Gas‐aerosol relationships of H<sub>2</sub>SO<sub>4</sub>, MSA, and OH: Observations in the coastal marine boundary layer at Mace Head, Ireland

Berresheim, H.; Elste, T.; Tremmel, H. G.; Allen, Andrew G.; Hansson, H. C.; Rosman, K.; Maso, Miikka Dal; Mäkelä, Jyrki M.; Kulmala, Markku; O’Dowd, Colin

doi:10.1029/2000jd000229

Cited by 165 publications

(179 citation statements)

References 61 publications

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“…Thus our model predicts that under some atmospheric conditions, particle formation from MSA should be similar in magnitude to that from sulfuric acid, as indicated by the field measurements (37,38). It is noteworthy that this consistency between the model predictions and field results arises even though atmospheric concentrations of MSA are typically ppt (28,32), as assumed in the model calculations, rather than ppb, which is experimentally accessible in our system. Once new particles have been formed from MSA, they can then grow by uptake of low and semivolatile gases formed in other atmospheric processes.…”

Section: Discussionmentioning

confidence: 55%

“…Although it is known that ammonia and amines enhance particle formation from sulfuric acid (14-19, 29, 30), the effect of amines on MSA chemistry has not been reported. Their impact on atmospheric particle formation could be important, given that there are many sources of amines in air (31) and gas-phase MSA is typically 10-100% of that of gas-phase H 2 SO 4 in the coastal marine boundary layer (32,33). MSA is commonly detected in atmospheric particles (34-36), and particulate methanesulfonate, dimethylamine (DMA), and cloud condensation nuclei (CCN) activity have been observed to be highly correlated (36).…”

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confidence: 99%

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Simplified mechanism for new particle formation from methanesulfonic acid, amines, and water via experiments and ab initio calculations

Dawson

Varner

Perraud

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

187

251

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Airborne particles affect human health and significantly influence visibility and climate. A major fraction of these particles result from the reactions of gaseous precursors to generate low-volatility products such as sulfuric acid and high-molecular weight organics that nucleate to form new particles. Ammonia and, more recently, amines, both of which are ubiquitous in the environment, have also been recognized as important contributors. However, accurately predicting new particle formation in both laboratory systems and in air has been problematic. During the oxidation of organosulfur compounds, gas-phase methanesulfonic acid is formed simultaneously with sulfuric acid, and both are found in particles in coastal regions as well as inland. We show here that: (i) Amines form particles on reaction with methanesulfonic acid, (ii) water vapor is required, and (iii) particle formation can be quantitatively reproduced by a semiempirical kinetics model supported by insights from quantum chemical calculations of likely intermediate clusters.Such an approach may be more broadly applicable in models of outdoor, indoor, and industrial settings where particles are formed, and where accurate modeling is essential for predicting their impact on health, visibility, and climate.kinetics modeling | multi-component nucleation | cluster enthalpy | flow tube reactor | atmospheric nanoparticles U nderstanding how gas phase precursors lead to the formation and growth of new particles that are important for scattering light, for serving as cloud condensation or ice nuclei, and for transport deep into the lung, is one of the most pressing scientific problems (1-5). The most studied system is the conversion of gas-phase SO 2 to sulfuric acid and sulfate particles, but even in this case, models typically underestimate particle formation by an order of magnitude or more (3, 4, 6). However, an accurate predictive capability based on molecular-level understanding is critical for projecting the impacts of particles and developing optimal control strategies.Classical nucleation theory (CNT) has been used for almost a century (7, 8) to predict new particle formation. At its heart, CNT is a thermodynamics approach that assumes that the precursor clusters have bulk liquid properties such as surface tension, and that addition to and evaporation from the clusters occurs via monomers. Modifications to CNT using kinetics approaches have been described (9, 10). More recently, dynamical nucleation theory (11-13) examined intermolecular interactions and used them to obtain rate constants for the individual steps through variational transition-state theory. This theory has been applied to particle formation in relatively simple systems and clusters of relatively few molecules. Recent data from field and laboratory studies, however, suggest that multicomponent systems with multiple reaction steps are likely involved in new particle formation in the atmosphere (14-22).We report here a combination of experimental and theoretical studies of new particle fo...

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Section: Discussionmentioning

confidence: 55%

mentioning

confidence: 99%

Simplified mechanism for new particle formation from methanesulfonic acid, amines, and water via experiments and ab initio calculations

Dawson

Varner

Perraud

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

187

251

View full text Add to dashboard Cite

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“…These observations also showed that [H 2 SO 4 ] values typically were at the 10 6 -10 7 cm −3 range at noon, depending on the season. There are also measurements that have shown that [H 2 SO 4 ] can be at the 10 8 cm −3 range in the polluted environment [Bardouki et al, 2003;Berresheim et al, 2002]. While these studies were mostly ground-based or in the boundary layer, H 2 SO 4 measurements also exist for the free troposphere [Clarke et al, 1998;Weber et al, 1998] and for the upper troposphere and lower stratosphere [Lee et al, 2003].…”

