NCD003446721_20040625_Celeanse Corporation - Shelby Fiber_FRBCERCLA SPD_Monitored Natural Attenuation Demonstration Project Workplan OU-1 - Revised-OCR

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Kubal-Furr & Associates
------------Envi.-011me11tal Management Services
Post Office Box 273210
Tampa, FL 33688-3210 ·
[phone]
FAX [phone]
Mr. Kenneth Lucas
Remedial Project Manager
U.S. Environmental Protection
Agency, Region IV
61 Forsyth Street
Atlanta, GA 30303
Dear Mr. Lucas:
June 25, 2004
Post Office Box 80247
Simpsonville, SC 29680-0247
[phone]
FAX [phone]
On behalf of CNA Holdings, Inc., we are pleased to enclose two copies of the report entitled:
"Monitored Natural Attenuation Demonstration Project Work Plan-Operable Unit 1-CNA
Holdings, Inc./Ticona-Shelby, North Carolina." By way of this letter, we have also transmitted
a copy of the report to David Mattison with NCDENR for his review.
The baseline MNA sampling event took place the last week of May as authorized in your
letter to Steve Olp dated May 20, 2004 granting conditional approval to implement the work plan
pending submittal of this revised document.
Please contact me at 813-265-2338, to discuss any questions you may have following your
review of this revised work plan.
Sincerely,
Kubal-Furr & Associates
left:~
President
cc: Mr. David Mattison, NCDENR
Mr. Steven F. Olp, Celanese Americas
Ms. PEM Carter, Ticona-Shelby ESHA
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Contents
Page
1.0 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Site History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 CERCLA-Related Remedial Actions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2.1 Review of Activities from 1986-1996 . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2.2 Review of Activities from 1996-Present . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3 Remedial Action Effectiveness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.4 MNA Work Plan Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.0 Conceptual Site Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.0 Initial MNA Data Collection Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.1 Work Performed ............................................... 9
3.2 Evaluation of the Initial MNA Data Set . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2.1 Ethylene Glycol Degradation Pathways . . . . . . . . . . . . . . . . . . . . . . . 11
3.2.2 Evaluation of Ethylene Glycol Degradation and MNA Potential
at the CFO Site . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.0 Proposed MNA Demonstration Project Work Plan . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.1 Ground-Water Flow Rate Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.2 MNA Monitoring Program and Data Analysis . . . . . . . . . . . . . . . . . . . . . . . . 15
4.3 Transport and Attenuation Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.4 Mid-Project Data Review and Evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.5 Project Reporting and Schedule . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 7
5 .0 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Tables
Table 1. Natural Attenuation Potential of Identified Constituents of Concern-Celanese{Ticoma
Shelby, North Carolina
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Figures
Figure 1. Site Location Map
Figure 2. Map Showing Deleted Portions of OU-1 and OU-2
Figure 3. Initial MNA Sampling Locations
Figure 4. Results of the MNA Sampling-Ethylene Glycol, Methane, MNA Screening Parameters
Figure 5. Results of the MNA Sampling-Total Manganese
Figure 6. Results of the MNA Sampling-Ferrous Iron
Figure 7. Results of the MNA Sampling-Nitrate
Figure 8. Results of the MNA Sampling-Sulfate
Figure 9. Proposed MNA Monitoring Locations
· Figure 10. Proposed MNA Demonstration Project Schedule
. Attachments
Attachment 1. Selected Water-Quality Plots
Attachment 2. Inner Tier Extraction Well Performance
Attachment 3. Letter from Jerry Kubal, Kubal-Furr & Associates to Giezelle Bennett, EPA (July 11,
2001)
Attachment 4. Potentiometric Surface Maps and Hydrogeologic Cross Sections
Attachment 5. Well Rehabilitation and Well Construction Details
Attachment 6. Summary of Initial MNA Analytical Data (September 2001)
Attachment 7. Selected Ethylene Glycol References
Attachment 8. Data Analysis Report from Robert C. Borden, P.E., Ph.D.
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CNA Holdi11gs, lllc.---Shelby, NC-MNA Demo11stration Project Work Pla11 (Rev 6/04) -Page I
1.0 Introduction
1.1 Site History
Ticona, an operating subsidiary of Celanese, owns and operates a polyester and engineering
plastics production facility in Shelby, North Carolina. CNA Holdings, Inc. (CNA), also a subsidiary of
Celanese, retains management of environmental matters for the corporation and thus, is responsible
for the work discussed in this plan. The site consists of an approximate 450-acre piece of property
which includes the main plant production area, wastewater treatment area, former waste disposal areas,
and recreational areas. The planr is located in south-central Cleveland County, bordered by NC
Highway 198 to the west and Lavender Road to the south, approximately one mile north of Earl and
six miles south of Shelby. A site plan showing the location of production areas, monitor wells,
extraction wells, and other significant features is shown on Figure 1.
Operations at the site were begun in 1960 by Fiber Industries, Inc. (Fil), a manufacturer of
polyester chips and filament yarn. Celanese Corporation bought the facility from FIi in 1983,
renaming it Celanese Fiber Operations (CFO), and continued the production and processing of
polyester polymer chips and fibers. The site has alternately been known as HNA Holdings, Inc.,
Hoechst Celanese Corporation, and Celanese Fiber Operations, the latter being the site name as listed
on the NPL. The site will be referred to herein as the CFO site.
Descriptions of the plant process system indicate that the principal organic compounds involved
as either feedstock or product are dimethyl terephthalate, ethylene glycol and 1,4 butanediol. A
mixture with the trade name Dowtherm A is used as a heat transfer medium. Other reagents and
intermediates and various industrial solvents are handled in smaller quantities.
1.2 CERCLA-Related Remedial Actions (1981-1996)
1.2.1 Review of Activities from 1981-1996
CNA and its predecessors have been conducting environmental investigations at the CFO site
since 1981. Remediation and clean-up activities based on these investigations have been on-going
since 1988. The site was proposed for listing on the NPL in October of 1984 and work conducted
after that time followed the formal RI/FS. (remedial investigation/feasibility study) and RD/RA
(remedial design/remedial action) processes under CERCLA. The site was formally placed on the
National Priorities List (NPL) in June of 1986.
A remedial investigation (RI) fo; the CFO site was completed in June of 1986. The conclusions
from the RI indicated the presence of organic and inorganic constituents in site soils, sediments and
ground water consisting of phthalates, phenols, polynuclear aromatic hydrocarbons, ethylene glycol,
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CNA Holdings, lnc.-Shelby, NC--,-MNA Demonstration Project Work Plan (Rev 6/04) -Page 2
and other semivolatile organics, volatile organics and metals. The RI concluded that the probable
sources of these constituents were from buried residual sludges from the Glycol Recovery Unit
(GRU) and from buried burn pit materials.
Remedial activities conducted at the site were broken into two operable units: Operable Unit 1
(OU-1), consisting of ground-water extraction, treatment and hydraulic control; and, Operable Unit 2
(OU-2), consisting of excavation, incineration, stabilization and reburial of treated sludge, other waste
materials and stream sediments. OU-1 construction activities began in October of 1988 and the
extraction well system was placed in operation in August of 1989. Actual remediation activities at
OU-2 began in January of 1991 and continued through August of 1992.
The OU-2 remedy consisted of the removal, incineration, stabilization and redisposal of more
than 7800 tons of source material which greatly reduced the mobility, toxicity and volume of
contaminants remaining in the system. The OU-2 remedy did not require "clean closure" (i.e.,
complete removal of source material and residual contamination). Rather, the readily identified
source materials were excavated along with obviously contaminated soils (based on visual
observation), to a depth of at least 1-ft below the buried wastes. The specific inten_t of the OU-2
remedy was to remove and treat the major source of ground-water contamination and thereby
enhance the effectiveness of the OU-1 remedy.
Residual contamination left in the former source area after the completion of the OU-2 remedy
was intended to be collected and treated by OU-1. OU-1 consists of nine shallow, saprolite extraction
wells adjacent to and. downgradient of the OU-2 source area (the "Inner Tier"), and nine deep,
bedrock wells along the eastern property boundary (the "Outer Tier") which were used to recover
relatively uncontaminated ground water and provide hydraulic control to prevent off-site migration
of constituents.
1.2.2 Review of Activities from 1996-Present
On April 21, 1998, OU-2 and the Outer Tier portion of OU-1 were shut down as part of a partial
delisting petition approved by the EPA effective April 17, 1998 (Figure 2). The basis for the delisting
of OU-2 included consideration of the fact that all CERCLA response activities had been concluded
at this operable unit and that the remedy was protective of human health and the environment.
The Outer Tier extraction well portion of OU-1 was deleted on the following basis:
• Off-site domestic well sampling reported no detectable levels of Target Compound List (TCL)
organic constituents.
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CNA Holdings, Jnc.-Shelby, NC-MNA Demonstration Project Work Plan (Rev 6/04) -Page 3
A voluntary initiative by Hoechst Celanese (now CNA), completed in April of 1996, provided
surrounding residents downgradient of the CFO site with municipal water. Further, these
domestic supply wells were plugged back thereby eliminating the human consumption
exposure scenario. A restriction prohibiting the installation of supply wells was also placed in
the deeds of the affected property owners.
It would conserve a valuable ground-water resource and enhance the natural attenuation of
constituents remaining in the ground-water system by decreasing hydraulic gradients and
increasing travel times from the former source area toward the Outer Tier.
The entire Outer Tier is being maintained in "stand-by status" as part of the delisting process
and can be brought on line within a relatively short period of time if it is found necessary to provide
hydraulic control along the property boundary.
With respect to long-term remedial actions at the site, two other significant CERCLA-related items
have been implemented since submittal of the original MNA Demonstration Project Work Plan in
December 2001. These include the following:
• Implementing EPA recommendations contained in an August 2001 Five-Year Review Report
for OU-1, on March 1, 2004, CNA turned off the Inner Tier recovery well system while it
implements and evaluates the MNA Demonstration Project. As part of the shutdown, the Inner
Tier wells have had the dedicated bladder/submersible pumps removed so that they can be
used as low-flow sampling points during the demonstration project. The entire Inner Tier
system is being maintained during the interim in the event active recovery resumes as part of
the site remedy.
In October 2003, CNA petitioned the EPA and DENR (North Carolina Department of
Environment and Natural Resources) to modify selected elements of the OU-1 ROD (Record
of Decision). The petition requested that CNA be allowed to biologically treat recovered
Inner Tier ground water in the site's existing wastewater treatment facility rather than in a
separate SBR (sequencing batch reactor) at the ground-water treatment building. CNA
demonstrated that the requested modification would provide an equivalent level of treatment
of the ground water, and proposed no other modifications to the site clean-up levels,
monitoring program, or ultimate discharge point. The EPA found the change to be
significant but not fundamental and an ESD (Explanation of Significant Differences) was
utilized to effectuate the modification which became effective on April 23, 2004. Since that
time, the SBR and other appertanences at the ground-water treatment facility have been
decommissioned but are being maintained in the event the system ever needs to be restarted
in the future.
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CNA Holdings, /nc.-Shelby, NC-MNA Demonstration Project Work Plan (Rev 6/04) -Page 4
With the Inner and Outer Tiers shut down and the ground-water treatment system
decommissioned, current long-term remedial actions at the site consist of: (1) maintaining these
systems for possible future service; (2) collecting quarterly ground-water levels and samples from
selected monitor wells; (3) reporting on the status of these activities to the EPA and DENR on a
semiannual basis; and, (4) quarterly sampling, analysis and evaluation of MNA as a potential site
remedy as described in the present demonstration project work plan.
1.3 Remedial Action Effectiveness
As discussed earlier, the OU-2 remedy was successful in removing more than 7800 tons of source
material which greatly reduced the mobility, toxicity and volume of contaminants remaining in the
system. It is estimated that as many as 10,000,000 gallons of ground water were recovered by the
Inner Tier extraction well system and treated through the SBR during its 174 months of operation
(August 1989 through February 2004).
The reduction in contaminant concentrations is apparent from many of the long-term plots of
water-quality data at selected monitor wells and process points (Attachment 1). A number of these
plots are reproduced and updated in each_ semiannual report, while several were previously provided
in the Five Year Review Report for OU-2 (Kubal-Furr, August 1995). Superimposed on the plots are
key dates in site remediation including start-up of OU-1, initiation of the OU-2 remedy, and the
completion of the OU-2 remedy. The choice of locations and constituents was based on a review of
the water-quality database, in particular those locations having any meaningful data to plot. In
general, only those locations within a few hundred feet of the former OU-2 source area have any
significant number of water-quality constituents reported above the detection limits.
In December 1999, Kubal-Furr prepared a preliminary evaluation of the Inner Tier ground-water
extraction system and concluded that the Inner Tier system remains protective, but not effective, as a
long-term remedy. It noted that extraction rates are very low, maintenance is a chronic problem, and
achieving the MCLs through this mechanism would be measured in the hundreds of years. At the
time, Kubal-Furr prepared several figures showing the decline in performance of the Inner Tier
extraction well system since 1994. Two of these are shown as Figures 3 and 4 in Attachment 2.
Figure 3 (Attachment 2) is a plot of monthly ground-water pumpage from the Inner Tier from
August of 1994 through June of 1999, the time at which the evaluation took place. Also shown on
this figure is a three month moving avarage and a linear trend line fit through the plotted data. These
data clearly show a declining trend in the Inner Tier's ability to effectively recover ground water even
following major maintenance activities such as well replacement and a significant well rehabilitation
project.
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CNA Holdings, lnc.---Shelby, NC-MNA Demonstration Project Work Plan (Rev 6/04) -Page 5
Figure 4 (Attachment 2) shows the cumulative extraction volumes from 1994 to 1999 compared
to an optimal pumping rate of 2500 gallons per day, the volume which the SBR is capabale of
processing on a daily basis. The optimal pumpage during this period would have been 4,485,000
gallons versus the actual pumpage of 3,854,998 gallons, a difference of 630,002 gallons. This
departure from optimal is the equivalent to having the Inner Tier shut down for 252 days during the
review period; roughly one day per week every week.
The decline in Inner Tier production is due to a combination of physical, chemical and biological
factors. Physically, the upper water bearing formation in which the Inner Tier wells are installed is
composed of saprolite, a residual clayey material resulting from the weathering of the native bedrock.
Although this formation contains water, it is not considered an aquifer in the classical sense because
it's incapable of producing water at appreciable rates. Chemically, high iron and manganese
concentrations have caused the submersible pumps in several of the wells to freeze up. Biologically,
the principal contaminant, ethylene glycol, is readily degradable and has caused biofouling and
bacterial build-up outside the well casings and along the well screens. This combination of factors has
produced a pump and treat remedy which is inefficient.
The report concluded that considering the nature of the remammg principal contaminant,
ethylene glycol, which is readily degradable aerobically and anaerobically, that a monitored natural
attenuation remedy may be as successful in achieving the ground-water endpoints as the current
ground-water extraction approach.
1.4 MNA Work Plan Development
As part of its Five-Year Review of OU-1, the EPA and DENR conducted a site visit of the CFO site
in June of 2001. During this visit, the current site conditions and remedy were discussed in detail
along with a request for consideration of an MNA demonstration project. On July 11, 2001,
following the site visit, a letter report was prepared by Kubal-Furr which provided a rationale for
EPA's and DENR's consideration of an MNA demonstration project (Attachment 3). The EPA and
DENR concurred with the recommendation and, in an August 2001 Five-Year Review Report, the
EPA made the following recommendations specifically related to the MNA project:
•
•
Grant the PRPs request to determine if monitored natural attenuation would be effective at the
site.
"Turn off' the ground-water pump-and-treat system for a period of twenty-four (24)
months to allow the aquifer to recover and to investigate other potential remedies.
In December 2001, Kubal-Furr prepared, on behalf of Celanese, a document entitled:
"Monitored Natural Attenuation Demonstration Project Work Plan-Operable Unit 1-Celanese
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CNA Holdings, lnc.---Shelby, NC-MNA Demonstration Project Work Plan (Rev 6/04) -Page 6
North America Holdings, Inc.-Shelby, North Carolina." This plan was submitted to the EPA and
DENR for review. The agencies submitted comments on the December 2001 plan on January 30,
2002. In response to the agencies comments, a revised work plan was prepared and submitted in April
2002. The agencies reviewed the revised plan and submitted comments on June 5, 2002.
CNA deferred a formal response to the EPA's June 5, 2002 comments and requested that the
work plan be removed from further consideration while CNA implemented recommendations in the
EPA Five Year Review Report (August 2001) and pursued an ESD to modify the ground-water
treatment system selected in the ROD for OU-1. This work has since been accomplished as discussed
in more detail in Section 1.2.2.
In subsequent discussions during a conference call with the EPA and DENR, CNA requested
reconsideration of the MNA demonstration project. The agencies proposed that CNA reinitiate the
process by submitting a formal response to the June 5, 2002 work plan comments. The requested
response was prepared by Kubal-Furr on behalf of CNA and submitted to the EPA on April 1, 2004.
A meeting and site visit with the agencies, CNA, Ticona and Kubal-Furr occurred on May 19, 2004, at
which time the work plan, comments and other issues were resolved such that CNA would be able to
implement the plan while finalizing the document to incorporate the agencies recommendations.
In a letter from Mr. Ken Lucas, EPA, to Mr. Steve Olp, Celanese, dated May 20, 2004, EPA
authorized implementation of the MNA Demonstration Project, based on CNA's agreement to
modify the work plan to address comments in the letter and discussed in the May 19, 2004 meeting
and site visit. The current document has been prepared to satisfy this contingent authorization.
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CNA Holdings, Jnc.--Shelby, NC-MNA Demonstration Project Work Plan (Rev 6/04) ~age 7
2.0 Conceptual Site Model
The geology at the site consists principally of a low permeability saprolite overlying bedrock.
The saprolite is generally thickest beneath the plant site, thinning toward the east and in the vicinity of
the adjacent streams, which in many areas have been excised down to bedrock. Ground water occurs
in the saprolite under water table conditions and in water filled fractures in the bedrock. The direction
of movement in both the saprolite and bedrock aquifers is generally from upgradient areas west of
the plant toward the east, to discharge areas along the intermittent, unnamed streams and Buffalo
Creek.
As part of the CERCLA quarterly ground-water monitoring program, CNA has been collecting
water levels from approximately 100 monitor wells, extraction wells and piezometers for the past 9
years. These data are used to construct potentiometric surface maps and hydrogeologic cross sections
and are included with each semiannual report submitted to the agencies. The maps from the most
recent semiannual report are provided in Attachment 4.
The shallow saprolite maps (Figures 2 and 5, Attachment 4) show water-level contours and
ground-water movement in the uppermost water-bearing zone beneath the site. The direction of
movement in this zone is to the east from upgradient areas along NC 198, towards discharge areas
along the unnamed tributaries of Buffalo Creek. Drawdown and a capture zone are apparent on these
figures situated around the Inner Tier extraction system which was still in operation when the water-
level measurements were made.
An attempt was made to separate the uppermost water-bearing zone from the deeper saprolite and
upper bedrock zone. While these maps (Figures 3 and 6, Attachment 4) present a reasonable picture
of ground-water movement in this zone, it should be pointed out that it is giving a somewhat more
generalized picture of ground-water movement because of the well construction techniques used in
many of the wells and piezometers. The typical construction for most of these wells was to have
relatively long screens and extremely long sand packs in the annular space above the screens. As a
result, the lower saprolite/upper bedrock maps have a number of composite head values measured
along a longer screened interval. Nonetheless, the maps are felt useful for determining the general
direction of ground-water movement.
To confirm inferences made about the direction of movement and hydraulic control exerted by
the Inner Tier system, hydrogeologic cross sections were also constructed (Figures 4 and 7,
Attachment 4). The location of the cross section is shown on the site location map, Figure 1, and is
constructed through the plant from upgradient areas west of the plant to downgradient, off-site areas
east of the plant. These east-west hydrogeologic cross sections indicate flow is predominantly
horizontal across the site, from upgradient areas west of the plant toward downgradient areas to the
. east.
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CNA Holdings, lnc.-Shelby, NC-MNA Demonstration Project Work Plan (Rev 6/04) -Page 8
Based on the nature of the formation and hydraulic gradients in the shallow saprolite, ground-
water movement is expected to be measured in the tens of feet per year. The slow rate of ground-
water movement is also supported by the empirical data which show constituents in the uppermost
water bearing zone to be below detect within a few hundred feet of the former source area even
though the plant has been in operation for more than 40 years.
Considering the direction of ground-water movement, final receptors for constituents migrating
from the CFO site would include off-site residents to the northeast that may consume ground water
but who were not part of the voluntary watering initiative (none known at this time); children wading
in the adjacent creeks; anyone eating fish caught in the creeks (unlikely); and, any ecological
receptors in the adjacent creeks. Because of different retardation factors, degradation rates, etc., the
buffer zone between the final receptors and the "plume' would depend on the specific constituent of
concern. For some constituents, the buffer zone might be several hundred feet whereas for others, it
might be several thousand. In the case of ethylene glycol, which has been detected in only a very
small area around the former source area, the buffer extends at least 1500 feet downgradient, which is
the distance to the nearest property boundary.
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CNA Holdings, /11c.---Shelby, NC-MNA Demonstration Project Work Plan (Rev 6/04) -Page 9
3.0 Initial MNA Data Collection
3.1 Work Performed
After the EPA had concluded its Five-Year Review Report for the CFO site which supported
consideration of the effectiveness of MNA as a site remedy, an initial MNA sampling event, under
pumping conditions, was completed by Kubal-Furr in September of 2001. In planning the sampling
program, it was determined that a majority of site monitoring wells were more than 15 years old and
that many had not been sampled for several years. Further, sampling methods differed from well to
well, with some wells equipped with dedicated sampling equipment (QED Environmental Well
Wizard®) and others with dedicated bailers. A decision was made to consistently sample wells using
low-flow purging techniques and the initial activity of the MNA sampling was a well rehabilitation
program. The program included all monitor wells except for those installed in 1998 during due
diligence related to sale of part of the plant to KOSA.
Well rehabilitation consisted of removing Well Wizards® or dedicated bailers, surging wells with a
surge-block, brushing well screens, and pumping to redevelop wells. Thirty-two (32) Well Wizards®
were removed completely from the monitoring wells. In three monitor wells, the Well Wizards® could
not be retrieved and only tubing was removed, leaving the lower part of the Well Wizard® in the
bottom of the well. A total of 49 monitor wells were surged and redeveloped using decontaminated
Grundfos® pumps or 12V wailer pumps depending on the specifics of well (size, depth to water,
etc.). The well rehabilitation program lasted from September 4 through September 11, 2001 and a
summary of the activities performed at the individual monitor wells is provided as Table 1 in
Attachment 5. A table summarizing construction details for all monitor wells, piezometers and
extraction wells is provided as Table 2 in Attachment 5.
The initial MNA ground-water quality sampling activities were conducted from September 11 to
September 27, 2001. Nine ground-water extraction wells and 25 ground-water monitor wells were
sampled for MNA evaluation parameters. The wells sampled, shown on Figure 3, included:
Extraction wells: IT-1, IT-2, IT-3, IT-4, IT-5, IT-6, IT-7, IT-8R, IT-9.
Monitor wells: A-39, C-49, CC-33, D-27, F-55, G-50, G-88, 1-57, J-28, K-28, N-29, 0-25,
Q-33, S-50, T-17, T-35, T-58, TD-3, TD-4, TI-1, TI-2, U-38, V-23, W-23, Z-78.
All monitoring wells were sampled using low flow purging and sampling procedures. A peristaltic
pump, or a decontaminated Grundfos® pump, each with dedicated tubing and a Horiba U-22 meter
with flow through cell were used throughout low flow sampling. Drawdown and field measurements
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of temperature, pH, specific conductivity, turbidity, DO (dissolved oxygen) and ORP (oxidation
reduction potential) were recorded at 5-minute intervals at each monitoring well during purging. All
extraction wells were sampled using grab sampling methods consistent with the current sampling and
analysis plan. Measurements of ferrous iron and sulfide were also collected in the field.
Initial MNA sampling included laboratory analysis of alkalinity, ammonia, carbon dioxide,
carbon monoxide, ethane, ethene, ethylene glycol, methane, nitrate, nitrogen gas, oxygen gas, sulfate,
sulfide, total aerobic plate count, total anaerobic plate count, total arsenic, total kjeldahl nitrogen, total
manganese, TOC (total organic carbon), and total phosphorus.
Samples were analyzed in accordance with EP A/DENR approved methodology by Davis & Floyd,
Inc., of Greenwood, SC, with analyses of gases subcontracted to Microseeps of Pittsburgh, PA.
Samples were also analyzed for aerobic and anaerobic plate count by Duke Power Company under
subcontract to Pace Analytical Services, Inc., both of Huntersville, NC. A summary of the results of
the initial MNA analyses is provided in Attachment 6.
Regarding the initial sampling event, the field sampling logs indicate a number of wells exceeded
the EPA turbidity guideline of 10 NTUs during low-flow sampling. Since this initial sampling, the
techniques used to purge the wells have improved considerably and most turbidities are now within
the low-flow sampling guidelines. Every attempt will be made during the course of the MNA
demonstration project to maintain or improve the physical quality of the collected samples although
some of the monitor wells are screened in such fine grained materials that the 10 NTU guidelines
may still be exceeded on occasion. For the most part, the parameters being analyzed during the
demonstration project would not be significantly affected by slightly elevated turbidities and CNA
may need to request a variance to the very specific 10 NTU criteria. This need will be evaluated
during subsequent sampling events and will be proposed, if necessary, at an appropriate time.
3.2 Evaluation of the Initial MNA Data Set
Although other constituents have been detected in monitor wells near the former source area, in
terms of constituent concentrations, ethylene glycol is the principal contaminant remaining at the site.
A list of constituents found near the former source area along with an indication as to how amenable
they are to natural attenuation is summarized in Table 1. While the focus of the work plan has been
oriented toward the degradation of ethylene glycol, it should be noted that all constituents listed in
Table 1 in excess of remedial goals will be remediated to the satisfaction of all ARARs (applicable,
relevant and appropriate requirements) as specified in the ROD.
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3.2.1 Ethylene Glycol Degradation Pathways
Ethylene glycol is readily degradable both aerobically and anaerobically. Under aerobic
conditions, ethylene glycol (C2H6O2) will degrade into carbon dioxide and water. Under anaerobic
conditions, ethylene glycol can degrade into ethanol, acetate and methane. The ethanol produced can
be further oxidized to acetate, with methane being the final end product.
While ethylene glycol has been found to be readily degradable biologically, few natural
attenuation field investigations have been conducted to address ethylene glycol specifically. Most of
the published literature has focused on attenuation ·of fuel hydrocarbons and chlorinated organics.
One investigation at the Naval Air Warfare Center in Lakehurst, New Jersey (Flathman, et. al) reported
on biological techniques used to remediate ground water contaminated with ethylene glycol resulting
from leakage of an estimated 4000 gallons from a surface storage lagoon. Concentrations of ethylene
glycol as high as 2100 ppm were remediated using a combination of ground-water extraction and ex-
situ treatment combined with reinjection and in-situ treatment following pH adjustment and mineral
nutrient and oxygen additions. Although this reference describes an aerobic process of ethylene
degradation, it cross references another paper dealing specifically with the anaerobic degradation of
ethylene glycol (Dwyer and Tiedje, 19ll3). Copies of both of these references are provided in
Attachment 7.
While ethylene glycol is readily biodegradable under both aerobic and anaerobic conditions, the
extent of aerobic biodegradation in the aquifer at the CFO site will likely be limited by the relatively
high concentrations of ethylene glycol present (> 1000 mg/L) and the low rate of oxygen transfer in
most aquifers. In general, aquifer conditions are more appropriate to support a variety of anaerobic
biotransformation processes including reduction of nitrate, manganese, iron, and sulfate and
methanogenesis. However, the actual significance of specific biotransformation processes will be
limited by the availability of appropriate electron acceptors.
3.2.2 Evaluation of Ethylene Glycol Degradation and MNA Potential at the CFO Site
At the CFO site, the initial MNA monitoring data were reviewed to identify parameters indicative
of the rate and/or the extent of ethylene glycol biotransformation in the subsurface. Robert C.
Borden, PE, Ph.D., a professor at N.C. State University and a nationally-recognized expert in natural
attenuation and bioremediation, was retained. by Kubal-Furr to assist with review of the initial MNA
water-quality data for evidence of ethylene glycol biodegradation. A complete copy of Dr. Borden's
analysis is included in Attachment 8 and is summarized below.
In its review of an earlier version of the work plan, EPA suggested that the initial MNA data set be
reviewed with respect to the screening parameters contained in EPA MNA guidance documents (EPA,
1998). The process involves comparing the site data to a screening table which assigns a numerical
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value to each data point, higher values being more indicative of the potential for anaerobic
degradation of constituents. The values for each parameter for each well are then summed and
produce a total score which, if high enough, is suggestive of conditions conducive to natural
attenuation. Although not directly applicable to ethylene glycol degradation, the screening criteria
were applied to the initial data set to produce the conditions depicted on Figure 4 which would
indicate that conditions in the former source area are favorable for natural attenuation to occur.
