ABSTRACT This manuscript describes an analytical method for the quantitative determination of 16-polycyclic aromatic hydrocarbons (PAHs) using accelerated solvent extraction (ASE), followed by purification on a silica cartridge, and subsequent measurement by gas chromatograph coupled to a mass spectrometer (GC-MS). The solvent extraction parameters (T = 100 oC, P = 1500 psi, t = 30 min, V = 30 ml) are optimized with dichloromethane (DCM) in order to avoid fractionation effect, thereby achieving quantitative mass recovery of PAHs. The purification of PAHs on silica cartridge eliminates the matrix effect, facilitates their enrichment from extracted solution and quantitative deter-mination in presence of an internal-standard (Pyrene-D10). The analytical protocol has been successfully used for the quantification of 16-PAHs and their isomer ratios in atmospheric aerosols collected from northern India dominated by agricultural- waste (post-harvest paddy and wheat residue) burning emissions. Based on the analysis of ambient aerosols, collected from different sites, the overall recovery efficiency for 2- to 3-ring PAHs is 85% and near 100% recovery for 4- to 6-ring compounds.
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nullP. Rajput, M. Sarin and R. Rengarajan, "High-Precision GC-MS Analysis of Atmospheric Polycyclic Aromatic Hydrocarbons (PAHs) and Isomer Ratios from Biomass Burning Emissions," Journal of Environmental Protection, Vol. 2 No. 4, 2011, pp. 445-453. doi: 10.4236/jep.2011.24051.
 O. L. Mayol-Bracero, P. Guyon, B. Graham, G. Roberts, M. O. Andreae, S. Decesari, M. C. Facchini, S. Fuzzi and P. Artaxo, “Water-Soluble Organic Compounds in Biomass Burning Aerosols over Amazonia 2. Apportionment of the Chemical Composition and Importance of the Polyacidic Fraction,” Journal of Geophysical Research, Vol. 107, No. D20, 2002. doi:10.1029/2001JD000522
 R. Rengarajan, M. M. Sarin and A. K. Sudheer, “Carbonaceous and Inorganic Species in Atmospheric Aerosols during Wintertime over Urban and High-Altitude Sites in North India,” Journal of Geophysical Research, Vol. 112, No. D21307, 2007.
 K. Ram and M. M. Sarin, “Spatio-Temporal Variability in Atmospheric Abundances of EC, OC and WSOC over Northern India,” Journal of Aerosol Science, Vol. 41, No. 1, 2010, pp. 88-98. doi:10.1016/j.jaerosci.2009.11.004
 J. H. Seinfeld and J. F. Pankow, “Organic Atmospheric Particulate Material,” Annual Review of Physical Chemistry, Vol., 54, 2003, pp. 121-140.
 J. H. Seinfeld and S. N. Pandis, “Atmospheric Chemistry and Physics—From Air Pollution to Climate Change,” 2nd Edition, John Wiley & Sons, New York, 2006.
 S. O. Baek, M. E. Goldstone, P. W. W. Kirk, J. N. Lester and R. Perry, “Phase Distribution and Particle Size Dependency of Polycyclic Aromatic Hydrocarbons in the Urban Atmosphere,” Chemosphere, Vol. 22, No. 5-6, 1991, pp. 503-520. doi:10.1016/0045-6535(91)90062-I
 Y. Rudich, N. M. Donahue and T. F. Mentel, “Aging of Organic Aerosol: Bridging the Gap Between Laboratory and Field Studies,” Annual Review of Physical Chemistry, Vol. 58, 2007, pp. 321-352.
