References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-9-3347-2009

Source apportionment of elevated wintertime PAHs by compound-specific radiocarbon analysis

Sheesley

R. J.

¹ Kruså

¹ Krecl

¹ Johansson

¹ Gustafsson

Ö.

Department of Applied Environmental Science (ITM), Stockholm University, 10691 Stockholm, Sweden

25 05 2009

9 10 3347 3356

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.

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Natural abundance radiocarbon analysis facilitates distinct source apportionment between contemporary biomass/biofuel (14C "alive") versus fossil fuel (14C "dead") combustion. Here, the first compound-specific radiocarbon analysis (CSRA) of atmospheric polycyclic aromatic hydrocarbons (PAHs) was demonstrated for a set of samples collected in Lycksele, Sweden a small town with frequent episodes of severe atmospheric pollution in the winter. Renewed interest in using residential wood combustion (RWC) means that this type of seasonal pollution is of increasing concern in many areas. Five individual/paired PAH isolates from three pooled fortnight-long filter collections were analyzed by CSRA: phenanthrene, fluoranthene, pyrene, benzo[b+k]fluoranthene and indeno[cd]pyrene plus benzo[ghi]perylene; phenanthrene was the only compound also analyzed in the gas phase. The measured Δ14C for PAHs spanned from −138.3&permil; to 58.0&permil;. A simple isotopic mass balance model was applied to estimate the fraction biomass (fbiomass) contribution, which was constrained to 71–87% for the individual PAHs. Indeno[cd]pyrene plus benzo[ghi]perylene had an fbiomass of 71%, while fluoranthene and phenanthrene (gas phase) had the highest biomass contribution at 87%. The total organic carbon (TOC, defined as carbon remaining after removal of inorganic carbon) fbiomass was estimated to be 77%, which falls within the range for PAHs. This CSRA data of atmospheric PAHs established that RWC is the dominating source of atmospheric PAHs to this region of the boreal zone with some variations among RWC contributions to specific PAHs.

References 1

Bench, G., Fallon, S., Schichtel, B., Malm, W., and McDade, C.: Relative contributions of fossil and contemporary carbon sources to PM$_2.5$ aerosols at nine Interagency Monitoring for Protection of Visual Environments (IMPROVE) network sites, J. Geophys. Res.-Atmos., 112, D10205, doi:10.1029/2006JD007708, 2007.

Benner, B. A., Wise, S. A., Currie, L. A., Klouda, G. A., Klinedinst, D. B., Zweidinger, R. B., Stevens, R. K., and Lewis, C. W.: Distinguishing the contributions of residential wood combustion and mobile source emissions using relative concentrations of dimethylphenanthrene isomers, Environ. Sci. Technol., 29(9), 2382–2389, 1995.

Breivik, K., Vestreng, V., Rozovskaya, O., and Pacyna, J. M.: Atmospheric emissions of some POPs in Europe: a discussion of existing inventories and data needs, Environ. Sci. Policy, 9(7–8), 663–674, doi:10.1016/j.envsci.2006.09.001, 2006.

Broman, D., Naf, C., and Zebuhr, Y.: Long-term high-volume and low-volume air sampling of polychlorinated dibenzo-para-dioxins and dibenzofurans and polycyclic aromatic-hydrocarbons along a transect from urban to remote areas on the Swedish Baltic Coast, Environ. Sci. Technol., 25(11), 1841–1850, 1991.

Busby, W. F., Smith, H., Plummer, E. F., Lafleur, A. L., Mulder, P. P. J., Boere, B. B., Cornelisse, J., and Lugtenburg, J.: Mutagenicity of cyclopenta-fused polynuclear aromatic hydrocarbons and a non-polar fraction from a fuel combustion sample in a Salmonella forward mutation assay without exogenous metabolic activation, Mutation Research-Genetic Toxicology and Environmental Mutagenesis, 391(3), 117–125, 1997.

Choi, H., Jedrychowski, W., Spengler, J., Camann, D. E., Whyatt, R. M., Rauh, V., Tsai, W. Y., and Perera, F. P.: International studies of prenatal exposure to polycyclic aromatic hydrocarbons and fetal growth, Environ. Health Perspect., 114(11), 1744–1750, 2006.

