References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-12-3273-2012

Primary and secondary sources of formaldehyde in urban atmospheres: Houston Texas region

Parrish

D. D.

¹ Ryerson

T. B.

¹ Mellqvist

² Johansson

² Fried

³ Richter

³ Walega

J. G.

³ Washenfelder

R. A.

¹ ⁴ de Gouw

J. A.

¹ ⁴ Peischl

¹ ⁴ Aikin

K. C.

¹ ⁴ McKeen

S. A.

¹ ⁴ Frost

G. J.

¹ ⁴ Fehsenfeld

F. C.

¹ ⁴ Herndon

S. C.

⁵

NOAA ESRL Chemical Sciences Division, 325 Broadway, Boulder, CO, USA

Earth and Space Sciences, Chalmers University of Technology, Gothenburg, Sweden

Earth Observing Laboratory, National Center for Atmospheric Research, Boulder, CO, USA

CIRES, University of Colorado, Boulder, CO, USA

Aerodyne Research, Inc., Billerica, Massachusetts, USA

05 04 2012

12 7 3273 3288

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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We evaluate the rates of secondary production and primary emission of formaldehyde (CH2O) from petrochemical industrial facilities and on-road vehicles in the Houston Texas region. This evaluation is based upon ambient measurements collected during field studies in 2000, 2006 and 2009. The predominant CH2O source (92 ± 4% of total) is secondary production formed during the atmospheric oxidation of highly reactive volatile organic compounds (HRVOCs) emitted from the petrochemical facilities. Smaller contributions are primary emissions from these facilities (4 ± 2%), and secondary production (~3%) and primary emissions (~1%) from vehicles. The primary emissions from both sectors are well quantified by current emission inventories. Since secondary production dominates, control efforts directed at primary CH2O emissions cannot address the large majority of CH2O sources in the Houston area, although there may still be a role for such efforts. Ongoing efforts to control alkene emissions from the petrochemical facilities, as well as volatile organic compound emissions from the motor vehicle fleet, will effectively reduce the CH2O concentrations in the Houston region. We do not address other emission sectors, such as off-road mobile sources or secondary formation from biogenic hydrocarbons. Previous analyses based on correlations between ambient concentrations of CH2O and various marker species have suggested much larger primary emissions of CH2O, but those results neglect confounding effects of dilution and loss processes, and do not demonstrate the causes of the observed correlations. Similar problems must be suspected in any source apportionment analysis of secondary species based upon correlations of ambient concentrations of pollutants.

References 1

Anderson, L. G., Lanning, J. A., Barrell, R., Miyagishima, J., Jones, R. H., and Wolfe, P.: Sources and sinks of formaldehyde and acetaldehyde: An analysis of Denver's ambient concentration data, Atmos. Environ., 3, 2113–2123, 1996.

Baker, A. K., Beyersdorf, A. J., Doezema, L. A., Katzenstein, A., Meinardi, S., Simpson, I. J., Blake, D. R., and Rowland, F. S.: Measurements of nonmethane hydrocarbons in 28 United States cities, Atmos. Environ., 42, 170–182, http://dx.doi.org/10.1016/j.atmosenv.2007.09.007doi:10.1016/j.atmosenv.2007.09.007, 2008.

Ban-Weiss, G. A., McLaughlin, J. P., Harley, R. A., Kean, A. J., Grosjean, E., and Grosjean, D.: Carbonyl and nitrogen dioxide emissions from gasoline- and diesel-powered motor vehicles, Environ. Sci. Technol., 42, 3944–3950, 2008.

Baylor University: Analysis of airborne data collected during 2006 to characterize HCHO emissions and sources in the Houston area, Final Report Project H-103B, Texas Environmental Research Consortium: Houston, TX, 2009.

Bevington, P. R.: Data reduction error analysis for the physical sciences, McGraw-Hill Book Company, New York, 1969.

