Short Course 3 Thermal Treatment Technologies - November 2011

Thermal Treatment Technologies:
Lessons Learned
THERMAL TREATMENT TECHNOLOGIES:
LESSONS LEARNED
Start End Topic
Welcome & Introduction
10:30 AM 10:35 AM
(Dr. Hans Stroo)
Overview and State of the Practice Summary
10:35 AM 11:00 AM
(D Paul
(Dr. P l Johnson)
J h )
Measuring and Modeling Thermal Treatment at Naval Air
11:00 AM 11:25 AM Warfare Center
((Dr. Bernie Kueper)
p )
11:25 AM 11:35 AM Questions and Open Discussion
Simulating Thermal Treatment of Fractured Rock
11:35 AM 12:05 PM
(Dr Ronald Falta)
(Dr.
Effects of Thermal Treatment on the Microbial Reductive
12:05 PM 12:20 PM Dechlorination Process
((Dr. Frank Löffler))
12:20 PM 12:30 PM Questions and Open Discussion
12:30 PM Adjourn 2
LESSONS LEARNED
Start End Topic
10:30 AM 10:35 AM
(Dr. Hans Stroo)
10:35 AM 11:00 AM
(D Paul
(Dr. P l Johnson)
J h )
p )
11:35 AM 12:05 PM
(Dr Ronald Falta)
(Dr.
12:30 PM Adjourn 3
Critical Evaluation of State-of-the-Art In Situ
Thermal Treatment Technologies for DNAPL
S
Source Zone
Z Treatment
T t t
ER-200314
Jennifer Kingston1,2, , Paul Dahlen1, Paul
Johnson1
1 - Arizona State University
2 – Haley & Aldrich
Project Team
● Principal Investigators
 Paul C. Johnson – Arizona State University
 Eric Foote - Battelle
● Others
 Jennifer Triplett Kingston – Arizona State University / Haley &
Aldrich
 Paul R. Dahlen – Arizona State University
 Shane Williams - Battelle
5
Technical Objective
Develop a tool that can be used by practitioners, regulators, and site
owners to
t anticipate
ti i t the
th likely
lik l d
design
i andd performance
f off th
thermal-
l
based DNAPL treatment technologies at their sites, including:
• how the technology gy has been applied
pp in that type
yp of
setting,
• the designs employed,
• the operating conditions
conditions,
• the performance monitoring that results are based on,
• the performance observed,
• indicators
i di t off success att other
th sites,
it andd
• reasonable bounds on expected performance.
In this project, the performance metrics focus on improvement to
groundwater quality and reduction in mass discharge (flux).
6
Final Product/Tech-Transfer Concept
p
Physical Technology Application Experience/
Scenarios Summary Performance Summary
Scenario Technology # of # of # of Full- # of
Sites Pilot Scale Systems
Tests Systems Since 2000
Generalized Scenario A: Steam Heating 7 5 2 2

relatively homogeneous and Resistance Heating 4 3 0 1
permeable unconsolidated Other 9 7 1 1
Generalized Scenario C: Steam Heating 4 0 3 1

largely permeable sediments Resistance Heating 12 3 7 3
with interbedded lenses of low Other 7 2 5 3
Generalized Scenario D: Steam Heating 17 6 8 7

largely impermeable sediments Resistance Heating 15 4 8 7
with interbedded layers of higher Other 15 5 9 2
Generalized Scenario E: Steam Heating 3 1 1 1

competent, but fractured Resistance Heating 0 0 1 0
bedrock Other 0 0 0 0
Steam Heating 2 2 0 2
Generalized Scenario F: karst
Resistance Heating 0 0 0 0
and/or weathered bedrock
Other 0 0 0 0
Steam Heatingg 15 2 5 2
Generalized Scenario G:
Resistance Heating 6 0 0 0
unknown
Other 7 3 2 0
This table and others summarize key design and performance attributes, including
numbers of energy delivery points, treatment times, temperatures reached, etc. 7
Technical Approach
Step 1: Collect, review, and compile historical performance data;
th
then, using
i professional
f i l judgment,
j d t decide
d id h how b
bestt tto capture
t th
the
information in user-friendly performance summary tables linked to
idealized conceptual models.
Step 2: Conduct supplemental post-treatment field investigations at

four to six sites identified in Task 1. Sites to be chosen to best
augment the information
f compiled in Task 1.
Step 3: Synthesize results – Utilize results from this study, other

SERDP/ESTCP projects,
j t etc.
t to t identify
id tif performance
f bounds
b d on
improvements to groundwater quality and contaminant mass
discharge (a.k.a. “mass flux”).
8
Summary of Applications Identified
Number
Number of Pilot- Full-
Technology Since Year
Applications Scale* Scale*
2000
Steam-Based 46 26 19 15
Electrical Resistance
Heating 87 23 56 48
Conduction 26 12 14 17
Other/Radio-
Frequency 23 14 9 4
Total 182 75 98 84
*Some sites have unknown application sizes and thus are not included in the Pilot- and Full-scale counts
9
Ch
Characterization
t i ti off Documentation
D t ti
Level of Data Number of
Description
Quantity Sites
- Application in progress 1
0 No documentation available at the time of this study 26
Insufficient data to assess pperformance of technology,
gy
1 78
but some design information
Limited performance data; some soils and/or
2 groundwater concentration data and some operating 37
data (e.g.,
(e g temperature information)
Good performance data record, but insufficient for
3 estimating differences between pre- and post mass 26
discharge from source zone
Data sufficient for full assessment of performance
4 14
(groundwater concentrations and mass discharge)
Total 182
Design and Operating Information Performance Information
10
Basic Design Information
Number of Sites With Density of
Number of Sites With Target
Energy Delivery Points
Treatment Zones With Sizes In
( l t d or wells)
(electrodes ll ) IIn thi
this R
Range
This Range [ft2]
[# per 100 ft2]
Technology
0.50
Unknown
Unknown
104
4x104
25
104 -
04
>0..5
0.25-0
<0.2
<10
<4x1
Steam-Based
16 6 4 20 20 2 4 20
H ti
Heating
Resistance Heating 36 24 0 27 10 23 27 27
Conductive Heating 19 6 0 1 1 1 23 1
Other (including
Mixing/Heating) 8 2 0 13 2 0 8 13
* For the three steam auger
g sites, the density
y is one energy
gy p
point p
per cell. This does not fit into the number calculation so it is
classified as <0.5.
<1/4 acre <15 ft spacing 11

Basic Operating Conditions
Number of Sites With Number of Sites With Number of Sites With
Temperatures in Target Active Heating Post-Treatment
Treatment Zone in Durations in These Monitoring in These
These Ranges [C] Ranges [y] Ranges [y]
Technology
nown
nown
nown
0.5 - 1.0
0.5 - 2.0
80 - 110
>110
0.5
1.0
0.5
2.0
80
<8
Unkn
Unkn
Unkn
<0
>1
<0
>2
Steam-Based Heating 7 13 1 25 14 0 3 29 2 0 0 44
Resistance Heating 9 37 0 41 38 2 0 47 1 5 1 80
Conductive Heating 0 11* 12* 4 18 3 0 5 1 1 0 24
Other (including
2 2 1 18 6 0 0 17 3 0 0 20
Mixing/Heating)
* One site had two different temperature values. The 80-110 C temperature was for the saturated zone and the >110 C temperature for the vadose zone.
Reflection of Durations often ?