Chow, J. C., Watson, J. G., Lowenthal, D. H., Chen, L. W. A., Zielinska, B., Mazzoleni, L. R., and Magliano, K. L.: Evaluation of organic markers for chemical mass balance source apportionment at the Fresno Supersite, Atmos. Chem. Phys., 7, 1741–1754, 2007.

Chowdhury, Z., Zheng, M., Schauer, J. J., Sheesley, R. J., Salmon, L. G., Cass, G. R., and Russell, A. G.: Speciation of ambient fine organic carbon particles and source apportionment of PM$_2.5$ in Indian cities, J. Geophys. Res.-Atmos., 112, D15, doi:10.1029/2007JD008386, 2007.

Coplen, T. B.: New guidelines for reporting stable hydrogen, carbon and oxygen isotope-ratio data, Geochim. Cosmochim. Acta, 60, 3359–3360, 1996.

Currie, L. A., Klouda, G. A., Benner, B. A., Garrity, K., and Eglinton, T. I.: Isotopic and molecular fractionation in combustion; three routes to molecular marker validation, including direct molecular `dating' (GC/AMS), Atmos. Environ., 33(17), 2789–2806, 1999.

Eglinton, T. I., Aluwihare, L. I., Bauer, J. E., Druffel, E. R. M., and McNichol, A. P.: Gas chromatographic isolation of individual compounds from complex matrices for radiocarbon dating, Anal. Chem., 68(5), 904–912, 1996.

Hays, M. D., Smith, N. D., Kinsey, J., Dong, Y. J., and 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(8), 1061–1084, 2003.

Hedberg, E. and Johansson, C.: Is levoglucosan a suitable quantitative tracer for wood burning? Comparison with receptor modeling on trace elements in Lycksele, Sweden, J. Air Waste Manage. Assoc., 56(12), 1669–1678, 2006.

Hildemann, L. M., Klinedinst, D. B., Klouda, G. A., Currie, L. A., and Cass, G. R.: Sources Of Urban Contemporary Carbon Aerosol, Environ. Sci. Technol., 28(9), 1565–1576, 1994.

Jaeckels, J. M., Bae, M. S., and Schauer, J. J.: Positive Matrix Factorization (PMF) analysis of molecular marker measurements to quantify the sources of organic aerosols, Environ. Sci. Technol., 41(16), 5763–5769, 2007.

Johansson, C., Hedberg, E., Olivares, G., et al.: Measurements and calculations of the effect of wood burning on air pollution levels. Part I. Lycksele, Department of Applied Environmental Science, Stockholm University, Stockholm, SwedenITM report-124, 2004.

Jordan, T. B., Seen, A. J., Jacobsen, G. E., and Gras, J. L.: Radiocarbon determination of woodsmoke contribution to air particulate matter in Launceston, Tasmania, Atmos. Environ., 40(14), 2575–2582, 2006.

Klinedinst, D. B. and Currie, L. A.: Direct quantification of PM$_2.5$ fossil and biomass carbon within the Northern Front Range Air Quality Study's domain, Environ. Sci. Technol., 33(23), 4146–4154, 1999.

Krecl, P., Strom, J., and Johansson, C.: Carbon content of atmospheric aerosols in a residential area during the wood combustion season in Sweden, Atmos. Environ., 41(33), 6974–6985, doi:10.1016/j.atmosenv.2007.06.025, 2007.

Krecl, P., Hedberg Larsson, E., Ström, J., and Johansson, C.: Contribution of residential wood combustion and other sources to hourly winter aerosol in Northern Sweden determined by positive matrix factorization, Atmos. Chem. Phys., 8, 3639–3653, 2008a.

Krecl, P., Strom, J., and Johansson, C.: Diurnal variation of atmospheric aerosol during the wood combustion season in Northern Sweden, Atmos. Environ., 42(18), 4113–4125, doi:10.1016/j.atmosenv.2008.01.026, 2008b.

