Summertime tropospheric ozone source apportionment study in Madrid (Spain)

de la Paz, David; Borge, Rafael; de Andrés, Juan Manuel; Tovar, Luis Miguel; Sarwar, Golam; Napelenok, Sergey L.

doi:https://doi.org/10.5194/egusphere-2023-2056

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https://doi.org/10.5194/egusphere-2023-2056

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06 Oct 2023

| 06 Oct 2023

Summertime tropospheric ozone source apportionment study in Madrid (Spain)

David de la Paz, Rafael Borge, Juan Manuel de Andrés, Luis Miguel Tovar, Golam Sarwar, and Sergey L. Napelenok

Abstract. The design of emission abatement measures to effectivly reduce high ground-level ozone (O₃) concentrations in urban areas is very complex. In addition to the strongly non-linear chemistry of this secondary pollutant, precursors can be released by a variety of sources in different regions and locally produced O₃ is mixed with that transported from the regional or continental scales. All of these processes depend also on the specific meteorological conditons and topography of the study area. Consequently, high-resolution comprehensive modeling tools are needed to understand the drivers of photochemical pollution and to assess the potential of local strategies to reduce adverse impacts from high tropospheric O₃ levels. In this study, we apply the Integrated Source Apportionment Method (ISAM) implemented in the Community Multiscale Air Quality (CMAQv5.3.2) model to investigate the origin of summertime O₃ in the Madrid region (Spain). Consistent with previous studies, our results confirm that O₃ levels are dominated by non-local contributions, representing around 70 % of mean values across the region. Nonetheless, precursors emitted by local sources, mainly road traffic, play a more important role during O₃ peaks, with contributions as high as 25 ppb. The potential impact of local measures is higher under unfavorable meteorological conditions associated with regional accumulation patterns. These findings suggest that this modeling system may be used in the future to simulate the potential outcomes of specific emission abatement measures to prevent high-O₃ episodes in the Madrid metropolitan area.

Received: 07 Sep 2023 – Discussion started: 06 Oct 2023

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29 Apr 2024

Summertime tropospheric ozone source apportionment study in the Madrid region (Spain)

David de la Paz, Rafael Borge, Juan Manuel de Andrés, Luis Tovar, Golam Sarwar, and Sergey L. Napelenok

Atmos. Chem. Phys., 24, 4949–4972, https://doi.org/10.5194/acp-24-4949-2024,https://doi.org/10.5194/acp-24-4949-2024, 2024

Short summary

David de la Paz, Rafael Borge, Juan Manuel de Andrés, Luis Miguel Tovar, Golam Sarwar, and Sergey L. Napelenok

