Articles | Volume 2, issue 2
https://doi.org/10.5194/ar-2-225-2024
© Author(s) 2024. 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-2-225-2024
© Author(s) 2024. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
18 Jul 2024
Research article |
| 18 Jul 2024
| 18 Jul 2024
Direct detection of polycyclic aromatic hydrocarbons on a molecular composition level in summertime ambient aerosol via proton transfer reaction mass spectrometry
Tobias Reinecke
IONICON Analytik GmbH, 6020 Innsbruck, Austria
Markus Leiminger
IONICON Analytik GmbH, 6020 Innsbruck, Austria
Andreas Klinger
IONICON Analytik GmbH, 6020 Innsbruck, Austria
IONICON Analytik GmbH, 6020 Innsbruck, Austria
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Cited articles
Agudelo-Castañeda, D. M., Teixeira, E. C., Schneider, I. L., Lara, S. R., and Silva, L. F. O.: Exposure to polycyclic aromatic hydrocarbons in atmospheric PM1.0 of urban environments: Carcinogenic and mutagenic respiratory health risk by age groups, Environ. Pollut., 224, 158–170, https://doi.org/10.1016/j.envpol.2017.01.075, 2017.
Arndt, D., Wachsmuth, C., Buchholz, C., and Bentley, M.: A complex matrix characterization approach, applied to cigarette smoke, that integrates multiple analytical methods and compound identification strategies for non-targeted liquid chromatography with high-resolution mass spectrometry, Rapid Commun. Mass Spectrom., 34, e8571, https://doi.org/10.1002/rcm.8571, 2020.
Borrás, E. and Tortajada-Genaro, L. A.: Characterisation of polycyclic aromatic hydrocarbons in atmospheric aerosols by gas chromatography-mass spectrometry, Anal. Chim. Acta, 583, 266–276, https://doi.org/10.1016/j.aca.2006.10.043, 2007.
Bosque, R. and Sales, J.: Polarizabilities of Solvents from the Chemical Composition, J. Chem. Inf. Comput. Sci., 42, 1154–1163, https://doi.org/10.1021/ci025528x, 2002.
Boutsidis, C. and Gallopoulos, E.: SVD based initialization: A head start for nonnegative matrix factorization, Pattern Recognition, 41, 1350–1362, https://doi.org/10.1016/j.patcog.2007.09.010, 2008.
Choi, H., Harrison, R., Komulainen, H., and Saborit, J. M. D.: Polycyclic aromatic hydrocarbons, in: WHO Guidelines for Indoor Air Quality: Selected Pollutants, World Health Organization, 289–346 pp., 2010.
Dorner, T. E., Brath, H., and Kautzky-Willer, A.: Sex-specific trends in smoking prevalence over seven years in different Austrian populations: results of a time-series cross-sectional analysis, BMJ Open, 10, e035235, https://doi.org/10.1136/bmjopen-2019-035235, 2020.
Dzepina, K., Arey, J., Marr, L. C., Worsnop, D. R., Salcedo, D., Zhang, Q., Onasch, T. B., Molina, L. T., Molina, M. J., and Jimenez, J. L.: Detection of particle-phase polycyclic aromatic hydrocarbons in Mexico City using an aerosol mass spectrometer, Int. J. Mass Spectro., 263, 152–170, https://doi.org/10.1016/j.ijms.2007.01.010, 2007.
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.
Eriksson, A. C., Nordin, E. Z., Nyström, R., Pettersson, E., Swietlicki, E., Bergvall, C., Westerholm, R., Boman, C., and Pagels, J. H.: Particulate PAH Emissions from Residential Biomass Combustion: Time-Resolved Analysis with Aerosol Mass Spectrometry, Environ. Sci. Technol., 48, 7143–7150, https://doi.org/10.1021/es500486j, 2014.
Graus, M., Müller, M., and Hansel, A.: High resolution PTR-TOF: Quantification and formula confirmation of VOC in real time, J. Am. Soc. Mass Spectrom., 21, 1037–1044, https://doi.org/10.1016/j.jasms.2010.02.006, 2010.
Gueneron, M., Erickson, M. H., VanderSchelden, G. S., and Jobson, B. T.: PTR-MS fragmentation patterns of gasoline hydrocarbons, Int. J. Mass Spectro., 379, 97–109, https://doi.org/10.1016/j.ijms.2015.01.001, 2015.
Hansel, A., Jordan, A., Holzinger, R., Prazeller, P., Vogel, W., and Lindinger, W.: Proton transfer reaction mass spectrometry: on-line trace gas analysis at the ppb level, Int. J. Mass Spectro. Ion Process., 149–150, 609–619, https://doi.org/10.1016/0168-1176(95)04294-U, 1995.
