Understanding the impact of recent advances in isoprene photooxidation on simulations of regional air quality

The CMAQ (Community Multiscale Air Quality) us model in combination with observations for INTEX-NA/ICARTT (Intercontinental Chemical Transport Experiment–North America/International Consortium for Atmospheric Research on Transport and Transformation) 2004 are used to evaluate recent advances in isoprene oxidation chemistry and provide constraints on isoprene nitrate yields, isoprene nitrate lifetimes, and NO_x recycling rates. We incorporate recent advances in isoprene oxidation chemistry into the SAPRC-07 chemical mechanism within the US EPA (United States Environmental Protection Agency) CMAQ model. The results show improved model performance for a range of species compared against aircraft observations from the INTEX-NA/ICARTT 2004 field campaign. We further investigate the key processes in isoprene nitrate chemistry and evaluate the impact of uncertainties in the isoprene nitrate yield, NO_x (NO_x = NO + NO_2) recycling efficiency, dry deposition velocity, and RO_2 + HO_2 reaction rates. We focus our examination on the southeastern United States, which is impacted by both abundant isoprene emissions and high levels of anthropogenic pollutants. We find that NO_x concentrations increase by 4–9% as a result of reduced removal by isoprene nitrate chemistry. O3 increases by 2 ppbv as a result of changes in NO_x. OH concentrations increase by 30%, which can be primarily attributed to greater HO_x production. We find that the model can capture observed total alkyl and multifunctional nitrates (∑ANs) and their relationship with O_3 by assuming either an isoprene nitrate yield of 6% and daytime lifetime of 6 hours or a yield of 12% and lifetime of 4 h. Uncertainties in the isoprene nitrates can impact ozone production by 10% and OH concentrations by 6%. The uncertainties in NO_x recycling efficiency appear to have larger effects than uncertainties in isoprene nitrate yield and dry deposition velocity. Further progress depends on improved understanding of isoprene oxidation pathways, the rate of NOx recycling from isoprene nitrates, and the fate of the secondary, tertiary, and further oxidation products of isoprene.

[1]  Yingjun Liu,et al.  Production of methyl vinyl ketone and methacrolein via the hydroperoxyl pathway of isoprene oxidation , 2012 .

[2]  J. Orlando,et al.  Laboratory Studies of Organic Peroxy Radical Chemistry: An Overview with Emphasis on Recent Issues of Atmospheric Significance , 2012 .

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

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

[5]  R. Cohen,et al.  Importance of biogenic precursors to the budget of organic nitrates: observations of multifunctional organic nitrates by CIMS and TD-LIF during BEARPEX 2009 , 2012 .

[6]  H. Kjaergaard,et al.  Atmospheric fate of methacrolein. 1. Peroxy radical isomerization following addition of OH and O2. , 2012, The journal of physical chemistry. A.

[7]  J. Lelieveld,et al.  Hydroxyl radical buffered by isoprene oxidation over tropical forests , 2012 .

[8]  E. Edgerton,et al.  Isoprene epoxydiols as precursors to secondary organic aerosol formation: acid-catalyzed reactive uptake studies with authentic compounds. , 2012, Environmental science & technology.

[9]  D. Henze,et al.  Impact of the isoprene photochemical cascade on tropical ozone , 2011 .

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

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

[12]  D. M. Brookes,et al.  Isoprene oxidation mechanisms: measurements and modelling of OH and HO 2 over a South-East Asian tropical rainforest during the OP3 field campaign , 2011 .

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

[14]  K. Baker,et al.  Photochemical modeling of the Ozark isoprene volcano: MEGAN, BEIS, and their impacts on air quality predictions. , 2011, Environmental science & technology.

[15]  Robin L. Dennis,et al.  A multi-resolution assessment of the Community Multiscale Air Quality (CMAQ) model v4.7 wet deposition estimates for 2002–2006 , 2010 .

[16]  W. Carter.  Development of the SAPRC-07 chemical mechanism , 2010 .

[17]  J. D. de Gouw,et al.  Contribution of isoprene-derived organosulfates to free tropospheric aerosol mass , 2010, Proceedings of the National Academy of Sciences.

[18]  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.

