Articles | Volume 15, issue 12
https://doi.org/10.5194/amt-15-3779-2022
© 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/amt-15-3779-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Ch3MS-RF: a random forest model for chemical characterization and improved quantification of unidentified atmospheric organics detected by chromatography–mass spectrometry techniques
Emily B. Franklin
CORRESPONDING AUTHOR
Department of Civil and Environmental Engineering, University of
California Berkeley, Berkeley 94720, USA
Lindsay D. Yee
Department of Environmental Science, Policy and Management, University of California Berkeley, Berkeley 94720, USA
Bernard Aumont
Université Paris-Est Créteil and Université de Paris, CNRS, LISA, 94010 Créteil, France
Robert J. Weber
Department of Environmental Science, Policy and Management, University of California Berkeley, Berkeley 94720, USA
Paul Grigas
Department of Industrial Engineering and Operations Research,
University of California Berkeley, Berkeley 94720, USA
Department of Civil and Environmental Engineering, University of
California Berkeley, Berkeley 94720, USA
Department of Environmental Science, Policy and Management, University of California Berkeley, Berkeley 94720, USA
Related authors
Delaney B. Kilgour, Gordon A. Novak, Jon S. Sauer, Alexia N. Moore, Julie Dinasquet, Sarah Amiri, Emily B. Franklin, Kathryn Mayer, Margaux Winter, Clare K. Morris, Tyler Price, Francesca Malfatti, Daniel R. Crocker, Christopher Lee, Christopher D. Cappa, Allen H. Goldstein, Kimberly A. Prather, and Timothy H. Bertram
Atmos. Chem. Phys., 22, 1601–1613, https://doi.org/10.5194/acp-22-1601-2022, https://doi.org/10.5194/acp-22-1601-2022, 2022
Short summary
Short summary
We report measurements of gas-phase volatile organosulfur molecules made during a mesocosm phytoplankton bloom experiment. Dimethyl sulfide (DMS), methanethiol (MeSH), and benzothiazole accounted for on average over 90 % of total gas-phase sulfur emissions. This work focuses on factors controlling the production and emission of DMS and MeSH and the role of non-DMS molecules (such as MeSH and benzothiazole) in secondary sulfate formation in coastal marine environments.
Erin F. Katz, Caleb M. Arata, Eva Y. Pfannerstill, Robert J. Weber, Darian Ng, Michael J. Milazzo, Haley Byrne, Hui Wang, Alex B. Guenther, Camilo Rey-Sanchez, Joshua Apte, Dennis D. Baldocchi, and Allen H. Goldstein
EGUsphere, https://doi.org/10.5194/egusphere-2025-2682, https://doi.org/10.5194/egusphere-2025-2682, 2025
This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
Short summary
Short summary
Terpenoids are organic gases that can originate from natural and human-caused sources, and their fast reactions in the atmosphere can cause air pollution. Emissions of organic gases in an urban environment were measured. For some terpenoids, human-caused sources were responsible for about a quarter of the emissions, while others were likely to be entirely from vegetation. The terpenoids contributed substantially to the potential to form secondary pollutants.
James D. A. Butler, Afsara Tasnia, Deep Sengupta, Nathan Kreisberg, Kelley C. Barsanti, Allen H. Goldstein, Chelsea V. Preble, Rebecca A. Sugrue, and Thomas W. Kirchstetter
EGUsphere, https://doi.org/10.5194/egusphere-2025-2295, https://doi.org/10.5194/egusphere-2025-2295, 2025
This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
Short summary
Short summary
Prescribed burns are controlled fires used to prevent wildfires. Smoke emissions were measured to characterize emission factors and optical properties of black and brown soot particles. Brown particles were emitted at 7–14 times that of black particles and contributed 82 % of atmospheric absorption by particles for ultraviolet light and 23 % for total solar radiation. These findings will improve inventories and climate models for prescribed burns.
Barbara Ervens, Andrew Rickard, Bernard Aumont, William P. L. Carter, Max McGillen, Abdelwahid Mellouki, John Orlando, Bénédicte Picquet-Varrault, Paul Seakins, William R. Stockwell, Luc Vereecken, and Timothy J. Wallington
Atmos. Chem. Phys., 24, 13317–13339, https://doi.org/10.5194/acp-24-13317-2024, https://doi.org/10.5194/acp-24-13317-2024, 2024
Short summary
Short summary
Chemical mechanisms describe the chemical processes in atmospheric models that are used to describe the changes in the atmospheric composition. Therefore, accurate chemical mechanisms are necessary to predict the evolution of air pollution and climate change. The article describes all steps that are needed to build chemical mechanisms and discusses the advances and needs of experimental and theoretical research activities needed to build reliable chemical mechanisms.