Brioude, J., Kim, S.-W., Angevine, W. M., Frost, G. J., Lee, S.-H., McKeen, S. A., Trainer, M., Fehsenfeld, F. C., Holloway, J. S., Ryerson, T. B., Williams, E. J., Petron, G., and Fast, J. D.: Top-down estimate of anthropogenic emission inventories and their interannual variability in Houston using a mesoscale inverse modeling technique, J. Geophys. Res., D20305, http://dx.doi.org/10.1029/2011JD016215doi:10.1029/2011JD016215, 2011.

Brown, S. S., Dube, W. P., Fuchs, H., Ryerson, T. B., Wollny, A. G., Brock, C. A., Bahreini, R., Middlebrook, A. M., Neuman, J. A., Atlas, E., Roberts, J. M., Osthoff, H. D., Trainer, M., Fehsenfeld, F. C., and Ravishankara, A. R.: Reactive uptake coefficients for N2O$_5$ determined from aircraft measurements during the Second Texas Air Quality Study: Comparison to current model parameterizations, J. Geophys. Res., 114, D00F10, http://dx.doi.org/10.1029/2008JD011679doi:10.1029/2008JD011679, 2009.

Brown, S. S., Dubé, W. P., Peischl, J., Ryerson, T. B., Atlas, E., Warneke, C., de Gouw, J., Te Lintel Hekkert, S., Brock, C. A., Flocke, F., Trainer, M., Parrish, D. D., Fehsenfeld, F. C., and Ravishankara, A. R.: Budgets for nocturnal VOC oxidation by nitrate radicals aloft during the 2006 Texas Air Quality Study, J. Geophys. Res., 116, D24305, http://dx.doi.org/10.1029/2011JD016544doi:10.1029/2011JD016544, 2011.

Buzcu Guven, B. and Olaguer, E. P.: Ambient formaldehyde source attribution in Houston during TexAQS II and TRAMP, Atmos. Environ., 45, 4272–4280, 2011.

Byun, D. W., Kim, S.-T., and Kim, S.-B.: Evaluation of air quality models for the simulation of a high ozone episode in the Houston metropolitan area, Atmos. Environ., 41, 837–853, http://dx.doi.org/10.1016/j.atmosenv.2006.08.038doi:10.1016/j.atmosenv.2006.08.038, 2007.

Cowling, E. B., Furiness, C., Dimitriades, B., and Parrish, D.: Final rapid synthesis report: Findings from the second Texas Air Quality Study (TexAQS II), Final Report, TCEQ Contract No. 582-4 65614, Texas Commission on Environmental Quality, Austin, Texas, 143 pp., 2007.

Daube Jr., B. C., Boering, K. A., Andrews, A. E., and Wofsy, S. C.: A high-precision fast-response airborne CO2 analyzer for in situ sampling from the surface to the middle stratosphere, J. Atmos. Oceanic Technol., 19, 1532–1543, http://dx.doi.org/10.1175/1520-0426(2002)019<1532:AHPFRA>2.0.CO;2doi:10.1175/1520-0426(2002)019<1532:AHPFRA>2.0.CO;2, 2002.

Daum, P. H., Kleinman, L. I., Springston, S. R., Nunnermacker, L. J., Lee, Y.-N., Weinstein-Lloyd, J., Zheng, J., and Berkowitz, C. M.: A comparative study of O3 formation in the Houston urban and industrial plumes during the 2000 Texas Air Quality Study, J. Geophys. Res., 108, 4715, http://dx.doi.org/10.1029/2003JD003552doi:10.1029/2003JD003552, 2003.

de Gouw, J. A. and Warneke, C.: Measurements of volatile organic compounds in the earth's atmosphere using proton-transfer-reaction mass spectrometry, Mass Spectrom. Rev., $26$, 223–257, http://dx.doi.org/10.1002/mas.20119doi:10.1002/mas.20119, 2007.

