Heather A. Parker, USCG D13 Greg Buie, USCG NPFC NRT RRT Co-Chairs Meeting, Mesa, Arizona April 13, 2010
Presentation Topics Purpose, Distinction Bioethanol vs Biodiesel Ethanol: Characteristics, Hazards, Spills Biodiesel: Characteristics, Hazards, Spills Funding Issues for Biofuels Planning Considerations Q&A, Group Discussion
Purpose of this talk: discuss some key points on Biofuels and responses to releases in the context of helping to plan for responses on a Regional and Area level. Distinction: Ethanol vs. Biodiesel Ethanol and Biodiesel fuels are very different Distinct and unique products Behave very differently when spilled into the marine, freshwater or terrestrial environments. Production, Transportation, Storage, and Use Two very distinct and dynamic economic, industrial, and regulatory regimes Result of laws enacted by Congress in an effort to achieve certain political and environmental objectives
Ethanol Characteristics and Hazards Ethanol or Ethyl Alcohol: E10, E85, E98 (fuel blends denatured with gasoline) Non-persistent product, very rapid rates of evaporation and dissolution once spilled especially with high degree of mixing energy Totally miscible in water, similar to mixing milk into coffee Once spilled will typically mix immediately into water column, with some evaporation Response Challenges: Fires and spills involving ethanol and ethanol/gasoline blends pose complex challenges for emergency responders Ethanol is a polar/water-miscible flammable liquid Degrades effectiveness of fire fighting foams that are not alcohol resistant Containment and recovery are usually not possible on water
Ethanol Spill Impacts to Organisms Resources Potentially Affected Habitat, Location Potential Impact (depends on exposure duration, life stage) ~ Recovery Time (Depends on severity of effect, duration of exposure, etc.) Microbes, Plankton Water surface, Upper water column Acute lethal in high doses, depends on duration of exposure Very short, on the order of hours to days because rapidly replaced Shellfish Intertidal, subtidal, benthic >Few hours, can have substantial acute effects, such a depressed activity, narcosis and other effects on various systems; can metabolize Depends on severity of effect, duration of exposure, etc. ~ weeks to months Fish Water column Larval, juveniles more susceptible than adults; 11200 ppm =24hr LC50 Rainbow Trout* Depends on severity of effect, duration of exposure, etc. ~ weeks, months, years. Ethanol trapped in sediments could affect eggs, larvae Birds Water Surface, Shoreline Low likelihood of exposure on water surface, subsurface plume. Long term exposure can cause substantial effects, including cardiomyopathy Depends on severity of effect, duration of exposure, etc. ~ likely years or one breeding cycle Mammals Water Surface, Shoreline Acute LD 50 mouse = 3450 ppm oral; acute LD 50 rabbit dermal = 20000 ppm Depends on severity of effect, duration of exposure, etc. ~ likely years or one breeding cycle
Biodiesel Characteristics Biodiesel = Fatty Acid Methyl Esters (FAME) (aka fatty acid esters or alkyl esters) Methanol and a catalyst, usually Sodium Hydroxide (NaOH), are mixed to react the two substances to form Methoxide. Methoxide mixed with source oils causes the Transesterification process and results in Glycerin and Biodiesel (Methyl Esters). Fatty Acid Methyl Esters = FAMEs Glycerol Biodiesel
Biodiesel Properties and Behavior Property High Boiling Point, Low Vapor Pressure Typical Flash Point ~ 150 C (302 F) Corresponding Behavior Remains in liquid phase under most environmental conditions Rather non-flammable Viscosity similar to diesel, 1.9 6.0 cst @ 40 C (vs 1.3-2.4) Speed of flow/flow potential are similar Specific Gravity ~0.86 Evaporation rates tend to be slower than diesels Light ends or the highly toxic, water-soluble BTEXs, and PAHs much less than diesel Lighter than water, floats Could affect persistence, although biodiesel biodegradation is ~ 5x faster than diesel Affects evaporation, persistence, toxicity
Petrodiesels are 5 10x MORE ACUTELY TOXIC to aquatic organisms. Biodiesel/petrodiesel blends up to 20% are similarly toxic to petrodiesel Toxicity for blends is not linear with blend concentration No strong correlations between solubility and toxicity Numerous lab tests show biodiesel very low toxicity to marine and aquatic organisms, but could present a smothering problem.
