Table of Contents TABLE OF TABLES VI TABLE OF FIGURES VIII CHAPTER 1: INTRODUCTION I 1.1 PROBLEM STATEMENT 1 1.2 PROJECT OBJECTIVES 1 1.3 PROJECT SCOPE 3 1.4 FORMAT AND CONVENTIONS 4 CHAPTER 2: CURRENT WATERCRAFT OPERATIONS ON CRATER LAKE—A BACKGROUND AND OVERVIEW 5 2.1 CRATER LAKE—BACKGROUND 5 2.1.1 Location and Lake Dimensions 5 2. 1.2 Limnology and Lake Trivia 5 2.1.3 Temperatures and Climate 6 2.1.4 Visitor Attendance Patterns 7 2.2 THE CURRENT PROBLEM 7 2.2.1 Fuel Pipeline Supply Issue 8 2.2.2 The Significance and Concern of Hydrocarbons in Crater Lake 9 2.3 CURRENT BOAT OPERATIONS 11 2.4 BIODEGRADATION POTENTIAL AT CRATER LAKE 14 2.5 PRESENCE OF BIODEGRADERS IN CRATER LAKE 14 2.6 AMIABILITY OF THE SURROUNDING ENVIRONMENT TO BIODEGRADATION 15 2.6.1 Temperature 16 2.62 Acceptability of Fuel Substrate for Biodegradation 16 2.6.3 Tests for Biodegradability 16 2.6.4 Tests for Toxicity 17 2.7 AN EMISSIONS PRIMER 18 2.7.1 Hydrocarbons (HC) 18 2.7.1.1 Non-Methane Hydrocarbons (NMHC) 19 2.7.1.2 Non-Methane Organic Gasses (NMOG) 19 2.7.2 Volatile Organic Compounds (VOC) 19 2.13 Aromatics 20 2.1 A Ozone (03) 21 2.1.5 Aldehydes 21 2.7.5 Olefins or Alkenes 23 2.7.6 Oxides of Nitrogen (NOx) 24 2.1.% Carbon Monoxide (CO) 24 2.1.9 Particulate Matter (PM) 25 2.7.10 Carbon Dioxide C02 26 2.7.11 Peroxyacetylnitrate (PAN) 26 2.7.12 Alcohols (Ethanol and Methanol) 26 CHAPTER 3: METHANOL FUEL AND METHANOL BLENDS 32 I 3.1 METHANOL PRODUCTION: RENEWABLE AND NON-RENEWABLE METHODS 33 3.2 METHANOL VENDORS, AVAILABILITY, TRANSPORTABILITY, AND FUEL COST 35 3.3 METHANOL AS AN ALTERNATIVE FUEL—FUEL PROPERTIES 36 3.3.1 Efficiency Benefits for Methanol in a Spark Ignition Internal Combustion Engine 36 33.2 Cold Starting Issues 39 3.3.3 Engine Conversion 40 3.4 METHANOL FUEL HAZARDS AND HANDLING ISSUES 41 3.4.1 Methanol Fuel Toxicity 41 3.4.1.1 Toxicity mechanism 42 3.4.1.2 Ingestion 44 3.4.1.3 Dermal Exposure 46 3.4.1.4 Inhalation 46 3.4.1.5 Biota Toxicity Limits 48 3.4.2 Methanol Fuel and Fire and Safety 50 3.4.2.1 Open-Air Flammability 50 3.4.2.2 Ullage-space Flammability 55 3.4.2.3 Fuel Luminosity 57 3.4.3 Handling Issues 57 3.4.3.1 Handling Safety 57 3.4.3.2 Corrosivity and Materials Compatibility Issues 58 3.4.3.3 Engine Wear and Benefits of Alcohol-compliant Crank Case Lubrication Oil 59 3.4.3.4 Water Tolerance for Blends— Phase Separation 60 3.4.3.5 Fuel Storage Tanks 61 3.5 FUEL EMISSIONS CHARACTERIZATION 61 3.5.1 Particulate Mater, Benzene, 1,3-butadiene emissions 63 3.5.2 Aldehyde Emissions: Formaldehyde and Acetaldehyde 63 3.5.3 Ozone forming potential 65 3.5.4 Evaporative emissions 66 3.5.5 NOx and CO emissions 67 3.5.6 Global Warming potential 68 3.5.7 Particulate Matter 69 3.5.8 Sulfur Oxides (SOx) 69 3.6 METHANOL BIODEGRADABILITY 69 3.6.1 Raw Fuel