United States
Environmental Protection
Agency
In-Situ DUOX™ Chemical Oxidation
Technology to Treat Chlorinated
Organics at the Roosevelt Mills Site,
Vernon, CT
Site Characterization and Treatability Study Report
SUPERFUND INNOVATIVE
TECHNOLOGY EVALUATION
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Notice
The information in this document has been funded by the U.S. Environmental Protection Agency
(EPA) under Contract Number 68-COO-179 to Science Applications International Corporation
(SAIC). It has been subjected to the Agency's peer and administrative reviews and has been
approved for publication as an EPA document. Mention of trade names or commercial products
does not constitute an endorsement or recommendation for use.
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Foreword
The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting
the Nation's land, air, and water resources. Under a mandate of national environmental laws, the
Agency strives to formulate and implement actions leading to a compatible balance between
human activities and the ability of natural systems to support and nurture life. To meet this
mandate, EPA's research program is providing data and technical support for solving
environmental problems today and building a science knowledge base necessary to manage our
ecological resources wisely, understand how pollutants affect our health, and prevent or reduce
environmental risks in the future.
The National Risk Management Research Laboratory (NRMRL) is the Agency's center for
investigation of technological and management approaches for preventing and reducing risks from
pollution that threaten human health and the environment. The focus of the Laboratory's research
program is on methods and their cost-effectiveness for prevention and control of pollution to air,
land, water, and subsurface resources; protection of water quality in public water systems;
remediation of contaminated sites, sediments and ground water; prevention and control of indoor
air pollution; and restoration of ecosystems. NRMRL collaborates with both public and private
sector partners to foster technologies that reduce the cost of compliance and to anticipate
emerging problems. NRMRL's research provides solutions to environmental problems by:
developing and promoting technologies that protect and improve the environment; advancing
scientific and engineering information to support regulatory and policy decisions; and providing the
technical support and information transfer to ensure implementation of environmental regulations
and strategies at the national, state, and community levels.
This publication has been produced as part of the Laboratory's strategic long-term research
plan. It is published and made available by EPA's Office of Research and Development to assist
the user community and to link researchers with their clients.
Sally Gutierrez, Director
National Risk Management Research Laboratory
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Abstract
A study was performed investigating the feasibility of applying the DUOX™ chemical oxidation
technology to chlorinated solvent contaminated media at the Roosevelt Mills site in Vernon,
Connecticut. The Roosevelt Mills site is a former woolen mill that included dry cleaning operations.
The plant also housed metal plating operations. The primary contaminants of concern are
chlorinated organic solvents: tetrachloroethene (PCE); trichloroethene, (TCE); cis-1,2-
dichloroethene (DCE); and vinyl chloride (VC). The DUOX™ technology, developed by researchers
at the Environmental Research Institute (ERI) at the University of Connecticut claims to provide a
cost-effective, in-situ oxidation process to neutralize chlorinated organic chemicals. The DUOX™
technology utilizes a combination of two types of oxidants to destroy unsaturated chlorinated
solvents. The oxidants belong to the persulfate and permanganate families of inorganic
compounds. Sodium persulfate is used to satisfy the soil oxidant demand (SOD) and minimize the
quantity of potassium permanganate needed to mineralize target compounds. This facilitates the
transport of permanganate through the aquifer, allowing for more uniform distribution of
permanganate and the use of a much smaller quantity. In turn, this alleviates problems caused by
excess permanganate (precipitated manganese dioxide that can result in reduced aquifer
permeability).
The study was performed under the auspices of the U.S. Environmental Protection Agency's
Superfund Innovative Technology Evaluation (SITE) program. The SITE study consisted of: (1) a
site characterization within and outside the Roosevelt Mills building to identify chlorinated source
material and characterize the extent of the dissolved phase plume, and (2) a laboratory treatability
study to evaluate the effectiveness of the DUOX™ technology on the impacted media at the site.
Results from the study are summarized below:
• A chlorinated solvent source area was located underneath the Roosevelt Mills building in a
portion of the foundation fill material (upper 1-3 ft). It appears that pure-phase PCE exists as
distinct globules within the coarse-grained fluidized zone.
• Groundwater results, both from inside and outside the building, indicate the presence of a
dissolved chlorinated solvent plume emanating from the vicinity of the source area identified in
the building.
• The near-surface fill material (source area matrix for the PCE) exhibits a very low soil oxidant
demand.
• Permanganate alone and in combination with persulfate is effective in reducing the levels of
chlorinated solvents in the site groundwater as well as in spiked soil samples simulating a free-
phase globular distribution.
• Persulfate alone, as tested, was ineffective in reducing the levels of chlorinated solvents in any of
the experiments. However, due to low SOD, there is no need to use persulfate for the chlorinated
solvent source area.
IV
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Contents
Notice ii
Foreword iii
Abstract iv
Tables vi
Figures vii
Abbreviations and Acronyms viii
Acknowledgements ix
1.0 Introduction 1-1
1.1 Background 1-1
1.2 Roosevelt Mills Site 1-1
1.3 DUOX™ Technology Description 1-2
2.0 Site Characterization 2-1
2.1 Site Characterization Objectives 2-1
2.2 Site Characterization Execution 2-1
2.3 Site Characterization Results 2-3
2.3.1 Source Area Delineation 2-3
2.3.2 Soil and Groundwater Characterization Results 2-5
2.4 Results from ERI's Field Investigation 2-5
3.0 Treatability Study 3-1
3.1 Purpose of the Treatability Study 3-1
3.2 Treatability Study Objectives 3-1
3.3 Treatability Study Experimental Design 3-1
3.3.1 Task 1 - Preparation and Characterization of Soil and Groundwater 3-2
3.3.2 Task 2 - Determination of Soil Oxidant Demand 3-2
3.3.3 Task 3 - Degradation of VOCs in Groundwater and Soil by KMnO4,
Na2S2O8 and the Dual Oxidants 3-3
3.4 Treatability Study Results and Conclusions 3-5
3.4.1 Task 1 Results and Conclusions 3-5
3.4.1.1 Particle Size Distribution 3-5
3.4.1.2 Characterization of Fill Material 3-5
3.4.1.3 Groundwater Characterization 3-5
3.4.2 Task2 Results and Conclusions 3-5
3.4.3 Tasks Results and Conclusions 3-9
3.4.3.1 Task 3-1 - Treatment of Contaminated Groundwater with
Oxidants 3-9
3.4.3.2 Task 3- 2 - Treatment of a Contaminated Groundwater in a
Soil Matrix with Oxidants 3-14
3.4.3.3 Task 3-3 - Treatment of Free Phase (Globular) PCE
Contaminated Soil/Groundwater Matrix with Oxidants 3-14
3.5 Treatability Study General Conclusions and Discussion 3-19
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Tables
2-1 Volatile Organic Compounds in Groundwater 2-6
2-2 Volatile Organic Compounds in Soil 2-7
2-3 Metals and Additional Analytes in Groundwater and Soil 2-8
2-4 ERI VOC Data (Detects) 2-11
3-1 Test Conditions of Batch Experiments for Soil Oxidant Demand (Task 2) 3-3
3-2 Test Conditions for Evaluating the Degradation of VOCs in Groundwater and Soil 3-4
3-3 Sieving Results forthe Fill Material 3-6
3-4 Fill Characterization Results 3-7
3-5 Background Groundwater Characteristics 3-8
3-6 Contaminated Groundwater Characteristics 3-9
3-7 Soluble Metals Before and After Ten Days of Oxidant Treatment 3-12
3-8 Results from Contaminated Groundwater Treatment 3-13
3-9 Chlorinated VOC Results from Spiked Groundwater/Soil 3-15
3-10 Other Analytes Results from Spiked Groundwater/Soil 3-16
3-11 Results from Free-Phase (Globular) PCE Contaminated Soil/Groundwater 3-18
VI
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Figures
1-1 Roosevelt Mills site map 1-3
2-1 Conceptual model of suspected chlorinated solvent source areas 2-2
2-2 Proposed outside sampling locations 2-2
2-3 CRT push locations inside the building 2-4
2-4 Globules of PCE in the near-surface fill material (from Video-CRT) 2-5
2-5 Soil and groundwater results from inside the building 2-9
2-6 Predicted PCE groundwater plume 2-10
2-7 ERI's sampling locations 2-14
3-1 Oxidant consumption over time - Potassium Permanganate (alone) 3-10
3-2 Oxidant consumption overtime -Sodium Persulfate (alone) 3-10
3-3 Oxidant consumption over time - Potassium Permanganate with 1 g/L
Sodium Persulfate 3-11
3-4 Oxidant consumption over time - Potassium Permanganate with 72 hour 1 g/L
Sodium Persulfate pretreatment 3-11
VII
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Abbreviations and Acronyms
ARA Applied Research Associates
BTSA Brownfields Targeted Site Assessment
CRT Cone penetrometer
DCE Dichloroethene
DNAPL Dense non-aqueous phase liquid
EPA U.S. Environmental Protection Agency
ERI Environmental Research Institute
mg/Kg Milligrams per kilogram
mg/L Milligrams per liter
ml Milliliter
MMFC Mark Metal Finishing Corporation
NA Not analyzed
ND Non-detectable, or not detected at or above the method detection limit
ORD Office of Research and Development (EPA)
ORP Oxidation reduction potential
OSWER Office of Solid Waste and Emergency Response (EPA)
PAHs Polyaromatic hydrocarbons
PCE Tetrachloroethene
PSD Particle size distribution
RCRA Resource Conservation and Recovery Act
SARA Superfund Amendments and Reauthorization Act
SAIC Science Applications International Corporation
SOD Soil oxidant demand
SITE Superfund Innovative Technology Evaluation
SVOCs Semivolatile organic compounds
S.U. Standard units
TCE Trichloroethene
TOG Total organic carbon
ug/Kg Micrograms per kilogram
ug/L Micrograms per liter
urn Micron
USTs Underground storage tanks
TPH Total petroleum hydrocarbons
VOA Volatile organic analysis
VOCs Volatile organic compounds
VC Vinyl chloride
VIM
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Acknowledgments
This report was prepared under the direction of Mr. Paul Randall, the EPA Technical Project Manager
for this SITE demonstration.
The demonstration required the combined services of several individuals from Science Applications
International Corporation (SAIC), Applied Research Associates (ARA), the Environmental Research
Institute (ERI), and the Town of Vernon Connecticut. Dr. Scott Beckman of SAIC served as the SITE
work assignment manager for the implementation of site characterization and treatability study
activities as well as the completion of this report. Dr. Joel Hayworth served as the project manager for
ARA. Dr. Amine Dahmani of the Environmental Research Institute of the University of Connecticut
provided assistance in the collection of samples and execution of the treatability study. Mr. Larry
Shaffer of the Town of Vernon provided access assistance to the Roosevelt Mills site. The treatability
study was performed at ARA's facility in Panama City, Florida. The cooperation and efforts of these
organizations and individuals are gratefully acknowledged.
This report was prepared by Dr. Scott Beckman and Ms. Rita Stasik of SAIC. Ms. Stasik also served
as the SAIC Quality Assurance (QA) Coordinator for data review and validation.
IX
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Section 1.0
Introduction
1.1 Background
A study was performed investigating the feasibility of
applying the DUOX™ chemical oxidation technology to
chlorinated solvent contaminated media at the Roosevelt
Mills site in Vernon, Connecticut. The DUOX™
technology, developed by researchers at the
Environmental Research Institute (ERI) at the University
of Connecticut (referred to as the developer), claims to
provide a cost-effective, in-situ oxidation process to
neutralize chlorinated organic chemicals. The study was
performed under the auspices of the U.S. Environmental
Protection Agency's Superfund Innovative Technology
Evaluation (SITE) program. The SITE Program is a
formal program established by the EPA's Office of Solid
Waste and Emergency Response (OSWER) and Office
of Research and Development (ORD) in response to the
Superfund Amendments and Reauthorization Act of
1986 (SARA). The SITE Program promotes the
development, demonstration, and use of new or
innovative technologies to clean up Superfund sites
across the country.