According to Dr. Borden, there is strong evidence that ethylene glycol is being anaerobically
degraded in the subsurface using nitrate, manganese, iron and sulfate as the terminal electron
acceptors. Figure 4 shows the concentration of ethylene glycol compared to methane and in relation
to the MNA screening parameters.
The initial MNA data indicate that ethylene glycol is biodegraded, resulting in methane
production in the most highly contaminated portions of the aquifer. An initial review of the
monitoring data suggested that methanogenic fermentation might be inhibited in this aquifer by the
low pH (4.9 to 6.1) since methanogenic processes often slow below a pH less than 7. However the
monitoring data (Figure 4) show that the ground water contains elevated levels of methane in the
areas with high ethylene glycol, indicating a very active methanogenic population.
Although the oxidized form of manganese is essentially insoluble, ethylene glycol
biodegradation using manganese as the electron acceptor converts the solid, oxidized manganese to
soluble, reduced manganese which is then detected in monitoring wells (Figure 5). The very high
concentrations of manganese observed in wells with high ethylene glycol concentrations indicate that
manganese is an important electron acceptor at this site.
A similar process occurs with iron (Fe) where bacterial degradation of ethylene glycol results in
the conversion of insoluble ferric iron (Fe3+) to soluble ferrous iron (Fe2+ ). The amount of iron
being used as an electron acceptor, however, can only be estimated, as the field test kits used during
the baseline MNA monitoring were limited to a 10 mg/L upper detection limit (Figure 6). According
to MNA protocols (EPA, 1996) the presence of ferrous iron in concentrations greater than 1 part per
million suggests: (1) the contaminant plume has impacted the biogeochemical conditions and utilized
Fe3+ to produce Fe2+; and, (2) a reductive pathway is possible. In the case of the MNA baseline data,
a 10 mg/L or higher accumulation (i.e., above the upper detection limits of the field test kit) of
ferrous iron should be sufficient to determine that iron-reducing conditions are occurring. If ferrous
iron continues to be an issue, an alternate constituent for which there are no analytical detection
problems (i.e., manganese) will be used for evaluation purposes.
Weaker evidence of ethylene glycol degradation is apparent in the sulfate and nitrate analyses. In
most cases, whenever ethylene glycol is present above the analytical detection limit of 5 mg/L, nitrate
has been depleted to less than 0.5 mg/L (Figure 7). Sulfate is generally present in high concentrations
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when ethylene glycol is below the analytical detection limit and sulfate depletes to less than 5 mg/L
when ethylene glycol is between 7 mg/L and 1,000 mg/L (Figure 8). Increases in sulfate
concentrations noted when ethylene glycol exceeds 1000 mg/L may be attributable to the fact that at
these concentrations ethylene glycol inhibits or slows the rate of sulfate reduction or produces
interferences in the sulfate measurement technique. Subsequent sampling events will incorporate
quality assurance checks in an attempt to resolve/quantify the sulfate interferences.
In summary, the initial MNA data contains multiple evidence that natural attenuation of the
ethylene glycol is occurring at the site. Tabulated below is a summary of the selected natural
attenuation indicators, from upgradient areas at well Tl-1; through the plume as shown in wells V-23
and IT-6, to downgradient areas as shown by wells 0-25 and W-23. These results are generally
consistent with the expected findings that as ethylene glycol increases, nitrate and sulfate will
decrease, while Fe2+, manganese, and methane will increase.
--------Background---------------Plume Area--------------Downgradien t-------
Well TI-1 U-38 V-23 IT-6 0-25 W-23
Eth.Glycol <5 <5 5040 5450 <5 <5
Nitrate 2.9 1.9 < 0.05 < 0.25 < 0.05 0.4
Manganese 0.03 0.0078 858 834 0.52 2.9
Fe2+ < 0.1 0.1 > 10 > 10 < 0.1 < 0.1
Sulfate < 1.1 < 2.1 41.6 < 12 453 64
Methane < 0.00011 < 0.00061 16 13 1.1 0.066
(All concentrations reported in milligrams per liter)
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4.0 Proposed MNA Demonstration Project Work Plan
Monitored natural attenuation is being considered at the CFO site because ethylene glycol is
biodegradable and the initial MNA data set indicates that biological activities at the site can support
degradation by using ethylene glycol as an electron donor and organic substrate.
A work plan describing the MNA demonstration project is presented below. The plan consists of
the implementation of several tasks including: (1) "shut down" of the Inner Tier extraction well
system; (2) "shut down" of the sequencing batch reactor (SBR) that treats recovered Inner Tier
ground water; (3) aquifer testing and flow rate analysis; ( 4) collection of quarterly water-quality data
for key MNA indicator parameters at selected monitor well locations; (5) modeling of the aquifer
system using numerical models to provide additional support and evaluation of MNA conditions; (6)
mid-project data review and evaluation of natural attenuation progress; and, (7) preparation of status
and end-of-project summary reports documenting the potential of using monitored natural
attenuation as a preferred site remedy.
As described in earlier sections, items 1 and 2 above have already been implemented. The Inner \
Tier was shut down on March 1, 2004. Decommissioning of the SBR and ground-water treatment
building followed shortly thereafter with approval of the ESD on April 23, 2004. A summary report
describing the SBR shu.t down activities will be included in the next semiannual monitoring report.
4.1 Ground-Water Flow Rate Analysis
With the Inner Tier extraction system shut down, aquifer testing will be performed to determine
the hydraulic parameters for the shallow, saprolite aquifer. A review will also be conducted of any
aquifer testing or determination of hydraulic charatceristics of the bedrock aquifer that may have
been performed during the remedial investigation, feasibility study, or during installation and testing
of the extraction well systems.
Slug tests will be conducted at all of the MNA monitoring wells under both rising head ("slug
out") and falling head ("slug in") conditions. A pressure transducer/data logger will be lowered into
each well to be tested and once the water level has stabilized, a manual water-level measurement will
be taken prior to the test run. After the water level has equilibrated, the data logger will be started and
the "slug in" test will begun by lowering a soHd slug into the well with a nylon rope. The slug will be
constructed of teflon, PVC or metal pipe, filled with deionized water, capped on both ends, and
decontaminated before insertion.
When the transducer readings equilibrate again, the "slug in" portion of the test will be
considered complete and the data logger will continue to record water levels as the slug is removed,
beginning the "slug out" portion of the test. Readings during the slug out portion of the test will
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continue until the water levels equilibrate. All slug test data will be compensated for barometric
pressure and will evaluated using the most appropriate evaluation method ( e.g., Bouwer & Rice,
Hvorslev, etc.) module of the "Super Slug™" aquifer slug test analysis software (Starpoint Software,
Inc.).
The hydraulic conductivity data developed for the saproilite aquifer during this part of the
project and any previous aquifer characteristics for the bedrock aquifer will be used as input to the
MODFLOW model that will be used in evaluating flow, contaminant transport and degradation rates.
4.2 MNA Monitoring Program and Data Analysis
The proposed MNA monitoring program will include quarterly sampling and analysis of select
monitoring wells and Inner Tier extraction wells (under non-pumping conditions) for the MNA
indicator parameters (Figure 9). Wells will be sampled and analyzed following the same EPA-
approved, low-flow procedures and analytical methodologies used during the initial MNA
investigation (except at F-55 as noted below). The proposed monitoring network includes the
following wells:
• Monitor wells: F-55, TI-1, U-38, J-28, V-23, V-65, CC-33, 0-25, K-28, N-29, W-23 and Q-33
Inner Tier wells: IT-1, IT-2, IT-3, IT-4, IT-5, IT-6, IT-7, IT-8R and IT-9
Monitor well V-65 has been added to the network during this work plan revision. It is a deeper'
well in the former source area that was installed since the original work plan was submitted in
December 2001. It will be used to evaluate the vertical distribution of ethylene glycol in the former
source area and for further information on the MNA indicator parameters at depth.
Well F-55 was added at the EPA's request during early reviews of the work plan. Small
accumulations of free product DowTherm have been reported at this location during quarterly PEW
(polymer extraction well) sampling events. The product is recovered each quarter and the quantity is
recorded in each semiannual monitoring report. Because of the difficulty of deconning sampling
equipment which may come in contact with DowTherm, this well will need to be evacuated and
sampled using a disposable bailer rather than low flow protocols used for the other monitor wells,
The proposed MNA indicator parameters include laboratory analysis of ethylene glycol, TOC,
alkalinity, nitrate, iron, sulfate, manganese, methane, sulfide and carbon dioxide and field analysis of
ferrous iron, DO, pH, specific conductivity, ORP and temperature. Samples will be collected from
each well for eight consecutive quarters beginning with the first quarterly sampling event after
approval of this work plan. At the completion of each quarterly monitoring event, the water-quality
data will be reviewed, validated, summarized and compiled into the ground-water data base. These
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data will also be provided to the EPA and the DENR in graphical and tabular form along with brief
interpretative letter reports.
4.3 Transport and Attenuation Modeling
In preparation of the mid-project and final MNA demonstration project reports, slug test data and
MNA water-quality data will be initially evaluated using BIOSCREEN. BIOSCREEN is based on an
analytical solute transport model and is designed to adequately screen a site's MNA potential by
providing terminal electron acceptor (TEA) data (i.e., oxygen, nitrate, Fe+2, sulfate and methane),
contaminant concentrations and kinetic rate information. BIOSCREEN is commonly used to model
BTEX transport but its use need not be limited to BTEX constituents (benzene, toluene, ethylbenzene,
xylenes). When constituents other than BTEX are modeled, the utilization factors will be changed or
the TEAs will be modified accordingly to reflect utilization factors (BIOSCREEN User's Manual).
Ethylene glycol, a C2 compound with two hydroxylic groups and solubility of " 10g/100ml, should
be suitable for the use of BIOSCREEN. An alternative evaluation, using MODFLOW, described below
will also be used and therefore, if it appears BIOSCREEN is not a useful tool, it will not be carried
forward any further in the analysis.
Once the initial review is completed, MODFLOW will be used to create a model calibrated to the
site. MODFLOW can be used to represent the effects of wells, rivers, streams, drains, horizontal flow
barriers, evapotranspiration, and recharge on flow systems with heterogeneous aquifer properties and
complex boundary conditions to simulate ground-water flow. RT3D is a software add-on package for
MODFLOW used to simulate three-dimensional, multispecies, reactive transport in ground water.
RT3D can simulate a multitude of scenarios including natural attenuation processes or an active
remediation involving contaminants such as heavy metals, explosives, petroleum hydrocarbons, and/or
chlorinated solvents.
4.4 Mid-Project Data Review and Evaluation
This work plan has presented the results of an initial set of monitored natural attenuation
parameters. The purpose of the initial sampling was to gain an understanding of current conditions
and assess whether there was sufficient evidence of ethylene glycol degradation to warrant full scale
implementation of a demonstration project. For purposes of evaluating the degradation rates and
progress in remediating the ground water, however, the first set of samples following Inner Tier shut
down will be considered as the baseline upon which to judge a successful outcome of the MNA
demonstration project.
Successful implementation and evaluation of the success of a monitored natural attenuation
remedy at the CFO site will be based on "lines-of-evidence" during the two year demonstration
project. In preparing these lines of evidence, Kubal-Furr will rely heavily on the protocols and
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proceedures presented in the various EPA MNA guidance documents. Items to be considered in
developing such evidence include:
•
•
•
Is the monitor well network and constituent list adequate to demonstrate that natural
attenuation is occurring?
Are constituent concentrations decreasing, and if so, are corresponding increases noted in
indicator constituents that would indicate transformation or degradation rather than
dispersion and dilution of the ethylene glycol and other constituents?
Have constituent concentrations found in monitor wells downgradient from the former source
area remained below any risk-based levels of concern from a human health or ecological
standpoint?
Are calculated degradation rates likely to reduce constituent concentrations to acceptable
levels in a reasonable amount of time?
It is understood that the addition of nutrients and oxygen-saturated water or an oxygen release
compound can enhance the degradation of ethylene glycol because aerobic conditions are always
energetically-favorable for bacteria: However, before deciding to add amendments, consideration will
be given to what the remedial objectives are; where the final receptors are; what the distance (buffer
zone) is between the plume and final receptors; and, the ethylene degradation rate. The addition of
oxygen or other amendments can always be considered if ethylene glycol needs to be remediated at a
faster rate. This assessment will be part of the on-going evaluation of MNA data collected during the
proposed demonstration project and will be proposed in the mid-course report as appropriate.
4.5 Project Reporting and Schedule
CNA will implement the MNA demonstration project upon review and approval of this work plan
by the EPA and DENR. Initial activities planned for the first quarter following approval include
shutting down the Inner Tier extraction well system and SBR (already acomplished); performing slug
tests; and, collection of the initial, non-pumping baseline MNA samples.
A schedule of MNA sampling and rep.orting activities is presented in Figure 10. Brief data
summary reports will be submitted at the completion of each quarterly sampling event. These
documents will include the field records, complete laboratory data packages, a data assessment
summary, tabular data summaries, graphical data plots (e.g., electron acceptor, ethylene glycol and
methane isopleth maps; time-concentration plots; etc.) and any recommendations for modifications
to the plan.
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After the fourth quarterly sample is collected, an expanded, mid-project summary report will be
prepared. Using the evaluation criteria described in Section 4.5, an assessment will be presented as to
how effective natural attenuation has been in reducing constituent concentrations, whether the
monitoring network and parameters are adequate to assess the rate of natural degradation, evaluate
how the addition of amendments could enhance the rate of natural degradation and any
recommendations for changes to the work plan to be evaluated during the remainder of the
demonstration project period.
The final MNA Demonstration Project Report will be submitted within 90 days of receipt of the
final quarterly sampling event. The report will summarize the work performed, the results of aquifer
analysis and water-quality sampling data, modeling results, and recommendations for additional data
collection, restart of the Inner Tier extraction well system, or replacement of the Inner Tier remedy
with natural attenuation via a ROD modification.
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5.0 References
Alleman, B.C., and Leeson, A. (Eds.), 1999, Bioremediation of Nitroaromatic and Haloaromatic
Compounds: Battelle Press, 302p.
Dwyer, D.F., and Tiedje, J.M., 1983, Degradation of Ethylene Glycol and Polyethylene Glycols by
Methanogenic Consortia: Journal of Applied and Environmental Microbiology, pp 185-190.
Flathman, P.E., and Bottomley, L.S., 1994, Bioremediation of Ethylene Glycol-Contaminated
Groundwater at the Naval Air Warfare Center in Lakehurst, New Jersey, in: Bioremediation Field
Experience, Ch. 23, pp 491-500.
U.S. Environmental Protection Agency, 1996, Bioremediation of Hazardous Waste Sites: Practical
Approaches to Implementation (Seminar): EP N625/K-96/001.
U.S. Environmental Protection Agency, 1998, Technical Protocol for Evaluating Natural Attenuation
of Chlorinated Solvents in Ground Water: EPN600/R-98/128, 248p.
U.S. Environmental Protection Agency, 1999, Use of Monitored Natural Attenuation at Superfund,
RCRA Corrective Action, and Underground Storage Tank Sites: OSWER Directive 9200.4-l?P,
32p.
U.S. Environmental Protection Agency Region 4, 1999, Draft EPA Region 4 Suggested Practices for
Evaluation of a Site For Natural Attenuation (Biological Degradation) of Chlorinated Solvents:
EPA Region 4, Version 3.1, 40p.
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CAS No
92-52-4
75-34-3
71-55-6
95-50-1
107-06-2
156-59-2
540-59-0
106-46-7
123-91-1
78-93-3
591-78-6
91-57-6
7005-72-3
50-29-3
67-64-1
-- - - - - --- -
Table 1. Natural Attenuation Potential of Identified Constituents of Concern
Celanese/Ticona-Shelby, North Carolina
Parameter Natural Attenuation Potential Comment
low ( potentially biodegradable under
1, 1-Biphenyl controlled aerobic conditions, no data limited field and laboratory
available under field or anaerobic data
conditions)
1 , 1-Dichloroethane moderate to high under anaerobic MNA is well documented conditions
1, 1, 1-Trichloroethane moderate to high under anaerobic MNA is well documented conditions
1,2-Dichlorobenzene moderate to high (biodegradable under biodegradability is well
aerobic and anaerobic conditions) documented
1,2-Dichtoroethane moderate to high under anaerobic MNA is well documented conditions
cis-1 ,2-Dichloroethene moderate to high under anaerobic MNA is well documented conditions
1,2-Dichloroethene (total} moderate to high under anaerobic MNA is well documented conditions
1,4-Dichlorobenzene moderate (biodegradable under aerobic and biodegradability is well
anaerobic conditions) documented
1,4-Dioxane low limited field and laboratory
data
2-Butanone (MEK) high under aerobic conditions and moderate biodegradability is well
to high under anaerobic conditions documented
2-Hexanone high under aerobic conditions and moderate biodegradability is well
to high under anaerobic conditions documented
fate and transport
-
2-Methylnaphthalene low mechanisms are governed by
sorption on natural organic
matter (NDM)
4-Chlorophenyl phenyl ether low limited field and laboratory
data
4,4'-DDT moderate to low under aerobic conditions biodegradability is well
and low under anaerobic conditions documented
Acetone high under both aerobic and anaerobic biodegradability is well
conditions documented
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CAS No
71-43-2
108-90-7
67-66-3
106-44-5
319-86-8
.
132-64-9
101-84-8
100-41-4
107-21-1
91-20-3
108-95-2
127-18-4
108-88-3
79-01-6
1330-20-7
.
- - -- - - ---- -
Table 1. Natural Attenuation Potential of Identified Constituents of Concern
Celanese/Ticona-Shelby, North Carolina
Parameter Natural Attenuation Potential Comment
Benzene high under aerobic and anaerobic conditions MNA is well documented
Chlorobenzene high under aerobic conditions and moderate biodegradability is well
to high under anaerobic conditions documented
Chloroform moderate to low under anaerobic conditions biodegradability is well
documented
p-Cresol moderate to high under both aerobic and biodegradability is well
anaerobic conditions documented
limited field and laboratory
delta-Hexachlorocyclohexane moderate to high under anaerobic data (biodegradability is well
(delta-BHC) conditions documented for Undane
(gamma-BHC))
fate and transport
Oibenzofuran low mechanisms are governed by
sorption on NOM
low ( potentially biodegradable under
Diphenyl ether controlled aerobic conditions, no data limited field and laboratory
available under field or anaerobic data
conditions)
Ethyl benzene high under aerobic conditions, moderate to MNA is well documented high under anaerobic conditions
Ethylene glycol high under both aerobic and anaerobic biodegradability is well
conditions documented
fate and transport
Naphthalene low mechanisms are governed by
sorption on NOM
Phenol high under both aerobic and anaerobic biodegradability is well
conditions documented
T etrachloroethene high under anaerobic conditions MNA is well documented
Toluene high under aerobic conditions, moderate to MNA is well documented high under anaerobic conditions
Trichloroethene high under anaerobic conditions MNA is well documented
Xylenes, Total high under aerobic conditions, moderate to MNA is well documented high under anaerobic conditions
NOM: Natural Organic Matter
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0 350 700
--- - - - -
Legend
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& Piezometer
& SUlface Water Location
♦ Outer Tier Extraction Well
• Inner Tier Ex1raction Well
■ PEW Extradlon Well
a Residential Wei
,,.._.,,, Craek / Stn,am
■ Building / Structure
Kubal-Furr & Associates
-Environmental Consultants-
Figure 1. Site Location Map
CNA Holdings, lnc.mcona
Shelby. North Carolina
--- -- -
Stream/Creek
□ HCC Bulldlng/Structure
♦ Abandoned Outer Tier Well
+ Inner Tier Extraction Well
♦ Outer Tier Extraction Well
Cl Domestic Supply Well
1K Abandoned Inner Tier Well
-
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~ f ~ Deleted Areas
• ,' -L_ (OU-~
--
Scale In Feet
600 1200
-
, ,
' ,
--- - ----,.. .. -... --•
0
Fonner Sourw ArN and R_C,_.
(OU-2)~
□ Ou• Tier Extraction Sya1am (OU-1) Deltad.
Deleted Area ---t---,,100-1 Outer Tier) ---
-..... ----~-...
Kubal-Furr & Associates
-Environmental Consultants -
---
Figure 2-Map Showing Deleted Portions
of OU-1 & OU-2
CNA Holdings, Inc. I Ticona
Shelby, North Carolina
-
- -- - - - -- - - - -
N Legend
l
o--==4:::ilOO-c:::::::iao~eet
$ Monitor Wells Sampled for MNA Parameters Buildings/Structures
.A. Inner Tier Wells Sampled for MNA Parameters -Creeks/Streams
-Roads •Basins/Ponds
-+ Railroads (g]Property
P:/GIS/C AIMNA!Figure3.mxd
-- - -- -
Kubal-Furr & Associates
-Environmental ConsulJants-
Figure 3
Inital MNA
Sampling Locations
CNA Holdings, Inc. I Ticona
Shelby, North Carolina
-
- -- - - - -
Ethylene Glycol
0
I
N
l
500 1,000
I
C:/GIS/CNA/MNA.mxd
2001 Ethylene Glycol
Concentration (mg/L)
1
10
100
1000
Feet -10000
- - - - -- --- - - -
Methane MNA Screening Parameters
2001 Methane
Concentration (mg/L)
•0.0001
0.001
•0.01
•0.1
1
10
MNA Screening Parameters
5-9
->10 !DI Parcel Boundaries
Monitor Wells Sampled for MNA Parameters
A Inner Tier Wells Sampled for MNA Parameters
-Creeks I Streams D Buildings/ Structures
Kubal-Furr & Associates
-Environmental Consultants-
Igure 4
Results of the MNA Sampling
Ethylene Glycol, Methane,
and Screening Parameters
September 2001
CNA Ho/dings, Inc. I T/cona
Shelby, North Caro/Ina
- -
N
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0 200
- -
400 Feet
P:/GIS/CNNMNNFigureS.mxd
- -
Legend
- -
LT~
35.3 ...
v.23 .& IT-5
858, 100
IT-6 IT-7 834 A 447
IT-SRA IT-9
71.8 .&75.6
-
~
0.52 EB
- - - -
EB Monitoring Wells Sampled for MNA Parameters Buildings/Structures 2001 Total Manganese
.A. Inner Tier Wells Sampled for MNA Parameters -Creeks/Streams Concentration (mg/L)
-Roads •Basins/Ponds 0.01
-Railroads [Q]Property •O. l
l
10
100
- - - - -
Kubal-Furr & Associates
-Environmental ConsultanJs-
Figure 5
Results of MNA Sampling
Total Manganese (September 2001)
CNA Holdings. Inc. I Ticoru1
Shelby, North Carolina
-
- -
N
t
0 200
--
400 Feet
P:/GIS/CNA/MNA/Figure6.nnd
- - -- - - -- -
Legend
$ Monitoring Wells Sampled for MNA Parameters Buildings/Structures 2001Ferrous Iron
.A. Inner Tier Wells Sampled for MNA Parameters -Creeks/Streams Concentration (mg/L)
-Roads •Basins/Ponds •0.1
-. Railroads c Property 1
10
- - - - -
Kubal-Furr & Associates
-Environmental, ConsrdlanJs-
Figure 6
Results of MNA Sampling
Ferrous Iron (September 2001)
CNA Holdings, Inc. I Ticona
Shelby, North Carolina
-
- - - - - --- - - - --
N
1
Legend
E& Monitoring Wells Sampled for MNA Parameters Buildings/Structures 2001 Nitrate
.A Inner Tier Wells Sampled for MNA Parameters -Creeks/Streams Concentration (mg/L)
-Roads •Basins/Ponds •O.l
0 200 400 •c:::iilc=:::i Feet
-+ Railroads [Q]Property I
10
P:IGIS/CNA/MNA/Figure7.mxd
- - - - -
Kubal-Furr & Associates
-Environrrumtal ConsulJanJs-
Figure 7
Results ofMNA Sampling
Nitrate (September 2001)
CNA Holdings, Inc. I Ticona
Shelby, North Carolina
-
- --- - - -- - - - --
N
i
0 200 40~eet
P:/GIS/CNA/MNA/Figure8.mxd
Legend
V-23 A IT-5
41 .6 1 <3
rT-8 ...
<1 2 A IT-7
<3
IT-8R A IT-9
<3 <3
E9
E9
0-25
453
E9 Monitoring Wells Sampled for l\1NA Parameters Buildings/Structures 2001 Sulfate
..A Inner Tier Wells Sampled for MNA Parameters -Creeks/Streams Concentration (mg/L)
-Roads •Basins/Ponds I
-Rail roads IQProperty 10
100
- - - - -
Kubal-Furr & Associates
-Environnumlal Consultants-
Figure 8
Results of MNA Sampling
Sulfate (September 2001)
CNA Holdings, Inc . I Ticona
Shelby, North Carolina
-
-------------------
0
N
i
125 250 iFeet
P:/GIS/CNA/MNA/Figure9.mxd
Legend
EB Monitoring Wells Sampled for MNA Parameters Buildings/Structures
.A. Inner Tier Wells Sampled for MNA Parameters -Creeks/Streams
-Roads
-+ Rail roads
•Basins/Ponds
(g)Property
Kubal-Furr & Associates
-Environmental Consu/Jants-
Figure 9
Proposed MNA
Monitoring Locaitons
CNA Holdings, Inc. I Ticona
Shelby, North Carolina
- -- --
Task
Quarterly Sampling (1)
Data Re ort 1
Quarterly Sampling (2)
Data Re ort 2
Quarterly Sampllng (3)
Data Re art 3
Quarterly Sampling ( 4)
Mid-Project Review[Evaluatlon
Quarterly Sampling (5)
Data Re ort 5
Quarterly Sampling (6)
Data Re ort 6
Quarterly Sampling (7)
Data Re ort 7
Quarterly Sampling (8)
Final Pro·ect Review/Evaluation
- - -- -- - -
Figure 1 O. Proposed MNA Demonstration Project Schedule
CFO Slte/Shebly, North Carolina
-
Q2 2004 Q3 2004 Q4 2004 Ql 2005 Q2 2005 Q3 2005
v
v
v
v
v
v
v
v
v
v
v
-- -- -
Q4 2005 Ql 2006 Q2 2006
v
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I Attachment 1
I Selected Water-Quality Plots
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-------------------
~
E -C
3500 -------------------
3000 ------------------
2500
.g 2000 "' . ~ -C ., u §
u 1500
ITCI TOC Data
1000 -------------------·--------------------------------------------------
500 ---------------------------------------------------------------------------------------------------------
0+----------t---------t--------+----------+--------+-__J
1/1/93 3/1 2/95 5/20/97 7/29/99 10/6/01 1 2/1 5/03
Date
-------------------
ITCI Ethylene Glycol Data
4000 ~---------------------------------------------,
3500
2500
(Unfilled data points represent qualified data
or values below the detection level.)
.g 2000
E -------------------------------------------------------------------------------------------------------... C .,
u C 8 1500
1000 · · · · ·
500
0+------+-=-------J----+-----1---------1-----1-----+-------1-----1-----
10/5/94 10/5/95 10/4/96 10/4/97 10/4/98 10/4/99 10/3/00 10/3/01 10/3/02 10/3/03 10/2/04
Date
-------------------
V-23 TOC Data
14000 .--------------------------------------------~
12000
10000
'.J'
'in 8000 E ~
C 0 ·.:,
~ .. C ~ 6000 8
4000
2000
(Unfilled data points represent qualified data
or values below the detection level.)
0U-2 End --------. ----------·l----
OU-1 Start
i
0U-2 Start
0+------t------+-----+------"'-----1-----+--------+------+-----+---'
1/1/8S 5/1 /87 8/28/89 12/26/91 4/24/94
Date
8/21/96 12/19/98 4/17/01 8/15/03
-------------------
V-23 Acetone Data
1.4-.------------------------------------------------,
OU-2 End
1.2 --------------------l---------------------------------------
OU-2 Start
OU-1 Start
0.4 ---------
0.2 - - - - - - - - - - - - - - -
(Unfilled data points represent qualified data
or values below the detection level.)
0 +---___Ju_-+-----+---:u___ __ ___.4--__ ---'--------'f--__l;I--_Q_-+-------+-----+cle=e{].. _ _J
6/1/89 6/1/91 5/31/93 5/31/95 5/30/97
Date
5/30/99 5/29/01 5/29/03
-------------------
C
V-23 Benzene Data
0.3 .-------------------------------------------~
(Unfilled data points represent qualified data
or values below the detection level.}
0.25 - - - -----· ------ --- - - ------
0.2 - - - - - - - - - - - - - --- - - - - - - - -
.g 0.15
f! ~ C Q) u C
8 OU-1 Start OU-2 End
0.1
0.05
I
----------... ---·1· ------------------------------------------------. -------------------------
OU-2 Start l · . . . . . ..................................................................... .
