References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-10-21567-2010

Measurement of fossil fuel derived carbon dioxide and other anthropogenic trace gases above Sacramento, California in Spring 2009

Turnbull

J. C.

¹ ² Karion

¹ ³ Fischer

M. L.

⁴ Faloona

⁵ Guilderson

⁶ Lehman

S. J.

² Miller

B. R.

¹ ³ Miller

J. B.

¹ ³ Montzka

¹ Sherwood

⁷ Saripalli

⁷ Sweeney

¹ ³ Tans

P. P.

NOAA/ESRL, 325 Broadway, Boulder, CO 80305, USA

INSTAAR, University of Colorado at Boulder, Boulder, CO 80309-0450, USA

CIRES, University of Colorado at Boulder, Boulder, CO 80309-0216, USA

Lawrence Berkeley Laboratory, 1 Cyclotron Rd, Berkeley, CA 94720, USA

Dept. of Land, Air and Water Resources, University of California, Davis, CA 95616-8627, USA

Lawrence Livermore National Laboratories, Center for Accelerator Mass Spectrometry, Livermore, CA 94551, USA

KalScott Engineering, 811 E 28th St, Lawrence, KS 66046, USA

10 09 2010

10 9 21567 21613

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Direct quantification of fossil fuel CO2 (CO2ff) in atmospheric samples can be used to examine several carbon cycle and air quality questions. We collected in-situ CO2, CO, and CH4 measurements and flask samples in the boundary layer and free troposphere over Sacramento, California, USA, during two aircraft flights over and downwind of this urban area during spring of 2009. The flask samples were analyzed for Δ14CO2 and CO2 to determine the recently added CO2ff mole fraction. A suite of additional greenhouse gases including hydrocarbons and halocarbons were measured in the same samples. Strong correlations were observed between CO2ff and numerous trace gases associated with urban emissions. From these correlations we estimate emission ratios between CO2ff and these species, and compare these with bottom-up inventory-derived estimates. Recent county level inventory estimates for carbon monoxide (CO) and benzene from the California Air Resources Board CEPAM database are in good agreement with our measured emission ratios, whereas older emissions inventories appear to overestimate emissions of these gases. For most other trace species, there are substantial differences between our measured emission ratios and those derived from available emission inventories. For the first flight, we combine in situ CO measurements with the measured CO:CO2ff emission ratio of 14±2 ppbCO/ppmCO2 to derive an estimate of CO2ff mole fraction throughout this flight, and also estimate the biospheric CO2 mixing ratio (CO2bio) from the difference of total and fossil CO2. The resulting CO2bio varies substantially between air in the urban plume and the surrounding boundary layer air. Finally, we use the in situ estimates of CO2ff mole fraction to infer total fossil fuel CO2 emissions from the Sacramento region, using a mass balance approach. However the resulting emissions are uncertain to within a factor of two due to uncertainties in wind speed and boundary layer height. Nevertheless, this first attempt to estimate urban-scale CO2ff from atmospheric radiocarbon measurements shows that CO2ff can be used to verify and improve emission inventories for many poorly known anthropogenic species, separate biospheric CO2, and indicates the potential to constrain the CO2ff emissions if transport uncertainties are reduced.

References 1

Andreae, M. O. and Merlet, P.: Emission of trace gases and aerosols from biomass burning, Global Biogeochem. Cy., 15, 955–966, 2001.

Atkinson, R., Arey, J., and Achmann, S. M.: Atmospheric chemistry of alkanes: Review and recent developments, Atmos. Environ., 42, 5859–5871, 2007.

Baker, A. K., Beyersdorf, A. J., Doezema, L. A., Katzenstein, A., Meinardi, S., Simpson, I. J., Blake, D. R., and Rowland, S.: Measurements of nonmethane hydrocarbons in 28 United States cities, Atmos. Environ., 42, 170–182, 2008.

Bakwin, P. S., Tans, P. P., White, J. W. C., and Andres, R. J.: Determination of the isotopic ($^13$C/$^12$C) discrimination by terrestrial biology from a global network of observations, Global Biogeochem. Cy., 12, 555–562, 1998.

