RemOx® EC Stabilization Reagent for In Situ

RemOx® EC Stabilization Reagent for In
Situ Biogeochemical Stabilization and Flux
Reduction of NAPL
K. Frasco and M. Dingens
Carus Corporation
J. Mueller, F. Lakhwala and A. Seech
Adventus Americas Inc.
D. Foster and J Zubrow
Key Environmental
M. Brourman and M. Slenska
Beazer East, Inc.
The Challenge
Primary Sources - Excavation and Disposal
$100 to $250/yd3
Secondary Sources – More Challenging
>$250/yd3
What is In Situ Bio-Geochemical
Stabilization (ISBS)?
In situ biogeochemical stabilization (ISBS)
describes an emerging remedial
technology that entails the use of a
modified permanganate based solution
called RemOx® EC Stabilization Reagent.
ISBS Technology Specifics
• Encapsulation of the contaminant(s) of concern
• Flux reduction of the aquifer
• Limited mass destruction
• Enhanced bioremediation after the stabilization
is complete
Technology Development
1997 - Conceptualization
1998 – 2000 Proof of Concept R&D at UW and Adventus
2000 - 2001 Pilot studies Camp Borden
2002 - 2003 Phase I Pilot Denver
2004 - Phase II Full Scale Denver; Bench testing Gainesville
2005 - MGP NE Utilities; New ISBS Reagents (patent
pending)
2006-Present – Licensed to Carus as RemOx EC; Field
implementation in Alabama, Florida; Others pending
This work piqued our interest in the technology
SEM DATA
Soil Treated with
RemOx® EC
Untreated Soil
Birnessite
is an oxide of Mn and Mg
along with Na, Ca and K with the composition:
(Na,Ca,K)(Mg,Mn)Mn6O14.5H2O
Longevity of (X)FeMnO2
Mars Blueberries
Petroglyphs
Crust Longevity
• Kinetic geochemical
modeling suggest
crust life ~ 400 years
(> 2,000 pore-volume
flushes).
• This may be overestimated because it
assumes Eh (-700 mV)
and pH (11)
Eh-pH diagram from Hem (1985)
More soluble
Denver, CO Site
Previous NAPL Recovery Efforts
• Approximately 6,300 gal residual NAPL
• Manual bailing (< 200 gal)
• Low-flow skimmer pumps (< 10 gal)
• 800-ft long recovery trench (< 55 gal)
5 g/kg vs. 18 g/kg NOD
Denver, CO Site
Soil Sample Prior to Treatment
With RemOx® EC
Soil Treated With
RemOx® EC
Samples taken from same depth three feet apart
Mass Removal
COI (mg/kg)
LMW PAHS
Average (n=4)
Background
7,633.50
Average (n=4)
Treated
5,996.75
%
Reduction
21
HMW PAHs
1,961.55
1,744.55
10
TOTAL PAHs
9,595.05
7,771.30
19
* PENTA
236.00
55.67
76
* TOTAL CPs
284.48
59.25
79
* Excludes sample IB05A-14 to 14.5 ft bgs (80 v. 8 ppm dppenta + 296 ppm total penta)
Flux Reduction
COI (mg/L)
LMW PAHS
Average
Background
34.41
Average
Treated
12.75
%
Reduction
73
HMW PAHs
6.05
0.11
99
TOTAL PAHs
40.46
12.86
79
* PENTA
18.91
9.66
49
* TOTAL CPs
23.38
10.41
56
* Excludes sample IB05A-14 to 14.5 ft bgs (80 v. 8 ppm dppenta + 296 ppm total penta)
Woodward Coke Site –
Alabama
• Former Coke plant demolished in 1998
• Coke/coal fines are present near surface over a large
portion of the site underlain by clay residuum and
dolomite with karst related features (e.g. solution voids)
• Localized areas of NAPL- impacted soil and
groundwater are present
• Higher dissolved phase concentrations correlate with
presence of NAPL/Tar
RemOx EC Area M-65R/B
• Fracture zone between 28
and 30 ft bgs
• Sample from fracture zone
well indicated BTEX (473
ug/L), Naphthalene (5,000
ug/L) and other PAHs
(2,500 ug/L)
• Groundwater TOC (10.3
mg/L) consistent with
expected COI
concentrations
• Soil NOD testing indicates
low oxidant demand (1.5 to
1.6 mg/L KMnO4)
10 Day Column
• 1% RemOx EC
Solution
• 85% Reduction in
SVOC concentrations
in column leachate
ISBS
Treatment
Control
Naphthalene
9.55
58
2-Methylnaphthalene
2.35
16
Acenaphthylene
ND (1.0)
ND (0.93)
Acenaphthene
ND (1.0)
ND (0.93)
Dibenzofuran
0.405
2.70
Phenanthrene
ND (1.0)
1.10
Anthracene
ND (1.0)
ND (0.93)
0.195
1.30
Pyrene
ND (1.0)
0.45
Benzo(a)anthracene
ND (0.20)
ND (0.19)
Chrysene
ND (0.50)
0.45
Benzo(b)fluoranthene
ND (0.20)
0.72
Benzo(k)fluoranthene
ND (0.20)
ND (0.19)
Total SVOC
12.50
80.72
SVOCs in Leachate
(ppb)
Fluoranthene
10 Day Column
• 1% RemOx EC
Solution
• 41% Reduction in
SVOC soil
concentrations
ISBS
Treatment
Control
Naphthalene
9.55
58
2-Methylnaphthalene
