Technical note: Effects of storage conditions on molecular-level composition of organic aerosol particles

Resch, Julian; Wolfer, Kate; Barth, Alexandre; Kalberer, Markus

doi:https://doi.org/10.5194/egusphere-2023-840

Preprints

https://doi.org/10.5194/egusphere-2023-840

Preprints

28 Apr 2023

| 28 Apr 2023

Technical note: Effects of storage conditions on molecular-level composition of organic aerosol particles

Julian Resch, Kate Wolfer, Alexandre Barth, and Markus Kalberer

Abstract. A significant fraction of atmospheric aerosol particles, which affect both the Earth’s climate and human health, can be attributed to organic compounds and especially secondary organic aerosol (SOA). To better understand the sources and processes generating organic aerosol particles, detailed chemical characterization is necessary, and particles are often collected onto filters and subsequently analyzed by liquid chromatography mass spectrometry (LC-MS). A downside of such offline analysis techniques is the uncertainty regarding artefactual changes in composition occurring during sample collection, storage, extraction and analysis. The goal of this work was to characterize how storage conditions and storage time may affect the chemical composition of SOA generated from β-pinene and naphthalene, as well as from urban atmospheric aerosol samples. SOA samples were produced in the laboratory using an aerosol flow tube and collected on PTFE filters, whereas ambient samples were collected onto quartz filters with a high-volume air sampler. To characterize temporal changes of SOA composition, all samples were extracted and analyzed immediately after collection, but were also stored as aqueous extracts or as filters for 24 hours and up to 4 weeks at three different temperatures of +20 °C, -20 °C or -80 °C, to assess whether a lower storage temperature would be favorable. Analysis was conducted using ultra high-performance liquid chromatography high resolution mass spectrometry (UHPLC-HRMS). Both principal component analysis (PCA) and time series of selected compounds were analyzed to identify the compositional changes over time. We illustrate that the chemical composition of organic aerosols remained stable during low temperature storage conditions, while storage at room temperature led to significant changes over time, even at short storage times of only one day. This indicates that it is necessary to freeze samples immediately after collection, and this requirement is especially important when automated ambient sampling devices are used where filters might be stored in the device for several days before being transferred to a laboratory.

Received: 26 Apr 2023 – Discussion started: 28 Apr 2023

Download & links

Preprint (PDF, 993 KB)

Notice on discussion status
The requested preprint has a corresponding peer-reviewed final revised paper. You are encouraged to refer to the final revised version.
Preprint (993 KB)

Supplement (943 KB)

Download & links

The requested preprint has a corresponding peer-reviewed final revised paper. You are encouraged to refer to the final revised version.

Journal article(s) based on this preprint

21 Aug 2023

Effects of storage conditions on the molecular-level composition of organic aerosol particles

Julian Resch, Kate Wolfer, Alexandre Barth, and Markus Kalberer

Atmos. Chem. Phys., 23, 9161–9171, https://doi.org/10.5194/acp-23-9161-2023,https://doi.org/10.5194/acp-23-9161-2023, 2023

Short summary

Julian Resch et al.

Interactive discussion

Status: closed

RC1:
'Comment on egusphere-2023-840', Anonymous Referee #1, 03 May 2023

This study of filter stability before the analysis has been long overdue, and I am really happy the authors found the time to do it, and do it well! The conclusion is something people suspected but had no proof for: filters and extracts stored at room temperature change in composition significantly on a times scale of a day or so. This is important, and I expected many offline studies of aerosols to cite this study in the future. I recommend publishing after minor revisions.

I do not think this has to be be a technical note, it can also be a regular paper, especially if the authors can offer a hypothesis or a possible explanation for why aging processes in solution are different from those on a filter (Figures 1 and 3).

Technical:

If it is practical I would make the X- and Y-scales on all PCA figures (Figures 1, 3, 5, S2, S5, S6, S7, S8) the same

Legend labels in Figures 5, S6, S7, S8 should say -20C and -80C instead of 20 and 80 (as they do in the rest of the PCA figures)

Line 166 and line 236: Intensity of 7E5 is not too meaningful – it is better to specify it in relationship to the peak signal (such as X% of the largest observed peak). Similar comment for line 292.