Bergamaschi, P., Hein, R., Heimann, M., and Crutzen, P. J.: Inverse modeling of the global CO cycle 1. Inversion of CO mixing ratios, J. Geophys. Res., 105, 1909–1927, 2000.

Bishop, G. A. and Stedman, D. H.: A decade of on-road emissions measurements, Environ. Sci. Technol., 42, 1651–1656, 2008.

Boden, T. A., Marland, G., and Andres, R. J.: Global, regional and national fossil-fuel CO2 emissions, Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, US Department of Energy, Oak Ridge, Tenn., USA, 2009.

Bousquet, P., Ciais, P., Miller, J. B., Dlugokencky, E. J., Hauglustaine, D., Prigent, C., van der Werf, G. R., Peylin, P., Brunke, E.-G., Carouge, C., Langenfelds, R. L., Lathiere, J., Papa, F., Ramonet, M., Schmidt, M., Steele, L. P., Tyler, S. C., and White, J. W. C.: Contribution of anthropogenic and natural sources to atmospheric methane variability, Nature, 443, 439–443, doi:10.1038/nature05132, 2006.

Chen, H., Winderlich, J., Gerbig, C., Hoefer, A., Rella, C. W., Crosson, E. R., Van Pelt, A., Steinbach, J., Kolle, O., Beck, V., Daube, B. C., Gottlieb, E. W., Chow, V., Santoni, G., and Wofsy, S. C.: High-accuracy continuous airborne measurements of greenhouse gases (CO2 and CH4) using the cavity ring-down spectroscopy (CRDS) technique, Atmos. Meas. Technol., 3, 375–286, 2010.

Crosson, E. R.: A cavity ring-down analyzer for measuring atmospheric levels of methane, carbon dioxide, and water vapor, Appl. Phys. B: 92, 403–408, 2008.

Draxler, R., and Rolph, G.: HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectory) Model access via NOAA ARL READY Website (http://ready.arl.noaa.gov/HYSPLIT.php), 2010.

Frey, H. C. and Small, M. J.: Uncertainty in emission factors and emission inventories, J. Indust. Ecol., 7, 9–11, 2003.

Frost, G. J., McKeen, S. A., Trainer, M., Ryerson, T. B., Neuman, J., Roberts, J., Swanson, A., Holloway, J., Sueper, D., Fortin, T., Parrish, D. D., Fehsenfeld, F., Flocke, F., Peckham, S., Grell, G., Kowal, D., Cartwright, J., Auerbach, N., and Habermann, T.: Effects of changing power plant NOx emissions on ozone in the eastern United States: Proof of concept, J. Geophys. Res., 111, D12306, doi:10.1029/2005JD006354, 2006.

Geller, L. S., Elkins, J. W., Lobert, J. M., Clarke, A. D., Hurst, D. F., Butler, J. H., and Myers, R. C.: Tropospheric SF$_6$: Observed latitudinal distribution and trends, derived emissions and interhemispheric exchange time, Geophys. Res. Lett., 24, 675–678, 1997.

Gerbig, C., Lin, J., Wofsy, S. C., Daube, B. C., Andrews, A. E., Stephens, B. B., Bakwin, P. S., and Grainger, C.: Toward constraining regional-scale fluxes of CO2 with atmospheric observations over a continent: 2. Analysis of COBRA data using a receptor-oriented framework, J. Geophys. Res., 108, 4757, doi:10.1029/2003JD003770, 2003.

Gerbig, C., Schmitgen, S., Kley, D., Volz-Thomas, A., Dewey, K., and Haaks, D.: An improved fast-response vacuum-UV resonance fluorescence CO instrument, J. Geophys. Res., 104, 1699–1704, 1999.

Graven, H. D., Guilderson, T. P., and Keeling, R. F.: Methods for high-precision $^14$C AMS measurement of atmospheric CO2 at LLNL, Radiocarbon, 49, 349–356, 2007.

Graven, H. D., Stephens, B. B., Guilderson, T. P., Campos, T. L., Schimel, D. S., Campbell, J. E., and Keeling, R. F.: Vertical profiles of biospheric and fossil fuel-derived CO2 and fossil fuel CO2 : CO ratios from airborne measurements of $\Delta^14$C, CO2 and CO above Colorado, USA, Tellus, 61, 53–546, 2009.

