| 1. |
- Graham, Emelie L., 1989-, et al.
(author)
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Volatility of aerosol particles from NO3 oxidation of various biogenic organic precursors
- 2023
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In: Atmospheric Chemistry And Physics. - 1680-7316 .- 1680-7324. ; 23, s. 7347-7362
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Journal article (peer-reviewed)abstract
- Secondary organic aerosol (SOA) is formed through the oxidation of volatile organic compounds (VOCs), which can be of both natural and anthropogenic origin. While the hydroxyl radical (OH) and ozone (O3) are the main atmospheric oxidants during the day, the nitrate radical (NO3) becomes more important during the nighttime. Yet, atmospheric nitrate chemistry has received less attention compared to OH and O3. The Nitrate Aerosol and Volatility Experiment (NArVE) aimed to study the NO3-induced SOA formation and evolution from three biogenic VOCs (BVOCs), namely isoprene, α-pinene, and β-caryophyllene. The volatility of aerosol particles was studied using isothermal evaporation chambers, temperature-dependent evaporation in a volatility tandem differential mobility analyzer (VTDMA), and thermal desorption in a filter inlet for gases and aerosols coupled to a chemical ionization mass spectrometer (FIGAERO-CIMS). Data from these three setups present a cohesive picture of the volatility of the SOA formed in the dark from the three biogenic precursors. Under our experimental conditions, the SOA formed from NO3+α-pinene was generally more volatile than SOA from α-pinene ozonolysis, while the NO3 oxidation of isoprene produced similar although slightly less volatile SOA than α-pinene under our experimental conditions. β-Caryophyllene reactions with NO3 resulted in the least volatile species. Four different parameterizations for estimating the saturation vapor pressure of the oxidation products were tested for reproducing the observed evaporation in a kinetic modeling framework. Our results show that the SOA from nitrate oxidation of α-pinene or isoprene is dominated by low-volatility organic compounds (LVOCs) and semi-volatile organic compounds (SVOCs), while the corresponding SOA from β-caryophyllene consists primarily of extremely low-volatility organic compounds (ELVOCs) and LVOCs. The parameterizations yielded variable results in terms of reproducing the observed evaporation, and generally the comparisons pointed to a need for re-evaluating the treatment of the nitrate group in such parameterizations. Strategies for improving the predictive power of the volatility parameterizations, particularly in relation to the contribution from the nitrate group, are discussed.
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| 2. |
- Gramlich, Yvette, 1993-, et al.
(author)
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Impact of Biomass Burning on Arctic Aerosol Composition
- 2024
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In: ACS Earth and Space Chemistry. - 2472-3452.
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Journal article (peer-reviewed)abstract
- Emissions from biomass burning (BB) occurring at midlatitudes can reach the Arctic, where they influence the remote aerosol population. By using measurements of levoglucosan and black carbon, we identify seven BB events reaching Svalbard in 2020. We find that most of the BB events are significantly different to the rest of the year (nonevents) for most of the chemical and physical properties. Aerosol mass and number concentrations are enhanced by up to 1 order of magnitude during the BB events. During BB events, the submicrometer aerosol bulk composition changes from an organic- and sulfate-dominated regime to a clearly organic-dominated regime. This results in a significantly lower hygroscopicity parameter κ for BB aerosol (0.4 ± 0.2) compared to nonevents (0.5 ± 0.2), calculated from the nonrefractory aerosol composition. The organic fraction in the BB aerosol showed no significant difference for the O:C ratios (0.9 ± 0.3) compared to the year (0.9 ± 0.6). Accumulation mode particles were present during all BB events, while in the summer an additional Aitken mode was observed, indicating a mixture of the advected air mass with locally produced particles. BB tracers (vanillic, homovanillic, and hydroxybenzoic acid, nitrophenol, methylnitrophenol, and nitrocatechol) were significantly higher when air mass back trajectories passed over active fire regions in Eastern Europe, indicating agricultural and wildfires as sources. Our results suggest that the impact of BB on the Arctic aerosol depends on the season in which they occur, and agricultural and wildfires from Eastern Europe have the potential to disturb the background conditions the most.
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| 3. |
- Gramlich, Yvette, 1993-, et al.
