Influence of Poly(ethylenimine) on the Monolayer of Oleic Acid at the Air/Water Interface

2000 ◽  
Vol 226 (1) ◽  
pp. 98-104 ◽  
Author(s):  
Tai Hwan Ha ◽  
Dai Kyu Kim ◽  
Myung-Un Choi ◽  
Kwan Kim
Keyword(s):  
Oleic Acid ◽  
Water Interface ◽  
Air Water Interface

scholarly journals Nighttime oxidation of surfactants at the air–water interface: effects of chain length, head group and saturation

2018 ◽  
Vol 18 (5) ◽  
pp. 3249-3268 ◽  
Author(s):  
Federica Sebastiani ◽  
Richard A. Campbell ◽  
Kunal Rastogi ◽  
Christian Pfrang
Keyword(s):  
Oleic Acid ◽  
Double Bond ◽  
Methyl Ester ◽  
Reaction Kinetics ◽  
Chain Length ◽  
Rate Coefficients ◽  
Head Group ◽  
Water Interface ◽  
Organic Monolayers ◽  
Air Water Interface

Abstract. Reactions of the key atmospheric nighttime oxidant NO3 with organic monolayers at the air–water interface are used as proxies for the ageing of organic-coated aqueous aerosols. The surfactant molecules chosen for this study are oleic acid (OA), palmitoleic acid (POA), methyl oleate (MO) and stearic acid (SA) to investigate the effects of chain length, head group and degree of unsaturation on the reaction kinetics and products formed. Fully and partially deuterated surfactants were studied using neutron reflectometry (NR) to determine the reaction kinetics of organic monolayers with NO3 at the air–water interface for the first time. Kinetic modelling allowed us to determine the rate coefficients for the oxidation of OA, POA and MO monolayers to be (2.8±0.7) × 10−8, (2.4±0.5) × 10−8and (3.3±0.6) × 10−8 cm2 molecule−1 s−1 for fitted initial desorption lifetimes of NO3 at the closely packed organic monolayers, τd, NO3, 1, of 8.1±4.0, 16±4.0 and 8.1±3.0 ns, respectively. The approximately doubled desorption lifetime found in the best fit for POA compared to OA and MO is consistent with a more accessible double bond associated with the shorter alkyl chain of POA facilitating initial NO3 attack at the double bond in a closely packed monolayer. The corresponding uptake coefficients for OA, POA and MO were found to be (2.1±0.5) × 10−3, (1.7±0.3) × 10−3 and (2.1±0.4) × 10−3, respectively. For the much slower NO3-initiated oxidation of the saturated surfactant SA we estimated a loss rate of approximately (5±1) × 10−12 cm2 molecule−1 s−1, which we consider to be an upper limit for the reactive loss, and estimated an uptake coefficient of ca. (5±1) × 10−7. Our investigations demonstrate that NO3 will contribute substantially to the processing of unsaturated surfactants at the air–water interface during nighttime given its reactivity is ca. 2 orders of magnitude higher than that of O3. Furthermore, the relative contributions of NO3 and O3 to the oxidative losses vary massively between species that are closely related in structure: NO3 reacts ca. 400 times faster than O3 with the common model surfactant oleic acid, but only ca. 60 times faster with its methyl ester MO. It is therefore necessary to perform a case-by-case assessment of the relative contributions of the different degradation routes for any specific surfactant. The overall impact of NO3 on the fate of saturated surfactants is slightly less clear given the lack of prior kinetic data for comparison, but NO3 is likely to contribute significantly to the loss of saturated species and dominate their loss during nighttime. The retention of the organic character at the air–water interface differs fundamentally between the different surfactant species: the fatty acids studied (OA and POA) form products with a yield of  ∼ 20 % that are stable at the interface while NO3-initiated oxidation of the methyl ester MO rapidly and effectively removes the organic character ( ≤ 3 % surface-active products). The film-forming potential of reaction products in real aerosol is thus likely to depend on the relative proportions of saturated and unsaturated surfactants as well as the head group properties. Atmospheric lifetimes of unsaturated species are much longer than those determined with respect to their reactions at the air–water interface, so they must be protected from oxidative attack, for example, by incorporation into a complex aerosol matrix or in mixed surface films with yet unexplored kinetic behaviour.

