Biofuelsand Emerging IssuesforEmergency RespondersAn introduction to basic response guides and case studyexamples from biofuel spills.Jeff Kimble, OSC, Region 5Jeff Kimble, OSC, Region 5Kimble.Jeffrey@epa.govKimble.Jeffrey@epa.govGOALSDiscuss hazards and clean uptechniques for biodiesel andDiscuss hazards and clean uptechniques for biodiesel andethanol spillsethanol spillsDiscuss otherDiscuss otherbiofuelsbiofuelshazardshazardsLook at what the response community is actually dealingLook at what the response community is actually dealingwithPresent response guides as a tool for respondersPresent response guides as a tool for respondersDiscuss possible alternative approaches to responseDiscuss possible alternative approaches to responseETHANOLETHANOLMANUFACTURINGMANUFACTURINGFACILITY RESPONSEFACILITY RESPONSEOVERVIEWOVERVIEWDescription of Ethanol Fuel andDescription of Ethanol Fuel andthe Production Processthe Production ProcessEthanol, which contains hydrogn, carbon, and oxygen in itsEthanol, which contains hydrogen, carbon, and oxygen in itschemical structure, is also known as ethyl alcohol or grain alcochemical structure, is also known as ethyl alcohol or grain alcohol.Ethanol can be used as a fuel for sparkEthanol can be used as a fuel for spark-ignited internalignited internalcombustion engines. When burned in engines without activecombustion engines. When burned in engines without activecatalytic converters on the engine exhaust, the presence of oxygcatalytic converters on the engine exhaust, the presence of oxygenallows ethanol to burn with lower carbon monoxide emissionsallows ethanol to burn with lower carbon monoxide emissionsthan gasoline, although aldehyde emissions tend to be higher.than gasoline, although aldehyde emissions tend to be higher.In the U.S., ethanol is primarilyproduced from corn. To prevenIn the U.S., ethanol is primarilyproduced from corn. To preventingestion, ethanol is denaturedat the plant by mixing the ethaningestion, ethanol is denatured atthe plant by mixing the ethanolwith some type of hydrocarbon,such as gasoline. Denaturedwith some type of hydrocarbon,such as gasoline. Denaturedethanol may contain 2ethanol may contain 2-percent (%) gasoline, making it an15percent (%) gasoline, making it anethanol and gasoline fuel blend. For example, ethanol Eethanol and gasoline fuel blend. For example, ethanol E-85contains 85% ethanol and 15% gascontains 85% ethanol and 15% gasoline.The ethanolproduction process takes place through two methods:The ethanolproduction process takes place through two methods:lling and wet milling. The dry milling method is moredry milling and wet milling. The dry milling method is morecommon and accounts for 82 %of U.S. ethanol production.common and accounts for 82 %of U.S. ethanol production.Dry Mill ProcessDry Mill ProcessSource: Nebraska Department of Environmental QualityCO–carbon monoxiderbon monoxidePM5–particulate matter less than five micrometersDDGS-Dried Distillers Grains with Solublesd Distillers Grains with SolublesPM10–particulate matter less than ten micrometersH2S–hydrogen sulfidedrogen sulfideSOx–oxides of sulfures of sulfurNOx–oxides of nitrogenxides of nitrogenVOCs–atile organic compoundsvolMajor Chemicals Involved inMajor Chemicals Involved inEthanol ProductionEthanol ProductionCorn–Used productUsed productdium HydroxideSodium Hydroxide–pH control during fermentationpH control during fermentationAmmoniaAmmonia–pH control and yeast nutrientduring fermentationpH control and yeast nutrient during fermentationSulfuric AcidSulfuric Acid––separates corn into starch, germ, fiber, and pseparates corn into starch, germ, fiber, and proteinFuel for process heatFuel for process heatYeast––used infermentationused infermentationEnzymes (amylase)Enzymes (amylase)–converts starch todextroseconverts starch todextroseAntibiotic such as penicillinAntibiotic such as penicillin––controls bacteria during fermentcontrols bacteria during fermentationCarbon DioxideCarbon Dioxide-byproductbyproductHydrogen SulfideHydrogen Sulfide–process emissionprocess emissionSulfur dioxideSulfur dioxide–process emissionprocess emissionNitric oxideNitric oxide––process emissionprocess emissionVOCs–process