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SUPERFUND TREATABILITT CLEARINGHOUSE ABSTRACT
Treatment Process: Biological - Aerobic and Anaerobic
Media: Soil/Generic
Document Reference: NUS Corporation. "Leetown Pesticide Site
Treatability Study." Four progress reports in
internal memorandum form. 62 pp. (total). Written
under EPA Contract. July 1986 - January 1987.
Document Type: Contractor/Vendor Treatability Study
Contact: William Hagel
Regional Project Manager
U.S. EPA - Region III
841 Chestnut Street
Philadelphia, PA 19107
215-597-9800
Site Name: Leetown Pesticide Site, Leetown, WV (NPL)
Location of Test: NUS, Pittsburgh, PA
BACKGROUND; This document is composed of a series of progress reports
pertaining to a bench-scale treatability study which utilized biodegrada-
tion to remediate pesticide contaminated soils (DDT and DDE) at the Leetown
Pesticide NPL site. Treatment consisted of aerobic, anaerobic and fungal
processes to biodegrade the DDT and DDE.
OPERATIONAL INFORMATION; Nutrients such as manure, sewage sludge and wood
chips were added to the soils to promote the growth of microbes capable of
degrading the pesticides. More than 400 biodegradation cells were used over
4 test periods. Efforts to control temperature, pH and moisture content
yere attempted during the study. One report states that DDT degradation
appears to take place at 35 under anaerobic conditions and that DDE
degradation takes place in acidic media. The microbes used in the test
were not specified but are indigenous to the site. Baseline DDT and DDE
levels were approximately 7,000 ug of DDT per Kg soil and 1000 ug of DDE
per Kg of soil.
An extraction procedure with hexane done on the soil to analyze for DDT
was criticized for being a quick and dirty extraction with no cleanup of
the extract. Other concerns reported were strongly sorbed compounds may
not be detected, interference from naturally occurring organic matter could
skew the results and lack of standard analytical protocols could introduce
extraneous variables into the data. Specific information pertaining to the
quantity or type of contaminated soils was not included in the report.
PERFORMANCE; In December of 1986 an analysis of variance (ANOVA) of the
results was conducted to determine if there is any statistically signifi-
cant difference between the various samples collected from each of the
different treatment cells and to determine if there is a significant
difference in DDT and DDE concentrations from one cell treatment to the
next. The ANOVA indicated there is no significant difference between the
3/89-21 Document Number: EZUU
NOTE: Quality assurance of data may not be appropriate for all uses.
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various cell configurations. Hence the average concentration calculated
for each cell configuration is representative of the population mean. A
review of the sampling data reported in the December 30th progress report
suggests that anaerobic vessels operating under incubated conditions
represented the best method of degrading DDT in the soils. The authors
report that the indigenous microbial populations can be used to degrade DDT
at the Leetown Pesticide Site. A preliminary estimate of the time for this
process to reduce DDT plus DDE to desired action levels of 300 ug/kg of
total DDT and metabolites was 8 months. Both DDT and DDE are degraded
under anaerobic conditions, and anaerobic vessels operating under incubated
conditions represent the best method of degrading DDT. Further work was
recommended on the toxicity and environmental mobility of the metabolites
present from the recommended composting scheme as well as controlled bench
and pilot testing.
No QA/QC procedures were reported; however, quality control issues
were discussed and this work was done under an EPA contract.
CONTAMINANTS;
Analytical data is provided in the treatability study report. The
breakdown of the contaminants by treatability group is:
Treatability Group
WOl-Halogenated
Nonpolar Aromatic
Compounds
CAS Number
50-29-3
72-55-9
Contaminant
l,l,l-trichloro-2,2-bis
(4-chlorophenyl)ethane
(4,4-DDT)
l,l-dichloro-2,2-bis
(4-chlorophenyl)e thene
(4,4-DDE)
3/89-21 Document Number: EZUU
NOTE: Quality assurance of data may not be appropriate for all uses.
