References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

Atmos. Chem. Phys. Discuss.

1680-7375

Göttingen, Germany

10.5194/acpd-12-5389-2012

Quantification of diesel exhaust gas phase organics by a thermal desorption proton transfer reaction mass spectrometer

Erickson

M. H.

¹ Wallace

H. W.

¹ Jobson

B. T.

Laboratory for Atmospheric Research, Washington State University, Pullman, WA, USA

20 02 2012

12 2 5389 5423

2012

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A new approach was developed to measure the total abundance of long chain alkanes (C12 and above) in urban air using thermal desorption with a proton transfer reaction mass spectrometer (PTR-MS). These species are emitted in diesel exhaust and may be important precursors to secondary organic aerosol production in urban areas. Long chain alkanes undergo dissociative proton transfer reactions forming a series of fragment ions with formula CnH2n+1. The yield of the fragment ions is a function of drift conditions. At a drift field strength of 80 Townsends, the most abundant ion fragments from C10 to C16 n-alkanes were m/z 57, 71 and 85. The PTR-MS is insensitive to n-alkanes less than C8 but displays an increasing sensitivity for larger alkanes. Higher drift field strengths yield greater normalized sensitivity implying that the proton affinity of the long chain n-alkanes is less than H2O. Analysis of diesel fuel shows the mass spectrum was dominated by alkanes (CnH2n+1), monocyclic aromatics, and an ion group with formula CnH2n−1 (m/z 97, 111, 125, 139). The PTR-MS was deployed in Sacramento, CA during the Carbonaceous Aerosols and Radiative Effects Study field experiment in June 2010. The ratio of the m/z 97 to 85 ion intensities in ambient air matched that found in diesel fuel. Total diesel exhaust alkane concentrations calculated from the measured abundance of m/z 85 ranged from the method detection limit of ~1 μg m−3 to 100 μg m−3 in several air pollution episodes. The total diesel exhaust alkane concentration determined by this method was on average a factor of 10 greater than the sum of alkylbenzenes associated with spark ignition vehicle exhaust.

References 1

Arnold, S. T., Viggiano, A. A., and Morris, R. A.: Rate Constants and Product Branching Fractions for the Reactions of H3O+ and NO+ with C2-C12 Alkanes, J. Phys. Chem., A 102, 8881–8887, <a href="http://dx.doi.org/10.1021/jp9815457">https://doi.org/10.1021/jp9815457</a>, 1998.

Bohme, D. K., Mackay, G. I., and Tanner, S. D.: An Experimental Study of the Gas-Phase Kinetics of Reactions with Hydrated H3O+ Ions ($n=1$–3) at 298 K, J. Am. Chem. Soc., 101, 3724–3730, 1979.

De Gouw, J. A., Middlebrook, A. M. Warneke, C., Goldan, P. D., Kuster, W. C., Roberts, J. M., Fehsenfeld, F. C., Worsnop, D. R., Canagaratna, J. M., Pszenny, A. A. P., Keene, W. C., Marchewka, M., Bertman, S. B., and Bates, T. S.: Budget of organic carbon in a polluted atmosphere: Results from the New England Air Quality Study in 2002, J. Geophys. Res.-Atmos., 110, D16305, <a href="http://dx.doi.org/10.1029/2004JD005623">https://doi.org/10.1029/2004JD005623</a>, 2005.

Fast, J. D., Gustafson Jr., W. I., Berg, L. K., Shaw, W. J., Pekour, M., Shrivastava, M., Barnard, J. C., Ferrare, R. A., Hostetler, C. A., Hair, J. A., Erickson, M., Jobson, B. T., Flowers, B., Dubey, M. K., Springston, S., Pierce, R. B., Dolislager, L., Pederson, J., and Zaveri, R. A.: Transport and mixing patterns over Central California during the Carbonaceous Aerosol and Radiative Effects Study (CARES), Atmos. Chem. Phys. Discuss., 11, 29949–30008, <a href="http://dx.doi.org/10.5194/acpd-11-29949-2011">https://doi.org/10.5194/acpd-11-29949-2011</a>, 2011.