Interactive discussion

Status: closed

RC1: 'Comment on egusphere-2023-2056', Anonymous Referee #1, 01 Nov 2023

The manuscript “summertime tropospheric ozone source apportionment study in Madrid (Spain) by de la Paz et al. presents a ozone source apportionment study using ISAM in the CMAQ model over the Madrid region for July 2016.
While the topic of the paper is very interesting and fits into the scope of ACP, the manuscript lacks many important information and the results are discussed in an insufficient way. Therefore, I recommend to reject the manuscript. Please find below a more detailed review given some major and minor comments the authors should consider before the plan to resubmit the publication.
Reading the paper I had several major concerns which needs to be clarified.
1) The authors apply a new version of ISAM in CMAQ 5.3.2 which (to my knowledge) has not been used in similar publications before. According to the authors this new version attributes ozone to all involved precursors and NOT to the limiting precursor (e.g. NOx or VOC). Sadly, the manuscript is lacking any details on the new method. I guess the method is somehow similar to the method presented by Grewe et al., 2017? The results presented in the manuscript heavily depend on this method. Therefore, the method either needs to be presented before in a scientific publication (e.g. an update of Kwok et al., 2015 and not a youtube video) which is cited by the authors or the manuscripts needs to include a detailed presentation/discussion of the revised method.
2) Given the new method, I am missing a detailed discussion of the method and the results in comparison to previous publications ( see for example Butler et al., 2018 for a detailed discussion of many ozone tagging methods). Moreover, I am missing a critical discussion of the model results. As example, Fig.4 shows a contributions of more than 14 % of SNAP6 (solvents) to ozone over the mountain range north of Madrid. Given my understanding of the method and results of similar methods I wonder about this high contribution. How can this be explained? Moreover, I wonder about the small contribution of biogenic emissions, even though they account for a large fraction of the VOC emissions. If the method attributed ozone to all precursors, they should account for a larger fraction (?) Please clarify. In addition, the manuscript is lacking an overview of the definition of the different source attribution sectors (e.g. as table etc). From Fig 11 it seems that 12 different source sectors are considered.
3) I am missing any new results. The large importance of boundary conditions to ozone levels over the Iberian Peninsula have been reported by e.g. Pay et al., 2019. Also the larger importance of regional emissions to high ozone values have been presented in previous publications (maybe not focusing on Madrid). I like the detailed investigation of source attribution results for specific weather patterns, however, for a scientific publication in ACP more detailed analyses are needed in my opinion and the author need to highlight new findings in more detail.
4) The authors mix the physical quantities “concentration” and “mixing ratio”. They use the term concentration and use the unit ppb which suggest a (volume) mixing ratio. Please clarify the used physical quantity. Similarly, Fig. 2 does not give any physical quantities for the emissions. In addition, please clarify what emissions of NOx and VOC are. Are they given in amount of N, NO, NO2 and C or NMHC?
5) Parts of the manuscript are confusing and missing a proper proof-reading. As example, on P5l197 the authors write that Fig. 4 shows “average contributions”. The description of Fig.4, however, indicates that contribution to the 90^th percentile of ozone are given. Moreover, I find it very confusing, that the authors only show contributions to ozone attributed to anthropogenic origin. I suggest to always show contributions with respect to total ozone. Otherwise results are very hard to compare to other studies and readers might be confused.
6) In the last subsections the authors present a comparison with measurements. This comparison shows an underestimation of ozone simulated by the model under accumulation conditions during 13 -19 UTC, however the authors do not discuss this model bias. How does it affect the source apportionment results? It seems that the model underestimated local ozone production under this stagnant conditions. To my opinion, the manuscript should start with a model evaluation and discuss the source attribution results critically with respect to the model performance.
7) Given the importance of emissions from the previous day for ozone formation I wonder why the authors attribute them to “IC”. Wouldn’t it be better to account them also sectorwise?
8) Some of the reference seems to be not adequate. As an example, P3l118 cites Borgee et al., 2022 (https://doi.org/10.1016/j.scitotenv.2013.07.093), but I can’t find “tagging” nor “ISAM” in the whole paper. Maybe I misunderstood something, but the authors should check the manuscript carefully.
Some minor comments:
- Introduction: I am missing a discussion of similar source attribution studies (globally, for Europe) and a discussion of comparable source attribution methods.
- Fig 2: COVs instead of VOC
-p5l183 I wonder why the contribution of biogenic emissions is so small (see also major comments above).
- P3l109 What is the temporal resolution of the boundary conditions?
- p2l45 You mean STE is projected to increase? Please clarify.
- P2l47ff I am missing a discussion of the role of the non linearity of the ozone chemistry which lead to an increase of the ozone production efficiency when emissions are reduced. The authors should consider to add this point including a discussion of the relevant literature.
- p2l58 Please fix, should be Paoletti et. al, 2014
- p5l160 How is soil-NOx handled?
- p5l185 But Pay et al, 2019 applies the “old” ISAM tagging, right? So I would expect a difference with the new approach? Please discuss.
References:
Butler, T., Lupascu, A., Coates, J., and Zhu, S.: TOAST 1.0: Tropospheric Ozone Attribution of Sources with Tagging for CESM 1.2.2, Geosci. Model Dev., 11, 2825–2840, https://doi.org/10.5194/gmd-11-2825-2018, 2018
Grewe, V., Tsati, E., Mertens, M., Frömming, C., and Jöckel, P.: Contribution of emissions to concentrations: the TAGGING 1.0 submodel based on the Modular Earth Submodel System (MESSy 2.52), Geosci. Model Dev., 10, 2615–2633, https://doi.org/10.5194/gmd-10-2615-2017, 2017.