The purpose of the study was to: (1) perform a site
characterization of the Roosevelt Mills site to gain an
understanding of the extent of groundwater chlorinated
solvent contamination and the location of a potential
chlorinated solvent source area. The site
characterization would be used to assist in determining
site-specific parameters associated with the application
of the DUOX™ technology, and (2) perform treatability
studies on contaminated soil and groundwater from the
site that represent potential matrices and conditions that
may be considered for subsequent pilot-scale testing at
Roosevelt Mills.
This report will present background information on the
Roosevelt Mills site and the DUOX™ technology,
discuss the results from the site characterization and
rationale for selecting media for study, and present the
results and conclusions from the treatability study.
1.2 Roosevelt Mills Site
The Roosevelt Mills site is a former woolen mill that
included dry cleaning operations. The plant also housed
metal plating operations. The primary contaminants of
concern are chlorinated organic solvents:
tetrachloroethene (PCE); trichloroethene, (TCE); c/s-1,2-
dichloroethene (DCE); and vinyl chloride (VC).
Roosevelt Mills, now owned by the Roosevelt
Acquisition Corporation, operated as a woolen mill from
the mid-1800s to the late 1980s. The 7-acre site
contains four main buildings (see Figure 1-1): a three-
story Granite Mill Building, constructed in 1836; a one-
story addition to the Granite Mill Building, constructed in
1937; a five-story Factory Building, constructed in 1907;
and a Boiler House, also constructed in 1906. The
Hockanum River has been channeled into two pathways
(canal outlet and wasteway) that flow beneath the
Granite Mill Building and the Factory Building. A pump-
house is adjacent to the Factory Building at the east
bank of the Hockanum River. Shenipsit Lake and a
water treatment plant that is operated by the Connecticut
Water Company border the northern portion of
Roosevelt Mills. Groundwater beneath the site and
within a 0.5-mile radius of the site is classified as GA
(water suitable for drinking without treatment). Shenipsit
Lake is utilized as a public water supply reservoir.
Operations conducted at Roosevelt Mills included wool
carding, picking, dyeing, knitting, button manufacturing,
and dry cleaning. Wool dyeing was conducted in the
dye house north of the Granite Mill Building until 1937,
then in the "1937 addition" until 1972, when the addition
was leased to the Mark Metal Finishing Corporation
(MMFC). Aluminum anodizing and electroplating were
the two main activities of the MMFC conducted in the
"1937 addition" from 1972 to 1996. Dyeing continued in
the west basement area of the Factory Building after
1972. Past waste disposal practices by Roosevelt Mills
are not known; however, it is probable that the mill
discharged waste products to the Hockanum River.
Potential sources of site contamination (Figure 1-1)
include: floor pits; dyeing area; dry-cleaning area; floor
1-1
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trench that discharged to the river; chemical storage
area; electroplating area; former pond and waste house,
contaminated soil with boiler slag and ash; fuel oil
underground storage tanks (USTs); and a former drum
storage area. Roosevelt Mills ceased operations in the
mid-1980s, and the site is currently abandoned.
According to a December 1998 Roy F. Weston Inc.
report entitled "Roosevelt Mills Site, Brownfields
Targeted Site Assessment", EPA-Region I conducted in
1988 an emergency removal of containerized waste and
raw materials left in the basement of the factory building
when site operations ceased in the mid-1980s. It was
noted that PCE was used as a dry-cleaning solvent in
the basement dry-cleaning area of the factory building
and that raw materials were stored in the basement
dyeing and dry-cleaning area of the factory building.
Drummed wastes removed during the removal action
included several hundred 5 to 55-gallon drums of
chemicals associated with dyeing and wool treatment.
The drums contained petroleum naphtha, sodium
chlorite, sodium acetate, sodium hypochlorite, sodium
bisulfate, copper sulfate, sodium sulfate, tetrasodium
pyrophosphate, acetic acid, formic acid, sodium
hydroxide, hydrochloric acid, botylcarnityl (a pesticide),
organic dyes, and pigments.
Other than the 1988 emergency removal, the only
remediation measure implemented to date was the
removal and replacement of the leaking USTs in the
early 1980s. Approximately 1000 cubic yards of
petroleum-contaminated soil was excavated, stockpiled
on-site, and subsequently removed from the site.
Another 10,000-gallon LIST discovered leaking in 1985
was replaced with another 10,000 gallon LIST.
Historical site characterization and assessment activities
at the Roosevelt Mills site include limited soil sampling in
the factory and boiler house (1988), installation of
groundwater monitoring wells (1990), Phase I and II site
assessments (1995), and a Brownfield Targeted Site
Assessment (BTSA, 1997). Of theses activities, the
BTSA conducted in 1997 provided the most complete
picture of the site to date, and provides a starting point
for developing a strategy for additional field sampling.
The Roosevelt Mills Brownfields Targeted Site
Assessment (BTSA) was conducted by Roy F. Weston,
Inc. in two Phases. Phase I sampling was performed in
August, 1997; Phase II sampling was performed in April,
1998. During Phase I work, 21 soil samples, 6 sediment
samples, and 8 groundwater samples were collected.
During Phase II work, 22 soil samples and 7
groundwater samples were collected. Phase I and II
samples were analyzed for potential contaminants of
concern, including VOCs, SVOCs, TPH, RCRA Metals,
PAHs, and Cyanide.
Results of groundwater samples collected during the
BTSA reveal the presence of tetrachloroethene (PCE),
trichloroethene (TCE), dichloroethene (DCE), and vinyl
chloride (VC) at the site. These compounds are found
within the near-surface aquifer primarily underlying the
mill and main factory buildings. The presence of DCE
and VC in the groundwater is evidence that PCE and
TCE are being anaerobically biodegraded at the site.
Further, the lateral distribution of these compounds
follows the direction of groundwater flow and is
consistent with migration away from a source region of
active biodegradation .
1.3 DUOX™ Technology Description
The DUOX™ technology utilizes a combination of two
types of oxidants to destroy unsaturated chlorinated
solvents. The oxidants belong to the persulfate and
permanganate families of inorganic compounds. The
most economical oxidants from each class of oxidants
are sodium persulfate (Na2S2O8) and potassium
permanganate (KMnO4). This in-situ chemical oxidation
process involves injecting a solution of one or more
oxidants in series or simultaneously into the subsurface
to mineralize the target contaminants.
In a typical process application, sodium persulfate is first
injected into the subsurface and consumed by the
combined effect of mineralizing target contaminants and
satisfying soil oxidant demand (SOD) (due to reduced
conditions and/or high background levels of natural
organic matter). The primary purpose of sodium
persulfate is to satisfy the SOD and minimize the
quantity of potassium permanganate needed to
mineralize target compounds. This facilitates the
transport of permanganate through the aquifer, allowing
for more uniform distribution of permanganate and the
use of a much smaller quantity of permanganate. In
turn, this alleviates problems caused by excess
permanganate (precipitated manganese dioxide that can
result in reduced aquifer permeability). This sequential
dual treatment protocol can be repeated as many times
as necessary to reduce contaminant concentrations to
site target levels.
For the proper application and success of this
technology, injection well location and oxidant injection
rates must be based on a thorough evaluation of the site
hydrogeologic conditions and the nature of the organic
matter present at the site. An understanding of the
extent of contamination at the site is, therefore, an
1-2
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integral part of this technology. Thus, a careful
evaluation of the site-specific parameters, and the extent
of contamination, is needed for the proper application
and success of this remedial technology.
PROPERTY -
BOUNDARY
Figure 1-1. Roosevelt Mills site map.
1-3
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Section 2.0
Site Characterization
2.1 Site Characterization Objectives
The site characterization objectives, as well as sampling
and analysis methodologies, is described in the
document: "Quality Assurance Project Plan for the SITE
Demonstration of In-Situ DUOX™ Chemical Oxidation
Technology to Treat Chlorinated Organics at the
Roosevelt Mills Site, Vernon, CT (October 2001)" The
two main goals of the site characterization were to: (1)
Retrieve soil and groundwater samples to perform the
treatability tests from both the contaminant source area
(soil) and the dissolved groundwater plume that meet
the following criteria: Soil PCE concentrations of 500-
10,000 mg/Kg; Groundwater PCE concentrations of >50
mg/L, and (2) Characterize in sufficient detail to
implement, if deemed feasible from the treatability study,
a field demonstration of the DUOX™ technology.
Characterization goals consist of locating and
delineating PCE source areas believed to be beneath
the building, defining the extent and concentration of the
VOC contaminant plume, and determining the
hydrogeologic properties that would be necessary to
apply the DUOX™ technology at the Roosevelt Mills
site.
Additional goals for the site characterization included: (1)
determining the location and delineation of a potential
TCE source area if one exists, (2) assessing background
levels of metals in the groundwater and soil, and (3)
determining the extent and distributions of non-critical
VOCs (e.g., acetone) that may be present in the
groundwater and/or soil.
2.2 Site Characterization Execution
Site characterization activities were initiated on January
14, 2002 and ended on January 28, 2002. The field
activities focused on the collection of groundwater and
soil samples both within the structure of the mill and
outside the building. In addition to the collection of
groundwater and soil samples, the field investigation
focused on the collection of field parameters for
groundwater (dissolved oxygen, ORP, pH), as well as
the collection of subsurface geophysical and visual
information via CPT sensors (piezocone and videocone).
Site characterization employed the use of a cone
penetrometer (CPT) outfitted with several subsurface
sensors and sample acquisition tools. CPT sensors and
tools utilized were: (1) a standard piezocone for
evaluating the site hydrogeological properties, (2) a
Video-CPT for visually identifying the presence of pure-
phase chlorinated solvents, (3) a Conesipper tool to
collect groundwater samples, and (4) a VERTEK soil
sampler to collect discrete soil samples as well as cores
for use during the treatability study. Hydrogeological
properties at all sample locations were assessed by the
use of a standard piezocone. The piezocone determines
soil stratigraphy, relative density, strength and
hydrogeologic information. At selected depth intervals,
pore water pressure was monitored over time to
determine relative hydraulic conductivity and hydrostatic
head. The video-CPT tool was used to discern the
presence of pure-phase solvent by providing a visual
assessment of free product which shows up as visually
discernable globules.
Initial site characterization activities were focused on
determining the location and extent of free product within
the building. Based on a conceptual model of the
contaminant distribution developed prior to the field
investigation, candidate site locations within the building
were probed using the Video-CPT tool for the source
area. Figure 2-1 depicts the probable source areas for
the chlorinated solvents, and served as the starting
locations for exploratory drilling. Locating the source
area was the critical first step in defining the remainder
of the investigation, and for collecting groundwater and
soil samples for the treatability study. Once the source
area was located, attention turned to the collection of
groundwater samples both inside the building and
outside the mill. Figure 2-2 depicts the locations of the
proposed sampling points outside of the mill building.
These samples were used to assess the magnitude and
extent of the dissolved plume emanating from the source
area. It is important to note that samples from several of
the outside locations were difficult to obtain due to
2-1
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ESTIMATED DIRECTION OF
GROUND WATER FLOW
Groundwater Flow Direction & Lateral
Distribution of PCE, TCE, DCE, and VC
Figure 2-1. Conceptual model of suspected chlorinated solvent source areas.
/ CPT Push Locations-Source Area Delineation,
* Soil sampling, & Treatability Core Collection
22
CPT Push Locations-Aqijifer Hydraulics
& Groundwater Contamination Distribution
Figure 2-2. Proposed outside sampling locations.
