References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-11-6945-2011

Observations of the temperature dependent response of ozone to NOx reductions in the Sacramento, CA urban plume

LaFranchi

B. W.

¹ ⁵ Goldstein

A. H.

² ³ Cohen

R. C.

¹ ⁴

Department of Chemistry, University of California, Berkeley, CA, USA

Department of Environmental Science, Policy, and Management, University of California, Berkeley, CA, USA

Department of Civil and Environmental Engineering, University of California, Berkeley, USA

Department of Earth and Planetary Science, University of California, Berkeley, USA

now at: Center for Accelerator Mass Spectrometry, Lawrence Livermore National Laboratory, Livermore, CA, USA

18 07 2011

11 14 6945 6960

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/11/6945/2011/acp-11-6945-2011.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/6945/2011/acp-11-6945-2011.pdf

Observations of NOx in the Sacramento, CA region show that mixing ratios decreased by 30 % between 2001 and 2008. Here we use an observation-based method to quantify net ozone (O3) production rates in the outflow from the Sacramento metropolitan region and examine the O3 decrease resulting from reductions in NOx emissions. This observational method does not rely on assumptions about detailed chemistry of ozone production, rather it is an independent means to verify and test these assumptions. We use an instantaneous steady-state model as well as a detailed 1-D plume model to aid in interpretation of the ozone production inferred from observations. In agreement with the models, the observations show that early in the plume, the NOx dependence for Ox (Ox = O3 + NO2) production is strongly coupled with temperature, suggesting that temperature-dependent biogenic VOC emissions and other temperature-related effects can drive Ox production between NOx-limited and NOx-suppressed regimes. As a result, NOx reductions were found to be most effective at higher temperatures over the 7 year period. We show that violations of the California 1-h O3 standard (90 ppb) in the region have been decreasing linearly with decreases in NOx (at a given temperature) and predict that reductions of NOx concentrations (and presumably emissions) by an additional 30 % (relative to 2007 levels) will eliminate violations of the state 1 h standard in the region. If current trends continue, a 30 % decrease in NOx is expected by 2012, and an end to violations of the 1 h standard in the Sacramento region appears to be imminent.

References 1

Archibald, A. T., Cooke, M. C., Utembe, S. R., Shallcross, D. E., Derwent, R. G., and Jenkin, M. E.: Impacts of mechanistic changes on HOx formation and recycling in the oxidation of isoprene, Atmos. Chem. Phys., 10, 8097–8118, http://dx.doi.org/10.5194/acp-10-8097-2010doi:10.5194/acp-10-8097-2010, 2010.

Ashmore, M. R.: Assessing the future global impacts of ozone on vegetation, Plant Cell Environ., 28, 949–964, 2005.

Ban-Weiss, G. A., McLaughlin, J. P., Harley, R. A., Lunden, M. M., Kirchstetter, T. W., Kean, A. J., Strawa, A. W., Stevenson, E. D., and Kendall, G. R.: Long-term changes in emissions of nitrogen oxides and particulate matter from on-road gasoline and diesel vehicles, Atmos. Environ., 42, 220–232, http://dx.doi.org/10.1016/j.atmosenv.2007.09.049doi:10.1016/j.atmosenv.2007.09.049, 2008.

Bouvier-Brown, N. C., Goldstein, A. H., Gilman, J. B., Kuster, W. C., and de Gouw, J. A.: In-situ ambient quantification of monoterpenes, sesquiterpenes, and related oxygenated compounds during BEARPEX~2007: implications for gas- and particle-phase chemistry, Atmos. Chem. Phys., 9, 5505–5518, http://dx.doi.org/10.5194/acp-9-5505-2009doi:10.5194/acp-9-5505-2009, 2009.

CARB – California Air Resources Board Air Quality Database, http://www.arb.ca.gov/aqd/aqdcd/aqdcd.htm, last access: 15~September, 2009.

Carroll, J. J., and Dixon, A. J.: Regional scale transport over complex terrain, a case study: tracing the Sacramento plume in the Sierra Nevada of California, Atmos. Environ., 36, 3745–3758, 2002.

CIMIS – California Irrigation Management Information System: http://www.cimis.water.ca.gov/cimis/welcome.jsp, last access: 15~September, 2009.

