Semivolatile behavior of dicarboxylic acids and other polar organic species at a rural background site (Nylsvley, RSA)

Limbeck, Andreas; Puxbaum, Hans; Otter, L.; Scholes, Mary

doi:10.1016/s1352-2310(00)00497-0

Cited by 166 publications

(123 citation statements)

References 37 publications

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“…The products from monoterpene oxidation with molecular weights between 130 and 200 have indeed been observed in the gas and in the aerosol phase (Yu et al, 1999). The same is true for PAH and dicarboxylic acids with up to 10 carbon atoms (Fernández et al, 2002;Limbeck et al, 2001;Kavouras and Stephanou, 2002).…”

Section: Observationsmentioning

confidence: 71%

Internal mixing of the organic aerosol by gas phase diffusion of semivolatile organic compounds

Marcolli¹,

Luo²,

Peter³

et al. 2004

Atmos. Chem. Phys.

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Abstract. This paper shows that most of the so far identified constituents of the tropospheric organic particulate matter belong to a semivolatile fraction for which gas phase diffusion in the lower troposphere is sufficiently fast to establish thermodynamic equilibrium between aerosol particles. For the first time analytical expressions for this process are derived. Inspection of vapor pressure data of a series of organic substances allows a rough estimate for which substances this mixing process must be considered. As general benchmarks we conclude that for typical aerosol radii between 0.1 and 1 µm this mixing process is efficient at 25 • C for polar species with molecular weights up to 200 and for non-polar species up to 320. At −10 • C, these values are shifted to 150 for polar and to 270 for non-polar substances. The extent of mixing of this semivolatile fraction is governed by equilibrium thermodynamics, leading to a selectively, though not completely, internally mixed aerosol. The internal mixing leads to a systematic depression of melting and deliquescence points of organic and mixed organic/inorganic aerosols, thus leading to an aerosol population in the lower troposphere which is predominantly liquid.

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Section: Observationsmentioning

confidence: 71%

Internal mixing of the organic aerosol by gas phase diffusion of semivolatile organic compounds

Marcolli¹,

Luo²,

Peter³

et al. 2004

Atmos. Chem. Phys.

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“…[1][2][3][4][5][6] Mono-and di-carboxylic acids are important groups of organic compounds identified in the atmospheric particles. 7,8 Formic and acetic acids, the dominant species of organic acids in tropospheric aqueous and gaseous phases, are also ubiquitous in aerosol particles. Oxalic acid has been detected as the major fraction of water-soluble organic compounds in urban, rural and even in remote areas.…”

Section: Introductionmentioning

confidence: 99%

“…16,17 Carboxylic acids in atmospheric aerosols have been investigated in several studies. 5,8,[18][19][20][21][22][23][24][25][26] The main natural emission sources are the biosynthesis of Size-Segregated Particulate Matter and Carboxylic Acids over Urban and Rural Sites in Londrina City, Brazil J. Braz. Chem.…”

Section: Introductionmentioning

confidence: 99%

Size-segregated particulate matter and carboxylic acids over urban and rural sites in Londrina City, Brazil

Freitas¹,

Martins

Solci³

2012

J. Braz. Chem. Soc.

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Amostragens simultâneas de material particulado (PM) de 0,25 a 10 mm foram realizadas entre os meses de março e abril de 2007 em área urbana e rural de Londrina (Paraná). Os resultados indicaram que o material particulado fino (PM 2,5 ) representa uma significativa porção da massa de material particulado PM 10 (70 e 67% na área urbana e rural, respectivamente). Ácidos dicarboxílicos foram encontrados em maior concentração respondendo por 78% e 69% da massa de PM 2,5 na área urbana e rural, respectivamente, sendo que o oxalato e succinato foram os mais abundantes. A distribuição de massa do oxalato em área urbana apresentou picos dominantes em 0,25-0,5 µm. A razão de massa de acetato e formato indicou as emissões veiculares primarias como fonte dominante de ácidos carboxílicos em Londrina. Além disso, análises das trajetórias indicaram a ocorrência de transporte de poluentes do estado de São Paulo para a região de estudo.Samplings of atmospheric particulate matter (PM) from 0.25 to 10 µm were performed between the months of March and April 2007, simultaneously in urban and rural areas of Londrina City (Paraná State, Brazil). Results indicated that the fine fraction (PM 2.5 ) represents a significant portion of the PM 10 mass (70 and 67% in urban and rural areas, respectively). Dicarboxylic acids were found in larger concentration, contributing to the PM 2.5 fraction with 78% in urban and 69% in rural areas, being oxalate and succinate the most abundant species. Mass size distribution of oxalate in urban site was presented as the dominant mode, with peaks at 0.25-0.5 µm. Acetate-to-formate mass ratio indicated the primary vehicular emissions as dominant source of carboxylic acids in Londrina. Moreover, backward trajectories indicated the transport of pollutants from São Paulo State to Londrina region.Keywords: size-segregated particulate matter, carboxylic acids, PM 2.5 , urban and rural aerosols IntroductionThe occurrence and abundance of carboxylic acids in atmospheric particulate matter (PM) depend on meteorological conditions and characteristics of the ambient. The carboxylic acids represent a major fraction of the organic acids present in the atmospheric particulate matter. Among them, the oxalic acid has been the main species, followed by succinic and malonic acids. [1][2][3][4][5][6] Mono-and di-carboxylic acids are important groups of organic compounds identified in the atmospheric particles. 7,8 Formic and acetic acids, the dominant species of organic acids in tropospheric aqueous and gaseous phases, are also ubiquitous in aerosol particles. Oxalic acid has been detected as the major fraction of water-soluble organic compounds in urban, rural and even in remote areas. [3][4][5][6] Since carboxylic acids are highly water-soluble, they have the potential to modify the hygroscopic properties of atmospheric particles, including their ambient size and cloud condensation nuclei activity. 9,10 Weak organic acids could contribute ca. 40 and 60% to the free acidity in precipitation in urban and remote areas, respe...