Herring, C. L., Faiola, C. L., Massoli, P., Sueper, D., Erickson, M. H., McDonald, J. D., Simpson, C. D., Yost, M. G., Jobson, B. T., and VanReken, T. M.: New Methodology for Quantifying Polycyclic Aromatic Hydrocarbons (PAHs) Using High-Resolution Aerosol Mass Spectrometry, Aerosol Sci. Technol., 49, 1131–1148, https://doi.org/10.1080/02786826.2015.1101050, 2015.
Karl, T., Gohm, A., Rotach, M. W., Ward, H. C., Graus, M., Cede, A., Wohlfahrt, G., Hammerle, A., Haid, M., Tiefengraber, M., Lamprecht, C., Vergeiner, J., Kreuter, A., Wagner, J., and Staudinger, M.: Studying Urban Climate and Air Quality in the Alps: The Innsbruck Atmospheric Observatory, B. Am. Meteorol. Soc., 101, E488–E507, https://doi.org/10.1175/BAMS-D-19-0270.1, 2020.
Kaur, S., Senthilkumar, K., Verma, V. K., Kumar, B., Kumar, S., Katnoria, J. K., and Sharma, C. S.: Preliminary Analysis of Polycyclic Aromatic Hydrocarbons in Air Particles (PM10) in Amritsar, India: Sources, Apportionment, and Possible Risk Implications to Humans, Arch. Environ. Contam. Toxicol., 65, 382–395, https://doi.org/10.1007/s00244-013-9912-6, 2013.
Laskin, J., Laskin, A., and Nizkorodov, S. A.: Mass Spectrometry Analysis in Atmospheric Chemistry, Anal. Chem., 90, 166–189, https://doi.org/10.1021/acs.analchem.7b04249, 2018.
Leglise, J., Müller, M., Piel, F., Otto, T., and Wisthaler, A.: Bulk Organic Aerosol Analysis by Proton-Transfer-Reaction Mass Spectrometry: An Improved Methodology for the Determination of Total Organic Mass, O:C and H:C Elemental Ratios, and the Average Molecular Formula, Anal. Chem., 91, 12619–12624, https://doi.org/10.1021/acs.analchem.9b02949, 2019.
Lung, S.-C. C. and Liu, C.-H.: Fast analysis of 29 polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs with ultra-high performance liquid chromatography-atmospheric pressure photoionization-tandem mass spectrometry, Sci. Rep., 5, 12992, https://doi.org/10.1038/srep12992, 2015.
Müller, M., Mikoviny, T., Jud, W., D'Anna, B., and Wisthaler, A.: A new software tool for the analysis of high resolution PTR-TOF mass spectra, Chemometr. Intell. Lab., 127, 158–165, https://doi.org/10.1016/j.chemolab.2013.06.011, 2013.
Müller, M., Eichler, P., D'Anna, B., Tan, W., and Wisthaler, A.: Direct Sampling and Analysis of Atmospheric Particulate Organic Matter by Proton-Transfer-Reaction Mass Spectrometry, Anal. Chem., 89, 10889–10897, https://doi.org/10.1021/acs.analchem.7b02582, 2017.
Müller, M., Piel, F., Gutmann, R., Sulzer, P., Hartungen, E., and Wisthaler, A.: A novel method for producing NH
Passig, J., Schade, J., Irsig, R., Kröger-Badge, T., Czech, H., Adam, T., Fallgren, H., Moldanova, J., Sklorz, M., Streibel, T., and Zimmermann, R.: Single-particle characterization of polycyclic aromatic hydrocarbons in background air in northern Europe, Atmos. Chem. Phys., 22, 1495–1514, https://doi.org/10.5194/acp-22-1495-2022, 2022.
Patel, A. B., Shaikh, S., Jain, K. R., Desai, C., and Madamwar, D.: Polycyclic Aromatic Hydrocarbons: Sources, Toxicity, and Remediation Approaches, Front. Microbiol., 11, 562813, https://doi.org/10.3389/fmicb.2020.562813, 2020.
Piel, F., Müller, M., Mikoviny, T., Pusede, S. E., and Wisthaler, A.: Airborne measurements of particulate organic matter by proton-transfer-reaction mass spectrometry (PTR-MS): a pilot study, Atmos. Meas. Tech., 12, 5947–5958, https://doi.org/10.5194/amt-12-5947-2019, 2019.
