Measurement and interpretation of gas phase formaldehyde concentrations obtained during the CHABLIS campaign in coastal Antarctica

Salmon, Richard; Bauguitte, Stéphane; Bloss, William J.; Hutterli, Manuel A.; Jones, A. E.; Read, Katie A.; Wolff, Eric W.

doi:10.5194/acp-8-4085-2008

Cited by 25 publications

(47 citation statements)

References 47 publications

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“…Kinetic measurements of the self reaction HO 2 + HO 2 have revealed the chaperone effect of water vapour enhancing the rate coefficient (Stone and Rowley, 2005). It has also been shown that the rate coefficient of the reaction HO 2 +NO 2 increase by 50 % from dry to humid atmospheric conditions (Sander and Peterson, 1984). In the Li et al (2014) study it was postulated that the reaction converts NO 2 to HONO with a yield of 100 % and this allowed a model to reproduce the observed levels of HONO, albeit under free-tropospheric conditions away from surfaces.…”

Section: Hono Box Model Approachmentioning

confidence: 99%

Detailed budget analysis of HONO in central London reveals a missing daytime source

et al. 2016

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Abstract. Measurements of HONO were carried out at an urban background site near central London as part of the Clean air for London (ClearfLo) project in summer 2012. Data were collected from 22 July to 18 August 2014, with peak values of up to 1.8 ppbV at night and non-zero values of between 0.2 and 0.6 ppbV seen during the day. A wide range of other gas phase, aerosol, radiation, and meteorological measurements were made concurrently at the same site, allowing a detailed analysis of the chemistry to be carried out. The peak HONO / NO x ratio of 0.04 is seen at ∼ 02:00 UTC, with the presence of a second, daytime, peak in HONO / NO x of similar magnitude to the night-time peak, suggesting a significant secondary daytime HONO source. A photostationary state calculation of HONO involving formation from the reaction of OH and NO and loss from photolysis, reaction with OH, and dry deposition shows a significant underestimation during the day, with calculated values being close to 0, compared to the measurement average of 0.4 ppbV at midday. The addition of further HONO sources from the literature, including dark conversion of NO 2 on surfaces, direct emission, photolysis of ortho-substituted nitrophenols, the postulated formation from the reaction of HO 2 × H 2 O with NO 2 , photolysis of adsorbed HNO 3 on ground and aerosols, and HONO produced by photosensitized conversion of NO 2 on the surface increases the daytime modelled HONO to 0.1 ppbV, still leaving a significant missing daytime source. The missing HONO is plotted against a series of parameters including NO 2 and OH reactivity (used as a proxy for organic material), with little correlation seen. Much better correlation is observed with the product of these species with j (NO 2 ), in particular NO 2 and the product of NO 2 with OH reactivity. This suggests the missing HONO source is in some way related to NO 2 and also requires sunlight. Increasing the photosensitized surface conversion rate of NO 2 by a factor of 10 to a mean daytime first-order loss of ∼ 6 ×10 −5 s −1 (but which varies as a function of j (NO 2 )) closes the daytime HONO budget at all times (apart from the late afternoon), suggesting that urban surfaces may enhance this photosensitized source. The effect of the missing HONO to OH radical production is also investigated and it is shown that the model needs to be constrained to measured HONO in order to accurately reproduce the OH radical measurements.

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Section: Hono Box Model Approachmentioning

confidence: 99%

Detailed budget analysis of HONO in central London reveals a missing daytime source

et al. 2016

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“…Formaldehyde measurements were made using an Aerolaser analyzer (Model AL 4021) that has a quantification limit of less than 50 pptv. The technique has been described in detail elsewhere [ Riedel et al , 1999; Salmon et al , 2008]. In brief, gaseous HCHO is scrubbed into a diluted sulfuric acid solution followed by reaction with the Hantzsch reagent, a dilute mixture of acetyl acetone, acetic acid, and ammonium acetate.…”

