Biofuels and Emerging Iss

for 

Emergency Responders

An introduction to basic response guides and 

examples from biofuel spills.

Jeff Kimble, OSC, Region 5 Jeff Kimble, OSC, Region 5

Kimble.Jeffrey@epa.gov Kimble.Jeffrey@epa.gov
GOALS

 Discuss hazards and clean up Discuss hazards and clean up techniques 

techniques 

ethanol spills ethanol spills

 Discuss other Discuss other biofuels biofuels hazards hazards Look at what the response community is 

Look at what the response community is 

with

 Present response guides as a tool for resp

Present response guides as a tool for resp

 Discuss possible alternative approaches t

Discuss possible alternative approaches t
ETHANOL ETHANOL 

MANUFACTURIN

MANUFACTURIN

FACILITY RESPO

FACILITY RESPO

OVERVIEW OVERVIEW
Description of Ethanol Fu

Description of Ethanol Fu

the Production Process the Production Process

 Ethanol, which contains hydrog Ethanol, which contains hydrogen, carbon, an

n, carbon, an

chemical structure, is also know chemical structure, is also known as ethyl alco

n as ethyl alco

 Ethanol can b Ethanol can be used as a fuel for spark e used as a fuel for spark-ignited 

ignited 

combustion engines. When burn combustion engines. When burned in engines 

ed in engines 

catalytic converters on the engine exhaust, the 

catalytic converters on the engine exhaust, the 

allows ethanol to burn with lo allows ethanol to burn with lower carbon mon

wer carbon mon

than gasoline, although aldehyde emissions te

than gasoline, although aldehyde emissions te

 In the U.S., ethanol is primarily In the U.S., ethanol is primarily produced from 

produced from 

ingestion, ethanol is denatured at ingestion, ethanol is denatured at the plant by 

 the plant by 

with some type of hydro with some type of hydrocarbon, carbon, such as gasoli

such as gasoli

ethanol may contain 2 ethanol may contain 2-15 percent (%) gasoline

percent (%) gasoline

ethanol and gasoline fuel blen ethanol and gasoline fuel blend. For example, 

d. For example, 

contains 85% ethanol and 15% gas contains 85% ethanol and 15% gasoline.

 The ethanol The ethanol production process ta production process takes place th

kes place th

dry milling and wet milling. Th lling and wet milling. The dry milling m

e dry milling m

common and accounts for 82 % common and accounts for 82 % of U.S. ethano

of U.S. ethano
Dry Mill Process Dry Mill Process

 Source: Nebraska Department of Environmental Quality

 CO –carbon monoxide rbon monoxide PM5 –particulate m

 DDGS -Dried Distillers Grains with Solubles d Distillers Grains with Solubles

PM10 –

particulate 

 H2S –hydrogen sulfide drogen sulfide SOx –oxides of sulf

es of sulf

 NOx –oxides of nitrogen xides of nitrogen VOCs –volatile org
Major Chemicals Involve

Major Chemicals Involve

Ethanol Production Ethanol Production

 Corn –Used product Used product Sodium Hydroxide dium Hydroxide –pH control during fermentati

pH control during fermentati

 Ammonia Ammonia –pH control and yeast nutrient during fe

pH control and yeast nutrient during f

 Sulfuric Acid Sulfuric Acid – 

– separates corn into starch separates corn into starch, germ, fib

, germ, fib

 Fuel for process heat Fuel for process heat  Yeast – 

– used in used in fermentation fermentation

 Enzymes (amylase) Enzymes (amylase) –converts starch to converts starch to dextrose dextrose

 Antibio Antibiotic such as penicillin tic such as penicillin – 

– controls bacteria dur

controls bacteria dur

 Carbon Dioxide Carbon Dioxide -byproduct byproduct Hydrogen Sulfide Hydrogen Sulfide –process emission process emission Sulfur dioxide Sulfur dioxide –process emission process emission Nitric oxide Nitric oxide – 

– process emission process emission

 VOCs–process emission process emission

 Ethanol Ethanol –final product final product Gasolin Gasoline –final product additive (if used) final product additive (if used) Denatured Ethanol Denatured Ethanol – 

– final blended product final blended product
Appropriate Mitigation M

Appropriate Mitigation M

for Release of Ethanol Fu

for Release of Ethanol Fu

 Proper Air Monitoring Equipment Proper Air Monitoring Equipment 

 Combustible Gas Indicator (CGI) an Combustible Gas Indicator (CGI) and Flame Io

d Flame Io

or MultiRAE Plus Five or MultiRAE Plus Five-Gas Air Monitoring Inst

Gas Air Monitoring Inst

Ionizing Det Ionizing Detector (PID). Must review response 

ector (PID). Must review response 

PID.

