Seasonal variations in photooxidant formation and light absorption in aqueous extracts of ambient particles

Ma, Lan; Worland, Reed; Heinlein, Laura; Guzman, Chrystal; Jiang, Wenqing; Niedek, Christopher; Bein, Keith J.; Zhang, Qi; Anastasio, Cort

doi:https://doi.org/10.5194/egusphere-2023-861

Preprints

https://doi.org/10.5194/egusphere-2023-861

Preprints

11 May 2023

| 11 May 2023

Seasonal variations in photooxidant formation and light absorption in aqueous extracts of ambient particles

Lan Ma, Reed Worland, Laura Heinlein, Chrystal Guzman, Wenqing Jiang, Christopher Niedek, Keith J. Bein, Qi Zhang, and Cort Anastasio

Abstract. Atmospheric waters – including fog/cloud drops and aerosol liquid water – are important sites for the transformations of atmospheric species, largely through reactions with photoformed oxidants such as hydroxyl radical (^●OH), singlet molecular oxygen (¹O₂*), and oxidizing triplet excited states of organic matter (³C*). Despite this, there are few measurements of these photooxidants, especially in extracts of ambient particles, and very little information about how oxidant levels vary with season or particle type. To address this gap, we collected ambient PM_2.5 from Davis, California over the course of a year and measured photooxidant concentrations in dilute aqueous extracts of the particles. We categorized samples into four groups: Winter & Spring (Win-Spr), Summer & Fall (Sum-Fall) without wildfire influence, fresh biomass burning (FBB), and aged biomass burning (ABB). FBB contains significant amounts of brown carbon (BrC) from wildfires, and the highest mass absorption coefficients (MAC) normalized by dissolved organic carbon, with an average (± 1 σ) value of 3.3 (± 0.4) m² (g C)⁻¹ at 300 nm. Win-Spr and ABB have similar MAC averages, 1.9 (± 0.4) and 1.5 (± 0.3) m² (g C)⁻¹, respectively, while Sum-Fall has the lowest MACDOC (0.65 (± 0.19) m² (g C)⁻¹). ^●OH concentrations in extracts range from (0.2–4.7) × 10⁻¹⁵ M and generally increase with concentration of dissolved organic carbon (DOC), although this might be because DOC is a proxy for extract concentration. The average quantum yield for ^●OH formation (ΦOH) across all sample types is 3.7 (± 2.4) %, with no statistical difference among sample types. ¹O₂* concentrations have a range of (0.7−45) × 10⁻¹³ M, exhibiting a good linearity with DOC that is independent of sample type (R² = 0.93). Fresh BB samples have the highest [¹O₂*] but the lowest average Φ_1O2*, while Sum-Fall samples are the opposite. Φ_1O2* is negatively correlated with MAC_DOC, indicating that less light-absorbing samples form ¹O₂* more efficiently. We quantified³C* concentrations with two triplet probes: syringol (SYR), which captures both strongly and weakly oxidizing triplets, and (phenylthio)acetic acid (PTA), which is only sensitive to strongly oxidizing triplets. Concentrations of ³C* are in the range of (0.03–7.9) × 10⁻¹³ M and linearly increase with DOC (R² = 0.85 for SYR and R² = 0.80 for PTA); this relationship for [³C*]_SYR is independent of sample type. The average ratio of [³C*]_PTA/[³C*]_SYR is 0.58 (± 0.38), indicating that roughly 60 % of oxidizing triplets are strongly oxidizing. Win-Spr samples have the highest fraction of strongly oxidizing ³C*, with an average of 86 (± 43) %. Φ_3C*,SYR is in the range of (0.6–8.8) %, with an average value, 3.3 (± 1.9) %, two times higher than Φ_3C*,PTA. FBB has the lowest average Φ_3C*, while the aging process tends to enhance Φ_3C*, as well as Φ_1O2*.

To estimate photooxidant concentrations in particle water, we extrapolate the photooxidant kinetics in our dilute particle extracts to aerosol liquid water (ALW) conditions of 1 µg PM/µg H₂O for each sample type. The estimated ALW ^●OH concentration is 7 × 10⁻¹⁵ M when including mass transport of gas-phase ^●OH to the particles. ¹O₂* and ³C* concentrations in ALW have ranges of (0.6–7) × 10⁻¹² M and (0.08–1) × 10⁻¹² M, respectively. In the Win-Spr and Sum-Fall samples, photooxidant concentrations increase significantly from lab particle extracts to ALW, while the changes for the FBB and ABB samples are minor. The small increases in ¹O₂* and ³C* from extract to ALW for the biomass burning particles are likely due to the high amounts of organic compounds in the extracts, which lead to strong quenching of these oxidants even under our dilute conditions. Compared to the photooxidant concentration estimates in Kaur et al. (2019), our updated ALW estimates show higher ^●OH (by roughly a factor of 10), higher ³C* (by factors of 1–5) and lower ¹O₂* concentrations (by factors of 20–100). Our results indicate that³C* and ¹O₂* in ALW dominate the processing of organic compounds that react quickly with these oxidants (such as phenols and furans, respectively), while ^●OH is more important for less reactive organics.