0-t------r-----+=-----+----~f---------+-------f---"l----+----_J
6/1/89 6/1/91 5/31/93 5/31/95 5/30/97
Sample Date
5/30/99 5/29/01 5/29/03
- - - - - - - - ---- - - - - - - - -
V-23 2-Butanone (MEK) Data
4-.-----------------------------------------------,
(Unfilled data points represent qualified data
or values below the detection level.)
3.5 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - --- - - - - - - - - - - - - - - - --- - - - - - - - - - - - - --- - - - - - - - - - - - - - --- - - - - - - - -
3
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6/1/89 6/1/91 5/31 /93 5/31 /95 5/30/97
Date
5/30/99 5/29/01 5/29/03
-------------------
~
K-28 TOC Data
9000 ~-----------------------------------------,
(Unfilled data points represent qualified data
or values below the detection level.}
8000 --------------------------------------------------------------------------------------------------------
7000 -------------------------------------------------------------------------------------------------------
6000
5 5000
C 0 . .,
E ...
~ 4000
C
8
3000
2000
1000
OU-1 Start
o U--W---1-------+----+-----+--=----~it-a-... ~..-.~'--"---.-'i'.~-111l-lW---_J
8/14/81 5/10/84 2/4/87 10/31/89 7127192
Date
4/23/95 1/17/98 10/13/00 7/10/03
- - - - - - - - - - - - ----- - - -
K-28 Benzene Data
0.035 -r-------------------------------------------~
0.03
0.025
(Unfilled data points represent qualified data
or values below the detection level.)
OU-1 Start
~ E 0.02
~ a .,
E ... C: ., g 0.015
8
0.01
OU-2 Start
0.005 ---------------· -----------------------------------
0+------+-------+-------+-------+--------l----------+-------+----~
6/1/89 6/1/91 5/31/93 5/31 /95 5/30/97
Date
5/30/99 5/29/01 5/29/03
Test Resi:i!tr ii\gflZ 0 N .;,. O> 00 0 O> z4,/ilov:a1 +----+--+---=-f-----+--+---+---+---+-----i .-,,.-.. •·· .. 0_4,M;:,r:az 09~)unc82 99:S~p-'82 QjCSep,83
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Monitor Well CC-33 Benzene Data
Locatioa Oate. ~ Unit
CC-33 8/4/89 0.085 mg/L
11 /8/89 0.08 mg/L
2/14/90 0.081 mg/L CC-33 Benzene Data
5/4/90 0.079 mg/L 0.16 ·-·--··-·-··
8/9/90 0.096 mg/L Begin 0U-2 End 0U-2
11/6/90 0.073 mg/L Remediation Remediation
2/6/91 0.095 mg/L 0.14 r -: :r::::::::::::::::::::::::::::::::: _: 5/2/91 0.089 mg/L
8/8/91 0.08 mg/L
11/4/91 0.14 mg/L 0.12 -----------
2/4/92 0.11 mg/L
5/4/92 0.11 mg/L s 0.1 ,. ----------------------------------8/7/92 0.1 mg/L "';C)
£
11 /5/92 0.086 mg/L ._,.
'rC
2/3/93 0.052 mg/L ;o. . ., 0.08 - -. ----------------------------------------
5/5/93 0.055 mg/L ;-~ ... l . C:
8/5/93 0.059 mg/L ,':Q,J'. ,u
11 /2/93 0.055 • C: 0.06 I mg/L '8' - -------------------------------!
2/2/94 0.045 ' mg/L !
8/4/94 0.026 mg/L Inner Tier
3/9/95 0.014 mg/L 0.04 Start-Up --------------------------------------------
8/24/95 0.0176 mg/L
1/17/96 0.01 mg/L 0.02 -------------------------------------------------7/12/96 0.0128 mg/L
1/17/97 0.005 mg/L <
7/22/97 0.01 mg/L 0
1/22/98 0.005 mg/L 6/1/89 6/1/91 5/31/93 5/31/95 5/30/97 7/21/98 0.005 mg/L < Date 1/14/99 0.005 mg/L <
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Attachment 2
Inner Tier Extraction Well Performance
Kubal-Furr & Associates
-
~
Cl)
C: .2 ;;;
C> ~ .,
C> "' C.
E ir.
"iii ..,
~
---... -
Figure 3. Inner Tier Monthly Ground-Water Extraction Volumes
100000 ,------------------------------------~
90000 r------------------1f-------Inner Tier Well f---------------------1
Rehab Project
\ I ' I 70000 -I ---{ --I \; I I ,
60000 I I -I , -~~ I
50000
40000 Well lT-8
replaced Total Flow
3 per. Mov. Avg. (Total.Flow)
-·Linear (Total Flow) 30000
,;, ,;, ,;, LI') LI') LI') LI') LI') LI') <.<J <.<J <.<J <.<J <.<J <.<J ,.._ en en en en en en en en en en en ,.._ ,.._ ,.._ ,.._ ,.._ co co co co co co en en en
----------------------------
en en en en en en en en en en en en en en en en en en en
--------------------------------------------------------------------------------------------
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ----d ----------------------------co N --------------------------------------------------------N ,;, <.<J co 0 N N ,;, <.<J co 0 ----------------------------N N ,;, <.<J co 0 N N '<t <.<J co 0 N N '<t <.<J ~ ~
Month
5000000
4500000
4000000
'iii' 3500000
C: ..2 oi .9 3000000 .,
Cl "' Q. E 2500000 :,
Cl. .,
> 2000000 :;:; "' "S
E :, 1500000 u
1000000
500000
0
st-st-"' a, a, a,
---------------------------co N
Figure 4. Inner Tier-Departure from Optimal Pumpage
Well lT-8
Replaced
"' "' "' a, a, a,
---------------
------------"' co
Optimal Pumpage
@ 2500 gpd
"' "' "' a, a, a,
---------------------------N "' co
"' r--. a, a,
------------------N
Month
! Actual Pumpage !
r--. r--. r--. co co co co a, a, a, a, a, a, a, a, a,
------------------------------------------------------------------------"' co N "' co N -
a, a,
-----
----"'
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Attachment 3
Letter from Jerry Kubal, Kubal-Furr & Associates,
to Giezelle Bennett, EPA (July 11, 2001)
Kubal-Furr & Associates
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Post Office Box 273210
Tampa, FL 33688-3210
[phone]
FAX [phone]
[e-mail]
Ms. Giezelle S. Bennett
U.S. Environmental Protection
Agency, Region IV
61 Forsyth Street
Atlanta, GA 30303
Dear Ms. Bennett:
UC II/ 0 ·;;.u.12 ':J 16 -0 o '-1 '1 ,
Kubal-Furr & Associates
Environmental Management Services
July 11, 2001
Post Office Box 80247
Simpsonville, SC 29680-0247
[phone]
FAX [phone]
[e-mail]
During the June 21, 2001 Ticona-Shelby site visit for the Five-Year Review, you requested
that Ticona prepare a brief Jetter summarizing the justification for its recommendation to
discontinue pumping from the Inner Tier recovery wells. On behalf of Ticona, I have prepared
this letter in response to your request.
The following items have been considered in Ticona's recommendation that EPA revisit the
remedy selected in the record of decision and that it allow Ticona to implement a monitored
natural attenuation demonstration project:
• The Inner Tier extraction well system is intended specifically to recover residual ground-
water contamination from around the former OU-2 source area. Although OU-2 was not
clean-closed, remediation consisted of excavation to a depth 1-ft below the obviously
contaminated soil, followed by incineration, stabilization and reburial of the treated
sludges and other waste materials. While some residual soil and ground-water
contamination remain, there is no continuing source of release to the ground water from
the former OU-2 area and it has subsequently been delisted from the NPL.
• As the Inner Tier extracts ground water, it creates a cone of depression around each well
which extends toward the former source area. This produces an unsaturated zone above
the water table which still contains residual soil contamination. When the pumps are shut
off, the area becomes saturated, residual contamination is released to the ground-water
system and concentrations of constituents at monitor wells rebound to levels that may
exceed remedial goals. A monitored natural attenuation approach proposed by Ticona
would address this residual source material and may be a preferable remedy in
combination with periodic or cyclic pumping to remove contaminated ground water.
• While the Inner Tier pumping remains protective, it is not particularly efficient. The
Inner Tier has shown a steady decline in its ability to recover residual ground-water
contamination despite repeated attempts by Ticona to maintain and upgrade system
performance including redeveloping and rehabilitating all wells; installing larger
diameter, higher capacity replacement wells; and, replacing the problematic bladder
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Ms. Giezelle Bennett -2-July 11, 2001
pumps with different types of submersible pumps. Maintenance difficulties associated
with the Inner Tier have been reported in the routine semiannual reports, while the
declining performance of the Inner Tier in general has been described in detail in the
draft Five-Year Review Report (Kubal-Furr & Associates, December 1999).
• The principal risk posed by the residual ground-water contamination at the former source
area is currently to the on-site worker having to maintain the system trying to keep it
operational. Routine replacement of bladder pumps, clearing of air lines, reworking of
screens, etc. expose the workers to contamination brought to the surface during
maintenance activities which they would not normally be exposed to. This worker
exposure increases coincidentally with the continued decline in performance of the Inner
Tier system.
• The decline in Inner Tier production is due to a combination of physical, chemical and
biological factors. Physically, the upper water bearing formation in which the Inner Tier
wells are installed is composed of saprolite, a residual clayey material resulting from the
weathering of the native bedrock. Although this formation contains water, it is not
considered an aquifer in the classical sense because it's incapable of producing water at
appreciable rates. Chemically, iron and manganese cause the submersible pumps to
freeze up. Biologically, the principal contaminant, ethylene glycol, is readily degradable
and has caused biofouling and bacterial build-up outside the well casings and along the
well screens. This combination of factors has produced a pump and treat remedy which is
inefficient.
While pump and treat was a presumptive remedy in the 1980's at virtually every Superfund
site with ground-water contamination, it has been demonstrated in a majority of cases to be less
than effective in remediating aquifer systems. This was the basis for EPA's Directive 9200.0-22
entitled "Superfund Reforms: Updating Remedy Decisions." This directive encourages the
Regions to: " ... take a close look at, and modify as appropriate, past remedy decisions where
those decisions are substantially out of date with the current state of knowledge in remediation
science and technology, and thus are not as effective from a technical or cost perspective as they
could be."
Specifically, one of the principal types of remedy updates anticipated in this directive were:
"Modification of the remediation objectives due to physical limitations posed by site conditions
or the nature of the contamination." We feel the Ticona site is exactly the type of site that the
directive on updating remedy decisions was intended to revisit, and we respectively request that
you consider the site in this context as you conduct your Five-Year Review.
As we discussed in detail during your site visit, Ticona feels a monitored natural attenuation
(MNA) approach to remediating the residual contamination around the former source area will
be as effective as the current pump and treat remedy. Ticona is requesting that EPA and DENR
agree to the following plan of action:
1) Ticona will collect a baseline set of MNA ground-water data, under pumping conditions,
from the following locations: Inner Tier wells, around the former OU-2 source area and
in selected background locations.
Kubal-Furr & Associates
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Ms. Giezelle Bennett -3 -July 11, 2001
2) Ticona will be permitted to shut down the Inner Tier wells, allow the system to
equilibrate and, for a period of from 18-24 months, begin collecting routine data to
evaluate the effectiveness of MNA as a remedy. Because the ground-water flow rate in
the saprolite is very low (less than a few feet per year), shutting down the wells will have
a negligible effect on contaminant migration during the evaluation phase.
3) Ticona will submit routine status reports to the EPA and DENR presenting the MNA
data. At the end of the demonstration period, Ticona will prepare a final summary report
evaluating the MNA remedy. Implementation of this project would provide Ticona ample
time to generate sufficient data to support a formal ROD amendment or modification
which both the EPA and DENR could support.
Ticona is preparing a draft site-wide sampling plan for Shelby which includes, as an element,
the proposed MNA baseline sampling program. This plan will be finalized by August 10, 2001,
and Ticona would like to get EPA and DENR's concurrence to implement the above-described
plan of action by September 3, 2001.
I'd be glad to answer any questions you may have following your review of this information.
Please give me a call at 813-265-2338.
Sincerely,
Kubal-Furr & Associates
/}/✓ L ... ,_., c/c ,'.J/1. { __
I
Jerry p. Kubal, P.G.
President
cc: Mr. McKenzie Mallary, USEPA
Mr. Grover Nicholson, NCDENR
Mr. Steve Olp, Celanese Acetate
Mr. Jerry McMurray, Ticona-Shelby ESHA
Mr. Everett Glover, P.E., EarthTech
Kubal-Furr & Associates
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Attachment 4
Potentiometric Surface Maps and Hydrogeologic Cross Sections
Kubal-Furr & Associates
-
•
--
...
I ..
Legend --Water-Level (ft msl)
e Inner Tier Extraction 'v\le!I
/78¥~~~:;:! f.c,;i!ioor
.,,,---.-,, Creek I Stream
~ Buiding I Structure
-- -----
0 350 700
-- -
\
\
\ I
I I
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~
I 6
--- -
lnner..Tierbtraction Well
Water.=.Le.v.e.LElevations
IT-1 = 788.60
IT-2 = <775.55
IT-3 = Not Measured
IT-4 = 778.03
IT-5 = 779.74
IT-6 = 777 .05
IT-7 = 788.67 IT-BR= 797.99
JT-9 = Not Measured
Hfi.411 EJ
71ij~
Kubal-Furr & Associates
-Environmental Consultants-
Figure 2. Potentiometric Surface Map
Shallow Saprolite-July 31, 2003
CNA Holding~. Im:.· 7ico11u
ShelhJ: North ( .'omlina
-
-- ---- - --
.. ...
I
t=
0
-
~ .... $ ~ ~ I
-- -
"·
--
' \
~ \
\ ,--~--'b~\~,;.
, I
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350 700
\
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- - --
\
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\
Legend
• """"""" water.Level (II msl) .... .,.._..,
• Outer Thtr Extlac:tion Well
■ PEW Ertradlon Wei ,,..,,.,., water-Leval Contoo, ___ .,.
,,---.../ Creek!Stleam
I!) Building I Structure
I
Kubal-Furr & Associates
-Environmental Consultants-
Figure 3. Potentiometric Surface Map
Deep Saprolitc /Upper Bedrock-July 31, 2003
CNA Holdings, lnc./Ticona
Shelby, North Carolina
-
850.00 A -~•~=-=-=-=-=-=-=-=-=-=-=--::~'=•~nt~A~r~•;:•::=======~!:::::::::::~---------4/VastewaterTreatmentArea-------------<>
830 oof--j-~!----
810.00
790.00
770.00
750.00
730.00
710.00
690.00
670.00
0-27
829.80
D-35
829.41
D-56
829.30
Legend
-a10..I Line of equal fluid potential (ft msl) E2J Bedrock
(das.hed wile~ io!erred)
Potentiometric Surface Saprolite
G-50
813.38
Inferred direction of ground-water
movement
Screened Interval of Well --Horizontal Scale in Feet
0 400
l"""""'"""'"""'"""''iiiiiiiiiiiiiiiiiii
800
A' 850.00
830.00
810.00
790.00
770.00
750.00
730.00
•
710.00
690.00
670.00
Kubal-Furr & Associates
-E1rniro11111ent11l Co11s11ltm1ts -
Figure 4-Hydrogeologic Cross-Section
A-A'-July 31,03
CNA Holding.I', lncllkona
Shelby. North Carolina
-
I\\ ..
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•
•
Legend
Monitor.Well
'Nater--level (ft msl)
Inner Tiet Extraction Well
......-,sv w.:~=~ Se~~~
,.,,.,.-.--' Creek I Stream
~ Building/ Structure
~~ ~ \
\
'
0
-:..
' '
~ ' ' \ ' \ ....
ill .... ....
....
'
350 700
-:-.
\
\
' ' -~,
t....
07~9,3
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lnner_Tier.Extraction.Well
Watef=Le:lllllEleYations
IT-1 = <781.80
IT-2 = <775.74
IT-3 = 783.41
IT-4 = 779.65
IT-5 = 785.16
IT-6 = 779.50
IT-7 = 790.81
IT-BR= 797.21
IT-9 = Not Measured
Kubal-Furr & Associates
-Envirownental Consultants-
Figure 5. Potentiometric Surface Map
Shallow Saprolitc-October 8. 2003
CNA Holdings, Jnc.mcona
Shelby, North Carolina
-
.. ...
I
\
0 350 700
-.:i':.-es
121.S2\
_,
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Monitor \Nell water-Level (ft msl)
Piezometer
•
•
Outer Tier Extraction \Nell
PEW Extraction Well
_,,--.,./
il
Creek I Stream
Building I Structure
/ I / / !l /
'~•"""'Ii!] '1a7!$57 / / I ~:'"----I
PZ-1 NM ~ /
,. ,1 ,' "'-----,..,
I~
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Kubal-Furr & Associates
-Environmental Consultants-
Figure 6. Potentiometric Surface Map
Deep Saprolite/Upper Iledrock-Octobcr 8, 2003
CNA Holdings, fnc./Ticona
Shelby, North Carolina
-
85000 A ..:.+~•:-:-:-:-:-:-:-:-:-:-:-'~'~•~nt~A~r~•=•'.::=======:!..f::::::::-::----------vvastewaterTreatmentArea------------e
830.00 •
D-27 ·
828.94
D-35 810.00 828.58
790.00 D-56
828.64
no.oo
750.00
730.00
710.00
690.00
670.00
Legend
-a10✓ Line of equal fluid potential (ft msl) ~
(da51led .,,,,twe interred)
r -Potentiometric Surface
Inferred direction of ground-water
movement
Bedrock
Saprolite
G-50
814.37
Screened Interval of \t\lell
J-29
810.36
·~
Horizontal Scale in Feet
0 400 800
~ C :;;;
i: ~ ~ e "-
I
A' 850.00
830.00
810.00
790.00
770.00
750.00
730.00
710.00
690.00
670.00
Kubal-Furr & Associates
-Envircmme11t11J Co11s11lta11ts -
Figure 7-Hydrogeologic Cross-Section
A-A'-October8, 2003
CNA 1/o/dinxs. Inc J1icona
Shelby. North Carolina
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I Attachment 5
I Well Rehabilitation and Well Construction Details
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I Kubal-Furr & Associates
I
I Well Date
Number Installed
I A-39 9/21/81
8-34 9/22/81
C-49 10/6/81
D-27 4/3/86
D-35 11/17/81
I D-56 4/8/86
D-88 4/15/86
F-55 11/12/81
G-50 11/11/81
I G-88 10/7/81
H-59 2f7/85
H-79 10/6/81
1-57 9/30/81
J-28 11/9/81
I J-59 10/1/81
K-28 10/5/81
K-58 9/29/81
M-28 11/10/81
I M-44 10/2/81
N-29 11/11/81
N-53 9/25/81
0-25 11/12/81
I 0-59 2/11/85
P-31 9/25/81
P-58 4/12/86
0-33 9/23/81
I R-17 10/8/81
R-42 9/29/81
S-50 10/5/81
T-17 10/1/81
I T-35 4/14/86
T-58 4/24/86
U-38 2/13/85
V-23 2/13/85
I W-23 2/6/85
X-32 2/6/85
Y-38 2/11/85
Y-74 2/10/85
I Z-78 2/8/85
AA-41 4/10/86
AA-54 4/9/86
88-18 4/4/86
I CC-33 4/4/86
CC-64 4/12/86
DD-58 5/1/86
EE-58 4/14/86 I FF-23 4/25/86
FF-34 4/24/86
FF-62 4/23/86
GG-25 4/25/86
I GG-39 4/25/86
GG-61 4/30/86
HH-48 5/2/86
HH-77 4/30/86
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Table 1. Summary of Well Rehabilitation Activities
CNA Holdings, lnc.lTlcona/ Shelby
Date of Well Wizard Rehabiliation
Rehabilitation Action Acton
9/6/01 Well Wizard Removed Swabbed and Developed
9/6/01 Well Wizard Removed Swabbed and Developed
9/5/01 Well Wizard Removed Swabbed and Developed
9/5/01 Well Wizard Removed Swabbed and Developed
9/4/01 Well Wizard Removed Swabbed and Developed
9/5/01 Well Wizard Removed Swabbed and Developed
9/11/01 Welt Wizard Tubing Removed Not Developed
9/11/01 No Well Wizard Swabbed and Developed
9/10/01 No Well Wizard Swabbed and Developed
9/10/01 Well Wizard Removed Swabbed and Developed
9/10/01 No Well Wizard Swabbed and Developed
9/10/01 No Well Wizard Swabbed and Developed
9/6/01 No Well Wizard Swabbed and Developed
9/7/01 No Well Wizard Swabbed and Developed
9/7/01 & 9/11/01 No Well Wizard Swabbed and Developed
9/11/01 Well Wizard Removed Swabbed and Developed
9(7/01 Well Wizard Removed Swabbed and Developed
9/7/01 No Well Wizard Swabbed -Well Dry
9/7/01 Well Wizard Removed Swabbed and Developed
9(7/01 No Well Wizard Swabbed and Developed
9f7/01 Well Wizard Removed Swabbed and Developed
9/7/01 Well Wizard Removed Swabbed and Developed
9/7/01 & 9/11/01 Well Wizard Removed Swabbed and Developed
9/6/01 No Well Wizard Swabbed and Developed
9/6/01 Well Wizard Removed Swabbed and Developed
9/6/01 No Well Wizard Swabbed and Developed
9/6/01 No Well Wizard Swabbed and Developed
9/6/01 No Well Wizard Swabbed and Developed
9/7/01 Well Wizard Removed Swabbed and Developed
9/5/01 No Well Wizard Swabbed and Developed
9/5/01 Well Wizard Removed Swabbed and Developed
9/5/01 Well Wizard Removed Swabbed and Developed
9/10/01 Well Wizard Removed Swabbed and Developed
9/10/01 Well Wizard Removed Swabbed and Developed
9/6/01 No Well Wizard Swabbed and Developed
9/6/01 No Well Wizard Swabbed and Developed
9/6/01 No Well Wizard Swabbed and Developed
9/6/01 Well Wizard Removed Swabbed and Developed
9/6/01 No Well Wizard Swabbed and Developed
9/11/01 Well Wizard Removed Swabbed and Developed
9/5/01 Well Wizard Removed Swabbed and Developed
9/6/01 No Well Wizard Swabbed and Developed
9/10/01 Well Wizard Removed Swabbed and Developed
9/10/01 Well Wizard Removed Swabbed and Developed
9/11/01 Well Wizard Tubing Removed Not Developed
9/5/01 Well Wizard Removed Swabbed and Developed
9/6/01 Well Wizard Removed Swabbed and Developed
9/6/01 Well Wizard Removed Swabbed and Developed
9/11/01 Well Wizard Removed Swabbed and Developed
9/11/01 Well Wizard Tubing Removed Not Developed
9/5/01 Well Wizard Removed Swabbed and Developed
9/5/01 Well Wizard Removed Swabbed and Developed
9/5/01 Well Wizard Removed Swabbed and Developed
9/11 /01 Well Wizard Tubin~ Removed Not Develooed
Kubal-Furr Associates
Gallons Water Turbidity I Removed after Develooina
25 Cloudy
16 Clear
28 Clear
8 Clear
20 Clear
25 Clear
0 NIA
10 Clear w/ Product Globules
18 Clear
35 Milky
7.5 Clear
32 Clear
25 Clear
10 Clear
17.5 Cloudy
3.5 Clear
10 Cloudy
0 Dry
15 Clear
10 Clear
27 Clear
13 Clear
14.5 Clear
10 Clear
30 Clear
13 Clear
10 Clear
30 Clear
23 Clear
18 Clear
9 Cloudy
34 Clear
18 Clear
5 Clear
11 Clear
15 Clear
11 Clear
40 Clear
20 Clear
4 Cloudy
5 Cloudy
12 Clear
15 Clear
37 Clear
0 N/A
15 Clear
23 Clear
15 Clear
15 Cloudy
0 N/A
16 Clear
38 Clear
6 Clear
0 N/A
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Well
Number
'Monitor Wells
A-39
B-34
C-49
D-27
D-35
D-56
D-88
F-55
G-50
G-88
H-59
H-79
1-57
J-28
J-59
K-28
K-58
M-28
M-44
N-29
N-53
0-25
0-59
P-31
P-58
0-33
R-17
R-42
S-50
T-17
T-35
T-58
U-38
V-23
V-65
W-23
X-32
Y-38
Y-74
Z-78
AA-41
AA-54
BB-18
CC-33
CC-64
DD-58
EE-58
FF-23
FF-34
FF-62
GG-25
GG-39
GG-61
HH-48
HH-77
Date
Installed
21-Sep-81
22-Sep-81
6-Oct-81
3-Apr-86
17-Nov-81
8-Apr-86
15-Apr-86
12-Nov-81
11-Nov-81
7-Oct-81
7-Feb-85
6-Oct-81
30-Sep-81
9-Nov-81
1-Oct-81
5-Oct-81
29-Sep-81
10-Nov-81
2-Oct-81
11-Nov-81
··25-Sep-81
12-Nov-81
11-Feb-85
25-Sep-81
.. 12-Apr-86 ....
23-Sep-81
8-Oct-81
29-Sep-81
5-Oct-81
1-Oct-81
14-Apr-86
24-Apr-86
13-Feb-85
13-Feb-85
20-May-02
6-Feb-85
6-Feb-85
11-Feb-85
10-Feb-85
8-Feb-85
10-Aer-86
9-Apr-86
4-Apr-86
4-Apr-86
12-Apr-86
1-May-86
14-Apr-86
25-Apr-86
24-Apr-86
23-Apr-86
25-Aer-86
25-Apr-86
30-Apr-86
2-May-86
30-Aor-86
Table 2 -Well Construction Details
CNA Holdings, Inc. -Shelby, NC
Surtace Casing Casing Total
Elevation (ft Material size /in\ Death (ft)
820.7 PVC 2.0 39.0
787.6 PVC 2.0 35.0
861.1 PVC 2.0 5o.o·
842.7 ss 2.0 30.0
....... ~4?.4 ...... PVC 2.0 ........ 35.0
843.1 ss 2.0 57.0
843.6 ss 2.0 89.5
846.2 PVC 2.0 55.0
845.5 PVC 2.0 50.0
845.5 PVC 2.0 89.0
843.7 ss 2.0 60.5
843.0 PVC 2.0 80.0
834.4 PVC 2.0 60.0
821.7 PVC 2.0 29
821.6 PVC 2.0 ............ 60 ....
808.3 PVC 2.0 28
808.3 PVC 2.0 60
804.2 PVC 2.0 28
804.6 · PVC 2.0 45
800.9 PVC 2.0 29
801.0 PVC 2.0 54
804.5 PVC 2.0 25
804.9 PVC 2.0 63.5
786.5 PVC 2.0 32
786.4 PVC 2.0 58.4
779.8 PVC 2.0 34
776.5 PVC 2.0 17
776.4 PVC 2.0 44
823.1 PVC 2.0 50
775.1 PVC 2.0 17.5
774.5 Stainless 2.0 37
774.5 Stainless 2.0 58.5
825.1 Stainless 2.0 53
810.2 Stainless 2.0 28
810.12 PVC 2.0 65
799.1 Stainless 2.0 24.4
794.9 Stainless 2.0 33.3
792.9 Stainless 2.0 40.5
793.2 Stainless 2.0 80.7
795.6 Stainless 2.0 79.3
782.0 Stainless 2.0 42
781.7 Stainless 2.0 54.7
770.3 Stainless 2.0 18.5
810.7 Stainless 2.0 33
810.6 Stainless 2.0 66.5
794.3 Stainless 2.0 §9.4 ...
792.5 Stainless 2.0 61.9
771.2 Stainless 2.0 25
770.7 Stainless 2.0 34.5
770.6 Stainless 2.0 62.7
769.2 Stainless 2.0 26.5
769.2 Stainless 2.0 39.5
769.4 Stainless 2.0 61
753.8 Stainless 2.0 48
753.3 Stainless 2.0 77.9
Kubal-Furr and Associates
MPE Well Screen
(ft msl\ Interval rtt msl\
823.36 787.2 -782.2
790.62 758.1 -753.1
864.11 817.1 -812.1
845.50 823.0 -818.0
845.69 . ... 812.4 -807.4 ..
