References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-8-2313-2008

Receptor modeling of C2–C7 hydrocarbon sources at an urban background site in Zurich, Switzerland: changes between 1993–1994 and 2005–2006

Lanz

V. A.

¹ Hueglin

¹ Buchmann

¹ Hill

¹ Locher

² Staehelin

³ Reimann

Empa, Swiss Federal Laboratories for Materials Testing and Research, Laboratory for Air Pollution and Environmental Technology, 8600 Duebendorf, Switzerland

ZHAW, School of Engineering, Institute of Data Analysis and Process Design IDP, 8401 Winterthur, Switzerland

Institute for Atmospheric and Climate Science, ETH Zurich, 8092 Zurich, Switzerland

05 05 2008

8 9 2313 2332

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/8/2313/2008/acp-8-2313-2008.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/8/2313/2008/acp-8-2313-2008.pdf

Hourly measurements of 13 volatile hydrocarbons (C2–C7) were performed at an urban background site in Zurich (Switzerland) in the years 1993–1994 and again in 2005–2006. For the separation of the volatile organic compounds by gas-chromatography (GC), an identical chromatographic column was used in both campaigns. Changes in hydrocarbon profiles and source strengths were recovered by positive matrix factorization (PMF). Eight and six factors could be related to hydrocarbon sources in 1993–1994 and in 2005–2006, respectively. The modeled source profiles were verified by hydrocarbon profiles reported in the literature. The source strengths were validated by independent measurements, such as inorganic trace gases (NOx, CO, SO2), methane (CH4), oxidized hydrocarbons (OVOCs) and meteorological data (temperature, wind speed etc.). Our analysis suggests that the contribution of most hydrocarbon sources (i.e. road traffic, solvents use and wood burning) decreased by a factor of about two to three between the early 1990s and 2005–2006. On the other hand, hydrocarbon losses from natural gas leakage remained at relatively constant levels (−20%). The estimated emission trends are in line with the results from different receptor-based approaches reported for other European cities. Their differences to national emission inventories are discussed.

References 1

Anttila, P., Paatero, P., Tapper, U., and Järvinen, O.: Source identification of bulk wet deposition in Finland by positive matrix factorization, Atmos. Environ., 29, 1705–1718, 1995.

Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem. Rev., 103, 4605–4638, 2003.

BAFU: Luftschadstoff-Emissionen des Stassenverkehrs 1950–2020. Nachtrag. Schriftenreihe UMWELT Nr. 225, Swiss Federal Office for the Environment FOEN, Bern, 2000.

BAFU: Abschätzung der Altlastenrelevanz von Methyl-tert-butylether (MTBE). Swiss Federal Office for the Environment FOEN, Bern, available at: http://www.bafu.admin.ch/php/ modules/shop/files/pdf/phpyeb9SE.pdf, 2002.

BAFU: Anthropogene VOC-Emissionen Schweiz 1998, 2001 und 2004, Swiss Federal Office for the Environment FOEN, Bern, available at: http://www.bafu.admin.ch/voc/03756/03758/index.html?lang=de, 2007.

Barrefors, G. and Petersson, G.: Volatile hydrocarbons from domestic wood burning, Chemosphere, 30, 1551–1556, 1995.

Bartenbach, S., Williams, J., Plass-Duelmer, C., Berresheim, H., and Lelieveld, J.: In-situ measurement of reactive hydrocarbons at Hohenpeissenberg with comprehensive two-dimensional gas chromatography (GCxGC-FID): use in estimating HO and NO3, Atmos. Chem. Phys., 7, 1-14, 2007.

Blifford, I. H. and Meeker, G. O.: A factor analysis model of large scale pollution, Atmos. Environ., 1, 147–157, 1967.

Borbon, A., Coddeville, P., Locoge, N., and Galloo, J.-C.: Characterising sources and sinks of rural VOC in eastern France, Chemosphere, 57, 931–942, 2004.

Buset, K. C., Evans, G. J., Leaitch, W. R., Brook, J. R., Toom-Sauntry, D.: Use of advanced receptor modelling for analysis of an intensive 5-week aerosol sampling campaign, Atmos. Environ., 40, Suppl 2, 482–499, 2006.

Buzcu, B. and Frazier, M. P.: Source identification and apportionment of volatile organic compounds in Houston, TX, Atmos. Environ., 40, 2385–2400, 2006.