Gurney, K. R., Law, R. M., Denning, A. S., Rayner, P. J., Baker, D., Bousquet, P., Bruhwiler, L., Chen, Y.-H., Ciais, P., Fan, S., Fung, I. Y., Gloor, M., Heimann, M., Higuchi, K., John, J., Maki, T., Maksyutov, S., Masarie, K. A., Peylin, P., Prather, M., Pak, B. C., Randerson, J., Sarmiento, J. L., Taguchi, S., Takahashi, T., and Yuen, C.-W.: Towards robust regional estimates of CO2 sources and sinks using atmospheric transport models, Nature, 415, 626–630, 2002.

Gurney, K. R., Mendoza, D. L., Zhou, Y., Fischer, M. L., Miller, C. C., Geethakumar, S., and de la Rue du Can, S.: High resolution fossil fuel combustion CO2 emission fluxes for the United States, Environ. Sci. Technol., 43, 5535–5541, doi:10.1021/es900806c, 2009.

Hirsch, A. I., Michalak, A. M., Bruhwiler, L. M., Peters, W., Dlugokencky, E. J., and Tans, P. P.: Inverse modeling estimates of the global nitrous oxide surface flux from 1998-2001, Global Biogeochem. Cy., 20, GB1008, doi:10.1029/2004GB002443, 2006.

Hudman, R., Murray, L., Jacob, D. J., Millet, D., Turquety, S., Wu, S., Blake, D. R., Goldstein, A., Holloway, J., and Sachse, G. W.: Biogenic versus anthropogenic sources of CO in the United States, Geophys. Res. Lett., 35, L04801, doi:10.1029/2007GL032393, 2008.

IPCC: Good practice guidance and uncertainty management in national greenhouse gas inventories, IPCC, 2000.

Karion, A.: Local signals of CO2, CH4 and N2O in the San Francisco and Sacramento regions of California, in preparation, 2010.

Lehman, S. J., Miller, J. B., Turnbull, J. C., Southon, J. R., Tans, P. P., and Sweeney, C.: $^14$CO2 measurements in the NOAA/ESRL Global Co-operative Sampling Network: An update on measurements and data quality, Expert Group Recommendations from the 15th WMO/IAEA Meeting of Experts on Carbon Dioxide, Other Greenhouse Gases and Related Tracer Measurement Techniques, Jena, Germany, 2010.

Levin, I. and Karstens, U.: Inferring high-resolution fossil fuel CO2 records at continental sites from combined $^14$CO2 and CO observations, Tellus, 59B, 245–250, doi:10.1111/j.1600-0889.2006.00244.x. , 2007.

Mays, K. L., Shepson, P. B., Stirm, B. H., Karion, A., Sweeney, C., and Gurney, K. R.: Aircraft-based measurements of the carbon footprint of Indianapolis, Environ. Sci. Technol., 43, 7316–7823, 2009.

McCulloch, A., Midgley, P. M., and Ashford, P.: Releases of refrigerant gases (CFC-12, HCFC-22 and HFC-134a) to the atmosphere, Atmos. Environ., 37, 889–902, 2003.

Mesinger, F., DiMego, G., Kalnay, E., Mitchell, K., Shafran, P. C., Ebisuzaki, W., Jovic, D., Woollen, J., Rogers, E., Berbery, E. H., Ek, M. B., Fan, Y., Grumbine, R., Higgins, W., Li, H., Lin, Y., Manifin, G., Parrish, D. D., and Shi, W.: North American Regional reanalysis, Bull. Am. Meteorol. Soc., 87, 343–360, doi:10.1175/BAMS-87-3-343, 2006.

Montzka, S. A., Myers, R. C., Butler, J. H., Elkins, J. W., and Cummings, S.: Global tropospheric distribution and calibration scale of HCFC-22, Geophys. Res. Lett., 20, 703–706, 1993.

Ohara, T., Akimoto, H., Kurokawa, J.-i., Horii, N., Yamaji, K., Yan, X., and Hayasaka, T.: An Asian emission inventory of anthropogenic emission sources for the period 1980-2020, Atmos. Chem. Phys., 7, 4419–4444, doi:10.5194/acp-7-4419-2007, 2007.