Section: Opale 2010–2011 Site Location and Instrumental Techniquesmentioning

confidence: 99%

Oxidant Production over Antarctic Land and its Export (OPALE) project: An overview of the 2010–2011 summer campaign

Preunkert¹,

Ancellet²,

Legrand³

et al. 2012

J. Geophys. Res.

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[1] This paper summarizes the objectives and setting of the OPALE (Oxidant Production over Antarctic Land and its Export) project during summer 2010/2011 at Dumont d'Urville. The primary goal of the campaign is to characterize the oxidizing environment of the atmospheric boundary layer along the coast of East Antarctica. A summary of the relevant field chemical measurements is presented including the carbon monoxide and ammonia records that are used here to identify local influences due to station activities and penguin emissions. An overview of the basic meteorological conditions experienced by the site is presented including the results from the trajectory/dispersion model FLEXPART to highlight which types of air mass were sampled (marine boundary layer versus continental Antarctic air). The results of the FLEXPART analysis demonstrate that high ozone levels and related changes in the OH concentrations are associated with the transport of continental air to DDU. Finally, three companion papers are introduced. A first paper is dedicated to the impact of local penguin emissions on the atmospheric budget of several oxygenated volatile organic compounds. The second paper reports on HONO levels that were measured for the first time in Antarctica by using the long path absorption photometer (LOPAP) technique. Finally, in a third paper, major findings on the HO x levels are detailed, leading to the overall conclusion that the photochemistry at coastal East Antarctica is strongly driven by an efficient HO x chemistry compared to the situation at other coastal Antarctic regions.

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“…These studies suggest that snowpack is a source of organic carbon to the atmosphere through possible outgassing and/or photochemical processes von Schneidemesser et al (2008) attributed the absence of a seasonal pattern in organic compounds in Greenland snow (hopanes, PAHs, alkanes, alkanoic acids) to possible post-depositional processing occurring in the snowpack. Other studies also point to the fact that concentrations of gas phase formaldehyde (HCHO) measured in the Arctic (Mabilia et al, 2007) and in Antarctica (Salmon et al, 2008) cannot be explained by known gas-phase chemistry without considering an additional source of HCHO from the snowpack, in support of previous observations Sumner and Shepson, 1999). In further support of these observations, Barret et al (2011a) showed that the seasonal snowpack near Barrow, Alaska, was a source of HCHO and that, while most of the HCHO produced was released to the atmosphere, a small fraction was incorporated into surface snow crystals by solid state diffusion.…”

Section: Atmosmentioning

confidence: 99%

Organics in environmental ices: sources, chemistry, and impacts

et al. 2012

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Abstract. The physical, chemical, and biological processes involving organics in ice in the environment impact a number of atmospheric and biogeochemical cycles. Organic material in snow or ice may be biological in origin, deposited from aerosols or atmospheric gases, or formed chemically in situ. In this manuscript, we review the current state of knowledge regarding the sources, properties, and chemistry of organic materials in environmental ices. Several outstanding questions remain to be resolved and fundamental data gathered before an accurate model of transformations and transport of organic species in the cryosphere will be possible. For example, more information is needed regarding the quantitative impacts of chemical and biological processes, ice morphology, and snow formation on the fate of organic material in cold regions. Interdisciplinary work at the interfaces of chemistry, physics and biology is needed in order to fully characterize the nature and evolution of organics in the cryosphere and predict the effects of climate change on the Earth's carbon cycle.

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Measurement and interpretation of gas phase formaldehyde concentrations obtained during the CHABLIS campaign in coastal Antarctica

Cited by 25 publications

References 47 publications

Detailed budget analysis of HONO in central London reveals a missing daytime source

Detailed budget analysis of HONO in central London reveals a missing daytime source

Oxidant Production over Antarctic Land and its Export (OPALE) project: An overview of the 2010–2011 summer campaign

Organics in environmental ices: sources, chemistry, and impacts

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