Transcript ITRC EISB Internet Training - CLU-IN

Welcome to ITRC’s
Internet Training
ITRC Technical and Regulatory Guidance Document:
“Enhanced In Situ Bioremediation of Chlorinated
Solvents in Ground Water”
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Copyright 2007 Interstate Technology & Regulatory Council, 444
North Capitol Street, NW, Suite 445, Washington, DC 20001
Enhanced In Situ Bioremediation of Solvents in Ground Water
EISB Presentation Overview
 Regulatory Issues
 Chemical Terminology
 Microbial Processes / Degradation
Pathways
 Questions & Answers
 Amendments & Delivery
 Field Pilots / Technical
Requirements
 Benefits / Rules of Thumb
 Questions & Answers
 Links to additional resources
 Your feedback
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Logistical Reminders
 Phone Audience
 Keep phone on mute
 * 6 to mute your phone
and again to un-mute
 Do NOT put call on hold
 Simulcast Audience

Use
at top of each
slide to submit questions
Today’s Presenters
 Ron Buchanan - Instructor

Principal Consultant, Dupont
 [email protected]
 Guy Tomassoni – Instructor

Environmental Protection Specialist, EPA
Office of Solid Waste / Corrective Actions

[email protected]
 Mary Yelken - Moderator

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Environmental Programs Advisor, WGA/ITRC
 [email protected]
What is EISB?
 Engineered technique for optimizing subsurface
conditions (hydrogeological, geochemical, microbial)
to biodegrade contaminants in situ
 Includes injecting substrate and nutrients
(i.e., amendments)
 Creates in situ conditions conducive to microbes
 May include extracting and recirculating amended
groundwater
 Establishes/accelerates contaminant biodegradation
in situ
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Regulatory Issues
EISB is a complex regulatory process
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regulatory
authorities
regulatory
status of contaminated groundwater
regulation
status of amendments
Regulatory Authorities
Regulatory Authority/Authorities
 RCRA (Subtitle C) or CERCLA (Section 104 or
106)
 Safe Drinking Water Act - 40 CFR Section 144
Underground Injection Control Program
 State Cleanup programs
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Regulatory Status of Contaminated Ground
Water
 Contaminated media, including ground water, may
“contain” hazardous wastes and therefore be subject
to regulation under RCRA subtitle C (contained-in
policy)
 If ground water contains HW we must understand
application of;



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Land Disposal Restrictions (LDRs)
Minimum Technological Standards (MTRs)
Permitting
Application of RCRA Subtitle C
(continued)
 Land Disposal Restrictions

RCRA Section 3020(b) clarification (EPA Guidance
Memorandum “Applicability RCRA Section 3020 to InSitu Treatment of Ground Water, Dec. 27, 2000”)
 Treatment standards for waste waters
 Site-specific treatment variance (if applicable)
 Management that does not constitute “placement”

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e.g., some NPDES permitting
Application of RCRA Subtitle C
(Cont’d)
 Minimum Technological Standards


different standards apply to different types of units
consider “temporary units”
 Permitting

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EPA, under CERCLA, and many states, under their
own programs, exempt from administrative permitting
requirements on-site cleanup provided substantive
standards are achieved
Application of Underground Injection
Control Programs
Class IV


waived under 40 CFR Part 144 .13 & must obtain
waiver in each case
NJDEP intent to issue “General NJPDES Permit”
where only amendments are added
Class V Wells


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Federal Performance Standards
State Standards
Regulatory Status of Injection of
Amendments
RCRA Subtitle C


Generally not regulated under Subtitle C
Exception is if amendment is a hazardous waste
Underground Injection Control Programs