Kumata, H., Uchida, M., Sakuma, E., Uchida, T., Fujiwara, K., Tsuzuki, M., Yoneda, M., and Shibata, Y.: Compound class specific C-14 analysis of polycyclic aromatic hydrocarbons associated with PM$_10$ and PM$_1.1$ aerosols from residential areas of suburban Tokyo, Environ. Sci. Technol., 40(11), 3474–3480, 2006.

Larsen, R. K. and Baker, J. E.: Source apportionment of polycyclic aromatic hydrocarbons in the urban atmosphere: A comparison of three methods, Environ. Sci. Technol., 37(9), 1873–1881, doi:10.1021/es0206184, 2003.

Levin, I., Kromer, B., Schmidt, M., and Sartorius, H.: A novel approach for independent budgeting of fossil fuel CO2 over Europe by (CO2)-C-14 observations, Geophys. Res. Lett., 30, 23, doi:10.1029/2003GL018477, 2003.

Levin, I. and Kromer, B.: The tropospheric (CO2)-C-14 level in mid-latitudes of the Northern Hemisphere (1959–2003), Radiocarbon, 46(3), 1261–1272, 2004.

Lima, A. L. C., Farrington, J. W., and Reddy, C. M.: Combustion-derived polycyclic aromatic hydrocarbons in the environment – A review, Environ. Forensics, 6(2), 109–131, 2005.

Lough, G. C. and Schauer, J. J.: Sensitivity of source apportionment of urban particulate matter to uncertainty in motor vehicle emissions profiles, J. Air Waste Manage. Assoc., 57(10), 1200–1213, 2007.

Mandalakis, M. and Gustafsson, O.: Optimization of a preparative capillary gas chromatography-mass spectrometry system for the isolation and harvesting of individual polycyclic aromatic hydrocarbons, J. Chromatogr. A, 996(1–2), 163–172, 2003.

Mandalakis, M., Gustafsson, O., Reddy, C. M., and Li, X.: Radiocarbon apportionment of fossil versus biofuel combustion sources of polycyclic aromatic hydrocarbons in the Stockholm metropolitan area, Environ. Sci. Technol., 38(20), 5344–5349, 2004a.

Mandalakis, M., Zebuhr, Y., and Gustafsson, O.: Efficient isolation of polyaromatic fraction from aliphatic compounds in complex extracts using dimethylformamide-pentane partitionings, J. Chromatogr. A, 1041(1–2), 111–117, 2004b.

Mandalakis, M., Gustafsson, O., Alsberg, T., Egeback, A. L., Reddy, C. M., Xu, L., Klanova, J., Holoubek, I., and Stephanou, E. G.: Contribution of biomass burning to atmospheric polycyclic aromatic hydrocarbons at three European background sites, Environ. Sci. Technol., 39(9), 2976–2982, 2005.

McDonald, J. D., Zielinska, B., Fujita, E. M., Sagebiel, J. C., Chow, J. C., and Watson, J. G.: Emissions from charbroiling and grilling of chicken and beef, J. Air Waste Manage. Assoc., 53(2), 185–194, 2003.

Pearson, A., McNichol, A. P., Schneider, R. J., Von Reden, K. F., and Zheng, Y.: Microscale AMS C-14 measurement at NOSAMS, Radiocarbon, 40(1), 61–75, 1998.

Ravindra, K., Sokhi, R., and Van Grieken, R.: Atmospheric polycyclic aromatic hydrocarbons: Source attribution, emission factors and regulation, Atmos. Environ., 42(13), 2895–2921, doi:10.1016/j.atmosenv.2007.12.010, 2008.

Reddy, C. M., Pearson, A., Xu, L., McNichol, A. P., Benner, B. A., Wise, S. A., Klouda, G. A., Currie, L. A., and Eglinton, T. I.: Radiocarbon as a tool to apportion the sources of polycyclic aromatic hydrocarbons and black carbon in environmental samples, Environ. Sci. Technol., 36(8), 1774–1782, 2002.

Reddy, C. M., Xu, L., and O'Connor, R.: Using radiocarbon to apportion sources of polycyclic aromatic hydrocarbons in household soot, Environ. Forensics, 4(3), 191–197, 2003.

