Atmospheric oxidation chemistry and ozone production: Results from SHARP 2009 in Houston, Texas

Ozone (O3) and secondary fine particles come from the atmospheric oxidation chemistry that involves the hydroxyl radical (OH) and hydroperoxyl radical (HO2), which are together called HOx. Radical precursors such as nitrous acid (HONO) and formaldehyde (HCHO) significantly affect the HOx budget in urban environments. These chemical processes connect surface anthropogenic and natural emissions to local and regional air pollution. Using the data collected during the Study of Houston Atmospheric Radical Precursors (SHARP) in spring 2009, we examine atmospheric oxidation chemistry and O3 production in this polluted urban environment. A numerical box model with five different chemical mechanisms was used to simulate the oxidation processes and thus OH and HO2 in this study. In general, the model reproduced the measured OH and HO2 with all five chemical mechanisms producing similar levels of OH and HO2, although midday OH was overpredicted and nighttime OH and HO2 were underpredicted. The calculated HOx production was dominated by HONO photolysis in the early morning and by the photolysis of O3 and oxygenated volatile organic compounds (OVOCs) in the midday. On average, the daily HOx production rate was 24.6 ppbv d−1, of which 30% was from O3 photolysis, 22% from HONO photolysis, 15% from the photolysis of OVOCs (other than HCHO), 14% from HCHO photolysis, and 13% from O3 reactions with alkenes. The O3 production was sensitive to volatile organic compounds (VOCs) in the early morning but was sensitive to NOx for most of afternoon. This is similar to the behavior observed in two previous summertime studies in Houston: the Texas Air Quality Study in 2000 (TexAQS 2000) and the TexAQS II Radical and Aerosol Measurement Project in 2006 (TRAMP 2006). Ozone production in SHARP exhibits a longer NOx‐sensitive period than TexAQS 2000 and TRAMP 2006, indicating that NOx control may be an efficient approach for the O3 control in springtime for Houston. Results from this study provide additional support for regulatory actions to reduce NOx and reactive VOCs in Houston in order to reduce O3 and other secondary pollutants.

[1]  V. L. Orkin,et al.  Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies: Evaluation Number 18 , 2015 .

[2]  Stanley P. Sander,et al.  NASA Data Evaluation: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies , 2014 .

[3]  M. Oinonen,et al.  Evidence of the solar Gleissberg cycle in the nitrate concentration in polar ice , 2014 .

[4]  Daniel R. Marsh,et al.  Climate change from 1850 to 2005 simulated in CESM1(WACCM) , 2013 .

[5]  J. Dibb,et al.  The preservation of atmospheric nitrate in snow at Summit, Greenland , 2013 .

[6]  R. Neale,et al.  The Mean Climate of the Community Atmosphere Model (CAM4) in Forced SST and Fully Coupled Experiments , 2013 .

[7]  E. Kyrölä,et al.  Observed effects of solar proton events and sudden stratospheric warmings on odd nitrogen and ozone in the polar middle atmosphere , 2013 .

[8]  S. Solomon,et al.  Simulation of polar stratospheric clouds in the specified dynamics version of the whole atmosphere community climate model , 2013 .

[9]  W. Stockwell,et al.  The regional atmospheric chemistry mechanism, version 2 , 2013 .

[10]  S. Tilmes,et al.  Evaluation of Whole Atmosphere Community Climate Model simulations of ozone during Arctic winter 2004–2005 , 2013 .

[11]  A. Hofzumahaus,et al.  Missing OH source in a suburban environment near Beijing: observed and modelled OH and HO 2 concentrations in summer 2006 , 2013 .

[12]  P. Démoulin,et al.  The standard flare model in three dimensions II: upper limit on solar flare energy , 2012, 1212.2086.

[13]  M. Frey,et al.  Relationship between snow microstructure and physical and chemical processes , 2012 .

[14]  E. Rozanov,et al.  Influence of a Carrington-like event on the atmospheric chemistry, temperature and dynamics: revised , 2012 .

