and-moisture exchangers: effects of saturation and flow rate/profile.

PubMed

Lucato, Jeanette Janaina Jaber; Tucci, Mauro Roberto; Schettino, Guilherme Paula Pinto; Adams, Alexander B; Fu, Carolina; Forti, Germano; de Carvalho, Carlos Roberto Ribeiro; de Souza, Rogério

2005-05-01

When endotracheal intubation is required during ventilatory support, the physiologic mechanisms of heating and humidifying the inspired air related to the upper airways are bypassed. The task of conditioning the air can be partially accomplished by heat-and-moisture exchangers (HMEs). To evaluate and compare with respect to imposed resistance, different types/models of HME: (1) dry versus saturated, (2) changing inspiratory flow rates. Eight different HMEs were studied using a lung model system. The study was conducted initially by simulating spontaneous breathing, followed by connecting the system directly to a mechanical ventilator to provide pressure-support ventilation. None of the encountered values of resistance (0.5\\N3.6 cm H(2)O/L/s) exceeded the limits stipulated by the previously described international standard for HMEs (International Standards Organization Draft International Standard 9360-2) (not to exceed 5.0 cm H(2)O with a flow of 1.0 L/s, even when saturated). The hygroscopic HME had less resistance than other types, independent of the precondition status (dry or saturated) or the respiratory mode. The hygroscopic HME also had a lesser increase in resistance when saturated. The resistance of the HME was little affected by increases in flow, but saturation did increase resistance in the hydrophobic and hygroscopic/hydrophobic HME to levels that could be important at some clinical conditions. Resistance was little affected by saturation in hygroscopic models, when compared to the hydrophobic or hygroscopic/hydrophobic HME. Changes in inspiratory flow did not cause relevant alterations in resistance.

Mulching as a means of exploiting dew for arid agriculture?

NASA Astrophysics Data System (ADS)

Graf, Alexander; Kuttler, Wilhelm; Werner, Julius

2008-03-01

A traditional mulching technique used in Lanzarote, Canary Islands, allows dry farming as well as pronounced water savings in irrigation. It is known to reduce evaporational losses, but is also supposed to enhance the nocturnal condensation of water vapour from the atmosphere. The mulch layer consists of porous volcanic rock fragments abundantly available on the island. The mulched surface is believed to cool rapidly and to be more hygroscopic than a bare soil surface. This was investigated during a field experiment conducted over 68 nights during different seasons in 2001 and 2002, as well as some simple laboratory measurements. It was found that nocturnal condensation on the mulch surface (max 0.33 mm) was lower than on the bare soil surface (max 0.57 mm) or any one of three alternative mulch substrates. However, a slightly stronger nocturnal cooling of the mulched as compared to the bare surface was present. It is shown that these contrary findings can be explained by the higher hygroscopicity of the dry loam soil, resulting in condensation gains beyond the strict definition of dew. Differences in plant-availability of non-hygroscopic dew water and hygroscopic water uptakes are discussed, and conditions under which mulching would show positive condensation effects are defined. This includes a theoretical section demonstrating that non-hygroscopic mulch layers of a proper thickness can provide small amounts of dew to plant roots at the mulch-soil interface. This condensation could also happen during the day and would be favoured by a high amplitude of the diurnal atmospheric moisture cycle.

Cloud residues and interstitial aerosols from non-precipitating clouds over an industrial and urban area in northern China

NASA Astrophysics Data System (ADS)

