Chemical processes at the air-sea interface: The behavior of fluorine

Wilkniss, P. E.; Bressan, D. J.

doi:10.1029/jc076i003p00736

Cited by 24 publications

(11 citation statements)

References 9 publications

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“…The box model results show that HF should remain in the gas phase, being much less soluble than HCI. This important result appears to confirm the suggestion of Cadle (1980) and Wilkniss and Bressan (1971) that HF might be degassed with HC1 from acidified aerosols in the atmosphere. This is investigated in more detail below since these calculations do not take into account the complexation of F-ions in real seawater solutions, or the fact that HF is a weak acid.…”

Section: Strong Acids In the Marine Atmospheresupporting

confidence: 78%

The solubility and behaviour of acid gases in the marine aerosol

1988

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The following Henry's law constants (K H/mol 2 kg -2atm -I ) for HNO 3 and the hydrohalic acids have been evaluated from available partial pressure and other thermodynamic data from 0°-40 °C, I atm total pressure: HN03, 40 °C -5.85 x 105; 30 °C -1.50x 106; 25 *C -2.45 x 106; 20 °C -4.04 x l06 ; 10 °C -1.15 X 10 7 ; 0 °C -3.41 x 10 7. HF, 40 °C -3.2; 30 °C -6.6; 25 °C -9.61; 20 °C -14.0; l0 °C -32.0; 0 °C -76. HCI, 40 °C -4.66 x l05 ; 30 °C -1.23 x l06 ; 25 °C -2.04 x 106 ; 20 °C -3.37 x l06 ; l0 "C -9.71 x l06 ; 0 °C -2.95 x 107 . HBr, 40 °C -2.5 x 108 ; 30 °C -7.5 x l08 ; 25°C-1.32x109;200C-2.37x109;10.C-8.10xl09;0°C-3.0xl0 l°. HI, 40 .C -5.2 x108 ; 300C-1.5x109;25°C-2.5X109;20°C-4.5x109;10°C-l.5xl0m;0°C-5.0xl0re.Simple equilibrium models suggest that HNO 3, CH3SO3H and other acids up to 10x less soluble than HCl displace it from marine seasalt aerosols. HF is displaced preferentially to HCI by dissolved acidity at all relative humidities greater than about 80%, and should be entirely depleted in aged marine aerosols.

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Section: Strong Acids In the Marine Atmospheresupporting

confidence: 78%

The solubility and behaviour of acid gases in the marine aerosol

1988

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“…Following Carpenter's analysis and his suggestion that F-is enriched in a sea surface process fractionation, Wilkniss and Bressan [1971] examined marine aerosols and laboratory-generated aerosols. They found that marine aerosols (diameter over 2/•) are enriched with respect to C1-about 100% over the F/C1 value of seawater but that laboratory aerosols generated from seawater showed a small F-deficit with respect to C1-.…”

Section: Is I and Presumably Also For Is ømentioning

confidence: 99%

“…Global scale motions can be deduced from the measurements as can the averaged concentrations of certain reactants like tropospheric OH from CH3CC13 data [Singh, 1977;Lovelock, 1977]. [ Wilkniss and Bressan, 1971]. Recently, Barnard and Nordstrom [1980] presented data and analysis to support the view that industtial Fg i and fluorides might dominate the fluorine budgets of ifidusttialized continents.…”

Section: Key Processes and Species: Iodine A Gas-phase Iodine Speciementioning

confidence: 99%

Halogens in the atmosphere

Cicerone¹

1981

Reviews of Geophysics

206

129

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Extant data from measurements of halogens in the atmosphere are reviewed in the following categories: gaseous chlorine compounds (inorganic and organic), particulate chloride and chloride in precipitation, gaseous bromine compounds (inorganic and organic), particulate bromide and bromide in precipitation, gaseous iodine compounds (inorganic and organic), iodine in particles and in precipitation, gaseous fluorine compounds (inorganic and organic), and fluoride in particles and precipitation. The roles that these data and other unavailable data play in defining global cycles of the halogens are discussed. Speciation of the halogen gases in the troposphere is very uncertain: the only inorganic species detected by species-specific methods are HC1 and SF6. More specific data are available on organic forms that contain halogens. Key species of gaseous halogens, either established or suspected to be important, are listed along with key processes that need investigation. Heterogeneous reactions, both gas-to-particle and particle-to-gas processes, precipitation removal, and sea-salt aerosol generation and fractionation processes need quantitative investigation to allow progress in estimating halogen sources and sinks. Where practical, as with stratospheric inorganic chlorine gases, quantitative comparisons are made between measured and predicted concentrations.

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“…This factor can be considered as the factor of marine spray owing to the high loadings of Na + and Cl -, the proxy species for sea salt. On the coarse mode F -can be present in sea salt through the bubble bursting phenomenon at the air-sea interface which deposits the terrigenous F -at the ocean surface, to the sea salt aerosol (Wilkniss and Bressan, 1971). Moreover NO 3 -of marine origin can be scavenged by sea salt particles due to their alkaline nature (Andreae et al, 2000).…”

Section: Coarse Mode Aerosolsmentioning

confidence: 99%

Latitudinal and Size Segregated Compositional Variability of Aerosols over the Indian and Southern Ocean during 2010 Austral Summer

Thakur

Thamban

2014

Aerosol Air Qual. Res.

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To characterize the spatial variations in size segregated aerosols, samples were collected over the Indian and Southern oceans (7°N to 68°S) during the Indian expedition to Southern Ocean (January-February 2010). The chemical and mass concentrations of ions were measured in nine size classes (0.4-> 10 µm) of aerosols through ion-exchange chromatographic system and gravimetric estimates, respectively. Mass concentrations of coarse aerosols increase towards the Antarctic coast which is well correlated with the increasing humidity suggesting growth of particles. The study area was found to be predominately impacted by sea salt aerosols with a sea salt load of 91%. F -, Cl -and NO 3 -reflected anthropogenic impact within the fine mode aerosols but the marine influence dominated the coarse mode. Methanesulphonic (MSA) was predominantly of biogenic origin but a substantially low MSA/nssSO 4 2-ratio suggested that DMS contribution to the total nssSO 4 2-concentration was low. NH 4 + concentrations showed a shift from fine to coarse particles, with a trimodal distribution over the Southern Ocean. Our study reports a significant Cl -depletion in the aerosols and the degree of Cl -deficit was size-dependent, increasing with decreasing particle sizes. The neutralization ratios suggested differential behavior of ions with respect to the prevailing meteorological conditions. The coarse mode aerosols were neutralized by ammonia leading to the formation of NH 4 NO 3 particles. The fine modes were predominately composed of NH 4 HSO 4 and its formation is favored by the high humidity and foggy conditions over the study area. Factor analysis support that the Southern Indian Ocean (10°S to 59°S) had the highest loading of anthropogenic and sea salt aerosols, which lead to the formation of secondary aerosols through gas to particle transformations. The rocky Antarctic coastline, act as a source of coarse crustal aerosols over the Southern Ocean (60°S to 65°S).

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Chemical processes at the air-sea interface: The behavior of fluorine

Cited by 24 publications

References 9 publications

The solubility and behaviour of acid gases in the marine aerosol

The solubility and behaviour of acid gases in the marine aerosol

Halogens in the atmosphere

Latitudinal and Size Segregated Compositional Variability of Aerosols over the Indian and Southern Ocean during 2010 Austral Summer

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