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1.
J Phys Chem A ; 124(18): 3652-3661, 2020 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-32281376

RESUMO

Water and organics are omnipresent in the atmosphere, and their interactions influence the properties and lifetime of both aerosols and clouds. Nopinone is one of the major reaction products formed from ß-pinene oxidation, a compound emitted by coniferous trees, and it has been found in both gas and particle phases in the atmosphere. Here, we investigate the interactions between water molecules and nopinone surfaces by combining environmental molecular beam (EMB) experiments and molecular dynamics (MD) simulations. The EMB method enables detailed studies of the dynamics and kinetics of water interacting with solid nopinone at 170-240 K and graphite coated with a molecularly thin nopinone layer at 200-270 K. MD simulations that mimic the experimental conditions have been performed to add insights into the molecular-level processes. Water molecules impinging on nopinone surfaces are efficiently trapped (≥97%), and only a minor fraction scatters inelastically while maintaining 35-65% of their incident kinetic energy (23.2 ± 1.0 kJ mol-1). A large fraction (60-80%) of the trapped molecules desorbs rapidly, whereas a small fraction (20-40%) remains on the surface for more than 10 ms. The MD calculations confirm both rapid water desorption and the occurrence of strongly bound surface states. A comparison of the experimental and computational results suggests that the formation of surface-bound water clusters enhances water uptake on the investigated surfaces.

2.
Nat Commun ; 10(1): 4442, 2019 09 30.
Artigo em Inglês | MEDLINE | ID: mdl-31570718

RESUMO

Particles formed in the atmosphere via nucleation provide about half the number of atmospheric cloud condensation nuclei, but in many locations, this process is limited by the growth of the newly formed particles. That growth is often via condensation of organic vapors. Identification of these vapors and their sources is thus fundamental for simulating changes to aerosol-cloud interactions, which are one of the most uncertain aspects of anthropogenic climate forcing. Here we present direct molecular-level observations of a distribution of organic vapors in a forested environment that can explain simultaneously observed atmospheric nanoparticle growth from 3 to 50 nm. Furthermore, the volatility distribution of these vapors is sufficient to explain nanoparticle growth without invoking particle-phase processes. The agreement between observed mass growth, and the growth predicted from the observed mass of condensing vapors in a forested environment thus represents an important step forward in the characterization of atmospheric particle growth.

3.
Indoor Air ; 29(6): 913-925, 2019 11.
Artigo em Inglês | MEDLINE | ID: mdl-31420890

RESUMO

This study aimed to better understand and quantify the influence of ventilation strategies on occupant-related indoor air chemistry. The oxidation of human skin oil constituents was studied in a continuously ventilated climate chamber at two air exchange rates (1 h-1 and 3 h-1 ) and two initial ozone mixing ratios (30 and 60 ppb). Additional measurements were performed to investigate the effect of intermittent ventilation ("off" followed by "on"). Soiled t-shirts were used to simulate the presence of occupants. A time-of-flight-chemical ionization mass spectrometer (ToF-CIMS) in positive mode using protonated water clusters was used to measure the oxygenated reaction products geranyl acetone, 6-methyl-5-hepten-2-one (6-MHO) and 4-oxopentanal (4-OPA). The measurement data were used in a series of mass balance models accounting for formation and removal processes. Reactions of ozone with squalene occurring on the surface of the t-shirts are mass transport limited; ventilation rate has only a small effect on this surface chemistry. Ozone-squalene reactions on the t-shirts produced gas-phase geranyl acetone, which was subsequently removed almost equally by ventilation and further reaction with ozone. About 70% of gas-phase 6-MHO was produced in surface reactions on the t-shirts, the remainder in secondary gas-phase reactions of ozone with geranyl acetone. 6-MHO was primarily removed by ventilation, while further reaction with ozone was responsible for about a third of its removal. 4-OPA was formed primarily on the surfaces of the shirts (~60%); gas-phase reactions of ozone with geranyl acetone and 6-MHO accounted for ~30% and ~10%, respectively. 4-OPA was removed entirely by ventilation. The results from the intermittent ventilation scenarios showed delayed formation of the reaction products and lower product concentrations compared to continuous ventilation.


