Sunrise ozone destruction found in the sub‐tropical marine boundary layer

Nagao, Ippei; Matsumoto, Kiyoshi; Tanaka, Hiroshi

doi:10.1029/1999gl010836

Cited by 61 publications

(47 citation statements)

References 26 publications

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“…When we compare the sunrise rates of ozone change with those observed around midday, when the HOx destruction is dominant in Figures i and 2, it appears that ozone destruction at sunrise is comparable in rate with ozone destruction by HO• chemistry centred around midday. Recently, similar ozone loss has been observed at a sub-tropical island site [Nagao et al, 1999]. If this destruction is characteristic of the open ocean as well as coastal sites then the ozone loss in the remote MBL has been underestimated by around a factor of two.…”

Section: Discussionmentioning

confidence: 68%

Mid‐latitude marine boundary‐layer ozone destruction at visible sunrise observed at Cape Grim, Tasmania, 41°S

Galbally¹,

Bentley²,

Meyer³

2000

Geophysical Research Letters

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Abstract. An analysis is made of 13 years of observations of ozone concentrations in the remote marine boundary layer at Cape Grim, Tasmania 41øS. These data reveal a decrease in ozone concentration in the first few hours following sunrise at a rate of around 0.1 ppb h -z in mid-summer and in mid-winter. This ozone destruction phenomenon causes an asymmetry in the daily ozone loss rate with enhanced destruction following sunrise, is statistically distinguishable from the 03 -HOx destruction cycle that peaks at midday, and occurs at similar rates in mid-summer and in midwinter.The cause of this sunrise ozone decrease is examined using the conservation equation for ozone. We speculate that ozone destruction at sunrise arises due to halogen chemistry. The absence of sunrise ozone decrease in models of marine boundary-layer photochemistry means that the ozone destruction rate in the remote marine boundary layer is underestimated by perhaps a factor of two.

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Section: Discussionmentioning

confidence: 68%

Mid‐latitude marine boundary‐layer ozone destruction at visible sunrise observed at Cape Grim, Tasmania, 41°S

Galbally¹,

Bentley²,

Meyer³

2000

Geophysical Research Letters

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“…At sunrise, these compounds photolyse freeing NO 2 and halogenated oxides that may trigger and amplify the catalytic destruction of ozone. Such a process is what is suggested by the so-called "sunrise ozone destruction" reported by different authors (Nagao et al, 1999;Galbally et al, 2000;Watanabe et al, 2005). Such a morning peak of ozone depletion was already reported for a close site (Gerosa et al, 2005 and it occurred again during this campaign.…”

Section: Canopy Wetness Frequencymentioning

confidence: 72%

Interactions among vegetation and ozone, water and nitrogen fluxes in a coastal Mediterranean maquis ecosystem

et al. 2009

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Abstract. Ozone, water and energy fluxes were measured over a Mediterranean maquis ecosystem from 5 May until 31 July 2007 by means of the eddy covariance technique. Additional measurements of NO x fluxes were performed by the aerodynamic gradient technique. Stomatal ozone fluxes were obtained from water fluxes by a Dry Deposition Inferential Method based on a big leaf concept.The maquis ecosystem acted as a net sink for ozone. The different water availability between late spring and summer was the major cause of the changes observed in stomatal fluxes, which decreased, together with evapotranspiration, when the season became drier. NO x concentrations were significantly dependent on the local meteorology. NO x fluxes resulted less intense than the ozone fluxes. However an average upward flux of both NO and NO 2 was measured.The non-stomatal pathways of ozone deposition were investigated. A correlation of non-stomatal deposition with air humidity and, in a minor way, with NO 2 fluxes was found.Ozone risk assessment was performed by comparing the exposure and the dose metrics: AOT40 (Accumulated dose over a threshold of 40 ppb) and AF st 1.6 (Accumulated stomatal flux of ozone over a threshold of 1.6 nmol m −2 s −1 ). AOT40, both at the measurement height and at canopy height was greater than the Critical Level for the protection of forests and semi-natural vegetation (5000 ppb h) adopted by UN-ECE. Also the AF st 1.6 value (12.6 mmol m −2 PLA, Projected Leaf Area) was higher than the provisional critical dose of 4 mmol m −2 PLA for forests. The cumulated dose showed two different growth rates in the spring and in the summer periods, while the exposure showed a more irregular behavior in both periods.

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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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Sunrise ozone destruction found in the sub‐tropical marine boundary layer

Cited by 61 publications

References 26 publications

Mid‐latitude marine boundary‐layer ozone destruction at visible sunrise observed at Cape Grim, Tasmania, 41°S

Mid‐latitude marine boundary‐layer ozone destruction at visible sunrise observed at Cape Grim, Tasmania, 41°S

Interactions among vegetation and ozone, water and nitrogen fluxes in a coastal Mediterranean maquis ecosystem

Enhanced surface photochemistry in chloride–nitrate ion mixtures

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