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Class IV wells
Class V Wells
Regulatory Issues Summary
Regulatory authorities
Regulatory status of contaminated ground
water
Regulation of injection of amendments
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Key Definitions
PCE
TCE
DCE
VC
CT
CF
DCM
TCA
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-
Tetrachloroethylene
Trichloroethylene
Dichloroethylene
Vinyl chloride
Carbon tetrachloride
Chloroform
Dichloromethane
1,1,1 Trichloroethane
C2Cl4
C2HCl3
C2H2Cl2
C2H3Cl
CCl4
CHCl3
CH2Cl2
C2H3Cl3
Preferred Electron Donors/Acceptors
 Electron Donors: small, simple molecules like
sugars, organic acids, alcohols, alkanes, aromatics;
man-made organic compounds, and natural organic
carbon can be used.
 Electron Acceptors: Oxygen, nitrate, Mn(IV),
Fe(III), chlorinated solvents, sulfate, and CO2
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Electron Donor Biochemical Reactions
 Lactate and hydrogen reactions
2CH3CH2OCOO- + 2H20 --> 4H2 + 2CH3COO- + 2CO2
TCE + H2 --> cDCE + Cl- + H+
cDCE + H2 -->VC + Cl- + H+
VC + H2 --> ETH + Cl- + H+
Overall:
TCE + 3H2 --> ETH + 3Cl- + 3H+
 Theoretically requires approx. 1.3 moles of lactate to
drive hydrogen mediated microbial reactions
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Degradation Processes
Three Major Degradation Mechanisms
1) Reductive Anaerobic Dechlorination
2) Aerobic Cometabolism
3) Oxidation - reactions may be used for the
destruction of vinyl chloride, dichloromethane,
1,2 DCA, 1,2 DCE
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Degradation Pathway
H
Cl 2H HClCl
H 2H HCl H
H 2H HCl H
H 2H HCl H
C C
C C
C C
C C
C C
H
H
Cl
Cl
Cl
Cl
Cl
Cl
Cl
H
Cl
PCE
TCE
DCEs
VC
ETH
Relative Degradation Rates:
PCE >TCE > VC > DCE
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Degradation Processes
“Reductive Anaerobic Dechlorination”
1) Reductive Anaerobic Dechlorination:
Process:
R-Cl + H2 + 2e-
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R-H + Cl- + H+

dechlorination involves a series of reductions

reductions = gain of electrons

electron transfer may provide energy

organic substrate supplies H2 and electrons
Mass Balancing Dechlorination
Reactions
 Example: reductive dechlorination of TCE

TCE  DCE  VC  ETH
 In gram moles:


C2HCl3 + 3 H2  C2H4 + 3 HCl
131.5g TCE + 6g H2  28g Ethene + 109.5g HCl
 TCE : H2 ratio is 21.9 : 1
 H2 solubility is 1.7 ppm, so you can degrade
37.2 ppm of TCE
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Degradation Processes
“Reductive Anaerobic Dechlorination”
 Potential Problems:
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
Low hydraulic conductivity zones

biofouling

over abundance of electron acceptors
Degradation Processes
“Aerobic Cometabolism”
2) Aerobic Cometabolism:
highly chlorinated compounds such as PCE and CCl4 do
not appear to be susceptible to aerobic cometabolic
degradation

non-specific oxygenase enzymes help metabolize
substrate(s)


bacteria incidentally oxidize chlorinated compounds
process usually requires oxygen addition for aerobic
bacteria

process usually requires a substrate such as methane,
phenol, or toluene

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Cometabolic Degradation
 A fortuitous aerobic reaction carried out by enzymes
designed to metabolize a different compound the bacteria
normally grows on.
 Bacteria are presumed to gain nothing from the reaction
and in fact, may be harmed by intermediates that are
formed
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Cometabolic Biodegradation
 Mechanism for ethenes is epoxidation:
O
/ \
-C = C- => -C - C- => CO2 , other products
Example: TCE
O
/ \
Cl2-C=C-Cl => Cl2-C-C-Cl => CO2 , (small amounts of Cl2-CCOOH, dichloroacetic acid)
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Cometabolic Degradation
 Compounds documented in the literature
supporting aerobic cometabolic reactions:
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
methane (Wilson and Wilson, 1985), other shortchained alkanes like ethane, propane (Wackett et.
al., 1989),

simple aromatic ring compounds: toluene, phenol
(Nelson et. al., 1986)

NH4+ (Arciero et. al., 1989)
Mass Balancing Cometabolic
Reactions
 Example: co-oxidation of TCE

2 C2HCl3 + 21 O2 + 2 C7H8 --> 6 HCl + 18 CO2 + 6 H2O
 In gram moles:

263g TCE + 672g O2 + 184g C7H8 ----> 219g HCl + 792g CO2 +
108g H2O
 TCE to O2 ratio is 0.39 : 1
 Water with 10 ppm dissolved oxygen can degrade a max of
3.9 ppm TCE
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Degradation Processes
“Aerobic Cometabolism (Cont’d)”
 Potential Problems:
process does not work on highly chlorinated
compounds


cost of maintaining aerobic conditions
intermediates may be toxic to bacteria (i.e..
epoxide)

substrate amendments maybe RCRA regulated
compounds

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Degradation Processes
“Oxidation”
3) Oxidation:
 used on dichloromethane (DCM), vinyl
chloride,chloroethane, and chloromethane
 Process:
 oxidizing agent (amendment) / reducing agent
(contaminant)
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
elemental oxygen and or hydroxyl radical replace
chloride

oxidizing agent supplied directly or indirectly (i.e. O2,
H2O2)
Direct Aerobic
Biodegradation
 Aerobic bacteria “grow” on the compound by using it
as their carbon and energy source (electron donor).
 Process is rapid, compound almost always degraded
to CO2, degradation intermediates may be formed.
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1,2-DCA Degradation Pathways
Aerobic Conditions
Anaerobic Conditions
1,2-Dichloroethane
(1,2-DCA)
hydrolysis
Chloroethanol
reductive
dechlorination
Vinyl Chloride
(VC)
Chloroethane
(CA)
Chloroacetate
Ethanol
reductive
dechlorination
Ethene
CO2
Ethane
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CO2
Mass Balancing Oxidation Reactions
 Example: oxidation of VC

