Assessing acetone for the GISS ModelE2.1 Earth system model

Rivera, Alexandra; Tsigaridis, Kostas; Faluvegi, Gregory; Shindell, Drew

doi:https://doi.org/10.5194/egusphere-2023-110

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https://doi.org/10.5194/egusphere-2023-110

Preprints

12 Jun 2023

| 12 Jun 2023

Assessing acetone for the GISS ModelE2.1 Earth system model

Alexandra Rivera, Kostas Tsigaridis, Gregory Faluvegi, and Drew Shindell

Abstract. Acetone is an abundant volatile organic compound in the atmosphere with important influence on ozone and oxidation capacity. Direct sources include anthropogenic, terrestrial vegetation, oceanic, and biomass burning emissions. Acetone is also produced chemically from other volatile organic compounds. Sinks include deposition onto the land and ocean surfaces, as well as chemical loss. Acetone’s lifetime is long enough to allow transport and reactions with other compounds remote from its sources. The latest NASA Goddard Institute for Space Studies (GISS) Earth System Model, ModelE2.1, simulates a variety of Earth system interactions. Previously, acetone had a very simplistic representation in the ModelE chemical scheme. This study assesses a more sophisticated acetone scheme, in which acetone is a full 3-dimensional tracer, with explicit sources, sinks and atmospheric transport. We evaluate the new global acetone budget in the context of past literature. Anthropogenic emissions, vegetation emissions, biomass burning, and deposition representations agree well with previous studies. Chemistry and the ocean contribute to both sources and sinks of acetone, with their net values agreeing with the literature, although their individual source and sink terms appear to be overestimated for chemistry and underestimated for ocean fluxes. We find the production of acetone from precursor hydrocarbon oxidation has strong leverage on the overall chemical source, indicating the importance of accurate molar yields for this source. Spatial distributions reveal that ocean uptake of acetone is strongest in northern latitudes, while production is mainly in mid-southern latitudes. The seasonality of acetone-related processes was also studied in conjunction with field measurements around the world. These comparisons show promising agreement, but have shortcomings at urban locations, since the model’s resolution is too coarse to capture behavior in high-emission areas. Overall, our analysis of the acetone budget aids the development of this tracer in the GISS ModelE2.1, a crucial step to understanding the role of acetone in the atmosphere.

Received: 10 Feb 2023 – Discussion started: 12 Jun 2023

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Journal article(s) based on this preprint

02 May 2024

Assessing acetone for the GISS ModelE2.1 Earth system model

Alexandra Rivera, Kostas Tsigaridis, Gregory Faluvegi, and Drew Shindell

Geosci. Model Dev., 17, 3487–3505, https://doi.org/10.5194/gmd-17-3487-2024,https://doi.org/10.5194/gmd-17-3487-2024, 2024

Short summary

Alexandra Rivera, Kostas Tsigaridis, Gregory Faluvegi, and Drew Shindell

Interactive discussion

Status: closed

RC1:
'Comment on egusphere-2023-110', Anonymous Referee #1, 01 Aug 2023
This paper presents an improved representation of acetone in GISS ModelE2.1 and evaluates it with observations. I don’t understand why this is submitted to GMD considering that there is no originality or particular difficulty on the model development front – the approach replicates what has routinely been used by other models to describe acetone sources and sinks, without any tangible improvement. From a model development standpoint the implementation is trivial. I could see the value of documenting in GMD a major update to GISS ModelE chemistry affecting the simulation of species relevant to chemistry-climate interactions, but acetone is not important enough to rise to that standard, and the paper does not discuss how improved simulation of acetone affects the model’s chemistry – presumably not much.
In my opinion, this paper is not a significant contribution to model development and is well below the standard of papers published in GMD. Publishing it might actually do some harm because it might be perceived as a new take on the global budget of acetone, which has not been revisited for some years, but in fact there is no innovation here aside from the evaluation with ATom measurements, and anthropogenic emission inventories are for 2000 which is dated. The evaluation with ATom is in my view the most interesting part of the paper but the interpretation is cursory.
A few specific comments:
Line 39: acetone is not highly water-soluble by atmospheric standards.

Line 40: oxidation of acetone by OH is not a net source of radicals.

