Articles | Volume 15, issue 17
https://doi.org/10.5194/amt-15-5061-2022
© 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-15-5061-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
05 Sep 2022
Research article |
| 05 Sep 2022
| 05 Sep 2022
Comprehensive detection of analytes in large chromatographic datasets by coupling factor analysis with a decision tree
Sungwoo Kim
Charles E. Via Jr. Department of Civil and Environmental Engineering, Virginia Tech, Blacksburg, VA 24061, USA
Brian M. Lerner
Aerodyne Research, Inc., Billerica, MA 01821, USA
Donna T. Sueper
Aerodyne Research, Inc., Billerica, MA 01821, USA
Charles E. Via Jr. Department of Civil and Environmental Engineering, Virginia Tech, Blacksburg, VA 24061, USA
Related authors
No articles found.
Yugo Kanaya, Roberto Sommariva, Alfonso Saiz-Lopez, Andrea Mazzeo, Theodore K. Koenig, Kaori Kawana, James E. Johnson, Aurélie Colomb, Pierre Tulet, Suzie Molloy, Ian E. Galbally, Rainer Volkamer, Anoop Mahajan, John W. Halfacre, Paul B. Shepson, Julia Schmale, Hélène Angot, Byron Blomquist, Matthew D. Shupe, Detlev Helmig, Junsu Gil, Meehye Lee, Sean C. Coburn, Ivan Ortega, Gao Chen, James Lee, Kenneth C. Aikin, David D. Parrish, John S. Holloway, Thomas B. Ryerson, Ilana B. Pollack, Eric J. Williams, Brian M. Lerner, Andrew J. Weinheimer, Teresa Campos, Frank M. Flocke, J. Ryan Spackman, Ilann Bourgeois, Jeff Peischl, Chelsea R. Thompson, Ralf M. Staebler, Amir A. Aliabadi, Wanmin Gong, Roeland Van Malderen, Anne M. Thompson, Ryan M. Stauffer, Debra E. Kollonige, Juan Carlos Gómez Martin, Masatomo Fujiwara, Katie Read, Matthew Rowlinson, Keiichi Sato, Junichi Kurokawa, Yoko Iwamoto, Fumikazu Taketani, Hisahiro Takashima, Mónica Navarro-Comas, Marios Panagi, and Martin G. Schultz
Earth Syst. Sci. Data, 17, 4901–4932, https://doi.org/10.5194/essd-17-4901-2025, https://doi.org/10.5194/essd-17-4901-2025, 2025
Short summary
Short summary
The first comprehensive dataset of tropospheric ozone over oceans/polar regions is presented, including 77 ship/buoy and 48 aircraft campaign observations (1977–2022, 0–5000 m altitude), supplemented by ozonesonde and surface data. Air masses isolated from land for 72+ hours are systematically selected as essentially oceanic. Among the 11 global regions, they show daytime decreases of 11–16 % in the tropics, while near-zero depletions are rare, unlike in the Arctic, implying different mechanisms.
Ying Zhang, Yuwei Wang, Chuang Li, Yueyang Li, Sijia Yin, Megan S. Claflin, Brian M. Lerner, Douglas Worsnop, and Lin Wang
Atmos. Meas. Tech., 18, 3547–3568, https://doi.org/10.5194/amt-18-3547-2025, https://doi.org/10.5194/amt-18-3547-2025, 2025
Short summary
Short summary
This study provides insight into how individual ions measured by proton-transfer-reaction (PTR) mass spectrometry are produced by multiple volatile organic compounds (VOCs). A reference table is provided for attributing the PTR signal to contributing VOC species. The signals are grouped according to the complexity of their potential identities. We find that a number of signal ions such as C6H7+ for benzene and C5H9+ for isoprene merely give an upper limit of their corresponding concentrations.
Namrata Shanmukh Panji, Deborah F. McGlynn, Laura E. R. Barry, Todd M. Scanlon, Manuel T. Lerdau, Sally E. Pusede, and Gabriel Isaacman-VanWertz
Atmos. Chem. Phys., 24, 12495–12507, https://doi.org/10.5194/acp-24-12495-2024, https://doi.org/10.5194/acp-24-12495-2024, 2024
Short summary
Short summary
Climate change will bring about changes in parameters that are currently used in global-scale models to calculate biogenic emissions. This study seeks to understand the factors driving these models by comparing long-term datasets of biogenic compounds to modeled emissions. We note that the light-dependent fractions currently used in models do not accurately represent regional observations. We provide evidence for the time-dependent variation in this parameter for future modifications to models.