Citation: https://doi.org/10.5194/egusphere-2023-2056-RC1
RC2: 'Comment on egusphere-2023-2056', Anonymous Referee #2, 23 Nov 2023

Please find the review comments attached.
Thanks,

Citation: https://doi.org/10.5194/egusphere-2023-2056-RC2
AC1: 'Comment on egusphere-2023-2056: final response from authors', Rafael Borge, 24 Jan 2024

Dear editor, thank you for the opportunity to revise our submission and provide responses to the points raised by both anonymous reviewers. We acknowledge them for fruitful critics and for their suggestions that helped us to improve our work.
In the document attached we provide point-to-point responses to each of their questions and comments. The author comments are structured according to ACP guidelines and follow the recommended sequence: comments from the referees (RC1 and RC2) are shown in blue, then we provide our responses in black and the main changes made in the manuscript are included in red. We respond to both reviewers in the same document. Although we provide a common response to the points raised in some cases we duplicate the corresponding explanations to facilitate the work of both reviewers.
Since we made substantial changes throughout the document, we include the revised version of our submission in full (manuscript and supplementary material with changes highlighted in red) at the end of this document for the sake of clarity.

Citation: https://doi.org/10.5194/egusphere-2023-2056-AC1

Interactive discussion

Status: closed

RC1: 'Comment on egusphere-2023-2056', Anonymous Referee #1, 01 Nov 2023

The manuscript “summertime tropospheric ozone source apportionment study in Madrid (Spain) by de la Paz et al. presents a ozone source apportionment study using ISAM in the CMAQ model over the Madrid region for July 2016.
While the topic of the paper is very interesting and fits into the scope of ACP, the manuscript lacks many important information and the results are discussed in an insufficient way. Therefore, I recommend to reject the manuscript. Please find below a more detailed review given some major and minor comments the authors should consider before the plan to resubmit the publication.
Reading the paper I had several major concerns which needs to be clarified.
1) The authors apply a new version of ISAM in CMAQ 5.3.2 which (to my knowledge) has not been used in similar publications before. According to the authors this new version attributes ozone to all involved precursors and NOT to the limiting precursor (e.g. NOx or VOC). Sadly, the manuscript is lacking any details on the new method. I guess the method is somehow similar to the method presented by Grewe et al., 2017? The results presented in the manuscript heavily depend on this method. Therefore, the method either needs to be presented before in a scientific publication (e.g. an update of Kwok et al., 2015 and not a youtube video) which is cited by the authors or the manuscripts needs to include a detailed presentation/discussion of the revised method.
2) Given the new method, I am missing a detailed discussion of the method and the results in comparison to previous publications ( see for example Butler et al., 2018 for a detailed discussion of many ozone tagging methods). Moreover, I am missing a critical discussion of the model results. As example, Fig.4 shows a contributions of more than 14 % of SNAP6 (solvents) to ozone over the mountain range north of Madrid. Given my understanding of the method and results of similar methods I wonder about this high contribution. How can this be explained? Moreover, I wonder about the small contribution of biogenic emissions, even though they account for a large fraction of the VOC emissions. If the method attributed ozone to all precursors, they should account for a larger fraction (?) Please clarify. In addition, the manuscript is lacking an overview of the definition of the different source attribution sectors (e.g. as table etc). From Fig 11 it seems that 12 different source sectors are considered.
3) I am missing any new results. The large importance of boundary conditions to ozone levels over the Iberian Peninsula have been reported by e.g. Pay et al., 2019. Also the larger importance of regional emissions to high ozone values have been presented in previous publications (maybe not focusing on Madrid). I like the detailed investigation of source attribution results for specific weather patterns, however, for a scientific publication in ACP more detailed analyses are needed in my opinion and the author need to highlight new findings in more detail.
