the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
| 06 Feb 2024
Measurement report: Rapid oxidation of phenolic compounds by O3 and HO•: effects of air-water interface and mineral dust in tropospheric chemical processes
Abstract. Environmental media affect the atmospheric oxidation processes of phenolic compounds (PhCs) released from biomass burning in the troposphere. Phenol (Ph), 4-hydroxybenzaldehyde (4-HBA), and vanillin (VL) are chosen as model compounds to investigate their reaction mechanism and kinetics at the air-water (A-W) interface, on TiO2 clusters, in the gas phase, and in bulk water using a combination of molecular dynamics simulation and quantum chemical calculations. Of them, Ph was the most reactive one. The occurrence percentages of Ph, 4-HBA, and VL staying at the A-W interface are ~72 %, ~68 %, and ~73 %, respectively. As the size of (TiO2)n clusters increases, the adsorption capacity decreases until n > 4, and beyond this, the capacity remains stable. A-W interface and TiO2 clusters facilitate Ph and VL reactions initiated by the O3 and HO•, respectively. However, oxidation reactions of 4-HBA are little affected by environmental media because of its electron-withdrawing group. The O3- and HO•-initiated reaction rate constant (k) values follow the order of PhA-W > VLTiO2 > VLA-W > 4-HBAA-W > 4-HBATiO2 > PhTiO2 and VLTiO2 > PhA-W > VLA-W > 4-HBATiO2 > PhTiO2 > 4-HBAA-W, respectively. Some byproducts are more harmful than their parent compounds, so should be given special attention. This work provides key evidence for the rapid oxidation observed in the O3/HO• + PhCs experiments at the A-W interface. More importantly, differences in oxidation of PhCs by different environmental media due to the impact of substituent groups were also identified.
- Preprint
(1938 KB) - Metadata XML
-
Supplement
(2138 KB) - BibTeX
- EndNote
Status: final response (author comments only)
-
RC1: 'Comment on egusphere-2023-2856', Anonymous Referee #1, 19 Mar 2024
The authors applied a combination of molecular dynamics simulation and quantum chemical calculations to systematically investigate the atmospheric transformation processes and environmental impacts in different environmental media of three phenolic compounds (PhCs). In addition, the authors assessed the ecological exposure risk of phenol (Ph), 4-hydroxybenzaldehyde (4-HBA), and vanillin (VL) and their transformation products based on predicted toxicological data. The results are important for well understanding the transition and fate the gas-phase reaction processes of PhCs. The expression and analysis of this paper are intelligible and logical. Nevertheless, the current manuscript still has several areas for improvement. The authors are advised to revise the manuscript according to the following suggestions.
- Why did you choose phenol (Ph), 4-hydroxybenzaldehyde (4-HBA), and vanillin (VL) as model compounds? It is better to explain in the introduction.
- In calculation methods, it is required for illustrating the reliability of the chosen methods and the used models. Moreover, the possible error bars should be further discussed. For example, in gas phase kinetics calculations, the recrossing effects, anharmonicity, and torsional anharmonicity are not considered. How do these factors influence the calculated results? In addition, what is the possible accuracy for electronic structure calculations?
- Have you scaled the calculated frequencies? Have you considered the stability of wave function in DFT calculations?
- It is necessary for explaining that TiO2 clusters can be used to model the mineral dust in the atmosphere. It is well known that there are abundant water in the atmosphere. Do TiO2 clusters react with water?
- In the manuscript, the discussion on the toxicity of the substances studied is highly relevant and informative. To enhance the readability and accessibility of this crucial information, it might be beneficial to consider listing the detailed toxicity data in the supplementary materials. This approach would provide those interested with easy access to the comprehensive data.
- The term "Criegee intermediate" in its singular form typically refers to a specific type of intermediate, while the plural form, "Criegee intermediates," refers to multiple types of Criegee intermediates. Therefore, if referring to a particular intermediate, the singular form should be used; if discussing multiple different intermediates, the plural form should be applied. Line 321, please check "Criegee intermediate".
- Please give more explanations for atmospheric implications for present results. Have field measurements supported this calculated conclusions?