Lauri Franzon, Marie Camredon, Richard Valorso, Bernard Aumont, and Theo Kurtén
Atmos. Chem. Phys., 24, 11679–11699, https://doi.org/10.5194/acp-24-11679-2024, https://doi.org/10.5194/acp-24-11679-2024, 2024
Short summary
Short summary
In this article we investigate the formation of large, sticky molecules from various organic compounds entering the atmosphere as primary emissions and the degree to which these processes may contribute to organic aerosol particle mass. More specifically, we qualitatively investigate a recently discovered chemical reaction channel for one of the most important short-lived radical compounds, peroxy radicals, and discover which of these reactions are most atmospherically important.
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
Short summary
Short summary
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.
Qindan Zhu, Rebecca H. Schwantes, Matthew Coggon, Colin Harkins, Jordan Schnell, Jian He, Havala O. T. Pye, Meng Li, Barry Baker, Zachary Moon, Ravan Ahmadov, Eva Y. Pfannerstill, Bryan Place, Paul Wooldridge, Benjamin C. Schulze, Caleb Arata, Anthony Bucholtz, John H. Seinfeld, Carsten Warneke, Chelsea E. Stockwell, Lu Xu, Kristen Zuraski, Michael A. Robinson, J. Andrew Neuman, Patrick R. Veres, Jeff Peischl, Steven S. Brown, Allen H. Goldstein, Ronald C. Cohen, and Brian C. McDonald
Atmos. Chem. Phys., 24, 5265–5286, https://doi.org/10.5194/acp-24-5265-2024, https://doi.org/10.5194/acp-24-5265-2024, 2024
Short summary
Short summary
Volatile organic compounds (VOCs) fuel the production of air pollutants like ozone and particulate matter. The representation of VOC chemistry remains challenging due to its complexity in speciation and reactions. Here, we develop a chemical mechanism, RACM2B-VCP, that better represents VOC chemistry in urban areas such as Los Angeles. We also discuss the contribution of VOCs emitted from volatile chemical products and other anthropogenic sources to total VOC reactivity and O3.
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
Short summary
Short summary
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.
Clara M. Nussbaumer, Bryan K. Place, Qindan Zhu, Eva Y. Pfannerstill, Paul Wooldridge, Benjamin C. Schulze, Caleb Arata, Ryan Ward, Anthony Bucholtz, John H. Seinfeld, Allen H. Goldstein, and Ronald C. Cohen
Atmos. Chem. Phys., 23, 13015–13028, https://doi.org/10.5194/acp-23-13015-2023, https://doi.org/10.5194/acp-23-13015-2023, 2023
Short summary
Short summary
NOx is a precursor to hazardous tropospheric ozone and can be emitted from various anthropogenic sources. It is important to quantify NOx emissions in urban environments to improve the local air quality, which still remains a challenge, as sources are heterogeneous in space and time. In this study, we calculate NOx emissions over Los Angeles, based on aircraft measurements in June 2021, and compare them to a local emission inventory, which we find mostly overpredicts the measured values.
Eva Y. Pfannerstill, Caleb Arata, Qindan Zhu, Benjamin C. Schulze, Roy Woods, John H. Seinfeld, Anthony Bucholtz, Ronald C. Cohen, and Allen H. Goldstein
Atmos. Chem. Phys., 23, 12753–12780, https://doi.org/10.5194/acp-23-12753-2023, https://doi.org/10.5194/acp-23-12753-2023, 2023
Short summary
Short summary
The San Joaquin Valley is an agricultural area with poor air quality. Organic gases drive the formation of hazardous air pollutants. Agricultural emissions of these gases are not well understood and have rarely been quantified at landscape scale. By combining aircraft-based emission measurements with land cover information, we found mis- or unrepresented emission sources. Our results help in understanding of pollution sources and in improving predictions of air quality in agricultural regions.
Yutong Liang, Rebecca A. Wernis, Kasper Kristensen, Nathan M. Kreisberg, Philip L. Croteau, Scott C. Herndon, Arthur W. H. Chan, Nga L. Ng, and Allen H. Goldstein
Atmos. Chem. Phys., 23, 12441–12454, https://doi.org/10.5194/acp-23-12441-2023, https://doi.org/10.5194/acp-23-12441-2023, 2023
Short summary
Short summary
We measured the gas–particle partitioning behaviors of biomass burning markers and examined the effect of wildfire organic aerosol on the partitioning of semivolatile organic compounds. Most compounds measured are less volatile than model predictions. Wildfire aerosol enhanced the condensation of polar compounds and caused some nonpolar (e.g., polycyclic aromatic hydrocarbons) compounds to partition into the gas phase, thus affecting their lifetimes in the atmosphere and the mode of exposure.