emissionprocess emissionEthanolEthanol–final productfinal productGasolinGasoline–final product additive (if used)final product additive (if used)Denatured EthanolDenatured Ethanol––final blended productfinal blended productAppropriate Mitigation MeasuresAppropriate Mitigation Measuresfor Release of Ethanol Fuelfor Release of Ethanol FuelProper Air Monitoring EquipmentProper Air Monitoring EquipmentCombustible Gas Indicator (CGI) and Flame Ionizing Detector (FIDCombustible Gas Indicator (CGI) and Flame Ionizing Detector (FID)or MultiRAE Plus Fiveor MultiRAE Plus Five-Gas Air Monitoring Instrument; PhotoGas Air Monitoring Instrument; PhotoIonizing Detector (PID). Must review response factors prior to uIonizing Detector (PID). Must review response factors prior to usingPID.Proper Spill ContainmentProper Spill ContainmentVentilate area and eliminate ignition sources. FireVentilate area and eliminate ignition sources. Fire-fighting measuresfighting measuresmust useALCOHOLALCOHOL-RESISTANT FOAMSRESISTANT FOAMS.Containment/response should follow typical containment procedureContainment/response should follow typical containment procedures.Example: use nonExample: use non-combustible oilcombustible oil-dry, absorbent socks, booms, etcdry, absorbent socks, booms, etcthatareALCOHOLALCOHOL-RESISTANTRESISTANT. Avoid entry into sewers and. Avoid entry into sewers andwaterways due to flammability hazards, potential aquatic toxicitwaterways due to flammability hazards, potential aquatic toxicity, andpotential microbial upsets atwastewater treatment plants. Wastepotential microbial upsets at waer treatment plants. Wasgenerated from the cleangenerated from the clean-up may exhibit the flammabilityup may exhibit the flammabilitycharacteristic for hazardous waste.characteristic for hazardous waste.Note: The Response Overview includes measures for the other majoNote: The Response Overview includes measures for the other majorchemicals involved in the manufacturing process.chemicals involved in the manufacturing process.EXPECTED FATE OF ETHANOLEXPECTED FATE OF ETHANOLRelease in SoilRelease in Soil-Ethanol is rapidly biodegradedEthanol is rapidly biodegradedin soil.in soil.Release in WaterRelease in Water-Fuel ethanol will mix with water,Fuel ethanol will mix with water,high enoughand athigh enoughconcentrations of water, theconcentrations of water, theethanol will separate from theethanol will separate from thegasoline. Ethanol is rapidlygasoline. Ethanol is rapidlybiodegraded in groundwater andbiodegraded in groundwater andsurface water. However, somesurface water. However, somestudies are focusing on thestudies are focusing on thepossibility of ethanol inducingpossibility of ethanol inducingthe transport of other chemicalsthe transport of other chemicalssuch as benzene.such as benzene.Release in Air as result ofRelease in Air as result ofspill/firespill/fire-Ethanol vapor, like gasolineEthanol vapor, like gasolinevapor, is denser than air andvapor, is denser than air andtends to settle in low areas.tends to settle in low areas.However, ethanol vaporHowever, ethanol vapordisperses rapidly.disperses rapidly.Release to storm/sanitaryRelease to storm/sanitarysewers-anol released to water willEthanol released to water willvolatilize and rapidly biodegrade.volatilize and rapidly biodegrade.The potential decrease inThe potential decrease indissolved oxygen as a result ofdissolved oxygen as a result ofethanol degradation can upsetethanol degradation can upsetmicrobial functions atmicrobial functions atastewater treatment plants. Thewastewater treatment plants. Thepotential flammability hazardpotential flammability hazardmust be addressed when ethanolmust be addressed when ethanolis released to a sanitary or stormis released to a sanitary or stormsystem.system.Overall Health Risks of EthanolOverall Health Risks of EthanolHuman Health EffectsHuman Health EffectsExposure to fuel ethanol can occurExposure to fuel ethanol can occurby breathing its vaporsby breathing its vapors(inhalation), getting it on the skin(inhalation), getting it on the skinor in the eyes (skin absorptionor in the eyes (skin absorption), oraccidentallyaccidentallyswallowing itswallowing it(ingestion).