Figure 3: this figure can be much improved – the traces can be split into separate stacked panels, the text labels can be more readable, and the four most intense peaks mentioned in line 192 of the paper can be explicitly identified.

Citation: https://doi.org/10.5194/egusphere-2023-840-RC1
- AC1: 'Reply on RC1', Julian Resch, 22 Jun 2023
  
  We thank the reviewer for the detailed and positive comments. Please see in the attachment point-by-point answers, addressing the all the comments. All of our answers are given in blue below and we indicate the lines changed in the revised manuscript.
  
  Citation: https://doi.org/10.5194/egusphere-2023-840-AC1
RC2:
'Comment on egusphere-2023-840', Anonymous Referee #2, 30 May 2023
This technical note presents the effect of the storage in different conditions on the molecular composition of aerosol produced in chamber and collected from ambient air. I absolutely agree with the authors on the crucial need to understand the effect of storage on the organic matter composition and I particularly appreciate the dual approach, taking into account the trends of specific m/z and on the global composition of the samples. The objectives of the study are clear and the methodology is well written and detailed. This work deserves to be published.
Nevertheless, few points can be improved:
The authors investigate 3 storage conditions for filters and extracts: room temperature, -20°C and -80°C. I would have added also 4°C. This could be extremely interesting for the extracts, because it is the temperature of the autosampler for many instruments (LC-MS, IC-MS…). Do the authors have an idea of the effect of storage in refrigerated conditions?

Regarding the storage conditions, at lines 56-61, the authors reported that storage conditions were evaluated for inorganic ions, EC and OC analysis. No references are reported. What are the current guidelines from research infrastructures? Are they comparable with those presented in this work?

SOA samples seems more perishable than ambient aerosol samples: few hours of sampling are enough to change the composition of the organic matter. Sampling in chamber should be performed in refrigerated conditions?

The extraction procedure reported at line 98-99 is reported in previous studies or was designed for this study in particular?

The PCA enables a global view of the variation of the composition of the samples with storage. However, I miss some details of the statistic study, like the methodology for the normalization of the intensity of the peaks. This is essential when the analysis is performed on a large database like mass spectrometry results. I also feel that the PCA can be better exploited to understand the effect of the storage: is there a trend in the clusters? For example, looking at the room temperature extracts in Fig 1, I would expect that short storage times would be closer to the initial sample.

I found very interesting the behaviour of cis-pinonic acid. May it be considered as a proxy to study the desorption or the sublimation of semivolatile organic compounds?

HVAS = ? high volume aerosol sample, I imagine

I think that the objective of this study is to provide some guidelines on the storage of filters and extracts for aerosol samples. I expected to find these guidelines in the conclusions but I didn’t. In my opinion, the authors should put the basis for a standardization of the methodologies in aerosol sampling for molecular characterisation and clearly state the procedure to adopt in order to improve the comparison of samples.
Citation: https://doi.org/10.5194/egusphere-2023-840-RC2
- AC2: 'Reply on RC2', Julian Resch, 22 Jun 2023
  
  We thank the reviewer for the detailed and positive comments. Please see in the attachment point-by-point answers, addressing the all the comments. All of our answers are given in blue below and we indicate the lines changed in the revised manuscript.
  
  Citation: https://doi.org/10.5194/egusphere-2023-840-AC2
RC3:
'Comment on egusphere-2023-840', Anonymous Referee #3, 14 Jun 2023

The manuscript by Resch et al. presents an interesting novel study on the influence of storage conditions on chemical composition of collected aerosol filter samples.

In general the manuscript is well written and presents the results in a straightforward way. But it still needs a careful language check. I have pointed to some suggestions for this, but an additional check is needed.

My main concern is the lack of detailed description of laboratory sample generation and conditions during collection from ambient air, as well as considerations of the difference in chemical composition between laboratory generated SOA and ambient aerosols as described in details below.

L. 12: I suggest to include here which oxidants were used to generate the SOA.

L20: It is not clear what you mean by “illustrate”. Please use a more scientific description. Please add information about the temperatures.

