Articles | Volume 3, issue 2
https://doi.org/10.5194/ar-3-557-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/ar-3-557-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
27 Nov 2025
Research article |
| 27 Nov 2025
| 27 Nov 2025
A simple, versatile approach for coupling a liquid chromatograph and chemical ionization mass spectrometer for offline analysis of organic aerosol
Andre F. Schaum
Department of Chemistry, University of Colorado, Boulder, Colorado 80309, United States
Cooperative Institute for Research in Environmental Sciences (CIRES), Boulder, Colorado 80309, United States
Kelvin H. Bates
Department of Mechanical Engineering, University of Colorado Boulder, Boulder, Colorado 80309, United States
Kyung-Eun Min
Cooperative Institute for Research in Environmental Sciences (CIRES), Boulder, Colorado 80309, United States
Department of Energy and Engineering, Gwangju Institute of Science and Technology, 61005, Gwangju, South Korea
Faith Myers
Cooperative Institute for Research in Environmental Sciences (CIRES), Boulder, Colorado 80309, United States
Emmaline R. Longnecker
Department of Chemistry, University of Colorado, Boulder, Colorado 80309, United States
Cooperative Institute for Research in Environmental Sciences (CIRES), Boulder, Colorado 80309, United States
Manjula R. Canagaratna
Aerodyne Research Inc., Billerica, Massachusetts 01821, United States
Mitchell W. Alton
Aerodyne Research Inc., Billerica, Massachusetts 01821, United States
Department of Chemistry, University of Colorado, Boulder, Colorado 80309, United States
Cooperative Institute for Research in Environmental Sciences (CIRES), Boulder, Colorado 80309, United States
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Arttu Ylisirniö, Noora Hyttinen, Zijun Li, Mitchell Alton, Aki Nissinen, Iida Pullinen, Pasi Miettinen, Taina Yli-Juuti, and Siegfried Schobesberger
Atmos. Meas. Tech., 18, 6449–6464, https://doi.org/10.5194/amt-18-6449-2025, https://doi.org/10.5194/amt-18-6449-2025, 2025
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This study increases the knowledge of the low-volatility organic compounds observed in ambient aerosol particles by providing new volatility information about compounds used for calibrating volatility measurement instruments. Previously, such information was not available, and calibration of the instrument had to be extrapolated to cover the whole measurement range. Results of this study will provide the scientific community with better tools for investigating the complexity of ambient aerosols.
Aoxing Zhang, Tzung-May Fu, Yuhang Wang, Enyu Xiong, Wenlu Wu, Yumin Li, Lei Zhu, Wei Tao, Kelley C. Wells, Dylan B. Millet, Zhe Wang, Bin Yuan, Min Shao, Christophe Lerot, Thomas Danckaert, Ruixiong Zhang, and Kelvin H. Bates
EGUsphere, https://doi.org/10.5194/egusphere-2025-5083, https://doi.org/10.5194/egusphere-2025-5083, 2025
This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
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Glyoxal, a product of volatile organic compound oxidation, influences atmospheric oxidation and aerosol formation but is underestimated in models. By improving emissions, chemistry, and marine sources in GEOS-Chem, we better reproduce observed glyoxal over land and ocean, which strengthens global oxidation capacity and aerosol formation. The results highlight glyoxal's role as a proxy of atmospheric oxidation, and emphasize the needs of accurately representing glyoxal chemistry.
Allison R. Moon, Leyang Liu, Xuan Wang, Yuk-Chun Chan, Alyson Fritzmann, Ryan Pound, Amy Lees, Lewis Marden, Mat Evans, Lucy J. Carpenter, Jochen Stutz, Joel A. Thornton, Gordon Novak, Andrew Rollins, Gregory P. Schill, Xu-cheng He, Henning Finkenzeller, Margarita Reza, Rainer Volkamer, Kelvin H. Bates, Alfonso Saiz-Lopez, Anoop S. Mahajan, and Becky Alexander
EGUsphere, https://doi.org/10.5194/egusphere-2025-4725, https://doi.org/10.5194/egusphere-2025-4725, 2025
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Global chemical transport models previously treated aerosols as a sink for reactive iodine (Iy); however, aerosol iodide is also a source of Iy via heterogeneous reactions involving hypohalous acids and halogen nitrates. We implemented this chemistry into GEOS-Chem, in addition to explicitly representing three aerosol iodine types: soluble organic iodine (SOI), iodide, and iodate. We found that aerosol recycling of iodide to form Iy is more than twice as fast as the other Iy sources combined.
Benjamin C. Sapper, Sean Youn, Daven K. Henze, Manjula Canagaratna, Harald Stark, and Jose L. Jimenez
Geosci. Model Dev., 18, 2891–2919, https://doi.org/10.5194/gmd-18-2891-2025, https://doi.org/10.5194/gmd-18-2891-2025, 2025
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Positive matrix factorization (PMF) has been used by atmospheric scientists to extract underlying factors present in large datasets. This paper presents a new technique for error-weighted PMF that drastically reduces the computational costs of previously developed algorithms. We use this technique to deliver interpretable factors and solution diagnostics from an atmospheric chemistry dataset.
Nadia K. Colombi, Daniel J. Jacob, Xingpei Ye, Robert M. Yantosca, Kelvin H. Bates, Drew C. Pendergrass, Laura Hyesung Yang, Ke Li, and Hong Liao
EGUsphere, https://doi.org/10.5194/egusphere-2025-1799, https://doi.org/10.5194/egusphere-2025-1799, 2025
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Surface ozone pollution in East Asia is among the highest in the world and has risen steadily over the past two decades. Using aircraft observations and a global 3-D chemical transport model, we show that ozone in the lower atmosphere in East Asia has risen in part due to intensified transport from the upper atmosphere. This rising natural background limits the effectiveness of local pollution controls, with major implications for air quality policy.
Alfred W. Mayhew, Lauri Franzon, Kelvin H. Bates, Theo Kurtén, Felipe D. Lopez-Hilfiker, Claudia Mohr, Andrew R. Rickard, Joel A. Thornton, and Jessica D. Haskins
EGUsphere, https://doi.org/10.5194/egusphere-2025-1922, https://doi.org/10.5194/egusphere-2025-1922, 2025
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This work outlines an investigation into an understudied atmospheric chemical reaction pathway with the potential to form particulate pollution that has important impacts on air quality and climate. We suggest that this chemical pathway is responsible for a large fraction of the atmospheric particulate matter observed in tropical forested regions, but we also highlight the need for further ambient and lab investigations to inform an accurate representation of this process in atmospheric models.
Ursula A. Jongebloed, Jacob I. Chalif, Linia Tashmim, William C. Porter, Kelvin H. Bates, Qianjie Chen, Erich C. Osterberg, Bess G. Koffman, Jihong Cole-Dai, Dominic A. Winski, David G. Ferris, Karl J. Kreutz, Cameron P. Wake, and Becky Alexander
Atmos. Chem. Phys., 25, 4083–4106, https://doi.org/10.5194/acp-25-4083-2025, https://doi.org/10.5194/acp-25-4083-2025, 2025
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Marine phytoplankton emit dimethyl sulfide (DMS), which forms methanesulfonic acid (MSA) and sulfate. MSA concentrations in ice cores decreased over the industrial era, which has been attributed to pollution-driven changes in DMS chemistry. We use a model to investigate DMS chemistry compared to observations of DMS, MSA, and sulfate. We find that modeled DMS, MSA, and sulfate are influenced by pollution-sensitive oxidant concentrations, characterization of DMS chemistry, and other variables.