(ingestion).The following symptoms ofThe following symptoms ofexposure to fuel ethanol mayexposure to fuel ethanol mayappear immediately: Dullness ofappear immediately: Dullness ofmemory and concentration;memory and concentration;impaired motor coordination; andimpaired motor coordination; anddrowsiness, stupor, and finallydrowsiness, stupor, and finally. May cause skin irritation ascoma. May cause skin irritation asa result of defatting.a result of defatting.Carcinogenic compounds are notCarcinogenic compounds are notpresent in pure ethanol; however,present in pure ethanol; however,ecause gasoline is used in thebecause gasoline is used in theblend, E85 is considered to beblend, E85 is considered to bepotentially carcinogenic.potentially carcinogenic.Ecological EffectsEcological EffectsPure ethanol hasPure ethanol hasdemonstrated lethaldemonstrated lethalconcentrations for fishconcentrations for fish(rainbow trout) at 11,200 to(rainbow trout) at 11,200 to15,300 milligrams per liter15,300 milligrams per liter(mg/L).(mg/L).Pure ethanol is expected toPure ethanol is expected tobiodegrade rapidly andbiodegrade rapidly andbioaccumulation orbioaccumulation orconcentration in thconcentration in the foodchain is notexpected.chain is notexpected.However, the biodegradationHowever, the biodegradationmay decrease the dissolvedmay decrease the dissolvedoxygen in surface wateroxygen in surface waterresulting in fish kills.resulting in fish kills.July 7, 2008July 7, 2008-Report from Hancock Co. EMAof yellow substance in aReport from Hancock Co. EMAof yellow substance in aroadside ditchroadside ditchOwner of adjacent property dumped 5,000 gallons of CDLS (byproduOwner of adjacent property dumped 5,000 gallons of CDLS (byproductof ethanol production)of ethanol production)Corn distiller was rejected at disposal facility and sold to locCorn distiller was rejected at disposal facility and sold to local farmer toal farmer tofeed deerfeed deerEthanol Plant onEthanol Plant on-site to providesite to provide“Technical AssistanceTechnical Assistance”discovers up to 1,000 deadfish downstream of spill siteODNRdiscovers up to 1,000 deadfish downstream of spill sitePRP hired an environmental contractor toPRP hired an environmental contractor toRemove gross contamination from spill siteRemove gross contamination from spill siteProvide aeration to tributaryProvide aeration to tributaryRemove dead fish from downstreamDispose of contaminated soilDispose of contaminated soilDirect reading in tributary showedDirect reading in tributary showedDO Levels @ 0 mg/LDO Levels @ 0 mg/LWoods Ethanol SpillWoods Ethanol SpillWoods Ethanol SpillWoods Ethanol SpillWoods Ethanol SpillWoods Ethanol SpillWoods Ethanol SpillWoods Ethanol SpillCurrent Ethanol PlantsCurrent Ethanol Plantshttp://www.card.iastate.edu/research/bio/tools/ethanol.aspxhttp://www.card.iastate.edu/research/bio/tools/ethanol.aspxas of 01/16/2008as of 01/16/2008BIODIESELBIODIESELMANUFACTURINGMANUFACTURINGFACILITY RESPONSEFACILITY RESPONSEOVERVIEWOVERVIEWDescription of Biodiesel Fuel andDescription of Biodiesel Fuel andthe Biodiesel Production Processthe Biodiesel Production ProcessMajor Chemicals InvolvedMajor Chemicals Involvedin Biodiesel Productionin Biodiesel ProductionSoybean hulls and finesSoybean hulls and finesHexane–extracts soybean oilextracts soybean oilSodium and Potassium HydroxideSodium and Potassium Hydroxide––removesremovesfatty acids from soybean oilfatty acids from soybean oilMethanolMethanol–replaces glycerol in soybean oil toreplaces glycerol in soybean oil tomake oil less viscous (make oil less viscous (transesterificationtransesterification)GlycerolGlycerol–byproduct ofbyproduct oftransesterificationtransesterificationFuel for process heat (i.e. natural gas,Fuel for process heat (i.e. natural gas,propane, etc.)propane, etc.)Appropriate Mitigation MeasuresAppropriate Mitigation Measuresfor Release of Biodiesel Fuelfor Release of Biodiesel FuelProper Air Monitoring EquipmentProper Air Monitoring EquipmentBiodiesel fuel has a very lowvolatility at normal ambientBiodiesel fuel has a very lowvolatility at normal ambienttemperatures and vapors are nottypically an issue. However,temperatures and vapors are