Li, Weijun; Li, Peiren; Sun, Guode; Zhou, Shengzhen; Yuan, Qi; Wang, Wenxing

2011-05-01

Most studies of aerosol-cloud interactions have been conducted in remote locations; few have investigated the characterization of cloud condensation nuclei (CCN) over highly polluted urban and industrial areas. The present work, based on samples collected at Mt. Tai, a site in northern China affected by nearby urban and industrial air pollutant emissions, illuminates CCN properties in a polluted atmosphere. High-resolution transmission electron microscopy (TEM) was used to obtain the size, composition, and mixing state of individual cloud residues and interstitial aerosols. Most of the cloud residues displayed distinct rims which were found to consist of soluble organic matter (OM). Nearly all (91.7%) cloud residues were attributed to sulfate-related salts (the remainder was mostly coarse crustal dust particles with nitrate coatings). Half the salt particles were internally mixed with two or more refractory particles (e.g., soot, fly ash, crustal dust, CaSO 4, and OM). A comparison between cloud residues and interstitial particles shows that the former contained more salts and were of larger particle size than the latter. In addition, a somewhat high number scavenging ratio of 0.54 was observed during cloud formation. Therefore, the mixtures of salts with OMs account for most of the cloud-nucleating ability of the entire aerosol population in the polluted air of northern China. We advocate that both size and composition - the two influential, controlling factors for aerosol activation - should be built into all regional climate models of China.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Dynamics of Phase Transitions in a Snow Mass Containing Water-Soluble Salt Particles

NASA Astrophysics Data System (ADS)

Zelenko, V. L.; Heifets, L. I.; Orlov, Yu. N.; Voskresenskiy, N. M.

2018-07-01

A macrokinetic approach is used to describe the dynamics of phase transitions in a snow mass containing water-soluble salt particles. Equations are derived that describe the rate of salt granule dissolution and the change in the phase composition and temperature of a snow mass under the conditions of heat transfer with an isothermal surface. An experimental setup that models the change in the state of a snow mass placed on an isothermal surface is created to verify theoretical conclusions. Experimental observations of the change in temperature of the snow mass are compared to theoretical calculations. The mathematical model that is developed can be used to predict the state of a snow mass on roads treated with a deicing agent, or to analyze the state of snow masses containing water-soluble salt inclusions and resting on mountain slopes.

Concurrent measurements of size-segregated particulate sulfate, nitrate and ammonium using quartz fiber filters, glass fiber filters and cellulose membranes

NASA Astrophysics Data System (ADS)

Tian, Shili; Pan, Yuepeng; Wang, Jian; Wang, Yuesi

2016-11-01

Current science and policy requirements have focused attention on the need to expand and improve particulate matter (PM) sampling methods. To explore how sampling filter type affects artifacts in PM composition measurements, size-resolved particulate SO42-, NO3- and NH4+ (SNA) were measured on quartz fiber filters (QFF), glass fiber filters (GFF) and cellulose membranes (CM) concurrently in an urban area of Beijing on both clean and hazy days. The results showed that SNA concentrations in most of the size fractions exhibited the following patterns on different filters: CM > QFF > GFF for NH4+; GFF > QFF > CM for SO42-; and GFF > CM > QFF for NO3-. The different patterns in coarse particles were mainly affected by filter acidity, and that in fine particles were mainly affected by hygroscopicity of the filters (especially in size fraction of 0.65-2.1 μm). Filter acidity and hygroscopicity also shifted the peaks of the annual mean size distributions of SNA on QFF from 0.43-0.65 μm on clean days to 0.65-1.1 μm on hazy days. However, this size shift was not as distinct for samples measured with CM and GFF. In addition, relative humidity (RH) and pollution levels are important factors that can enhance particulate size mode shifts of SNA on clean and hazy days. Consequently, the annual mean size distributions of SNA had maxima at 0.65-1.1 μm for QFF samples and 0.43-0.65 μm for GFF and CM samples. Compared with NH4+ and SO42-, NO3- is more sensitive to RH and pollution levels, accordingly, the annual mean size distribution of NO3- exhibited peak at 0.65-1.1 μm for CM samples instead of 0.43-0.65 μm. These methodological uncertainties should be considered when quantifying the concentrations and size distributions of SNA under different RH and haze conditions.

Meteorological and Aerosol effects on Marine Cloud Microphysical Properties

NASA Astrophysics Data System (ADS)

Sanchez, K. J.; Russell, L. M.; Modini, R. L.; Frossard, A. A.; Ahlm, L.; Roberts, G.; Hawkins, L. N.; Schroder, J. C.; Wang, Z.; Lee, A.; Abbatt, J.; Lin, J.; Nenes, A.; Wonaschuetz, A.; Sorooshian, A.; Noone, K.; Jonsson, H.; Albrecht, B. A.; Desiree, T. S.; Macdonald, A. M.; Seinfeld, J.; Zhao, R.