L21: I suggest to add more information about your results here to describe what you mean by “significant”.

L53-61: This section contains speculations and broad criticism of previous studies. I suggest to change the wording to avoid these broad accusations of unspecified previous studies.

L70: Please state purities if known.

Section 2.2: The conditions for laboratory generation of SOA samples should be described in much more detail including the OCU in the main manuscript. How much ageing does this compare to (oxidant concentrations, days)?

Furthermore the dates of ambient sampling should be listed, as well as supporting measurements such as PM levels.

L90: Please provide this information, maybe in the SI.

L101-102: What was the precision of these volumes? Please give the appropriate number of digits.

L113-115: These lines need revision regarding: liquid chromatographic measurements, split sampler, for separations. Please rewrite to clarify and improve the (scientific) language.

Section 3.3. It is important to consider the influence of the time of year on the results.

It is very interesting that the conclusion in section 3.3 is that ambient samples are less affected by the storage conditions. Could this difference be due to a high content of freshly formed reactive species (HOMs, peroxides etc.) in the laboratory-generated SOA?

Conclusion L359: This sentence seems quite speculative.

Fig S4: Which type of SOA is shown?

Fig. S2 and S5: Numbers in dark blue markers are not visible.
Minor comments:

Line 10 artefactual – please check that this is a correct word

L18: Seems that a word is missing after chromatography – with? coupled to?

L50: exhibit -> show?

L62: define – I assume you mean “identify” or “characterize”.

L127: AGC target of 3E6 – please clarify

L164: I suggest to mention the oxidants again.

L297: generates -> generated

Citation: https://doi.org/10.5194/egusphere-2023-840-RC3
- AC3: 'Reply on RC3', Julian Resch, 22 Jun 2023
  
  We thank the reviewer for the detailed and positive comments. Please see in the attachment point-by-point answers, addressing the all the comments. All of our answers are given in blue below and we indicate the lines changed in the revised manuscript.
  
  Citation: https://doi.org/10.5194/egusphere-2023-840-AC3

Interactive discussion

Status: closed

RC1:
'Comment on egusphere-2023-840', Anonymous Referee #1, 03 May 2023

This study of filter stability before the analysis has been long overdue, and I am really happy the authors found the time to do it, and do it well! The conclusion is something people suspected but had no proof for: filters and extracts stored at room temperature change in composition significantly on a times scale of a day or so. This is important, and I expected many offline studies of aerosols to cite this study in the future. I recommend publishing after minor revisions.

I do not think this has to be be a technical note, it can also be a regular paper, especially if the authors can offer a hypothesis or a possible explanation for why aging processes in solution are different from those on a filter (Figures 1 and 3).

Technical:

If it is practical I would make the X- and Y-scales on all PCA figures (Figures 1, 3, 5, S2, S5, S6, S7, S8) the same

Legend labels in Figures 5, S6, S7, S8 should say -20C and -80C instead of 20 and 80 (as they do in the rest of the PCA figures)

Line 166 and line 236: Intensity of 7E5 is not too meaningful – it is better to specify it in relationship to the peak signal (such as X% of the largest observed peak). Similar comment for line 292.

Figure 3: this figure can be much improved – the traces can be split into separate stacked panels, the text labels can be more readable, and the four most intense peaks mentioned in line 192 of the paper can be explicitly identified.

Citation: https://doi.org/10.5194/egusphere-2023-840-RC1
- AC1: 'Reply on RC1', Julian Resch, 22 Jun 2023
  
  We thank the reviewer for the detailed and positive comments. Please see in the attachment point-by-point answers, addressing the all the comments. All of our answers are given in blue below and we indicate the lines changed in the revised manuscript.
  
