Kinetics of the reaction of chlorine atoms with nitrosyl chloride and nitryl chloride and the photochemistry of nitryl chloride

Nelson, H. H.; Johnston, Herrick L.

doi:10.1021/j150625a036

Cited by 40 publications

(50 citation statements)

References 2 publications

(2 reference statements)

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“…1 A and B, where N 2 O 5 and ClNO 2 mixing ratios track one another for much of the night, peaking at midnight. As expected, N 2 O 5 mixing ratios drop sharply to zero at sunrise due to rapid photolysis of the nitrate radical (NO 3 ), which is in thermal equilibrium with N 2 O 5 , whereas ClNO 2 decays to zero with a time constant (τ = 2.71 h) consistent with its photolysis lifetime (26). The magnitude of the N 2 O 5 and ClNO 2 mixing ratios are comparable with those found in previous studies in coastal California (27).…”

Section: Significancesupporting

confidence: 62%

A controlling role for the air−sea interface in the chemical processing of reactive nitrogen in the coastal marine boundary layer

Kim

Farmer

Bertram

2014

Proc. Natl. Acad. Sci. U.S.A.

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The lifetime of reactive nitrogen and the production rate of reactive halogens in the marine boundary layer are strongly impacted by reactions occurring at aqueous interfaces. Despite the potential importance of the air−sea interface in serving as a reactive surface, few direct field observations are available to assess its impact on reactive nitrogen deposition and halogen activation. Here, we present direct measurements of the vertical fluxes of the reactant−product pair N 2 O 5 and ClNO 2 to assess the role of the ocean surface in the exchange of reactive nitrogen and halogens. We measure nocturnal N 2 O 5 exchange velocities (V ex = −1.66 ± 0.60 cm s −1 ) that are limited by atmospheric transport of N 2 O 5 to the air−sea interface. Surprisingly, vertical fluxes of ClNO 2 , the product of N 2 O 5 reactive uptake to concentrated chloride containing surfaces, display net deposition, suggesting that elevated ClNO 2 mixing ratios found in the marine boundary layer are sustained primarily by N 2 O 5 reactions with aerosol particles. Comparison of measured deposition rates and in situ observations of N 2 O 5 reactive uptake to aerosol particles indicates that N 2 O 5 deposition to the ocean surface accounts for between 26% and 42% of the total loss rate. The combination of large V ex, N2O5 and net deposition of ClNO 2 acts to limit NO x recycling rates and the production of Cl atoms by shortening the nocturnal lifetime of N 2 O 5 . These results indicate that air−sea exchange processes account for as much as 15% of nocturnal NO x removal in polluted coastal regions and can serve to reduce ClNO 2 concentrations at sunrise by over 20%.heterogeneous chemistry | halogen chemistry | atmospheric chemistry T he production rate of tropospheric ozone (O 3 ), a criteria air pollutant, depends critically on the concentrations of nitrogen oxides (NO x ≡ NO + NO 2 ), volatile organic compounds (VOCs), trace oxidants (e.g., OH, NO 3 , and Cl), and the wavelength-dependent actinic flux. Accurate model representation of O 3 mixing ratios and the sensitivity of O 3 to changes in NO x and VOC emissions rely heavily on a complete description of the factors that control NO x lifetimes and, in turn, the concentrations of atmospheric oxidants. Modeling studies, constrained by laboratory and field observations, suggest that nocturnal processes involving the nitrate radical (NO 3 ) and N 2 O 5 , both products of NO x oxidation, can account for as much as 50% of the NO x removal (1). Incorporation of the heterogeneous reaction of N 2 O 5 on chloride containing aerosol particles (2, 3) serves as both an efficient NO x recycling and halogen activation mechanism via the production of photolabile nitryl chloride (ClNO 2 ) in both coastal (4) and continental air masses (5).To date, study of the impact of nocturnal processes on the lifetime of NO x and the production of reactive halogen species in the marine boundary layer has concentrated on gas-phase reactions and heterogeneous and multiphase processes occurring on/within aerosol particles, w...

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Section: Significancesupporting

confidence: 62%

A controlling role for the air−sea interface in the chemical processing of reactive nitrogen in the coastal marine boundary layer

Kim

Farmer

Bertram

2014

Proc. Natl. Acad. Sci. U.S.A.

