Henry's law and the behavior of weak acids and bases in fog and cloud

Winiwarter, Wilfried; Fierlinger, H.; Puxbaum, Hans; Facchini, M. C.; Arends, B. G.; Fuzzi, S.; Schell, D.; Kaminski, U.; Pahl, S.; Schneider, Thomas; Berner, A.; Solly, I.; Kruisz, C.

doi:10.1007/bf00696588

Cited by 51 publications

(28 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…For NH + 4 , such sub-saturation of the liquid phase was already observed in Voisin et al (2000). The subsaturation of the liquid phase is likely resulting from mass transfer limitation between gaseous and liquid phase as proposed by Ricci et al (1998) and Winiwarter et al (1994). However, we observe that for higher pH, both theoretical and measured liquid fraction of NH 3 / NH + 4 decreases.…”

Section: Monocarboxylic Acids and Nhsupporting

confidence: 70%

“…Our results show that a high pH, this contribution is lower, as expected from thermodynamics. The studies of Laj et al (1997) and Winiwarter et al (1994), showed that NH + 4 subsaturation increases with increasing pH. The pH dependence of the subsaturation could be an artifact resulting from the fact that transfer through nucleation scavenging is not pH dependent.…”

Section: Figmentioning

confidence: 96%

“…This assumption, however, does not appear to be fully supported by experimental studies in fog and cloud systems. Deviations from theoretical equilibrium of several orders of magnitude have been found for gases such as SO 2 , NH 3 or HCOOH, showing either sub-or super-saturation of the liquid phase of clouds (Facchini et al, 1992a;Facchini et al, 1992b;Keene et al, 1995;Laj et al, 1997;Munger et al, 1995;Noone et al, 1991;Rao and Collett, 1995;Richards et al, 1983;Winiwarter et al, 1988;Winiwarter et al, 1994). Such deviations are not easily explained neither by additional equilibrium nor by in-cloud formation of new compounds , nor by sampling artifact due to long integration time or droplet heterogeneity (Ricci et al, 1998, Pandis andSeinfeld, 1991;Winiwarter et al, 1992).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Contribution of gaseous and particulate species to droplet solute composition at the Puy de Dôme, France

et al. 2003

View full text Add to dashboard Cite

Abstract. Chemical reactions of dissolved gases in the liquid phase play a key role in atmospheric processes both in the formation of secondary atmospheric compounds and their wet removal rate but also in the regulation of the oxidizing capacity of the troposphere. The behavior of gaseous species and their chemical transformation in clouds are difficult to observe experimentally given the complex nature of clouds.During a winter field campaign at the summit of the Puy de Dôme (central France, 1465 m a.s.l), we have deployed an experimental set-up to provide a quantification of phase partitioning of both organic (CH 3 COOH, HCOOH, H 2 C 2 O 4 ) and inorganic (NH 3 , HNO 3 , SO 2 , HCl) species in clouds.We found that nitric and hydrochloric acids can be considered close to Henry's law equilibrium, within analytical uncertainty and instrumental errors. On another hand, for NH 3 and carboxylic acids, dissolution of material from the gas phase is kinetically limited and never reaches the equilibrium predicted by thermodynamics, resulting in significant sub-saturation of the liquid phase. On the contrary, S IV is supersaturated in the liquid phase, in addition to the presence of significant aerosol-derived S VI transferred through nucleation scavenging.Upon droplet evaporation, a significant part of most species, including S IV , tends to efficiently return back into the gas phase. Overall, gas contribution to the droplet solute concentration ranges from at least 48.5 to 98% depending on the chemical species. This is particularly important considering that aerosol scavenging efficiencies are often calculated assuming a negligible gas-phase contribution to the solute concentration. Our study emphasizes the need to account for the in-cloud interaction between particles and gases to provide an adequate modeling of multiphase chemistry systems and its impact on the atmospheric aerosol and gas phases.

show abstract

Section: Monocarboxylic Acids and Nhsupporting

confidence: 70%

Section: Figmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Contribution of gaseous and particulate species to droplet solute composition at the Puy de Dôme, France

et al. 2003

View full text Add to dashboard Cite

show abstract

“…The water fluxes were very similar for the three events, making chemical concentrations directly comparable without taking into account dilution effects. Table 1 [Winiwarter et al, 1994, and references therein). Liquid phase production will be essentially dependent on the pH of the solution and the initial gas phase concentrations, with production of HCOOH favored over that of CH3COOH [Chebbi and Carlief, 1996].…”