technology capabilities decided a priori
12
Geologic Scenarios
● Scenario A: relatively homogeneous and permeable
unconsolidated sediments (mixtures of sands, gravels
and silts,
silts etc
etc.))
● Scenario B: largely impermeable sediments with inter-
bedded layers of higher permeability material
● Scenario C: largely permeable sediments with inter-
bedded lenses of low permeability material
● Scenario D: competent,
competent but fractured bedrock (i
(i.e.
e
crystalline rock)
● Scenario E: weathered bedrock, limestone, sandstone
13
Thermal Geologic Settings
● The majority of recent thermal applications were
conducted in settings matching Generalized Scenario
B and C
C.
● Scenario B accounts for 43% (36 of 84) of thermal
treatments two
treatments, two-thirds
thirds of which are ERH applications
applications.
● Scenario C accounts for roughly another one-third
(29%) of all applications.
14
Supplemental Field Investigations
Selection Criteria:
1
1. The hydrogeology of the site was
reasonably well-characterized;
Fort Lewis
2. The aerial extent of the source zone
was reasonably defined prior to
treatment;
3. The depth to groundwater was <20 ft; Camp
Lejeune
4
4. The total depth to impacted
groundwater was <40 ft;
5. There was access immediately down- NAS
gradient of the treatment zone for Alameda Hunter
Army
drilling;
Airfield
Air Force
6. Direct-push technology could be used; Plant 4
and,
7. Local site personnel were present to
facilitate the logistics associated with
15
the sampling events.
Field Data Collection Approach
pp
Supplemental data collection emphasizes post-treatment groundwater
quality and quantification of mass discharge to the aquifer
GW flow
Shadow of
treatment zone with
respect to GW flow
direction
Mass
discharge
transect
16
Site Characteristics
eology at This Site is
orinated
umber of Perrmanent
etroleum
cenario1
erval [ft]
W-Wood-treatting, O-
of Target
Treatment Area [ft2]
micals
Depth to Water [ft]

Wells
This
ons,
Size of Tarrget
Technology
Monitoring W
of Chem
Most Like T
Trreated (C-chlo
hydrocarbo
Trreatment Inte
onceptual Sc
Site ID
olvents, P-pe
other)
Thickness
Type
T
Co
Nu
W
Ge
T
so
Hunter Army Airfield
ERH A 12 P, O 30,000 8 13
Former Pumphouse #2
Air Force Plant 4
ERH B 21 C 21,780 37 30
Bldg 181
Bldg.
NAS
ERH C 15 C 14,520 20 6
Building 5, Site 5-1
ERH C 17 C, P 18,200 30 N/A

EDGY Area 3
ERH C 26 C 15,873 21 5
Site 89
1Scenario Descriptors (for the target treatment zone)
A - relatively homogeneous and permeable unconsolidated sediments (sands, etc.)
B - largely impermeable sediments with interbedded layers of higher permeable material
C - largely permeable sediments with interbedded lenses of low permeable material
D - Competent, but fractured bedrock
E - Weathered Bedrock
ERH - Electrical resistance heating
N/A - Not Available
17
Mass Discharge Sampling
Number of Vertical Number of
Transect Number of Aquifer
Transect Sampling
p g Depth-
p
Site ID Length Specific Capacity
Specific-Capacity
Sampling Interval Specific GW
(ft) Tests
Locations (ft bgs) Samples

10 400 12 - 22 48 47
Former
o e Pumphouse
u p ouse # #2
Air Force Plant 4
10 170 29 - 35 13 9
Bldg 181
NAS
7 115 6.5 - 21 39 39
Site 5-1, Bldg. 5
7 255 3 - 40 78 62
Site 89
N/A N/A N/A N/A N/A
EGDY Area 3*
ft - Feet
bgs – Below ground surface
N/A – Not applicable to this site –
Note: All analysis were performed via groundwater samples from permanent monitoring wells collected by the Corp of Engineers and were sent
directly to ASU for analysis. Analyses were performed pre-, during, and post-treatment to gauge how contaminant flux changed while treatment
was occurring.
g
18
Example 1
Camp Lejeune
•ERH Treatment 9/03 - 5/04
•DNAPL source
•43 deep/48 shallow electrodes
19
Example
p 1: Sampling
p g Locations
Supplemental data collection emphasizes post-treatment groundwater
quality and quantification of mass discharge to the aquifer
GW flow
Shadow of
treatment zone with
respect to GW flow
direction
Mass
discharge
transect
20
Example 1 – Field Work
Activities at Camp
p Lejeune:
j
• Generic Demo Plan submitted Sept. 2005
• Site-specific Demo Plan Feb. 2006
• Field Activities 2/23/06 - 3/3/06
• 60+ hydraulic conductivity tests
performed in 14 wells at 8 locations
• Continuous soil core collected at transect
location
• 26 groundwater samples collected from
26 wells at 16 locations
• 78 depth
depth-specific
specific groundwater samples
collected from 7 direct-push locations;
aquifer characterization mini-pump tests
performed at each depth
p p
• pH, EC, Temp., DO, ORP, PCA, TCA,
PCE, TCE, DCE isomers, VC
21
Concentration Transect
Camp Lejeune: TCE concentrations measured along the transect
perpendicular to groundwater flow on the down-gradient edge of the source
zone.
Shadow of treatment zone with
respect to GW flow direction TCE [ug/L]]
urface [ft]
ow Ground Su
Depth Belo
Distance along Transect [ft]

22
Estimating Mass Discharge
Data Presentation: hydraulic conductivities [cm/s] posted on top of TCE
concentration contours [ug/L] along the transect perpendicular to groundwater
fl
flow on the
th ddown-gradient
di t edge
d off th
the source zone
Mass Discharge Calculation: estimated to be about 30 kg/y using the ESTCP-
sponsored Mass Flux Toolkit Software from GSI
Shadow of treatment zone with
respect to GW flow direction TCE [ug/L]]
w Ground Surrface [ft]
Depth Below
Distance along Transect [ft] 23

Example 1 - Conclusion
It is difficult to determine
treatment effectiveness at this TCE
[ug/L]
site because impacts from
DNAPL residuals outside of the
treatment zone ((that were not
fully-delineated prior to the ERH
design and application) are
masking the treatment effect.
Shallow
DNAPL wells
(plan
view)
24
Example 2
NAS Alameda
•ERH
ERH TTreatment
t t 7/04 - 11/04
•DNAPL source
•35 Energy delivery points with 4
sheet
h t piles
il making-up
ki an electrode
l t d
25
NAS Alameda ERH System Layout
Mass
discharge
transect
GW Flow
26
Example 2 – Field Work
Activities at NAS Alameda:
• Generic Demo Plan submitted Sept.Sept 2005
• Site-specific Demo Plan May 2006
• Field Activities 6/1/06 – 6/9/06
• 40+ hydraulic conductivity tests
performed in
• 2 continuous soil core collected at
transect location
• 11 groundwater samples collected from
11 wells at 7 locations
• 29 depth-specific groundwater samples
collected from 7 direct-push locations;
aquifer characterization mini-pump tests
performed at each depth
• pH,
H EC
EC, T
Temp., DO
DO, ORP
ORP, TCA,
TCA PCE,
PCE
TCE, DCA, DCE isomers, VC
27
Concentration Transect
NAS Alameda: TCE concentrations measured along the transect
perpendicular to groundwater flow on the down-gradient
down gradient edge of the
source zone.
TCE [ug/L]]
Shadow of treatment zone with respect to GW flow direction
-5
Surface [ft]
0 8.8 1.3 0.7 45

8.3 14 0.9
16 1 0.6 0.2 0.9 25

ow Ground S
-10 34 49
21 18 16 0.3 6.8
13.5 11.5 10
-15
Depth Belo
37
3.7 03
0.3 0
0.5 5
0.3
0.1 0 0 0.1
0.2 0 1
-20
0.4 0 0 0
0.2 1.5
0
-60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 0

28
Estimating
g Mass Discharge
g
Data Presentation: hydraulic conductivities [cm/s] posted on top of TCE
concentration contours [ug/L] as measured along the transect perpendicular to
groundwater flow on the down-gradient
g g edgeg of the source zone
Mass Discharge Calculation: estimated to be about 5.72E-03 kg/y using the
ESTCP-sponsored Mass Flux Toolkit Software from GSI
Sh d
Shadow off treatment
t t t zone with
ith respectt to
t GW flow
fl direction
di ti TCE [ug/L]
-5
ace [ft]
5.6E-003 5.1E-003 3.3E-003 1.7E-002 45

6.8E-003 5.7E-003 4.4E-003
Ground Surfa
3.4E-003 1.5E-003 1.8E-003 1.6E-004 5.7E-004

-10 2.3E-003 4.9E-004 25
5.0E-004 1.6E-003 3.8E-004 1.4E-003 6.6E-003

1.1E-003 4.2E-003 10
Depth Below G
15
-15
6.2E-004 2.4E-004 5.2E-004
2.2E-005
1.8E-004 5
7.3E-004 1.5E-003 2.5E-003 2.0E-004