Section: Introductionmentioning

confidence: 99%

Correlation of aerosol nucleation rate with sulfuric acid and ammonia in Kent, Ohio: An atmospheric observation

Erupe¹,

Benson²,

Li³

et al. 2010

J. Geophys. Res.

115

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[1] New particle formation (NPF) occurs in various atmospheric environments, and these newly formed particles have the potential to grow to cloud condensation nuclei. But at present it is unclear which chemical species are involved in aerosol nucleation and growth, in part because there are only a limited number of simultaneous measurements of aerosol precursors and aerosol size distributions. Observations of ambient aerosol size distributions, sulfuric acid, and ammonia were made for over a year in Kent, Ohio, a relatively less polluted continental environment. Particle sizes in the diameter range from 3 to 1000 nm were measured continuously through the whole year, while sulfuric acid and ammonia were measured seasonally with two chemical ionization mass spectrometers. Strong NPF events were more frequently found during the spring and fall and less frequently during the summer and winter. The median of measured sulfuric acid was higher in spring (5.2 × 10 6 cm −3 ) and summer (2.9 × 10 6 cm −3 ) than in winter (6 × 10 5 cm −3 ) and fall (5 × 10 5 cm −3 ). We have used the inverse model Particle Growth and Nucleation to derive aerosol nucleation and growth rates from the measured aerosol size distributions. Nucleation rates derived during the NPF events ranged from 1.4 to 12.9 cm −3 s −1 and were proportional to the measured sulfuric acid concentration with a power of 0.6-2.3. Our results show that sulfuric acid is an important aerosol nucleation precursor, but only a small fraction of the aerosol growth rates could be explained by the condensation of sulfuric acid alone. Ammonia mixing ratios did not have a diurnal trend but had some seasonal variations, higher in spring than in fall and winter, typically at sub-ppbv level; aerosol nucleation rates did not show a clear correlation with ammonia at least at this sub-ppbv level, mostly because the ammonia mixing ratios were nearly constant. Our observations also indicate that the role that ammonia plays in aerosol nucleation is more complicated than is currently understood by the aerosol nucleation theories.Citation: Erupe, M. E., et al. (2010), Correlation of aerosol nucleation rate with sulfuric acid and ammonia in Kent, Ohio: An atmospheric observation,

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“…However, in coastal areas, sulfuric acid does not correlate with new particle formation or tidal cycles. [1,2] The measurement of iodine in the ultrafine particle composition [3] during coastal nucleation events has focused attention on organic and inorganic emissions from seaweed as potential iodine sources. Molecular iodine [4] and CH 2 I 2 [5] are likely precursors, since they rapidly photolyze to give iodine atoms, which are converted to the IO radical by reaction with ozone.…”

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confidence: 99%

Marine Organic Halide and Isoprene Emissions Near Mace Head, Ireland

2005

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Environmental Context.Atmospheric aerosols have received increasing attention, not only because they include cloud condensation nuclei, essential for precipitation, but also because of their absorption and scattering of radiation, which may affect climate. The process of aerosol formation, however, is not well understood. This paper describes measurements of the fluxes into the atmosphere of several possible biogenic precursors to primary aerosol production. Abstract.Vertical profiles of the concentration of several alkyl halides, as well as isoprene, were made from the surface to 200 m, using a tethered balloon platform, near Mace Head, Ireland in September–October 2003. Profiles indicate a surface source of several alkyl halides. Alkyl halides have been proposed as a source of new particles in the atmosphere. Estimates of emission rates (μg m−2 h−1) were made using a flux-gradient technique for CH2Br2 (0.8), CHBr3 (6), CH2IBr (0.1), CH2I2 (0.1), and isoprene (24).

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Gas‐aerosol relationships of H₂SO₄, MSA, and OH: Observations in the coastal marine boundary layer at Mace Head, Ireland

Cited by 165 publications

References 61 publications

Simplified mechanism for new particle formation from methanesulfonic acid, amines, and water via experiments and ab initio calculations

Simplified mechanism for new particle formation from methanesulfonic acid, amines, and water via experiments and ab initio calculations

Correlation of aerosol nucleation rate with sulfuric acid and ammonia in Kent, Ohio: An atmospheric observation

Marine Organic Halide and Isoprene Emissions Near Mace Head, Ireland

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Gas‐aerosol relationships of H2SO4, MSA, and OH: Observations in the coastal marine boundary layer at Mace Head, Ireland

Cited by 165 publications

References 61 publications

Simplified mechanism for new particle formation from methanesulfonic acid, amines, and water via experiments and ab initio calculations

Simplified mechanism for new particle formation from methanesulfonic acid, amines, and water via experiments and ab initio calculations

Correlation of aerosol nucleation rate with sulfuric acid and ammonia in Kent, Ohio: An atmospheric observation

Marine Organic Halide and Isoprene Emissions Near Mace Head, Ireland

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Product

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Gas‐aerosol relationships of H₂SO₄, MSA, and OH: Observations in the coastal marine boundary layer at Mace Head, Ireland