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1.
PNAS Nexus ; 2(2): pgac301, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36743472

RESUMO

An accepted murine analogue for the environmental behavior of human SARS coronaviruses was aerosolized in microdroplets of its culture media and saliva to observe the decay of its airborne infectious potential under relative humidity (RH) conditions relevant to conditioned indoor air. Contained in a dark, 10 m3 chamber maintained at 22°C, murine hepatitis virus (MHV) was entrained in artificial saliva particles that were aerosolized in size distributions that mimic SARS-CoV-2 virus expelled from infected humans' respiration. As judged by quantitative PCR, more than 95% of the airborne MHV aerosolized was recovered from microdroplets with mean aerodynamic diameters between 0.56 and 5.6 µm. As judged by its half-life, calculated from the median tissue culture infectious dose (TCID50), saliva was protective of airborne murine coronavirus through a RH range recommended for conditioned indoor air (60% < RH < 40%; average half-life = 60 minutes). However, its average half-life doubled to 120 minutes when RH was maintained at 25%. Saliva microaerosol was dominated by carbohydrates, which presented hallmarks of vitrification without efflorescence at low RH. These results suggest that dehydrating carbohydrates can affect the infectious potential coronaviruses exhibit while airborne, significantly extending their persistence under the drier humidity conditions encountered indoors.

2.
J Gastrointest Surg ; 25(12): 3198-3207, 2021 12.
Artigo em Inglês | MEDLINE | ID: mdl-34668165

RESUMO

BACKGROUND: Understanding the drivers of patient engagement and adherence is critical to developing and implementing preoperative optimization programs. The aim of this project is to determine whether existing health beliefs are associated with engagement and adherence in a home-based online prehabilitation program. METHODS: Patients undergoing abdominal colorectal operations were enrolled in an online nutrition and exercise program. We collected baseline health beliefs and mindsets, daily exercises, and weekly diet recalls. Multivariable binary logistic regression predicted engagement, multivariable ordinary least squares regression predicted diet adherence, and generalized linear models with a binomial distribution predicted engagement and exercise adherence. RESULTS: Of the 227 patients who agreed to participate, 75% activated their accounts; of those, 75% used the program. Engagement with the program was unrelated to health beliefs or mindsets. Positive diet-related health beliefs and a growth mindset were associated with positive diet behaviors and inversely associated with negative diet behaviors. Exercise-related health beliefs and mindsets were not associated with exercise adherence. Patients enrolled within 4 weeks of surgery used the program more than those enrolled more than 4 weeks from surgery. CONCLUSIONS: This app-based prehabilitation program demonstrated moderate acceptability, engagement, and adherence. Addressing health beliefs and mindsets may be an effective way of increasing adherence to diet recommendations. To increase adherence to exercise recommendations, further assessment of potential barriers is critical. While an online platform is a highly promising scalable strategy, more customization and user engagement are necessary to make it an effective way of delivering a preoperative health behavior change intervention.


Assuntos
Cirurgia Colorretal , Procedimentos Cirúrgicos do Sistema Digestório , Humanos , Internet , Cuidados Pré-Operatórios , Exercício Pré-Operatório
3.
J Phys Chem A ; 125(39): 8668-8679, 2021 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-34553594

RESUMO

Atmospheric aerosols are complex with both inorganic and organic components. The soluble inorganics can transition between aqueous and crystalline phases through efflorescence and deliquescence. This study focuses on the efflorescence of (NH4)2SO4/organic particles by seeded crystal growth through contact with a crystal of (NH4)2SO4. Seeded crystal growth is known to effectively shut down supersaturation of aqueous aerosols. Here, we investigate whether organics can inhibit seeded crystal growth. We demonstrate that poly(ethylene glycol) 400 (PEG-400), which phase-separates from the aqueous (NH4)2SO4 and forms a core-shell structure, did not inhibit seeded crystal growth of (NH4)2SO4 at all relative humidity (RH) values below deliquescence RH. The PEG-400 layer was not viscous enough to prevent the diffusion of species through the coating. In contrast, we find that although raffinose, which stays homogeneously mixed with (NH4)2SO4, did not inhibit seeded crystal growth at RH > 45%, it did inhibit heterogeneous efflorescence at lower humidities. Viscosity measurements using an electrodynamic balance show a significant increase in viscosity as humidity was lowered, suggesting that inhibited diffusion of water and ions prevented efflorescence. The observed efflorescence at the higher RH also demonstrates that collisions can induce efflorescence of mixed aerosols that would otherwise not homogeneously effloresce.