 Proper Spill Containment Proper Spill Containment

 Ventilate area and eliminate ignition sources. F

Ventilate area and eliminate ignition sources. F

must use ALCOHOL ALCOHOL-RESISTANT FOAMS RESISTANT FOAMS. Containment/ Containment/response should follow typical co

response should follow typical co

Example: use non Example: use non-combustible oil combustible oil-dry, absorbe

dry, absorbe

that are ALCOHOL ALCOHOL-RESISTANT RESISTANT. Avoid entr

. Avoid entr

waterways due to flammability ha waterways due to flammability hazards, potent

zards, potent

potential microbial upsets at wa potential microbial upsets at wastewater treatm

er treatm

generated from the clean generated from the clean-up may exhibit the fla

up may exhibit the fla

characteristic for hazardous waste. characteristic for hazardous waste.

Note: T Note: The Response Overview incl he Response Overview includes measures f

udes measures 

chemicals involved in th chemicals involved in the manufacturing proce

e manufacturing proce
EXPECTED FATE OF ET

EXPECTED FATE OF ET

 Release in Soil Release in Soil

-Ethanol is rapidly biodegraded Ethanol is rapidly biodegraded in soil. in soil.

 Release in Water Release in Water

-Fuel et Fuel ethanol will mix with water, hanol will mix with water, and at high enough high enough concentrations of wat concentrations of water, the er, the ethanol will separate from the ethanol will separate from the gasoline. Ethanol is rapidly gasoline. Ethanol is rapidly biodegraded in groundwater and biodegraded in groundwater and surface water. However, some surface water. However, some studies are focusin studies are focusing on the g on the possibility of ethanol inducing possibility of ethanol inducing the transport of other chemicals the transport of other chemicals such as benzene. such as benzene. 

 Release i

Release i

spill/fire spill/fire-Ethanol v

Ethanol v

vapor, is d

vapor, is d

tends to se

tends to se

However, e

However, e

disperses r

disperses r

 Release t

Release t

sewers-Ethanol re

anol r

volatilize a

volatilize a

The pot The potent

ent

dissolved o

dissolved o

ethanol de

ethanol de

microbial f

microbial f

wastewate

astewate

potential fl

potential f

must be ad

must be ad

is released 

is released 

system. system. 
Overall Health Risks of E

Overall Health Risks of E

 Human Health Effects Human Health Effects

 Exposure to fuel ethanol can occur Exposure to fuel ethanol can occur by breathing its vapors by breathing its vapors (inhalat (inhalation), getting it on the skin ion), getting it on the skin or in the eyes (skin absorption or in the eyes (skin absorption), or accidentally accidentally swallowing it swallowing it (ingestion). (ingestion). 

 The following symptoms of The following symptoms of exposure to fuel ethanol may exposure to fuel ethanol may appear immediately: Dullness of appear immediately: Dullness of memory and concentration; memory and concentration; impaired motor coordination; and impaired motor coordination; and drowsiness, stupor, and finally drowsiness, stupor, and finally 

coma. May cause skin irritation as . May cause skin irritation as a result of defatting. a result of defatting. 

 Carcinogenic compounds are not Carcinogenic compounds are not present in pure ethanol; however, present in pure ethanol; however, 

because gasoline is used in the ecause gasoline is used in the blend, E85 is considered to be blend, E85 is considered to be potentially carcinogenic. potentially carcinogenic.

 Ecologica

Ecologica

 Pure e

Pure e

demon

demon

concen

concen

(rainb

(rainb

15,300 

15,300 

(mg/L

(mg/L

 Pure e

Pure e

biodeg

biodeg

bioacc

bioacc

concen

concen

chain 

chain 

Howev

Howev

may d

may d

oxygen 

oxygen 

resulti

resulti
 July 7, 2008 July 7, 2008-Report from Hancock Co. EMA Report from Hancock Co. EMA of yell

of yell

roadside ditch roadside ditch

 Owner of adjacent property dumped 5,000 gallons 

Owner of adjacent property dumped 5,000 gallons 

of ethanol production) of ethanol production)