(author)
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Revealing the chemical characteristics of Arctic low-level cloud residuals – in situ observations from a mountain site
- 2023
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In: Atmospheric Chemistry And Physics. - 1680-7316 .- 1680-7324. ; 23:12, s. 6813-6834
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Journal article (peer-reviewed)abstract
- The role aerosol chemical composition plays in Arctic low-level cloud formation is still poorly understood. In this study we address this issue by combining in situ observations of the chemical characteristics of cloud residuals (dried liquid cloud droplets or ice crystals) and aerosol particles from the Zeppelin Observatory in Ny-Ålesund, Svalbard (approx. 480 m a.s.l.). These measurements were part of the 1-year-long Ny-Ålesund Aerosol and Cloud Experiment 2019–2020 (NASCENT). To obtain the chemical composition of cloud residuals at molecular level, we deployed a Filter Inlet for Gases and AEROsols coupled to a Chemical Ionization Mass Spectrometer (FIGAERO-CIMS) with iodide as the reagent ion behind a ground-based counterflow virtual impactor (GCVI). The station was enshrouded in clouds roughly 15 % of the time during NASCENT, out of which we analyzed 14 cloud events between December 2019 and December 2020. During the entire year, the composition of the cloud residuals shows contributions from oxygenated organic compounds, including organonitrates, and traces of the biomass burning tracer levoglucosan. In summer, methanesulfonic acid (MSA), an oxidation product of dimethyl sulfide (DMS), shows large contributions to the sampled mass, indicating marine natural sources of cloud condensation nuclei (CCN) and ice nucleating particle (INP) mass during the sunlit part of the year. In addition, we also find contributions of the inorganic acids nitric acid and sulfuric acid, with outstanding high absolute signals of sulfuric acid in one cloud residual sample in spring and one in late summer (21 May and 12 September 2020), probably caused by high anthropogenic sulfur emissions near the Barents Sea and Kara Sea. During one particular cloud event, on 18 May 2020, the air mass origin did not change before, during, or after the cloud. We therefore chose it as a case study to investigate cloud impact on aerosol physicochemical properties. We show that the overall chemical composition of the organic aerosol particles was similar before, during, and after the cloud, indicating that the particles had already undergone one or several cycles of cloud processing before being measured as residuals at the Zeppelin Observatory and/or that, on the timescales of the observed cloud event, cloud processing of the organic fraction can be neglected. Meanwhile, there were on average fewer particles but relatively more in the accumulation mode after the cloud. Comparing the signals of sulfur-containing compounds of cloud residuals with aerosols during cloud-free conditions, we find that sulfuric acid had a higher relative contribution to the cloud residuals than to aerosols during cloud-free conditions, but we did not observe an increase in particulate MSA due to the cloud. Overall, the chemical composition, especially of the organic fraction of the Arctic cloud residuals, reflected the overall composition of the general aerosol population well. Our results thus suggest that most aerosols can serve as seeds for low-level clouds in the Arctic.
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| 4. |
- Haslett, Sophie, 1988-, et al.
(author)
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Nighttime NO emissions strongly suppress chlorine and nitrate radical formation during the winter in Delhi
- 2023
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In: Atmospheric Chemistry And Physics. - 1680-7316 .- 1680-7324. ; 23:16, s. 9023-9036
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Journal article (peer-reviewed)abstract
- Atmospheric pollution in urban regions is highly influenced by oxidants due to their important role in the formation of secondary organic aerosol (SOA) and smog. These include the nitrate radical (NO3), which is typically considered a nighttime oxidant, and the chlorine radical (Cl), an extremely potent oxidant that can be released in the morning in chloride-rich environments as a result of nocturnal build-up of nitryl chloride (ClNO2). Chloride makes up a higher percentage of particulate matter in Delhi than has been observed anywhere else in the world, which results in Cl having an unusually strong influence in this city. Here, we present observations and model results revealing that atmospheric chemistry in Delhi exhibits an unusual diel cycle that is controlled by high concentrations of NO during the night. As a result of this, the formation of both NO3 and dinitrogen pentoxide (N2O5), a precursor of ClNO2 and thus Cl, are suppressed at night and increase to unusually high levels during the day. Our results indicate that a substantial reduction in nighttime NO has the potential to increase both nocturnal oxidation via NO(3 )and the production of Cl during the day.
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| 5. |
- Huang, Wei, et al.