Line 170: what spectroscopic and quantum yield data are used for acetone photolysis? There has been some work done on that recently.

Line 180: Where does the fixed ocean concentration of 15 nM come from? What is the justification for assuming a fixed concentration? This obviously effects the sign and geographical distribution of the air-sea acetone fluxes mentioned in the abstract.

Lines 228-229, 257-258: documenting the improvement over the previous GISS ModelE parameterization of acetone is of little interest considering that the previous parameterization was so crude by current model standards.

Line 325: why would there be non-linearities in the system? I presume that the acetone simulations use the full chemistry mechanism (although that’s not clear – it could also be done with archived OH fields and production rates) but since acetone is in general a minor player in oxidant chemistry I don’t see why there would be significant non-linearities. The asymmetry in response to doubling/halving is not necessarily a sign of non-linearity in the presence of other sources/sinks. If there is indeed significant non-linearity the authors should explain why.

Lines 383-384: analysis of the evaluation with ATom observation is limited to uninstructive throwaway statements. The authors should do better. Would correlations with other chemical species be insightful?
Citation: https://doi.org/10.5194/egusphere-2023-110-RC1
- AC1: 'Reply on RC1', Kostas Tsigaridis, 13 Dec 2023
  
  The comment was uploaded in the form of a supplement: https://egusphere.copernicus.org/preprints/2023/egusphere-2023-110/egusphere-2023-110-AC1-supplement.pdf
  
  Citation: https://doi.org/10.5194/egusphere-2023-110-AC1
RC2:
'Comment on egusphere-2023-110', Anonymous Referee #2, 12 Sep 2023

Acetone is an important molecule in troposphere chemistry cycles and to model it correctly a rather sophisticated scheme is needed because of the complex sources and sinks including biological, chemical and physical processes. Also to note is that acetone has been well studied but recent widespread measurements provide an opportunity to further refine models.
Significant effort was put into the work described in this paper and the authors made good progress toward improving their GISS model representation of acetone. If this is sufficient for publication in this journal then fine and I can provide a more thorough review. However if, to be published in this journal, (which I am not very familiar with) there is a requirement that the paper provides an important contribution to our understanding of acetone in the atmosphere then it falls short because, although significant progress was made on this model, the work does not represent an improvement over previous modeling efforts. If this is the case I would recommend rejecting the paper. The editor will have to make the call on this.
There are some things in the paper that cause concern on my part. One is that the derived chemical lifetime from the expression (burden (Tg) /sink (Tg/year)) is too short. (Also, the burden units are wrong on line 203). The kinetics of the reaction of acetone with OH is well known and the authors have the correct expressions on line 169. Based on the OH reaction, if one assumes that the diurnal [OH] is 0.7E * 05, then the chemical lifetime derived due to OH reaction is 95 days. The lifetime with respect to Cl is significantly longer than this and the lifetime with respect to photolysis is also longer than this. So combined the actual atmospheric chemical lifetime is most likely > 40 days. However the derived value in the paper from burden/sink is 20 days which to me indicates a problem with the formulation of either the burden or the sink terms that needs to be investigated further.
Another shortcoming is the chemical representation in the model. The chemical scheme appears to be rudimentary and also seems to have errors.
The authors state: “Initial tests using a yield of 0.72 resulted in an overestimated chemistry source, leading us to re-evaluate this yield for the specific mixture of VOCs represented in the GISS ModelE2.1. Estimated mole fractions of propane (11%), butane (22%) and pentane (21%) in anthropogenic emissions were multiplied by each compound’s acetone molar yield (0.73, 0.95, 0.63, respectively), determining that 42% of paraffin from anthropogenic sources becomes acetone”.
The authors don’t reference where they got their estimated mole fractions from anthropogenic emissions or where they got the molar yield of acetone for each compound. Furthermore the molar yields are incorrect. Although propane does in fact form acetone with a significant yield, butane and pentane do not.
In summary, I refer to my comments above in the second paragraph.