845.19 791.9 -786.9
845.52 760.6 -755.6
849.19 796.2 • 791.2
848.48 800.5 -795.5
848.26 762.0 • 757.0
845.25 789.7 • 784.7
846.53 768.5 -763.5
837.63 781.9 -776.9
825.18 798.2 -793.2
825.01 767.1 -762.1
811.2 785.3 • 780.3
811.39 755.3 -750.3
806.72 781.2 -776.2
806.71 765.1 -760.1
803.38 776.9 -771.9
803.82 . 752.5 -747.5
807.54 784.5 • 779.5
806.61 750.7 -745.7
790.00 760.0 -755.0
788.12 732.9 • 727.0
783.48 751.3 -746.3
779.31 764.5 -759.5
778.81 738.9 -733.9
826.02 778.1 • 773.1
777.9 763.1 -758.1
777.38 743.8 -738.8
776.03 721.0 • 716.0
826.55 791.5 -786.5
811.89 791.9 -786.9
812.1 755.12 • 745.12
800.91 780.9 • 775.9
796.96 767.0 • 762.0
794.52 759.1 -754.1
794.87 723.8 -718.8
797.08 722.2 -717.2
783.68 746.0 -741.0
782.16 732.7 • 727.7
771.73 756.8 • 751.8
812.68 782.7 -777.7
811.37 751.6 • 746.6
796.1 741.3 -736.3
794.48 739.5 -734.5
772.33 752.6 • 747.6
772.73 741.7-736.7
772.19 713.2 -708.2
771.64 748.9 -743.9
770.44 735.2 -730.2
771.78 713.4 -708.4
755.44 710.8 -705.8
755.87 680.9 -675.9
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Well Date
Number Installed
t Piezometerl
PZ-1(Lambert) 25-Oct-88
PZ-2 (Stine) 25-Oct-88
PZ-3 10-Nov-88
PZ-4 11-Nov-88
PZ-5A 22-Aor-89
PZ-58 22-Apr-89
PZ-6A 18-Apr-89
PZ-68 17-Apr-89
PZ-7A 19-Apr-89
PZ-78 18-Apr-89 rz:a 26-Jun-90
PZ-9 26-Jun-90
PZ-10 26-Jun-90
PZ-11 26-Jun-90
PZ-12 26-Jun-90
PZ-13 28-Jun-90
'Due Di/ioence Monitor Wells
TD-1 28-Jun-98
TD-2 28-Jun-98
TD-3 30-Jun-98
TD-4 29-Jun-98
T-1 26-Jun-98
T-2 26-Jun-98
Tl-1 25-Jun-98
Tl-2 24-Jun-98
S-1 28-Jun-98
'Outer Tier Extraction We/Isl
OT-1R 28-Jun-95
OT-2R 30-Apr-96
OT-3 27-Oct-88
OT-4 26-Oct-88
OT-5 18-Feb-88
OT-6 26-Oct-88
OT-6A 30-Jun-90
OT-7 28-Oct-88
OT-7A 28-Jun-90
OT-8 26-Oct-88
OT-10 30-Jun-95
'Inner Tier Extraction We/Isl
IT-1 29-Oct-88
IT-2 29-Oct-88
IT-3 29-Oct-88
IT-4 29-Oct-88
IT-5 29-Oct-88
IT-6 29-Oct-88
IT-7 29-Oct-88
IT-SR 21-Jul-95
IT-9 29-Oct-88
'PEW Extraction We/Isl
PEW-1 16-Aug-93
PEW-2 23-Aug-93
PEW-3 17-Aug-93
PEW-4 17-Aua-93
Table 2 -Well Construction Details
CNA Holdings, Inc. -Shelby, NC
Surface Casing Casing Total
Elevation (ft Material size lin\ Denth (ft)
774.14 PVC 1.0 62.5
795.91 PVC 1.0 62.5
786.75 PVC 1.0 62.5
750.13 PVC 1.0 62.5
788.74 PVC 1.0 64
777.61 PVC 1.0 65
795.13 PVC 1 .0 65
796.91 PVC 1.0 62
780.48 PVC 1.0 62
784.48 PVC 1.0 65
765.69 PVC 1.0 67.5
788.61 PVC 1.0 68
782.65 PVC 1.0 68
803.38 PVC 1 .0 68
747.31 PVC 1 .0 68
773.61 PVC 1.0 35
PVC 2.0 19.3
PVC 2.0 38.5
PVC 2.0 45.10
PVC 2.0 79.30
PVC 2.0 27
PVC 2.0 73.40
PVC 2.0 42.65
PVC 2.0 70.95
PVC 2.0 29.75
-PVC 6.0 71.5
-PVC 6.0 67
790.88 Carbon Steel 6.0 68
788.28 Carbon Steel 6.0 65
782.15 Carbon Steel 4.0 66
783.45 Carbon Steel 6.0 66
796.68 Carbon Steel 6.0 84
780.16 Carbon Steel 6,0 68
780.52 Carbon Steel 6.0 64
779.26 Carbon Steel 6.0 67
PVC 6.0 98
814.20 Stainless 2.0 42.5
813.85 Stainless 2.0 42.5
809.66 Stainless 2.0 42.5
809.08 Stainless 2.0 42.5
810.64 Stainless 2.0 42.5
812.20 Stainless 2.0 42.5
813.52 Stainless 2.0 42.5
-PVC 4.0 44.2
808.73 Stainless 2.0 42.5
845.15 Stainless 6.0 92.00
847.22 Stainless 6.0 98
847.55 Stainless 6.0 100.5
846.44 Stainless 6.0 94
Kubal-Furr and Associates
MPE Well Screen
(ft msl\ Interval (ft msll
773.99 734.14 -714.14
795.81 755.91 -735.91
786.82 746.75 -726.75
750.07 710.15-690.15
788.72 734.74 -724.74 ....
777.59 722.61 -712.61
795.11 740.13-730.13
796.89 744.91 -734.91
780.46 728.48 -718.48
784.46 729.48 -718.48 ...........
767.99 710.69 - 700.69
788.96 733.61 -722.61
784.65 726.65-716.65
805.48 748.38 -737.38
749.41 692.31 -682.31
776.51 751.61 -741.61
771.44 729.92 -699.94
773.55 736.55 -706.55
792.88 742.88 -722.88
790.28 743.28 -723.28
784 738.65 -718.65
787.45 737.45 -717.45
798.68 722.68 -712.68
782.16 732.16-712,16
782.52 737.52 -717.52
782.26 732.26 • 712.26
804.08 745.58 -703.58
814.2 784.20 -774.20
813.85 783.85 -773.85
809.66 779.66 -769.66
809.08 779.08 -769.08
810.64 780.64 -770.64
812.2 782.20 -772.20
813.52 783.52 -773.52
813.04 793.34 -770.34
808.73 778. 73 -768. 73
846.85 786.85 -755.55
848.92 783.42 -752.12
849.25 786.05 -754.25
848.14 786.14 -754.84
Z of 2
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I Attachment 6
I Summary of Initial MNA Analytical Data
I
(December 2001)
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I Kubal-Furr & Associates
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
A-39 9/27/01 Alkalinity 1.5 mg/L
I A-39 9/27/01 Ammonia Nitrogen < 0.1 mg/L
A-39 9/27/01 Carbon dioxide < 18 mg/L u
A-39 9/27/01 Carbon monoxide < 0.4 mg/L
A-39 9/27/01 Dissolved Oxygen 7.17 mg/L
A-39 9/27/01 Ethane < 0.000005 mg/L
I A-39 9/27/01 Ethene < 0.000005 mg/L
A-39 9/27/01 Ethylene glycol < 5 mg/L
A-39 9/27/01 Ferrous Iron < 0.1 mg/L
A-39 9/27/01 Methane < 0.00011 mg/L u
I A-39 9/27/01 Nitrate 11.9 mg/L
A-39 9/27/01 Nitrogen gas < 18 mg/L u
A-39 9/27/01 Oxygen gas < 9.6 mg/L u
A-39 9/27/01 pH 4.81 SU
I A-39 9/27/01 Redox Potential 357 mv
A-39 9/27/01 Specific Conductivity 174 umhostcm
A-39 9/27/01 Sulfate < 0.87 mg/L u
A-39 9/27/01 Sulfide < 0.1 mg/L
I A-39 9/27/01 . Temperature 16.6 degrees C
A-39 9/27/01 Total Aerobic Plate Count 500 cfu/ml
A-39 9/27/01 Total Anaerobic Plate Count 4 cfu/ml
A-39 9/27/01 Total Arsenic < 0.005 mg/L
I A-39 9/27/01 Total Kjeldahl Nitrogen 0.17 mg/L
A-39 9/27/01 Total Manganese 0.01 mg/L
A-39 9/27/01 Total Organic Carbon < 9.3 mg/L u
A-39 9/27/01 Total Phosphorus 0.031 mg/L
I C-49 9/19/01 Alkalinity < 1 mg/L
C-49 9/19/01 Ammonia Nitrogen < 0.1 mg/L
C-49 9/19/01 Carbon dioxide < 20 mg/L u
I C-49 9/19/01 Carbon monoxide < 0.4 mg/L
C-49 9/19/01 Dissolved Oxygen 7.80 mg/L
C-49 9/19/01 Ethane < 0.000011 mg/L u
C-49 9/19/01 Ethene < 0.0000083 mg/L u
I C-49 9/19/01 Ethylene glycol < 5 mg/L
C-49 9/19/01 Ferrous Iron 0.1 mg/L
C-49 9/19/01 Methane < 0.0049 mg/L u
C-49 9/19/01 Nitrate 0.82 mg/L
I C-49 9/19/01 Nitrogen gas < 20 mg/L u
C-49 9/19/01 Oxygen gas < 9.3 mg/L u
C-49 9/19/01 pH 4.54 SU
C-49 9/19/01 Redox Potential 339 mv
I C-49 9/19/01 Specific Conductivity 26 umhos/cm
C-49 9/19/01 Sulfate < 0.5 mg/L
C-49 9/19/01 Sulfide < 0.1 mg/L
C-49 9/19/01 Temperature 22.9 degrees C
I C-49 9/19/01 Total Aerobic Plate Count 11000 cfu/ml
C-49 9/19/01 Total Anaerobic Plate Count 82 cfu/ml
C-49 9/19/01 Total Arsenic < 0.005 mg/L
C-49 9/19/01 Total Kjeldahl Nitrogen < 0.1 mg/L
C-49 9/19/01 Total Manganese 0.082 mg/L
I C-49 9/19/01 Total Organic Carbon < 1 mg/L
C-49 9/19/01 Total Phosphorus < 0.03 mg/L
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Kubal-Furr and Associates 1 of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
I CC-33 9/18/01 Alkalinity 39.7 mg/L
CC-33 9/18/01 Ammonia Nitrogen < 0.1 mg/L
CC-33 9/18/01 Carbon dioxide < 69 mg/L u
CC-33 9/18/01 Carbon monoxide < 0.4 mg/L
I CC-33 9/18/01 Dissolved Oxygen 2.39 mg/L
CC-33 9/18/01 Ethane < 0.000012 mg/L u
CC-33 9/18/01 Ethene < 0.000012 mg/L u
CC-33 9/16/01 Ethylene glycol < 5 mgil
I CC-33 9/16/01 Ferrous Iron > 10 mg/L
CC-33 9/16/01 Methane 0.44 mg/L
CC-33 9/16/01 Nitrate < 0.05 mg/L
CC-33 9/16/01 Nitrogen gas < 17 mg/L u
I CC-33 9/16/01 Oxygen gas < 0.94 mg/L u
CC-33 9/16/01 pH 6.10 SU
CC-33 9/16/01 Redox Potential -69 mv
CC-33 9/16/01 Specific Conductivity 369 umhos/cm
I CC-33 9/16/01 Sulfate 5.3 mg/L
CC-33 9/16/01 Sulfide < 0.1 mg/L
CC-33 9/16/01 Temperature 16.6 degrees C
CC-33 9/18/01 Total Aerobic Plate Count 79 cfu/ml
CC-33 9/16/01 Total Anaerobic Plate Count < 1 cfu/ml
I CC-33 9/16/01 Total Arsenic 0.015 mg/L
CC-33 9/18/01 Total Kjeldahl Nitrogen < 0.1 mg/L
CC-33 9/16/01 Total Manganese 3.9 mg/L
CC-33 9/16/01 Total Organic Carbon < 2.6 mg/L u
I CC-33 9/16/01 Total Phosphorus < 0.03 mg/L
D-27 9/19/01 Alkalinity 22.6 mg/L
I D-27 9/19/01 Ammonia Nitrogen < 0.1 mg/L
D-27 9/19/01 Carbon dioxide 260 mg/L
D-27 9/19/01 Carbon monoxide < 0.4 mg/L
D-27 9/19/01 Dissolved Oxygen 6.70 mgil
I D-27 9/19/01 Ethane < 0.000022 · mg/L u
D-27 9/19/01 Ethene < 0.000014 mg/L u
D-27 9/19/01 Ethylene glyccl < 5 mg/L
D-27 9/19/01 Ferrous Iron < 0.1 mg/L
I D-27 9/19/01 Methane < 0.00061 mg/L u
D-27 9/19/01 Nitrate 0.44 mg/L
D-27 9/19/01 Nitrogen gas < 14 mg/L u
D-27 9/19/01 Oxygen gas < 5.6 mg/L u
I D-27 9/19/01 pH 4.36 SU
D-27 9/19/01 Redox Potential 345 mv
D-27 9/19/01 Specific Conductivity 309 umhos/cm
D-27 9/19/01 Sulfate < 2 mg/L u
D-27 9/19/01 Sulfide < 0.1 mg/L
I D-27 9/19/01 Temperature 19.5 degrees C
D-27 9/19/01 Total Aerobic Plate Count 2500 cfu/ml
D-27 9/19/01 Total Anaerobic Plate Count < 1 cfu/ml
D-27 9/19/01 Total Arsenic < 0.005 mg/L
I D-27 9/19/01 Total Kjeldahl Nitrogen 0.11 mg/L
D-27 9/19/01 Total Manganese 0.067 mg/L
D-27 9/19/01 Total Organic Carbon < 1 mg/L
D-27 9/19/01 Total Phosphorus < 0.03 mg/L
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Kubal-Furr and Associates 2 of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
I F-55 9/20/01 Alkalinity 639 mg/L
F-55 9/20/01 Ammonia Nitrogen 2 mg/L
F-55 9/20/01 Carbon dioxide 220 mg/L
F-55 9/20/01 Carbon monoxide < 0.4 mg/L
I F-55 9/20/01 Chloride 3.4 mg/L
F-55 9/19/01 Dissolved Oxygen 2.57 mg/L
F-55 9/20/01 Ethane 0.2 mg/L
F-55 9/20/01 Ethene 0.0007 mg/L
I F-55 9/20/01 Ethylene glycol 155 mg/L
F-55 9/19/01 Ferrous Iron > 10 mg/L
F-55 9/20/01 Methane 3.2 mg/L
F-55 9/20/01 Nitrate < 0.25 mg/L
I F-55 9/20/01 Nitrogen gas < 10 mg/L u
F-55 9/20/01 Oxygen gas < 0.64 mg/L u
F-55 9/19/01 pH 5.38 SU
F-55 9/19/01 Redox Potential -19 mv
I F-55 9/19/01 Specific Conductivity 1960 umhos/cm
F-55 9/20/01 Sulfate < 3 mg/L
F-55 9/19/01 Sulfide < 0.1 mg/L
F-55 9/19/01 Temperature 21.5 degrees C
I F-55 9/20/01 Total Aerobic Plate Count 22 cfu/ml
F-55 9/20/01 Total Anaerobic Plate Count 6 cfu/ml
F-55 9/20/01 Total Arsenic 0.0085 mg/L
F-55 9/20/01 Total Kjeldahl Nitrogen 2.1 mg/L
I F-55 9/20/01 Total Manganese 139 mg/L
F-55 9/20/01 Total Organic Carbon 730 mg/L
F-55 9/20/01 Total Phosphorus < 0.03 m9/L
I G-50 9/25/01 Alkalinity 44.3 mg/L
G-50 9/25/01 Ammonia Nitrogen < 0.1 mg/L
G-50 9/25/01 Carbon dioxide 120 mg/L
G-50 9/25/01 Carbon monoxide < 0.4 mg/L
I G-50 9/25/01 Chloride 45.6 mg/L
G-50 9/25/01 Dissolved Oxygen 2.12 mg/L
G-50 9/25/01 Ethane < 0.0000078 mg/L u
G-50 9/25/01 Ethene < 0.0000072 mg/L u
I G-50 9/25/01 Ethylene glycol < 5 mg/L UJ
G-50 9/25/01 Ferrous Iron 4 mg/L
G-50 9/25/01 Methane < 0.00016 mg/L u
G-50 9/25/01 Nitrate 0.087 mg/L
I G-50 9/25/01 Nitrogen gas < 17 mg/L u
G-50 9/25/01 Oxygen gas < 8 mg/L u
G-50 9/25/01 pH 5.63 SU
G-50 9/25/01 Redox Potential 37 mv
I G-50 9/25/01 Specific Conductivity 307 umhos/cm
G-50 9/25101 Sulfate < 2.1 mg/L u
G-50 9/25101 Sulfide < 0.1 mg/L
G-50 9/25/01 Temperature · 28.9 degrees C
G-50 9/25/01 Total Aerobic Plate Count 7400 cfu/ml
I G-50 9/25/01 Total Anaerobic Plate Count 45 cfu/ml
G-50 9/25/01 Total Arsenic < 0.005 mg/L
G-50 9/25/01 Total Kjeldahl Nitrogen 0.22 mg/L
G-50 9/25/01 Total Manganese 8.3 mg/L
I G-50 9/25/01 Total Organic Carbon < 2.4 mg/L u
G-50 9/25/01 Total Phosphorus < 0.03 mg/L
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Kubal-Furr and Associates 3 of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
I G-88 9/25/01 Alkalinity 29.8 mg/L
G-88 9/25/01 Ammonia Nitrogen < 0.1 mg/L
G-88 9/25/01 Carbon dioxide 140 mg/L
G-88 9/25/01 Carbon monoxide < 0.4 mg/L
I G-88 9/25/01 Chloride 0.91 mg/L
G-88 9/25/01 Dissolved Oxygen 5.00 mg/L
G-88 9/25/01 Ethane 0.03 mg/L
G-88 9/25/01 Ethene < 0.00003 mg/L u
G-88 9/25/01 Ethylene glycol < 5 mg/L UJ
I G-88 9/25/01 Ferrous Iron < 0.1 mg/L
G-88 9/25/01 Methane 0.45 mg/L
G-88 9/25/01 Nitrate 0.2 mg/L
G-88 9/25/01 Nitrogen gas < 19 mg/L u
I G-88 9/25/01 Oxygen gas < 2.4 mg/L u
G-88 9/25/01 pH 5.88 SU
G-88 9/25/01 Redox Potential 223 mv
G-88 9/25/01 Specific Conductivity 71 umhos/cm
I G-88 9/25/01 Sulfate < 0.76 mg/L u
G-88 9/25/01 Sulfide < 0.1 mg/L
G-88 9/25/01 Temperature 25.8 degrees C
G-88 9/25/01 Total Aerobic Plate Count 43700 cfu/ml
I G-88 9/25/01 Total Anaerobic Plate Count 24 cfu/ml
G-88 9/25/01 Total Arsenic < 0.005 mg/L
G-88 9/25/01 Total Kjeldahl Nitrogen < 0.1 mg/L
G-88 9/25/01 Total Manganese 0.033 mg/L
I G-88 9/25/01 Total Organic Carbon < 1.1 mg/L u
G-88 9/25/01 Total Phosphorus 0.064 mg/L
1-57 9/25/01 Alkalinity 4.6 mg/L
I 1-57 9/25/01 Ammonia Nitrogen < 0.1 mg/L
1-57 9/25/01 Carbon dioxide < 27 mg/L u
1-57 9/25/01 Carbon monoxide < 0.4 mg/L
1-57 9/25/01 Dissolved Oxygen 4.25 mg/L
I 1-57 9/25/01 Ethane < 0.000044 mg/L u
1-57 9/25/01 Ethene < 0.000031 mg/L u
1-57 9/25/01 Ethylene glycol < 5 mg/L UJ
1-57 9/25/01 Ferrous Iron < 0.1 mg/L
I 1-57 9/25/01 Methane 0.014 mg/L
1-57 9/25/01 Nitrate 0.65 mg/L
1-57 9/25/01 Nitrogen gas < 20 mg/L u
1-57 9/25/01 Oxygen gas < 5 mg/L u
I 1-57 9/25/01 pH 4.80 SU
1-57 9/25/01 Redox Potential 319 mv
1-57 9/25/01 Specific Conductivity 29 umhos/cm
1-57 9/25/01 Sulfate < 0.51 mg/L u
I 1-57 9/25/01 Sulfide < 0.1 mg/L
1-57 9/25/01 Temperature 21.6 degrees C
1-57 9/25/01 Total Aerobic Plate Count 8500 cfu/ml
1-57 9/25/01 Total Anaerobic Plate Count 13 cfu/ml
1-57 9/25/01 Total Arsenic < 0.005 mg/L
I 1-57 9/25/01 Total Kjeldahl Nitrogen < 0.1 mg/L
1-57 9/25/01 Total Manganese 0.Q18 mg/L
1-57 9/25/01 Total Organic Carbon < 1 mg/L
1-57 9/25/01 Total Phosphorus < 0.03 mg/L
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Kubal-Furr and Associates 4 of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
IT-1 9/24/01 Alkalinity 2460 mg/L
I IT-1 9/24/01 Ammonia Nitrogen < 1 mg/L
IT-1 9/24/01 Carbon dioxide 130 mg/L
IT-1 9/24/01 Carbon monoxide < 0.4 m9/L
IT-1 9/24/01 Dissolved Oxygen 7.62 mg/L
I IT-1 9/24/01 Ethane < 0.00014 mg/L u
IT-1 9/24/01 Ethene 0.0019 mg/L
IT-1 9/24/01 Ethylene glycol 25000 mg/L J
IT-1 9/24/01 Ferrous Iron > 10 mg/L
IT-1 9/24/01 Methane 15 mg/L
I IT-1 9/24/01 Nitrate < 0.25 mg/L
IT-1 9/24/01 Nitrogen gas < 4.7 mg/L u
IT-1 9/24/01 Oxygen gas < 0.32 mg/L u
IT-1 9/24/01 pH 5.05 SU
I IT-1 9/24/01 Redox Potential 62 mv
IT-1 9/24/01 Specific Conductivity 6460 umhos/cm
IT-1 9/24/01 Sulfate 28.6 mg/L
IT-1 9/24/01 Sulfide < 0.1 mg/L
I IT-1 9/24/01 TemPerature 19.9 degrees C
IT-1 9/24/01 Total Aerobic Plate Count 113 cfu/ml J
IT-1 9/24/01 Total Anaerobic Plate Count 36 cfu/ml J
IT-1 9/24/01 Total Arsenic 0.17 mg/L
I IT-1 9/24/01 Total Kjeldahl Nitrogen < 0.1 mg/L
IT-1 9/24/01 Total Manganese 102 mg/L
IT-1 9/24/01 Total Organic Carbon 18200 mg/L
IT-1 9/24/01 Total Phosphorus 0.16 mg/L
I IT-2 9/24/01 Alkalinity 650 mg/L
IT-2 9/24/01 Ammonia Nitrogen < 1 mg/L
IT-2 9/24/01 Carbon dioxide 230 mg/L
I IT-2 9/24/01 Carbon monoxide < 0.4 mg/L
IT-2 9/24/01 Dissolved Oxygen 8.09 mg/L
IT-2 9/24/01 Ethane 0.002 mg/L
IT-2 9/24/01 Ethene 0.00017 mg/L
I IT-2 9/24/01 Ethylene glycol 405 mg/L J
IT-2 9/24/01 Ferrous Iron > 10 mg/L
IT-2 9/24/01 Methane 14 mg/L
IT-2 9/24/01 Nitrate < 0.25 mg/L
I IT-2 9/24/01 Nitrogen gas < 5.3 mg/L u
IT-2 9/24/01 Oxygen gas < 0.44 mg/L u
IT-2 9/24/01 pH 4.85 SU
IT-2 9/24/01 Redox Potential 47 mv
I IT-2 9/24/01 Specific Conductivity 2760 umhos/cm
IT-2 9/24/01 Sulfate < 3 mg/L
IT-2 9/24/01 Sulfide < 0.1 mg/L
IT-2 9/24/01 Temperature 20.4 degrees C
I IT-2 9/24/01 Total Aerobic Plate Count 150 cfu/ml J
IT-2 9/24/01 Total Anaerobic Plate Count 110 cfu/ml J
IT-2 9/24/01 Total Arsenic 0.024 mg/L
IT-2 9/24/01 Total Kjeldahl Nitrogen 0.8 mg/L
I IT-2 9/24/01 Total Manganese 10.1 mg/L
IT-2 9/24/01 Total Organic Carbon 2000 mg/L
IT-2 9/24/01 Total Phosphorus 0.09 mg/L
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Kubal-Furr and Associates S of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
IT-3 9/24/01 Alkalinity 3830 mg/L
I IT-3 9/24/01 Ammonia Nitrogen < 1 mg/L
IT-3 9/24/01 Carbon dioxide < 50 mg/L u
IT-3 9/24/01 Carbon monoxide < 0.4 mg/L
IT-3 9/24/01 Dissolved Oxygen 3.40 mg/L
I IT-3 9/24/01 Ethane < 0.000005 mg/L
IT-3 9/24/01 Ethene 0.00012 mg/L
IT-3 9/24/01 Ethylene glycol 723 mg/L J
IT-3 9/24/01 Ferrous Iron Not analyzed mg/L
IT-3 9/24/01 Methane 17 mg/L
I IT-3 9/24/01 Nitrate < 0.25 mg/L
IT-3 9/24/01 Nitrogen gas < 7.6 mg/L u
IT-3 9/24/01 Oxygen gas < 0.38 mg/L u
IT-3 9/24/01 pH 5.43 SU
I IT-3 9/24/01 Redox Potential 3 mv
IT-3 9/24/01 Specific Conductivity 7940 umhos/cm
IT-3 9/24/01 Sulfate < 12 mg/L
IT-3 9/24/01 Sulfide Not analyzed mg/L
I IT-3 9/24/01 Temperature 21.3 degrees C
IT-3 9/24/01 Total Aerobic Plate Count 230 cfu/ml JX
IT-3 9/24/01 Total Anaerobic Plate Count 500 cfu/ml JX
IT-3 9/24/01 Total Arsenic 0.071 mg/L
I IT-3 9/24/01 Total Kjeldah1 Nitrogen 1 mg/L
IT-3 9/24/01 Total Manganese 214 mg/L
IT-3 9/24/01 Total Organic Carbon 6030 mg/L
IT-3 9/24i01 Total Phosphorus 2.1 mg/L
I IT-4 9/24/01 Alkalinity 203 mg/L
IT-4 9/24/01 Ammonia Nitrogen 0.18 mg/L
IT-4 9/24/01 Carbon dioxide 94 mg/L
I IT-4 9/24/01 Carbon monoxide < 0.4 mg/L
IT-4 9/24/01 Dissolved Oxygen 8.70 mg/L
IT-4 9/24/01 Ethane < 0.000071 mg/L u
IT-4 9/24/01 Ethene < 0.00003 mg/L u
I IT-4 9/24/01 Ethylene glycol 111 mg/L J
IT-4 9/24/01 Ferrous Iron > 10 mg/L
IT-4 9/24/01 Methane 6.7 mg/L
IT-4 9/24/01 Nitrate 0.28 mg/L
I IT-4 9/24/01 Nitrogen gas < 11 mg/L u
IT-4 9/24/01 Oxygen gas < 0.57 mg/L u
IT-4 9/24/01 pH 5.71 SU
IT-4 9/24/01 Redox Potential 120 mv
I IT-4 9/24/01 Specific Conductivity 717 umhos/cm
IT-4 9/24/01 Sulfate < 3 mg/L
IT-4 9/24/01 Sulfide < 0.1 mg/L
IT-4 9/24/01 Temperature 19.2 degrees C
I IT-4 9/24/01 Total Aerobic Plate Count 58800 cfu/ml J
IT-4 9/24/01 Total Anaerobic Plate Count 124 cfu/ml J
IT-4 9/24/01 Total Arsenic 0.024 mg/L
IT-4 9/24/01 Total Kjeldahl Nitrogen 1.4 mg/L
I IT-4 9/24/01 Total Manganese 35.3 mg/L
IT-4 9/24/01 Total Organic Carbon 314 mg/L
IT-4 9/24/01 Total Phosphorus 0.085 mg/L
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Kubal-Furr and Associates 6 of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
IT-5 9/24/01 Alkalinity 629 mg/L
I IT-5 9/24101 Ammonia Nitrogen 0.22 mg/L
IT-5 9/24101 Carbon dioxide 140 mg/L
IT-5 9/24101 Carbon monoxide < 0.4 mg/L
IT-5 9/24/01 Dissolved Oxygen 7.61 mg/L
IT-5 9/24/01 Ethane < 0.000005 mg/L
I IT-5 9/24/01 Ethene < 0.000049 mg/L u
IT-5 9/24101 Ethylene glycol 205 mg/L J
IT-5 9/24/01 Ferrous Iron > 10 mg/L
IT-5 9/24101 Methane 12 mg/L
I IT-5 9/24/01 Nitrate 0.48 mg/L
IT-5 9/24/01 Nitrogen gas < 7.3 mg/L u
IT-5 9/24101 Oxygen gas < 0.56 mg/L u
IT-5 9/24101 pH 5.35 SU
I IT-5 9/24101 Redox Potential 47 mv
IT-5 9/24/01 Specific Conductivity 1488 umhos/cm
IT-5 9/24/01 Sulfate < 3 mg/L
IT-5 9/24/01 Sulfide < 0.1 mg/L
I IT-5 9/24/01 Temperature 20.0 degrees C
IT-5 9124/01 Total Aerobic Plate Count 9800 cfu/ml J