[19]  J. Müller,et al.  Improved global modelling of HO x recycling in isoprene oxidation: evaluation against the GABRIEL and INTEX-A aircraft campaign measurements , 2010 .

[20]  Golam Sarwar,et al.  Model representation of secondary organic aerosol in CMAQv4.7. , 2010, Environmental science & technology.

[21]  R. Derwent,et al.  Impacts of mechanistic changes on HO x formation and recycling in the oxidation of isoprene , 2010 .

[22]  D. M. Rowley,et al.  Kinetic and Mechanistic Studies of the Reactions of Cyclopentylperoxy and Cyclohexylperoxy Radicals with HO2. , 2010 .

[23]  P. Shepson,et al.  Isoprene nitrates: preparation, separation, identification, yields, and atmospheric chemistry , 2010 .

[24]  J. Peischl,et al.  Biogenic emission measurement and inventories determination of biogenic emissions in the eastern United States and Texas and comparison with biogenic emission inventories , 2010 .

[25]  T. Wallington,et al.  Investigation of the radical product channel of the CH(3)OCH(2)O(2) + HO(2) reaction in the gas phase. , 2010, The journal of physical chemistry. A.

[26]  J. Seinfeld,et al.  Reactive intermediates revealed in secondary organic aerosol formation from isoprene , 2009, Proceedings of the National Academy of Sciences.

[27]  Christine Wiedinmyer,et al.  A Preliminary Synthesis of Modeled Climate Change Impacts on U.S. Regional Ozone Concentrations , 2009 .

[28]  Jeffrey Young,et al.  Incremental testing of the Community Multiscale Air Quality (CMAQ) modeling system version 4.7 , 2009 .

[29]  P. Artaxo,et al.  Rapid formation of isoprene photo-oxidation products observed in Amazonia , 2009 .

[30]  T. Pugh,et al.  Atmospheric Chemistry and Physics Simulating Atmospheric Composition over a South-east Asian Tropical Rainforest: Performance of a Chemistry Box Model T. A. M. Pugh Et Al.: Simulating Atmospheric Composition over a Tropical Rainforest , 2022 .

[31]  R. Cohen,et al.  Isoprene oxidation by nitrate radical: alkyl nitrate and secondary organic aerosol yields , 2009 .

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

[33]  P. Shepson,et al.  A product study of the isoprene+NO 3 reaction , 2009 .

[34]  A. Goldstein,et al.  Observations of NO x , ΣPNs, ΣANs, and HNO 3 at a Rural Site in the California Sierra Nevada Mountains: summertime diurnal cycles , 2009 .

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

[36]  A. Ravishankara,et al.  Nocturnal isoprene oxidation over the Northeast United States in summer and its impact on reactive nitrogen partitioning and secondary organic aerosol , 2009 .

[37]  J. Seinfeld,et al.  Isoprene photooxidation: new insights into the production of acids and organic nitrates , 2009 .

[38]  Alice B. Gilliland,et al.  A method for evaluating spatially-resolved NO x emissions using Kalman filter inversion, direct sensitivities, and space-based NO 2 observations , 2008 .

[39]  T. J. Dillon,et al.  Direct detection of OH formation in the reactions of HO 2 with CH 3 C(O)O 2 and other substituted peroxy radicals , 2008 .

[40]  J. Lelieveld,et al.  Hydroxyl radicals in the tropical troposphere over the Suriname rainforest: comparison of measurements with the box model MECCA , 2008 .

[41]  J. Lelieveld,et al.  Improved simulation of isoprene oxidation chemistry with the ECHAM5/MESSy chemistry-climate model: lessons from the GABRIEL airborne field campaign , 2008 .

[42]  John H. Seinfeld,et al.  Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO 3 ) , 2008 .

[43]  D. Blake,et al.  Airborne observations of total RONO2: new constraints on the yield and lifetime of isoprene nitrates , 2008 .

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

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

[46]  John H Seinfeld,et al.  Effect of acidity on secondary organic aerosol formation from isoprene. , 2007, Environmental science & technology.

[47]  J. Lamarque,et al.  Observational constraints on the chemistry of isoprene nitrates over the eastern United States , 2007 .

[48]  T. Wallington,et al.  Investigation of the radical product channel of the CH3COO2 + HO2 reaction in the gas phase. , 2007, Physical chemistry chemical physics : PCCP.