- Some details need to be modified. In line 384, change "k" to italic "k". In line 121 currently lacks a leading space. Please insert a space at the beginning of this paragraph to maintain the uniform indentation level throughout the document. Consistency in formatting contributes to the overall readability and professional appearance of your manuscript. The term "A-Winterface" mentioned in line 240 appears to be a typographical error. Please correct it to "A-W interface" to ensure clarity and correct representation of the term. In line 278, "titanium atom" should be changed to "Ti atom". There is an inconsistency in the format of the thermodynamic symbols in line 337. Specifically, "ΔrG" and "DG‡" use different styles for the delta symbol (Δ). Please standardize the formatting of these symbols to ensure uniformity throughout the document. In line 546, please check "68%". In line 916, do not italicize the subscript of k, such as "ktotal-A-W, cal".
Citation: https://doi.org/10.5194/egusphere-2023-2856-RC1 -
RC2: 'Comment on egusphere-2023-2856', Anonymous Referee #2, 25 Mar 2024
The article written by Huo et al., is generally well written and present theoretical investigations of the three selected aromatic compounds regarding their degradation mechanism and reactivity initiated by ozone and OH radicals at different environmental media.
Please revise the manuscript according to following comments and advices:
- The numbers, percentages and any value included in the paper should present a range of uncertainties if the value are coming from experimental investigations
- The selection of the model compounds is not enough explained. Increasing number of constituents on the aromatic ring would affect the reactivity and would lead to complex compounds following reaction addition and/or open ring pathway.
- Please follow with attention the way of presenting the interaction of the phenolics with environmental media. The use of subscripts for this should be kept for all of them.
- Please add minimum information in the article body as the supplementary text would help understanding on main article but not replace it. As an example, a sentence about the kinetic calculation would be necessary in the main text with additional material in SM.
- The ozone concentration is known to be variable, however new reference data regarding the more recent measurements of the ozone concentration are necessary.
- The gas-phase degradation mechanism initiated by Ozone requires much more attention. Simply Criegee pathway as in the text is not valid, but cleavage of the double bond following a Criegee mechanism from the cyclic adduct would be possible. Please revise the mechanism in details.
- The concentration of OH radicals is also outdated. Please use more recent information: Lelieveld, J., Gromov, S., Pozzer, A., and Taraborrelli, D.: Global tropospheric hydroxyl distribution, budget and reactivity, Atmos. Chem. Phys., 16, 12477–12493, https://doi.org/10.5194/acp-16-12477-2016, 2016.
- Please add reference in the text every time you add information about products formation, kinetic constants, etc. For example, for catechol formation in gas-phase
- Please relate the findings more in detail with experimental data.
- In the environments where the phenolic compounds are released, the presence of NOx is well represented. Please describe the mechanistic implication of the NOx system in the degradation product formation. Discuss about the nitroaromatic formation and their atmospheric behaviour.
- The article considers multiple oxidation and final formation of benzene hexaol. Is this feasible energetically? Could be formed in the gas-phase?
- Please add information regarding the equilibrium of the gas-particle composition of the three selected aromatics and the importance of them for secondary organic aerosol formation.
- Please present the degradation mechanism for the reaction of vanillin too.
Line 281 – “phosphorus” ?
Line 349 – Authors are mentioning the ozone reaction. Is that true?
Line 348-350 – Please revise the sentence since there is a mix between OH and O3 reactions.
Line 380 – “Phe + O3 reactions”
Citation: https://doi.org/10.5194/egusphere-2023-2856-RC2 -
RC3: 'Comment on egusphere-2023-2856', Anonymous Referee #3, 07 Apr 2024
General Comments:
The manuscript uses molecular dynamics simulation and quantum chemical calculations to explore the effect of selected environments on the initial reaction of three phenols (phenol, vanillin, and 4-hydroxybenzaldehyde) with ozone and OH radical. There are multiple concerns listed in the major comments that will require extensive work for the manuscript to be considered for publication in ACP. In its current form, the manuscript cannot be recommended for publication.
Major Comments:
1) The manuscript that does not seem to fit the “Measurement report” type expected for the peer review in Atmospheric Chemistry and Physics (ACP). Such type of manuscript should present substantial new results from measurements of atmospheric properties and processes from field and laboratory experiments. There are no field observations or laboratory experiment measurements in this manuscript that could be modeled to gain new insights to advance the field.
