Uptake of formaldehyde by sulfuric acid solutions: Impact on stratospheric ozone

Tolbert, Margaret A.; Pfaff, Jeanne; Jayaweera, Indira; Prather, Michael J.

doi:10.1029/92jd02386

Cited by 31 publications

(33 citation statements)

References 27 publications

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“…Currently, there are no other measurements of reactive uptake coefficients for pinonaldehyde on any surface type. The values obtained here are generally smaller than those measured for glyoxal on aerosols [ Liggio et al , 2005] or other carbonyl species on sulfuric acid films [ Iraci and Tolbert , 1997] or bulk solutions [ Tolbert et al , 1993]. The differences between the values reported in Table 3 are consistent with the effect of aerosol acidity as described above, as the largest uptake coefficients (1.1 × 10 −3 ) were associated with the most acidic aerosols (experiment 1).…”

Section: Uptake Coefficientssupporting

confidence: 70%

Reactive uptake of pinonaldehyde on acidic aerosols

Liggio

2006

J. Geophys. Res.

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[1] The reactive uptake of pinonaldehyde, a monoterpene oxidation product, on aerosols has been studied in a reaction chamber. Monodisperse inorganic seed aerosols, consisting of acidic mixtures of (NH 4 ) 2 SO 4 and H 2 SO 4 , were exposed to gaseous pinonaldehyde for several hours within the chamber under relative humidity conditions of 3-65%. The aerosol inorganic and organic mass were quantitatively monitored in real time with an aerosol mass spectrometer (AMS) which also measured the mass spectra of the aerosols. Numerous fragments in the mass spectra were observed with masses greater than what can be accounted for by pinonaldehyde alone and have arisen from oligomerization in reactive uptake processes. The evolution of the mass spectra also revealed a progression toward larger oligomers over time. Significant organic mass was added to the aerosols in most experiments immediately upon exposure, resulting in maximum organic mass loadings from 3.5-110 mgm À3 depending on the experiments. Organic mass to seed aerosol SO 4 = ratios were also highly variable (0.06-4.75), resulting in particles ranging in composition from primarily inorganic to mostly organic. This reactive uptake was highly dependent upon the aerosol water activity, and hence acidity and did not occur on neutral (NH 4 ) 2 SO 4 aerosols suggesting that acidity is necessary. Reactive uptake coefficients (g) of pinonaldehyde were calculated by fitting a model of organic mass growth to the data. The coefficients spanned two orders of magnitude (1.2 Â 10 À5 -1.3 Â 10 À3 ) and were primarily dependent upon aerosol water activity and acidity but independent of gas phase pinonaldehyde concentrations. These coefficients indicated that the heterogeneous reactions of pinonaldehyde are of little importance as a gas phase loss mechanism but potentially of major importance as a source of secondary organic aerosols (SOA). Estimates of SOA production via pinonaldehyde, using the derived g, suggest that 1-750 ng m À3 of organic material can be formed in a short time, consistent with ambient measurements.

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Section: Uptake Coefficientssupporting

confidence: 70%

Reactive uptake of pinonaldehyde on acidic aerosols

Liggio

2006

J. Geophys. Res.

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“…However, the range of observed γ is also consistent with those for other carbonyl compounds reported in literature, on a variety of substrates. The formaldehyde/sulfuric acid system has been the most common system studied to date, with uptake coefficients measured on sulfuric acid films (γ ∼ 2 × 10 −3 ) [ Iraci and Tolbert , 1997], droplets (γ = 2.7 × 10 −3 − 2.7 × 10 −2 ) [ Jayne et al , 1996], and bulk solution (γ = 1 × 10 −2 − 8 × 10 −2 ) [ Tolbert et al , 1993]. Uptake coefficients for other carbonyls including acetaldehyde, acetone and propionaldehyde, on mineral oxide particles have also been reported (γ ∼ 10 −4 − 10 −6 ) [ Li et al , 2001] and are significantly lower.…”

Section: Resultsmentioning

confidence: 99%

“…The elevated gas phase and particle concentrations associated with such experiments make a simple extrapolation to the ambient conditions difficult. More rigorous kinetic experiments have also been performed, primarily involving the reactive uptake of carbonyl species such as formaldehyde and acetone on aqueous droplets, sulfuric acid films or bulk solution [ Duncan et al , 1999; Iraci and Tolbert , 1997; Jayne et al , 1996; Tolbert et al , 1993]. The kinetics for the reactive uptake of glyoxal onto particles more closely simulating ambient material would be a useful tool in an assessment of the atmospheric importance of this process.…”