Assuntos
Poluentes Atmosféricos/análise , Poluição do Ar em Ambientes Fechados/análise , Ozônio/análise , Pele/química , Ventilação/métodos , Aldeídos/análise , Ambiente Construído , Vestuário , Monitoramento Ambiental/métodos , Humanos , Cetonas/análise , Espectrometria de Massas/métodos , Oxirredução , Terpenos/análise
4.
Nature ; 565(7741): 587-593, 2019 01.
Artigo em Inglês | MEDLINE | ID: mdl-30700872

RESUMO

Secondary organic aerosol contributes to the atmospheric particle burden with implications for air quality and climate. Biogenic volatile organic compounds such as terpenoids emitted from plants are important secondary organic aerosol precursors with isoprene dominating the emissions of biogenic volatile organic compounds globally. However, the particle mass from isoprene oxidation is generally modest compared to that of other terpenoids. Here we show that isoprene, carbon monoxide and methane can each suppress the instantaneous mass and the overall mass yield derived from monoterpenes in mixtures of atmospheric vapours. We find that isoprene 'scavenges' hydroxyl radicals, preventing their reaction with monoterpenes, and the resulting isoprene peroxy radicals scavenge highly oxygenated monoterpene products. These effects reduce the yield of low-volatility products that would otherwise form secondary organic aerosol. Global model calculations indicate that oxidant and product scavenging can operate effectively in the real atmosphere. Thus highly reactive compounds (such as isoprene) that produce a modest amount of aerosol are not necessarily net producers of secondary organic particle mass and their oxidation in mixtures of atmospheric vapours can suppress both particle number and mass of secondary organic aerosol. We suggest that formation mechanisms of secondary organic aerosol in the atmosphere need to be considered more realistically, accounting for mechanistic interactions between the products of oxidizing precursor molecules (as is recognized to be necessary when modelling ozone production).

5.
J Environ Sci (China) ; 73: 69-77, 2018 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-30290873

RESUMO

Particle density is an important physical property of atmospheric particles. The information on high time-resolution size-resolved particle density is essential for understanding the atmospheric physical and chemical aging processes of aerosols particles. In the present study, a centrifugal particle mass analyzer (CPMA) combined with a differential mobility analyzer (DMA) was deployed to determine the size-resolved effective density of 50 to 350nm particles at a rural site of Beijing during summer 2016. The measured particle effective densities decreased with increasing particle sizes and ranged from 1.43 to 1.55g/cm3, on average. The effective particle density distributions were dominated by a mode peaked at around 1.5g/cm3 for 50 to 350nm particles. Extra modes with peaks at 1.0, 0.8, and 0.6g/cm3 for 150, 240, and 350nm particles, which might be freshly emitted soot particles, were observed during intensive primary emissions episodes. The particle effective densities showed a diurnal variation pattern, with higher values during daytime. A case study showed that the effective density of Aitken mode particles during the new particle formation (NPF) event decreased considerably, indicating the significant contribution of organics to new particle growth.


Assuntos
Poluentes Atmosféricos/análise , Atmosfera/química , Monitoramento Ambiental , Material Particulado/análise , Aerossóis/análise , Pequim
6.
Environ Sci Technol ; 52(14): 7720-7728, 2018 07 17.
Artigo em Inglês | MEDLINE | ID: mdl-29894174