Qindan Zhu, Bryan Place, Eva Y. Pfannerstill, Sha Tong, Huanxin Zhang, Jun Wang, Clara M. Nussbaumer, Paul Wooldridge, Benjamin C. Schulze, Caleb Arata, Anthony Bucholtz, John H. Seinfeld, Allen H. Goldstein, and Ronald C. Cohen
Atmos. Chem. Phys., 23, 9669–9683, https://doi.org/10.5194/acp-23-9669-2023, https://doi.org/10.5194/acp-23-9669-2023, 2023
Short summary
Short summary
Nitrogen oxide (NOx) is a hazardous air pollutant, and it is the precursor of short-lived climate forcers like tropospheric ozone and aerosol particles. While NOx emissions from transportation has been strictly regulated, soil NOx emissions are overlooked. We use the airborne flux measurements to observe NOx emissions from highways and urban and cultivated soil land cover types. We show non-negligible soil NOx emissions, which are significantly underestimated in current model simulations.
Rebecca A. Wernis, Nathan M. Kreisberg, Robert J. Weber, Greg T. Drozd, and Allen H. Goldstein
Atmos. Chem. Phys., 22, 14987–15019, https://doi.org/10.5194/acp-22-14987-2022, https://doi.org/10.5194/acp-22-14987-2022, 2022
Short summary
Short summary
We measured volatile and intermediate-volatility gases and semivolatile gas- and particle-phase compounds in the atmosphere during an 11 d period in a Bay Area suburb. We separated compounds based on variability in time to arrive at 13 distinct sources. Some compounds emitted from plants are found in greater quantities as fragrance compounds in consumer products. The wide volatility range of these measurements enables the construction of more complete source profiles.
Yutong Liang, Christos Stamatis, Edward C. Fortner, Rebecca A. Wernis, Paul Van Rooy, Francesca Majluf, Tara I. Yacovitch, Conner Daube, Scott C. Herndon, Nathan M. Kreisberg, Kelley C. Barsanti, and Allen H. Goldstein
Atmos. Chem. Phys., 22, 9877–9893, https://doi.org/10.5194/acp-22-9877-2022, https://doi.org/10.5194/acp-22-9877-2022, 2022
Short summary
Short summary
This article reports the measurements of organic compounds emitted from western US wildfires. We identified and quantified 240 particle-phase compounds and 72 gas-phase compounds emitted in wildfire and related the emissions to the modified combustion efficiency. Higher emissions of diterpenoids and monoterpenes were observed, likely due to distillation from unburned heated vegetation. Our results can benefit future source apportionment and modeling studies as well as exposure assessments.
Mike J. Newland, Camille Mouchel-Vallon, Richard Valorso, Bernard Aumont, Luc Vereecken, Michael E. Jenkin, and Andrew R. Rickard
Atmos. Chem. Phys., 22, 6167–6195, https://doi.org/10.5194/acp-22-6167-2022, https://doi.org/10.5194/acp-22-6167-2022, 2022
Short summary
Short summary
Alkene ozonolysis produces Criegee intermediates, which can act as oxidants or decompose to give a range of closed-shell and radical products, including OH. Therefore it is essential to accurately represent the chemistry of Criegee intermediates in atmospheric models in order to understand their impacts on atmospheric composition. Here we provide a mechanism construction protocol by which the central features of alkene ozonolysis chemistry can be included in an automatic mechanism generator.
Andrew J. Lindsay, Daniel C. Anderson, Rebecca A. Wernis, Yutong Liang, Allen H. Goldstein, Scott C. Herndon, Joseph R. Roscioli, Christoph Dyroff, Ed C. Fortner, Philip L. Croteau, Francesca Majluf, Jordan E. Krechmer, Tara I. Yacovitch, Walter B. Knighton, and Ezra C. Wood
Atmos. Chem. Phys., 22, 4909–4928, https://doi.org/10.5194/acp-22-4909-2022, https://doi.org/10.5194/acp-22-4909-2022, 2022
Short summary
Short summary
Wildfire smoke dramatically impacts air quality and often has elevated concentrations of ozone. We present measurements of ozone and its precursors at a rural site periodically impacted by wildfire smoke. Measurements of total peroxy radicals, key ozone precursors that have been studied little within wildfires, compare well with chemical box model predictions. Our results indicate no serious issues with using current chemistry mechanisms to model chemistry in aged wildfire plumes.