Section: Resultsmentioning

confidence: 99%

Biomass burning signatures in the atmosphere of central Greenland

Jaffrezo¹,

Davidson²,

Kuhns³

et al. 1998

J. Geophys. Res.

View full text Add to dashboard Cite

Abstract. Daily atmospheric concentrations of particulate oxalate measured at the Summit of the Greenland Ice Sheet are presented for the summers 1992 -1995. We believe that four episodes of elevated concentrations are due to biomass burning plumes passing over the site. In at least two cases the source regions of the fires are located in northern Canada. Further characteristics of the aerosol are examined during one of these events. A large increase of particle number concentrations in the accumulation mode can be observed, while the increase is much more limited for total particle number. The suite of chemical species enriched in the aerosol includes typical biomass burning tracers like fine K, large concentrations of ammonium, particulate formate and acetate, as well as other organic species like glycolate. The size distributions of K, oxalate, and glycolate are skewed toward the accumulation mode and exhibit the very same shape as sulfate, suggesting internal mixing of these species in the same particles. Molar ratios S/K indicate incorporation of S during transport, most probably by production of sulfate. Concentrations of these species were measured in fog samples for radiative events that occurred during the plume passage. There is a good agreement in the relative variation of concentrations between the aerosol and fog for oxalate and glycolate, while the gas phase probably dominates incorporation in the fog droplets for acetate, formate, chloride, nitrate, and sulfate (incorporated as SO2, which is further oxidized). The complexity of the transfer of the organic acids from the atmosphere to fog is underlined.

show abstract

“…Our current knowledge of cloud chemistry and composition beyond acidity and major ions remains poor. Limited observational data exist on trace metals (e.g., Cini et al 2002;Collett et al 2002;Husain et al 2004;Plessow et al 2001;Siefert et al 1998), organic species (e.g., Anastasio et al 2000;Collett et al 2002;Decesari et al 2005;Herckes et al 2007;Anastasio 2001, 2003a, b), and volatile species in clouds (Aneja 1993;Ervens et al 2003;Moore et al 2004;Valsaraj et al 1993;Winiwarter et al 1994). Detailed characterization efforts have been concentrated in a few locations such as the Central Valley of California, the East Coast Mountains in the USA, and the Po Valley in Italy.…”

Section: Introductionmentioning

confidence: 97%

The Chemistry of Intercepted Clouds in Northern Arizona during the North American Monsoon Season

Hutchings

Robinson

McIlwraith

et al. 2008

Water Air Soil Pollut

View full text Add to dashboard Cite

Cloudwater samples have been collected for the first time at a high-elevation site in the US interior Southwest. Cloud samples were collected at the summit of Mt. Elden near Flagstaff, Arizona. The samples were analyzed for pH, ionic composition, trace metals, organic carbon content, and volatile organic compounds. All of the samples showed high pH values (5.12-6.66), which appear to be the result of soil/crustal acid-neutralizing components. Ammonium and nitrate were the dominant ionic species. Organic carbon concentrations ranged from 3 to 18 mg/l. Volatile aromatic compounds (toluene, ethylbenzene, and xylenes) were detected, although they did not contribute significantly to the dissolved organic matter (<1% of dissolved organic carbon). Still, their aqueous-phase concentrations were substantially higher than equilibrium partitioning from the gas phase would suggest. Metal concentrations were high when compared to other cloud studies in remote areas. Overall, with the exception of pH, the cloud chemistry showed marked inter-event variability. The source of the variability was investigated using NOAA HYSPLIT dispersion calculations. Like the cloud composition, the air mass back trajectories differed widely from event to event, and consistently, air masses that passed over highly urbanized areas had higher trace metal, organic, and ion concentrations than more pristine air masses.

show abstract

Henry's law and the behavior of weak acids and bases in fog and cloud

Cited by 51 publications

References 31 publications

Contribution of gaseous and particulate species to droplet solute composition at the Puy de Dôme, France

Contribution of gaseous and particulate species to droplet solute composition at the Puy de Dôme, France

Biomass burning signatures in the atmosphere of central Greenland

The Chemistry of Intercepted Clouds in Northern Arizona during the North American Monsoon Season

Contact Info

Product

Resources

About