Spill on Water 74 3.6.2 Raw Fuel Spill on Land 77 3.6.3 Ultimate Fuel Fate in the Environment 78 3.6.4 Methanol Blends and Their Impacts 79 3.7 FUTURE POTENTIAL AND TRENDS OF METHANOL 80 3.8 SUMMARY AND CLOSING REMARKS ON METHANOL 81 CHAPTER 4: ETHANOL FUEL AND ETHANOL BLENDS 96 4.1 TERMINOLOGY 96 4.2 ETHANOL PRODUCTION 97 4.2.1 Ethanol Vendors, Availability, Transportability, and Fuel Cost 101 4.3 ETHANOL AS AN ALTERNATIVE FUEL 103 4.3.1 Engine Efficiency 104 4.3.2 Cold Start 106 4.3.3 Gasoline to Ethanol Conversions 106 4.3.4 Aquanol—Aqueous Ethanol 107 4.4 ETHANOL FUEL HAZARDS AND HANDLING ISSUES 110 4.4.1 Ethanol Fuel Toxicity 110 4 .4.2 Ethanol Fuel Fire and Safety 116 4.4.3 Handling Issues 117 n 4.4.3.1 Water Contamination—Phase Separation 118 4.4.3.2 Materials Compatibility Issues 118 4.4.3.3 Other Considerations 119 4.5 ETHANOL BlODEGRADABILITY 120 4.5.1 Raw Fuel Spill on Water 122 4.5.2 Raw Fuel Spill on Land 124 4.5.3 Ethanol Blends and Their Impacts 124 4.6 EMISSION CHARACTERIZATION 126 4.6.1 Evaporative Emissions 128 A.6.2 Benzene, Polycyclic Organic Matter (POM), 1,3-butadiene, Particulate Matter, Polycyclic aromatic hydrocarbons (PAH), Volatile Organic Compounds 128 4.6.3 Smog and Ozone Forming Impacts from emissions 129 4.6.4 Oxides of Nitrogen (NOx) 130 4.6.5 Carbon Monoxide Emissions (CO) 130 4.6.6 Greenhouse Impact from Emissions 131 4.6.7 Acetaldehyde and Formaldehyde Emissions 131 4.7 FUTURE POTENTIAL AND TRENDS OF ETHANOL 132 4.8 SUMMARY AND CLOSING REMARKS ON ETHANOL 134 CHAPTER 5: BIO-DIESEL—METHYL AND ETHYL ESTERS 148 5.1 TERMINOLOGY 149 5.2 PRODUCTION 149 5.2.1 Production Methods, Feedstocks, andRenewability 150 5.2.1.1 Feedstock 150 5.2.1.2 Production Methods 152 5.2.2 Vendors, Availability, Transportability, and Cost 156 5.3 FUEL PROPERTIES—BIODIESEL AS AN ALTERNATIVE FUEL 160 5.3.1 Concerns with Biodiesel 163 53.2 Energy Density 164 5.3.3 Cold Start and Cold Flow Issues 165 53 A Practical Experience with Biodiesel 166 5.3.4.1 Biodiesel Used in Marine Engine to Circumnavigate the World 167 5.3.4.2 Biodiesel in the NPS: Biodiesel Truck in Yellowstone and Other Projects 167 5.3.4.3 Other Experiences 171 5.3.5 Engine Wear 172 53.6 Other Issues 172 5.4 FUEL HAZARDS AND HANDLING ISSUES 173 5.4.1 Fuel Toxicity 174 5 A.2 Fuel Fire Danger and Safety 175 5.4.3 Handling Issues 176 5.4.3.1 Materials Compatibility Issues 176 5.4.3.2 Fuel Storage and Delivery System 177 5.4.3.3 Biodiesel-Biota Interaction 179 5.5 FUEL FATE, BIODEGRADABILITY, AND ENVIRONMENTAL IMPACT 179 5.5.1 Raw Fuel Spills to Water 181 5.5.2 Raw Fuel Spills to Land 183 5.6 BIODIESEL EMISSIONS 184 5.6.1 Compression Ignition versus Spark Ignition 186 5.6.2 Emissions and Altitude 188 5.6.3 Greenhouse Gas Emissions and Process Wastes 189 5.6.4 Smoke, Soot, and