de Gouw, J. A., Middlebrook, A. M., Warneke, C., Goldan, P. D., Kuster, W. C., Roberts, J. M., Fehsenfeld, F. C., Worsnop, D. R., Canagaratna, M. R., Pszenny, A. A. P., Keene, W. C., Marchewka, M., Bertman, S. B., and Bates, T. S.: Budget of organic carbon in a polluted atmosphere: Results from the New England Air Quality Study in 2002, J. Geophys. Res., 110, D16305, http://dx.doi.org/10.1029/2004JD005623doi:10.1029/2004JD005623, 2005.

de Gouw, J. A., Johansson, J., Mellqvist, J., Samuelsson, J., Offerle, B., and Rappenglück, B.: Airborne measurements of ethene from industrial sources using laser photo-acoustic spectroscopy, Environ. Sci. Technol, 43, 2437–2442, 2009.

Eom, I.-Y., Li, Q., Li, J., Dasgupta, P. K.: Robust hybrid flow analyzer for formaldehyde, Environ. Sci. Technol., 42, 1221–1226, 2008.

Friedfeld, S., Fraser, M., Ensor, K., Tribble, S., Rehle, D., Leleux, D., and Tittel, F.: Statistical analysis of primary and secondary atmospheric formaldehyde, Atmos. Environ., 36, 4767–4775, 2002.

Garcia, A. R., Volkamer, R., Molina, L. T., Molina, M. J., Samuelson, J., Mellqvist, J., Galle, B., Herndon, S. C., and Kolb, C. E.: Separation of emitted and photochemical formaldehyde in Mexico City using a statistical analysis and a new pair of gas-phase tracers, Atmos. Chem. Phys., 6, 4545–4557, http://dx.doi.org/10.5194/acp-6-4545-2006doi:10.5194/acp-6-4545-2006, 2006.

Gilman, J. B., Kuster, W. C., Goldan, P. D., Herndon, S. C., Zahniser, M. S., Tucker, S. C., Brewer, W. A., Lerner, B. M., Williams, E. J., Harley, R. A., Fehsenfeld, F. C., Warneke, C., and de Gouw, J. A.: Measurements of volatile organic compounds during the 2006 TexAQS/GoMACCS campaign: Industrial influences, regional characteristics, and diurnal dependencies of the OH reactivity, J. Geophys. Res., 114, D00F06, http://dx.doi.org/10.1029/2008JD011525doi:10.1029/2008JD011525, 2009.

Grosjean, D.: Formaldehyde and other carbonyls in Los Angeles ambient air, Environ. Sci. Technol,, 16, 254–262, 1982.

Holloway, J. S., Jakoubek, R. O., Parrish, D. D., Gerbig, C., Volz-Thomas, A., Schmitgen, S., Fried, A., Wert, B., Henry, B., and Drummond, J. R.: Airborne intercomparison of vacuum ultraviolet fluorescence and tunable diode laser absorption measurements of tropospheric carbon monoxide, J. Geophys. Res., 105, 24251–24261, http://dx.doi.org/10.1029/2000JD900237doi:10.1029/2000JD900237, 2000.

Jiang, G. and Fast, J. D.: Modeling the effects of VOC and NO$_X$ emission sources on ozone formation in Houston during the TexAQS 2000 field campaign, Atmos. Environ., 38, 5071–5085, http://dx.doi.org/10.1016/j.atmosenv.2004.06.012doi:10.1016/j.atmosenv.2004.06.012, 2004.

Johansson, J., Mellqvist, J., Samuelsson, J., Offerle, B., and Rappenglück, B.: Investigation of VOC radical sources in the Houston Area by the Solar Occultation Flux (SOF) method and Mobile DOAS, Abstract A31B-0034 presented at 2010 Fall Meeting, AGU, San Francisco, Calif., 13–17 December 2010.

