The Influence of Organic Films at the Air−Aqueous Boundary on Atmospheric Processes

Donaldson, D. J.; Vaida, Veronica

doi:10.1021/cr040367c

Cited by 339 publications

(480 citation statements)

References 309 publications

Supporting

Mentioning

474

Contrasting

Order By: Relevance

“…200,201 Some involve relatively thick (several mm) organic films on solid substrates, while others use monolayers on liquid solutions or on solid substrates. Self-assembled monolayers (SAMs) are particularly appealing as a model system because there are …”

Section: Oxidation Of Surface Organicsmentioning

confidence: 99%

Reactions at surfaces in the atmosphere: integration of experiments and theory as necessary (but not necessarily sufficient) for predicting the physical chemistry of aerosols

Finlayson-Pitts

2009

Phys. Chem. Chem. Phys.

231

272

View full text Add to dashboard Cite

show abstract

Section: Oxidation Of Surface Organicsmentioning

confidence: 99%

Reactions at surfaces in the atmosphere: integration of experiments and theory as necessary (but not necessarily sufficient) for predicting the physical chemistry of aerosols

Finlayson-Pitts

2009

Phys. Chem. Chem. Phys.

231

272

View full text Add to dashboard Cite

show abstract

“…[13] The air-water interface, having different chemical, physical and biological properties from subsurface waters, plays a significant role in biogeochemical processes on a global scale, a role that needs to be better understood for fundamental research on marine chemistry. [15] Sea spray aerosol has been shown to comprise more than just sodium chloride; it contains other inorganic salts as well as biologically produced organic species. [16] While the majority of submicrometre SSA particles contain mostly sea salts (i.e.…”

Section: Introductionmentioning

confidence: 99%

Impact of anions on the surface organisation of lipid monolayers at the air–water interface

Wang

2017

Environ. Chem.

View full text Add to dashboard Cite

Environmental context. Lipids released from lysis of phytoplankton cells are enriched in the sea surface microlayer. Such surface-active organics can be transferred through bursting bubbles to sea-spray aerosols where they can influence atmospheric chemistry. The results presented here suggest that phospholipids combine more readily with SO 4 2À than with Br À , leading to enrichment of organic-coated sulfate salts in marine aerosols.Abstract. Inorganic salts and organic matter are known to be present at higher levels in the sea surface microlayer and marine aerosols; however, the impact of common anions on their surface properties is not well understood. Here, a 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) monolayer was enriched with the sodium and ammonium salts of different anions (Br À , Cl À , NO 3 À , SO 4 2À , CH 3 COO À , and HCO 3 À ), and the effects on the surface properties of the monolayer were investigated. The monolayer phase behaviour and the structure of the lipid phases were studied by surface pressure-area (p-A) isotherms and infrared reflection-absorption spectroscopy (IRRAS). The presence of salts in the subphase was found to increase the surface pressure of the DPPC monolayer at a fixed area per molecule. The effect of the anions follows the order of the Hofmeister series. The higher concentration of salt solution caused the p-A isotherm to shift to larger area. The IRRAS spectra demonstrate that the ordering of the DPPC molecules in the liquid condensed phase remains essentially unaffected, even at higher electrolyte concentrations. DPPC molecules combined with SO 4 2À could be transferred from the ocean to sea spray aerosol. The present study finds that the anions have significant influence on the surface organisation and, consequently, the interfacial properties, of the surface-active species at the air-water interface, a finding that has further implications for atmospheric aerosol nucleation.

show abstract

“…In addition, organic molecules serve as cloud condensation nuclei [14][15][16] , and nucleation due to sulphuric acid particles is enhanced by the presence of organic compounds [17][18][19] . Therefore, the effect of organic layers on water aerosols in the atmosphere has been the subject of research for several decades, for reviews on the subject see references [20][21][22] .…”

Section: Introductionmentioning

confidence: 99%

Organic molecules on the surface of water droplets – an energetic perspective

Hub

Caleman

Spoel

2012

Phys. Chem. Chem. Phys.

100

View full text Add to dashboard Cite

The solubility of organic molecules is a well established property, founded on decades of measurements, the results of which have been tabulated in handbooks. Under atmospheric conditions water droplets may form containing small amounts of other molecules. Such droplets typically have a very large area to volume ratio, which may shift the solvation equilibrium towards molecules residing on the droplet surface. The presence of organic molecules on droplet surfaces is extremely important for reactivity -it is well established that certain chemical reactions are more prevalent under atmospheric conditions than in bulk. Here we present a thermodynamic rationalization of the surface solvation properties of methanol, ethanol, propanoic acid, nbutylamine, diethyl ether, and neopentane based on potential of mean force (PMF) calculations -we have previously demonstrated that an energetic description is a very powerful means of disentangling the factors governing solvation (Caleman et al., Proc. Natl. Acad. Sci. U.S.A. 108 (2011) 6838-6842). All organic molecules investigated here are preferentially solvated on the surface of the droplets rather than in the inside, yet the magnitude of surface preference may differ by orders of magnitude. In order to dissect the energetic contributions that govern surface preference, we decompose the PMF into enthalpic and entropic components, and, in a second step, into contributions from water-water and solute-water interactions. The analysis demonstrates that surface preference is primarily an enthalpic effect, but the magnitude of surface preference of solutes containing large apolar groups is enhanced due to entropy. We introduce an analysis of the droplet PMFs that allows one to extrapolate the results to larger droplets. From this we can estimate the solubility of the solutes in water droplets, demonstrating that the solubility in droplets can be orders of magnitude larger than in bulk water. Our findings have implications for understanding the process of electrospray ionization, an important technique in biological mass spectrometry, since our work strongly suggests that in equilibrium biomolecules would be adsorbed on the droplet surface as well.

show abstract

The Influence of Organic Films at the Air−Aqueous Boundary on Atmospheric Processes

Cited by 339 publications

References 309 publications

Reactions at surfaces in the atmosphere: integration of experiments and theory as necessary (but not necessarily sufficient) for predicting the physical chemistry of aerosols

Reactions at surfaces in the atmosphere: integration of experiments and theory as necessary (but not necessarily sufficient) for predicting the physical chemistry of aerosols

Impact of anions on the surface organisation of lipid monolayers at the air–water interface

Organic molecules on the surface of water droplets – an energetic perspective

Contact Info

Product

Resources

About