Formation of nitrosyl chloride from salt particles in air

Schroeder, W. H.; Urone, Paul

doi:10.1021/es60093a015

Cited by 79 publications

(64 citation statements)

References 4 publications

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“…Thus the presence of chloride ions appears to minimize segregation of the anions and the resulting rates of NO 2 production reflect those from well-mixed salts. The similarity of the rate of production of NO 2 between the ternary mixture and NaBr-NaNO 3 . b Rates from binary NaCl-NaNO 3 and NaBr-NaNO 3 mixtures measured previously 99,100 were normalized to correspond to the present experiments.…”

Section: Resultsmentioning

confidence: 99%

“…Fig. 5a shows a direct comparison of the solvation of nitrate ions in the bulk and at the surface for NaCl-NaNO 3 the high chloride experiments, the water solvent cage of nitrate is reduced from twenty-one water molecules (bulk) to seventeen at 3 Å below the GDS and to twelve water molecules at the GDS. Calculations for the high bromide system (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…The loss of nitrogen species to sea salt aerosols through heterogeneous reactions is an important removal pathway for NO y (N 2 O 5 , NO 2 , HNO 3 and ClONO 2 ) in the marine troposphere. Nitrate formed from these reactions is a common constituent of sea salt aerosols (100-400 mM) 30 and is one of the most abundant soluble anions in high-latitude snow and ice.…”

Section: Introductionmentioning

confidence: 99%

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Production of gas phase NO2 and halogens from the photolysis of thin water films containing nitrate, chloride and bromide ions at room temperature

Richards-Henderson

Callahan

Nissenson

et al. 2013

Phys. Chem. Chem. Phys.

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aNitrate and halide ions coexist in particles generated in marine regions, around alkaline dry lakes, and in the Arctic snowpack. Although the photochemistry of nitrate ions in bulk aqueous solution is well known, there is recent evidence that it may be more efficient at liquid-gas interfaces, and that the presence of other ions in solution may enhance interfacial reactivity. This study examines the 311 nm photolysis of thin aqueous films of ternary halide-nitrate salt mixtures (NaCl-NaBr-NaNO 3 ) deposited on the walls of a Teflon chamber at 298 K. The films were generated by nebulizing aqueous 0.25 M NaNO 3 solutions which had NaCl and NaBr added to vary the mole fraction of halide ions. Molar ratios of chloride to bromide ions were chosen to be 0.25, 1.0, or 4.0. The subsequent generation of gas phase NO 2 and reactive halogen gases (Br 2 , BrCl and Cl 2 ) were monitored with time. The rate of gas phase NO 2 formation was shown to be enhanced by the addition of the halide ions to thin films containing only aqueous NaNO 3 .] r 1.0, the NO 2 enhancement was similar to that observed for binary NaBr-NaNO 3 mixtures, while with excess chloride NO 2 enhancement was similar to that observed for binary NaCl-NaNO 3 mixtures. Molecular dynamics simulations predict that the halide ions draw nitrate ions closer to the interface where a less complete solvent shell allows more efficient escape of NO 2 to the gas phase, and that bromide ions are more effective in bringing nitrate ions closer to the surface. The combination of theory and experiments suggests that under atmospheric conditions where nitrate ion photochemistry plays a role, the impact of other species such as halide ions should be taken into account in predicting the impacts of nitrate ion photochemistry.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Production of gas phase NO2 and halogens from the photolysis of thin water films containing nitrate, chloride and bromide ions at room temperature

Richards-Henderson

Callahan

Nissenson

et al. 2013

Phys. Chem. Chem. Phys.

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] The particle composition has been observed to range from no Cl À depletion (fresh sea salt) to complete Cl À depletion (heavily processed sea salt), and a strong anticorrelation of Cl À with NO 3 À has been reported. 4,7,8 As a result, the ratio of Cl À to NO 3 À in sea salt-derived aerosol decreases as air masses move downwind in coastal urban regions.…”

Section: Introductionmentioning

confidence: 99%

Enhanced surface photochemistry in chloride–nitrate ion mixtures

Wingen

Moskun

Johnson

et al. 2008

Phys. Chem. Chem. Phys.

116

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Heterogeneous reactions of sea salt aerosol with various oxides of nitrogen lead to replacement of chloride ion by nitrate ion. Studies of the photochemistry of a model system were carried out using deliquesced mixtures of NaCl and NaNO 3 on a Teflon s substrate. Varying molar ratios of NaCl to NaNO 3 (1 : 9 Cl À : NO 3 À , 1 : 1 Cl À : NO 3 À , 3 : 1 Cl À : NO 3 À , 9 : 1 Cl À : NO 3 À) and NaNO 3 at the same total concentration were irradiated in air at 299 AE 3 K and at a relative humidity of 75 AE 8% using broadband UVB light (270-380 nm). Gaseous NO 2 production was measured as a function of time using a chemiluminescence NO y detector. Surprisingly, an enhanced yield of NO 2 was observed as the chloride to nitrate ratio increased. Molecular dynamics (MD) simulations show that as the Cl À : NO 3 À ratio increases, the nitrate ions are drawn closer to the interface due to the existence of a double layer of interfacial Cl À and subsurface Na + . This leads to a decreased solvent cage effect when the nitrate ion photodissociates to NO 2 +O À , increasing the effective quantum yield and hence the production of gaseous NO 2 . The implications of enhanced NO 2 and likely OH production as sea salt aerosols become processed in the atmosphere are discussed.

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“…If their proton and sodium adducts are below the mass range (m/z Z 500) probed by MALDI-TOF-MS, they would not have been observed in the mass spectra but would be evident in the DRIFTS spectra. The formation of NO 3 À is caused by reaction of the NaCl substrate 19,20,48 with NO 2 and HNO 3 that are formed in secondary chemistry following IPN photolysis. In principle, products such as organic nitrates and NO 3 À could be destroyed by photolysis simultaneously while they are being formed.…”

mentioning

confidence: 99%