IT-5 9/24/01 Total Anaerobic Plate Count < 1 cfu/ml UJ
IT-5 9/24101 Total Arsenic 0.016 mg/L
I IT-5 9/24101 Total Kjeldahl Nitrogen 0.49 mg/L
IT-5 9124101 Total Manganese 100 mg/L
IT-5 9124101 Total Organic Carbon 717 mg/L
IT-5 9124101 Total Phosphorus 1.1 mg/L
I IT-6 9124101 Alkalinity 2150 mg/L
IT-6 9/24/01 Ammonia Nitrogen < 1 mg/L
IT-6 9/24/01 Carbon dioxide 120 mg/L
I IT-6 9/24/01 Carbon monoxide < 0.4 mg/L
IT-6 9/24101 Dissolved Oxygen 6.43 mg/L
IT-6 9124101 Ethane < 0.00011 mg/L u
IT-6 9124/01 Ethene 0.00042 mg/L
I IT-6 9124101 Ethylene glycol 5450 mg/L J
IT-6 9/24/01 Ferrous Iron > 10 mg/L
IT-6 9/24/01 Methane 13 mg/L
IT-6 9124101 Nitrate < 0.25 mg/L
I IT-6 9124101 Nitrogen gas < 8.8 mg/L u
IT-6 9124101 Oxygen gas < 0.65 mg/L u
IT-6 9/24/01 pH 5.01 SU
IT-6 9/24/01 Redox Potential 74 mv
I IT-6 9/24/01 Specific Conductivity 4830 umhos/cm
IT-6 9/24/01 Sulfate < 12 mg/L
IT-6 9/24/01 Sulfide < 0.1 mg/L
IT-6 9/24/01 Temperature 20.2 degrees C
I IT-6 9/24/01 Total Aerobic Plate Count 2240 cfu/ml J
IT-6 9/24/01 Total Anaerobic Plate Count < 1 cfu/ml UJ
IT-6 9/24/01 Total Arsenic 0.096 mg/L
IT-6 9/24/01 Total Kjeldahl Nitrogen 0.38 mg/L
IT-6 9/24/01 Total Manganese 834 mg/L
I IT-6 9/24/01 Total Organic Carbon 7310 mg/L
IT-6 9/24/01 Total Phosphorus 0.35 mg/L
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Kubal-Furr and Associates 7 of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
IT-7 9/24/01 Alkalinity 1060 mg/L
I IT-7 9/24/01 Ammonia Nitrogen < 1 mg/L
IT-7 9/24/01 Carbon dioxide 99 mg/L
IT-7 9/24/01 Carbon monoxide < 0.4 mg/L
IT-7 9/24/01 Dissolved Oxygen 8.70 mg/L
I IT-7 9/24/01 Ethane < 0.000011 mg/L u
IT-7 9/24/01 Ethene 0.00021 mg/L
IT-7 9/24/01 Ethylene glycol 982 mg/L J
IT-7 9/24/01 Ferrous Iron > 10 mg/L
IT-7 9/24/01 Methane 14 mg/L
I IT-7 9/24/01 Nitrate < 0.05 mg/L
IT-7 9/24/01 Nitrogen gas < 6.2 mg/L u
IT-7 9/24/01 Oxygen gas < 0.34 mg/L u
IT-7 9/24/01 pH 4.83 SU
I IT-7 9/24/01 Redox Potential 109 mv
IT-7 9/24/01 Specific Conductivity 2870 umhos/cm
IT-7 9/24/01 Sulfate < 6 mg/L
IT-7 9/24/01 Sulfide < 0.1 mg/L
I IT-7 9/24/01 Temperature 21.0 degrees C
IT-7 9124101 Total Aerobic Plate Count 1300 cfulml J
IT-7 9124/01 Total Anaerobic Plate Count < 1 cfulml UJ
IT-7 9124/01 Total Arsenic 0.039 mg/L
I IT-7 9124/01 Total Kjeldahl Nitrogen 0.45 mg/L
IT-7 9124101 Total Manganese 447 mg/L
IT-7 9124101 Total Organic Carbon 3780 mg/L
IT-7 9124101 Total Phosphorus 0.11 mg/L
I IT-8 9/24/01 Alkalinity 761 mg/L
IT-8 9124/01 Ammonia Nitrogen < 1 mg/L
IT-8 9/24/01 Carbon dioxide 92 mg/L
I IT-8 9124/01 Carbon monoxide < 0.4 mg/L
IT-8 9124/01 Dissolved Oxygen 5.60 mg/L
IT-8 9124/01 Ethane < 0.000087 mg/L u
IT-8 9/24/01 Ethene 0.00023 mg/L
I IT-8 9124101 Ethylene glycol 368 mg/L J
IT-8 9124101 Ferrous Iron > 10 mg/L
IT-8 9124101 Methane 18 mg/L
IT-8 9/24101 Nitrate < 0.05 mg/L UJ
I IT-8 9124101 Nitrogen gas < 4.7 mg/L u
IT-8 9/24101 Oxygen gas < 0.34 mg/L u
IT-8 9/24101 pH 5.88 SU
IT-8 9/24/01 Redox Potential -37 mv
I IT-8 9/24101 Specific Conductivity 1987 umhos/cm
IT-8 9/24/01 Sulfate < 3 mg/L
IT-8 9124/01 Sulfide < 0.1 mg/L
IT-8 9124/01 Temperature 22.8 degrees C
I IT-8 9124/01 Total Aerobic Plate Count 6600 cfu/ml J
IT-8 9124101 Total Anaerobic Plate Count 500 cfu/ml J
IT-8 9124101 Total Arsenic 0.014 mg/L
IT-8 9/24101 Total Kjeldahl Nitrogen · 0.57 mg/L
I IT-8 9/24101 Total Manganese 71.8 mg/L
IT-8 9/24101 Total Organic Carbon 1420 mg/L
IT-8 9/24101 Total Phosphorus < 0.03 mg/L
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Kubal-Furr and Associates 8 of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
IT-8 (dup) 9/24/01 Alkalinity 812 mg/L
I IT-8 (dup) 9/24/01 Ammonia Nitrogen < 1 mg/L
IT-8 (dup) 9/24/01 Carbon dioxide 82 mg/L
IT-8 (dup) 9/24/01 Carbon monoxide < 0.4 mg/L
IT-8 (dup) 9/24/01 Ethane < 0.00013 mg/L u
I
IT-8 (dup) 9/24/01 Ethene 0.00025 mg/L
IT-8 (dup) 9/24/01 Ethylene glycol 375 mg/L J
IT-8 (dup) 9/24/01 Methane 16 mg/L
IT-8 (dup) 9/24/01 Nitrate 0.052 mg/L J
IT-8 (dup) 9/24/01 Nitrogen gas < 5.6 mg/L u
I IT-8 (dup) 9/24/01 Oxygen gas < 0.38 mgll u
IT-8 (dup) 9/24/01 Sulfate < 3 mg/L
IT-8 (dup) 9/24/01 Total Aerobic Plate Count 6300 cfu/ml J
IT-8 (dup) 9/24/01 Total Anaerobic Plate Count 131 cfu/ml J
I IT-8 (dup) 9/24/01 Total Arsenic 0.013 mg/L
IT-8 (dup) 9/24/01 Total Kjeldahl Nitrogen 0.47 mg/L
IT-8 (dup) 9/24/01 Total Manganese 74 mg/L
IT-8 (dup) 9/24/01 Total Organic Carbon 1230 mg/L
I IT-8 (dup) 9/24/01 Total Phosphorus < 0.03 mg/L
IT-9 9/24/01 Alkalinity 223 mg/L
I IT-9 9/24/01 Ammonia Nitrogen 0.11 mg/L
IT-9 9/24/01 Carbon dioxide 89 mg/L
IT-9 9/24/01 Carbon monoxide < 0.4 mg/L
IT-9 9/24/01 Dissolved Oxygen 4.30 mg/L
I IT-9 9/24/01 Ethane 0.00059 mgll
IT-9 9/24/01 Ethene 0.0013 mg/L
IT-9 9/24/01 Ethylene glycol 7.6 mg/L UJ
IT-9 9/24/01 Ferrous Iron > 10 mg/L
IT-9 9/24/01 Methane 14 mg/L
I IT-9 9/24/01 Nitrate < 0.05 mg/L
IT-9 9/24/01 Nitrogen gas < 7.1 mg/L u
IT-9 9/24/01 Oxygen gas < 0.76 mg/L u
IT-9 9/24/01 pH 5.86 SU
I IT-9 9/24/01 Redox Potential -2 mv
IT-9 9/24/01 Specific Conductivity 729 umhos/cm
IT-9 9/24/01 Sulfate < 3 mg/L
IT-9 9/24/01 Sulfide < 0.1 mg/L
I IT-9 9/24/01 Temperature 23.2 degrees C
IT-9 9/24/01 Total Aerobic Plate Count 6000 cfu/ml "J
IT-9 9/24/01 Total Anaerobic Plate Count 420 cfu/ml J
IT-9 9/24/01 Total Arsenic 0.015 mg/L
I IT-9 9/24/01 Total Kjeldahl Nitrogen 0.12 mg/L
IT-9 9/24/01 Total Manganese 75.6 mg/L
IT-9 9/24/01 Total Organic Carbon 198 mg/L
IT-9 9/24/01 Total Phosphorus < 0.03 mg/L
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Kubal-Furr and Associates 9 of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
J-28 9/20/01 Alkalinity 355 mg/L
I J-28 9/20/01 Ammonia Nitrogen < 0.1 mg/L
J-28 9/20/01 Carbon dioxide 120 mg/L
J-28 9/20/01 Carbon monoxide < 0.4 mg/L
J-28 9/20/01 Dissolved Oxygen 2.16 mg/L
I J-28 9/20/01 Ethane < 0.000014 mg/L u
J-28 9/20/01 Ethene < 0.000013 mg/L u
J-28 9/20/01 Ethylene glycol < 5 mg/L
J-28 9/20/01 Ferrous Iron < 0.1 mg/L
J-28 9/20/01 Methane < 0.00083 mg/L u
I J-28 9/20/01 Nitrate 6.5 mg/L
J-28 9/20/01 Nitrogen gas < 21 mg/L u
J-28 9/20/01 Oxygen gas < 2.8 mg/L u
J-28 9/20/01 pH 6.50 SU
I J-28 9/20/01 Redox Potential 166 mv
J-28 9/20/01 Specific Conductivity 937 umhos/cm
J-28 9/20/01 Sulfate 38.2 mg/L
J-28 9/20/01 Sulfide < 0.1 mg/L
I J-28 9/20/01 Temperature 18.9 degrees C
J-28 9/20/01 Total Aerobic Plate Count 6 cfu/ml
J-28 9/20/01 Total Anaerobic Plate Count < 1 cfu/ml
J-28 9/20/01 Total Arsenic < 0.005 mg/L
I J-28 9t2p101 Total Kjeldahl Nitrogen < 0.1 mg/L
J-28 9/20/01 Total Manganese 0.31 mg/L
J-28 9/20/01 Total Organic Carbon < 1.4 mg/L u
J-28 9/20/01 Total Phosphorus < 0.03 mg/L
I J-28 (dup) 9/20/01 Alkalinity 406 mg/L
J-28 (dup) 9/20/01 Ammonia Nitrogen < 0.1 mg/L
J-28 (dup) 9/20/01 Carbon dioxide 120 mg/L
I J-28 (dup) 9/20/01 Carbon monoxide < 0.4 mg/L
J-28 (dup) 9/20/01 Ethane < 0.00001 mg/L u
J-28 (dup) 9/20/01 Ethene < 0.000011 mg/L u
J-28 (dup) 9/20/01 Ethylene glycol < 5 mg/L
I J-28 (dup) 9/20/01 Methane < 0.00089 mg/L u
J-28 (dup) 9/20/01 Nitrate 6.5 mg/L
J-28 (dup) 9/20/01 Nitrogen gas < 21 mg/L u
J-28 (dup) 9/20/01 Oxygen gas < 2.7 mg/L u
I J-28 (dup) 9/20/01 Sulfate 38.7 mg/L
J-28 (dup) 9/20/01 Total Aerobic Plate Count 7 cfu/ml
J-28 (dup) 9/20/01 Total Anaerobic Plate Count < 1 cfu/ml
J-28 (dup) 9/20/01 Total Arsenic < 0.005 mg/L
I J-28 (dup) 9/20/01 Total Kjeldahl Nitrogen < 0.1 mg/L
J-28 (dup) 9/20/01 Total Manganese 0.3 mg/L
J-28 (dup) 9/20/01 Total Organic Carbon < 2.6 mg/L u
J-28 (dup) 9/20/01 Total Phosphorus < 0.03 mg/L
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Kubal-Furr and Associates 10 of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
K-28 9/18/01 Alkalinity 974 mg/L
•·
K-28 9/18/01 Ammonia Nitrogen < 0.1 mg/L
K-28 9/18/01 Carbon dioxide 170 mg/L
K-28 9/18/01 Carbon monoxide < 0.4 mg/L
K-28 9/18/01 Dissolved Oxygen 2.09 mg/L
K-28 9/18/01 Ethane < 0.000005 mg/L
I K-28 9/18/01 Ethene < 0.000005 mg/L
K-28 9/18/01 Ethylene glycol 384 mg/L
K-28 9/18/01 Ferrous Iron > 10 mg/L
K-28 9/18/01 Methane 9.4 mg/L
I K-28 9/18/01 Nitrate < 0.05 mg/L
K-28 9/18/01 Nitrogen gas < 2.4 mg/L u
K-28 9/18/01 Oxygen gas < 0.24 mg/L u
K-28 9/18/01 pH 6.10 SU
I K-28 9/18/01 Redox Potential -121 mv
K-28 9/18/01 Specific Conductivity 3510 umhos/cm
K-28 9/18/01 Sulfate 4.4 mg/L
K-28 9/18/01 Sulfide < 0.1 mg/L
I K-28 9/18/01 Temperature 17.7 degrees C
K-28 9/18/01 Total Aerobic Plate Count 400 cfu/ml
K-28 9/18/01 Total Anaerobic Plate Count 8 cfu/ml
K-28 9/18/01 Total Arsenic 0.025 mg/L
I K-28 9/18/01 Total Kjeldahl Nitrogen < 0.1 mg/L
K-28 9/18/01 Total Manganese 11 mg/L
K-28 9/18/01 Total Organic Carbon 1110 mg/L
K-28 9/18/01 Total Phosphorus < 0.03 mg/L
I N-29 9/24/01 Alkalinity 5.6 mg/L
N-29 9/24/01 Ammonia Nitrogen 0.6 mg/L
N-29 9/24/01 Carbon dioxide 120 mg/L
I N-29 9/24/01 Carbon monoxide < 0.4 mg/L
N-29 9/24/01 Dissolved Oxygen 2.43 mg/L
N-29 9/24/01 Ethane < 0.000052 mg/L u
N-29 9/24/01 Ethene < 0.000014 mg/L u
I . N-29 9/24/01 Ethylene glycol <· 5 mg/L UJ
N-29 9/24/01 Ferrous Iron < 0.1 mg/L
N-29 9/24/01 Methane 0.65 mg/L
N-29 9/24/01 Nitrate 1.1 mg/L
I N-29 9/24/01 Nitrogen gas < 18 mg/L u
N-29 9/24/01 Oxygen gas < 2.1 mg/L u
N-29 9/24/01 pH 4.48 SU
N-29 9/24/01 Redox Potential 505 mv
I N-29 9/24/01 Specific Conductivity 72 umhos/cm
N-29 9/24/01 Sulfate < 2.7 mg/L u
N-29 9/24/01 Sulfide < 0.1 mg/L
N-29 9/24/01 Temperature 17.1 degrees C
I N-29 9/24/01 Total Aerobic Plate Count 43 cfu/ml J
N-29 9/24/01 Total Anaerobic Plate Count < 1 cfu/ml UJ
N-29 9/24/01 Total Arsenic < 0.005 mg/L
N-29 9/24/01 Total Kjeldahl Nitrogen 0.79 mg/L
N-29 9/24/01 Total Manganese 0.19 mg/L
I N-29 9/24/01 Total Organic Carbon < 1 mg/L
N-29 9/24/01 Total Phosphorus < O.Q3 mg/L
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Kubal-Furr and Associates 11 of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
0-25 9/24/01 Alkalinity 46.1 mg/L J
I 0-25 9/24/01 Ammonia Nitrogen 33 mg/L
0-25 9/24/01 Carbon dioxide < 38 mg/L u
0-25 9/24/01 Carbon monoxide < 0.4 mg/L
0-25 9/24/01 Dissolved Oxygen 2.38 mg/L
I
0-25 9/24/01 Ethane 0.0053 mg/L
0-25 9/24/01 Ethene 0.00044 mg/L J
0-25 9/24/01 Ethylene glycol < 5 mg/L UJ
0-25 9/24/01 Ferrous Iron < 0.1 mg/L
0-25 9/24/01 Methane 1.1 mg/L J
I 0-25 9/24/01 Nitrate < 0.05 mg/L UJ
0-25 9/24/01 Nitrogen gas < 18 mg/L u
0-25 9/24/01 Oxygen gas < 0:58 mg/L u
0-25 9/24/01 pH 6.34 SU
I 0-25 9/24/01 Redox Potential -115 mv
0-25 9/24/01 Specific Conductivity 1350 umhos/cm
0-25 9/24/01 Sulfate 453 mg/L
0-25 9/24/01 Sulfide < 0.1 mg/L
I 0-25 9/24/01 Temperature 18.1 degrees C
0-25 9/24/01 Total Aerobic Plate Count 1530 cfu/ml J
0-25 9/24/01 Total Anaerobic Plate Count 190 cfu/ml J
0-25 9/24/01 Total Arsenic 0.026 mg/L
I 0-25 9/24/01 Total Kjeldahl Nitrogen 33.1 mg/L
0-25 9/24/01 Total Manganese 0.52 mg/L
0-25 9/24/01 Total Organic Carbon 30.2 mg/L
0-25 9/24/01 Total Phosphorus 0.057 mg/L
I 0-25 (dup) 9/24/01 Alkalinity 35.7 mg/L J
0-25 (dup) 9/24/01 Ammonia Nitrogen 31.7 mg/L
0-25 (dup) 9/24/01 Carbon dioxide < 46 mg/L u
I 0-25 (dup) 9/24/01 Carbon monoxide < 0.4 mg/L
0-25 (dup) 9/24/01 Ethane 0.0065 mg/L
0-25 (dup) 9/24/01 Ethene 0.00055 mg/L J
0-25 (dup) 9/24/01 Ethylene glycol < 5 mg/L UJ
I 0-25 (dup) 9/24/01 Methane 1.4 mg/L J
0-25 (dup) 9/24/01 Nitrate 0.052 mg/L J
0-25 (dup) 9/24/01 Nitrogen gas < 22 mg/L u
0-25 (dup) 9/24/01 Oxygen gas < 0.88 mg/L u
I 0-25 (dup) 9/24/01 Sulfate 422 mg/L
0-25 (dup) 9/24/01 Total Aerobic Plate Count 6700 cfu/ml J
0-25 (dup) 9/24/01 Total Anaerobic Plate Count 80 cfu/ml J
0-25 (dup) 9/24/01 Total Arsenic 0.027 mg/L
I 0-25 (dup) 9/24/01 Total Kjeldahl Nitrogen 32.9 mg/L
0-25 (dup) 9/24/01 Total Manganese 0.53 mg/L
0-25 (dup) 9/24/01 Total Organic Carbon 30.3 mg/L
0-25 (dup) 9/24/01 Total Phosphorus 0.054 mg/L
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Kubal-Furr and Associates 12 of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
Q-33 9/27/01 Alkalinity 113 rng/L
I Q-33 9/27/01 Ammonia Nitrogen 0.14 rng/L
Q-33 9/27/01 Carbon dioxide 110 rng/L
Q-33 9/27/01 Carbon monoxide < 0.4 rng/L
Q-33 9/27/01 Dissolved Oxygen 1.91 rng/L
Q-33 9/27/01 Ethane < 0.000041 rng/L u
I Q-33 9/27/01 Ethene < 0.000005 rng/L
Q-33 9/27/01 Ethylene glycol < 5 rng/L
Q-33 9/27/01 Ferrous Iron 0.2 rng/L
Q-33 9/27/01 Methane 0.024 rng/L
I Q-33 9/27/01 Nitrate < 0.05 rng/L
Q-33 9/27/01 Nitrogen gas < 19 rng/L u
Q-33·-· • 9/27/01 Oxygen gas < 3.4 rng/L u
Q-33 9/27/01 pH 5.73 SU
I Q-33 9/27/01 Redox Potential 183 rnv
Q-33 9/27/01 Specific Conductivity 934 umhos/cm
Q-33 9/27/01 Sulfate 103 rng/L
Q-33 9/27/01 Sulfide < 0.1 rng/L
I Q-33 9/27/01 Temperature 17.4 degrees C
Q-33 9/27/01 Total Aerobic Plate Count 380 cfu/ml
Q-33 9/27/01 Total Anaerobic Plate Count < 1 cfu/rnl
Q-33 9/27/01 Total Arsenic < 0.005 rng/L
I Q-33 9/27/01 Total Kjeldahl Nitrogen 0.38 rng/L
Q-33 9/27/01 Total Manganese 0.11 rng/L
Q-33 9/27/01 Total Organic Carbon < 3.6 rng/L u
Q-33 9/27/01 Total Phosphorus 0.031 rng/L
I S-50 9/25/01 Alkalinity 31.1 rng/L
S-50 9125/01 Ammonia Nitrogen < 0.1 rng/L
S-50 9/25/01 Carbon dioxide < 25 rng/L u
I S-50 9/25/01 Carbon monoxide < 0.4 rng/L
S-50 9/25/01 Dissolved Oxygen 5.98 rng/L
S-50 9/25/01 Ethane < 0.000037 rng/L u
S-50 9/25/01 Ethene < 0.000045 rng/L u
I S-50 9/25/01 Ethylene glycol < 5 rng/L UJ
S-50 9/25/01 Ferrous Iron < 0.1 rng/L
S-50 9/25/01 Methane 0.014 rng/L
S-50 9/25/01 Nitrate 1.1 rng/L
I S-50 9125/01 Nitrogen gas < 21 rng/L u
S-50 9125/01 Oxygen gas < 6.2 rng/L u
S-50 9125/01 pH 8.46 SU
S-50 9/25/01 Redox Potential 288 rnv
I S-50 9/25/01 Specific Conductivity 93 umhos/cm
S-50 9/25/01 Sulfate < 1.4 rng/L u
S-50 9/25/01 Sulfide < 0.1 rng/L
S-50 9/25/01 Temperature 17.4 degrees C
I S-50 9/25/01 Total Aerobic Plate Count 17800 cfu/rnl J
S-50 9/25/01 Total Anaerobic Plate Count 3 cfu/ml J
S-50 9/25/01 Total Arsenic < 0.005 rng/L
S-50 9/25/01 Total Kjeldahl Nitrogen < 0.1 rng/L
S-50 9/25/01 Total Manganese < 0.01 rng/L
I S-50 9/25/01 Total Organic Carbon < 1 rng/L
S-50 9/25/01 Total Phosphorus 0.077 rng/L
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Kubal-Furr and Associates 13 of 20
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I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result· Units Flag
T-17 9120101 Alkalinity 31.8 mg/L
I T-17 9120101 Ammonia Nitrogen < 0.1 mg/L
T-17 9120101 Carbon dioxide 240 mg/L
T-17 9120101 Carbon monoxide < 0.4 mg/L
T-17 9120101 Chloride 87.2 mg/L
I T-17 9120101 Dissolved Oxygen 2.21 mg/L
T-17 9120101 Ethane < 0.000058 mg/L u
T-17 9120101 Ethene < 0.000013 mg/L u
T-17 9120101 Ethylene glycol < 5 mg/L
T-17 9120101 Ferrous Iron < 0.1 mg/L
I T-17 9120101 Methane 0.014 mgll
T-17 9120101 Nitrate 0.18 mgll
T-17 9120101 Nitrogen gas < 17 mg/L u
T-17 9120101 Oxygen gas < 2 mg/L u
I T-17 9120101 pH 4.91 SU
T-17 9120101 Redox Potential 470 mv
T-17 9120101 Specific Conductivity 571 umhos/cm
T-17 9120101 Sulfate 36.3 mgll
I T-17 9120101 Sulfide < 0.1 mg/L
T-17 9120/01 Temperature 19.0 degrees C
T-17 9/20/01 Total Aerobic Plate Count 13 cfu/ml
T-17 9/20101 Total Anaerobic Plate Count 2 cfu/ml
I T-17 9/20101 Total Arsenic < 0.005 mg/L
T-17 9/20/01 Total Kjeldahl Nitrogen 0.12 mg/L
T-17 9/20/01 Total Manganese 2 mg/L
T-17 9120101 Total Organic Carbon < 3.9 mg/L u
I T-17 9120101 Total Phosphorus < 0.03 mg/L
T-35 9118101 Alkalinity 44.7 mg/L
T-35 9118101 Ammonia Nitrogen < 0.1 mg/L
I T-35 9118/01 Carbon dioxide 230 mg/L
T-35 9118101 Carbon monoxide < 0.4 mg/L
T-35 9118101 Chloride 93.6 mg/L
T-35 9118101 Dissolved Oxygen 3.06 mg/L
I T-35 9118101 Ethane < 0.000058 mg/L u
T-35 9118101 Ethene < 0.0000071 mg/L u
T-35 9118101 Ethylene glycol < 5 mg/L
T-35 9118101 Ferrous Iron 1 mg/L
I T-35 9118101 Methane < 0.00096 mg/L u
T-35 9/18/01 Nitrate < 0.05 mg/L
T-35 9/18/01 Nitrogen gas < 12 mg/L u
T-35 9/18/01 Oxygen gas < 1.6 mg/L u
I T-35 9/18/01 pH 5.50 SU
T-35 9/18101 Redox Potential 120 mv
T-35 9/18/01 Specific Conductivity 605 umhos/cm
T-35 9/18/01 Sulfate 38 mg/L
I T-35 9118101 Sulfide < 0.1 mg/L
T-35 9118101 Temperature 20.8 degrees C
T-35 9118101 Total Aerobic Plate Count 560 cfulml
T-35 9118101 Total Anaerobic Plate Count 11 cfu/ml
T-35 9118101 Total Arsenic < 0.005 mg/L
I T-35 9118101 Total Kjeldahl Nitrogen 0.12 mg/L
T-35 9118101 Total Manganese 1.1 mg/L
T-35 9/18101 Total Organic Carbon < 8 mg/L u
T-35 9118101 Total Phosphorus < 0.03 mg/L
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Kubal-Furr and Associates 14 of 20
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I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
T-58 9/19/01 Alkalinity 124 mg/L
I T-58 9/19/01 Ammonia Nitrogen 0.11 mg/L J
T-58 9/19/01 Carbon dioxide 180 mg/L
T-58 9/19/01 Carbon monoxide < 0.4 mg/L
T-58 9/19/01 Chloride 70.1 mg/L
T-58 9/19/01 Dissolved Oxygen 2.38 mg/L
I T-58 9/19/01 Ethane < 0.00022 mg/L u
T-58 9/19/01 Ethene 0.00012 mg/L
T-58 9/19/01 Ethylene glycol < 5 mg/L
T-58 9/19/01 Ferrous Iron 10 mg/L
I T-58 9/19/01 Methane 0.4 mg/L
T-58 9/19/01 Nitrate < 0.05 mg/L
T-58 9/19/01 Nitrogen gas < 19 mg/L u
T-58 9/19/01 Oxygen gas < 0.85 mg/L u
I T-58 9/19/01 pH 5.48 SU
T-58 9/19/01 Redox Potential 1 mv
T-58 9/19/01 Specific Conductivity 636 umhos/cm
T-58 9/19/01 Sulfate 27.3 mg/L
I T-58 9/19/01 Sulfide < 0.1 mg/L
T-58 9/19/01 Temperature 22.0 degrees C
T-58 9/19/01 Total Aerobic Plate Count 950 cfutml J
T-58 9/19/01 Total Anaerobic Plate Count 8 cfu/ml J
I T-58 9/19/01 Total Arsenic < 0.005 mg/L
T-58 9/19/01 Total Kjeldahl Nitrogen 0.17 mg/L
T-58 9/19/01 Total Manganese 0.73 mg/L
T-58 9/19/01 Total Organic Carbon < 3.9 mg/L u
I
T-58 9/19/01 Total Phosphorus 0.049 mg/L
T-58 (dup) 9/19/01 Alkalinity 128 mg/L
T-58 (dup) 9/19/01 Ammonia Nitrogen 0.14 mg/L J
I T-58 (dup) 9/19/01 Carbon dioxide 170 mg/L
T-58 (dup) 9/19/01 Carbon monoxide < 0.4 mg/L
T-58 (dup) 9/19/01 Chloride 71 mg/L
T-58 (dup) 9/19/01 Ethane < 0.0002 mg/L u
I T-58 (dup) 9/19/01 Ethene 0.00011 mg/L
T-58 (dup) 9/19/01 Ethylene glycol < 5 mg/L
T-58 (dup) 9/19/01 Methane 0.33 mg/L
T-58 (dup) 9/19/01 Nitrate < 0.05 mg/L
I T-58 (dup) 9/19/01 Nitrogen gas < 16 mg/L u
T-58 (dup) 9/19/01 Oxygen gas < 0.66 mg/L u
T-58 (dup) 9/19/01 Sulfate 27.9 mg/L
T-58 (dup) 9/19/01 Total Aerobic Plate Count 1200 cfu/ml J
I T-58 (dup) 9/19/01 Total Anaerobic Plate Count 10 cfu/ml J
T-58 (dup) 9/19/01 Total Arsenic < 0.005 mg/L
T-58 (dup) 9/19/01 Total Kjeldahl Nitrogen 0.17 mg/L
