the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
The impacts of pollution sources and temperature on the light absorption of HULIS were revealed by UHPLC-HRMS/MS at the molecular structure level
Abstract. Atmospheric humic-like substances (HULIS), a key component of brown carbon (BrC), significantly promote the light absorption of aerosols. However, their linkages to pollution sources and ambient temperature in cold environments remain unresolved. Here, we analyze wintertime urban aerosol samples in Changchun, Northeast China, using ultrahigh performance liquid chromatography coupled with high-resolution tandem mass spectrometry (UHPLC-HRMS/MS). HULIS show a high light absorption efficiency (MAE365 = 1.81 ± 0.24 m2 gC-1) and high mass concentration (2.97 ± 1.54 μgC m-3), exceeding values reported from other global regions. Through UHPLC-HRMS/MS characterization, we identify 264 compounds at the molecular structure level, accounting for 38.2–78.1 % of the total HULIS mass. Compositional analysis demonstrates biomass burning and coal combustion are the main BrC sources during haze events. We screen out 39 strong BrC chromophores, mainly nitrophenols, that contribute 28.9 ± 10.4 % of the total light absorbance at 365 nm. Low ambient temperatures potentially enhance the accumulation of these strong BrC chromophores in the aerosol particles by suppressing photobleaching processes and altering thermodynamic reaction equilibria. These findings emphasize the potential of BrC to exert a more significant and persistent environmental effect in the cold region atmosphere.
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RC1: 'Comment on egusphere-2025-1808', Anonymous Referee #1, 01 May 2025
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This work investigated the impact of low temperature on the formation of strong BrC chromophores in HULIS and proposed two mechanisms, one is that the low temperature may lead to a non-liquid phase state of ambient particles, potentially introducing kinetic limitation on the diffusion of reactive species from gas phase into the bulk aerosol and second low temperature promoted the reaction of phenols with NOx radicals while inhibited the atmospheric oxidation of nitrophenols, thus facilitating the accumulation of BrC chromophores such as nitrophenols in HULIS. Overall, the paper was well-organized, and the results are of broad interest. I would recommend the paper be accepted after revision, as outlined below.
1 line 48-50. Please elaborate further on the assertion that HULIS is under low-temperature conditions for the majority of its atmospheric lifetime. This statement serves as a critical foundation for the research motivation and requires more evidenced or references to support it.
2 line 83-84 and Text S1. This semi-quantification strategy was based on the experiment experience that substances with similar structures and equal concentrations yield comparable signal intensities in mass spectrometry. Please specify the criteria for selecting the semi-quantification proxy compounds. Additionally, a thorough discussion on the uncertainties associated with this semi-quantification approach should be provided.
3 Move compound identification and quantification from SI to the main text and a discussion of semi-quantification errors, as suggested above, should be incorporated into the manuscript (either in the main text or the SI).
4 Section 3.2. In the discussion on the potential sources of HULIS, the authors selected two PM haze events instead of high HULIS episodes. What’s HULIS concentration during these two PM pollution events. Additionally, please include the mass spectra of HULIS samples from non-haze days for comparison with those in Event I and II. This would clarify whether the identified sources were specific to HULIS or more generally associated with PM2.5.
5 Section 3.3. The discussion of the effect of temperature on BrC chromophore formation is arguably the most important aspect of this study. As the author proposed, low temperature promoted the exothermic process (e.g., reaction of phenols with NOx radicals) and hindered the endothermic chemical reactions (e.g., atmospheric oxidation of nitrophenols), thus facilitating the accumulation of BrC chromophores in HULIS. In addition to this qualitative thermodynamic explanation, a more in-depth discussion is encouraged. Specifically, how does low temperature alter the overall atmospheric chemistry and also any comparable results/findings/ mechanistic insights from previous literature that support your conclusions.
Citation: https://doi.org/10.5194/egusphere-2025-1808-RC1 -
RC2: 'Comment on egusphere-2025-1808', Anonymous Referee #2, 05 May 2025
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This study collected atmospheric PM2.5 samples during wintertime in Changchun and identified the molecular structures in HULIS, providing a new insight into the potential sources and temperature effects on the light-absorption properties of HULIS. We have gained some new insights through this study, but there is still room for improvement.
Is the temperature division in Figure 3 based on the daily average temperature? Studying the impact of temperature on HULIS based on daily average temperature may be too crude. In addition, the temperature in the sampling area is generally low. How to compare the impact of high temperature on the formation of HULIS, because the so-called high temperature during the sampling period is far from the general high temperature, such as 20℃ or even 30℃ or above. Please clarify. Warm and cold need to be indicated the temperature range in the Graphical abstract.
The average concentration and standard deviation of PM2.5 during the entire sampling period need to be reported in order to reflect the rationality of the selection of two typical haze events. The PM2.5 concentration of Event II is not high. Please indicate the basis for selecting these two events. The daily meteorological data and mean values of the entire sampling process also need to be presented in the attachment.
Table S5 only shows the concentrations of K+ and SO2 for two pollution events and does not compare them with other non-polluting days. How can you know that these two pollution events were strongly contributed by biomass and coal combustion?
Can the mechanism of low temperatures reducing the photobleaching of brown carbon be further explored? And is it related to relative humidity?
Citation: https://doi.org/10.5194/egusphere-2025-1808-RC2
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