Citation: https://doi.org/10.5194/egusphere-2023-110-RC2
- AC2: 'Reply on RC2', Kostas Tsigaridis, 13 Dec 2023
  
  The comment was uploaded in the form of a supplement: https://egusphere.copernicus.org/preprints/2023/egusphere-2023-110/egusphere-2023-110-AC2-supplement.pdf
  
  Citation: https://doi.org/10.5194/egusphere-2023-110-AC2

Interactive discussion

Status: closed

RC1:
'Comment on egusphere-2023-110', Anonymous Referee #1, 01 Aug 2023
This paper presents an improved representation of acetone in GISS ModelE2.1 and evaluates it with observations. I don’t understand why this is submitted to GMD considering that there is no originality or particular difficulty on the model development front – the approach replicates what has routinely been used by other models to describe acetone sources and sinks, without any tangible improvement. From a model development standpoint the implementation is trivial. I could see the value of documenting in GMD a major update to GISS ModelE chemistry affecting the simulation of species relevant to chemistry-climate interactions, but acetone is not important enough to rise to that standard, and the paper does not discuss how improved simulation of acetone affects the model’s chemistry – presumably not much.
In my opinion, this paper is not a significant contribution to model development and is well below the standard of papers published in GMD. Publishing it might actually do some harm because it might be perceived as a new take on the global budget of acetone, which has not been revisited for some years, but in fact there is no innovation here aside from the evaluation with ATom measurements, and anthropogenic emission inventories are for 2000 which is dated. The evaluation with ATom is in my view the most interesting part of the paper but the interpretation is cursory.
A few specific comments:
Line 39: acetone is not highly water-soluble by atmospheric standards.

Line 40: oxidation of acetone by OH is not a net source of radicals.

Line 170: what spectroscopic and quantum yield data are used for acetone photolysis? There has been some work done on that recently.

Line 180: Where does the fixed ocean concentration of 15 nM come from? What is the justification for assuming a fixed concentration? This obviously effects the sign and geographical distribution of the air-sea acetone fluxes mentioned in the abstract.

Lines 228-229, 257-258: documenting the improvement over the previous GISS ModelE parameterization of acetone is of little interest considering that the previous parameterization was so crude by current model standards.

Line 325: why would there be non-linearities in the system? I presume that the acetone simulations use the full chemistry mechanism (although that’s not clear – it could also be done with archived OH fields and production rates) but since acetone is in general a minor player in oxidant chemistry I don’t see why there would be significant non-linearities. The asymmetry in response to doubling/halving is not necessarily a sign of non-linearity in the presence of other sources/sinks. If there is indeed significant non-linearity the authors should explain why.

Lines 383-384: analysis of the evaluation with ATom observation is limited to uninstructive throwaway statements. The authors should do better. Would correlations with other chemical species be insightful?
Citation: https://doi.org/10.5194/egusphere-2023-110-RC1
- AC1: 'Reply on RC1', Kostas Tsigaridis, 13 Dec 2023
  
  The comment was uploaded in the form of a supplement: https://egusphere.copernicus.org/preprints/2023/egusphere-2023-110/egusphere-2023-110-AC1-supplement.pdf
  
  Citation: https://doi.org/10.5194/egusphere-2023-110-AC1
RC2:
'Comment on egusphere-2023-110', Anonymous Referee #2, 12 Sep 2023