Hendrik Fuchs, Aaron Stainsby, Florian Berg, René Dubus, Michelle Färber, Andreas Hofzumahaus, Frank Holland, Kelvin H. Bates, Steven S. Brown, Matthew M. Coggon, Glenn S. Diskin, Georgios I. Gkatzelis, Christopher M. Jernigan, Jeff Peischl, Michael A. Robinson, Andrew W. Rollins, Nell B. Schafer, Rebecca H. Schwantes, Chelsea E. Stockwell, Patrick R. Veres, Carsten Warneke, Eleanor M. Waxman, Lu Xu, Kristen Zuraski, Andreas Wahner, and Anna Novelli
Atmos. Meas. Tech., 18, 881–895, https://doi.org/10.5194/amt-18-881-2025, https://doi.org/10.5194/amt-18-881-2025, 2025
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Significant improvements have been made to the instruments used to measure OH reactivity, which is equivalent to the sum of air pollutant concentrations. Accurate and precise measurements with a high time resolution have been achieved, allowing use on aircraft, as demonstrated during flights in the USA.
Benjamin A. Nault, Katherine R. Travis, James H. Crawford, Donald R. Blake, Pedro Campuzano-Jost, Ronald C. Cohen, Joshua P. DiGangi, Glenn S. Diskin, Samuel R. Hall, L. Gregory Huey, Jose L. Jimenez, Kyung-Eun Min, Young Ro Lee, Isobel J. Simpson, Kirk Ullmann, and Armin Wisthaler
Atmos. Chem. Phys., 24, 9573–9595, https://doi.org/10.5194/acp-24-9573-2024, https://doi.org/10.5194/acp-24-9573-2024, 2024
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Ozone (O3) is a pollutant formed from the reactions of gases emitted from various sources. In urban areas, the density of human activities can increase the O3 formation rate (P(O3)), thus impacting air quality and health. Observations collected over Seoul, South Korea, are used to constrain P(O3). A high local P(O3) was found; however, local P(O3) was partly reduced due to compounds typically ignored. These observations also provide constraints for unmeasured compounds that will impact P(O3).
Katherine R. Travis, Benjamin A. Nault, James H. Crawford, Kelvin H. Bates, Donald R. Blake, Ronald C. Cohen, Alan Fried, Samuel R. Hall, L. Gregory Huey, Young Ro Lee, Simone Meinardi, Kyung-Eun Min, Isobel J. Simpson, and Kirk Ullman
Atmos. Chem. Phys., 24, 9555–9572, https://doi.org/10.5194/acp-24-9555-2024, https://doi.org/10.5194/acp-24-9555-2024, 2024
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Human activities result in the emission of volatile organic compounds (VOCs) that contribute to air pollution. Detailed VOC measurements were taken during a field study in South Korea. When compared to VOC inventories, large discrepancies showed underestimates from chemical products, liquefied petroleum gas, and long-range transport. Improved emissions and chemistry of these VOCs better described urban pollution. The new chemical scheme is relevant to urban areas and other VOC sources.
Matthew J. Rowlinson, Mat J. Evans, Lucy J. Carpenter, Katie A. Read, Shalini Punjabi, Adedayo Adedeji, Luke Fakes, Ally Lewis, Ben Richmond, Neil Passant, Tim Murrells, Barron Henderson, Kelvin H. Bates, and Detlev Helmig
Atmos. Chem. Phys., 24, 8317–8342, https://doi.org/10.5194/acp-24-8317-2024, https://doi.org/10.5194/acp-24-8317-2024, 2024
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Ethane and propane are volatile organic compounds emitted from human activities which help to form ozone, a pollutant and greenhouse gas, and also affect the chemistry of the lower atmosphere. Atmospheric models tend to do a poor job of reproducing the abundance of these compounds in the atmosphere. By using regional estimates of their emissions, rather than globally consistent estimates, we can significantly improve the simulation of ethane in the model and make some improvement for propane.
Tommaso Galeazzo, Bernard Aumont, Marie Camredon, Richard Valorso, Yong B. Lim, Paul J. Ziemann, and Manabu Shiraiwa
Atmos. Chem. Phys., 24, 5549–5565, https://doi.org/10.5194/acp-24-5549-2024, https://doi.org/10.5194/acp-24-5549-2024, 2024
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Secondary organic aerosol (SOA) derived from n-alkanes is a major component of anthropogenic particulate matter. We provide an analysis of n-alkane SOA by chemistry modeling, machine learning, and laboratory experiments, showing that n-alkane SOA adopts low-viscous semi-solid or liquid states. Our results indicate few kinetic limitations of mass accommodation in SOA formation, supporting the application of equilibrium partitioning for simulating n-alkane SOA in large-scale atmospheric models.
Melinda K. Schueneman, Douglas A. Day, Dongwook Kim, Pedro Campuzano-Jost, Seonsik Yun, Marla P. DeVault, Anna C. Ziola, Paul J. Ziemann, and Jose L. Jimenez
Aerosol Research, 2, 59–76, https://doi.org/10.5194/ar-2-59-2024, https://doi.org/10.5194/ar-2-59-2024, 2024
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Our study presents a novel method for quantifying mass spectrometer responses to molecular species in organic aerosols. Traditional calibrations often fail for complex mixtures like secondary organic aerosol. We combined chromatography with statistical component analysis to improve separation and quantification, achieving promising agreement with direct calibration. Our findings offer a new approach to assess aerosol composition, especially beneficial for complex mixtures.
Mahen Konwar, Benjamin Werden, Edward C. Fortner, Sudarsan Bera, Mercy Varghese, Subharthi Chowdhuri, Kurt Hibert, Philip Croteau, John Jayne, Manjula Canagaratna, Neelam Malap, Sandeep Jayakumar, Shivsai A. Dixit, Palani Murugavel, Duncan Axisa, Darrel Baumgardner, Peter F. DeCarlo, Doug R. Worsnop, and Thara Prabhakaran
Atmos. Meas. Tech., 17, 2387–2400, https://doi.org/10.5194/amt-17-2387-2024, https://doi.org/10.5194/amt-17-2387-2024, 2024
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In a warm cloud seeding experiment hygroscopic particles are released to alter cloud processes to induce early raindrops. During the Cloud–Aerosol Interaction and Precipitation Enhancement Experiment, airborne mini aerosol mass spectrometers analyse the particles on which clouds form. The seeded clouds showed higher concentrations of chlorine and potassium, the oxidizing agents of flares. Small cloud droplet concentrations increased, and seeding particles were detected in deep cloud depths.
Jian Zhao, Valter Mickwitz, Yuanyuan Luo, Ella Häkkinen, Frans Graeffe, Jiangyi Zhang, Hilkka Timonen, Manjula Canagaratna, Jordan E. Krechmer, Qi Zhang, Markku Kulmala, Juha Kangasluoma, Douglas Worsnop, and Mikael Ehn
Atmos. Meas. Tech., 17, 1527–1543, https://doi.org/10.5194/amt-17-1527-2024, https://doi.org/10.5194/amt-17-1527-2024, 2024
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Organic aerosol constitutes a significant portion of atmospheric fine particles but is less characterized due to its vast number of constituents. Recently, we developed a system for online measurements of particle-phase highly oxygenated organic molecules (HOMs). In this work, we systematically characterized the system, developed a new unit to enhance its performance, and demonstrated the essential role of thermograms in inferring volatility and quantifying HOMs in organic aerosols.
