WI0800235_Application Attachment_20100504 (2)

Demonstration Plan
ER-0912 Cooperative Technology Demonstration:
Polymer-Enhanced Subsurface Delivery
and Distribution of Permanganate
March 2010

Contents
List of Tables ii
List of Figures iii
Acronyms iv
1.0 Introduction 1
1.1 Background 1
1.2 Objective of the Demonstration 1
1.3 Regulatory Drivers 1
2.0 Technology 3
2.1 Technology Description 3
2.2 Advantages and Limitations of the Technology 17
3.0 Performance Objectives 18
3.1 Evaluate Occurrence of Contaminant Rebound Post-Treatment 19
3.2 Improved Contaminant Treatment Effectiveness 20
3.3 Increassed Penetration of Permanganate into Lower
Permeability Layers/Strata 20
3.4 Decreased Flow Bypassing of Areas of High Contaminant Mass 22
3.5 Decrease Impact of Mn02 Deposition on Injection Pressures 22
3.6 Improved Understanding of Impacts of the Enhanced Delivery
Approach on Groundwater Quality 23
4.0 Site Description 24
4.1 Site Selection 24
4.2 Site Location and History 24
4.3 Site Geology/Hydrogeology 27
4.4 Contaminant Distribution 40
5.0 Site Design 45
5.1 Conceptual Experimental Design 45
5.2 Baseline Characterization Activities 45
5.3 Design and Layout of Technology Components 52
5.4 Field Testing 62
5.5 Sampling Plan 65
5.6 Data Analyses 68
6.0 Cost Assessment 72
7.0 Schedule of Activities 74
8.0 Management and Staffing 76
9.0 References 78
Appendix A—Site Selection Memorandum
Appendix B—Health and Safety Plan (HASP)
Appendix C —Spill Prevention, Control, and Countermeasure (SPCC) Plan
Appendix D—Points of Contact
i

List of Tables
Table 2-1. Impacts of MnO2 on Subsurface Permeability: Laboratory and Field
Evaluations
Table 2-2. Experimental Conditions
Table 2-3. Range of Response Values and Statistical Significance of Reaction Variables
Table 2-4. Advantages and Limitations of Enhanced Permanganate ISCO using Water
Soluble Polymers
Table 3-1. Demonstration Performance Objectives
Table 4-1. Hydraulic Conductivity Calculated at Each Slug Test Location
Table 4-2. Analytical Results for Contaminants (GC-MS)in Soils
Table 4-3. Analytical Results for Contaminants (GC-MS)in Groundwater
Table 4-4. Site Characterization Summary
Table 5-1. Summary of Injection Testing Flow Rate (gpm)
Table 5-2. Schedule of Plot Testing and Sampling
Table 5-3. Total Number and Types of Samples to be Collected
Table 5-4. Analytical Methods for Sample Analysis
Table 5-5. Xanthan Control Plot Operation
Table 5-6. SHMP Test Plot Operation
Table 5-7. Xanthan Test Plot Operation
Table 5-8. Project Schedule
Table 5-9. QA/QC Samples
Table 5-10. Demonstration Performance and Success Criteria
Table 6-1. Cost Model for Polymer-Enhanced Permanganate ISCO
Table 7-1. Schedule of Activities
ii

List of Figures
Figure 2-1. Simplified illustration of the cross-flow mechanism.
Figure 2-2. Viscosity-time plot.
Figure 2-3. PCE Concentration time plot.
Figure 2-4. Results of 1-D transport experiments for Xanthan/KMnO4 solutions.
Figure 2-5. 2-D tank experiment showing xanthan biopolymer improving sweep
efficiency within a fining downward heterogeneity structure.
Figure 2-6. 2-D tank experiment showing xanthan biopolymer improving sweep
efficiency within a fining 5 layered heterogeneity structure.
Figure 2-7. UTCHEM simulation showing the potential benefits of polymer addition at
the NTC Orlando-SA17 area.
Figure 2-8. Demonstration of 418 nm Response Metrics.
Figure 2-9. Percentage of particles < 0.10 µm for all sample conditions at high
stabilization aid concentration and t= 24 hours.
Figure 2-10. Average particle size and zeta potential for each stabilization aid condition at
pH 7 with base groundwater.
Figure 2-11. Representative data for 525 nm measurements (to determine permanganate
concentration) vs. time.
Figure 2-12. Mass of Mn (as MnO2)per kg of media with distance from 1-D column
influent.
Figure 2-13. Percent decrease in MnO2 deposition in source zone w/1,000 mg/L SHMP.
Figure 4-1. Test area at MCB CamLej, North Carolina, OU 15, Site 88.
Figure 4-2. Closer view of test area located within and immediately west of the footprint
of the former Building 25.
Figure 4-3. Test Area Conceptual Site Model.
Figure 4-4. Test Geologic Cross Section.
Figure 4-5. Example HRP results.
Figure 4-6. Boring log for DPTO1.
Figure 4-7. Grain size analysis for surficial aquifer media.
Figure 4-8. Geologic cross-section within the test area based on most recent
characterization activities.
Figure 4-9. Potentiometric map of the Surficial Aquifer.
Figure 4-10. Potentiometric map of the Upper Castle Hayne Aquifer.
Figure 4-11. PCE concentrations in the Surficial Aquifer (2007).
Figure 4-12. PCE concentrations in the Upper Castle Hayne Aquifer (2007).
Figure 5-1. Plot Test System Layout.
Figure 5-2. Injection well design.
Figure 5-3. Conventional monitoring well design.
Figure 5-4. MLS monitoring well design.
Figure 5-5. Process and instrumentation diagram.
Figure 5-6. Schematic of field core sample transects and example permanganate
distribution cross-sections used to estimate permanganate vertical sweep
efficiencies for the polymer and no-polymer treatment plots.
Figure 8-1. Project organization.
iii

Acronyms
APHA American Public Health Association
AST Aboveground storage tank
bgs Below ground surface
CDISCO Conceptual design for ISCO (modeling tool)
COC Contaminant of concern OR Chain of custody
CEC Cation exchange capacity
CPT Cone penetrometer test
CSM Conceptual site model
CSP Certified safety professional
CVOC Chlorinated volatile organic compound
C.Y. Cubic yard
c-DCE cis-dichloroethylene
DNAPL Dense nonaqueous phase liquid
DO Dissolved Oxygen
DoD Department of Defense
DOT Department of Transportation
DPT Direct push technology
EC Electrical conductivity
ECD Electrical conductivity detector
ERD Enhanced reductive dechlorination
EPA Environmental Protection Agency
FS Feasibility study
GC-MS Gas chromatography—mass spectroscopy
gpm gallon per minute
HASP Health and Safety Plan
HMP Hexametaphosphate (used interchangeably with SHMP)
HDPE High density polyethylene
HRP High-resolution piezocone
ID Inner diameter
IDW Investigative derived waste
ISCO In situ chemical oxidation
k Hydraulic conductivity
KMn04 Potassium permanganate
LPM Low permeability media
MCB Marine Corps base
MCL Maximum contaminant level
MIP Membrane interface probe
MLS Multi-level sampling
Mn Manganese
Mn02 Manganese dioxide
Mn04 Permanganate anion
mV Millivolts
iv

MW Monitoring well
NAPL Nonaqueous phase liquid
NCAD North Carolina Administrative Code
NOD Natural oxidant demand
ORP Oxidation/Reduction potential
OU Operable unit
PCE Tetrachloroethylene (perchloroethylene)
PH Negative base-10 logarithm of hydronium ion activity
PI Principal investigator
PITT Partitioning interwell tracer test
PLC Process logic controlled
PPE Personal protection equipment
psig pounds per square inch gauge
PVC Polyvinyl chloride
QA/QC Quality assurance/quality control
RABITT Reductive Anaerobic In Situ Treatment Technology
RI Remedial investigation
SEAR Surfactant enhanced aquifer remediation
SERDP Strategic Environmental Research and Development Program
SHMP Sodium hexametaphosphate
SPCC Spill Prevention, Control, and Countermeasure Plan
SS Suspended solids
TCE Trichloroethylene
TOC Total organic carbon
TCE Trichloroethylene
TTI Target treatment interval
UST Underground storage tank
VC Vinyl chloride
VOC Volatile organic chemical
VSE Vertical sweep efficiency
ZVI Zero valent iron
v

1.0 INTRODUCTION
1.1 BACKGROUND
In situ chemical oxidation (ISCO) using permanganate is an established remediation technology
being applied at hazardous waste sites throughout the United States and abroad. Field
applications of ISCO continue to grow and have demonstrated that ISCO can achieve destruction
of contaminants and achieve clean-up goals. However, some field-scale applications have had
uncertain or poor in situ treatment performance. Poor performance is often attributed to poor
uniformity of oxidant delivery caused by zones of low permeability media (LPM) and site
heterogeneity and excessive oxidant consumption by natural subsurface materials. A second
permanganate ISCO challenge is the management of manganese dioxide (Mn02)particles, which
are a byproduct of the reaction of permanganate with organic contaminants and naturally-
reduced subsurface materials. These particles have the potential to deposit in the well and
subsurface and impact flow in and around the well screen, filter pack, and the surrounding
subsurface formation. This is a particular challenge for sites with excessive oxidant consumption
due to the presence of natural materials or large masses of non-aqueous phase liquids (NAPLs).
This project focuses on (1) diminishing the detrimental effects of site heterogeneities with
respect to the uniformity of oxidant delivery, and (2) managing Mn02 aggregation and
deposition.
1.2 OBJECTIVES OF THE DEMONSTRATION
This project will demonstrate and validate the use of a water-soluble polymer with permanganate
for in situ chemical oxidation (ISCO) of organic contaminants with the dual primary objectives
of(1) improving the sweep efficiency of permanganate through heterogeneous media containing
lower permeability media, and (2) controlling manganese dioxide (Mn02) particles to improve
oxidant delivery and flow, thereby enhancing contaminant destruction. A secondary project
objective is to compare post-delivery/treatment groundwater quality for "permanganate only"
and "permanganate + polymer" test areas. Results of this demonstration will allow for the
development of guidance for transfer to the DoD user community.
1.3 REGULATORY DRIVERS
This project addresses contaminants amenable to ISCO using permanganate; most commonly
chlorinated solvents such as trichloroethylene (TCE) and tetrachloroethylene (PCE). Over 3,000
DoD sites are contaminated by chlorinated solvents, including dense nonaqueous phase liquid
(DNAPL) present at high mass density, which challenges many remediation technologies, as
well as very low concentrations emanating from contaminant trapped in lower permeability
layers that the majority of treatment technologies have difficulty accessing. The U.S.
Environmental Protection Agency's (EPA's) maximum contaminant level for TCE and PCE is 5
µg/L. This concentration is lower than typically present at sites containing even very dilute
concentrations of these contaminants. These MCLs, and others related to contaminants
amenable to permanganate ISCO, are the regulatory driver for advancing approaches for their
treatment.
1

Specific to the site for this particular demonstration, Camp Lejeune, remediation activities are
being conducted in accordance with the North Carolina Groundwater Quality Standards specified
in 15A North Carolina Administrative Code (NCAC) 2L .0202.
2

2.0 TECHNOLOGY
2.1 TECHNOLOGY DESCRIPTION
2.1.1 Challenges to ISCO using Permanganate
In situ chemical oxidation (ISCO) using permanganate is an established remediation technology
being applied at hazardous waste sites throughout the United States and abroad. A wide variety
of organic contaminants have been successfully oxidized by permanganate, with high treatment
effectiveness (e.g., > 90% mass destruction) for common contaminants such as chlorinated
ethenes (e.g., TCE, PCE) with very fast reaction rates (e.g., 90% destruction in minutes). Field
applications of ISCO continue to grow and have demonstrated that ISCO can achieve destruction
of contaminants and achieve clean-up goals. However, some field-scale applications have had
uncertain or poor in situ treatment performance. Two challenges with any in situ remediation
technology are (1) treatment amendment delivery limitations due to site heterogeneities, and (2)
minimizing unfavorable impacts of technology implementation. With respect to permanganate in
situ chemical oxidation (ISCO), these challenges specifically relate to (1) the ability to deliver
into low permeability media (LPM) (vs. preferential flow and bypassing of the LPM), and (2)
deposition of oxidation reaction byproduct manganese dioxide (Mn02) particles, preventing
effective distribution and contact with contaminants.
Poor amendment (i.e., permanganate) sweep efficiencies are typically the result of the injection
process whereby the injected amendments are delivered into preferential flow paths within zones
of higher permeability. This leads to the treatment amendment bypassing LPM and rebounding
contaminant concentrations within a groundwater aquifer following treatment. The efficiency
and efficacy of engineered remediation strategies that involve the introduction of chemical
amendments such as oxidants into the subsurface is dependent on achieving an efficient
subsurface sweep applied amendment within the contaminated zone. When injected under an
applied pressure gradient the resulting subsurface distribution is impacted greatly by the
architecture of the subsurface permeability field because the amendments will seek preferential
flow paths through more permeable media, resulting in a less efficient sweep of the target zone
by the injected amendments. The extent to which this occurs in a given heterogeneous system
largely depends on the physicochemical properties of the injected fluid, the mode of introduction
(e.g., injection rates, orientation and placement of well screens), the permeability distribution, the
location of the contaminant zone (in high-permeability zones, within clay zones, etc), and the
interaction of the fluid with the solid media at the pore-scale. Therefore, understanding the
interplay between the site-specific heterogeneity of the subsurface and the injected remediation
fluids is crucial to optimizing the distribution of applied amendments in the subsurface, thereby
enhancing the contact between the amendment and the target contaminant. Mobility control
methods exist that can mitigate the effects of permeability heterogeneity.
In addition to difficulties due to naturally existing site heterogeneities, Mn02 particles, a product
of the reaction of permanganate with organic materials (Eqn. 2-1), can create secondary site
heterogeneities that may provide an added hindrance to the technology's effectiveness.
3

2KMnO4+ C2HC13 4 2CO2 +2Mn02+ 2K++H++ 30- [2-1]
Mn02 particles are of interest because they have the potential to deposit in the well and
subsurface and impact the flow regime in and around the permanganate injection system,
including the well screen, filter pack, and the surrounding subsurface formation. Permeability
changes may result due to Mn02 particle deposition, which has been observed in laboratory and
field evaluations (e.g., West et al., 1998, 2000; Li and Schwartz, 2000; Lowe et al., 2000;
Reitsma and Marshall, 2000; Lee et al., 2003). It is postulated that differences observed in Mn02
deposition and permeability effects are attributable to differences in natural and design
conditions associated with these studies. The degree to which the particles can impact
permeability appears to be related to the amount of contaminant in the reaction zone, as well as
the reaction rate, which are interrelated. Table 2-1 presents a summary of laboratory and field
evaluations where impacts of Mn02 deposition have been observed and documented.
Table 2-1. Impacts of Mn02 on Subsurface Permeability: Laboratory& Field Evaluations
Study Description Impacts of Mn02 Reference
Field evaluation: A 5-spot recirculation After approximately 5 days of operation,increasing Lowe et al.,
network was employed to deliver 3000 injection well pressures(up to 18 psig)caused reduced 2000
mg/L NaMn04 to treat up to 600 mg/L recirculation rates(down to 4 gpm). Redevelopment of
TCE in groundwater. NaMn04 was added the injection well recovered the well efficiency,
to contaminated groundwater above however increasing injection pressures and reduced
ground,filtered at 5 and 1 um respectively, recirculation rates were again rapidly observed.
then injected into a central injection well.
Field evaluation: 2-4 wt%of KMn04 was Hydraulic conductivities measured 10 months after West et al.,
used to treat TCE at 100 to 800 mg/L in completion of the ISCO test showed order of 1998,2000
groundwater. magnitude decreases in several wells,especially the
oxidant injection well.
Laboratory study: 1-D column and 2-D The distribution of Mn02 in column studies indicates Li and
test cell studies were conducted to examine that the majority of Mn was located close to or at the Schwartz,
flushing efficiencies resulting from DNAPL zone. Precipitates tended to plug the column 2000
reaction of permanganate with typical —flushing become more difficult as the experiment
aquifer materials containing dense progressed. The 2-dimensional studies demonstrated
nonaqueous phase liquid(DNAPL) flow bypass zones with high DNAPL saturation once
contamination. The distribution of Mn02 the permanganate initially came into contact with the
was evaluated. DNAPL. Contaminant removal efficiencies were less
in 2D systems where flow was able to bypass areas
with Mn02 build-up.
Laboratory study: 2-D experimental Substantial Mn02 build-up was observed around the Reitsma
studies examined flow processes during DNAPL emplacement zone. With lower initial and
DNAPL oxidation,with varying rates of permanganate concentration and slower reaction rates, Marshall,
reaction due to varied initial permanganate more Mn02 was deposited downgradient from the 2000
concentrations introduced to the system. point of contact of oxidant with the DNAPL. Flow-
regimes were impacted by the Mn02 deposition.
Laboratory study: 3-D experimental The DNAPL oxidation process became less efficient Lee et al.,
studies examined DNAPL contaminant with time,likely due to reduction in permeability 2003
destruction and Mn02 deposition with caused by increasing Mn02 deposition that inhibited
treatment using 1250 mg/L KMn04. contact between the permanganate and DNAPL. Large
amounts of unreacted permanganate left the treatment
zone during oxidant flushing.
4

The stability of these Mn02 particles in solution, which is an indicator of their potential to be
controlled and transported with groundwater flow, can be impacted by several reaction matrix
conditions. These include reactant/particle concentrations, pH, turbulence, the presence of
anions/cations in solution, and the presence of stabilizing colloids or polymers (Morgan and
Stumm 1964; Perez Benito et al. 1989, 1990, 1991, 1992a,b; Insausti et al. 1992, 1993; Doona
and Schneider 1993; Chandrakanth and Amy 1996), providing a foundation for managing
particle aggregation and deposition.
2.1.2 Enhanced Permanganate ISCO
Methods to mitigate the potential for preferential flow and bypassing effects would increase
remediation effectiveness and reduce costs of environmental restoration efforts through reduced
occurrence of rebound. This project seeks to validate the use of water-soluble polymers with
permanganate for in situ chemical oxidation (ISCO) of organic contaminants with the dual
objectives of(1) improving the sweep efficiency of permanganate through heterogeneous media
containing LPM, and (2) controlling manganese dioxide (Mn02) particles to improve oxidant
delivery and flow, thereby enhancing contaminant destruction. A secondary project objective is
to compare post-delivery/treatment groundwater quality for "permanganate only" and
"permanganate+polymer"test areas.
Obiective 1: Improve oxidant sweep efficiency. Mobility control defines a class of strategies
involving the modification of in-situ fluid viscosities. This strategy was developed by the
petroleum industry for enhanced oil recovery to overcome preferential flow and other by-passing
effects produced by geological heterogeneities. Mobility control mechanisms have been used by
the petroleum industry since the 1960's to improve chemical flood efficiency and maximize oil
production from lower permeability strata. Traditional mobility control techniques in petroleum
reservoir engineering have involved the use of polymers, which increase the viscosity of the
injected solutions. The increased viscosity of the injected fluid minimizes the effects of the
aquifer heterogeneities by promoting strong transverse fluid movement, or cross-flow, across
heterogeneous reservoir units (Lake, 1989: Sorbie, 1991), providing an enhanced sweep
efficiency. The occurrence and benefits of cross-flow during polymer flooding for oil recovery is
well documented (see Seright and Martin, 1991, Sorbie, 1991 and references therein) and a
summary of recent applications in environmental restoration may be found in Jackson et al.
(2003).
A simplified illustration of the cross-flow mechanism is provided below (Figure 2-1) for linear
flow of a viscous Newtonian fluid in a two-layered aquifer system(permeability kl>k2).
5

A El Viscous Fluid Water 1 /
0.9 Linear Flow,k1/k2=10 /
rQ L 0.8
i /
0.7 �
/
�API� k, ,m' 0.6 With /
q1 a
0.5 Cross-Flow/ B
0.4
0.3
/
eP2� /
kz 0.2 1,=ithout
Cross-Flow
0.1
/
For vertical equilibrium AP,=ePZ o
k1eP1 k2AP2 qZ k2Rf 1 2 3 4 5 6 7 8 9 10
k1>kZ q1= FAQ qz= NWL q1 k1 Resistance Factor
Figure 2-1. Simplified illustration of the cross-flow mechanism(from Seright and Martin,
1991). kl >k2. The cross-flow condition occurs more readily with injected polymer.
When a viscous fluid is injected into the subsurface, a transverse pressure gradient is induced
between higher and lower permeability strata causing fluid to flow from the more permeable
strata into less permeable strata in an attempt to attain vertical equilibrium (i.e., API =AP2). The
result is a smoothing of the viscous liquid frontal advance within heterogeneous porous media
and diminished viscous fingering (i.e., enhanced sweep efficiency) as the fluid propagates away
from the point of injection. The effects of the cross-flow mechanism are better shown in Figure
2-1B, where the calculated ratio of the positions of the viscous fronts in both layers (L2/Ll, see
Figure 1) are plotted for the case of no cross-flow versus that with unrestrained cross-flow for an
increasing resistance factor (Rf). Rf is the ratio of the fluid injectivity (Q divided by the
difference in pressure between the point of injection and a defined distant point of reference) of
water to that of the viscous fluid and can be thought of as a fluid-specific measure of resistance
to flow. As shown, an increase in the amendment resistance to flow decreases the relative
positions of the viscous fronts between layers when cross-flow occurs (i.e., L2/L1 approaches
unity). The effect of cross-flow in real geologic systems would fall between these two curves
because the resistance to transverse flow is not negligible. The net result is that preferential flow
and by-passing of low permeability media is reduced, improving amendment sweep efficiency.
Technically, the term "mobility control" relates to defining an optimum mobility ratio (i.e.,
mobility of injected fluid greater than that of the displaced fluid) to displace a viscous pore fluid
(oil or viscous NAPLs) from porous media. When a viscous fluid is used to displace pore water
and promote lateral dispersion of the injected fluid within variable permeability media (as is the
case in this research), the term "heterogeneity control" is more appropriate. Viscosity
modification of engineered remediation amendments, whether by the addition of polymers or
other modifications to amendment formulations, should promote similarly favorable
heterogeneity control results for amendment emplacement in environmental systems as those
observed in the petroleum industry. Moreover, heterogeneity control strategies can be applied to
improve the efficiency of a variety of in situ remediation technologies, including in situ chemical
oxidation.
6

