California Biobutanol Multimedia Evaluation Tier II Work Plan Prepared By Butamax™ Advanced Biofuels, LLC for the California Environmental Protection Agency Multimedia Working Group July 2013 Biobutanol Multimedia Evaluation Tier II Work Plan Table of Contents Table of Contents ........................................................................... 2 Table of Tables ............................................................................... 6 Table of Figures.............................................................................. 7 1. Executive Summary ................................................................. 8 1.1. Scope ................................................................................................................. 8 1.2. Background ....................................................................................................... 8 2. Tier I Conclusions .................................................................. 10 2.1. Conclusions of the Tier I Report ..................................................................... 10 2.2. Formulation of the Tier II Work Plan ............................................................. 11 3. Impact of Biobutanol on Elastomers .................................... 12 3.1. Statement of the Knowledge Gap ................................................................... 12 3.2. Test Plan.......................................................................................................... 13 4. Impact of Biobutanol on Fiberglass Resins and Sealants .. 15 4.1. Statement of the Knowledge Gap ................................................................... 15 4.2. Test Plan.......................................................................................................... 15 5. Electrical Conductivity of iso-Butanol/Gasoline Blends .... 17 5.1. Statement of the Knowledge Gap ................................................................... 17 5.2. Test Plan.......................................................................................................... 17 6. Terminal Vapor Recovery Requirements............................ 18 6.1. Statement of the Knowledge Gap ................................................................... 18 6.2. Overview ......................................................................................................... 18 6.3. Vapor recovery systems .................................................................................. 19 Page 2 Biobutanol Multimedia Evaluation Tier II Work Plan 6.4. Vapor combustion ........................................................................................... 20 6.5. Vapor Balance ................................................................................................. 21 6.6. Membrane and hybrid technologies ................................................................ 21 6.7. Other requirements......................................................................................... 21 6.8. Gasoline Bulk Terminal Emission Requirements and Limitations................. 22 6.9. Assessment of the Impact of Biobutanol on Terminal Emissions .................. 22 7. Impact of Biobutanol on Exhaust and Evaporative Emissions ................................................................................. 27 7.1. Statement of the Knowledge Gap ................................................................... 27 7.2. Test Fuels and Vehicles .................................................................................. 27 7.3. Vehicle Exhaust Emissions Test Program ...................................................... 28 7.4. Vehicle Evaporative Emissions Test Program ................................................ 32 7.5. Data Analysis and Reporting .......................................................................... 36 8. Impact of Biobutanol on Toxic Air Pollutants .................... 37 8.1. Statement of the Knowledge Gap ................................................................... 37 8.2. Test Fuels and Vehicle .................................................................................... 37 8.3. Test Plan.......................................................................................................... 37 8.4. Analysis of emissions ..................................................................................... 39 8.5. Data Analysis and Reporting .......................................................................... 50 9. Impact of Biobutanol on Gasoline Headspace .................... 51 9.1. Statement of the Knowledge Gap ................................................................... 51 9.2. Test Procedure ................................................................................................ 51 9.3. Test Matrix / Permutations.............................................................................. 53 9.4. Data Analysis and Report ............................................................................... 53 10. Impact of Biobutanol on Permeation Emissions ................. 54 Page 3 Biobutanol Multimedia Evaluation Tier II Work Plan 10.1. Statement of the Knowledge Gap ................................................................... 54 10.2. Work Plan ....................................................................................................... 54 10.3. Data Analysis and Reporting .......................................................................... 58 11. Environmental Fate of Biobutanol ....................................... 60 11.1. Statement of the Knowledge Gap ................................................................... 60 11.2. Biodegradation of Iso-Butanol Blended Gasoline under Different Environmental Conditions .............................................................................. 61 11.3. Degradation Pathways and Kinetics of Iso-Butanol ....................................... 65 11.4. Environmental Transport of Iso-Butanol and BTEX from Spills and Leaking USTs ............................................................................................................... 67 11.5. Sorption Coefficients of Pure Iso-butanol and Iso-butyric Acid in Soil ......... 74 11.6. Modelling ........................................................................................................ 90 12. Lifecycle Analysis of Biobutanol........................................... 94 12.1. Statement of the Knowledge Gap ................................................................... 94 12.2. Work Plan ....................................................................................................... 94 13. Management of Genetically Modified Microorganisms..... 95 13.1. Statement of Knowledge Gap ......................................................................... 95 13.2. Description of Country Specific Regulatory Framework and Requirements . 95 13.3. Work Plan ....................................................................................................... 99 14. Certification of Fuel-Dispensing Equipment and Compatibility of UST Leak Detection Systems ................. 100 14.1. Statement of Knowledge Gap ....................................................................... 100 14.2. Overview ....................................................................................................... 100 14.3. UL Guidance for Isobutanol Fuels ................................................................ 101 14.4. Fuel-Dispensing Equipment Compatibility Testing ..................................... 102 14.5. Leak Detection Equipment Testing .............................................................. 104 Page 4 Biobutanol Multimedia Evaluation Tier II Work Plan 15. References ............................................................................. 106 16. Appendices ............................................................................ 109 16.1. Appendix A: Draft Product Specification ..................................................... 109 16.2. Appendix B – E-Fate Modeling Proposal from Professor Pedro Alvarez .... 110 Page 5 Biobutanol Multimedia Evaluation Tier II Work Plan Table of Tables Table 3.1 Test Fuels for Elastomers Testing .................................................................... 14 Table 6.1. California Local Air Districts ......................................................................... 22 Table 7.1 Test Fuels .......................................................................................................... 28 Table 7.2 Vehicle Fleet for Emissions Testing ................................................................. 28 Table 8.1 Test Fuels for 211(b) Testing............................................................................ 37 Table 8.2 Test Vehicle for EPA 211(b) Testing ............................................................... 37 Table 8.3 Sampling Methodologies ................................................................................. 39 Table 8.4 TACs Quatified ................................................................................................. 41 Table 8.5. C5 - C12 Species Quantified .......................................................................... 43 Table 8.6 Selected C1 to C6 Alcohols and Ethers That Have Some Solubility in Water . 45 Table 9.1 Test Fuels and Temperatures ........................................................................... 53 Table 10.1 Vehicle Fleet for Permeation Study ...............................................................