T-58 (dup) 9/19/01 Total Manganese 0.7 mg/L
T-58 (dup) 9/19/01 Total Organic Carbon < 4 mg/L u
I T-58 (dup) 9/19/01 Total Phosphorus 0.046 mg/L
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Kubal-Furr and Associates 15 of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
TD-3 9/26/01 Alkalinity 3 mg/L
I TD-3 9/26/01 Ammonia Nitrogen < 0.1 mg/L
TD-3 9/26/01 Carbon dioxide < 0.6 mg/L
TD-3 9/26/01 Carbon monoxide < 0.4 mg/L
TD-3 9/26/01 Chloride 8 mg/L
I TD-3 9/26/01 Dissolved Oxygen 2.31 mg/L
TD-3 9/26/01 Ethane < 0.000026 mg/L u
TD-3 9/26/01 Ethene < 0.000025 mg/L u
TD-3 9/26/01 Ethylene glycol < 5 mg/L
TD-3 9/26101 Ferrous Iron < 0.1 mgll
I TD-3 9126101 Methane < 0.00046 mg/L u
TD-3 9/26101 Nitrate 2.5 mg/L
TD-3 9126101 Nitrogen gas < 18 mg/L u
TD-3 9126/01 Oxygen gas < 9.7 mg/L u
I TD-3 9126101 pH 4.68 SU
TD-3 9/26101 Redox Potential 299 mv
TD-3 9126/01 Specific Conductivity 87 umhos/cm
TD-3 9126101 Sulfate < 2.7 mgll u
I TD-3 9126/01 Sulfide < 0.1 mg/L
TD-3 9126101 Temperature 27.0 degrees C
TD-3 9126/01 Total Aerobic Plate Count 92 cfulml
TD-3 9/26/01 Total Anaerobic Plate Count < 1 cfulml
I TD-3 9/26/01 Total Arsenic < 0.005 mg/L
TD-3 9/26101 Total Kjeldahl Nitrogen < 0.1 mg/L
TD-3 9126101 Total Manganese 0.07 mgll
TD-3 9126101 Total Organic Carbon < 1 mgll
I TD-3 9126101 Total Phosphorus 0.11 mg/L
TD-4 9126101 Alkalinity 21.3 mg/L
TD-4 9/26/01 Ammonia Nitrogen < 0.1 mgll
I TD-4 9/26/01 Carbon dioxide 140 mgll
TD-4 9126101 Carbon monoxide < 0.4 mg/L
TD-4 9126/01 Chloride 0.83 mg/L
TD-4 9126/01 Dissolved Oxygen 6.06 mgll
I TD-4 9126/01 Ethane 0.00054 mg/L
TD-4 9126101 Ethene < 0.000045 mg/L u
TD-4 9126/01 Ethylene glycol < 5 mg/L
TD-4 9126101 Ferrous Iron < 0.1 mgll
I TD-4 9126101 Methane 0.32 mgll
TD-4 9126101 Nitrate 0.93 mgll
TD-4 9/26/01 Nitrogen gas < 18 mgll u
TD-4 9/26101 Oxygen gas < 1.7 mgll u
I TD-4 9/26101 pH 6.05 SU
TD-4 9/26/01 Redox Potential 342 mv
TD-4 9126101 Specific Conductivity 76 umhos/cm
TD-4 9126101 Sulfate < 2.8 mg/L u
I TD-4 9/26/01 Sulfide < 0.1 mg/L
TD-4 9/26/01 Temperature 23.0 degrees C
TD-4 9126101 Total Aerobic Plate Count 11000 cfulml
TD-4 9126101 Total Anaerobic Plate Count 4 cfu/ml
TD-4 9126101 Total Arsenic < 0.005 mg/L
I TD-4 9/26101 Total Kjeldahl Nitrogen 0.26 mgll
TD-4 9126101 Total Manganese 0.17 mgll
TD-4 9126101 Total Organic Carbon < 1 mgll
TD-4 9126101 Total Phosphorus < 0.03 mg/L
I
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Kubal-Furr and Associates 16 of 20
I
I Summary of Initial MNA Monitoring Data .,
I Sample ID Sample Date Parameter Modifier Result Units Flag
Tl-1 9/26/01 Alkalinity 12.7 mg/L
I Tl-1 9/26/01 Ammonia Nitrogen < 0.1 mg/L
Tl-1 9/26/01 Carbon dioxide < 0.6 mg/L
Tl-1 9/26/01 Carbon monoxide < 0.4 mg/L
Tl-1 9/26/01 Dissolved Oxygen 1.00 mg/L
Tl-1 9/26/01 Ethane < 0.0000087 mg/L u
I Tl-1 9/26/01 Ethene < 0.000021 mg/L u
Tl-1 9/26/01 Ethylene glycol < 5 mg/L
Tl-1 9/26/01 Ferrous Iron < 0.1 mg/L
Tl-1 9/26/01 Methane < 0.00011 mg/L u
I Tl-1 9/26/01 Nitrate 2.9 mg/L
Tl-1 9/26/01 Nitrogen gas < 19 mg/L u
Tl-1 9/26/01 Oxygen gas < 9.2 mg/L u
Tl-1 9/26/01 pH 5.16 SU
I Tl-1 9/26/01 Redox Potential 1.68 mv
Tl-1 9/26/01 Specific Conductivity 96 umhos/cm
Tl-1 9/26/01 Sulfate < 1.1 mg/L u
Tl-1 9/26/01 Sulfide < 0.1 mg/L
I Tl-1 9/26/01 Temperature 27.0 degrees C
Tl-1 9/26/01 Total Aerobic Plate Count 43 cfu/ml J
Tl-1 9/26/01 Total Anaerobic Plate Count 5 cfu/ml J
Tl-1 9/26/01 Total Arsenic < 0.005 mg/L
I Tl-1 9/26/01 Total Kjeldahl Nitrogen < 0.1 mg/L
Tl-1 9/26/01 Total Manganese 0.03 mg/L
Tl-1 9/26/01 Total Organic Carbon < 1 mg/L
Tl-1 9/26/01 Total Phosphorus < 0.03 mg/L
I Tl-2 9/26/01 Alkalinity 22.3 mg/L
Tl-2 9/26/01 Ammonia Nitrogen < 0.1 mg/L
Tl-2 9/26/01 Carbon dioxide < 55 mg/L UJ
I Tl-2 9/26/01 Carbon monoxide < 0.4 mg/L UJ
Tl-2 9/26/01 Dissolved Oxygen 4.03 mg/L
Tl-2 9/26/01 Ethane < 0.000005 mg/L
Tl-2 9/26/01 Ethene < 0.000005 mg/L UJ
I Tl-2 9/26/01 Ethylene glycol < 5 mg/L
Tl-2 9/26/01 Ferrous Iron < 0.1 mg/L
Tl-2 9/26/01 Methane < 0.000031 mg/L UJ
Tl-2 9/26/01 Nitrate 0.73 mg/L
I Tl-2 9/26/01 Nitrogen gas < 21 mg/L u
Tl-2 9/26/01 Oxygen gas < 5.8 mg/L u
Tl-2 9/26/01 pH 5.84 SU
Tl-2 9/26/01 Redox Potential 253 mv
I Tl-2 9/26/01 Specific Conductivity 65 umhos/cm
Tl-2 9/26/01 Sulfate < 0.71 mg/L u
Tl-2 9/26/01 Sulfide < 0.1 mg/L
Tl-2 9/26/01 Temperature 21.3 degrees C
I Tl-2 9/26/01 Total Aerobic Plate Count 3000 cfu/ml
Tl-2 9/26/01 Total Anaerobic Plate Count 4 cfu/ml
Tl-2 9/26/01 Total Arsenic < 0.005 mg/L
Tl-2 9/26/01 Total Kjeldahl Nitrogen < 0.1 mg/L
Tl-2 9/26/01 Total Manganese 0.19 mg/L
I Tl-2 9/26/01 Total Organic Carbon < 1 mg/L
Tl-2 9/26/01 Total Phosphorus < 0.03 mg/L
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Kubal-Furr and Associates 17 of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
I Tl-2 (dup) 9/26/01 Alkalinity 22.3 mg/L
Tl-2 (dup) 9/26/01 Ammonia Nitrogen < 0.1 mg/L
Tl-2 (dup) 9/26/01 Carbon dioxide 120 m9/L J
Tl-2 (dup) 9/26/01 Carbon monoxide < 0.4 mg/L
Tl-2 (dup) 9/26/01 Ethane < 0.00032 mg/L u
I Tl-2 (dup) 9/26/01 Ethene 0.0002 mg/L J
Tl-2 (dup) 9/26/01 Ethylene glycol < 5 mg/L
Tl-2 (dup) 9/26/01 Methane 0.046 mg/L J
Tl-2 (dup) 9/26/01 Nitrate 0.79 mg/L
I Tl-2 (dup) 9/26/01 Nitrogen gas < 22 mg/L u
Tl-2 (dup) 9/26/01 Oxygen gas < 1.4 mg/L u
Tl-2 (dup) 9/26/01 Sulfate < 0.53 mg/L u
Tl-2 (dup) 9/26/01 Total Aerobic Plate Count 2900 cfu/ml
I Tl-2 (dup) 9/26/01 Total Anaerobic Plate Count 2 cfu/ml
Tl-2 (dup) 9/26/01 Total Arsenic < 0.005 mg/L
Tl-2 (dup) 9/26/01 Total Kjeldahl Nitrogen < 0.1 mg/L
Tl-2 (dup) 9/26/01 Total Manganese 0.19 mg/L
I Tl-2 (dup) 9/26/01 Total Organic Carbon < 1 mg/L
Tl-2 (dup) 9/26/01 Total Phosphorus < 0.03 mg/L
I U-38 9/26/01 Alkalinity 3.6 mg/L
U-38 9/26/01 Ammonia Nitrogen < 0.1 mg/L
U-38 9/26/01 Carbon dioxide < 19 mg/L u
U-38 9/26/01 Carbon monoxide < 0.4 mg/L
I U-38 9/26/01 Dissolved Oxygen 4.52 mg/L
U-38 9/26/01 Ethane < 0.000035 mg/L u
U-38 9/26/01 Ethene < 0.000076 mg/L u
U-38 9/26/01 Ethylene glycol < 5 mg/L
U-38 9/26/01 Ferrous Iron < 0.1 mg/L
I U-38 9/26/01 Methane < 0.00061 mg/L u
U-38 9/26/01 Nitrate 1.9 mg/L
U-38 9/26/01 Nitrogen gas < 21 mg/L u
U-38 9/26/01 Oxygen gas < 7.4 mg/L u
I U-38 9/26/01 pH 4.13 SU
U-38 9/26/01 Redox Potential 405 mv
U-38 9/26/01 Specific Conductivity 80 umhos/cm
U-38 9/26/01 Sulfate < 2.1 mg/L u
I U-38 9/26/01 Sulfide < 0.1 mg/L
U-38 9/26/01 Temperature 19.7 degrees C
U-38 9/26/01 Total Aerobic Plate Count 470 cfu/ml
U-38 9/26/01 Total Anaerobic Plate Count < 1 cfu/ml
I U-38 9/26/01 Total Arsenic < 0.005 mg/L
U-38 9/26/01 Total Kjeldahl Nitrogen < 0.1 mg/L
U-38 9/26/01 Total Manganese 0.078 mg/L
U-38 9/26/01 Total Organic Carbon < 1 mg/L
U-38 9/26/01 Total Phosphorus < 0.03 mg/L
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Kubal-Furr and Associates 18 of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
V-23 9/18/01 Alkalinity 2460 mg/L
I V-23 9/18/01 Ammonia Nitrogen < 0.1 mg/L
V-23 9/18/01 Carbon dioxide 240 mg/L
V-23 9/18/01 Carbon monoxide < 0.4 mg/L
V-23 9/18/01 Dissolved Oxygen 2.86 mg/L
V-23 9/18/01 Ethane < 0,000005 mg/L
I V-23 9/18/01 Ethene 0.00032 mg/L
V-23 9/18/01 Ethylene glycol 5040 mg/L
V-23 9/18/01 Ferrous Iron > 10 mg/L
V-23 9/18/01 Methane 16 mg/L
I V-23 9/18/01 Nitrate < 0.05 mg/L
V-23 9/18/01 Nitrogen gas < 2 mg/L u
V-23 9/18/01 Oxygen gas < 0.23 mg/L u
V-23 9/18/01 pH 5.29 SU
I V-23 9/18/01 Redox Potential 27 mv
V-23 9/18/01 Specific Conductivity 5290 umhos/cm
V-23 9/18/01 Sulfate 41.6 mg/L
V-23 9/18/01 Sulfide < 0.1 mg/L
I V-23 9/18/01 Temperature 21.0 degrees C
V-23 9/18/01 Total Aerobic Plate Count 550 cfu/ml
V-23 9/18/01 Total Anaerobic Plate Count < 1 cfu/ml
V-23 9/18/01 Total Arsenic 0.1 mg/L
I V-23 9/18/01 Total Kjeldahl Nitrogen 1.1 mg/L
V-23 9/18/01 Total Manganese 858 mg/L
V-23 9/18/01 Total Organic Carbon 7850 mg/L
V-23 9/18/01 Total Phosphorus 0.97 mg/L
I W-23 9/24/01 Alkalinity 144 mg/L
W-23 9/24/01 Ammonia Nitrogen 1.8 mg/L
W-23 9/24/01 Carbon dioxide 270 mg/L
I W-23 9/24/01 Carbon monoxide < 0.4 mg/L
W-23 9/24/01 Dissolved Oxygen 2.52 mg/L
W-23 9/24/01 Ethane < 0.00016 mg/L u
W-23 9/24/01 Ethene < 0.000025 mg/L u
I W-23 9/24/01 Ethylene glycol < 5 mg/L UJ
W-23 9/24/01 Ferrous Iron < 0.1 mg/L
W-23 9/24/01 Methane 0.066 mg/L
W-23 9/24/01 Nitrate 0.4 mg/L
I W-23 9/24/01 Nitrogen gas < 17 mg/L u
W-23 9/24/01 Oxygen gas < 2.1 mg/L u
W-23 9/24/01 pH 5.62 SU
W-23 9/24/01 Redox Potential 136 mv
I W-23 9/24/01 Specific Conductivity 834 umhos/cm
W-23 9/24/01 Sulfate 64 mg/L
W-23 9/24/01 Sulfide < 0.1 mg/L
W-23 9/24/01 Temperature 19.0 degrees C
I W-23 9/24/01 Total Aerobic Plate Count 43 cfu/ml J
W-23 9/24/01 Total Anaerobic Plate Count < 1 cfu/ml UJ
W-23 9/24/01 Total Arsenic < 0.005 mg/L
W-23 9/24/01 Total Kjeldahl Nitrogen 1.8 mg/L
W-23 9/24/01 Total Manganese 2.9 mg/L
I W-23 9/24/01 Total Organic Carbon < 6.4 mg/L u
W-23 9/24/01 Total Phosphorus < 0.03 mg/L
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Kubal-Furr and Associates 19 of 20
I
I Summary of Initial MNA Monitoring Data
I Sample ID Sample Date Parameter Modifier Result Units Flag
Z-78 9/20/01 Alkalinity 31.1 mg/L
I Z-78 9/20/01 Ammonia Nitrogen < 0.1 mg/L
Z-78 9/20/01 Carbon dioxide < 21 mg/L u
Z-78 9/20/01 Carbon monoxide < 0.4 mg/L
Z-78 9/20/01 Dissolved Oxygen 2.66 m9/L
Z-78 9/20/01 Ethane < 0.000011 mg/L u
I Z-78 9/20/01 Ethene < 0.0000051 mg/L u
Z-78 9/20/01 Ethylene glycol < 5 mg/L
Z-78 9/20/01 Ferrous Iron < 0.1 mg/L
Z-78 9/20/01 Methane < 0.0049 mg/L u
I Z-78 9/20/01 Nitrate < 0.05 mg/L
Z-78 9/20/01 Nitrogen gas < 26 mg/L u
Z-78 9/20/01 Oxygen gas < 2.5 mg/L u
Z-78 9/20/01 pH 6.13 SU
I Z-78 9/20/01 Redox Potential 150 mv
Z-78 9/20/01 Specific Conductivity 124 umhos/cm
Z-78 9/20/01 Sulfate 7.8 mg/L
Z-78 9/20/01 Sulfide < 0.1 mg/L
I Z-78 9/20/01 Temperature 19.0 degrees C
Z-78 9/20/01 Total Aerobic Plate Count 5400 cfu/ml J
Z-78 9/20/01 Total Anaerobic Plate Count 6 cfu/ml J
Z-78 9/20/01 Total Arsenic < 0.005 mg/L
I Z-78 9/20/01 Total Kjeldahl Nitrogen < 0.1 mg/L
Z-78 9/20/01 Total Manganese 0.1 mg/L
Z-78 9/20/01 Total Organic Carbon < 1 mg/L
Z-78 9/20/01 Total Phosphorus < 0.03 mg/L
I IIP BLANK 91, 9/20/01 Alkalinity < 1 mg/L
IIP BLANK 9/, 9/20/01 Ammonia Nitrogen < 0.1 mg/L
IIP BLANK 9/, 9/20/01 Carbon dioxide 0.81 mg/L
I IIP BLANK 9/, 9/20/01 Carbon monoxide < 0.4 mg/L
IIP BLANK 9/, 9/20/01 Chloride < 0.5 mg/L
IIP BLANK 9/, 9/20/01 Ethane 0.00008 mg/L
IIP BLANK 9/, 9/20/01 Ethene 0.000016 mg/L
I IIP BLANK 9/, 9/20/01 Ethylene glycol < 5 mg/L
IIP BLANK 9/, 9/20/01 Methane 0.0024 mg/L
IIP BLANK 9/, 9/20/01 Nitrate < 0.05 mg/L
IIP BLANK 9/, 9/20/01 Nitrogen gas 16 mg/L
I IIP BLANK 9/, 9/20/01 Oxygen gas 7.8 mg/L
IIP BLANK 9/, 9/20/01 Sulfate < 0.5 mg/L
IIP BLANK 9/, 9/20/01 Total Arsenic < 0.005 mg/L
IIP BLANK 9/, 9/20/01 Total Kjeldahl Nitrogen < 0.1 mg/L
I IIP BLANK 9/, 9/20/01 Total Manganese < 0.01 mg/L
IIP BLANK 9/, 9/20/01 Total Organic Carbon 1.6 mg/L
IIP BLANK 9/, 9/20/01 Total Phosphorus < 0.03 mg/L
IIP BLANK 9/, 9/25/01 Alkalinity < 1 mg/L
IIP BLANK 91, 9/25/01 Ammonia Nitrogen < 0.1 mg/L
I IIP BLANK 9/, 9/25/01 Carbon dioxide 15 mg/L
IIP BLANK 91, 9/25/01 Carbon monoxide < 0.4 mg/L
IIP BLANK 9/, 9/25/01 Chloride < 0.5 mg/L
IIP BLANK 91, 9/25/01 Ethane 0.000064 mg/L
I IIP BLANK 91, 9/25/01 Ethene 0.000014 mg/L
IIP BLANK 9/, 9/25/01 Ethylene glycol < 5 mg/L UJ
IIP BLANK 9/, 9/25/01 Methane 0.00035 mg/L
IIP BLANK 9/, 9/25/01 Nitrate < 0.05 mg/L
I IIP BLANK 91, 9/25/01 Nitrogen gas 19 mg/L
IIP BLANK 9/, 9/25/01 Oxygen gas 8.7 mg/L
IIP BLANK 91, 9/25/01 Sulfate 0.56 mg/L
IIP BLANK 9/, 9/25/01 Total Arsenic < 0.005 mg/L
I IIP BLANK 9/, 9/25/01 Total Kjeldahl Nitrogen < 0.1 mg/L
IIP BLANK 9/, 9/25/01 Total Manganese < 0.01 mg/L
IIP BLANK 91, 9/25/01 Total Organic Carbon < 1 mg/L
IIP BLANK 9/, 9/25/01 Total Phosphorus < 0.03 mg/L
I
Kubal-Furr and Associates 20 of 20
I
Attachment 7
Selected Ethylene Glycol References
Kubal-Furr & Associates
9t1~f,
; t 1::
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J\rl'I.IED ANO ENVIRONMENTAi. MICRIIRIOl.O(;Y, July 19!0, p. JR5-J9(1 0099-2240/83/070 I 85-0(i$02 . (l()/1) Vol. 46. No. I
Copyright 0 I9RJ, American Society for Mit:rohiology
Degradation of Ethylene Glycol and Polyethylene Glycols by Methanogenic Consortiat
DARYL F. DWYER ANI> JAMES M. TIEDJE'
Vl'partmcnt of Mic-mhioloRy aud l'uMic lfra/rl,, Miclti~a11 Stal(' Uufrcrsiry, l:asr l.ansing, Michi,mn 48824
Received I March l98J/An:eplcd 2 ~fay 19~0
Methanogenic cnrichmenls capable of degrading polyethylene glycol and ethyl-ene glycol were obtained from sewage sludge. Erhanol. acetate, methane. and (in the case of polyethylene glycols) ethylene glycol were detected as prod11cts. The seq11ence of prod11ct forrnation s11ggestcd that the ethylene oxide 11nit IHO-(CH,-CH,-0-)JII was dism11tatcd to acetate and elhanol; clhanol was subscq11enlly oxidized to acetate by a syntrophic association that produced methane. The rates of degradation for clhylene, dielhylenc, and polyethylene glycol with molecular weights of 4011. 1,0110, and 20,11110, respcclivcly', were inversely related lo the number of ethylene oxide monomers per molecule and ranged from O.R4 lo 0.1 J mM ethylene oxide units degraded per h. The enrichments were shown lo best metabolize glycols close to the molecular weight of the suhstrate on which 1f1cy were enriched. The anaerobic degradation of polyethylene glycol (molecular weight. 20,01}()) may he importanl in the light of the general resistance of polyethylene glycols lo aerohit: degradation.
Ethylene glycol (EU: 1.2-clhancdiol) and ils oligomcrs and polymers arc used in the produc-tion of substances such ;is surfactants, explo-sives. cosmetics, heat transfer fluids, solvents, lubricants, and plastics (I, 3). Lillie allcntion has hccn given to their fotc in ano,xic hnhitats, such as those in waste tre.il ment. sediments, and landfills, even though billions of pounds arc manufactured and disd1argcd into the environ-ment anmrnlly, and the high-molecular-weight
polymers (up to 25,000) arc relatively rcsislant to aerobic biodegradation 0). In foci. the bin-degradation of most polymers. especially of syn-thclic polymers. by ohligalc anaerobes is poorly understood. We fell thal the gc11cral resistance of polyethylene glycols (l'EUs) In r.ipid aerobic dcgrad~ltion, along wirh their heavy use. made it important to establish whether or 1101 they can he degraded anaerobically nnd, ir so. lo co111pare the rates and products of degradation wilh !hose for aerobic systems.
Aerobic microorganisms use hoth ECi and PJ~Gs as sources of carbon and energy (8. 13, 20, 21 ). The aerobic metabolism of EU is relatively common, and the pathways of its metabolism are known (2,· 7, 16, 20, 22, 2.l). However, !he ether hond of the oligomcrs and polymers is comparatively resistant to microbial attack. This is especially true for the degradation of PEG wilh a molecular weight of 20,000 I PEG-2tUl00;
t f'uhli:,;hct.1 as journal mtidc n(l. 10785 of lhc l\fichi!,!a11 Agriculturnl Experiment Station.
18.5
IIO-(Cll,-CH2-0-)4511 H /. Haines and Alexander (6) reported the isolation of several monocul-tures of aerobic bacleria able to grow on PEG-20,000, hul did not report carbon balances or demonstrate !he extcnl of polymer degradation.
The only olhcr report of PEG020,000 degrada-tion involves the coculture (Jf a Flm1oluwtcrium sr. and a P.vcudomonas sp. (9), in which neither microorganism alone degraded lhc polymer. In this case. signifkanl degradation of the polymer was not verified.
The anaerobic metabolism of EG has been reported. The fermentation of EG by Closlridi-
11111 Rlycolicum yields equimolar amounts of ace-lale and elhanol (5); !he metabolism of EG by a Flm·ohaclt'rium sp. under micruaerophilic con-ditions follows the sequence acetyl-CoA, ace1yl-phosrha1c. and acetate (23). The only apparent
example of anaerobic PEG degradation is for l'EG-400 in anaerobic sludge reactors, where enhanced methane production was nolccl (11 ). We were able to enrich for glycol-degrading
cons1..lrtia from sludge on EU. diethylcne glycol (DEUl. l'EG-400, PEG-1000, and PEG-20J)()O.
We report here on the degradation rates, inter-mediate products. specificity of enrichment for polymer lenglh, and extent of substrate conver-sion In gaseous prc1dt1cts for each of the five glycols.
MATEIUALS ANH METIIOUS
{~ultur('s. Glycol-degrading h:icterial const1rti.1 were obtained from sludge of a municipal nnaerobic digestor
I
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' i 11
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186 DWYER AND TIEDJE
in Mason, Mich. Serum hottles ( I Ml ml) were nushcd
with a 90% N2•l0% CO2 gas mixture which had been
passed over hot copper filings to remove traces of
oxygen. During flushing. JO ml of sludge was added
with 90 ml of reduced medium. The hottlcs were then
scaled with black butyl rubber stoppers ( Bcllco Glass.
Inc.) and crimped with aluminum sc,ds lo maintain
mmcrohic conditions. Enrichmcnls were mainlaincd
hy the weekly transfer of IO ml of cmidmu:nt lo 90 ml
of fresh medium. lncuhati1111 was al J7"C and st:ilic.
The hasic minimal medium (D. R. Shelton. personal
communication) was composed of (per liter): 0.J0 g of
Kll,PO4 , 0.35 g of K2HPO4, 0.5 g of NH,CI. 0.1 g
MgCI,. 70 mg ofCnCI, · 2H,O, 20 mg of FeCI, · 411,0,
I ml of trace metals solution 125). 1.2 g of NallCO-1,
120 mg of Na2S · 9H 2O, .incl 1 111! <1f vitamin B solution
(18). The· substrate was added lo give a 0.2% flnal
concentration. The enrichment suhslrales \\.'ere eilher
EG (Mallinckrodt. Inc.I. DEG U. T. !taker Chcmkal
Co.I. PEG-400 (Fisher Scic11(ilic Co.). PECi-1000, or
PE(i-20,000 (hoth from J. T. Baker Chemical Co.I.
Substrates al a 0.2% concentration arc equivalent to 16
mM EG 06 mM ethylene oxide unils). 21 mM DEG
(42 mM ethylene oxide units). 5 mM PEG-400. 2 mM
PEG-1000, and 0.1 mM PEG-20,0110 (4.5 mM ethylene
oxide units each). PEG-20,000. manufactured by
Union Carbide Corp., is termed PECI compound 20M
and is formed hy joining 8,000-molccnlar-weight poly-
mers with a diepoxide. It has an average appro;,;imated
molcn1lar weight of 20,000. hut the mole(:ular weight
dislrihution is from 5,000 lo 80,000. with the largest
portion heing unreacled 8.000-molecular-weight
monomer (L. F. Theiling, Union C:,rhide Corp .. per-
sonal communication).