2-2
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accessibility issues. Subsequent to the January 2001
field effort, ERI performed a site characterization to
obtain some of the samples that were not recovered in
January. In addition to the collection of samples for
analysis, soil cores and contaminated groundwater was
recovered for the subsequent treatability study.
Site characterization activities were impacted by the
physical conditions associated with sampling and
working within the building and subsurface conditions
related to the sub-basement. Noteworthy conditions
consisted of: (1) a lack of reliable sub-floor plans which
required very careful consideration of probe-hole
placement and resulted in numerous zones of refusal (2)
several areas within the work space that contained
asbestos including construction debris and large mill
equipment that required re-evaluation of the sampling
layout and rig movement, and (3) cold conditions in the
building causing ice hazards. In spite of these
challenging sample conditions, the source area was
delineated and samples were acquired and analyzed to
meet the project objectives.
2.3 Site Characterization Results
As previously discussed, the site characterization
focused on identification of the source area within the
building, and the assessment of the magnitude and
extent of soil and groundwater contamination. The
following sections will present the results from these two
efforts.
2.3.1 Source Area Delineation
Initial efforts focused on the detection and delineation of
probable source areas within the building. To
accomplish this task, the Video-CRT tool, along with the
piezocone tool, were utilized. Figure 2-3 depicts the
push locations inside the building. These locations have
the prefix "I" in the text to denote samples taken inside
the building. The process consisted of advancing these
CRT tools, and visually assessing in real-time, the
presence of free phase material. Once detected, a core
could be recovered and analyzed for Dense Non-
Aqueous Phase Liquid (DNAPL) VOCs from the zones
of interest. It was anticipated that the DNAPL source
area would be encountered in the deeper strata
underlying the building floor. This was based on the
tendency for denser-than-water chlorinated solvents to
accumulate within the basal sections of aquifers.
Contrary to this supposition, no DNAPL was found at
depth at the push locations investigated.
The chlorinated solvent source area was located within
the basal portion of foundation fill material (upper 1-3 ft)
near sample locations 18 and 110. It appears that pure-
phase PCE exists as distinct globules within this
fluidized zone rather than as a residual phase trapped
by pore tension. This is supported by the video cone
results and material cores. Figure 2-4 is a screen
capture of the Video-CPT and illustrates the globular
nature of the PCE distributed within the coarse grained
fill matrix. There is no evidence that the source area
exists to the east at or past 17, and to the south past 111.
The source area exists within a poorly sorted, fluidized
zone which begins under the building foundation and
extends to approximately 3 ft below the ground surface.
Below the upper fill zone is a more consistent aquifer
composed primarily of distinct sand layers interbedded
with silty sand and gravel-sand layers (native material).
The upper and underlying systems are hydraulically
connected and so the groundwater within each is
contaminated. However, PCE within the upper zone
cannot overcome the pore pressures within the lower
system and thus do not appear contaminated as free
product. This is supported by video cone results,
several core samples, and groundwater samples.
The globular nature of the PCE in the fill material results
in a very heterogeneous distribution. Soil samples taken
from this zone support the heterogeneous distribution of
the source area. A soil sample from 110 in the 1-3' fill
material exhibited a tetrachloroethene (PCE)
concentration of 1,720 ug/Kg, while a soil sample from
the same interval from adjacent 111 exhibited no
detectable VOCs. Furthermore, analysis of this fill
material is difficult due to the coarse nature and the
globular distribution of the PCE within the pore space.
In order to assess the level of contamination in this
zone, a large volume of material should be extracted
and analyzed.
Although there is no evidence of free product in the
underlying native material, there are significant levels of
dissolved chlorinated volatile organic compounds in the
groundwater. These compounds represent both
dissolved PCE as well as PCE degradation products
derived from reductive dechlorination. It is postulated
that PCE has diffused, in a dissolved state, from the
overlying fill material into the native material and is being
transported in the groundwater system. Reductive
dechlorination is occurring in portions of the underlying
groundwater system.
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2-4
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Figure 2-4. Globules of PCE in the near-surface fill material (from Video-CPT).
2.3.2 So/7 and Groundwater Characterization
Results
Tables 2-1 and 2-2 presents the results of the volatile
organic compounds in groundwater and soil from both
inside and outside of the building. Table 2-3 presents
the results of metals and other analytes from the soil and
groundwater. Figure 2-5 depicts the distribution of soil
and groundwater contamination within the building.
The results from the VOC data, both from inside and
outside the building, indicate the presence of a dissolved
chlorinated solvent plume emanating from the vicinity of
the source area identified in the building. There are
several noteworthy characteristics of the solvent plume:
(1) concentrations of PCE and chlorinated solvent
daughter products are highest directly beneath the
source area with concentrations of several hundred ppb,
(2) there is evidence that reductive dechlorination is
occurring due to the presence of PCE daughter
products, and (3) the plume is migrating to the
southwest and is consistent with the general
groundwater flow. Figure 2-6 depicts the predicted
movement of PCE based on a groundwater model using
data from this study as well as regional groundwater flow
data.
Groundwater and soil samples acquired from outside of
the building to the northeast do not contain significant
levels of volatile organic compounds. This area was a
potential area of concern due to the reported storage of
drums containing hazardous materials. No significant
chlorinated solvents were detected, and minor hits of
petroleum-based hydrocarbons were encountered.
2.4 Results from ERI's Field Investigation
The Environmental Research Institute of the University
of Connecticut, performed a field investigation
subsequent to SAIC's field deployment in January. The
purpose of ERI's investigation was to further delineate
the concentration and extent of chlorinated solvent
contamination inside and outside of the building. The
results from ERI's characterization confirm and are
consistent with the information gathered in January
2002.
ERI's data is presented in Table 2-4. Figure 2-7 depicts
sample locations. Note: ERI's data has not been
evaluated by the EPA and is presented here for data
comparisons.
2-5
-------
Table 2-1. Volatile Organic Compounds in Ground water
SAMPLE ID
Matrix Units
H-(7-9)-GW
!2-(1-4)-GW
!5-(2.5-4)-GW
!7-(7-10)-GW
!8-(4-6.5)-GW
!9-(3-5.5)-GW
HO-(6-9)-GW
IH-(4-7)-GW
IH-(4-7)-Gwdup
H2-(7-9)-GW
H3-(3-6)-GW
018-(10-13)-GW
022-(6-9)
024-(4-7)-GW
026-(6-9)-GW
027-(12.5-15.5)-GW
028-(12-15)-GW
029-(10-13)-GW
029-(10-13)-GW-dup
030-(17-20)-GW
GW
GW
GW
GW
GW
GW
GW
GW
GW
GW
GW
GW
GW
GW
GW
GW
GW
GW
GW
GW
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
ug/L
4 U
101
4 U
4 U
4 U
4 U
4 U
4 U
4 U
55
149
4 U
4 U
4 U
4 U
4 U
4 U
4 U
4 U
4 U
1 U
1 U
1 U
1 U
0.1 J
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
2 U
1 U
2 U
2 U
2 U
2 U
1 U
1 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
1 U
1 U
1 U
1 U
1.6
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
0.2 J
1 U
1 U
0.3 J
1 U
1 U
0.3 J
0.2 J
0.2 J
1 U
1 U
0.5 J
1 U
1 U
0.3 J
0.3 J
0.2 J
1 U
1 U
0.4 J
1 U
1 U
U
1 U
1.5
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
32
1 U
1 U
0.2 J
1 U
2.9
36
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1.1
1 U
1 U
1 U
1 U
1 U
1.1
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
1 U
14
0.9 J
1 U
231
60
20
323
127
172
69
1 U
1 U
1 U
0.3 J
1 U
0.2 J
1 U
1 U
1 U
1 U
15
1 U
1 U
1 U
1 U
1 U
1 U
1 U
2.2
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
2.7
0.2 J
0.2 J
0.5 J
1 U
1 U
0.2 J
1 U
0.4 J
1 U
0.3 J
1 U
1.9
1 U
1 U
1 U
0.2 J
1 U
1 U
1 U
1
1 U
1 U
50
3.1
0.4 J
1.4
1.6
4.3
115
1 U
1 U
1 U
0.3 J
1 U
1 U
1 U
1 U
1 U
2 U
2 U
2 U
2 U
4.1
2 U
2 U
2 U
2 U
2 U
0.7 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
2 U
3 U
47
3 U
3 U
0.3 J
3 U
3 U
3 U
3 U
8.7
3 U
3 U
3 U
3 U
3 U
3 U
3 U
3 U
3 U
3 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
1 U
U = Not Detected at the concentration indicated (e.g. 4U means not detected at a 4 ug/L detection limit)
J = Estimated Value
2-6
-------
Table 2-2. Volatile Organic Compounds in Soil.
SAMPLE ID
Matrix Units
M-(8-10)-S
!7-(6-8)-S
!8-(4.5-6.5)-S
MO-(7-9)-S
MO-(7-9)-Sdup
M1-(5-7)-S
M2-(7-9)-S
M3-(2-4)-S
!2-(1-3)-S
O24-(6-7.7)-S
O27-(5-7)-S
O28-(13-15)-S
O29-(9-10.5)-S
O30-(15-17)-S
O18-(12-14)-S
O19-(10-12)-S
O20-(5-7)-S
O21-(6-8)-S
O23-(2-4)-S
O25-(8-10)-S
O25-(8-10)-Sdup
O26-(3-5)-S
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
ug/Kg
320 U
220 U
220 U
220 U
17 U
240 U
220 U
240 U
220 U
34 U
14 U
14 U
19 U
17 U
260 U
260 U
240 U
280 U
240 U
260 U
260 U
240 U
81 U
56 U
54 U
56 U
56 U
58 U
56 U
62 U
55 U
56 U
59 U
57 U
57 U
55 U
66 U
64 U
62 U
69 U
60 U
64 U
64 U
7 J
160 U
110 U
110 U
110 U
28 J
120 U
110 U
120 U
110 U
110 U
120 U
110 U
110 U
110 U
37 J
130 U
120 U
140 U
120 U
130 U
130 U
120 U
81 U
56 U
54 U
56 U
56 U
58 U
56 U
62 U
55 U
56 U
59 U
57 U
57 U
55 U
66 U
64 U
62 U
69 U
60 U
64 U
64 U
61 U
39 J
56 U
20 J
56 U
56 U
58 U
58 U
30 J
55 U
56 U
59 U
57 U
57 U
55 U
66 U
64 U
62 U
69 U
60 U
64 U
64 U
61 U
81 U
56 U
54 U
56 U
56 U
58 U
58 U
62 U
55 U
56 U
59 U
57 U
57 U
55 U
66 U
64 U
62 U
69 U
60 U
64 U
64 U
61 U
81 U
56 U
54 U
56 U
56 U
58 U
58 U
62 U
55 U
56 U
59 U
57 U
57 U
55 U
66 U
64 U
62 U
69 U
60 U
64 U
64 U
61 U
81 U
56 U
54 U
56 U
56 U
58 U
58 U
62 U
55 U
56 U
59 U
57 U
57 U
55 U
66 U
64 U
62 U
69 U
60 U
64 U
64 U
61 U
160 U
110 U
110 U
110 U
8.7 J
120 U
110 U
120 U
110 U
17 J
7.1 J
7.1 J
9.6 J
8.5 J
130 U
130 U
120 U
140 U
120 U
130 U
130 U
120 U
34 J
56 U
54 U
22 J
56 U
58 U
58 U
300
270
56 U
59 U
57 U
57 U
55 U
66 U
64 U
62 U
69 U
60 U
64 U
64 U
61 U
81 U
56 U
54 U
56 U
56 U
58 U
58 U
62 U
63
8 J
59 U
57 U
57 U
55 U
66 U
64 U
62 U
69 U
60 U
64 U
64 U
16 J
81 U
56 U
54 U
56 U
56 U
58 U
58 U
62 U
12 J
27 J
59 U
57 U
57 U
55 U
66 U
64 U
62 U
69 U
60 U
64 U
64 U
48 J
81 U
56 U
54 U
56 U
56 U
58 U
58 U
37 J
16 J
49 J
44 J
38 J
36 J
36 J
66 U
64 U
62 U
69 U
60 U
64 U
64 U
61 U
160 U
110 U
110 U
110 U
110 U
120 U
110 U
120 U
110 U
110 U
120 U
110 U
110 U
110 U
130 U
130 U
120 U
140 U
120 U
130 U
130 U
120 U
240 U
170 U
160 U
170 U
170 U
170 U
170 U
190 U
160 U
27 J
180 U
170 U
170 U
160 U
200 U
190 U
190 U
210 U
240 U
190 U
190 U
80 J
81 U
56 U
54 U
56 U
56 U
58 U
58 U
62 U
55 U
3.7 J
3.9 J
57 U
57 U
3.3 J
66 U
64 U
62 U
69 U
60 U
64 U
64 U
61 U
U = Not Detected at the concentration indicated (e.g. 220U means not detected at a 200 ug/Kg detection limit)
J = Estimated Value
2-7
-------
Table 2-3. Metals and Additional Analytes in Groundwater and Soil.