Han, M., Assanis, D. N., Jacobs, T. J., and Bohac, S. V.: Method and Detailed Analysis of Individual Hydrocarbon Species From Diesel Combustion Modes and Diesel Oxidation Catalyst, J. Eng. Gas. Turb. Power, 130, 042803-1–042803-10, 2008.

Heald, C. L., Jacob, D. J., Park, R. J., Russel, L. M., Huebert, B. J., Seinfeld, J. H., Liao, H., and Weber, R. J.: A large organic aerosol source in the free troposphere missing from current models, Geophys. Res. Lett., 32, L18809, <a href="http://dx.doi.org/10.1029/2005GL023831">https://doi.org/10.1029/2005GL023831</a>, 2005.

Hoekman, S. K.: Speciated Measurements and Calculated Reactivities of Vehicle Exhaust Emissions from Conventional and Reformulated Gasolines, Environ. Sci. Technol., 26, 1206–1216, <a href="http://dx.doi.org/10.1021/es50002a610">https://doi.org/10.1021/es50002a610</a>, 1992.

Hunter, K. C. and East, A. L. L.: Properties of C-C Bonds in n-alkanes: Relevance to Cracking Mechanisms, J. Phys. Chem. A., 106, 1346–1356, <a href="http://dx.doi.org/10.1021/jp0129030">https://doi.org/10.1021/jp0129030</a>, 2002.

Jobson, B. T. and McCoskey, J. K.: Sample drying to improve HCHO measurements by PTR-MS instruments: laboratory and field measurements, Atmos. Chem. Phys., 10, 1821–1835, <a href="http://dx.doi.org/10.5194/acp-10-1821-2010">https://doi.org/10.5194/acp-10-1821-2010</a>, 2010.

Jobson, B. T., Alexander, M. L., Maupin, G. D., and Muntean, G. G.: On-line analysis of organic compounds in diesel exhaust using a proton transfer reaction mass spectrometer (PTR-MS), Int. J. Mass. Spectrom., 245, 78–89, <a href="http://dx.doi.org/10.1016/j.ijms.2005.05.009">https://doi.org/10.1016/j.ijms.2005.05.009</a>, 2005.

Johnson, K. S., Zuberi, B., Molina, L. T., Molina, M. J., Iedema, M. J., Cowin, J. P., Gaspar, D. J., Wang, C., and Laskin, A.: Processing of soot in an urban environment: case study from the Mexico City Metropolitan Area, Atmos. Chem. Phys., 5, 3033–3043, <a href="http://dx.doi.org/10.5194/acp-5-3033-2005">https://doi.org/10.5194/acp-5-3033-2005</a>, 2005.

Jordan, C. E., Ziemann, P. J., Griffin, R. J., Lim Y. B., Atkinson, R., and Arey, J.: Modeling SOA formation from OH reactions with C8–C17 n-alkanes, Atmos. Environ., 42, 8015–8026, <a href="http://dx.doi.org/10.1016/j.atmosenv.2008.06.017">https://doi.org/10.1016/j.atmosenv.2008.06.017</a>, 2008.

Lai, C. H., Chen, K. S., Ho, Y. T., and Chou, M. S.: Characteristics of C2–C15 hydrocarbons in the air of urban Kaohsiung, Taiwan, Atmos. Environ., 28, 1997–2011, <a href="http://dx.doi.org/10.1016/j.atmosenv.2003.11.041">https://doi.org/10.1016/j.atmosenv.2003.11.041</a>, 2004.

Lewis, A. C., Carslaw, N., Marriott, P. J., Kinghorn, R. M., Morrison, P., Lee, A. L., Bartle, K. D., and Pilling, M. J.: A larger pool of ozone forming carbon compounds in urban atmospheres, Nature, 405, 778–781, 2000.