Section: Introductionmentioning

confidence: 99%

Reactive uptake of glyoxal by particulate matter

Li²,

2005

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[1] The uptake of gaseous glyoxal onto particulate matter has been studied in laboratory experiments under conditions relevant to the ambient atmosphere using an aerosol mass spectrometer. The growth rates and reactive uptake coefficients, g, were derived by fitting a model of particle growth to the experimental data. Organic growth rates varied from 1.05 Â 10 À11 to 23.1 Â 10 À11 mg particle À1 min À1 in the presence of $5 ppb glyoxal. Uptake coefficients (g) of glyoxal varied from 8.0 Â 10 À4 to 7.3 Â 10 À3 with a median g = 2.9 Â 10 À3 , observed for (NH 4 ) 2 SO 4 seed aerosols at 55% relative humidity.Increased g values were related to increased particle acidity, indicating that acid catalysis played a role in the heterogeneous mechanism. Experiments conducted at very low relative humidity, with the potential to be highly acidic, resulted in very low reactive uptake. These uptake coefficients indicated that the heterogeneous loss of glyoxal in the atmosphere is at least as important as gas phase loss mechanisms, including photolysis and reaction with hydroxyl radicals. Glyoxal lifetime due to heterogeneous reactions under typical ambient conditions was estimated to be t het = 5-287 min. In rural and remote areas the glyoxal uptake can lead to 5-257 ng m À3 of secondary organic aerosols in 8 hours, consistent with recent ambient measurements.Citation: Liggio, J., S.-M. Li, and R. McLaren (2005), Reactive uptake of glyoxal by particulate matter,

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“…Jayne eta!. (1996) measured mass accommodation coefficients of formaldehyde by H2SO4+ H20 and H2SO4+ H20+ HNO3 over broad concentration ranges and at temperatures between 230 and 298 K. Tolbert et al (1993) studied formaldehyde uptake by 60-75 wt. % H2SO4 at considerably lower temperatures, between 208 and 233 K. Under these conditions, uptake was irreversible, with efficiencies as large as 0.08.…”

Section: Introductionmentioning

confidence: 99%

A new sulfate‐mediated reaction: Conversion of acetone to trimethylbenzene in the presence of liquid sulfuric acid

Duncan¹,

Schindler²,

Roberts³

1998

Geophysical Research Letters

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Abstract. A new heterogeneous reaction, namely the sulfate-Unfortunately, virtually all studies of H2SO4-catalyzed and mediated conversion of acetone to 4-methyl-3-penten-2-one and promoted reactions have been carried out under conditions far trimethylbenzene, is reported. The reaction products were observed in their absorbed states by Fourier transform infrared spectroscopy and in the gas phase by mass spectrometry. In addition, protonated, absorbed acetone was observed under certain conditions. The reaction exhibits a strong concentration and / or temperature dependence, with non-reactive uptake as protonated acetone dominating at low temperatures and sulfate concentrations and reactive uptake occurring above 200 K and 75 wt. % H2SO 4. Under conditions where reactive uptake occurs, the steady-state acetone loss probability is roughly 40%.removed from those in the upper troposphere: at room temperature, in concentrated (>96 wt. %) solution, and not via accommodation of the reactants from the gas phase.In this work, we present initial results of a study of the interaction of one tropospherically abundant compound, acetone [(CH3)2CO], with sulfate. The experiments were carried out on ultrathin sulfate films (--100 monolayers thick) of composition between 60 and 96 wt. % H2SO 4 and at temperatures between 180 and 250 K. Infrared spectroscopy and mass spectrometry were used to identify the absorbed and gas-phase reaction It was not possible in this study to assess the relative effects of products, respectively. temperature and concentration on the reactivity of sulfate toward acetone.

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Uptake of formaldehyde by sulfuric acid solutions: Impact on stratospheric ozone

Cited by 31 publications

References 27 publications

Reactive uptake of pinonaldehyde on acidic aerosols

Reactive uptake of pinonaldehyde on acidic aerosols

Reactive uptake of glyoxal by particulate matter

A new sulfate‐mediated reaction: Conversion of acetone to trimethylbenzene in the presence of liquid sulfuric acid

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