2015-12-01

Both meteorology and microphysics affect cloud formation and consequently their droplet distributions and shortwave reflectance. The Eastern Pacific Emitted Aerosol Cloud Experiment (EPEACE) and the Stratocumulus Observations of Los-Angeles Emissions Derived Aerosol-Droplets (SOLEDAD) studies provide detailed measurements in 6 case studies of both cloud thermodynamic properties and initial particle number distribution and composition, as well as the resulting cloud drop distribution and composition. This study uses simulations of a detailed chemical and microphysical aerosol-cloud parcel (ACP) model with explicit kinetic drop activation to reproduce the observed cloud droplet distribution and composition. Four of the cases examined had a sub-adiabatic lapse rate, which was shown to have fewer droplets due to decreased maximum supersaturation, lower LWC and higher cloud base height, consistent with previous findings. These detailed case studies provided measured thermodynamics and microphysics that constrained the simulated droplet size distribution sufficiently to match the droplet number within 6% and the size within 19% for 4 of the 6 cases, demonstrating "closure" or consistency of the measured composition with the measured CCN spectra and the inferred and modeled supersaturation. The contribution of organic components to droplet formation shows small effects on the droplet number and size in the 4 marine cases that had background aerosol conditions with varying amounts of coastal, ship or other non-biogenic sources. In contrast, the organic fraction and hygroscopicity increased the droplet number and size in the cases with generated smoke and cargo ship plumes that were freshly emitted and not yet internally mixed with the background particles. The simulation results show organic hygroscopicity causes small effects on cloud reflectivity (<0.7%) with the exception of the cargo ship plume and smoke plume which increased absolute cloud reflectivity fraction by 0.02 and 0.20 respectively. In addition, the ACP model simulations are compared to those from a numerical parameterization of cloud droplet activation that is suitable for GCMs and show droplet concentrations are comparable between the two methods.

Preformulation characterization and in vivo absorption in beagle dogs of JFD, a novel anti-obesity drug for oral delivery.

PubMed

Fan, Yunzhou; Yang, Meiyan; Wang, Yuli; Li, Yanyou; Zhou, Yuanda; Chen, Xiaoping; Shan, Li; Wei, Jun; Gao, Chunsheng

2015-05-01

JFD (N-isoleucyl-4-methyl-1,1-cyclopropyl-1-(4-chlorine)phenyl-2-amylamine·HCl) is a novel investigational anti-obesity drug without obvious cardiotoxicity. The objective of this study was to characterize the key physicochemical properties of JFD, including solution-state characterization (ionization constant, partition coefficient, aqueous and pH-solubility profile), solid-state characterization (particle size, thermal analysis, crystallinity and hygroscopicity) and drug-excipient chemical compatibility. A supporting in vivo absorption study was also carried out in beagle dogs. JFD bulk powders are prismatic crystals with a low degree of crystallinity, particle sizes of which are within 2-10 μm. JFD is highly hygroscopic, easily deliquesces to an amorphous glass solid and changes subsequently to another crystal form under an elevated moisture/temperature condition. Similar physical instability was also observed in real-time CheqSol solubility assay. pK(a) (7.49 ± 0.01), log P (5.10 ± 0.02) and intrinsic solubility (S0) (1.75 μg/ml) at 37 °C of JFD were obtained using potentiometric titration method. Based on these solution-state properties, JFD was estimated to be classified as BCS II, thus its dissolution rate may be an absorption-limiting step. Moreover, JFD was more chemically compatible with dibasic calcium phosphate, mannitol, hypromellose and colloidal silicon dioxide than with lactose and magnesium stearate. Further, JFD exhibited an acceptable pharmacokinetic profiling in beagle dogs and the pharmacokinetic parameters T(max), C(max), AUC(0-t) and absolute bioavailability were 1.60 ± 0.81 h, 0.78 ± 0.47 μg/ml, 3.77 ± 1.85 μg·h/ml and 52.30 ± 19.39%, respectively. The preformulation characterization provides valuable information for further development of oral administration of JFD.