scholarly journals Time resolved study of hydroxyl radical oxidation of oleic acid at the air-water interface

2017 ◽  
Vol 683 ◽  
pp. 76-82 ◽  
Author(s):  
Xinxing Zhang ◽  
Kevin M. Barraza ◽  
Kathleen T. Upton ◽  
J.L. Beauchamp
Keyword(s):  
Oleic Acid ◽  
Hydroxyl Radical ◽  
Water Interface ◽  
Time Resolved ◽  
Radical Oxidation ◽  
Air Water Interface

Interaction of nitrogen dioxide (NO2) with a monolayer of oleic acid at the air–water interface – A simple proxy for atmospheric aerosol

2010 ◽  
Vol 44 (14) ◽  
pp. 1822-1825 ◽  
Author(s):  
Martin D. King ◽  
Adrian R. Rennie ◽  
Christian Pfrang ◽  
Arwel V. Hughes ◽  
Katherine C. Thompson
Keyword(s):  
Oleic Acid ◽  
Nitrogen Dioxide ◽  
Atmospheric Aerosol ◽  
Water Interface ◽  
Air Water Interface

scholarly journals The reaction of oleic acid monolayers with gas-phase ozone at the air water interface: the effect of sub-phase viscosity, and inert secondary components

2020 ◽  
Vol 22 (48) ◽  
pp. 28032-28044
Author(s):  
Martin D. King ◽  
Stephanie H. Jones ◽  
Claire O. M. Lucas ◽  
Katherine C. Thompson ◽  
Adrian R. Rennie ◽  
...  
Keyword(s):  
Oleic Acid ◽  
Reaction Kinetics ◽  
Gas Phase ◽  
Surface Coverage ◽  
Water Interface ◽  
Air Water Interface ◽  
Product Film

Reaction of gas-phase ozone with oleic acid monolayer at the air–water interface leaves no product film. Reaction kinetics change with surface coverage but not with addition of unreactive material or with change of viscosity of the water.

Oxidation of oleic acid at the air–water interface and its potential effects on cloud critical supersaturations

2009 ◽  
Vol 11 (35) ◽  
pp. 7699 ◽  
Author(s):  
Martin D. King ◽  
Adrian R. Rennie ◽  
Katherine C. Thompson ◽  
Fleur N. Fisher ◽  
Chu Chuan Dong ◽  
...  
Keyword(s):  
Oleic Acid ◽  
Water Interface ◽  
Air Water Interface

scholarly journals Night - time oxidation of surfactants at the air–water interface: effects of chain length, head group and saturation

2017 ◽  
Author(s):  
Federica Sebastiani ◽  
Richard A. Campbell ◽  
Kunal Rastogi ◽  
Christian Pfrang
Keyword(s):  
Oleic Acid ◽  
Methyl Ester ◽  
Reaction Kinetics ◽  
Chain Length ◽  
Rate Coefficients ◽  
Head Group ◽  
Water Interface ◽  
Organic Monolayers ◽  
Night Time ◽  
Air Water Interface