Fundamental study of the applicability of heterogeneity control within near-surface geologic
systems was completed under SERDP Project ER-1486 at the Colorado School of Mines. The
principal goal of the project was to examine the fundamental processes associated with polymer-
enhanced sweep efficiencies as a means to promote enhanced contact between the injected
amendments and the target contamination. An additional objective of ER-1486 was to examine
the compatibility of polymers and two remediation amendment categories (i.e., chemical
oxidants and bioamendments).
Xanthan gum has been identified a highly promising polymer for use with permanganate oxidant
solutions, in that it maintains a stable and predictable viscosity within the oxidant solution
(Figure 2-2), and exhibits a low oxidant demand for permanganate (Smith et al., 2008). When
the xanthan gum/permanganate solution contacts PCE (aqueous or non-aqueous phase liquid),
solution viscosity rapidly decreases (Figure 2-2). This coupled with the low oxidant demand for
the polymer suggests that the oxidation of PCE initiates partial oxidation of the xanthan molecule
at specific locations along the polymer chain, impacting the viscosity. However, as a part of
design, during subsurface injection a continuous and stable bank of xanthan/permanganate
solution will exist behind the PCE contact zone that will continue to impart heterogeneity control
within the aquifer.
700
600
cai 500
T
.N
o 400
N
300
3 1 N
m 200
1 -0--Xanthan solutoin(XXX ppm)
100 l Xanthan/KMn04
1 Xanthan/KMn04/PCE
0
0 2 4 6 8 10 12 14 16 18 20 22 24
Time(hrs)
Figure 2-2. Viscosity-time plot.
Figure 2-3 shows that xanthan gum does not greatly inhibit PCE oxidation. Calculated second
order rate constants for the PCE/KMnO4/xanthan gum system averaged around 0.036 M-1 sec-1
for xanthan concentrations between 1600 and 142 mg/L. This is nearly the same as that
determined for the no-xanthan case (PCE/KMnO4 system) where the rate constant was 0.04 M-1
sec-1. Both measured rate constants are consistent with those reported in the scientific literature.
7

Of additional importance to polymer/oxidant compatibility, and to implementation design, is to
assess the comparative transport of xanthan gum and permanganate within porous media when
introduced together in solution. The results of a I-D column experiments have shown that
polymer and oxidant transport similarly, and conservatively, within a clean silica sand.
Observed sharpening of the polymer and oxidant breakthrough profiles, compared to the
conservative tracer, reflects the polymer mitigating pore-scale heterogeneities within the column.
These results are presented as Figure 2-4. Similar column experiments were performed in
natural soil possessing elevated natural oxidant demand (NOD) characteristics. The results of
these experiments are also presented in Figure 2-4. The observed early breakthrough for both
the conservative tracer and xanthan gum elution profiles, and tailing of the xanthan gum elution
profile, are indicative of a reduction in media permeability due to manganese dioxide (Mn02)
precipitation as a result of oxidation of natural organic matter. This slight permeability reduction
resulted in some mechanical filtering of xanthan gum which temporarily delayed its approach to
C/Co = I (i.e., the time needed for effluent xanthan concentrations to equal that of the influent).
However, the viscosity of the effluent did reach its inlet value at 2.5 pore volumes, suggesting
that the oxidation of NOD ultimately did not affect the viscosity of the polymer during transport.
These results also indicate that although the strength of the polymer front was 80% reduced
during the initial flushed pore volumes, as a result of retention, the continued introduction of
xanthan gum/KMn04 solution restored the integrity of the polymer bank within this new
permeability condition. It should be noted that the media used in these experiments was collected
from within a sewage wastewater leach field and therefore possessed a significantly greater NOD
than would reasonably exist within a groundwater aquifer. Additional experiments such as these
have been budgeted as a part of this proposal using site media so as to assess and potentially
incorporate the mechanics of these phenomena within an implementation design basis.
0
-0.1
-0.2 I Note: In all cases initial PCE,
0 3 KMn04, and xanthan concentrations
were 142 ppm, 1000 ppm, and 1600 ppm,
-0.4 respectively.
w
a -0.5
rn
o -0.6
J
0 I 0 Xanthan/PCE
PCE/KMn04
-0.8- Xanthan/PCE/KMnO4
-0.9
0 2 4 6 8 10 12 14 16 18 20 22 24
Time(hrs)
Figure 2-3. PCE Concentration time plot.
8

li+i'
08
I o U IPA Tracer
U •[WO4J
• •E10u"t Viet
U 0.4
0.2 F Clean Sand
0
0 0.5 1 1.5 2 2.1
°q High NOM �� M• �'►
•
Sand
0
U 0.4
U D IPA Tracer
0.2 ♦E10ue°I Viet
a�
0
0.0 0.5 1,0 15 2.0 2.5
Pore Volume
Figure 2-4. Results of 1-D transport experiments for xanthan/KMn04 solutions. Xanthan
biopolymer transport in clean sand was found to be similar to that of a conservative tracer(i.e.,
no unexpected retention of polymer).
An example of polymer-improved sweep efficiency in a 2-D experimental tank is presented in
Figure 2-5. Here, the permeability structure is layered in a fining downward sequence.
Permeabilities varied over three orders of magnitude (i.e., 100 — 1 darcy). The addition of 800
ppm xanthan gum is shown to provide a sweep efficiency (i.e., swept area of the tank divided by
the total tank area) of 92% at 2 pore volumes, compared to the no polymer case of 61%.
Furthermore, there was a 500% sweep efficiency improvement of the lowest permeability layer
after 2 pore volumes flushing. These results indicate that the addition of polymers to remediation
amendments can greatly improve amendment delivery efficiency to lower permeability strata and
reduce the volume of amendment required to achieve such delivery. Results of an additional 2-D
tank experiment are presented in Figure 2-6.
Tracer:1PV Polymer:1PV
Sweep Efficiency=42% Sweep Efficiency=769%.
Tracer:2PV Polymer:2PV
Sweep Efficiencyq1%6PSweepfficiencyM929%16
Figure 2-5. 2-D tank experiment showing xanthan biopolymer improving sweep efficiency
within a fining downward heterogeneity structure (3-order of magnitude permeability contrast,
500% sweep improvement of lowest permeability layer. Numerical simulation of this experiment
is also presented.
9

Darcy
10 Darcy
00 Darcy
10 Darcy
Darcv
Figure 2-6. 2-D tank experiment showing xanthan improving sweep efficiency within a fining 5-
layered heterogeneity structure (3-order of magnitude permeability contrast). The addition of
polymer improved the sweep efficiency of this system by 103% and 80% at 1 and 2 pore
volumes,respectively.
To further demonstrate the benefits of polymer addition on the resulting distribution of KMnO4,
the UTCHEM simulator was used to simulate fluids propagation (with and without polymer
addition) within a contaminated aquifer section at the NTC Orlando-SA17 Area (Figure 2-7).
Model input parameters were based on those measured as a part of SERDP project ER-1486.
The permeability field consisted of three continuous layers of silty fine-sand (k= 100 millidarcy)
surrounded by a fine-med sand (k= 1000 millidarcy). The frontal advance rate was 20 ft/day and
the simulation time was 2 days. As shown in Figures A4, the addition of xanthan gum greatly
improves the distribution of oxidant in this system and forces oxidant into the lower permeability
media (LPM). Slower frontal advance rates and/or elevated polymer concentrations will
improve oxidant sweep efficiencies further. Ultimately, simulations like these are critical to tailor
polymer solution characteristics and injection rates to a specific site as a part of implementation
design to maximize the benefits of polymer-induced heterogeneity control.
10

i Simulated Region
(Wt,)
....-........................................
Central Injector(fully penetrating) Polymer-induced cross-flow into LPM
No Polymer
Poor Oxidant Sweep
10 ft. 100 ft.
Figure 2-7.UTCHEM simulation showing the potential benefits of polymer addition at the NTC
Orlando-SA17 area.
Obiective 2: Control Manzanese Dioxide Particles. SERDP Project ER-1484 recently
determined that Mn02 particles in groundwater can be controlled using polymers to specifically
allow for their facilitated transport through porous media. Since it is not particle size alone that
determines the ability of these particles to be transported, physico-chemical interactions must be
considered; therefore the experimental studies examined the interactions of potential stabilization
aids (e.g., ionic/nonionic, organic/inorganic water soluble polymers) with Mn02 particles, as
well as the interactions of potential stabilization aids with porous media and groundwater. The
ideal particle stabilizer will (1) interact minimally with porous media, (2) react minimally with
the oxidant permanganate, (3) interact minimally with other groundwater components, (4) be
acceptable to the regulatory community, and(5)be cost-effective.
Batch experimental studies were conducted to evaluate four polymer stabilization aids with
respect to particle stability in solution over time and the influence groundwater conditions have
on stabilization (experimental conditions included in Table 2-2). Measurements of each reaction
solution included spectrophotometric evaluation of particle behavior (optical measurement of
particle suspension and settling), particle filtration (filtered at each pore size of 5, 1, 0.4 and 0.1
µm), and optical (laser)measurement of particle size and zeta potential.
Table 2-2. Ex erimental Conditions
Variable Condition A Condition B Condition C
Particle concentration 10 mg/L 100 mg/L ---
pH 7 3 ---
Ionic variation Base groundwater Base groundwater+Ca2+ Base groundwater+P043-
Solids content None 20 wt.% ---
Redox conditions 1:1 initial ratio of Mn04 to Oxidizing(excess Mn04) Reducing(excess reductant)
reductant
Stabilization Aids Dowfax Hexametaphosphate Gum arabic Xanthan Gum
Stabilization Aid 23,540 3,300 1,000 100 1,000 100 25 10
Concentration(mg/L)
11

Spectrophotometric measurements were made at 418 nm and assessed for multiple responses.
Because the 418 nm data reflect the measurement of particles suspended in solution, they
provide a qualitative indication of particle behavior. An increase in the 418 nm measurements
indicates an increasing concentration of suspended particles, whereas a decrease indicates that
particles have settled from solution. An ideal stabilization aid will prevent particle settling.
Responses measured using the 418 nm data include (1) maximum absorbance value (Amax), (2)
time of maximum absorbance (Tmax), (3)time of maximum absorbance minus time of minimum
absorbance (Tmax-Tmin), and (4) particle settling rate (ks-obs) (Figure 2-8). A higher maximum
absorbance value indicates a higher concentration of particles suspended in solution. Tmax and
Tmax-Tmin characterize the particle growth and settling behavior. Favorable particle
stabilization is indicated by a highly positive value for the Tmax-Tmin, corresponding with a
relatively late Tmax value in general (i.e.,particles are suspended for a longer duration). Particle
settling rates were calculated by fitting the 418 nm data after the reaction between oxidant and
reductant was complete (-4 hours) to a power curve; y= AxB, where y is absorbance at 418 nm,
x is time, A and B are model fitting parameters, and B provides the rate of particle settling in
terms of decreasing 418 nm absorbance vs. time. Values for these indicator measurements are
included in Table 2-3. Sodium hexametaphosphate (SHMP), gum arabic, and xanthan gum all
improve particle stability as evidenced by higher Amax values, higher Tmax values, higher
Tmax-Tmin values, and lower ks_obs values.
Favorable Unfavorable
Amax Amax
E E ks-obs
c c
00 00 IF
m m
U U
� C
f6 f0
L L
O O
U)
Q Tmax Q Tmax
Time Time
Tmax - Tmin Tmax- Tmin
Figure 2-8. Demonstration of 418 nm response metrics.
12

Table 2-3. Range of Response Values and Statistical Significance of Reaction Variables(check
indicates the condition or interaction has a statistically significant impact on the response)
Amax Tmax Tmax-Tmin KS-obsa
Response range 0.2—1.2 2-8 -71—-50 0.75—1.02
Particle Conc(PC)
No pH
Stabilization Groundwater(GW)
PC x pH(interaction)
PC x GW
pH x GW
Response range 0.5—3.2 1—21 -71—-30 0.5—1.10
PC
pH
GW
Dowfax Conc(D-C)
Dowfax PC x pH
PC x GW
PC x D-C
pH x GW
pH x D-C
GW x D-C
Response range 0.3—2.0 10—40 -20-+10 0.1—0.7
PC
pH
GW
SHMP Cone(SHMP-C)
SHMP PC x pH
PC x GW
PC x SHMP-C
pH x GW
pH x SHMP-C
GW x SHMP-C
Response range 1.0—3.6 20—44 +5—+38 -0.1—+0.4
PC
pH
GW
Gum Arabic Conc(GA-C)
Gum aabic PC x pH
PC x GW
PC x GA-C
pH x GW
pH x GA-C
GW x GW-C
Response range 0.7—3.4 10—58 -50—+55 0.15—0.80
PC
pH
GW
Xanthan Conc(X-C)
Xanthan gum PC x pH
PC x GW
PC x X-C
pH x GW
pH x X-C
GW x X-C
aA positive ks b,value,as applied here,indicates particle settling has occurred during the 72 hour reaction period,whereas a negative k,.b.value
indicates particle growth continues through reaction.
13

The particle filtration and optical measurement data concur with the conclusions of the
spectrophotometric evaluations. The use of SHMP, gum arabic, and xanthan gum result in a
greater percentage of particles < 0.10 µm (Figure 2-9) under a range of experimental
conditions; as well as a smaller average MnO2 particle size and more favorable (highly negative)
zeta potential for particle stabilization (Figure 2-10). While results are similar and favorable for
several stabilization aids, SHMP is of particular interest because it does not exert a non-
productive demand for permanganate (Figure 2-111).
XG,pH7
GA,pH7 pH 7
PP,pH7
Dow,pH7
None,pH7 GW+P043-
............................................................................................................
XG,pH3
GA,pH3 pH 3
PP,pH3
Dow,pH3
None,pH3
.............. ....................................................................................................................... .
XG,pH7
GA,pH7
PP,pH7 pH 7
Dow,pH7
None,pH7 GW+Ca2+
............................................................................................................
XG,pH3
GA,pH3
PP,pH3 pH 3
Dow,pH3
None,pH3
..... 19....... .......................................................................................................................
XG,pH7
GA,pH7
PP pH7 pH 7
Dow,pH7
None,pH7 ...................................................... GW
XG,pH3
GA,pH3
PP,pH3 pH 3
Dow,pH3
None,pH3 IF
0.00 20.00 40.00 60.00 80.00 100.00
%Particles< 0.1 um
Figure 2-9. Percentage of particles < 0.10 µm for all sample conditions at high stabilization aid
concentration and t=24 h. None=no stabilization aid; Dow=Dowfax; PP =polyphosphate (or
sodium hexametaphosphate (SHMP)); GA=gum arabic; XG=xanthan gum.
14

30 Particle Size (µm)
N 20 ❑ Zeta Potential (mV)
in
V 10
m
a
-0
5 No .A. Do fa SH P Gm Xan ha
Arabic G m
10
C
-20
Q
a
�a
d -30
N
Figure 2-10. Average particle size and zeta potential for each stabilization aid condition at pH 7
with base groundwater. High particle concentration samples are presented.
Permanganate Depletion vs.Time +no S.A.
�1b
0.4 2b
E 0.35 +3b
r t 4b
0.3
N
^ 0.25
u 0.2
c
0.15
°� 0.1
Q 0.05
0
0 10 20 30 40 50 60 70 80
Time(hrs)
Figure 2-11. Representative data for 525 nm measurements (to determine permanganate
concentration) vs. time. "No S.A."refers to no stabilization, "lb"refers to Dowfax, "2b" is
SHMP, "3b" is gum arabic, and"4b" is xanthan gum. All samples are for the base groundwater
condition(no excess Cat+or P043-) at pH 3. SHMP results mimic those of the "no stabilization"
condition, indicating it does not exert a demand for the permanganate.
The batch experimental studies have established the proof of concept for using polymers to
improve particle stability in solution, enhancing their potential to be more readily transported in
groundwater. Additional experiments evaluated transport of MnO2 both with and without SHMP
in 1-D transport systems of varied media content (i.e., organic matter, clay, mineralogy) to
determine if the enhanced stability is maintained during transport through porous media. Figure
2-12 shows deposition of MnO2 with distance from the influent end TCE NAPL source. Note
that the majority of deposition occurs in or near the NAPL source with some differences in
deposition based on media type. Figure 2-13 shows the decrease of MnO2 deposition in the
source zone (which is Section 1 of Figure 2-12) with use of 1,000 mg/L of SHMP with the
permanganate solution.
15

14
12
■Sand
u v 7 Sand+1%FeO(OH)
7o d 10 IN Sand+05%organic carbon
o ❑Sand+20%clay
c m 6
� E
e 4
E-
2
1 2 3 4 5 6 7 9 9 10 11 12
Sectioned distance(each section-5 cm length)
Figure 2-12. Mass of Mn(as Mn02) per kg of media with distance from 1-D column influent.
Each section is approximately 5 cm of column length. Results are normalized for the total mass
of permanganate delivered to the column. Delivery mass differed for columns due to plugging
and restricted flow in Sand+Goethite and Sand+ Clay columns.
100
80
at
p" 60
L C
aa)) 40
0
20
0
Sand Sand+1% Sand+0.5% Sand+20%
FeO(OH) Oc clay
Media Type
Figure 2-13. Percent decrease in Mn02 deposition in source zone with 1,000 mg/L SHMP
Summary. This project focuses on (1) diminishing the effects of site heterogeneities with respect
to the uniformity of oxidant delivery, and(2) managing Mn02 aggregation and deposition, which
is a significant challenge for sites with excessive oxidant consumption due to the presence of
natural materials or large masses of dense non-aqueous phase liquids (DNAPLs). We are
demonstrating/validating the use of water-soluble polymers (xanthan gum and sodium
hexametaphosphate (SHMP)) to improve the delivery and distribution of permanganate oxidant
solutions within heterogeneous contaminated aquifers. Xanthan gum biopolymers have a long
history of use in the petroleum industry, and their contribution toward improving the sweep
efficiency of injected fluids by minimizing the effects of the aquifer heterogeneities is well-
documented (Lake, 1989; Sorbie, 1989 and references therein). SERDP Project ER-1486 has
verified that xanthan gum can significantly enhance the sweep efficiency of permanganate
through heterogeneous media. Additionally, SERDP Project ER-1484 has found SHMP to
stabilize Mn02 particles in solution, preventing particle aggregation and inhibiting permeability
reductions due to in situ deposition. Both of these projects have shown xanthan gum and SHMP
to be compatible with permanganate solutions and amenable to co-injection.
16

2.2 ADVANTAGES AND LIMITATIONS OF THE TECHNOLOGY
Table 2-4 summarizes the advantages and limitations associated with introducing each polymer
to a standard permanganate ISCO operation.
Table 2-4. Advantages and Limitations of Enhanced Permanganate ISCO using Water
Soluble Polymers
Xanthan Gum
Improves injected fluids sweep efficiency within heterogeneous porous media.Increased
injection fluid viscosity promotes mobility reduction in the principal flow direction(longitudinal
for vertically installed wells)and encourages transverse fluid movement(or cross-flow)of
fluids between strata of differing permeability.
Improved sweep efficiency results in improved distribution of co-injected remediation agent and
Advantages im roved contact between the amendment and the target contaminant
In the presence of permanganate,xanthan gum will slowly oxidize into simple sugars.During
our Treatability Study we found that,depending on the specific concentrations of oxidant and
polymer,the co-injected solution will lose roughly half its initial viscosity in one week after
emplacement. Initially,the enhanced viscosity will hydraulically isolate the treatment zone,
improving contact times. As the polymer is oxidized the hydraulic properties of the treatment
area should be largely restored.
Increased injected fluid viscosity results in reduced fluid mobility during transport within
porous media. "Mobility"refers to the fluid-specific component of hydraulic conductivity.
Therefore,a reduction in mobility results in a reduction in hydraulic conductivity. This
hydraulic conductivity reduction can limit the rate of fluid injection within shallow aquifer
systems
Larger polymer molecules can become trapped within narrow pores during
transport with porous media, reducing the permeability to polymer and in severe
cases to water. This entrapment mechanism becomes more pronounced as the
Limitations intrinsic permeability of the porous media decreases and the mean pore diameter
approaches the effective hydrodynamic diameter of the polymer molecule
(which is generally considered to be about 1 micron(Dominguez and Willhite,
1977). Permeability reduction compounds the reduced injectivity of the
polymer-amended fluid resulting from the increased viscosity. Therefore, the
effects of mobility reduction and permeability reduction must be accounted for
during implementation design
Polymer mixing and filtration equipment are necessary and must be added to the design and
treatment costs.
SHMP
Maintains Mn02 particles suspended in solution,inhibiting their deposition in the subsurface.
This can result in improved contact with contaminant and increased remediation efficiency.
Does not react with permanganate therefore there is no additional unproductive demand for
Advantages oxidant.
Aside from an additional line to introduce SHMP to permanganate solution prior to subsurface
delivery,there are no additional modifications to a typical permanganate system design for
implementation.
The impacts of adding excess"salt"to the subsurface system are expected to be minimal and
Limitations
harmless,yet they have not been investigated.
The addition of SHMP will increase total dissolved solids concentrations in the treatment zone
and possibl down gradient.
17