nottypically an issue. However,vapors/mists may be generated when heated above ~266 degreesvapors/mists may be generated when heated above ~266 degreesFahrenheit (Fahrenheit (oF).Proper Spill ContainmentProper Spill ContainmentContainment/response should follow typical oil containmentContainment/response should follow typical oil containmentprocedures. Example: use oilprocedures. Example: use oil-, petroleumdry-mpatible absorbentcompatible absorbentsocks, booms, etc; the absorbentmaterial used should be resistasocks, booms, etc; the absorbentmaterial used should be resistant toalcohol in the eventmethanol has further commingled with thealcohol in the eventmethanol has further commingled with thebiodiesel release. Disposal of biodieselbiodiesel release. Disposal of biodiesel-contaminated soil or procontaminated soil or productscan be considered nocan be considered non-hazardous provided methanol and/or hexanehazardous provided methanol and/or hexanehave not commingled with the release to meet the flammabilityhave not commingled with the release to meet the flammabilitycharacteristic for hazardous waste.characteristic for hazardous waste.Note: The Response Overview includes measures for the other majoNote: The Response Overview includes measures for the other majorchemicals involved in the manufacturing process.chemicals involved in the manufacturing process.EXPECTED FATE OF BIODIESELEXPECTED FATE OF BIODIESELRelease in SoilRelease in Soil-Biodegradation occursBiodegradation occursrapidly, with faster ratesrapidly, with faster ratesunder aerobic conditions thanunder aerobic conditions thananaerobic conditions.anaerobic conditions.Release in WaterRelease in Water-Insoluble in water. DegradesInsoluble in water. Degradesrapidly and fairly extensivelyrapidly and fairly extensivelyin aquatic environments.in aquatic environments.Estimated to degrade at a rateEstimated to degrade at a rateapproximately four timesapproximately four timesthan petroleum dieselfasterthan petroleum diesel–85% of pure biodiesel85% of pure biodieselexpected to degrade within 28expected to degrade within 28days.Release in Air as result ofRelease in Air as result ofspill/firespill/fire-Combustion produces carbonCombustion produces carbonmonoxide, carbon dioxidemonoxide, carbon dioxidealong with thick smoke.along with thick smoke.Release to storm/sanitaryRelease to storm/sanitarysewers-May be high in free fattyMay be high in free fattyacids and glycerol, and canacids and glycerol, and canhave a high biochemicalhave a high biochemicaloxygen demand (BOD). Theseoxygen demand (BOD). Thesecan disrupt wastewatercan disrupt wastewatertreatment plant operations.treatment plant operations.Overall Health Risks of aOverall Health Risks of aBiodiesel ReleaseBiodiesel ReleaseHuman Health EffectsHuman Health EffectsInhalation effects are negligibleInhalation effects are negligibleunless heated to produce vapors.unless heated to produce vapors.If biodiesel fuel were to be ingested,If biodiesel fuel were to be ingested,enzymes in the body called esterenzymes in the body called esteraseswould break the biodiesel fuelwould break the biodiesel fuelmolecules into the component fattymolecules into the component fattyacids and alcohol molecules. Theacids and alcohol molecules. Thealcohol is usually methanol andalcohol is usually methanol andmethanol is toxic. Thus, methanolmethanol is toxic. Thus, methanoltoxicity could be a concern fortoxicity could be a concern foringestion of biodiesel fuel.ingestion of biodiesel fuel.Neat biodiesel fuel is approximatelyNeat biodiesel fuel is approximately11 percent methanol by weight, so11 percent methanol by weight, soingestion of 100 gramsof biodieselingestion of 100 gramsof biodieselwould release 11 gramswould release 11 grams, or14milliliters (milliliters (mLof methanol. For a)of methanol. For a70 kilogram (kg)t, the fatal dose70 kilogram (kg)adult, the fatal doseof methanol rangesfrom 60 to 160of methanol rangesfrom 60 to 160mL.Ecological EffectsEcological EffectsBiodiesel biodegrades much moreBiodiesel biodegrades much morerapidly than conventional diesel.rapidly than conventional diesel.When biodiesel is present in bulk inWhen biodiesel is present in bulk