Acetone is an important molecule in troposphere chemistry cycles and to model it correctly a rather sophisticated scheme is needed because of the complex sources and sinks including biological, chemical and physical processes. Also to note is that acetone has been well studied but recent widespread measurements provide an opportunity to further refine models.
Significant effort was put into the work described in this paper and the authors made good progress toward improving their GISS model representation of acetone. If this is sufficient for publication in this journal then fine and I can provide a more thorough review. However if, to be published in this journal, (which I am not very familiar with) there is a requirement that the paper provides an important contribution to our understanding of acetone in the atmosphere then it falls short because, although significant progress was made on this model, the work does not represent an improvement over previous modeling efforts. If this is the case I would recommend rejecting the paper. The editor will have to make the call on this.
There are some things in the paper that cause concern on my part. One is that the derived chemical lifetime from the expression (burden (Tg) /sink (Tg/year)) is too short. (Also, the burden units are wrong on line 203). The kinetics of the reaction of acetone with OH is well known and the authors have the correct expressions on line 169. Based on the OH reaction, if one assumes that the diurnal [OH] is 0.7E * 05, then the chemical lifetime derived due to OH reaction is 95 days. The lifetime with respect to Cl is significantly longer than this and the lifetime with respect to photolysis is also longer than this. So combined the actual atmospheric chemical lifetime is most likely > 40 days. However the derived value in the paper from burden/sink is 20 days which to me indicates a problem with the formulation of either the burden or the sink terms that needs to be investigated further.
Another shortcoming is the chemical representation in the model. The chemical scheme appears to be rudimentary and also seems to have errors.
The authors state: “Initial tests using a yield of 0.72 resulted in an overestimated chemistry source, leading us to re-evaluate this yield for the specific mixture of VOCs represented in the GISS ModelE2.1. Estimated mole fractions of propane (11%), butane (22%) and pentane (21%) in anthropogenic emissions were multiplied by each compound’s acetone molar yield (0.73, 0.95, 0.63, respectively), determining that 42% of paraffin from anthropogenic sources becomes acetone”.
The authors don’t reference where they got their estimated mole fractions from anthropogenic emissions or where they got the molar yield of acetone for each compound. Furthermore the molar yields are incorrect. Although propane does in fact form acetone with a significant yield, butane and pentane do not.
In summary, I refer to my comments above in the second paragraph.

Citation: https://doi.org/10.5194/egusphere-2023-110-RC2
- AC2: 'Reply on RC2', Kostas Tsigaridis, 13 Dec 2023
  
  The comment was uploaded in the form of a supplement: https://egusphere.copernicus.org/preprints/2023/egusphere-2023-110/egusphere-2023-110-AC2-supplement.pdf
  
  Citation: https://doi.org/10.5194/egusphere-2023-110-AC2

Peer review completion

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

AR by Kostas Tsigaridis on behalf of the Authors (13 Dec 2023) Author's response Author's tracked changes Manuscript

ED: Publish subject to minor revisions (review by editor) (26 Jan 2024) by Sergey Gromov

Dear Kostas Tsigaridis and co-authors,

Thank you for submitting the revised version of your manuscript. I find the reviewers’ comments have resulted in a perceptible increase in the manuscript quality. I do not share reviewers’ criticism regarding the suitability of this study publication for GMD (we need to document model development in either way), however I very second them in the opinion that the very “climatological” design of the model simulations and limited analysis depth do not allow any new insights on atmospheric acetone.
The latter is also the reason why I cannot suggest you resubmitting this manuscript to, e.g., the ACP. Furthermore, the presented analysis is overburden with figures and statements, yet it lacks in-depth discussion on processes (e.g. chemical feedbacks claimed) and thus offers only limited insights about what could be improved in the future in modelling acetone with this or another modelling system.
However, I see the way for this study being published here, provided that you address all the specific comments outlined below (please find copies of the manuscript/supplement with respective statements highlighted). These address presentation issues, overstated claims and reduction of the amount of presented material. Provided that all these remarks are addressed, I will be ready to reconsider the publication of the revised manuscript.

With best regards,
S. Gromov

General remarks
L23-24 This is an overstatement, as you do not present an analysis offering a “crucial step to umderstding the role of acetone in the atmosphere”. Please reformulate accordingly, i.e. stating that the new implementation results in acetone budget/turnover in line with previous studies.
L533-534 Neither reviewers nor myself can confirm your being extensive, please reformulate accordingly or remove the sentence.
L540-541 Same as above, consider removing this sentence.