3.0 PERFORMANCE OBJECTIVES
Detailed demonstration performance criteria, data required, and success criteria related to these
objectives are presented in Table 3-1.
Table 3-1. Demonstration Performance Objectives
Performance Criteria Data Requirements Success Criteria
(with use of polymer)
Quantitative Performance Objectives
Evaluate long-term • Contaminant concentrations in • Data collected and are representative of
potential for and short-term groundwater over time and distance test plots
occurrence of contaminant . Contaminant concentrations in soil cores • Post-treatment groundwater monitoring
rebound within 2-months pre-and post-treatment results remain below baseline
post-treatment . Diffusion of contaminant out of soil concentrations and validate reduction of
cores in the laboratory post-treatment contaminant rebound that would
otherwise be predicted from the soil
samples alone
Improved contaminant • Contaminant concentrations in • Statistically significant reduction in
treatment effectiveness groundwater over time and distance from contaminant mass as compared to a
injection control plot
• Contaminant mass in soil over time and
distance
Increased penetration of • Examination of soil cores for evidence of • 50%longer distance of permanganate
oxidant into lower permanganate(purple color,or penetration into lower permeability
permeability layers/strata byproduct,Mn02,brown)in lower layers/strata
permeability layers/strata . 25%higher permanganate concentration
• If LPM of thickness appropriate for at expected(as observed in control plot)
discrete groundwater sampling is present, time of arrival in each monitoring well
then Mn04/1\4n02 concentrations . Demonstrated improvement in vertical
measured in groundwater over space and sweep efficiency of permanganate
time within lower permeability layers/strata
• Demonstrated improvement in overall
vertical sweep efficiency of
permanganate within the test lot(s)
Decreased flow bypassing . Examination of soil cores for evidence of • 50%lower mass of Mn02 in given mass
(increased lateral sweep Mn02(dark brown)in media with high of media(indicative of inhibition of
efficiency)of areas of high contaminant concentration deposition that can increase bypass)
contaminant mass . Soil core extractions for Mn02 and • 25%greater mobile Mn02 concentration
spectrophotometric measurements for at given time point in monitoring well
Mn04 and Mn02 in groundwater over • 50%lower mass of contaminant in high
time and distance from injection concentration cores
• Soil core extractions for contaminant
with distance from injection
Qualitative Performance Objectives
Decreased impact of Mn02 . Injection well pressure over time • No increase in injection pressure
deposition on injection . Pre-and post-injection slug tests attributable to Mn02(compared to
pressure pressures expected via simulation
Improved understanding of • pH,ORP,key metals,solids • Note differences
impacts of the enhanced concentrations,conductivity,bioactivity
delivery approach on
groundwater quality
18

3.1 PERFORMANCE OBJECTIVE: EVALUATE OCCURRENCE OF CONTAMINANT REBOUND
POST-TREATMENT
Contaminant rebound at a site is often attributable to poor distribution of treatment amendments.
Poor distribution is a function of site heterogeneity, depletion of amendment as it moves through
the subsurface, or impacts from reaction byproducts that may be generated/formed; or both the
physical and chemical processes occurring. With respect to permanganate ISCO, flow bypass of
the oxidant can result from physical heterogeneities causing flow bypass around areas of lower
permeability media where contaminant may be entrapped, or it can also result from flow around
areas where Mn02 solids reaction byproduct deposit, typically around areas of high contaminant
saturation or in media that exerts an extensive natural demand for oxidant (i.e., highly reduced).
By diminishing the impact of site heterogeneities with polymers, it is feasible to diminish or
eliminate associated contaminant rebound. While the duration of this demonstration (monitoring
up to 8 weeks post-demonstration) will limit the ability to assess complete elimination of
rebound, we will be able to make several measurements that will allow us to assess the potential
for rebound to occur in both the permanganate only and permanganate +polymer test plots.
3.1.1 Data Requirements
Rebound potential will be evaluated using several approaches:
1. Examination of contaminant concentrations in groundwater over distance measured at
the site pre-, during- and post-treatment. Post-treatment monitoring data will be
compared to pre- and during-treatment data for both the test (oxidant + polymer) and
control (oxidant only)plots to determine if the addition of polymer impacted rebound.
2. Measurement of contaminant concentrations in soil cores pre and post-treatment. Data
will be compared for the test and control plots.
3. Pre- and post-treatment cores will be sectioned and sub-sections will be exposed, intact
as best possible, to a deionized (DI) water solution. Concentrations of contaminant
accumulating in the DI water will be measured over time in the laboratory.
3.1.2 Success Criteria
The primary criterion for success, because the goal is to evaluate occurrence of rebound, is that
the data collected are representative of the conditions within the treatment and control plots. We
hope to assess, using that data, the rebound potential in the test vs. control plots. A decrease in
the rebound potential with the use of polymer will be considered met if at least one of the
following occurs: (1) there are measurable contaminant concentrations in groundwater in the
oxidant-only control plot, but no contaminant concentrations in groundwater in the oxidant +
polymer test plot; (2) there is a statistically significant difference between concentrations
measured in the oxidant-only control vs. oxidant + polymer test plots AND the measured
concentrations in the test plot can be attributed to factors other than rebound (i.e., migration of
contaminant from upgradient); (3) there are measureable contaminant concentrations in the
oxidant-only control plot porous media, and contaminant concentrations in the oxidant_polymer
test plot are statistically lower than the control plot. A decrease in rebound potential will not be
considered met if both the test and control plots show either (1) no statistically significant
difference in post-treatment concentrations in soil or groundwater, or (2) no measurable
19

contaminant concentrations in either plot. While the latter of these two does not point to an
unsuccessful demonstration, it would not be possible to attribute a success to polymer
application, therefore other performance criteria would be relied upon to evaluate demonstration
success.
3.2 PERFORMANCE OBJECTIVE: IMPROVED CONTAMINANT TREATMENT EFFECTIVENESS
While improved contaminant treatment effectiveness is linked to the rebound assessment
objective, it is listed and will be evaluated as a separate criterion as it is possible to improve
contaminant treatment effectiveness without impacting rebound during a short-term, pilot-scale
demonstration.
3.2.1 Data Requirements
Treatment effectiveness will be evaluated through examination of both groundwater and soil core
contaminant concentrations measured with distance from injection pre-, during-, and post-
treatment with permanganate. Groundwater samples will be collected from a monitoring
network with radial distance from oxidant delivery and at several depths. Continuous soil core
samples will be collected from points adjacent to and corresponding with groundwater samples.
Post-treatment data will be compared to pre- and during-treatment data for both the test (oxidant
+ polymer) and control (oxidant only) plots to determine if the addition of polymer impacted
treatment effectiveness.
3.2.2 Success Criteria
The objective will be considered to be met if there is a statistically significant lower total mass of
contaminant is measured in soil and groundwater in the polymer + oxidant test plot vs. the
oxidant-only control plot. The criteria will not be considered met if both the test and control
plots show either(1) no statistically significant difference in post-treatment concentrations, or(2)
no measurable contaminant concentrations in either plot. While the latter of these two does not
point to an unsuccessful demonstration, it would not be possible to attribute success to polymer
application, therefore other performance criteria would be relied upon to evaluate demonstration
success.
3.3 PERFORMANCE OBJECTIVE: INCREASED PENETRATION OF PERMANGANATE INTO
LOWER PERMEABILITY LAYERS/STRATA
One means by which polymers are anticipated to improve permanganate delivery is to control
fluid mobility and normalize the advance of injected fluids within media of varying permeability
via modification of fluid viscosity. This impact, because of permanganate's purple coloring, is
expected to be both observable upon inspection of soil cores and potentially measurable in
groundwater if it is feasible to position multi-level monitoring well points within strata of
varying permeability.. At the bulk scale, this normalization of flow is expected to translate to an
overall enhanced sweep efficiency (increased percentage of pore volume contacted by oxidant
solution) of the treatment area.
20

3.3.1 Data Requirements
Oxidant penetration and sweep efficiency will be evaluated through examination of both
groundwater samples and soil cores. If monitoring wells can be screened over discrete intervals
of media permeability (feasibility unknown until site characterization activities are complete),
then permanganate concentrations in groundwater will be examined with distance and time, with
particular attention to concentrations measured in the target lower permeability strata. It is
anticipated that oxidant concentrations will be greater in the lower permeability strata in the
oxidant + polymer test plot vs. the oxidant-only control plot during both short-term and longer-
term monitoring timeframes. Groundwater monitoring data will also be used to assess oxidant
sweep efficiency. Permanganate concentration data from all available soil and groundwater
samples collected will be used to prepare vertical concentration distribution profiles for sweep-
efficiency analysis. Vertical sweep-efficiency will then be determined as the integrated profile
area contacted by permanganate divided by the total area of the profile generated. Sweep-
efficiencies calculated for the no-polymer case and the polymer amended cases will be compared
to determine permanganate sweep-efficiency improvement. A real-time monitoring program for
specific conductivity and oxidation reduction potential (ORP) will be implemented using
downhole sensors and data loggers within the permeable and LPM materials to observe
permanganate distribution. This data will be used to optimize the delivery timeframe. A
membrane interface probe — electrical conductivity (MIP-EC) survey will be conducted after
delivery is complete to ascertain permanganate distribution based on EC response. After
distribution is confirmed, then groundwater samples will be collected from a monitoring network
with radial distance from oxidant delivery and at several depths. Continuous soil core samples
will also be collected from points adjacent to and corresponding with groundwater samples.
Post-treatment data will be compared to pre- and during-treatment data for both the test (oxidant
+ polymer) and control (oxidant only) plots to determine if the addition of polymer impacted
oxidant penetration and sweep efficiency.
3.3.2 Success Criteria
The objective will be considered to be met if all of the criteria listed below that can be measured
are met. It is important to consider that these factors are qualitative indicators (i.e., surrogates)
of success and are actually measures of delivery and reaction longevity.
• Oxidant permeates lower permeability media strata/layers 50% greater in the oxidant +
polymer test plot vs. the oxidant-only control plot in a statistically relevant portion of
samples/layers collected/observed.
• Oxidant concentrations are 25% greater in a statistically relevant portion of groundwater
samples for the oxidant + polymer test plot vs. the oxidant-only control plot (again, this
criterion may not be relevant if media cannot be discretely screened).
• Observable improvement in oxidant penetration into lower permeability strata/layers for
the oxidant+polymer case vs. the no-polymer case.
• Observable sweep-efficiency improvement for the oxidant + polymer test plot vs. the
oxidant-only control plot as defined in Section 4.3.1.
21

3.4 PERFORMANCE OBJECTIVE: DECREASED FLOW BYPASSING OF AREAS OF HIGH
CONTAMINANT MASS
Another means by which polymers are anticipated to improve permanganate delivery is to
mitigate the effects Mn02 (permanganate oxidation byproduct) can have on permanganate
distribution. Negative impacts are due to deposition of Mn02, filling soil pores and causing flow
bypass. These effects can be mitigated by the addition of polymer that will impact particle-
particle and particle-soil surface interactions, inhibiting their deposition. The effect is most
pronounced in areas of high contaminant saturation, simply because of the excess Mn02 that can
be generated within these areas. The impact of polymer, because of permanganate's purple
coloring and Mn02's dark brown coloring, along with Mn02's contribution to solids
concentrations in groundwater, is expected to be observable upon inspection of soil cores and
measurable in groundwater.
3.4.1 Data Requirements
Oxidant penetration and sweep efficiency will be evaluated through examination of both
groundwater samples and soil cores. Soil cores will be visually inspected for the dark brown
Mn02 signature, particularly in areas of high contaminant saturation. Cores will also be
quantitatively extracted for Mn02. Contaminant will also be extracted from the core to assess
impact on mass treated. Additionally, Mn02 will be measured in groundwater samples both in
terms of total solids/suspended solids evidence and more directly via spectrophotometric
measurement. Continuous soil core samples will be collected from points adjacent to and
corresponding with groundwater samples.
Post-treatment data will be compared to pre-treatment data for both the test (oxidant + polymer)
and control (oxidant only) plots to determine if the addition of polymer impacted Mn02
deposition.
3.4.2 Success Criteria
The objective will be considered to be met if all of the following criteria are met:
• Soil cores have 50% lower mass of Mn02 per mass of media in the oxidant + polymer
test plot vs. the oxidant-only control plot in a statistically relevant portion of samples.
• Mn02 concentrations in groundwater are 25% greater (i.e., more mobile) in the oxidant+
polymer test plot vs. the oxidant-only control plot in a statistically relevant portion of
samples.
• Contaminant mass, where initially present at relatively high saturation, is 50% lower in
the oxidant +polymer test plot vs. the oxidant-only control plot in a statistically relevant
portion of samples.
3.5 PERFORMANCE OBJECTIVE: DECREASE IMPACT OF MN02 DEPOSITION ON INJECTION
PRESSURES
During subsurface treatment with permanganate, Mn02 deposits can potentially impact the
injectivity of the solution as a result of a reduction in media permeability (i.e., a reduction in
22

effective pore diameters due to Mn02 deposition). The degree to which this occurs is dependent
on soil surface chemical properties and the intrinsic permeability of the media. This process can
result in an increase in injection pressures needed to maintain design injection flow rates. The
proposed polymer for Mn02 deposition control is hexametaphosphate (HMP) which does not
increase solution viscosities as would the proposed heterogeneity control polymer xanthan gum.
If Mn02 deposition at our test site is sufficient to demonstrate an increase in injection pressures
for the control plot (no-polymer case), the addition of HMP is expected to mitigate this pressure
increase within the test plot (oxidant + HMP case). In both cases pressures at the injection wells
and subsurface pressures at distance from the injection wells will be monitored to assess the
potential for permeability reduction and the potential for HMP to mitigate permeability
reduction. The utility of these measurements will be determined following the proposed site
characterization activities.
3.5.1 Data Requirements
Field subsurface and injection pressures will be monitored before, during, and after treatment
within the control plot (oxidant-only) and test plots (oxidant + polymer). These results will be
compared to assess the potential for HMP to mitigate reduction in media permeability due to
Mn02 deposition effects as described.
3.5.2 Success Criteria
The objective will be considered to be met if site conditions are favorable in that there is a
discernable difference in injection pressures due to Mn02 deposition during treatment between
the control plot and the test plot.
3.6 PERFORMANCE OBJECTIVE: IMPROVED UNDERSTANDING OF IMPACTS OF THE
ENHANCED DELIVERY APPROACH ON GROUNDWATER QUALITY
Because the use of polymers with oxidant has not been evaluated in the field, it would be
generally beneficial to improve the understanding of potential effects of polymer addition on
groundwater quality.
3.6.1 Data Requirements
With both distance and time, the following indicators will be evaluated in soil and/or
groundwater: pH, ORP, key metals, solids concentrations, conductivity, and bioactivity.
3.6.2 Success Criteria
The objective will be considered met upon completion of all sampling rounds and data analysis.
23

4.0 Site Description
4.1 SITE SELECTION
Marine Corps Base Camp Lejeune (MCB CamLej), Operable Unit (OU) 15, Site 88 was selected
for the technology demonstration because it best fulfilled the preferred technical criteria,
including chloroethene concentration, depth to groundwater, minimum interference, utility
access, bulk hydraulic conductivity, and heterogeneous lithology. Selection of Site 88 for the
technology demonstration is detailed in the Site Selection Memorandum, provided in Appendix
A.
4.2 SITE LOCATION AND HISTORY
The test area is located at MCB CamLej in Jacksonville, North Carolina. MCB CamLej covers
approximately 236 square miles and is a training base for the United States Marine Corps. The
test area is located within OU 15, Site 88, which consists of the former Base Dry Cleaning
facility (former Building 25), located approximately 500 feet east of the intersection of Post Lane
Road and McHugh Boulevard(Figure 4-1). The test area is located within and immediately west
of the footprint of the former Building 25 (Figure 4-2).
Former Building 25 operated as a dry cleaning facility from the 1940s until 2004 when
operations ceased and the building was demolished. Five 750-gallon underground storage tanks
(USTs) were installed on the north side of the building to store dry cleaning fluids. Initially,
VarsolTM, a petroleum hydrocarbon-based stoddard solvent, was used in dry cleaning operations
at Building 25. Due to flammability concerns, Varsol's use was discontinued in the 1970s and
was replaced with tetrachloroethene (PCE). PCE was stored in a 150-gallon aboveground storage
tank (AST) adjacent to the north wall of Building 25, in the same vicinity as the USTs. PCE was
reportedly stored in the AST from the 1970s until the mid-1990s. Facility employees have
reported that during this time, spent PCE was disposed of in floor drains that discharged into the
sanitary sewer system on the north side of the building (Figure 4-2).
In December 1986 and again in March 1995, self-contained dry cleaning machines were installed
in Building 25, eliminating the need for bulk storage of PCE. The USTs and AST were removed
in November 1995.
During removal of the USTs and ASTs, chlorinated volatile organic compounds (VOCs) were
detected in soil and groundwater samples. Subsequent investigations conducted in 1996 and
1997 identified subsurface soil contamination under and near Building 25, and along a line of
borings paralleling the underground sanitary sewer line north of Building 25, which was
attributed to the leakage of solvent-contaminated wastewater (Baker, 1998a). Groundwater
analytical results identified wide-spread chlorinated solvent contamination (PCE, trichloroethene
[TCE], and cis-1,2-dichloroethene [cis-1,2-DCE]), which had impacted the Surficial Aquifer
(less than 25 ft below ground surface [bgs]) and the upper portion of the Castle Hayne Aquifer
(25-80 ft bgs). A distinct contaminant plume was identified, which suggested Building 25 was
the source area. The results also suggested the presence of a dense non-aqueous phase liquid
(DNAPL) in this area.
24

Y'.lA#s=ec .awf eeumL Jc FB.ESCP FYtl�m- �rca la.t4-nnv�
i
Ihst.VLN
In MV _•N�I vAV
mm
�t,:t,>s'+'- m . ..-. .iM�� w M'gv�iN�,4���\ - +wir � � •
WWI-
R4� rt _ F-MN.PN �. e / r -♦
ti FasMNae
�.._ P_YNn
47(�e�J(3TN t ` Q / 1 NV.iGN
n1Q4� � Nt t 9 Mw>;y IFe.MW lv`S Ias�MN
r�
rl Itt 1 r ,,,77Y In s1AY ^` 9
s
fTt r� '007rrN� in,s wiierN
•1 I-=_MN rNA la w 1.W 3i Fl W,-aw j - .`.r IftB6MN Jl 1
4O rILR MY.MV. �� J I♦(4 41
t�`�' 4
�� �. t �t V IA MN e�..W TRg-1rw s.i�" •\fin Vl�`Y'.�-� 1r �_
weaMw�!N Test Area
k iassvr M
Mh NVI'F __YN:bNIRaa' =SN 11�tLg. tZ ♦ '�R..,;
T • F MN r �y
r MN IN s�+�£� - _,�6 r1 -•OW Inca MNio1Y IR NSPV' •,y r r J
Stems +rr'- •4�� t .- Y M A
w \ ILp C
Legend Figure 4-1
e Shallow Monitoring Well Location Test Area Location
Intermediate Monitoring Well Location MCB CamLej
3 De Monitoring Well Location a Too _ North Carolina
ep
9 Very Dew Monitoring Well Location
Surface Water Centerline
C!Test Area 1 itch=200 feet
Site Ba Boundary '10
Figure 4-1. Test area at MCB CamLej,North Carolina, OU 15, Site 88
25

'VYIPS, �YIPu .j��' �.i
l r •_ ���.
11 `1 .Yla,s R6MYmeN
.Yx_,. anwmM
YlR-Wr
SlN YP i MP". • m 11M� !
` 1• n
tjrRD, YIB4YYn y, K.MIG_-ti}rPID'� -
• a16�/301N _
to
JII r it!' YIYPs� ylPl•
IiM
f 1 �
lk
1 IN, w `
1 OPrM rii-XYJ Yi
�X rMn
Catch Bain I .a rvit
. mWnIft
t`. lire 1�• o- !
� _ QIResNVR /
y: IRISYwaSITY �� - r \
�IRes YwasrN _ �
• .� •�Xee-YWOS l
fool
CIT
~, .• -IRBaYiIMIM�
legend Figure 4-2
• Slug Test Location • Shallow Monitonng Well Location Wastewater Utility Line Test Area Site Character¢ation
DPT Location 8 Intermediate Monitoring Well Location—Approximate location of wastewater line from Building 25 N MCB CamLej
• HRP Location o Deep Monitonng Well Location Surface Water Centerline o 1815 37.5 75 North Carolina
• MIP Location ---Steam Line p Potential Treatment Areas Feet
C PT,-MIP Locations —Storm Saver Utility Lune L]Sod Aifoiig Boundary
Htstoncal Sample Locations Electrical Utility Line O Former Building 25 1 inch=37.5 feet
--Water Utility Line Site as Boundary CX3MNILL
Figure 4-2. Closer view of test area located within and immediately west of the footprint of the former Building 25.
26