  Citation: https://doi.org/10.5194/egusphere-2023-840-AC1
RC2:
'Comment on egusphere-2023-840', Anonymous Referee #2, 30 May 2023
This technical note presents the effect of the storage in different conditions on the molecular composition of aerosol produced in chamber and collected from ambient air. I absolutely agree with the authors on the crucial need to understand the effect of storage on the organic matter composition and I particularly appreciate the dual approach, taking into account the trends of specific m/z and on the global composition of the samples. The objectives of the study are clear and the methodology is well written and detailed. This work deserves to be published.
Nevertheless, few points can be improved:
The authors investigate 3 storage conditions for filters and extracts: room temperature, -20°C and -80°C. I would have added also 4°C. This could be extremely interesting for the extracts, because it is the temperature of the autosampler for many instruments (LC-MS, IC-MS…). Do the authors have an idea of the effect of storage in refrigerated conditions?

Regarding the storage conditions, at lines 56-61, the authors reported that storage conditions were evaluated for inorganic ions, EC and OC analysis. No references are reported. What are the current guidelines from research infrastructures? Are they comparable with those presented in this work?

SOA samples seems more perishable than ambient aerosol samples: few hours of sampling are enough to change the composition of the organic matter. Sampling in chamber should be performed in refrigerated conditions?

The extraction procedure reported at line 98-99 is reported in previous studies or was designed for this study in particular?

The PCA enables a global view of the variation of the composition of the samples with storage. However, I miss some details of the statistic study, like the methodology for the normalization of the intensity of the peaks. This is essential when the analysis is performed on a large database like mass spectrometry results. I also feel that the PCA can be better exploited to understand the effect of the storage: is there a trend in the clusters? For example, looking at the room temperature extracts in Fig 1, I would expect that short storage times would be closer to the initial sample.

I found very interesting the behaviour of cis-pinonic acid. May it be considered as a proxy to study the desorption or the sublimation of semivolatile organic compounds?

HVAS = ? high volume aerosol sample, I imagine

I think that the objective of this study is to provide some guidelines on the storage of filters and extracts for aerosol samples. I expected to find these guidelines in the conclusions but I didn’t. In my opinion, the authors should put the basis for a standardization of the methodologies in aerosol sampling for molecular characterisation and clearly state the procedure to adopt in order to improve the comparison of samples.
Citation: https://doi.org/10.5194/egusphere-2023-840-RC2
- AC2: 'Reply on RC2', Julian Resch, 22 Jun 2023
  
  We thank the reviewer for the detailed and positive comments. Please see in the attachment point-by-point answers, addressing the all the comments. All of our answers are given in blue below and we indicate the lines changed in the revised manuscript.
  
  Citation: https://doi.org/10.5194/egusphere-2023-840-AC2
RC3:
'Comment on egusphere-2023-840', Anonymous Referee #3, 14 Jun 2023

The manuscript by Resch et al. presents an interesting novel study on the influence of storage conditions on chemical composition of collected aerosol filter samples.

In general the manuscript is well written and presents the results in a straightforward way. But it still needs a careful language check. I have pointed to some suggestions for this, but an additional check is needed.

My main concern is the lack of detailed description of laboratory sample generation and conditions during collection from ambient air, as well as considerations of the difference in chemical composition between laboratory generated SOA and ambient aerosols as described in details below.

L. 12: I suggest to include here which oxidants were used to generate the SOA.

L20: It is not clear what you mean by “illustrate”. Please use a more scientific description. Please add information about the temperatures.

L21: I suggest to add more information about your results here to describe what you mean by “significant”.

L53-61: This section contains speculations and broad criticism of previous studies. I suggest to change the wording to avoid these broad accusations of unspecified previous studies.

L70: Please state purities if known.

Section 2.2: The conditions for laboratory generation of SOA samples should be described in much more detail including the OCU in the main manuscript. How much ageing does this compare to (oxidant concentrations, days)?

Furthermore the dates of ambient sampling should be listed, as well as supporting measurements such as PM levels.

L90: Please provide this information, maybe in the SI.

L101-102: What was the precision of these volumes? Please give the appropriate number of digits.

L113-115: These lines need revision regarding: liquid chromatographic measurements, split sampler, for separations. Please rewrite to clarify and improve the (scientific) language.

Section 3.3. It is important to consider the influence of the time of year on the results.

