Special Issue "Physical Chemistry of the Air-Water Interface"

A special issue of Atmosphere (ISSN 2073-4433). This special issue belongs to the section "Biosphere/Hydrosphere/Land - Atmosphere Interactions".

Deadline for manuscript submissions: closed (15 October 2018)

Special Issue Editor

Guest Editor
Prof. Dr. Agustin J. Colussi

Linde Center for Global Environmental Science, California Institute of Technology, Pasadena, CA 91125, USA
Website | E-Mail
Interests: interfacial Criegee chemistry; heterogeneous chemistry of China Haze Events; long-range ion–ion interactions at the air–water interface; properties of percolating hydrogen-bonding networks on aqueous surfaces; interfacial Fenton chemistry on aqueous organic aerosols

Special Issue Information

Dear Colleagues,

Interfacial water is not thin ‘water’. In the steep water density gradient present at the air–water interface (AWI), extreme anisotropy coexists with a hydrogen-bonding network constrained by the lack of inversion symmetry. These features give rise to unprecedented, unanticipated and often unimagined phenomena from what we know about bulk water. The composition of interfacial layers can also be very different from that of the bulk solutions beneath. The fascinating physical chemistry associated with these observations, however, will be not just another frontier research topic because it matters to what happens on the aerial surfaces of lungs, oceans, clouds and atmospheric aerosols. Understanding what determines the interfacial propensities of ions and molecules, how the interfacial hydrogen-bonding network mediates specific interactions between distant solutes, and how decreased hydration influences equilibria, reactivity and selectivity at the AWI are some of the outstanding issues in this field. Awareness that the AWI may appear different when probed from above and below the surface should inform the conclusions derived from future experiments. Approaches based on molecular dynamic calculations should deal with and possibly account for the collective, long-range interactions apparent in both bulk and interfacial water. Fundamental new concepts are likely to emerge from these studies.

Prof. Dr. Agustin J. Colussi
Guest Editor

Manuscript Submission Information

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Keywords

  • Non-linear surface spectroscopy
  • Online electrospray ionization mass spectrometry
  • Cooperative effects in water
  • Hydrogen bonding in interfacial water
  • Interfacial atmospheric chemistry
  • Interfacial chemistry of lung epithelial fluids
  • Chemical equilibria in interfacial water
  • Ion hydration in interfacial water

Published Papers (3 papers)