Christensen, W. F., Schauer, J. J., and Lingwall, J. F.: Iterated confirmatory factor analysis for pollution source apportionment, Environmetrics, 17, 663–681, 2006.

Colberg, C. A., Tona, B., Stahel, W. A., Meier, M., and Staehelin, J.: Comparison of a road traffic emission model (HBEFA) with emissions derived from measurements in the Gubrist road tunnel, Switzerland, Atmos. Environ., 39, 4703–4714, 2005.

Derwent, R. G., Davies, T. J., Delaney, M., Dollard, G. J., Field, R. A., Dumitrean, P., Nason, P. D., Jones, B. M. R., and Pepler, S. A.: Analysis and interpretation of the continuous hourly monitoring data for 26 C2–C$_8$ hydrocarbons at 12 United Kingdom sites during 1996, Atmos. Environ., 34, 297–312, 2000.

Dollard, G. J., Dumitrean, P., Telling, S., Dixon, J., and Derwent, R. G: Observed trends in ambient concentrations of C2–C$_8$ hydrocarbons in the United Kingdom over the period from 1993 to 2004, Atmos. Environ., 41, 2559–2569, 2007.

Eggertsen, F. T. and Nelsen, F. M.: Gas chromatographic analysis of engine exhaust and atmopshere. Determination of C2–C$_5$ hydrocarbons, Anal. Chem., 30, 1040–1043, 1958.

Empa: Technischer Bericht zum Nationalen Beobachtungsnetz für Luftfremdstoffe (NABEL), available at: http://www.empa.ch/nabel, Dübendorf, Switzerland, 2006.

Forster, P., Ramaswamy, V., Artaxo, P., Berntsen, T. , Betts, R., Fahey, D.W., Haywood, J., Lean, J., Lowe, D. C., Myhre, G., Nganga, J., Prinn, R., Raga, G., Schulz, M., and Van Dorland, R.: Changes in atmospheric constituents and in radiative forcing, in: Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, edited by: Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K. B., Tignor, M., and Miller, H. L., Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA, 2007.

Fujita, E. M., Campbell, D. E., Zielinska, B., Sagebiel, J. C., Bowen, J. L., Goliff, W. S., Stockwell, W. S., and Lawson, D. R.: Diurnal and weekday variations in the source contributions of ozone precursors in California's South Coast Air Basin, J. Air Waste Manage., 53, 844–863, 2003.

Fuzzi, S., Andreae, M. O., Huebert, B. J., Kulmala, M., Bond, T. C., Boy, M., Doherty, S. J., Guenther, A., Kanakidou, M., Kawamura, K., Kerminen, V.-M., Lohmann, U., Russell, L. M., and Pöschl, U.: Critical assessment of the current state of scientific knowledge, terminology, and research needs concerning the role of organic aerosols in the atmosphere, climate, and global change, Atmos. Chem. Phys., 6, 2017–2038, 2006.

Hakola, H., Hellén, H., and Laurila, T.: Ten years of light hydrocarbons (C2–C$_6$) concentration measurements in background air in Finland, Atmos. Environ., 40, 3621–3630, 2006.

HBEFA: Handbuch für Emissionsfaktoren des Strassenverkehrs (handbook of emission factors for road traffic), Umweltbundesamt Berlin, Bundesamt für Umwelt, Wald und Landschaft Bern, Infras AG, Bern (published on CD-ROM, also available at: www.hbefa.net), 2004.

Hellén, H., Hakola, H., Pirjola, L., Laurila, T., and Pystynen, K.-H.: Ambient air concentrations, source profiles, and source apportionment of 71 Different C2–C$_10$ volatile organic compounds in urban and residential areas of Finland, Environ. Sci. Technol., 40, 103–108, 2006.

Henry, R. C., Lewis, C. W., Hopke, P. K., and Williamson, H. J.: Review of receptor model fundamentals, Atmos. Environ., 18, 1507–1515, 1984.

Henry, R. C.: Multivariate receptor modelling by N-dimensional edge detection, Chemometr. Intell. Lab., 65, 179–189, 2003.

Hopke, P. K.: Target transformation factor analysis as an aerosol mass apportionment method: A review and sensitivity analysis, Atmos. Environ., 22, 1777-1792, 1988.