2 C2H3Cl + 5 O2 ---> 4 CO2 + 2 HCl +2 H2O
 In gram moles:

125g VC + 160g O2 ---> 176g CO2 + 73g HCl + 36g H2O
 VC : O2 ratio is 0.78 : 1
 Water with 10 ppm dissolved oxygen can degrade a max
of 7.8 ppm VC
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Degradation Processes
“Oxidation (cont’d)”
 Potential Problems:
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
low hydraulic conductivity

Oxygen transport in ground water

high levels of naturally occurring organic carbon
Chlorinated Solvent Degradation
PROCESS
PCE
TCE
c-DCE
VC
TCA
DCA
CT
CF
DCM
Direct Aerobic
N
N
Y&N
Y
N
N
N
N
Y
Cometabolic w/ CH4
N
Y
Y
Y
Y&N
N*
N
Y
NR
Cometabolic w/
toluene
N
Y
Y
Y
N
N*
N
Y&N
NR
Cometabolic w/ NH4
N
Y
Y
Y
Y
N*
N
Y
NR
Direct Anaerobic
Anaerobic/
Denitrification
N
N
N
Y
N
N
N
N
Y
Y&N
Y&N
N*
N*
N*
N*
Y
Y&N
NR
Anaerobic/Sulfate
reduction
Y
Y
Y
Y
Y
Y
Y
Y
NR
Anaerobic/
Methanogenic
Y
Y
Y
Y
Y
Y
Y
Y
NR
N: Not documented in the literature
Y: Documented in the literature many times; concensus opinion
Y&N: Documented in the literature more than once of both occurrence and absence
N*: Not documented in the literature to date, but not investigated significantly
NR: Process may occur but Not Relevant since competing process occurs more rapidly
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“Technical and Regulatory Requirements
for Enhanced In Situ Bioremediation of
Chlorinated Solvents in Ground Water”
Question & Answer
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Amendment Delivery Systems
Effective EISB requires delivery of amendments to
the targeted portion of the plume
A) Dual Well or Trench Recirculation
 extraction and reinjection of groundwater
 effective mixing of amendments and water
 forms a treatment zone
B) Injection Only Systems
 gravity or forced injection
 lack of hydraulic containment
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Delivery Systems (Cont’d)
C) Gas Injection Systems
 injection of vapor phase amendment(s)
D) Passive Systems
 no forced injection or recirculation
 amendments added within or in the path of a plume
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Amendments for
Microbial Growth
A) Substrate
 growth source and electron donor
 vary from site to site
 example: Na lactate
B) Nutrients
 ground water analysis for needed inorganics
 monitoring of concentration levels
 example: P, N
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Amendments for
Microbial Growth (cont’d)
C) Electron Acceptors
 associated with aerobic cometabolism or direct
oxidation
 O2, H2O2
D) Bioaugmentation
 introduction of non-native bacteria
 duration
 short lived, outcompeted easily by indigenous
microbes
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When is EISB Appropriate?
 To reduce chlorinated solvent levels below regulatory
requirements
 As a polishing step
 When reduction-oxidation (redox) potential is low
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EISB Flowchart
Precursor
Assessment
Lab
Optimization
Study
Hydrogeology
Modeling
Field Tracer
Test
Field Pilot
Test
Scale-up
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Technical Requirements
A) Site Assessment
41

review of previous site data

development of site characterization work plans

hydrogeologic and geochemical characterization
Technical Requirements
(cont’d)
A) Site Assessment (cont’d)
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
source area characterization

plume characterization

conceptual model and site evaluation
“Technical and Regulatory Requirements
for Enhanced In Situ Bioremediation of
Chlorinated Solvents in Ground Water”
Not
it
Ethene
Chlorine
Hydrogen
Carbon
Vinyl Chloride
Bond
Cis-1,2-Dichloroethene
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43
Trichloroethene
Technical Requirements
(cont’d)
B) Laboratory Treatability Test Phase
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
laboratory treatability studies

analysis

evaluating laboratory treatability results
Technical Requirements
(cont’d)
B) Laboratory Treatability Test Phase cont’d)