4.0E-004 3.0E-003
-20 1
9.0E-005 1.8E-004 1.8E-004 3.4E-004
1 8E-004
1.8E 004 9 7E-005
9.7E 005
D
1.4E-004
-60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60
0
29
Example 2 - Conclusion
ERH treatment resulted in a significant reduction in contaminant
concentrations throughout the 20 ft depth of treatment. Monitoring well
concentrations for TCE ranged from 80 to 1 ug/L
ug/L, while the direct push
concentrations for TCE ranged from 49 ug/L to non-detect. Pre-treatment
concentrations were in the range of 1,000 – 10,000 ug/L before full-scale
treatment.
treatment
30
Summary of Mass Discharge Results
Post-treatment
Pre-treatment
Post-treatment
Post treatment Mass Mass Discharge
Site Contaminant Discharge
Discharge (kg/y)2 per Linear Foot
(kg/y)1
(kg/y/ft)
5.2 x 101 1.9 x 10-1 1.1 x 10-3
Former Pumphouse
p 2*
Air Force Plant 4 2.1 x 101 1.4 x 10-1
Bldg 181** Total 6.0 x 101 4.9 3.4 x 10-2
NAS Alameda
Contaminant 4.9 x 101 1.3 x 10-1 9.6 x 10-4
Site 5-1, Bldg.
g 5*
Camp LeJeune
Flux 6.8 x 102 8.2 x 101 5.5 x 10-1
Site 89*
Ft. Lewis
3.2 x 101 2.1 1.9 x 10-2
EGDY Area 3***
N t
Notes:
1 Mass discharge calculations were based on monitoring well data from the documentation.
2 Mass discharge calculations were based on discrete-depth sampling data, or a combination of discrete-depth sampling data and
monitoring well data.
* Mass discharge calculations were base on discrete-depth sampling data only.
** Mass discharge calculations were performed for discrete-depth sampling data only and discrete-depth sampling data with monitoring
well data.
*** Mass discharge calculations were based on monitoring well data analyzed by ASU personnel.
31
P tT t
Post-Treatment
t Reductions
R d ti
Dissolved Mass Discharge Reduction
Site Heating Groundwater
Generalized Scenario/Site
No. Technology Concentration <10x 10x 100x 1000x >1000x
Reduction
1 ERH Generalized Scenario A (SDC) 10x x
2 ERH Generalized Scenario B+ (SDC) <10x x x
3 ERH Generalized Scenario C 10x x
4 ERH Generalized Scenario C* (SDC) >10x to <100x x
5 ERH Generalized Scenario C ^ <10x x
6 ERH Generalized Scenario C ^ <10x x x
7 ERH Generalized Scenario C <10x x
8 ERH Generalized Scenario C (SDC) 10x x
9 ERH Generalized Scenario C (SDC) 100x x
10 ERH Generalized Scenario C 1000x x
11 SEE Generalized Scenario C 100x x
12 SEE Generalized Scenario C 10x x
13 SEE Generalized Scenario C ^ 10000x x x
14 SEE Generalized Scenario D* <10x x
* Pilot application appeared to encompass the entire source zone based on documentation reviewed.
+ Mass discharge assessment involved two calculations using first only the post-treatment field investigation data and then the post-treatment
field investigation data supplemented with data from a set of monitoring wells that were directly in line with the field investigation transect.
^ Site used two different vertical intervals to calculate mass discharge: 1) Only shallow geology and 2) shallow and deep geology.
SDC – supplemental data collection site for this project
32
Mass Discharge Summary – All Sites
Site Heating Pre-treatment Discharge Post-treatment

Site Contaminant
No. Technology (kg/y) Discharge (kg/y)
1 ERH Generalized Scenario A 5.2 x 101 1.9 x 10-1

2.1 x 101
2 ERH Generalized Scenario B 6.0 x 101 4.9
3 ERH Generalized Scenario C 4.0 x 10-1 3.1 x 10-2
Total Contaminant
4 ERH Generalized Scenario C Mass Discharge (sum 6.8 x 102 8.2 x 101
of all components)
1.7 6.0 x 10-1
5 ERH Generalized Scenario C 2.4 9.7 x 10-1
9.4 2.7 x 10-2
6 ERH Generalized Scenario C 4.9 1.6
9.3 1.7 x 10-2
33
M
Mass Discharge
Di h Summary
S – All Sit
Sites
Pre-treatment
Pre treatment
Site Heating Post-treatment
Site Contaminant Discharge
No. Technology Discharge (kg/yr)
(kg/yr)
8 ERH Generalized Scenario C 3.2 x 101 2.1
9 ERH Generalized Scenario C 4.9 x 101 1.3 x 10-1

Total Contaminant Mass
11 SEE Generalized Scenario C Discharge (sum of all 4.6 7.3 x 10-2
components)
12 SEE Generalized Scenario C 1.3 2.8
1.9 x 10-2 1.8 x 10-7
13 SEE Generalized Scenario C 2.9 x 10-4 1.1 x 10-7
14 SEE Generalized Scenario D 9.7 x 10-2 6.1 x 10-2
34
Key Observations
● Data Collection:
 182 applications conducted between 1988 and 2007 were
identified and reviewed,
reviewed including
 87 electrical resistance heating,
 46 steam-based heating,
 26 conductive
d ti h heating,
ti and
d
 23 other heating technology applications.
 This information indicates that a significant number of
applications
li ti have
h occurred
d andd it reflects
fl t ththe acceptance
t off iin
situ thermal technologies as viable source zone treatment
options.
35
Key Observations
● Trends in Current Applications

 Approximately half of the 182 applications have been
implemented since 2000 and over half of those have
been ERH systems.
 ERH applications
pp outnumber all other applications
pp
since 2000 by about a factor of three.
 There appears to be a recent trend in the increasing
use of conductive heating and decreasing use of
steam-based heating.
36
Key Observations
● Operating Conditions
 Steam and ERH systems are inherently limited to
operating temperatures at about the atmospheric
boiling point of water (100 C) or lower, and most
systems operate close to that range.
 Conductive heating is the only option for achieving
significantly higher temperatures than that.
37
Key Observations
● Energy Delivery Design

 There appears convergence towards relatively
closel spaced energ
closely-spaced energy deli
delivery
er points in the design of
ERH and conductive heating systems.
 Spacing
p g for most ERH and conductive energy
gy delivery
y
points was less than 20 ft (6 m).
 Steam application well spacing was usually greater
than 20 ft (6 m).
m)
38
Key Observations
● Treatment Zone Size

 117 of 121 treated areas were <4x104 ft2 (<4000 m2 or
an acre) and two-thirds of those were <104 ft2 (<1000 m2
or one-quarter acre treatment areas)
 It is
i also
l apparentt that
th t the
th spatialti l extents
t t off many
source zones are likely ill-defined prior to treatment.
 This results in under
under-sized
sized target treatment zones
zones,
untreated source zone areas, and minimal beneficial
impact to groundwater quality and mass discharge.
39
Key Observations
● Geologic Setting Effects

 The effect of geologic setting on performance is
difficult to discern in this data set.
 Most treatment systems were installed in layered settings,
characterized as either primarily fine
fine-grained
grained materials with
higher permeability lenses (Generalized Scenario B) or
primarily permeable materials with finer-grained lenses
(Generalized Scenario C).
40
Key Observations
● Application Operating Times