Melissa A. Morris, Demetrios Pagonis, Douglas A. Day, Joost A. de Gouw, Paul J. Ziemann, and Jose L. Jimenez
Atmos. Meas. Tech., 17, 1545–1559, https://doi.org/10.5194/amt-17-1545-2024, https://doi.org/10.5194/amt-17-1545-2024, 2024
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Polymer absorption of volatile organic compounds (VOCs) is important to characterize for atmospheric sampling setups (as interactions cause sampling delays) and indoor air quality. Here we test different polymer materials and quantify their absorptive capacities through modeling. We found the main polymers in carpets to be highly absorptive, acting as large reservoirs for indoor pollution. We also demonstrated how polymer tubes can be used as a low-cost gas separation technique.
Kelvin H. Bates, Mathew J. Evans, Barron H. Henderson, and Daniel J. Jacob
Geosci. Model Dev., 17, 1511–1524, https://doi.org/10.5194/gmd-17-1511-2024, https://doi.org/10.5194/gmd-17-1511-2024, 2024
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Accurate representation of rates and products of chemical reactions in atmospheric models is crucial for simulating concentrations of pollutants and climate forcers. We update the widely used GEOS-Chem atmospheric chemistry model with reaction parameters from recent compilations of experimental data and demonstrate the implications for key atmospheric chemical species. The updates decrease tropospheric CO mixing ratios and increase stratospheric nitrogen oxide mixing ratios, among other changes.
Matthew M. Coggon, Chelsea E. Stockwell, Megan S. Claflin, Eva Y. Pfannerstill, Lu Xu, Jessica B. Gilman, Julia Marcantonio, Cong Cao, Kelvin Bates, Georgios I. Gkatzelis, Aaron Lamplugh, Erin F. Katz, Caleb Arata, Eric C. Apel, Rebecca S. Hornbrook, Felix Piel, Francesca Majluf, Donald R. Blake, Armin Wisthaler, Manjula Canagaratna, Brian M. Lerner, Allen H. Goldstein, John E. Mak, and Carsten Warneke
Atmos. Meas. Tech., 17, 801–825, https://doi.org/10.5194/amt-17-801-2024, https://doi.org/10.5194/amt-17-801-2024, 2024
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Mass spectrometry is a tool commonly used to measure air pollutants. This study evaluates measurement artifacts produced in the proton-transfer-reaction mass spectrometer. We provide methods to correct these biases and better measure compounds that degrade air quality.
Andrew T. Lambe, Bin Bai, Masayuki Takeuchi, Nicole Orwat, Paul M. Zimmerman, Mitchell W. Alton, Nga L. Ng, Andrew Freedman, Megan S. Claflin, Drew R. Gentner, Douglas R. Worsnop, and Pengfei Liu
Atmos. Chem. Phys., 23, 13869–13882, https://doi.org/10.5194/acp-23-13869-2023, https://doi.org/10.5194/acp-23-13869-2023, 2023
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We developed a new method to generate nitrate radicals (NO3) for atmospheric chemistry applications that works by irradiating mixtures containing ceric ammonium nitrate with a UV light at room temperature. It has several advantages over traditional NO3 sources. We characterized its performance over a range of mixture and reactor conditions as well as other irradiation products. Proof of concept was demonstrated by generating and characterizing oxidation products of the β-pinene + NO3 reaction.
Mitchell W. Alton, Harald J. Stark, Manjula R. Canagaratna, and Eleanor C. Browne
Atmos. Meas. Tech., 16, 3273–3282, https://doi.org/10.5194/amt-16-3273-2023, https://doi.org/10.5194/amt-16-3273-2023, 2023
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Mass spectrometric measurements of atmospheric composition routinely detect hundreds of different ions of varying chemical composition, creating challenges for visualization and data interpretation. We present a new analysis technique to facilitate visualization, while providing greater chemical insight. Additionally, it can aid in identifying the chemical composition of ions. A graphical user interface for performing the analysis is introduced and freely available, enabling broad applications.
Daniel John Katz, Aroob Abdelhamid, Harald Stark, Manjula R. Canagaratna, Douglas R. Worsnop, and Eleanor C. Browne
Atmos. Chem. Phys., 23, 5567–5585, https://doi.org/10.5194/acp-23-5567-2023, https://doi.org/10.5194/acp-23-5567-2023, 2023
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Ambient ion chemical composition measurements provide insight into trace gases that are precursors for the formation and growth of new aerosol particles. We use a new data analysis approach to increase the chemical information from these measurements. We analyze results from an agricultural region, a little studied land use type that is ~41 % of global land use, and find that the composition of gases important for aerosol formation and growth differs significantly from that in other ecosystems.
Jian Zhao, Ella Häkkinen, Frans Graeffe, Jordan E. Krechmer, Manjula R. Canagaratna, Douglas R. Worsnop, Juha Kangasluoma, and Mikael Ehn
Atmos. Chem. Phys., 23, 3707–3730, https://doi.org/10.5194/acp-23-3707-2023, https://doi.org/10.5194/acp-23-3707-2023, 2023
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Based on the combined measurements of gas- and particle-phase highly oxygenated organic molecules (HOMs) from α-pinene ozonolysis, enhancement of dimers in particles was observed. We conducted experiments wherein the dimer to monomer (D / M) ratios of HOMs in the gas phase were modified (adding CO / NO) to investigate the effects of the corresponding D / M ratios in the particles. These results are important for a better understanding of secondary organic aerosol formation in the atmosphere.
Laura Hyesung Yang, Daniel J. Jacob, Nadia K. Colombi, Shixian Zhai, Kelvin H. Bates, Viral Shah, Ellie Beaudry, Robert M. Yantosca, Haipeng Lin, Jared F. Brewer, Heesung Chong, Katherine R. Travis, James H. Crawford, Lok N. Lamsal, Ja-Ho Koo, and Jhoon Kim
Atmos. Chem. Phys., 23, 2465–2481, https://doi.org/10.5194/acp-23-2465-2023, https://doi.org/10.5194/acp-23-2465-2023, 2023
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A geostationary satellite can now provide hourly NO2 vertical columns, and obtaining the NO2 vertical columns from space relies on NO2 vertical distribution from the chemical transport model (CTM). In this work, we update the CTM to better represent the chemistry environment so that the CTM can accurately provide NO2 vertical distribution. We also find that the changes in NO2 vertical distribution driven by a change in mixing depth play an important role in the NO2 column's diurnal variation.
Amir H. Souri, Matthew S. Johnson, Glenn M. Wolfe, James H. Crawford, Alan Fried, Armin Wisthaler, William H. Brune, Donald R. Blake, Andrew J. Weinheimer, Tijl Verhoelst, Steven Compernolle, Gaia Pinardi, Corinne Vigouroux, Bavo Langerock, Sungyeon Choi, Lok Lamsal, Lei Zhu, Shuai Sun, Ronald C. Cohen, Kyung-Eun Min, Changmin Cho, Sajeev Philip, Xiong Liu, and Kelly Chance
Atmos. Chem. Phys., 23, 1963–1986, https://doi.org/10.5194/acp-23-1963-2023, https://doi.org/10.5194/acp-23-1963-2023, 2023
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We have rigorously characterized different sources of error in satellite-based HCHO / NO2 tropospheric columns, a widely used metric for diagnosing near-surface ozone sensitivity. Specifically, the errors were categorized/quantified into (i) an inherent chemistry error, (ii) the decoupled relationship between columns and the near-surface concentration, (iii) the spatial representativeness error of ground satellite pixels, and (iv) the satellite retrieval errors.