Abstract. Reactions of the key atmospheric night-time oxidant NO3 with organic monolayers at the air–water interface are used as proxies for the ageing of organic-coated aqueous aerosols. The surfactant molecules chosen for this study are oleic acid (OA), palmitoleic acid (POA), methyl oleate (MO) and stearic acid (SA) to investigate the effects of chain length, head group and degree of unsaturation on the reaction kinetics and products formed. Fully and partially deuterated surfactants were studied using neutron reflectometry (NR) to determine the reaction kinetics of organic monolayers with NO3 at the air–water interface for the first time. Kinetic modelling allowed us to determine the rate coefficients for the oxidation of OA, POA and MO monolayers to be (2.8 ± 0.7) × 10-8 cm2 molecule−1 s−1, (2.4 ± 0.5) × 10−8 cm2 molecule−1 s−1 and (3.3 ± 0.6) × 10−8 cm2 molecule−1 s−1, respectively. The corresponding uptake coefficients were found to be (2.1 ± 0.5) × 10−3, (1.7 ± 0.3) × 10−3 and (2.1 ± 0.4) × 10−3. For the much slower NO3-initiated oxidation of the saturated surfactant SA we found a loss rate of (5 ± 1) × 10−12 cm2 molecule−1 s−1 which we consider to be an upper limit for the reactive loss, and estimated an uptake coefficient of (5 ± 1) × 10−7. Our investigations demonstrate that NO3 will contribute substantially to the processing of unsaturated surfactants at the air–water interface during night-time given its reactivity is ca. two orders of magnitude higher than that of O3. Furthermore, the relative contributions of NO3 and O3 to the oxidative losses vary massively between species that are closely related in structure: NO3 reacts ca. 400 times faster than O3 with the common model surfactant oleic acid, but only ca. 60 times faster with its methyl ester MO. It is therefore necessary to perform a case-by-case assessment of the relative contributions of the different degradation routes for any specific surfactant. The overall impact of NO3 on the fate of saturated surfactants is slightly less clear given the lack of prior kinetic data for comparison, but NO3 is likely to contribute significantly to the loss of saturated species and dominate their loss during night-time. The retention of the organic character at the air–water interface differs fundamentally between the different surfactant species: the fatty acids studied (OA and POA) form products with a yield of ca. 20 % that are stable at the interface while NO3-initiated oxidation of the methyl ester MO rapidly and effectively removes the organic character (≤ 3 % surface-active products). The film-forming potential of reaction products in real aerosol is thus likely to depend on the relative proportions of saturated and unsaturated surfactants as well as the head group properties. Atmospheric lifetimes of unsaturated species are much longer than those determined with respect to their reactions at the air–water interface, so that they must be protected from oxidative attack e.g. by incorporation into a complex aerosol matrix or in mixed surface films with yet unexplored kinetic behaviour.

Sampling and analysis of the air-water interface with SEM and EDS of microlayers

1989 ◽  
Vol 47 ◽  
pp. 1004-1005
Author(s):  
Randall W. Smith ◽  
John Dash
Keyword(s):  
Heavy Metals ◽  
Surface Microlayer ◽  
Surface Films ◽  
Water Interface ◽  
Physical Processes ◽  
Infrared Spectroscopic Analysis ◽  
Eds Analysis ◽  
Air Water Interface ◽  
Significant Area ◽  
Bulk Chemical

The structure of the air-water interface forms a boundary layer that involves biological ,chemical geological and physical processes in its formation. Freshwater and sea surface microlayers form at the air-water interface and include a diverse assemblage of organic matter, detritus, microorganisms, plankton and heavy metals. The sampling of microlayers and the examination of components is presently a significant area of study because of the input of anthropogenic materials and their accumulation at the air-water interface. The neustonic organisms present in this environment may be sensitive to the toxic components of these inputs. Hardy reports that over 20 different methods have been developed for sampling of microlayers, primarily for bulk chemical analysis. We report here the examination of microlayer films for the documentation of structure and composition.Baier and Gucinski reported the use of Langmuir-Blogett films obtained on germanium prisms for infrared spectroscopic analysis (IR-ATR) of components. The sampling of microlayers has been done by collecting fi1ms on glass plates and teflon drums, We found that microlayers could be collected on 11 mm glass cover slips by pulling a Langmuir-Blogett film from a surface microlayer. Comparative collections were made on methylcel1ulose filter pads. The films could be air-dried or preserved in Lugol's Iodine Several slicks or surface films were sampled in September, 1987 in Chesapeake Bay, Maryland and in August, 1988 in Sequim Bay, Washington, For glass coverslips the films were air-dried, mounted on SEM pegs, ringed with colloidal silver, and sputter coated with Au-Pd, The Langmuir-Blogett film technique maintained the structure of the microlayer intact for examination, SEM observation and EDS analysis were then used to determine organisms and relative concentrations of heavy metals, using a Link AN 10000 EDS system with an ISI SS40 SEM unit. Typical heavy microlayer films are shown in Figure 3.

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