 Most applications (independent of specific
technology) lasted less than 6 months
 There was little documentation as to the criteria or
rationale used to determine the duration of operation.
p
 There was little indication that the duration of
operation was linked to mass removal-, groundwater
quality-,
lit or soilil concentration-based
t ti b d criteria.
it i
41
Performance Expectations
● Supplemental
pp data collection indicated that a 100x reduction
was achievable if the source zone was adequately delineated
and fully encompassed during treatment and if the system
was operated
p for a sufficient p
period of time.
 Reductions of less than 100x were seen if the system was not operated
for a sufficient period of time, and at sites where the source zone was
not fullyy encompassed
p a reduction of <10x was typical.
yp
● For sites with a concentration reduction of 100x or more, the

final groundwater concentrations could be less than 100 ug/L
for individual constituents which then could correspond to a
mass discharge of 1E-01 kg/y or less.
42
C
Correlations
l ti
● M
Mass discharge
di h reduction
d ti tto ttemperature
t
 Available data suggests that achieving a target
t
temperature
t is
i insufficient
i ffi i t to
t achieve
hi good
d clean-up,
l
and that application duration, in combination with the
treatment zone temperature
p and treatment zone size
likely control the performance.
43
Technology
gy Transfer
State-of-the-Practice Overview
Combined results from this project of the Use of In Situ Thermal
and vendor-authored/ASU-edited Technologies For
NAPL Source Zone Cleanup
state-of-the-practice write-ups for key
thermal treatment technologies in a
users guide targeting program
manager, consultant, and regulator
audiences.
Thermal tech-transfer meeting in WA Jennifer Triplett Kingston 1, Paul R. Dahlen, and Paul C. Johnson
Arizona State University
in early stages of the project. Eric Foote and Shane Williams
Battelle Memorial Institute
With contributions from:
Gorm Heron, Ralph Baker, and Gregory Crisp (TerraTherm)

Articles in press and under review in Greg Smith (Thermal Remediation Services, Inc.)
Phil La Mori and Elgin Kirkland ( FECC Corporation)
GWMR
GWMR.
May 2009
1 Now with Haley and Aldrich, Lenexa, Kansas

44
Acknowledgements
The ASU and Battelle team would The ASU and Battelle team would
like to thank the following vendors like to thank the following people for
and companies for their help with th i help
their h l in
i accessingi field
fi ld sites:
it
this project:
● Ron Kenyon (Shaw)
● TerraTherm ((R. Baker, G. Heron)) ● Daniel Hood (Navy)
● Shaw Environmental ● Bob Lowder (Marines)
● URS ● Steven Peck (Navy)
● CES ● Doug Delong (Navy)
● TRS ● John McGuire (Shaw)
● Haley and Aldrich (M. Basel) ● Rick Wice (Shaw)
● ERM ● George Walters (AF)
● Army Corps of Engineers ● Randall McDaniel (Shaw)
● McMillian-McGee ● Algeana Stevenson (AF)
● EPA ● Phil La Mori (BEM Systems)
● Department of Defense – Military ● Mark Kershner (AF)
branches
● Emile Pitre (USACE)
● Department of Energy
● Kira Lynch (USACE)
● And the numerous consulting firms
involved in thermal applications that
helped us with documentation
45
LESSONS LEARNED
Start End Topic
10:30 AM 10:35 AM
(Dr. Hans Stroo)
10:35 AM 11:00 AM
(Dr. Paul Johnson)
(Dr. Bernie Kueper)
11:35 AM 12:05 PM
(Dr. Ronald Falta)
Eff t off Thermal
Effects Th l Treatment
T t t on the
th Microbial
Mi bi l Reductive
R d ti
(Dr. Frank Löffler)
12:30 PM Adjourn
46
Measuring and Modeling Thermal
Treatment at Naval Air Warfare
Center
Project # ER-200715
Professor Bernie Kueper

Department of Civil Engineering
Engineering, Queen’s
Queen s University
C. Lebron, G. Heron, J. Lachance, D. Rodriquez, D.

Baston, A. Wemp, P. Lacombe, others. . .
47
Th
Thermal
lCConductive
d ti H Heating
ti (TCH) in
i
Fractured Rock
● Introduction to TCH
● TOPIC #1 - Influence
I fl off inflowing
i fl i cold
ld
groundwater in fractures
● TOPIC #2 - Ability
Abilit tto observe
b b
boiling
ili iin rock
k
matrix
● TOPIC #3 – NAWC Site pilot test results
● TOPIC #4 - Field parameters to measure
48
Thermal Conductive Heating
Thermal Thermal
Blanket Wells
49
Compliments of Terratherm
T h l
Technology Description
D i ti - Field
Fi ldTreated vapor
to atmosphere
Vapor
t t
treatment
t
Power
Heater and Knockout
vacuum wells pot
Heat Blower
Power distribution exchanger
system
P
Pump
Water treatment
Discharge
Temperature and pressure

monitoring holes (1 of many)
Treatment area foot-print
Compliments of Terratherm 50
TCH Heaters
Protected by U.S. and International Patents
Compliments of Terratherm 51
TOPIC #1 - Assess influence of inflowing cold
groundwater on ability to reach boiling in rock
Baston, D., Heron, G. and Kueper, B.H., 2007. Screening level modeling of thermal conductive heating in
fractured rock. Proceedings, USEPA/NGWA Fractured Rock Conference, Portland, ME.
Baston, D.P. and Kueper, B.H., 2009. Thermal conductive heating in fractured bedrock: screening
calculations to assess the effect of groundwater influx. Advances in Water Resources, 32, pp. 231-238.
52
Temperature Between Thermal Wells
(q = 33.7 L/m2·day) 2
e g  e 
Kb   
120 Increasing fracture aperture 12  s 
100
& spacing (Kb fixed)
& spacing (K
re (°C)
80
Tempertur
60 0.25 m
1.0 m
40
2 5 m spacing
2.5
T
20 5.0 m
10 m
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Time (years) 53
TOPIC #1 - Conclusions
● Inflowing cold groundwater can prolong time required to

reach boiling in rock
● Site characterization should focus on
 Bulk K of rock (hydraulic testing),
 Fracture spacing (e.g.,downhole televiewer),
 Hydraulic gradient
54
TOPIC #2 - Assess
A iinfluence
fl off rock
k properties
ti on ability
bilit
to reach boiling in rock matrix
symmetry boundary y
heater
wells x
(6)
flow
symmetry boundary
T = To
P = P0
heater‐extraction θ = 30°
well (1) model boundary
3 m well spacing
3 m well spacing
Treatment Zone 55
350 Boiling in fracture
f and matrix
300
250
start of boiling in
fracture end of boiling
end of boiling
erature (°C)
200 in matrix
start of boiling in
start of boiling in
Tempe
150
matrix
100
end of boiling
end of boiling
in fracture Matrix
50
Fracture
0
0 50 100 150 200 250 300 350
Heating Time (days) 56
Pressure spike in matrix
corresponding to boiling
35
30 φ = 0.005
φ = 0.01
25
ssure (barr)
φ 0 03
φ = 0.03
20 increasing φ = 0.05
15 porosity φ = 0.10
Pres
10
0
0 100 200 300 400 500
Heating Time (da
(days)
s)
57
TOPIC #2 - Conclusions
● It may
ma be difficult
diffic lt to monitor progress of heating
in bedrock because of:
(i) Variability of boiling point in the rock matri
Variabilit matrix (T
function of P)
(ii) Lack of well defined temperature plateau indicating
boiling in matrix,
● Pressure monitoring may be beneficial
Baston, D.P., Falta, R.W. and Kueper, B.H., 2010. Numerical modeling of
thermal conductive heating in bedrock. Journal of Ground Water.
58
TOPIC #3 – NAWC Pilot Test
● Jet engine
g testing
g facility,
y,
1950’s to 1990’s, West Trenton,
NJ
● Decommissioned in 1998
~1990 ● Pump & treat since mid-1990’s
● 2001: NAWC chosen as
fractured rock hydrology
research site under USGS
Toxics Substances Hydrology
Program.
● TCE > 20 mg/L
g
Today From USGS 59

N
Liquid
Li id
Discharge
Heater Well Field
Line
Elec. Equip. Off-gas

Treatment
60
TCH Pilot
Test Location
61
160 -10
36BR 73BR 70BR 71BR 15BR -8
155 81BR -6
150
L-21 80BR 82BR 25BRshift Land Surface -4
-2
0
145 L-20 Fill 2
4
140 L-19 6
8
10
135 L-18
Mas.124
Weathered
12
14
130 16
Bedrock 18
20
125 22
24
120 26
Mas.263 28
Carb.159 30
DEPTH BELOW LAND SURFACE IN FEET