Chuanyang Shen, Xiaoyan Yang, Joel Thornton, John Shilling, Chenyang Bi, Gabriel Isaacman-VanWertz, and Haofei Zhang
Atmos. Chem. Phys., 24, 6153–6175, https://doi.org/10.5194/acp-24-6153-2024, https://doi.org/10.5194/acp-24-6153-2024, 2024
Short summary
Short summary
In this work, a condensed multiphase isoprene oxidation mechanism was developed to simulate isoprene SOA formation from chamber and field studies. Our results show that the measured isoprene SOA mass concentrations can be reasonably reproduced. The simulation results indicate that multifunctional low-volatility products contribute significantly to total isoprene SOA. Our findings emphasize that the pathways to produce these low-volatility species should be considered in models.
Delaney B. Kilgour, Gordon A. Novak, Megan S. Claflin, Brian M. Lerner, and Timothy H. Bertram
Atmos. Chem. Phys., 24, 3729–3742, https://doi.org/10.5194/acp-24-3729-2024, https://doi.org/10.5194/acp-24-3729-2024, 2024
Short summary
Short summary
Laboratory experiments with seawater mimics suggest ozone deposition to the surface ocean can be a source of reactive carbon to the marine atmosphere. We conduct both field and laboratory measurements to assess abiotic VOC composition and yields from ozonolysis of real surface seawater. We show that C5–C11 aldehydes contribute to the observed VOC emission flux. We estimate that VOCs generated by the ozonolysis of surface seawater are competitive with biological VOC production and emission.
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.
James F. Hurley, Alejandra Caceres, Deborah F. McGlynn, Mary E. Tovillo, Suzanne Pinar, Roger Schürch, Ksenia Onufrieva, and Gabriel Isaacman-VanWertz
Atmos. Meas. Tech., 16, 4681–4692, https://doi.org/10.5194/amt-16-4681-2023, https://doi.org/10.5194/amt-16-4681-2023, 2023
Short summary
Short summary
Volatile organic compounds (VOCs) have a wide range of sources and impacts on environments and human health that make them spatially, temporally, and chemically varied. Current methods lack the ability to collect samples in ways that provide spatial and chemical resolution without complex, costly instrumentation. We describe and validate a low-cost, portable VOC sampler and demonstrate its utility in collecting distributed coordinated samples.
Namrata Shanmukh Panji and Gabriel Isaacman-VanWertz
Atmos. Meas. Tech., 16, 4319–4330, https://doi.org/10.5194/amt-16-4319-2023, https://doi.org/10.5194/amt-16-4319-2023, 2023
Short summary
Short summary
Measuring volatile organic compounds (VOCs) in the atmosphere is crucial for understanding air quality and environmental impact. Since these compounds are present in low concentrations, preconcentration of samples is often necessary for accurate detection. To address this issue, we have developed a novel inlet that uses selective permeation to concentrate organic gases in small sample flows. This device offers a promising approach for accurately detecting low levels of VOCs in the atmosphere.
Michael P. Vermeuel, Gordon A. Novak, Delaney B. Kilgour, Megan S. Claflin, Brian M. Lerner, Amy M. Trowbridge, Jonathan Thom, Patricia A. Cleary, Ankur R. Desai, and Timothy H. Bertram
Atmos. Chem. Phys., 23, 4123–4148, https://doi.org/10.5194/acp-23-4123-2023, https://doi.org/10.5194/acp-23-4123-2023, 2023
Short summary
Short summary
Reactive carbon species emitted from natural sources such as forests play an important role in the chemistry of the atmosphere. Predictions of these emissions are based on plant responses during the growing season and do not consider potential effects from seasonal changes. To address this, we made measurements of reactive carbon over a forest during the summer to autumn transition. We learned that observed concentrations and emissions for some key species are larger than model predictions.