2) The covered manuscript theme of phenols’ reactions with O3 and OH radical at the air-water interface has been extensively studied in the literature. However, such material is poorly covered in the manuscript, with the relevant literature missing from the bibliography. The resulting manuscript provided is a very incomplete account of relevant works of phenols’ reactions with O3 and OH radical at the air-water interface, in water, and in the gas phase. The manuscript did not appropriately connect the introduction, discussion, and conclusions sections to the published peer-review literature.
3) The abstract needs to be completely rewritten for clarity as detailed in the next points 4 through 7.
4) l. 24-30: The text did not acknowledge that the mechanisms and kinetics for the reactions of phenol, vanillin, and 4-hydroxybenzaldehyde at the air-water interface, in the gas-phase, and in bulk water have been studied experimentally in detail recently. Therefore, what is the novelty of performing molecular dynamics simulations and quantum chemical calculations here?
5) l. 31-33: It is completely unclear where the said occurrence percentages of the 3 phenols at the air-water interface come from and their validity. What is a (TiO2)n cluster and why should the reader of ACP care about it? What do the authors mean by “adsorption capacity” and “the capacity” and why is it relevant here? The text lacks focus and clarity.
6) l. 36-38: What environmental media do the authors refer to? None is distinguished in the statement. What specific rate constants for O3 and OH radical initiated reactions (of the many possible based on the literature but not covered in the manuscript) are compared? The provided comparison of the presented calculations without a connection to the scientific literature is of no value to advance this field.
7) l. 40-46: The text should have first defined the products or byproducts that could be more harmful than their parent compounds. A better comparison among media would be beneficial here.
8) l. 50-110 (Introduction): The section needs to be completely rewritten and incorporate many key missing papers in the topic including those form searching in the Web of Science and SciFinder-n of key terms that is presented below. The twenty-six papers1-26 presented below in revere chronological order are not all missing works but just serve as an example of selected literature that needs to be covered in this manuscript:
- Zhang, J.; Shrivastava, M.; Ma, L.; Jiang, W. Q.; Anastasio, C.; Zhang, Q.; Zelenyuk, A., Modeling Novel Aqueous Particle and Cloud Chemistry Processes of Biomass Burning Phenols and Their Potential to Form Secondary Organic Aerosols. Environmental Science & Technology 2024, 58, (8), 3776-3786.
- Rana, M. S.; Bradley, S. T.; Guzman, M. I., Conversion of Catechol to 4-Nitrocatechol in Aqueous Microdroplets Exposed to O3 and NO2. ACS ES&T Air 2024, 1, (2), 80-91.
- Ma, L.; Worland, R.; Heinlein, L.; Guzman, C.; Jiang, W. Q.; Niedek, C.; Bein, K. J.; Zhang, Q.; Anastasio, C., Seasonal variations in photooxidant formation and light absorption in aqueous extracts of ambient particles. Atmospheric Chemistry and Physics 2024, 24, (1), 1-21.
- Ma, L.; Worland, R.; Jiang, W. Q.; Niedek, C.; Guzman, C.; Bein, K. J.; Zhang, Q.; Anastasio, C., Predicting photooxidant concentrations in aerosol liquid water based on laboratory extracts of ambient particles. Atmospheric Chemistry and Physics 2023, 23, (15), 8805-8821.
- Jiang, W. Q.; Niedek, C.; Anastasio, C.; Zhang, Q., Photoaging of phenolic secondary organic aerosol in the aqueous phase:evolution of chemical and optical properties and effects of oxidants. Atmospheric Chemistry and Physics 2023, 23, (12), 7103-7120.
- Rana, M. S.; Guzman, M. I., Surface Oxidation of Phenolic Aldehydes: Fragmentation, Functionalization, and Coupling Reactions. Journal of Physical Chemistry A 2022, 126, (37), 6502-6516.
- Rana, M. S.; Guzman, M. I., Oxidation of Catechols at the Air-Water Interface by Nitrate Radicals. Environmental Science & Technology 2022, 56, (22), 15437-15448.
- Rana, M. S.; Guzman, M. I., Oxidation of Phenolic Aldehydes by Ozone and Hydroxyl Radicals at the Air-Solid Interface. ACS Earth and Space Chemistry 2022, 6, (12), 2900-2909.