Anaerobic Laboratory Treatability Studies
Cookson, John T. - Bioremediation Engineering, Design
and Application, 1995, McGraw-Hill
Harkness (et al., 1998) - Stimulation of complete reductive
dechlorination of TCE in Strother Soil: Microcosm
and column studies.
ITRC In Situ Bioremediation Team (1998) - Technical and
Regulatory Requirements for Enhanced In Situ
Bioremediation of Chlorinated Solvents in Ground Water
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Technical Requirements
(cont’d)
C) Field Pilot Test Phase
46

permitting and regulatory acceptance

preliminary site selection

focused hydrogeologic study
Pilot Location and Geology
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Pilot Study Plume Configuration
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Typical Lab Results: Microcosms
CE (uM)
50
40
TCE
DCE
VC
Ethene
30
20
10
0
0
50
100
Days
49
150
Hydrogeologic Modeling
“EISB Recirculation System”
N
24.5
24.0
23.5
Injection Well
23
Treatment Zone
22.5
22.0
21.5
21.0
20.5
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Extraction Well
From Recovery Wells
Pilot System
Flow Meters
“Schematic”
Globe Valves
Mixing Tank
Metering Pump
Filter
Mixing Tank
Metering Pump
Globe Valves
Flow Meters
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To Injection Wells
Pilot Flowfield
52
52
Pilot Piping
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Amendments &
Metering Pumps
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Bioaugmentation: Dehalococcoides
Ethenogenes
Thin-section electron micrographs showing coccoid and elongated cells
Courtesy of Steve Zinder, Cornell University
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t
Summary of Dehalorespirating Organisms Detected at
Several Chloroethene Contaminated Sites
D. ethenogenes D. restrictus D. multivorans D. dehalogenans
Pinellas culture
New Jersey
New Jersey 2
Dover AFB
Dover bioaug well
Stanford (Victoria)
Mississippi
Kelly AFB, TX
S. Texas
Cornell
Cape Canaveral
Toronto
Ohio
Au Sable River, MI
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X
X
X
X
X
X
X
X
X
X
X
X
X
TCE to Ethene
X
X
X
X
X
X
X
X
X
X
X
X
X
X
SpeciesSpecificAssay
Assay For
For
PCRPCR
SpeciesSpecific
D. Ethenogenes:
16SrRNA
Dehalococcoides
ethenogenes
Dover Bioaugmentation Pilot Microcosms
1µL of Microcosm
D3
D6
D9
D12 D15
1 µL of 500 µL Genomic Extract
423 bp
Product
D3
D6
D9
D12
D15
1 µL of 10 mL Genomic Extract
423 bp
Product
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D3
D15
423 bp
Product
Soil Samples from Pilot
D3 = 1.0 m dg.
D6 = 4.0 m dg.
D9 = 8.0 m dg.
D12 = 14.0 m dg.
D15 = 5.0 m ug.
60
50
TCE
40
30
20
10
0
0
100
200
300
400
500
60
50
40
30
20
10
0
600
cDCE
0
100
200
300
400
500
60
600
VC
50
40
30
20
10
0
0
100
200
300
400
500
600
60
Ethene
50
40
30
20
10
0
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0
100
200
300
400
500
600
Technical
TechnicalRequirements
Requirements
(cont’d)
(cont’d)
C) Field Pilot Test Phase (cont’d)
 Engineering design



COOKSON, John T. - Bioremediation Engineering,Design and Application, 1995
McGraw-Hill
AFCEE - Aerobic Cometabolic In Situ Bioremediation Technology Guidance
Manual and Screening Software Users Guide: Installation Restoration Program
ITRC In Situ Bioremediation Team (1998) - Technical and Regulatory
Requirements for Enhanced In Situ Bioremediation of Chlorinated Solvents in
Ground Water
 Evaluating pilot test results

59
Ellis, D.E., Lutz, E.J.,Odom, J.M., Buchanan, R.J., Bartlett, C., Lee, M.D.,
Harkness, M., Deweerd, K., Bioaugmentation For Accelerated In Situ Anaerobic
Bioremediation, Environmental Sci. & Technology, Vol. 34, No. 11, 2000, Pg.
2254-2260.
Benefits of the
Technology
 Less Expensive form of treatment
 Field-Pilot Scale vs. Full Scale
 Less complex design (“ the enhancement of a natural
process”)
 Remediate a specific and/or multiple portions of a plume
 Avoid extra cost associated with treatment of created
by-products
60
Rules of Thumb
 Correct Environmental Conditions (pH, Eh, N, P)
 Transforming Microbes Present
 Suitable e - Donor Present
61
Wrap-up
QUESTIONS AND
ANSWERS
Thank you for attending
this ITRC training course.
62
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Thank You!
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