[15]  F. Keutsch,et al.  Insights into hydroxyl measurements and atmospheric oxidation in a California forest , 2012 .

[16]  Yuhang Wang,et al.  Summertime photochemistry during CAREBeijing-2007: ROx budgets and O3 formation , 2012 .

[17]  M. Santee,et al.  Formation of stratospheric nitric acid by a hydrated ion cluster reaction: Implications for the effect of energetic particle precipitation on the middle atmosphere: FORMATION OF STRATOSPHERIC NITRIC ACID , 2012 .

[18]  J. Seinfeld,et al.  Peroxy radical chemistry and OH radical production during the NO 3 -initiated oxidation of isoprene , 2012 .

[19]  M. Frezzotti,et al.  Nitrate in Polar Ice: A New Tracer of Solar Variability , 2012 .

[20]  C. J. Schrijver,et al.  Estimating the frequency of extremely energetic solar events, based on solar, stellar, lunar, and terrestrial records , 2012, 1206.4889.

[21]  H. Oerter,et al.  9,400 years of cosmic radiation and solar activity from ice cores and tree rings , 2012, Proceedings of the National Academy of Sciences.

[22]  Karl E. Taylor,et al.  An overview of CMIP5 and the experiment design , 2012 .

[23]  Jack E. Dibb,et al.  The Carrington event not observed in most ice core nitrate records , 2012 .

[24]  J. Lamarque,et al.  CAM-chem: description and evaluation of interactive atmospheric chemistry in the Community Earth System Model , 2012 .

[25]  P. Riley.  On the probability of occurrence of extreme space weather events , 2012 .

[26]  Miguel Ángel Martínez,et al.  Comparisons of observed and modeled OH and HO 2 concentrations during the ambient measurement period of the HO x Comp field campaign , 2011 .

[27]  Manuel López-Puertas,et al.  Composition changes after the "Halloween" solar proton event: the High Energy Particle Precipitation in the Atmosphere (HEPPA) model versus MIPAS data intercomparison study , 2011 .

[28]  Jessica L. Neu,et al.  Toward a more physical representation of precipitation scavenging in global chemistry models: cloud overlap and ice physics and their impact on tropospheric ozone , 2011 .

[29]  M. Lockwood,et al.  Predicting space climate change , 2011 .

[30]  C. E. Jones,et al.  Quantifying the magnitude of a missing hydroxyl radical source in a tropical rainforest , 2011 .

[31]  S. Schubert,et al.  MERRA: NASA’s Modern-Era Retrospective Analysis for Research and Applications , 2011 .

[32]  D. Marsh,et al.  Northern Hemisphere atmospheric influence of the solar proton events and ground level enhancement in January 2005 , 2011 .

[33]  A. Hofzumahaus,et al.  Detection of HO 2 by laser-induced fluorescence: calibration and interferences from RO 2 radicals , 2011 .

[34]  G. König‐Langlo,et al.  Continuous 25-yr aerosol records at coastal Antarctica – I: inter-annual variability of ionic compounds and links to climate indices , 2011 .

[35]  G. Meehl,et al.  SOLAR INFLUENCES ON CLIMATE , 2010 .

[36]  M. Storini,et al.  The hydroxyl radical as an indicator of SEP fluxes in the high-latitude terrestrial atmosphere , 2010 .

[37]  G. J. Fochesatto,et al.  Deposition of dinitrogen pentoxide, N 2 O 5 , to the snowpack at high latitudes , 2010 .

[38]  J. Peeters,et al.  HO(x) radical regeneration in isoprene oxidation via peroxy radical isomerisations. II: experimental evidence and global impact. , 2010, Physical chemistry chemical physics : PCCP.

[39]  Barry Lefer,et al.  Photochemical and meteorological relationships during the Texas-II Radical and Aerosol Measurement Project (TRAMP) , 2010 .