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INTERNAL CORRESPONDENCE
TO: FILE DATE: JULY 9, 1986
FROM: *HKRT J. HUBBARDX$^ COPIES: D. BRENNEMAN
/ D. MACINTYRE
/ H. ROFFMAN
J. GEORGE
SUBJECT: LEETOHN PESTICIDE SITE TREATABILITY STUDY PROGRESS REPORT
EPA WORK ASSIGNMENT NUMBER 65-3152
NUS PROJECT NUMBER S794.14
A brief synopsis of the status of the Leetown Pesticide Site Treatablllty
Study follows:
t One hundred and thirty (130) reaction vessels (blodegradatlon cells) were
generated from June 25 through June 28, 1986.
t Twenty cells were deleted from the original scope of work as a result of
the offensive nature of the matrix (I.e., odlferous aerobic sewage sludge
cells were eschewed).
t Generation of all other cells proceeded without difficulty with the
following exception: gypsum was found to be an Inappropriate
acidification substance. On reexamlnation 1s Is recognized that this
salt (calcium sulfate) Is generated from both a strong base and a strong
add. Hence, the pH of the soil matrix achieved through addition of this
substance was 1n the neutral range (pH » 6.5). Aluminum sulfate was sub-
stituted as an ac1d1f1er. Aluminum Ions successfully compete with
hydronium Ions for available exchange sites. Soil reaction of pH * 4.5
was easily achieved through addition of aluminum sulfate.
0 The heat Input to the Incubation vessel was gradually adjusted until a
constant temperature of 94 °F was achieved. The aerobic reaction vessels
experienced loss of soil moisture over the first four or five days of the
study. This required addition of additional deionized water. This
moisture loss has been mitigated through capping. Mason jar Hds have
been placed loosely over the vessels. The lids are removed once dally
(during daily inspection) to Introduce new air to the vessels.
No loss of soil moisture 1s evident In the ambient (bench top) vessels.
The pre-humidified air supplied to the enclosures 1s working as planned.
To date, no evidence of gas generation 1s evident in any of the flooded
(anaerobic) vessels.
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t Evidence of growth of Microorganisms Is evident In a number of the
aerobic cells, however. Mycelium are apparent 1n a number of the pH *
4.5 cells (I.e., the fungal cells). A crusty substance similar to a
lichen 1n appearance has been noted In several of the pH * 7.0 cells.
Although no evidence of degradation will be available until the first
samples are analyzed In late July, the growth of the different organisms
under the different conditions appears promising.
The results for the Initial (t * 0) samples are attached. Note the
consistency 1n the results between replicates for each sample batch. This
Is considered an Indication that the mixing process was thorough and
adequate to assure statistically useful results.
A lab logbook 1s being kept that contains more detailed Information regarding
the study. I have learned that our laboratory has an NRC license, thus we
should have no difficulty 1n obtaining the radlolabeled pesticides for the
carbon 14 study. As Indicated 1n the work plan, this phase of the study will
not be undertaken until the results at the end of the first 30-day period
(approximately July 30) have been obtained. This should give us some Insight
as to which combination of variables warrants more explicit study.