Surface energy characteristics of zeolite embedded PVDF nanofiber films with electrospinning process

NASA Astrophysics Data System (ADS)

Kang, Dong Hee; Kang, Hyun Wook

2016-11-01

Electrospinning is a nano-scale fiber production method with various polymer materials. This technique allows simple fiber diameters control by changing the physical conditions such as applied voltage and polymer solution viscosity during the fabrication process. The electrospun polymer fibers form a thin porous film with high surface area to volume ratio. Due to these unique characteristics, it is widely used for many application fields such as photocatalyst, electric sensor, and antibacterial scaffold for tissue engineering. Filtration is one of the main applications of electrospun polymer fibers for specific application of filtering out dust particles and dehumidification. Most polymers which are commonly used in electrospinning are hard to perform the filtering and dehumidification simultaneously because of their low hygroscopic property. To overcome this obstacle, the desiccant polymers are developed such as polyacrylic acid and polysulfobetaine methacrylate. However, the desiccant polymers are generally expensive and need special solvent for electrospinning. An alternating way to solve these problems is mixing desiccant material like zeolite in polymer solution during an electrospinning process. In this study, the free surface energy characteristics of electrospun polyvinylidene fluoride (PVDF) film with various zeolite concentrations are investigated to control the hygroscopic property of general polymers. Fundamental physical property of wettability with PVDF shows hydrophobicity. The electrospun PVDF film with small weight ratio with higher than 0.1% of zeolite powder shows diminished contact angles that certifying the wettability of PVDF can be controlled using desiccant material in electrospinning process. To quantify the surface energy of electrospun PVDF films, sessile water droplets are introduced on the electrospun PVDF film surface and the contact angles are measured. The contact angles of PVDF film are 140° for without zeolite and 80° for with 5 wt% of zeolite respectively. As a result, the surface energy of PVDF film can be controlled by embedding zeolite particles in electrospinning process and applied to filtration application of dust filtering and dehumidification simultaneously with low manufacturing cost.

Aerosol optical properties in the Marine Environment during the TCAP-I campaign

NASA Astrophysics Data System (ADS)

Chand, D.; Berg, L. K.; Barnard, J.; Berkowitz, C. M.; Burton, S. P.; Chapman, E. G.; Comstock, J. M.; Fast, J. D.; Ferrare, R. A.; Connor, F. J.; Hair, J. W.; Hostetler, C. A.; Hubbe, J.; Kluzek, C.; Mei, F.; Pekour, M. S.; Sedlacek, A. J.; Schmid, B.; Shilling, J. E.; Shinozuka, Y.; Tomlinson, J. M.; Wilson, J. M.; Zelenyuk-Imre, A.

2013-12-01

The role of direct radiative forcing by atmospheric aerosol is one of the largest sources of uncertainty in predicting climate change. Much of this uncertainty comes from the limited knowledge of observed aerosol optical properties. In this presentation we discuss derived aerosol optical properties based on measurements made during the summer 2012 Two-Column Aerosol Project-I (TCAP) campaign and relate these properties to the corresponding chemical and physical properties of the aerosol. TCAP was designed to provide simultaneous, in-situ observations of the size distribution, chemical properties, and optical properties of aerosol within and between two atmospheric columns over the Atlantic Ocean near the eastern seaboard of the United States. These columns are separated by 200-300 km and were sampled in July 2012 during a summer intensive operation period (IOP) using the U.S. Department of Energy's Gulfstream-1 (G-1) and NASA's B200 aircraft, winter IOP using G-1 aircraft in February 2013, and the surface-based DOE Atmospheric Radiation Measurement (ARM) Mobile Facility (AMF) located on Cape Cod. In this presentation we examine the spectral dependence of the aerosol optical properties measured from the aircraft over the TCAP-I domain, with an emphasis on in-situ derived intensive properties measured by a 3-λ Nephelometer, a Particle Soot Absorption Photometer (PSAP), a humidograph (f(RH)), and a Single Particle Soot Photometer (SP2). Preliminary results indicate that the aerosol are more light-absorbing as well as more hygroscopic at higher altitudes (2-4 km) compared to the corresponding values made within residual layers near the surface (0-2 km altitude). The average column (0-4 km) single scattering albedo (ω) and hygroscopic scattering factor (F) are found to be ~0.96 and 1.25, respectively. Additional results on key aerosol intensive properties such as the angstrom exponent (å), asymmetry parameter (g), backscattering fraction (b), and gamma parameter (γ) will be presented and discussed.