It is very interesting that the conclusion in section 3.3 is that ambient samples are less affected by the storage conditions. Could this difference be due to a high content of freshly formed reactive species (HOMs, peroxides etc.) in the laboratory-generated SOA?

Conclusion L359: This sentence seems quite speculative.

Fig S4: Which type of SOA is shown?

Fig. S2 and S5: Numbers in dark blue markers are not visible.
Minor comments:

Line 10 artefactual – please check that this is a correct word

L18: Seems that a word is missing after chromatography – with? coupled to?

L50: exhibit -> show?

L62: define – I assume you mean “identify” or “characterize”.

L127: AGC target of 3E6 – please clarify

L164: I suggest to mention the oxidants again.

L297: generates -> generated

Citation: https://doi.org/10.5194/egusphere-2023-840-RC3
- AC3: 'Reply on RC3', Julian Resch, 22 Jun 2023
  
  We thank the reviewer for the detailed and positive comments. Please see in the attachment point-by-point answers, addressing the all the comments. All of our answers are given in blue below and we indicate the lines changed in the revised manuscript.
  
  Citation: https://doi.org/10.5194/egusphere-2023-840-AC3

Peer review completion

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

AR by Julian Resch on behalf of the Authors (22 Jun 2023) Author's response Author's tracked changes Manuscript

ED: Referee Nomination & Report Request started (07 Jul 2023) by Theodora Nah

RR by Anonymous Referee #1 (09 Jul 2023)

ED: Publish as is (16 Jul 2023) by Theodora Nah

AR by Julian Resch on behalf of the Authors (24 Jul 2023) Manuscript

Journal article(s) based on this preprint

21 Aug 2023

Effects of storage conditions on the molecular-level composition of organic aerosol particles

Julian Resch, Kate Wolfer, Alexandre Barth, and Markus Kalberer

Atmos. Chem. Phys., 23, 9161–9171, https://doi.org/10.5194/acp-23-9161-2023,https://doi.org/10.5194/acp-23-9161-2023, 2023

Short summary

Julian Resch et al.

Supplement

https://doi.org/10.5194/egusphere-2023-840-supplement

Julian Resch et al.

Viewed

Total article views: 770 (including HTML, PDF, and XML)

HTML	PDF	XML	Total	Supplement	BibTeX	EndNote
574	172	24	770	77	10	10

HTML: 574
PDF: 172
XML: 24
Total: 770
Supplement: 77
BibTeX: 10
EndNote: 10

Views and downloads (calculated since 28 Apr 2023)

Month	HTML	PDF	XML	Total
Apr 2023	87	24	5	116
May 2023	237	62	9	308
Jun 2023	143	44	8	195
Jul 2023	72	27	2	101
Aug 2023	35	15	0	50

Cumulative views and downloads (calculated since 28 Apr 2023)

Month	HTML	PDF	XML	Total
Apr 2023	87	24	5	116
May 2023	237	62	9	308
Jun 2023	143	44	8	195
Jul 2023	72	27	2	101
Aug 2023	35	15	0	50

Viewed (geographical distribution)

Total article views: 800 (including HTML, PDF, and XML) Thereof 800 with geography defined and 0 with unknown origin.

Country	#	Views	%

Latest update: 21 Aug 2023

Download

The requested preprint has a corresponding peer-reviewed final revised paper. You are encouraged to refer to the final revised version.

Preprint (993 KB)
Metadata XML

Short summary

Detailed chemical analysis of organic aerosol is necessary to better understand their effects on climate and health. Aerosol samples are often stored for days to months before analysis. We examined effects of storage conditions (i.e., time, temperature and aerosol storage on filters or as solvent extracts) on composition and found significant changes in the concentration of individual compounds, indicating that sample storage can strongly affect the detailed chemical particle composition.


Total:	0
HTML:	0
PDF:	0
XML:	0

Technical note: Effects of storage conditions on molecular-level composition of organic aerosol particles

Journal article(s) based on this preprint

Interactive discussion

Interactive discussion

Peer review completion

Suggestions for revision or reasons for rejection

Journal article(s) based on this preprint

Supplement

Viewed

Viewed (geographical distribution)