Articles | Volume 22, issue 9
https://doi.org/10.5194/acp-22-5943-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-22-5943-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Enhanced photodegradation of dimethoxybenzene isomers in/on ice compared to in aqueous solution
Ted Hullar
Department of Land, Air and Water Resources, University of
California, Davis, One Shields Avenue, Davis, CA 95616, USA
Theo Tran
Department of Land, Air and Water Resources, University of
California, Davis, One Shields Avenue, Davis, CA 95616, USA
Zekun Chen
Department of Chemistry, University of California, Davis, One
Shields Avenue, Davis, CA 95616, USA
Fernanda Bononi
Department of Chemistry, University of California, Davis, One
Shields Avenue, Davis, CA 95616, USA
Oliver Palmer
Department of Land, Air and Water Resources, University of
California, Davis, One Shields Avenue, Davis, CA 95616, USA
now at: TeraPore Technologies, 407 Cabot Road, South San Francisco,
CA 94080, USA
Davide Donadio
Department of Chemistry, University of California, Davis, One
Shields Avenue, Davis, CA 95616, USA
Department of Land, Air and Water Resources, University of
California, Davis, One Shields Avenue, Davis, CA 95616, USA
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Ted Hullar and Cort Anastasio
The Cryosphere, 10, 2057–2068, https://doi.org/10.5194/tc-10-2057-2016, https://doi.org/10.5194/tc-10-2057-2016, 2016
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We study chemical reactions in snow and ice by freezing solutions in the laboratory. Although it is important to know where these chemicals are in the frozen sample (at the surface or buried in the ice), we do not understand this well. In this paper, we used X-rays to look at the chemical location in frozen samples. We found chemical location is sensitive to freezing method, sample container, and chemical characteristics, requiring careful experimental design and interpretation of results.
Michael Oluwatoyin Sunday, Laura Marie Dahler Heinlein, Junwei He, Allison Moon, Sukriti Kapur, Ting Fang, Kasey C. Edwards, Fangzhou Guo, Jack Dibb, James H. Flynn III, Becky Alexander, Manabu Shiraiwa, and Cort Anastasio
EGUsphere, https://doi.org/10.5194/egusphere-2024-3272, https://doi.org/10.5194/egusphere-2024-3272, 2024
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Hydrogen peroxide (HOOH) is an important oxidant that forms atmospheric sulfate. We demonstrate that illumination of brown carbon can rapidly form HOOH within particles, even under the low sunlight conditions of Fairbanks, Alaska during winter. This in-particle formation of HOOH is fast enough that it forms sulfate at significant rates. In contrast, the formation of HOOH in the gas phase during the campaign is expected to be negligible because of high NOx levels.
Stephanie Arciva, Lan Ma, Camille Mavis, Chrystal Guzman, and Cort Anastasio
Atmos. Chem. Phys., 24, 4473–4485, https://doi.org/10.5194/acp-24-4473-2024, https://doi.org/10.5194/acp-24-4473-2024, 2024
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We measured changes in light absorption during the aqueous oxidation of six phenols with hydroxyl radical (●OH) or an organic triplet excited state (3C*). All the phenols formed light-absorbing secondary brown carbon (BrC), which then decayed with continued oxidation. Extrapolation to ambient conditions suggest ●OH is the dominant sink of secondary phenolic BrC in fog/cloud drops, while 3C* controls the lifetime of this light absorption in particle water.
Aaron Lieberman, Julietta Picco, Murat Onder, and Cort Anastasio
Atmos. Chem. Phys., 24, 4411–4419, https://doi.org/10.5194/acp-24-4411-2024, https://doi.org/10.5194/acp-24-4411-2024, 2024
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We developed a method that uses aqueous S(IV) to quantitatively convert NO2 to NO2−, which allows both species to be quantified using the Griess method. As an example of the utility of the method, we quantified both photolysis channels of nitrate, with and without a scavenger for hydroxyl radical (·OH). The results show that without a scavenger, ·OH reacts with nitrite to form nitrogen dioxide, suppressing the apparent quantum yield of NO2− and enhancing that of NO2.
Lan Ma, Reed Worland, Laura Heinlein, Chrystal Guzman, Wenqing Jiang, Christopher Niedek, Keith J. Bein, Qi Zhang, and Cort Anastasio
Atmos. Chem. Phys., 24, 1–21, https://doi.org/10.5194/acp-24-1-2024, https://doi.org/10.5194/acp-24-1-2024, 2024
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We measured concentrations of three photooxidants – the hydroxyl radical, triplet excited states of organic carbon, and singlet molecular oxygen – in fine particles collected over a year. Concentrations are highest in extracts of fresh biomass burning particles, largely because they have the highest particle concentrations and highest light absorption. When normalized by light absorption, rates of formation for each oxidant are generally similar for the four particle types we observed.