Received: 29 Apr 2023 – Discussion started: 11 May 2023

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02 Jan 2024

Seasonal variations in photooxidant formation and light absorption in aqueous extracts of ambient particles

Lan Ma, Reed Worland, Laura Heinlein, Chrystal Guzman, Wenqing Jiang, Christopher Niedek, Keith J. Bein, Qi Zhang, and Cort Anastasio

Atmos. Chem. Phys., 24, 1–21, https://doi.org/10.5194/acp-24-1-2024,https://doi.org/10.5194/acp-24-1-2024, 2024

Short summary

Lan Ma et al.

Interactive discussion

Status: closed

RC1:
'Comment on egusphere-2023-861', Anonymous Referee #1, 25 May 2023
The manuscript aims at measuring the seasonal variation in photooxidant formation and concentration in atmospheric water and to predict the lifetime of 5 compounds in the atmosphere. Overall, I found the article well written and would support its publication as it brings interesting information to the community.
I did not find major issues in the article, here is my list of comments and corrections:
Abstract and introduction
The abstract and introduction are clear. In addition to singlet oxygen, excited triplet states and hydroxyl radical, the authors could also mention in the introduction other photooxidants that were not considered in the study but that may play a role in the transformation of some classes of contaminants. E.g., Halides radicals may play a role in the transformation of electron rich compounds (Marine Chemistry 115 (2009) 134–144) or long-lived photooxidant could be important for the transformation of phenols or anilines (Water Research 213 (2022) 118095).
L25. It looks to me that the OH quantum yield value is too high and does not correspond to the values presented in the article (Table S3).
L.79. I would switch organic compounds for DOM as the quoted studies presents correlations between 3DOM* quantum yields and factors correlating with the molecular weight / aromaticity.
Material and methods
L.141. I would indicate the spectrophotometer cuvette pathlength.
l.146 I would add in the SI the arc lamp spectra, that is important to evaluate nitrate photolysis.
Results and discussion
The results are presented in a logical order, I have two main comments on the results:
Hydroxyl radical quantum yields are presented. The fact that hydroxyl radicals are produced by many pathways in the atmospheric aqueous phase, and that each pathway has its own quantum yield, makes the numbers difficult to compare to other studies and not that useful. The quantum yield numbers would depend on the extract’s composition (nitrate, nitrite, iron) but also on the irradiation wavelength distribution.

Part 3.5. It looks like the authors use Henry constants to evaluate the partition of 5 compounds between the atmospheric aqueous phase and the gas phase. The use of Henry constants is fine for dilute solutions, but I fear that for concentrated solution (1ug PM/ug H2O), the actual partition may be different from the one calculated using Henry constants. I think that the authors should at least acknowledge the problem. If the authors are aware of methods or measurements to evaluate the actual partition coefficients to use them instead of Henry constants.

Figures, the date format may confuse non-American reader (e.g., one can read the first date as November first 2019 or January 11^th 2019). I would suggest writing the months to be clearer. Also, the numbers on the y-axis could be written as 1×10^-15 (and not 1E-15).
L.306. “fresh BB are fragmented during aging”, it could be noted that ozone exposure also induces and increase of E2/E3 (Leresche et al. quoted in the manuscript) and that ozone indeed also induce a decrease in mean molecular weight indicating that fragmentation occurs during ozonation (Environmental Science & Technology, 2023 57 (14), 5603-5610).
L.347. DDT assay, the abbreviation is not defined, switch for the full name.
L.450. Do the authors think that there are anilines moieties in PME ? I would suggest withdrawing the mention to anilines.
L.508. The second-order rate constant between singlet oxygen and water was reevaluated to be of 2.76*10⁵ M^-1 s^-1 (Environ. Sci.: Processes Impacts, 2017, 19, 507–516) I would suggest using the more recent value.
L.552. ³C* fraction that produces singlet oxygen (fΔ). This fraction was recently measured for Suwannee River fulvic acid to be of 0.34 (Environ. Sci. Technol. 2017, 51, 13151−13160). The value from McNeill and Canonica is a rule of thumb I believe. It would be worth mentioning this 0.34 value.
L.678. “Estimated concentrations of ¹O₂, ³C*, and OH in ALW are on the order of 10-12 - 10-11, 10-13 - 10-12 and 10-14 M”. I would suggest putting the respective number range next to the corresponding reactive species, as it is, it is difficult to see which numbers correspond to what.
L.993 and L.66, it should be Hoigné and not Hoigne.
Citation: https://doi.org/10.5194/egusphere-2023-861-RC1
RC2:
'Comment on egusphere-2023-861', Anonymous Referee #2, 28 Jun 2023
Overview:
The authors of this manuscript present OH, 3C* and 1O2* measurements of 18 filters taken from Nov 2019 to Oct 2020 in Davis already described and published in (Jiang et al., 2023). In Jiang et al., the concentrations of OH, 3C* and 1O2* are presented for each filter in Figures 5, 6, S11, S12.