Cleary, P. A., Murphy, J. G., Wooldridge, P. J., Day, D. A., Millet, D. B., McKay, M., Goldstein, A. H., and Cohen, R. C.: Observations of total alkyl nitrates within the Sacramento Urban Plume, Atmos. Chem. Phys. Discuss., 5, 4801–4843, http://dx.doi.org/10.5194/acpd-5-4801-2005doi:10.5194/acpd-5-4801-2005, 2005.

Cleary, P. A., Wooldridge, P. J., Millet, D. B., McKay, M., Goldstein, A. H., and Cohen, R. C.: Observations of total peroxy nitrates and aldehydes: measurement interpretation and inference of OH radical concentrations, Atmos. Chem. Phys., 7, 1947–1960, http://dx.doi.org/10.5194/acp-7-1947-2007doi:10.5194/acp-7-1947-2007, 2007.

Cox, P., Delao, A., Komorniczak, A., and Weller, R.: The California Almanac of Emissions and Air Quality, California Air Resources Board, 2009.

Da Silva, G., Graham, C., and Wang, Z. F.: Unimolecular beta-Hydroxyperoxy Radical Decomposition with OH Recycling in the Photochemical Oxidation of Isoprene, Environ. Sci. Technol., 44, 250–256, http://dx.doi.org/10.1021/es900924ddoi:10.1021/es900924d, 2010.

Day, D. A., Wooldridge, P. J., and Cohen, R. C.: Observations of the effects of temperature on atmospheric HNO3, $§igma$ANs, $§igma$PNs, and NOx: evidence for a temperature-dependent HOx source, Atmos. Chem. Phys., 8, 1867–1879, http://dx.doi.org/10.5194/acp-8-1867-2008doi:10.5194/acp-8-1867-2008, 2008.

Day, D. A., Farmer, D. K., Goldstein, A. H., Wooldridge, P. J., Minejima, C., and Cohen, R. C.: Observations of NOx, $§igma$PNs, $§igma$ANs, and HNO3 at a Rural Site in the California Sierra Nevada Mountains: summertime diurnal cycles, Atmos. Chem. Phys., 9, 4879–4896, http://dx.doi.org/10.5194/acp-9-4879-2009doi:10.5194/acp-9-4879-2009, 2009.

Dillon, M., Lamanna, M., Schade, G., Goldstein, A., and Cohen, R.: Chemical evolution of the Sacramento urban plume: Transport and oxidation, J. Geophys. Res., 107, 4046, doi:4010.1029/2001JD000969, 2002.

Dreyfus, G. B., Schade, G. W., and Goldstein, A. H.: Observational constraints on the contribution of isoprene oxidation to ozone production on the western slope of the Sierra Nevada, California, J. Geophys. Res., 107, 4365, doi:4310.1029/2001JD001490, 2002.

Dunlea, E. J., Herndon, S. C., Nelson, D. D., Volkamer, R. M., San Martini, F., Sheehy, P. M., Zahniser, M. S., Shorter, J. H., Wormhoudt, J. C., Lamb, B. K., Allwine, E. J., Gaffney, J. S., Marley, N. A., Grutter, M., Marquez, C., Blanco, S., Cardenas, B., Retama, A., Ramos Villegas, C. R., Kolb, C. E., Molina, L. T., and Molina, M. J.: Evaluation of nitrogen dioxide chemiluminescence monitors in a polluted urban environment, Atmos. Chem. Phys., 7, 2691–2704, http://dx.doi.org/10.5194/acp-7-2691-2007doi:10.5194/acp-7-2691-2007, 2007.

Farmer, D. K. and Cohen, R. C.: Observations of HNO3, $§igma$AN, $§igma$PN and NO2 fluxes: evidence for rapid HOx chemistry within a pine forest canopy, Atmos. Chem. Phys., 8, 3899–3917, http://dx.doi.org/10.5194/acp-8-3899-2008doi:10.5194/acp-8-3899-2008, 2008.

Feng, Z. Z. and Kobayashi, K.: Assessing the impacts of current and future concentrations of surface ozone on crop yield with meta-analysis, Atmos. Environ., 43, 1510–1519, http://dx.doi.org/10.1016/j.atmosenv.2008.11.033doi:10.1016/j.atmosenv.2008.11.033, 2009.