4.
Nat Commun ; 11(1): 4526, 2020 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-32913208

RESUMO

Volcanic ash is often neglected in climate simulations because ash particles are assumed to have a short atmospheric lifetime, and to not participate in sulfur chemistry. After the Mt. Kelut eruption in 2014, stratospheric ash-rich aerosols were observed for months. Here we show that the persistence of super-micron ash is consistent with a density near 0.5 g cm-3, close to pumice. Ash-rich particles dominate the volcanic cloud optical properties for the first 60 days. We also find that the initial SO2 lifetime is determined by SO2 uptake on ash, rather than by reaction with OH as commonly assumed. About 43% more volcanic sulfur is removed from the stratosphere in 2 months with the SO2 heterogeneous chemistry on ash particles than without. This research suggests the need for re-evaluation of factors controlling SO2 lifetime in climate model simulations, and of the impact of volcanic ash on stratospheric chemistry and radiation.

5.
Environ Sci Technol ; 54(8): 4781-4789, 2020 04 21.
Artigo em Inglês | MEDLINE | ID: mdl-32227881

RESUMO

Oxalic acid and sulfate salts are major components of aerosol particles. Here, we explore the potential for their respective precursor species, glyoxal and SO2, to form atmospheric brown carbon via aqueous-phase reactions in a series of bulk aqueous and flow chamber aerosol experiments. In bulk aqueous solutions, UV- and visible-light-absorbing products are observed at pH 3-4 and 5-6, respectively, with small but detectable yields of hydroxyquinone and polyketone products formed, especially at pH 6. Hydroxymethanesulfonate (HMS), C2, and C3 sulfonates are major products detected by electrospray ionization mass spectrometry (ESI-MS) at pH 5. Past studies have assumed that the reaction of formaldehyde and sulfite was the only atmospheric source of HMS. In flow chamber experiments involving sulfite aerosol and gas-phase glyoxal with only 1 min residence times, significant aerosol growth is observed. Rapid brown carbon formation is seen with aqueous aerosol particles at >80% relative humidity (RH). Brown carbon formation slows at 50-60% RH and when the aerosol particles are acidified with sulfuric acid but stops entirely only under dry conditions. This chemistry may therefore contribute to brown carbon production in cloud-processed pollution plumes as oxidizing volatile organic compounds (VOCs) interact with SO2 and water.


Assuntos
Carbono , Glioxal , Aerossóis , Espectrometria de Massas por Ionização por Electrospray , Água
6.
Astrobiology ; 20(5): 658-669, 2020 05.
Artigo em Inglês | MEDLINE | ID: mdl-32159384

RESUMO

Atmospheric organic hazes are common in planetary bodies in our solar system and likely exoplanet atmospheres as well. In addition, geochemical data support the existence of an organic haze in the early Earth's atmosphere. Much of what is known about organic haze formation derives from studies of Saturn's moon Titan. It is believed that on Titan ions play an important role in haze formation. It is possible, by using Titan as an analog for the Archean Earth, to consider that an Archean haze could have formed by similar processes. Here, we examine the anion chemistry that occurs during laboratory simulations of early Earth haze formation and measure the composition of gaseous anions as a function of O2 mixing ratio. Gaseous anion composition and relative abundances are measured by an atmospheric pressure interface time-of-flight mass spectrometer and are compared to previous photochemical haze mass loading measurements. Numerous anions are observed spanning from mass-to-charge ratio 26 to 246, with a majority of the identified anions containing carbon, hydrogen, nitrogen, and/or oxygen. A shift in the anion composition occurs with increasing the precursor O2 mixing ratio. With 0-20 ppmv O2 in CH4/CO2/N2 mixtures, ions contain mostly organic nitrogen, with CNO- being the most intense ion peak. As the precursor O2 is increased to 200 and 2000 ppmv, inorganic nitrogen ions become the dominant chemical group, with NO3- having the most intense ion signal. The clear shift in the ionic composition could be indicative of a modification to the gas-phase chemistry that occurs in the transition from an anoxic atmosphere to an oxygen-containing atmosphere, with potential astrobiological significance.