115 32
Mas.160 Lay.272 34
110 36
Mas.273 38
ALTITUDE, IN FEET
Lay.165 40
105
Carb 172
Carb.172 42
100 Red.279 44
Fractured 46
Mas.173 48
95 Bedrock 50
packer--> 52
90 54
Lay.178 Mas.290 56
85 58
Carb.190 60
Lay.301 62
80 64
Mas.191 66
75 Mas.304 68
Lay 312
Lay.312 70
70 Lay.201 72
74
76
65 Mas.207 Mas.314 78
80
60 82
Lay.213 84
55 Red.323 86
Mas.216 88
Lay.227 90
50 Carb.233 Water 92
<--Bearing 94
45 Mas.234 96
Fracture 98
40 Lam.244 100
Carb.246 102
104
35 Mas.247 106
108
30 110
Lay.251 112
25 114
Carb.262 116
118
20 120
122
15 124
126
10 128
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240
5 15 25 35 45 55 65 75 85 95 105 115 125 135 145 155 165 175 185 195 205 215 225 235
Toxics/Sections/Drilling2007/serdp36x15.sgr 62
Performance Assessment:
Physical Properties
Fraction organic carbon (Foc)
8.E-03
7.E-03
6 E-03
6.E 03
5.E-03
4.E-03 Dolostone
Sandstone
3.E-03
Limestone
2.E-03 Siltstone
Black Mudstone
1.E-03
Grey Mudstone
0.E+00
1 Red Mudstone
2
3
63
Performance Assessment:
Physical Properties
Matrix Porosity (%)
10
6
Dolostone
5
Sandstone
4 Limestone
3 Siltstone
2 Black Mudstone
1
Grey Mudstone
0
1 Red Mudstone
2
3
64
Performance Assessment: Field Demo
65
Well Configuration
66
Fi ld Demo
Field D R kT
Rock Temperatures
t –
Averages per depth
250
Depth (ft)
5.0
10.0
200
15.0
ature (F)
20.0
25.0
Tempera
150 30.0
35.0
40.0
45.0
100
50.0
Good heating
g from 5-35 ft Average
Somewhat cooler 35-50 ft

50
4/9 4/16 4/23 4/30 5/7 5/14 5/21 5/28 6/4 6/11 6/18 6/25 7/2 7/9 7/16 7/23 67
Fluids Extracted
68
Performance Assessment
Field Demo VOC mass removal
500 2,000
Est. Total VOCs (TCE based on PID) [lbs] 500 lbs
450 PID as TCE [ppmV] 1,800
400 1,600
350 1,400
s (lbs)
300 1,200
VOC mass removed:
V)
PID (ppmV
Mass of VOCs
250 1,000
In vapor: 500 lbs
200
In liquid: 33 lbs 800
Total: 530 lbs

150 600
100 400
50 200
0 0
4/9 4/16 4/23 4/30 5/7 5/14 5/21 5/28 6/4 6/11 6/18 6/25 7/2 7/9 7/16 7/23 69
P f
Performance A
Assessment
t
Collection & Analysis of Rock Samples for Treatment Confirmation
70
Performance Assessment: Field Demo
71
Collection & Analysis of Rock Samples for Treatment
Confirmation
Rock crusher
(Queen’s University) 72
P f
Performance A
Assessment S
Summary
Collection & Analysis of Rock Samples for Treatment Confirmation
C
Crushed
h d samples
l
73
TCE Concentration in Rock Samples
TCE (mg/kg) TCE (mg/kg)
0 50 100 150 200 250 300 0 50 100 150 200 250 300
0 0
BR - 1 BR - 3
5 BRP - 1 5 BRP - 3
10 10
15 15
20 20
25 25
Depth (ft)
Depth (ft)
30 30
35 35
40 40 Average reduction
Averages BR-1: in TCE:
45 45
Before: 37 mg/kg
50 50 84% BR-1
After: 5 mg/kg 69% overall
55 55
74
Rock Matrix Clean-up Goals
Compliance
Concentration
Matrix clean-up goal?
velocity S
e
75
Example Output
(z = 100 m, S = 5 m, e = 142 um, matrix porosity = 3.3%, matrix foc = 0.008)
Rodriguez and Kueper, 2011 76

TOPIC #4 – Field parameters to measure
77
TOPIC #4 – Field parameters to measure in
evaluating use of a thermal remedy in bedrock
● Bulk hydraulic conductivity (hydraulic testing)

● H d li gradient
Hydraulic di t
● Fracture spacing (aperture can be calculated)
● Matrix porosity,
porosity permeability,
permeability and fraction organic carbon
● VOC concentrations in matrix
● Thermal pproperties
p of rock matrix
78
LESSONS LEARNED
Start End Topic
10:30 AM 10:35 AM
(Dr. Hans Stroo)
10 3 AM 11:00
10:35 11 00 AM
(Dr. Paul Johnson)
(D B
(Dr. Bernie
i K
Kueper))
11:35 AM 12:05 PM
(Dr. Ronald Falta)
12:30 PM Adjourn
79
LESSONS LEARNED
Start End Topic
10:30 AM 10:35 AM
(Dr. Hans Stroo)
10 3 AM 11:00
10:35 11 00 AM
(Dr. Paul Johnson)
(D B
(Dr. Bernie
i K
Kueper))
11:35 AM 12:05 PM
(D R
(Dr. Ronald
ld F
Falta)
lt )
12:30 PM Adjourn 80
Simulating Thermal Treatment of Fractured
Rocks
Ron Falta
Clemson University
faltar@clemson.edu
Fractured Porous Media
Unfractured soil layer
Fractured rock
(limestone, sandstone,
basalt volcanic tuff) or
basalt,
unconsolidated material
(clay, silt)
Unfractured
U f t d rock k or
sediment layer
Shortly after a DNAPL spill Later time – mostly dissolved
82
OUTLINE
● Key Processes
 Energy balance and cost to heat to boiling temperature
 Energy required to boil off water
 Steam stripping of dissolved chlorinated solvents
● Numerical Multiphase Flow Models

 Existing models and capabilities
 Simulation of Clemson laboratory experiments
● Field Scale Simulations

 Challenges and approaches
 Multiple Interacting Continua (MINC)
 Simulation examples
83
E
Energy Balance:
B l heating
h ti up to
t boiling
b ili
temperature
M  (1   )  R CR T   S w  wCw T
h
  porosity (.01-.4)
( 01 4)
 R  rock grain density 2300-2700 kg/m 3
 w  liquid water density 1000 kg/m 3
CR  rock grain heat capacity 800 1200 J/kgoC

800-1200
Cw  liquid water heat capacity 4200 J/kgoC
S w  water saturation (0-1)

84
Example: cost to heat 1 cubic meter
M h  (1   )  R CR T   S w  wCw T
= (1-.2)(2650)(1000)(90) + (.2)(1)(1000)(4200)(90)
= 191 MJ/m
MJ/ 3 + 76 MJ/m
MJ/ 3 = 267 MJ/m
MJ/ 3
One kW-hr = 3.6 MJ, so 74 kW-hr to heat 1 m3
At $0.10/kW-hr, this would cost $7.40/m3
85
Typical heating pattern with time
200
Dry-out
rature, C
100
B ili
Boiling
Temper
T
15
Ambient
Time
86
Boiling
B ili temperature
t t depends
d d on pressure
(and dissolved components)
● Under vacuum
Boiling Temperature with depth conditions, the boiling
assuming hydrostatic pressure
250
point is lower:
200
0.7 atm – boiling at 90 C
boiling temperatture, C
150
0.5 atm – boiling at 80 C
100
50
Dissolved volatile
0 compounds and gases
0 200 400 600 800 1000
depth, ft also depress the boiling

temperature
87
St
Steam stripping
t i i off di
dissolved
l d volatiles:
l til
Udell’s 1996 analysis
Assume equilibrium batch conditions in some control volume. Steam vapor is
generated by boiling, and leaves the volume, carrying contaminant vapors
1 d ( M wH 2O Cwc ) 1 dM wH 2O c
 Cg
w dt  g dt
rate of change of rate of volumetric
dissolved contaminant steam generation x gas concentration
=
mass
M wH 2O  mass of liquid water

Cwc  dissolved concentration
Cgc  gas concentration
88
After some calculus and algebra…
 H w 
 1
Cwc  M wH 2O   g 
 
  H 2O 
Cw,0  M w,0
c

H  Henry ' s const.