Hopke, P. K.: Recent developments in receptor modeling, Chemometr. Intell. Lab., 17, 255–265, 2003.

Jorquera, H. and Rappenglück, B.: Receptor modeling of ambient VOC at Santiago, Chile, Atmos. Environ., 38, 4243–4263, 2004.

Junninen, H., Niska, H., Tuppurainen, K., Ruuskanen, J., and Kolehmainen, M.: Methods for imputation of missing values in air quality data sets, Atmos. Environ., 38, 2895–2907, 2004.

Kunert, U. and Kuhfeld, H.: The diverse structures of passenger car taxation in Europe and the EU Commissions proposal for reform, Transp. Policy, 14, 306–316, 2007.

Lanz, V. A., Alfarra, M. R., Baltensperger, U., Buchmann, B., Hueglin, C., and Prevot, A. S. H.: Source apportionment of submicron organic aerosols at an urban site by factor analytical modelling of aerosol mass spectra, Atmos. Chem. Phys., 7, 1503-1522, 2007.

Lanz, V. A., Alfarra, M. R., Baltensperger, U., Buchmann, B., Hueglin, C., Szidat, S., Wehrli, M. N., Wacker, L., Weimer, S., Caseiro, A., Puxbaum, H., and Prevot, A. S. H.: Source attribution of submicron organic aerosols during wintertime inversions by advanced factor analysis of aerosol mass spectra, Environ. Sci. Technol., 42, 214–220, 2008.

Latella, A., Stani, G., Cobelli, L., Duane, M., Junninen, H., Astorga, C., and Larsen, B. R.: Semicontinuous GC analysis and receptor modelling for source apportionment of ozone precursor hydrocarbons in Bresso, Milan, 2003, J. Chrom. A, 39, 29–39, 2005.

Lee, E., Chan, C., and Paatero, P.: Application of positive matrix factorization in source apportionment of particulate pollutants in Hong Kong, Atmos. Environ., 33, 3201–3212, 1999.

Legreid, G., Reimann, S., Steinbacher, M., Staehelin, J., Young, D., and Stemmler, K.: Measurements of OVOCs and NMHCs in a Swiss highway tunnel for estimation of road transport emissions, Environ. Sci. Technol., 41, 7060–7066, 2007a.

Legreid, G., Balzani Lööv, J., Staehelin, J., Hueglin, C., Hill, M., Buchmann, B., Prevot, A. S. H., and Reimann, S.: Oxygenated volatile organic compounds (OVOCs) at an urban background site in Zürich (Europe): Seasonal variation and source allocation, Atmos. Environ., 41, 8409–8423, 2007b.

Li, Z., Hopke, P. K., Husain, L., Qureshi, S., Dutkiewicz, V. A., Schwab, J. J., Drewnick, F., and Demerjian, K. L.: Sources of fine particle composition in New York City, Atmos. Environ., 38, 6521–6529, 2004.

Matson, P., Lohse, K. A., and Hall, S. J.: The globalization of nitrogen deposition: Consequences for terrestrial ecosystems, Ambio, 31, 113–119, 2002.

McKendry, I. G., Steyn, D. G., Lundgren, J., Hoff, R. M., Strapp, W., Anlauf, K., Froude, F., Martin, J. B., Banta, R. M., and Olivier, L. D.: Elevated ozone layers and vertical down-mixing over the Lower Fraser Valley, BC, Atmos. Environ., 31, 2135-2146, 1997.

MEF: MEF, Risk assessment of methyl tertiary-butyl ether (MTBE), EINECS No 216-653-1, carried out in the framework of European Council Regulation (EEC) 793/93 on the evaluation and control of the risks of existing substances, Ministry of the Environment Finland, Helsinki, Final Draft 06/2001, 328, 2001.

Miller, S. L., Anderson, M. J., Daly, E. P., and Milford, J. B.: Source apportionment of exposures to volatile organic compounds. I. Evaluation of receptor models using simulated exposure data, Atmos. Environ., 36, 3629–3641, 2002.

Nel, A.: Air pollution-related illness: effects of particles, Science, 308, 804–806, 2005.

Niedojadło, A., Becker, K. H., Kurtenbach, R., and Wiesen, P.: The contribution of traffic and solvent use to total NMVOC emission in a German city derived from measurements and CMB modelling, Atmos. Environ., 41, 7108–7126, 2007.

