References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-4331-2010

Technical Note: Fast two-dimensional GC-MS with thermal extraction for anhydro-sugars in fine aerosols

¹ ³ Hays

M. D.

¹ Geron

C. D.

¹ Walker

J. T.

¹ Gatari Gichuru

M. J.

National Risk Management Research Laboratory, United States Environmental Protection Agency, Research Triangle Park, North Carolina 27711, USA

Institute of Nuclear Science & Technology, College of Architecture and Engineering, University of Nairobi, Nairobi, Kenya

currently at: California Air Resources Board, 9528 Telstar Avenue, El Monte, CA 91731, USA

07 05 2010

10 9 4331 4341

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/10/4331/2010/acp-10-4331-2010.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/4331/2010/acp-10-4331-2010.pdf

A fast two-dimensional gas chromatography (GC-MS) method that uses heart-cutting and thermal extraction (TE) and requires no chemical derivatization was developed for the determination of anhydro-sugars in fine aerosols. Evaluation of the TE-GC-GC-MS method shows high average relative accuracy (≥90%), reproducibility (≤10% relative standard deviation), detection limits of less than 3 ng/μL, and negligible carryover for levoglucosan, mannosan, and galactosan markers. TE-GC-GC-MS- and solvent extraction (SE)-GC-MS-measured levoglucosan concentrations correlate across several diverse types of biomass burning aerosols. Because the SE-GC-MS measurements were taken 8 years prior to the TE-GC-GC-MS ones, the stability of levoglucosan is established for quartz filter-collected biomass burning aerosol samples stored at ultra-low temperature (−50 °C). Levoglucosan concentrations (w/w) in aerosols collected following atmospheric dilution near open fires of varying intensity are similar to those in biomass burning aerosols produced in a laboratory enclosure. An average levoglucosan-mannosan-galactosan ratio of 15:2:1 is observed for these two aerosol sets. TE-GC-GC-MS analysis of atmospheric aerosols from the US and Africa produced levoglucosan concentrations (0.01–1.6 μg/m<sup>3</sup>) well within those reported for aerosols collected globally and examined using different analytical techniques (0.004–7.6 μg/m<sup>3</sup>). Further comparisons among techniques suggest that fast TE-GC-GC-MS is among the most sensitive, accurate, and precise methods for compound-specific quantification of anhydro-sugars. In addition, an approximately twofold increase in anhydro-sugar determination may be realized when combining TE with fast chromatography.

References 1

Branca, C., Giudicianni, P., and Di Blasi, C.: GC/MS characterization of liquids generated from low-temperature pyrolysis of wood, Ind. Eng. Chem. Res., 42(14), 3190–3202, 2003.

Caseiro, A., Bauer, H., Schmidl, C., Pio, C. A., Puxbaum, H.: Wood burning impact on PM10 in three Austrian regions, Atmos. Environ., 43, (13), 2186–2195, 2009.

Chow, J. C., Yu, J. Z., Watson, J. G., Ho, S. S. H., 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 A., 42, (11), 1521–1541, 2007.

Dixon, R. W. and Baltzell, G.: Determination of levoglucosan in atmospheric aerosols using high performance liquid chromatography with aerosol charge detection, J. Chromatogr. A, 1109, 214–221, 2006.

Dye, C. and Yttri, K. E.: Determination of monosaccharide anhydrides in atmospheric aerosols by use of high-performance liquid chromatography combined with high-resolution mass spectrometry, Anal. Chem., 77, 1853–1858, 2005.

Elias, V., Simoneit, B., Cordeiro, R., and Turcq, B.: Evaluating levoglucosan as an indicator of biomass burning in Carajas, Amazonia: A comparison to the charcoal record, Geochim. Cosmochim. Acta, 65, 267–272, 2001.

Engling, G., Carrico, C. M., Kreidenweis, S. M., Jeffrey L. Collett, J., Day, D. E., Malm, W. C., Lincoln, E., Hao, W. M., Iinuma, Y., and Herrmann, H.: Determination of levoglucosan in biomass combustion aerosol by high-performance anion-exchange chromatography with pulsed amperometric detection, Atmos. Environ., 40, 299–311, 2006.

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(11), 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(13), 2665–2675, 2001.

Fine, P. M., Cass, G. R., and Simoneit, B. R. T.: Chemical characterization of fine particulate 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 particulate emissions from the fireplace combustion of woods grown in the midwestern and western United States, Environ. Eng. Sci., 21, 387–409, 2004a.

Fine, P. M., Cass, G. R., and Simoneit, B. R. T.: Chemical characterisation of fine particle emissions from the wood stove combustion of prevalent United States tree species, Environ. Eng. Sci., 21, 705–721, 2004b.

Fine, P. M., Chakrabarti, B., Krudysz, M., Schauer, J. J., and Sioutas, C.: Diurnal variations of individual organic compound constituents of ultrafine and accumulation mode particulate matter in the Los Angeles basin, Environ. Sci. Technol., 38, 1296–1304, 2004c.