RESUMO

The potential effect of changing to a nonfossil fuel vehicle fleet was investigated by measuring primary emissions (by extractive sampling of bus plumes) and secondary mass formation, using a Gothenburg Potential Aerosol Mass (Go:PAM) reactor, from 29 in-use transit buses. Regarding fresh emissions, diesel (DSL) buses without a diesel particulate filter (DPF) emitted the highest median mass of particles, whereas compressed natural gas (CNG) buses emitted the lowest (MdEFPM 514 and 11 mg kgfuel-1, respectively). Rapeseed methyl ester (RME) buses showed smaller MdEFPM and particle sizes than DSL buses. DSL (no DPF) and hybrid-electric RME (RMEHEV) buses exhibited the highest particle numbers (MdEFPN 12 × 1014 # kgfuel-1). RMEHEV buses displayed a significant nucleation mode ( Dp< 20 nm). EFPN of CNG buses spanned the highest to lowest values measured. Low MdEFPN and MdEFPM were observed for a DPF-equipped DSL bus. Secondary particle formation resulting from exhaust aging was generally important for all the buses (79% showed an average EFPM:AGED/EFPM:FRESH ratio >10) and fuel types tested, suggesting an important nonfuel dependent source. The results suggest that the potential for forming secondary mass should be considered in future fuel shifts, since the environmental impact is different when only considering the primary emissions.


Assuntos
Poluentes Atmosféricos , Corrida , Biocombustíveis , Veículos Automotores , Gás Natural , Emissões de Veículos
7.
J Phys Chem A ; 122(18): 4470-4480, 2018 May 10.
Artigo em Inglês | MEDLINE | ID: mdl-29659281

RESUMO

The OH-initiated atmospheric degradation of tert-butylamine (tBA), (CH3)3CNH2, was investigated in a detailed quantum chemistry study and in laboratory experiments at the European Photoreactor (EUPHORE) in Spain. The reaction was found to mainly proceed via hydrogen abstraction from the amino group, which in the presence of nitrogen oxides (NO x), generates tert-butylnitramine, (CH3)3CNHNO2, and acetone as the main reaction products. Acetone is formed via the reaction of tert-butylnitrosamine, (CH3)3CNHNO, and/or its isomer tert-butylhydroxydiazene, (CH3)3CN═NOH, with OH radicals, which yield nitrous oxide (N2O) and the (CH3)3C radical. The latter is converted to acetone and formaldehyde. Minor predicted and observed reaction products include formaldehyde, 2-methylpropene, acetamide and propan-2-imine. The reaction in the EUPHORE chamber was accompanied by strong particle formation which was induced by an acid-base reaction between photochemically formed nitric acid and the reagent amine. The tert-butylaminium nitrate salt was found to be of low volatility, with a vapor pressure of 5.1 × 10-6 Pa at 298 K. The rate of reaction between tert-butylamine and OH radicals was measured to be 8.4 (±1.7) × 10-12 cm3 molecule-1 s-1 at 305 ± 2 K and 1015 ± 1 hPa.

8.
J Phys Chem A ; 121(35): 6614-6619, 2017 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-28792755

RESUMO

Water and organic molecules are omnipresent in the environment, and their interactions are of central importance in many Earth system processes. Here we investigate molecular-level interactions between water and a nopinone surface using an environmental molecular beam (EMB) technique. Nopinone is a major reaction product formed during oxidation of ß-pinene, a prominent compound emitted by coniferous trees, which has been found in both the gas and particle phases of atmospheric aerosol. The EMB method enables detailed studies of the dynamics and kinetics of D2O molecules interacting with a solid nopinone surface at 202 K. Hyperthermal collisions between water and nopinone result in efficient trapping of water molecules, with a small fraction that scatter inelastically after losing 60-80% of their incident kinetic energy. While the majority of the trapped molecules rapidly desorb with a time constant τ less than 10 µs, a substantial fraction (0.32 ± 0.09) form strong bonds with the nopinone surface and remain in the condensed phase for milliseconds or longer. The interactions between water and nopinone are compared to results for recently studied water-alcohol and water-acetic acid systems, which display similar collision dynamics but differ with respect to the kinetics of accommodated water. The results contribute to an emerging surface science-based view and molecular-level description of organic aerosols in the atmosphere.