Kim, S.-W., McKeen, S. A., Frost, G. J., Lee, S.-H., Trainer, M., Richter, A., Angevine, W. M., Atlas, E., Bianco, L., Boersma, K. F., Brioude, J., Burrows, J. P., de Gouw, J., Fried, A., Gleason, J., Hilboll, A., Mellqvist, J., Peischl, J., Richter, D., Rivera, C., Ryerson, T., te Lintel Hekkert, S., Walega, J., Warneke, C., Weibring, P., and Williams, E.: Evaluations of NOx and highly reactive VOC emission inventories in Texas and their implications for ozone plume simulations during the Texas Air Quality Study 2006, Atmos. Chem. Phys., 11, 11361–11386, http://dx.doi.org/10.5194/acp-11-11361-2011doi:10.5194/acp-11-11361-2011, 2011.

Kleinman, L. I., Daum, P. H., Imre, D., Lee, Y.-N., Nunnermacker, L. J., Springston, S. R., Weinstein-Lloyd, J., and Rudolph, J.: Ozone production rate and hydrocarbon reactivity in 5 urban areas: A cause of high ozone concentration in Houston, Geophys. Res. Lett., $29$, 1467, http://dx.doi.org/10.1029/2001GL014569doi:10.1029/2001GL014569, 2002.

Kleinman, L. I., Daum, P. H., Imre, D., Lee, Y.-N., Nunnermacker, L. J., Springston, S. R., Weinstein-Lloyd, J., and Rudolph, J.: Correction to "Ozone production rate and hydrocarbon reactivity in 5 urban areas: A cause of high ozone concentration in Houston," Geophys. Res. Lett., 30, 1639, http://dx.doi.org/10.1029/2003GL017485doi:10.1029/2003GL017485, 2003.

Lefer, B. and Rappenglück, B.: Preface: The TexAQS-II radical and aerosol measurement project (TRAMP), Atmos. Environ., 44, 3997–4004, 2010.

Li, S. M., Anlauf, K. G., Wiebe, H. A., Bottenheim, J. W., Shepson, P. B., and Biesenthal, T.: Emission ratios and photochemical production efficiencies of nitrogen oxides, ketones, and aldehydes in the Lower Fraser Valley during the summer Pacific 1993 oxidant study, Atmos. Environ., 31, 2037–2048, 1997.

Liu, Y., Shao, M., Kuster, W. C., Goldan, P. D., Li, X., Lu, S., and de Gouw, J. A.: Source identification of reactive hydrocarbons and oxygenated VOCs in the summertime in Beijing, Environ. Sci. Technol, 43, 75–81, http://dx.doi.org/10.1021/es801716ndoi:10.1021/es801716n, 2009.

Martin, R. V., Parrish, D. D., Ryerson, T. B., Nicks Jr., D. K., Chance, K., Kurosu, T. P., Jacob, D. J., Sturges, E. D., Fried, A., and Wert, B. P.: Evaluation of GOME satellite measurements of tropospheric NO2 and HCHO using regional data from aircraft campaigns in the southeastern United States, J. Geophys. Res., 109, D24307, http://dx.doi.org/10.1029/2004JD004869doi:10.1029/2004JD004869, 2004.

Mellqvist, J.: Application of infrared and UV-visible remote sensing techniques for studying the stratosphere and for estimating anthropogenic emissions, Ph.D. Thesis, Chalmers University of technology, Gothenburg, Sweden, 1999.

Mellqvist, J., Samuelsson, J., Johansson, J., Rivera, C., Lefer, B., Alvarez, S., and Jolly, J.: Measurements of industrial emissions of alkenes in Texas using the solar occultation flux method, J. Geophys. Res., 115, D00F17, http://dx.doi.org/10.1029/2008JD011682doi:10.1029/2008JD011682, 2012a.

Mellqvist, J., Johansson, J., Samuelsson, J., Offerle, B., Rappenglück, B., Wilmot, C.-S., and Fuller, R.: Investigation of VOC radical sources in the Houston area by the Solar Occultation Flux (SOF) method, mobile DOAS (SOF-II) and mobile extractive FTIR, Final Report Project H-102, Texas Environmental Research Consortium: Houston, TX, 2010b.