[40]  M. Leuchner,et al.  Measurements of primary trace gases and NOY composition in Houston, Texas , 2010 .

[41]  B. Rappenglück,et al.  The TexAQS-II radical and aerosol measurement project (TRAMP) , 2010 .

[42]  W. Brune,et al.  Atmospheric oxidation capacity in the summer of Houston 2006: Comparison with summer measurements in other metropolitan studies , 2010 .

[43]  B. Rappenglück,et al.  Nocturnal NO3 radical chemistry in Houston, TX , 2010 .

[44]  W. Brune,et al.  A comparison of chemical mechanisms based on TRAMP-2006 field data , 2010 .

[45]  B. Rappenglück,et al.  Simultaneous DOAS and mist-chamber IC measurements of HONO in Houston, TX , 2010 .

[46]  A. Goldstein,et al.  Measurement of atmospheric nitrous acid at Bodgett Forest during BEARPEX2007 , 2010 .

[47]  W. Brune,et al.  Measurement of Ozone Production Sensor , 2009 .

[48]  M. Shea,et al.  Interhemispheric observations of impulsive nitrate enhancements associated with the four large ground-level solar cosmic ray events (1940–1950) , 2009 .

[49]  W. Brune,et al.  Deciphering the Role of Radical Precursors during the Second Texas Air Quality Study , 2009, Journal of the Air & Waste Management Association.

[50]  S. Meinardi,et al.  Measurements of OH and HO 2 concentrations during the MCMA-2006 field campaign - Part 2: Model comparison and radical budget , 2009 .

[51]  J. Lamarque,et al.  Description and evaluation of the Model for Ozone and Related chemical Tracers, version 4 (MOZART-4) , 2009 .

[52]  J. Seinfeld,et al.  Unexpected Epoxide Formation in the Gas-Phase Photooxidation of Isoprene , 2009, Science.

[53]  J. Peeters,et al.  HOx radical regeneration in the oxidation of isoprene. , 2009, Physical chemistry chemical physics : PCCP.

[54]  Y. Kondo,et al.  Amplified Trace Gas Removal in the Troposphere , 2009, Science.

[55]  Rolando R. Garcia,et al.  Long‐term middle atmospheric influence of very large solar proton events , 2009 .

[56]  M. Leuchner,et al.  VOC source–receptor relationships in Houston during TexAQS-II , 2009 .

[57]  K. Makishima,et al.  An Antarctic ice core recording both supernovae and solar cycles , 2009, 0902.3446.

[58]  T. Clarmann,et al.  About the increase of HNO3 in the stratopause region during the Halloween 2003 solar proton event , 2008 .

[59]  A. Jones,et al.  The interpretation of spikes and trends in concentration of nitrate in polar ice cores, based on evidence from snow and atmospheric measurements , 2008 .

[60]  D. Blake,et al.  Airborne measurement of OH reactivity during INTEX-B , 2008 .

[61]  Miguel Ángel Martínez,et al.  Atmospheric oxidation capacity sustained by a tropical forest , 2008, Nature.

[62]  R. Long,et al.  HOx chemistry during INTEX-A 2004: Observation, model calculation, and comparison with previous studies , 2008 .

[63]  Rolando R. Garcia,et al.  Modeling the whole atmosphere response to solar cycle changes in radiative and geomagnetic forcing , 2007 .

[64]  Y. Yokouchi,et al.  Urban photochemistry in central Tokyo 1. Observed and modeled OH and HO2 radical concentrations during the winter and summer of 2004 , 2007 .

[65]  T. Diehl,et al.  Sensitivity of chemical tracers to meteorological parameters in the MOZART-3 chemical transport model , 2007 .

[66]  J. Dibb,et al.  Seasonal variations in the soluble ion content of snow at Summit. Greenland: Constraints from three years of daily surface snow samples , 2007 .

[67]  J. Dibb.  Vertical mixing above Summit, Greenland: Insights into seasonal and high frequency variability from the radionuclide tracers 7Be and 210Pb , 2007 .