Olson, M.: Wheat straw and peat fuel pellets - organic compounds from combustion, Biomass Bioenerg., 30, 555–564, 2006.

Paatero, P. and Tapper, U.: Positive matrix factorization: a non-negative factor model with optimal utilization of error estimates of data values, Environmetrics, 5, 111–126, 1994.

Paatero, P.: Least squares formulation of robust non-negative factor analysis, Chemometr. Intell. Lab., 37, 23–35, 1997.

Paatero, P.: User's guide for positive matrix factorization programs PMF2 and PMF3, part 1: tutorial, University of Helsinki, Finland, 2007.

Paatero, P., Hopke, P. K., Begum, B. A., and Biswas, S. K.: A graphical diagnostic method for assessing the rotation in factor analytical models of atmospheric pollution, Atmos. Environ., 39, 193–201, 2005.

Poulopoulos, S. and Philippopoulos, C.: Influence of MTBE addition into gasoline on automotive exhaust emissions, Atmos. Environ., 34, 4781–4786, 2000.

Primerano, P., Marino, G., Di Pasquale, S., Mavilia, L., and Corigliano, F.: Possible alteration of monuments caused by particles emitted into the atmosphere carrying strong primary acidity, Atmos. Environ., 34, 3889–3896, 2000.

Ruffieux, D., Nash, J., Jeannet, P., and Agnew, J. L.: The COST 720 temperature, humidity, and cloud profiling campaign: TUC, Meteorol. Z., 15, 5-10, 2006.

Schauer, J. J., Rogge, W. F., Hildemann, L. M., Mazurek, M. A., and Cass, G. R.: Source apportionment of airborne particulate matter using organic compounds as tracers, Atmos. Environ., 30, 3837–3855, 1996.

Seinfeld, J. H. and Pandis, S. N.: Atmospheric chemistry and physics, John Wiley and Sons, Inc., New York, 1998.

Staehelin, J., Keller, C., Stahel, W., Schläpfer, K., and Wunderli, S.: Emission factors from road traffic from a tunnel study (Gubrist tunnel, Switzerland), Part III: Results of organic compounds, SO2, and speciation of oranic exhaust emission, Atmos. Environ., 32, 999–1009, 1998.

Staehelin, J., Locher, R., Mönkeberg, S., and Stahel, W. A.: Contribution of road traffic emissions to ambient air concentrations of hydrocarbons: the interpretation of monitoring measurements in Switzerland by Principal Component Analysis and road tunnel measurements, Int. J. Vehicle Des., 27, 161–172, 2001.

Strader, R., Lurmann, F., and Pandis, S. N.: Evaluation of secondary organic aerosol formation in winter, Atmos. Environ., 33, 4849–4863, 1999.

Theloke, J. and Friedrich, R.: Compilation of a database on the composition of anthropogenic VOC emissions for atmospheric modeling in Europe, Atmos. Environ., 41, 4148–4160, 2007.

Vestreng, V., Rigler, E., Adams, M., Kindbom, K., Pacyna, J. M., Denier van der Gon, H., Reis, S., and Travnikov, O.: Inventory review 2006, Emission data reported to LRTAP and NEC Directive, Stage 1, 2 and 3 review and Evaluation of inventories of HM and POPs. EMEP/MSC-W Technical Report 1/2006 ISSN 1504-6179, available at: http://www.emep.int, 2006.

VOCV: http://www.admin.ch/ch/d/sr/c814_018.html, 1997.

Wåhlin, P.: COPREM – A multivariate receptor model with a physical approach, Atmos. Environ., 37, 4861-4667, 2003.

Watson, J. G.: Visibility: science and regulation, J. Waste Air Manage., 52, 628–713, 2002.

WHO: Benzene (Environmental Health Criteria, No. 150), Geneva, World Health Organization, 1993.

Winchester, J. W. and Nifong, G. D.: Water pollution in Lake Michigan by trace elements from pollution aerosol fallout, Water Air Soil Poll., 1, 51–64, 1971.

Zhao, W., Hopke, P. K., and Karl, T.: Source Identification of volatile organic compounds in Houston, TX, Environ. Sci. Technol., 38, 1338–1347, 2004.