Particulate Matter 189 5.6.5 Hydrocarbon Emissions (HC) 193 5.6.6 Carbon Monoxide (CO) 194 iii 5.6.1 Oxides of Nitrogen (NOx) 195 5.6.8 Polycyclic Aromatic Hydrocarbons (PAHs) 196 5.6.9 Other Emissions 197 5.7 FUTURE POTENTIAL AND TRENDS 197 5.8 CLOSING NOTES 201 CHAPTER 6: BIODEGRADABLE FOUR-STROKE ENGINE LUBRICANTS 216 6.1 THE NEED FOR A BIODEGRADABLE LUBRICANT 216 6.2 'ENVIRONMENTALLY FRIENDLY' LUBRICANTS 220 6.3 TYPES OF LUBRICANTS: CONVENTIONAL VS. SYNTHETIC VS. NATURAL BASE 222 6.3.1 Mineral Oils—Conventional Lubricants 222 632 Synthetic Lubricants 223 6.3.3 Natural Base Oils—Natural Lubricants 227 6.4 A BIODEGRADABLE LUBRICANT—AMG2000 228 6.5 CLOSING NOTES 231 CHAPTER 7: MARINE ENGINES, EMISSIONS, EMISSION STANDARDS, AND POLLUTION CONTROL DEVICES 235 7.1 How CURRENT MARINE ENGINES WORK 235 7.1.1 Two-Stroke Outboard SI Engines 236 7 A.2 Four-stroke SI Outboard Engines 238 7.1.3 Inboard Four-stroke SI Engines 238 7.1.4 Diesel Four-Stroke Inboard and Outboards 239 7.2 THE CURRENT STATE OF THE ART IN MARINE ENGINES 240 7.2.1 SI Outboard Engines 240 1.22 SI Inboard and Sterndrive Engines 244 123 Compression Ignition Engine 244 13 MARINE ENGINE EMISSIONS 246 7.3.1 Marine SI Engine Emissions 246 7.3.2 Diesel Engine Emissions 249 7.4 CURRENT AND PROJECTED EMISSIONS STANDARDS 249 7.4.1 EPA Outboard Engine Emissions Regulations 250 7.4.2 CARB 2008 California Outboard Engine Emissions Regulations 250 1.43 Future EPA Inboard Engine Regulations 252 1AA Bodanasee Emission Standards—(BSO) Bodensee-Schiffahrts-Ordnug 253 7.4.5 IMO and EPA Tier 1 and 2 Marine Diesel Engine Emission Regulations 254 1.4.5 Blue Sky Voluntary Marine Diesel Emission Standards 257 7.5 CATALYTIC CONVERTER TYPES 258 7.6 MARINE ENGINE CATALYSTS 259 7.6.1 Safety Issues 260 7.6.2 Technical Issues 261 1.1 CATALYST POTENTIAL 264 7.8 EMISSIONS CONTROL DEVICES FOR DIESEL ENGINES 265 7.8.1 Particulate Filters 267 7.8.2 Water Scrubbing 270 7.8.3 Oxidation Catalytic Converters 271 7.8.4 Engine Modifications and Air Enhancement Technologies 273 7.8.5 Intake Air Membrane Filter 274 7.8.6 Selective Catalytic Reduction 277 7.9 COMMENTS AND SUMMARY 278 CHAPTER 8: SUMMARY AND CONCLUSIONS 295 IV 8.1 SUMMARY 295 8.2 CONCLUDING REMARKS 297 8.2.1 The Use of an Eco-Friendly Lubricant 297 8.2.2 Concluding Remarks Regarding the Alternative Fuels Studied 297 8.2.2.1 The Methanol Fuel System 298 8.2.2.2 The Ethanol Fuel System 302 8.2.2.3 The Aquanol Fuel System 306 8.2.2.4 The Biodiesel Fuel System 309 8.2.3 Comments Regarding Marine Internal Combustion Engines 312 8.2.4 Implement a Monitoring and/or Test System 314 8.2.5 Forward Looking Options and Additional Considerations 314 8.,2.6 Recommendations and Opinions 314 BIBLIOGRAPHY 321 APPENDIX A: OVERHEADS USED IN THESIS RELATED PRESENTATIONS 340 v