Olaguer, E. P., Rappenglück, B., Lefer, B., Stutz, J., Dibb, J., Griffin, R., Brune, W. H., Shauck, M., Buhr, M., Jeffries, H., Vizuete, W., and Pinto, J. P.: Deciphering the role of radical precursors during the second Texas air quality study, J. Air Waste Manage. Assoc., 59, 1258–1277, http://dx.doi.org/10.3155/1047-3289.59.11.1258doi:10.3155/1047-3289.59.11.1258, 2009.

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

Parrish, D. D., Allen, D. T., Bates, T. S., Estes, M., Fehsenfeld, F. C., Feingold, G., Ferrare, R., Hardesty, R. M., Meagher, J. F., Nielsen-Gammon, J. W., Pierce, R. B., Ryerson, T. B., Seinfeld, J. H., and Williams, E. J.: Overview of the Second Texas Air Quality Study (TexAQS II) and the Gulf of Mexico Atmospheric Composition and Climate Study (GoMACCS), J. Geophys. Res., 114, D00F13, http://dx.doi.org/10.1029/2009JD011842doi:10.1029/2009JD011842, 2009.

Peischl, J., Ryerson, T. B., Holloway, J. S., Parrish, D. D., Trainer, M., Frost, G. J., Aikin, K. C., Brown, S. S. Dubé, W. P., Stark, H., and Fehsenfeld, F. C.: A top-down analysis of emissions from selected Texas power plants during TexAQS 2000 and 2006, J. Geophys. Res., 115, D16303, http://dx.doi.org/10.1029/2009JD013527doi:10.1029/2009JD013527, 2010.

Possanzini, M., Di Palo, V., Petricca, M., Fratarcangeli, R., and Brocco, D.: Measurements of lower carbonyls in Rome ambient air, Atmos. Environ., 30, 3757–3764, 1996.

Rappenglück, B., Dasgupta, P. K., Leuchner, M., Li, Q., and Luke, W.: Formaldehyde and its relation to CO, PAN, and SO2 in the Houston-Galveston airshed, Atmos. Chem. Phys., 10, 2413–2424, http://dx.doi.org/10.5194/acp-10-2413-2010doi:10.5194/acp-10-2413-2010, 2010.

Rivera, C., Mellqvist, J., Samuelsson, J., Lefer, B., Alvarez, S., and Patel, M. R.: Quantification of NO2 and SO2 emissions from the Houston Ship Channel and Texas City industrial areas during the 2006 Texas Air Quality Study, J. Geophys. Res., 115, D08301, http://dx.doi.org/10.1029/2009JD012675doi:10.1029/2009JD012675, 2010.

Ryerson, T. B., Buhr, M. P., Frost, G. J., Goldan, P. D., Holloway, J. S., Hübler, G., Jobson, B. T., Kuster, W. C., McKeen, S. A., Parrish, D. D., Roberts, J. M., Sueper, D. T., Trainer, M., Williams, J., and Fehsenfeld, F. C.: Emissions lifetimes and ozone formation in power plant plumes, J. Geophys. Res., $103$, 22569–22583, http://dx.doi.org/10.1029/98JD01620doi:10.1029/98JD01620, 1998. \hack

Ryerson, T. B., Huey, L. G., Knapp, K., Neuman, J. A., Parrish, D. D., Sueper, D. T., and Fehsenfeld, F. C.: Design and initial characterization of an inlet for gas-phase NO$_\texty$ measurements from aircraft, J. Geophys. Res., 104, 5483–5492, http://dx.doi.org/10.1029/1998JD100087doi:10.1029/1998JD100087, 1999.

Ryerson, T. B., Williams, E. J., and Fehsenfeld, F. C.: An efficient photolysis system for fast-response NO2 measurements, J. Geophys. Res., 105, 26447–26461, http://dx.doi.org/10.1029/2000JD900389doi:10.1029/2000JD900389, 2000.