Deborah F. McGlynn, Graham Frazier, Laura E. R. Barry, Manuel T. Lerdau, Sally E. Pusede, and Gabriel Isaacman-VanWertz
Biogeosciences, 20, 45–55, https://doi.org/10.5194/bg-20-45-2023, https://doi.org/10.5194/bg-20-45-2023, 2023
Short summary
Short summary
Using a custom-made gas chromatography flame ionization detector, 2 years of speciated hourly biogenic volatile organic compound data were collected in a forest in central Virginia. We identify diurnal and seasonal variability in the data, which is shown to impact atmospheric oxidant budgets. A comparison with emission models identified discrepancies with implications for model outcomes. We suggest increased monitoring of speciated biogenic volatile organic compounds to improve modeled results.
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
Short summary
Short summary
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.
Deborah F. McGlynn, Laura E. R. Barry, Manuel T. Lerdau, Sally E. Pusede, and Gabriel Isaacman-VanWertz
Atmos. Chem. Phys., 21, 15755–15770, https://doi.org/10.5194/acp-21-15755-2021, https://doi.org/10.5194/acp-21-15755-2021, 2021
Short summary
Short summary
We present 1 year of hourly measurements of chemically resolved Biogenic volatile organic compound (BVOCs) between 15 September 2019 and 15 September 2020, collected at a research tower in central Virginia. Concentrations of a range of BVOCs are described and examined for their impact on atmospheric reactivity. The majority of reactivity comes from α-pinene and limonene, highlighting the importance of both concentration and structure in assessing atmospheric impacts of emissions.
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
Short summary
Short summary
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.
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
Short summary
Short summary
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.
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.
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
Short summary
Short summary
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
Amigo, J. M., Popielarz, M. J., Callejon, R. M., Morales, M. L., Troncoso, A. M., Petersen, M. A., and Toldam-Andersen, T. B.:
Comprehensive analysis of chromatographic data by using PARAFAC2 and principal components analysis, J. Chromatogr. A, 1217, 4422–4429, https://doi.org/10.1016/j.chroma.2010.04.042, 2010.
Anderson, A. H., Gibb, T. C., and Littlewood, A. B.:
Computer Resolution of Unresolved Convoluted Gas-Chromatographic Peaks, J. Chromatogr. Sci., 8, 640–646, https://doi.org/10.1093/chromsci/8.11.640, 1970.
Apel, E. C., Hills, A. J., Lueb, R., Zindel, S., Eisele, S., and Riemer, D. D.:
A fast-GC/MS system to measure C2 to C4 carbonyls and methanol aboard aircraft, J. Geophys. Res., 108, 8794, https://doi.org/10.1029/2002JD003199, 2003.
Bertsch, W.:
Two-Dimensional Gas Chromatography. Concepts, Instrumentation, and Applications – Part 1: Fundamentals, Conventional Two-Dimensional Gas Chromatography, Selected Applications, J. High Res. Chromatog., 22, 647–665, https://doi.org/10.1002/(SICI)1521-4168(19991201)22:12<647::AID-JHRC647>3.0.CO;2-V, 1999.
Blaško, J., Kubinec, R., Ostrovský, I., Pavlíková, E., Krupčík, J., and Soják, L.:
Chemometric deconvolution of gas chromatographic unresolved conjugated linoleic acid isomers triplet in milk samples, J. Chromatogr. A, 1216, 2757–2761, https://doi.org/10.1016/j.chroma.2008.11.019, 2009.
Claeys, M., Wang, W., Ion, A. C., Kourtchev, I., Gelencsér, A., and Maenhaut, W.:
Formation of secondary organic aerosols from isoprene and its gas-phase oxidation products through reaction with hydrogen peroxide, Atmos. Environ., 38, 4093–4098, https://doi.org/10.1016/j.atmosenv.2004.06.001, 2004.
Department of Energy Atmospheric Radiation Measurement (DOE ARM): Observations and modeling of the Green Ocean AMAZON (GOAMAZON), DOE ARM, https://iop.archive.arm.gov/arm-iop/2014/mao/goamazon/T3/goldstein-svtag/,
last access: 13 August 2022.
Di Marco, V. B. and Bombi, G. G.:
Mathematical functions for the representation of chromatographic peaks, J. Chromatogr. A, 931, 1–30, https://doi.org/10.1016/S0021-9673(01)01136-0, 2001.
Eilers, P. H. C.:
Parametric Time Warping, Anal. Chem., 76, 404–411, https://doi.org/10.1021/ac034800e, 2004.
