Chemical controls on ozone deposition to water

Martino, Manuela; Lézé, Bertrand; Baker, Alex R.; Liss, Peter S.

doi:10.1029/2011gl050282

Cited by 23 publications

(33 citation statements)

References 28 publications

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“…13 Observed oceanic O 3 deposition velocities measured by eddy covariance from both fixed tower platforms 41,55 or by turbulent aircraft measurements 40,56 are approximately double that calculated from the presence of iodide alone in coastal waters. 25,32 This is consistent with recent laboratory measurements by Martino et al, 33 who demonstrated that natural DOC (sourced from the Suwannee River) and iodide at naturally occurring concentrations contribute similarly to the chemical enhancement of ozone deposition to surface waters. As shown in Figure 1 25,57 Thus, our laboratory measurements suggest that an additional components of coastal seawater, most likely DOC, is an important chemical control of O 3 deposition over coastal waters.…”

Section: ■ Introductionsupporting

confidence: 90%

Modification of Ozone Deposition and I₂ Emissions at the Air–Aqueous Interface by Dissolved Organic Carbon of Marine Origin

Shaw

Carpenter

2013

Environ. Sci. Technol.

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The reaction between gaseous ozone (O3) and aqueous iodide (I(-)) at the surface microlayer (SML) is believed to be a major chemical contributor to the oceanic dry deposition of O3 over open ocean waters and has also recently been shown to produce environmentally significant quantities of gaseous molecular iodine (I2). Here we investigate how this reaction is affected by the presence of dissolved organic carbon (DOC) of marine origin, using a heterogeneous flow reactor and detection of gaseous I2 by solvent trapping and UV/vis spectroscopy. Ozone deposition measurements over coastal seawater implied an O3 reactivity (λ) toward coastal marine DOC of ∼500 (420-580) s(-1), 2-5 times higher than that toward iodide at typical ocean concentrations (∼0.5-1 × 10(-7) M). We added varying amounts of highly concentrated DOC extracted from coastal seawater to I(-) solutions (1 × 10(-5) M) such that the relative reactivities of DOC and I(-) toward O3 (λDOC/λI) were in the expected range for natural seawater. The evolution of gaseous I2 and the loss of aqueous I(-) both reduced as DOC concentrations increased, with an overall suppression of I2 emissions of about a factor of 2 under conditions of λDOC/λI representative of open ocean waters (0.5-1). A kinetic model of the SML suggested that neither competition of DOC with I(-) for reaction with interfacial O3, nor direct loss of I2 and hypoiodous acid (HOI) through reaction with increasing quantities of DOC, can fully explain these results. We conclude that the suppression of I2 emissions by DOC is largely a physical effect arising from a decrease in the net transfer of I2 from the aqueous to gas phase, as suggested by recent laboratory studies.

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Section: ■ Introductionsupporting

confidence: 90%

Modification of Ozone Deposition and I₂ Emissions at the Air–Aqueous Interface by Dissolved Organic Carbon of Marine Origin

Shaw

Carpenter

2013

Environ. Sci. Technol.

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“…The Fairall parameterisation, including chemical reactivity was further developed based on the laboratory studies [12,17] in which the chemical enhancement of the ozone deposition velocity was quantified for iodide and DOC reactants. The reaction rate for ozone and DOC, k DOCuM-O3 , was calculated by comparing the results from ozone-iodide reactions with the Fairall dry deposition theory and known ozone-iodide reaction kinetics [18] and determining systematic constants for the experimental setup.…”

Section: Model Developmentmentioning

confidence: 99%

“…Combining R a and the rate constant used in Magi et al [18] for sea-surface O 3 -I reactions, we can define the experimental setup in terms of Fairall's dry deposition velocity equation. A surface turbulence term (τ) is required to be combined with R w to replicate the Martino et al [12] experiments. Consequently, the dry deposition velocity to seawater can be written as follows:…”

Section: Model Developmentmentioning

confidence: 99%

“…The parameterisation was also adapted to account for variability of ozone diffusivity, solubility, and reactivity with sea surface temperature and to estimate emissions of volatile organoiodine (VOI) vapours following 2 Advances in Meteorology reactions of ozone with iodide and DOC (e.g., [11]). In the present study, the Fairall parameterisation was further developed to parameterise ozone-DOC reactions with a second-order reaction rate empirically derived from the laboratory work of [12]. Box model results of the updated Fairall parameterisation are compared to in situ ozone gradient fluxes measured at Mace Head.…”

Section: Introductionmentioning

confidence: 99%

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Photochemical Impact on Ozone Fluxes in Coastal Waters

Coleman¹,

McVeigh²,

Berresheim³

et al. 2012

Advances in Meteorology

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Ozone fluxes, derived from gradient measurements in Northeast Atlantic coastal waters, were observed to depend on both tide height and solar radiation. Peak ozone fluxes of −0.26 ± 0.04 μg m −2 s −1 occurred during low-tide conditions when exposed microalgae fields contributed to the flux footprint. Additionally, at mid-to-high tide, when water surfaces contribute predominantly to the flux footprint, fluxes of the order of −0.12 ± 0.03 μg m −2 s −1 were observed. Considering only fluxes over water covered surfaces, and using an advanced ozone deposition model that accounts for surface-water chemistry enhancing the deposition sink, it is demonstrated that a photochemical enhancement reaction with dissolved organic carbon (DOC) is required to explain the enhanced ozone deposition during daylight hours. This sink amounts to an ozone loss rate of up to 0.6 ppb per hour under peak solar irradiance and points to a missing sink in the marine boundary layer ozone budget.