9.
Sci Rep ; 6: 35038, 2016 10 13.
Artigo em Inglês | MEDLINE | ID: mdl-27733773

RESUMO

Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.

10.
Proc Natl Acad Sci U S A ; 113(6): 1516-21, 2016 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-26811465

RESUMO

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

12.
J Phys Chem B ; 118(47): 13427-34, 2014 Nov 26.
Artigo em Inglês | MEDLINE | ID: mdl-25139130

RESUMO

The detailed interactions of nitrogen oxides with ice are of fundamental interest and relevance for chemistry in cold regions of the atmosphere. Here, the interactions of NO, NO2, N2O4, and N2O5 with ice surfaces at temperatures between 93 and 180 K are investigated with molecular beam techniques. Surface collisions are observed to result in efficient transfer of kinetic energy and trapping of molecules on the ice surfaces. NO and NO2 rapidly desorb from pure ice with upper bounds for the surface binding energies of 0.16 ± 0.02 and 0.26 ± 0.03 eV, respectively. Above 150 K, N2O4 desorption follows first-order kinetics and is well described by the Arrhenius parameters Ea = 0.39 ± 0.04 eV and A = 10((15.4±1.2)) s(-1), while a stable N2O4 adlayer is formed at lower temperatures. A fraction of incoming N2O5 reacts to form HNO3 on the ice surface. The N2O5 desorption rates are substantially lower on pure water ice (Arrhenius parameters: Ea = 0.36 ± 0.02 eV; A = 10((15.3±0.7)) s(-1)) than on HNO3-covered ice (Ea = 0.24 ± 0.02 eV; A = 10((11.5±0.7)) s(-1)). The N2O5 desorption kinetics also sensitively depend on the sub-monolayer coverage of HNO3, with a minimum in N2O5 desorption rate at a low but finite coverage of HNO3. The studies show that none of the systems with resolvable desorption kinetics undergo ordinary desorption from ice, and instead desorption likely involves two or more surface states, with additional complexity added by coadsorbed molecules.

13.
Environ Sci Technol ; 48(11): 6168-76, 2014 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-24810838

RESUMO

Formation and evolution of secondary organic aerosols (SOA) from biogenic VOCs influences the Earth's radiative balance. We have examined the photo-oxidation and aging of boreal terpene mixtures in the SAPHIR simulation chamber. Changes in thermal properties and chemical composition, deduced from mass spectrometric measurements, were providing information on the aging of biogenic SOA produced under ambient solar conditions. Effects of precursor mixture, concentration, and photochemical oxidation levels (OH exposure) were evaluated. OH exposure was found to be the major driver in the long term photochemical transformations, i.e., reaction times of several hours up to days, of SOA and its thermal properties, whereas the initial concentrations and terpenoid mixtures had only minor influence. The volatility distributions were parametrized using a sigmoidal function to determine TVFR0.5 (the temperature yielding a 50% particle volume fraction remaining) and the steepness of the volatility distribution. TVFR0.5 increased by 0.3±0.1% (ca. 1 K), while the steepness increased by 0.9±0.3% per hour of 1×10(6) cm(-3) OH exposure. Thus, aging reduces volatility and increases homogeneity of the vapor pressure distribution, presumably because highly volatile fractions become increasingly susceptible to gas phase oxidation, while less volatile fractions are less reactive with gas phase OH.


Assuntos
Poluentes Atmosféricos/química , Terpenos/química , Aerossóis/análise , Aerossóis/química , Poluentes Atmosféricos/análise , Gases/química , Oxirredução , Processos Fotoquímicos , Terpenos/análise , Volatilização
14.
J Phys Chem A ; 117(40): 10346-58, 2013 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-24001129

