Preprints
https://doi.org/10.5194/egusphere-2026-3716
https://doi.org/10.5194/egusphere-2026-3716
27 Jul 2026
 | 27 Jul 2026
Status: this preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).

Supercooled nitrate solution on ice at 232 K: Enhanced HONO yields

Yanisha Manoharan, Zoë M. Golay, Jérôme P. Gabathuler, Anthony Boucly, Luca Artiglia, Markus Ammann, and Thorsten Bartels Rausch

Abstract. Snowpack nitrate photolysis is a major source of nitrogen oxides and nitrous acid that control atmospheric oxidants in polar environments. It remains unclear at what temperature nitrate salts crystalize in snow and how this impacts the photolysis product yields. Here we show, using near‑edge X‑ray absorption fine structure (NEXAFS) spectroscopy, that sodium nitrate does not precipitate at temperatures down to 23 K below the eutectic temperature at ice surfaces, but does so in absence of ice. This indicates that strong interfacial supercooling or liquid‑like solvation persists. Complementary snow photolysis experiments demonstrate that such liquid-like nitrate shows a higher HONO to NO2 emission ratio than precipitated nitrate, which is consistent with the enhanced role of secondary chemistry in the aqueous phase. These findings show that supercooled nitrate might be present over wide ranges of Arctic, Antarctic, and upper tropospheric temperatures with a significant impact on the HONO and NO2 fluxes and thus the composition and chemistry in the air above snow or in contact with ice clouds.

Competing interests: At least one of the (co-)authors is a member of the editorial board of Atmospheric Chemistry and Physics.

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Yanisha Manoharan, Zoë M. Golay, Jérôme P. Gabathuler, Anthony Boucly, Luca Artiglia, Markus Ammann, and Thorsten Bartels Rausch

Status: open (until 07 Sep 2026)

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Yanisha Manoharan, Zoë M. Golay, Jérôme P. Gabathuler, Anthony Boucly, Luca Artiglia, Markus Ammann, and Thorsten Bartels Rausch
Yanisha Manoharan, Zoë M. Golay, Jérôme P. Gabathuler, Anthony Boucly, Luca Artiglia, Markus Ammann, and Thorsten Bartels Rausch
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Latest update: 27 Jul 2026
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Short summary
Nitrate in polar snow releases reactive gases when exposed to sunlight, influencing polar air chemistry. We studied whether nitrate crystallizes at low temperatures and how this affects its reactivity. X-ray spectroscopy revealed that nitrate stays liquid-like at ice surfaces, even 23 degrees below its expected freezing point. Sunlight experiments show that liquid-like nitrate releases much more nitrous acid than crystallized nitrate. This has implications for polar atmospheric chemistry models.
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