Qing Ye, Matthew B. Goss, Jordan E. Krechmer, Francesca Majluf, Alexander Zaytsev, Yaowei Li, Joseph R. Roscioli, Manjula Canagaratna, Frank N. Keutsch, Colette L. Heald, and Jesse H. Kroll
Atmos. Chem. Phys., 22, 16003–16015, https://doi.org/10.5194/acp-22-16003-2022, https://doi.org/10.5194/acp-22-16003-2022, 2022
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The atmospheric oxidation of dimethyl sulfide (DMS) is a major natural source of sulfate particles in the atmosphere. However, its mechanism is poorly constrained. In our work, laboratory measurements and mechanistic modeling were conducted to comprehensively investigate DMS oxidation products and key reaction rates. We find that the peroxy radical (RO2) has a controlling effect on product distribution and aerosol yield, with the isomerization of RO2 leading to the suppression of aerosol yield.
Woohui Nam, Changmin Cho, Begie Perdigones, Tae Siek Rhee, and Kyung-Eun Min
Atmos. Meas. Tech., 15, 4473–4487, https://doi.org/10.5194/amt-15-4473-2022, https://doi.org/10.5194/amt-15-4473-2022, 2022
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We describe our vibration-resistant instrument for measuring ambient NO3, NO2, and H2O based on cavity-enhanced absorption spectroscopy. By simultaneous retrieval of H2O with the other species using a measured H2O absorption spectrum, direct quantifications among all species are possible without any pre-treatment for H2O. Our instrument achieves the effective light path to ~101.5 km, which allows the sensitive measurements of NO3 and NO2 as 1.41 pptv and 6.92 ppbv (1σ) in 1 s.
Kyung-Eun Min, Junphil Mun, Begie Perdigones, Soojin Lee, and Kyung-Hwan Kwak
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2022-205, https://doi.org/10.5194/acp-2022-205, 2022
Revised manuscript not accepted
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For knowing the accurate amount of human-induced CO2, emission strengths of individual activities were assessed via direct eddy-covariance observations at urban-atmosphere interface. This work extracted emission factors (EFs) with minimized seasonal effects through day of the week difference with varying wind sectors. Our work urges the need for not only emission inventory validation but also seasonal bias free EFs estimations for establishing effective climate mitigation strategies.
Lu Shen, Daniel J. Jacob, Mauricio Santillana, Kelvin Bates, Jiawei Zhuang, and Wei Chen
Geosci. Model Dev., 15, 1677–1687, https://doi.org/10.5194/gmd-15-1677-2022, https://doi.org/10.5194/gmd-15-1677-2022, 2022
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The high computational cost of chemical integration is a long-standing limitation in global atmospheric chemistry models. Here we present an adaptive and efficient algorithm that can reduce the computational time of atmospheric chemistry by 50 % and maintain the error below 2 % for important species, inspired by machine learning clustering techniques and traditional asymptotic analysis ideas.
Kelvin H. Bates, Guy J. P. Burke, James D. Cope, and Tran B. Nguyen
Atmos. Chem. Phys., 22, 1467–1482, https://doi.org/10.5194/acp-22-1467-2022, https://doi.org/10.5194/acp-22-1467-2022, 2022
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The main nighttime sink of α-pinene, a hydrocarbon abundantly emitted by plants, is reaction with NO3 to form nitrooxy peroxy radicals (nRO2). Using uniquely designed chamber experiments, we show that this reaction is a major source of organic aerosol when nRO2 reacts with other nRO2 and forms a nitrooxy hydroperoxide when nRO2 reacts with HO2. Under ambient conditions these pathways are key loss processes of atmospheric reactive nitrogen in areas with mixed biogenic and anthropogenic influence.
Dongwook Kim, Changmin Cho, Seokhan Jeong, Soojin Lee, Benjamin A. Nault, Pedro Campuzano-Jost, Douglas A. Day, Jason C. Schroder, Jose L. Jimenez, Rainer Volkamer, Donald R. Blake, Armin Wisthaler, Alan Fried, Joshua P. DiGangi, Glenn S. Diskin, Sally E. Pusede, Samuel R. Hall, Kirk Ullmann, L. Gregory Huey, David J. Tanner, Jack Dibb, Christoph J. Knote, and Kyung-Eun Min
Atmos. Chem. Phys., 22, 805–821, https://doi.org/10.5194/acp-22-805-2022, https://doi.org/10.5194/acp-22-805-2022, 2022
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CHOCHO was simulated using a 0-D box model constrained by measurements during the KORUS-AQ mission. CHOCHO concentration was high in large cities, aromatics being the most important precursors. Loss path to aerosol was the highest sink, contributing to ~ 20 % of secondary organic aerosol formation. Our work highlights that simple CHOCHO surface uptake approach is valid only for low aerosol conditions and more work is required to understand CHOCHO solubility in high-aerosol conditions.
Kelvin H. Bates, Daniel J. Jacob, Ke Li, Peter D. Ivatt, Mat J. Evans, Yingying Yan, and Jintai Lin
Atmos. Chem. Phys., 21, 18351–18374, https://doi.org/10.5194/acp-21-18351-2021, https://doi.org/10.5194/acp-21-18351-2021, 2021
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Simple aromatic compounds (benzene, toluene, xylene) have complex gas-phase chemistry that is inconsistently represented in atmospheric models. We compile recent experimental and theoretical insights to develop a new mechanism for gas-phase aromatic oxidation that is sufficiently compact for use in multiscale models. We compare our new mechanism to chamber experiments and other mechanisms, and implement it in a global model to quantify the impacts of aromatic oxidation on tropospheric chemistry.
Dongyu S. Wang, Chuan Ping Lee, Jordan E. Krechmer, Francesca Majluf, Yandong Tong, Manjula R. Canagaratna, Julia Schmale, André S. H. Prévôt, Urs Baltensperger, Josef Dommen, Imad El Haddad, Jay G. Slowik, and David M. Bell
Atmos. Meas. Tech., 14, 6955–6972, https://doi.org/10.5194/amt-14-6955-2021, https://doi.org/10.5194/amt-14-6955-2021, 2021
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To understand the sources and fate of particulate matter in the atmosphere, the ability to quantitatively describe its chemical composition is essential. In this work, we developed a calibration method for a state-of-the-art measurement technique without the need for chemical standards. Statistical analyses identified the driving factors behind instrument sensitivity variability towards individual components of particulate matter.
Chenyang Bi, Jordan E. Krechmer, Graham O. Frazier, Wen Xu, Andrew T. Lambe, Megan S. Claflin, Brian M. Lerner, John T. Jayne, Douglas R. Worsnop, Manjula R. Canagaratna, and Gabriel Isaacman-VanWertz
Atmos. Meas. Tech., 14, 6835–6850, https://doi.org/10.5194/amt-14-6835-2021, https://doi.org/10.5194/amt-14-6835-2021, 2021
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Iodide-adduct chemical ionization mass spectrometry (I-CIMS) has been widely used to analyze airborne organics. In this study, I-CIMS sensitivities of isomers within a formula are found to generally vary by 1 and up to 2 orders of magnitude. Comparisons between measured and predicted moles, obtained using a voltage-scanning calibration approach, show that predictions for individual compounds or formulas might carry high uncertainty, yet the summed moles of analytes agree reasonably well.
Chenyang Bi, Jordan E. Krechmer, Manjula R. Canagaratna, and Gabriel Isaacman-VanWertz
Atmos. Meas. Tech., 14, 6551–6560, https://doi.org/10.5194/amt-14-6551-2021, https://doi.org/10.5194/amt-14-6551-2021, 2021
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Calibration techniques have been recently developed to log-linearly correlate analyte sensitivity with CIMS operating conditions particularly for compounds without authentic standards. In this work, we examine the previously ignored bias in the log-linear-based calibration method and estimate an average bias of 30 %, with 1 order of magnitude for less sensitive compounds in some circumstances. A step-by-step guide was provided to reduce and even remove the bias.