2.35
16
Acenaphthylene
ND (1.0)
ND (0.93)
Acenaphthene
ND (1.0)
ND (0.93)
Dibenzofuran
0.405
2.70
Phenanthrene
ND (1.0)
1.10
Anthracene
ND (1.0)
ND (0.93)
0.195
1.30
Pyrene
ND (1.0)
0.45
Benzo(a)anthracene
ND (0.20)
ND (0.19)
Chrysene
ND (0.50)
0.45
Benzo(b)fluoranthene
ND (0.20)
0.72
Benzo(k)fluoranthene
ND (0.20)
ND (0.19)
Total SVOC
12.50
80.72
SVOCs in Leachate
(ppb)
Fluoranthene
• MW-65B
• Screened 21-31 ft bgs
• DTW ca. 8 to 12 ft bgs
• Historical DNAPL in
fractured dolomite @ 25
to 30 ft bgs
3 Injection Points
2 Extraction Points
MW-04
Water Storage Tank
IW-05
IW-01
Rail
Tracks
1,000 G RemOx EC Mix Tank
20 Skids of
RemOx EC
MW65
IW-02
MW-03
RemOx EC Field Injections
May 2007
• Traditional 5 point injection scheme into fractured
Bedrock Geology
• Target interval 20 – 30 feet below grade; 1,500 m3 area
• 80 Drums (37,500 lbs) of RemOx EC 4.5% solution
• 4 Drums to 1,000 gallons of water for 20,000 USG of
~1% injection solution
•Average 20 PSI injection pressure. Permitted up to 50
PSI
• Average 1,000 USG in 1 hour 15 minutes (~13 gpm)
Injection Set Up Overview
Water Storage Tank
Middle Injection Well
1,000 G Mix Tank
Centrifical Pump
Full Site Overview
Top Left Injection Well
Data To Date – Slug Tests
Gainesville, FL Site
• 90 acre site; P&T in place
• 2nd NAPL issues; Grouting, steam, ISBS
8-days ISBS using
Catalyzed NaMnO4
• COI mass reduced <10%
• Flux of HMW PAHs
reduced 60% (69 to 28
ppb)
• Flux of LMW PAHs
reduced 52% (1,836 to
894 ppb)
• Flux of CP reduced 96%
(212 to 9 ppb)
Transmissivity
• Column Leaching with
“cores”
• Buffered, Catalyzed
NaMnO4
Figure 1 Cummulative volume of solution that leached through 200 g of site soil after 7 and 8
days
500
450
400
• Soil “permeability”
reduced 98%
Volume (mL)
350
300
250
200
150
100
50
0
Control
1% NaMnO4
ISBS #1
ISBS #2
Treatment
Day 7
Day 8
ISBS #3
Gainesville, FL Site
Gainesville, FL Site
Direct Push Injections
DIP Parameter
Value
Treatment area
2,000 ft2
Thickness of treatment interval
20 ft
Soil density (estimated)
94.4 lbs/ft3
Soil mass within treatment area
3,778,000 lbs
NaMnO4 to soil mass
3.8 g NaMnO4 / kg soil
Mass NaMnO4 required
14,400 lbs
Soil NOD
122 g MnO4 / Kg soil
Application rate
10 % of soil pore vol
Total vol 4.5% solution to inject
6,200 USG
Number of injection points
10
Volume 4.5% solution per point
620 USG
Volume 4.5% NaMnO4 solution 155 USG
per layer
Direct Push Injections
Temporary Injection Points
TIP Parameter
Value
Treatment area
ca. 500 ft2
Thickness of treatment interval
20 ft
Soil density (estimated)
94.4 lbs/ft3
Soil mass within treatment area 944,000 lbs
MnO4 to soil mass
3.2 g MnO4 / kg soil
NaMnO4 to soil mass
3.8 g NaMnO4 / kg soil
Mass NaMnO4
3,600 lbs
Application rate
4 % of soil pore vol
Number of TIPs
2
Mass 10% RemOx EC solution
4,800 lbs
Total vol 10% solution to inject
500 USG
Volume 10% NaMnO4 solution 250 USG
per point
Temporary Injection Points
RemOx EC Material Cost
Denver, CO
Dolomite, AL
Gainesville, FL
TOD = 18 g/kg
TOD = 1 g/kg
TOD = 122 g/kg
Dense Alluvium
KMnO4 @ 4.5 g/kg
Injection Wells
Fractured Karst
RemOx EC
Push-Pull
Sand/Silt
RemOx EC
Direct Push and
Injection wells
1,273 m3 area
3% solutions
1,850 USG/IP
2-5 gpm (20 psi)
1,500 m3 soil area
1% solutions
20,000 USG
13 gpm (20-50 psi)
1,415 m3 soil
4.5 % solutions
620 USG/DIP
2-5 gpm (<50 psi)
Cost = $40 - 50/m3
$31 -38/yd3
Cost = $45 - 50/m3
$34 -38/yd3
Cost = $60 - 75/m3
$50 -60/yd3
Pore Volume Impacts
• Gainesville TIP - 4% PV with 10% RemOx EC
(special case – not typical application)
• Gainesville DIP - 10% PV with 4.5% RemOx EC
• Denver injection wells - 20% PV with RemOx EC
• Dolomite push-pull - 11% PV with 1% RemOx EC
RemOx EC Material Cost Estimates
(125 m3; n=30%)
PV Replaced
(vol required)
1% Solution
4.5% Solution
5% (495 USG)
917 lbs RemOx EC
$1,650 ($10 yd3)
4,444 lbs RemOx EC
$7,999 ($49 yd3)
10% (990 USG)
1,835 lbs RemOx EC
$3,303 ($20 yd3)
8,888 lbs RemOx EC
$15,988 ($98 yd3)
15% (1,485 USG)
917 lbs RemOx EC
$4,954 ($30 yd3)
13,332 lbs RemOx EC
$23,998 ($147 yd3)
• $1.80 / lb; Volume discounts not applied.
• > 20% PV = NAPL mobilization issues
QUESTIONS?