Assuntos
Atmosfera/química , Planeta Terra , Oxigênio/química , Ânions , Espectrometria de Massas
7.
J Womens Health (Larchmt) ; 29(10): 1319-1327, 2020 10.
Artigo em Inglês | MEDLINE | ID: mdl-31800360

RESUMO

Purpose: To test a novel bladder health tutorial on use of the Knack for overcoming bladder control challenges. The Knack-tutorial is a self-administered vignette-based instructional program on preempting bladder challenges in daily life (urgency, stress-leakage, or urge-leakage) through anticipatory, well-timed pelvic floor muscle contraction at the moment of challenge. Materials and Methods: This is a randomized controlled trial pilot test of 108 women with stress or mixed urinary incontinence. The Knack-tutorial group saw a 15-minute slide show with 10 vignettes portraying use of the Knack in daily life. The slide show format used inserted narrated videos, dubbed and animation enhanced pictures and cartoons, and automatic slide advancement. A control group saw a similarly constructed slide show on incorporating good diet/exercise habits. Outcomes were self-perceived improvement (yes/no, and as 0%-100%) 1 month after viewing the tutorial. Results: We enrolled 123 women, randomizing 64 to Knack-tutorial group and 59 to diet/exercise tutorial group. Eleven and one participant, respectively, did not return. Three did not fill out the self-perceived improvement report. Significant improvement was reported by 71% in the Knack-tutorial group compared to 25% in the diet/exercise group (p < 0.001). Self-perceived improvement was 21%-22% higher (Model I Est: 21.01, SE: 4.25, p < 0.001) in the Knack-tutorial group. Conclusions: An electronic tutorial viewed independent of a health care provider with vignettes showing Knack application to manage the everyday bladder challenges women face shows benefit of a magnitude that warrants more widespread use and rigorous testing. A professional remake of the intervention is now available (www.myconfidentbladder.com).


Assuntos
Terapia por Exercício/métodos , Diafragma da Pelve/fisiopatologia , Incontinência Urinária por Estresse/terapia , Feminino , Humanos , Educação de Pacientes como Assunto , Projetos Piloto , Resultado do Tratamento
8.
J Phys Chem A ; 122(5): 1303-1311, 2018 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-29332388

RESUMO

The phase state of inorganic salt aerosols impacts their properties, including the ability to undergo hygroscopic growth, catalyze heterogeneous reactions, and act as cloud condensation nuclei. Here, we report the first observation of contact efflorescence by mineral dust aerosol. The efflorescence of aqueous ammonium sulfate ((NH4)2SO4) and sodium chloride (NaCl) droplets by contact with three types of mineral dust particles (illite, montmorillonite, and NX illite), were examined using an optical levitation chamber. Immersion mode efflorescence was also studied for comparison. We find that in the presence of mineral dust particles, crystallization occurred at a higher relative humidity (RH) when compared to the homogeneous phase transition. Additionally, crystallization by contact mode efflorescence occurred at a higher RH than the corresponding immersion mode. Crystallization efficiencies in the contact mode exhibited an ion-specific trend consistent with the Hoffmeister series. Estimates for lifetimes of a salt droplet to collide with dust particles suggests that collisions between the two aerosol types are likely to occur before the salt aerosol is removed by other atmospheric processes. Such collisions could then lead to the crystallization of salt droplets that would otherwise have remained liquid, changing the overall impact that salt aerosols have on atmospheric chemistry and climate.

9.
J Geophys Res Planets ; 123(5): 1156-1167, 2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-33294305

RESUMO

The Mars Science Laboratory (MSL) Rover Environmental Monitoring Station (REMS) has now made continuous in situ meteorological measurements for several Martian years at Gale crater, Mars. Of importance in the search for liquid formation are REMS' measurements of ground temperature and in-air measurements of temperature and relative humidity, which is with respect to ice. Such data can constrain the surface and subsurface stability of brines. Here we use updated calibrations to REMS data and consistent relative humidity comparisons (i.e., with respect to liquid versus with respect to ice) to investigate the potential formation of surface and subsurface liquids throughout MSL's traverse. We specifically study the potential for the deliquescence of calcium perchlorate. Our data analysis suggests that surface brine formation is not favored within the first 1648 sols as there are only two times (sols 1232 and 1311) when humidity-temperature conditions were within error consistent with a liquid phase. On the other hand, modeling of the subsurface environment would support brine production in the shallow subsurface. Indeed, we find that the shallow subsurface for terrains with low thermal inertia (Γ â‰² 300 J m-2 K-1 s-1/2) may be occasionally favorable to brine formation through deliquescence. Terrains with Γ â‰² 175 J m-2 K-1 s-1/2 and albedos of ≳0.25 are the most apt to subsurface brine formation. Should brines form, they would occur around Ls 100°. Their predicted properties would not meet the Special nor Uncertain Region requirements, as such they would not be potential habitable environments to life as we know it.

10.
Astrobiology ; 17(10): 997-1008, 2017 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-29048223

RESUMO

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. Key Words: Raman microscopy-Mars-Planetary protection-Salts-Water activity. Astrobiology 17, 997-1008.