Louise N. Jensen, Manjula R. Canagaratna, Kasper Kristensen, Lauriane L. J. Quéléver, Bernadette Rosati, Ricky Teiwes, Marianne Glasius, Henrik B. Pedersen, Mikael Ehn, and Merete Bilde
Atmos. Chem. Phys., 21, 11545–11562, https://doi.org/10.5194/acp-21-11545-2021, https://doi.org/10.5194/acp-21-11545-2021, 2021
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This work targets the chemical composition of α-pinene-derived secondary organic aerosol (SOA) formed in the temperature range from -15 to 20°C. Experiments were conducted in an atmospheric simulation chamber. Positive matrix factorization analysis of data obtained by a high-resolution time-of-flight aerosol mass spectrometer shows that the elemental aerosol composition is controlled by the initial α-pinene concentration and temperature during SOA formation.
Benjamin A. Nault, Duseong S. Jo, Brian C. McDonald, Pedro Campuzano-Jost, Douglas A. Day, Weiwei Hu, Jason C. Schroder, James Allan, Donald R. Blake, Manjula R. Canagaratna, Hugh Coe, Matthew M. Coggon, Peter F. DeCarlo, Glenn S. Diskin, Rachel Dunmore, Frank Flocke, Alan Fried, Jessica B. Gilman, Georgios Gkatzelis, Jacqui F. Hamilton, Thomas F. Hanisco, Patrick L. Hayes, Daven K. Henze, Alma Hodzic, James Hopkins, Min Hu, L. Greggory Huey, B. Thomas Jobson, William C. Kuster, Alastair Lewis, Meng Li, Jin Liao, M. Omar Nawaz, Ilana B. Pollack, Jeffrey Peischl, Bernhard Rappenglück, Claire E. Reeves, Dirk Richter, James M. Roberts, Thomas B. Ryerson, Min Shao, Jacob M. Sommers, James Walega, Carsten Warneke, Petter Weibring, Glenn M. Wolfe, Dominique E. Young, Bin Yuan, Qiang Zhang, Joost A. de Gouw, and Jose L. Jimenez
Atmos. Chem. Phys., 21, 11201–11224, https://doi.org/10.5194/acp-21-11201-2021, https://doi.org/10.5194/acp-21-11201-2021, 2021
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Secondary organic aerosol (SOA) is an important aspect of poor air quality for urban regions around the world, where a large fraction of the population lives. However, there is still large uncertainty in predicting SOA in urban regions. Here, we used data from 11 urban campaigns and show that the variability in SOA production in these regions is predictable and is explained by key emissions. These results are used to estimate the premature mortality associated with SOA in urban regions.
Eleni Dovrou, Kelvin H. Bates, Jean C. Rivera-Rios, Joshua L. Cox, Joshua D. Shutter, and Frank N. Keutsch
Atmos. Chem. Phys., 21, 8999–9008, https://doi.org/10.5194/acp-21-8999-2021, https://doi.org/10.5194/acp-21-8999-2021, 2021
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We examined the mechanism and products of oxidation of dissolved sulfur dioxide with the main isomers of isoprene hydroxyl hydroperoxides, via laboratory and model analysis. Two chemical mechanism pathways are proposed and the results provide an improved understanding of the broader atmospheric chemistry and role of multifunctional organic hydroperoxides, which should be the dominant VOC oxidation products under low-NO conditions, highlighting their significant contribution to sulfate formation.
Chenyang Bi, Jordan E. Krechmer, Graham O. Frazier, Wen Xu, Andrew T. Lambe, Megan S. Claflin, Brian M. Lerner, John T. Jayne, Douglas R. Worsnop, Manjula R. Canagaratna, and Gabriel Isaacman-VanWertz
Atmos. Meas. Tech., 14, 3895–3907, https://doi.org/10.5194/amt-14-3895-2021, https://doi.org/10.5194/amt-14-3895-2021, 2021
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Measurement techniques that can achieve molecular characterizations are necessary to understand the differences of fate and transport within isomers produced in the atmospheric oxidation process. In this work, we develop an instrument to conduct isomer-resolved measurements of particle-phase organics. We assess the number of isomers per chemical formula in atmospherically relevant samples and examine the feasibility of extending the use of an existing instrument to a broader range of analytes.
Mutian Ma, Laura-Hélèna Rivellini, YuXi Cui, Megan D. Willis, Rio Wilkie, Jonathan P. D. Abbatt, Manjula R. Canagaratna, Junfeng Wang, Xinlei Ge, and Alex K. Y. Lee
Atmos. Meas. Tech., 14, 2799–2812, https://doi.org/10.5194/amt-14-2799-2021, https://doi.org/10.5194/amt-14-2799-2021, 2021
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Chemical characterization of organic coatings is important to advance our understanding of the physio-chemical properties and atmospheric processing of black carbon (BC) particles. This work develops two approaches to improve the elemental analysis of oxygenated organic coatings using a soot-particle aerosol mass spectrometer. Analyzing ambient data with the new approaches indicated that secondary organics that coated on BC were likely less oxygenated compared to those externally mixed with BC.
Haiyan Li, Manjula R. Canagaratna, Matthieu Riva, Pekka Rantala, Yanjun Zhang, Steven Thomas, Liine Heikkinen, Pierre-Marie Flaud, Eric Villenave, Emilie Perraudin, Douglas Worsnop, Markku Kulmala, Mikael Ehn, and Federico Bianchi
Atmos. Chem. Phys., 21, 4123–4147, https://doi.org/10.5194/acp-21-4123-2021, https://doi.org/10.5194/acp-21-4123-2021, 2021
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For the first time, we performed binPMF analysis on the complex mass spectra acquired with the Vocus PTR-TOF in two European pine forests and identified various primary emission sources and secondary oxidation processes of atmospheric organic vapors, i.e., terpenes and their oxidation products, with varying oxidation degrees. Further insights were gained regarding monoterpene and sesquiterpene reactions based on the interpretation results.
Megan S. Claflin, Demetrios Pagonis, Zachary Finewax, Anne V. Handschy, Douglas A. Day, Wyatt L. Brown, John T. Jayne, Douglas R. Worsnop, Jose L. Jimenez, Paul J. Ziemann, Joost de Gouw, and Brian M. Lerner
Atmos. Meas. Tech., 14, 133–152, https://doi.org/10.5194/amt-14-133-2021, https://doi.org/10.5194/amt-14-133-2021, 2021
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We have developed a field-deployable gas chromatograph with thermal desorption preconcentration and detector switching between two high-resolution mass spectrometers for in situ measurements of volatile organic compounds (VOCs). This system combines chromatography with both proton transfer and electron ionization to offer fast time response and continuous molecular speciation. This technique was applied during the 2018 ATHLETIC campaign to characterize VOC emissions in an indoor environment.
Cited articles
Aljawhary, D., Lee, A. K. Y., and Abbatt, J. P. D.: High-resolution chemical ionization mass spectrometry (ToF-CIMS): application to study SOA composition and processing, Atmos. Meas. Tech., 6, 3211–3224, https://doi.org/10.5194/amt-6-3211-2013, 2013.
Alton, M., Canagaratna, M., Avery, A., Lambe, A., Kangasluoma, J., Ehn, M., Mickwitz, V., Zhao, J., and Worsnop, D.: Measurements of Atmospheric Aerosol with the Vaporization Inlet for Aerosols and the Filter Inlet for Gases and Aerosols on a Bipolar Multi-Reagent Chemical Ionization Mass Spectrometer, EGU General Assembly 2024, Vienna, Austria, 14–19 April 2024, EGU24-12470, https://doi.org/10.5194/egusphere-egu24-12470, 2024.