Delaney B. Kilgour, Gordon A. Novak, Jon S. Sauer, Alexia N. Moore, Julie Dinasquet, Sarah Amiri, Emily B. Franklin, Kathryn Mayer, Margaux Winter, Clare K. Morris, Tyler Price, Francesca Malfatti, Daniel R. Crocker, Christopher Lee, Christopher D. Cappa, Allen H. Goldstein, Kimberly A. Prather, and Timothy H. Bertram
Atmos. Chem. Phys., 22, 1601–1613, https://doi.org/10.5194/acp-22-1601-2022, https://doi.org/10.5194/acp-22-1601-2022, 2022
Short summary
Short summary
We report measurements of gas-phase volatile organosulfur molecules made during a mesocosm phytoplankton bloom experiment. Dimethyl sulfide (DMS), methanethiol (MeSH), and benzothiazole accounted for on average over 90 % of total gas-phase sulfur emissions. This work focuses on factors controlling the production and emission of DMS and MeSH and the role of non-DMS molecules (such as MeSH and benzothiazole) in secondary sulfate formation in coastal marine environments.
Rebecca A. Wernis, Nathan M. Kreisberg, Robert J. Weber, Yutong Liang, John Jayne, Susanne Hering, and Allen H. Goldstein
Atmos. Meas. Tech., 14, 6533–6550, https://doi.org/10.5194/amt-14-6533-2021, https://doi.org/10.5194/amt-14-6533-2021, 2021
Short summary
Short summary
cTAG is a new scientific instrument that measures concentrations of organic chemicals in the atmosphere. cTAG is the first instrument capable of measuring small, light chemicals as well as heavier chemicals and everything in between on a single detector, every hour. In this work we explain how cTAG works and some of the tests we performed to verify that it works properly and reliably. We also present measurements of alkanes that suggest they have three dominant sources in a Bay Area suburb.
Zhe Peng, Julia Lee-Taylor, Harald Stark, John J. Orlando, Bernard Aumont, and Jose L. Jimenez
Atmos. Chem. Phys., 21, 14649–14669, https://doi.org/10.5194/acp-21-14649-2021, https://doi.org/10.5194/acp-21-14649-2021, 2021
Short summary
Short summary
We use the fully explicit GECKO-A model to study the OH reactivity (OHR) evolution in the NO-free photooxidation of several volatile organic compounds. Oxidation progressively produces more saturated and functionalized species, then breaks them into small species. OHR per C atom evolution is similar for different precursors once saturated multifunctional species are formed. We also find that partitioning of these species to chamber walls leads to large deviations in chambers from the atmosphere.
Isaac Kwadjo Afreh, Bernard Aumont, Marie Camredon, and Kelley Claire Barsanti
Atmos. Chem. Phys., 21, 11467–11487, https://doi.org/10.5194/acp-21-11467-2021, https://doi.org/10.5194/acp-21-11467-2021, 2021
Short summary
Short summary
This is the first mechanistic modeling study of secondary organic aerosol (SOA) from the understudied monoterpene, camphene. The semi-explicit chemical model GECKO-A predicted camphene SOA yields that were ~2 times α-pinene. Using 50/50 α-pinene + limonene as a surrogate for camphene increased predicted SOA mass from biomass burning fuels by up to ~100 %. The accurate representation of camphene in air quality models can improve predictions of SOA when camphene is a dominant monoterpene.
Tommaso Galeazzo, Richard Valorso, Ying Li, Marie Camredon, Bernard Aumont, and Manabu Shiraiwa
Atmos. Chem. Phys., 21, 10199–10213, https://doi.org/10.5194/acp-21-10199-2021, https://doi.org/10.5194/acp-21-10199-2021, 2021
Short summary
Short summary
We simulate SOA viscosity with explicit modeling of gas-phase oxidation of isoprene and α-pinene. While the viscosity dependence on relative humidity and mass loadings is captured well by simulations, the model underestimates measured viscosity, indicating missing processes. Kinetic limitations and reduction in mass accommodation may cause an increase in viscosity. The developed model is powerful for investigation of the interplay among gas reactions, chemical composition and phase state.
Gabriel Isaacman-VanWertz and Bernard Aumont
Atmos. Chem. Phys., 21, 6541–6563, https://doi.org/10.5194/acp-21-6541-2021, https://doi.org/10.5194/acp-21-6541-2021, 2021
Short summary
Short summary
There are tens of thousands of different chemical compounds in the atmosphere. To tackle this complexity, there are a wide range of different methods to estimate their physical and chemical properties. We use these methods to understand how much the detailed structure of a molecule impacts its properties, and the extent to which properties can be estimated without knowing this level of detail. We find that structure matters, but methods lacking that level of detail still perform reasonably well.
Yutong Liang, Coty N. Jen, Robert J. Weber, Pawel K. Misztal, and Allen H. Goldstein
Atmos. Chem. Phys., 21, 5719–5737, https://doi.org/10.5194/acp-21-5719-2021, https://doi.org/10.5194/acp-21-5719-2021, 2021
Short summary
Short summary
This article reports the molecular composition of smoke particles people in SF Bay Area were exposed to during northern California wildfires in Oct. 2017. Major components are sugars, acids, aromatics, and terpenoids. These observations can be used to better understand health impacts of smoke exposure. Tracer compounds indicate which fuels burned, including diterpenoids for softwood and syringyls for hardwood. A statistical analysis reveals a group of secondary compounds formed in daytime aging.
