Environmental Chemistry Environmental Chemistry Society
Environmental problems - Chemical approaches
RESEARCH ARTICLE (Open Access)

Investigating the photo-oxidative and heterogeneous chemical production of HCHO in the snowpack at the South Pole, Antarctica

P. D. Hamer A B E , D. E. Shallcross A , A. Yabushita C , M. Kawasaki C , V. Marécal B and C. S. Boxe D
+ Author Affiliations
- Author Affiliations

A School of Chemistry, University of Bristol, Cantock’s Close, Bristol, BS8 1TS, UK.

B Centre National de Recherches Météorologiques-Groupe d’étude de l’Atmosphérè Météorologique, Météo-France and CNRS, UMR3589, F-31000 Toulouse, France.

C Department of Molecular Engineering, Kyoto University, Kyoto 615-8510, Japan.

D Department of Physical, Environmental and Computer Science, Medgar Evers College-City University of New York, 1650 Bedford Avenue, Brooklyn, NY 11235, USA.

E Corresponding author. Email: paul.d.hamer@gmail.com

Environmental Chemistry 11(4) 459-471 https://doi.org/10.1071/EN13227
Submitted: 17 December 2013  Accepted: 2 May 2014   Published: 12 August 2014

Environmental context. Snowpacks present a surprisingly active environment for photochemistry, leading to sunlight-induced oxidation of deposited organic matter and the subsequent emission of a variety of photochemically active trace gases. We seek to address questions regarding the ultimate fate of organic matter deposited onto snow in the remote regions of the world. The work is relevant to atmospheric composition and climate change.

Abstract. We investigate snowpack fluxes of formaldehyde (HCHO) into the South Pole boundary layer using steady-state photochemical models. We study two chemical sources of HCHO within the snowpack. First, we study chemical production of HCHO from the processing of methyl hydroperoxide (CH3OOH): photolysis, reaction with the hydroxyl radical (OH), and by an acid catalysed rearrangement. Assuming surface layer concentration effects for acidic solutes, we show that the acid catalysed production of HCHO within ice could contribute a non-negligible source to the snowpack HCHO budget. This novel source of HCHO complements existing explanations of HCHO fluxes based on physical emission of HCHO from snow. Secondly, we investigate HCHO production from the oxidation of organic matter (OM) by OH within snow to explain observed fluxes of photochemical origin from the South Pole snowpack. This work shows that laboratory-derived photochemical production rates of HCHO and our standard model are inconsistent with field observations, which has implications for the distribution of OM relative to oxidants within ice particles. We resolve this inconsistency using new laboratory measurements of the molecular dynamics of the OH photofragment from hydrogen peroxide (H2O2) and nitrate (NO3) photolysis, which show that only OH produced in the outermost monolayers can contribute to gas phase and surface layer chemistry. Using these new measurements in conjunction with realistic treatments of ice grain size, H2O2 and NO3 distribution within ice grains, diffusion of gas species within solid ice, and observed OM particle size distributions yields snowpack HCHO photochemical production rates more consistent with observations.

Additional keywords: hydrogen peroxide, hydroxyl radical, ice chemistry, methyl peroxide, organic matter.


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