Fuhrer, J.: Ozone risk for crops and pastures in present and future climates, Naturwissenschaften, 96, 173–194, http://dx.doi.org/10.1007/s00114-008-0468-7doi:10.1007/s00114-008-0468-7, 2009.

Grosjean, D. and Harrison, J.: Response of chemi-luminescence NOx analyzers and ultraviolet ozone analyzers to organic air-pollutants, Environ. Sci. Technol., 19, 862–865, 1985.

Harley, R. A., Marr, L. C., Lehner, J. K., and Giddings, S. N.: Changes in motor vehicle emissions on diurnal to decadal time scales and effects on atmospheric composition, Environ. Sci. Technol., 39, 5356–5362, 2005.

Herman, D. J., Halverson, L. J., and Firestone, M. K.: Nitrogen dynamics in an annual grassland: oak canopy, climate, and microbial population effects, Ecol. Appl., 13, 593–604, 2003.

Hofzumahaus, A., Rohrer, F., Lu, K. D., Bohn, B., Brauers, T., Chang, C. C., Fuchs, H., Holland, F., Kita, K., Kondo, Y., Li, X., Lou, S. R., Shao, M., Zeng, L. M., Wahner, A., and Zhang, Y. H.: Amplified Trace Gas Removal in the Troposphere, Science, 324, 1702–1704, http://dx.doi.org/10.1126/science.1164566doi:10.1126/science.1164566, 2009.

Kleinman, L. I., Daum, P. H., Lee, J. H., Lee, Y. N., Nunnermacker, L. J., Springston, S. R., Newman, L., WeinsteinLloyd, J., and Sillman, S.: Dependence of ozone production on NO and hydrocarbons in the troposphere, Geophys. Res. Lett., 24, 2299–2302, 1997.

Kurpius, M. R. and Goldstein, A. H.: Gas-phase chemistry dominates O3 loss to a forest, implying a source of aerosols and hydroxyl radicals to the atmosphere, Geophys. Res. Lett., 30, 1371, 2003.

Lamanna, M. and Goldstein, A.: In situ measurements of C-2-C-10 volatile organic compounds above a Sierra Nevada ponderosa pine plantation, J. Geophys. Res., 104, 21247–21262, 1999.

Lelieveld, J., Butler, T. M., Crowley, J. N., Dillon, T. J., Fischer, H., Ganzeveld, L., Harder, H., Lawrence, M. G., Martinez, M., Taraborrelli, D., and Williams, J.: Atmospheric oxidation capacity sustained by a tropical forest, Nature, 452, 737–740, 2008.

McClellan, R. O., Frampton, M. W., Koutrakis, P., McDonnell, W. F., Moolgavkar, S., North, D. W., Smith, A. E., Smith, R. L., and Utell, M. J.: Critical considerations in evaluating scientific evidence of health effects of ambient ozone: a conference report, Inhal. Toxicol., 21, 1–36, http://dx.doi.org/10.1080/08958370903176735doi:10.1080/08958370903176735, 2009.

Morgan, P. B., Ainsworth, E. A., and Long, S. P.: How does elevated ozone impact soybean? A meta-analysis of photosynthesis, growth and yield, Plant Cell Environ., 26, 1317–1328, 2003.

Muller, N., Tong, D., and Mendelsohn, R.: Regulating NOx and SO2 Emissions in Atlanta, B. E. J. Econ. Anal. Pol., 9, Art 3, 2009.

Murphy, J. G., Day, D. A., Cleary, P. A., Wooldridge, P. J., and Cohen, R. C.: Observations of the diurnal and seasonal trends in nitrogen oxides in the western Sierra Nevada, Atmos. Chem. Phys., 6, 5321–5338, http://dx.doi.org/10.5194/acp-6-5321-2006doi:10.5194/acp-6-5321-2006, 2006a.

Murphy, J. G., Day, D. A., Cleary, P. A., Wooldridge, P. J., Millet, D. B., Goldstein, A. H., and Cohen, R. C.: The weekend effect within and downwind of Sacramento: Part 2 Observational evidence for chemical and dynamical contributions, Atmos. Chem. Phys. Discuss., 6, 11971–12019, http://dx.doi.org/10.5194/acpd-6-11971-2006doi:10.5194/acpd-6-11971-2006, 2006b.