 M. C. Jacobson, H. C. Hansson, K. J. Noone and R. J. Charlson, “Organic Atmospheric Aerosols: Review and State of the Science,” Reviews of Geophysics, Vol. 38, No. 2, 2000, pp. 267-294. doi:10.1029/1998RG000045
 E. Perraudin, H. Budzinski and E. Villenave, “Analysis of Polycyclic Aromatic Hydrocarbons Adsorbed on Particles of Atmospheric Interest using Pressurised Fluid Extraction,” Analytical Bioanalytical Chemistry, Vol. 383, No. 1, 2005, pp. 122-131. doi:10.1007/s00216-005-3398-7
 K. Miet, K. Le Menach, P. M. Flaud, H. Budzinski and E. Villenave, “Heterogeneous Reactivity of Pyrene and 1-Nitropyrene with NO2: Kinetics, Product Yields and Mechanism,” Atmospheric Environment, Vol. 43, No. 4, 2009, pp. 837-843. doi:10.1016/j.atmosenv.2008.10.041
 K. Miet, K. Le Menach, P. M. Flaud, H. Budzinski and E. Villenave, “Heterogeneous Reactions of Ozone with Pyrene, 1-Hydroxypyrene and 1-Nitropyrene Adsorbed on Particles,” Atmospheric Environment, Vol. 43, No. 24, 2009, pp. 3699-3707.
 B. E. Richter, B. A. Jones, J. L. Ezzell, N. L.Porter, N. Avdalovic and C. Pohl, “Accelerated Solvent Extraction: A Technique for Sample Preparation,” Analytical Chemistry, Vol. 68, No. 6, 1996, pp. 1033-1039.
 G. Kiss, Z. Varga-Puchony and J. Hlavay, “Determination of Polycyclic Aromatic Hydrocarbons in Precipitation using Solid-Phase Extraction and Column Liquid Chromatography,” Journal of Chromatography A, Vol. 725, No. 2, 1996, pp. 261-272.
 S. A. Wise, L. C. Sander, M. M. Schantz, M. J. Hays and B. A. Benner, “Recertification of Standard Reference Material (SRM) 1649, Urban Dust, for the Determination of Polycyclic Aromatic Hydrocarbons (PAHs),” Polycyclic Aromatic Compounds, Vol. 13, No. 4, 2000, pp. 419-456. doi:10.1080/10406630008233854
 M. M. Schantz, J. J. Nichols and S. A. Wise, “Evaluation of Pressurized Fluid Extraction for the Extraction of Environmental Matrix Reference Materials,” Analytical Chemistry, Vol. 69, No. 20, 1997, pp. 4210-4219. doi:10.1021/ac970299c
 N. Alexandrou, M. Smith, R. Park, K. Lumb and K. Brice, “The Extraction of Polycyclic Aromatic Hydrocarbons from Atmospheric Particulate Matter Samples by Accelerated Solvent Extraction (ASE),” International Journal of Environmental Analytical Chemistry, Vol. 81, No. 4, 2001, pp. 257 - 280. doi:10.1080/03067310108044248
 G. Kiss, A.Gelencsér, Z. Krivácsy and J. Hlavay, “Occurrence and Determination of Organic Pollutants in Aerosol, Precipitation, and Sediment Samples Collected at Lake Balaton,” Journal of Chromatography A, Vol. 774, Nos. 1-2, 1997, pp. 349-361.
 S. A. Wise, B. A. Benner, S. N. Chesler, L. R. Hilpert, C. R. Vogt and W. E. May, “Characterization of the Polycyclic Aromatic Hydrocarbons from Two Standard Reference Material Air Particulate Samples,” Analytical Chemistry, Vol. 58, No. 14, 1986, pp. 3067-3077.
 J. Duan, X. Bi, J. Tan, G. Sheng and J. Fu, “The Differences of the Size Distribution of Polycyclic Aromatic Hydrocarbons (PAHs) between Urban and Rural Sites of Guangzhou, China,” Atmospheric Research, Vol. 78, Nos. 3-4, 2005, pp. 190-203.
 M. Mandalakis, ?. Gustafsson, T. Alsberg, A.-L. Egeb?ck, C. M. Reddy, L. Xu, J. Klanova, I. Holoubek and E. G. Stephanou, “Contribution of Biomass Burning to Atmospheric Polycyclic Aromatic Hydrocarbons at Three European Background Sites,” Environmental Science & Technology, Vol. 39, No. 9, 2005, pp. 2976-2982.