Encapsulation of Ibuprofen in CD-MOF and Related Bioavailability Studies.

PubMed

Hartlieb, Karel J; Ferris, Daniel P; Holcroft, James M; Kandela, Irawati; Stern, Charlotte L; Nassar, Majed S; Botros, Youssry Y; Stoddart, J Fraser

2017-05-01

Although ibuprofen is one of the most widely used nonsteroidal anti-inflammatory drugs (NSAIDs), it exhibits poor solubility in aqueous and physiological environments as a free acid. In order to improve its oral bioavailability and rate of uptake, extensive research into the development of new formulations of ibuprofen has been undertaken, including the use of excipients as well as ibuprofen salts, such as ibuprofen lysinate and ibuprofen, sodium salt. The ultimate goals of these studies are to reduce the time required for maximum uptake of ibuprofen, as this period of time is directly proportional to the rate of onset of analgesic/anti-inflammatory effects, and to increase the half-life of the drug within the body; that is, the duration of action of the effects of the drug. Herein, we present a pharmaceutical cocrystal of ibuprofen and the biocompatible metal-organic framework called CD-MOF. This metal-organic framework (MOF) is based upon γ-cyclodextrin (γ-CD) tori that are coordinated to alkali metal cations (e.g., K + ions) on both their primary and secondary faces in an alternating manner to form a porous framework built up from (γ-CD) 6 cubes. We show that ibuprofen can be incorporated within CD-MOF-1 either by (i) a crystallization process using the potassium salt of ibuprofen as the alkali cation source for production of the MOF or by (ii) absorption and deprotonation of the free-acid, leading to an uptake of 23-26 wt % of ibuprofen within the CD-MOF. In vitro viability studies revealed that the CD-MOF is inherently not affecting the viability of the cells with no IC 50 value determined up to a concentration of 100 μM. Bioavailability investigations were conducted on mice, and the ibuprofen/CD-MOF pharmaceutical cocrystal was compared to control samples of the potassium salt of ibuprofen in the presence and absence of γ-CD. From these animal studies, we observed that the ibuprofen/CD-MOF-1 cocrystal exhibits the same rapid uptake of ibuprofen as the ibuprofen potassium salt control sample with a peak plasma concentration observed within 20 min, and the cocrystal has the added benefit of a 100% longer half-life in blood plasma samples and is intrinsically less hygroscopic than the pure salt form.

Synthesis of LaMnO3 in molten chlorides: effect of preparation conditions.

PubMed

Vradman, Leonid; Zana, Jonatan; Kirschner, Alon; Herskowitz, Moti

2013-07-14

LaMnO3 perovskite was successfully synthesized in molten chlorides. In order to explore the effect of the molten salt type, NaCl-KCl and LiCl-KCl eutectic mixtures were employed as a liquid medium for the perovskite formation process. The synthesis included heating the La-nitrate, Mn-nitrate and chlorides mixture to above the melting point of the corresponding chlorides. This procedure yielded a LaMnO3 phase integrated in the fused chloride matrix. Washing with water removed the salts completely, yielding pure LaMnO3 perovskite crystals. The synthesis without molten salt at 800 °C yielded several by-products in addition to the LaMnO3 phase, while with LiCl-KCl the pure perovskite phase was obtained at temperatures as low as 600 °C. Variation of temperature in the range 600-800 °C for LiCl-KCl and 700-800 °C for NaCl-KCl had no significant effect either on the morphology or on the particle size of the product. On the other hand, the effect of the molten salt type on the morphology and size of perovskite particles was remarkable. The synthesis in NaCl-KCl resulted in sub-micron LaMnO3 particles with shapes that range from truncated hexahedrons to spheres, while in LiCl-KCl mostly cubic particles of up to 2-microns were obtained. The effect of the molten salt type on LaMnO3 perovskite formation is explained based on the nucleation and crystal growth model and difference in the melting point of eutectic mixtures.