Apffel, A., Fischer, S., Goldberg, G., Goodley, P. C., and Kuhlmann, F. E.: Enhanced sensitivity for peptide mapping with electrospray liquid chromatography-mass spectrometry in the presence of signal suppression due to trifluoroacetic acid-containing mobile phases, J. Chromatogr. A., 712, 177–190, https://doi.org/10.1016/0021-9673(95)00175-M, 1995.
ASCENT: La Casa, https://ascent.research.gatech.edu/la-casa, last access: 9 December 2024.
Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem. Rev., 103, 4605–4638, https://doi.org/10.1021/cr0206420, 2003.
Bateman, A. P., Nizkorodov, S. A., Laskin, J., and Laskin, A.: Photolytic processing of secondary organic aerosols dissolved in cloud droplets, Phys. Chem. Chem. Phys., 13, 12199–12212, https://doi.org/10.1039/c1cp20526a, 2011.
Bi, C., Krechmer, J. E., Frazier, G. O., Xu, W., Lambe, A. T., Claflin, M. S., Lerner, B. M., Jayne, J. T., Worsnop, D. R., Canagaratna, M. R., and Isaacman-VanWertz, G.: Coupling a gas chromatograph simultaneously to a flame ionization detector and chemical ionization mass spectrometer for isomer-resolved measurements of particle-phase organic compounds, Atmos. Meas. Tech., 14, 3895–3907, https://doi.org/10.5194/amt-14-3895-2021, 2021a.
Bi, C., Krechmer, J. E., Frazier, G. O., Xu, W., Lambe, A. T., Claflin, M. S., Lerner, B. M., Jayne, J. T., Worsnop, D. R., Canagaratna, M. R., and Isaacman-VanWertz, G.: Quantification of isomer-resolved iodide chemical ionization mass spectrometry sensitivity and uncertainty using a voltage-scanning approach, Atmos. Meas. Tech., 14, 6835–6850, https://doi.org/10.5194/amt-14-6835-2021, 2021b.
Bones, D. L., Henricksen, D. K., Mang, S. A., Gonsior, M., Bateman, A. P., Nguyen, T. B., Cooper, W. J., and Nizkorodov, S. A.: Appearance of strong absorbers and fluorophores in limonene-O3 secondary organic aerosol due to NH
Brown, S. S. and Stutz, J.: Nighttime radical observations and chemistry, Chem. Soc. Rev., 41, 6405–6447, https://doi.org/10.1039/c2cs35181a, 2012.
Cai, J., Daellenbach, K. R., Wu, C., Zheng, Y., Zheng, F., Du, W., Haslett, S. L., Chen, Q., Kulmala, M., and Mohr, C.: Characterization of offline analysis of particulate matter with FIGAERO-CIMS, Atmos. Meas. Tech., 16, 1147–1165, https://doi.org/10.5194/amt-16-1147-2023, 2023.
Canagaratna, M. R., Jayne, J. T., Jimenez, J. L., Allan, J. D., Alfarra, M. R., Zhang, Q., Onasch, T. B., Drewnick, F., Coe, H., Middlebrook, A., Delia, A., Williams, L. R., Trimborn, A. M., Northway, M. J., DeCarlo, P. F., Kolb, C. E., Davidovits, P., and Worsnop, D. R.: Chemical and microphysical characterization of ambient aerosols with the aerodyne aerosol mass spectrometer, Mass Spectrom. Rev., 26, 185–222, https://doi.org/10.1002/mas.20115, 2007.
Claeys, M., Iinuma, Y., Szmigielski, R., Surratt, J. D., Blockhuys, F., Van Alsenoy, C., Böge, O., Sierau, B., Gómez-González, Y., Vermeylen, R., Van Der Veken, P., Shahgholi, M., Chan, A. W. H., Herrmann, H., Seinfeld, J. H., and Maenhaut, W.: Terpenylic acid and related compounds from the oxidation of α-pinene: Implications for new particle formation and growth above forests, Environ. Sci. Technol., 43, 6976–6982, https://doi.org/10.1021/es9007596, 2009.
Colorado Department of Public Health and Environment: Air Quality Reports [data set], https://www.colorado.gov/airquality/report.aspx (last access: 21 March 2025), 2025.
Devault, M. P. and Ziemann, P. J.: Gas- and particle-phase products and their mechanisms of formation from the reaction of Δ-3-carene with NO3 radicals, J. Phys. Chem. A., 125, 10207–10222, https://doi.org/10.1021/acs.jpca.1c07763, 2021.
Devault, M. P., Ziola, A. C., and Ziemann, P. J.: Chemistry of secondary organic aerosol formation from reactions of monoterpenes with OH radicals in the presence of NOx, J. Phys. Chem. A, 126, 7719–7736, https://doi.org/10.1021/acs.jpca.2c04605, 2022a.
Devault, M. P., Ziola, A. C., and Ziemann, P. J.: Products and mechanisms of secondary organic aerosol formation from the NO3 radical-initiated oxidation of cyclic and acyclic monoterpenes, ACS Earth Space Chem., 6, 2076–2092, https://doi.org/10.1021/acsearthspacechem.2c00130, 2022b.
Docherty, K. S. and Ziemann, P. J.: Reaction of oleic acid particles with NO3 radicals: Products, mechanism, and implications for radical-initiated organic aerosol oxidation, J. Phys. Chem. A, 110, 3567–3577, https://doi.org/10.1021/jp0582383, 2006.
Docherty, K. S., Kumboonlert, K., Lee, I. J., and Ziemann, P. J.: Gas chromatography of trimethylsilyl derivatives of α-methoxyalkyl hydroperoxides formed in alkene-O3 reactions, J. Chromatogr. A., 1029, 205–215, https://doi.org/10.1016/j.chroma.2003.12.014, 2004.
Eichler, P., Müller, M., D'Anna, B., and Wisthaler, A.: A novel inlet system for online chemical analysis of semi-volatile submicron particulate matter, Atmos. Meas. Tech., 8, 1353–1360, https://doi.org/10.5194/amt-8-1353-2015, 2015.
Faxon, C., Hammes, J., Le Breton, M., Pathak, R. K., and Hallquist, M.: Characterization of organic nitrate constituents of secondary organic aerosol (SOA) from nitrate-radical-initiated oxidation of limonene using high-resolution chemical ionization mass spectrometry, Atmos. Chem. Phys., 18, 5467–5481, https://doi.org/10.5194/acp-18-5467-2018, 2018.
Finewax, Z., Jimenez, J. L., and Ziemann, P. J.: Development and application of a low-cost vaporizer for rapid, quantitative, in situ addition of organic gases and particles to an environmental chamber, Aerosol Sci. Tech., 54, 1567–1578, https://doi.org/10.1080/02786826.2020.1808186, 2020.
Gkatzelis, G. I., Coggon, M. M., McDonald, B. C., Peischl, J., Aikin, K. C., Gilman, J. B., Trainer, M., and Warneke, C.: Identifying volatile chemical product tracer compounds in U.S. cities, Environ. Sci. Technol., 55, 188-199, https://doi.org/10.1021/acs.est.0c05467, 2021.
Goldstein, A. H. and Galbally, I. E.: Known and unexplored organic constituents in the earth's atmosphere, Environ. Sci. Technol., 41, 1514–1521, https://doi.org/10.1021/es072476p, 2007.
Häkkinen, E., Zhao, J., Graeffe, F., Fauré, N., Krechmer, J. E., Worsnop, D., Timonen, H., Ehn, M., and Kangasluoma, J.: Online measurement of highly oxygenated compounds from organic aerosol, Atmos. Meas. Tech., 16, 1705–1721, https://doi.org/10.5194/amt-16-1705-2023, 2023.
