ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-8977-2011 Technical Note: In-situ derivatization thermal desorption GC-TOFMS for direct analysis of particle-bound non-polar and polar organic species Orasche J. 1 2 3 Schnelle-Kreis J. 2 Abbaszade G. 2 Zimmermann R. 2 3 Department of Sedimentology & Environmental Geology, Georg-August-University, Göttingen, Germany Joint Mass Spectrometry Centre – Cooperation Group "Comprehensive Molecular Analytics", Helmholtz Zentrum München, Neuherberg, Germany Joint Mass Spectrometry Centre – Institute of Chemistry, Division of Analytical and Technical Chemistry, University of Rostock, Rostock, Germany 02 09 2011 11 17 8977 8993 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/11/8977/2011/acp-11-8977-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/8977/2011/acp-11-8977-2011.pdf

An in-situ derivatization thermal desorption method followed by gas chromatography and time-of-flight mass spectrometry (IDTD-GC-TOFMS) was developed for determination of polar organic compounds together with non-polar compounds in one measurement. Hydroxyl and carboxyl groups of compounds such as anhydrous sugars, alcohols and phenols, fatty acids and resin acids are targets of the derivatization procedure. Derivatization is based on silylation with N-Methyl-N-trimethylsilyl-trifluoroacetamide (MSTFA) during the step of thermal desorption. The high temperature of 300 °C during desorption is utilized for the in-situ derivatization on the collection substrate (quartz fibre filters) accelerating the reaction rate. Thereby, the analysis time is as short as without derivatization. At first the filter surface is dampened with derivatization reagent before insertion of the sample into the thermal desorption unit. To ensure ongoing derivatization during thermal desorption the carrier gas is enriched with MSTFA until the desorption procedure is finished. The precisions of all studied analytes were below 17 % within a calibration range from 22 pg (abietic acid) up to 342 ng (levoglucosan). Limits of quantification (LOQ) for polycyclic aromatic hydrocarbons (PAH) were between 1 pg (fluoranthene) and 8 pg (indeno[1,2,3-cd]pyrene), for resin acids 37–102 pg and for studied phenols 4–144 pg. LOQ for levoglucosan was 17 pg.

 References Bari, M. A., Baumbach, G., Kuch, B., and Scheffknecht, G.: Wood smoke as a source of particle-phase organic compounds in residential areas, Atmos. Environ., 43, 4722–4732, 2009. Bates, M., Bruno, P., Caputi, M., Caselli, M., de Gennaro, G., and Tutino, M.: Analysis of polycyclic aromatic hydrocarbons (PAHs) in airborne particles by direct sample introduction thermal desorption GC/MS, Atmos. Environ., 42, 6144–6151, 2008. Beiner, K., Plewka, A., Haferkorn, S., Iinuma, Y., Engewald, W., and Herrmann, H.: Quantification of organic acids in pariculate matter by coupling of thermally assisted hydrolysis and methylation with thermodesorption-gas chromatography-mass spectrometry, J. Chromatogr. A, 1216, 6642–6650, 2009. Blau, K. and King, G. S.: Handbook of Derivatives for Chromatography, Heyden & Son Ltd., London, UK, 1977. Böge, O., Miao, Y., Plewka, A., and Herrmann, H.: Formation of secondary organic particle phase compounds from isoprene gas-phase oxidation products: An aerosol chamber and field study, Atmos. Environ., 40, 2501–2509, 2006. Chandramouli, B., Jang, M., and Kamens, R. M.: Gas-particle partitioning of semivolatile organic compounds (SOCs) on mixtures of aerosols in a smog chamber, Environ. Sci. Technol., 37, 4113–4121, 