RESUMO

The influence of water and radicals on SOAs produced by ß-pinene ozonolysis was investigated at 298 and 288 K using a laminar flow reactor. A volatility tandem differential mobility analyzer (VTDMA) was used to measure the evaporation of the SOA, enabling the parametrization of its volatility properties. The parameters extracted included the temperature at which 50% of the aerosol had evaporated (T(VFR0.5)) and the slope factor (S(VFR)). An increase in S(VFR) indicates a broader distribution of vapor pressures for the aerosol constituents. Reducing the reaction temperature increased S(VFR) and decreased T(VFR0.5) under humid conditions but had less effect on T(VFR0.5) under dry conditions. In general, higher water concentrations gave lower T(VFR0.5) values, more negative S(VFR) values, and a reduction in total SOA production. The radical conditions were changed by introducing OH scavengers to generate systems with and without OH radicals and with different [HO2]/[RO2] ratios. The presence of a scavenger and lower [HO2]/[RO2] ratio reduced SOA production. Observed changes in S(VFR) values could be linked to the more complex chemistry that occurs in the absence of a scavenger and indicated that additional HO2 chemistry gives products with a wider range of vapor pressures. Updates to existing ozonolysis mechanisms with routes that describe the observed responses to water and radical conditions for monoterpenes with endocyclic and exocyclic double bonds are discussed.


Assuntos
Poluentes Atmosféricos/química , Compostos Bicíclicos com Pontes/química , Monoterpenos/química , Ozônio/química , Água/química , Aerossóis , Monoterpenos Bicíclicos , Depuradores de Radicais Livres/química , Umidade , Radical Hidroxila/antagonistas & inibidores , Radical Hidroxila/química , Temperatura , Volatilização
15.
Environ Sci Technol ; 47(2): 773-80, 2013 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-23163334

RESUMO

In this study nanoparticle emissions have been characterized onboard a ship with focus on number, size, and volatility. Measurements were conducted on one of the ship's four main 12,600 kW medium-speed diesel engines which use low sulfur marine residual fuel and have a Selective Catalytic Reduction (SCR) system for NO(X) abatement. The particles were measured after the SCR with an engine exhaust particle sizer spectrometer (EEPS), giving particle number and mass distributions in the size range of 5.6-560 nm. The thermal characteristics of the particles were analyzed using a volatility tandem DMA system (VTDMA). A dilution ratio of 450-520 was used which is similar to the initial real-world dilution. At a stable engine load of 75% of the maximum rated power, and after dilution and cooling of the exhaust gas, there was a bimodal number size distribution, with a major peak at ∼10 nm and a smaller peak at around 30-40 nm. The mass distribution peaked around 20 nm and at 50-60 nm. The emission factor for particle number, EF(PN), for an engine load of 75% in the open-sea was found to be 10.4 ± 1.6 × 10(16) (kg fuel)(-1) and about 50% of the particles by number were found to have a nonvolatile core at 250 °C. Additionally, 20 nm particles consist of ∼40% of nonvolatile material by volume (evaporative temperature 250 °C), while the particles with a particle diameter <10 nm evaporate completely at a temperature of 130-150 °C. Emission factors for NO(X), CO, and CO(2) for an engine load of 75% in the open-sea were determined to 4.06 ± 0.3 g (kg fuel)(-1), 2.15 ± 0.06 g (kg fuel)(-1), and 3.23 ± 0.08 kg (kg fuel)(-1), respectively. This work contributes to an improved understanding of particle emissions from shipping using modern pollution reduction measures such as SCR and fuel with low sulfur content.


Assuntos
Gasolina/análise , Nanopartículas/análise , Material Particulado/análise , Navios/instrumentação , Emissões de Veículos/análise , Óxido Nítrico/química , Tamanho da Partícula , Enxofre/análise , Dióxido de Enxofre/química , Ureia/química , Volatilização
16.
Environ Sci Technol ; 46(21): 11660-9, 2012 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-22985264