The authors of this manuscript present MAC values for their extracts, the same values as in (Jiang et al., 2023). They also discuss the AMS data from (Jiang et al., 2023). The quantum yields are also discussed in (Jiang et al., 2023). Finally, the authors extrapolate the OH, 3C* and 1O2* concentrations to aerosol liquid water content, which they already did for 2 of the same samples in (Ma et al., 2023b).

Therefore, this paper is not publishable as all the data has been previously published across two papers by the same authors: (Ma et al., 2023b; Jiang et al., 2023).

Comments:
Nevertheless, the techniques used, although uncommon in the community (like use of D2O for FFA, use of double probe for 3C* - although that’s building on their own previous work in (Ma et al., 2023a) which has interesting merit -, acidifying to pH4.2 with no clear understanding of the impact of pH), have been reported in other publications by the same authors. The data are listed in tables in the SI in a good and extensive matter (but missing LOD info). Unfortunately, there is no new key message or finding in this submitted manuscript in comparison to previously published work by the same group, and the paper has important issues that would need to be resolved.

General issues with this paper beyond the lack of new data/results are listed here:
Raw data of all the BA, FFA, SYR and PTA probe decays for all the samples is missing.
There is one example of the BA decay which for the 121719 and the 030420 samples is clearly not linear. This observation is concerning as the deviation from linearity indicates that the oxidant is no longer under pseudo-first order rate kinetics! What do the probe kinetics look like for other oxidants and other filters?

A number of incorrect statements are used to motivate the study, often based on “things being unknown”. Here are examples:
Lines 68-69: So much is known about measured and modeled OH radical concentrations in the gas phase and its seasonality (Martin et al., 2003; Fan and Li, 2022) and so simply by partitioning, one could estimate what the seasonality might be (I would agree with a statement about OH radical concentrations being variable due to different sinks, but the word “unknown” is a disservice to the OH radical community (ex: Comprehensive OH seasonality by (Pfannerstill et al., 2021) and OH has been quantified at the global scale: (Thames et al., 2020) and (Pimlott et al., 2022) are examples.

References are an issue throughout the text where multiple papers (5-6) are referenced without identify the contribution of each and thereby missing the opportunity to build upon previous work. Here are a few examples to support this claim:
Lines 53-55: 6 seemingly random references are listed to support the fact that OH, 3C* and 1O2* are important oxidants. Reviews such as (McNeill and Canonica, 2016; Ossola et al., 2021; Hems et al., 2021) are more appropriate

Statement on Lines 98-99 is inaccurate as (Bogler et al., 2022) addresses both the seasonality and the particle type.

Line 263: a study from 2001 and from 2013 were chosen to discuss organic carbon content in biomass burning, when there are more recent references: to name a few: (Fang et al., 2023; Di Lorenzo et al., 2017; Lee et al., 2016; Bikkina and Sarin, 2019; Forrister et al., 2015)

Same point is true for line 281-283 where the 4 references listed are not representative of the statement, see for example (Fleming et al., 2020; Lee et al., 2014; Laskin et al., 2014)

Another example on lines 284-285

The authors chose to focus on a seasonality story line, but was 2020 representative? There were massive wildfires in Fall 2020 in northern California.
Where did the PM2.5 data in Figure 1 come from? (I found it at the bottom of Table S1 in footnote b…but it should be in the text and appropriately referenced with multiyear data)

What is the seasonal PM2.5 profile in northern California? Was 2020 representative of PM mass?

The methods sampled PM10 – how different/similar are PM10 to PM2.5 in Davis.

There were no samples taken between March 4^th 2020 and July 7^th 2020 (Table S1) and there are therefore no spring samples. The use of spring seasonality is therefore unjustified throughout the text.

The authors motivate their work discussing Fenton OH chemistry (lines 61-64) but how do they take this chemistry into account in their own measurements of OH steady state concentration calculations?

Relevant work that should have been built upon to connect to ROS and EPFRs (also from ambient Californian samples): (Fang et al., 2023)

No mention of limits of detection. What are the minimum concentrations that the authors are able to quantify (3 sigma above background)?

The authors decided to divide their concentrations by 7 for comparing filters collected for 7 days and filters collected for 1 day. This division is an oversimplification of the complex mixture of brown carbon and is not justified.

