Walker, HL, Heal, MR, Braban, CF et al. (2 more authors) (2022) Evaluation of local measurement-driven adjustments of modelled cloud-free atmospheric photolysis rate coefficients. Environmental Science: Atmospheres, 2 (6). pp. 1411-1427. ISSN 2634-3606
Abstract
Photolysis rate constants (j-values) play a crucial role in atmospheric chemistry modelling, but capturing the variability in local conditions needed for their accurate simulation is computationally challenging. One approach is to adjust modelled clear-sky estimates using ratios of measured-to-modelled j-values of a reference photolysis, typically j(NO₂) or j(O¹D). However, application of such adjustments to other photolysis reactions introduces uncertainty. Using spectral radiometer data from the UK, this study examines how hourly measurement driven adjustment factors (MDAF) across a set of 12 photolysis reactions group together using cluster analysis, and evaluates the uncertainties in using j(NO₂) and j(O¹D)-derived MDAF values to adjust modelled j-values of other photolysis reactions. The NO₂-MDAF reference is suitable for adjusting photolysis reactions that absorb at λ > 360 nm (HONO, methylglyoxal, ClNO₂, ClONO₂ → Cl), which are largely independent of solar zenith angle and total ozone column (<31% error). In particular, NO₂-MDAF is a good reference for j(HONO) and j(ClNO₂). The O¹D-MDAF performed better at adjusting modelled j-values for species that predominantly photodissociate at λ < 350 nm, such as HNO₃, H₂O₂, CH₃CHO, HCHO → H, HCHO → H₂ and ClONO₂ → ClO (errors ≤ 30%). However, j(O¹D) radiometers require more data processing to account for local conditions. The maximum error determined using NO₂-MDAF was within a factor of two (91% for j(H₂O₂)), which may still be acceptable in some instances. It is important that MDAFs are used to improve accuracy and uncertainty in simulated j-values caused by variation in local conditions.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2022 The Author(s). Published by the Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Physical Chemistry (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 17 Oct 2022 11:57 |
Last Modified: | 14 Dec 2022 15:32 |
Status: | Published |
Publisher: | Royal Society of Chemistry |
Identification Number: | 10.1039/d2ea00072e |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:192020 |