Fraser, M. and Lakshmanan, K.: Using levoglucosan as a molecular marker for the long-range transport of biomass combustion aerosols, Environ. Sci. Technol., 34(21), 4560–4564, 2000.

Gambaro, A., Zangrando, R., Gabrielli, P., Barbante, C., and Cescon, P.: Direct Determination of Levoglucosan at the Picogram per Milliliter Level in Antarctic Ice by High-Performance Liquid Chromatography/Electrospray Ionization Triple Quadrupole Mass Spectrometry, Anal. Chem., 80(5), 1649–1655, 2008.

Gao, S., Hegg, D. A., Hobbs, P. V., Kirchstetter, T. W., Magi, B. I., and Sadilek, M.: Water-soluble organic components in aerosols associated with savanna fires in southern Africa: identification, evolution, and distribution, J. Geophys. Res., 108(D13), 8491, doi:10.1029/2002JD002324, 2003.

Garcia, C. D., Engling, G., Herckes, P., Collett, J. L., and Henry, C. S.: Determination of levoglucosan from smoke samples using microchip capillary electrophoresis with pulsed amperometric detection, Environ. Sci. Technol., 39, 618–623, 2005.

Graham, B., Guyon, P., Taylor, P., Artaxo, P., Maenhaut, W., Glovsky, M., Flagan, R., and Andreae, M.: Organic compounds present in the natural Amazonian aerosol: Characterization by gas chromatography-mass spectrometry, J. Geophys. Res. Atmos., 108(D24), 4677, doi:10.1029/2003JD003990, 2003.

Graham, B., Mayol-Bracero, O., Guyon, P., Roberts, G., Decesari, S., Facchini, M., Artaxo, P., Maenhaut, W., Koll, P., and Andreae, M.: Water-soluble organic compounds in biomass burning aerosols over Amazonia 1. Characterization by NMR and GC-MS, J. Geophys. Res., 107(D20), 8047, doi:10.1029/2001JD000336, 2002.

Gravitis, J., Zandersons, J., Vedernikov, N., Kruma, I., and Ozols-Kalnins, V.: Clustering of bio-products technologies for zero emissions and eco-efficiency, Ind. Crops Products, 20, 169–180, 2004.

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, 2004.

Hays, M. D., Fine, P. M., Geron, C. D., Kleeman, M. J., and Gullett, B. K.: Open burning of agricultural biomass: Physical and chemical properties of particle-phase emissions, Atmos. Environ., 39, 6747–6764, 2005.

Hays, M. D., Geron, C. D., Linna, K. J., Smith, N. D., and Schauer, J. J.: Speciation of gas-phase and fine particle emissions from burning of foliar fuels, Environ. Sci. Technol., 36(11), 2281–2295, 2002.

Hays, M. D., N. D. Smith, J. Kinsey, Y. Dong, and P. H. Kariher: Polycyclic aromatic hydrocarbon size distribution in aerosols from appliances of residential wood combustion as dertermined by direct thermal desorption-GC/MS, J. Aerosol Sci., 34, 1061–1084, 2003.

Hildemann, L. M., Cass, G. R., and Markowski, G. R.: A dilution stack sampler for collection of organic aerosol emissions: design, characterization and field tests, Aerosol Sci. Technol., 10, 193–204, 1989.

Hope, J. L., Prazen, B. J., Nilsson, E. J., Lidstrom, M. E., and Synovec, R. E.: Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry detection: analysis of amino acid and organic acid trimethylsilyl derivatives, with application to the analysis of metabolites in rye grass samples, Talanta, 65(2), 380–388, 2005.

Iinuma, Y., Brueggemann, E., Gnauk, T., Mueller, K., Andreae, M. O., Helas, G., Parmar, R., and Herrmann, H.: Source characterization of biomass burning particles: the combustion of selected European conifers, African hardwood, savanna grass, and German and Indonesian peat, J Geophys. Res., 112(D8), D08209/1–D08209/26, 2007.

Kallio, M., Hyötyläinen, T., Lehtonen, M., Jussila, M., Hartonen, K., Shimmo, M., and Riekkola, M.-L.: Comprehensive two-dimensional gas chromatography in the analysis of urban aerosols, J. Chromatogr. A, 1019, 251–260, 2003.

Kituyi, E., Marufu, L., Huber, B., Wandiga, S. O., Jumba, I. O., Andreae, M. O., and Helas, G.: Biofuel consumption rates and patterns in Kenya, Biomass Bioener., 20, 83–99, 2001.

Kleeman, M. J., Robert, M. A., Riddle, S. G., Fine, P. M., Hays, M. D., Schauer, J. J., and Hannigan, M. P.: Size distribution of trace organic species emitted from biomass combustion and meat charbroiling, Atmos. Environ., 42(13), 3059–3075, 2008.