Line 15: The abstract mentions that; “there are few measurements of these photoxidants…” which is not accurate. There are likely over a dozen: (Faust and Allen, 1992; Anastasio and McGregor, 2001; Albinet et al., 2010; Hong et al., 2018; Cote et al., 2018; Manfrin et al., 2019; Kaur et al., 2019; Leresche et al., 2021; Jiang et al., 2023; Bogler et al., 2022; Lyu et al., 2023; Ma et al., 2023b)!

The mathematical equations representing the projected concentrations in AWL are missing.

Presentation of wildfire information in lines 231-236 but making no connection to the oxidant data.
Wouldn’t a discussion on the different BBOA samples have been more worthwhile for the community?

There is considerable research undertaken to study the impact of solvent extraction on filters that the authors should be building upon: (Chen et al., 2022) and references therein. (referring to line 314)

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Hong, J., Liu, J., Wang, L., Kong, S., Tong, C., Qin, J., Chen, L., Sui, Y., and Li, B.: Characterization of reactive photoinduced species in rainwater, Environ. Sci. Pollut. Res., 25, 36368–36380, https://doi.org/10.1007/s11356-018-3499-4, 2018.
Jiang, W., Ma, L., Niedek, C., Anastasio, C., and Zhang, Q.: Chemical and Light-Absorption Properties of Water-Soluble Organic Aerosols in Northern California and Photooxidant Production by Brown Carbon Components, ACS Earth Space Chem., https://doi.org/10.1021/acsearthspacechem.3c00022, 2023.
Kaur, R., Labins, J. R., Helbock, S. S., Jiang, W., Bein, K. J., Zhang, Q., and Anastasio, C.: Photooxidants from brown carbon and other chromophores in illuminated particle extracts, Atmospheric Chem. Phys., 19, 6579–6594, https://doi.org/10.5194/acp-19-6579-2019, 2019.
Laskin, J., Laskin, A., Nizkorodov, S. A., Roach, P., Eckert, P., Gilles, M. K., Wang, B., Lee, H. J., and Hu, Q.: Molecular Selectivity of Brown Carbon Chromophores, Env. Sci Technol, 48, 12047, 2014.
Lee, A. K. Y., Willis, M. D., Healy, R. M., Wang, J. M., Jeong, C.-H., Wenger, J. C., Evans, G. J., and Abbatt, J. P. D.: Single-particle characterization of biomass burning organic aerosol (BBOA): evidence for non-uniform mixing of high molecular weight organics and potassium., Atmospheric Chem. Phys., 16, 5561–5572, https://doi.org/10.5194/acp-16-5561-2016, 2016.
Lee, H. J. (Julie), Aiona, P. K., Laskin, A., Laskin, J., and Nizkorodov, S. A.: Effect of Solar Radiation on the Optical Properties and Molecular Composition of Laboratory Proxies of Atmospheric Brown Carbon, Environ. Sci. Technol., 48, 10217–10226, https://doi.org/10.1021/es502515r, 2014.
Leresche, F., Salazar, J. R., Pfotenhauer, D. J., Hannigan, M. P., Majestic, B. J., and Rosario-Ortiz, F. L.: Photochemical Aging of Atmospheric Particulate Matter in the Aqueous Phase, Environ. Sci. Technol., https://doi.org/10.1021/acs.est.1c00978, 2021.
Lyu, Y., Lam, Y. H., Li, Y., Borduas-Dedekind, N., and Nah, T.: Efficient production of singlet oxygen and organic triplet excited states in aqueous PM_2.5 in Hong Kong, South China, EGUsphere, 1–28, https://doi.org/10.5194/egusphere-2023-739, 2023.
Ma, L., Worland, R., Tran, T., and Anastasio, C.: Evaluation of Probes to Measure Oxidizing Organic Triplet Excited States in Aerosol Liquid Water, Environ. Sci. Technol., https://doi.org/10.1021/acs.est.2c09672, 2023a.
Ma, L., Worland, R., Jiang, W., Niedek, C., Guzman, C., Bein, K. J., Zhang, Q., and Anastasio, C.: Predicting photooxidant concentrations in aerosol liquid water based on laboratory extracts of ambient particles, EGUsphere, 1–36, https://doi.org/10.5194/egusphere-2023-566, 2023b.
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Pfannerstill, E. Y., Reijrink, N. G., Edtbauer, A., Ringsdorf, A., Zannoni, N., Araújo, A., Ditas, F., Holanda, B. A., Sá, M. O., Tsokankunku, A., Walter, D., Wolff, S., Lavrič, J. V., Pöhlker, C., Sörgel, M., and Williams, J.: Total OH reactivity over the Amazon rainforest: variability with temperature, wind, rain, altitude, time of day, season, and an overall budget closure, Atmospheric Chem. Phys., 21, 6231–6256, https://doi.org/10.5194/acp-21-6231-2021, 2021.
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Citation: https://doi.org/10.5194/egusphere-2023-861-RC2
AC1: 'Comment on egusphere-2023-861', Cort Anastasio, 19 Aug 2023

Our response to reviewer comments is uploaded in the form of a supplement.