 Corn distiller was rejected at dis Corn distiller was rejected at disposal facility and s

posal facility and s

feed deer feed deer

 Ethanol Plant on Ethanol Plant on-site to provide site to provide “Technical Assista

Technical Assista

 ODNR discovers up to 1,000 dead discovers up to 1,000 dead fish downstream 

fish downstream 

 PRP hired an environmental contractor to PRP hired an environmental contractor to

 Remove gross contamination from spill site Remove gross contamination from spill site Provide aeration to tributary Provide aeration to tributary Remove dead fish from downstream Dispose of contaminated soil Dispose of contaminated soil

 Direct reading in tributary showed Direct reading in tributary showed

 DO Levels @ 0 mg/L DO Levels @ 0 mg/L

Woods Ethanol Spill Woods Ethanol Spill
Woods Ethanol Spill Woods Ethanol Spill
Woods Ethanol Spill Woods Ethanol Spill
Woods Ethanol Spill Woods Ethanol Spill
Current Ethanol Plan

Current Ethanol Plan

http://w http://www.card.iastate.edu/res ww.card.iastate.edu/research/bio/tools/ethanol.aspx earch/bio/tools/ethanol.aspx as of 01/16/

as of 01/16/
BIODIESEL BIODIESEL 

MANUFACTURIN

MANUFACTURIN

FACILITY RESPO

FACILITY RESPO

OVERVIEW OVERVIEW
Description of Biodiesel F

Description of Biodiesel F

the Biodiesel Production 

the Biodiesel Production 
Major Chemicals Inv

Major Chemicals Inv

in Biodiesel Producti

in Biodiesel Product

 Soybean hulls and fines Soybean hulls and fines Hexane –extracts soybean oil extracts soybean oil Sodium and Potassium Hydroxid

Sodium and Potassium Hydroxid

fatty acids from soybean oil fatty acids from soybean oil

 Methanol Methanol –replaces glycerol in s

replaces glycerol in s

make oil less viscous ( make oil less viscous (transester

transester

 Glycerol Glycerol –byproduct of byproduct of transeste

transeste

 Fuel for process heat (i.e. natura

Fuel for process heat (i.e. natura

propane, etc.) propane, etc.)
Appropriate Mitigation M

Appropriate Mitigation M

for Release of Biodiesel F

for Release of Biodiesel F

 Proper Air Monitoring Equipment Proper Air Monitoring Equipment 

 Biodiesel fuel has a very low Biodiesel fuel has a very low volatility at norma

volatility at norma

temperatures and vapors are not temperatures and vapors are not typically an is

typically an is

vapors/mists may be generated wh vapors/mists may be generated when heated ab

en heated ab

Fahrenheit ( Fahrenheit (

oF).

 Proper Spill Containment Proper Spill Containment

 Containment/ Containment/response should follow typical oi

response should follow typical oi

procedures. Example: use oil procedures. Example: use oil-dry, petroleum-cosocks, booms, etc; the absorbent socks, booms, etc; the absorbent material used 

material used 

alcohol in the event alcohol in the event methanol has further comm

methanol has further comm

biodiesel release. Disposal of biodiesel biodiesel release. Disposal of biodiesel-contam

contam

can be considered no can be considered non-hazardous provided met

hazardous provided me

have not commingled with the re have not commingled with the release to meet t

lease to meet t

characteristic for hazardous waste. characteristic for hazardous waste.

Note: T Note: The Response Overview incl he Response Overview includes measures f

udes measures 

chemicals involved in th chemicals involved in the manufacturing proce

e manufacturing proce
EXPECTED FATE OF BIO

EXPECTED FATE OF BIO

 Release in Soil Release in Soil

-Biodegradation occurs Biodegradation occurs rapidly, with faster rates rapidly, with faster rates under aerobic conditions than under aerobic conditions than anaerobic conditions. anaerobic conditions. 

 Release in Water Release in Water

-Insoluble in water. Degrades Insoluble in water. Degrades rapidly and fairly extensively rapidly and fairly extensively in aquatic environments. in aquatic environments. Estimated to degrade at a rate Estimated to degrade at a rate approximately four times approximately four times faster than petroleum diesel than petroleum diesel –85% of pure biodiesel 85% of pure biodiesel expected to degrade within 28 expected to degrade within 28 days. 