He, S., Liu, Y., Song, M., Li, X., Lou, S., Ye, C., Liu, Y., Liu, Y., Ye, J., Lu, S., Zhou, W., Qiu, X., Zhu, T., and Zeng, L.: Empirical approach to quantifying sensitivity in different chemical ionization techniques for organonitrates and nitroaromatics constrained by ion-molecule reaction and transmission efficiency, Anal. Chem., 96, 16882–16890, https://doi.org/10.1021/acs.analchem.4c03751, 2024.
Hearn, J. D. and Smith, G. D.: A chemical ionization mass spectrometry method for the online analysis of organic aerosols, Anal. Chem., 76, 2820–2826, https://doi.org/10.1021/ac049948s, 2004.
Heaton, K. J., Sleighter, R. L., Hatcher, P. G., Hall IV, W. A., and Johnston, M. V.: Composition domains in monoterpene secondary organic aerosol, Environ. Sci. Technol., 43, 7797–7802, https://doi.org/10.1021/es901214p, 2009.
Hildmann, S. and Hoffmann, T.: Characterisation of atmospheric organic aerosols with one- and multidimensional liquid chromatography and mass spectrometry: State of the art and future perspectives, Trends Anal. Chem., 175, 117698, https://doi.org/10.1016/j.trac.2024.117698, 2024.
Hoffmann, T., Bandur, R., Marggraf, U., and Linscheid, M.: Molecular composition of organic aerosols formed in the α-pinene/O3 reaction: Implications for new particle formation processes, J. Geophys. Res. Atmos., 103, 25569–25578, https://doi.org/10.1029/98JD01816, 1998.
Huang, W., Saathoff, H., Pajunoja, A., Shen, X., Naumann, K.-H., Wagner, R., Virtanen, A., Leisner, T., and Mohr, C.: α-Pinene secondary organic aerosol at low temperature: chemical composition and implications for particle viscosity, Atmos. Chem. Phys., 18, 2883–2898, https://doi.org/10.5194/acp-18-2883-2018, 2018.
Kenseth, C. M., Hafeman, N. J., Rezgui, S. P., Chen, J., Huang, Y., Dalleska, N. F., Kjaergaard, H. G., Stoltz, B. M., Seinfeld, J. H., and Wennberg, P. O.: Particle-phase accretion forms dimer esters in pinene secondary organic aerosol, Science, 382, 787–792, https://doi.org/10.1126/science.adi0857, 2023.
Krechmer, J. E., Groessl, M., Zhang, X., Junninen, H., Massoli, P., Lambe, A. T., Kimmel, J. R., Cubison, M. J., Graf, S., Lin, Y.-H., Budisulistiorini, S. H., Zhang, H., Surratt, J. D., Knochenmuss, R., Jayne, J. T., Worsnop, D. R., Jimenez, J.-L., and Canagaratna, M. R.: Ion mobility spectrometry–mass spectrometry (IMS–MS) for on- and offline analysis of atmospheric gas and aerosol species, Atmos. Meas. Tech., 9, 3245–3262, https://doi.org/10.5194/amt-9-3245-2016, 2016.
Kristensen, K., Watne, Å. K., Hammes, J., Lutz, A., Petäjä, T., Hallquist, M., Bilde, M., and Glasius, M.: High-molecular weight dimer esters are major products in aerosols from α-pinene ozonolysis and the boreal forest, Environ. Sci. Technol. Lett., 3, 280–285, https://doi.org/10.1021/acs.estlett.6b00152, 2016.
Kroll, J. H. and Seinfeld, J. H.: Chemistry of secondary organic aerosol: Formation and evolution of low-volatility organics in the atmosphere, Atmos. Environ., 42, 3593–3624, https://doi.org/10.1016/j.atmosenv.2008.01.003, 2008.
Lee, B. H., Lopez-Hilfiker, F. D., Mohr, C., Kurtén, T., Worsnop, D. R., and Thornton, J. A.: An iodide-adduct high-resolution time-of-flight chemical-ionization mass spectrometer: Application to atmospheric inorganic and organic compounds, Environ. Sci. Technol., 48, 6309–6317, https://doi.org/10.1021/es500362a, 2014.
Lee, B. H., Mohr, C., Lopez-Hilfiker, F. D., and Thornton, J. A.: Highly functionalized organic nitrates in the southeast united states: contribution to secondary organic aerosol and reactive nitrogen budgets, P. Natl. Acad. Sci., 113, 1516–1521, https://doi.org/10.1073/pnas.1508108113, 2016.
Lobrutto, R., Jones, A., Kazakevich, Y. V., and Mcnair, H. M.: Effect of the eluent pH and acidic modifiers in high-performance liquid chromatography retention of basic analytes, J. Chromatogr. A, 913, 173–187, https://doi.org/10.1016/S0021-9673(00)01012-8, 2001.
Lopez-Hilfiker, F. D., Mohr, C., Ehn, M., Rubach, F., Kleist, E., Wildt, J., Mentel, Th. F., Lutz, A., Hallquist, M., Worsnop, D., and Thornton, J. A.: A novel method for online analysis of gas and particle composition: description and evaluation of a Filter Inlet for Gases and AEROsols (FIGAERO), Atmos. Meas. Tech., 7, 983–1001, https://doi.org/10.5194/amt-7-983-2014, 2014.
Luo, H., Guo, Y., Shen, H., Huang, D. D., Zhang, Y., and Zhao, D.: Effect of relative humidity on the molecular composition of secondary organic aerosols from α-pinene ozonolysis, Environ. Sci.: Atmos., 4, 519–530, https://doi.org/10.1039/d3ea00149k, 2024.
Ma, Y., Luciani, T., Porter, R. A., Russell, A. T., Johnson, D., and Marston, G.: Organic acid formation in the gas-phase ozonolysis of α-pinene, Phys. Chem. Chem. Phys., 9, 5084–5087, https://doi.org/10.1039/b709880d, 2007a.
Ma, Y., Willcox, T. R., Russell, A. T., and Marston, G.: Pinic and pinonic acid formation in the reaction of ozone with α-pinene, Chem. Commun., 1328–1330, https://doi.org/10.1039/b617130c, 2007b.
Mauderly, J. L. and Chow, J. C.: Health effects of organic aerosols, Inhal. Toxicol., 20, 257–288, https://doi.org/10.1080/08958370701866008, 2008.
Pöschl, U.: Atmospheric aerosols: Composition, transformation, climate and health effects, Angew. Chem. Int. Ed., 44, 7520–7540, https://doi.org/10.1002/anie.200501122, 2005.
Reinnig, M. C., Müller, L., Warnke, J., and Hoffmann, T.: Characterization of selected organic compound classes in secondary organic aerosol from biogenic VOCs by HPLC/MSn, Anal. Bioanal. Chem., 391, 171–182, https://doi.org/10.1007/s00216-008-1964-5, 2008.
Riva, M., Pospisilova, V., Frege, C., Perrier, S., Bansal, P., Jorga, S., Sturm, P., Thornton, J. A., Rohner, U., and Lopez-Hilfiker, F.: Evaluation of a reduced-pressure chemical ion reactor utilizing adduct ionization for the detection of gaseous organic and inorganic species, Atmos. Meas. Tech., 17, 5887–5901, https://doi.org/10.5194/amt-17-5887-2024, 2024.
Robinson, M. A., Roberts, J. M., Neuman, J. A., Jernigan, C. M., Xu, L., Coggon, M. M., Stockwell, C. E., Warneke, C., Peischl, J., Gilman, J. B., Lamplugh, A., Rollins, A. W., Zuraski, K., Rivera-Rios, J. C., Wang, Y., Ng, N. L., Liu, S., Brown, S. S., and Veres, P. R.: Online calibration of a chemical ionization mass spectrometer for multifunctional biogenic organic nitrates, ACS ES&T Air, 1, 1066–1083, https://doi.org/10.1021/acsestair.4c00056, 2024.