Michael E. Jenkin, Richard Valorso, Bernard Aumont, Mike J. Newland, and Andrew R. Rickard
Atmos. Chem. Phys., 20, 12921–12937, https://doi.org/10.5194/acp-20-12921-2020, https://doi.org/10.5194/acp-20-12921-2020, 2020
Short summary
Short summary
Unsaturated organic compounds are emitted in large quantities from natural and human-influenced sources. Atmospheric removal occurs significantly by reaction with ozone, initiating reaction sequences forming free radicals and organic pollutants in the gaseous and particulate phases. Due to their very large number, it is impossible to study the reaction rate for every compound, and most have to be estimated. Updated and extended estimation methods are reported for use in atmospheric models.
Cited articles
Bé, A. G., Chase, H. M., Liu, Y., Upshur, M. A., Zhang, Y., Tuladhar, A., Chase, Z. A., Bellcross, A. D., Wang, H. F., Wang, Z., Batista, V. S., Martin, S. T., Thomson, R. J., and Geiger, F. M.: Atmospheric â-caryophyllene-derived ozonolysis products at interfaces, ACS Earth Sp. Chem., 3, 158–169, https://doi.org/10.1021/acsearthspacechem.8b00156, 2019.
Bentéjac, C., Csörgõ, A., and Martínez-Muñoz, G.: A
comparative analysis of gradient boosting algorithms, Artif. Intell. Rev.,
54, 1937–1967, https://doi.org/10.1007/s10462-020-09896-5, 2021.
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, 2021.
Breiman, L.: Random Forests, Mach. Learn., 45, 5–32,
https://doi.org/10.1023/A:1010933404324, 2001.
Compernolle, S., Ceulemans, K., and Müller, J.-F.: EVAPORATION: a new vapour pressure estimation methodfor organic molecules including non-additivity and intramolecular interactions, Atmos. Chem. Phys., 11, 9431–9450, https://doi.org/10.5194/acp-11-9431-2011, 2011.
Ditto, J. C., Barnes, E. B., Khare, P., Takeuchi, M., Joo, T., Bui, A. A.
T., Lee-Taylor, J., Eris, G., Chen, Y., Aumont, B., Jimenez, J. L., Ng, N.
L., Griffin, R. J., and Gentner, D. R.: An omnipresent diversity and
variability in the chemical composition of atmospheric functionalized
organic aerosol, Commun. Chem., 1, 75, https://doi.org/10.1038/s42004-018-0074-3, 2018.
Donahue, N. M., Robinson, A., Stanier, C. O., and Pandis, S. N.: Coupled
Partitioning, Dilution, and Chemical Aging of Semivolatile Organics,
Environ. Sci. Technol., 40, 2635–2643, https://doi.org/10.1021/ES052297C, 2006.
Eghbaldar, A., Forrest, T. P., and Cabrol-Bass, D.: Development of neural
networks for identification of structural features from mass spectral data,
Anal. Chim. Acta, 359, 283–301, https://doi.org/10.1016/S0003-2670(97)00663-6, 1998.
Franklin, E. B.: ebarnesey/Ch3MS-RF: Pre-Publication Main Release (v1.1.1), Zenodo [code, data set], https://doi.org/10.5281/zenodo.6320122, 2022.
Franklin, E. B., Alves, M. R., Moore, A. N., Kilgour, D. B., Novak, G. A.,
Mayer, K., Sauer, J. S., Weber, R. J., Dang, D., Winter, M., Lee, C., Cappa,
C. D., Bertram, T. H., Prather, K. A., Grassian, V. H., and Goldstein, A. H.:
Atmospheric Benzothiazoles in a Coastal Marine Environment, Environ. Sci.
Technol., 55, acs.est.1c04422, https://doi.org/10.1021/ACS.EST.1C04422, 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.
Goldstein, A. H., Worton, D. R., Williams, B. J., Hering, S. V, Kreisberg,
N. M., Panićpanić, O., and Górecki, T.:
Thermal desorption comprehensive two-dimensional gas chromatography for
in-situ measurements of organic aerosols, J. Chromatogr. A, 1186, 340–347,
https://doi.org/10.1016/j.chroma.2007.09.094, 2008.
Hamilton, J. F., Webb, P. J., Lewis, A. C., Hopkins, J. R., Smith, S., and Davy, P.: Partially oxidised organic components in urban aerosol using GCXGC-TOF/MS, Atmos. Chem. Phys., 4, 1279–1290, https://doi.org/10.5194/acp-4-1279-2004, 2004.