Lias, S. G., Liebman, J. F., and Levin, R. D.: Evaluated Gas Phase Basicities and Proton Affinities of Molecules; Heats of Formation of Protonated Molecules, J. Phys. Chem. Ref. Data, 13, 695–808, 1984.

Lim, Y. B. and Ziemann, P. J.: Products and Mechanism of Secondary Organic Aerosol Formation from Reactions of n-alkanes with OH radicals in the Presence of NOx, Environ. Sci. Technol., 39, 9229–9236, <a href="http://dx.doi.org/10.1021/es051447g">https://doi.org/10.1021/es051447g</a>, 2005.

McClenny, W. A., Daughtrey Jr., E. H., Adams, J. R., Oliver, K. D., and Kronmiller, K. G.: Volatile organic compound concentration patterns at the New Hendersonville monitoring site in the 1995 Southern Oxidants Study in the Nashville, Tennessee, area, J. Geophys. Res., 103, 22509–22518, 1998.

Presto, A. A., Miracolo, M. A., Kroll, J. H., Worsnop, D. R., Robinson, A. L., and Donahue, N. M.: Intermediate- Volatility Organic Compounds: A Potential Source of Ambient Oxidized Organic Aerosol, Environ. Sci. Technol., 43, 4744–4749, <a href="http://dx.doi.org/10.1021/es803219q">https://doi.org/10.1021/es803219q</a>, 2009.

Robinson, A. L., Donahue, N. M., Shrivastava, M. K., Weitkamp, E. A., Sage, A. M., Grieshop, A. P., Lane, T. E., Pierce, J. R., and Pandis, S. N.: Rethinking Organic Aerosol: Semivolatile Emissions and Photochemical Aging, Science, 315, 1259–1262, <a href="http://dx.doi.org/10.1126/science.1133061">https://doi.org/10.1126/science.1133061</a>, 2007.

Samy, S. and Zielinska, B.: Secondary organic aerosol production from modern diesel engine emissions, Atmos. Chem. Phys., 10, 609–625, <a href="http://dx.doi.org/10.5194/acp-10-609-2010">https://doi.org/10.5194/acp-10-609-2010</a>, 2010.

Schauer, J. J., Kleeman, M. J., Cass, G. R., and Simoneit, B. R. T.: Measurement of Emissions from Air Pollution Sources. 2. C1 through C30 Organic Compounds from Medium Duty Diesel Trucks, Environ. Sci. Technol., 33, 1578–1587, <a href="http://dx.doi.org/10.1021/es980081n">https://doi.org/10.1021/es980081n</a>, 1999.

Schmitz, T., Hassel, D., and Weber, F.-J.: Determination of VOC-components in the exhaust of gasoline and diesel passenger cars, Atmos. Environ., 34. 4639–4647, 2000.

Schulz, H., Bandeira del Melo, G., and Ousmanov, F.: Volatile Organic Compounds and Particulates as Components of Diesel Engine Exhaust Gas, Combust. Flame, 118, 179–190, 1999.

Siegl, W. O., Hammerle, R. H., Herrmann, H. M., Wenclawiak, B. W., and Luers-Jongen, B.: Organic emissions profile for a light-duty diesel vehicle, Atmos. Environ., 33, 797–805, 1999.

Spanel, P. and Smith, D.: Selected ion flow tube studies of the reactions of H3O+, NO+, and O2+ with several aromatic and aliphatic hydrocarbons, Int. J. Mass Spectrom., 181, 1–10, 1998.

Vendeuvre, C., Ruiz-Guerrero, R., Bertoncini, F., Duval, L., Thiebaut, D., and Hennion, M. C.: Characterization of middle-distillates by comprehensive two-dimensional gas chromatography (GC×GC): A powerful alternative for performing various standard analysis of middle-distillates, J. Chromatogr. A, 1086, 21–28, <a href="http://dx.doi.org/10.1016/j.chroma.2005.05.106">https://doi.org/10.1016/j.chroma.2005.05.106</a>, 2005.