In 2005, shallow soil mixing with clay and zero valent iron (ZVI) was implemented at Site 88 in
the vicinity of former Building 25, as shown on Figures 4-2 and 4-3, to contain and treat the
DNAPL source area. Approximately 7,050 cubic yards of impacted soil was treated. Within the
soil mixing zone, PCE concentrations in the soil were reduced by greater than 99 percent.
Despite the significant source area mass flux reduction, residual groundwater contamination
remains over a large portion of the surrounding and downgradient areas.
Additional investigation and remediation activities conducted at Site 88 include:
• Free Phase DNAPL Recovery, 1998: Conducted north of Building 25
• Partitioning Inter-well Tracer Test(PITT), 1998: Conducted adjacent to the north wall of Bldg. 25
• Surfactant-Enhanced Aquifer Remediation (SEAR), 1998-1999: Conducted adjacent to the north
wall of Building 25
• Reductive Anaerobic In-Situ Treatment Technology (RABITT), 2001: Conducted at monitoring
wells IR88-MW05 and IR88-MW051W, approximately 200 ft northwest of the test area
Site 88 is currently in the remedial investigation (RI)/feasibility study (FS) phase of the
CERCLA process. A pilot study is planned for the summer of 2010 to evaluate in-situ chemical
oxidation (ISCO) and enhanced reductive dechlorination (ERD) in the downgradient plume
(approximately 400 feet downgradient of the test area). The test area, located within the source
zone, will not be affected by on-going site activities.
4.3 SITE GEOLOGY AND HYDROGEOLOGY
4.3.1 Geology
Southeastern North Carolina and MCB CamLej are within the Tidewater region of the Atlantic
Coastal Plain physiographic province. The MCB CamLej area is underlain by a westward
(inland) thinning wedge of marine and non-marine sediments ranging in age from early
Cretaceous to Holocene. Along the coastline, several thousands of feet of interlayered,
unconsolidated sediment are present, consisting of gravel, sand, silt, clay deposits, calcareous
clays, shell beds, sandstone and limestone that was deposited over pre-Cretaceous crystalline
basement rock.
Site 88 is underlain by a thick sequence of coastal plain soils consisting of unconsolidated sands,
silts, clays, and partially indurated shelly sands. Soils within the Surficial Aquifer are generally
comprised of silty sands, ranging in thickness from 20 to 30 feet, which overlie a discontinuous
layer of clayey silt or clay approximately 20 ft bgs. A clayey silt and clay confining layer,
ranging in thickness from 4 to 10 feet, underlies the former location of Building 25 at a depth of
approximately 20 ft bgs and extends westward as far as Building 3, whereupon it pinches out and
is not encountered again until the 88MW-15 well cluster (Figure 4-1). Within the Castle Hayne
Aquifer, a fine grained layer overlies massive beds of fine to medium grained sand with sporadic
zones of partial cementation and shell fragments extending to a depth of roughly 180 feet bgs.
At Site 88, the Castle Hayne Aquifer is divided into the upper Castle Hayne (25-80 feet), the
middle Castle Hayne (80-130 feet), and the lower Castle Hayne (130-180 feet). A plastic clay
layer, known as the Beaufort confining unit, was encountered beneath the Castle Hayne Aquifer;
the Beaufort confining unit defines the vertical limit of subsurface investigation at Site 88.
27

NP15,
�
a��eI 11�5� m fW 125 �r ••j 02 - `.
..R�v • \\\ 57
I
113 � 1 � � � 133 1' 103
3E fbta ta1Y,9ar„
134
2. �.
25 .?. .. 1
1„ DNAPC
I Back aflusun
e �
mA
Legend
sdi 6aing ivea hAmnledule PCE Contour = Pomde water Main
rroworaoer Flae LYreubn ,S1alOatl:"y94 atn:eamrOnnage ryclem FF 43
�.a7ygL :7. 192 Ter A,D :n:ep.�a ai'=_%1—
p>70 4L 77.00c PgL —Consal0.lea Waiewa�r
r._ah cr ru
mnsmo+aun gn«ausltel4ardear OIS10a
Figure 4-3. Test area conceptual site model
28

The general geologic setting in the vicinity of the test area is presented on Figure 4-4. The
lithology in the test area was further investigated during site characterization activities conducted
in Nov and Dec 2009. Cone penetrometer testing (CPT) was conducted at locations M2, M4, M5
and M6, shown on Figure 4-2, to delineate stratigraphic layers in the subsurface. High-resolution
piezocone (HRP) profiling was conducted at location HI to obtain detailed lithologic and
hydraulic information. Example HRP results are provided in Figure 4-5. Additionally, a
continuous soil core was collected from 10 to 50 ft bgs via direct push technology (DPT) at soil
boring location DPTO1, as shown on Figure 4-2. The boring log for DPTOI is provided in
Figure 4-6.
The data collected during site characterization indicates alternating fine grained silty sand and
sand to approximately 20 ft bgs in the vicinity of the test area. Soil particle size analysis has
been completed for this shallower area. These data are included as Figure 4-7. The fine grained
sediments are underlain by a more dense silty clay and clay layer approximately 7 to 12 feet
thick to a depth of approximately 30 ft bgs. Below this unit are alternating layers of silty sand
and sand. The sands become more dominate with depth and fewer fines are present, generally
between 40 to 60 ft bgs. The boring log for deep monitoring well 88-MW02DW, located
adjacent to the test area, indicates that fine grained silty sand is again present between 60 to 88 ft
bgs, which is underlain by a layer of partially cemented sand and shells exists from 88 to 90 ft. A
geologic cross-section within the vicinity of the test area based on site characterization activities
is presented in Figure 4-8.
4.3.2 Hydrogeology
The hydrogeologic setting at Site 88 is that of a two aquifer system, the Surficial Aquifer and the
Castle Hayne Aquifer, with the two aquifers typically separated by a low permeability clayey silt
aquitard(Duke, 1999). This low permeability unit is present under former Building 25 within the
test area, and, as noted above, is discontinuous to the west of former Building 25.
In November 2009, depth-to-water measurements were taken across Site 88. In the vicinity of the
test area, the water table was found to occur from 7.25 to 10.10 ft bgs. The depth to water in
monitoring wells screened within the Upper Castle Hayne Aquifer in the vicinity of the test area,
ranged from 14.46 to 15.62 ft bgs.
Figure 4-9 shows the potentiometric surface of the Surficial Aquifer measured in November
2009, as represented by the shallow monitoring wells (less than 25 ft bgs). Figure 4-9 shows a
highly variable water table surface, which is likely due in part to the heterogeneous nature of the
shallow sediments, and also the anthropogenic effects relating to the soil mixing activities. The
soil mixing involved addition of a mixture of zero-valent iron and bentonite clay that
significantly reduced the hydraulic conductivity of the mixed soil. Shallow groundwater flow in
the test area is to the southwest, with a horizontal hydraulic gradient of approximately 0.002 ft/ft.
A downward vertical hydraulic gradient of approximately 0.25 ft/ft between the Surficial Aquifer
and the Upper Castle Hayne Aquifer in the test area was calculated, based on the November
2009 depth-to-water measurements collected in the IR88-MWO2 cluster.
29

YY North—South
40
# b 5� 7 40
Surftcial ter
20 20 Notes:
TICECE�ti PM 12.tM t.Tile depth aid 1111" ss Oi the slnGW"
PCE m.i :<li TM Md strata MOIrated on Ills section(prorlleI were
TCE m.L .aeE:tM .acE:H ood neiraCPorn and Inte aled oetY en
.4)M m d t
.[ VC:Hi VC:O,0
VC:m test locations Infonitatlon onacWa
PCE:m.L slnslcrace conditions apples only to the
Silt TCE:m.t specnc baton and dates ndcated.
o-CE:m.f fazsurrace Oondwris and water lels at
0 VC:m.L 0 other locations may MW thorn conditions
occurring a the Indicated W-adon_
PC@ mM Upper Castle 2.AnayCcal resuts are ftht the August 200;
p^ )M AM HaY1C pqudx rerreaa Meedgatlon.
re:aML
3.COIKONefil ConCernra10f16 Af
rcE;aM PCE m.[ tetracttrdretlele(PCE),
-20 PCE:0-MJ rcE IMJ TCE m.s -20 ifIUlgldedleYle fTCE�
PCE:q.L TCE 0 0. e-0CE:QM i-oCE:Q6 J d61.2-0 e crlorowne c-DCEI.
Toe,2.1 WOCE:t m m.L VC:QM VC:m.c ( .
aace:.M V .c J and Ary ctYortde NC i are presented In ug'L
vc<as
d..,-Reporle0 taus Is eLvnated-
40 40
foaifow2 Svd
PCE:
PVCCE:m m.Ls PVCCE:m 1.6 TCE 1.2
T m6 1
&0 1.6 J
aCE id 3.6 Vcm6
w&.1:1:=121Y•=
Cene-aW_W PCE-•sc _ VE=10,
TCE�z-c
> E 2L
Sold ❑C�
=2•JloL 3stl
�v_•trCl 9!"d
100 -100
a'O[C1[r IRnM
P'CE M zM Figure 4i
120 rcE:M 120 ,r v a.T>ere sr•,� Test Area Ged ogic Cross Seurat
Hd
Mx:�13 rats CamLry
El NaAI Carolina
p 200 400 000 800 106 1200 1400 CWLWM1LL
Distance in Feet
EFY193W13•PIE Fyr H Jk_Y�S�I 013.•:9s
Figure 4-4. General geologic setting in vicinity of test area
30

= IRECT H-1A
SENSING
Site 88 H-IA Final Site 88 HAA Final Site 88 HAA Final Site 88 H-1A Final Site 88 H-1A Final
Soil Class(load cell) K(Robertson) K(Parez 8 Fauriel) Porosity 2000
a v a i Disslpabon 14:45 11112I2009
J
C O O O O O O O 0 0 0 1 1 1
°' �,m 2,'m>✓ c—a' C E A ti b ti d o 0 0 o i ti ti w d d+ o 0 0 m o r ,n o .n .o 1600 - --�---'J - - -----'-----'---'}-
O U N U N N N N 2 1A t> — — 0 0 0 O — — 0 0 0 0 N N p p N J
I , I 1 1 42.421<.
0'_r--r—fir'-f—r—r—•r—' 0�
1400 I , _
I I I I I 1 , I ! I I I I 1 I I I I 1 1■ 1 I I I 1 1200 ' 1
I
1000 1 ---J-----1----I-
I L_ ---_-• ---
I 1 I I 1 I I I 1 I I 1 1 1 I 1 I I 1 1 1 1 I I -- - -
I I I I 1 1 -1-_ I 1 I I 1 1 1 I 1 I I 1 1 1 , I 1 1 .� ■ I I
10 -I-i'i i-r-i'1 I 10 -'I---l-i-l'- 10 -r-i-i-i I■-I-,'�- 10 -i-i-i-I- i-l-
, I I I I 1 1 I I I I I I 1 I 1 I 1 I I I 1 1 I I 1 � I I I I
I 1 1 1 I I I t I 11 , I 11 I I r t 1 I 11 1 1 600 --"1'T=-=-r ■
I I I I I I I I 1 1 1 I 1 I■I 1 1 1 I 1 I I 1 I 1
I , I I I I I I 1 1 1 I 1 ■ I 1 � , 1 I 1 I 1 • ��_� I ,
I I 1 I I I I I 1 I I I I 1 400
, I , r i l l ■ I I 1 1 11 1 1 i I
20 J_ _ _ J_L!__ 20 _J_J_J_J__ 20■ -_1__I__'_J_J_J_J__ 20 t._I _J_ 1_ ;_J_J__
I I1I 1I, IIII IIII 111I ,11I 1I,, I,II II ,II ,II, 1I III II1I 1, ■■ 11, ,II1 ,11I IIII ,III 111 111 11I t 1 I I1 II ,1150_000 ¢
200 150 300
T50:0-65sesto508-000(@ 717.006 psi)Pressure(psi)vs.Time(secs)
I I I I 1 1 1 I I I I I I I I • I I I I I 1 t 1 1 I I 1
I I 1 I I I I 1 I ■ I I 1 I I 1 1■ 1 I 1 1 I I I I Site 88 H4A Final
' 30
[i■■• 111r 1111I11IIII IIIlIII1II1 IIl11111111 ■�IlIII1 IIlI11i `1ri1 t1IIr�■.■
30
Y _sM_J111II reJ IIIIIII s_u-reJ
I1I
-_
--
34217.
■I 32 3 .643
34
3 --"---6 1 1
341
40 40 40 40 40 __L__1__
ft.
I ,
I 1 I , I , , I I , I I 1 1 I 1 1 I 1 • 1 I I I I , I _1 I 1 , , I , I
42 -'---'---'---
1 I I I I I I , I I I I I 1 1 1 I I I 1 ■ , , I I I 1 1 I I 1 1 44 ---r--i--------�--1--1- -1---1---
50 50 -'--'----'--1- -'+-+-- 50 -�'I--1--1'-'- - 50 46 I i i -i--i---i-- 1 ---
1 1 I 1 I I I 1 I I 1 I I 1 1 1 I 1 I I 1 1 1
--r----------
I I I 1 I I I 1 I I 1 I I I 1 1 I 1 I I I 1 1 I 1 1 I 1 1 I I I, I
'4e -
1
1 I I I I 1 1 1 I I I I 1 1 1 i i i 59
450 550 650 750 850 950
500 600 700 800 900
pore pressure ' ' estlma116DBS.20.03 ft. Hydrostatic:739.54 psi. Water Table:-20.03 R. Sloe 0.030 Correlation:9,
50 80 80 80 P P :
soil Class vs.it. cmisec vs ft, cmisec vs.ft. Porosity(%)vs ft. Depth(feet)vs.Final Pressure(psi)
Figure 4-5. Example HRP results
31

40 C1-12MHILL Boring Number: DPT-01 Sheet: 1 of
AW
Driller:Drill Pro
Client: Clarkson University Drilling Method:DPT
Project: ESTCP Sampling Method:macro-core
Location: Site 88. MCB Camp Lejeune Logged by:B.Propst
Project Number: StarLtFinish Date: 11-12-09
Sample Information
a F Soil Description Comments
s .2 m
E c a c
OvZ rr Cn Ui
Ground Sur'ace
Sittr Sand(SM)
Brown,dry loose,fine grained
HA 100
No saniple ooSecled
Sand(SP)
~, TanAxvm,wet,loose.fine grained
DP-1 DP 100 4.�' Sand(SP)
x: Cray wet,loose ne grained
15
DP-2 DP 100
W.
20 Silty Sand(SM)
Light brown,wet,loose fine grained
DP-3 DP 100
Sandy Clay(CL)
!<. Lght brown,wet.sort fine grained
` Clay(CH)
Light gray.high piastoty,soft to rr E-c,-n stff
DP-A DP 100
Sandy Clay(CL)
B•own,wet,stiP
Figure 4-6. Boring Log for DPTO1
32

CN2MHILL Boring Number: DPT-01 Sheet:2of2
Driller:Drill Pro
Client:Clarkson University Drilling Method:DPT
Project: ESTCP Sampling Method:macro-core
Location:Site 88,MCB Camp Lejeune Logged by:B.Propst
Project Number: StarLtFinish Date: 11-12-09
Sample Information
E a F Soil Description Comments
E E
Sand(SP)
Lght gray,wet,medium dense,fine grained
Silty Sand(SM)
DP-5 DP 1 DO Brown,wet,medium dense,fine grained
35
Silly Sand(SM1
Gray,wet,loose to medium dense,fine grained
DP-8 DP 1DO
Sand(SP)
Otnre gray,wet,loose to medium dense,fine
grained
DP-7 DP 1 DO
Fi
Sand(SP)
Gray,wet,loose,medium grained
DP-8 DP 1O0 ;
:i
x:
-- Terminate boring at 54"bgs
Figure 4-6. Boring log for DPTO1 (cont'd)
33

Particle Size Distribution Report
Project: Soil Laboratory Testing Report No.: CT2989SL-01-01-10
Client: Date: 1/29/10
Sample No: CT2989S 1 Source of Sample: Not Specified
Location: -- Elev./Depth:
s
100
90 I I I
I I 1 I 1 1 1 I I 1 I I I I
80 I I I 1 1
1 1 1 I 1 1 1 1 1 I I I I I
70 I 1 I I I I I I
Z I I I I I 1 1 I 1 1 I I I I
1 1 1 I I 1 1 I 1 1 I I I I
I 1 1 I I 1 I I 1 I I I I
Q so
1 1 I I 1 1 1 I 1 I I I 1
a I I I I I 1 1 I 1 I I I 1
1 I 1 I I 1 1 1 1 I I I 1
50 1 1 1 I 1 1 1 I I I I I 1
Z I 1 1 I 1 1 1 1 I I I I I 1
ll.l 1 I I I I 1 I 1 1 I I I I 1
U40 I 1 I I 1 1 1 1 I I 1 I I 1
LL I I 1 1 1 I I I I I
W 30 i i i 1 i i i
0_
1 1 I 1 I I 1 1 I I I I
20 1 1 I I 1 I 1 I I I 1 I
I I I I I I I 1 I I 1 I I I
10
I 1 I I I I I I I I I I 1
O I 1 1 I I I I I I 1 I
500 100 10 1 0.1 0.01 0.001
GRAIN SIZE-mm
%COBBLES %GRAVEL %SAND %FINES
CRS. FINE CRS. MEDIUM FINE SILT CLAY
0 0 0 0 1 78 14 7
SIEVE PERCENT SPEC! OUT OF Soil Description
SIZE FINER PERCENT SPEC.(X) Brown mf+SAND;little SILT;trace CLAY
#4 100
#10 100
#20 100
#40 99 Atterbern Limits
#80 78 PL= -- LL= -- PI= --
#140 30
#200 21 Coefficients
D85= 0.221 D60= 0.152 D50= 0.137
D30= 0.106 D15= 0.0316 D10= 0.0131
Cu= 11.55 Cc= 5.63
Classification
USCS= SM AASHTO=
Remarks
Sample delivered by B.Klock on 1/26/10.
R (no specification provided)
ATLANTIC TESTING LABORATORIES,LIMITED
Reviewed by: Dater f
Figure 4-7. Grain size analysis for surficial aquifer media.
34

Legend
Green Plume----PI Response Above 500,000 uV
White Boxes-----Target Treatment Areas
a
Light Blue Line Water Table
JBlue Arrow- Groundwater Flow Direction
Red Line Test Area Cross Section
rw w
A a A
f f
ZO
Lithology
-- 71-
1D -^ -r- - - - -- ---------- M+rrrrr�rr eocw�- ----- --- Silty Sand
Sand
Silty Clay
� 0
W � T
4 ECD
w -10 -------------- -- --------- ---- ------ 10,000,000 uV
5,000.000 uV
- 2,000,000 uV
-30 1.000,000 u`✓
500.000 uV
Z Scale 1:1
Section A-A'
Figure 4-5
Test Area Geologic Cross Section and MIP Results
MCB CamLej
North Carolina
Figure 4-8. Geologic cross-section within the test area based on most recent characterization activities
35

f
V w r
It
�ry:e�� n '"-
m
,s T, • i + 'ir3`k c- -iilRsa �tJ,,• r—Ojv
qk
'jA l :Syr RUBfor - �,y< t ,\► .+ y "1AeaArvy1'�: �"
cent rf� �*" t - � u �► � t`� - � f. � �
IRs.AfOlw
At WL
� -. ,. � M,.VFr s� � r i l�Ji�F•��
Ito< � '1'tlFa a f•I SPEE, `/ 7 rw'� R M1 • � � k ,. l e� t L
K'�•vf! ti,
1 t
Legend Figure 4-6
e Shallow Monitoring Well Location Potentiometric Map
Shallow Aquifer PotentionnetricContour NIL Not Located — SufiaalAquifer
--Shallow Aquifer Potentiometric Contour(inferred) MCg CarnLej
♦Groundwater Flow Direction
— Faet North Carolina
Surface Water Centerline
Site 88 Boundary O Test Area 1 Inch_-200 feet
Soil Mixing Boundary
Cream or.aooxe ProMPOLJ Che&,tl t1y:Ken HarbwgraT
Figure 4-9. Potentiometric map of the Surficial Aquifer
36