Hatch, L. E., Luo, W., Pankow, J. F., Yokelson, R. J., Stockwell, C. E., and Barsanti, K. C.: Identification and quantification of gaseous organic compounds emitted from biomass burning using two-dimensional gas chromatography–time-of-flight mass spectrometry, Atmos. Chem. Phys., 15, 1865–1899, https://doi.org/10.5194/acp-15-1865-2015, 2015.
Heald, C. L., Kroll, J. H., Jimenez, J. L., Docherty, K. S., DeCarlo, P. F.,
Aiken, A. C., Chen, Q., Martin, S. T., Farmer, D. K., and Artaxo, P.: A
simplified description of the evolution of organic aerosol composition in
the atmosphere, Geophys. Res. Lett., 37, https://doi.org/10.1029/2010GL042737, 2010.
Hunter, J. F., Day, D. A., Palm, B. B., Yatavelli, R. L. N., Chan, A. W. H.,
Kaser, L., Cappellin, L., Hayes, P. L., Cross, E. S., Carrasquillo, A. J.,
Campuzano-Jost, P., Stark, H., Zhao, Y., Hohaus, T., Smith, J. N., Hansel,
A., Karl, T., Goldstein, A. H., Guenther, A., Worsnop, D. R., Thornton, J.
A., Heald, C. L., Jimenez, J. L., and Kroll, J. H.: Comprehensive
characterization of atmospheric organic carbon at a forested site, Nat. Geosci., 10, 748–753, https://doi.org/10.1038/NGEO3018, 2017.
Isaacman, G., Kreisberg, N. M., Yee, L. D., Worton, D. R., Chan, A. W. H., Moss, J. A., Hering, S. V., and Goldstein, A. H.: Online derivatization for hourly measurements of gas- and particle-phase semi-volatile oxygenated organic compounds by thermal desorption aerosol gas chromatography (SV-TAG), Atmos. Meas. Tech., 7, 4417–4429, https://doi.org/10.5194/amt-7-4417-2014, 2014.
Isaacman-VanWertz, G. and Aumont, B.: Impact of organic molecular structure on the estimation of atmospherically relevant physicochemical parameters, Atmos. Chem. Phys., 21, 6541–6563, https://doi.org/10.5194/acp-21-6541-2021, 2021.
Isaacman-VanWertz, G., Yee, L. D., Kreisberg, N. M., Wernis, R., Moss, J.
A., Hering, S. V., De Sá, S. S., Martin, S. T., Alexander, M. L., Palm,
B. B., Hu, W., Campuzano-Jost, P., Day, D. A., Jimenez, J. L., Riva, M.,
Surratt, J. D., Viegas, J., Manzi, A., Edgerton, E., Baumann, K., Souza, R.,
Artaxo, P., and Goldstein, A. H.: Ambient Gas-Particle Partitioning of
Tracers for Biogenic Oxidation, Environ. Sci. Technol., 50, 9952–9962,
https://doi.org/10.1021/acs.est.6b01674, 2016.
Isaacman-Vanwertz, G., Massoli, P., O'Brien, R., Lim, C., Franklin, J. P.,
Moss, J. A., Hunter, J. F., Nowak, J. B., Canagaratna, M. R., Misztal, P.
K., Arata, C., Roscioli, J. R., Herndon, S. T., Onasch, T. B., Lambe, A. T.,
Jayne, J. T., Su, L., Knopf, D. A., Goldstein, A. H., Worsnop, D. R., and
Kroll, J. H.: Chemical evolution of atmospheric organic carbon over multiple
generations of oxidation, Nat. Chem., 10, 462–468,
https://doi.org/10.1038/s41557-018-0002-2, 2018.
Jen, C. N., Hatch, L. E., Selimovic, V., Yokelson, R. J., Weber, R., Fernandez, A. E., Kreisberg, N. M., Barsanti, K. C., and Goldstein, A. H.: Speciated and total emission factors of particulate organics from burning western US wildland fuels and their dependence on combustion efficiency, Atmos. Chem. Phys., 19, 1013–1026, https://doi.org/10.5194/acp-19-1013-2019, 2019.
Jimenez, J. L., Canagaratna, M. R., Donahue, N. M., Prevot, A. S. H., Zhang,
Q., Kroll, J. H., DeCarlo, P. F., Allan, J. D., Coe, H., Ng, N. L., Aiken,
A. C., Docherty, K. S., Ulbrich, I. M., Grieshop, A. P., Robinson, A. L.,
Duplissy, J., Smith, J. D., Wilson, K. R., Lanz, V. A., Hueglin, C., Sun, Y.
L., Tian, J., Laaksonen, A., Raatikainen, T., Rautiainen, J., Vaattovaara,
P., Ehn, M., Kulmala, M., Tomlinson, J. M., Collins, D. R., Cubison, M. J.,
E., Dunlea, J., Huffman, J. A., Onasch, T. B., Alfarra, M. R., Williams, P.
