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Investigation of Atmospheric Ozone Impacts of 3-Methoxy-3-Methyl-1-Butanol

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Investigation of Atmospheric Ozone Impacts of 3-Methoxy-3-Methyl-1-Butanol INVESTIGATION OF ATMOSPHERIC OZONE IMPACTS OF 3-METHOXY-3-METHYL-1-BUTANOL Final Report to the Kuraray Co. Ltd Contract UCR- 09070726 By William P. L. Carter1, Wendy S. Goliff1, Roger Atkinson,2 Janet Arey2 and Sara M. Aschmann2 July 8, 2010 1Center for Environmental Research and Technology College of Engineering University of California Riverside, California 92521 2Air Pollution Research Center University of California Riverside, California 92521 ABSTRACT An experimental and modeling study was carried out to assess the impacts of 3-Methoxy-3- methyl-1-butanol (MMB) on ground-level ozone formation. The rate constant for the reaction of MMB with OH radicals was measured to be (1.64 ± 0.06) × 10-11 cm3 molecule-1 s-1 at 296 ± 2 K, which is over a factor of 2 higher than previously estimated. Acetone, methyl acetate, and 3 methoxy-3-methylbutanal were identified as products of this reaction, with yields of 3 ± 1%, 34 ± 8, and approximately 33-47%, respectively. Glycolaldehyde was also observed but was not quantified. These data were used to derive a mechanism for the atmospheric reactions of MMB, for use in calculating its atmospheric ozone impacts using the SAPRC-07 mechanism. To evaluate the predictive capability of this mechanism, incremental reactivity environmental chamber experiments were carried out to determine the effects of adding MMB to irradiations of reactive organic gas (ROG) surrogate - NOx mixtures representing ambient conditions. The results were reasonably consistent with the new MMB mechanism derived in this work. This mechanism was then used to calculate the atmospheric ozone impact of MMB in the MIR and other SAPRC-07 ozone reactivity scales. The MIR calculated for MMB was 2.78 grams O3 per gram VOC, which is higher than calculated for it previously using an estimated mechanism, but slightly lower than the MIR for the mixture used to represent anthropogenic VOCs from all sources in the reactivity calculations. The environmental chamber experiments also indicated that MMB does not form measurable secondary organic aerosol under the conditions of our experiments. ii ACKNOWLEDGEMENTS AND DISCLAIMERS This work was funded by Kuraray Co. Ltd. through contract UCR- 09070726. The environmental chamber experiments for this project were carried out at the College of Engineering Center for Environmental Research and Technology (CE-CERT) at the University of California at Riverside (UCR) under the supervision of William Carter and Wendy Goliff. The experiments at CE-CERT were carried out primarily by Qi Li and Kurt Bumiller. Mr. Dennis Fitz also provided assistance in administering this project at CE-CERT, and Ms. Kathy Cocker provided assistance in conducting the experiments and processing the data. The kinetic and mechanistic experiments were carried out by Roger Atkinson, Janet Arey and Sara Aschmann at the Air Pollution Research Center (APRC) at UCR. We also wish to thank Mr. Wally Albers of CBC America Corporation for supporting this project and for helpful discussions. Although Kuraray Co. Ltd. funded this work, the contents of this report reflect only the opinions and conclusions of the primary author. Mention of trade names and commercial products does not constitute endorsement or recommendation for use. iii TABLE OF CONTENTS INTRODUCTION ........................................................................................................................................ 1 EXPERIMENTAL METHODS.................................................................................................................... 3 Kinetic and Mechanistic Studies ............................................................................................................ 3 Kinetic Experiments......................................................................................................................... 3 Product Determination Experiments................................................................................................ 3 Materials .......................................................................................................................................... 4 Environmental Chamber Experiments ................................................................................................... 4 Chamber Description ....................................................................................................................... 4 Analytical Instrumentation............................................................................................................... 6 Sampling methods............................................................................................................................ 9 Characterization Methods ................................................................................................................ 9 Experimental Procedures ............................................................................................................... 10 Materials ........................................................................................................................................ 11 KINETIC AND MECHANISTIC RESULTS ............................................................................................ 12 Kinetics of OH + 3-Methoxy-3-methyl-1-butanol ............................................................................... 12 Products of OH + 3-Methoxy-3-methyl-1-butanol............................................................................... 12 MECHANISM AND MODELING METHODS........................................................................................ 17 Base Mechanism................................................................................................................................... 17 Mechanism for 3-Methoxy-3-Methyl-1-Butanol.................................................................................. 18 Representation of Chamber Conditions................................................................................................ 26 Atmospheric Reactivity Simulations.................................................................................................... 26 RESULTS AND DISCUSSION ................................................................................................................. 27 Characterization Results....................................................................................................................... 27 Incremental Reactivity and Mechanism Evaluation Results ................................................................ 30 Atmospheric Reactivity Calculation..................................................................................................... 33 Effects of MMB on Secondary Aerosol Formation.............................................................................. 37 CONCLUSIONS......................................................................................................................................... 39 REFERENCES ........................................................................................................................................... 40 APPENDIX A. BASE MECHANISM LISTING....................................................................................... 44 iv LIST OF TABLES Table 1. List of analytical and characterization instrumentation for the UCR EPA chamber................. 7 Table 2. Estimated rate constants for OH radical abstractions from various positions in the 3- methoxy-3-methyl-1-butanol molecule.................................................................................. 18 Table 3. Mechanism used for the atmospheric reactions of 3-methoxy-3-methyl-1-butanol................ 19 Table 4. Products predicted to be formed in the atmospheric reactions of 3-methoxy-3-methyl- 1-butanol and the model species used to represent their subsequent reactions...................... 22 Table 5. Mechanism used for the atmospheric reactions of the MMB oxidation product 3- methoxy-3-methyl butyraldehyde. ......................................................................................... 24 Table 6. Products predicted to be formed in the atmospheric reactions of CH3OC(CH3)(CH3)CH2CHO and the model species used to represent their subsequent reactions. ............................................................................................................. 25 Table 7. Summary of experiments carried out for this project.............................................................. 28 Table 8. Summary of initial concentrations and selected gas-phase results of the incremental reactivity experiments. ........................................................................................................... 30 Table 9. Summary of conditions of scenarios used for reactivity assessment....................................... 34 Table 10. Calculated atmospheric incremental reactivities for 3-methoxy-3-methyl-1-butanol and the base ROG mixture ..................................................................................................... 36 Table A-1. List of model species used in the base SAPRC-07 mechanism, including the VOC species used in the chamber and atmospheric reactivity simulations. ................................... 44 Table A-2. Reactions and rate constants in the base SAPRC-07 mechanism used in this work. See Carter (2009a) for documentation. .................................................................................. 48 Table A-3. Summary of photolysis rates used in chamber
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