RESUMO

Limonene has a strong tendency to form secondary organic aerosol (SOA) in the atmosphere and in indoor environments. Initial oxidation occurs mainly via ozone or OH radical chemistry. We studied the effect of O(3) concentrations with or without a OH radical scavenger (2-butanol) on the SOA mass and thermal characteristics using the Gothenburg Flow Reactor for Oxidation Studies at Low Temperatures and a volatility tandem differential mobility analyzer. The SOA mass using 15 ppb limonene was strongly dependent on O(3) concentrations and the presence of a scavenger. The SOA volatility in the presence of a scavenger decreased with increasing levels of O(3), whereas without a scavenger, there was no significant change. A chemical kinetic model was developed to simulate the observations using vapor pressure estimates for compounds that potentially contributed to SOA. The model showed that the product distribution was affected by changes in both OH and ozone concentrations, which partly explained the observed changes in volatility, but was strongly dependent on accurate vapor pressure estimation methods. The model-experiment comparison indicated a need to consider organic peroxides as important SOA constituents. The experimental findings could be explained by secondary condensed-phase ozone chemistry, which competes with OH radicals for the oxidation of primary unsaturated products.


Assuntos
Butanóis/química , Cicloexenos/química , Radical Hidroxila/química , Oxidantes/química , Ozônio/química , Terpenos/química , Aerossóis , Simulação por Computador , Limoneno , Modelos Químicos , Temperatura , Volatilização , Água/química
17.
J Environ Monit ; 14(9): 2488-96, 2012 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-22858604

RESUMO

Ultrafine particles have a significant detrimental effect on both human health and climate. In order to abate this problem, it is necessary to identify the sources of ultrafine particles. A parameterisation method is presented for estimating the levels of traffic-emitted ultrafine particles in terms of variables describing the ambient conditions. The method is versatile and could easily be applied to similar datasets in other environments. The data used were collected during a four-week period in February 2005, in Gothenburg, as part of the Göte-2005 campaign. The specific variables tested were temperature (T), relative humidity (RH), carbon monoxide concentration (CO), and the concentration of particles up to 10 µm diameter (PM(10)); all indicators are of importance for aerosol processes such as coagulation and gas-particle partitioning. These variables were selected because of their direct effect on aerosol processes (T and RH) or as proxies for aerosol surface area (CO and PM(10)) and because of their availability in local monitoring programmes, increasing the usability of the parameterization. Emission factors are presented for 10-100 nm particles (ultrafine particles; EF(ufp)), for 10-40 nm particles (EF(10-40)), and for 40-100 nm particles (EF(40-100)). For EF(40-100) no effect of ambient conditions was found. The emission factor equations are calculated based on an emission factor for NO(x) of 1 g km(-1), thus the particle emission factors are easily expressed in units of particles per gram of NO(x) emitted. For 10-100 nm particles the emission factor is EF(ufp) = 1.8 × 10(15) × (1 - 0.095 × CO - 3.2 × 10(-3) × T) particles km(-1). Alternative equations for the EFs in terms of T and PM(10) concentration are also presented.


Assuntos
Poluentes Atmosféricos/análise , Poluição do Ar/estatística & dados numéricos , Monitoramento Ambiental , Material Particulado/análise , Emissões de Veículos/análise , Tamanho da Partícula
18.
Proc Natl Acad Sci U S A ; 109(34): 13503-8, 2012 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-22869714

RESUMO

The Multiple Chamber Aerosol Chemical Aging Study (MUCHACHAS) tested the hypothesis that hydroxyl radical (OH) aging significantly increases the concentration of first-generation biogenic secondary organic aerosol (SOA). OH is the dominant atmospheric oxidant, and MUCHACHAS employed environmental chambers of very different designs, using multiple OH sources to explore a range of chemical conditions and potential sources of systematic error. We isolated the effect of OH aging, confirming our hypothesis while observing corresponding changes in SOA properties. The mass increases are consistent with an existing gap between global SOA sources and those predicted in models, and can be described by a mechanism suitable for implementation in those models.