Murphy, J. G., Day, D. A., Cleary, P. A., Wooldridge, P. J., Millet, D. B., Goldstein, A. H., and Cohen, R. C.: The weekend effect within and downwind of Sacramento - Part~1: Observations of ozone, nitrogen oxides, and VOC reactivity, Atmos. Chem. Phys., 7, 5327–5339, http://dx.doi.org/10.5194/acp-7-5327-2007doi:10.5194/acp-7-5327-2007, 2007.

Parrish, D. D., Millet, D. B., and Goldstein, A. H.: Increasing ozone in marine boundary layer inflow at the west coasts of North America and Europe, Atmos. Chem. Phys., 9, 1303–1323, http://dx.doi.org/10.5194/acp-9-1303-2009doi:10.5194/acp-9-1303-2009, 2009.

Parrish, D. D., Aikin, K. C., Oltmans, S. J., Johnson, B. J., Ives, M., and Sweeny, C.: Impact of transported background ozone inflow on summertime air quality in a California ozone exceedance area, Atmos. Chem. Phys., 10, 10093–10109, http://dx.doi.org/10.5194/acp-10-10093-2010doi:10.5194/acp-10-10093-2010, 2010.

Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kurten, A., St Clair, J. M., Seinfeld, J. H., and Wennberg, P. O.: Unexpected Epoxide Formation in the Gas-Phase Photooxidation of Isoprene, Science, 325, 730–733, 2009.

Peeters, J., Nguyen, T. L., and Vereecken, L.: HOx radical regeneration in the oxidation of isoprene, Phys. Chem. Chem. Phys., 11, 5935–5939, http://dx.doi.org/10.1039/b908511ddoi:10.1039/b908511d, 2009.

Perez, I. M.: The Photochemical Evolution of the Sacramento Urban Plume: a Guide to Controlling Ozone now and in a Warmer Climate, Department of Chemistry, University of California at Berkeley, Berkeley, CA, 155 pp., 2008.

Pérez, I. M., LaFranchi, B. W., and Cohen, R. C.: Nitrogen oxide chemistry in an urban plume: investigation of the chemistry of peroxy and multifunctional organic nitrates with a Lagrangian model, Atmos. Chem. Phys. Discuss., 9, 27099–27165, http://dx.doi.org/10.5194/acpd-9-27099-2009doi:10.5194/acpd-9-27099-2009, 2009.

Ren, X. R., Olson, J. R., Crawford, J. H., Brune, W. H., Mao, J. Q., Long, R. B., Chen, Z., Chen, G., Avery, M. A., Sachse, G. W., Barrick, J. D., Diskin, G. S., Huey, L. G., Fried, A., Cohen, R. C., Heikes, B., Wennberg, P. O., Singh, H. B., Blake, D. R., and Shetter, R. E.: HOx chemistry during INTEX-A~2004: Observation, model calculation, and comparison with previous studies, J. Geophys. Res., 113, D05310, http://dx.doi.org/10.1029/2007JD009166doi:10.1029/2007JD009166, 2008.

Rubin, J. I., Kean, A. J., Harley, R. A., Millet, D. B., and Goldstein, A. H.: Temperature dependence of volatile organic compound evaporative emissions from motor vehicles, J. Geophys. Res. - Atmos., 111, D03305, http://dx.doi.org/10.1029/2005jd006458doi:10.1029/2005jd006458, 2006.

Russell, A. R., Valin, L. C., Bucsela, E. J., Wenig, M. O., and Cohen, R. C.: Space-based Constraints on Spatial and Temporal Patterns of NOx Emissions in California, 2005–2008, Environ. Sci. Technol., 44, 3608–3615, http://dx.doi.org/10.1021/es903451jdoi:10.1021/es903451j, 2010.

Schade, G. W., Goldstein, A. H., Gray, D. W., and Lerdau, M. T.: Canopy and leaf level 2-methyl-3-buten-2-ol fluxes from a ponderosa pine plantation, Atmos. Environ., 34, 3535–3544, 2000.

Sillman, S.: The Use of NOy, H2O2, and HNO3 as Indicators for Ozone-NOx-Hydrocarbon Sensitivity in Urban Locations, J. Geophys. Res.-Atmos., 100, 14175–14188, 1995.