Citation: https://doi.org/10.5194/egusphere-2023-861-AC1

Interactive discussion

Status: closed

RC1:
'Comment on egusphere-2023-861', Anonymous Referee #1, 25 May 2023
The manuscript aims at measuring the seasonal variation in photooxidant formation and concentration in atmospheric water and to predict the lifetime of 5 compounds in the atmosphere. Overall, I found the article well written and would support its publication as it brings interesting information to the community.
I did not find major issues in the article, here is my list of comments and corrections:
Abstract and introduction
The abstract and introduction are clear. In addition to singlet oxygen, excited triplet states and hydroxyl radical, the authors could also mention in the introduction other photooxidants that were not considered in the study but that may play a role in the transformation of some classes of contaminants. E.g., Halides radicals may play a role in the transformation of electron rich compounds (Marine Chemistry 115 (2009) 134–144) or long-lived photooxidant could be important for the transformation of phenols or anilines (Water Research 213 (2022) 118095).
L25. It looks to me that the OH quantum yield value is too high and does not correspond to the values presented in the article (Table S3).
L.79. I would switch organic compounds for DOM as the quoted studies presents correlations between 3DOM* quantum yields and factors correlating with the molecular weight / aromaticity.
Material and methods
L.141. I would indicate the spectrophotometer cuvette pathlength.
l.146 I would add in the SI the arc lamp spectra, that is important to evaluate nitrate photolysis.
Results and discussion
The results are presented in a logical order, I have two main comments on the results:
Hydroxyl radical quantum yields are presented. The fact that hydroxyl radicals are produced by many pathways in the atmospheric aqueous phase, and that each pathway has its own quantum yield, makes the numbers difficult to compare to other studies and not that useful. The quantum yield numbers would depend on the extract’s composition (nitrate, nitrite, iron) but also on the irradiation wavelength distribution.

Part 3.5. It looks like the authors use Henry constants to evaluate the partition of 5 compounds between the atmospheric aqueous phase and the gas phase. The use of Henry constants is fine for dilute solutions, but I fear that for concentrated solution (1ug PM/ug H2O), the actual partition may be different from the one calculated using Henry constants. I think that the authors should at least acknowledge the problem. If the authors are aware of methods or measurements to evaluate the actual partition coefficients to use them instead of Henry constants.

Figures, the date format may confuse non-American reader (e.g., one can read the first date as November first 2019 or January 11^th 2019). I would suggest writing the months to be clearer. Also, the numbers on the y-axis could be written as 1×10^-15 (and not 1E-15).
L.306. “fresh BB are fragmented during aging”, it could be noted that ozone exposure also induces and increase of E2/E3 (Leresche et al. quoted in the manuscript) and that ozone indeed also induce a decrease in mean molecular weight indicating that fragmentation occurs during ozonation (Environmental Science & Technology, 2023 57 (14), 5603-5610).
L.347. DDT assay, the abbreviation is not defined, switch for the full name.
L.450. Do the authors think that there are anilines moieties in PME ? I would suggest withdrawing the mention to anilines.
L.508. The second-order rate constant between singlet oxygen and water was reevaluated to be of 2.76*10⁵ M^-1 s^-1 (Environ. Sci.: Processes Impacts, 2017, 19, 507–516) I would suggest using the more recent value.
L.552. ³C* fraction that produces singlet oxygen (fΔ). This fraction was recently measured for Suwannee River fulvic acid to be of 0.34 (Environ. Sci. Technol. 2017, 51, 13151−13160). The value from McNeill and Canonica is a rule of thumb I believe. It would be worth mentioning this 0.34 value.
L.678. “Estimated concentrations of ¹O₂, ³C*, and OH in ALW are on the order of 10-12 - 10-11, 10-13 - 10-12 and 10-14 M”. I would suggest putting the respective number range next to the corresponding reactive species, as it is, it is difficult to see which numbers correspond to what.
L.993 and L.66, it should be Hoigné and not Hoigne.
Citation: https://doi.org/10.5194/egusphere-2023-861-RC1
RC2:
'Comment on egusphere-2023-861', Anonymous Referee #2, 28 Jun 2023
Overview:
The authors of this manuscript present OH, 3C* and 1O2* measurements of 18 filters taken from Nov 2019 to Oct 2020 in Davis already described and published in (Jiang et al., 2023). In Jiang et al., the concentrations of OH, 3C* and 1O2* are presented for each filter in Figures 5, 6, S11, S12.