The exponent is huge because liquid water is ~ 1600 times
denser than steam vapor. Typical values for H at steam
p
temperatures are about 0.3 to 7 depending
p g on the chemical
89
Steam Stripping
● Steam stripping results in geometric reductions in
dissolved concentrations of volatiles
● The stripping effect only occurs as liquid water is
converted to vapor, and leaves the system
● A system
y mayy be at the boilingg temperature, with
highly variable rates of water phase change – this
has tremendous impact on contaminant removal!
90
Entire rock mass heated to
Once the rock is hot, boiling steam temperature
starts. Details of the boiling are
very important
● Contaminant
C t i t removall only
l
occurs in the locations
where liquid
q water is being g
converted to vapor
● The boiling may be well
distributed in the rock
rock, or it
may be localized around the
fractures
91
1D S
Simulations
u at o s ((T2VOC)
OC)
fracture maintained at a
● 1 m3 block of rock with a vacuum of 0.3 ATM
single fracture. Fracture and
t i iinitially
matrix iti ll saturated
t t d with
ith
water containing 10 ppm
TCE.
● Heat the block with 200 W
power.
● Drop pressure in fracture and Cw=10 PPM
simulate mass in matrix with k=10-15 m2
(1 millidarcy)
time Sw=1
1
T=20 oC
Consider three conditions: sandstone

matrix
a.) steam is mobile in matrix
b.) steam is immobile in matrix
Add 200 W power
c.) intermediate vapor mobility uniformly
if l to
t matrix
t i (simulating
( i l ti
electrical resistance heating)
92
RESULTS: 1-D
1 D Simulations
Vapor phase forms as isolated
TCE Mass During Boiling bubbles in matrix, pushing liquid
1.0E-02
water into fracture where it boils.
H t tto sustain
Heat t i ffracture
t b
boiling
ili
comes from thermal conduction.
1.0E-03
Matrix, kg
TCE mass, krg=0,

1.0E-04 liquid
q water is mobile
TCE Mass in M
TCE mass, typical

krg(Sg), krw(Sw)
1.0E-05
TCE mass, krw=0,
gas is mobile krg
1.0E-06
1.0E 06
1.0E-07
0 20 40 60 80
Time since start of heating, days Sg
Vapor forms in matrix and is mobile,
flowing freely to fracture. All boiling Initially vapor phase pushes liquid water
occurs in matrix, and steam stripping into fracture where it boils. Later, vapor
effect is similar to Udell (1996) model phase
h becomes
b more mobile
bil andd flows
fl outt
to fracture. Boiling moves from fracture to
matrix with time
93
Energy required to boil away pore water
● The heat of vaporization of water is about 2,260,000 J/kg
● From the previous heating example, there was about
192 kg of liquid water in each cubic meter of rock
● to boil away 50% of this water would require 217 MJ, or
about 60 kW-hr. At $0.10/kw-hr, this would cost
$6.00/m3 which is comparable to the cost to raise the
temperature up to the normal boiling point
● Our laboratory experiments and numerical simulations
show excellent contaminant removal with 40-60% liquid
water removal during heating.
94
Numerical Models for Steam Remediation
● There are many existing multiphase flow codes that can
be used for modeling thermal remediation in fractured
heterogeneous porous media
media. A partial list:
 T2VOC (Falta et al., 1992; Falta et al., 1995)
 NUFT (Nitao, 1993)
 COMPFLOW (Forsyth,
(F th 1994)
 MUFTE (Helmig et al., 1994)
 MAGNAS (Panday et al., 1995)
 STOMP (White and Oostrom, 1996)
 TMVOC (Pruess and Battistelli, 2002)
These codes have similar numerical formulations and process

capability 95
TMVOC (Pruess and Battistelli, 2002)
● 3D integral finite difference ● Multiphase diffusion with
formulation for fractured and tortuosity effects
heterogeneous media ● Assumes local (gridblock)
● 3 phase flow (gas, aqueous, chemical equilibrium with
NAPL) linear adsorption isotherms,
● Full heat transfer and first order decay of dissolved
thermodynamics with contaminants
t i t
evaporation, boiling and ● Includes noncondensible
condensation of water and gases (air, etc), and can
multicomponent
lti t NAPL
NAPLs simulate
i l t d dry superheated
h t d
● Temperature dependent vapor conditions
pressure, solubility, and ● Maximum temperature is
H
Henry’s’ constants
t t forf li it d to
limited t critical
iti l point
i t off water
t
contaminants (374 oC)
96
A GUI for TMVOC is available (PetraSim)
97
Simulation
Si l ti off Laboratory
L b t Experiments
E i t
(SERDP ER-1553)
Field Scale Fracture-matrix
Fracture matrix interaction
is locally ~ 1-D
Simulated fracture Unfractured matrix material (silt,

on one end clay, limestone, sandstone, etc.)
98
Experimental Setup
Da
ata port
ta
ca
ble
Da
Fluid in
during circulation
Pressure
transducer
Fluid recovery
able
Ribbon heater wrapped
e r c
Power Pow around sample
Flange with pass-throughs for

data, fluids and power
99
Experimental
p Results
Chen et al., 2010
100
TMVOC model: 2d rr-z
z model.
model Simulating
end effects is critical here
S bd
Subdomain
i P
Porosity
it Permeability
P bilit Density
D it Thermall
Th
(m2) (kg/m3) conductivity
(W/m°C)
Berea 0.167 1.5×10-13 2491 3.57 (wet)

sandstone
d 11.75
75 (dry)
(d )
Heater 0.001 1.0×10-18 501.2 1.07
Porous disk 0.16 1.0×10-10 3950.0 41.22
Aluminum 0.001 1.0×10-18 2702 237

end-cap
Outlet tube 0.0559 1.46×10-10 8730 60
Condenser 0.0559 1.46×10-10 1.0×1010 60
Inlet Tube 0.14 3.15×10-10 8940 400
Teflon Plate 0.001 1.0×10-18 2200 0.5
Insulation 0.01 1.0×10-18 100 0.28

Layer
Chen et al., 2011 101

Simulation Results: temperature and condensate
production
140
(a) (b)
120
Temperature (°C)
100
80 T2_Exp
T2_Sim
60
T1_Exp
Produced (mL)
T1_Sim
1 Si
40
100
20
140
(c) (d) Simulated
120 80 Experimental
Temperaturre (°C)
100
Cumulative Condensate P
T3_Exp
3
80 T4_Exp
T3_Sim
T4_Sim 60
60
40
20
40
140
Time (h)
(e) (f)
120
20
Temperature (°C)
100
80
60
T5_Exp
T6_Exp 0
T6_Sim
40
T5_Sim
0 1 2 3 4 5 6
20
140 Time (h)
(g) (h)
120
Temperaature (°C)
100
80
60
Chen et al., 2011

T7_Exp
40 T7_Sim
20
0 2 4 6 0 2 4 6 102
Time (h) Time (h)
Simulation Results: temperature and
condensate production
Chen et al., 2011
● Model is predicting a slower

transition to vapor flow
conditions
● Likely due to fact that we used
measured air relative
permeability; steam vapor
relative permeability is
probably
b bl hi
higher
h
● Simulation and experiment
both show complete DCA
removall att 40% pore volume
l
produced
103
Fi ld scale
Field l simulations
i l ti off fractured
f t d
systems
● Numerically challenging due to small size of fractures
compared to large size of model
● Large contrasts in permeability and capillary pressure
between fractures and rock matrix
● Discretization issues – need to discretize both the
fractures (very small) and the matrix (very large), with
transitions in size between the two
● Starting from liquid water conditions
conditions, gas phase
evolution occurs in all boiling gridblocks – possibility of
unstable phase transitions
104
Discrete fracture model
● Normal discretization of
fractures and matrix,
small elements near
fractures
● Most realistic model, but
practically limited to
simple fracture geometry
● Best for parallel sets of
fractures due to
computational limits
Wemp et al., 2011 105