- Guzman, M. I.; Pillar-Little, E. A.; Eugene, A. J., Interfacial Oxidative Oligomerization of Catechol. ACS Omega 2022.
- Arciva, S.; Niedek, C.; Mavis, C.; Yoon, M.; Sanchez, M. E.; Zhang, Q.; Anastasio, C., Aqueous middotOH Oxidation of Highly Substituted Phenols as a Source of Secondary Organic Aerosol. Environmental Science & Technology 2022, 56, (14), 9959-9967.
- Al-Abadleh, H. A.; Motaghedi, F.; Mohammed, W.; Rana, M. S.; Malek, K. A.; Rastogi, D.; Asa-Awuku, A. A.; Guzman, M. I., Reactivity of aminophenols in forming nitrogen-containing brown carbon from iron-catalyzed reactions. Communications Chemistry 2022, 5, (1).
- Ma, L.; Guzman, C.; Niedek, C.; Tran, T.; Zhang, Q.; Anastasio, C., Kinetics and Mass Yields of Aqueous Secondary Organic Aerosol from Highly Substituted Phenols Reacting with a Triplet Excited State. Environmental Science & Technology 2021, 55, (9), 5772-5781.
- Rana, M. S.; Guzman, M. I., Oxidation of Phenolic Aldehydes by Ozone and Hydroxyl Radicals at the Air-Water Interface. Journal of Physical Chemistry A 2020, 124, (42), 8822-8833.
- Pillar-Little, E. A.; Guzman, M. I., An Overview of Dynamic Heterogeneous Oxidations in the Troposphere. Environments 2018, 5, (9).
- Kaur, R.; Anastasio, C., First Measurements of Organic Triplet Excited States in Atmospheric Waters. Environmental Science & Technology 2018, 52, (9), 5218-5226.
- Jurak, M.; Mroczka, R.; Lopucki, R., Properties of Artificial Phospholipid Membranes Containing Lauryl Gallate or Cholesterol. Journal of Membrane Biology 2018, 251, (2), 277-294.
- Huang, D. D.; Zhang, Q.; Cheung, H. H. Y.; Yu, L.; Zhou, S.; Anastasio, C.; Smith, J. D.; Chan, C. K., Formation and Evolution of aqSOA from Aqueous-Phase Reactions of Phenolic Carbonyls: Comparison between Ammonium Sulfate and Ammonium Nitrate Solutions. Environmental Science & Technology 2018, 52, (16), 9215-9224.
- Pillar, E. A.; Guzman, M. I., Oxidation of Substituted Catechols at the Air-Water Interface: Production of Carboxylic Acids, Quinones, and Polyphenols. Environmental Science & Technology 2017, 51, (9), 4951-4959.
- Lin, P. C.; Wu, Z. H.; Chen, M. S.; Li, Y. L.; Chen, W. R.; Huang, T. P.; Lee, Y. Y.; Wang, C. C., Interfacial Solvation and Surface pH of Phenol and Dihydroxybenzene Aqueous Nanoaerosols Unveiled by Aerosol VUV Photoelectron Spectroscopy. Journal of Physical Chemistry B 2017, 121, (5), 1054-1067.
- Kaur, R.; Anastasio, C., Light absorption and the photoformation of hydroxyl radical and singlet oxygen in fog waters. Atmospheric Environment 2017, 164, 387-397.
- Yu, L.; Smith, J.; Laskin, A.; George, K. M.; Anastasio, C.; Laskin, J.; Dillner, A. M.; Zhang, Q., Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation. Atmospheric Chemistry and Physics 2016, 16, (7), 4511-4527.
- Pillar, E. A.; Zhou, R. X.; Guzman, M. I., Heterogeneous Oxidation of Catechol. Journal of Physical Chemistry A 2015, 119, (41), 10349-10359.
- Chen, C. M.; Chen, H. S.; Yu, J.; Han, C.; Yan, G. X.; Guo, S. H., p-Nitrophenol Removal by Bauxite Ore Assisted Ozonation and its Catalytic Potential. Clean-Soil Air Water 2015, 43, (7), 1010-1017.
- Smith, J. D.; Sio, V.; Yu, L.; Zhang, Q.; Anastasio, C., Secondary Organic Aerosol Production from Aqueous Reactions of Atmospheric Phenols with an Organic Triplet Excited State. Environmental Science & Technology 2014, 48, (2), 1049-1057.
