The formation of organic sulfate esters in the limonene ozonolysis secondary organic aerosol (SOA) under acidic conditions

Iinuma, Yoshiteru; Müller, Conny; Böge, Olaf; Gnauk, T.; Herrmann, Hartmut

doi:10.1016/j.atmosenv.2007.03.007

Cited by 141 publications

(169 citation statements)

References 41 publications

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“…For experiments without OH scavenger the effect was pronounced and the SOA yield was higher by a factor of about 2. The effects at 303 K thus resemble previous observations for α-pinene and other endocyclic terpenes Docherty et al, 2005;Iinuma et al, 2005;Jonsson et al, 2008a). At 243 K the influence of the scavenger shows the same trend but the differences in SOA yield, especially compared to the case without scavenger, seem to be smaller at low temperatures (Jonsson et al, 2008b) although Tillmann et al (2009) provide clear evidence that OH radicals are formed in the ozonolysis reaction of α-pinene even at the lowest temperatures.…”

Section: Role Of Humidity and Oh Scavengersupporting

confidence: 71%

“…There has been a considerable amount of work on aerosol yields from the ozonolysis of α-pinene or limonene near room temperature (290-303 K) e.g. (Hoffmann et al, 1997;Griffin et al, 1999a;Hoppel et al, 2001;Cocker et al, 2001;Berndt et al, 2003;Iinuma et al, 2004;Presto and Donahue, 2006;Northcross and Jang, 2007;Pathak et al, 2007a;Iinuma et al, 2007;Johnson and Marston, 2008;Shilling et al, 2008). Studies covering more extended temperature ranges are less abundant (Sheehan and Bowman, 2001;Takekawa et al, 2003;Offenberg et al, 2006;Pathak et al, 2007b).…”

Section: Introductionmentioning

confidence: 99%

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Temperature dependence of yields of secondary organic aerosols from the ozonolysis of <i>α</i>-pinene and limonene

Saathoff¹,

Naumann²,

Möhler³

et al. 2009

Atmos. Chem. Phys.

191

181

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Abstract. Secondary organic aerosol (SOA) formation has been investigated as a function of temperature and humidity for the ozone-initiated reaction of the two monoterpenes α-pinene (243-313 K) and limonene (253-313 K) using the 84.5 m 3 aerosol chamber AIDA. This paper gives an overview of the measurements done and presents parameters specifically useful for aerosol yield calculations. The ozonolysis reaction, selected oxidation products and subsequent aerosol formation were followed using several analytical techniques for both gas and condensed phase characterisation. The effective densities of the SOA were determined by comparing mass and volume size distributions to (1.25±0.10) g cm −3 for α-pinene and (1.3±0.2) g cm −3 for limonene. The detailed aerosol dynamics code COSIMA-SOA proved to be essential for a comprehensive evaluation of the experimental results and for providing parameterisations directly applicable within atmospheric models. The COSIMA-assisted analysis succeeded to reproduce the observed time evolutions of SOA total mass, number and size distributions by adjusting the following properties of two oxidation product proxies: individual yield parameters (α i ), partitioning coefficients (K i ), vapour pressures (p i ) and effective accommodation coefficients (γ i ). For these properties temperature dependences were derived and parameterised. Vapour pressures and partitioning coefficients followed classical Clausius -Clapeyron temperature dependences. From this relationship enthalpies of vaporisation were derived for the two more and less volatile product proxies of α-pinene: (59±8) kJ mol −1 and (24±9) kJ mol −1 , and limonene: (55±14) kJ mol −1 and (25±12) kJ mol −1 . The more volatile proxy components had a notably low enthalpy Correspondence to: H. Saathoff (harald.saathoff@imk.fzk.de) of vaporisation while the less volatile proxy components gave enthalpies of vaporisation comparable with those of typical products from α-pinene oxidation, e.g. pinonaldehyde and pinonic acid.

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Section: Role Of Humidity and Oh Scavengersupporting

confidence: 71%

Section: Introductionmentioning

confidence: 99%

Temperature dependence of yields of secondary organic aerosols from the ozonolysis of <i>α</i>-pinene and limonene

Saathoff¹,

Naumann²,

Möhler³

et al. 2009

Atmos. Chem. Phys.