2003. Chiappini, L., Perraudin, E., Durand-Jolibois, R., and Doussin, J.: Development of a supercritical fluid extraction–gas chromatography–mass spectrometry method for the identification of highly polar compounds in secondary organic aerosols formed from biogenic hydrocarbons in smog chamber experiments, Analyt. Bioanalyt. Chem., 386, 1749–1759, 2006. Chow, J. C., Yu, J. Z., Watson, J. G., Hang Ho, S. S., Bohannan, T. L., Hays, M. D., and Fung, K. K.: The application of thermal methods for determining chemical composition of carbonaceous aerosols: A review, J. Environ. Sci. Health, 42, 1521–1541, 2007. Ding, L. C., Ke, F., Wang, D. K. W., Dann, T., and Austin, C. C.: A new direct thermal desorption-GC/MS method: Organic speciation of ambient particulate matter collected in Golden, BC, Atmos. Environ., 43, 4894–4902, 2009. Donahue, N. M., Robinson, A. L., and Pandis, S. N.: Atmospheric organic particulate matter: From smoke to secondary organic aerosol, Atmos. Environ., 43, 94–106, 2009. Dutton, S. J., Williams, D. E., Garcia, J. K., Vedal, S., and Hannigan, M. P.: PM$_2.5$ characterization for time series studies: Organic molecular marker speciation methods and observations from daily measurements in denver, Atmos. Environ., 43, 2008–2013, 2009. Edney, E. O., Kleindienst, T. E., Conver, T. S., McIver, C. D., Corse, E. W., and Weathers, W. S.: Polar organic oxygenates in PM$_2.5$ at a southeastern site in the United States, Atmos. Environ., 37, 3947–3965, 2003. Edney, E. O., Kleindienst, T. E., Jaoui, M., Lewandowski, M., Offenberg, J. H., Wang, W., Claeys, M.: Formation of 2-methyl tetrols and 2-methylglyceric acid in secondary organic aerosol from laboratory irradiated isoprene/NO<sub>x</sub>/SO<sub>2</sub>/air mixtures and their detection in ambient PM$_2.5$ samples collected in the eastern United States, Atmos. Environ., 39, 5281–5289, 2005. Fabbri, D., Prati, S., and Vassura, I.: Molecular characterisation of organic material in air fine particles (PM$_10)$ using conventional and reactive pyrolysis-gas chromatography-mass spectrometry, J. Environ. Monitor., 4, 210–215, 2002. Falkovich, A. H. and Rudich, Y.: Analysis of semivolatile organic compounds in atmospheric aerosols by direct sample introduction thermal desorption GC/MS, Environ. Sci. Technol., 35, 2326–2333, 2001. Fine, P. M., Cass, G. R., and Simoneit, B. R. T.: Chemical characterization of fine particle emissions from fireplace combustion of woods grown in the northeastern United States, Environ. Sci. Technol., 35, 2665–2675, 2001. Fine, P. M., Cass, G. R., and Simoneit, B. R. T.: Chemical characterization of fine particle emissions from the fireplace combustion of woods grown in the southern United States, Environ. Sci. Technol., 36, 1442–1451, 2002. Fine, P. M., Cass, G. R., and Simoneit, B. R. T.: Chemical characterization of fine particle emissions from the fireplace combustion of wood types grown in the midwestern and western United States, Environ. Eng. Sci., 21, 387–409, 2004. Gil-Moltó, J., Vareaa, M., Galindoa, N., and Crespo, J.: Application of an automatic thermal desorption-gas chromatography-mass spectrometry system for the analysis of polycyclic aromatic hydrocarbons in airborne particulate matter, J. Chromatogr. A, 1216, 1285–1289, 2009. Goldstein, A. H., Worton, D. R., Williams, B. J., Hering, S. V., Kreisberg, N. M., Panic, O., Gorecki, T.: Thermal desorption comprehensive two-dimensional gas chromatography for in-situ measurements of organic aerosols, J. Chromatogr. A, 1186, 340–347, 