Laboratory study of nitrate photolysis in Antarctic snow: II. Isotopic effects and wavelength dependence

Tesfaye A. Berhanu; Carl Meusinger; Joseph Erbland; Rémy Jost; S.K. Bhattacharya; Matthew Stanley Johnson; Joël Savarino

doi:10.1063/1.4882899

Laboratory study of nitrate photolysis in Antarctic snow: II. Isotopic effects and wavelength dependence

Tesfaye A. Berhanu, Carl Meusinger, Joseph Erbland, Rémy Jost, S.K. Bhattacharya, Matthew Stanley Johnson, Joël Savarino

Department of Chemistry

30 Citations (Scopus)

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 (¹⁵N, ¹⁷O, and ¹⁸O) 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 ¹⁵N, δ ¹⁸O, and Δ ¹⁷O). From these measurements an average photolytic isotopic fractionation of ¹⁵ε = (- 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 ¹⁵ε = (- 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 ¹⁴NO₃ ^- and ¹⁵NO ₃ ^- 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.

Original language	English
Article number	244306
Journal	Journal of Chemical Physics
Volume	140
Issue number	24
Number of pages	14
ISSN	0021-9606
DOIs	https://doi.org/10.1063/1.4882899
Publication status	Published - 28 Jun 2014

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@article{c9f6d5b781d64bba9552fcbbe4fe6ffd,

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 (15N, 17O, and 18O) 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 15N, δ 18O, and Δ 17O). From these measurements an average photolytic isotopic fractionation of 15ε = (- 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 15ε = (- 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 14NO3 - and 15NO 3 - 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.",

author = "Berhanu, {Tesfaye A.} and Carl Meusinger and Joseph Erbland and R{\'e}my Jost and S.K. Bhattacharya and Johnson, {Matthew Stanley} and Jo{\"e}l Savarino",

year = "2014",

month = jun,

day = "28",

doi = "10.1063/1.4882899",

language = "English",

volume = "140",

journal = "Journal of Chemical Physics",

issn = "0021-9606",

publisher = "American Institute of Physics",

number = "24",

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TY - JOUR

T1 - Laboratory study of nitrate photolysis in Antarctic snow

T2 - II. Isotopic effects and wavelength dependence

AU - Berhanu, Tesfaye A.

AU - Meusinger, Carl

AU - Erbland, Joseph

AU - Jost, Rémy

AU - Bhattacharya, S.K.

AU - Johnson, Matthew Stanley

AU - Savarino, Joël

PY - 2014/6/28

Y1 - 2014/6/28

N2 - 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 (15N, 17O, and 18O) 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 15N, δ 18O, and Δ 17O). From these measurements an average photolytic isotopic fractionation of 15ε = (- 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 15ε = (- 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 14NO3 - and 15NO 3 - 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.

AB - 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 (15N, 17O, and 18O) 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 15N, δ 18O, and Δ 17O). From these measurements an average photolytic isotopic fractionation of 15ε = (- 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 15ε = (- 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 14NO3 - and 15NO 3 - 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.

U2 - 10.1063/1.4882899

DO - 10.1063/1.4882899

M3 - Journal article

C2 - 24985637

AN - SCOPUS:84903695621

SN - 0021-9606

VL - 140

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 24

M1 - 244306

ER -

Laboratory study of nitrate photolysis in Antarctic snow: II. Isotopic effects and wavelength dependence

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