Figure 4-10 shows the potentiometric surface of the Upper Castle Hayne Aquifer in November
2009, as represented by the intermediate zone wells (45 to 55 ft bgs). The groundwater flow
pattern for this aquifer is less complex than that of the Surficial Aquifer, with groundwater flow
generally to the west, with an approximate horizontal hydraulic gradient in the vicinity of the test
area of 0.0004 ft/ft. A downward vertical gradient of 0.0015 ft/ft between the Upper Castle
Hayne and Middle Castle Hayne Aquifers within the test area was calculated, based on the
November 2009 depth-to-water measurements collected in the IR88-MW02 cluster.
Aquifer testing was conducted during site characterization activities in November and December
2009. A pneumatic slug test method was employed through DPT-installed steel rod piezometers
at three locations across the test area, ST-1, ST-2, ST-3, shown on Figure 4-2. A groundwater
sampler equipped with a screen was pushed using DT to the terminating depth of the testing
interval. The drill rods were then pulled up to expose two feet of the screen and conduct the slug
test.
Hydraulic conductivity was calculated using the Hvorslev method. The hydraulic conductivity
values calculated at each slug test location are summarized in Table 4-1. The hydraulic
conductivity in the Surficial Aquifer ranged from 1.5 ft/day to 5.2 ft/day, with an average
hydraulic conductivity of 2.8 ft/day. The hydraulic conductivity in the Upper Castle Hayne
Aquifer just below the confining unit ranged from 0.9 ft/day to 4.9 ft/day, with an average
hydraulic conductivity of 2.5 ft/day.
As previously mentioned, HRP profiling was conducted at location HI to obtain detailed
hydraulic information. HRP technology involves the advancement of a probe that continuously
logs pore pressure (measured as hydraulic head) and periodically logs pore pressure dissipation
during stoppage time. The data are then electronically processed and used to estimate vertical
gradients, soil type, and hydraulic conductivity. HRP conductivity values generally ranging from
1 x 10-5 centimeters per second (cm/s) (0.03 ft/day) to 0.001 cm/s (3 ft/day) in the Surficial
Aquifer. In the Upper Castle Hayne Aquifer, HRP conductivity values were generally higher,
ranging from 1 x 10-4 cm/s (0.3 ft/day)to 0.01 cm/s (30 ft/day).
37

r
IY 7,
s .
�YrrN
�:_tt t' iT ,+K +./• 'fit a ` ''� iRasw/',�nv a •', �.
.0 Its t 1'_.� '�. .• HP,:S s .nb'%� a'%'Q.aaiV"" I -. Mx�e1x z .... �' � .,.r 'yy __ ��:'
FA
t '7 tIS�Realf/d3xrA - :�' PB&1IA� �� , 1
Its t ,• r'9•Af
NL�L�J�ly l v. itxf
•. Y
40
IL
s. r�'� � _ � • R, IQ�Ia�,t a '^ 15 H� , �' 1
legend Figure 4-7
d Monitoring Weil NM=Not Measured Potentiometric Map
—Intermediate Aquifer Poteneometric Contour NIL=Nol Located N' Upper Castle Hayne Aquifer(40-50 it bgs)
Intermediate Aquifer PotentiomeMc Contour(inferred) 100 -0 4w MCB Camt-ej
Fl♦Groundwater ow Direction
—Surface Water Centedine FogNorth Carolina
Site 88 Boundary Test Area 1 inch-200 feet
p Sod Mixing Boundary
�'e3te]br-&Odle PrgwVGT.TCrwOwc1 bV Ken Ha1&,g'aT
Figure 4-10. Potentiometric map of the Upper Castle Hayne Aquifer
38

Table 4-1. H draulic Conductivity Calculated at Each Slu Test Location
Location Interval Dept t gs Test Conductivity Results t ayAverage Conductivity t ay
1 4.9
33-35 2 4.8 4.6
3 4.2
1 2.6
ST-1 38-40 2 2.5 2.5
3 2.5
1 9.8
43-45 2 9.8 9.8
3 9.8
1 2.2
14-16 2 1.5 2.0
3 2.1
1 0.9
33-35 3 1.0 1.0
4 1.0
1 6.1
2 6.1
42-44 3 5.9 6.0
4 5.9
5 6.0
ST-2 1 10.7
47-49 3 100.7 10.9
4 11.0
1 8.7
2 8.7
54-56 4 9.1 9.0
5 9.2
6 9.2
1 2.3
61-63 3 2.4 2.8
2.8
4 3.7
14-16 2 5.2 4.0
2.33-35 2 1.5 1.5
1.4
1 16.6
45-47 2 16.4 17.0
ST-3 3 18.1
1 8.2
2 7.5
54-56 3 8.0 7.4
4 6.9
5 6.3
60-62 2 3.5 3.2
2.1 0.6
ST-4(offset from ST-1) 14-16 3 0.6 0.6
4 0.5
39

4.4 CONTAMINANT DISTRIBUTION
Based on the chemical data gathered for Site 88, former Building 25 is the source of the
chlorinated VOCs that are currently observed in the groundwater within the shallow,
intermediate, deep and very deep aquifer zones. The contaminants of concern (COCs) for Site 88
are PCE and its anaerobic biodegradation daughter products TCE, cis-1,2-DCE, and vinyl
chloride.
Data obtained from groundwater samples collected as part of the RI in August 2007, indicate the
maximum chlorinated VOC concentration within the shallow aquifer in the vicinity of former
Building 25 and the test area, was reported at well IR88-MW02 with PCE and cis-1,2-DCE
concentrations of 12,000 micrograms per liter (µg/L) and 13,000 µg/L respectively.
Concentrations in the source area decrease significantly with depth, as shown by the 88-MW02
cluster, on Figure 4-4. Figures 4-11 and 4-12 show the post-treatment distribution of PCE in
the Surficial and Upper Castle Hayne Aquifers across the test area and Site 88 (2007).
During site characterization activities conducted in November and December 2009, membrane
interface probe (MIP) profiling was conducted at six locations, M 1 through M6 shown on Figure
4-4, to delineate contaminant concentrations within the test area. Analytical results are shown on
Figure 4-8. MIP results indicate that the highest contaminant concentrations in the Surficial
Aquifer exist from 16 to 18 ft bgs at location Ml, immediately above an apparent confining unit.
MIP results in this area are indicative of DNAPL. Results suggest that contamination in the
shallow zone extends approximately 45 feet to the southeast towards location M2. MIP results
consistently indicate higher contaminant concentrations throughout the Upper Castle Hayne
Aquifer between 40 and 50 ft bgs at locations Ml, M2, and M3. Again, the highest contaminant
concentrations were detected at location M1 from approximately 33 to 35 ft bgs, immediately
below an apparent confining unit. In both the Surficial and Upper Castle Hayne Aquifers,
contaminant concentrations appear to decrease significantly to the west towards location M6.
Two groundwater and three soil samples were collected from soil boring DPTO L DPT soil
samples were obtained using a 5-foot long, 1.5-inch inner diameter (ID) acetate macro-core
sampler. As each borehole was advanced, continuous soil cores were collected and soil samples
were collected directly from the acetate liners. The groundwater samples were collected by
pushing the groundwater sampler equipped with a screen to the terminating depth of the
sampling interval. The drill rods were then pulled up to expose two feet of the screen. A
peristaltic pump was used to purge the groundwater and collect the groundwater sample.
DNAPL, which was dark in color, was observed in the groundwater sample collected in the
shallow interval (14-16), immediately above the confining unit. The DNAPL was collected and
submitted for laboratory analysis.
40

A'WIOXTe.PRWJJSN4YFACENODOW.CAM-LEJELIESMPFIE MITE BILES CP FIELD IN5TRUCTIpB.F 4 B x..i S�tW CWxrmG
CAW
Ifs
1
tf I713�gR � '
.�tU'e, err 0 .
.tit E�> C . na r-. ^mot . 1
♦ ;
ttY
r.,
tol
'r Y $W 040*
IPt25 R y:li1'w �..R•-1�' } 1,.'/r
nta ,r aae;wr,
t* v7 rT]
ge
<,16• vet t!•M \ ?��:M� .
JOi - ss
ie
1`\ '+y..><:•L*� tti - . r '�EEt ,.� Q F •, r
v _ ; y -"t s•�17• 1i�
' '�'" a-;, , ,� .tt��'E`' ems, '� •r _ g� , � �'
Legend Shallow PCE Contours Now --cncen*.raticn ccnours have been interpolated between Figure,
tb Shallav Monitoring Well Location NC2L Standard:0.7 pg L monitonng well locations.Actual concentrations may differ from Tetrachloroethe
Surface Water Centerline o> 0 Ng L those shown on this figure. Surficial A ui
70 pg L L 7
Site 88 Boundary > 7.000 o ,oo MCB C ml
I Test Area o> Ng > ply L .._-I North Caroli
Q Soil WIN Boundary
t inch - 200 feet
Figure 4-11. PCE concentrations in the Surficial Aquifer (2007)
41

'.'A MDDTFPRW.,)SNN' CEIACOMGIMRE-EUEURPFLEb14�W.-Et21=_C hS L)C-OhSF IM 4•i PCE L C-IG H ro A ub nc
131 ` r .'MP- -�t 0
1 ♦ .
�� _X,11t,,-��`�l Nw����1�!'•�c� — -• F �1� ',tcC ��' �.� �r�� • t ReaYN�_yVl
r„ #i
.• .R ` tee r
e saa
ON% a , r
ea 0 `s _
Pa_a 1Aw 11 1W
-r • e �Y .,r ` IRti_MN33Irl R WI1 SIM - •.'(�.
16
to
i:1Avj
14P125r d}�lkt+� . _' -
`•.4. '� J. Rae_22 oa1V�� Yet rA r f .
'� - - — IR1io-►rW,srW [ -x� FA&MwO21WJ
r, Rsa Mwmrw _�,yC" R -. ewo { --•.IR_a& 01
_ - 'y - L
..r, �fRwkfW2irW t IRB6Irl a11W1
o>
VSA
ES z3: GO
'-r.� Q
•C r 7
.1 jr It
rov,� t1.�, 1,1.MF�hRX . R, vyt �]!. � , e � ,s � { �1�.,` - •'^ -
Legend Intermediate PCE Contours Note:Concentration contours have been interpolated between Figure 4-9
Intermediate Monitoring Well Location NC21-Standard:0.7 pg't monitoring well locations.Actin concentrations may differ from Tetrachloroethene
Sudace Water Centerline o>0.7 pg L m>700 pg L those shown on this figure. NJ Upper Castle Hayne Aquifer
Site 88 Boundary p>70 pq L =>7,000 pg L 13oo ago aoo MCB CamLej
Test Area Feet North Carolina
f]Soil Mocing Boundary
1 inch=200 feet
40.
Figure 4-12. PCE concentrations in the Upper Castle Hayne Aquifer(2007)
42

Analytical results are summarized in Tables 4-2 and 4-3. PCE and cis-1,2-DCE were detected at
maximum concentrations of 7,100 micrograms per kilogram (µg/kg) and 10,000 µg/kg,
respectively, in the soil sample collected immediately above the confining unit. Below the
confining unit, PCE ranged from below the laboratory detection limit (720 µg/kg) to 1,300 µg/kg
and cis-1,2-DCE ranged from below the laboratory detection limit (5.2 µg/kg) to 22 µg/kg. PCE
was detected in the groundwater sample collected immediately above the confining unit(14-16 ft
bgs) at a concentration of 220,000 µg/L. Below the confining unit (33-35 ft bgs), PCE was
detected at a concentration of 230,000 µg/L. These groundwater concentrations are indicative of
DNAPL, which is consistent with observed site conditions described above and the results of the
MIP data collected from M1 adjacent to DPTOL Site characterization results for the test area
are summarized in Table 4-4.
Table 4-2. Analytical Results for Contaminants (GC-MS) in Soils
Sample ID DPT01-16-18 DPT01-33-35 DPT01-53-55
Sample Date 11/12/2009 11/12/2009 11/12/2009
Volatile Organic Compounds(µg/kg)
2-Butanone 49 14 U 10 U
Acetone 2300 U 48 40
Carbon Disulfide 14 14 U 10
etrachloroethene 7,100 720 U 1,300
Toluene 7.6 6.9 U 5.2 U
richloroethene 600 12 540 U
cis-1,2-Dichloroethene 10,000 22 5.2 U
rans-1,2-Dichloroethene 21 6.9 U 5.2 U
,Vinyl Chloride 38 1 6.9 U 5.2 U
Notes:
U-Analyte not detected
Table 4-3. Analytical Results for Contaminants (GC-MS) in Groundwater
Sample ID DPT01-14-16 I DPT01-33-35
Sample Date 11/12/2009 1 11/12/2009
Chemical Name
Volatile Organic Compounds(µg/L)
Acetone 75,000 50,000 U
Tetrachloroethene 220,000 230,000
Trichloroethene 10,000 U 13,000 U
cis-1,2-Dichloroethene 10,000 U 13,000 U
Vinyl Chloride 10,000 U 13,000 U
Notes:
U-Analyte not detected
43

Table 4-4. Site Characterization Summary
Depth Interval of Study Area 7 ft bgs to 18 ft bgs 33 ft bgs to 62 ft bgs
Predominant Soil Type Sand Sand
Fine-grained Soil Type Silty Sand (7 to 11 ft bgs) Silty Sand (33 to 40 ft)
Sand (11 to 18 ft bgs) Sand (40 to 60 ft bgs)
Depth to Water,ft bgs 7.5 15.5
Hydraulic Conductivity,ft/day 0.5 to 5.2 0.9 to 18.1
Average: 1.8 Average:6.6
Heterogeneity: 10.4 Heterogeneity: 20.1
Vertical Conductivity:0.00013
Anisotropy: 13,846
Hydraulic Gradient,ft/ft Horizontal:0.002,southwest Horizontal: 0.0004,west
Vertical:0.25,downward Vertical:0.0015,downward
PCE Concentration in Groundwater, µg/L 220,000 230,000
PCE Concentration in Soil, µg/kg 7,100(16-18 ft bgs) ND<720(33-35 ft bgs)
1,300(53-55 ft bgs)
Depth Interval with Greatest Mass of 16 to 18 33 to 35
Contaminant as indicated by MIP,ft bgs
Visual or Analytical Evidence of DNAPL? Yes No
44

5.0 TEST DESIGN
The objectives for this demonstration are: (1) diminishing the detrimental effects of site
heterogeneities with respect to the uniformity of permanganate delivery using the
polymer xanthan gum, and (2) managing Mn02 aggregation and deposition using the
polymer SHMP. A secondary project objective is to compare post-delivery/treatment
groundwater quality for "permanganate only" and "permanganate + polymer" test areas.
The two separate overall objectives will be pursued in two separate intervals of treatment
and control plots (Figure 5-1): a shallow zone (within the Surficial aquifer, where highest
contaminant concentrations exist) and an intermediate zone (where target anisotropy
exists with the Upper Castle Hayne). The intermediate zone of the site has characteristics
suitable for the demonstration related to Objective 1, while the shallow zone of the site
has characteristics suitable for the demonstration related to Objective 2. This section
provides a detailed description of the system design and testing to be conducted to
address these objectives. Laboratory studies supporting the design have been completed
and are available in the project's Treatability Study Report.
5.1 CONCEPTUAL DESIGN
Four plots will be utilized to implement the demonstration and achieve the project
objectives. One will be a control plot for SHMP (shallow depth, permanganate only),
one will be a control plot xanthan gum (intermediate depth, permanganate only), one will
be a SHMP test plot (shallow depth, permanganate + SHMP), and the fourth will be a
xanthan test plot (intermediate depth, permanganate + xanthan) (Figure 5-1). An
injection well will be installed in the center of each test plot for substrate delivery.
Conventional and multi-level sampling (MLS) wells will be installed at various distances
from the injection wells and screened at various intervals to monitor the water quality of
the targeted zones prior to system startup and for two months afterward.
5.2 BASELINE CHARACTERIZATION ACTIVITIES
Prior to implementation of the demonstration and in order to further refine the design,
baseline characterization activities will be conducted to monitor pre-treatment conditions.
These activities include the following:
5.2.1 Baseline Soil Sampling
During well installation, baseline cores will be collected from each plot to characterize
pre-treatment conditions. Soil samples will be analyzed for VOCs, natural oxidant
demand, total organic carbon (TOC), grain size distritubution, pH, ORP, cation exchange
capacity (CEC), microbial density, diversity, and activity, and manganese content. At
Site 88, a confining unit separates the Surficial Aquifer from the Upper Castle Hayne
Aquifer at approximately 25 ft bgs. All borings to be advanced beyond this depth (all
those associated with xanthan test and control plots) will require the installation of
isolation casings from the ground surface into the confining unit (at least one foot) to
prevent cross-contamination.
45

on 11-1 -a. in: _
IRee .L�" MD:S
IRaa#\Mt7
IRMJaN7DM
lips
1
f-- •4 mDJ'1
•I'll P 17 / �lMD7Jr MP37
N1-A MS Penaae aMefalor
ST2
�Mt aff1T Injection 9/stem footprint and
Secondary Containment t
I
I SHMP lest Plot I'I�p°f - KMnOd Drum Slorepe Area
� feeder
�1
Portable Lighting t
� ` MP16 M2'MI
- KMn04
Xt�
Catch 8851n MP75
hill IRa6-MLM3l R1
PT01 9 MP26 Q�IR$$-MPl31 qi,-IRaB-hNfY
5T-1
" SHMP
MP01
� f
MP22 'a
Poneble Liyhhn�l <i MIPJ2
t MIPJB
Q3
P Ia MIPJ6
M2
MP11
IRfm-11at1, aw
SHMP and XG I
Test Plot % _
IRAJalY02
MP41
XG Test Plot _ Im 02W
SeJ 0
ST3
MP37
I
}
i
tt j
Legend Figure�t
• Slug Test Location Proposed Shallow DPTAAlaterloo Sample Approximate location ofwastewater M Injection System Units
CPTAAIP Locations • Locations Approximately 1S20It bgs line from Building 25 O Potential Treatment Areas 1 Pilot Test System Layout and Well Locations
o OPT Location Proposed Deep OPT/Waterloo Sample —Temporary ryFencin for Exclusion zone Soil l Mixing Boundary MCB CamL
el
• HRP Location 0 Locations Approximately 15-20It bgs —Traffic Barricade Site 88 Boundary 0 7.5 15 30 North Carolina
• MIP Location 00 Proposed CMT Wells --•Steam Line ID Former Building 25 Feet
O Historical Sample Locations la Proposed Conventional Monitoring Wells Storm Sewer Utility Line Note.
lb Shallow Monitoring Well Location ® Proposed Injection Wells —Electrical Utility Line XG-Xanthan Gum 1 inch= 15 feet
0 Intermediate Monitoring Well Location—Fire Hose --Water Utility Line KMnO4-Potassium Permanganate n
(1 Deep Monitoring Well Location —Approximate Feld Piping Layout Wastewater Utility Line SHMP-Sodium Hexametaphosphate
bgs-below ground surface
Figure 5-1. Plot Test System Layout
46

5.2.2 Potable Water Injection Testing
Potable water injection testing will be conducted on each of the four injection wells to
evaluate the initial hydraulic properties of each plot and to optimize injection flow rates
to be used during the demonstration.
Approximately one pore volume of potable water will be injected into each of the four
injection wells using a fire hydrant source and the demonstration process equipment,
including a flow meter/totalizer, a flow control valve, and a pressure gauge. For the
shallow SHMP control and test injection wells, approximately 10,000 gallons of water
will be injected for the tests. For the xanthan gum control and test injection wells, 40,000
gallons of water will be injected for the test. The injection rate, pressure, and duration are
dependent on soil transmissivity. To optimize the flow rate for the demonstration, low,
average, and high flow rates for each plot will be upward step tested in the field, as
summarized on Table 5-1. Injection pressures between 5 and 30 pounds per square inch
gauge (psig) are expected, although pressures will be kept below those that createshort
circuiting of the injected fluids, or formation fracturing. During potable water injection
testing, injection pressures will be closely observed to assess the impact on the aquifer
and water distribution.
Table 5-1. Summary of Injection Testing
Flow Rate (gpm)
Test Plot Low Average High
SHMP 0.5 1 5
Xanthan Gum 1 7 10
Changes in groundwater quality will be monitored in wells within each plot using with a
combination of down-hole specific conductivity electrodes with data-logging capability
and the ex situ field chloride measurement of water samples. Monitoring will continue
until breakthrough occurs at the distal monitoring wells at the edge of the expected 15-
foot ROI. Breakthrough will be measured as indicated by specific conductivity and
chloride concentrations that are representative of the potable water..
5.2.3 Slug Testing
Baseline (pre-injection) rising and falling head slug tests will be performed in each of the
four injection wells to evaluate aquifer hydraulic conductivity and transmissivity in the
vicinity of each well. Slug tests will be performed prior to and after the potable water
injection tests to measure the impacts, if any, from the injectability tests. If dramatic
effects are noted, then injection well re-development may be implemented.
The slug test will consist of submerging a PVC or stainless steel cylinder of known
volume (slug), allowing the static water level to equilibrate, rapidly removing the slug,
47

and recording changes in head over time using a pressure transducer data logger. The test
will continue until the water level returns to within 10% of the original static water level.
Equipment used for the slug test will include a data logger and pressure transducer, a
nylon rope, and a solid PVC or stainless-steel slug.
The data will be reduced by plotting the change in head versus time on a semi-
logarithmic graph and using a method of analysis appropriate for each aquifer (e.g., the
Bouwer and Rice method of analysis, applicable to the shallow unconfined aquifer
[Bouwer, 1987]).
5.2.4 Baseline Groundwater Sampling
Prior to implementation of the demonstration, groundwater samples will be collected
from each monitoring well and MLS well within each plot to measure pre-treatment
water quality (see Tables 5-2, 5-3, and 5-4).
Groundwater samples will be collected from each monitoring well and MLS well using
the low-flow sampling techniques that are standard for MCB Camp Lejeuene. In addition,
water quality parameters (color, specific conductance, pH, turbidity, temperature,
dissolved oxygen [DO], and oxidation-reduction potential [ORP]) will be collected
during purging activities. Depth to water measurements will be measured and recorded
prior to and during purging and sampling.
5.2.5 Investigative Derived Waste
Investigative derived waste (IDW) soil, water, and personal protective equipment (PPE)
generated from well installation, drilling, sampling, and decontamination activities will
be segregated, characterized and disposed of in accordance to all local, state, and federal
regulations. Soil cuttings and PPE generated from well installation will be temporarily
stored in a lined (and covered)roll-off container. Following drilling activities, composite
soil characterization samples will be collected from the roll-off to determine if the waste
is hazardous. All soil cuttings and PPE will be disposed of at a certified and DoD-
approved off-site facility. Aqueous IDW generated from groundwater sampling and
decontamination activities will be temporarily stored in a secure frac tank and disposed of
at the onsite waste water treatment plant. Common trash (non contaminated paper and
plastic) will be recycled or disposed of at an onsite trash receptacle.
48