The authors of this manuscript present MAC values for their extracts, the same values as in (Jiang et al., 2023). They also discuss the AMS data from (Jiang et al., 2023). The quantum yields are also discussed in (Jiang et al., 2023). Finally, the authors extrapolate the OH, 3C* and 1O2* concentrations to aerosol liquid water content, which they already did for 2 of the same samples in (Ma et al., 2023b).

Therefore, this paper is not publishable as all the data has been previously published across two papers by the same authors: (Ma et al., 2023b; Jiang et al., 2023).

Comments:
Nevertheless, the techniques used, although uncommon in the community (like use of D2O for FFA, use of double probe for 3C* - although that’s building on their own previous work in (Ma et al., 2023a) which has interesting merit -, acidifying to pH4.2 with no clear understanding of the impact of pH), have been reported in other publications by the same authors. The data are listed in tables in the SI in a good and extensive matter (but missing LOD info). Unfortunately, there is no new key message or finding in this submitted manuscript in comparison to previously published work by the same group, and the paper has important issues that would need to be resolved.

General issues with this paper beyond the lack of new data/results are listed here:
Raw data of all the BA, FFA, SYR and PTA probe decays for all the samples is missing.
There is one example of the BA decay which for the 121719 and the 030420 samples is clearly not linear. This observation is concerning as the deviation from linearity indicates that the oxidant is no longer under pseudo-first order rate kinetics! What do the probe kinetics look like for other oxidants and other filters?

A number of incorrect statements are used to motivate the study, often based on “things being unknown”. Here are examples:
Lines 68-69: So much is known about measured and modeled OH radical concentrations in the gas phase and its seasonality (Martin et al., 2003; Fan and Li, 2022) and so simply by partitioning, one could estimate what the seasonality might be (I would agree with a statement about OH radical concentrations being variable due to different sinks, but the word “unknown” is a disservice to the OH radical community (ex: Comprehensive OH seasonality by (Pfannerstill et al., 2021) and OH has been quantified at the global scale: (Thames et al., 2020) and (Pimlott et al., 2022) are examples.

References are an issue throughout the text where multiple papers (5-6) are referenced without identify the contribution of each and thereby missing the opportunity to build upon previous work. Here are a few examples to support this claim:
Lines 53-55: 6 seemingly random references are listed to support the fact that OH, 3C* and 1O2* are important oxidants. Reviews such as (McNeill and Canonica, 2016; Ossola et al., 2021; Hems et al., 2021) are more appropriate

Statement on Lines 98-99 is inaccurate as (Bogler et al., 2022) addresses both the seasonality and the particle type.

Line 263: a study from 2001 and from 2013 were chosen to discuss organic carbon content in biomass burning, when there are more recent references: to name a few: (Fang et al., 2023; Di Lorenzo et al., 2017; Lee et al., 2016; Bikkina and Sarin, 2019; Forrister et al., 2015)

Same point is true for line 281-283 where the 4 references listed are not representative of the statement, see for example (Fleming et al., 2020; Lee et al., 2014; Laskin et al., 2014)

Another example on lines 284-285

The authors chose to focus on a seasonality story line, but was 2020 representative? There were massive wildfires in Fall 2020 in northern California.
Where did the PM2.5 data in Figure 1 come from? (I found it at the bottom of Table S1 in footnote b…but it should be in the text and appropriately referenced with multiyear data)

What is the seasonal PM2.5 profile in northern California? Was 2020 representative of PM mass?

The methods sampled PM10 – how different/similar are PM10 to PM2.5 in Davis.

There were no samples taken between March 4^th 2020 and July 7^th 2020 (Table S1) and there are therefore no spring samples. The use of spring seasonality is therefore unjustified throughout the text.

The authors motivate their work discussing Fenton OH chemistry (lines 61-64) but how do they take this chemistry into account in their own measurements of OH steady state concentration calculations?

Relevant work that should have been built upon to connect to ROS and EPFRs (also from ambient Californian samples): (Fang et al., 2023)

No mention of limits of detection. What are the minimum concentrations that the authors are able to quantify (3 sigma above background)?

The authors decided to divide their concentrations by 7 for comparing filters collected for 7 days and filters collected for 1 day. This division is an oversimplification of the complex mixture of brown carbon and is not justified.

Line 15: The abstract mentions that; “there are few measurements of these photoxidants…” which is not accurate. There are likely over a dozen: (Faust and Allen, 1992; Anastasio and McGregor, 2001; Albinet et al., 2010; Hong et al., 2018; Cote et al., 2018; Manfrin et al., 2019; Kaur et al., 2019; Leresche et al., 2021; Jiang et al., 2023; Bogler et al., 2022; Lyu et al., 2023; Ma et al., 2023b)!