Pacala, S. W., Breidenich, C., Brewer, P. G., Fung, I. Y., Gunson, M. R., Heddle, G., Law, B. E., Marland, G., Paustian, K., Prather, M., Randerson, J. T., Tans, P. P., and Wofsy, S. C.: Verifying greenhouse gas emissions: Methods to support international climate agreements, Committee on Methods for Estimating Greenhouse Gas Emissions; National Research Council, 2010.

Parrish, D. D.: Critical evaluation of US on-road vehicle emission inventories, Atmos. Environ., 40, 2288–2300, 2006.

Peylin, P., Houweling, S., Krol, M. C., Karstens, U., Rödenbeck, C., Geels, C., Vermeulen, A., Badawy, B., Aulagnier, C., Pregger, T., Delage, F., Pieterse, G., Ciais, P., and Heimann, M.: Importance of fossil fuel emissions uncertainties over Europe for CO2 modeling: model intercomparison, Atmos. Chem. Phys. Discuss., 9, 7457–7503, doi:10.5194/acp-9-7457-2009, 2009.

Potosnak, M. J., Wofsy, S. C., Denning, A. S., Conway, T. J., Munger, J. W., and Barnes, D. H.: Influence of biotic exchange and combustion sources on atmospheric CO2 concentrations in New England from observations at a forest flux tower, J. Geophys. Res., 104, 9561–9569, 1999.

Pozzer, A., Pollmann, J., Taraborrelli, D., J�ckel, P., Helmig, D., Tans, P., Hueber, J., and Lelieveld, J.: Observed and simulated global distribution and budget of atmospheric C2-C5 alkanes, Atmos. Chem. Phys., 10, 4403–4422, doi:10.5194/acp-10-4403-2010, 2010.

Press, W. H. and Teukolsky, S.: Fitting straight line data with errors in both coordinates, Comp. Phys., 6, 274–276, 1992.

Rivier, L., Ciais, P., Hauglustaine, D., Bakwin, P. S., Bousquet, P., Peylin, P., and Klonecki, A.: Evaluation of SF$_6$, C2Cl4 and CO as surrogate tracers for fossil fuel CO2 in the Northern Hemisphere using a chemistry transport model, J. Geophys. Res., 111, D16311, doi:10.1029/2005JD006725, 2006.

Ryerson, T. B., Trainer, M., Holloway, J., Parrish, D. D., Huey, L., Sueper, D., Frost, G. J., Donnelly, S., Schauffler, S., Atlas, E., Kuster, W., Golden, P., Hubler, G., Meagher, J., and Fehsenfeld, F.: Observations of ozone formation in power plant plumes and implications for ozone control strategies, Science, 292, 719–723, 2001.

Spivakovsky, C. M., Logan, J. A., Montzka, S. A., Balkanski, Y. J., Foreman-Fowler, M., Jones, D., Horowitz, L., Fusco, A., Brenninkmeijer, C. A. M., Prather, M. J., Wofsy, S. C., and McElroy, M. B.: Three-dimensional climatological distribution of tropospheric OH: Update and evaluation, J. Geophys. Res., 105, 8931–8980, 2000.

Stephens, B. B., Gurney, K. R., Tans, P. P., Sweeney, C., Peters, W., Bruhwiler, L., Ciais, P., Ramonet, M., Bousquet, P., Nakazawa, T., Aoki, S., Machida, T., Inoue, G., Vinnichenko, N., Lloyd, J., Jordan, A., Heimann, M., Shibistowa, O., Langenfelds, R. L., Steele, l. P., Francey, R. J., and Denning, A. S.: Weak northern and strong tropical land carbon uptake from vertical profiles of atmospheric CO2, Science, 316, 1732–1735, 2007.

TEAP: Task force on emissions discrepancies report, UNEP, Montreal Protocol on substances that deplete the ozone layer, 2006.

Trainer, M., Ridley, B., Buhr, M., Kok, G., Walega, J., Hübler, G., Parrish, D. D., and Fehsenfeld, F.: Regional ozone and urban plumes in the southeastern United States: Birmingham, a case study, J. Geophys. Res., 100, 18823–18834, 1995.