4) The authors mix the physical quantities “concentration” and “mixing ratio”. They use the term concentration and use the unit ppb which suggest a (volume) mixing ratio. Please clarify the used physical quantity. Similarly, Fig. 2 does not give any physical quantities for the emissions. In addition, please clarify what emissions of NOx and VOC are. Are they given in amount of N, NO, NO2 and C or NMHC?
5) Parts of the manuscript are confusing and missing a proper proof-reading. As example, on P5l197 the authors write that Fig. 4 shows “average contributions”. The description of Fig.4, however, indicates that contribution to the 90^th percentile of ozone are given. Moreover, I find it very confusing, that the authors only show contributions to ozone attributed to anthropogenic origin. I suggest to always show contributions with respect to total ozone. Otherwise results are very hard to compare to other studies and readers might be confused.
6) In the last subsections the authors present a comparison with measurements. This comparison shows an underestimation of ozone simulated by the model under accumulation conditions during 13 -19 UTC, however the authors do not discuss this model bias. How does it affect the source apportionment results? It seems that the model underestimated local ozone production under this stagnant conditions. To my opinion, the manuscript should start with a model evaluation and discuss the source attribution results critically with respect to the model performance.
7) Given the importance of emissions from the previous day for ozone formation I wonder why the authors attribute them to “IC”. Wouldn’t it be better to account them also sectorwise?
8) Some of the reference seems to be not adequate. As an example, P3l118 cites Borgee et al., 2022 (https://doi.org/10.1016/j.scitotenv.2013.07.093), but I can’t find “tagging” nor “ISAM” in the whole paper. Maybe I misunderstood something, but the authors should check the manuscript carefully.
Some minor comments:
- Introduction: I am missing a discussion of similar source attribution studies (globally, for Europe) and a discussion of comparable source attribution methods.
- Fig 2: COVs instead of VOC
-p5l183 I wonder why the contribution of biogenic emissions is so small (see also major comments above).
- P3l109 What is the temporal resolution of the boundary conditions?
- p2l45 You mean STE is projected to increase? Please clarify.
- P2l47ff I am missing a discussion of the role of the non linearity of the ozone chemistry which lead to an increase of the ozone production efficiency when emissions are reduced. The authors should consider to add this point including a discussion of the relevant literature.
- p2l58 Please fix, should be Paoletti et. al, 2014
- p5l160 How is soil-NOx handled?
- p5l185 But Pay et al, 2019 applies the “old” ISAM tagging, right? So I would expect a difference with the new approach? Please discuss.
References:
Butler, T., Lupascu, A., Coates, J., and Zhu, S.: TOAST 1.0: Tropospheric Ozone Attribution of Sources with Tagging for CESM 1.2.2, Geosci. Model Dev., 11, 2825–2840, https://doi.org/10.5194/gmd-11-2825-2018, 2018
Grewe, V., Tsati, E., Mertens, M., Frömming, C., and Jöckel, P.: Contribution of emissions to concentrations: the TAGGING 1.0 submodel based on the Modular Earth Submodel System (MESSy 2.52), Geosci. Model Dev., 10, 2615–2633, https://doi.org/10.5194/gmd-10-2615-2017, 2017.

Citation: https://doi.org/10.5194/egusphere-2023-2056-RC1
RC2: 'Comment on egusphere-2023-2056', Anonymous Referee #2, 23 Nov 2023

Please find the review comments attached.
Thanks,

Citation: https://doi.org/10.5194/egusphere-2023-2056-RC2
AC1: 'Comment on egusphere-2023-2056: final response from authors', Rafael Borge, 24 Jan 2024

Dear editor, thank you for the opportunity to revise our submission and provide responses to the points raised by both anonymous reviewers. We acknowledge them for fruitful critics and for their suggestions that helped us to improve our work.
In the document attached we provide point-to-point responses to each of their questions and comments. The author comments are structured according to ACP guidelines and follow the recommended sequence: comments from the referees (RC1 and RC2) are shown in blue, then we provide our responses in black and the main changes made in the manuscript are included in red. We respond to both reviewers in the same document. Although we provide a common response to the points raised in some cases we duplicate the corresponding explanations to facilitate the work of both reviewers.
Since we made substantial changes throughout the document, we include the revised version of our submission in full (manuscript and supplementary material with changes highlighted in red) at the end of this document for the sake of clarity.