Heterogeneous freezing of droplets with immersed surface modified mineral dust particles

NASA Astrophysics Data System (ADS)

Hartmann, Susan

2010-05-01

In the framework of the international measurement campaign FROST II (FReezing Of duST), the heterogeneous freezing of droplets with an immersed surface modified size-segregated mineral dust particles was investigated at LACIS (Leipzig Aerosol Cloud Interaction Simulator, Stratmann et al. 2004). The following measurements were done: LACIS, CFDC (Continuous Flow thermal gradient Diffusion Chamber, Rogers (1988)) and FINCH (Fast Ice Nucleus Chamber Counter, Bundke et al (2008)) were used to analyze the immersion freezing behavior of the treated Arizona Test Dust (ATD) particles at different temperature regimes. The ability to act as IN (Ice Nucleus) in the deposition nucleation mode was quantified by the PINC (Portable Ice Nucleation Chamber) and the CFDC instrument. AMS (Aerosol Mass Spectrometers, e.g. Schneider et al. (2005)) and ATOFMS (Aerosol Time-Of-Flight Mass Spectrometer) measurements were applied to determine particle composition. The hygroscopic growth and the critical super-saturations needed for droplet activation were determined by means of an H-TDMA (Humidity-Tandem Differential Mobility Analyzer) and CCN counter (Cloud Condensation Nucleus counter, Droplet Measurement Technologies, Roberts and Nenes (2005)). The 300 nm ATD particles were chemically and physically treated by coating with sulphuric acid (H2SO4, three different coating thicknesses) and ammonium sulphate ((NH4)2SO4) or by thermal treatment with a thermodenuder operating at 250°C. The H2SO4 coating modified the particles by reacting with particle material, forming soluble sulfates and therefore changing surface properties. AMS showed free H2SO4 only for thick H2SO4 coatings. In the heated section of the thermodenuder coating materials were evaporated partly and the surface properties of the particles were additionally altered. Uncoated particles and those coated with thin coatings of H2SO4, showed almost no hygroscopic growth. Particles coated with thicker coatings of H2SO4 and of (NH4)2SO4 grew noticeably above 95% relative humidity. All investigated particles were found to activate at atmospherically relevant super-saturations. All kinds of treatment lower the IN-ability, whereas the deposition nucleation was more sensitive to treatments than the immersion freezing mode. Considering the immersion freezing behavior, pure ATD particles and particles coated with thin coatings of H2SO4 were more efficient IN, than particles with thick H2SO4 or (NH4)2SO4 coatings. Thermal treatments of the particles led to further decrease of the IN capability except for particles coated with (NH4)2SO4, where the heating did not effect the immersion freezing behavior likely due to their already reduced IN ability. In order to specify the temperature-dependent immersion freezing, two parameterization based on either stochastic or singular hypothesis were performed. From both theoretical approaches it can be concluded that the treatments lead to particle surface modifications lowering the nucleation efficiency. References: Bundke, U., B. Nillius, et al. (2008), The fast Ice Nucleus chamber FINCH, Atmospheric Research 90(2-4): 180-186. Rader, D. J. and P. H. McMurry (1986), Application of the Tandem Differential Mobility Analyzer to studies of droplet growth or evaporation, J. Aerosol Sci., Vol. 17, No. 5, pp. 771-787. Roberts, G., and A. Nenes (2005), A continuous-flow streamwise thermal-gradient CCN chamber for atmospheric measurements, Aerosol Sci. Technol., 39, 206-221. Schneider, J., N. Hock, S. Weimer, S. Borrmann, U. Kirchner, R. Vogt, and V. Scheer (2005), Nucleation particles in Diesel exhaust: Composition inferred from in situ mass spectrometric analysis, Environ. Sci. Technol., 39, 6153-6161. Rogers,D .C. (1988), Developmenot f a continuousflow thermal gradient diffusion chamber for ice nucleation studies. Atmospheric Research, 22, 149-181. Stratmann, F., A. Kiselev, S. Wurzler, M. Wendisch, J. Heintzenberg, R. J. Charlson, K. Diehl, H. Wex, and S. Schmidt (2004), Laboratory studies and numerical simulations of cloud droplet formation under realistic super-saturation conditions, J. Atmos. Oceanic Technol., 21, 876-887.