Filer, C. N.:
Isotopic fractionation of organic compounds in chromatography, J. Labelled Compd. Rad., 42, 169–197, https://doi.org/10.1002/(SICI)1099-1344(199902)42:2<169::AID-JLCR178>3.0.CO;2-0, 1999.
Goldan, P. D., Kuster, W. C., Williams, E., Murphy, P. C., Fehsenfeld, F. C., and Meagher, J.:
Nonmethane hydrocarbon and oxy hydrocarbon measurements during the 2002 New England Air Quality Study, J. Geophys. Res., 109, D21309, https://doi.org/10.1029/2003JD004455, 2004.
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.
Grace, D. N., Sebold, M. B., and Galloway, M. M.:
Separation and detection of aqueous atmospheric aerosol mimics using supercritical fluid chromatography–mass spectrometry, Atmos. Meas. Tech., 12, 3841–3851, https://doi.org/10.5194/amt-12-3841-2019, 2019.
Hamilton, J. F.:
Using Comprehensive Two-Dimensional Gas Chromatography to Study the Atmosphere, J. Chromatogr. Sci., 48, 274–282, https://doi.org/10.1093/chromsci/48.4.274, 2010.
Hoggard, J. C. and Synovec, R. E.:
Parallel Factor Analysis (PARAFAC) of Target Analytes in GC × GC-TOFMS Data: Automated Selection of a Model with an Appropriate Number of Factors, Anal. Chem., 79, 1611–1619, https://doi.org/10.1021/ac061710b, 2007.
Hornbrook, R. S., Blake, D. R., Diskin, G. S., Fried, A., Fuelberg, H. E., Meinardi, S., Mikoviny, T., Richter, D., Sachse, G. W., Vay, S. A., Walega, J., Weibring, P., Weinheimer, A. J., Wiedinmyer, C., Wisthaler, A., Hills, A., Riemer, D. D., and Apel, E. C.:
Observations of nonmethane organic compounds during ARCTAS – Part 1: Biomass burning emissions and plume enhancements, Atmos. Chem. Phys., 11, 11103–11130, https://doi.org/10.5194/acp-11-11103-2011, 2011.
Hubert, M., Van Kerckhoven, J., and Verdonck, T.:
Robust PARAFAC for incomplete data, J. Chemometr., 26, 290–298, https://doi.org/10.1002/cem.2452, 2012.
Hübschmann, H.-J.: Fundamentals, in: Handbook of GC‐MS, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany, 7-354, https://doi.org/10.1002/9783527674305.ch2, 2015.
Isaacman, G., Kreisberg, N. M., Worton, D. R., Hering, S. V., and Goldstein, A. H.:
A versatile and reproducible automatic injection system for liquid standard introduction: application to in-situ calibration, Atmos. Meas. Tech., 4, 1937–1942, https://doi.org/10.5194/amt-4-1937-2011, 2011.
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., Yee, L. D., Kreisberg, N. M., Wernis, R., Moss, J. A., Hering, S. V., de Sa, 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., Sueper, D. T., Aikin, K. C., Lerner, B. M., Gilman, J. B., de Gouw, J. A., Worsnop, D. R., and Goldstein, A. H.:
Automated single-ion peak fitting as an efficient approach for analyzing complex chromatographic data, J. Chromatogr. A, 1529, 81–92, https://doi.org/10.1016/j.chroma.2017.11.005, 2017.
Isaacman-VanWertz, G., Lerner, B. M., and Sueper, D. T.: TAG Explorer and iNtegration (TERN) (v.2.2.20-beta), Zenodo [code], https://doi.org/10.5281/zenodo.6940761, 2022.
Jeansonne, M. and Foley, J.: Review of the Exponentially Modified Gaussian (EMG) Function Since 1983, J. Chromatogr. Sci., 29, 258–266, https://doi.org/10.1093/chromsci/29.6.258, 1991.
Johnsen, L. G., Amigo, J. M., Skov, T., and Bro, R.:
Automated resolution of overlapping peaks in chromatographic data, J. Chemometr., 28, 71–82, https://doi.org/10.1002/cem.2575, 2013.
Kassidas, A., Macgregor, J. F., and Taylor, P. A.:
Synchronization of batch trajectories using dynamic time warping, AIChE J., 44, 864–875, 1998.