Citation: https://doi.org/10.5194/egusphere-2023-2056-AC1

Peer review completion

AR: Author's response | RR: Referee report | ED: Editor decision | EF: Editorial file upload

AR by Rafael Borge on behalf of the Authors (29 Jan 2024) Author's response Author's tracked changes Manuscript

ED: Referee Nomination & Report Request started (06 Feb 2024) by Tim Butler

RR by Johana Romero Alvarez (22 Feb 2024)

RR by Anonymous Referee #1 (23 Feb 2024)

Suggestions for revision or reasons for rejection

The authors have done a good job in revising the manuscript. Before I can recommend the manuscript for publication, however, a few details still need to be clarified:

1) Figure 2: Please add the unit (%) to the axis. Moreover, I wonder if it would be much more helpful for the reader if the figure would show the share of the emissions during the analyzed period and not for the whole year (the share of biogenic emissions might be much larger during summer as for the annual mean?).

2) To my opinion a table which lists all the tagged sectors including a short description would be very helpful. Figure 2 lists only the emissions, Fig. 12 lists all tagged sectors but using acronyms only i.e. the reader has to search for the meaning of “OTH” or “PVO3”. Also the tagged biogenic emissions are labeled SNAP10-11 in Figure 2 and BIO in Figure 12. Please use a unique naming scheme.

3) I think the newly added discussion on the contribution of biogenic emissions in Sect. 3.2 is interesting, but the section seems unbalanced to me. The authors write: “O3 apportionment to biogenic emissions is not considered in Figure 4 because i) they have less interest from the point of view of possible abatement measures (Oliveira et al., 2023) and ii) their contribution is relatively small”. After this statement they add one page of discussion on biogenic emissions and only after this discussion the figure is discussed further. I feel this newly added part would much better fit into a dedicated “Discussion” section (or at the end of Sect. 3.2)

4) Please clarify L426: “This relates to second-order interactions between sources (U.S. EPA, 2022). This represents a negligible fraction in this study, i.e. ISAM could attribute the virtual totality of O3 to any of the other sources” What is meant by “ second-order interactions between sources”?

5) Please fix wrong usage of citations with (author) instead of author (e.g. (Paoletti et al., 2014) )

Hide

ED: Publish subject to minor revisions (review by editor) (25 Feb 2024) by Tim Butler

AR by Rafael Borge on behalf of the Authors (06 Mar 2024) Author's response Author's tracked changes

EF by Sarah Buchmann (07 Mar 2024) Manuscript

EF by Sarah Buchmann (07 Mar 2024) Supplement

ED: Publish as is (12 Mar 2024) by Tim Butler

AR by Rafael Borge on behalf of the Authors (19 Mar 2024) Manuscript

Journal article(s) based on this preprint

29 Apr 2024

Summertime tropospheric ozone source apportionment study in the Madrid region (Spain)

David de la Paz, Rafael Borge, Juan Manuel de Andrés, Luis Tovar, Golam Sarwar, and Sergey L. Napelenok

Atmos. Chem. Phys., 24, 4949–4972, https://doi.org/10.5194/acp-24-4949-2024,https://doi.org/10.5194/acp-24-4949-2024, 2024

Short summary

David de la Paz, Rafael Borge, Juan Manuel de Andrés, Luis Miguel Tovar, Golam Sarwar, and Sergey L. Napelenok

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https://doi.org/10.5194/egusphere-2023-2056-supplement

David de la Paz, Rafael Borge, Juan Manuel de Andrés, Luis Miguel Tovar, Golam Sarwar, and Sergey L. Napelenok

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This modelling study shows that around 70 % of ground-level ozone (O₃) in Madrid (Spain) is transported from other regions. Nonetheless, local sources, mainly road traffic, play a significant role, specially under stagnation conditions associated to regional air recirculation. Our results suggest that local measures may be effective to reduce O₃ peaks (potentially, up to 30 %) and thus, reduce impacts from high-O₃ episodes in the Madrid metropolitan area.


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