inthe environment, itcan coat animalsthe environment, itcan coat animalsthat come in contact with it and maye in contact with it and mayreduce the ability ofoxygen to reachreduce the ability ofoxygen to reachaquatic systems. Inrespect, itsaquatic systems. Inthisrespect, itsaction is similar to petroleum dieselaction is similar to petroleum dieselfuel.Biodieseldoes nothave the toxicityBiodieseldoes nothave the toxicityand the solvent actionthat diesel fueland the solvent actionthat diesel fuelso its effects on animals arehas,so its effects on animals areexpected to be less severe.expected to be less severe.The treatment of oiled birds andThe treatment of oiled birds andanimals would be similar to theals would be similar to thetreatment providedwhen an oil spilltreatment providedwhen an oil spilloccurs.occurs.However, in water it has a highHowever, in water it has a highoxygen demand which can loxygen demand which can lead tomassive fish killsmassive fish killsInitial report called in to state:Initial report called in to state:COMPANY HAD ANCOMPANY HAD ANEXPLOSION. THERE ARE 2 LARGE TANKS ON SITEEXPLOSION. THERE ARE 2 LARGE TANKS ON SITECONTAINING GYLCERIN. SEWER BEING IMPACTEDCONTAINING GYLCERIN. SEWER BEING IMPACTEDWITH FF WATERWITH FF WATEROHIO EPA OSC respondedOHIO EPA OSC responded2 tanks were in fire (10,000 gallons & 4,000 gallons)2 tanks were in fire (10,000 gallons & 4,000 gallons)Only 1650 gallons of glycerin reported on handOnly 1650 gallons of glycerin reported on handAlso ~700 gallons of biodieselAlso ~700 gallons of biodiesel“Empty”55-gallon drumsgallon drumsRelease to ground and storm sewerRelease to ground and storm sewerRelease to threatened creek and river via storm sewerRelease to threatened creek and river via storm sewerDefiance Biofuel SpillDefiance Biofuel SpillDefiance Biofuel Spill (contDefiance Biofuel Spill (cont’d)Fire and release pointFire and release pointDefianceDefianceBiofuelBiofuelSpill (contSpill (cont’d)Ohio EPA responded and assessed situationOhio EPA responded and assessed situationCalled EPA spill phone duty officerCalled EPA spill phone duty officerDuty officer coordinated with OSCDuty officer coordinated with OSCBoth told Ohio EPA to respond as if diesel spillBoth told Ohio EPA to respond as if diesel spillWere not sure what regulations applied toWere not sure what regulations applied tobiodiesel productionbiodiesel productionBoth continued research that nightBoth continued research that nightAdvised state on limited info obtainedAdvised state on limited info obtainedOhio determined spill contained, but notOhio determined spill contained, but notcleaned upcleaned upThey decided to wait till morning for removalThey decided to wait till morning for removalDefianceDefianceBiofuelBiofuelSpill (contSpill (cont’d)-“fats” floated-3 layers in water observed-some suspended in water-“milky” layer observedResponse TechniquesResponse TechniquesOhio EPA made PRP hirea contractorOhio EPA made PRP hirea contractorOn-land spills were excavatedland spills were excavatedSpill to ditch was collected and put inSpill to ditch was collected and put infractanksAnalytical ofAnalytical offractank water revealed styrene andtank water revealed styrene andperchloroethyleneperchloroethyleneShows more thanShows more than“glyceringlycerin”spilledspilledSome wastes suspended in water column were lostSome wastes suspended in water column were lostRenewable Energy (IDEM)Renewable Energy (IDEM)Biofuels production facilityBiofuels production facilitySpill from 50,000 gallon tankSpill from 50,000 gallon tankSurface soils and ditch water impactedSurface soils and ditch water impactedWater in ditch aWater in ditch a“milky”whiteSoils excavatedSoils excavatedTile field drains intercepted and pluggedTile field drains intercepted and pluggedRenewable Energy (IDEM)Renewable Energy (IDEM)Private Garage (IDEM)Private Garage (IDSmall scale productionSmall scale productionUsed vegetable oilUsed vegetable oilNo tanks large enough for regulationNo tanks large enough for regulationHowever, 20 gallons spilled, some to sewerHowever, 20 gallons spilled, some to sewerIDEM advised resident on contingency plans andIDEM advised resident on contingency plans