[68]  Rolando R. Garcia,et al.  Simulation of secular trends in the middle atmosphere, 1950–2003 , 2007 .

[69]  P. Bernath,et al.  Energetic particle precipitation effects on the Southern Hemisphere stratosphere in 1992–2005 , 2007 .

[70]  G. Sachse,et al.  In situ evidence for renitrification in the Arctic lower stratosphere during the polar aura validation experiment (PAVE) , 2006 .

[71]  L. Froidevaux,et al.  EOS MLS observations of ozone loss in the 2004–2005 Arctic winter , 2006 .

[72]  Tami C. Bond,et al.  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 , 2005 .

[73]  W. Brune,et al.  Hydroxyl and Peroxy Radical Chemistry in a Rural Area of Central Pennsylvania: Observations and Model Comparisons , 2005 .

[74]  T. Clarmann,et al.  Observation of NO(x) Enhancement and Ozone Depletion in the Northern and Southern hemispheres after the October-November 2003 Solar Proton Events , 2005 .

[75]  Matthew T. DeLand,et al.  Neutral atmospheric influences of the solar proton events in October–November 2003 , 2005 .

[76]  M. Alexander,et al.  On-line analysis of organic compounds in diesel exhaust using a proton transfer reaction mass spectrometer (PTR-MS) , 2005 .

[77]  J. C. McConnell,et al.  Simulation of the October–November 2003 solar proton events in the CMAM GCM: Comparison with observations , 2005 .

[78]  Paul S Monks,et al.  Gas-phase radical chemistry in the troposphere. , 2005, Chemical Society reviews.

[79]  J. Zawodny,et al.  Stratospheric effects of energetic particle precipitation in 2003–2004 , 2005 .

[80]  Jack E. Dibb,et al.  Snow accumulation, surface height change, and firn densification at Summit, Greenland: Insights from 2 years of in situ observation , 2004 .

[81]  J. McConnell,et al.  Seasonal accumulation timing and preservation of nitrate in firn at Summit, Greenland , 2004 .

[82]  D. Jacob,et al.  Testing fast photochemical theory during TRACE‐P based on measurements of OH, HO2, and CH2O , 2004 .

[83]  P. Doskey,et al.  Chemical and meteorological characteristics associated with rapid increases of O3 in Houston, Texas , 2004 .

[84]  David Tan,et al.  A Laser-induced Fluorescence Instrument for Detecting Tropospheric OH and HO2: Characteristics and Calibration , 2004 .

[85]  D. Jacob,et al.  Peroxy radical behavior during the Transport and Chemical Evolution over the Pacific (TRACE-P) campaign as measured aboard the NASA P-3B aircraft , 2003 .

[86]  W. Brune,et al.  Intercomparison of peroxy radical measurements at a rural site using laser‐induced fluorescence and Peroxy Radical Chemical Ionization Mass Spectrometer (PerCIMS) techniques , 2003 .

[87]  J. Bassis,et al.  OH and HO2 concentrations, sources, and loss rates during the Southern Oxidants Study in Nashville, Tennessee, summer 1999 , 2003 .

[88]  W. Brune,et al.  OH and HO2 Chemistry in the urban atmosphere of New York City , 2003 .

[89]  U. Platt,et al.  OH formation by HONO photolysis during the BERLIOZ experiment , 2003 .

[90]  A. Hofzumahaus,et al.  Hydrocarbon measurements at Pabstthum during the BERLIOZ campaign and modeling of free radicals , 2003 .

[91]  U. Platt,et al.  Peroxy radicals during BERLIOZ at Pabstthum: Measurements, radical budgets and ozone production , 2003 .

[92]  A. Volz-Thomas,et al.  Inorganic trace gases and peroxy radicals during BERLIOZ at Pabstthum: An investigation of the photostationary state of NOx and O3 , 2003 .

[93]  R. Bradley Pierce,et al.  A climatology of stratospheric polar vortices and anticyclones , 2002 .

