Transcript Watervliet Arsenal Preliminary MIN3P Simulations (from

Case Study:
Permanganate Applied to VOCs
in Fractured Shale
Beth L. Parker, Ph.D.
Department of Earth Sciences
University of Waterloo
Presented at the EPA Symposium in Chicago
December 12, 2002
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Research Collaborators

Dr. Tom Al
– University of New Brunswick

Dr. Ulrich Mayer
– University of British Columbia

Drs. Ramon Aravena and John Cherry
– University of Waterloo

Kenneth Goldstein, CGWP
– Malcolm Pirnie, Inc

Grant Anderson, P.G.
– U.S. Army Corps of Engineers
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Watervliet Arsenal
in New York State
Watervliet
Arsenal
Hudson River
Troy
Shale
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Watervliet Arsenal
Building 40 Area
Hudson River
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DNAPL Passed Through
Overburden Into Shale
PCE
adapted from Mackay and Cherry, 1989
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The Problem
 Chlorinated
ethenes – as high as
150 mg/L
 Contamination
 All
VOC mass in fractured shale
 AOC
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down to 150 ft. bgs
is 200 ft west of Hudson River
Study Area
N
Building 40
AW-MW-59
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Identification of Major Transmissive
Zones Using Hydro-geophysics
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USGS, 2001
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USGS, 2001
Major Transmissive Zone Identified
Fractures, Transmissive Zones, and
Total VOCs from PACKER TESTING
Leakage
MW-71
mg/L
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5,150
5,310
93,600
USGS, 2001
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PCE and Degradation Products in Shale
North
South
PCE
DCE
From packer test intervals
during drilling
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Interconnected Fracture Network
with Two Major Transmissive Zones
Cross-section view
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1
2
2
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DNAPL was Initially Distributed
in Many Fractures
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ILLUSTRATION OF
MATRIX POROSITY
DETAIL A
mineral particle
A
Microscopic
view of rock
matrix
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DNAPL Phase Initially Resides
within Fractures
Fracture Aperture
2b
ff
fm
H 2O
DNAPL
Fracture Spacing
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Matrix porosity is
1000 times greater than
fracture porosity
DNAPL Disappearance by Diffusion
Parker et al. (1994)
Fracture Aperture
2b
ff
fm
Fracture
Spacing
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Early
ff
H2 O
DNAPL
fm
Dissolved
Phase
Intermediate
ff
fm
Dissolved
Phase
Later Time
Snake Hill Shale Formation
Watervliet Site
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Core Hole In Source Zone
cored
hole
vadose
zone
groundwater
zone
B.L. Parker, 2000
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Diffusion Into Rock Matrix
Porous Rock Matrix
Fracture
Diffusion
Halo
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Core Sampling for
Migration Pathway Identification
TCE mg/L
cored hole
rock core
fractures
1
0
core
samples
analyzed
1
10
100
non-detect
2
3
4
Fractures with
TCE migration
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6
B.L. Parker, 2000
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Overview
of the
Rock Core
Method
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Sample Length
~Two Inches
Core Diameter
3.2 Inches
Parker and Colleagues 1997
Two Rock Crushers
Rock Crusher
Crushing Cell
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MW-74
Dec. 2001 (preliminary data)
Rock Core
Profile
Dec 2001
0
CMT
PORTS
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PCE solubility (240 mg/L)
20
30
40
50
60
depth (ft)
Pre-KMnO4
Injection
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PCE – 8 ug/L
1 TCE – 5 ug/L
c-DCE – 350 ug/L
PCE – 4 ug/L
2 TCE – ND
c-DCE – 1088 ug/L
PCE – 458 ug/L
3 TCE – 123 ug/L
c-DCE – 2802 ug/L
80
4
90
PCE – 9183 ug/L
TCE – 382 ug/L
c-DCE – 524 ug/L
PCE – 13,988 ug/L
5 TCE – 3,699 ug/L
c-DCE – 15,155 ug/L
100
110
PCE – 172 ug/L
6 TCE – 259ug/L
c-DCE – 11,745 ug/L
120
130
140
PCE
TCE
c-DCE
150
160
0.01
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Aqueous
Concentrations
(Feb. 2002)
0.1
1
10
100
1000 10000 10000 1E+06
0
conc. VOC (ug/L)
®
WESTBAY MP SYSTEM
Tripod
Pressure
Probe
Cable Reel
2.5 ft.
Sample
Bottle
2.5 ft.
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®
SOLINST CMT SYSTEM
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Site Conceptual Model
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
VOC migration occurs in a large
number of interconnected
fractures

Nearly all VOC mass resides in
the rock matrix rather than in the
fractures
It is well established that
permanganate completely
destroys chlorinated ethenes
However, to do so,
it must be delivered to the
contaminant mass
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Can permanganate be
effective for remediating
chlorinated ethenes in
fractured sedimentary rock?
Important factors:

Delivery throughout fracture network

Diffusion rates into rock matrix

Oxidant Demand of Shale
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KMnO4 Injections at Watervliet
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Potassium Permanganate Injection
75 65 34
Phase 2
injection
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~145 feet bgs
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71 74
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Phase 1
injection
PILOT STUDY RESULTS in 2002
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Treatment Approach
Permanganate
• Permanganate oxidizes chlorinated ethenes
Solvent + MnO4-
MnO2(s) + Cl- + Acid
• 13C / 12C and Chloride used to confirm
destruction
• Stable chemistry in subsurface allows time
for diffusion into matrix
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Remediation in Fractured
Porous Media
KMnO4 in
fracture
Contaminated
clay/rock
Early
Time
Contaminated
clay/rock
Treatment
zone
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Later
Time
B.L. Parker, 1993
In Situ Oxidation in
Fractured Porous Media
• Diffusion of both reactants occurs in
opposite directions
• Readily destroys sorbed phase
contaminants
Greatly reduces time scale for remediation
B.L. Parker, 1993
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Analogy to Fractured Shale
Results from
Permanganate Field Tests
in Marine Clay
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Oxidized zone shows extent of diffusion invasion and
treatment by KMnO4
Top of clay
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Invasion front
B.L. Parker, 1996
KMnO4 Profile in Clay
3.8
3.9
Depth
(m)
4.0
147 days
Pease ISI-6
4.1
0
5
10
KMnO4 in pore water (g/l)
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15
Combined Profiles in Clay
3.8
3.9
Reaction interface
Depth
(m)
KMnO4
TCE
4.0
147 days
Pease ISI-6
4.1
0
5
10
Concentration
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Snake Hill Shale Formation
Watervliet Site
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Permanganate Diffusion
into Matrix from Fracture
2b = fracture aperture
z
diffusion
x
y
C/Co
mass
x
40
mass
x+
Elemental Manganese Profiles in Shale
Transects Normal to Fractures Propagating
in from Surface of Rock Sample
Shale sample in 10 g/L KMnO4 solution for ~6 weeks
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How long will MnO4 take to
remediate the source zone?

Answer being sought using
~ field data
~ laboratory tests
~ numerical models
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Preliminary MIN3P Simulations
Watervliet Arsenal
Model developed by
Dr. Ulrich Mayer (1999)
3D multicomponent reactive transport model
Now being modified for permanganate oxidation
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MIN3P Simulation
• Simulate 1D MnO4- invasion into shale matrix
•
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where PCE has been diffusing in for 40 years
to examine rates of matrix clean-up
Parameters:
• Site-specific f, De, foc
• MnO4- R = 1
• PCE R = 220 (estimated using foc=0.5%)
• Source [ PCE ] = 150 mg/L for 40 years
• Injection [ KMnO4 ] = 5 g/L
Chloride Diffusion Test Cell for Rock
Golder Associates, Toronto
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Initial Condition
40 years PCE Diffusion-In
MIN3P Model – Snake Hill Shale
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Matrix Profiles after 1 year
MnO4- Injection
MIN3P Model – Snake Hill Shale
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Matrix Profiles after 2 years
MnO4- Injection
MIN3P Model – Snake Hill Shale
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Matrix Profiles after 5 years
MnO4- Injection
MIN3P Model – Snake Hill Shale
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Partial Mass Destruction
Greatly diminishes VOC mass
flux into fracture network
after permanganate is gone
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PCE flux to fracture after
partial permanganate treatment
Frac3DVS Modeling Log - Log Scale
No MnO4 Case
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Preliminary Conclusions
Permanganate…
• Diffuses and reacts in low K matrix
• Prevents release of mass from matrix to flowing
groundwater while present in fractures
• Greatly reduces magnitude of flux from matrix
even after partial treatment
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How do we know that VOCs
are being destroyed ?
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
Chloride increases at many locations

Change in carbon isotope ratio of PCE
ON-GOING WORK

Rebound monitoring after pilot injections

Permanganate invasion tests
– Laboratory samples
– Field cores

Reactive transport modeling
– Single fractures and fracture networks

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Design of full-scale system and monitoring
Acknowledgements

Project Contributors:
~
~
~
~
~

Steven Chapman and Martin Guilbeault (UWaterloo)
Daria Navon and Andrew Vitolins (Malcolm Pirnie)
Stephen Wood (U.S. Army Corps of Engineers)
JoAnn Kellogg (Watervliet Arsenal)
John Williams and Fred Paillet (U.S.G.S)
Funding:
~ U.S. Army Corps of Engineers
~ Solvents-In-Groundwater Research Program
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The End
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