Professional Documents
Culture Documents
► Introduction
► Releases
► Fate and Transport
► Q&A Session #1
► Site Investigation
► Long-Term Response Strategies
► Summary
► Q&A Session #2
Dispensing
Dispenser Station
System
Vadose
Zone
Underground
Storage Tank
System (UST)
Capillary
Fringe
Aquifer
Groundwater
Flow Direction
5
What Are Biofuels?
► Catastrophic impact of
large releases
• Large releases from tank
car train derailments
• Massive fires 2009 train derailment in Rockford, IL
► Smaller releases resulting in 435,000-gallon DFE release.
WA
MT
OR MN
PA MA
MO
NM
LA
FL
HI
11
International Mandates
► European Union
• Directive 2003/30/EC
• Promotes biofuels use in
transportation sector
• Proposes non-mandatory
biofuels use targets
► Brazil
• Has required the use of
biofuels since 1976
12 ITRC Guidance: Biofuels: Release
Prevention, Environmental Behavior, and
Remediation
1. Biofuel basics
2. Release prevention and
response planning
3. Fate & transport (F&T) of
biofuels in the environment
4. Characterizing release
sites
5. Long-term response
strategies
6. Stakeholder concerns
13
What is Not Covered
D
DE
manufacturing processes
►
LU
End-user considerations
►
NC
Biofuel policies
► Fuel additives
TI
NO
14
Applying the ITRC Document Before a
Release
► Release prevention
• Ensure materials
compatibility
• Update best management
practices
► Release response
planning
• Fire/explosion threats
• Rapid containment
15
Biofuel Production Projections
(Figures 1-1 and 1-2)
15,000 6,000
5,000
10
12
14
16
18
20
20
20
20
20
4,000
3,000
10
12
14
16
18
20
20
20
20
20
16
Opportunities to Use this Document
in Your State
► Introduction
► Releases
► Fate and Transport
► Q&A Session #1
► Site Investigation
► Long-Term Response Strategies
► Summary
► Q&A Session #2
18
Biofuel Releases
(Section 2)
This section will cover
Evaluated based on the differences
Release Scenarios between petroleum and biofuel
and Frequencies supply chains
Release Causes
Prevention
Emergency
Response Planning
19
Petroleum vs. Biofuel Supply Chains
(Combined Figures 2-1 and 2-2)
Manufacturing Bulk Depot / Dispensing
Refinery –OR– Facility Supply Terminal Station
(Bulk) (Blended)
Transport Distribution
Pipeline Truck
► Applicable plans
• Spill Prevention Control and Countermeasures
(SPCC) regulations (40 CFR 112)
• Facility Response Plans (FRP)
► Additional Emergency Response considerations
• Common fire-fighting foams – less effective
• Appropriate foams – less available
• Sorbent booms – miscibility, sorption, etc.
• Impacts to sensitive receptors – oxygen demand,
biodegradability, etc.
24
Our Case Study: The Release
► Introduction
► Releases
► Fate and Transport
► Q&A Session #1
► Site Investigation
► Long-Term Response Strategies
► Summary
► Q&A Session #2
27
Fate and Transport
(Section 3)
This section will cover:
Biofuel
Properties
Surface and
subsurface
behavior
Effects on microbial
communities and
by-product formation
Impacts on petroleum
hydrocarbons and Use of the hypothetical case
NAPL study to help illustrate key points
28
Properties of Selected Fuel Components
(Table 3-1)
Henry’s
Vapor
Solubility Law Biodegradation
Pressure Implications
(mg/L) Constant Potential
(mm Hg)
(unitless)
Ethanol Infinite 2.1E-4 to 59 Aerobic: hours to Readily partitions to water
2.6E-4 days and dilutes according to
Anaerobic: days availability. Rapidly
to weeks biodegradable
Benzene 1,800 0.22 75 Aerobic: days to Readily partitions to vapor
months phase from NAPL and from
Anaerobic: years water
Unsaturated zone
Primary source (short term)
Trapped and sorbed residual
Volatilization
NAPL Groundwater source (longer term)
Capillary fringe
n
body
utio
sol
Aquifer
Dis
► In groundwater, rapid
biodegradation will
induce anaerobic
Dead paddlefish resulting from a
conditions release of Wild Turkey Bourbon
34
Biofuel Biodegradation
(Figure 3-2)
Methane
CO2 Ethanol
CO2
H2 Acetyl CoA Butyryl CoA Butyrate
CO2
Acetone AcetoacetylCoA Butanol
Acetate
Figure 3-2. Major routes of the
anaerobic fermentation of ethanol
Methane
35
Factors Affecting Biodegradation
Oxygen
Capable of forming
• Upper explosive limit (UEL) 12%
explosive mixtures
= 15% in atmosphere with air
► LEL equivalent concentration 8%
in groundwater
Not capable of
• 1 - 2 mg/L 4% forming explosive
• Dependent on temperature mixtures with air
0
0 4% 8% 12% 16% 20%
Methane
Figure source: Relationship Between Quantitative Composition
30 CFR 57.22003 and Explosivity of Mixtures of Methane and Air
37
Generation of Methane
(Figure 3-3)
► Media impacts to
vadose zone, capillary
fringe and
groundwater
• Capillary fringe can
act as a lingering
source area for
ethanol CH4
► Groundwater will
become anaerobic,
possibly leading to
methane generation
41
Fate and Transport Summary
► Introduction
► Releases
► Fate and Transport
► Q&A Session #1
► Site Investigation
► Long-Term Response Strategies
► Summary
► Q&A Session #2
43
Training Roadmap
► Introduction
► Releases
► Fate and Transport
► Q&A Session #1
► Site Investigation
► Long-Term Response Strategies
► Summary
► Q&A Session #2
44
Site Investigation
(Section 4)
This section will cover:
Risk
Drivers
Monitoring
CH4
Analytical
Methods
Site Closure
Use of the hypothetical case
Considerations