191

181

View full text Add to dashboard Cite

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“…The characterization of SOA formation from the degradation of cyclic hydrocarbons has therefore been the focus of numerous chamber investigations over the years (e.g., Hoffmann et al, 1997;Odum et al, 1997;Griffin et al, 1999). The more recent identification of oligomers and organosulfates in SOA formed in chambers and the atmosphere (Gao et al, 2004a(Gao et al, , b, 2006Kalberer et al, 2004;Iinuma et al, 2004Iinuma et al, , 2005Iinuma et al, , 2007aTolocka et al, 2004;Baltensperger et al, 2005;Samburova et al, 2005b;Dommen et al, 2006;Surratt et al, 2006Surratt et al, , 2007aSurratt et al, , b, 2008Denkenberger et al, 2007;Gómez-González et al, 2008) has established that SOA formation from VOC degradation is not solely driven by the volatility of the gas-phase products formed, but is also influenced by the propensity of degradation products to undergo further reactions in the condensed phase, and how this depends on conditions such as water content, dissolved ions and pH. Condensed-phase reactions that increase the MW can sharply reduce the volatility distribution of the organics.…”

Section: Atmospheric Degradation Mechanisms Of Soa Precursorsmentioning

confidence: 99%

“…LC is particularly suited to high-MW species and very polar molecules, without the need for derivatization prior to analysis. LC/MS is finding increasing use in the analysis of the small polar fraction of SOA formed in simulation chamber studies (Larsen et al, 2001;Gao et al, 2004a, b;Surratt et al, 2006Surratt et al, , 2007aSurratt et al, , 2008Iinuma et al, 2007a, b;Ng et al, 2008). LC/MS analyses have also been used to indicate that sulfate as well as nitrate groups could be incorporated in SOA as outlined in Sect.…”

Section: Off-line High Complexity Soa Measurementsmentioning

confidence: 99%

The formation, properties and impact of secondary organic aerosol: current and emerging issues

et al. 2009

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Abstract. Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed.

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“…Moreover, our somewhat higher PIXE results (Figure 1, Table 3) suggest that some S was also attributable to other compounds, possibly organosulfates (Blando et al 1998;Liggio and Li 2006;Romero and Oehme 2005). These organosulfates (also called sulfate esters) can form from reactions of acidic aerosol SO [2][3][4] with carbonyls in the atmosphere (Iinuma et al 2007;Surratt et al 2007). It has been suggested that conventional inorganic SO 2-4 chemical analysis may underestimate the total SO 2-4 mass in ambient aerosols (Liggio and Li 2006).…”

Section: Aerosol Nhmentioning

confidence: 99%

Aerosol Inorganic Composition at a Tropical Site: Discrepancies Between Filter-Based Sampling and a Semi-Continuous Method

Trebs

Andreae

Elbert

et al. 2008

Aerosol Science and Technology

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The concentrations of the water-soluble inorganic aerosol species, ammonium (NH ; when filter-based samplers measured on average 40-90% less than the WAD/SJAC. The differences were not due to consistent systematic biases of the analytical techniques, but were apparently a result of prevailing environmental conditions and different sampling procedures. For the transition period and wet season, the significance of our results is reduced by a low number of data points. We argue that the observed differences are mainly attributable to (a) positive and negative filter sampling artifacts, (b) presence of organic compounds and organosulfates on filter substrates, and (c) a SJAC sampling efficiency of less than 100%.

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The formation of organic sulfate esters in the limonene ozonolysis secondary organic aerosol (SOA) under acidic conditions

Cited by 141 publications

References 41 publications

Temperature dependence of yields of secondary organic aerosols from the ozonolysis of <i>α</i>-pinene and limonene

Temperature dependence of yields of secondary organic aerosols from the ozonolysis of <i>α</i>-pinene and limonene

The formation, properties and impact of secondary organic aerosol: current and emerging issues

Aerosol Inorganic Composition at a Tropical Site: Discrepancies Between Filter-Based Sampling and a Semi-Continuous Method

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The formation of organic sulfate esters in the limonene ozonolysis secondary organic aerosol (SOA) under acidic conditions

Cited by 141 publications

References 41 publications

Temperature dependence of yields of secondary organic aerosols from the ozonolysis of &lt;i&gt;α&lt;/i&gt;-pinene and limonene

Temperature dependence of yields of secondary organic aerosols from the ozonolysis of &lt;i&gt;α&lt;/i&gt;-pinene and limonene

The formation, properties and impact of secondary organic aerosol: current and emerging issues

Aerosol Inorganic Composition at a Tropical Site: Discrepancies Between Filter-Based Sampling and a Semi-Continuous Method

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Temperature dependence of yields of secondary organic aerosols from the ozonolysis of <i>α</i>-pinene and limonene

Temperature dependence of yields of secondary organic aerosols from the ozonolysis of <i>α</i>-pinene and limonene