Ruiz-Jiménez, J., Hautala, S., Parshintsev, J., Laitinen, T., Hartonen, K., Petäjä, T., Kulmala, M., and Riekkola, M. L.: Aliphatic and aromatic amines in atmospheric aerosol particles: comparison of three ionization techniques in liquid chromatography-mass spectrometry and method development, Talanta, 97, 55–62, https://doi.org/10.1016/j.talanta.2012.03.062, 2012.
Schueneman, M. K., Day, D. A., Kim, D., Campuzano-Jost, P., Yun, S., DeVault, M. P., Ziola, A. C., Ziemann, P. J., and Jimenez, J. L.: A multi-instrumental approach for calibrating real-time mass spectrometers using high-performance liquid chromatography and positive matrix factorization, Aerosol Research, 2, 59–76, https://doi.org/10.5194/ar-2-59-2024, 2024.
Schwarzenbach, R.: High-performance liquid chromatography of carboxylic acids, J. Chromatogr. A, 251, 339–358, https://doi.org/10.1016/S0021-9673(00)87024-7, 1982.
Shrivastava, M., Cappa, C. D., Fan, J., Goldstein, A. H., Guenther, A. B., Jimenez, J. L., Kuang, C., Laskin, A., Martin, S. T., Ng, N. L., Petaja, T., Pierce, J. R., Rasch, P. J., Roldin, P., Seinfeld, J. H., Shilling, J., Smith, J. N., Thornton, J. A., Volkamer, R., Wang, J., Worsnop, D. R., Zaveri, R. A., Zelenyuk, A., and Zhang, Q.: Recent advances in understanding secondary organic aerosol: implications for global climate forcing, Rev. Geophys., 55, 509–559, https://doi.org/10.1002/2016RG000540, 2017.
Skyttä, A., Gao, J., Cai, R., Ehn, M., Ahonen, L. R., Kurten, T., Wang, Z., Rissanen, M. P., and Kangasluoma, J.: Isomer-resolved mobility-mass analysis of α-pinene ozonolysis products, J. Phys. Chem. A, 126, 5040–5049, https://doi.org/10.1021/acs.jpca.2c03366, 2022.
Takeuchi, M., Berkemeier, T., Eris, G., and Ng, N. L.: Non-linear effects of secondary organic aerosol formation and properties in multi-precursor systems, Nat. Commun., 13, https://doi.org/10.1038/s41467-022-35546-1, 2022.
Tobias, H. J. and Ziemann, P. J.: Compound identification in organic aerosols using temperature-programmed thermal desorption particle beam mass spectrometry, Anal. Chem., 71, 3428–3435, https://doi.org/10.1021/ac990056f, 1999.
Vasquez, K. T., Allen, H. M., Crounse, J. D., Praske, E., Xu, L., Noelscher, A. C., and Wennberg, P. O.: Low-pressure gas chromatography with chemical ionization mass spectrometry for quantification of multifunctional organic compounds in the atmosphere, Atmos. Meas. Tech., 11, 6815–6832, https://doi.org/10.5194/amt-11-6815-2018, 2018.
Voisin, D., Smith, J. N., Sakurai, H., McMurry, P. H., and Eisele, F. L.: Thermal desorption chemical ionization mass spectrometer for ultrafine particle chemical composition, Aerosol Sci. Tech., 37, 471–475, https://doi.org/10.1080/02786820300959, 2003.
Wang, C. T., Ashworth, K., Wiedinmyer, C., Ortega, J., Harley, P. C., Rasool, Q. Z., and Vizuete, W.: Ambient measurements of monoterpenes near cannabis cultivation facilities in Denver, Colorado, Atmos. Environ., 232, https://doi.org/10.1016/j.atmosenv.2020.117510, 2020.
Warneke, C., De Gouw, J. A., Kuster, W. C., Goldan, P. D., and Fall, R.: Validation of atmospheric VOC measurements by proton-transfer-reaction mass spectrometry using a gas-chromatographic preseparation method, Environ. Sci. Technol., 37, 2494–2501, https://doi.org/10.1021/es026266i, 2003.
Warscheid, B. and Hoffmann, T.: On-line measurements of α-pinene ozonolysis products using an atmospheric pressure chemical ionisation ion-trap mass spectrometer, Atmos. Environ., 35, 2927–2940, https://doi.org/10.1016/S1352-2310(00)00513-6, 2001.
Yeh, G. K. and Ziemann, P. J.: Identification and yields of 1,4-hydroxynitrates formed from the reactions of C8–C16 n-alkanes with OH radicals in the presence of NOx, J. Phys. Chem. A, 118, 8797–8806, https://doi.org/10.1021/jp505870d, 2014.
Yu, J., Flagan, R. C., and Seinfeld, J. H.: Identification of products containing -COOH, -OH, and -C=O in atmospheric oxidation of hydrocarbons, Environ. Sci. Technol., 32, 2357–2370, https://doi.org/10.1021/es980129x, 1998.
Yu, J., Griffin, R. J., Cocker, D. R., Flagan, R. C., Seinfeld, J. H., and Blanchard, P.: Observation of gaseous and particulate products of monoterpene oxidation in forest atmospheres, Geophys. Res. Lett., 26, 1145–1148, https://doi.org/10.1029/1999GL900169, 1999.
Zhang, X., Lambe, A. T., Upshur, M. A., Brooks, W. A., Gray Bé, A., Thomson, R. J., Geiger, F. M., Surratt, J. D., Zhang, Z., Gold, A., Graf, S., Cubison, M. J., Groessl, M., Jayne, J. T., Worsnop, D. R., and Canagaratna, M. R.: Highly oxygenated multifunctional compounds in α-pinene secondary organic aerosol, Environ. Sci. Technol., 51, 5932–5940, https://doi.org/10.1021/acs.est.6b06588, 2017.
Zhao, J., Häkkinen, E., Graeffe, F., Krechmer, J. E., Canagaratna, M. R., Worsnop, D. R., Kangasluoma, J., and Ehn, M.: A combined gas- and particle-phase analysis of highly oxygenated organic molecules (HOMs) from α-pinene ozonolysis, Atmos. Chem. Phys., 23, 3707–3730, https://doi.org/10.5194/acp-23-3707-2023, 2023.
Zhao, J., Mickwitz, V., Luo, Y., Häkkinen, E., Graeffe, F., Zhang, J., Timonen, H., Canagaratna, M., Krechmer, J. E., Zhang, Q., Kulmala, M., Kangasluoma, J., Worsnop, D., and Ehn, M.: Characterization of the Vaporization Inlet for Aerosols (VIA) for online measurements of particulate highly oxygenated organic molecules (HOMs), Atmos. Meas. Tech., 17, 1527–1543, https://doi.org/10.5194/amt-17-1527-2024, 2024.
Ziemann, P. J. and Atkinson, R.: Kinetics, products, and mechanisms of secondary organic aerosol formation, Chem. Soc. Rev., 41, 6582–6605, https://doi.org/10.1039/c2cs35122f, 2012.
Short summary
Organic aerosols consist of complex chemical mixtures that are challenging to characterize using chemical ionization mass spectrometry alone. This study presents a method for coupling liquid chromatography and chemical ionization mass spectrometry for the offline analysis of organic aerosols. The evaluation of the method using standards and laboratory-generated and field-collected organic aerosols showed that it can provide detailed characterization of environmentally relevant mixtures.
Organic aerosols consist of complex chemical mixtures that are challenging to characterize using...
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