[94]  Hartmut Boesch,et al.  Validation of POAM III NO2 measurements , 2001 .

[95]  M. Shea,et al.  Solar cosmic ray events for the period 1561–1994: 2. The Gleissberg periodicity , 2001 .

[96]  K. G. McCracken,et al.  Solar cosmic ray events for the period 1561–1994: 1. Identification in polar ice, 1561–1950 , 2001 .

[97]  L. Kleinman,et al.  Sensitivity of ozone production rate to ozone precursors , 2001 .

[98]  D. Fahey,et al.  Severe and extensive denitrification in the 1999–2000 Arctic winter stratosphere , 2001 .

[99]  T. V. van Ommen,et al.  Ice‐core evidence for a small solar‐source of atmospheric nitrate , 2001 .

[100]  J. Lamarque,et al.  A global simulation of tropospheric ozone and related tracers: Description and evaluation of MOZART, version 2 , 2001 .

[101]  T. L. Thompson,et al.  The Detection of Large HNO3-Containing Particles in the Winter Arctic Stratosphere , 2001, Science.

[102]  M. Santee,et al.  UARS Microwave Limb Sounder observations of denitrification and ozone loss in the 2000 Arctic late winter , 2000 .

[103]  Y. Kondo,et al.  Denitrification and nitrification in the Arctic stratosphere during the winter of 1996–1997 , 2000 .

[104]  James N. Pitts,et al.  Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications , 1999 .

[105]  D. Blake,et al.  Assessment of upper tropospheric HOx sources over the tropical Pacific based on NASA GTE/PEM data: Net effect on HOx and other photochemical parameters , 1999 .

[106]  P. Crutzen,et al.  Arctic ozone loss due to denitrification , 1999, Science.

[107]  M. Legrand,et al.  High northern latitude forest fires and vegetation emissions over the last millennium inferred from the chemistry of a central Greenland ice core , 1998 .

[108]  Philip J. Rasch,et al.  Representations of transport, convection, and the hydrologic cycle in chemical transport models : Implications for the modeling of short-lived and soluble species , 1997 .

[109]  J. Kahl,et al.  Air mass trajectories to Summit, Greenland: A 44‐year climatology and some episodic events , 1997 .

[110]  F. Vitt,et al.  A comparison of sources of odd nitrogen production from 1974 through 1993 in the Earth's middle atmosphere as calculated using a two‐dimensional model , 1996 .

[111]  M. Legrand,et al.  Light carboxylic acids in Greenland ice: A record of past forest fires and vegetation emissions from the boreal zone , 1996 .

[112]  J. McConnell,et al.  BIOMASS BURNING SIGNATURES IN THE ATMOSPHERE AND SNOW AT SUMMIT, GREENLAND: AN EVENT ON 5 AUGUST 1994 , 1996 .

[113]  D. Allen,et al.  Missing chemistry of reactive nitrogen in the upper stratospheric polar winter , 1995 .

[114]  E. Zeller,et al.  Anomalous nitrate concentrations in polar ice cores—Do they result from solar particle injections into the polar atmosphere? , 1995 .

[115]  R. Hillamo,et al.  The contributions of snow, fog, and dry deposition to the summer flux of anions and cations at Summit, Greenland , 1995 .

[116]  M. Anklin,et al.  A continuous analysis technique for trace species in ice cores. , 1994, Environmental science & technology.

[117]  M. Legrand,et al.  Large perturbations of ammonium and organic acids content in the summit‐Greenland Ice Core. Fingerprint from forest fires? , 1992 .

[118]  P. Mayewski,et al.  An ice-core record of atmospheric response to anthropogenic sulphate and nitrate , 1990, Nature.

[119]  E. Zeller,et al.  Evidence of individual solar proton events in Antarctic snow , 1990 .

[120]  M. Legrand,et al.  Origins and variations of nitrate in south polar precipitation , 1990 .