 Release 

Release 

spill/fire spill/fire-Combust

Combust

monoxide

monoxide

along with 

along wit

 Release 

Release 

sewers-May be h

May be h

acids and 

acids and 

have a hig

have a hig

oxygen de

oxygen de

can disrup

can disru

treatment 

treatment 
Overall Health Risks 

Overall Health Risks 

Biodiesel Releas

Biodiesel Releas

 Human Health Effects Human Health Effects

 Inhalation effects are negligible Inhalation effects are negligible unless 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 ester enzymes in the body called esterases would break the biodiesel fuel would break the biodiesel fuel 

molecules into the component fatty molecules into the component fatty acids and alcohol molecules. The acids and alcohol molecules. The alcohol is usually methanol and alcohol is usually methanol and methanol is toxic. Thus, methanol methanol is toxic. Thus, methanol toxicity could be a concern for toxicity could be a concern for ingestion of biodiesel fuel. ingestion of biodiesel fuel. 

 Neat biodiesel fuel is approximately Neat biodiesel fuel is approximately 

11 perc 11 percent methanol by weight, so ent methanol by weight, so ingestion of 100 grams ingestion of 100 grams of biodiesel of biodiesel would release 11 grams would release 11 grams, or 14milliliters ( milliliters (mL) of methanol. For a of methanol. For a 70 kilogram (kg) 70 kilogram (kg) adult, the fatal dose t, the fatal dose of methanol ranges of methanol ranges from 60 to 160 from 60 to 160 mL.

 Ecological E

Ecological E

 Biodiese

Biodiese

rapidly th

rapidly th

 When bi

When bi

the envir

the envirthat com

reduce t

reduce t

aquatic s

aquatic s

action is 

action is 

fuel. 

 Biodiese

Biodiese

and the s

and the 

has, so i

 so i

expected 

expected 

 The trea

The treaanimals 

als 

treatmen

treatmen

occurs. occurs. 

 Howeve

Howeve

oxygen d

oxygen d

massive 

massive 
 Initial report called in to state: Initial report called in to state: COMPANY 

COMPANY 

EXPLOSION. THERE ARE 2 LARGE TAN

EXPLOSION. THERE ARE 2 LARGE TAN

CONTAINING GYLCERIN. SEWER BEIN

CONTAINING GYLCERIN. SEWER BEIN

WITH FF WATER WITH FF WATER

 OHIO EPA OSC responded OHIO EPA OSC responded 2 tanks were in fire (10,000 gallons & 4,00

2 tanks were in fire (10,000 gallons & 4,00

 Only 1650 gallons of glycerin reported on h

Only 1650 gallons of glycerin reported on h

 Also ~700 gallons of biodiesel Also ~700 gallons of biodiesel “Empty”55-gallon drums gallon drums

 Release to ground and storm sewer Release to ground and storm sewer Release to threatened creek and river via 

Release to threatened creek and river via 

Defiance Biofuel Spill Defiance Biofuel Spill
Defiance Biofuel Spill (cont Defiance Biofuel Spill (cont’d

Fire and release point Fire and release point
Defiance Defiance Biofuel Biofuel Spill (cont Spill (cont’d

 Ohio EPA responded and asses

Ohio EPA responded and asses

 Called EPA spill phone duty offi

Called EPA spill phone duty offi

 Duty officer coordinated with OS

Duty officer coordinated with OS

 Both told Ohio EPA to respond 

Both told Ohio EPA to respond 

 Were not sure what regulations 

Were not sure what regulations 

biodiesel production biodiesel production

 Both continued research that nigh

Both continued research that nigh

 Advised state on limited info obtai

Advised state on limited info obtai

 Ohio determined spill contained

Ohio determined spill contained

cleaned up cleaned up

 They decided to wait till morning 

They decided to wait till mornin
Defiance Defiance Biofuel Biofuel Spill (cont Spill (cont’d

-“fats” floate- 3 layers in - some susp-“milky” laye

 Response Techniques Response Techniques

 Ohio EPA made PRP hire Ohio EPA made PRP hire a contractor a contractor On-land spills were excavated land spills were excavated

 Spill to ditch was collected and put in Spill to ditch was collected and put in fracta

 Analytical of Analytical of fractank water revealed styrene 

tank water revealed styrene 

 Shows more than Shows more than “glycerin glycerin”spilled spilled

 Some wastes suspended in water column w

Some wastes suspended in water column w
Renewable Energy (IDEM) Renewable Energy (IDEM)

 Biofuels production facility Biofuels production facility Spill from 50,000 gallon tank Spill from 50,000 gallon tank Surface soils and ditch water impac