2008. Graham, B., Mayol-Bracero, O. L., Guyon, P., Roberts, G. C., Decesari, S., Facchini, M. C., Artaxo, P., Maenhaut, W., Köll, P., and Andreae, M. O.: Water-soluble organic compounds in biomass burning aerosols over amazonia – 1. Characterization by NMR and GC-MS, J. Geophys. Res., 107, 8047, http://dx.doi.org/10.1029/2001jd000336doi:10.1029/2001jd000336, 2002. Graham, B., Guyon, P., Taylor, P. E., Artaxo, P., Maenhaut, W., Glovsky, M. M., Flagan, R. C., and Andreae, M. O.: Organic compounds present in the natural amazonian aerosol: Characterization by gas chromatography-mass spectrometry, J. Geophys. Res., 108, 4766, http://dx.doi.org/10.1029/2003jd003990doi:10.1029/2003jd003990, 2003. Guenther, A., Hewitt, C. N., Erickson, D., Fall, R., Geron, C., Graedel, T., Harley, P., Klinger, L., Lerdau, M., McKay, W. A., Pierce, T., Scholes, B., Steinbrecher, R., Tallamraju, R., Taylor, J., and Zimmerman, P.: A global model of natural volatile organic compound emissions, J. Geophys. Res., 100, 8873–8892, 1995. Halket, J. M., Zaikin, V. G.: Derivatization in mass spectrometry – 1. Silylation, Europ. J. Mass Spectrom., 9, 1–21, 2003. Hallquist, M., Wenger, J. C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M., Dommen, J., Donahue, N. M., George, C., Goldstein, A. H., Hamilton, J. F., Herrmann, H., Hoffmann, T., Iinuma, Y., Jang, M., Jenkin, M. E., Jimenez, J. L., Kiendler-Scharr, A., Maenhaut, W., McFiggans, G., Mentel, T. F., Monod, A., Prévôt, A. S. H., Seinfeld, J. H., Surratt, J. D., Szmigielski, R., and Wildt, J.: The formation, properties and impact of secondary organic aerosol: Current and emerging issues, Atmos. Chem. Phys., 9, 5155–5236, http://dx.doi.org/10.5194/acp-9-5155-2009doi:10.5194/acp-9-5155-2009, 2009. Hays, M. D. and Lavrich, R. J.: Developments in direct thermal extraction gas chromatography-mass spectrometry of fine aerosols, Trends Analyt. Chem., 26, 88-102, 2007. Hays, M. D., Smith, N. D., Kinsey, J., Dong, Y., Kariher, P.: Polycyclic aromatic hydrocarbon size distributions in aerosols from appliances of residential wood combustion as determined by direct thermal desorption-GC/MS, J. Aerosol Sci., 34, 1061–1084, 2003. Ho, S. S. H. and Yu, J. Z.: In-injection port thermal desorption and subsequent gas chromatography-mass spectrometric analysis of polycyclic aromatic hydrocarbons and n-alkanes in atmospheric aerosol samples, J. Chromatogr. A, 1059, 121–129, 2004. Ho, S. S. H., Yua, J. Z., Chow, J. C., Zielinskaa, B., Watson, J. G., Leung Sit, E. H., and Schauer, J. J.: Evaluation of an in-injection port thermal desorption-gas chromatography/mass spectrometry method for analysis of non-polar organic compounds in ambient aerosol samples, J. Chromatogr. A, 1200, 217–227, 2008. Kourtchev, I., Ruuskanen, T., Maenhaut, W., Kulmala, M., and Claeys, M.: Observation of 2-methyltetrols and related photo-oxidation products of isoprene in boreal forest aerosols from Hyytiälä, Finland, Atmos. Chem. Phys., 5, 2761–2770, http://dx.doi.org/10.5194/acp-5-2761-2005doi:10.5194/acp-5-2761-2005, 2005. Kuo, L.-J., Herbert, B. E., and Louchouarn, P.: Can levoglucosan be used to characterize and quantify char/charcoal black carbon in environmental media?, Org. Geochem., 39, 1466–1478, 2008. Lambe, A. T., Chacon-Madrid, H. J., Nguyen, N. T., Weitkamp, E. A., Kreisberg, N. M., Hering, S. V., Goldstein, A. H., Donahue, N. M., and Robinson, A. L.: Organic aerosol speciation: Intercomparison of thermal desorption aerosol GC/MS (TAG) and filter-based techniques, Aerosol Sci. Technol., 44, 141–151, 2010. Larsen III, R. K., Schantz, M. M., and Wise, S. A.: Determination of levoglucosan in particulate matter reference materials, Aerosol Sci. Technol., 40, 781–787, 2006. Leithead, A., Li, S.