Piel, F., Müller, M., Winkler, K., Skytte af Sätra, J., and Wisthaler, A.: Introducing the extended volatility range proton-transfer-reaction mass spectrometer (EVR PTR-MS), Atmos. Meas. Tech., 14, 1355–1363, https://doi.org/10.5194/amt-14-1355-2021, 2021.
Poulain, L., Iinuma, Y., Müller, K., Birmili, W., Weinhold, K., Brüggemann, E., Gnauk, T., Hausmann, A., Löschau, G., Wiedensohler, A., and Herrmann, H.: Diurnal variations of ambient particulate wood burning emissions and their contribution to the concentration of Polycyclic Aromatic Hydrocarbons (PAHs) in Seiffen, Germany, Atmos. Chem. Phys., 11, 12697–12713, https://doi.org/10.5194/acp-11-12697-2011, 2011.
Reinecke, T., Leiminger, M., Jordan, A., Wisthaler, A., and Müller, M.: Ultrahigh Sensitivity PTR-MS Instrument with a Well-Defined Ion Chemistry, Anal. Chem., 95, 11879–11884, https://doi.org/10.1021/acs.analchem.3c02669, 2023.
Schade, J., Passig, J., Irsig, R., Ehlert, S., Sklorz, M., Adam, T., Li, C., Rudich, Y., and Zimmermann, R.: Spatially Shaped Laser Pulses for the Simultaneous Detection of Polycyclic Aromatic Hydrocarbons as well as Positive and Negative Inorganic Ions in Single Particle Mass Spectrometry, Anal. Chem., 91, 10282–10288, https://doi.org/10.1021/acs.analchem.9b02477, 2019.
Sekimoto, K., Li, S.-M., Yuan, B., Koss, A., Coggon, M., Warneke, C., and de Gouw, J.: Calculation of the sensitivity of proton-transfer-reaction mass spectrometry (PTR-MS) for organic trace gases using molecular properties, Int. J. Mass Spectro., 421, 71–94, https://doi.org/10.1016/j.ijms.2017.04.006, 2017.
Su, T. and Chesnavich, W. J.: Parametrization of the ion–polar molecule collision rate constant by trajectory calculations, The J. Chem. Phys., 76, 5183–5185, https://doi.org/10.1063/1.442828, 1982.
Thrane, K. E. and Mikalsen, A.: High-volume sampling of airborne polycyclic aromatic hydrocarbons using glass fibre filters and polyurethane foam, Atmos. Environ. (1967), 15, 909–918, https://doi.org/10.1016/0004-6981(81)90090-1, 1981.
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.
Wisthaler, A., Müller, M., Poulain, L., Piel, F., Gräfe, R., Spindler, G., Wiedensohler, A., and Herrmann, H.: Chemical Characterization of Particulate and Volatile Organic Compounds in the Rural Wintertime Atmosphere by CHARON PTR-ToF-MS, EGU General Assembly 2020, Online, 4–8 May 2020, EGU2020-19635, https://doi.org/10.5194/egusphere-egu2020-19635, 2020.
Xu, P., Yang, Y., Zhang, J., Gao, W., Liu, Z., Hu, B., and Wang, Y.: Characterization and source identification of submicron aerosol during serious haze pollution periods in Beijing, J. Environ. Sci., 112, 25–37, https://doi.org/10.1016/j.jes.2021.04.005, 2022.
Yassine, M. M., Harir, M., Dabek-Zlotorzynska, E., and Schmitt-Kopplin, P.: Structural characterization of organic aerosol using Fourier transform ion cyclotron resonance mass spectrometry: Aromaticity equivalent approach, Rapid Commun. Mass Spectro., 28, 2445–2454, https://doi.org/10.1002/rcm.7038, 2014.
Yuan, B., Koss, A. R., Warneke, C., Coggon, M., Sekimoto, K., and de Gouw, J. A.: Proton-Transfer-Reaction Mass Spectrometry: Applications in Atmospheric Sciences, Chem. Rev., 117, 13187–13229, https://doi.org/10.1021/acs.chemrev.7b00325, 2017.
Short summary
Condensed particulate polycyclic aromatic hydrocarbons (PAHs) are toxic compounds that may be detrimental to human health, even at low (sub-ng m-3) long-term exposure levels. The CHARON FUSION PTR-TOF 10k is capable of directly detecting PAHs on a chemical composition level at significantly lower mass concentrations. Herein, we report the time series of nine PAHs and identify three associated major sources and physicochemical processes for summertime aerosol in Innsbruck, Austria.
Condensed particulate polycyclic aromatic hydrocarbons (PAHs) are toxic compounds that may be...
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