The mathematical equations representing the projected concentrations in AWL are missing.

Presentation of wildfire information in lines 231-236 but making no connection to the oxidant data.
Wouldn’t a discussion on the different BBOA samples have been more worthwhile for the community?

There is considerable research undertaken to study the impact of solvent extraction on filters that the authors should be building upon: (Chen et al., 2022) and references therein. (referring to line 314)

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Bogler, S., Daellenbach, K. R., Bell, D. M., Prévôt, A. S. H., El Haddad, I., and Borduas-Dedekind, N.: Singlet Oxygen Seasonality in Aqueous PM10 is Driven by Biomass Burning and Anthropogenic Secondary Organic Aerosol, Environ. Sci. Technol., 56, 15389–15397, https://doi.org/10.1021/acs.est.2c04554, 2022.
Chen, K., Raeofy, N., Lum, M., Mayorga, R., Woods, M., Bahreini, R., Zhang, H., and Lin, Y.-H.: Solvent effects on chemical composition and optical properties of extracted secondary brown carbon constituents, Aerosol Sci. Technol., 56, 917–930, https://doi.org/10.1080/02786826.2022.2100734, 2022.
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Faust, B. C. and Allen, J. M.: Aqueous-phase photochemical sources of peroxyl radicals and singlet molecular oxygen in clouds and fog, J. Geophys. Res. Atmospheres, 97, 12913–12926, https://doi.org/10.1029/92JD00843, 1992.
Fleming, L. T., Lin, P., Roberts, J. M., Selimovic, V., Yokelson, R., Laskin, J., Laskin, A., and Nizkorodov, S. A.: Molecular Composition and Photochemical Lifetimes of Brown Carbon Chromophores in Biomass Burning Organic Aerosol, Atmos Chem Phys, 20, 1105, 2020.
Forrister, H., Liu, J., Scheuer, E., Dibb, J., Ziemba, L., Thornhill, K. L., Anderson, B., Diskin, G., Perring, A. E., Schwarz, J. P., Campuzano-Jost, P., Day, D. A., Palm, B. B., Jimenez, J. L., Nenes, A., and Weber, R. J.: Evolution of Brown Carbon in Wildfire Plumes, Geophys Res Lett, 42, 4623, 2015.
Hems, R. F., Schnitzler, E. G., Liu-Kang, C., Cappa, C. D., and Abbatt, J. P. D.: Aging of Atmospheric Brown Carbon Aerosol, ACS Earth Space Chem., 5, 722–748, https://doi.org/10.1021/acsearthspacechem.0c00346, 2021.
Hong, J., Liu, J., Wang, L., Kong, S., Tong, C., Qin, J., Chen, L., Sui, Y., and Li, B.: Characterization of reactive photoinduced species in rainwater, Environ. Sci. Pollut. Res., 25, 36368–36380, https://doi.org/10.1007/s11356-018-3499-4, 2018.
Jiang, W., Ma, L., Niedek, C., Anastasio, C., and Zhang, Q.: Chemical and Light-Absorption Properties of Water-Soluble Organic Aerosols in Northern California and Photooxidant Production by Brown Carbon Components, ACS Earth Space Chem., https://doi.org/10.1021/acsearthspacechem.3c00022, 2023.
Kaur, R., Labins, J. R., Helbock, S. S., Jiang, W., Bein, K. J., Zhang, Q., and Anastasio, C.: Photooxidants from brown carbon and other chromophores in illuminated particle extracts, Atmospheric Chem. Phys., 19, 6579–6594, https://doi.org/10.5194/acp-19-6579-2019, 2019.
Laskin, J., Laskin, A., Nizkorodov, S. A., Roach, P., Eckert, P., Gilles, M. K., Wang, B., Lee, H. J., and Hu, Q.: Molecular Selectivity of Brown Carbon Chromophores, Env. Sci Technol, 48, 12047, 2014.
Lee, A. K. Y., Willis, M. D., Healy, R. M., Wang, J. M., Jeong, C.-H., Wenger, J. C., Evans, G. J., and Abbatt, J. P. D.: Single-particle characterization of biomass burning organic aerosol (BBOA): evidence for non-uniform mixing of high molecular weight organics and potassium., Atmospheric Chem. Phys., 16, 5561–5572, https://doi.org/10.5194/acp-16-5561-2016, 2016.
Lee, H. J. (Julie), Aiona, P. K., Laskin, A., Laskin, J., and Nizkorodov, S. A.: Effect of Solar Radiation on the Optical Properties and Molecular Composition of Laboratory Proxies of Atmospheric Brown Carbon, Environ. Sci. Technol., 48, 10217–10226, https://doi.org/10.1021/es502515r, 2014.
Leresche, F., Salazar, J. R., Pfotenhauer, D. J., Hannigan, M. P., Majestic, B. J., and Rosario-Ortiz, F. L.: Photochemical Aging of Atmospheric Particulate Matter in the Aqueous Phase, Environ. Sci. Technol., https://doi.org/10.1021/acs.est.1c00978, 2021.
Lyu, Y., Lam, Y. H., Li, Y., Borduas-Dedekind, N., and Nah, T.: Efficient production of singlet oxygen and organic triplet excited states in aqueous PM_2.5 in Hong Kong, South China, EGUsphere, 1–28, https://doi.org/10.5194/egusphere-2023-739, 2023.
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Ma, L., Worland, R., Jiang, W., Niedek, C., Guzman, C., Bein, K. J., Zhang, Q., and Anastasio, C.: Predicting photooxidant concentrations in aerosol liquid water based on laboratory extracts of ambient particles, EGUsphere, 1–36, https://doi.org/10.5194/egusphere-2023-566, 2023b.
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Citation: https://doi.org/10.5194/egusphere-2023-861-RC2
AC1: 'Comment on egusphere-2023-861', Cort Anastasio, 19 Aug 2023