Sauvain, J. J., Duc, T. V., and Guillemin, M.: Exposure to carcinogenic polycyclic aromatic compounds and health risk assessment for diesel-exhaust exposed workers, Int. Arch. Occ. Env. Hea., 76(6), 443–455, 2003.

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(9), 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. C-1-C- 29 organic compounds from fireplace combustion of wood, Environ. Sci. Technol., 35(9), 1716–1728, 2001.

Schauer, J. J., Kleeman, M. J., Cass, G. R., and Simoneit, B. R. T.: Measurement of emissions from air pollution sources. 5. C-1-C- 32 organic compounds from gasoline-powered motor vehicles, Environ. Sci. Technol., 36(6), 1169–1180, 2002.

Schnelle-Kreis, J., Sklorz, M., Orasche, J., Stolzel, 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(11), 3821–3828, 2007.

Schwarze, P. E., Ovrevik, J., Hetland, R. B., Becher, R., Cassee, F. R., Lag, M., Lovik, M., Dybing, E., and Refsnes, M.: Importance of size and composition of particles for effects on cells in vitro, Inhalation Toxicology, 19, 17–22, 2007.

Sheesley, R. J., Schauer, J. J., Zheng, M., and Wang, B.: Sensitivity of molecular marker-based CMB models to biomass burning source profiles, Atmos. Environ., 41(39), 9050–9063, 2007.

Stuiver, M. and Polach, H. A.: Reporting Of C-14 Data – Discussion, Radiocarbon, 19(3), 355–363, 1977.

Szidat, S., Jenk, T. M., Gaggeler, H. W., Synal, H. A., Fisseha, R., Baltensperger, U., Kalberer, M., Samburova, V., Reimann, S., Kasper-Giebl, A., and Hajdas, I.: Radiocarbon (C-14)-deduced biogenic and anthropogenic contributions to organic carbon (OC) of urban aerosols from Zurich, Switzerland, Atmos. Environ., 38(24), 4035–4044, 2004a.

Szidat, S., Jenk, T. M., Gaggeler, H. W., Synal, H. A., Fisseha, R., Baltensperger, U., Kalberer, M., Samburova, V., Wacker, L., Saurer, M., Schwikowski, M., and Hajdas, I.: Source apportionment of aerosols by C-14 measurements in different carbonaceous particle fractions, Radiocarbon, 46(1), 475–484, 2004b.

Szidat, S., Prevot, A. S. H., Sandradewi, J., Alfarra, M. R., Synal, H. A., Wacker, L., and Baltensperger, U.: Dominant impact of residential wood burning on particulate matter in Alpine valleys during winter, Geophys. Res. Lett., 34, L05820, doi:10.1029/2006GL028325, 2007.

Yan, B. Z., Abrajano, T. A., Bopp, R. F., Chaky, D. A., Benedict, L. A., and Chillrud, S. N.: Molecular tracers of saturated and polycyclic aromatic hydrocarbon inputs into Central Park Lake, New York City, Environ. Sci. Technol., 39(18), 7012–7019, 2005.

Yunker, M. B., Macdonald, R. W., Vingarzan, R., Mitchell, R. H., Goyette, D., and Sylvestre, S.: PAHs in the Fraser River basin: a critical appraisal of PAH ratios as indicators of PAH source and composition, Org. Geochem., 33(4), 489–515, 2002.

Zencak, Z., Elmquist, M., and Gustafsson, O.: Quantification and radiocarbon source apportionment of black carbon in atmospheric aerosols using the CTO-375 method, Atmos. Environ., 41(36), 7895–7906, 2007a.

Zencak, Z., Klanova, J., Holoubek, I., and Gustafsson, O.: Source apportionment of atmospheric PAHs in the western balkans by natural abundance radiocarbon analysis, Environ. Sci. Technol., 41(11), 3850–3855, 2007b.

Zencak, Z., Reddy, C. M., Teuten, E. L., Xu, L., McNichol, A. P., and Gustafsson, O.: Evaluation of gas chromatographic isotope fractionation and process contamination by carbon in compound-specific radiocarbon analysis, Anal. Chem., 79(5), 2042–2049, 2007c.