Ryerson, T. B., Trainer, M., Angevine, W. M., Brock, C. A., Dissly, R. W., Fehsenfeld, F. C., Frost, G. J., Goldan, P. D., Holloway, J. S., Hübler, G., Jakoubek, R. O., Kuster, W. C., Neuman, J. A., Nicks Jr., D. K., Parrish, D. D., Roberts, J. M., Sueper, D. T., Atlas, E. L., Donnelly, S. G., Flocke, F., Fried, A., Potter, W. T., Schauffler, S., Stroud, V., Weinheimer, A. J., Wert, B. P., Wiedinmyer, C., Alvarez, R. J., Banta, R. M., Darby, L. S., and Senff, C. J.: Effect of petrochemical industrial emissions of reactive alkenes and NO$_\textx$ on tropospheric ozone formation in Houston, Texas; J. Geophys. Res., $108$, 4249, http://dx.doi.org/10.1029/2002JD003070doi:10.1029/2002JD003070, 2003.

Schauffler, S. M., Atlas, E. L., Blake, D. R., Flocke, F., Lueb, R. A., Lee-Taylor, J. M., Stroud, V., and Travnicek, W.: Distributions of brominated organic compounds in the troposphere and lower stratosphere, J. Geophys. Res., 104, 21513–21535, http://dx.doi.org/10.1029/1999JD900197doi:10.1029/1999JD900197, 1999.

Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, John Willey & Sons, Inc., New York, 1998.

Stutz, J., Pikelnaya, O., Mount, G., Spinei, E., Herndon, S., Wood, E., Oluwole, O., Vizuette, W., and Causo, E.: Quantification of Hydrocarbon, NO$_\textx$, and SO2 emissions from Petrochemical Facilities in Houston: Interpretation of the 2009 FLAIR dataset, Final Report for Air Quality Research Program, project~10-045, Texas Environmental Research Consortium: Houston, TX, 2011.

Warneke, C., McKeen, S. A., de Gouw, J. A., Goldan, P. D., Kuster, W. C., Holloway, J. S., Williams, E. J., Lerner, B. M., Parrish, D. D., Trainer, M., Fehsenfeld, F. C., 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, http://dx.doi.org/10.1029/2006JD007930doi:10.1029/2006JD007930, 2007.

Washenfelder, R. A., Trainer, M., Frost, G. J., Ryerson, T. B., Atlas, E. L., de Gouw, J. A., Flocke, F. M., Fried, A., Holloway, J. S., Parrish, D. D., Peischl, J., Richter, D., Schauffler, S. M., Walega, J. G., Warneke, C., Weibring, P., and Zheng, W.: Characterization of NO$_x$, SO2, ethene, and propene from industrial emission sources in Houston, Texas, J. Geophys. Res., 115, D16311, http://dx.doi.org/10.1029/2009JD013645doi:10.1029/2009JD013645, 2010.

Weibring, P., Richter, D., Walega, J. G., and Fried, A.:First demonstration of a high performance difference frequency spectrometer on airborne platforms, Optics Express, 15, 13476–13495, 2007.

Wert, B. P., Trainer, M., Fried, A., Ryerson, T. B., Henry, B., Potter, W., Angevine, W. M., Atlas, E., Donnelly, S. G., Fehsenfeld, F. C., Frost, G. J., Goldan, P. D., Hansel, A., Holloway, J. S., Hubler, G., Kuster, W. C., Nicks Jr., D. K., Neuman, J. A., Parrish, D. D., Schauffler, S., Stutz, J., Sueper, D. T., Wiedinmyer, C., and Wisthaler, A.: Signatures of terminal alkene oxidation in airborne formaldehyde measurements during TexAQS 2000; J. Geophys. Res., 108, 4104, http://dx.doi.org/10.1029/2002JD002502doi:10.1029/2002JD002502, 2003.