Formulation design for optimal high-shear wet granulation using on-line torque measurements.

PubMed

Cavinato, Mauro; Bresciani, Massimo; Machin, Marianna; Bellazzi, Guido; Canu, Paolo; Santomaso, Andrea C

2010-03-15

An alternative procedure for achieving formulation design in a high-shear wet granulation process has been developed. Particularly, a new formulation map has been proposed which describes the onset of a significant granule growth as a function of the formulation variables (diluent, dry and liquid binder). Granule growth has been monitored using on-line impeller torque and evaluated as changes in granule particle size distribution with respect to the dry formulation. It is shown how the onset of granule growth is denoted by an abrupt increase in the torque value requires the amount of binder liquid added to be greater than a certain threshold that is identified here as 'minimum liquid volume'. This minimum liquid volume is determined as a function of dry binder type, amount, hygroscopicity and particle size distribution of diluent. It is also demonstrated how this formulation map can be constructed from independent measurements of binder glass transition temperatures using a static humidity conditioning system. 2009 Elsevier B.V. All rights reserved.

Radiative effect of anthropogenic dust ageing

NASA Astrophysics Data System (ADS)

Klingmueller, K.; Lelieveld, J.; Karydis, V.; Stenchikov, G. L.

2017-12-01

The chemical ageing of mineral dust mixing due to the uptake of air pollution affects the optical and hygroscopical properties of the dust particles and their atmospheric residence time. This results in an anthropogenic radiative forcing associated with mineral dust despite the natural origin of most dust particles. Using the atmospheric chemistry-climate model EMAC with a detailed parametrisation of chemical ageing and an emission scheme accounting for the chemical composition of desert soils, we study the direct radiative forcing globally and regionally. Preliminary results indicate large positive and negative forcings, depending on the region. The predominantly negative top of atmosphere forcing over large parts of the dust belt, from West Africa to East Asia, reaches about -2 W / m2 south of the Sahel, in contrast to positive forcings over India and the western Atlantic. Globally averaged, these forcings partially counterbalance, resulting in a negative forcing of -0.04 to -0.05 W / m2, nevertheless representing a considerable fraction of the total dust forcing.

Photoelectron resonance capture ionization-aerosol mass spectrometry of the ozonolysis products of oleic acid particles: Direct measure of higher molecular weight oxygenates

NASA Astrophysics Data System (ADS)

Zahardis, James; Lafranchi, Brian W.; Petrucci, Giuseppe A.

2005-04-01

The heterogeneous reaction of particle-phase 9-octadecenoic acid (oleic acid) and gas-phase ozone in a flow reactor was studied by photoelectron resonance capture ionization (PERCI) mass spectrometry. This soft ionization technique facilitated one of the first simultaneous, direct observations of all four of the major products predicted for this reaction: nonanal, nonanoic acid, 9-oxononanoic acid, and azelaic acid. In addition, a series of higher molecular weight oxygenated compounds were observed directly for the first time. The proposed structures are all cyclic oxygenates and contain the oxygen-oxygen moiety, including secondary ozonides and cyclic geminal diperoxides. Mechanisms for the formation of these products are proposed. The mechanisms are generally 1,3-dipolar cycloadditions that lead to five- and six-member oxygen-containing rings. The mechanisms are shown to involve short-lived Criegee intermediates reacting with aldehydes and other Criegee intermediates. Atmospheric implications of these higher molecular weight compounds are suggested and include enhancing the fatty acid medium's capacity to act as a source of radicals due to the prominence of the peroxide moiety. The low volatility coupled with the high polarity of these compounds may alter particle phase hygroscopicity that can enhance the cloud condensation nuclei properties of these particles.