Our response to reviewer comments is uploaded in the form of a supplement.

Citation: https://doi.org/10.5194/egusphere-2023-861-AC1

Peer review completion

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

AR by Cort Anastasio on behalf of the Authors (19 Aug 2023) Author's response Author's tracked changes Manuscript

ED: Referee Nomination & Report Request started (08 Sep 2023) by Ryan Sullivan

RR by Anonymous Referee #1 (08 Sep 2023)

RR by Anonymous Referee #3 (17 Sep 2023)

Suggestions for revision or reasons for rejection

I read the revised version of this manuscript after it was reviewed by two reviewers. Reviewer 1 requested relatively minor changes. Reviewer 2 suggested that the presented data overlap with the already published results from the same group in Jiang et al. (2023) and Ma et al. (2023). The methods and results described in this paper are indeed linked to the results presented in Jiang et al. (2023) and Ma et al. (2023), especially the latter. However, the authors provided a convincing explanation in the response about how these three manuscripts are connected and how they are different. This is a very large data set resulting from years of work, so it is understandable that the authors are trying to split into more focused, digestible stories. I recommend publishing the revised paper. I have additional minor comments:

1. The abstract is unreasonably long, to the extent it had to be split in two paragraphs. While long abstracts have appeared in published in ACP papers, it is not in a general a good practice. I would strongly recommend condensing it to a more reasonable length focusing on the most important message of this paper and omitting less important details.

2. L120: I would mention that this work builds on the previous study by Kaur et al. (2019) since these data are used in the figures

3. L143: the unit for hour is “h” not “hr” (it is used correctly in most other places in the text)

4. L358 and Figure S13: is there a physical reason to expect a linear relationship here? And regardless of the model, should no the fitting curve pass through zero at zero PM/water ratio?

5. L494. “Figure S15 shows the equivalent plot of Figure 3”. I think you mean Figure 4. In the caption of figure S15, I would explain how it is different from figure 4.

6. L669 and below: instead of using “compound (X)” why not use the actual names of these compounds? It will not make the text longer but will make it easier to read. You can still use 1,2,3,4,5 in the figure since the structures are shown right there so the labels are not too confusing.

7. The same reference for Jiang (2023) in ACS Earth Space Chem. is listed twice in the reference section under indexes “a” and “b”. Please fix.

Hide

ED: Publish subject to minor revisions (review by editor) (04 Oct 2023) by Ryan Sullivan

AR by Cort Anastasio on behalf of the Authors (11 Oct 2023) Author's response Author's tracked changes Manuscript

ED: Publish as is (20 Oct 2023) by Ryan Sullivan

AR by Cort Anastasio on behalf of the Authors (23 Oct 2023) Manuscript

Journal article(s) based on this preprint

02 Jan 2024

Seasonal variations in photooxidant formation and light absorption in aqueous extracts of ambient particles

Lan Ma, Reed Worland, Laura Heinlein, Chrystal Guzman, Wenqing Jiang, Christopher Niedek, Keith J. Bein, Qi Zhang, and Cort Anastasio

Atmos. Chem. Phys., 24, 1–21, https://doi.org/10.5194/acp-24-1-2024,https://doi.org/10.5194/acp-24-1-2024, 2024

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We measured concentrations of three photooxidants – hydroxyl radical, triplet excited states of organic carbon, and singlet molecular oxygen – in fine particles collected over a year. Concentrations are highest in extracts of fresh biomass burning particles, largely because they have the highest particle concentrations and highest light absorption. When normalized by light absorption, rates of formation for each oxidant are generally similar for the four particle types we observed.


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