Table 5-2. Schedule of Plot Testing and Sampling
Time Since Treatment,t Activity Location Measurements
(weeks)
Pre-Demonstration Soil Core Collection by Sonic 5 SHMP Control Locations(to approximately 20 ft bgs) See Table 5-3.
t=-9 5 SHMP Test Locations(to approximately 20 ft bgs)
5 Xanthan Control Locations(to approximately 60 ft bgs)
5 Xanthan Test Locations(to approximately 60 ft bgs)
Injectability Testing SHMP Control-Injection Well Flow vs.Time
t=-4 (3 flow rate tests per well) SHMP Test-Injection Well
SHMP Test-Injection Well
Xanthan Control-Injection Well
t=-1 Slug Testing SHMP Control-Injection Well Depth-to-Water(DTW)vs.Time
(1 test per well) SHMP Test-Injection Well
SHMP Test-Injection Well
Xanthan Control-Injection Well
t=-1 Well Sampling SHMP Control-Injection Well;6 Monitoring Wells See Table 5-3.
SHMP Test-Injection Well;4 Monitoring Wells;2 MILS wells(1 sample each)
Xanthan Control-Injection Well;2 MILS wells(4 samples each)
Xanthan Test-Injection Well;1 Monitoring Well;2 MILS wells(4 samples each)
Delivery Performance Well Sampling SHMP Control-Injection Well;6 Monitoring Wells See Table 5-3.
t=0 SHMP Test-Injection Well;4 Monitoring Wells;2 MILS wells(1 sample each)
Xanthan Control-Injection Well;2 MILS wells(4 samples each)
Xanthan Test-Injection Well;1 Monitoring Well;2 MLS wells(4 samples each)
t=1 Soil Core Collection by DPT 16 SHMP Control Locations(to approximately 20 ft bgs) See Table 5-3.
16 SHMP Test Locations(to approximately 20 ft bgs)
16 Xanthan Control Locations(to approximately 60 ft bgs)
16 Xanthan Test Locations(to approximately 60 ft bgs)
Post-Demonstration Slug Testing SHMP Control-Injection Well DTW vs.Time
t=8 (1 test per well) SHMP Test-Injection Well
SHMP Test-Injection Well
Xanthan Control-Injection Well
t=1,3,5,7,9 Well Sampling SHMP Control-Injection Well;6 Monitoring Wells See Table 5-3.
SHMP Test-Injection Well;4 Monitoring Wells;2 MILS wells(1 sample each)
Xanthan Control-Injection Well;2 MILS,wells(4 samples each)
Xanthan Test-Injection Well;1 Monitoring Well;2 MILS wells(4 samples each)
t=9 Soil Core Collection by DPT 5 SHMP Control Locations(to approximately 20 ft bgs) See Table 5-3.
5 SHMP Test Locations(to approximately 20 ft bgs)
5 Xanthan Control Locations(to approximately 60 ft bgs)
5 Xanthan Test Locations(to approximately 60 ft bgs)
49

Table 5-3. Total Number and Types of Samples to be Collected
Component Test Plot Matrix Number of Analytes Location
Samples
Pre- SHMP Control Groundwater 7 TCL VOCs,pH,ORP,total solids,suspended solids, 1 injection well;6 monitoring wells
Demonstration major cations/metals,major anions,total organic
Sampling carbon
Soil 5 Soil cores from 5locations,each to approximately 20 ft
TCL VOCs,NOD,TOC,grain size,bulk density, bgs
porosity,pH,ORP,cation exchange capacity,
microbial density,diversity,activity,Mn speciation
SHMP Test Groundwater 7 TCL VOCs,pH,ORP,total solids,suspended solids, 1 injection well;4 monitoring wells;2 MLS wells(1
major cations/metals,major anions,total organic sample each)
carbon
Soil 5 Soil cores from 5locations,each to approximately 20 It
TCL VOCs,NOD,TOC,grain size,bulk density, bgs
porosity,pH,ORP,cation exchange capacity,
microbial density,diversity,activity,Mn speciation
Xanthan Control Groundwater 10 TCL VOCs,pH,ORP,total solids,suspended solids, 1 injection well;1 monitoring well;2 MLS wells(4
major cations/metals,major anions,total organic samples each)
carbon
Soil 5 Soil cores from 5locations,each to approximately 60 It
TCL VOCs,NOD,TOC,grain size,bulk density, bgs
porosity,PH,ORP,cation exchange capacity,
microbial density,diversity,activity,Mn speciation
Xanthan Test Groundwater 9 TCL VOCs,pH,ORP,total solids,suspended solids, 1 injection well;2 MLS wells(4 samples each)
major cations/metals,major anions,total organic
carbon
Soil 5 Soil cores from 5 locations,each to approximately 60 ft
TCL VOCs,NOD,TOC,grain size,bulk density, bgs
porosity,pH,ORP,cation exchange capacity,
microbial density,diversity,activity,Mn speciation
Delivery SHMP Control Groundwater 6 MnO.TCL VOCs,pH,ORP,total solids,suspended 6 monitoring wells
Performance solids,major cations/metals,major anions,total
Sampling organic carbon
Soil 16 Soil cores from 16 locations,each to approximately 20
TCL VOCs,NOD,TOC,grain size,bulk density, ft bgs
porosity,pH,ORP,cation exchange capacity,
microbial density,diversity,activity,Mn speciation
SHMP Test Groundwater 6 MnO4,TCL VOCs,pH,ORP,total solids,suspended 4 monitoring wells;2 MLS wells(1 sample each)
solids,major cations/metals,major anions,total
organic carbon
Soil 16 Soil cores from 16 locations,each to approximately 20
TCL VOCs,NOD,TOC,grain size,bulk density, ft bgs
porosity,pH,ORP,cation exchange capacity,
microbial density,diversity,activity,Mn speciation
Xanthan Control Groundwater 9 MnO4,TCL VOCs,PH,ORP,total solids,suspended 1 monitoring well;2 MLS wells(4 samples each)
solids,major cations/metals,major anions,total
organic carbon
Soil 16 Soil cores from 16 locations,each to approximately 60
TCL VOCs,NOD,TOC,grain size,bulk density, ft bgs
porosity,pH,ORP,cation exchange capacity,
microbial density,diversity,activity,Mn speciation
Xanthan Test Groundwater 8 MnO4,TCL VOCs,pH,ORP,total solids,suspended 2 MLS wells(4 samples each)
solids,major cations/metals,major anions,total
organic carbon
Soil 16 Soil cores from 16 locations,each to approximately 60
TCL VOCs,NOD,TOC,grain size,bulk density, ft bgs
porosity,pH,ORP,cation exchange capacity,
microbial density,diversity,activity,Mn speciation
Post- SHMP Control Groundwater 7 MnO4,TCL VOCs,pH,ORP,total solids,suspended 1 injection well;6 monitoring wells
Demonstration solids,major cations/metals,major anions,total
Sampling organic carbon
Soil 5 Soil cores from 5 locations,each to approximately 20 ft
TCL VOCs,NOD,TOC,grain size,bulk density, bgs
porosity,pH,ORP,cation exchange capacity,
microbial density,diversity,activity,Mn speciation
SHMP Test Groundwater 7 MnO4,TCL VOCs,pH,ORP,total solids,suspended 1 injection well;4 monitoring wells;2 MLS wells(1
solids,major cations/metals,major anions,total sample each)
organic carbon
Soil 5 Soil cores from 5locations,each to approximately 20 ft
TCL VOCs,NOD,TOC,grain size,bulk density, bgs
porosity,pH,ORP,cation exchange capacity,
microbial density,diversity,activity,Mn speciation
Xanthan Control Groundwater 10 MnO4,TCL VOCs,pH,ORP,total solids,suspended 1 deep injection well;1 monitoring well;2 MLS wells(4
solids,major cations/metals,major anions,total samples each)
organic carbon
Soil 5 Soil cores from 5locations,each to approximately 60 ft
TCL VOCs,NOD,TOC,grain size,bulk density, bgs
porosity,pH,ORP,cation exchange capacity,
microbial density,diversity,activity,Mn speciation
Xanthan Test Groundwater 9 MnO4,TCL VOCs,pH,ORP,total solids,suspended 1 injection well;2 MLS wells(4 samples each)
solids,major cations/metals,major anions,total
organic carbon
Soil 5 Soil cores from 5 locations,each to approximately 60 ft
TCL VOCs,NOD,TOC,grain size,bulk density, bgs
porosity,PH,ORP,cation exchange capacity,
microbial density,diversity,activity,Mn speciation
Notes:
Field measurements of dissolved oxygen,pH,ORP,specific conductivity,temperature,and turbidity will be collected using a portable multi-parameter meter and flow-through cell.
50

Table 5-4. Analytical Methods for Sample Analysis
Matrix Analyte Method Container Preservative Holding Time
Groundwater MnO, APHA 4500 Spec vial None Immediate
TCL VOCs EPA 8260E and 5030 (3)40-ml Vial HCI pH<2; Cool to 40C 7 Days
pH,ORP APHA 4500, 2580 Cool to 40C 3 Days
Total Solids
Suspended Solids APHA 2540 Cool to 40C ASAP (7 days max)
Major Cations/Metals APHA 3125 (1)250-m1 poly Cool to 40C 30 Days
Major Anions APHA 4110 Cool to 40C 2 Days
Total Organic Carbon APHA 5310B Cool to 40C 15 Days
Field Parameters, including:
MnO2 Field spectrometer at 418 nm
MnO4 Field spectrometer at 525 nm
Chloride Chloride-specific probe -- --
Xanthan gum viscosity Viscometer
ORP/temperature/pH/specific Multi-parameter meter with
conductivity/turbidity flow-through cell
Soil
TCL VOCs EPA 8260B and 5035 (3)Encore Samplers Cool to 40C 48 hours
NOD Siegrist et al.,2009 Cool to 40C 30 Days
TOC,Grain Size, Bulk Density,
Porosity EPA 9060 Cool to 40C 30 Days
pH,ORP EPA 9045D Cool to 40C 3 Days
Cation Exchange Capacity Sparks et al., 1996 (3)4-oz jar, minimum Cool to 40C 10 Days
Kieft and Phelps(1997); Phelps et
Microbial Density, Diversity, al. (1 994a,1 994b)Weaver et al.
Activity (1994) Cool to 40C 3 Days
Mn Speciation Chao, 1972 Cool to 4°C 30 Days
51

5.3 DESIGN AND LAYOUT OF TECHNOLOGY COMPONENTS
Four plots of approximately 30-feet in diameter will be installed, operated, and monitored during
the demonstration(see Figure 5-1), as described above in Section 5.1.
5.3.1 SHMP Control Plot
The well network associated the SHMP control plot includes one injection well and six
conventional monitoring wells, spaced at five-foot intervals along two radii from the injection well
at a distance of 15-feet from the injection well. The injection well and all monitoring wells will be
screened from 15 to 20 ft bgs, immediately above the silt/clay confining unit..
5.3.2 Xanthan Gum Control Plot
The xanthan gum control plot will include one injection well located at the center of the plot, one
existing monitoring well (IR88-MW02DW), and two MLS wells (Solinst CMT wells) each located
at a distance of approximately 15 feet from the injection well. The injection well will be screened
from 35 to 55 feet bgs and both MLS wells will have approximately four sampling ports with the
injection well screen interval as determined in the field based upon stratigraphy. MLS well screens
will target individual isolated lithologic units and/or zones with unique permeability.
5.3.3 SHMP and Xanthan Gum Test Plot
The central vertically stacked test plot will include two injection wells (shallow and intermediate
zones), four conventional monitoring wells (shallow zone only), and two MLS wells (intermediate
zone only). Both injection wells will be located in the center of the test plot; one screened within
the intermediate zone (35 to 55 feet bgs) for the xanthan gum test and one screened in the shallow
zone (15 to 20 feet bgs) for the SHMP test. The conventional monitoring wells will be spaced at
five-foot intervals along two radii out to 10-feet from the shallow injection well and each screened
at a depth of 15 to 20 feet bgs. The two MLS wells will be installed at a distance 15 feet from the
injection wells and will have five sampling ports: one associated with the SHMP shallow zone and
four associated with the intermediate zone xanthan test. The depths and screen lengths of the MLS
wells sampling ports will be determined in the field based on site stratigraphy. Similar to the
control plots, the MLS well screens will target individual isolated lithologic units and/or zones
with unique permeability.
5.3.4 Well Specifications
All wells will be installed and developed using Roto-sonic drilling technology. During installation,
soil will be logged from ground surface to the total depth of the well. Injection wells will be
constructed with 4-inch diameter stainless steel screens (20-slot) affixed to schedule 80 polyvinyl
chloride (PVC) risers and completed above grade with process equipment to monitor and control
the injection rates (see Figure 5-2). The conventional monitoring wells will be constructed of 2-
inch diameter schedule 40 PVC screens (10-slot) and completed flush with ground surface (Figure
5-3). Each MLS well (see Figure 5-4) will be fabricated in the field by manually cutting sampling
ports at the desired depth and length after the borehole is logged and desired screen intervals are
52

identified. Each sampling port will be isolated from the port above by installing water-tight
packers. After installation and prior to sampling, all wells will be developed according to local and
state requirements and horizontal and vertical controls established (e.g., XYZ coordinates) by a
licensed surveyor.
5.3.5 Design and Layout of Process Equipment
Process equipment with components for delivering KMnO4, xanthan polymer, and SHMP to the
plots will be constructed following baseline characterization activities. The dosing equipment will
consist of standard off-the-shelf construction materials (e.g., PVC piping, flexible hosing with cam
lock fittings, and poly tanks), inline mixing and monitoring equipment, and basic controls for
automatic operation and shutdown. All equipment will be contained within a secondary
containment basin. Figure 5-5 presents a process and instrumentation diagram of the process
equipment. Operational flow rates will vary, but are expected to be within the range of 0.5 to 12
gallons per minute (gpm) and under 25 psig. Tables 5-5, 5-6, and 5-7 summarize the range of
possible operating conditions for the control, SHMP test, and xanthan test plots, respectively.
Process locations are identified on Figure 5-5. Chemical usage for each process operation is also
summarized in the tables. Provisions will be made for the High-Dose operating conditions. This
includes a total of 22,000 lbs of KMnO4, 3,000 lbs of SHMP, and 6000 lbs. of xanthan gum.
Water source. A fire hydrant located approximately 250 feet away from the plots will be used as
the water source for the injection system and will be equipped with a back-flow preventer and a
pressure reduction valve that is certified by a local technician. The fire hydrant will provide
enough pressure to drive the permanganate feed eductor.
Potassium Permanganate Miring Unit. Water will be delivered from the fire hydrant to the
potassium permanganate and xanthan gum mixing equipment through flexible hose. The
potassium permanganate mixing equipment will consist of two parallel Merrick screw feeders with
a common mixing bucket and eductor designed to deliver the proper powdered potassium
permanganate mass into the water stream. Each feeder has a single drum (330 lb) hopper and a
manual drum handler/inverter will be used to replace the permanganate drums as needed. A local
control panel for the permanganate feeders will indicate when the drums need to be replaced. The
system will be capable of over-night unattended operation.
Xanthan Mixing Unit. The xanthan process equipment will be comprised of a polymer mixing
unit, a 500-gallon supplemental mixing tank, a 2,600-gallon primary polymer mixing and storage
tank, a circulation pump, and a progressive cavity dosing pump. The polymer mixing unit consists
of a stainless steel hopper, educator, an internal shearing device, and a gear pump to drive fluids
through the shear mixer. Xanthan will be manually mixed to a concentration of up 8,000 mg/L and
circulated through the 2,600-gallon tank to achieve the desired viscosity. As needed, smaller 500
gallon batches of polymer will be prepared and transferred to the concentrate tank. This solution
will be dosed into the main process line at a point downstream of the permanganate feeder bucket
and further mixed using an in-line mixer. Further downstream, a relaxation tank (55 gallon drum
with mixer) will be used to allow the xanthan to be re-mixed (if needed) and an additional
progressive cavity injection pump will be used to deliver the xanthan/permanganate solution to the
well heads.
53

NEEDLE VALVE FLOW AND
CHECK VALVE PRE.49URE
INDICATOR
4'TO I S REDUCER
C ABOVE GROUND WELL MONUMENT
CONCRETE WELL PAD
i'
SCH W PVC RISER
o cEMENr GRGLrr
I
3' NTOMTE SEAL
6AI•D FILTER PACK
STAINLESS STEEL
01M0'SLOT SCREEN
CH2MHILL
Figure 5-2. Injection well design.
54

B'ROUND STEEL MANHOLE COVER
NCRETE WELL PAD
1'
COMING WELL EXPANSION PLUG
SAND
2"SCH 40 PVC RISER
\ u /
u
ORTLAND CEMENT GROUT
2'
ENTONITESEAL
2'
10120 SAND FILTER PACK
5'
.010"SLOT 2'PVC SCREEN
B'
CH2MHILL J
Figure 5-3. Conventional monitoring well design.
55

S'ROUND STEEL MANHOLE COVER
ONCRETE WELL PAD
1'
SAMPLE PORT ADAPTER
SAND
1.7'POLYETHYLENE TUBING
RTLAND CEMENT GROUT
ENTONITE SEAL
0
0
0
0
10/20 SAND FILTER PACK
ENTRALIZER
0
0
0
0
0
0
0
0
SAMPLE PORT
00
0
I—Ba
NOTE:SAMPLE PORT DEPTHS
ARE DEPENDENT ON LITHOLOGY
40 CH2MHILL J
Figure 5-4. MLS monitoring well design.
56

WASTE
WATER
DISCHARGE
TEAT
TANK
DRUM P3H
DPI 9 PI
CINVERTER O
FEELER ^ PI �_\ �CNNP
WASH 120V ) s p -
DPI SI IMP
HOPPER EL ( S \ O '�MDER �' Yn .t3M`"r TEST
p\ �� 120V b /fl 1 PI
\ TZ \J CFI (^ r4z W"►XANTHAN
coNTRaI
CPS, ' �Y �✓ s BY.PASS p\ -
lSH S 1P8H} \
X2' 'aADv r a` •IV ,oJP"h`"' ��ST
NTHAN
BY.PASS
INJECTION
$ PUMP-
PROGRESSIVE
2000
00 CAVITY
M F 'O� O- P 3 —
`I( TI .
2cy �CO� 4dOVl O
MIK
1 � INJECTION
- PUMP• A
170VI PROGRESSVA?:
iLlzx
CAVITY
�,_! P-2 p{
_ FIX
TRANSFER TANK 170V
PUMP
P-1 SHMP MIXING UNIT T-1 TANK
SECONDARY CONTAINMENT WALL 4 P.1 INI NP PUMP
I�
L I 121YV VOLTAGHPOWFR
REQUIREMENTS
LEGEND
SH PRESSURE SWITCH HIGH
LOW LEVEL ALARM � OIFFERENTAL PRESSURE
U WATER SOURCEMYORANT FLOW INDICATOR TRANSMITTER `/ FLEX TUBING PORTABLE SUMP PUMP ELECTRIC INDICATOR
I= BACKFLOW PREVENTOR i VALVE ® STATIC MLXER
MANIFOLD � CAMLOCK FlREH09E PVC COUPLER
1 Si BALANCE PORT n \
FLOWING CATOR
^.-11. ..^FIRE HOSE I CHFMICAI NFTFMW,P,)MP VA-1 �I
f�
EDUCTOR LJ ROW INDICATOR&FLOW TOTALIZER LSH LEVEL SWRCN HIGH
DQ DATE VALVE
1 112'PVC 9CH 40 � PUMP
WATER FLOW PRV MEDIAFILTERS
BALL VALVE VALVE
CHECK VALVE VALVE 55 GAI I ON DRUM W/MIXFR RE RELEASE
PROCESS
(0) FLOW TOTALIZER y PI ' PRESSURE INDICATOR H LOCATION
FLOWCUNTR(X%WYF MOTOR17FO AIR COMPRESSOR TO OPERATF P IDENTIFIER
SITE 88, CAMP LEJEUNE NORTH CAROLINA PERMANGANATE, SHMP, AND
d_TAY ESTCP PROTECT ER-0912 XANTHAN 'GUM' PROCESS
COOPGRATIVE TECHNOLOGY DEMONSTRATION - POLYGL- ENHANCED AND INSTRUMENTATION
wre.�MnR 1° DELIVERY OF PERMANGANATE DIAGRAM
Figure 5-5. Process and instrumentation diagram.
57