andcontractorscontractorsMichigan Paint ShopReported as small biodiesel spillReported as small biodiesel spillActually a paint shopActually a paint shopUSCG was in area and offered to check on spillUSCG was in area and offered to check on spillUSCG and MDEQ met on siteUSCG and MDEQ met on siteSmall spill observedSmall spill observedDid not see any coming out of sewerDid not see any coming out of sewerUSCG left, conditions changedUSCG left, conditions changedMDEQ noted emerging issues at shift changeMDEQ noted emerging issues at shift changeNoted entering waterway, low flowNoted entering waterway, low flow“Milky”white throughout the water columnwhite throughout the water columnMDEQ and EPA discussed optionsMDEQ and EPA discussed optionsCapture and removal not possibleCapture and removal not possibleLittle impact to fish observedLittle impact to fish observedConditions did not change much due tono flowConditions did not change much due tono flow••Decided to purge ditch and flushDecided to purge ditch and flush••Flushing somewhat effectiveFlushing somewhat effective•Heavy rains completed the flushingHeavy rains completed the flushingMichigan Paint ShopMilky WhiteThe following are Federal regulations that would apply toThe following are Federal regulations that would apply tobiofuelsbiofuelsmanufacturing facilities when they meet themanufacturing facilities when they meet thethresholds for the requirementshe regulation. Note thatthresholds for the requirementsof the regulation. Note thatstate-specific regulations may also applyspecific regulations may also applyEmergency Planning and Community Right Know ACTEmergency Planning and Community Right Know ACT(EPCRA)(EPCRA)U.S. EPA Oil Pollution Control/Federal WaterU.S. EPA Oil Pollution Control/Federal WaterPollution Control ActPollution Control ActClean Water ActClean Water ActOil Pollution Act of 1990 (OPA 90)Oil Pollution Act of 1990 (OPA 90)Resource Conservation and Recovery Act (RCRA)Resource Conservation and Recovery Act (RCRA)Clean Air Act (CAA)Clean Air Act (CAA)DOT Hazardous Materials Regulations (HMR); asDOT Hazardous Materials Regulations (HMR); asamended by Homeland Security Act of 2002amended by Homeland Security Act of 2002Current Biodiesel PlantsCurrent Biodiesel PlantsResponse GuidesResponse GuidesLayout – intended for responders•Description of Process•The chemicals involved (1stimportant table)•How releases may occur (what to look for)•Responding to releases (and byproduct releases, 2ndtable)•Environmental receptors/concerns (3rdtable)•Health risks•Summary of applicable regulationsResponse GuidesUse – want more functionality•Tables were included for quick location of info•Many spills are not the end product•Tables reflect the “may be” scenario of spills•Need your input•got tohttp://www.epaosc.org/site_profile.asp?site_id=4022Biofuels degrade fasterBiofuels degrade fasterCauses extreme DO issues in creeksCauses extreme DO issues in creeksNot great for water treatment plantsNot great for water treatment plantsOther removal/cleanup techniquesOther removal/cleanup techniquesAny ideas for treatingAny ideas for treating“in streamin stream”besidesbesidesaeration?aeration?Other sorbent technologies?Other sorbent technologies?Fast degradation can make cleanupsFast degradation can make cleanupsfasterBiofuel spills are many times notBiofuel spills are many times notbiodiesel or ethanol, but productionbiodiesel or ethanol, but productionproducts and byproductsproducts and byproductsSummaryBiofuel production can be anywhereBiofuel production can be anywhere“ManufacturersManufacturers”are heavily ignorant ofare heavily ignorant ofregulationsregulationsIn R5, many facilities are beingIn R5, many facilities are beingabandoned or going bankrupt due toabandoned or going bankrupt due tomarket fluctuationsmarket fluctuationsGlycerin spills seem to be prevalentGlycerin spills seem to be prevalentOutput from theOutput from thetransesterificationtransesterificationNot that much use for it as productNot that much use for it as productPeople are storing it and not disposingPeople are storing it and not disposingof itSome waiting forSome waiting for“value”to increaseto increaseSummaryQUESTIONS ???QUESTIONS ???