[121]  M. Legrand,et al.  A model study of the stratospheric budget of odd nitrogen, including effects of solar cycle variations , 1989 .

[122]  M. Legrand,et al.  Relative contributions of tropospheric and stratospheric sources to nitrate in Antarctic snow , 1986 .

[123]  T. Dunkerton,et al.  Evolution of potential vorticity in the winter stratosphere of January‐February 1979 , 1986 .

[124]  B. Parker,et al.  Nitrate ion in Antarctic firn as a marker for solar activity , 1981 .

[125]  Paul J. Crutzen,et al.  The effect of particle precipitation events on the neutral and ion chemistry of the middle atmosphere: II. Odd hydrogen , 1981 .

[126]  J. Frederick,et al.  Production of odd nitrogen in the stratosphere and mesosphere: An intercomparison of source strengths , 1980 .

[127]  H. Porter,et al.  Efficiencies for production of atomic nitrogen and oxygen by relativistic proton impact in air , 1976 .

[128]  P. Crutzen,et al.  Solar Proton Events: Stratospheric Sources of Nitric Oxide , 1975, Science.

[129]  W. Brune,et al.  Interactive comment on “ Direct measurement of ozone production rates in Houston in 2009 and comparison with two estimation methods ” , 2012 .

[130]  H. Kjaergaard,et al.  Electronic Supporting Information ( ESI ) Peroxy radical isomerization in the oxidation of isoprene , 2011 .

[131]  A. Hofzumahaus,et al.  Detection of HO2 by laser-induced fluorescence: calibration and interferences from RO2 radicals , 2011 .

[132]  Janie M. Chermak,et al.  Online supplementary materials , 2010 .

[133]  R. Volkamer.  Atmospheric Chemistry and Physics Discussions Interactive comment on “ Oxidative capacity of the Mexico City atmosphere – Part 1 : A radical source perspective , 2007 .

[134]  William P. L. Carter,et al.  Development of the SAPRC-07 chemical mechanism and updated ozone reactivity scales , 2007 .

[135]  © Author(s) 2007. This work is licensed under a Creative Commons License. Atmospheric Chemistry and Physics , 2006 .

[136]  L. Kleinman.  The dependence of tropospheric ozone production rate on ozone precursors , 2005 .

[137]  R. Volkamer,et al.  University of Birmingham Development of a detailed chemical mechanism (MCMv3.1) for the atmospheric oxidation of aromatic hydrocarbons , 2005 .

[138]  V. L. Orkin,et al.  Chemical kinetics and photochemical data for use in atmospheric studies. Evaluation No. 14 (JPL Publication 02-25) , 2003 .

[139]  R. Röthlisberger,et al.  Nitrate in Greenland and Antarctic ice cores: a detailed description of post-depositional processes , 2002, Annals of Glaciology.

[140]  B. Finlayson‐Pitts.  CHAPTER 7 – Chemistry of Inorganic Nitrogen Compounds , 2000 .

[141]  R. Röthlisberger,et al.  Technique for continuous high-resolution analysis of trace substances in firn and ice cores , 2000 .

[142]  D. Ehhalt.  Photooxidation of trace gases in the troposphere Plenary Lecture , 1999 .

[143]  M. Sturm,et al.  Vapor transport, grain growth and depth-hoar development in the subarctic snow , 1997, Journal of Glaciology.

[144]  M. Legrand,et al.  Acidic Gases (HCl, HF, HN03, HCOOH, and CH3COOH): A Review of Ice Core Data and Some Preliminary Discussions on their Air-Snow Relationships , 1996 .

[145]  M. Legrand,et al.  A Preliminary Study of the Air-Snow Relationship for Nitric Acid in Greenland , 1995 .

[146]  E. Wolff.  Nitrate in Polar Ice , 1995 .

[147]  J. Dibb,et al.  Recent climate anomalies and their impact on snow chemistry at South Pole , 1987 .

[148]  Robert J. O'Brien,et al.  Tropospheric free radical determination by FAGE , 1984 .