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“…Dicarboxylic acids are present in various concentrations in different terrestrial environments, e.g. marine, rural, and urban (Kawamura et al, 2005;Yu and Fraser, 2004;Limbeck et al, 2001), and their formation in the atmosphere is likely due to photochemical reactions in the gaseous phase involving VOCs (in particular aliphatic and aromatic hydrocarbons) of biogenic and anthropogenic origin. In particular, they play an important role on physical-chemical reactions involving aerosol particles that may be gathered in agglomerates (submicron-sized), and represent an important component of the atmospheric aerosol particles, both in remote and urban areas (Rohrl and Lammel, 2001).…”

Section: Introductionmentioning

confidence: 99%

Piezoelectric crystal microbalance measurements of enthalpy of sublimation of C<sub>2</sub>–C<sub>9</sub> dicarboxylic acids

et al. 2016

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Abstract. We present here a novel experimental set-up that is able to measure the enthalpy of sublimation of a given compound by means of piezoelectric crystal microbalances (PCMs). The PCM sensors have already been used for space measurements, such as for the detection of organic and nonorganic volatile species and refractory materials in planetary environments. In Earth atmospherics applications, PCMs can be also used to obtain some physical-chemical processes concerning the volatile organic compounds (VOCs) present in atmospheric environments. The experimental set-up has been developed and tested on dicarboxylic acids. In this work, a temperature-controlled effusion cell was used to sublimate VOC, creating a molecular flux that was collimated onto a cold PCM. The VOC recondensed onto the PCM quartz crystal, allowing the determination of the deposition rate. From the measurements of deposition rates, it has been possible to infer the enthalpy of sublimation of adipic acid, i.e. H sub : 141.6 ± 0.8 kJ mol −1 , succinic acid, i.e. 113.3 ± 1.3 kJ mol −1 , oxalic acid, i.e. 62.5 ± 3.1 kJ mol −1 , and azelaic acid, i.e. 124.2 ± 1.2 kJ mol −1 . The results obtained show an accuracy of 1 % for succinic, adipic, and azelaic acid and within 5 % for oxalic acid and are in very good agreement with previous works (within 6 % for adipic, succinic, and oxalic acid and within 11 % or larger for azelaic acid).

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Semivolatile behavior of dicarboxylic acids and other polar organic species at a rural background site (Nylsvley, RSA)

Cited by 166 publications

References 37 publications

Internal mixing of the organic aerosol by gas phase diffusion of semivolatile organic compounds

Internal mixing of the organic aerosol by gas phase diffusion of semivolatile organic compounds

Size-segregated particulate matter and carboxylic acids over urban and rural sites in Londrina City, Brazil

Piezoelectric crystal microbalance measurements of enthalpy of sublimation of C<sub>2</sub>–C<sub>9</sub> dicarboxylic acids

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Semivolatile behavior of dicarboxylic acids and other polar organic species at a rural background site (Nylsvley, RSA)

Cited by 166 publications

References 37 publications

Internal mixing of the organic aerosol by gas phase diffusion of semivolatile organic compounds

Internal mixing of the organic aerosol by gas phase diffusion of semivolatile organic compounds

Size-segregated particulate matter and carboxylic acids over urban and rural sites in Londrina City, Brazil

Piezoelectric crystal microbalance measurements of enthalpy of sublimation of C&lt;sub&gt;2&lt;/sub&gt;–C&lt;sub&gt;9&lt;/sub&gt; dicarboxylic acids

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Piezoelectric crystal microbalance measurements of enthalpy of sublimation of C<sub>2</sub>–C<sub>9</sub> dicarboxylic acids