the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Composition and reactivity of volatile organic compounds in the South Coast Air Basin and San Joaquin Valley of California
Shang Liu
Barbara Barletta
Rebecca S. Hornbrook
Alan Fried
Jeff Peischl
Simone Meinardi
Matthew Coggon
Aaron Lamplugh
Jessica B. Gilman
Georgios I. Gkatzelis
Carsten Warneke
Eric C. Apel
Alan J. Hills
Ilann Bourgeois
James Walega
Petter Weibring
Dirk Richter
Toshihiro Kuwayama
Michael FitzGibbon
Donald Blake
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- Final revised paper (published on 29 Aug 2022)
- Supplement to the final revised paper
- Preprint (discussion started on 07 Jun 2022)
- Supplement to the preprint
Interactive discussion
Status: closed
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RC1: 'Comment on acp-2022-399', Anonymous Referee #1, 23 Jun 2022
This study contrasts airborne VOC concentrations and reactivity in the SJV and SOCAB regions of California with a focus on the implications for O3 in the region. The study is straight-forward and the manuscript was a pleasure to read – well organized and clear. I have only a few comments and suggestions.
- Rather than “total” OHR, I strongly suggest that the authors use the term “calculated”, as in for example, Thames et al, ACP, 2020. The manuscript does not include OHR measurements and referring to “total measured OHR” as in the abstract (line 20) could be misleading.
- This study is based on only two flights. It raises the question of representativeness of the measurements shown here. I suggest that the authors discuss this directly in the conclusions and also consider softening some statements, particularly those that rely on the distribution of values. For example, line 140 “O3 in the SoCAB may be more”
- The authors provide some contrast with previous studies, including CalNex (ines 259-261), but it would be informative to include even more discussion of how the SoCAB measurements in 2019 compare to the conditions in 2010 (and the earlier surface measurements in California listed in Table S1). In particular, it would be useful to discuss the relative decreases in VOCs and NOx, the impact on OHR, and any implications for the O3 production regime. There were also a couple of specific interesting differences from CalNex (as described in Heald et al., 2020) that would be useful to discuss the potential causes of: (a) ethanol:methanol > 2 in CalNex whereas this study reports that methanol concentrations exceed ethanol in the SoCAB in 2019 (b) limonene is below DL in this study (but comparable to methacrolein in 2010) – this seems interesting in light of the emphasis that this study places on the need to understand BVOC impacts on O3.
Minor comments/corrections:
- Line 25: “BVOCs were important”
- Line 42: “relatively high O3 background” – relative to what? I suggest that the authors modify to provide specific numbers (i.e. Fig 1 of Parrish et al. indicates 20-40 ppb, varying by season). Parrish et al., 2017 also show that the background is decreasing which would be worth stating here as well.
- Figure 1: it’s not really possible to distinguish the red and blue lines for flight 1 and 2 given the data overplotted. Perhaps for clarity the authors might consider removing those lines in Figure 1 and adding a figure in the SI that more clearly shows the two flight tracks.
- Table 1, entry #1: first name is “Thomas”
- Line 88-89: why is the slope on Fig S1 1.07? One would not expect mean values to be modified by merging to a different time base. Does this also reflect the filtering? If so, perhaps clarify this in the text.
- Line 93: were the higher altitude points also removed from Fig 1? If so, I suggest stating that here.
- Table 2: either footnote c or the top row should indicate that kOH is given at 298K. Footnote c should also state that references for reaction rates are given in the text, as readers may look for those here.
- Figure 4 discussion: The NOx OHR vs O3 relationship is very different between SJV and SoCAB – given that this is shown on the figure, it bears some discussion in the text.
- Line 253: you showed in Figure 3 that “the overall OHR in the SoCAB was 30% higher than in the SJV”, so perhaps “confirming as in Fig. 3” rather than “suggesting” would be appropriate here.
