title: Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence.
abstract: Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. ["Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry," J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate ((15)N, (17)O, and (18)O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ(15)N, δ(18)O, and Δ(17)O). From these measurements an average photolytic isotopic fractionation of (15)ɛ = (-15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of (15)ɛ = (-47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from -40 to -74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of (14)NO3 (-) and (15)NO3 (-) in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the shift in width and center well reproduced the values obtained in the laboratory study. These cross sections can be used in isotopic models to reproduce the stable isotopic composition of nitrate found in Antarctic snow profiles.
authors.affiliation: Laboratoire de Glaciologie et Géophysique de l'Environnement, CNRS, F-38041 Grenoble, France.
authors.forename: Tesfaye A
authors.initials: TA
authors.lastname: Berhanu
authors.affiliation: Copenhagen Center for Atmospheric Research (CCAR), Department of Chemistry, University of Copenhagen, Copenhagen, Denmark.
authors.forename: Carl
authors.initials: C
authors.lastname: Meusinger
authors.affiliation: Laboratoire de Glaciologie et Géophysique de l'Environnement, CNRS, F-38041 Grenoble, France.
authors.forename: Joseph
authors.initials: J
authors.lastname: Erbland
authors.affiliation: Laboratoire de Interdisciplinaire de Physique (LIPHY) Univ. de Grenoble, Grenoble, France.
authors.forename: Rémy
authors.initials: R
authors.lastname: Jost
authors.affiliation: Research Center for Environmental Changes, Academia Sinica, Nangang, Taipei 115, Taiwan.
authors.forename: S K
authors.initials: SK
authors.lastname: Bhattacharya
authors.affiliation: Copenhagen Center for Atmospheric Research (CCAR), Department of Chemistry, University of Copenhagen, Copenhagen, Denmark.
authors.forename: Matthew S
authors.initials: MS
authors.lastname: Johnson
authors.affiliation: Laboratoire de Glaciologie et Géophysique de l'Environnement, CNRS, F-38041 Grenoble, France.
authors.forename: Joël
authors.initials: J
authors.lastname: Savarino