Assuntos
Aerossóis/química , Compostos Orgânicos/química , Atmosfera , Radicais Livres , Radical Hidroxila , Espectrometria de Massas/métodos , Modelos Químicos , Oxigênio/química , Ozônio , Reprodutibilidade dos Testes , Solventes/química , Raios Ultravioleta
19.
J Phys Chem A ; 115(42): 11671-7, 2011 Oct 27.
Artigo em Inglês | MEDLINE | ID: mdl-21910406

RESUMO

Amines are widely used and originate from both anthropogenic and natural sources. Recently, there is, in addition, a raised concern about emissions of small amines formed as degradation products of the more complex amines used in CO(2) capture and storage systems. Amines are bases and can readily contribute to aerosol mass and number concentration via acid-base reactions but are also subject to gas phase oxidation forming secondary organic aerosols. To provide more insight into the atmospheric fate of the amines, this paper addresses the volatility properties of aminium nitrates suggested to be produced in the atmosphere from acid-base reactions of amines with nitric acid. The enthalpy of vaporization has been determined for the aminium nitrates of mono-, di-, trimethylamine, ethylamine, and monoethanolamine. The enthalpy of vaporization was determined from volatility measurements of laboratory generated aerosol nanoparticles using a volatility tandem differential mobility analyzer set up. The determined enthalpy of vaporization for aminium nitrates range from 54 up to 74 kJ mol(-1), and the calculated vapor pressures at 298 K are around 10(-4) Pa. These values indicate that aminium nitrates can take part in gas-to-particle partitioning at ambient conditions and have the potential to nucleate under high NO(x) conditions, e.g., in combustion plumes.


Assuntos
Aerossóis/química , Poluentes Atmosféricos/química , Aminas/química , Atmosfera/química , Monitoramento Ambiental/métodos , Nanopartículas/química , Atmosfera/análise , Gases , Nitratos/química , Ácido Nítrico/química , Óxidos de Nitrogênio/química , Oxirredução , Tamanho da Partícula , Termodinâmica , Volatilização
20.
J Phys Chem A ; 114(13): 4586-94, 2010 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-20235543

RESUMO

The enthalpy of sublimation has been determined for nine carboxylic acids, two cyclic (pinonic and pinic acid) and seven straight-chain dicarboxylic acids (C(4) to C(10)). The enthalpy of sublimation was determined from volatility measurements of nano aerosol particles using a volatility tandem differential mobility analyzer (VTDMA) set-up. Compared to the previous use of a VTDMA, this novel method gives enthalpy of sublimation determined over an extended temperature range (DeltaT approximately 40 K). The determined enthalpy of sublimation for the straight-chain dicarboxylic acids ranged from 96 to 161 kJ mol(-1), and the calculated vapor pressures at 298 K are in the range of 10(-6)-10(-3) Pa. These values indicate that dicarboxylic acids can take part in gas-to-particle partitioning at ambient conditions and may contribute to atmospheric nucleation, even though homogeneous nucleation is unlikely. To obtain consistent results, some experimental complications in producing nanosized crystalline aerosol particles were addressed. It was demonstrated that pinonic acid "used as received" needed a further purification step before being suspended as a nanoparticle aerosol. Furthermore, it was noted from distinct differences in thermal properties that aerosols generated from pimelic acid solutions gave two types of particles. These two types were attributed to crystalline and amorphous configurations, and based on measured thermal properties, the enthalpy of vaporization was 127 kJ mol(-1) and that of sublimation was 161 kJ mol(-1). This paper describes a new method that is complementary to other similar methods and provides an extension of existing experimental data on physical properties of atmospherically relevant compounds.


Assuntos
Aerossóis/química , Atmosfera/química , Ácidos Dicarboxílicos/química , Aerossóis/análise , Poluentes Atmosféricos/análise , Poluentes Atmosféricos/química , Ácidos Dicarboxílicos/análise , Ácidos Graxos/análise , Ácidos Graxos/química , Estrutura Molecular , Ácidos Pimélicos/análise , Ácidos Pimélicos/química , Termodinâmica , Volatilização
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