Experimental procedures. Each consorlia used in the
experimenl twd undergone .10 weekly lransfr:rs afler
their initial cstahlishment. The suhslmlc range of each
emichment was determined by transferring HJ ml of
actively mclaholizing culture to 90 1111 of' medium
containing one of the five suhstrntes. Separate cultures
were estahlished to determine the mies of product
formation and EG and DEG utilizaton hy each hactcri-
al consortium grown on its own substrate. All e.xpcri-
ments were done in triplicate and repeated.
Since the polymeric suhstrates cannol be quantified
easily. the mies of degradation were assessed ,1s rates
of product formation for DEG. PE(i-400. PEG-1000.
and l'EG-20.000. EU was easily and accurntely quanti-
fied; therefore. lhe degrndalion rntc of EG was hased
on a gas chromatographic assay of EG. For the
compmison of rates. all vnlues arc e;,;pressed as milli-
rnolar ethylene o:<idc unils dcgrndcd. which corre-
spond lo the two-carbon products ethanol and acetate.
A rate of producl formation of 0.5 mM m:etatc and 0 . .5
mM ethanol per h, therefore, was presumed lo indicate
a rnle or 1.0 mM ethylene <nide units metabolized per
h.
Analytical melhnds. Aqueous s:i111ples (2 ml) were
pc,fodirnlly withdrawn hy syringe from the incubated
bottles. filtered lhrough a 0.4.5 Jll1l filter (Millipore
Corp.) into glass vials . .ind frozen until analyses \Vere
done. At time zero and after 12<, h. we took I-ml
st11nples to determine protein conccnlration by the
method of Lowry et al. (24). using hovinc scrum
albumin as the standard. lfocterial prolein w.is made
soluble hy heating the samples in 0 . .<i N NaOI I at 90"C
for 10 min. Growth yields (Y-suhstnile) for the per-
APPL. ENVIRON. MICROBIOI..
centage of substrate degraded were expressed as mi•
crograms of protein formed per millimolc of ethylene
oxide unit degraded.
EU. DEG. and ethanol were measured with a i)er-
kin-Elmcr 900 gas chromatograph equipped with n 2-m
Chromosnrh IOI packed glass column (Anspec Co ..
Inc.) and u lbme ionization detector. N! was the
c;u-ricr i;as al a flow ralc of 50 ml/min. For DEG. the
i1~icct11r, C(1!11nm. and manifold lcmpcratures were
:!.5fl"l'. For EG and ethanol. !he column temperature
was i 51fC. ;\cctale was as~aycd with a 2-m, C:irbo-
pack C-0.Y)~· CW 20 M-1% H_11'0,. packed glass cnl-
unm (Suprlco. Inc.). The samples were acidified with
formic acid before i1ticction. The injector. column. and
manifold te111pcrntun:s were set at 125"C. Mclhane
was q11:llltiflcd hy in_jecling 0.2 ml of cullure head space
ga.s into a Carle model 8500 gas chromalograph
equipped wilh a Ptm1pak Q column (;\nspcc Co .. Inc.)
am\ a micrnlhermistor detector. When methane de•
rived from acetate oxidation was used in calculations
or producl :iccumulation. the methane value was rc-
dm:cd hy four~fifths. :11HI the remaining amount was
used lo inf'cr !he amount 11f;1cetalc oxidized hecausc of
the sloichiomctry 411O-Cl-1 2-OM + l·IC01 ~ + II' ....,.. ,c:11., + co,.
Microscopy was by phase contrast and nuorcsccnce
with a Leitz Orthulu;,; microscope. The nuorc:-;cence
was used to identify melhanogcnic hacleria as de•
scribed by Mink and Dugan (12).
RESULTS
(;IJTol degradation. Bacterial enrichments
were successfully established on each substrate.
E<i. DEG. l'EG-400, l'EG-1000, and PEG-
20.000. as evidenced hy an increase in lurhidily
and the production of methane. Microscopic
examination revealed Iha! lhe EG, DEG. and
PEG-400 consortia were dominated hy two mor-
plwlogical types of bacteria. These were is(1lated
from the DEG consortia and tentatively i(lcnti•
lied as a fi,frtlwnohactcrium sp. and a De.rn(f(,ri.
hrio sp. The loss of !he mclhanogen occurred
sporadically in some of the cultures. which
resulled in a loss of c11l111re viahilily. A h1rther
characterization of this apparent synlrophic re•
lationship is bciug conducled. The PEG-1000
and PEG-20,000 consortia exhibiled less dislinc-
tivC. more varied morphologies of hactcria. One
\\leek after tr;rnsfcr to fresh medium. both c11l-
ll1rcs in the high•molcculw·-wcight substrates
conlained a large number ofnuorcscent bacteria
rcscmhling !11<'1/wno.wrdna sr.
Figure I depicls lhc formalion of degradalion
prnducls hy the consorlia enriched on EG and
DEG. The parallel fnrmalion of ethanol and
acetale suggesls Iha! lhe glycol monomer uni!
was dismulated. Afler 70 h. the conversion of
ethanol to acetate with concurrent methane for-
malion was readily apparenl in the EG consor-
lia: EG degradalion appeared complcle before
ethanol oxidation commenced. In contrast. the
DEG consorlia (Fig. I) appeared to oxidize
cthannl during DEG use. and ethanol was never
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V01 .. 46, 198) ANAEROBIC DEGRADt'JON OF ETHYLENE GLYCOLS 187 4o,:::;,c---.,-,,-,,-a-,-.-,,-
00-,-------,•.o substrLes is also shown by the 5-day Y-suh-strate Values (Table I). The reported DEG con-sortit1~ growth yield may he too low since .z ethanol \Vas 1101 totally oxidized to acetate (Fig.
30
'-Acetate 3.0
0 1 ). whCrcas in lhc other consortia it was. Three
I 20
Elhenol
2·0 j differcnl DEG consorlia were st1hscq11cntly grown 11111il cthan(ll oxidation was complete; the Y-suhsl,rnlc calc11latcd was 213 µg of protein per mmol of ethylene oxide unit degraded. This is slill sig11ilican1/y lower lhan the Y-substratc for the PEG-1000 and PEG-20.000 consortia.
30
::! 20 E
10
26
r-~"-.!''....
Olethylene gl)'cOI
52 78 104
HOURS
1.0
0
3.0 .,
:,:
0
2.0 0 E E
1.0
0
130
Fl(i I. Tcmpln;,I formation of degradation prnd-11c!s hy fhc 1.:onsorlia enriched 1m f.:c; :ind IJl·Ji.
completely oxidized lo acetate. In :.1 IO0-ml culture. the dismutatiun of 40 111M ethylene glycol units would produce 20 mM ethanol and 20 111M acetate: a final methane qu:111tity of I .II 0111101 could theoretically be rroduced: 4HO-CH,-CH,-OH _, 2CH3CH,OH + 2CH,COOII: 2CH,Cll,OH + 2H,O -> 2CH,COOI I + 411,: and 4112 + CO2 -, CH, + 21120. As c·.xpccled. lhe amount of methane in both cnnsortia was onc-four1h lhat of the final acelc1lc conccnlration and, lhercforc. is evidence that mclhanc was produced only as a product of ethanol oxidation. Similar .studies wilh the PECi-400 consortia showed (lflly a trnnsicnt. low level of ethanol accun111l.1tion ( 18 to 66 h). Methane and ellrnnol were first dclcctcd al the same sampling 1irnc: the amount of methane produced s11hscq11cntly increased until ethanol disappeared (data not shown). This is further evidence that for these consortia, methane was produced only as a product of ethannl oxidation. Methane. ethanol. acclate. and EG (4 tu 5 mMJ were rrodr1ccd in the l'EG-1000 and PEG-20,000 consortia. Etha-nol was present only in trace quantilics. proha-bly because the rate-limiting step ,,r l'E<,-101111 and PEG-20.000 degradation was polymer hy-drolysis. J\t I 2fl h. thL· anwunr of llll'lhane produced w:is again one-fourth that nf the final conccnlralion of acetate.
Rate's of PE(; degradation and ,::rowth _rield,c;. A general decrease in lhc overall ralc of dcgrada-lion occurred with increases in PEG n10/ccul:1r weight (Table I). The utilizati()n of glycols as
Speci~cifJ of consortia for polJmcr length. Two general observations are evident from the study o'n substrate specificity (Table 2). First. neither the EG nor DEG consortia were able to significantly attack glycols of higher molecular weight. Second. each PEG enrichment effective-ly used bEG. perhaps explaining why we were unable 1;, detect DEG as an intermediate. The PEG-20,0011 consortia displayed slower degrada-tion of the lower-molecular.weight suhstralcs as compared with tl1c rest of the consortia (e.g .. cf. 5-day data on DEG ITahle 21). This may be due to either ~1 lag period in suhslratc use or to a low relative density of bacteria ahlc to use glycols; micwscopic examination of the PEG-20.000 consortia·, revealed few of the bacterial types which dominated lhc enrichments metabolizing low-nwlecular-wcight glycols.
The pe/-cenl degradation for the PEG-l000 and PEG-20,o'oo consortia was based largely on lhe accumulation of mclhane, as the other products were mos.tly oxidized by day 12 (Table 2). As noted aho'vc. hoth consortia contained Afetlwn-o.rnrcina Jp .. which may he responsible for the removal of the acetate. The EG. DEG. and PEG-400 ~onsortia ~1ccunH1httcd acetate with no
TABLE,/. Rates or rroducl formalion, carhun recovery. arld growth yield of e;1ch enrichment on its ' glycol suhstr:ilc
Hate nf ~;;, Carbon Y-suhslralc Enrichment 1
1
rwduct recovered in lµg tlf and substrate I fonnn!ion 1, prntcin/mmol
1~u-·---.. ·-·-·-·1' •1;·,;: <~ :;1;;~· --"~:~;:, ___ nr ;~4u,· .. DEG 0.7J ± 0.05 85-89 148 PEG-400 0.66 ± 0.0J 69-75 I 82 PEG-I 000 !U6 ± 11.04 59-6.l 4.17 PEG-20,0l~l 0.IJ ± 0.01 84-87 512
"The mies· of prmlm:I fonnnti<ln (clhanPI, accl.ilc) arc expressed as !he mean ± the sl;111Jmd t..levialion (11 = J) an<l were' ccdc11l;1IL'd for the lime period in which a near-constanl'rale or rrnducl formation w.is {1hscrved. ,, The pcrcc'n1 carbon recovered in product is for !he period of constanl rale and is less lhan the lot.ii carhon recnvered in rrmluct value round after a long im:uha-fion (Table 2J.
,-Y-suh.stratc w;1s c;1lcul:11cd at 126 h. The mean is given (11 = 3).:
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188 DWYER AND TIEDJE APPL ENVIRON. MICRODIOL
TABLE 2. Specificity of each consortium for polymer length
Consortimn % Suh ... tratc mclaholi1.cd after 12 days ··-·--·-·---------•-------·-------------~-
EG" DEG" PEG-400" l'Eti-1000.., PEG-20.0otl' ----------
EG IOO 1011 (21( 7 7 7
DEG 100 100111101 9 0 0
PEG-4110 86 toll (100) 100 62 50 (14)
PEG-IOIIO 44 IOI) i8J) 60 82 0
PEG-20.IJIKl 55 toll ((,{l) 90 8J 82 (33)
" Based on suhstrate disappearance.
h Based on the accumulation of ethanol, acetate. amt methane.
,. The data given within parentheses nre the results nftcr 5 days or incubation ;:ind show the slow adaptation or
the consorlia to the given substrates.
subsequent oxidation. The pH of these consortia
fell to 6.ll during !heir growth period. whereas
that of the PEG-1000 and PEG-20.000 consorlia
remained near 7.0 to 7.2. This may have selected
against the A1etha110.Hll'ci11a sp.
IIISCUSSION
This study demonstrates significant rates of
anacrohic biodcgradation of EGs and. most im~
portantly, of the recalcitrant PEG-20,000 poly-
mer. llcrctoforc. research has demonstrated the
aerobic degradation of PEGs with molecular
weights of only 6,000 I 16) and less (211) with
activated. acclimated sludge. 111 :iddilion. Cox
and Conway (4) found that PEG-15411 was con-
sumed in 2 days. wchreas Pitter ( 17) found that
the degradation of 1% PEG-600 and PEG-800
enrichments look 30 days and that of PEG-I 1100
and PEG-15<Ml enrichments took 55 and 75 days,
respectively. Maines and· Alexander (6), using
aerobic soil isolates. found that I 'Hi concentra-
tions of PEG-400 were degraded in 5 days and
those of PEG-1000 were degraded in 10 days.
Our study showed at least an 82% degradation of
PEG-20,000 and an 83% degradation of PEG-
l000 in 12 days and a 100% degradation of PEG-
400 in less than 4 days. Unfortunately, the
141
FIG. 2. Proposed pathway for degradation or EU
by methanogcnic consortium.
comparison of our rates of degradation with
those obtained aerobically is dimcult since the
latter data '1rc l'iom biological oxygen demand
studies or from the loss of total organic carhon
(and thus not specific for substrate conversion),
whereas ours rely upon a determination using
product recovery. Nonetheless. tile substantial
rates of anaerobic hiodegradation of PEGs by
our enrichmcnls obtained from sewage sludge
demonstrate a good potential for using anaerobic
organisms in l'EG removal. Considering the
higher cost of aerobic lrcatment systems. the
anaerobic process may be advantageous for the
removal of this and perhaps other synthetic
polymers.
Based on the identity and sequence of the
products formed. we arc pnlposing the degrada-
tion wutc for EO in mcthanogcnic consortia
shown in Fig. 2. Reactions 111 and 121 have hccn
proposed previously hy Wicganl and DcBonl
(22) for Myrnhacrcri,1111 E44. which metabolizes
EG acrohically. For our rinacrubic consortia.
acetaldehyde is suggested as the electron sink in
a dismutation producing acetate and ethanol:
reaction 131 thus would account for the early
formation of ethanol. The subsequent consump-
tion of ethanol with a concomitant production of
acetate and methane is described by reaction 141.
Whereas reactions 11 J throngh 13 J arc cncrgcli-
cally favorable ( 19), reaction 14 J, the oxidation
of ethanol to acetate, is only favorable if the
hydrogen concentration is kept low. This pre-
sumably was accomplished by the mcthano-
gen(s) and suggests a syntrophic association.
The stoichiometry and sequence of the products
that wc observed (Fig. I) make any other dcgra-
dative pathway unlikely, although another possi-
bility does exist. EG could be hydrogenated lo
ethanol (u G"' = -21 kcal lea. -87.9 kJJ) with
the hydrogen derived from acetaldehyde oxida-
tion to acetate, but this would require the pres-
ence of novel cnzymc(s) and. therefore. is less
likely.
The ahility of our PEG consortia to.accumu-
late EG and to use EG and DEG (Table 2)
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Vm .. 46, 1983 ANAEROBIC DEGRADATION OF ETHYLENE GLYCOLS 189
suggests that glycol units were released from the
polymer hy hydrolysis before suhscquenl me-
tabolism to acetate, ethanol. and methane. This
is similar to the examples of the aerobic, hydro-
lytic microorganisms which also use EG and
were studied by Haines and Alexander (6). In
contrast, other aerobic dcpt,lyn1crizatilH1S ap-
pear to involve either an initial dehydration of
the terminal glycol unit ( I<,) nr ;i tlehydrogcna-
tion (9. 10, 15). in which case. the microorga-
nisms appear unable to use EG. Bcl'ausc the
glycol polymers arc degraded hy a rate one-sixth
that of monomer degradation (Table 2), it ap-
pears that the polymer first must he hydrolyzed
into fragments, from which monomers can then
he hydrolytically removed. If enzymatic attack
occurred only from the cm.ls. we would expect
the degradation rate of the PE(,-20,000 polymer
IHO-(CH,-CH2-O-)45oHI to he less than one-
sixth that of the monomer.
Our results !]emonstrated an inability of the
EG and DEG consortia (where selection was for
non-dcpolymcrizing bacteria) to metabolize
polymers. This is comparable to earlier research
with acrohic hacteria (14), which showed that
the ahility to grow on oligon1crs. hut not roly-
mers, of EG is due to an inability of :ippropriatc
enzyme(s) to reach the polymer substrate. We
have also demonstrated that each co11sorti11rn,
although adapted lo metabolizing glycols with a
molecular weight similar lo that of its own
substrate, also was able to use DEG cniciently.
The hydrolytic cleavage of polymers may ex-
plain the DEG metabolism. and a difference in
the conformational structure of polymers may
dictate substrate specificity. Cox (3) noted that
PEG biodegradability may depend on the con-
formation of the molecule, which appears to be
helical in solution (I), whereas low-111olec11lar-
weight PEG (<400) has a zig-zag pattern. Such
conformational differences could influence the
activity of an enzyme and inliihil. for example,
PEG-20,(XI0 utilization hy the bacteria of the
PEU-400 consortia. In this way. conformational
differences could explain the relatively greater
ability of the PEG-400 and PEG-1000 consortia
to <lcgradc their own respective polymer.
The relatively greater growl h yields obtained
for high-molecular-weight polymers, as mea-
sured by protein concentrations. were unexpect-
ed. The results may have been due to either an
increase in yield from some ncctalc metabolism
in lhe consortia or lo a difference in metaholism
between the dominate bacterial types. Pure-
culture studies may help clarify this by separat-
ing nlhcr members of the consortia from lhc
glycol degraders.
ACKN()Wl,1-:ll(;l\lENT
We thank IJ. R. Shellon for his cmly ohscn·a1ions 11n
methane rroduclion from the glycol.s l'>y .c.cw:tl?C sludge.
LITERATURE CITED
I. Rnlley, F. F.., .Jr-., and.). V. Kole.<ike. 1976. Poly(ethylene
11~idc). Academic Pres.~. Inc .• New York.
2. Child, J., and A. Willetts. 1978. Micrt•bial metal:wlism of
aliph:iric glyc11ls. Hacterial mclaholism of clhylcne glycol.
niochirn. Biophys. /\eta .5JR:Jl6-J27.
J. Cox, ll. I'. !97R. The biodcgrndatic,n of r11lycfhylenc
glycols. Adv. Appl. Microhiol. 2J:17J-194.
4. Co.,, IL I'., and R. A. Cmrnn.,.-. 1976. Micn,t,i:d dcgnida-
tion of some polyclhylene glycols, p. 8'.'15-841. In J.M.
Sha1pky and /\. M. Kaplan (ed.l. l'n1eecdi11gs nf !he
Thi1d lnternaliu11al Bi11degradatinn Symposium. Applictl
Sciem:c<.; l'ublishers. Ltd .. London.
5. (;a.,lon. I,. W., and E. R. Sladlman. 1%J. Fermentation
of ethylene gly1,.·ol by Cfo.1tridi11111 Rf.vn,lin1m .~f' N . .I.
Bacterinl. 85:.15(1-J62.
f,. Haines, .I. R., n11d 1\-1. All''ll.nnder. 1975. Mic11)hial t.lcgrada-
lion of pnlycthylene glycols. Appl. Microhiol. 29:621-625.
7. Harada. T., nnd \". Nagnshima. 1975. Utilization of alky-
lcther co111pn1111ds by soil haclcri.i. J. Ferment. Techuol.
!iJ:218-222.
H. llusu~'ll, II., N. l\tiJarnki, Y. SuRisaki, E. Takanashi, M.
T~urufuJi, l\1. \'nmasnkl, and G. Tamura. 1978. llaclel'ial
degrndalil1n of synthetic polymers and oligt1mcrs with the
speci.il reference to the case 1•f polyethylene glycol.
Agrii.:. Biol. Chern. 42:1.'i45-1552.
Q, K:rnai, F .• T. Kimura, l\l. Fukaya, \'. Tani, K. Ogato, T.
l11'1m, and II. Fnk:nnl. 197H. 13.idcrial oxidalion of p11ly-
cthykne E=lycnl. Appl. Envi1on. f\.licn1hiol. .15:679-f,84.
Ill. Kmrni, F., T. Khnurn, Y. Tani, II. Yamada, aml M.
K11n1d1I. 19HO. l'milka1i1111 anti characleri.>:alnn of pol}'-
elh}'lcm· glyc11I 1khyd1of!e11asc i11volvc1I in the hacterial
mctaholism ufpolycthylt·ne glycol. Appl. Envi1on. Micni-
bic,I. 411:7111-711.'i.
11. Mill.,. E . .)., nnd \'. T. Stnt'k. l9.'i4. Biolllgical o:ddation nf
syulheric rnganic chcrnical,;. Eng. Bull. Pmtlue Univ.
E,1g. Exl. Ser. 87:449-464.
12. !\link, R. W., and I'. R. IJui:::m. 1977. Tcnlative idenlilica-
lion of mctharwgenic bacteria hy nuorcscencc micn1sco•
py. Appl. En\'iron. Miert•hiol. JJ:71J-717.
IJ. Oi::ata, K., F. Kawai, F. l\hlshlro, and Y. Tani. 1975.
Isolation of ptilycthylcne glycols-assimilable bacteria . .I.
Ferment. Te..:hnul. 5.1:757-761.
1,1. r:i~·m·. \\'. J. 1%J. Pure culture studies of the degradation
of dctc1gcnt compounds. Hiotechnol. Bioeng. S:J5."i-.V1:'i.
l."i. 1':1.rnt', W. J., and R. L. 'f'odd. 1966. Flavin-linked dehy-
d111gcnatio11 nf ether glycols by cell-free c:-:tracts of a soil
hnc1t:ri11m. J. llactc1iol. 91:l:'i.lJ-15.1(,.
16. Pcnrce, B. A., and M. T. lleydeman. 19R0. Melabolism of
tli(ethylcnc glycol) l2-C'-hytlroxyelh11xy)ethanol/ am!
other slmrl ptily(ethylcne glyeol_ls hy gram negative bacte-
ria. J. Gen. Micr.1hiol. 118:21-27.
17. l'illu, I'. l97J. Rclalion between structure and himlcgrnd-
ability of organic compounds. II. Biological dcgrndahility
of polyethylene J!lycnls. Sh. Vys. Sk. Chem. Technol.
Prnze Tech,wl. Vtidy 18:41-75. fTakcn fn1rn Chem.
Ah,.lr. Hl:241. 1974. ahslr. no. '29235).
18. Sharak Genthner, B. R., C. L. lla,·i.,, and M. r. DrJant.
1981. Features of rumen and sludge strains of E11ht1c·tn•
i11111 limo.rnm. a mclhannl•;md-ll:-CO1-ulilizing species.
Appl. Envinin. Micrnhiol. 42:12-19.
19. Thaurr, R. K .• K . .lungermann1 and K. Uerker. 1977.
Energy ci1nscrva1i1111 in chemt1lrophic anaerohic hacleria.
Bacleliul. Rev. 41:I00-180.
20. Thelu, J., L. Medina, und J. l'elmunf. 1980. (hidalitin 11f
polyoxycthylcne oligomer.s hy an indocihlc enzyme from
/',H·11do111111111.t /'400. FEMS Lett. R:1~7-190.
21. Wn(,;1111, G. K., and N. Jonl's. 1977. The hiodef?rat.l:ilion of
pt•lrc-thylene glycols by sewage h:icteria. Water Res.
11:95-100.
22. \\'iegant, W. M., nnd J. A. l\1. DeBont. 1980. A new route
for ethylene glycol mclnholism in Mycoht1cleri11m E44. J.
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190 DWYER AND TIEDJE
Gen. Microbiol. 1211:325-3.lJ.
2J. Willetts, A. 1981. Bacterial mctnholism of ethylene g1ycn1.
Birn.:him. 11il1rhys. Acta 677:194-199.
24. Wond. W. ,\. 19X\. Physical methods. p. JSX. In I'.
Gcrhanh led.). Manual or methods for general hadc1 iolo-
Arri.. ENVIRON. MICRODIOL
En'-Amcrirnn Sticicty for Microhhilugy, Washington.
ll.C.
25. Zehmkr. A. J. n .. :11111 K. Wuhrman. 1977. Physiology of
/\fr1/11111nh1c1c•ri11111 strain AZ. An.:h. t,..fo:rnhiol. J: 199-
:!0.:'i.
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CHAPTER 23
Bioremediation of Ethylene Glycol-
Contaminated Groundwater at the Naval Air
Warfare Center in Lakehurst, New Jersey
Paul E. Flathman and Lucy S. Bottomley
INTRODUCTION
Biological techniques were used to remediate ethylene glycol-contaminated
groundwater following the loss of an estimated 4000 gal (15,000 L) of cooling
water from a lined surface storage lagoon at the Naval Air Warfare Center
(NA WC) in Lakehurst, NJ, which until recently was known as the Naval Air
Engineering Center. The cooling water at the site was estimated to contain 25%
(v/v) ethylene glycol. The problem developed on January 5, 1982, when a
break occurred in the lined lagoon. A subsequent investigative program con-
finned soil contamination around the lagoon and identified a 180-ft (55-m)
long by 45-ft (14-m) wide contaminant plume extending to the east. The
cooling water had moved through 30 ft (9 m) of porous sandy soil to contami-
nate groundwater. At the start of the project, average ethylene glycol concen-
tration in groundwater was 1440 ppm (n = 20, s = 132 ppm). Approximately
85 to 93% of the ethylene glycol was removed from ground~ater within the
first 26 days of biological treatment. By the completion of the project, ethylene
glycol was reduced to below the analytical limit of detection (LOD = 50 ppm)
in all production wells at the site.
0.87 311-740-61941$0.00+S.50
C 1994 by Lewis P11blishers 491
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492 BIOREMEDIATION: FIELD EXPERIENCE
Ethylene glycol has been shown to support microbial growth under aerobic conditions.'_. The aerobic metabolism of ethylene glycol is relatively common. and the pathways of its metabolism are known.<-11 Caskey and Taber demon-strated that the most likely pathway of ethylene glycol catabolism by bacterium T-52 was sequential oxidation to glycolate and glyoxylate.5 By reaction with acetyl-CoA, glyoxylate would form malate, a TCA cycle intermediate. Anaerobic metabolism of ethylene glycol has been reported by Dwyer and Tiedje.12 Using a sewage sludge inoculum under methanogenic conditions, ethylene glycol was converted to ethanol, acetate, and methane. The ethanol produced was further oxidized to acetate, with methane as the final end product. Clostridium glycolicum fermentation of ethylene glycol has been shown to yield equimolar amounts of acetate and ethanol.13 The metabolism of ethylene glycol by Flavobacterium sp. under microaerophilic conditions fol-lows the sequence acetyl-CoA, acetylphosphate, and acetate.11 Thus, ethylene glycol mineralization can occur in both ae~obic and anaerobic environments.
LABORATORY TflEATABILITV STUDY
The objective of the laboratory study was to determine the potential to biologically remediate ethylene glycol contamination in groundwater at the site. Prior to initiation of the laboratory study, the following screening analyses were performed on representative soil and groundwater samples collected at the site:
• ethylene glycol
heavy metals (As, Cd, Cr, and Pb)
heterotrophic bacterial population density ; pH
NH4-N and P04-P available mineral nutrient concentrations
Ethylene glycol concentration in groundwater was determined by direct aque~us injection into a Hewlett-Packard 5880 gas chromatograph (GC) (Hewlett-Packard Co., Palo Alto, CA), equipped with a 30-m DB-5 fused silica capillary column (Supelco Inc., Bellefonte, PA) and a flame ionization detector (FID). The limit of detection for the method was 50 ppm in water. Based on analytical results for 20 groundwater samples collected within the spill area and contaminant plume, average ethylene glycol concentration within the treatment zone at the site was 1440 ± 132 ppm (x ± s). Those samples were composited equally by volume and were used to determine biodegradation potential of ethylene glycol.
Appreciable concentrations of heavy metals, as determined by atomic absorption spectrophotometry, were not detected in any of the groundwater samples analyzed (As <0.05 ppm, Cd <0.5 ppm, Cr <l ppm, and Pb <5ppm). Laboratory analyses also· indicated that the soil/groundwater environment
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ETHYLENE GLYCOL-CONTAMINATED GROUNDWATER 493
contained a viable bacterial population. Groundwater samples were found to contain bacterial population densities ranging from I02 to IO" colony-form-ing units (cfu) per milliliter (mL). Population densities in the soil samples collected within the spill area ranged from IO' to 106 cfu/g oven-dry soil. Those results suggested that the environment was not toxic to bacterial growth.