[49]  M. Pennino,et al.  Direct kinetics study of the product-forming channels of the reaction of isoprene-derived hydroxyperoxy radicals with NO , 2007 .

[50]  R. Cohen,et al.  Observations of HNO 3 , ΣAN, ΣPN and NO 2 fluxes: evidence for rapid HO x chemistry within a pine forest canopy , 2007 .

[51]  J. Penner,et al.  Effects of additional nonmethane volatile organic compounds, organic nitrates, and direct emissions of oxygenated organic species on global tropospheric chemistry , 2007 .

[52]  D. Jacob,et al.  Why are there large differences between models in global budgets of tropospheric ozone , 2007 .

[53]  J. Offenberg,et al.  Ozone‐isoprene reaction: Re‐examination of the formation of secondary organic aerosol , 2007 .

[54]  Philip B. Russell,et al.  Overview of the Summer 2004 Intercontinental Chemical Transport Experiment–North America (INTEX-A) , 2006 .

[55]  Philip B. Russell,et al.  International Consortium for Atmospheric Research on Transport and Transformation (ICARTT): North America to Europe—Overview of the 2004 summer field study , 2006 .

[56]  E. M. Bailey,et al.  Treatment of clouds and the associated response of atmospheric sulfur in the Community Multiscale Air Quality (CMAQ) modeling system , 2006 .

[57]  P. Palmer,et al.  Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature) , 2006 .

[58]  D. Byun,et al.  Review of the Governing Equations, Computational Algorithms, and Other Components of the Models-3 Community Multiscale Air Quality (CMAQ) Modeling System , 2006 .

[59]  John H Seinfeld,et al.  Secondary organic aerosol formation from isoprene photooxidation. , 2005, Environmental science & technology.

[60]  M. Claeys,et al.  Formation of 2-methyl tetrols and 2-methylglyceric acid in secondary organic aerosol from laboratory irradiated isoprene/NOX/SO2/air mixtures and their detection in ambient PM2.5 samples collected in the eastern United States , 2005 .

[61]  A. Goldstein,et al.  Observations of total alkyl nitrates within the Sacramento Urban Plume , 2005 .

[62]  L. Horowitz,et al.  Evaluating the contribution of changes in isoprene emissions to surface ozone trends over the eastern United States , 2005 .

[63]  P. Shepson,et al.  Comparison of the measured and simulated isoprene nitrate distributions above a forest canopy , 2005 .

[64]  J. Orlando,et al.  A product yield study of the reaction of HO2 radicals with ethyl peroxy (C2H5O2), acetyl peroxy (CH3C(O)O2), and acetonyl peroxy (CH3C(O)CH2O2) radicals , 2004 .

[65]  P. Shepson,et al.  A comparison of isoprene nitrate concentrations at two forest-impacted sites , 2004 .

[66]  J. Thornton,et al.  Observations of total alkyl nitrates during Texas Air Quality Study 2000: Implications for O3 and alkyl nitrate photochemistry , 2004 .

[67]  M. Andreae,et al.  Formation of Secondary Organic Aerosols Through Photooxidation of Isoprene , 2004, Science.

[68]  J. Thornton,et al.  On alkyl nitrates, O3, and the “missing NOy” , 2003 .

[69]  P. Crutzen,et al.  Sensitivities in global scale modeling of isoprene , 2003 .

[70]  Paul J. Crutzen,et al.  A model for studies of tropospheric ozone and nonmethane hydrocarbons: Model description and ozone results , 2003 .

[71]  A. A. Boyd,et al.  Rate Constants for RO2 + HO2 Reactions Measured under a Large Excess of HO2 , 2003 .

[72]  R. Derwent,et al.  Atmospheric Chemistry and Physics Protocol for the Development of the Master Chemical Mechanism, Mcm V3 (part B): Tropospheric Degradation of Aromatic Volatile Organic Compounds , 2022 .

[73]  James G. Anderson,et al.  Product analysis of the OH oxidation of isoprene and 1,3‐butadiene in the presence of NO , 2002 .

[74]  P. Stevens,et al.  Measurements of the kinetics of the OH‐initiated oxidation of isoprene , 2002 .

[75]  J. Thornton,et al.  Ozone production rates as a function of NOx abundances and HOx production rates in the Nashville urban plume , 2002 .

