the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Short lifetimes of organic nitrates in a sub-urban temperate forest indicate efficient assimilation of reactive nitrogen by the biosphere
Abstract. Alkyl nitrates (ANs) and peroxycarboxylic nitric anhydrides (PANs) are important reservoirs of reactive nitrogen that contribute significantly to the rate of formation and growth of secondary organic aerosols and support the transport of reactive nitrogen from polluted areas to remote areas. It is therefore critical to understand their sources and sinks in different environments. In this study we use measurements of OH, O3, NO3 reactivity, VOCs, ∑ANs and ∑PANs during the ACROSS campaign to investigate different production and loss processes of ANs and PANs in a temperate forest. At daytime OH-initiated processes were the dominant source of ANs (69–72 %) followed by NO3 (18–20 %) and O3 (8–12 %). At nighttime the contribution from OH decreased to 43–53 %, and NO3 increased to 26–40 % with that of O3 largely unchanged. Of the measured ∑PANs, 48–78 % was modelled to be peroxyacetic nitric anhydride (PAN). Physical loss (e.g. deposition) was an important sink for both ANs and PANs and contributed significantly to the very short lifetimes of 1.5 ± 1 h for ANs and 0.08–1.5 h for PANs observed during the campaign.
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CC1: 'Comment on egusphere-2024-3437', Domenico Taraborrelli, 18 Nov 2024
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In this study the box model CAABA/MECCA has been used. Its chemical scheme includes the gas-phase oxidation of over 40 emitted VOCs including APINENE,
BPINENE, C3H8, C5H8, CH3CHO, CH4, LIMONENE, and NC4H10. The scheme considers the alkyl nitrate yields as a function of heavy atoms number, functional groups, temperature and pressure (Sander et al. 2019). The updates, corrections and additions to the mechanism in the version 4.7.0 have recently been presented by Wieser et al. (2024). The authors have not used this VOC oxidation mechanism. Instead they have used MCM v3.3.1. The latter has constant alkyl nitrate yields pre-calculated at 298K and and many oxidation pathways have not been updated in a while. Can the authors comment on why they chose MCM for the analysis?References
Wieser, F., Sander, R., Cho, C., Fuchs, H., Hohaus, T., Novelli, A., Tillmann, R., and Taraborrelli, D.: Development of a multiphase chemical mechanism to improve secondary organic aerosol formation in CAABA/MECCA (version 4.7.0), Geosci. Model Dev., 17, 4311–4330, https://doi.org/10.5194/gmd-17-4311-2024, 2024.
Citation: https://doi.org/10.5194/egusphere-2024-3437-CC1 -
CC2: 'Reply on CC1', Rolf Sander, 19 Nov 2024
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We'd like to thank Domenico Taraborrelli for his comment. Indeed, the mechanism presented by Wieser et al. improves the modeling of alkyl nitrates. Unfortunately, however, the final version of the mechanism by Wieser et al. was not yet available when we performed the model simulations for our manuscript. In fact, merging the improved alkyl-nitrate chemistry into the main branch of the MECCA code is still work in progress.
We think that using the MCM mechanism for our study is an adequate choice because we focus on PANs, not on alkyl nitrates. We don't expect any major changes for the PANs when upgrading to the new mechanism by Wieser et al.
Citation: https://doi.org/10.5194/egusphere-2024-3437-CC2 -
CC3: 'Reply on CC2', Domenico Taraborrelli, 20 Nov 2024
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I would like to thank Rolf Sander for the prompt reply.
He is right saying that the mechanism by Wieser et al. (2024) is not yet final and included in the main equation file of MECCA. Nevertheless, it is already available in the model version 4.7.0 and I think it would have as well been an adequate mechanism for the analysis presented in this manuscript. If the focus of the latter is really on PANs I would expect anyway some differences compared to the results with MCM. Indeed in an idealized setup Sander et al. (2019) has already shown that the default mechanism predicted about 25% less PAN than MCM. Part of the reason is surely a different set of rate constants and branching ratios for the reactions involving CH3CO3. I would not exclude even larger differences under different conditions.
Another remark
L379 - L384 The authors state that the reason for the model-observation discrepancy for XO2 is not known. Vereecken et al. (2021) has shown that many isomers of XO2s from the NO3-initiated oxidation of isoprene are produced and that a large portion cannot be detected by LIF systems. As also shown by Wieser et al. (2024), model-observations discrepancies for XO2 can be very large. However, in L509 - L516 the authors suggest that in the high precursor day their large model-observation discrepancy is not a measurement issue. Therefore, the new NO3-isoprene chemistry seems to have the potential for reducing the model-observation gap presented in Fig. S6 especially for the nighttime.
References
Vereecken, L., Carlsson, P., Novelli, A., Bernard, F., Brown, S., Cho, C., Crowley, J., Fuchs, H., Mellouki, W., Reimer, D., Shenolikar, J., Tillmann, R., Zhou, L., Kiendler-Scharr, A., and Wahner, A.: Theoretical and experimental study of peroxy and alkoxy radicals in the NO3-initiated oxidation of isoprene, Phys. Chem. Chem. Phys., 23, 5496–5515, https://doi.org/10.1039/D0CP06267G, 2021.
Citation: https://doi.org/10.5194/egusphere-2024-3437-CC3
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CC3: 'Reply on CC2', Domenico Taraborrelli, 20 Nov 2024
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CC2: 'Reply on CC1', Rolf Sander, 19 Nov 2024
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Data sets
ACROSS_MPIC_RambForest_5ch-PNs-ANs_10min_L2 S. T. Andersen and J. N. Crowley https://doi.org/10.25326/706
ACROSS_MPIC_RambForest_5ch-NO2_1min_L2 S. T. Andersen and J. N. Crowley https://doi.org/10.25326/705
ACROSS_MPIC_RambForest_O3_10min_L1 J. N. Crowley https://doi.org/10.25326/707
ACROSS_CNRM_RambForest_MTO-1MIN_L2 C. Denjean https://doi.org/10.25326/437
ACROSS_MPIC_RambForest_ KNO3_10min_L2 P. Dewald and J. N. Crowley https://doi.org/10.25326/545
ACROSS_LPC2E_Rambforest_OH_L2 A. Kukui https://doi.org/10.25326/510
ACROSS_LPC2E_Rambforest_RO2_L2 A. Kukui https://doi.org/10.25326/509
ACROSS_2022_RambForest_LISA_PTRMS_VOCs_Belowcanopy_10min_20220617 - 20220723 V. Michoud et al. https://doi.org/10.25326/685
ACROSS_ICARE_RambForest_NO_L2 C. Xue et al. https://doi.org/10.25326/512
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