SAMPLE ID
M-(7-9)-GW
!5-(2.5-4)-GW
!7-(7-10)-GW
!8-(4-6.5)-GW
!9-(3.0-5.5)-GW
M-(8-10)-S
MO-(7-9)-S
M1-(5-7)-S
M2-(7-9)-S
M3-(2-4)-S
!2-(1-3)-S
!7-(6-8)-S
!8(4.5-6.5)-S
O18-(12-14)-S
O19-(10-12)-S
O20-(5-7)-S
O21-(6-8)-S
O23-(2-4)-S
O24-(6-7.7)-S
O25-(8-10)-S
O25-(8-10)-S(dup)
O26-(3-5)-S
O27-(5-7)-S
O28-(13-15)-S
O29-(9-10.5)-S
O30-(15-17)-S
M2-(7-9)-S
O28-(13-15)-S
Matrix
GW
GW
GW
GW
GW
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
SPLP
SPLP
Units
mg/L
mg/L
mg/L
mg/L
mg/L
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
mg/Kg
As
0.014
0.14
0.034
0.14
0.098
3.1U
2.1U
2.2U
2.1U
2.4U
2.1U
2.2U
2.1U
2.4U
2.4U
1.9U
2.3U
2.3U
3.9
2.4U
2.4U
13
2.4U
2.1U
2.2U
2.2U
0.02U
0.02U
Cr
0.12
0.45
0.23
0.93
0.47
39
11
8.7
9.7
11
6.4
5.6
12
13
22
19
15
13
7.9
8.5
12
27
9.3
17
11
19
0.01U
0.01U
Fe
90
740
590
660
670
28000
28000
29000
30000
31000
11000
20000
16000
13000
19000
24000
80
14000
23000
20000
25000
11000
24000
3.5
0.02U
Pb
0.049
0.53
0.26
1.3
0.43
3.1
1.1U
1.1U
1.1U
2.4
4.2
1.1U
1.0U
3.6
5.9
4.7
3.4
1.1
3
1.2
3.7
26
2.4
3.1
3.3
2.2
0.01U
0.01U
Mn Se K
1.4 0.01 U 4.5
28 0.01U 210
19 0.01U 230
43 0.01 U 160
29 0.01U 120
3.1U
3.2
3.2
2.1U
4.7
3.2
2.2U
4.1
2.4U
2.4U
1.9U
2.3U
2.3U
3
2.4U
2.4U
3.7
2.4U
2.1
2.2U
3.3
0.02U
0.02U
Na Sulfide
11
56
18
36
17
SOU
SOU
SOU
SOU
SOU
SOU
SOU
SOU
SOU
SOU
sou
sou
60U
SOU
sou
sou
sou
sou
TOC pH
27200 6.76
320U
340U
370U
1480
290U 6.11
290U 8.47
280U
290U
400U
280U
430U
4500
3600
85000
4500
260U
330U
410U
Total
Solids
61.7
89.7
86.2
89.3
80.2
91.1
89.4
91.8
75.3
78.4
80.7
72.9
83
90
78.4
82
84.2
87
87.2
91.6
U = Not Detected at the concentration indicated (e.g. 3.1U means not detected at a 3.1 mg/Kg detection limit)
2-8
-------
5
ELEVATED SLAB OVER
HOCKANUM RIVER
B -
ELEVATOR SHAFT
STAIRWELL
1-3'
Tetrachloroethene 1720
Trichloroethene 55
4-6.5'
Carbon Disulfide 1.6
1,1-Dichloroethene 1.5
cis-1,2-Dichloroethene 32
trans-1,2-Dichloroethene 1.1
Tetrachloroethene 231
Trichloroethene 50
Vinyl chloride 4.1
3-6'
Acetone 149
cis-1,2-Dichloroethene 36
trans-1,2-Dichloroethene 1.1
Tetrachloroethen
3-5.5'
cis-1,2-Dichloroethene 2.1
Tetrachloroethene 60
Trichloroethene 3.1
7-9'
Acetone 55
cis-1,2-Dichloroethene 2.9
Ethyibenezene 2.2
Tetrachloroethene 172
Trichloroethene 4.3
Xylenes 8.7
WOOD STAIRWELL
ELEVATOR SHAFT
-6.5'
I Depth
I Analytes fug/Kg)
i ,
Groundwater
Soil
ROOSEVELT MILLS
Figure 2-5. Soil and groundwater results from inside the building.
2-9
-------
Note: Yellow and
orange areas indicate
probable higher
concentrations, while
green and blue areas
indicate probable lower
concentrations.
Figure 2-6. Predicted PCE groundwater plume.
2-10
-------
Table 2-4. ERI VOC Data.
Sample#
Sampling date
Compound
Trichloroethene
Tetrachloroethene
(Cis)- 1 ,2-Dichloroethene
Chloroethene (Vinyl
Chloride)
4-iso-Propyltoluene
Naphthalene
(trans)- 1,2-
Dichloroethene
MTBE
RM4-9-7.5*
2/19/02
8.6
44.9
RM8-8
2/11/02
36.1
30.7
17.1
1.2
10.8
3.6
RM9-12
2/12/02
5
2.1
1.9
1.3
RM9-15
2/12/02
18.4
31.6
3
RM10-
12
2/13/02
^ j***
RM10-14
2/13/02
j 2***
RM11-1-
23-22
2/14/02
2.5
RM11-1-
26-25
2/14/02
4
RMB28
-14-13
5/8/02
10.7
27.2
13.6
0.8
Sample#
Sampling date
Compound
Trichloroethene
Tetrachloroethene
(Cis)- 1 ,2-Dichloroethene
Chloroethene (Vinyl
Chloride)
Sample#
Sampling date
Compound
Trichloroethene
Tetrachloroethene
(Cis)- 1 ,2-Dichloroethene
RMB24-13-10**
5/30/02
7.4
24
12.6
RMB 13-8-5
6/10/02
679
RMB20-7-4
5/31/02
6.5
RMB13-15-
12
6/10/02
4
RMB20-10-
7
5/31/2002
9.8
RMB 12-8-5
6/11/02
164
RMB 14-8-5
6/10/02
3.4
9.5
2.3
1.4
RMB 12-15-
12
6/11/02
3.3
RMB 11
-8-5-G
6/11/02
776
RMB11-13-
10-G
6/11/02
235
RMB 10-
8-5
6/12/02
2.4
14.4
RMB9-6-4
6/12/02
3.4
6.9
2.7
2-11
-------
Table 2.4 (cont'd
Sample#
Sampling date
Compound
Trichloroethene
Tetrachloroethene
(Cis)- 1 ,2-Dichloroethene
(trans)- 1,2-
Dichloroethene
1 , 1 -Dichloroethene
Sample#
Sampling date
Comvound
Trichloroethene
Tetrachloroethene
(Cis)- 1 ,2-Dichloroethene
RMB6-7-4
6/13/02
211
321
154
1.3
RMB23-8-5
6/5/02
3.7
32.5
1.1
RMB 15-10-
7
6/3/02
2.4
RMB23-11-
8
6/5/02
3.6
39.8
RMB 15-6-3
6/3/02
15.5
19.4
3.1
RMB22-8-5
6/5/02
5.9
70.8
1.2
RMB 15-7-6
6/3/02
5.4
7.5
1.4
RMB22-11-
8
6/5/02
3.7
51.4
RMB 17
-6-4
6/4/02
4.3
7.4
RMB27
-12-9
5/29/02
2.2
4.8
RMB 18-5-3
6/4/02
346
287
41.1
1.1
RMB21-11-
8
5/30/02
1.3
13
RMB 18-
14-10
6/4/02
4.6
RMB21-
8-5
5/30/02
2.7
33
RMB26-
12-9
5/29/02
4.2
RMB26
-9-6
5/29/02
1.4
9.4
Sample#
Sampling date
Comvound
Chloroethene (Vinyl
Chloride)
Acetone
Dichloromethane
Naphthalene
Methyl Ethyl Ketone
(MEK)
020603-TB
6/3/02
5
3
020604-TB
6/4/02
6
1
3
LAB BLK
6/6/02
2
020614-FB
6/14/02
4
020614-
TB
6/14/02
4
1
020613-FB
6/13/02
6
020605-
TB
6/5/02
3
020611-TB
6/11/02
4
2
2
LAB
BLK
6/18/02
2
020529-
TB
5/29/02
4
1
2-12
-------
Table 2.4 (cont'd
Sample#
Sampling date
Compound
Tetrachloroethene
Acetone
Dichloromethane
Methyl Ethyl Ketone
(MEK)
020612-TB
6/12/02
4
020612-FB
6/12/02
4
020613-TB
6/13/02
4
020530-TB
5/30/02
3
020531-
TB
5/31/02
4
3
020610-TB
6/10/02
4
1
2
020211-
FB
2/11/02
0.6
020213-
TB
2/13/02
3
020213-
FB
2/13/02
1.1
5
020212-
FB
2/12/02
6
* RM4-9-7.5 means RM at SAIC location 4 from 9 to 7.5 ft BGS
**RMB24-13-10 means RMB at ERI location 24 from 10 to 13 BGS
***FBhas l.lppbofPCE
TB is trip blank
FB is field blank
List of Non-Detect Samples
Field samples
RMB24-9-6
RMB14-12-9
RMB10-9-7
RMB7-11-7
RMB5-7-3
RMB4-4-2
RMB3-5-4
RMB16-18-14
RMB13-25-21
RMB13-25-21-B
RMB16-8
RMB16-11
RM12-31-30-A(unfiltered)
RM12-31-30-A (filtered)
RMB17-7-6
Blanks
020531-FB
020530-FB
020529-FB
Lab Blank 6/3/02
020610-FB
020611-FB
020211-TB
Lab Blank 2/11/02
Lab Blank 2/15/02
020212-TB
020214-TB
020214-FB
Lab Blank 2/15/02
Lab Blank 2/22/02
020215-TB
020215-FB
Shallow refusal locations
020219-FB
020219-TB
020218-FB
020218-TB
020605-FB
020610-FB
RMB1
RMB2
RMB8
RMB19
RMB25
refusal at 1.5'
refusal at 1'
refusal at 2'
refusal at 3'
refusal at 3'
2-13
-------
ELEVATED SLAB OVER
HOCKANUM RIVER
B -
ELEVATOR SHAFT -
STAIRWELL —
[S- - — Q B- ~ —
10
O
GO
© •
-------
Section 3.0
Treatability Study
3.1 Purpose of the Treatability Study
The usability and benefits of the DUOX™ technology are
dependent on the types and concentrations of the
contaminants of concern, as well as characteristics of
the associated matrix (soil and groundwater). Therefore,
laboratory-based treatability studies are necessary prior
to field implementation of the technology. Several
treatability tests can be performed. Dosing experiments
are needed to determine adequate oxidant types and
concentrations in order to assure complete oxidation of
the chlorinated organics (in soil and groundwater)
without overdosing. Overdosing is undesirable from a
cost perspective as well as potentially interfering with
beneficial downgradient naturally-occurring reductive
dechlorination processes. Dosing experiments
addressing soil oxidant demand (SOD) are also
beneficial for determining the expenditure of oxidants
due to soil characteristics (oxidizable minerals and
organic carbon compounds). SOD expenditure is a key
feature of the DUOX™ technology, since low-cost
oxidants are used to expend SOD. Finally, optimized
oxidant candidates are tested on retrieved materials
from the site to simulate treatment and determine
reduction rates and efficiencies. For the Roosevelt Mills
study, it was necessary to develop and test a spiked
soil-fill matrix based on the results from the site
characterization study. The findings from the site
characterization study indicated that the source of the
PCE was associated with a near-surface, coarse-
grained fill material containing heterogeneously
distributed globules of PCE. It was impossible to set-up
identical replicates for the treatability study due to the
inherent heterogeneity of the contaminated fill material.