Sillman, S., Logan, J. A., and Wofsy, S. C.: The Sensitivity of Ozone to Nitrogen-Oxides and Hydrocarbons in Regional Ozone Episodes, J. Geophys. Res.-Atmos., 95, 1837–1851, 1990.

Spaulding, R. S., Schade, G. W., Goldstein, A. H., and Charles, M. J.: Characterization of secondary atmospheric photooxidation products: Evidence for biogenic and anthropogenic sources, J. Geophys. Res., 108, 4247, http://dx.doi.org/10.1029/2002JD002478doi:10.1029/2002JD002478, 2003.

Stavrakou, T., Peeters, J., and Müller, J.-F.: Improved global modelling of HOx recycling in isoprene oxidation: evaluation against the GABRIEL and INTEX-A aircraft campaign measurements, Atmos. Chem. Phys., 10, 9863–9878, http://dx.doi.org/10.5194/acp-10-9863-2010doi:10.5194/acp-10-9863-2010, 2010.

Steinbacher, M., Zellweger, C., Schwarzenbach, B., Bugmann, S., Buchmann, B., Ordonez, C., Prevot, A. S. H., and Hueglin, C.: Nitrogen oxide measurements at rural sites in Switzerland: Bias of conventional measurement techniques, J. Geophys. Res.-Atmos., 112, D11307, http://dx.doi.org/10.1029/2006jd007971doi:10.1029/2006jd007971, 2007.

Steiner, A. L., Tonse, S., Cohen, R. C., Goldstein, A. H., and Harley, R. A.: Influence of future climate and emissions on regional air quality in California, J. Geophys. Res., 111, D18303, doi:18310.11029/12005JD006935, 2006.

Steiner, A. L., Cohen, R. C., Harley, R. A., Tonse, S., Millet, D. B., Schade, G. W., and Goldstein, A. H.: VOC reactivity in central California: comparing an air quality model to ground-based measurements, Atmos. Chem. Phys., 8, 351–368, http://dx.doi.org/10.5194/acp-8-351-2008doi:10.5194/acp-8-351-2008, 2008.

Tang, G., Li, X., Wang, Y., Xin, J., and Ren, X.: Surface ozone trend details and interpretations in Beijing, 2001-2006, Atmos. Chem. Phys., 9, 8813–8823, http://dx.doi.org/10.5194/acp-9-8813-2009doi:10.5194/acp-9-8813-2009, 2009.

Thornton, J., Wooldridge, P., and Cohen, R.: Atmospheric NO2: In situ laser-induced fluorescence detection at parts per trillion mixing ratios, Anal. Chem., 72, 528-539, 2000.

Thornton, J. A., Wooldridge, P. J., Cohen, R. C., Martinez, M., Harder, H., Brune, W. H., Williams, E. J., Roberts, J. M., Fehsenfeld, F. C., Hall, S. R., Shetter, R. E., Wert, B. P., and Fried, A.: Ozone production rates as a function of NOx abundances and HOx production rates in the Nashville urban plume, J. Geophys. Res., 107, 4146, doi:4110.1029/2001JD000932, 2002.

Trasande, L. and Thurston, G. D.: The role of air pollution in asthma and other pediatric morbidities, J. Allergy Clin. Immun., 115, 689–699, http://dx.doi.org/10.1016/j.jaci.2005.01.056doi:10.1016/j.jaci.2005.01.056, 2005.

Uysal, N. and Schapira, R. M.: Effects of ozone on lung function and lung diseases, Curr. Opin. Pulm. Med., 9, 144–150, 2003.

Winer, A. M., Peters, J. W., Smith, J. P., and Pitts, J. N.: Response of commercial chemiluminescent NO-NO2 analyzers to other notrogen-containing compounds, Environ. Sci. Technol., 8, 1118–1121, 1974.

Yang, W. and Omaye, S. T.: Air pollutants, oxidative stress and human health, Mutat. Res.-Gen. Tox. En., 674, 45–54, http://dx.doi.org/10.1016/j.mrgentox.2008.10.005doi:10.1016/j.mrgentox.2008.10.005, 2009.

Zavala, M., Lei, W., Molina, M. J., and Molina, L. T.: Modeled and observed ozone sensitivity to mobile-source emissions in Mexico City, Atmos. Chem. Phys., 9, 39–55, http://dx.doi.org/10.5194/acp-9-39-2009doi:10.5194/acp-9-39-2009, 2009.