-M., Hoff, R., Cheng, Y., and Brook, J.: Levoglucosan and dehydroabietic acid: Evidence of biomass burning impact on aerosol in the lower fraser valley, Atmos. Environ., 40, 2721–2734, 2006. Little, J. L.: Artifacts in trimethylsilyl derivatization reactions and ways to avoid them, J. Chromatogr. A, 844, 1–22, 1999. Liu, Y., Sklorz, M., Schnelle-Kreis, J., Orasche, J., Ferge, T., Kettrup, A., and Zimmermann, R.: Oxidant denuder sampling for analysis of polycyclic aromatic hydrocarbons and their oxygenated derivates in ambient aerosol: Evaluation of sampling artefact, Chemosphere, 62, 1889–1898, 2006. Louchouarn, P., Kuo, L.-J., Wade, T. L., and Schantz, M.: Determination of levoglucosan and its isomers in size fractions of aerosol standard reference materials, Atmos. Environ., 43, 5630–5636, 2009. Ma, Y. and Hays, M. D.: Thermal extraction-two-dimensional gas chromatography-mass spectrometry with heart-cutting for nitrogen heterocyclics in biomass burning aerosols, J. Chromatogr. A, 1200, 228–234, 2008. Ma, Y., Hays, M. D., Geron, C. D., Walker, J. T., and Gatari Gichuru, M. J.: Technical Note: Fast two-dimensional GC-MS with thermal extraction for anhydro-sugars in fine aerosols, Atmos. Chem. Phys., 10, 4331–4341, http://dx.doi.org/10.5194/acp-10-4331-2010doi:10.5194/acp-10-4331-2010, 2010. Medeiros, P. M. and Simoneit, B. R. T.: Analysis of sugars in environmental samples by gas chromatography-mass spectrometry, J. Chromatogr. A, 1141, 271–278, 2007. Medeiros, P. M., Conte, M. H., Weber, J. C., and Simoneit, B. R. T.: Sugars as source indicators of biogenic organic carbon in aerosols collected above the howland experimental forest, maine, Atmos. Environ., 40, 1694–1705, 2006. Nolte, C. G., Schauer, J. J., Cass, G. R., and Simoneit, B. R. T.: Highly polar organic compounds present in wood smoke and in the ambient atmosphere, Environ. Sci. Technol., 35, 1912–1919, 2001. Nolte, C. G., Schauer, J. J., Cass, G. R., and Simoneit, B. R. T.: Trimethylsilyl derivatives of organic compounds in source samples and in atmospheric fine particulate matter, Environ. Sci. Technol., 36, 4273–4281, 2002. Oliveira, C., Pio, C., Alves, C., Evtyugina, M., Santos, P., Gonçalves, V., Nunes, T., Silvestre, A. J. D., Palmgren, F., Wåhlin, P., and Harrad, S.: Seasonal distribution of polar organic compounds in the urban atmosphere of two large cities from the north and south of europe, Atmos. Environ., 41, 5555–5570, 2007. Pashynska, V., Vermeylen, R., Vas, G., Maenhaut, W., and Claeys, M.: Development of a gas chromatographic/ion trap mass spectrometric method for the determination of levoglucosan and saccharidic compounds in atmospheric aerosols. Application to urban aerosols, J. Mass Spectrom., 37, 1249–1257, http://dx.doi.org/10.1002/jms.391doi:10.1002/jms.391, 2002. Schkolnik, G. and Rudich, Y.: Detection and quantification of levoglucosan in atmospheric aerosols: A review, Anal. Bioanal. Chem., 385, 26–33, 2006. Schnelle-Kreis, J., Sklorz, M., Peters, A., Cyrys, J., Zimmermann, R.: Analysis of particle-associated semi-volatile aromatic and aliphatic hydrocarbons in urban particulate matter on a daily basis, Chemosphere, 39, 7702–7714, 2005a. Schnelle-Kreis, J., Welthagen, W., Sklorz, M., Zimmermann, R.: Application of direct thermal desorption gas chromatography and comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry for analysis of organic compounds in ambient aerosol particles, J. Sep. Sci., 28, 1648–1657, 2005b. Schnelle-Kreis, J., Sklorz, M., Orasche, J., Stölzel, M., Peters, A., and Zimmermann, R.: Semi volatile organic compounds in ambient PM$_2.5$. Seasonal trends and daily resolved source contributions, Environ. Sci. Technol., 41, 3821–3828, 2007. Sheesley, R. J., DeMinter, J. T., Meiritz, M., Snyder, D. C., and Schauer, J. J.: Temporal trends in motor vehicle and secondary organic tracers using in situ methylation thermal desorption GCMS, Environ. Sci. Technol., 44, 9398–9404, 2010. Simoneit, B. R. T., Schauer, J. J., Nolte, C. G., Oros, D. R., Elias, V. O., Fraser, M. P., Rogge, W. F., and Cass, G. R.: Levoglucosan, a tracer for cellulose in biomass burning and atmospheric particles, Atmos. Environ., 33, 173–182, 1999. Simoneit, B. R. T., Elias, V. O., Kobayashi, M., Kawamura, K., Rushdi, A. I., Medeiros, P. M., Rogge, W. F., Didyk, Borys M. : Sugars dominant water-soluble organic compounds in soils and characterization as tracers in atmospheric particulate matter, Environ. Sci. Technol., 38, 5939–5949, 2004. Simpson, C. D., Dills, R. L., Katz, B. S., and Kalman, D. A.: Determination of levoglucosan in atmospheric fine particulate matter, J. Air Waste Manage. Assoc., 54, 689–694, 2004. Sklorz, M., Schnelle-Kreis, J., Liu, Y., Orasche, J., and Zimmermann, R.: Daytime resolved analysis of polycyclic aromatic hydrocarbons in urban aerosol samples – impact of sources and meteorological conditions, Chemosphere, 67, 934–943, 2007. van Drooge, B. L., Nikolova, I., and Ballesta, P. P.: Thermal desorption gas chromatography–mass spectrometry as an enhanced method for the quantification of polycyclic aromatic hydrocarbons from ambient air particulate matter, J. Chromatogr. A, 1216, 4030–4039, 2009. Vedal, S., Hannigan, M. P., Dutton, S. J., Miller, S. L., Milford, J. B., Rabinovitch, N.,Kim, S.-Y., and Sheppard L.: The denver aerosol sources and health (dash) study: Overview and early findings, Atmos. Environ., 43, 1666–1673, 2009. Waterman, D., Horsfield ,B., Leistner, F., Hall, K., and Smith, S.: Quantification of polycyclic aromatic hydrocarbons in the nist standard reference material (SRM1649a) urban dust using thermal desorption GC/MS, Anal. Chem., 72, 3563–3567, 2000. Waterman, D., Horsfield, B., Hall, K., and Smith, S.: Application of micro-scale sealed vessel thermal desorption–gas chromatography–mass spectrometry for the organic analysis of airborne particulate matter: Linearity, reproducibility and quantification, J. Chromatogr. A, 912, 143–150, 2001. Williams, B. J., Goldstein, A. H., Kreisberg, N. M., and Hering, S. V.: An in-situ instrument for speciated organic composition of atmospheric aerosols: Thermal desorption aerosol GC/MS-FID (TAG), Aerosol Sci. Technol., 40, 627–638, 2006. Williams, B. J., Goldstein, A. H., Kreisberg, N. M., Hering, S. V., Worsnop, D. R., Ulbrich, I. M., Docherty, K. S., and Jimenez, J. L.: Major components of atmospheric organic aerosol in southern California as determined by hourly measurements of source marker compounds, Atmos. Chem. Phys., 10, 11577–11603, http://dx.doi.org/10.5194/acp-10-11577-2010doi:10.5194/acp-10-11577-2010, 2010. Zdrahal, Z., Oliveira, J., Vermeylen, R., Claeys, M., and Maenhaut, W.: Improved method for quantifying levoglucosan and related monosaccharide anhydrides in atmospheric aerosols and application to samples from urban and tropical locations, Environ. Sci. Technol., 36, 747–753, 2002.