I., Bower, K., Kondo, Y., Schneider, J., Drewnick, F., Borrmann, S., Weimer,
S., Demerjian, K., Salcedo, D., Cottrell, L., Griffin, R., Takami, A.,
Miyoshi, T., Hatakeyama, S., Shimono, A., Sun, J. Y., Zhang, Y. M., Dzepina,
K., Kimmel, J. R., Sueper, D., Jayne, J. T., Herndon, S. C., Trimborn, A.
M., Williams, L. R., Wood, E. C., Middlebrook, A. M., Kolb, C. E.,
Baltensperger, U., and Worsnop, D. R.: Evolution of Organic Aerosols in the
Atmosphere, Science, 326, 1525–1529, https://doi.org/10.1126/SCIENCE.1180353, 2009.
Kroll, J. H., Donahue, N. M., Jimenez, J. L., Kessler, S. H., Canagaratna,
M. R., Wilson, K. R., Altieri, K. E., Mazzoleni, L. R., Wozniak, A. S.,
Bluhm, H., Mysak, E. R., Smith, J. D., Kolb, C. E., and Worsnop, D. R.:
Carbon oxidation state as a metric for describing the chemistry of
atmospheric organic aerosol, Nat. Chem., 3, 133–139,
https://doi.org/10.1038/nchem.948, 2011.
Li, Y., Pöschl, U., and Shiraiwa, M.: Molecular corridors and parameterizations of volatility in the chemical evolution of organic aerosols, Atmos. Chem. Phys., 16, 3327–3344, https://doi.org/10.5194/acp-16-3327-2016, 2016.
Liang, Y., Jen, C. N., Weber, R. J., Misztal, P. K., and Goldstein, A. H.: Chemical composition of PM2.5 in October 2017 Northern California wildfire plumes, Atmos. Chem. Phys., 21, 5719–5737, https://doi.org/10.5194/acp-21-5719-2021, 2021.
Martin, S. T., Artaxo, P., Machado, L. A. T., Manzi, A. O., Souza, R. A. F., Schumacher, C., Wang, J., Andreae, M. O., Barbosa, H. M. J., Fan, J., Fisch, G., Goldstein, A. H., Guenther, A., Jimenez, J. L., Pöschl, U., Silva Dias, M. A., Smith, J. N., and Wendisch, M.: Introduction: Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5), Atmos. Chem. Phys., 16, 4785–4797, https://doi.org/10.5194/acp-16-4785-2016, 2016.
Martin, S. T., Artaxo, P., Machado, L., Manzi, A. O., Souza, R. A. F.,
Schumacher, C., Wang, J., Biscaro, T., Brito, J., Calheiros, A., Jardine,
K., Medeiros, A., Portela, B., De Sá, S. S., Adachi, K., Aiken, A. C.,
Alblbrecht, R., Alexander, L., Andreae, M. O., Barbosa, H. M. J., Buseck,
P., Chand, D., Comstmstmstock, J. M., Day, D. A., Dubey, M., Fan, J.,
Fastst, J., Fisch, G., Fortner, E., Giangrande, S., Gilllles, M.,
Goldststein, A. H., Guenther, A., Hubbbbe, J., Jensen, M., Jimenez, J. L.,
Keutstsch, F. N., Kim, S., Kuang, C., Laskskin, A., McKinney, K., Mei, F.,
Millller, M., Nascimento, R., Pauliquevis, T., Pekour, M., Peres, J.,
Petäjä, T., Pöhlklker, C., Pöschl, U., Rizzo, L., Schmid,
B., Shilllling, J. E., Silva Dias, M. A., Smith, J. N., Tomlmlinson, J. M.,
Tóta, J., and Wendisch, M.: The Green Ocean Amazon Experiment
(GoAmazon2014/5) Observes Pollution Affecting Gases, Aerosols, Clouds, and
Rainfall over the Rain Forest, B. Am. Meteorol. Soc., 98, 981–997,
https://doi.org/10.1175/BAMS-D-15-00221.1, 2017.
Nannoolal, Y., Rarey, J., and Ramjugernath, D.: Estimation of pure component
properties: Part 3. Estimation of the vapor pressure of non-electrolyte
organic compounds via group contributions and group interactions, Fluid
Phase Equilib., 269, 117–133, https://doi.org/10.1016/J.FLUID.2008.04.020, 2008.
Nozière, B., Kalberer, M., Claeys, M., Allan, J., D'Anna, B., Decesari,
S., Finessi, E., Glasius, M., Grgiæ, I., Hamilton, J. F., Hoffmann, T.,
Iinuma, Y., Jaoui, M., Kahnt, A., Kampf, C. J., Kourtchev, I., Maenhaut, W.,
Marsden, N., Saarikoski, S., Schnelle-Kreis, J., Surratt, J. D., Szidat, S.,
Szmigielski, R., and Wisthaler, A.: The Molecular Identification of Organic
Compounds in the Atmosphere: State of the Art and Challenges, Chem. Rev.,
115, 3919–3983, https://doi.org/10.1021/CR5003485, 2015.