Lerner, B. M.: aerodyneresearch/TERN: Version 2.2.20, beta (Igor 9 compatible) (v.2.2.20-beta), Zenodo [code], https://doi.org/10.5281/zenodo.6940761, 2022.
Lerner, B. M., Gilman, J. B., Aikin, K. C., Atlas, E. L., Goldan, P. D., Graus, M., Hendershot, R., Isaacman-VanWertz, G. A., Koss, A., Kuster, W. C., Lueb, R. A., McLaughlin, R. J., Peischl, J., Sueper, D., Ryerson, T. B., Tokarek, T. W., Warneke, C., Yuan, B., and de Gouw, J. A.:
An improved, automated whole air sampler and gas chromatography mass spectrometry analysis system for volatile organic compounds in the atmosphere, Atmos. Meas. Tech., 10, 291–313, https://doi.org/10.5194/amt-10-291-2017, 2017.
Li, H., Almeida, T. G., Luo, Y., Zhao, J., Palm, B. B., Daub, C. D., Huang, W., Mohr, C., Krechmer, J. E., Kurtén, T., and Ehn, M.:
Fragmentation inside proton-transfer-reaction-based mass spectrometers limits the detection of ROOR and ROOH peroxides, Atmos. Meas. Tech., 15, 1811–1827, https://doi.org/10.5194/amt-15-1811-2022, 2022.
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.
Meyer, M. R., Peters, F. T., and Maurer, H. H.:
Automated Mass Spectral Deconvolution and Identification System for GC-MS Screening for Drugs, Poisons, and Metabolites in Urine, Clin. Chem., 56, 575–584, https://doi.org/10.1373/clinchem.2009.135517, 2010.
Mydlová-Memersheimerová, J., Tienpont, B., David, F., Krupcik, J., and Sandra, P.:
Gas chromatography of 209 polychlorinated biphenyl congeners on an extremely efficient nonselective capillary column, J. Chromatogr. A, 1216, 6043–6062, https://doi.org/10.1016/j.chroma.2009.06.049, 2009.
Naish, P. J. and Hartwell, S.:
Exponentially Modified Gaussian functions – A good model for chromatographic peaks in isocratic HPLC?, Chromatographia, 26, 285–296, https://doi.org/10.1007/BF02268168, 1988.
Nielsen, N.-P. V., Carstensen, J. M., and Smedsgaard, J.:
Aligning of single and multiple wavelength chromatographic profiles for chemometric data analysis using correlation optimised warping, J. Chromatogr. A, 805, 17–35, https://doi.org/10.1016/S0021-9673(98)00021-1, 1998.
Paatero, P.:
Least squares formulation of robust non-negative factor analysis, Chemometr. Intell. Lab., 37, 23–35, https://doi.org/10.1016/S0169-7439(96)00044-5, 1997.
Paatero, P. and Hopke, P. K.:
Rotational tools for factor analytic models, J. Chemometr., 23, 91–100, https://doi.org/10.1002/cem.1197, 2009.
Paatero, P. and Tapper, U.:
Positive matrix factorization: A non-negative factor model with optimal utilization of error estimates of data values, Environmetrics, 5, 111–126, https://doi.org/10.1002/env.3170050203, 1994.
Phillips, J. and Beens, J.:
Comprehensive Two-dimensional Gas Chromatography: A Hyphenated Method with Strong Coupling between the Two Dimensions, J. Chromatogr. A, 856, 331–347, https://doi.org/10.1016/S0021-9673(99)00815-8, 1999.
Potgieter, H., Bekker, R., Govender, A., and Rohwer, E.:
Two-dimensional gas chromatography-online hydrogenation for improved characterization of petrochemical samples, J. Chromatogr. A, 1445, 118–125, https://doi.org/10.1016/j.chroma.2016.03.024, 2016.
Skov, T. and Bro, R.:
Solving fundamental problems in chromatographic analysis, Anal. Bioanal. Chem., 390, 281–285, https://doi.org/10.1007/s00216-007-1618-z, 2008.
Stein, S. E.:
Estimating probabilities of correct identification from results of mass spectral library searches, J. Am. Soc. Mass Spectr., 5, 316–323, https://doi.org/10.1016/1044-0305(94)85022-4, 1994.
Stein, S. E.:
National Institute and Standards and Technology (NIST) Mass Spectral Search Program, National Institute of Standards and Technology, https://chemdata.nist.gov/mass-spc/ms-search/docs/Ver20Man.pdf (last access: 10 February 2022), 2008.