Analytical results from laboratory analyses also indicated that pH adjust-ment and NH4-N and PO,-P nutrient addition would be necessary for biological treatment of ethylene glycol at the site. The average (geometric mean) pH of the 13 samples analyzed was 4.5. The heterotrophic bacteria responsible for the biodegradation of most spilled organic compounds generally have an optimum pH range for growth between 6.0 and 8.0, with minimum and maximum values of 4.5 and 9.0, respectively.14 Inorganic nitrogen is assimilated during micro-bial growth and is required in quantities approximately 10 times greater than phosphorus. 15
In addition to the screening analyses, groundwater samples collected from four representative wells within the spill area were extracted and analyzed utilizing U.S. EPA Method 625-Base/Neutrals, Acids, and Pesticides (Federal Register, December 3, 1979). Gas chromatographic techniques were used to analyze the samples. Significant extractable contaminant concentrations (<0.5 ppm) were not detected in any of the groundwater samples analyzed. The electrolytic respirometer (A.RF. Products, Raton, NM) and static flask culture techniques were used to establish biodegradation potential and to define biodegradation rate of ethylene glycol in the composite groundwater sample. Electrolytic respirometer treatment vessels (Figure I) were prepared according to the procedures of Young and Baumann.16 The static flask techniques have been previously described.17-18 Analytical results obtained using those tech-niques were similar to those acquired with the electrolytic respirometer. The electrolytic respirometer provided a direct and continuous measurement of oxygen uptake by indigenous microbial populations within closed treatment vessels, with oxygen generated within the closed system. Oxygen uptake by indigenous· microflora was a direct measurement of biodegradation taking place within the groundwater matrix.
The experimental design for the biodegradation study is presented in Table I. Vessel I demonstrated the biodegradation potential of ethylene glycol by indigenous microflora already present in groundwater at the site. A comparison of the rates of oxygen uptake in vessels 2 and 3 was utilized to determine if significant quantities of substances toxic or inhibitory to microbial growth existed in groundwater at the site. Vessel 4 served as an abiotic control to quantify nonbiological loss of ethylene glycol from treatment vessels. The final volume in each treatment vessel was I L.
Ammonium nitrate was added to each treatment vessel to a final concen-tration of 1.0 g/L to provide the inorganic nitrogen necessary to support microbial growth. To inhibit nitrification, JO mg of 2-chloro-6-
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494 BIOREMEDIATION: FIELD EXPERIENCE
GLASS FIBER WICK
OXYGEN
ELECTRODE-----~
SWITCH ElEC1'ROOE
Figure 1. An electrolytic resplrometer treatm8nt vessel.
H\'OROGEN ElECTRODE
TREATMENT
VESSEL
KOH
SOLlffiON
STIR BAR
(trichloromethyl) pyridine (TCMP) was added to treatment vessels. Oxygen uptake was, therefore, the result of a carbonaceous demand. Sodium dihydrogen phosphate (monohydrate) neutralized to pH 7.2 with-potassium hydroxide served as a buffer and as a source of PO,-P 10· support enhanced growth on ethylene glycol. The phosphate salt was added to each treatment vessel to a final concentration of 0.02 M.
Glucose was added to a final concentration of· 1.0 g/L in the toxicity/ inhibition·control (vessels 2 ·and 3). The abiotic control receiv~d the microbial poisons HgC12, KCN, and NaN, to respective final concentrations of 100, 320, and 320 ppm.19 Stirring speed in each treatment vessel was adjusted to maintain a 3-in. vortex.
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ETHYLENE GLYCOL-CONTAMINATED GROUNDWATER 495
Table 1. Experimental Design for Treatments In Electrolytic Resplrometer
Treatment Vessels Used to Determine Biodegradatlon Potential of
Ethylene Glycol In the Composite Groundwater Sample
Vessel number
2
3
4
Treatment
Natural bacterial flora
Groundwater + basal salts + TCMP
Toxicity/inhibition control
Groundwater + basal salts + TCMP + glucose
Laboratory grade water + basal salts + TCMP + glucose
+ inoculum of indigenous bacteria
Ablotic control
Groundwater + basal salts + TCMP + poisons
Biochemical oxygen demand (BOD) for the composite groundwater sample in
vessel I is presented in Figure 2. A loss of ethylene glycol was not observed in the
abiotic control (vessel 4). The theoretical oxygen demand (ThOD) for aerobic
mineralization of ethylene glycol was calculated from the following relationship:
2000
1500
~ 0 OU 0~
Q]C,'i'
1000 al w n. ~~~
J;;
500
0
2(CH20H)2 + 5 0 2 = 4 CO2 + 6 H20
•
• • • •
•
10
DAYS
... •
20
• TOTAL BOD n .. 40
r2 .. 0.959 BOO a 1740 -4460e -O.JOOI
• ETHYLENE GLYCOL
" -5 r2a 0.813
In C • In 44100 -0.799t
30
Figure 2. Ethylene glycol concentration and total BOD as a function of time In an
electrolytic respirometer treatment vessel (vessel 1) containing the composite
groundwater sample.
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496 BIOAEMEDIATION: FIELD EXPERIENCE
ThOD is 1.29 mg 0,1mg of ethylene glycol. With an initial concentration of 1440 mg/L ethylene glycol, 1860 mg 0 2 would be required for complete oxidation. The ultimate BOD (BODu) in the composite groundwater sample in vessel I was determined by fitting oxygen uptake data to a modified crescent curve:20
BOD = A + Be -Kl
where BOD = the amount of BOD expressed at time t (ppm) .
A
B
K
= =
= =
BO Du, the ultimate amo•nt of oxygen uptake to be expressed (ppm) a lag period parameter (ppm) (Note: IA/= /Bl if the fitted crescent curve intersects the origin)
the first-order rate constant (day -1) time (days)
BOD~ is defined as the total amount of oxygen required to biodegrade the immediately available organic matter present in a sample." Using the following relationship, ii was calculated that 94% of the ThOD for ethylene glycol biodegradation was met:
(BODu/ThOD) 100
Those results suggested that ethylene glycol was completely oxidized to carbon dioxide and water without the accumulation of incomplete oxidation products. With a BODu of 1700 ppm, an estimated minimum of 170 ppm NH,-N and 17 ppm PO,-P would be required to prevent nitrogen and phosphorus from lim-iting microbial growth during biological treatment." Bi_odegradation of ethylene glycol by indigenous microtlora in the compos-ite groundwater sample (vessel I) was assumed to be first-order (Figure 2).21 The first-order rate constant was determined by linear regression using least squares. The lack of a significant lag period in both oxygen uptake and ethylene glycol deg(adation indicated that the indigenous microtlora were adapted to ethylene glycol. The groundwater appeared to be slightly stimulatory to bac-terial growth, as evidenced by the slightly greater rate of oxygen uptake in the composite groundwater sample compared to the glucose-basal salts control (Figure 3). Initial oxygen uptake data in vessels 2 and 3 of the toxicity/ inhibition control (Table I) were compared. On a semilog plot, a comparison was made of the slopes of the line-of-best-fit through the linear portion of the natural log transformed oxygen uptake data. In the linear portion of the semilog plot, the rate of oxygen uptake in the glucose-containing·composite groundwater sample was 1.2 times greater than in the glucose-basal salts control. Evidence for an environment toxic or inhibitory to microbial growth was, therefore, not found.
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ETHYLENE GLYCOL-CONTAMINATED GROUNDWATER
1000
900
800
700
600
500
:, 400 a. ec,
0 0 "' 300
~
500
100
0 10
.... -.---•·· VESSEL J
• COMPOSITE GROUND WATER SAMPLE + BASAL SALTS + GLUCOSE
n -7
r2• 0.998
In 800 -In 99.4 + 0.0557t
■ BASAL SALTS + GLUCOSE + MICROBIAL INOCULUM
n -7 r2-.. 0.999
In BOD -In 88.1 + 0.0479t
·20 JO 40 50 60
HOURS
497
Figure 3. Total BOD as a function ol time In the composite groundwater sample
containing glucose (vessel 2) and In a glucose-basal salts control (vessel 3).
Evaluation of treatability study results indicated that in situ biological
treatment was a viable option for remediation of ethylene glycol contami-
nation in the spill area and in the contaminant plume. The management
approach for the project would be to enhance the natural biodegradation
rate.
FIELD IMPLEMENTATION
Biological treatment at the site was divided into a 14-day operational phase,
a 3-month monitoring phase, and a 9-month maintenance program. The opera-
tional phase was primarily designed to provide maximum recovery and treat-
ment of ethylene glycol in soil and groundwater, both within the spill area and
within the contaminant plume (Figure 4). Initial efforts during that phase also
addressed the highly contaminated soil below the storage lagoon. The monitor-
ing program was designed to assess the ethylene glycol degradation rate in
groundwater following nitrogen and phosphorus mineral nutrient addition, pH
adjustment, and enhanced microbial growth. The maintenance program was
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498
/J. RECOVERY WELL
O SOIL BORING
e SOIL BORING/MONITOR WELL
BIOREMEDIATION: FIELD EXPERIENCE
s C A L C
TO 20 MET£RS
S C AL E
0
Figure 4. Schematic of the cooling water storage lagoon and the contaminant ground water plume.
designed to provide an environment suitable for continued biological treatment of any residual ethylene glycol remaining in the groundwater environment. Ethylene glycol had contaminated the vadose zone in the spill area, where it was retained through capillary action. The highest concentration detected in that zone was 4900 ppm. Surface contamination was also identified following analysis of shallow samples (0 to 2 ft; 0 to 0.6 m) collected adjacent to the storage lagoon. The second zone of contamination was the groundwater. Groundwater samples within the spill area had ethylene glycol concentrations . ranging as high as 2 I 00 ppm. Monitoring wells were installed to provide sampling points, and subsequent analyses indicated significant groundwater contamination. A downgradient contaminant plume was identified east of the lagoon. The plume was estimated to be 180 ft (55 m) long by45 ft (14 m) wide. A two-phased technical approach was implemented to deal with both soil and groundwater contamination. Using injection and recovery wells, initial effons addressed the highly contaminated soil underlying the storage lagoon. The second phase of the operation focused on groundwater cleanup and was implemented to prevent further migration of contaminated groundwater and to treat any contamination that would be released during treatment of the unsaturated zone.
The injection system was used to adjust pH of the soil/groundwater environ-ment, as well as to provide the oxygen and nitrogen/phosphorus mineral nutrients required to suppon enhanced microbial growth on ethylene glycol. The recovery
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ETHYLENE GLYCOL-CONTAMINATED GROUNDWATER 499
system withdrew contaminated water from the ground for above-ground treat-
ment in a biological treatment system. Effluent from the treatment system was
then reinjected into the vadose zone, creating a closed-loop system. Aow rate
through the system approximated 20 gal/min (76Umin). Biodegradation of the
spilled ethylene glycol took place in the soil/groundwater environmen~ as well
as aboveground in the biological treatment system.
Based on information obtained from site investigations conducted by NA WC
and OHM personnel, five recovery wells were installed to recover contami-
nated groundwater (Figure 4). These recovery wells were positioned near the
lagoon to provide zones of attraction for injected water. Two recovery wells
were positioned east of the lagoon to recover contaminated water from the
contaminant plume and to aid in the distribution of the reinjected water into
that area.
Following pH adjustment of and mineral nutrient and oxygen additions to
recovered groundwater in the above-ground treatment system, effluent from
the system was incorporated into a three-phase injection system. A lagoon
injection system was employed to flush contaminated soil and thereby transfer
contaminated water to the three recovery wells located in the vicinity of the
lagoon. The plume injection system was similar to the lagoon system in both
construction and operation. The primary functions of the plume injection
system were to enhance microbial growth· through pH adjustment and mineral
nutrient/oxygen addition and to create a gradient from the fringe of the plume
toward the two recovery wells located at the center of the contaminant plume.
The third injection system was implemented through surface application. Sur-
face application was primarily used in the lagoon area to flush the unsaturated
zone and to enhance microbial. growth in the contaminated soil.
The biological treatment system was designed to reduce ethylene glycol using
the indigenous bacterial flora (Figure 5). Nitrogen and phosphorus mineral
nutrient additions and pH adjustments were made to the recovered groundwater
through the use of a premix tank to the bioreactor. From the bioreactor, the
treated groundwater was pumped into a settling chamber. A portion of the settled
sludge was recycled into the bioreactor with the remainder used, as needed, in the
three-phase injection system.
Throughout the operational phase, treatment system and recovery well
samples were analyzed for aerobic heterotrophic bacteria, pH, dissolved oxy-
gen, inorganic nitrogen and phosphorus nutrient concentrations, and ethylene
glycol. Based on the results of those analyses, environmental parameters were
modified on an as-needed basis to maintain an enhanced rate of biological
treatment in the soil/groundwater environment. During the monitoring phase,
those same parameters were quantified on a monthly basis from recovery well
samples.
In those initial phases of treatment, ethylene glycol concentrations in two
plume recovery wells were reduced from 690 and 420 ppm io below the limit of
detection (LOD = 50 ppm) within 26 days of treatment. These represent >92 and
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500 BIOREMEDIATION: FIELD EXPERIENCE
RECOVERY WELLS AERATED >-------, INJECTION SYSTEt,j BIOREACTOR
RETURN SLUDGE WASTE SLUOCE FOR SURFACE APPLICATION
Figure 5. Process flow diagram for aboveground biological treatment of ethylene gly· col-contaminated groundwater.
88% reductions in ethylene glycol concentrations, respectively. With the excep-tion of one monitoring phase data point (day 40), ethylene glycol concentration remained below the detection limit. As shown in Figure 6, following adjustment, groundwater pH was maintained with an optimum range for bacterial growth (i.e., pH 6 to 7). In response to pH adjustment and mineral nutrient/oxygen addition to the contaminated groundwater environment, bacterial population density increased more than a millionfold. Following remediation of that environment, bacterial population density began to return to background levels. In the two downgradient recovery wells adjacent to the storage lagoon, concentrations of ethylene glycol in groundwater were reduced by >85 and 92% within the first 26 days of treatment (Figure 7). Initial concentrations were
2000 • CTHYl..ENE GLYCOL 12
0 8ELOW OETECTION LIMIT
,.
■ MJCROBW. POPIJI..A,TIQN • 1000
10f A,H 0 " 1 ~ a-~ 800 , m" 10 f Iffi
o" I tJ
6 ai ~ • 600
h ~o ' i ~o
~ ~~ 400 • • 0 " ~ 200
2 •
0 0 0 20 40 " " 100 120 435
OA,s
Figure 6. Ethylene glycol concentration, aerobic heterotrophlc bacterial population density, and pH as a function of time for a contaminant plume production well.
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ETHYLENE GLYCOL-CONTAMINATED GROUNDWATER 501
2000 • ETHYLENE GLYCOL " ,. 0 BELOW DETECTION UMIT
■ MICROBIAL POPULATION
10 f 1000 • pH 0
" ,-~ • o-
!!, 800 8 ~ ~
J
10 0 X ffi
~ u"
i 0 600 ~ 6 iii 2
i
~u
• ~g
'°" • t-• r' 0
' • " >
200 2
•
0 0
0 20 40 6-0 80 ,00 '20 .,,
DAYS
Figure 7. Ethylene glycol concentration, aerobic heterotrophlc bacterial population
density, and pH as a function of time for a downgradient spill area production
well.
3400 and 1110 ppm, respectively. In the one upgradient recovery well adjacent
to· the lagoon, ethylene glycol concentration had increased from 100 ppm on
day Oto 880 ppm by Day 13. From that peak on Day 13, monitoring data had
shown a continued decrease in ethylene glycol concentration. That increase in
ethylene glycol concentration reflected the project's aggressive operational
phase, in which the injection system had flushed pockets of contamination
from the unsaturated zone into groundwater for recovery and treatment. As in
the contaminant plume, following pH adjustment and mineral nutrient/oxygen
addition, bacterial population density in the spill area increased more than a
millionfold and began to return to background levels following biological
treatment of ethylene glycol.
The maintenance program, which was manned by NA WC personnel, focused
on removal of those remaining pockets of contamination, particularly in the spill
area. As part of that program, both limestone and diarnmonium phosphate were
applied to the soil surface in the lagoon and contaminant plume areas, and
oxygen was sparged into groundwater through the recovery wells to maintain an
aerobic groundwater environment. Limestone was added to maintain the pH of
·the soil/groundwater environment within a range favorable for enhanced bacte-
rial growth. Diarnmonium phosphate, a readily available source of nitrogen and
phosphorus, was added to support enhanced growth on ethylene glycol.
By the completion of the project, ethylene glycol was reduced to below
detection limits in all production wells at the site. Analytical results a_fter 435
days of biological treatment for soil and groundwater at the site assured
compliance with all regulations concerning contamination. The project cost
was $91,700 (U.S.).
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502 BIOREMEDIATION: FIELD EXPERIENCE
ACKNOWLEDGMENTS
For preparation of this paper, the authors would like to thank Laura L. Duhigg, who prepared the figures, and Anne L. Hermiller, who did the typing.
REFERENCES
I.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15 .
16.
17.
Claus, D. and W. Hempel. "Specific Substrates for Isolation and Differentiation of Azotobacter vinelandii," Arch. Microbiol. 73:90-96 (I 970). Fincher, E.L. and W J. Payne. "Bacte,ial Utilization of Ether Glycols," Appl. Microbiol. 10:542-547 (1962).
Gonzalez, C.F., W.A. Taber, and M.A. Zeitoun. "Biodegradation of Ethylene Glycol by a Salt-Requiring Bacterium," Appl. Microbiol. 24:911-919 ( 1972). Thelu, J., L. Medina, and J. Pelmont. "Oxidation of Polyoxyethylene Oligomers by an Inducible Enzyme from Pseudomonas P400," Fed. Eur. Microbial. Soc. Microbiol. Lett. 8:187-190 (1980).
Caskey, W.H. and W.A. Taber. "Oxidation of Ethylene Glycol by a Salt-Requir-ing Bacterium," Appl. Environ. Microbiol. 42:180-183 (1981). Child, J. and A. Willetts. "Microbial Metabolism of Aliphatic Glycols. Bacterial Metabolism of Ethylene Glycol," Biochim. Biophys. Acta 538:316-327 (1978). Harada, T. and Y. Nagashima. "Utilization of Alkylether Compounds by Soil Bacteria," J. Fermentation Technol. 53:218-222 (1975). Jones, N. and G.K. Watson. "Ethylene Glycol and Polyethylene Glycol Catabo-lism by a Sewage Bacterium," Biochem. Soc. Trans. 4:891-892 (1976). Pearce, B.A. and M.T. Heydeman. "Metabolism of Di(ethylene glyco1)[2-(2'-hydroxyethoxy)ethanol] and Other Short Poly(ethylene glycol)s by Gram-Nega-tive Bacteria," J. Gen. Microbiol. I 18:21-27 (1980). Wiegant, W.M. and J.A.M. De Boni. "A New Roule for Ethylene Glycol Me-tabolism in Mycobacterium E44," J. Gen. Microbiol. 120:325-331 (1980). Willetts, A. "Bacterial Metabolism of Ethylene Glycol", Biochim. Biophys. Acta 677: 1.94-199 ( I 98 I).
Dwyer, D.F. and J.M. Tiedje. "Degradation of Ethylene Glycol and Polyethylene Glycols by Methanogenic Consortia," Appl Environ. Microbiol. 46: 185-190 ( I 983). Gaston, L.W. and E.R. Stadtman. "Fertnentation of Ethylene Glycol by Clostridium glycolicum sp. N," J. Bacteriol. 85:356-362 (1963). Atlas, R.M. and R. Bartha. Microbial Ecology: Fundamentals an.d Applications, 2nd ed. (Reading, MA: The Benjamin/Cummings Publishing Company, Inc., 1987).
Mitchell, R. Introduction to Environmental Microbiology (Englewood Cliffs, NJ: Prentice-Hall, Inc., 1974) ..
Young, J.C. and E.R. Baumann. "The Electrolytic Respirometer. I. Factors Affecting Oxygen Uptake Measurements," Water Res. I0:1031-1040 (1976). Flathman, P.E., D.E. Jerger, and L.S. Bottomley ... Remediation of Contaminated Ground Water Using Biologi_cal Techniques," Ground Water Monitoring Rev. 9(1):l05-119 (1989).
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ETHYLENE GLYCOL-CONTAMINATED GROUNDWATER 503
18. Flathman, P.E., J.R. Quince, and L.S. Bottomley. "Biological Treatment of
Ethylene Glycol-Contaminated Ground Water at Naval Air Engineering Center,
Lakehurst, New Jel"Sey," in Proceedings of the Fourth National Symposium and
Exposition on Aquifer Restoration and Ground Water Monitoring (Dublin, OH:
National Water Well Association, 1984), pp. 111-119.
19. Liu, D., W.M.J. Stracham, K. Thomson, and K. Kwasniewska. 'Tietennination
of the Biodegradability of Organic Compounds," Environ. Sci. Technol. 15:788-
793 (1981).
20. Shammas, N.C. Modified Crescent Curve Fitting, Program Number 34IC,
Users' Library, Hewlett-Packard Co., Corvallis, OR, 1984.
21. Larson, R.J. "Role of BiodegradatiOn Kinetics in Predicting Environmental
Fate," in Biotransformations and Fate of Chemicals in the Aquaric Environment,
A.W. Maki, K.L. Dickson, and J. Cairns, Jr., Eds. (Washington, DC: American
Society for Microbiology, 1980), pp. 67-86.
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Attachment 8
Data Analysis Report from Robert C. Borden, PE, Ph.D.
Kubal-Furr & Associates
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Analysis of Monitored Natural Attenuation Parameters at
Ticona/Celanese Facility in Shelby, NC
Robert C. Borden, PE, Ph.D.
5017 Theys Road, Raleigh, NC 27695
December 19, 200 I
An analysis was performed to evaluate the likely impact of monitored natural attenuation
on the migration of dissolved ethylene glycol (EG) in groundwater in the event that the
Inner Tier extraction wells system was temporarily or permanently shut down. Chemical
and biological parameters indicative of contaminant biotransformation processes were
monitored in 34 wells at the Ticona/Celanese facility in Shelby, NC in September 2001.
Parameters monitored included alkalinity, carbon dioxide (CO2), carbon monoxide (CO),
chloride (Cl), ethylene glycol (EG), total organic carbon (TOC), dissolved oxygen (DO),
nitrate-nitrogen (NO3-N), total manganese (Mn), ferrous Iron (Fe[II]), sulfate (SO4),
sulfide, methane, (CH4), ethane, ethene, total aerobic plate count (aerobes), total
anaerobic plate count (anaerobes), total Kjeldahl nitrogen (TKN), ammonia-nitrogen
(NH4-N), total phosphorus (TP), pH, redox potential (redox), and specific conductivity.
The monitoring data were reviewed to identify parameters indicative of the rate and or
extent of EG biotransformation in the subsurface. EG is readily biodegradable under
both aerobic and anaerobic conditions. However the extent of aerobic biodegradation in
the aquifer will likely be limited by the relatively high concentrations of EG present and
the low rate of oxygen transfer to most aquifers. In general, aquifer conditions are
appropriate to support a variety of anaerobic biotransformation processes including
reduction of nitrate, manganese, iron, and sulfate and methanogenic fermentation.
However the actual significance of specific biotransformation processes will be limited
by the availability of appropriate electron acceptors.
Figures 4 to 9 show the variation in indicator parameter concentrations with ethylene
glycol (EG) concentration in monitoring wells where measurements are available. When
a parameter is less than the analytical detection limit, the result is plotted at the detection
limit on the appropriate plot. In all of the plots, there is a large cluster of measurements
at 5 mg/LEG which is the analytical detection limit for EG.
There is no clear relationship between groundwater dissolved oxygen (DO) and EG
concentrations with very high and low DO measurements throughout the full range of EG
concentrations (Figure I). This kind of pattern is extremely unlikely given the very rapid
aerobic bi ode gradation of EG and the strong evidence for anaerobic biodegradation in
Figures 2 to 6 (discussed below). We believe there were problems with DO measurement
procedure and many if not all of the DO measurements are not valid. Errors in DO
measurement can be associated with problems with the commonly available DO meters
and with oxygen introduction from the atmosphere during sampling.
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In contrast to DO, there is a very clear and distinct relationship between nitrate and EG in
groundwater (Figure 2). Whenever EG is present above the analytical detection limit of 5
mg/L, nitrate has been depleted to less than 0.5 mg/L. This is strong evidence that EG is
being anaerobically degraded in the subsurface using nitrate as the terminal electron
acceptor.
There is also strong evidence for EG biodegradation using manganese (Figure 3) and iron
(Figure 4) as terminal electron acceptors. The oxidized form of manganese is essentially
insoluble. However EG biodegradation using manganese (Mn) as the electron acceptor
converts the solid, oxidized Mn to soluble, reduced Mn +l which is then detected in
monitoring wells. The very high concentrations of Mn observed in \veils with high EG
concentrations indicate that Mn is an important electron acceptor at this site. A similar
process occurs with iron (Fe) where bacterial degradation ofEG results in the conversion
of insoluble ferric iron (Fe[III]) to soluble ferrous iron (Fe[II]). In this project, Fe[ll]
concentrations were measured using a field test kit with a maximum measurable
concentration of 10 mg/L. As a consequence, it is not possible to evaluate the relative
importance of Fe reduction in comparison to Mn reduction. At many sites, Fe is a more
important electron acceptor than Mn suggesting that dissolved Fe concentrations maybe
comparable to the Mn concentrations.
The monitoring data indicates that in a substantial portion of the aquifer, EG is being
biodegraded using sulfate as a terminal electron acceptor (Figure 5). Sulfate is only
present in high concentrations when EG is below the analytical detection limit and sulfate
declines to less than 5 mg/L when EG is between 7 and 1000 mg/L. When EG is greater
than 1000 mg/L, this appears to correspond with an increase in sulfate. The reason for
this apparent increase is not clear. One possibility is that very high EG concentrations
slow or inhibit sulfate reduction. A second possibility is that high EG concentrations
interfere with the sulfate measurement technique resulting in a positive sulfate
measurement when sulfate is actually below detection. In future sampling, samples with
know sulfate concentrations should be spiked with EG to determine if there is an
interference in the analytical technique.
The groundwater monitoring data indicate that EG is being biodegraded producing
methane in the most highly contaminated portions of the aquifer (Figure 6). An initial
review of the monitoring data suggested that methanogenic fermentation might be
inhibited in this aquifer by the low pH (4.9 to 6.1) since methanogenic processes often
slow below a pH less than 7. However the groundwater monitoring data show that the
groundwater is completely saturated with methane in the areas with high EG indicating a
very active methanogenic population. The actual extent of methanogenic fermentation of
EG'riThy'be greater than that shown in Figure 6 since any additional methane produced
will be released from the groundwater as bubbles of methane gas.
Summarv and Recommendations for Future Work
There is strong evidence for the anaerobic biodegradation of ethylene glycol in the
aquifer at the CNA Facility by naturally occurring microorganisms. The most important
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evidence for these processes is changes in major electron acceptors and metabolic
products including nitrate, manganese, iron, sulfate and methane. In future sampling, an
analytical technique that can measure the full range of dissolved iron concentrations
should be used. In addition, the potential for ethylene glycol to interfere in the sulfate
analyses should be investigated. In the September sampling, dissolved oxygen
concentrations were not a useful indicator of biotransformation processes, possibly due to
issues with the field instrumentation or sample exposure to atmospheric oxygen. These
issues should be resolved or the dissolved oxygen measurements should be eliminated.
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Figure 1
Figure 2
10
9 ::r 8 c,
.§. 7
C:
QJ 6 Cl >, 5 )(
0
"O 4
... ...
•
1 ... ...
~ ... ...
i. -QJ
.2 3 . ...
0 II) 2 .!!1 -t ... -•
Cl . -
0
1 10 100 1000 10000 100000
Ethylene Glycol (rng/L)
Variation in dissolved oxygen concentration with ethylene glycol
concentration in MNA monitor wells.
14
12 -
-10 ..J c, 8 .§.
QJ 6 -"'
.. ... ;!: z 4
2
0 • .................. • • '
1 10 100 1000 10000 100000
Ethylene Glycol (rng/L)
Variation in nitrate concentration with ethylene glycol concentration in
MNA monitor wells.
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Figure 3
Figure 4
1000 • ...
J ... -Cl ... .§. 100 ., ...
"' ., ... C: "' Cl C: "' 10 :a;;
"' -t 0 I-...
10 100 1000 10000 100000
Ethylene Glycol (mg/L)
Variation in total manganese concentration with ethylene glycol
concentration in MNA monitor wells.
12
10 . . . . -------

-
J c, 8 .§.
C: 0 6 -= "' :,
0 4 ... ... . -., ...
2
0
10 100 1000 10000 100000
Ethylene Glycol (mg/L)
Variation in ferrous iron concentration with ethylene glycol concentration
in MNA monitor wells.
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Figure 5
Figure 6
:::r c,
.§. ., ... ~ :::,
V)
:::, a, .s .,
C:
"" .c: -.,
:.
150
125
100 •
75
50
25
0
10 100 1000 10000 100000
Ethylene Glycol (mg/L)
Variation in sulfate concentration with ethylene glycol concentration in
MNA monitor wells.
20
•• • 15
.
• • • • •
10 •
•
5 •
0 t
'
10 100 1000 10000 100000
Ethylene Glycol (mg/L)
Variation in methane concentration with ethylene glycol concentration in
MNA monitor wells.