Therefore, uncontaminated fill material was retrieved
from the site, screened, and spiked with appropriate
levels of PCE to simulate globular-phase contamination.
The following sections discuss the treatability study
objectives, experimental design, and results and
conclusions.
3.2 Treatability Study Objectives
The objectives of the treatability study focused on
evaluating the ability of the DUOX™ technology to treat
both dissolved chlorinated organics in the groundwater
as well as the globular free-phase PCE in the shallow fill
material. Therefore, two primary objectives were
established for the treatability study, and are
summarized below:
1. Groundwater treatment - Concentrations of each of
the target VOCs (PCE, TCE, DCE, VC), present in
the groundwater, will reach 5 ug/l or less at the end
of a 120 hr batch test using an optimized oxidant
mixture (determined during optimization
experiments) employing both oxidant solutions in
series or combination.
2. Soil/Groundwater treatments - Achieve a 90 %
reduction in the mass of PCE (based on the
comparison of the post-treatment soil/water matrix)
from the final experiments (performed in triplicate)
employing both oxidant solutions in combination,
with the calculated spiked concentrations based on
the amount of PCE or chlorinated VOCs added to
the soil/water system.
Secondary objectives for the treatability study included
the evaluation of the behavior of heavy metals in the
contaminated matrix when treated by the DUOX™
technology and the monitoring of pH, ORP, anions
(chloride and sulfate), particle size distribution (PSD),
oxidant concentrations and TOG.
3.3 Treatability Study Experimental
Design
The project objectives were evaluated by a series of
tasks and experiments. These tasks were sequentially
performed in order to: (1) characterize groundwater and
fill material from the site for use in the evaluation
experiments (Task 1), (2) determine the soil oxidant
demand (SOD) of candidate oxidants alone and in
combination as a means of determining the optimal
oxidant solution for the subsequent evaluation (Task 2) ,
and (3) using the information from Tasks 1 and 2,
perform the evaluation for the project objectives (Task
3). The three tasks are discussed in the following sections:
3-1
-------
3.3.1 Task 1 - Preparation and Characterization of
Soil and Groundwater
In order to generate a suitable and reproducible soil
matrix for the evaluation experiment in Task 3, it was
necessary to determine the grain size distribution of the
fill material. Since the fill material is poorly-sorted and
heterogeneous, containing excessively large cobbles,
using this material without screening would require very
large sample sizes to ensure a representative,
reproducible sample for testing. Approximately 75 Kg of
uncontaminated fill material was collected from the
Roosevelt Mills site, characterized, and split into
replicates for testing under Tasks 2 and 3.
Roosevelt Mills site groundwater was used in the
treatability study. Both clean and contaminated
groundwater were collected in a manner minimizing the
soil particle content. Contaminated groundwater was
collected just prior to the start of the groundwater
treatability tests, and stored in 1-L VOCs-compatible
Tedlar bags from the hot/treatment zones of the site
while the clean groundwater was collected in 1-gallon
amber glass bottles from areas absent of VOCs. Prior to
use, triplicate groundwater samples (for both clean and
contaminated groundwater) were characterized for
parameters including VOCs, TOG, pH, metal content
[including Na, K, Ca, Mg, Fe, Al, Mn, Cr, As, Se and Pb],
alkalinity and anions (chloride and sulfate).
3.3.2 Task 2 - Determination of Soil Oxidant
Demand
The results from this task provided data on the soil
oxidant demand for individual oxidants and
combinations. Potential cost reduction by applying the
dual oxidants in combination or in sequence was
evaluated based on the data obtained from this set of
experiments. The source soil prepared in Task 1 was
used to determine the soil oxidant demand under
various testing conditions (e.g., different oxidant/soil
ratios). Tests were performed in duplicate using a set of
amber jar reactors on a rotator system used to enhance
the contact between soil particles and the oxidant during
the test.
Soil oxidant demand (SOD) was determined by oxidizing
a certain amount (e.g., 50 g) of soil with the appropriate
volume (e.g., 250 ml) of oxidant solutions in a desired
oxidant/soil ratio (i.e., 0.5, 1, 3, 5, and 10 g/Kg). Two
oxidants (i.e., KMnO4 and Na2S2O8) were applied
separately, in sequence and in combination.
The oxidant concentrations in the reactors were
periodically monitored during a test period of 10 days.
The tests were run in duplicate to ascertain the
reproducibility and reliability of the experimental data.
The oxidant solutions used in the tests include 0.1, 0.2,
0.6, 1.0 and 2.0 g/L, corresponding to the oxidant/soil
ratio of 0.5, 1, 3, 5 and 10 g/Kg, respectively (Table 3-1).
In addition, duplicate control experiments (i.e., oxidant
solutions in the absence of the soil as shown in Tests
1F, 2F, 3F and 4F in Table 3-1) were run to estimate the
amount of oxidant consumption due to auto-
decomposition during the test. Variation in the oxidant
concentration with time was established by monitoring a
data point every 2 days during the test. The SOD was
determined using the following equation.
SOD = V(Co-Cs)/msoil
where V = the total volume of oxidant solution in the
reactor; C0 = initial oxidant concentration; Cs = the
oxidant concentration at the time of sample collection;
msoi| = the mass of dry soil used in the reaction.
Because both the studied oxidants are light sensitive,
experiments were conducted in a manner minimizing
light exposure (e.g., wrapping the reactors with
aluminum foil or using amber reaction jars) to limit any
photo-catalyzed decomposition.
An additional control experiment (i.e., Test 1G) was
used to establish the baseline of metal ions (i.e., Cr, As,
Pb and Fe), in order to understand the impact of
chemical injection on the Roosevelt Mills site soil matrix
(by comparing the levels of targeted metal ions between
the soil-DI water mixture and the soil-oxidant mixture).
The impacts of chemical oxidation with KMnO4 and
Na2S2O8 on the leaching of selected metals (e.g., As, Cr,
Pb and Fe,) from the soil were examined. This was
accomplished by determining the increase in dissolved
metal ions (collected by filtering samples with 0.45 |im
filters) in the samples at the end of the selected
oxidation tests. The amount of the increase in dissolved
metal ions was determined by comparing the metal ion
concentrations of control samples (i.e., Task 2-1 G) with
those of the oxidant-containing samples (i.e., Tasks 2-
1D, 2-2D and 2-3D). The pH and oxidation-reduction
potential of all samples were measured so that a
correlation between metal leaching with pH, oxidation
reduction potential (ORP) and oxidant concentration can
be established.
3-2
-------
Table 3-1. Test Conditions of Batch Experiments for Soil Oxidant Demand (Task 2)
Test
2-1A
2-1 B
2-1C
2-1 D
2-1 E
2-1 F
2-1G
Test
2-2A
2-2B
2-2C
2-2D
2-2E
2-2F
Test
2-3A
2-3B
2-3C
2-3D
2-3E
2-3F
Test
2-4A
2-4B
2-4C
2-4D
2-4E
2-4F
Total Oxidant
Solution Vol.,
ml
250
250
250
250
250
250
250
Total Oxidant
Solution Vol.,
ml
250
250
250
250
250
250
Total Oxidant
Solution Vol.,
ml
250
250
250
250
250
250
Total Oxidant
Solution Vol.,
ml
250
250
250
250
250
250
Initial KMnO4 Cone., g/L
0.1
0.2
0.6
1.0
2.0
1.0
Dl water (no oxidant)
Initial Na2S2O8 Cone.
9/L
0.1
0.2
0.6
1.0
2.0
1.0
Initial KMnO4 Cone.
g/L (with 1 g/L Na2S2O8)
0.1
0.2
0.6
1.0
2.0
1.0
Initial KMnO4 Cone. g/L
(with pretreatment by
1 g/L Na2S2O8 for 72 h)
0.1
0.2
0.6
1.0
2.0
1.0
KMnO4/Soil ratio
g/kg-dry soil
0.5
1
3
5
10
No soil
No KMnO4
Na2S2O8/Soil
ratio
g/kg-dry soil
0.5
1
3
5
10
No soil
KMnO4/Soil ratio
g/kg-dry soil
0.5
1
3
5
10
No soil
KMnO4/Soil ratio
g/kg-dry soil
0.5
1
3
5
10
No soil
Water/Dry-soil
Ratio
5:1
5:1
5:1
5:1
5:1
NA
5:1
Water/Dry-soil
ratio
5:1
5:1
5:1
5:1
5:1
NA
Water/Dry-soil
ratio
5:1
5:1
5:1
5:1
5:1
NA
Water/Dry-soil
ratio
5:1
5:1
5:1
5:1
5:1
NA
Notes: 1. All experiments were conducted in duplicate
3.3.3 Task 3 - Degradation of VOCs in
Groundwater and Soil by KMnO4, Na2S2O8
and the Dual Oxidants
In Task 3, the ability of KMnO4 and Na2S2O8 to degrade
the targeted VOCs in the Roosevelt Mills site
groundwater and prepared soil matrix was investigated.
Three sets of batch experiments (Tasks 3-1, 3-2 and 3-
3) were used to evaluate the effectiveness of degrading
VOCs (in aqueous phase and in pure phase) with
chemical oxidation under various media: (1)
contaminated groundwater (2) soil with "contaminated"
groundwater mixture (i.e., soil + clean groundwater
spiked with targeted VOCs at 10 mg/L), and (3) soil with
"free product" mixture (i.e., soil spiked with pure PCE).
The oxidant dose was determined from the Task 2
results.
Experiments were conducted under headspace free and
relatively constant temperature conditions using
appropriate reactors (e.g., 40-mL volatile organic
analysis (VOA) vials and a vial rotator system for
3-3
-------
mixing). A list showing experimental conditions and
monitored parameters for Task 3 is presented in Table
3-2. The experiments were operated for a reaction
period of 120 hours. The experimental procedures are
described below.
In Task 3-1, the site VOC contaminated groundwater
was used to determine the effectiveness of the DUOX™
technology in treated soluble chlorinated solvents in
groundwater. The following experimental design was
used:
• 6 vials used to determine initial (3 vials) and final
(3 vials) VOCs levels as a control (Test 3-1D),
• vials (1 test in triplicate) used to determine VOC
degradation by KMnO4 oxidation (3-1 A),
• vials (1 test in triplicate) used to determine VOC
degradation by Na2S2O8 oxidation (3-1B),
• vials (1 test in triplicate) for determining VOC
degradation by KMnO4/Na2S2O8 oxidation (3-
1C),
• vials used to determine the initial pH, ORP,
chloride and oxidant levels (for 3-1 D)
• another 6 vials (two for each oxidant) used to
determine final pH, ORP, chloride production
and oxidant concentrations at the end of the
tests (3-1A, 3-1B, 3-1C).