TABLE 5.5
XANTHAN CONTROL PLOT OPERATION-ENHANCED-DELIVERY PERMANGANATE INJECTION PROCESS DESIGN
ESTCP Project ER-0912
Site 88,Camp Lejeune,North Carolina
Process Location ID
Fire Hydrant Potable Water Supply A
Xanthan Feed B
Permanganate Feed C
Process-Post-PermanganaleFeed D
Tracer Feed E
Process-Post-Tracer Feed F
Process-Post-Mix G
SHMP Feed H
Process-Post-SHMPFeed I
Process-Posl-Fifterinjectate i
Injection to Both Control Plots
XANFHAN CONTROL PLOT OPERATION Process Location A(hydrant Sup*) Process Location B(XanthanFeed) Process Location C(OxldantFeed) Process Location Process LocatlonE Process Location F(SHMPFeed) Process Location ProcesslocadonH(lnjectate)
Design Parameter Low-Dose Avg-Dose High-Dose Low-Dose Avg-Dose High-Dose Low-Dose Avg-Dose High-Dos e Low-Dose Ava-Dose High-Dose Low-Dose Ave-Dose High-Dose Low-Dose Ave-Dose High-Dose Low-Dose Ave-Dose High-Dose LowwDose A -Dose Ei¢ ose
Flow Rate(gpm)= 1.5 8.0 12 0.0 0.0 0.0 1.5 2.8 4.0 1.5 8.0 12 1.5 8. 12 0.0 0.0 0.0 1.5 8.0 12 1.5 8.0 12
Daily Flow Duration(hrs/day)= 12 18 24 12 18 24 12 18 24 12 18 24 12 18 24 12 18 24 12 18 24 12 18 24
Total Flow(gah/day)= 1,080 8,640 17,280 0 0 0 1,080 2,970 5,760 L080 8,640 17,280 1,08D 8,640 17,280 0 0 0 1,080 8,640 17280 1,080 8,640 17280
Required Pressure(psig)= 2.2 4.3 6.5 0.0 1.1 2.2 0.0 0.0 0.0 1.6 32 4.9 0.4 1.1 1.7 1.0 13 1.0 13 25 0.0 ZS 15
[KMnO4](met)= 1,300 19,491 40,500 %300 6,700 13,500 L300 6,700 13,500 - 1,300 6,700 13,500 1,300 6,700 13,500
KMnO4 Loading Rate(lbs/day)= 12 482 1943 12 482 1,943 12 482 1,943 12 482 1,943 12 482 1,943
[Mn04](mel-) 978 14,669 30,480 978 5,042 10,160 978 5,042 10,160 978 5,042 10,160 978 5,042 10,160
MnO4 Loading Rate(lbVday)= 8.8 363 1462 8.8 363 1462 88 363 1462 8.8 363 1462 8.8 363 1462
llJ Tracer(mg7Q= 322 4,622 10,020 322 1,658 3,340 322 1,658 3,340 322 1,658 3,340 322 1,658 3,340
[K]Tracer Loading Rate(lbVday)= 2.9 119 481 1 2.9 119 481 1 29 119 481 L 119 481 1 2.9 119 481
Low-Dose Average-Dose High-Dose
22CESSMA55&ILANCEL2C In s Outputs Delta tn�uts Ou ruts Delta In-uts Ou is Delta
Flow Rate(gpm)= 15 1.5 0 8.0 8.0 0 12 12 0
Total Flow(gah/day)= 1,080 1,080 0 8,640 8,640 0 17,280 17,280 0
KMnO4 Loading Rate(lbs/day)= 12 12 0 482 482 0 1,943 1,943 0
MnO4 Loading Rate(lbs/day)= 8.8 8.8 0 363 363 0 L462 1,462 0
[KI Tracer loading Rate llbs/day)= 1 2.9 2.9 0 1 119 119 0 1 481 481 0
PROCESS WATERAND CHEMICAL TOTAL DEMAND
Duration of Operation(d*)= 5 (assumes concurrent control plot operation)
Low-Dose A%R-Dose flkkM
Total Flow(gallons)= 5,400 43,200 86,400
KMnO4 Demand(lbs)= 58 2,410 9,713
Xardhan Loading Rate(lbs)= 0 0 0
SHMP Demand(lbs)= 0 0 0
58

TABLE 5.6
SHMP TEST PLOT OPERATION-ENHANCED-DELIVERY PERMANGANATE INJECTION PROCESS DESIGN
ESTCP Project ER•0912
Site 88,Camp Lejeune,North Carolina
rlrel drarl Potable waterSu A
XaMunfeed R
Primanganalefeed
Pm(ess Post IMmx)n alsdeleed D
Isar m f rrd r
Ptoum INO harm Iced I
Process Pnsl MIX G
SHMP Fred II
Proms MI91MP1erd I
Ptoceu P e l l Rim In e(tate 1
SHMP TEST PLOT OPERATION Process Locodm A(Hydrmt Fm m location 81)(anthon Feed) proem London C(OXldont ked) %ours Location process LotoBa)E process LoroBon F(SHMP Feed) Protest Location IS Protest Lat000nNM
D"If"parimofr With- I h w A - I I A -Dose HI h0ow I A
I low itate(gpm) O.S 1.0 5.0 0.0 0.0 0.0 U.SU 1.1 1.1 050 IA 5.0 0.50 1.0 5.0 0.001 nnm, o', 0.50 1.0 S.0 U.50 1.0 5.0
DallyIMlwDmallan(hn/day) 17718 1 )4 12 18 24 12 1R M 1) 18 14 12 18 14 12 IR M v 18 24 1) lK 14
Inlallluw(MK/day)= W) I'M /,118 0 0 0 160 I'll/ 1'41) 3S9 11015 I'm 359 I'm 1,118 07 S,4 72 360 1,080 1,200 360 1,080 I'mo
RequiredP)esswe(psig) 2.1 1 4.1 1 6.S 0.0 1 1.1 2.2 0.0 0.0 0.0 th 3.2 4.9 0.4 1.1 1 1.1 1.0 13 25 1D 13 25 0.0 1.5 15
(KMn(NI(mg/1)- 1,100 6,141 40,119 1,303 6,734 13,636 1,103 6,734 llh16 1,300 6,700 13,So0 1.300 1 6,700 1 13,500
KMnO4loading Rate(Iln/day)= - 3.9 60 809 3.9 60 M9 39 60 809 - - 19 60 809 39 60 809
IMn(Al IMg/I) 918 4,626 30,138 980 5,068 10,26.1 980 5,068 10,163 - 91g 5,042 10,160 W11 S,(A) 10,160
MnU4 loading Rate(Ibs/day) - - 2.9 45 609 2.9 45 609 ).9 45 (09 - 2.9 45 609 1.9 45 Log
(SHMPI(mg/I)= 1,000,000 1,000,000 1,000,000 2,000 5,oOo lo,nno 2,000 S,Doo 10,000
SIIMP loading Rate(lbs/day) - 6D 45 600 6.0 45 600 6.0 45 600
(K)T6nm(mg/l)- 311 11521 9,940 322 11666 3,374 32) 1,666 3,174 - 122 1,658 3,340 322 1,658 1,340
IKl ham Loading Rate Ibs/day= D% IS 200 D96 IS 200 1 096 15 200 1 0% 15 200 1 0.96 15 200
Low Dose Average Dose 1,10411ow
PROCESS MASS M I h Out uh Delta Apm Out uts Delta hi puts Outputs Delta
Hmv Rate(RPm)- n 50 0'a) 0 111 10 0 50 s 0 0
IOtalI low(gah/day) 160 360 0 1,030 1,090 0 I'lou 1,100 0
KMMMIoading Rate(IbVday) 319 3.9 0 (10 60 0 809 809 0
MnO4Ioading Rate(II)gday)= 2,9 1.9 0 45 45 0 609 609 0
SIIMP Ioadingllale(lbs/&y) 6.0 6.0 0 4S 45 0 600 600 0
(K)Tratrika.1mgRate Ibqday) 0,% ox 0 1 iS IS 0 20D 200 0
SS WATER AND CHEMICAL TOTAL DEMAND
Uwalbn of Upmalgn(dar)
tow-Dos Aw-Dou High 1 Dose
TotalFYnv(gallom)- IHIXI 5100 '%'IXlll
KMnU4 Dena(lbs)- 19 Sul 4,(AI
XanlhanloadingRale(lb%) 0 0 0
SIIMP Demand jib,)- 10 )75 ),998
59

TABLE 5-7
XANTHAN TEST PLOT OPERATION-ENHANCED-DELIVERY PERMANGANATE INJECTION PROCESS DESIGN
ESTCP Project ER-0912
Site 88,Camp Lejeune,North Carolina
Process Location ID
Fire Hydrant Potable WaterSuppty A
Xanthan Feed B
Permanganate Feed C
Process-Post-Permanganate Feed D
Tracer Feed E
Process-Post-Tracer Feed F
Process-Post-Moe G
SHMP Feed H
Process-Post-SHMPFeed I
Process-Post-Fifterinjectate 1
XANTHAN TEST PLOTOPERATION Process Location A(Hydrant Supply) Process Location 8(Xanthan Feed) Process Location C(Oridant Feed) Process Location D Process Location E Process Location F(SHMP Feed) Process Location G Process Location H(Injectate)
Design Parameter Low-Dose Avg-Dose High-Dose Low-Dose AW-Dose High-Dose Low-Dose Avg Dose High Dose Low Dose Avg-Dose High-Dose Low-Dose Avg-Dose High-Dose Low-Dose Avg-Dose High Dos Low Dose AW-Dose High Dose Low-Dose Ave-Dose Hleh-Dose
Flow Rate(gpm)= 1-0 6.5 8.8 0.020 0.54 1.3 1.0 2.2 3A 1.0 7.0 10 1.0 %.II 10 0.0 0.0 1.0 7.0 10 1.0 0 110
Dail Flow Duration(hrVday)= 12 18 24 12 18 24 12 18 24 12 18 24 12 18 24 12 18 2a 12 18 24 12 18 24
Total Flow(gals/day)= 706 6,977 12,600 14 583 1,800 720 2,360 4,853 720 7,%0 14,400 720 7560 14,400 0 0 9 720 7,%0 14,400 720 7,%0 14,400
Required Pressure(psig)= 2 4 1 6 0.0 1 1.1 1 2.2 0.0 0.0 0.0 1.6 32 4.9 OA 1.1 1 1.7 1.0 11 1.0 13 25 0.0 7.5 15
[KMn04j(mg(L)= - - - - - - 1,300 21,465 40,059 1,300 6,700 13,500 1,300 6,700 13,500 - - - 1,300 6,700 13,500 1,300 1 6,700 13,500
KMn04 Loading Rate(Ibs/day)= - - - - - 7.8 422 1,619 7.8 422 1,619 7.8 422 1,619 - 7.8 422 1,619 7.8 422 1,619
[MnO4)(mg/Q= 978 16,154 30,148 978 5,042 10,160 978 5,042 10,160 978 5,042 10,160 978 5,042 10,160
Mn04 Loading Rate(lbVday)= - - - - - - 5.9 317 1,218 5.9 317 1,218 5.9 317 1,218 - - - 5.9 317 %218 5.9 317 1218
Vanthan](mg/L)= 5,000 6,481 8,000 - - - 100 500 1,000 100 SOO LOBO 100 500 1,000 100 500 T 1,000
Xanthan Loading Rate(lbs/day)= 0.6 31 120 - - - 0.6 31 120 0.6 31 120 - - 0.60 31 120 0.6 31 120
(K]Tracer(mg/L)= - - - - - - 322 5,310 9,911 322 1,658 3,340 322 1,658 3,340 - - - 322 1,658 3,340 322 1,658 3,340
(KJTracer Loading Rate(Ibs/day)= - - - - - - 19 104 400 19 104 400 1.9 104 400 - - - 19 104 400 1.9 104 400
Low-Dose Average-Dose High-Dose
PROCESS MASS BALANCE Inputs Outputs Delta Inputs Outputs Delta Inputs Outputs Delta
Flow Rate(gpm)= 1-0 LO 0 7.0 7 0 0 10 10 0
Total Flow(gals/day)= 720 720 0 7,560 7,%0 0 14,400 14,400 0
KMn04 Loading Rate(IbVday)= 78 78 0 422 422 0 L619 1,619 0
MnO4 Loading Rate(IbVday)= 59 5.9 0 317 317 0 1218 1,218 0
Xandhan Loading Rate(lbs/day)= 0.6 0.6 0 31 31 0 120 120 0
[K]Tracer Loading Rate(IbVday)= 19 1.9 0 104 104 0 400 400 0
PROCESS WATER AND CHEMICAL TOTAL DEMAND
Duration of Operation(days)= ❑5
Low-Dose Avg-Dos e High-Dose
Total Flow(gallons)= 3.600 37,800 72.000
KMnO4 Demand(Ibs)= 39 2,109 8,094
Xanthan Loading Rate(lbs)= 3.0 157 600
SHMP Demand(Ibs)= 0 0 0
60

SHMP Mixing Unit. The SHMP process equipment will consist of a small mixing tank
(approximately 250 gallons) and a chemical metering pump that delivers the 1,000,000 mg/L
stock concentration of SHMP to the injection wells.
Media filters. Prior to reaching the injection wells, all substracte and permanganate solution will
pass through one of two parallel media (sand) filters. When exhausted, the media filters will be
taken off-line and the media replaced with fresh sand.
Injection wells. An injection manifold (2 lines) will be built that includes instrumentation to
monitor and control the injection flow rate. Instrumentation includes a flow control valve, flow
indicator transmitter/totalizer, pressure gauge, and sample port.
Secondary Containment and Site Facilities. A secondary containment unit constructed of
bermed high-density polyethylene (HDPE), designed to capture a worst case scenario spill and
24-hour/25-year rain storm event, will house each of the tanks and major process equipment. A
project-specific Spill Prevention Control and Countermeasure Plan (SPCC) has been prepared
and is attached as Appendix C.
Equipment will be powered using a rented portable 3-phase generator will be used to run all of
the electrical components and system control. Portable light stands, temporary fencing, and
traffic control will be used for health and safety considerations and to prevent disruption of the
injections.
Controls. Instrumentation and controls will be provided to automatically regulate the injection
flow rate and provide failsafe to allow unattended overnight operation. The primary controls
include the following:
■ The 2,600 gallon xanthan gum storage tank, 55-gallon relaxation tank, and secondary
containment sump will be equipped with a high level float switch for automatic
shutdown if they achieve a high-high level.
■ The media filter delivery line will be equipped with a high pressure switch for
automatic shutdown if both media filters become plugged.
■ The permanganate feed system will be equipped with a low level switch for automatic
shutdown if both feeders become empty.
■ The permanganate screw feeders and wash hopper will be controlled using a local
control panel with a timer switch. A low level alarm is built into the screw feeders to
signal drum replacement
■ A master control panel will control flow into the injection wells using flow control
valves (at the well head and on the fire hydrant supply) and an adjustable speed drive
on the injection pump. The primary goal is to deliver a constant flow rate to each
injection well for the duration of the plot operation. If the injection well begins to
plug, the process logic controlled (PLC) in the master control panel will respond by
opening the well flow control valve. If the desired flow rate can't be achieved, then
the speed of the injection pump may be increased. If this happens, then the flow
control valve on the fire hydrant will be opened to maintain a constant fluid level in
the relaxation drum.
61

■ Secondary containment is equipped with a high level switch to operate a sump pump.
The media filters will be equipped with differential pressure gauges to indicate when
media needs replacement.
5.4 FIELD TESTING
Control and test plots will be operated and monitored to observe the effect of injecting potassium
permanganate and potassium permanganate with SHMP and with xanthan gum. During this time,
system operational parameters will be monitored and modified accordingly to optimize injection
rates and distribution. Injection will last approximately 5 days per plot, operating at 24 hours per
day. The schedule for these tests is provided in Section 7.0 and summarized in Table 5-8.
Details on each configuration as well as tests to be conducted are described below.
5.4.2 Control Testing
Approximately one month following the potable water injectability tests (see Section 5.3),
simultaneous injection of potassium permanganate will begin in the SHMP (shallow) and
xanthan gum (intermediate) control plots at conditions summarized in Table 5-5. The duration
of this injection is expected to last for approximately five days. During injection, process line
pressure and flow measurements and permanganate injection concentrations will be monitored
and adjusted as needed.
Field analyses will be conducted during injections to measure changes in specific conductivity
and ORP to understand break through time and color to measure lag time of the potassium
permanganate behind the hydraulic delivery front. Samples will be collected from the process
pipelines and monitoring and MLS wells for field and laboratory analysis to confirm these results
and ensure process controls are functioning.
As summarized in Table 5-3, groundwater samples will be collected from all monitoring wells
and MLS wells within each control plot using low-flow sampling techniques to evaluate the
performance of permanganate delivery. Also as summarized in Table 5-3, soil cores will be
collected from both control plots immediately following the demonstration for physical and
chemical testing to evaluate permanganate distribution. Soil borings in each plot will be
advanced using DPT with continuous sampling. Soil and groundwater samples will be analyzed
for the constituents listed in Table 5-4.
5.4.3 SHMP Test Plot
Following the control plots operation, the SHMP test plot injection will be commenced. A
solution of SHMP and potassium permanganate will be injected into the shallow zone at
conditions summarized in Table 5-6. During injection, process line pressure and flow
measurements and permanganate and SHMP injection concentrations will be monitored and
adjusted as needed. The duration of this injection is expected to be five days.
62

Table 5-8. Project Schedule
per K. .yi1kq
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pdi--d P——pi- 23.5 d­ hbn 7112110 M.—10
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SH MPnjediens 11, M-7-0 Sun 725r16
....A Groundwater Sam pi,.g(.11 MUU and MLS 5d, M.h7AQMO ..71— eM
hPTS.iIS..p1mg(.—d p—,—..)(2­) ...7-M. Th.7-0 HILL g..I.g,A,&.d
01 1.S. y 05days Th.-0 F—U10 CI 2M HILL geologiS
—than G..—Pid Op—h..antl—t.—B 11 1-110 —-11D
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D P T S.,I S—ph.g(,—d p.t d—)(2,, 5d, M..­0 Mon Baia —1.—R-kC 12M HILL
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j6 8/16110 ThU 1-110
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Page 1
63

Groundwater will be collected from all monitoring and MLS wells within the SHMP test plot
using low-flow sampling techniques to evaluate the performance of permanganate and SHMP
delivery, as described in Table 5-3. Soil cores will be collected immediately following SHMP
test plot operation for physical and chemical testing to evaluate permanganate and MnO2
distribution, as summarized in Table 5-3. Soil borings will be advanced using DPT with
continuous sampling. Each soil boring will be logged by the field geologist specifically noting
the color index and signs of permanganate and MnO2 solids. All soil and groundwater samples
will analyzed for the constituents listed in Table 5-4.
5.4.4 Xanthan Gum Test Plot
Following the SHMP test plot operation, xanthan gum and potassium permanganate will be
injected into the intermediate zone. During injection, process line pressure and flow
measurements, permanganate concentration and polymer viscosity will be monitored and
adjusted as needed. Groundwater samples will be collected from the MLS wells within the
xanthan gum test plot using low-flow sampling techniques to evaluate the performance of
permanganate and xanthan gum delivery, as described in Table 5-3. Groundwater samples will
analyzed for the constituents listed in Table 5-4. Immediately following injection operations,
continuous soil cores will be collected from within the treatment zone (between 33 and 55 ft bgs)
within acetate sleeves using direct push sampling techniques, as described in Table 5-3. These
cores will be sampled and vertically logged in the field for the presence or absence of
permanganate (or MnO2 oxidation by-product) as described in Table 5-4. These cores will be
collected along two transects within the treatment zone, intersecting the injection well, to provide
sufficient data to reconstruct the subsurface distribution of permanganate and perform vertical
sweep efficiency calculations as described in Section 5.6. It is anticipated that up to 16 individual
corings will be required to meet these data objectives. However, the actual number of cores
needed will be evaluated on-site as a dynamic data collection approach. The same soil sampling
approach will be used immediately following the Xanthan control plot as described in Section
5.4.2.
5.4.5 Post-Demonstration Testing
Post-demonstration Slug Testing. As was conducted for baseline conditions, slug tests will be
repeated in each of the four injection wells to evaluate any the post-treatment properties of each
injection well and test plot. Slug tests will be conducted by implementing the procedures
described above for baseline monitoring.
Post Demonstration Sampling. Following completion of all plot operation and monitoring,
groundwater samples will be collected bi-weekly for two months from all monitoring wells and
MLS wells within each plot to evaluate post-treatment conditions using low flow sampling
techniques (see Table 5-3). Groundwater samples will be analyzed for the constituents listed in
Table 5-4.
Additionally, up to five soil cores will be collected using DPT technology from each plot to
further define post-treatment conditions. Soil borings will be advanced within the SHMP control
and test plots to approximately 20 ft bgs and advanced within the xanthan gum control and test
64

plots to approximately 60 ft bgs. Each soil boring will be logged by the field geologist and sent
for laboratory analysis of the analytes listed in Table 5-4.
At Site 88, a confining unit separates the Surficial Aquifer from the Upper Castle Hayne Aquifer
at approximately 25 ft bgs. All borings to be advanced beyond this depth (all borings associated
with the xanthan gum control and test plots)will require the installation of isolation casings from
the ground surface into the confining unit(at least one foot)to prevent cross-contamination.
5.5 SAMPLING PLAN
The complete sampling plan is provided in Tables 5-2, 5-3, and 5-4.
5.5.1 Monitoring Objectives
The objectives of this sampling plan are to evaluate the delivery and treatment performance for
"permanganate only" and "permanganate + polymer" test areas. Physical and chemical testing
will be conducted to evaluate the effect of xanthan gum on the distribution of permanganate in
heterogeneous lithologies, the effect of SHMP on the aggregation and deposition of Mn02, and
to compare post-delivery/treatment groundwater quality for each test area.
5.5.2 Overview of Monitoring Approach
As discussed in Sections 5.2 and 5.4, physical and chemical tests will be conducted prior to,
during, and following the demonstration to evaluate potassium permanganate delivery and
treatment of site contaminants.
Prior to the demonstration, injectability tests and slug tests will be conducted in each of the four
injection wells to determine the initial hydraulic properties of each plot. Groundwater samples
will be collected from all monitoring wells and MLS wells within each plot to capture baseline
conditions. Soil core samples will be collected from all plots to further define baseline
conditions.
During the demonstration, groundwater samples will be collected from all monitoring wells and
MLS wells within each test plot. Soil cores will be collected using DPT for physical and
analytical testing to evaluate the distribution of potassium permanganate.
Following the demonstration, slug tests will be repeated in each of the injection wells to evaluate
post-treatment properties of each injection well and plot. Groundwater samples will be collected
from all monitoring wells and MLS wells within each plot. Groundwater grab samples and soil
cores will be collected using DPT for physical and chemical testing to determine the extent of
potassium permanganate delivery.
65