M lti l IInteracting
Multiple t ti Continua
C ti (MINC) discretization
di ti ti
matrix blocks
Vacuum Well
Electrode Electrode
Insulating Cover
Water Table
Groundwater
contaminated with Fractured Limestone
10 PPM of TCE in
both fractures
and matrix
16 m
Spatial domain is discretized

fractures
normally into volume elements
The fracture elements are globally Each gridblock is subdivided into a fracture
connected in all directions. element, and multiple nested matrix
elements. The fracture and matrix
This is similar to a dual porosity formulation, but elements
l t are llocally
ll connected
t d tto each
h
gradients in the matrix are resolved much more other in 1-D
accurately
106
Fi ld Si
Field Simulation
l i Example
E l
Idealized field scale
simulation – single element Vacuum Well
of a repeated 6-phase electrical Electrode Electrode
heating pattern.
Insulating Cover
3-D orthogonal set of 200
micron fractures with 1m
Water Table
spacing, matrix k=10-15 m2;
model uses MINC for matrix
blocks.
Groundwater
contaminated with
Add 800 kW power for 15 days, 10 PPM of TCE in
Fractured Limestone
then pump vacuum well at 0.5 both fractures

ATM for 1 year. Re-energize for and matrix
3 days and pump vacuum well
for another year
16 m
107
Simulation Result
120 700 10000 1
110 0.9
ction Rate, Liters//min

600
Average TCE Concentration, ug//l

100 1000 08
0.8
eTemperature, C
Water Saturation
500
e-energize
90
0.7
80
400 100 0.6
70
0.5
ze
300
Re-energiz
Average W
Re
Steam Extrac
60
Average
10 0.4
TCE
50 200
0.3
40 Temperature Sw
100 1 0.2
30 Steam Extraction
Rate 0.1
20 0
0 100 200 300 400 500 600 700 0.1 0
0 100 200 300 400 500 600 700
time, days
time, days
108
Summary
● Experiments and simulations show good removal of

volatile contaminants with about 40-50% removal of pore
water by thermal treatment
● Several numerical models are available for simulating
thermal remediation. These codes should be able to
capture the key heat and mass transfer effects that
occur.
● Field scale models of fractured systems are challenging
b
because off scale
l effects
ff t and d the
th strong
t interaction
i t ti
between the fractures and matrix
● MINC discretization appears to be the most practical way
to setup most large field simulations
109
LESSONS LEARNED
Start End Topic
10:30 AM 10:35 AM
(Dr. Hans Stroo)
10:35 AM 11:00 AM
(D P
(Dr. Paull J
Johnson)
h )
p )
11:35 AM 12:05 PM
(Dr Ronald Falta)
(Dr.
11:50 AM 12:00 PM Questions and Open Discussion
12:00 PM Adjourn 110
THE UNIVERSITY of TENNESSEE
KNOXVILLE
Departments
p of Microbiology
gy and of Civil & Environmental Engineering
g g
Oak Ridge National Laboratory, Environmental Sciences Division
Effects of Thermal Treatment on the

Microbial Reductive
Dechlorination Process
F
Frank
kEE. Löffl
Löffler
Mi
Microbial
bi l Reductive
R d ti Dechlorination
D hl i ti att
Elevated T
Thermal
Treatment
Dissolved - Phase Plume

DNAPL
Source Pooled DNAPL
Downgradient
Zone Groundwater
Flow
T
Temperature Gradients
G di
112
Key Questions
1. Are reductively dechlorinating (i.e., organohalide-respiring)
bacteria active at elevated temperatures?
2. Do reductively dechlorinating bacteria recover activity
following exposure to elevated temperatures?
3. Does thermal treatment increase soil organic carbon
(i.e., electron donor) bioavailability to sustain the reductive
dechlorination process?
4. Does thermal treatment provide opportunities for post-
treatment bioremediation to control residual contaminants?
113
1. Microbial Reductive Dechlorination at
Elevated T
● Reductive dechlorination of chlorinated solvents demonstrated at
mesophilic temperatures (10-35 oC)
● Occurs in
O i coldld (4 oC) aquifers
if
(Bradley et al. 2005, Appl. Environ. Microbiol. 71:6414-6417)
● A thermophilic PCE-to-cis-DCE-dechlorinating
PCE to cis DCE dechlorinating mixed culture containing a
Dehalobacter sp. obtained from Rhine River sediment (60-65 oC)
(Kengen et al. 1999, Appl. Environ. Microbiol. 65:2312-2316)
● Enrichment of PCE dechlorinators from geothermal areas not successful

(unpubl. results)
● Screening of metagenome libraries established with DNA from geothermal

environments did not detect reductive dehalogenase genes (unpubl.
results)
114
Mi
Microbial
bi l Reductive
R d ti Dechlorination
D hl i ti att
Elevated T
An enrichment culture
derived from Rhine River
PCE dechlorinated
sediment dechlorinated PCE

e]
moles/bottle
to cis-DCE ay 60 oC. A
bacterium related to
Dehalobacter was detected.
[µm
Temperature (oC)
Kengen et al. 1999, Appl. Environ. Microbiol. 65:2312-2316
115
Reductive Dechlorination at Elevated T
Laboratory experiments with the PCE-to-ethene-dechlorinating
PCE to ethene dechlorinating consortium BDI
Dechlorination to ethene in Accumulation of VC in BDI

18 18
hene
BDI cultures incubated at 30 oC cultures incubated at 35 oC

nes and Eth
15 15
es/bottle]
12 12
PC DCE VC Ethen
9 9
E e
[μmole
Chloroethen
6 6
3 3
0 0
C
0 5 10 15 20 25 30 0 10 20 30 40
Incubation Time (Days) Incubation Time (Days)
No dechlorination at 40 oC
Fletcher et al. 2011, ES&T
Potential for VC accumulation 45:712-718
116
1. Microbial Reductive Dechlorination at
Elevated T
● A single study reports reductive dechlorination of PCE to cis-DCE
at temperatures of 60-65oC. This culture was derived from a “cold”
river
i sediment.
di t
● Search for thermophilic microbes capable of reductive

dechlorination has not been successful to date
date. The efforts to date
were limited in scope and the search should continue.
● Metagenome
g information is currently
yggenerated from many
y
environments, including thermophilic habitats. Screening of these
data sets for reductive dehalognease genes will reveal their
presence in thermophilic environments and can guide enrichment
efforts.
117
2. Recovery of Reductive Dechlorination Activity
Incubation at 40oC for 24 days prior to cooling to 24oC
ons [μmolees/bottle]
40 TCE DCE VC Ethen

henes and Ethene
40°C 24°C e
30 24 d
20 Dechlorination of VC
to
oeethene
e eaafter
e coo
cooling
g
Chloroeth
Concentrati
10
Fletcher et al. 2011, ES&T
45:712-718
0
0 20 40 60
C
Incubation Time (Days)
118
Incubation at 40oC for 49 days prior to cooling to 24oC
ions [μmoles/bottle]
40
TCE DCE VC Ethen
Chloroethenes and Ethene
40°C 24°C
e
30 49 d No dechlorination of
VC to ethene after
20 cooling
10 Fletcher et al. 2011, ES&T

S&
Concentrat
45:712-718
0
0 20 40 60 80 100
C
Incubation Time (Days)
119
PCE TCE cis-DCE

Sulfurospirillum Desulfitobacterium
Sulfurospirillum, Desulfitobacterium, Dehalobacter,
Dehalobacter Desulfuromonas
Desulfuromonas, Geobacter
Geobacter, Clostridium
Isolation and Characterization of a Tetrachloroethylene A PCE-dechlorinating

Dechlorinating Bacterium, Clostridium bifermentans DPH-1 spore former would be
Chang et al. 2000, J. Biosci. Bioeng. 89:489-491 able to survive high T
Resolution of Culture Clostridium bifermentans DPH-1 into No PCE-dechlorinating