These vials were injected with appropriate amounts of
oxidant solutions to initiate the reactions. After the
addition of the desired amount of oxidant, vials were
placed in a rotator/shaker placed in an incubator set at
20 °C for 120 hours.
In Tasks 3-2 and 3-3 (see Table 3-2), procedures similar
to the Task 3-1 experiments were followed with the
following differences. For Task 3-2, a selected amount
of soil and appropriate amounts of clean groundwater
spiked with VOCs at the desired concentration (mixed to
distribute the VOCs), was placed in each of the 23 vials
or appropriate reactors, and an appropriate amount of
the oxidant was added. For Task 3-3, a selected
amount of soil was placed into each of the 23 vials or
reactors, then pure-phase PCE was added to the soil.
Distilled water was added to maintain a 5:1 water:soil
ratio. Oxidants were added as above. This last task (3-
3) was meant to simulate "pockets" of free product found
in the soil void spaces, as observed during the site
characterization efforts. The amount of pure product
spiked during the third test of the treatability study is the
estimated amount expected to produce free-product
globules of a similar size and proportion (water-filled
pore space versus PCE-filled pore space) as those
observed during the site characterization. Spiking 10 ul
of pure PCE into a treatability test sample of 8 grams for
a concentration of approximately 2000 mg/Kg, met this
requirement.
Table 3-2: Test Conditions for Evaluating the Degradation of VOCs in Groundwater and Soil
Task
3-1A
3-1 B
3-1C
3-1 D
3-2A
3-2B
3-2C
3-2D
3-3A
3-3B
3-3C
3-3D
Reaction media
Contaminated groundwater
Soil/groundwater spiked with
10mg/L targeted VOCs
(PCE, TCE and cis-DCE)
Soil spiked with pure PCE;
distilled water
Oxidant(s)
0.6 g/L
concentration
KMnO4
Na2S2O8
KMnO4/ Na2S2O8
None
(Control experiment)
KMnO4
Na2S2O8
KMnO4/ Na2S2O8
None
(Control experiment)
KMnO4
Na2S2O8
KMnO4/ Na2S2O8
None
(Control experiment)
No. of
Reaction Vials
5
5
5
8
5
5
5
8
5
5
5
8
Aq/soil
ratio
No soil
No soil
No soil
No soil
5:1
5:1
5:1
5:1
5:1
5:1
5:1
5:1
NOTE: Reaction time (120 hrs) and temperature (20 degrees C) constant for all tests
3-4
-------
3.4 Treatability Study Results and
Conclusions
The following sections present the results from the three
experimental tasks and discuss these results in relation
to the usability of the DUOX™ technology at the
Roosevelt Mills site.
3.4.1 Task 1 Results and Conclusions
3.4.1.1 Particle Size Distribution
The results from the particle size distribution (Task 1-A)
are presented in Table 3-3. Approximately 100 grams of
material was sampled from the near-surface shallow
material and sieved through four sieves (10, 40, 100 and
200). The sieving operation was replicated four times,
and reproducibility between replicates was good. Based
on these results, it was decided that sieving through a
No. 8 sieve (2.36 mm) would remove the oversize
material and provide a suitable matrix for the testing in
terms of reproducibility, and would be representative of
the fill material.
3.4.1.2 Characterization of Fill Material
The clean fill material was characterized for metals,
TOG, pH, total chloride, percent moisture and select
chlorinated VOCs to: (1) determine the levels of metals
and organic components that may expend oxidants, and
(2) confirm that the material is clean relative to the
chlorinated volatile organics. Results from the
characterization are presented in Table 3-4. Three
samples were analyzed for the analytes discussed
above. Overall, reproducibility between the samples
was good. The analysis for metals and TOG did not
indicate the presence of compounds that would
significantly expend the oxidant solutions. The analysis
for VOCs did not indicate the presence of significant
chlorinated materials that would influence the spiking
experiment under Task 3.
3.4.1.3 Groundwater Characterization
Clean and contaminated groundwater from the
Roosevelt Mills site was collected and analyzed for the
purpose of determining inorganic and organic
characteristics for Task 3 experiments. Results are
presented in Table 3-5 for the background area and in
Table 3-6 for the contaminated area. Three replicates
were analyzed from both areas. The replicate data
indicate good reproducibility. The results indicate that
the groundwater sampled from the background area did
not contain detectable levels of chlorinated solvents.
The groundwater collected from the contaminated area
at the site contained approximately 200 ug/L of PCE and
was deemed appropriate for testing under Task 3.
3.4.2 Task 2 Results and Conclusions
Soil oxidant demand was evaluated on non-
contaminated near-surface fill material to determine the
levels and types of oxidants that would be most
applicable for testing under Task 3. Under Task 2, two
oxidants (potassium permanganate and sodium
persulfate) were evaluated alone and in combination at
five different concentration levels (0.1 g/L, 0.2 g/L, 0.6
g/L, 1.0 g/L, and 2.0 g/L) over a ten-day period. The
oxidant concentrations were periodically measured over
the ten-day period. The amount of oxidant consumed
over the ten days is an indication of the soil oxidant
demand (excluding auto-decomposition). Figures 3-1
through 3-4 depict the results of the soil oxidant demand
experiments for: (1) potassium permanganate (at the
five concentrations), (2) sodium persulfate (at the five
concentrations), (3) potassium permanganate (at the five
concentrations) with 1 g/L of sodium persulfate, and (4)
potassium permanganate (at the five concentrations)
with a 72 hour pretreatment with 1 g/L sodium
persulfate.
The experiments indicate that the near-surface fill
material exhibits minimal soil oxidant demand, as
demonstrated by the small decrease in oxidant
concentration over the ten-day period for all oxidants
and oxidant combinations. This is consistent with the
findings from the characterization analyses under Task 1
which demonstrated that the fill material has low total
organic carbon and low concentrations of metals that
would expend the oxidants.
Based on the results from these experiments, it was
decided that oxidant concentrations at 0.6 g/L would be
used for the Task 3 studies. This determination was
based on: (1) the levels of chlorinated solvents in the
contaminated media, and (2) the fact that approximately
90% of the oxidants remained after the ten-day study at
the 0.6 g/L concentration.
3-5
-------
Table 3-3. Sieving Results for the Fill Material
Test#1A-1
Soil Weight 100.4 grams
Time 40 minutes
Sieve NO
10
40
100
200
Bottom
Tare (g)
488.6
389.0
347.5
329.4
503.8
Sieved Weight (g)
507.6
441.5
373.5
331.3
504.5
Soil Retained (g)
19.0
52.5
26.0
1.9
0.7
% Retained
18.9
52.3
25.9
1.9
0.7
Particle Size Range (mm)
2 to 5
0.475 to 2
0.1 25 to 0.475
0.075 to 0.1 25
< 0.075
Total: 100.1
Test#1A-2
Soil Weight 101.0 grams
Time 40 minutes
Sieve NO
10
40
100
200
Bottom
Tare (g)
488.5
389.0
347.2
329.4
503.7
Sieved Weight (g)
508.4
439.6
374.5
331.4
504.5
Soil Retained (g)
19.9
50.6
27.3
2.0
0.8
% Retained
19.3
49.2
26.5
1.9
0.8
Particle Size Range (mm)
2 to 5
0.475 to 2
0.1 25 to 0.475
0.075 to 0.1 25
< 0.075
Total: 100.6
Test#1A-3
Soil Weight 102.9 grams
Time 40 minutes
Sieve NO
10
40
100
200
Bottom
Tare (g)
488.5
388.9
347.3
329.4
503.7
Sieved Weight (g)
508.7
446.4
369.8
331.0
504.4
Soil Retained (g)
20.2
57.5
22.5
1.6
0.7
% Retained
19.6
55.9
21.9
1.6
0.7
Particle Size Range (mm)
2 to 5
0.475 to 2
0.1 25 to 0.475
0.075 to 0.1 25
< 0.075
Total: 102.5
Test#1A-4
Soil Weight 100.7 grams
Time 40 minutes
Sieve NO
10
40
100
200
Bottom
Tare (g)
488.4
388.9
347.3
329.3
503.7
Sieved Weight (g)
510.2
439.6
373.2
330.9
504.3
Soil Retained (g)
21.8
50.7
25.9
1.6
0.6
% Retained
21.2
49.3
25.2
1.6
0.6
Particle Size Range (mm)
2 to 5
0.475 to 2
0.1 25 to 0.475
0.075 to 0.1 25
< 0.075
Total: 100.6
3-6
-------
Table 3-4. Fill Characterization Results
Metals (mg/kg dw)
Aluminum
Arsenic
Chromium
Iron
Lead
Manganese
Selenium
TOO (mg/kg, dw)
Total Chloride (mg/kg)
PH
Moisture (%)
Sample
1
Sample
2
Sample
3
40000
8.
5
100
97000
49
2300
<7.1
<510
70
9.
0.
75
67
26000
7
1
74
62000
44
2300
<7.1
<510
70
9
0
67
64
28000
9.4
80
68000
44
1500
<7.1
<510
70
9.67
0.66
VOCs
(ug/kg dw)
Sample 1
Sample 2
Sample 3
VC
<200
<200
<200
t-DCE
<200
<200
<200
C-DCE
<200
<200
<200
TCE
<200
<200
<200
PCE
<200
<200
<200
3-7
-------
Table 3-5. Background Groundwater Characteristics
Metals (mg/L)
Aluminum
Arsenic
Calcium
Chromium
Iron
Lead
Manganese
Magnesium
Sodium
Potassium
Selenium
TOO (mg/L)
Chloride (mg/L)
Sulphate (mg/L)
PH
ORP(mv)
Alkalinity (mg/L)
Replicate
1
<0.20
<0.010
12
<0.010
2.3
<0.0050
0.28
3.4
8.7
5.9
<0.010
1.6
3.6
19.5
8.45
862
55
Replicate
2
<0.20
<0.010
12
<0.010
2.5
<0.0050
0.29
3.6
9.1
6.1
<0.010
1.6
3.6
19.6
8.22
817
54
Replicate
3
<0.20
<0.010
12
<0.010
2.4
<0.0050
0.29
3.6
8.9
6
<0.010
1.5
3.4
19.5
8.1
800
53
VOCs (ug/L)
VC t-DCE c-DCE TCE PCE
Replicate 1 <4 <4 <4 <4 <4
Replicate 2 <4 <4 <4 <4 <4
Replicate 3 <4 <4 <4 <4 <4
3-8
-------
Table 3-6. Contaminated Groundwater Characteristics.
Metals (mg/L)
Aluminum
Arsenic
Calcium
Chromium
Iron
Lead
Manganese
Magnesium
Sodium
Potassium
Selenium
TOO (mg/L)
Chloride (mg/L)
Sulphate (mg/L)
PH
ORP(mv)
Alkalinity (mg/L)
Replicate
1
<0.20
<0.010
15
<0.010
<0.050
<0.0050
0.021
2.6
5.9
3.9
<0.010
<1.0
4.2
18.7
7.68
810
40
Replicate
2
<0.20
<0.010
14
<0.010
<0.050
<0.0050
0.021
2.5
5.8
3.9
<0.010
<1.0
4.2
18.7
7.66
827
41
Replicate
3
<0.20
<0.010
14
<0.010
<0.050
<0.0050
0.021
2.6
5.9
3.9
<0.010
<1.0
4.2
18.6
7.67
832
41
VOCs (ug/L)
VC t-DCE c-DCE TCE PCE
Replicate 1 <8 <8 <8 <8 212
Replicate 2 <8 <8 <8 <8 201
Replicate 3 <4 <4 <4 <4 223
In order to determine the potential effect of the oxidants
on metal solubilization, select experiments were
sampled for metals on initial oxidant addition and at the
end of the ten-day experiment. In addition, a Dl water
control (no oxidant) was sampled initially and at the end
of ten days. The samples were filtered through a
0.45um filter and analyzed to determine dissolved
metals. Results from the study are presented in Table
3-7. The study demonstrated that there were minor
increases in some soluble metals in some of the
experiments. Chromium increased (relative to the
control) in the experiments that used potassium
permanganate. Manganese also increased (relative to
the control) in the experiments that used potassium
permanganate.
