References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-9-3147-2009

The influence of traffic and wood combustion on the stable isotopic composition of carbon monoxide

Saurer

¹ Prévôt

A. S. H.

¹ Dommen

¹ Sandradewi

¹ Baltensperger

¹ Siegwolf

R. T. W.

Paul Scherrer Institut, 5232 Villigen PSI, Switzerland

15 05 2009

9 9 3147 3161

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Carbon monoxide in the atmosphere is originating from various combustion and oxidation processes. Recently, the proportion of CO resulting from the combustion of wood for domestic heating may have increased due to political measures promoting this renewable energy source. Here, we used the stable isotope composition of CO (δ13C and δ18O) for the characterization of different CO sources in Switzerland, along with other indicators for traffic and wood combustion (NOx-concentration, aerosol light absorption at different wavelengths). We assessed diurnal variations of the isotopic composition of CO at 3 sites during winter: a village site dominated by domestic heating, a site close to a motorway and a rural site. The isotope ratios of wood combustion emissions were studied at a test facility, indicating significantly lower δ18O of CO from wood combustion compared to traffic emissions. At the village and the motorway site, we observed very pronounced diurnal δ18O-variations of CO with an amplitude of up to 8&permil;. Solving the isotope mass balance equation for three distinct sources (wood combustion, traffic, clean background air) resulted in diurnal patterns consistent with other indicators for wood burning and traffic. The average night-time contribution of wood-burning to total CO was 70% at the village site, 49% at the motorway site and 29% at the rural site based on the isotope mass balance. The results, however, depend strongly on the pure source isotope values, which are not very well known. We therefore additionally applied a combined CO/NOx-isotope model for verification. Here, we separated the CO emissions into different sources based on distinct CO/NOx emissions ratios for wood combustion and traffic, and inserted this information in the isotope mass balance equation. Accordingly, a highly significant agreement between measured and calculated δ18O-values of CO was found (r=0.67, p<0.001). While different proxies for wood combustion all have their uncertainties, our results indicate that the oxygen isotope ratio of CO (but not the carbon isotope ratio) is an independent sensitive tool for source attribution studies.

References 1

Alfarra, M. R., Prévôt, A. S. H., Szidat, S., Sandradewi, J., Weimer, S., Lanz, V. A., Schreiber, D., Mohr, M., and Baltensperger, U.: Identification of the mass spectral signature of organic aerosols from wood burning emissions, Environ. Sci. Technol., 41, 5770–5777, 2007.

Barkan, E. and B. Luz: High precision measurements of $^17$O/$^16$O and $^18$O/$^16$O ratios in H2O, Rapid Comm. Mass Spectrom., 19(24), 3737–3742, 2005.

Brenninkmeijer, C. A. M., Röckmann, T., Bräunlich, M., Jöckel, P., and Bergamaschi, P.: Review of progress in isotope studies of atmospheric carbon monoxide, Chemosphere, 1, 33–52, 1999.

Crutzen, P. J. and Zimmermann, P. H.: The changing photochemistry of the troposphere, Tellus, 43, 136–151, 1991.

Dommen, J., Prévôt, A. S. H., Neininger, B., and Bäumle, M.: Characterization of the photooxidant formation in the metropolitan area of Milan from aircraft measurements, J. Geophys. Res., 107, 8197, doi:8110.1029/2000JD000283, 2002.

Gaeggeler, K., Prévôt, A. S. H., Dommen, J., Legreid, G., Reimann, S., and Baltensperger, U.: Residential wood burning in an Alpine valley as a source for oxygenated volatile organic compounds, hydrocarbons and organic acids, Atmos. Environ., 42, 8278–8287, doi:10.1016/j.atmosenv.2008.07.038, 2008

Gros, V., Jöckel, P., Brenninkmeijer, C. A. M., Röckmann, T., Meinhardt, F., and Graul, R.: Characterization of pollution events observed at Schauinsland, Germany, using CO and its stable isotopes, Atmos. Environ., 36, 2831–2840, 2002.

Huff, A. K. and Thiemens, M. H.: $^17$O/$^16$O and $^18$O/$^16$O isotope measurements of atmospheric carbon monoxide and its sources, Geophys. Res. Lett., 25, 3509–3512, 1998.

Jeong, C.-H., Hopke, P. K., Kim, E., and Lee, D.-W.: The comparison between thermal-optical transmittance elemental carbon and Aethalometer black carbon measured at multiple monitoring sites, Atmos. Environ., 38, 5193–5204, 2004.

Johansson, L. S., Leckner, B., Gustavsson, L., Cooper, D., Tullin, C., and Potter, A.: Emission characteristics of modern and old-type residential boilers fired with wood logs and wood pellets, Atmos. Environ., 38, 4183–4195, 2004.

Kato, S., Akimoto, H., Bräunlich, M., Röckmann, T., and Brenninkmeijer, C. A. M.: Measurements of stable carbon and oxygen isotopic compositions of CO in automobile exhausts and ambient air from semi-urban Mainz, Germany, Geochem. J., 33, 73–77, 1999a.

Kato, S., Akimoto, H., Röckmann, T., Bräunlich, M., and Brenninkmeijer, C. A. M.: Stable isotopic compositions of carbon monoxide from biomass burning experiments, Atmos. Environ., 33, 4357–4362, 1999b.