Vendeuvre, C., Ruiz-Guerrero, R., Bertoncini, F., Duval, L., and Thiebaut, D.: Comprehensive Two-Dimensional Gas Chromatography for Detailed Characterisation of Petroleum Products, Oil Gas Sci. Technol., 62, 43–55, <a href="http://dx.doi.org/10.1016/j.chroma.2005.05.106">https://doi.org/10.1016/j.chroma.2005.05.106</a>, 2007.

Volkamer, R., Jimenez, J. L., San Martini, F., Dzepina, K., Zhang, Q., Salcedo, D., Molina, L. T., Worsnop, D. R., and Molina, M. J.: Secondary organic aerosol formation from anthropogenic air pollution: Rapid and higher than expected, Geophys. Res. Lett., 33, L17811, <a href="http://dx.doi.org/10.1029/2006GL026899">https://doi.org/10.1029/2006GL026899</a>, 2006.

Wang, C.-Y. F., Qian, K., and Green, L. A.: GCxMS of Diesel: A Two-Dimensional Separation Approach, Anal. Chem., 77, 2777–2785, <a href="http://dx.doi.org/10.1021/ac0401624">https://doi.org/10.1021/ac0401624</a>, 2005.

Zaveri, R. A., Shaw, W. J., Cziczo, D. J., Schmid, B., Ferrare, R. A., Alexander, M. L., Alexandrov, M., Alvarez, R. J., Arnott, W. P., Atkinson, D. B., Baidar, S., Banta, R. M., Barnard, J. C., Beranek, J., Berg, L. K., Brechtel, F., Brewer, W. A., Cahill, J. F., Cairns, B., Cappa, C. D., Chand, D., China, S., Comstock, J. M., Dubey, M. K., Easter, R. C., Erickson, M. H., Fast, J. D., Floerchinger, C., Flowers, B. A., Fortner, E., Gaffney, J. S., Gilles, M. K., Gorkowski, K., Gustafson, W. I., Gyawali, M., Hair, J., Hardesty, R. M., Harworth, J. W., Herndon, S., Hiranuma, N., Hostetler, C., Hubbe, J. M., Jayne, J. T., Jeong, H., Jobson, B. T., Kassianov, E. I., Kleinman, L. I., Kluzek, C., Knighton, B., Kolesar, K. R., Kuang, C., Kubátová, A., Langford, A. O., Laskin, A., Laulainen, N., Marchbanks, R. D., Mazzoleni, C., Mei, F., Moffet, R. C., Nelson, D., Obland, M. D., Oetjen, H., Onasch, T. B., Ortega, I., Ottaviani, M., Pekour, M., Prather, K. A., Radney, J. G., Rogers, R. R., Sandberg, S. P., Sedlacek, A., Senff, C. J., Senum, G., Setyan, A., Shilling, J. E., Shrivastava, M., Song, C., Springston, S. R., Subramanian, R., Suski, K., Tomlinson, J., Volkamer, R., Wallace, H. W., Wang, J., Weickmann, A. M., Worsnop, D. R., Yu, X.-Y., Zelenyuk, A., and Zhang, Q.: Overview of the 2010 Carbonaceous Aerosols and Radiative Effects Study (CARES), Atmos. Chem. Phys. Discuss., 12, 1299–1400, <a href="http://dx.doi.org/10.5194/acpd-12-1299-2012">https://doi.org/10.5194/acpd-12-1299-2012</a>, 2012.

Zielinska, B., Sagebiel, J. C., Harshfield, G., Gertler, A. W., and Pierson, W. R.: Volatile Organic Compounds up to C20 Emitted from Motor Vehicles; Measurement Methods, Atmos. Environ., 30, 2269–2286, 1996.