3.4.3 Task 3 Results and Conclusions
Task 3 activities investigated the performance of the
DUOX™ technology for the treatment of chlorinated
solvents in groundwater and a soil/groundwater matrix.
Under this task, three sets of experiments were
performed. Task 3-1 investigated the ability of the
oxidants (alone and in combination) to treat PCE
contaminated groundwater from the Roosevelt Mills site.
Task 3-2 investigated the ability of the oxidants (alone
and in combination) to treat a spiked groundwater that
was added to the near-surface fill material. Task 3-3
evaluated the ability of the oxidants (alone and in
combination) to treat PCE as a free-phase globular
component in the near-surface fill material. Results from
these experiments are presented and discussed in the
following sections.
3.4.3.1 Task 3-1 - Treatment of Contaminated
Groundwater with Oxidants
Under this task, groundwater from the Roosevelt Mills
site, contaminated with approximately 130 ug/L of PCE,
was treated with potassium permanganate and sodium
persulfate, alone and in combination, for 120 hours to
determine the ability of the oxidants to degrade the PCE
3-9
-------
Potassium Permanganate (alone)
2.5
3 1.5
o
c
o
o
c
ra
^ 1
x
O
0.5
A---A-
A-
O
& O O
4 6
Day
10
Figure 3-1. Oxidant consumption over time - Potassium Permanganate (alone).
Sodium Persulfate (alone)
2.5
3 1.5
c
o
o
c
ra
;o
'x
O
0.5
^r—
-A A
o ............ o ............ o ............. o ............. ............
0
---?
0 2 4 6 8 10
Day
Figure 3-2. Oxidant consumption over time - Sodium Persulfate (alone).
3-10
-------
Potassium Permanganate with 1 g/L Sodium Persulfate
2.5
2.0
o
o
2 1.0
0.5
0.0
* -A A- ,
0--
-e-
w o
Q rn
+ '.EH
10
Day
Figure 3-3. Oxidant consumption over time -Potassium Permanganate with 1 g/L Sodium Persulfate.
Potassium Permanganate with 72 hour 1 g/L Sodium Persulfate Pretreatment
2.5
2.0
3 1.5
o
o
o
2 1.0
§
0.5
0.0
--A A- -A /
-A
G>
e-
o o
DayO Day 2 Day 4 Day 6 Days Day 10
Day
Figure 3-4. Oxidant consumption over time -Potassium Permanganate with 72 hour 1 g/L Sodium
Persulfate pretreatment.
3-11
-------
Table 3-7. Soluble Metals Before and After Ten Days of Oxidant Treatments
Sample
Control (no oxidant)
Control (no oxidant)
Permanganate (1 .0 g/L)
Permanganate (1 .0 g/L)
Persulfate (1 .0 g/L)
Persulfate (1 .0 g/L)
Permanganate (1 .0 g/L) and
Persulfate (1 .0 g/L)
Permanganate (1 .0 g/L) and
Persulfate (1 .0 g/L)
Permanganate (1 .0 g/L) and 72 hr
pretreat with persulfate (1 .0 g/L)
Permanganate (1 .0 g/L) and 72 hr
pretreat with persulfate (1 .0 g/L)
Stage
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Al
mg/L
0.34
1
0.46
0.37
0.43
0.83
<0.2
0.27
<0.2
0.31
As
mg/L
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
Cr
mg/L
<0.010
<0.010
<0.010
0.042
<0.010
<0.010
<0.010
0.04
<0.010
0.021
Fe
mg/L
0.062
<0.050
<0.050
<0.050
0.066
<0.050
<0.050
<0.050
<0.050
<0.050
Pb
mg/L
<0.0050
<0.0050
<0.0050
<0.0050
<0.0050
<0.0050
<0.0050
<0.0050
<0.0050
<0.0050
Mn
mg/L
1.4
<0.010
38
3.9
0.59
<0.010
49
44
2.7
22
Se
mg/L
<0.010
<0.010
0.018
<0.010
<0.010
<0.010
0.018
0.018
<0.010
0.012
to less than 5 ug/L.. Results from this task are
presented in Table 3.8.
Oxidants were added to the reaction vessels at a
concentration of 0.6 g/L and reacted at 20°C for 120
hours. Five reaction vessels were used for each oxidant
treatment and combination as well as a control (no
oxidants). Two of the vials were used to measure the
following parameters: pH, ORP, oxidant concentration,
chloride, and sulfate. Three vials were used to analyze
for chlorinated solvents. The vials were analyzed for
these parameters at the start of the reaction (0 hour) and
at the end of the reaction (120 hours), except for
chlorinated solvents which were only measured at the
end of the reaction. In addition, a control sample (no
oxidants) was analyzed at time 0 and at 120 hours.
Results from the control samples reveal that the
contaminated groundwater started at an average PCE
concentration of 131 ppb, and after 120 hours averaged
126 ppb, indicating that there was no significant loss in
volatiles over the course of the experiment. It is
important to note that the groundwater contained only
PCE as the chlorinated solvent, and the other VOCs
(VC, DCE, and TCE) were below the detectable levels of
5 ug/L. Results from the other analytes indicate minimal
changes over time. As a baseline, pH was
approximately 8.6, ORP around 900, chloride 3.5 mg/L,
and sulfate approximately 17 mg/L.
The potassium permanganate treatment successfully
reduced the PCE to less than 5 ug/L after 120 hours,
thereby meeting the project claim. In addition, there was
an increase in pH, as well as an increase in both
chloride and sulfate. In addition, there was no
discernable expenditure of oxidant over the 120 hours.
The sodium persulfate treatment did not reduce the
concentration of PCE to less than 5 ug/L, and therefore
the project objective was not met for this oxidant. The
concentration of PCE was reduced to approximately 40
ug/L after 120 hours. It is important to note that the lack
of a reduction to less than 5 ug/L is not totally
unexpected, since the main purpose of this oxidant is to
minimize or eliminate soil oxidant demand, as opposed
to being an oxidizing agent for the chlorinated solvents.
The combined oxidants (potassium permanganate and
sodium persulfate) successfully reduced the PCE to less
than 5 ug/L after 120 hours and met the project claim.
As with the potassium permanganate treatment, pH,
chloride, and sulfate increased. Again, there was no
discernable expenditure of oxidants over the 120 hours.
3-12
-------
Table 3-8. Results from Contaminated Groundwater Treatment
Initial
Oxidant Cone
(9/L)
Oxidant
Cone
(g/L)
Average
PCE Met
(ug/L) Claim
Chloride
(mg/L)
Sulfate PCE
(mg/L) (ug/L)
KMnO4 (0.6)
KMnO4 (0.6)
KMnO4 (0.6)
120hr
120hr
120hr
KMnO4 (0.6)
KMnO4 (0.6)
KMnO4 (0.6)
KMnO4 (0.6)
Na2S2O8 (0.6)
Na2S2O8 (0.6)
s (0.6)
Na2S2O8 (0.6)
Na2S2O8 (0.6)
Na2S2O8 (0.6)
Na2S2O8 (0.6)
Both (0.6)
Both (0.6)
Both (0.6)
120hr
120hr
120hr
Both (0.6)
Both (0.6)
Both (0.6)
Both (0.6)
None
(Control)
None
(Control)
None
(Control)
None
(Control)
None
(Control)
None
(Control)
None
(Control)
None
(Control)
None
(Control)
None
(Control)
3-13
-------
In summary, potassium permanganate, alone and in
combination with sodium persulfate, successfully
reduced the PCE contaminated groundwater from a
starting concentration of approximately 130 ug/L to less
than 5 ug/L over the 120 hour test. Sodium persulfate
alone did not reduce the PCE to less than 5 ug/L.
3.4.3.2 Task 3-2 - Treatment of Contaminated
Groundwater in a Soil Matrix With Oxidants
Task 3-2 evaluated the oxidants, alone and in
combination, to treat a spiked groundwater in a soil
(near-surface fill) matrix. For these experiments, 10
mg/L each of PCE, TCE, and DCE were added to 40 ml
of uncontaminated groundwater from the site. Eight
grams of the screened near-surface fill material (soil)
was added to the spiked groundwater. The
groundwater/soil matrix was reacted with the oxidants,
alone and in combination, for 120 hours. A control
sample with no oxidants was also run. The initial and
final samples (0 and 120 hours) were analyzed for pH,
ORP, chloride, and sulfate. The final samples were
analyzed for each of the chlorinated VOCs in both the
aqueous and solid phases and converted to mass in
order to calculate percent reduction. The control sample
was analyzed for chlorinated VOCs both at 0 hours and
at 120 hours.
Table 3-9 presents the results of the chlorinated VOC
reductions (as percent) after 120 hours of treatment.
Table 3-10 presents the results of the other
measurements and analytes.
The permanganate (alone) treatment achieved average
mass reductions of 99.5% for PCE, 99.5% for TCE, and
99.4% for DCE. Based on these mass reductions, the
permanganate treatment successfully met the project
objective of a 90% mass reduction for all three analytes.
There was also a reduction in the concentration of the
oxidant during the course of the experiment (average of
0.57 g/L at time 0 hour to 0.45 g/L at 120 hours). There
was also an increase in pH, chloride, and sulfate.
The persulfate (alone) treatment achieved average mass
reductions of 15% for PCE, 6% for TCE, and 14.3% for
DCE. Based on these mass reductions, the persulfate
treatment did not meet the project objective of a 90%
reduction in mass for any of the three analytes.
Furthermore, there was no discernable reduction in the
concentration of the oxidant over the course of the
experiment. There was also an increase in chloride and
sulfate from 0 hours to 120 hours.
The combined permanganate and persulfate treatment
achieved average mass reductions of 99.5% for PCE,
99.5% for TCE, and 99.4% for DCE. Based on these
mass reductions, the combined treatment successfully
met the project objective of a 90% mass reduction for all
three analytes. As with the permanganate (alone)
treatment, the combined treatment exhibited a reduction
in the concentration of oxidants over the course of the
experiment, indicating that the oxidants (predominately
permanganate) were expended during the oxidation of
the chlorinated VOCs. There was also an increase in
pH, chloride, and sulfate over the course of the
experiment.
It is important to note that the reductions shown in Table
3-9 for tests performed on the spiked groundwater/soil
matrix were determined based on a comparison of the
total final mass to the initial mass of the contaminant of
interest. The initial mass was determined by averaging
the results of the control test samples for the spiked
compounds PCE, TCE and DCE (three T=0 hours
analyses and three T120 analyses). The control
measurements were reproducible with average BSD
values for each analyte of approximately 10%. Final
mass was determined using the aqueous and soil
concentrations with the associated volumes and weights
for samples analyzed after 120 hours of treatment. For
samples with analyte concentrations that were reported
as non-detected, the detection limit value (0.005 mg/L
for the aqueous phase and 0.200 mg/Kg for the soil
phase) was used as the sample concentration for
calculating mass.
3.4.3.3 Task 3-3 - Treatment of Free-Phase (Globular)
PCE Contaminated Soil/Groundwater Matrix
with Oxidants
The site characterization study at Roosevelt Mills
identified a chlorinated solvent source area in the near-
surface, coarse-grained fill material. This fill material
was impacted by PCE primarily distributed as a globular
free-phase product within the large pore-spaces.
Therefore, a remedial action should consider treatment
of this material. Based on this need, the treatability
study investigated the applicability of the DUOX™
process for the treatment of this free-phase, globular
material within the saturated near-surface fill material.