Turnbull, J. C., Lehman, S. J., Miller, J. B., Sparks, R. J., Southon, J. R., and Tans, P. P.: A new high precision $^14$CO2 time series for North American continental air, J. Geophys. Res., 112, D11310, doi:10.1029/2006JD008184, 2007.

Turnbull, J. C., Lehman, S. J., Morgan, S., and Wolak, C.: A new automated extraction system for $^14$C measurement in atmospheric CO2, Radiocarbon, 52, 1261–1269, 2010.

Turnbull, J. C., Miller, J. B., Lehman, S. J., Tans, P. P., Sparks, R. J., and Southon, J. R.: Comparison of $^14$CO2, CO and SF$_6$ as tracers for determination of recently added fossil fuel CO2 in the atmosphere and implications for biological CO2 exchange, Geophys. Res. Lett., 33, L01817, doi:10.1029/2005GL024213, 2006.

Turnbull, J. C., Rayner, P. J., Miller, J. B., Naegler, T., Ciais, P., and Cozic, A.: On the use of$^ 14$CO2 as a tracer for fossil fuel CO2: quantifying uncertainties using an atmospheric transport model, J. Geophys. Res., 114, D22302, doi:10.1029/2009JD012308, 2009.

USEPA: Current methods used to estimate emissions, 1985-1999, Procedures Document for National Emission Inventory, Criteria Air Pollutants 1985–1999, USEPA, 2001.

USEPA: AP-42, Fifth Edition. Compilation of air pollutant emission factors, Volume 1: Point and area sources, USEPA (United States Environmental Protection Agency), Research Triangle Park, NC, USA, 2009.

Vaughn, B. H., Ferretti, D. F., Miller, J. B., and White, J. W. C.: Stable isotope measurements of atmospheric CO2 and CH4, in: Handbook of stable isotope analytical techniques, Elsevier BV, Amsterdam, The Netherlands, 2004.

Vogel, F. R., Hammer, S., Steinhof, A., Kromer, B., and Levin, I.: Implication of weekly and diurnal 14C calibration on hourly estimates of CO-based fossil fuel CO2 at a moderately polluted site in south-western Germany, Tellus, doi:10.1111/j.1600-0889.2010.00477.x, 2010.

Warneke, C., de Gouw, J., Stohl, A., Cooper, O., Goldan, P., Kuster, W., Holloway, J., Williams, E., Lerner, B., McKeen, S. A., Trainer, M., Fehsenfeld, F., Altas, E. L., Donnelly, S., Stroud, V., Lueb, A., and Kato, S.: Biomass burning and anthropogenic sources of CO over New England in the summer 2004, J. Geophys. Res., 111, D23S15, doi:10.1029/2005JD006878, 2006.

Warneke, C., McKeen, S. A., de Gouw, J., Goldan, P., Kuster, W., Holloway, J., Williams, E., Lerner, B., Parrish, D. D., Trainer, M., Fehsenfeld, F., Kato, S., Atlas, E. L., Baker, A., and Blake, D. R.: Determination of urban volatile organic compound emission ratios and comparison with an emissions database, J. Geophys. Res., 112, D10S47, doi:10.1029/2006JD007930, 2007.

White, W., Anderson, J., Blumenthal, D., Husar, R., Gillani, N., Husar, J., and Wilson, W., Jr: Formation and transport of secondary air pollutants: Ozone and aerosols in the St Louis urban plume, Science, 194, 187–189, 1976.

Wofsy, S. C., Fan, S.-M., Blake, D., Bradshaw, J., Sandholm, S., Singh, H., Sachse, G., and Harriss, R.: Factors influencing atmospheric composition over subarctic North America during summer, J. Geophys. Res., 99, 1887–1897, 1994.

Zhao, C., Andrews, A. E., Bianco, L., Eluszkiewicz, J., Hirsch, A., MacDonald, C., Nehrkorn, T., and Fischer, M. L.: Atmospheric inverse estimates of methane emissions from Central California, J. Geophys. Res., D114, 16302, 10.1029/2008JD011671, 2009.