Pankow, J. F. and Asher, W. E.: SIMPOL.1: a simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds, Atmos. Chem. Phys., 8, 2773–2796, https://doi.org/10.5194/acp-8-2773-2008, 2008.
Rokach, L.: Decision forest: Twenty years of research, Inf. Fusion, 27,
111–125, https://doi.org/10.1016/J.INFFUS.2015.06.005, 2016.
Vinaixa, M., Schymanski, E. L., Neumann, S., Navarro, M., Salek, R. M., and
Yanes, O.: Mass spectral databases for LC/MS- and GC/MS-based metabolomics:
State of the field and future prospects, TrAC Trends Anal. Chem., 78,
23–35, https://doi.org/10.1016/J.TRAC.2015.09.005, 2016.
Whitmore, L. S., Davis, R. W., McCormick, R. L., Gladden, J. M., Simmons, B.
A., George, A., and Hudson, C. M.: BioCompoundML: A General Biofuel Property
Screening Tool for Biological Molecules Using Random Forest Classifiers,
Energ. Fuel., 30, 8410–8418, https://doi.org/10.1021/acs.energyfuels.6b01952, 2016.
Worton, D. R., Kreisberg, N. M., Isaacman, G., Teng, A. P., McNeish, C.,
Górecki, T., Hering, S. V., and Goldstein, A. H.: Thermal Desorption
Comprehensive Two-Dimensional Gas Chromatography: An Improved Instrument for
In-Situ Speciated Measurements of Organic Aerosols, Aerosol Sci. Tech., 46, 380–393, https://doi.org/10.1080/02786826.2011.634452, 2011.
Worton, D. R., Decker, M., Isaacman-VanWertz, G., Chan, A. W. H., Wilson, K.
R., and Goldstein, A. H.: Improved molecular level identification of organic
compounds using comprehensive two-dimensional chromatography, dual
ionization energies and high resolution mass spectrometry, Analyst, 142,
2395–2403, https://doi.org/10.1039/C7AN00625J, 2017.
Yee, L. D., Isaacman-VanWertz, G., Wernis, R. A., Meng, M., Rivera, V., Kreisberg, N. M., Hering, S. V., Bering, M. S., Glasius, M., Upshur, M. A., Gray Bé, A., Thomson, R. J., Geiger, F. M., Offenberg, J. H., Lewandowski, M., Kourtchev, I., Kalberer, M., de Sá, S., Martin, S. T., Alexander, M. L., Palm, B. B., Hu, W., Campuzano-Jost, P., Day, D. A., Jimenez, J. L., Liu, Y., McKinney, K. A., Artaxo, P., Viegas, J., Manzi, A., Oliveira, M. B., de Souza, R., Machado, L. A. T., Longo, K., and Goldstein, A. H.: Observations of sesquiterpenes and their oxidation products in central Amazonia during the wet and dry seasons, Atmos. Chem. Phys., 18, 10433–10457, https://doi.org/10.5194/acp-18-10433-2018, 2018.
Zhang, H., Yee, L. D., Lee, B. H., Curtis, M. P., Worton, D. R.,
Isaacman-VanWertz, G., Offenberg, J. H., Lewandowski, M., Kleindienst, T.
E., Beaver, M. R., Holder, A. L., Lonneman, W. A., Docherty, K. S., Jaoui,
M., Pye, H. O. T., Hu, W., Day, D. A., Campuzano-Jost, P., Jimenez, J. L.,
Guo, H., Weber, R. J., Gouw, J. de, Koss, A. R., Edgerton, E. S., Brune, W.,
Mohr, C., Lopez-Hilfiker, F. D., Lutz, A., Kreisberg, N. M., Spielman, S.
R., Hering, S. V., Wilson, K. R., Thornton, J. A., and Goldstein, A. H.:
Monoterpenes are the largest source of summertime organic aerosol in the
southeastern United States, P. Natl. Acad. Sci. USA, 115, 2038–2043,
https://doi.org/10.1073/PNAS.1717513115, 2018.
Short summary
The composition of atmospheric aerosols are extremely complex, containing hundreds of thousands of estimated individual compounds. The majority of these compounds have never been catalogued in widely used databases, making them extremely difficult for atmospheric chemists to identify and analyze. In this work, we present Ch3MS-RF, a machine-learning-based model to enable characterization of complex mixtures and prediction of structure-specific properties of unidentifiable organic compounds.
The composition of atmospheric aerosols are extremely complex, containing hundreds of thousands...