Stein, S. E.: NIST/EPA/NIH Mass Spectral Library with Search Program Data Version: NIST v20 Software Version: 2.4, National Institute of Standards and Technology, https://doi.org/10.18434/T4H594, 2014.
Surratt, J. D., Chan, A. W. H., Eddingsaas, N. C., Chan, M., Loza, C. L., Kwan, A. J., Hersey, S. P., Flagan, R. C., Wennberg, P. O., and Seinfeld, J. H.:
Reactive intermediates revealed in secondary organic aerosol formation from isoprene, P. Natl. Acad. Sci. USA, 107, 6640, https://doi.org/10.1073/pnas.0911114107, 2010.
Tukey, J. W.:
Exploratory data analysis, Addison-Wesley series in behavioral science, Addison-Wesley Pub. Co., Reading, Mass., 1977.
Ulbrich, I. M., Canagaratna, M. R., Zhang, Q., Worsnop, D. R., and Jimenez, J. L.:
Interpretation of organic components from Positive Matrix Factorization of aerosol mass spectrometric data, Atmos. Chem. Phys., 9, 2891–2918, https://doi.org/10.5194/acp-9-2891-2009, 2009.
Valleix, A., Carrat, S., Caussignac, C., Leonce, E., and Tchapla, A.:
Secondary isotope effects in liquid chromatography behaviour of 2H and 3H labelled solutes and solvents, J. Chromatogr. A, 1116, 109–126, https://doi.org/10.1016/j.chroma.2006.03.078, 2006.
van Nederkassel, A. M., Daszykowski, M., Eilers, P. H., and Heyden, Y. V.:
A comparison of three algorithms for chromatograms alignment, J. Chromatogr. A, 1118, 199–210, https://doi.org/10.1016/j.chroma.2006.03.114, 2006.
Wang, W., Kourtchev, I., Graham, B., Cafmeyer, J., Maenhaut, W., and Claeys, M.:
Characterization of oxygenated derivatives of isoprene related to 2-methyltetrols in Amazonian aerosols using trimethylsilylation and gas chromatography/ion trap mass spectrometry, Rapid Commun. Mass Sp., 19, 1343–1351, https://doi.org/10.1002/rcm.1940, 2005.
Williams, B., Goldstein, A., Kreisberg, N., and Hering, S.:
An In-Situ Instrument for Speciated Organic Composition of Atmospheric Aerosols: Thermal Desorption A erosol G C/MS-FID (TAG), Aerosol Sci. Tech., 40, 627–638, https://doi.org/10.1080/02786820600754631, 2006.
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, 2012.
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.
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. d., 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.
Zhang, W., Wu, P., and Li, C.:
Study of automated mass spectral deconvolution and identification system (AMDIS) in pesticide residue analysis, Rapid Commun. Mass Sp., 20, 1563–1568, https://doi.org/10.1002/rcm.2473, 2006.
Zhang, Y., Williams, B. J., Goldstein, A. H., Docherty, K., Ulbrich, I. M., and Jimenez, J. L.:
A Technique for Rapid Gas Chromatography Analysis Applied to Ambient Organic Aerosol Measurements from the Thermal Desorption Aerosol Gas Chromatograph (TAG), Aerosol Sci. Tech., 48, 1166–1182, https://doi.org/10.1080/02786826.2014.967832, 2014.
Zhao, Y., Kreisberg, N. M., Worton, D. R., Teng, A. P., Hering, S. V., and Goldstein, A. H.:
Development of an In Situ Thermal Desorption Gas Chromatography Instrument for Quantifying Atmospheric Semi-Volatile Organic Compounds, Aerosol Sci. Tech., 47, 258–266, https://doi.org/10.1080/02786826.2012.747673, 2013.
Short summary
Atmospheric samples can be complex, and current analysis methods often require substantial human interaction and discard potentially important information. To improve analysis accuracy and computational cost of these large datasets, we developed an automated analysis algorithm that utilizes a factor analysis approach coupled with a decision tree. We demonstrate that this algorithm cataloged approximately 10 times more analytes compared to a manual analysis and in a quarter of the analysis time.
Atmospheric samples can be complex, and current analysis methods often require substantial human...