 S. B. Hawthorne, D. J. Miller, M. D. Burford, J. J. Langenfeld, S. Eckert-Tilotta and P. K. Louie, “Factors Controlling Quantitative Supercritical Fluid Extraction of Environmental Samples,” Journal of Chromatography A, Vol. 642, No. 1-2, 1993, pp. 301-317.
 O. Alvarez-Avilés, L. Cuadra-Rodríguez, F. González- Illán, J. Qui?ones-González and O. Rosario, “Optimization of a Novel Method for the Organic Chemical Characterization of Atmospheric Aerosols Based on Microwave-Assisted Extraction Combined with Stir Bar Sorptive Extraction,” Analytica Chimica Acta, Vol. 597, No. 2, 2007, pp. 273-281. doi:10.1016/j.aca.2007.07.004
 K. K. Chee, M. K. Wong and H. K. Lee, “Microwave-Assisted Solvent Extraction of Air Particulates for the Determination of PAHs,” Environmental Monitoring and Assessment, Vol. 44, Nos. 1-3, 1997, pp. 391-403.
 L. Turrio-Baldassarri, C. L. Battistelli and A. L. Iamiceli, “Evaluation of the Efficiency of Extraction of PAHs from Diesel Particulate Matter with Pressurized Solvents,” Analytical Bioanalytical Chemistry, Vol. 375, No. 4, 2003, pp. 589-595.
 D. L. Poster, M. M. Schantz, L. C. Sander and S. A. Wise, “Analysis of Polycyclic Aromatic Hydrocarbons (PAHs) in Environmental Samples: A Critical Review of Gas Chromatographic (GC) Methods,” Analytical Bioanalytical Chemistry, Vol. 386, No. 4, 2006, pp. 859-881.
 M. Punia, V. P. Nautiyal and Y. Kant, “Identifying Biomass Burned Patches of Agricultural Residue using Satellite Remote Sensing Data,” Current Science, Vol. 94, No. 9, 2008, pp. 1185-1190.
 P. K. Gupta, S. Sahai, N. Singh, C. K. Dixit, D. P. Singh, C. Sharma, M. K. Tiwari, R. K. Gupta and S. C. Garg, “Residue Burning in Rice-Wheat Cropping System: Causes and Implications,” Current Science, Vol. 87, No. 12, 2004, pp. 1713-1717.
 K. V. S. Badarinath, T. R. K. Chand and V. K. Prasad, “Agricultural Crop Residue Burning in the Indo-Gangetic Plains - A Study using IRS-P6 A WiFS Satellite Data,” Current Science, Vol. 91, No. 8, 2006, pp. 1085-1089.
 J. J. Schauer, B. T. Mader, J. T. DeMinter, G. Heidemann, M. S. Bae, J. H. Seinfeld, R. C. Flagan, R. A. Cary, D. Smith, B. J. Huebert, T. Bertram, S. Howell, J. T. Kline, P. Quinn, T. Bates, B. Turpin, H. J. Lim, J. Z. Yu, H. Yang and M. D. Keywood, “ACE-Asia Intercomparison of a Thermal-Optical Method for the Determination of Particle-Phase Organic and Elemental Carbon,” Environmental Science & Technology, Vol. 37, No. 5, 2003, pp. 993-1001. doi:10.1021/es020622f
 M. -X. Xie, F. Xie, Z.-W. Deng and G.-S. Zhuang, “Determination of Polynuclear Aromatic Hydrocarbons in Aerosol by Solid-Phase Extraction and Gas Chromatography-Mass Spectrum,” Talanta, Vol. 60, No. 6, 2003, pp. 1245-1257. doi:10.1016/S0039-9140(03)00224-8
 K. Ram, M. M. Sarin and P. Hegde, “Atmospheric Abundances of Primary and Secondary Carbonaceous Species at Two High-Altitude Sites in India: Sources and Temporal Variability,” Atmospheric Environment, Vol. 42, No. 28, 2008, pp. 6785-6796.