Surface soils and ditch water impac

 Water in ditch a Water in ditch a 

“milky”white

 Soils excavated Soils excavated Tile field drains intercepted and plug

Tile field drains intercepted and plu
Renewable Energy (IDEM) Renewable Energy (IDEM)
Private Garage (ID Private Garage (IDEM)

 Small scale production Small scale production Used vegetable oil Used vegetable oil No tanks large enough for regulation No tanks large enough for regulation However, 20 gallons spilled, some to se

However, 20 gallons spilled, some to se

 IDEM advised resident on contingency p

IDEM advised resident on contingency p

contractors contractors
Michigan Paint Shop

 Reported as small biodiesel spill Reported as small biodiesel spill Actually a paint shop Actually a paint shop USCG was in area and offered to check on spill USCG was in area and offered to check on spill USCG and MDEQ met on site USCG and MDEQ met on site

 Small spill observed Small spill observed Did not see any coming out of sewer Did not see any coming out of sewer

 USCG left, conditions changed USCG left, conditions changed MDEQ noted emerging issues at shift change MDEQ noted emerging issues at shift change Noted entering waterway, low flow Noted entering waterway, low flow

“Milky”white throughout the water column white throughout the water column

 MDEQ and EPA discussed options MDEQ and EPA discussed options Capture and removal not possible Capture and removal not possible

 Little impact to fish observed Little impact to fish observed Conditions did not change much due to Conditions did not change much due to no f

 no f

• 

• Decided to purge ditch and flush Decided to purge ditch and flush

• 

• Flushing somewhat effective Flushing somewhat effective

•Heavy rains completed the flushing Heavy rains completed the flushing
Michigan Paint Shop

Milky 
The following are Fe The following are Federal regulations that 

deral regulations that 

biofuels biofuels manufacturing facilities when t

manufacturing facilities when t

thresholds for the requirements thresholds for the requirements of the regul

he regu

state

-specific regulations may also 

specific regulations may also 

 Emergency Planning and Communit

Emergency Planning and Communit

(EPCRA) (EPCRA)

 U.S. EPA Oil Pollution Control/Fede

U.S. EPA Oil Pollution Control/Fede

Pollution Control Act Pollution Control Act 

 Clean Water Act Clean Water Act  Oil Pollution Act of 1990 (OPA 90) Oil Pollution Act of 1990 (OPA 90) Resource Conservation and Recover

Resource Conservation and Recover

 Clean Air Act (CAA) Clean Air Act (CAA) DOT Hazardous Materials Regulatio

DOT Hazardous Materials Regulatio

amended by Homeland Security Act 

amended by Homeland Security Act 
Current Biodiesel Pla

Current Biodiesel Pl
Response Guides
Response Guides

Layout – intended for responders• Description of Process• The chemicals involved (1st important 

• How releases may occur (what to look • Responding to releases (and byproduc

• Environmental receptors/concerns (3

• Health risks• Summary of applicable regulations
Response Guides

Use – want more functionality• Tables were included for quick location of • Many spills are not the end product• Tables reflect the “may be” scenario of spi• Need your input

• got to http://www.epaosc.org/site_profile.asp?site_
 Biofuels degrade faster Biofuels degrade faster

 Causes extreme DO issues 

Causes extreme DO issues 

 Not great for water treatmen

Not great for water treatmen

 Other removal/cleanup tech

Other removal/cleanup tech

 Any ideas for treating Any ideas for treating “in stre

in stre

aeration? aeration?

 Other sorbent technologies? Other sorbent technologies?

 Fast degradation can make 

Fast degradation can make 

faster

 Biofuel spills are many time

Biofuel spills are many time

biodiesel or ethanol, but pro

biodiesel or ethanol, but pro

products and byproducts products and byproducts

Summary
 Biofuel production can be an

Biofuel production can be an

 “Manufacturers Manufacturers”are heavily 

are heavily 

regulations regulations

 In R5, many facilities are bei

In R5, many facilities are bei

abandoned or going bankrup

abandoned or going bankrup

market fluctuations market fluctuations

 Glycerin spills seem to be pr

Glycerin spills seem to be pr

 Output from the Output from the transeste

transeste

 Not that much use for it as 

Not that much use for it as 

 People are storing it and n

People are storing it and n

of it

 Some waiting for Some waiting for “value”t

t

Summary
QUESTIONS ?

QUESTIONS