Lan Ma, Reed Worland, Wenqing Jiang, Christopher Niedek, Chrystal Guzman, Keith J. Bein, Qi Zhang, and Cort Anastasio
Atmos. Chem. Phys., 23, 8805–8821, https://doi.org/10.5194/acp-23-8805-2023, https://doi.org/10.5194/acp-23-8805-2023, 2023
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Although photooxidants are important in airborne particles, little is known of their concentrations. By measuring oxidants in a series of particle dilutions, we predict their concentrations in aerosol liquid water (ALW). We find •OH concentrations in ALW are on the order of 10−15 M, similar to their cloud/fog values, while oxidizing triplet excited states and singlet molecular oxygen have ALW values of ca. 10−13 M and 10−12 M, respectively, roughly 10–100 times higher than in cloud/fog drops.
Wenqing Jiang, Christopher Niedek, Cort Anastasio, and Qi Zhang
Atmos. Chem. Phys., 23, 7103–7120, https://doi.org/10.5194/acp-23-7103-2023, https://doi.org/10.5194/acp-23-7103-2023, 2023
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We studied how aqueous-phase secondary organic aerosol (aqSOA) form and evolve from a phenolic carbonyl commonly present in biomass burning smoke. The composition and optical properties of the aqSOA are significantly affected by photochemical reactions and are dependent on the oxidants' concentration and identity in water. During photoaging, the aqSOA initially becomes darker, but prolonged aging leads to the formation of volatile products, resulting in significant mass loss and photobleaching.
Richie Kaur, Jacqueline R. Labins, Scarlett S. Helbock, Wenqing Jiang, Keith J. Bein, Qi Zhang, and Cort Anastasio
Atmos. Chem. Phys., 19, 6579–6594, https://doi.org/10.5194/acp-19-6579-2019, https://doi.org/10.5194/acp-19-6579-2019, 2019
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We measured hydroxyl radical (•OH), singlet oxygen (1O2*), and organic triplets (3C*) in illuminated aqueous particle extracts. After measuring the impact of dilution on oxidant concentrations, we extrapolated our results to predict them in ambient particles – 1O2* and 3C* concentrations appear to be greatly enhanced, while •OH appears largely unchanged. Two of these oxidants (1O2*, 3C*) are not yet included in atmospheric models, and our results make it possible to include them in the future.
Richie Kaur, Brandi M. Hudson, Joseph Draper, Dean J. Tantillo, and Cort Anastasio
Atmos. Chem. Phys., 19, 5021–5032, https://doi.org/10.5194/acp-19-5021-2019, https://doi.org/10.5194/acp-19-5021-2019, 2019
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Organic triplets are an important class of aqueous photooxidants, but little is known about their reactions with most atmospheric organic compounds. We measured the reaction rate constants of a model triplet with 17 aliphatic alkenes; using their correlation with oxidation potential, we predicted rate constants for some atmospherically relevant alkenes. Depending on their reactivities, triplets can be minor to important sinks for isoprene- and limonene-derived alkenes in cloud or fog drops.
Ted Hullar and Cort Anastasio
The Cryosphere, 10, 2057–2068, https://doi.org/10.5194/tc-10-2057-2016, https://doi.org/10.5194/tc-10-2057-2016, 2016
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We study chemical reactions in snow and ice by freezing solutions in the laboratory. Although it is important to know where these chemicals are in the frozen sample (at the surface or buried in the ice), we do not understand this well. In this paper, we used X-rays to look at the chemical location in frozen samples. We found chemical location is sensitive to freezing method, sample container, and chemical characteristics, requiring careful experimental design and interpretation of results.
Zeyuan Chen, Liang Chu, Edward S. Galbavy, Keren Ram, and Cort Anastasio
Atmos. Chem. Phys., 16, 9579–9590, https://doi.org/10.5194/acp-16-9579-2016, https://doi.org/10.5194/acp-16-9579-2016, 2016
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We made the first measurements of the concentrations of hydroxyl radical (•OH), a dominant environmental oxidant, in snow grains. Concentrations of •OH in snow at Summit, Greenland, are comparable to values reported for midlatitude cloud and fog drops, even though impurity levels in the snow are much lower. At these concentrations, the lifetimes of organics and bromide in Summit snow are approximately 3 days and 7 h, respectively, suggesting that OH is a major oxidant for both species.
Lu Yu, Jeremy Smith, Alexander Laskin, Katheryn M. George, Cort Anastasio, Julia Laskin, Ann M. Dillner, and Qi Zhang
Atmos. Chem. Phys., 16, 4511–4527, https://doi.org/10.5194/acp-16-4511-2016, https://doi.org/10.5194/acp-16-4511-2016, 2016
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The chemical evolution of SOA formed during aqueous reactions of phenolic compounds is studied via combined bulk and molecular analysis. Phenolic SOA evolve dynamically during photochemical aging, with different reaction mechanisms (oligomerization, fragmentation, and functionalization) leading to different generations of products that span an enormous range in volatilities and a large range in oxidation state and composition. Aqueous reactions of phenols are likely an important source of ELVOC.