Specific remarks
Main text
L98-99 Please add which data product the ocean surface conditions are derived from.
L124,130,231 Please use correct statistical term, i.e. you are presenting interannual variations, not the variability (which is the measure of the true population spread you do not have information on).
L126 Same as above, perhaps use “differences between models”.
L131 From the figure caption it is ambiguous whether C3H6 or acetone emissions are shown. Do you present fluxes or acetone calculated from C3H6 fluxes? With which yield?
L152,167,etc. Please use standard mathematical notation (base 10 instead of engineering E+- exponent, e instead of exp()) in reaction rate expressions throughout the manuscript.
L182-182 To be precise, all atmospheric reactions are pressure- and temperature-dependent simply due to changes in air density. Please use “reaction rate” instead of just “reaction”.
L183 You imply photolysis quantum yields?
L198-199 Please refomulate sentence clearer. You are interested in sensitivity of simulated acetone burden/turnover to perturbations in a given parameter, I assume.
L199 By “sources” you rather mean “production”, please avoid potential misunderstanding as “surface sources” or “direct sources” (e.g. L202).
L218-220 Please do not use negative figures for categories already implying removal (chem. sink, deposition) to avoid ambiguity. Use brackets in negative net fluxes ranges, e.g. −(a−b).
L237-238 Please reformulate the sentence. It is not clear what you want to state. As of now, it appears that this comparison is not intended to corroborate your estimates, then what is it presented for?
L265 Omit either “negative” or the minus sign whilte reporting the flux here.
L262-270 Please remove Figure 4 (it contains the summary of the features seen in Figure 5 and described in this statement. Please reformulate the paragraph accordingly.
L291-300 Please combine Figures 6 and 7 into one, i.e. showing loss, source and net in one row next to each other.
L305-306 How high is “as high”? You likely imply “troposphere”, not “atmosphere”?
L317-318 It is an erroneous approach to average mixing ratios simply arithmetically because the air density changes significantly in the regarder altitude ranges. Please recalculate with mass-weighting of mixing ratios and replot.
L355-361 Please quote RMSE values in respective plot panels in the figure, similar to that in Figure 10.
L365 Please use the regular equal sign (“=”), use of “approximately equal” is inappropriate here.
L370-393 Please move Figures 12 and 13 to the Supplement.
L422-432 The analysis of chemistry sensitivity studies offers no insights (read is very shallow), at least explicate the mechanism responsible for the “feedbacks” (L424-428). Please mention results for Chem_Cl0 in the paragraph text, not the Figure 15 caption. Please move Figure 15 to the supplement.
L433-444 Move Figure 16 to the Supplement to accompany Fig. S14.
L459-462 Reformulate the sentence – you iterate “increase” 11 times here. E.g. strongest increase is seen in Ispra (38.4%), Kosetice (…) etc.
L503,510,517 Please use “observations” instead of “measurements” (the latter are the act of measuring, so you can’t “underestimate” these).
L521-523 This is a self-contradictory statement, please reformulate.
L527 Please amend the sentence, which “some conditions” are implied?
L557 Make sure the URL data to the Zenodo publication points at doi.org or zenodo.org (currently it points at some address starting with urldefense.com)

Figures 10, 18, S3−S5, S15
Currently the symbols for individual observations are barely distinguishable either on the screen or in hard-copy. Please re-plot figures with thicker symbols (you may also use pluses “+”) in better visible colours (e.g. red). Please use vector graphics for these comparison plots.

Supplement
Please number the sections sequentially, e.g. S1, S2 etc.

Comments to the Author: PDF

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AR by Kostas Tsigaridis on behalf of the Authors (16 Feb 2024) Author's response Author's tracked changes Manuscript

ED: Publish as is (29 Feb 2024) by Sergey Gromov

AR by Kostas Tsigaridis on behalf of the Authors (12 Mar 2024)

Journal article(s) based on this preprint

02 May 2024

Assessing acetone for the GISS ModelE2.1 Earth system model

Alexandra Rivera, Kostas Tsigaridis, Gregory Faluvegi, and Drew Shindell

Geosci. Model Dev., 17, 3487–3505, https://doi.org/10.5194/gmd-17-3487-2024,https://doi.org/10.5194/gmd-17-3487-2024, 2024

Short summary

Alexandra Rivera, Kostas Tsigaridis, Gregory Faluvegi, and Drew Shindell

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https://doi.org/10.5194/egusphere-2023-110-supplement

Alexandra Rivera, Kostas Tsigaridis, Gregory Faluvegi, and Drew Shindell

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This paper describes and evaluates an improvement to the representation of acetone in the GISS ModelE2.1 Earth system model. We simulate acetone's concentration and transport across the atmosphere, as well as its dependence on chemistry, the ocean, and various global emissions. Comparisons of our model’s estimates to past modeling studies and field measurements have shown encouraging results. Ultimately, this paper contributes to a broader understanding of acetone's role in the atmosphere.


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