Two Populations
Populations, a Clostridium sp.
sp and Tetrachloroethene-
Tetrachloroethene
Dechlorinating Desulfitobacterium hafniense Strain JH1.
spore formers
f have
h
Fletcher et al. 2008, Appl. Environ. Microbiol. 74:6141-6143 been identified to date
120
● No reductive dechlorination activity recovered from cultures

incubated at temperatures >40oC
● Duration of exposure to elevated temperatures affects
recovery of dechlorination activity
● The VC-to-ethene dechlorination step is most susceptible to
heat inactivation
 Increased potential for VC accumulation
● No spore-forming chlorinated solvent dechlorinators have
been described
121
3. Release of ED for Reductive Dechlorination
During/Following Thermal Treatment
Microcosm experiments with Ft. Lewis soil
Hydrogen production at different incubation temperatures
25000
Live
H2 Conccentration ((ppmv)
20000
killed
15000 H2 concentrations in live and

autoclaved Ft. Lewis microcosms
10000 after 28 days of incubation
5000 Fletcher, Water Research. In

Press.
0 * doi:10.1016/j.watres.2011.09.033
24 35 50 70 95
Incubation Temperature (°C)
122
16 Ft. Lewis - Live 16 Ft. Lewis - Microcosms established from Ft.
Autoclaved Lewis, WA, and Great Lakes, IL
12 12
Depicted is the electron donor
osm)
8 8
(ED) consumption in
Electrrons (µmoles/microco
4 4 reductive dechlorination
following thermal treatment.
0 0
24 35 50 70 95 24 35 50 70 95
Prior to bioaugmentation
300 Great Lakes - Live 300 Great Lakes - After bioaugmentation
250
* 250 Autoclaved After biostimulation I
200 200 After biostimulation II
150 * 150
 More reducing equivalents
100 100
directed towards reductive
50 50 dechlorination in microcosms
0 0 that had been incubated at
24 35 50 70 95 24 35 50 70 95
lower temperatures
Previous Incubation Previous Incubation
Temperature (oC) Temperature (oC) 123
Microcosms established from Ft.
300,000 300,000 Ft. Lewis -
Ft
Ft. Lewis - Live
Autoclaved
Lewis, WA, and Great Lakes, IL
250,000 250,000
200,000 200,000 Depicted is the electron donor
mv)
(ED) consumption in
H4 Concentration (ppm
150 000
150,000 150 000
150,000
methane formation following
100,000 100,000 thermal treatment.
50,000 50,000
0 0 Prior to biostimulation
24 35 50 70 95 24 35 50 70 95
After biostimulation I
400,000 Great Lakes - Live 400,000 Great Lakes -
After biostimulation II
Autoclaved
300,000 300,000
The majority of reducing
CH
200,000 200,000
equivalents released from
100,000 the soil matrix during heat
100,000
treatment are consumed in
0
0 methanogenesis rather than
24 35 50 70 95
24 35 50 70 95 reductive dechlorination
Previous Incubation Previous Incubation (i.e., <0.1%).
Temperature (oC) Temperature (oC) 124
● Thermal treatment increased the hydrogen flux
● At the two sites investigated, the amount of reducing equivalents

consumed d iin reductive
d ti d dechlorination
hl i ti negatively
ti l correlated
l t d with
ith
previous incubation temperature (i.e., fewer electrons consumed in
microcosms previously incubated at higher temperature)
● At both sites, biostimulation (i.e., the addition of electron donor)

was required to sustain reductive dechlorination and ethene
formation
● The majority of reducing equivalents was consumed in

methanogenesis
125
4. Opportunities for Enhanced Post-Thermal
Treatment Bioremediation
● Bioaugmentation with non-methanogenic consortia can increase the efficiency
of the reductive dechlorination process (i.e., a greater fraction of the available
reducing equivalents will be consumed in reductive dechlorination)
Before T After T Bioaugmentation after T
Niches Occupied
p Open
p Niches Colonialization of open
p
niches by bacteria in
the inoculum
126
Conclusions
● Residual contamination often remains following thermal treatment
● Subsequent bioremediation is a promising polishing step to meet
remediation g
goals  Combined Remedyy Approach
pp
● The known bacteria capable of reductive dechlorination cannot
tolerate elevated temperatures
● The VC-to-ethene step is most susceptible to temperature inhibition
● Thermal treatment increases electron donor (e.g., hydrogen) flux
● The majority of the hydrogen is consumed by methanogens
● Thermal treatment may offer unique opportunities for enhanced
bioremediation by using bioaugmentation inocula not containing
methanogens
127
Acknowledgements
● Kelly Fletcher (former PhD student)
● Nivedhya Ramaswamy (former MS student)
● J dC
Jed Costanza
t (U
(U.S.
S EPA)
● Natalie Capiro (Tufts University)
● Kurt Pennell (Tufts University)
SERDP Projects ER-1419 and ER-1586
128
LESSONS LEARNED
Start End Topic
10:30 AM 10:35 AM
(Dr. Hans Stroo)
10:35 AM 11:00 AM
(D P
(Dr. Paull J
Johnson)
h )
p )
11:35 AM 12:05 PM
(Dr Ronald Falta)
(Dr.
LESSONS LEARNED
Start End Topic
10:30 AM 10:35 AM
(Dr. Hans Stroo)
10:35 AM 11:00 AM
(Dr Paul
(Dr. Pa l Johnson)
p )
11:35 AM 12:05 PM
(Dr Ronald Falta)
(Dr.

Short Course 3 Thermal Treatment Technologies - November 2011

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Thermal Treatment Technologies:

Generalized Scenario A: Steam Heating 7 5 2 2

Generalized Scenario C: Steam Heating 4 0 3 1

Generalized Scenario D: Steam Heating 17 6 8 7

Generalized Scenario E: Steam Heating 3 1 1 1

Step 2: Conduct supplemental post-treatment field investigations at

Step 3: Synthesize results – Utilize results from this study, other

<1/4 acre <15 ft spacing 11

Conductive Heating 0 11* 12* 4 18 3 0 5 1 1 0 24

Reflection of Durations often ?

eology at This Site is

Depth to Water [ft]

ERH C 17 C, P 18,200 30 N/A

Hunter Army Airfield

Distance along Transect [ft]

Distance along Transect [ft] 23

0 8.8 1.3 0.7 45

16 1 0.6 0.2 0.9 25

Distance along Transect [ft]

5.6E-003 5.1E-003 3.3E-003 1.7E-002 45

3.4E-003 1.5E-003 1.8E-003 1.6E-004 5.7E-004

5.0E-004 1.6E-003 3.8E-004 1.4E-003 6.6E-003

7.3E-004 1.5E-003 2.5E-003 2.0E-004

Site Heating Pre-treatment Discharge Post-treatment

1 ERH Generalized Scenario A 5.2 x 101 1.9 x 10-1

8 ERH Generalized Scenario C 3.2 x 101 2.1

9 ERH Generalized Scenario C 4.9 x 101 1.3 x 10-1

10 ERH Generalized Scenario C 1.2 5.4 x 10-2

● Trends in Current Applications

● Energy Delivery Design

● Treatment Zone Size

● Geologic Setting Effects

● Application Operating Times

● For sites with a concentration reduction of 100x or more, the

With contributions from:

Gorm Heron, Ralph Baker, and Gregory Crisp (TerraTherm)

1 Now with Haley and Aldrich, Lenexa, Kansas

Professor Bernie Kueper

C. Lebron, G. Heron, J. Lachance, D. Rodriquez, D.

Temperature and pressure

Treatment area foot-print

Protected by U.S. and International Patents

● Inflowing cold groundwater can prolong time required to

Today From USGS 59

Elec. Equip. Off-gas

DEPTH BELOW LAND SURFACE IN FEET

Somewhat cooler 35-50 ft

Total: 530 lbs

Rodriguez and Kueper, 2011 76

● Bulk hydraulic conductivity (hydraulic testing)

Unfractured soil layer

Shortly after a DNAPL spill Later time – mostly dissolved

● Numerical Multiphase Flow Models

● Field Scale Simulations

 R  rock grain density 2300-2700 kg/m 3

 w  liquid water density 1000 kg/m 3

CR  rock grain heat capacity 800 1200 J/kgoC

Cw  liquid water heat capacity 4200 J/kgoC

S w  water saturation (0-1)

One kW-hr = 3.6 MJ, so 74 kW-hr to heat 1 m3

At $0.10/kW-hr, this would cost $7.40/m3

depth, ft also depress the boiling

M wH 2O  mass of liquid water