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INVESTIGATION of ATMOSPHERIC REACTIVITIES of SELECTED CONSUMER PRODUCT Voes

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INVESTIGATION of ATMOSPHERIC REACTIVITIES of SELECTED CONSUMER PRODUCT Voes INVESTIGATION OF ATMOSPHERIC REACTIVITIES OF SELECTED CONSUMER PRODUCT voes Final Report to California Air Resources Board Contract 95-308 By William P. L. Carter, Dongmin Luo, and Irina L. Malkina May 30, 2000 College of Engineering Center for Environmental Research and Technology University of California Riverside, California 92521 00-AP-RT4P-002-FR ABSTRACT A series of environmental chamber experiments and computer model calculations were carried out to assess the atmospheric ozone formation potentials of selected organic compounds representative of those emitted from consumer products. This information is needed to reduce the uncertainties of ozone reactivity scales for stationary source emissions. The compounds studied were cyclohexane, cyclohexane, isopropyl alcohol, the three octanol isomers, diethyl ether, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, ethyl acetate, methyl isobutyrate, n-butyl acetate, and propylene glycol methyl ether acetate. "Incremental reactivity" experiments were carried out to determine the effect of each compound on 0 3 formation, NO oxidation and integrated OH radical levels when added to irradiations of reactive organic gas (ROG) - NOx mixtures representing simplified polluted urban atmospheres. Differing ROG surrogates and ROG/NOx ratios were employed to test how the impacts of the compounds vary with chemical conditions. In addition, single compound - NOx irradiations were carried out for the various ketones, OH radical rate constants were measured for the octanol isomers and propylene glycol methyl ether acetate, and the yields of the C8 carbonyl products were determined for each of the octanol.isomers. The results of these experiments were used in the development and testing of the SAPRC-99 mechanism that is documented in detail in a separate report (Carter, 2000). The data obtained, in conjunction with results of industry-funded studies of related compounds, has resulted in significantly reduced uncertainties in estimates of ozone impacts of the wide variety of oxygenated compounds present in consumer product emissions inventories. However, uncertainties still remain, and information is still inadequate to estimate ozone impacts for other classes of emitted compounds, such as amines and halogenated organics. ii ACKNOWLEDGEMENTS The authors wish to acknowledge the major role played by Randy Pasek of California Air Resources Board (CARB) and the CARB's Reactivity Research Advisory Committee in overseeing this project and providing input on the choices of compounds to be studied. Helpful contributions and support by Eileen McCauley of the CARB during the later periods of this project are also gratefully acknowledged. The authors also thank Roger Atkinson of the Air Pollution Research Center at the University of California at Riverside (UCR) for helpful discussions and also for generously providing the methyl nitrite used in the kinetic and product yield studies. The following people contributed significantly to the experiments discussed in this report. Dennis Fitz provided major assistance to the administration of this program and oversight of the laboratory and the experiments. Kurt Bumiller assisted with the maintenance of the instrumentation and carrying out of many of the experiments. Jodi Powell did most of the experimental work on the kinetic and product yield studies. Kathalena M.Smihula, Amy Lishan Ng, Thomas Cheng assisted in carrying out the experiments at various times during the course of this project. This work was carried out under funding by the California Air Resources Board through Contract 95-308. However, the opinions and conclusions in this document are entirely those of the first author. Mention of trade names and commercial products does not constitute endorsement or recommendation for use. iii TABLE OF CONTENTS LIST OF TABLES ....................................................................................................................................... vi LIST OF FIGURES .....................................................................................................................................vii EXECUTNE SUMMARY ..........................................................................................................................ix I. INTRODUCTION .................................................................................................................................. 1 A. Background and Objectives ............................................................................................................. 1 B. Compounds Chosen for Study ..........................................................................................................2 IL METHODS .............................................................................................................................................5 A. Overall Experimental Approach ....................................................................................................... 5 1. Incremental Reactivity Experiments .......................................................................................... 5 a. Mini-Surrogate Experiments ...............................................................................................5 b. Full Surrogate Experiments .................................................................................................5 c. Low NOx Full Surrogate Experiments ................................................................................6 2. Single compound- NOx Experiments ........................................................................................ 6 3. Control and Characterization Runs ............................................................................................ 6 4. Kinetic and Product Yield Experiments .................................................................................... 7 B. Environmental Chambers ................................................................................................................. 8 C. Experimental Procedures .................................................................................................................. 9 1. Environmental Chamber Experiments ....................................................................................... 9 2. Kinetic Experiments ................................................................................................................ 10 3. Product Yield Experiments ...................................................................................................... 11 D. Analytical Methods ........................................................................................................................ 11 E. Characterization Methods .............................................................................................................. 12 1. Temperature ............................................................................................................................. 12 2. Xenon Arc Light Source .......................................................................................................... 12 3. Blacklight Light Source ........................................................................................................... 12 4. Dilution .................................................................................................................................... 14 F. Reactivity Data Analysis Methods ................................................................................................. 14 G. Modeling Methods ......................................................................................................................... 15 1. Gas-Phase Mechanism ............................................................................................................. 15 2. Environmental Chamber Simulations ...................................................................................... 16 III. RESULTS AND DISCUSSION ........................................................................................................... 19 A. Kinetic and Product Yield Studies ................................................................................................. 19 1. Relative Rate Constant Measurements .................................................................................... 20 2. Octanol Product Yield Measurements ..................................................................................... 25 B. Environmental Chamber Results .................................................................................................... 27 1. Characterization Results .......................................................................................................... 27 a. Light Characterization Results for the OTC .....................................................................27 b. Light Characterization Results for the CTC ......................................................................28 c. Radical Source Characterization Results ..........................................................................32 d. Results of Other Characterization and Control Runs ........................................................33 iv 2. Mechanism Evaluation Results ................................................................................................ 35 a. Cyclohexane ......................................................................................................................36 b. Methyl Ethyl Ketone .........................................................................................................39
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