Assuntos
Adaptação Fisiológica , Bacillus subtilis/fisiologia , Exobiologia/métodos , Meio Ambiente Extraterreno/química , Marte , Atmosfera/química , Percloratos/química , Salinidade , Esporos Bacterianos/fisiologia , Água/química
11.
Sci Adv ; 3(7): e1700425, 2017 07.
Artigo em Inglês | MEDLINE | ID: mdl-28776032

RESUMO

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

12.
Astrobiology ; 16(11): 822-830, 2016 11.
Artigo em Inglês | MEDLINE | ID: mdl-27870584

RESUMO

Despite the faint young Sun, early Earth might have been kept warm by an atmosphere containing the greenhouse gases CH4 and CO2 in mixing ratios higher than those found on Earth today. Laboratory and modeling studies suggest that an atmosphere containing these trace gases could lead to the formation of organic aerosol haze due to UV photochemistry. Chemical mechanisms proposed to explain haze formation rely on CH4 as the source of carbon and treat CO2 as a source of oxygen only, but this has not previously been verified experimentally. In the present work, we use isotopically labeled precursor gases and unit-mass resolution (UMR) and high-resolution (HR) aerosol mass spectrometry to examine the sources of carbon and oxygen to photochemical aerosol formed in a CH4/CO2/N2 atmosphere. UMR results suggest that CH4 contributes 70-100% of carbon in the aerosol, while HR results constrain the value from 94% to 100%. We also confirm that CO2 contributes approximately 10% of the total mass to the aerosol as oxygen. These results have implications for the geochemical interpretations of inclusions found in Archean rocks on Earth and for the astrobiological potential of other planetary atmospheres. Key Words: Atmosphere-Early Earth-Planetary atmospheres-Carbon dioxide-Methane. Astrobiology 16, 822-830.


Assuntos
Aerossóis/análise , Carbono/análise , Planeta Terra , Marcação por Isótopo/métodos , Isótopos de Carbono , Espectrometria de Massas
13.
Proc Natl Acad Sci U S A ; 112(52): 15815-20, 2015 Dec 29.
Artigo em Inglês | MEDLINE | ID: mdl-26668396

RESUMO

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.

14.
Anal Chem ; 87(12): 6186-94, 2015 Jun 16.
Artigo em Inglês | MEDLINE | ID: mdl-25961113

RESUMO

A novel optical trapping technique is described that combines an upward propagating Gaussian beam and a downward propagating Bessel beam. Using this optical arrangement and an on-demand droplet generator makes it possible to rapidly and reliably trap particles with a wide range of particle diameters (∼1.5-25 µm), in addition to crystalline particles, without the need to adjust the optical configuration. Additionally, a new image analysis technique is described to detect particle phase transitions using a template-based autocorrelation of imaged far-field elastically scattered laser light. The image analysis allows subtle changes in particle characteristics to be quantified. The instrumental capabilities are validated with observations of deliquescence and homogeneous efflorescence of well-studied inorganic salts. Then, a novel collision-based approach to seeded crystal growth is described in which seed crystals are delivered to levitated aqueous droplets via a nitrogen gas flow. To our knowledge, this is the first account of contact-induced phase changes being studied in an optical trap. This instrument offers a novel and simple analytical technique for in situ measurements and observations of phase changes and crystal growth processes relevant to atmospheric science, industrial crystallization, pharmaceuticals, and many other fields.

15.
Anal Chem ; 87(5): 2741-7, 2015 Mar 03.
Artigo em Inglês | MEDLINE | ID: mdl-25645140

RESUMO

Elemental analysis of unit-mass resolution (UMR) mass spectra is limited by the amount of information available to definitively elucidate the molecular formula of a molecule ionized by electron impact. The problem is compounded when a mixture of organic molecules (such as those found in organic aerosols) is analyzed without the benefit of prior separation. For this reason, quadrupole mass spectrometry is not usually suited to the elemental analysis of organic mixtures. Here, we present a mathematical method for the elemental analysis of UMR mass spectra of a complex organic aerosol through the use of isotopic labeling. Quadrupole aerosol mass spectrometry was used to obtain UMR data of (13)C-labeled and unlabeled aerosol generated by far ultraviolet (FUV) photochemistry of gas mixtures containing 0.1% of either CH4 or (13)CH4 in N2. In this method, the differences in the positions of ion groups in the resulting spectra are used to estimate the mass fraction of carbon in the aerosol, and estimation of the remaining elements follows. Analysis of the UMR data yields an elemental composition of 63 ± 7% C, 8 ± 1% H, and 29 ± 7% N by mass. Unlabeled aerosols formed under the same conditions are found by high-resolution time-of-flight aerosol mass spectrometry to have an elemental composition of 63 ± 3% C, 8 ± 1% H, 20 ± 4% N, and 9 ± 3% O by mass, in good agreement with the UMR method. This favorable comparison verifies the method, which expands the UMR mass spectrometry toolkit.