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“…The lifetime of N 2 O 5 to thermal decomposition to NO 2 and NO 3 is ∼ 10 min at 270 K. NO 3 is also lost to reaction with certain organic species, especially compounds with unsaturated carbon-carbon bonds and aldehydes. When reaction times are long, for example during long, dark winter nights and when unsaturated hydrocarbon emissions are low, the most important loss of NO 3 is via N 2 O 5 uptake onto aerosols (e.g., Dentener and Crutzen, 1993;Macintyre and Evans, 2010;Wagner et al, 2013), At sunrise, ClNO 2 photolyzes within a few hours (Nelson and Johnston, 1981), releasing NO 2 and Cl radical, the latter reacting rapidly with most gas-phase organic compounds. The heterogeneous loss rate of N 2 O 5 is a function of the total aerosol surface area and of the fraction of gas-particle collisions resulting in N 2 O 5 uptake.…”

Section: Chemistry In the Dynamic Near-surface Atmospherementioning

confidence: 99%

“…This interference is well documented and observed to be large during summer months, when more than 80 % of NH 4 NO 3 may be lost, but is estimated to be ∼ 20 % when relative humidities are high and temperatures are cold (Appel et al, 1981;Shaw Jr. et al, 1982;Hering and Cass, 1999). If we assume ambient conditions, as opposed to conditions internal to the instrument, drive the equilibrium (Appel et al, 1981;Shaw Jr. et al, 1982;Hering and Cass, 1999;Babich et al, 2000), we are able to estimate the interference using surface AMS observations of NO − 3 , NH + 4 , Cl − , and sulfate (SO 2− 4 ) and a particle into liquid sampler (PILS) of potassium (K + ) and magnesium (Mg + ) in Fresno during DISCOVER-AQ to constrain the thermodynamic model ISORROPIA II (Nenes et al, 1998;Fountoukis and Nenes, 2007). To do this, we set the total gas plus particle concentration equal to the ion data, running ISORROPIA II in the forward mode to simulate the gas-aerosol partitioning after the air stream passed through a denuder, consistent with all gases being captured by the denuder and all aerosol depositing on the filter.…”

Section: A1 Long-term Recordsmentioning

confidence: 99%

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On the effectiveness of nitrogen oxide reductions as a control over ammonium nitrate aerosol

et al. 2016

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Abstract. Nitrogen oxides (NO x ) have fallen steadily across the US over the last 15 years. At the same time, NO x concentrations decrease on weekends relative to weekdays, largely without co-occurring changes in other gas-phase emissions, due to patterns of diesel truck activities. These trends taken together provide two independent constraints on the role of NO x in the nonlinear chemistry of atmospheric oxidation. In this context, we interpret interannual trends in wintertime ammonium nitrate (NH 4 NO 3 ) in the San Joaquin Valley of California, a location with the worst aerosol pollution in the US and where a large portion of aerosol mass is NH 4 NO 3 . Here, we show that NO x reductions have simultaneously decreased nighttime and increased daytime NH 4 NO 3 production over the last decade. We find a substantial decrease in NH 4 NO 3 since 2000 and conclude that this decrease is due to reduced nitrate radical-initiated production at night in residual layers that are decoupled from fresh emissions at the surface. Further reductions in NO x are imminent in California, and nationwide, and we make a quantitative prediction of the response of NH 4 NO 3 . We show that the combination of rapid chemical production and efficient NH 4 NO 3 loss via deposition of gas-phase nitric acid implies that high aerosol days in cities in the San Joaquin Valley air basin are responsive to local changes in NO x within those individual cities. Our calculations indicate that large decreases in NO x in the future will not only lower wintertime NH 4 NO 3 concentrations but also cause a transition in the dominant NH 4 NO 3 source from nighttime to daytime chemistry.

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“…The discharge flow-resonance fluorescence study of Abbatt et al [4] provides the first reliable data on the temperature dependence. The laser photolysis-LMR study of Chasovnikov et al [246] provides rate data for each Cl atom spin state, and they attribute the low value reported by Nelson and Johnston [954] in a laser flash photolysis-resonance fluorescence study to reaction of the Cl 2 P 1/2 state. Adsorption and decomposition of ClNO on the walls of their static system may account for the very low value of Grimley and Houston [528].…”

Section: -81mentioning

confidence: 99%

Environmental effects of large igneous province magmatism: a Siberian perspective

Black

Lamarque

Shields

et al. 2015

Volcanism and Global Environmental Change

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Kinetics of the reaction of chlorine atoms with nitrosyl chloride and nitryl chloride and the photochemistry of nitryl chloride

Cited by 40 publications

References 2 publications

A controlling role for the air−sea interface in the chemical processing of reactive nitrogen in the coastal marine boundary layer

A controlling role for the air−sea interface in the chemical processing of reactive nitrogen in the coastal marine boundary layer

On the effectiveness of nitrogen oxide reductions as a control over ammonium nitrate aerosol

Environmental effects of large igneous province magmatism: a Siberian perspective

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