Lin, L., Lee, M. L., and Eatough, D. J.: Gas chromatographic analysis of organic marker compounds in fine particulate matter using solid-phase microextraction, J. Air Waste Manage. Assoc., 57, 53–58, 2007.

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(2), 228–234, 2008.

McLaren, A. D. and Peterson, G. H. (Eds.): Soil Biochemistry, Dekker, New York, USA, 509 pp., 1967.

Migliaccio, C. T., Bergauff, M. A., Palmer, C. P., Jessop, F., Noonan, C. W., and Ward, T. J.: Urinary levoglucosan as a biomarker of wood smoke exposure: observations in a mouse model and in children, Environ. Health Perspect., 117(1), 74–79, 2009.

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., 35, 1912–1919, 2001.

Otto, A., Gondokusumo, R., and Simpson, M. J.: Characterization and quantification of biomarkers from biomass burning at a recent wildfire site in Northern Alberta, Canada. Appl. Geochem., 21(1), 166–183, 2006.

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, 2002.

Poore, M. W.: Levoglucosan in PM2.5 at the fresno supersite, J. Air Waste Manage. Assoc., 52, 3–4, 2002.

Schauer, J. J. and Cass, G. R.: Source apportionment of wintertime gas-phase and particle-phase air pollutants using organic compounds as tracers, Environ. Sci. Technol., 34, 1821–1832, 2000.

Schauer, J. J., Kleeman, M. J., Cass, G. R., and Simoneit, B. R. T.: Measurement of emissions from air pollution sources. 3. C1–C29 organic compounds from fireplace combustion of wood, Environ. Sci. Technol., 35, 1716–1728, 2001.

Schkolnik, G., Falkovich, A. H., Rudich, Y., Maenhaut, W., and Artaxo, P.: New analytical method for the determination of levoglucosan, polyhydroxy compounds, and 2-methylerythritol and its application to smoke and rainwater samples, Environ. Sci. Technol., 39(8), 2744–2752, 2005.

Schkolnik, G. and Rudich, Y.: Detection and quantification of levoglucosan in atmospheric aerosols: A review, Anal. Bioanal. Chem., 385(1), 26–33, 2006.

Schmidl, C., Bauer, H., Dattler, A., Hitzenberger, R., Weissenboeck, G., Marr, I. L., and Puxbaum, H.: Chemical characterisation of particle emissions from burning leaves, Atmos. Environ., 42, 9070–9079, 2008.

Schmidl, C., Marr, I. L., Caseiro, A., Kotianova, P., Berner, A., Bauer, H., Kasper-Giebl, A., and Puxbaum, H.: Chemical characterization of fine particle emissions from wood stove combustion of common woods growing in mid-European Alpine regions, Atmos. Environ., 42, 126–141, 2009.

Shafidazeh, F.: The chemistry of pyrolysis and combustion, Adv. Chem. Ser., 207, 489–529, 1984.

Sheesley, R. J., Schauer, J. J., Chowdhury, Z., Cass, G. R., and Simoneit, B. R. T.: Characterization of organic aerosols emitted from the combustion of biomass indigenous to South Asia, J. Geophys. Res., 108(D9), 4285, doi:10.1029/2002JD002981, 2003.

Simoneit, B.: A review of biomarker compounds as source indicators and tracers for air pollution, Environ. Sci. Pollut. Res., 6, 159–169, 1999a.

Simoneit, B., Schauer, J., Nolte, C., Oros, D., Elias, V., Fraser, M., Rogge, W., and Cass, G.: Levoglucosan, a tracer for cellulose in biomass burning and atmospheric particles, Atmos. Environ., 33, 173–182, 1999b.

Simoneit, B. and Elias, V.: Detecting organic tracers from biomass burning in the atmosphere, Mar. Pollut. Bull., 42, 805–810, 2001.

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.

Wan, E. C. H. and Yu, J. Z.: Analysis of sugars and sugar polyols in atmospheric aerosols by chloride attachment in liquid chromatography /negative ion electrospray mass spectrometry, Environ. Sci. Technol., 41, 2459–2466, 2007.

Welthagen, W., Schnelle-Kreis, J., and Zimmermann, R.: Search criteria and rules for comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry analysis of airborne particulate matter, J. Chromatogr. A, 1019(1–2), 233–249, 2003.

Williams, B., Goldstein, A., Kreisberg, N., and Herring, S.: 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.

Yttri, K. E., Dye, C., Slordal, L. H., and Braathen, O.-A.: Quantification of monosaccharide anhydrides by liquid chromatography combined with mass spectrometry: Application to aerosol samples from an urban and a suburban site influenced by small-scale wood burning, J. Air Waste Manage. Assoc., 55, 1169–1177, 2005.

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.

Zheng, M., Cass, G. R., Schauer, J. J., and Edgerton, E. S.: Source apportionment of PM$_2.5$ in the southeastern United States using solvent-extractable organic compounds as tracers, Environ. Sci. Technol., 36, 2361–2371, 2002.