[76]  Ronald C. Cohen,et al.  A thermal dissociation laser‐induced fluorescence instrument for in situ detection of NO2, peroxy nitrates, alkyl nitrates, and HNO3 , 2002 .

[77]  P. Shepson,et al.  Measurements of isoprene nitrates above a forest canopy , 2001 .

[78]  Jeffrey M. Vukovich,et al.  Emission inventory development and processing for the Seasonal Model for Regional Air Quality (SMRAQ) project , 2000 .

[79]  Y. Rudich,et al.  Henry's law constants of some β-, γ-, and δ-hydroxy alkyl nitrates of atmospheric interest , 2000 .

[80]  John H. Seinfeld,et al.  Organic aerosol formation from the oxidation of biogenic hydrocarbons , 1999 .

[81]  P. Shepson,et al.  Measurement of the organic nitrate yield from OH reaction with isoprene , 1998 .

[82]  P. Shepson,et al.  Observations of isoprene chemistry and its role in ozone production at a semirural site during the 1995 Southern Oxidants Study , 1998 .

[83]  D. Kley,et al.  Long‐term measurements of alkyl nitrates in southern Germany: 1. General behavior and seasonal and diurnal variation , 1998 .

[84]  P. Shepson,et al.  Henry's Law Constants and Removal Processes for Several Atmospheric β-Hydroxy Alkyl Nitrates , 1996 .

[85]  M. Jenkin,et al.  Kinetics of Reactions of Primary, Secondary and Tertiary β- Hydroxy Peroxyl Radicals. Application to Isoprene Degradation , 1995 .

[86]  I. Barnes,et al.  Near UV absorption spectra and photolysis products of difunctional organic nitrates: Possible importance as NOx reservoirs , 1993 .

[87]  J. Seinfeld,et al.  Development and evaluation of a photooxidation mechanism for isoprene , 1992 .

[88]  D. M. Rowley,et al.  Kinetic and mechanistic studies of the reactions of cyclopentylperoxy and cyclohexylperoxy radicals with hydroperoxy radical , 1992 .

[89]  I. Barnes,et al.  Relative-rate study of the gas-phase reaction of hydroxy radicals with difunctional organic nitrates at 298 K and atmospheric pressure , 1991 .

[90]  I. Barnes,et al.  Kinetics and Products of the Reactions of NO3 with Monoalkenes, Dialkenes, and Monoterpenes , 1990 .

[91]  F. Fehsenfeld,et al.  Contribution of organic nitrates to the total reactive nitrogen budget at a rural eastern U.S. site , 1990 .

[92]  R. Atkinson,et al.  A product study of the gas-phase reaction of methacrolein with the OH radical in the presence of NOx , 1990 .

[93]  I. Barnes,et al.  Kinetics and products of the reactions of nitrate radical with monoalkenes, dialkenes, and monoterpenes , 1990 .

[94]  J. Roberts,et al.  UV absorption cross sections of organic nitrates of potential atmospheric importance and estimation of atmospheric lifetimes , 1989 .

[95]  D. Luecken,et al.  Interpreting predictions from the SAPRC07 mechanism based on regional and continental simulations , 2012 .

[96]  Lieven Clarisse,et al.  Satellite evidence for a large source of formic acid from boreal and tropical forests , 2012 .

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

[98]  R. Derwent,et al.  Impacts of mechanistic changes on HOx formation and recycling , 2010 .

[99]  J. Peeters,et al.  HOx Radical Regeneration in Isoprene Oxidation via Peroxy Radical Isomerisation. II: Experimental Evidence and Global Impact - Electronic Supporting Information (ESI) - , 2009 .

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

[101]  T. Berndt,et al.  GAS-PHASE REACTION OF NO3 RADICALS WITH ISOPRENE : A KINETIC AND MECHANISTIC STUDY , 1997 .

[102]  M. Jenkin,et al.  Kinetics of reactions of primary, secondary and tertiary β-hydroxy peroxyl radicals , 1995 .

[103]  G. Grell,et al.  A description of the fifth-generation Penn State/NCAR Mesoscale Model (MM5) , 1994 .

[104]  J. M. Hollis,et al.  Observations of HNO , 1992 .