5.5.3 Monitoring Schedule
The schedule of plot testing and sampling is summarized in Tables 5-2 and 5-8. A detailed
schedule of anticipated dates for the occurrence of the testing and sampling events is included in
Section 7.0.
5.5.4 General Procedures
Calibration of Analytical Equipment. All instruments will be calibrated as required by the
Standard Methods of analysis employed (e.g., APHA, USEPA, etc.) or as per the instrument
manufacturer's directions. Calibration verification will be conducted at least once per day or for
each analytical run. All field equipment will be pre- and post-calibrated. Calibration checks
using known standard solutions of the analyte of interest will be run as necessary during the day
and at the end of each sampling session.
Quality Assurance Sampling. Field blanks and duplicate samples will be collected and
submitted for laboratory analysis. Table 5-9 describes each quality assurance/quality control
(QA/QC) sample and the required frequency of collection.
Table 5-9. QA/QC Samples
Sample Type Description Frequency Analytes
Field Blank Designed to detect contamination in the One field blank TCL VOCs,MnO4
decontamination water. A field blank is from each source of
decontamination water collected directly decontamination
in the sample bottle. It is handled like a water for each
sample and transported to the laboratory sampling event,
for analysis. where a sampling
event is defined as
one week
Field Duplicate Designed to check precision of data in 10%of field TCL VOCs,MnO4
the laboratory. A field duplicate is a samples
sample collected in addition to the native
sample at the same sampling location
during the same sampling event.
Decontamination Procedures. Appropriate personnel, drilling and well equipment and
materials, and sampling equipment and materials decontamination procedures will be followed
as described below.
Personnel Decontamination
Personnel decontamination is discussed in the Health and Safety Plan (Appendix B).
Drilling Equipment and Well Construction Materials
Before mobilizing to the site, all drilling tools will be cleaned with a high-pressure hot-water
power washer or steam jenny, or hand washed with a brush using detergent to remove oil,
grease, and hydraulic fluid from the exterior of the unit. Degreasers will not be used. All
66

drilling tools will be decontaminated prior to installation of each monitoring well.
Decontamination of all equipment, tools, and well materials will consist of hot-water
pressure washing to remove all visible evidence of soil, encrustations, or films. Well
materials, augers, drill rods, and split-spoon samplers will be rinsed with de-ionized water
after pressure washing and prior to use.
Sampling Equipment
Any stainless-steel sampling equipment, if utilized, will be decontaminated prior to sampling
and between all samples to prevent the introduction of contaminants into the sample. This
will generally include washing equipment with a laboratory detergent, then rinsing with tap
water, de-ionized water, and isopropanol.
Water sampling, water level measuring, and sample preparation equipment brought onsite
will be cleaned prior to and after each use. During cleaning and decontamination operations,
the substitution of higher grade water for tap water is permitted and need not be noted as a
variation. Personnel will decontaminate PPE in accordance with the Health and Safety Plan
(Appendix B).
Sample Documentation. Each analytical sample collected will be assigned a unique number of
the following format:
IR88 -Media/Station#or QA/QC—Depth/Round;where:
Media IS=In-situ soil or groundwater sample collected by DPT
MW=Groundwater collected from a monitoring well
Station# Unique identification number for each collected sample
QA/QC D=Duplicate sample (following sample type/number)
e.g., IR88-MW123D-1
FB=Field blank
The blank QA/QC designation should be followed by the date the
sample was collected.
e.g.,IR88-FB082410
Depth/Round Depth or round indicators may be used for soil and groundwater
samples.
1 —Pre-Demonstration Sampling
2—Technology Performance Sampling
3 —Post-Demonstration Sampling
e.g.,IR88-MW123-1
Sample preservation occurs in the field immediately after collection. The containers supplied by
the laboratory will contain preservative, if appropriate. QA/QC samples will be collected in the
same type of containers with preservatives as the field samples. Preservatives and holding times
for each analysis is included in Table 5-4.
Samples collected during field activities will be shipped via an overnight courier to the analytical
laboratory. A cooler of suitable strength for packaging and shipping of samples will be used and
will be manifested to meet U.S. Department of Transportation (DOT) regulations. The bottom
and sides of each cooler will be lined with bubble wrap or other cushioning material. Each
sample jar or bottle will also be individually wrapped in bubble wrap to prevent breakage. All
samples will be kept upright in the cooler. Once the samples are in the cooler, any voids will be
67

filled with additional packaging material. Ice will be double-bagged in re-sealable bags and
placed in the cooler with the samples. A sufficient amount of ice will be added to the coolers to
ensure they arrive at the laboratory at a temperature of 4°C. The chain-of-custody (COC) record
will be placed in a watertight plastic bag and taped to the inside lid of the cooler. The cooler will
be secured with strapping tape and custody seals will be affixed to the front and back of the
cooler. The custody seals will be covered with wide, clear adhesive tape.
A COC form will be prepared for each cooler of samples shipped to the laboratory. At a
minimum, the following will be recorded on the COC:
• Site name
• Sampler name(s)
• Date and time of sample collection
• Identification code unique to each sample
• Number of containers with the same sample code
• Analyses requested for each sample (including the analytical method numbers)
• Signature of each individual who has custody of the sample(s)
Field documentation will consist of one or more site-specific field logbooks, field forms, sample
logs/labels, and an equipment calibration log. Each logbook will be identified uniquely by
project task and consecutively numbered. The responsible person for the field effort will
complete the logbook. Pages will not be removed from the document. Partially used pages will
be lined out, dated, and initialed to prevent data entry at a later date.
The front cover or first page of the logbook must list the project name, the project number, and
dates of use. Entries in the logbook must be continuous through the day. Logbook pages, as
well as the logbooks themselves, are numbered consecutively. The following items are to be
included, as appropriate to the work scope, in the logbook:
• Date, time of specific activities, and physical location
• Weather conditions
• Names, titles, and organization of personnel onsite, names and titles of visitors, and times
of visits
• Field changes or variances with references to the appropriate documentation of these
changes
• Specific comments related to peculiar problems that occurred during the day, if any, and
their resolution
• Field observations, including specific details on sampling activities (including type of
sampling, time of sampling, and sample numbers), a description of any field tests and
their results, and references to any field forms used and type of document generated
• A detailed description of samples collected and any splits, duplicates, or blanks that were
prepared. A list of sample identification numbers, packaging numbers, and COC record
numbers pertinent to each sample or referenced to the appropriate documentation should
be noted
• Specific problems, including equipment malfunctions and their resolutions
• List of times, equipment types, and decontamination procedures followed
68

• Photograph records (photographs will be taken during key field activities)
• Additional information, at the discretion of the logbook user
5.6 DATA ANALYSIS
Table 3-1 outlines in detail this demonstration's success criteria, which are also summarized
below in Table 5-10 for quick access, along with a summary of the general data analysis
approach. Section 5.6.1 is provided below for data analysis approaches requiring explanation
beyond that provided in Table 5-10.
5.6.1 Improved Sweep Efficiency Using Xanthan Gum
Immediately following injection operations for the control and test plots, continuous sediment
cores will be collected using direct-push methods in acetate sleeves. These sediment cores will
be characterized and logged on-site for the presence or absence of un-reacted permanganate
(purple color) or the oxidation by-product MnO2 (brown staining). These cores will also be
shipped to the laboratory for analysis of MnO2 concentration. The presence or absence of
permanganate will be vertically profiled along two transects across the treatment radius of each
plot. These data will be used to prepare cross-sections of the presence of permanganate via
numerical kriging. To address the success criteria outlined in Table 5-7, vertical sweep
efficiencies (VSE) for permanganate, with and without xanthan addition, will be calculated as
per Eqn. 5-1. A schematic example of this sampling approach is provided as Figure 5-6.
VSE = Integrated area swept by_permanganate [5-1]
Total area of the cross-section
VSE calculated for treatment with and without polymer addition will be used to determine the
percent improvement in VSE as in Eqn. 5-2.
%V SEImprovement = V SEWithPolymer—VSE t outfolyme X 100 [5-2]
V SEWAPolymer
In addition to investigating overall sweep efficiency improvement, we will use the soil cores
collected to assess the improvement of permanganate delivery into the lower permeability silt
and silty sand layers that exist within the treatment zones. Cores collected that include this lower
permeability stratum will be evaluated on site as to the depth of penetration of permanganate into
the lower permeability strata. Depths of penetration of permanganate will be determined for the
polymer and no-polymer cases and the results compared.
69

Table 5-10. Demonstration Performance and Success Criteria
Key Objective Performance Success Criteria Data Analysis*
Criteria F
Quantitative Performance Objectives
Improve sweep Evaluate long-term Data collected and are representative of test plots Data collected and evaluated for outliers relative to historical site data
efficiency and potential for and short-
control Mn02 term occurrence of
particles(xanthan contaminant rebound Post-treatment groundwater monitoring results remain below Determine if there is a statistically significant difference in
and SHMP) within 2-months post- baseline concentrations and validate reduction of contaminant contaminant concentrations in soil core sections and in waters into
treatment rebound that would otherwise be predicted from the soil which core contaminants are subjected to for diffusion assessment
samples alone
Improve sweep Improved contaminant Statistically significant reduction in contaminant mass as Determine if there is a statistically significant difference
efficiency and treatment effectiveness compared to a control plot
control Mn02
particles(xanthan
and SHMP
Improve sweep Increased penetration 50%longer distance of permanganate penetration into lower Measure permanganate penetration in soil cores focusing on key
efficiency of oxidant into lower permeability layers/strata strata;determine if there is a statistically significant difference
(xanthan) permeability 25%higher permanganate concentration at expected time of Measure permanganate concentration in groundwater for each
layers/strata arrival in each monitoring well sampling event;determine if there is a statistically significant
difference
Demonstrated improvement in vertical sweep efficiency of See Section 5.6.1
permanganate within lower permeability layers/strata
Demonstrated improvement in overall vertical sweep See Section 5.6.1
efficiency of permanganate within the test plot
Control Mn02 Decreased flow 50%lower mass of Mn02 in given mass of media Measure Mn02 in soil cores with distance from injection;determine if
particles(SHMP) bypassing(increased there is a statistically significant difference
lateral sweep 25%greater mobile Mn02 concentration at given time point in Measure Mn02 in groundwater with distance from injection;
efficiency)of areas of monitoring well determine if there is a statistically significant difference
high contaminant mass 50%lower mass of contaminant in high concentration cores Measure contaminant in soil cores with distance from injection;
determine if there is a statistically significant difference
Qualitative Performance Objectives
Control Mn02 Decreased impact of No increase in injection pressure attributable to Mn02 Measure pressure at the well head;determine if there a statistically
particles(SHMP) Mn02 deposition on significant difference
injection pressure
Compare post- Improved Note differences Note differences
delivery/treatment understanding of
groundwater impacts of approach
quality(xanthan on groundwater
and SHMPquality
*NOTE: difference refers to test vs. control plots
70

Test Plot (Polymer) Test Plot (No Polymer)
i v ♦ i v
i ru ♦ i
• ► • ►
Transect 1 ► Transect 3
• •
♦ i ♦ i
Clay
Sand(K1)
Ail
Silt(K)
Sand (K2>K1)
Figure 5-6. Schematic of field core sample transects and example permanganate distribution
cross-sections used to estimate permanganate vertical sweep efficiencies for the polymer and no-
polymer treatment plots.
71

6.0 COST ASSESSMENT
Table 6-1 shows the costs associated with developing and validating polymer-enhanced
permanganate ISCO. Cost elements and data to be tracked focus on the costs that are above-and-
beyond the costs of the typical permanganate-only ISCO approach. All costs will be tracked and
compared per plot and costs will be compared for each permanganate-only (control) and
permanganate + polymer (test) plot. With this approach any cost differences not anticipated
(Table 6-1)will still be captured.
Table 6-1. Cost Model for Polymer-Enhanced Permanganate ISCO
Cost Element Data to be Tracked Examples/Comments
Site • Detailed hydraulic and lithology • CPT with depth
characterization characterization required—costs will be • Pneumatic slug test for high resolution
tracked dissipation testing
Treatability test • Personnel and labor • Additional batch tests to optimize
• Materials oxidant/polymer mixture
• Analytical costs • Transport evaluations where permeability
may be of concern for delivery
Material cost • Polymer costs
• Polymer mixing and filtration
equipment costs
Installation • Installation method
• Mobilization costs
• Time
Operation and • Labor costs • Specialized polymer mixing and filtration
maintenance equipment
Long-term • Standard groundwater monitoring • Comprehensive water quality parameters
monitoring expected will be measured during demonstration—
any notable parameters that would trigger
extra monitoring will be subject to cost
tracking
6.1 COST ELEMENT: SITE CHARACTERIZATION
For polymer-enhanced permanganate ISCO (beyond permanganate-only ISCO), particularly for
improved sweep efficiency using xanthan polymer, it is important to have detailed
characterization of site lithology and hydraulic conductivity to assure heterogeneities are well-
understood for design purposes. For this demonstration, we are using detailed CPT profiling
with depth (well beyond the standard amount of data points with depth). Pre- and post-
demonstration slug testing will also be conducted to understand potential impacts of residual
polymer (xanthan plot) or Mn02 (SHMP and control plots) on hydraulic conductivity. Residual
xanthan may cause pore clogging and reduced conductivity. The ability to decrease or eliminate
the impacts of Mn02 on hydraulic conductivity using SHMP is a key performance objective.
These are evaluations that would be recommended for any demonstration using xanthan and
72

SHMP at any scale. Costs will be tracked by cubic yard (c.y.) of media targeted for
permanganate and polymer treatment.
6.2. COST ELEMENT: TREATABILITY TEST
While oxidant demand tests to determine the rate and extent of permanganate interaction with
natural subsurface media are recommended whether or not polymer amendments are added, the
use of polymer requires additional testing involving increased labor, materials, and analytical
costs. Additional testing includes the determination of optimal xanthan and SHMP
concentrations to use on a site-specific basis at the batch scale, characterization of concentration-
specific rates of reaction of xanthan and permanganate (albeit slow), and, ideally, 1-D transport
evaluations to assess potential impacts to conductivity and flow. Costs will be tracked on a per
site basis and will apply to a demonstration of any scale.
6.3 COST ELEMENT: MATERIAL COST
Excess materials for enhanced polymer ISCO include the polymers themselves, polymer mixing
equipment, extra piping for introducing polymer inline to the system design, and polymer
filtration (specific to xanthan) materials/equipment. Polymer costs will be tracked on a lb of
polymer per c.y. of media treated — site specific factors that could impact the extrapolation of
these results to other sites will be discussed. Other costs will be tracked on a cost per lb of
polymer material used basis.
6.4 COST ELEMENT: INSTALLATION
Any extra costs associated with installing the extra components of the treatment system (time
and mobilization costs) will be tracked on a per site basis. Issues of scaling from pilot to full
scale will be discussed.
6.5 COST ELEMENT: OPERATION AND MAINTENANCE
Specialized equipment will be used for polymer filtration and mixing. Any additional costs
associated with O&M of the specialized equipment (e.g., changing filter cartridges, etc.) will be
tracked on a"per hour of operation"basis.
6.6 COST ELEMENT: LONG-TERM MONITORING
Long-term monitoring (up to 8 weeks post-treatment) is planned for this demonstration to
monitor impacts on water quality and attenuation of such impacts. Any monitoring results that
"kick in" extra monitoring requirements or adjustment to conditions in the field will be subject to
cost-tracking on a "per occurrence" basis. These costs are not anticipated nor budgeted at this
time.
73

7.0 SCHEDULE OF ACTIVITIES
Figure 7-1 presents the project's original schedule of activities (on a project funding year
schedule from Feb of one year through Jan of the next). Site selection was completed in July
2009. Treatability study work was completed and the reported was submitted in January 2010.
Field implementation is to begin May 2010, starting with building the system on site, and all
post-demonstration monitoring will be completed in October 2010, two months after oxidant and
polymer injection, scheduled for July/August 2010. Data analysis will continue through
February 2011, followed by completion of the Cost and Performance Assessment and Final
Technical Report in May 2011.
Key milestones (see Table 5-8) that must be met to assure this schedule is followed include:
1. Delivery of system design equipment to the site by May 2010
2. Well installation and development by May 2010
3. Equipment testing by June 7, 2010
4. Chemical delivery by July 5, 2010
5. Potable water injection tests by June 14, 2010
6. Pre-demonstration testing and analysis by July 9, 2010
7. Control plot injections by July 27, 2010
8. SHMP test operation by July 30, 2010
9. Xanthan test operation by August 9, 2010
10. Post-demonstration testing and analysis by October 14, 2010
Each of the items 7-10 above has associated groundwater sampling, DPT soil sampling and
borehole surveys in addition to the oxidant (and polymer) injection. Items 5 and 10 both have
associated slug testing. Issues with instrumentation and/or equipment would be the most likely
causes of an offset to the schedule. If each of the summer and fall 2010 milestones can be met,
then a May 2011 project completion is anticipated.
74

Table 7-1. Schedule of Activities
YR1 3/09-1/10 YR2 2/10-1/11 YR3 2/11-5/11
MONTH M A M J J A S O N D J F M A M J J A S O N D J F M A M
Site Selection
Treatability stud
Demonstration Plan
Field Implementation
Data Analysis
Cost& Perf. Assessment
Reporting
75

8.0 MANAGEMENT & STAFFING
The project organization is presented in Figure 8-1.
Dr. Michelle Crimi is the Principal Investigator (PI) for the demonstration. She is a professor at
Clarkson University. She is responsible for coordinating and supervising field activities,
particularly those related to the SHMP application test plots. She will provide real time data
interpretation and will assess the need for changes to operation during the demonstration. She is
also responsible for supervising laboratory analyses and subsequent data interpretation and
reporting.
Dr. Jeffrey Silva is the Co-Principal Investigator (Co-PI) for the ESTCP Demonstration. He is a
researcher at the Colorado School of Mines (CSM). He is responsible for coordinating and
supervising field efforts related to the xanthan application test plots. He will provide real time
data interpretation and will assess the need for changes to operation during the demonstration.
He is also responsible for supervising laboratory analyses and subsequent data interpretation and
reporting.
Ms. Monica Fulkerson, Professional Engineer (P.E.) is the CH2M HILL Project Manager for
ESTCP Demonstration. She is the primary contact for MCB Camp Lejeune and is responsible for
the overall quality assurance and quality control (QA/QC) of site activities.
Mr. Tom Palaia, P.E. will serve as Senior Technical Consultant for the ESTCP Demonstration.
Mr. Palaia will review the technical aspects of the work from project scoping to project
completion.
Mr. Max Bertram, Certified Safety Professional (CSP), is the CH2M HILL Project Health and
Safety Manager. Mr. Bertram will determine appropriate hazardous control measures for
personnel on site.
76

Regulator and Stakeholder Agencies
United States Environmental Protection Agency Region 4
North Carolina Department of Environment and Natural Resources
i
i
i
MCB CamLej Environmental NAYFAC Mid-Atlantic Reme6al
Management Division -+--- Project Manager
Bob Lowder Dave Cleland
(910-461-9607) (757-322-48511
CH2M HILL Deputy CH2M HILL Activity Manager
Program Manager Matt LouthNBO
(757-671-8240)
Doug DronfieldlWDC CH2M HILL Deputy Activity
(703-37&5090) Manager ESTCP
Kim HandersonNeO
(757-671-62311
Clarkson University Project Colorado School of Mines
Manager Project Manager
Michelle Cnmi Jeff Stiva
CH2M HILL Senior CH2MHILL Heakh and (315-244-3125) (303-579-1275)
Technical Consultant Safety Manager
Tom Palaia/DEN r----____
Cad Woods(CIN
(303-679.2510) (513-889-5771)
CH2M HILL Project
Manager
Monica FUlkersorVCLT
(704-544-5177)
1
CH2MHILL Project CH2M HILL Quality
Assurance Manager
Delivery Manager ___
Chris Bozzird/CLT
Doug BittermanNBO
(7045445163)
1757-671-83111
CH2M HILL
Subcontractors CH2M HILL Field Staff
Utility Locator
- TBD
TBD
Driller
TBD
Surveyor
TBD
Investigation Derived Waste
Transport and Disposal
TBD
------ Lines of Communication
b Lines of Authority
Figure 8-1. Project organization.
77

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