Kirchstetter, T. W., Harley, R. A., Kreisberg, N. M., Stolzenburg, M. R., and Hering, S. V.: On-road measurement of fine particle and nitrogen oxide emissions from light- and heavy-duty motor vehicles Atmos. Environ., 33, 2955–2968, 1999.

Lanz, V. A., Alfarra, M. R., Baltensperger, U., Buchmann, B., Hueglin, C., and Prévôt, 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 Prévôt, 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.

Mak, J. E. and Yang, W. B.: Technique for analysis of air samples for $^13$C and $^18$O in carbon monoxide via continuous-flow isotope ratio mass spectrometry, Anal. Chem., 70, 5159–5161, 1998.

Pataki, D. E., Ehleringer, J. R., Flanagan, L. B., Yakir, D., Bowling, D. R., Still, C. J., Buchmann, N., Kaplan, J. O., and Berry, J. A.: The application and interpretation of Keeling plots in terrestrial carbon cycle research, Global Biogeochem. Cy., 1022, doi:10.1029/2001GB001850, 2003.

Prévôt, A. S. H., Dommen, J., and Bäumle, M.: Influence of road traffic on volatile organic compound concentrations in and above a deep Alpine valley, Atmos. Environ., 34, 4719–4726, 2000a.

Prévôt, A. S. H., Dommen, J., Bäumle, M., and Furger, M.: Diurnal Variations of volatile organic compounds and local circulation systems in an Alpine valley, Atmos. Environ., 34, 1413–1423, 2000b.

Röckmann, T., Jöckel, P., Gros, V., Bräunlich, M., Possnert, G., and Brenninkmeijer, C. A. M.: Using $^14$C, $^13$C, $^18$O and $^17$O isotopic variations to provide insights into the high northern latitude surface CO inventory, Atmos. Chem. Phys., 2, 147–159, 2002.

Sandradewi, J., Prévôt, A. S. H., Szidat, S., Perron, N., Alfarra, M. R., Lanz, V. A., Weingartner, E., and Baltensperger, U.: Using aerosol light absorption measurements for the quantitative determination of wood burning and traffic emission contributions to particulate matter, Environ. Sci. Technol., 42, 3316–3323, 2008a.

Sandradewi, J., Prévôt, A. S. H., Weingartner, E., Schmidhauser, R., Gysel, M., and Baltensperger, U.: A study of wood burning and traffic aerosols in an Alpine valley using a multi-wavelength Aethalometer, Atmos. Environ., 42, 101–112, doi:110.1016/j.atmosenv.2007.1009.1034, 2008b.

Saurer, M., Robertson, I., Siegwolf, R., and Leuenberger, M.: Oxygen isotope analysis of cellulose: An interlaboratory comparison, Anal. Chem., 70, 2074–2080, 1998.

Steinbacher, M., Zellweger, C., Schwarzenbach, B., Bugmann, S., Buchmann, B., Ordonez, C., Prévôt, A. S. H., and Hueglin, C.: Nitrogen oxide measurements at rural sites in Switzerland: Bias of conventional measurement techniques, J. Geophys. Res., 112, D11307, doi:10.1029/2006JD007971, 2007.

Stevens, C. M., Walling, D., Venters, A., Ross, L. E., Engelkem, A, and Krout, L.: Isotopic composition of atmospheric carbon monoxide, Earth. Planet. Sc. Lett., 16, 147–165, 1972.

Stevens, C. M. and Wagner, A. F.: The role of isotope fractionation effects in atmospheric chemistry, Z. Naturforsch., 44A, 376–384, 1989.

Szidat, S., Jenk, T. M., Synal, H.-A., Kalberer, M., Wacker, L., Hajdas, I., Kasper-Giebl, A., and Baltensperger, U.: Contribution of fossil fuel, biomass-burning, and biogenic emissions to carbonaceous aerosols in Zurich as traced by $^14$C, J. Geophys. Res., 111, D07206, doi:10.1029/2005JD006590, 2006.

Szidat, S., Prévôt, 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.

Theis, D. E., Saurer, M., Blum, H., Frossard, E., and Siegwolf, R. T. W.: A portable automated system for trace gas sampling in the field and stable isotope analysis in the laboratory, Rapid Commun. Mass Spectrom., 18, 2106–2112, 2004.

Tsunogai, U., Hachisu, Y., Komatsu, D. D., Nakagawa, F., Gamo, T., and Akiyama, K.: An updated estimation of the stable carbon and oxygen isotopic compositions of automobile CO emissions, Atmos. Environ., 37, 4901-4910, 2003.

Weimer, S., Alfarra, M. R., Schreiber, D., Mohr, M., Prévôt, A. S. H., and Baltensperger, U.: Organic aerosol mass spectral signatures from wood burning emissions: Influence of burning conditions and wood type, J. Geophys. Res., 113, D10304, doi:10.1029/2007JD009309, 2008.

Widory, D., Roy, S., Le Moullec, Y., Goupil, G., and Cocherie, A.: The origin of atmospheric particles in Paris: a view through carbon and lead isotopes, Atmos. Environ., 38, 953–961, 2004.