J. G. Charrier, N. K. Richards-Henderson, K. J. Bein, A. S. McFall, A. S. Wexler, and C. Anastasio
Atmos. Chem. Phys., 15, 2327–2340, https://doi.org/10.5194/acp-15-2327-2015, https://doi.org/10.5194/acp-15-2327-2015, 2015
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We measured the oxidative potential of airborne particles – a property that has been linked to health problems caused by particles – from different emission source mixtures in Fresno, CA. Copper was responsible for the majority of the oxidative potential (as measured by the DTT assay), followed by unknown species (likely organics) and manganese. Sources of copper-rich particles, including vehicles, had higher oxidative potentials.
L. Yu, J. Smith, A. Laskin, C. Anastasio, J. Laskin, and Q. Zhang
Atmos. Chem. Phys., 14, 13801–13816, https://doi.org/10.5194/acp-14-13801-2014, https://doi.org/10.5194/acp-14-13801-2014, 2014
Related subject area
Subject: Hydrosphere Interactions | Research Activity: Laboratory Studies | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
An 800-year high-resolution black carbon ice core record from Lomonosovfonna, Svalbard
Evaporating brine from frost flowers with electron microscopy and implications for atmospheric chemistry and sea-salt aerosol formation
A review of air–ice chemical and physical interactions (AICI): liquids, quasi-liquids, and solids in snow
Formation of gas-phase carbonyls from heterogeneous oxidation of polyunsaturated fatty acids at the air–water interface and of the sea surface microlayer
Dimitri Osmont, Isabel A. Wendl, Loïc Schmidely, Michael Sigl, Carmen P. Vega, Elisabeth Isaksson, and Margit Schwikowski
Atmos. Chem. Phys., 18, 12777–12795, https://doi.org/10.5194/acp-18-12777-2018, https://doi.org/10.5194/acp-18-12777-2018, 2018
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This study presents the first long-term and high-resolution refractory black carbon (rBC) ice core record from Svalbard, spanning the last 800 years. Our results show that rBC has had a predominant anthropogenic origin since the beginning of the Industrial Revolution in Europe and that rBC concentrations have been declining in the last 40 years. We discuss the impact of 20th century snowmelt on our record. We reconstruct biomass burning trends prior to 1800 by using a multi-proxy approach.
Xin Yang, Vilém Neděla, Jiří Runštuk, Gabriela Ondrušková, Ján Krausko, Ľubica Vetráková, and Dominik Heger
Atmos. Chem. Phys., 17, 6291–6303, https://doi.org/10.5194/acp-17-6291-2017, https://doi.org/10.5194/acp-17-6291-2017, 2017
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A unique environmental electron microscope was used for monitoring the evaporation of salty frost flowers. We observe a cohesive villous brine surface layer facilitating the formation of NaCl microcrystals at temperatures below −10°C as the brine oversaturation is achieved. This finding confirms the increased surface area and thus also the enhanced heterogeneous reactivity; however, no support for the easiness of fragmentation to produce aerosols can be provided.
T. Bartels-Rausch, H.-W. Jacobi, T. F. Kahan, J. L. Thomas, E. S. Thomson, J. P. D. Abbatt, M. Ammann, J. R. Blackford, H. Bluhm, C. Boxe, F. Domine, M. M. Frey, I. Gladich, M. I. Guzmán, D. Heger, Th. Huthwelker, P. Klán, W. F. Kuhs, M. H. Kuo, S. Maus, S. G. Moussa, V. F. McNeill, J. T. Newberg, J. B. C. Pettersson, M. Roeselová, and J. R. Sodeau
Atmos. Chem. Phys., 14, 1587–1633, https://doi.org/10.5194/acp-14-1587-2014, https://doi.org/10.5194/acp-14-1587-2014, 2014
S. Zhou, L. Gonzalez, A. Leithead, Z. Finewax, R. Thalman, A. Vlasenko, S. Vagle, L.A. Miller, S.-M. Li, S. Bureekul, H. Furutani, M. Uematsu, R. Volkamer, and J. Abbatt
Atmos. Chem. Phys., 14, 1371–1384, https://doi.org/10.5194/acp-14-1371-2014, https://doi.org/10.5194/acp-14-1371-2014, 2014
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Short summary
Chemicals are commonly found in snowpacks throughout the world and may be degraded by sunlight; some previous research has reported faster decay rates for chemicals on the surface of snow and ice compared to in water. We found photodegradation on snow can be as much as 30 times faster than in solution for the three dimethoxybenzene isomers. Our computational modeling found light absorbance by dimethoxybenzenes increases on the snow surface, but this only partially explains the decay rate.
Chemicals are commonly found in snowpacks throughout the world and may be degraded by sunlight;...
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