Prospects for simulating macromolecular surfactant chemistry at the ocean–atmosphere boundary

Biogenic lipids and polymers are surveyed for their ability to adsorb at the water–air interfaces associated with bubbles, marine microlayers and particles in the overlying boundary layer. Representative ocean biogeochemical regimes are defined in order to estimate local concentrations for the major...

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Main Authors: S Elliott, S M Burrows, C Deal, X Liu, M Long, O Ogunro, L M Russell, O Wingenter
Format: Article
Language:English
Published: IOP Publishing 2014-01-01
Series:Environmental Research Letters
Subjects:
Online Access:https://doi.org/10.1088/1748-9326/9/6/064012
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author S Elliott
S M Burrows
C Deal
X Liu
M Long
O Ogunro
L M Russell
O Wingenter
author_facet S Elliott
S M Burrows
C Deal
X Liu
M Long
O Ogunro
L M Russell
O Wingenter
author_sort S Elliott
collection DOAJ
description Biogenic lipids and polymers are surveyed for their ability to adsorb at the water–air interfaces associated with bubbles, marine microlayers and particles in the overlying boundary layer. Representative ocean biogeochemical regimes are defined in order to estimate local concentrations for the major macromolecular classes. Surfactant equilibria and maximum excess are then derived based on a network of model compounds. Relative local coverage and upward mass transport follow directly, and specific chemical structures can be placed into regional rank order. Lipids and denatured protein-like polymers dominate at the selected locations. The assigned monolayer phase states are variable, whether assessed along bubbles or at the atmospheric spray droplet perimeter. Since oceanic film compositions prove to be irregular, effects on gas and organic transfer are expected to exhibit geographic dependence as well. Moreover, the core arguments extend across the sea–air interface into aerosol–cloud systems. Fundamental nascent chemical properties including mass to carbon ratio and density depend strongly on the geochemical state of source waters. High surface pressures may suppress the Kelvin effect, and marine organic hygroscopicities are almost entirely unconstrained. While bubble adsorption provides a well-known means for transporting lipidic or proteinaceous material into sea spray, the same cannot be said of polysaccharides. Carbohydrates tend to be strongly hydrophilic so that their excess carbon mass is low despite stacked polymeric geometries. Since sugars are abundant in the marine aerosol, gel-based mechanisms may be required to achieve uplift. Uncertainties distill to a global scale dearth of information regarding two dimensional kinetics and equilibria. Nonetheless simulations are recommended, to initiate the process of systems level quantification.
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spelling doaj.art-da9ad000cc8c4660bbe05fc4f187b8232023-08-09T14:46:41ZengIOP PublishingEnvironmental Research Letters1748-93262014-01-019606401210.1088/1748-9326/9/6/064012Prospects for simulating macromolecular surfactant chemistry at the ocean–atmosphere boundaryS Elliott0S M Burrows1C Deal2X Liu3M Long4O Ogunro5L M Russell6O Wingenter7Climate Ocean Sea Ice Modeling (COSIM), Los Alamos National Laboratory, MS D-401, Los Alamos, NM 87545, USAAtmospheric Science and Global Change Division, Pacific Northwest National Laboratory, 3200 Q Avenue, Richland, WA 99352, USAInternational Arctic Research Center (IARC), University of Alaska , 930 Koyukuk Drive, Fairbanks, AK 99775, USAAtmospheric Science and Global Change Division, Pacific Northwest National Laboratory, 3200 Q Avenue, Richland, WA 99352, USAAtmospheric Chemistry Modeling Group, Harvard University , 29 Oxford Street, Cambridge, MA 02138, USAChemistry Department, New Mexico Institute of Mining and Technology, 801 Leroy Place, Socorro, NM 87801, USAScripps Institution of Oceanography, University of California San Diego , 9500 Gilman Drive, La Jolla, CA 92093, USAChemistry Department, New Mexico Institute of Mining and Technology, 801 Leroy Place, Socorro, NM 87801, USABiogenic lipids and polymers are surveyed for their ability to adsorb at the water–air interfaces associated with bubbles, marine microlayers and particles in the overlying boundary layer. Representative ocean biogeochemical regimes are defined in order to estimate local concentrations for the major macromolecular classes. Surfactant equilibria and maximum excess are then derived based on a network of model compounds. Relative local coverage and upward mass transport follow directly, and specific chemical structures can be placed into regional rank order. Lipids and denatured protein-like polymers dominate at the selected locations. The assigned monolayer phase states are variable, whether assessed along bubbles or at the atmospheric spray droplet perimeter. Since oceanic film compositions prove to be irregular, effects on gas and organic transfer are expected to exhibit geographic dependence as well. Moreover, the core arguments extend across the sea–air interface into aerosol–cloud systems. Fundamental nascent chemical properties including mass to carbon ratio and density depend strongly on the geochemical state of source waters. High surface pressures may suppress the Kelvin effect, and marine organic hygroscopicities are almost entirely unconstrained. While bubble adsorption provides a well-known means for transporting lipidic or proteinaceous material into sea spray, the same cannot be said of polysaccharides. Carbohydrates tend to be strongly hydrophilic so that their excess carbon mass is low despite stacked polymeric geometries. Since sugars are abundant in the marine aerosol, gel-based mechanisms may be required to achieve uplift. Uncertainties distill to a global scale dearth of information regarding two dimensional kinetics and equilibria. Nonetheless simulations are recommended, to initiate the process of systems level quantification.https://doi.org/10.1088/1748-9326/9/6/064012marinemacromoleculessurfactants
spellingShingle S Elliott
S M Burrows
C Deal
X Liu
M Long
O Ogunro
L M Russell
O Wingenter
Prospects for simulating macromolecular surfactant chemistry at the ocean–atmosphere boundary
Environmental Research Letters
marine
macromolecules
surfactants
title Prospects for simulating macromolecular surfactant chemistry at the ocean–atmosphere boundary
title_full Prospects for simulating macromolecular surfactant chemistry at the ocean–atmosphere boundary
title_fullStr Prospects for simulating macromolecular surfactant chemistry at the ocean–atmosphere boundary
title_full_unstemmed Prospects for simulating macromolecular surfactant chemistry at the ocean–atmosphere boundary
title_short Prospects for simulating macromolecular surfactant chemistry at the ocean–atmosphere boundary
title_sort prospects for simulating macromolecular surfactant chemistry at the ocean atmosphere boundary
topic marine
macromolecules
surfactants
url https://doi.org/10.1088/1748-9326/9/6/064012
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