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“…Prime candidates for the oceanic reactivity are the iodide ion (I À ) as well as organic constituents (Oh et al 2008). The results of a recent laboratory study indicate that these two reactants are about equally important in determining the deposition velocity of ozone (Martino et al 2012). Most likely, these reactions occur in the ocean surface microlayer or the immediately underlying seawater.…”

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confidence: 99%

Short-Lived Trace Gases in the Surface Ocean and the Atmosphere

Liss

Marandino

Dahl

et al. 2013

Springer Earth System Sciences

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The two-way exchange of trace gases between the ocean and the atmosphere is important for both the chemistry and physics of the atmosphere and the biogeochemistry of the oceans, including the global cycling of elements. Here we review these exchanges and their importance for a range of gases whose lifetimes are generally short compared to the main greenhouse gases and which are, in most cases, more reactive than them. Gases considered include sulphur and related compounds, organohalogens, non-methane hydrocarbons, ozone, ammonia and related compounds, hydrogen and carbon monoxide. Finally, we stress the interactivity of the system, the importance of process understanding for modeling, the need for more extensive field measurements and their better seasonal coverage, the importance of inter-calibration exercises and finally the need to show the importance of air-sea exchanges for global cycling and how the field fits into the broader context of Earth System Science. IntroductionDespite their seemingly low abundances, short-lived trace gases in the atmosphere critically influence global climate change, stratospheric ozone chemistry, and the oxidative capacity of the atmosphere. Because the ocean-atmosphere interface covers a large extent of the Earth's surface, the ocean is a major control on the atmospheric budget of many trace gases. Further, the chemical, biological, and physical processes that occur around this interface have a large impact on trace gas cycling between the oceanic and atmospheric reservoirs.In this chapter we present current knowledge on surface ocean cycling processes, atmospheric reactivity and importance, and the influence of air-sea exchange for a suite of trace gases which generally have shorter atmospheric lifetimes than those discussed in Chap. 3 (i.e. CO 2 , N 2 O and CH 4 ). We focus not only on research from the past 10 years, but also on topics where much uncertainty remains. Unfortunately, not all of the important issues can be addressed here. Notably missing is detailed information about trace gas cycling in polar regions and particularly over-ice processes, including the role of frost flowers.The chemical species discussed in the chapter are intimately related to the topics discussed in Chaps. 2, 4, and 5 of this book. More accurate parameterisations of gas exchange will allow for better calculations of 1 oceanic emissions and uptake (Chap. 2). Many of the gases described, such as sulphur gases and non-methane hydrocarbons, are important for marine boundary layer particle formation and cloud coverage (Chap. 4). And, finally, predictive tools for the impacts of future environmental variability on these gases are required (Chap. 5).In the chapter we have tried to rationalise the use of units wherever possible. However, different units are used by, for example, the atmospheric and ocean communities, the former often using volume units (e.g. ppt by volume), whereas the latter use mass or molar units (both of which are found widely). So, to avoid confusion, we have not tried t...

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Chemical controls on ozone deposition to water

Cited by 23 publications

References 28 publications

Modification of Ozone Deposition and I₂ Emissions at the Air–Aqueous Interface by Dissolved Organic Carbon of Marine Origin

Modification of Ozone Deposition and I₂ Emissions at the Air–Aqueous Interface by Dissolved Organic Carbon of Marine Origin

Photochemical Impact on Ozone Fluxes in Coastal Waters

Short-Lived Trace Gases in the Surface Ocean and the Atmosphere

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Chemical controls on ozone deposition to water

Cited by 23 publications

References 28 publications

Modification of Ozone Deposition and I2 Emissions at the Air–Aqueous Interface by Dissolved Organic Carbon of Marine Origin

Modification of Ozone Deposition and I2 Emissions at the Air–Aqueous Interface by Dissolved Organic Carbon of Marine Origin

Photochemical Impact on Ozone Fluxes in Coastal Waters

Short-Lived Trace Gases in the Surface Ocean and the Atmosphere

Contact Info

Product

Resources

About

Modification of Ozone Deposition and I₂ Emissions at the Air–Aqueous Interface by Dissolved Organic Carbon of Marine Origin

Modification of Ozone Deposition and I₂ Emissions at the Air–Aqueous Interface by Dissolved Organic Carbon of Marine Origin