- Pillar, E. A.; Camm, R. C.; Guzman, M. I., Catechol Oxidation by Ozone and Hydroxyl Radicals at the Air-Water Interface. Environmental Science & Technology 2014, 48, (24), 14352-14360.
- M'Hemdi, A.; Dbira, B.; Abdelhedi, R.; Brillas, E.; Ammar, S., Mineralization of Catechol by Fenton and Photo-Fenton Processes. Clean-Soil Air Water 2012, 40, (8), 878-885.
Many of the above papers should also be recalled in the results and discussion and conclusions sections.
9) l. 107: This was not an experimental measurement but a quantum chemical calculation. It seems incorrect to state that “Rate constants were measured …”.
10) l. 109-110, l. 502-524: The computational work of toxicological relevance is not of primary interest to the readers of ACP. Such work is out of scope for this journal and should be moved to the accompanying Supplementary Material document.
11) l. 124: A better contextual explanation to the selected dimensions is needed before the values of 4*4*9 nm^3 are provided.
12) l. 128-130: The statement is unclear for the general reader to understand its intent. The authors should more clearly state what the meaning of “… steer clear of the intersection of two A-W interface” is.
13) l. 130-131: The manuscript should state how the random selection was executed in this work.
14) l. 132: The manuscript should explain to the readers of ACP why such a short 150 ns period is relevant. The explanation should be followed by establishing the relevance of this period to what happens in the environment.
15) l. 133-134: Clearly state the pi-pi and H-bond molecular orbitals and/or atomic centers that are considered for these interactions of phenols.
16) l. 137-138: The text appears disconnected to the aimed description and the actual environment. There are no relevant nanobubbles in air to assume such a model of the air-water interface is of any atmospheric relevance.
17) l. 151 and l. 155: Indicate the “specifics” that can be found in the Supplementary Materials by completing the ideas in these statements. Similarly, in l. 174, expand the text to inform the readers of ACP what calculations are in the Supplementary Materials.
18) l. 157: What electrical structure do the authors refer to? Explain in the text.
19) l. 159: What is the meaning of “benchmarking” here? Clarify the text.
20) l. 162: In what sense and context is this “reliable” for phenols?
21) l. 163: Several levels were presented above so what is “this level” for the gas phase reactions?
22) l 185-185: Range of what? Complete the idea in the statement and preferably give the values in this range.
23) l. 188: The concept of “pure” water is completely wrong here.
24) l. 190-193: Explain why most of the phenols positioned themselves at the air-water interface.
25) 194-197: The concept of “nanoparticles” appears out of nowhere and is completely wrong.
26) l. 201- 206: A literature comparison to the free energy change of hydration values is needed.
27) l. 211-213: The text is confusing. Explain how an atom of hydrogen serves as an electron donor and state to what electron acceptor. Is the text referring to the hydrogen atom that should participate in hydrogen bonding?
28) l. 213: Why should the reader care about the return to the “bulk water”? Shouldn’t be more important the return to “air”? The model approached the irrelevant problem and missed the relevant problem questioning its validity.
29) l. 215, l. 302-305, l. 319-325, l. 344-359, l. 367-374, and l. 417-500: Bring here the information from the literature search provided in point 8 above to supplement the discussion with relevant experimental observations of interfacial reactivity and O3 and OH radical initiated reactions.
30) l. 217-218: Explain how you arrive at this conclusive statement for an increased concentration of phenols at the air-water interface and/or moderate its strength.
31) l. 219-249: The section about the interface properties of phenols is not key to the readers of ACP and should be completely moved to the Supplementary Materials document. A clarification of the meaning of “N value” will be needed. The interesting summary statements that should remain in the main manuscript are based on l. 231-234 and l. 242-245. A note should be added to indicate a full description of this part of the work is available in the Supplementary Materials.
32) l. 247-249: The statement is misleading. What happens if the functional groups are hydrophilic?
33) l. 251-257 and l. 268-279: The information is not key to the readers of ACP and should be moved to the Supplementary Materials document. Moreover, the statements in l. 268-279 should be rechecked for technical correction and the interactions of C-O and -OH groups should be re-evaluated.