(author)
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Variation in chemical composition and volatility of oxygenated organic aerosol in different rural, urban, and mountain environments
- 2024
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In: Atmospheric Chemistry and Physics. - 1680-7316 .- 1680-7324. ; 24:4, s. 2607-2624
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Journal article (peer-reviewed)abstract
- The apparent volatility of atmospheric organic aerosol (OA) particles is determined by their chemical composition and environmental conditions (e.g., ambient temperature). A quantitative, experimental assessment of volatility and the respective importance of these two factors remains challenging, especially in ambient measurements. We present molecular composition and volatility of oxygenated OA (OOA) particles in different rural, urban, and mountain environments (including Chacaltaya, Bolivia; Alabama, US; Hyytiälä, Finland; Stuttgart and Karlsruhe, Germany; and Delhi, India) based on deployments of a filter inlet for gases and aerosols coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (FIGAERO-CIMS). We find on average larger carbon numbers (nC) and lower oxygen-To-carbon (O:C) ratios at the urban sites (nC: 9.8±0.7; O:C: 0.76±0.03; average ±1 standard deviation) compared to the rural (nC: 8.8±0.6; O:C: 0.80±0.05) and mountain stations (nC: 8.1±0.8; O:C: 0.91±0.07), indicative of different emission sources and chemistry. Compounds containing only carbon, hydrogen, and oxygen atoms (CHO) contribute the most to the total OOA mass at the rural sites (79.9±5.2%), in accordance with their proximity to forested areas (66.2±5.5% at the mountain sites and 72.6±4.3% at the urban sites). The largest contribution of nitrogen-containing compounds (CHON) is found at the urban stations (27.1±4.3%), consistent with their higher NOx levels. Moreover, we parametrize OOA volatility (saturation mass concentrations, Csat) using molecular composition information and compare it with the bulk apparent volatility derived from thermal desorption of the OOA particles within the FIGAERO. We find differences in Csat values of up to 1/43 orders of magnitude and variation in thermal desorption profiles (thermograms) across different locations and systems. From our study, we draw the general conclusion that environmental conditions (e.g., ambient temperature) do not directly affect OOA apparent volatility but rather indirectly by influencing the sources and chemistry of the environment and thus the chemical composition. The comprehensive dataset provides results that show the complex thermodynamics and chemistry of OOA and their changes during its lifetime in the atmosphere. We conclude that generally the chemical description of OOA suffices to predict its apparent volatility, at least qualitatively. Our study thus provides new insights that will help guide choices of, e.g., descriptions of OOA volatility in different model frameworks such as air quality models and cloud parcel models.
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| 6. |
- Kommula, S. M., et al.
(author)
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Effect of Long-Range Transported Fire Aerosols on Cloud Condensation Nuclei Concentrations and Cloud Properties at High Latitudes
- 2024
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In: Geophysical Research Letters. - 0094-8276 .- 1944-8007. ; 51:6
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Journal article (peer-reviewed)abstract
- Active vegetation fires in south-eastern (SE) Europe resulted in a notable increase in the number concentration of aerosols and cloud condensation nuclei (CCN) particles at two high latitude locations—the SMEAR IV station in Kuopio, Finland, and the Zeppelin Observatory in Svalbard, high Arctic. During the fire episode aerosol hygroscopicity κ slightly increased at SMEAR IV and at the Zeppelin Observatory κ decreased. Despite increased κ in high CCN conditions at SMEAR IV, the aerosol activation diameter increased due to the decreased supersaturation with an increase in aerosol loading. In addition, at SMEAR IV during the fire episode, in situ measured cloud droplet number concentration (CDNC) increased by a factor of ∼7 as compared to non-fire periods which was in good agreement with the satellite observations (MODIS, Terra). Results from this study show the importance of SE European fires for cloud properties and radiative forcing in high latitudes.
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| 7. |
- Siegel, Karolina, 1990-, et al.
(author)
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Arctic observations of hydroperoxymethyl thioformate (HPMTF) – seasonal behavior and relationship to other oxidation products of dimethyl sulfide at the Zeppelin Observatory, Svalbard
- 2023
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In: Atmospheric Chemistry And Physics. - 1680-7316 .- 1680-7324. ; 23:13, s. 7569-7587
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Journal article (peer-reviewed)abstract
- Dimethyl sulfide (DMS), a gas produced by phytoplankton, is the largest source of atmospheric sulfur over marine areas. DMS undergoes oxidation in the atmosphere to form a range of oxidation products, out of which sulfuric acid (SA) is well known for participating in the formation and growth of atmospheric aerosol particles, and the same is also presumed for methanesulfonic acid (MSA). Recently, a new oxidation product of DMS, hydroperoxymethyl thioformate (HPMTF), was discovered and later also measured in the atmosphere. Little is still known about the fate of this compound and its potential to partition into the particle phase. In this study, we present a full year (2020) of concurrent gas- and particle-phase observations of HPMTF, MSA, SA and other DMS oxidation products at the Zeppelin Observatory (Ny-Ålesund, Svalbard) located in the Arctic. This is the first time HPMTF has been measured in Svalbard and attempted to be observed in atmospheric particles. The results show that gas-phase HPMTF concentrations largely follow the same pattern as MSA during the sunlit months (April–September), indicating production of HPMTF around Svalbard. However, HPMTF was not observed in significant amounts in the particle phase, despite high gas-phase levels. Particulate MSA and SA were observed during the sunlit months, although the highest median levels of particulate SA were measured in February, coinciding with the highest gaseous SA levels with assumed anthropogenic origin. We further show that gas- and particle-phase MSA and SA are coupled in May–July, whereas HPMTF lies outside of this correlation due to the low particulate concentrations. These results provide more information about the relationship between HPMTF and other DMS oxidation products, in a part of the world where these have not been explored yet, and about HPMTF's ability to contribute to particle growth and cloud formation.
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