16.
J Phys Chem A ; 118(38): 8787-96, 2014 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-25211030

RESUMO

Mineral dust aerosol is one of the largest contributors to global ice nuclei, but physical and chemical processing of dust during atmospheric transport can alter its ice nucleation activity. In particular, several recent studies have noted that sulfuric and nitric acids inhibit heterogeneous ice nucleation in the regime below liquid water saturation in aluminosilicate clay minerals. We have exposed kaolinite, KGa-1b and KGa-2, and montmorillonite, STx-1b and SWy-2, to aqueous sulfuric and nitric acid to determine the physical and chemical changes that are responsible for the observed deactivation. To characterize the changes to the samples upon acid treatment, we use X-ray diffraction, transmission electron microscopy, and inductively coupled plasma-atomic emission spectroscopy. We find that the reaction of kaolinite and montmorillonite with aqueous sulfuric acid results in the formation of hydrated aluminum sulfate. In addition, sulfuric and nitric acids induce large structural changes in montmorillonite. We additionally report the supersaturation with respect to ice required for the onset of ice nucleation for these acid-treated species. On the basis of lattice spacing arguments, we explain how the chemical and physical changes observed upon acid treatment could lead to the observed reduction in ice nucleation activity.

17.
Environ Sci Technol ; 48(3): 1675-82, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24410444

RESUMO

In this study, we have explored the phase behavior and the ice nucleation properties of secondary organic aerosol made from aqueous processing (aqSOA). AqSOA was made from the dark reactions of methylglyoxal with methylamine in simulated evaporated cloud droplets. The resulting particles were probed from 215 to 250 K using Raman spectroscopy coupled to an environmental cell. We find these particles are in a semisolid or glassy state based upon their behavior when exposed to mechanical pressure as well as their flow behavior. Further, we find that these aqSOA particles are poor depositional ice nuclei, in contrast to previous studies on simple mixtures of glassy organics. Additionally, we have studied the effect of ammonium sulfate on the phase, morphology, and ice nucleation behavior of the aqSOA. We find that the plasticizing effect of ammonium sulfate lowers the viscosity of the aqSOA, allowing the ammonium sulfate to effloresce within the aqSOA matrix. Upon humidification, the aqSOA matrix liquefies before it can depositionally nucleate ice, and the effloresced ammonium sulfate can act as an immersion mode ice nucleus. This change in the mode of nucleation is accompanied by an increase in the overall ice nucleation efficiency of the aqSOA particles.


Assuntos
Aerossóis/química , Poluentes Atmosféricos/química , Sulfato de Amônio/química , Gelo/análise , Análise Espectral Raman
18.
Environ Sci Technol ; 48(4): 2273-80, 2014 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-24428707

RESUMO

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.


Assuntos
Aerossóis/química , Simulação por Computador , Compostos Orgânicos/química , Água/química , Atmosfera/química , Metilaminas/química , Transição de Fase , Aldeído Pirúvico/química , Temperatura , Fatores de Tempo , Molhabilidade
19.
Environ Sci Technol ; 47(23): 13339-46, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-24144443

RESUMO

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.


Assuntos
Sulfato de Amônio/química , Atmosfera/química , Álcoois Graxos/química , Luz , Aerossóis , Modelos Químicos , Tamanho da Partícula , Fotoquímica , Análise Espectral/métodos , Água/química , Molhabilidade
20.
J Phys Chem A ; 116(25): 6817-22, 2012 Jun 28.
Artigo em Inglês | MEDLINE | ID: mdl-22646721

RESUMO

The heterogeneous ice nucleation efficiency of a series of thin C3-C6 monocarboxylic acid films between 180 and 200 K has been investigated using a Knudsen cell flow reactor. At each temperature, the critical ice saturation ratio for depositional nucleation as well as the effective contact angle was found to be strongly dependent on the chemical nature of the film. For the organic acids used in this study, increasing the O:C ratio lowered the supersaturation required for the onset of heterogeneous ice nucleation and decreased the effective angle of contact. This could be the result of an increase in surface hydrophilicity, which allows the film to better adsorb a metastable, icelike layer of water that serves as a template for the new phase of ice. These ice nucleation results are in excellent agreement with ice nucleation on laboratory generated α-pinene secondary organic aerosol as well as on predominantly organic particles collected in Mexico City.

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