- Line 269 vs lines 239-240: Earlier in the text the authors suggest that it’s difficult to compare ground and airborne, but then here in line 269 the airborne measurements are compared to two ground sites and a model(!) in other regions of the world. If the authors stand by their statement on 239-240, then perhaps a caveat is needed here.
- Line 276-277: The Steiner et al. (2008) study is representative of conditions over a decade prior to this study, and clearly emissions have changed substantially in California over that time period (as shown here in comparison with previous work), so I suggest re-rephrasing “our measurements support” to “our measurements are consistent with…from over a decade prior.”
- Line 346: says “studies” but only one citation provided. Modify for consistency.
Citation: https://doi.org/10.5194/acp-2022-399-RC1 -
RC2: 'Comment on acp-2022-399', Anonymous Referee #2, 27 Jul 2022
Review for Liu et al., “Composition and reactivity of volatile organic compounds in the south coast air basin and San Joaquin Valley of California”
Review Summary
Liu et al present atmospheric composition measurements collected during two flights associated with the FIREX-AQ campaign in 2019. They analyzed VOCs, CO, NOx, and ozone from measurements collected below 1.2 km altitude. They estimated total OH reactivity including contributions to OH reactivity by different chemical constituents. They found that VOCs accounted for most OH reactivity, and oxygenated VOCs, in particular, accounted for more than 60% of the OH reactivity attributed to VOCs. Biogenic VOCs comprised a minor portion of the total VOC mixing ratio but accounted for 21% of the OH reactivity from VOCs in the South Coast Air Basin. Biogenic VOCs contributed to less of the OH reactivity in the San Joaquin Valley on these flight days. A steeper gradient in OH reactivity was observed in the South Coast Air Basin than the San Joaquin Valley, the latter of which was more homogeneously distributed. The data-set is unique, valuable to the scientific community, and a good fit for the journal. The analysis and context of the measurements could be improved with some minor modifications that I describe below.
General Comments
The authors should comment on expected temporal variability throughout the year to provide some context for how representative these two flight days were. Would you expect BVOC and OVOC emissions to be higher or lower in the winter and spring? And why? Many of the plants in the region are drought deciduous and go dormant in the summer and fall. In the San Joaquin Valley, what is the context for agricultural activity on these two days? Are there times of year when the BVOCs from ag plants might have a stronger contribution to OH reactivity in this area?
The conclusions would be better supported with some simple box modeling to estimate how much of the VOCs could have reacted away by the time the air parcel reached the aircraft. The authors mention this in a qualitative sense, but knowing the reaction rate constants, assuming some oxidant concentration, and estimating the air parcel age would allow them to be more quantitative in this assessment. Even some range of values would be helpful. Has >80% of the BVOCs reacted away already? <20%? They state that the VOCs have undergone photochemical processing for minutes to several hours, but this could be translated into a more meaningful estimate of how this equates to estimated percent loss of VOCs vs OVOCs. You could even estimate how much of the HCHO was contributed by BVOC oxidation vs OVOC oxidation, etc.
Specific Comments
The authors mention they only included measurements collected below 1.2 km. Can they clarify the PBL height? Are these within the PBL or in the free troposphere?
Table 2 provides incredibly detailed measurement information, but it’s unclear to me why it is in the methods section instead of the results. Aren’t these results?
It’s unclear what the main takeaway is from Figure 4. Can the authors please strengthen the discussion of this figure, better highlight its relevance, or remove it if that is not possible? As far as I can tell, the figure isn’t referenced anywhere in the text directly.
On page 16, the authors make comparisons to OVOC contributions reported in mainland China, Seoul, and Mexico City. Can the authors clarify that these were also flight measurements at a similar altitude? Or were these surface measurements? It would be helpful to know to provide context for the comparison.
Citation: https://doi.org/10.5194/acp-2022-399-RC2 - AC1: 'Author Comment on acp-2022-399', Shang Liu, 13 Aug 2022