34) l. 258-267 and l. 281: A close examination of the literature cited in theses statements (Bai et al. and Qu and Kroes) shows there is no connection to “phosphorus atoms”. This reviewer finds these statements to compromise the intellectual integrity of the manuscript.
35) l. 286-287: The text appears contradictory as the authors are unaware of the differences between physisorption and chemical adsorption.
36) l. 293, l. 295 and l. 351: The manuscript does not present work with the molecule of “benzene”. Scientific accuracy is needed.
37) l. 309-311 and l. 315: At the air-water interface or in water? Clarification is needed in terms of the significant reduction in molecular energy mentioned.
38) l. 318: The idea is this statement is incomplete; provide the full range of relevant O3 molecules and update to more current references.
39) l. 336-339 and l. 340-343: It appears that based on the current work, the authors are unable to arrive at such a conclusion. How is the comparison for phenols oxidation based and among different media? What is the order of reaction in each media considered?
40) l. 352-355: Based on the current literature from point 8, this is misleading, and the reference used here is irrelevant.
41) l. 364: What do the authors mean by the “… TiO2 clusters are the most favorable”?
42) l. 419: These aromatic compounds do not react with O2. Scientific accuracy is needed.
43) l. 424-426” Why is this a “desirable outcome”? Why is this “most attractive”? Clarification is needed for the readers to understand what the points made are.
44) l. 430-431 and l. 460: This connection came unexpectedly. Improvements are needed to introduce the idea of reaction of “nitric oxide” with the radical. “NO” was not introduced earlier for this system. Why is “NO-O” abstraction a desirable choice?
45) l. 476-482: The manuscript should explain how valid these comparisons are. An expansion to include calculations of reaction rates is needed as constants alone do not communicate much for such systems. What reaction order is considered for each medium? What concentration of each oxidant should be assumed? Literature in point 8 has compared OH and O3 driven reactions at the air-water interface.
46) Fig. 2: Specify if you are dealing with the deltaG of hydration or what in the y-axes. The meaning of nanoparticles appears inappropriate for this field.
47) Fig. 3: The quality of this image is not the optimum expected for publication in ACP. Moreover, after improving it, this figure should be moved to the Supplementary Materials document.
48) Fig. 7: The resolution is poor for reading it. How are both “gas phase” and “bulk water” included together in panel (a)? How does the bottom reaction of panel (a) loose OH? It seems unlikely based on extensive studies in point 8. The final product should have one more OH.
How is the second reaction in the bottom of panel (b) capable of losing OH? The no go reaction (red cross) contradicts thermodynamic measurements that have been experimentally determined and are available in the literature of point 8. The material in the figure needs significant improvements as well as its discussion based on published literature that has not been included in the manuscript.
Similar comments from point 48 are valid also for Fig. S10.
49) Fig. 8: What phase/medium is this figure referring to? Many experimental values for such constants have been reported in the literature based on experimental work missing from this manuscript.
50) Once all the points above are addressed, the conclusions should be reconsidered and rewritten accordingly to be scientifically accurate and connect with relevant works in point 8.
Minor Comments:
1) l. 147: Insert “Fig. S1” after the word “coordinate”.
2) l. 293: Delete repeated “bonds”.
3) l. 341: dissolved?
4) l. 360: RAHben?
5) l. 376: RAHHsub?
6) l. 417: desiny?
Citation: https://doi.org/10.5194/egusphere-2023-2856-RC3
Data sets
Measurement report: Rapid oxidation of phenolic compounds by O3 and HO•: effects of air-water interface and mineral dust in tropospheric chemical processes Yanru Huo, Mingxue Li, Xueyu Wang, Jianfei Sun, Yuxin Zhou, Yuhui Ma, and Maoxia He https://doi.org/10.5281/zenodo.10614650
Viewed
| HTML | XML | Total | Supplement | BibTeX | EndNote | |
|---|---|---|---|---|---|---|
| 205 | 59 | 20 | 284 | 34 | 12 | 12 |
- HTML: 205
- PDF: 59
- XML: 20
- Total: 284
- Supplement: 34
- BibTeX: 12
- EndNote: 12
Viewed (geographical distribution)
| Country | # | Views | % |
|---|
| Total: | 0 |
| HTML: | 0 |
| PDF: | 0 |
| XML: | 0 |
- 1