the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
| 30 Jun 2025
Quantification of 21 sugars in tropospheric particulate matter by ultra-high-performance liquid chromatography tandem mass spectrometry
Abstract. Sugars compose an important class of compounds by mass in atmospheric particulate matter (PM), often with biogenic and anthropogenic sources, many of them still poorly characterized. These sugars are mainly analysed by gas-chromatography coupled to mass spectrometry (GC-MS) or ion chromatography coupled with pulsed amperometric detection (IC-PAD). However, these techniques present several disadvantages such as a complex preparation for GC-MS, or a limited range of possible analytes and elevated limits of quantification for IC-PAD. This hinders our capability to perform analyses of extensive time series, in order to develop our knowledge of the phenomenology of these species. In this paper, we present the validation of an ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method for the simultaneous quantification of 21 sugars in atmospheric PM. The sample preparation is simple, fast and safe, consisting of an aqueous extraction. The method was validated in terms of linearity, accuracy, repeatability, reproducibility, and recovery. This technique showed excellent linearity (r2>0.99), precision (relative standard deviation RSD<25 %) and extraction yields (results between 70 and 120 %). The suitability of the method for analyses of samples from sites with very low PM concentrations was demonstrated with samples from the High-Altitude Research Station Jungfraujoch (JFJ), Switzerland. A series of samples spanning a 6-year period is presented. Results for arabitol, levoglucosan and 2-methyl-tetrols display strong seasonality, due to seasonal variation in chemical production and boundary layer dynamics, with atmospheric convection and transport from the valleys to high altitudes mostly in summer. This simple and fast method facilitates the analysis of large sets of PM samples and sugar compounds, and opens the door to a better understanding and attribution of their sources.
- Preprint
(1069 KB) - Metadata XML
-
Supplement
(679 KB) - BibTeX
- EndNote
Status: closed
-
RC1: 'Comment on egusphere-2025-1951', Anonymous Referee #1, 18 Jul 2025
- AC1: 'Reply on RC1', Sophie Darfeuil, 05 Sep 2025
-
RC2: 'Comment on egusphere-2025-1951', Anonymous Referee #2, 27 Jul 2025
This manuscript presents the use of ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) as a tool to quantify sugars in atmospheric PM at very low concentrations. The authors provide a description of the preparation and measurement procedures and give an in-depth validation of the method’s standard analytical criteria. This technique was then applied to ambient samples from the high altitude station “Jungfraujoch”, providing a time series of five years. The authors demonstrate that sample preparation and analysis can be obtained in relatively short lab time. They show the observation of a seasonal cycle for three of the measured sugars and discuss their trends qualitatively.
Many different sugars have been measured in particulate matter but analysis is so far quite demanding due to the low concentrations and low selectivity of available analytical techniques. As sugars may comprise a large fraction of PM, more and better measurements are needed for quantification and tracking their origin. The authors show that UHPLC-MS/MS can be used to quantify a large range of sugars at very low concentrations. They tested 28 different sugars and show, that 21 of them can be used for quantitative analysis. The validation of the method is sound and the description of procedures and calculations sufficiently complete and precise to allow their reproduction by fellow scientists.
They apply the method to filter samples taken at “Jungfraujoch”, a relatively unpolluted environment, demonstrating that it also performs well at fairly low concentrations. The discussion of the results of this time series is reasonable, albeit only qualitative. It is mentioned that a more comprehensive analysis including other measured species will follow. The paper is clearly written and I recommend the manuscript to be published. I have only a few minor comments that should be considered.
Add the mass resolution of the mass spectrometer. In Table 1 m/z is reported in 3 digits. However, isomers show different m/z, although they should be the same (e.g. fructose, glucose). Probably mass resolution is not that high.
Equation 1and Table 2: Why do you use an absolute value for bias? Thus, the direction of the bias cannot be seen.
Table S2: You do not report the molecular mass but Q1. Clarify this.
Line 66; Sentence not clear (However…)
Line 80: replace tgenerally by generally
Line 120: replace “et” by and
Line 128: not correct units of MQ-water
Line 130: MIX-SI stands for mixture of internal standards. I recommend using MIX-IS. I assume you used the French abbreviation.
Line 305: others, replace by other
Citation: https://doi.org/10.5194/egusphere-2025-1951-RC2 - AC2: 'Reply on RC2', Sophie Darfeuil, 05 Sep 2025
Status: closed
-
RC1: 'Comment on egusphere-2025-1951', Anonymous Referee #1, 18 Jul 2025
- AC1: 'Reply on RC1', Sophie Darfeuil, 05 Sep 2025
-
RC2: 'Comment on egusphere-2025-1951', Anonymous Referee #2, 27 Jul 2025
This manuscript presents the use of ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) as a tool to quantify sugars in atmospheric PM at very low concentrations. The authors provide a description of the preparation and measurement procedures and give an in-depth validation of the method’s standard analytical criteria. This technique was then applied to ambient samples from the high altitude station “Jungfraujoch”, providing a time series of five years. The authors demonstrate that sample preparation and analysis can be obtained in relatively short lab time. They show the observation of a seasonal cycle for three of the measured sugars and discuss their trends qualitatively.
Many different sugars have been measured in particulate matter but analysis is so far quite demanding due to the low concentrations and low selectivity of available analytical techniques. As sugars may comprise a large fraction of PM, more and better measurements are needed for quantification and tracking their origin. The authors show that UHPLC-MS/MS can be used to quantify a large range of sugars at very low concentrations. They tested 28 different sugars and show, that 21 of them can be used for quantitative analysis. The validation of the method is sound and the description of procedures and calculations sufficiently complete and precise to allow their reproduction by fellow scientists.
They apply the method to filter samples taken at “Jungfraujoch”, a relatively unpolluted environment, demonstrating that it also performs well at fairly low concentrations. The discussion of the results of this time series is reasonable, albeit only qualitative. It is mentioned that a more comprehensive analysis including other measured species will follow. The paper is clearly written and I recommend the manuscript to be published. I have only a few minor comments that should be considered.
Add the mass resolution of the mass spectrometer. In Table 1 m/z is reported in 3 digits. However, isomers show different m/z, although they should be the same (e.g. fructose, glucose). Probably mass resolution is not that high.
Equation 1and Table 2: Why do you use an absolute value for bias? Thus, the direction of the bias cannot be seen.
Table S2: You do not report the molecular mass but Q1. Clarify this.
Line 66; Sentence not clear (However…)
Line 80: replace tgenerally by generally
Line 120: replace “et” by and
Line 128: not correct units of MQ-water
Line 130: MIX-SI stands for mixture of internal standards. I recommend using MIX-IS. I assume you used the French abbreviation.
Line 305: others, replace by other
Citation: https://doi.org/10.5194/egusphere-2025-1951-RC2 - AC2: 'Reply on RC2', Sophie Darfeuil, 05 Sep 2025
Viewed
| HTML | XML | Total | Supplement | BibTeX | EndNote | |
|---|---|---|---|---|---|---|
| 466 | 49 | 13 | 528 | 17 | 15 | 24 |
- HTML: 466
- PDF: 49
- XML: 13
- Total: 528
- Supplement: 17
- BibTeX: 15
- EndNote: 24
Viewed (geographical distribution)
| Country | # | Views | % |
|---|
| Total: | 0 |
| HTML: | 0 |
| PDF: | 0 |
| XML: | 0 |
- 1
Please see attached Report.