Ozone in the remote marine boundary layer: A possible role for halogens

Dickerson, Russell R.; Rhoads, Kevin P.; Carsey, Thomas P.; Oltmans, S. J.; Burrows, J. P.; Crutzen, Paul J.

doi:10.1029/1999jd900023

Cited by 144 publications

(145 citation statements)

References 49 publications

(9 reference statements)

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“…104,105 Bromide ion enhancement at the interface has been shown theoretically and experimentally to be greater than that for chloride ions. [29][30][31]34,37,106 It is therefore expected that bromide ions will be even more effective in pulling nitrate ions towards the interface through the double-layer effect and that the quantum yields will be greater than for the chloride-nitrate mixtures.…”

Section: Atmospheric Implicationsmentioning

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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Section: Atmospheric Implicationsmentioning

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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“…O 3 decreases in the lower troposphere of Bombay by around 5-7 ppbv (8-10%). However O 3 is still too high in the lower troposphere, perhaps reflecting a combination of local sea breeze not resolved at the coarse resolution of the model, missing halogen chemistry (Dickerson et al, 1999;Stehr et al, 2002), or inefficient O 3 production in urban areas .…”

Section: Evaluation With In Situ Datamentioning

confidence: 99%

Remote sensed and in situ constraints on processes affecting tropical tropospheric ozone

et al. 2007

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Abstract. We use a global chemical transport model (GEOSChem) to evaluate the consistency of satellite measurements of lightning flashes and ozone precursors with in situ measurements of tropical tropospheric ozone. The measurements are tropospheric O 3 , NO 2 , and HCHO columns from the GOME satellite instrument, lightning flashes from the OTD and LIS satellite instruments, profiles of O 3 , CO, and relative humidity from the MOZAIC aircraft program, and profiles of O 3 from the SHADOZ ozonesonde network. We interpret these multiple data sources with our model to better understand what controls tropical tropospheric ozone. Tropical tropospheric ozone is mainly affected by lightning NO x and convection in the upper troposphere and by surface emissions in the lower troposphere. Scaling the spatial distribution of lightning in the model to the observed flashes improves the simulation of O 3 in the upper troposphere by 5-20 ppbv versus in situ observations and by 1-4 Dobson Units versus GOME retrievals of tropospheric O 3 columns. A lightning source strength of 6±2 Tg N/yr best represents in situ observations from aircraft and ozonesonde. Tropospheric NO 2 and HCHO columns from GOME are applied to provide topdown constraints on emission inventories of NO x (biomass burning and soils) and VOCs (biomass burning). The topdown biomass burning inventory is larger than the bottom-up inventory by a factor of 2 for HCHO and alkenes, and by a factor of 2.6 for NO x over northern equatorial Africa. These emissions increase lower tropospheric O 3 by 5-20 ppbv, improving the simulation versus aircraft observations, and by 4 Dobson Units versus GOME observations of tropospheric O 3 columns. Emission factors in the a posteriori inventory are more consistent with a recent compilation from in situ measurements. The ozone simulation using two different dy-

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“…3 may be expected. The destruction of ozone by reactive halogens is another potential sink for the ozone in the marine boundary layer (Dickerson et al, 1999;Ali et al, 2009). During the pre-monsoon transition, surface winds are westerly at the northern AS with an anticyclonic pattern centred over the middle AS.…”

Section: Influences Of Meteorologymentioning

confidence: 99%

Tropospheric ozone maxima observed over the Arabian Sea during the pre-monsoon

Jia¹,

Ladstätter-Weißenmayer²,

Hou

et al. 2017

Atmos. Chem. Phys.

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Abstract. An enhancement of the tropospheric ozone column (TOC) over Arabian Sea (AS) during the pre-monsoon season is reported in this study. The potential sources of the AS spring ozone pool are investigated by use of multiple data sets (e.g., SCIAMACHY Limb-Nadir-Matching TOC, OMI/MLS TOC, TES TOC, MACC reanalysis data, MOZART-4 model and HYSPLIT model). Three-quarters of the enhanced ozone concentrations are attributed to the 0-8 km height range. The main source of the ozone enhancement is considered to be caused by long-range transport of ozone pollutants from India ( ∼ 50 % contributions to the lowest 4 km, ∼ 20 % contributions to the 4-8 km height range), the Middle East, Africa and Europe (∼ 30 % in total). In addition, the vertical pollution accumulation in the lower troposphere, especially at 4-8 km, was found to be important for the AS spring ozone pool formation. Local photochemistry, on the other hand, plays a negligible role in producing ozone at the 4-8 km height range. In the 0-4 km height range, ozone is quickly removed by wet deposition. The AS spring TOC maxima are influenced by the dynamical variations caused by the sea surface temperature (SST) anomaly during the El Niño period in 2005 and 2010 with a ∼ 5 DU decrease.

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Ozone in the remote marine boundary layer: A possible role for halogens

Cited by 144 publications

References 49 publications

Enhanced surface photochemistry in chloride–nitrate ion mixtures

Enhanced surface photochemistry in chloride–nitrate ion mixtures

Remote sensed and in situ constraints on processes affecting tropical tropospheric ozone

Tropospheric ozone maxima observed over the Arabian Sea during the pre-monsoon

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