B100 degraded between ~ 76-89% over 28d (aqueous system). Petrodiesels degraded only ~ 26%-50% (depending on study specifics) The higher the concentration of biodiesel in the petrodiesel blend, the higher the % of degradation; Biodiesel enhances the microbial breakdown of petrodiesel compounds Not considered Persistent Biodiesel particles are oxygenated so are much more biologically active. After 28 days (aqueous system) Biodiesel % % Degradation 100 84 80 68 50 52 20 36 0 18 (from Zhang et al, 1998)
Biodiesel Response Challenges Response could be Hazardous Substances or Oil discharge, or both. Methanol and NaOH are inhalation and dermal hazard, Sodium Methoxide even more so. Sorbents can be effective, as well as particular skimmers and vacuum devices Biodiesel can be corrosive to rubber, affects skimmer choice Biodiesel Forensics fingerprinting Biodiesels will naturally disperse > diesel Biodiesels are mild surfactants; Biodiesel blended with diesel, as low as B10 to B20, can cause dispersion of diesel into the water column
FUNDING ISSUES Distinction: Ethanol vs. Biodiesel Ethanol sector fairly mature, enjoys broad political support, tightly linked with the fuel refining, blending, and marketing segment of the oil industry. Poses less of a challenge to the RRTs and responders Biodiesel sector not mature, fewer linkages to established energy industries, markets, and regulatory regimes Poses more of a challenge to RRTs and responders
Ethanol Funding Issues Ethanol is not an oil Gasoline is an oil Ethanol denatured with gasoline is an oil The OSLTF can pay for responses to discharges of E98/E95/E85 to surface waters The OSLTF can pay for responses to mitigate substantial threats of discharges of E85/E95/E98 to surface waters OPA 90 Removal and Damage Claims? OPA 90 Natural Resource Damage Claims?
Biodiesel Funding Issues Biodiesel is classified as a fatty acid methyl ester (FAME) non-petroleum oil. Several FAME non-petroleum oils are listed on the Coast Guard s list of oils. The OSLTF can also be used to respond to discharges and substantial threats of discharges of on-spec biodiesel or blended biodiesel. These products are also known as B100 or ASTM D6751 biodiesel feedstock or ASTM D7467 Biodiesel Blends B6-B20 or B20, which is a common name for a blend of 20% biodiesel feedstock and 80% diesel fuel oil. Funding Summary: For responses to spills of - Biodiesel feedstock edible oils: OSLTF Process and waste liquids at biodiesel production facilities: It depends - might be OSLTF, might be CERCLA Commercial grade biodiesel or commercial biodiesel/diesel blends: OSLTF
Planning Considerations (1) Production facilities in many cases will fall under EPA jurisdiction, but some coastal facilities may have USCG FOSCs. Biofuels and production chemicals are transported by barge and vessel in some parts of the country in large volumes, spill from these vessels would most likely have a USCG FOSC. Transportation Issues ACs and RRTs need to know the volumes and modes of transport in their AORs, and associated risks of spills and explore contingencies and means to mitigate the risks. There are a number of guidance documents available to planners: NRT Quick Reference Guide: Fuel Grade Ethanol Spills (including E85) ETHANOL MANUFACTURING FACILITY RESPONSE OVERVIEW (EPA Reg5) BIODIESEL MANUFACTURING FACILITY RESPONSE OVERVIEW (EPA Reg5)
Ethanol risks are well known, production is highly regulated and producers are sophisticated. Biodiesel production is a bit more complicated, there are a lot of mom and pop producers (few large, well-capitalized ones) and with the flux in economy and market, could be a lot of abandoned facilities, or poor practices Because this industry is not yet mature in the U.S., the regulatory and response regimes are not yet mature, this creates challenges for planners. For the most part, biodiesel falls within the existing petroleum oil regulatory regime, with some special considerations: the feedstock and end products are oil but the production and intermediate products are hazardous substances
Biofuels Production/Transportation/Blending/Use Overview Oil Field Production Pipeline/Vessel Vessels with Crude Petroleum Oil as Cargo Animal Fats/Vegetable Oils (AFVO) Traditional Petroleum Refinery Terminal Company Biofuel Generator Biorefinery Ethanol Biodiesel Pipelines (under development) Railcar, Barge, Tanker Truck Denatured Fuel Ethanol Railcar Pipeline Blending Terminal Vessels with Petroleum Products as Cargo Dealer Company Dealers Railcar Transloading Denaturant Biodiesel Tanker Truck Truck Wholesale/Jobber Dealer Consumer adapted from EPA training materials, 13 th Annual OSC Readiness Training Program (Wilson, 2010)
Typical Biodiesel Generation Process Vegetable Oil NaOH Methanol Feedstock Preparation Transesterification Reaction Catalyst Preparation Acid Crude Biodiesel Phase Separation Glycerin Phase Acid Water Drying Neutralization Water Washing Finished Biodiesel Methanol Recovery Glycerin Refining Crude Glycerin Acidification & FFA Separation Purified Glycerin Free Fatty Acids FFA Legend Response Funding OSLTF? Yes! adapted from EPA training materials, 13 th Annual OSC Readiness Training Program (Wilson, 2010) OSLTF? No!