study to help illustrate key points
45
Risk Drivers for Site Investigation
► Surface water
• Ethanol can not be recovered due to solubility; biodiesel can be
recovered like petroleum
• Dissolved oxygen depletion – risk to aquatic species a significant
new concern
► Vadose zone
• Explosive risk from increased methane production – NO ODOR
• Potential increased vapor intrusion (VI) risk for petroleum VOCs
► Groundwater
• Risk to drinking water supplies due to plume elongation
• Biofuel degradation can produce taste and odor issues in
drinking water supplies
46
July 2008 – Lanesboro, MN
3,000 gals E95
47
Our Case Study: Site Investigation
(Section 4)
CH4
48
Site Investigation – What’s Different
► Groundwater
• Generally more reliable than soil gas for detection
• Well screen lengths may affect concentrations
• Must closely follow QA/QC sampling procedures
• Methane is easily lost during sampling
• Levels above 25 mg/L indicate saturated levels where
ebullition (bubbling) may be occurring
► Soil gas
• Sampling points and procedures same as VOCs (ITRC
2007, Vapor Intrusion Pathway: A Practical Guideline)
• If potential receptors are present at least one vapor
monitoring point should be placed in the release area
51
November 2006 - Cambria, MN
25,000 gals DFE (E95)
52
Delayed Methane Generation: Cambria, MN
Case Study July 2007 (Appendix D)
53
Delayed Methane Generation: Cambria, MN
Case Study December 2007 (Appendix D)
54
Ethanol Monitoring (Section 4.1.2)
► Vadose zone
• Soil gas monitoring same as VOCs
• Soils can be sampled using standard VOC methodology
► Capillary fringe
• Lysimeters have been used, but sampling capillary fringe not
necessary
► Groundwater
• Shorter monitoring well screens recommended to capture ethanol
draining, and/or leaching from the capillary fringe
• Multi-level wells may be needed
• Detection of ethanol in groundwater should not be used alone for
methane risk assessment
55
Cambria, MN Case Study
Soil Sample
6,340,000 ug/kg
CH4
► Introduction
► Releases
► Fate and Transport
► Q&A Session #1
► Site Investigation
► Long-Term Response Strategies
► Summary
► Q&A Session #2
65
Long-Term Response Strategies
(Section 5)
General
considerations
for remediation
Risk
management CH4
Remedial
selection Use of the hypothetical case
study to help illustrate key points
66
Our Case Study: Long-Term
Response Strategies (Section 5)
Requires consideration of: Case study:
• Type of biofuel • E85 spill
• Extent and magnitude of the • Media impacted:
release • Vadose zone
• Regulatory threshold for a • Capillary Fringe
COC(s)
• Groundwater
• Risk to identified receptors
• State regulations applicable to
gasoline components
• Dispensing station building and
surrounding residential area
CH4
67
Generalized Framework
(Figure 5-1)
Risk
Site Conceptual Sections acceptableSect 5.2.1 Sect 5.3
Model/Site 3 and 4
or
Characterization No Active
manageabl
e w/ Remedy
Above controls?
Sect 5.1 regulatory
threshold Yes Yes
Sect 5.2.2
and/or a No
Implement closure
potential Sect 5.3.3
monitoring and/or
hazard Meet
exists? controls
remedial
Yes
No endpoints
?
Meet Sect 5.4
No Further
closure
Action/Site Yes
requireme
Closure
nts? Yes
No
68
Risk Management
(Section 5.2.1; Table 5-1)
Benefits Limitations
Dissolved •High concentrations of some dissolved biofuel constituents (i.e.,
biofuel is ethanol) can be toxic to microorganisms
readily •Delayed biodegradation of more recalcitrant contaminants via
biodegradable preferential biodegradation of the biofuel
without •Does not address immediate risks
additional •High potential for methane generation
enhancement •Does not address LNAPL, although microbial processes can
enhance dissolution in groundwater
•Surface water may become anoxic, impacting aquatic species
and habitat
69
Selection of Remedial Technology
(Tables 5-2 and 5-3)
► Active remedy
• Eliminate or reduce the remediation driver or COC
► Remedial technologies
• Soils/Sediment (Table 5-2)
• Groundwater/Surface water (Table 5-3)
► Categorized as in situ or ex situ
► Subdivided within each category by dominant remedial
mechanism
• Biological technologies (e.g. enhanced aerobic biodegradation)
• Chemical (e.g. chemical oxidation)
• Physical (e.g. soil vapor extraction)
► Provides discussion on overall benefits and limitations of each
technology to help guide selection
70
Remedial Technology (Soils Example)
Table 5-2
► Biofuels evaluated
• Ethanol (Table 5-4a)
• Butanol (Table 5-4b)
• Biodiesel (Table 5-4c)
► Identifies targeted environmental media
► Evaluates technology by specific property (e.g. solubility) and
provides numerical values
► Compares efficiency to a reference petroleum hydrocarbon
compound
► Summarizes which compound (biofuel or reference
hydrocarbon) is favored by the remedial technology
72
Example Table 5-4a
(Figure 5-2)
► Introduction
► Releases
► Fate and Transport
► Q&A Session #1
► Site Investigation
► Long-Term Response Strategies
► Summary
► Q&A Session #2
77
Our Case Study: Summary
► Equipment compatibility
issues
► Biofuels fate & transport in
the environment
► Methane gas generation
► Site investigation design
► Monitoring in
CH
environmental media 4
► Long-term response
strategies
► Risk management
78
Overall Summary