Due to the heterogeneous distribution of this material at
the site, it was necessary to develop a soil/groundwater
matrix, spiked with PCE to simulate free-phase
distribution of the PCE.
The simulated soil/groundwater matrix was prepared by
spiking 10 ul of PCE into 8 grams of the screened fill
3-14
-------
Table 3-9. Chlorinated VOC Results from Spiked Groundwater/Soil.
Initial
Oxidant
Cone (g/L)
KMnO4 (0.6)
KMnO4 (0.6)
KMnO4 (0.6)
Na2S2O8
(0.6)
Na2S2O8
(0.6)
Na2S2O8
(0.6)
Both (0.6)
Both (0.6)
Both (0.6)
None
None
None
None
None
None
Time
120hr
120hr
120hr
120hr
120hr
120hr
120hr
120hr
120hr
120hr
120hr
120hr
Ohr
Ohr
Ohr
Initial Mass: 0.485 mg
Final PCE Average
Mass, Mass PCE Met
mg Red. Red. Claim
0.002 99.5 99.5 YES
0.002 99.5
0.002 99.6
0.440 9.4 15 NO
0.400 17.6
0.401 17.3
0.002 99.6 99.5 YES
0.002 99.5
0.002 99.5
0.525
0.473
0.384
0.506
0.553
0.472
Initial Mass: 0.415 mg
Final TCE Average
Mass, Mass TCE Met
mg Red. Red. Claim
0.002 99.5 99.5 YES
0.002 99.5
0.002 99.6
0.415 0 6 NO
0.377 9.1
0.378 8.8
0.002 99.5 99.5 YES
0.002 99.5
0.002 99.5
0.449
0.408
0.338
0.426
0.464
0.402
Initial Mass: 0.375 mg
Final DCE Average
Mass, Mass DCE Met
mg Red. Red. Claim
0.002 99.4 99.4 YES
0.002 99.4
0.002 99.5
0.337 10 14.3 NO
0.314 16.3
0.313 16.5
0.002 99.4 99.4 YES
0.002 99.4
0.002 99.4
0.399
0.359
0.312
0.395
0.415
0.369
Note: Initial mass determined as the average of the no treatment tests at T=0 and T=120 hours (6 samples)
Note: Detection limit values were used as the sample concentration to calculate final mass for samples with the analytes reported as
ND
3-15
-------
Table 3-10. Other Analytes Results from Spiked Groundwater/Soil.
Initial Oxidant Concentration (g/L)
Time
PH
ORP
(mV)
Oxidant
Cone
(g/L)
Cl
(mg/L)
S04
(mg/L)
KMnO4 (0.6)
KMnO4 (0.6)
KMnO4 (0.6)
KMnO4 (0.6)
KMnO4 (0.6)
120hr
120hr
KMnO4 (0.6)
KMnO4 (0.6)
Ohr
Ohr
7.9
8
866
879
0.615
0.523
40.1
40.1
32.3
30.1
Na2S2O8 (0.6)
Na2S2O8 (0.6)
Na2S2O8 (0.6)
Na2S2O8 (0.6)
Na2S2O8 (0.6)
Na2S2O8 (0.6)
Na2S2O8 (0.6)
Ohr
Ohr
8.9
8.6
746
742
0.622
0.623
12.9
12.2
31.0
29.9
Both (0.6)
Both (0.6)
Both (0.6)
3-16
-------
material, resulting in a concentration of approximately
2,000 mg/kg. Distilled water was then added to achieve
a 5:1 (w/w) ratio of aqueous to soil. As in Task 3-2,
oxidants alone and in combination, as well as a no
oxidant control, were evaluated to determine the mass
reduction in the PCE over a 120 hour period. This test
was considered the most challenging due to the
concentration and distribution of the free-phase PCE
within the soil matrix.
Table 3-11 presents the results of the PCE reductions
(as percent) after 120 hours of treatment, as well as the
initial and final analysis of oxidant concentration, pH,
ORP, chloride, and sulfate.
The permanganate (alone) treatment was able to
successfully degrade an average of 94.1% of the PCE
and met the project objective of a 90% or greater mass
reduction. It is important to note that the oxidant
consumption was high (0.55 g/L to 0.15 g/L),
presumably due to the relatively high concentration of
PCE in the experiment. Furthermore, the chloride
content increased from approximately 11 mg/L at the
beginning of the experiment to 212 mg/L at the end, and
may indicate the generation of chloride from the
degradation of the chlorinated PCE. In contrast to tests
run under Tasks 3-1 and 3-2, pH dropped from an
average of 9.6 to 7.6.
As seen in the previous tasks, the persulfate (alone)
treatment was not successful in meeting the project
objective. The average reduction in mass for the
persulfate was 0.8%, thereby not meeting the project
objective of a 90% reduction in the mass of PCE.
Furthermore, there was virtually no change in oxidant
consumption over the course of the experiment.
The combined permanganate and persulfate treatment
achieved an average mass PCE reduction of 91.4%, and
met the project objective for a 90% mass reduction. As
with the permanganate (alone) treatment, there was a
large expenditure of the oxidants, as well as a large
increase in the chloride concentration. The pH also was
lowered over the course of the demonstration. Based on
the previous experiments, it is probable that the
permanganate is the operative oxidant responsible for
the observed decomposition.
It is important to note that Table 3-11 presents
conservative estimates of the efficacy of the oxidant
treatment on free-phase PCE in the near-surface fill
material, based on several of the conditions placed on
the determinations. As noted for Task 3-2, initial mass
was determined by averaging the results of the control
test samples for the spiked compound PCE, which had
an RSD of <15% for all six values (three TO and three
T120 hour results). The QAPP specified that the initial
mass used in the determination of percent reduction
would be calculated based on the known spiked amount
(16.2 mg). However, using the observed initial mass as
measured from the controls (9.1 mg) provides a more
conservative estimate of efficiency. Furthermore,
calculations for the percent reduction in the treatment
systems using potassium permanganate alone and both
oxidants together were performed using an estimated
concentration for the aqueous phase that overestimated
the contribution of this phase to the total final mass. The
analysis of the aqueous samples for each of these tests
(three test vials for the permanganate and three vials for
the tests with both oxidants) resulted in PCE
concentrations that exceeded the upper range of the
analytical calibration curve. Since the entire sample was
consumed during the analysis, reanalyzing a diluted
sample was not possible. Results for other samples that
exceeded the calibration curve and were reanalyzed at a
higher dilution (e.g., the control samples which were
expected to be high and therefore analyzed initially at a
dilution and reanalyzed at a higher dilution as
necessary), indicated that concentration results were 50-
70% higher when the sample was reanalyzed at an
appropriate dilution. For the aqueous samples that
exceeded the calibration range for PCE, an estimated
concentration of five times the observed concentration
was used in determining the final mass of PCE for these
tests (e.g., sample 3-3A-2 had an observed PCE
concentration of 1.973 mg/L and a value of 9.865 mg/L
was used in the calculation of final mass).
3-17
-------
Table 3-11. Results from Free-Phase (Globular) PCE Contaminated Soil/Groundwater
Initial Oxidant
Cone (g/L)
KMnO4 (0.6)
KMnO4 (0.6)
KMnO4 (0.6)
KMnO4 (0.6)
KMnO4 (0.6)
KMnO4 (0.6)
KMnO4 (0.6)
Na2S2O8 (0.6)
Na2S2O8 (0.6)
Na2S2O8 (0.6)
Na2S2O8 (0.6)
Na2S2O8 (0.6)
Na2S2O8 (0.6)
Na2S2O8 (0.6)
Both (0.6)
Both (0.6)
Both (0.6)
Both (0.6)
Both (0.6)
Both (0.6)
Both (0.6)
None
None
None
None
None
None
None
None
None
None
Time
120hr
120hr
120hr
pH
r I
M
§ i
120hr 7.4
120hr 7.8
Ohr 9.7
Ohr 9.5
120hr ,
120hr i
120hr !
lOUMUf
pJ8fMtS
r
120hr 9.8
120hr 9.6
Ohr 9.6
Ohr 9.6
ORP
(mV)
!
878
933
832
922
Oxidant
Cone
(g/L)
0.123
0.178
0.537
0.567
Cl
(mg/L)
278.3
146.1
10.0
11.6
SO4
(mg/L)
49.3
35.8
8.2
7.0
i
946
818
890
945
0.645
0.702
0.695
0.574
22.6
23.6
9.4
8.9
46.9
43.2
10.9
10.0
120hr
120hr
HlSSBiWiM J|
120hr 1 §
120hr 7.3
120hr 6.5
Ohr 9.7
Ohr 9.8
120hr
120hr
120hr
Ohr
Ohr
Ohr '
( i
i i
1
i |
Uuuuuf
1 1
120hr 9.86
120hr 9.91
Ohr 10.1
Ohr 10.1
852
947
776
762
0.142
0.095
0.614
0.605
243.4
279.7
9.3
2.9
Final
PCE
Mass,
mg
PCE Average
Mass PCE Met
Red. Red. Claim
0.338* 94.3 94.1 YES
0.355* 94
0.389* 93.9
I i
10.8 -18.5 0.8 NO
7.91 13
8.41 7.6
0.358* 92.2 91.4 YES
0.401* 90.5
0.175* 91.6
jjammnwaamnwaam^
46.8 I I
TO moMS!W(MaraoMsraoMaraoMssff|
41.5 I i
9.6
5.6
I
823
814
766
785
I— I
15.8
15.1
8.6
9.4
35.9
29.6
6.4
7.2
|__|
10.4
8
10.4
7.23
8.04
10.4
Note: Initial mass determined as the average of the no treatment tests at T=0 and T=120 hours (6 samples)
Note: Detection limit values were used as the sample concentration to calculate final mass for samples
With the analytes reported as ND
*Note: For tests with aqueous sample concentrations that exceeded calibration range, an estimate of 5 times
the observed concentration was used (see text discussion) to calculate final mass.
3-18
-------
3.5 Treatability Study General Conclusions and
Discussion
The following general conclusions can be drawn from
this treatability study:
1. The near-surface fill material (source area matrix for
the PCE) exhibits a very low soil oxidant demand.
2. Permanganate alone and in combination with
persulfate is effective in reducing the levels of
chlorinated solvents in the site groundwater as well
as in spiked soil samples simulating a free-phase
globular distribution.
3. Persulfate alone was ineffective in reducing the
levels of chlorinated solvents in any of the
experiments.
There were minor increases in some soluble metals in
some of the experiments.
Based on these conclusions, the chlorinated solvent
contamination in both the soil and groundwater can be
effectively treated by using permanganate as an oxidant.
However, due to the low soil oxidant demand of the soil
(near-surface fill), the rationale for using a dual oxidant
approach (DUOX™) is unnecessary. Persulfate would
only be necessary if there was a need to expend the soil
oxidant demand before using a more costly oxidant such
as permanganate.
The study also demonstrated the appropriate dosing
required to treat the more difficult free-phase distributed
PCE in the fill matrix. A remedial solution for this site
could include a source removal or treatment strategy.
The use of the permanganate could potentially be used
as a source treatment for the near-surface contaminated
fill material, as well as the groundwater, assuming that
an appropriate means of introducing the oxidant into the
subsurface can be implemented.
This study at Roosevelt Mills was not able to fully
demonstrate the potential of the DUOX™ technology for
the treatment of chlorinated solvents in soil and
groundwater. The major benefit of the DUOX™
process, as compared to single phase oxidation
technologies, is in the treatment of impacted media with
significant soil oxidant demand. Since the media
evaluated during this study did not exhibit significant soil
oxidant demand, the full utility of the process was not
demonstrated. The technology may have merit at other
sites where significant soil oxidant demand would benefit
from a DUOX™ approach.
3-19
------- |