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Research

Open AccessArticle Night-Time Oxidation of a Monolayer Model for the Air–Water Interface of Marine Aerosols—A Study by Simultaneous Neutron Reflectometry and in Situ Infra-Red Reflection Absorption Spectroscopy (IRRAS)
Atmosphere 2018, 9(12), 471; https://doi.org/10.3390/atmos9120471
Received: 12 September 2018 / Revised: 12 November 2018 / Accepted: 24 November 2018 / Published: 30 November 2018
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Abstract
This paper describes experiments on the ageing of a monolayer model for the air–water interface of marine aerosols composed of a typical glycolipid, galactocerebroside (GCB). Lipopolysaccharides have been observed in marine aerosols, and GCB is used as a proxy for these more complex
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This paper describes experiments on the ageing of a monolayer model for the air–water interface of marine aerosols composed of a typical glycolipid, galactocerebroside (GCB). Lipopolysaccharides have been observed in marine aerosols, and GCB is used as a proxy for these more complex lipopolysaccharides. GCB monolayers are investigated as pure films, as mixed films with palmitic acid, which is abundant in marine aerosols and forms a stable attractively mixed film with GCB, particularly with divalent salts present in the subphase, and as mixed films with palmitoleic acid, an unsaturated analogue of palmitic acid. Such mixed films are more realistic models of atmospheric aerosols than simpler single-component systems. Neutron reflectometry (NR) has been combined in situ with Fourier transform infra-red reflection absorption spectroscopy (IRRAS) in a pioneering analysis and reaction setup designed by us specifically to study mixed organic monolayers at the air–water interface. The two techniques in combination allow for more sophisticated observation of multi-component monolayers than has previously been possible. The structure at the air–water interface was also investigated by complementary Brewster angle microscopy (BAM). This study looks specifically at the oxidation of the organic films by nitrate radicals (NO3•), the key atmospheric oxidant present at night. We conclude that NO3• oxidation cannot fully remove a cerebroside monolayer from the surface on atmospherically relevant timescales, leaving its saturated tail at the interface. This is true for pure and salt water subphases, as well as for single- and two-component films. The behaviour of the unsaturated tail section of the molecule is more variable and is affected by interactions with co-deposited species. Most surprisingly, we found that the presence of CaCl2 in the subphase extends the lifetime of the unsaturated tail substantially—a new explanation for longer residence times of materials in the atmosphere compared to lifetimes based on laboratory studies of simplified model systems. It is thus likely that aerosols produced from the sea-surface microlayer at night will remain covered in surfactant molecules on atmospherically relevant timescales with impact on the droplet’s surface tension and on the transport of chemical species across the air–water interface. Full article
(This article belongs to the Special Issue Physical Chemistry of the Air-Water Interface)
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Open AccessArticle Spectroscopic BIL-SFG Invariance Hides the Chaotropic Effect of Protons at the Air-Water Interface
Atmosphere 2018, 9(10), 396; https://doi.org/10.3390/atmos9100396
Received: 13 September 2018 / Revised: 1 October 2018 / Accepted: 3 October 2018 / Published: 11 October 2018
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Abstract
The knowledge of the water structure at the interface with the air in acidic pH conditions is of utmost importance for chemistry in the atmosphere. We shed light on the acidic air-water (AW) interfacial structure by DFT-MD simulations of the interface containing one
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The knowledge of the water structure at the interface with the air in acidic pH conditions is of utmost importance for chemistry in the atmosphere. We shed light on the acidic air-water (AW) interfacial structure by DFT-MD simulations of the interface containing one hydronium ion coupled with theoretical SFG (Sum Frequency Generation) spectroscopy. The interpretation of SFG spectra at charged interfaces requires a deconvolution of the signal into BIL (Binding Interfacial Layer) and DL (Diffuse Layer) SFG contributions, which is achieved here, and hence reveals that even though H 3 O + has a chaotropic effect on the BIL water structure (by weakening the 2D-HBond-Network observed at the neat air-water interface) it has no direct probing in SFG spectroscopy. The changes observed experimentally in the SFG of the acidic AW interface from the SFG at the neat AW are shown here to be solely due to the DL-SFG contribution to the spectroscopy. Such BIL-SFG and DL-SFG deconvolution rationalizes the experimental SFG data in the literature, while the hydronium chaotropic effect on the water 2D-HBond-Network in the BIL can be put in perspective of the decrease in surface tension at acidic AW interfaces. Full article
(This article belongs to the Special Issue Physical Chemistry of the Air-Water Interface)
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Graphical abstract

Open AccessArticle The FuGas 2.3 Framework for Atmosphere–Ocean Coupling: Comparing Algorithms for the Estimation of Solubilities and Gas Fluxes
Atmosphere 2018, 9(8), 310; https://doi.org/10.3390/atmos9080310
Received: 8 May 2018 / Revised: 19 July 2018 / Accepted: 2 August 2018 / Published: 9 August 2018
Cited by 1 | PDF Full-text (2005 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Accurate estimates of the atmosphere–ocean fluxes of greenhouse gases and dimethyl sulphide (DMS) have great importance in climate change models. A significant part of these fluxes occur at the coastal ocean which, although much smaller than the open ocean, have more heterogeneous conditions.
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Accurate estimates of the atmosphere–ocean fluxes of greenhouse gases and dimethyl sulphide (DMS) have great importance in climate change models. A significant part of these fluxes occur at the coastal ocean which, although much smaller than the open ocean, have more heterogeneous conditions. Hence, Earth System Modelling (ESM) requires representing the oceans at finer resolutions which, in turn, requires better descriptions of the chemical, physical and biological processes. The standard formulations for the solubilities and gas transfer velocities across air–water surfaces are 36 and 24 years old, and new alternatives have emerged. We have developed a framework combining the related geophysical processes and choosing from alternative formulations with different degrees of complexity. The framework was tested with fine resolution data from the European coastal ocean. Although the benchmark and alternative solubility formulations generally agreed well, their minor divergences yielded differences of up to 5.8% for CH4 dissolved at the ocean surface. The transfer velocities differ strongly (often more than 100%), a consequence of the benchmark empirical wind-based formulation disregarding significant factors that were included in the alternatives. We conclude that ESM requires more comprehensive simulations of atmosphere–ocean interactions, and that further calibration and validation is needed for the formulations to be able to reproduce it. We propose this framework as a basis to update with formulations for processes specific to the air–water boundary, such as the presence of surfactants, rain, the hydration reaction or biological activity. Full article
(This article belongs to the Special Issue Physical Chemistry of the Air-Water Interface)
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