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NUS
CORPORATION C-34-8-6-182
J&RK WEST TWO
TTSBUFIGH, PENNSYLVANIA 1 SE75-1 O71
C.4ia)7BB-1O8O
August 14, 1986
NUS Project No. S794.14
Ms. Laura Booranzian
Regional Site Project Officer
U.S. Environmental Protection Agency
Region III
841 Chestnut Street
Philadelphia, Pennsylvania 19107
Subject: Leetown Pesticide Site, WV
EPA Work Assignment No. 95-3L52.1
Treatabilty Study Status Meeting -
August 13, 1986
Dear Laura:
This correspondence includes a brief summary of the points raised during our
meeting on August 13, 1986, regarding the ongoing treatability study of
microbial degradation of pesticides in the Leetown Site soils. This meeting
was attended by the following:
Ms. Laura Boornazian EPA Region III Regional Site Project Officer
Dr. Richard Brunker EPA Region III Toxicologist
Mr. Robert Hubbard NUS Chemical Engineer, Technical Project Lead
Mr. John George NUS Project Manager
Dr. Brunker generally approved of the experimental set-up in the NUS
Laboratory Services (LSD) facility, and of the manner in which Mr. Hubbard had
documented the study thus far. One area of concern appeared to be the
assurance that soil reaction (pH) in the test cells was being adequately
maintained. NUS should verify that the buffers used remain effective in
maintaining the desired pH over the course of the study by periodic pH
measurements. In addition, NUS should validate the procedure used to
determine soil pH; in particular, NUS should investigate whether the quantity
of soil used in making up the slurry for pH testing has any bearing on the pH
measured. Cells should also be configured and exposed to sunlight to test the
utility of photolytic degradation of the pesticides as a treatment technology.
This will be done by placing soil in aluminum roasting pans, covered with a
celophane wrap and exposing them to sunlight with frequent mixing of the
soils.
Administratively, we agreed that NUS would continue the present study, with
sample collection from the cells at the end of August and during mid-
September, in anticipation of possible termination or interruption of the
study with the close of the REM/FIT Contract on September 30. The EPA trailer
which houses the GC used in analyzing the samples will be returned to the EPA
A Halliburton Company
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C-34-8-6-182
Ms. Laura Boornazian
U.S. Environmental Protection Agency, Region III
August 14, 1986 - Page Two
in mid-September. An adequate allowance will be made in scheduling sample
collection in September to ensure that these samples can be analyzed via the
EPA lab. NUS is investigating the possible use of a similar GC owned by NUS
and presently onsite in Michigan. Under REM III, use of this equipment
requires negotiation of a rental rate with EBASCO and the EPA.
Although preliminary quantitative results were incomplete from the analysis of
the first set of soil samples (t = 30 days), there appears to be some evidence
of decay in the initial pesticide concentrations in some of the cells. Final
preliminary quantitative results should be available by today. However,
adequate data are not expected to enable NUS to establish a time rate of decay
of the pesticides in order to determine whether the treatability study can be
terminated with sample collection in mid-September. The likelihood is that
at least some facet of the study will need to be continued beyond the end of
the present REM/FIT Contract. It will be necessary for us to discuss the
mechanism for transition of this work into REM III under EBASCO as soon as
possible to avoid interruption of the work. I realize, however, that no firm
commitments can be made by the Agency until the issue of Superfund
reauthorization is resolved.
We committed to submittal of a report of the initial and t = 30 days
analytical results within approximately two weeks.
The remainder of our meeting was devoted to a discussion of the experimental
protocols for the radio-isotope study. Dr. Brunker indicated that the
protocols presented by Mr. Hubbard, based on a search of the literature,
appeared to be appropriate to the study. The issue of what material to use to
trap the C0£ off-gas (e.g., potassium hydroxide, phenylethyl amine) should be
resolved by contacting applications personnel at New England Nuclear. NUS
should be aware that the C02 trapping material may react with the
scintillation cocktail to produce "chemoluminesence" which may result in
aberrant (high) scintillation counts. The occurrence of this phenomenon will
be evaluated initially by conducting "aged" counts on a single sample to see
if counts drop off after time, indicative of the phenomenon.
We then discussed the amount of the isotope to use. NUS will be obtaining
uniformly ring-labeled DDT and DDE. Approximately one micro-Curie of each
will be obtained. When ready for use, the radio-isotopes will be mixed with
distilled water and diluted to a concentration sufficient to produce about 100
counts per minute (cpm) in the C02 collected. The actual amount of the
isotope/distilled water mixture to be added to the soil samples will be
dependent upon the concentration of the mixture, the assumed decay rate (and
thus the labeled C02 generation rate) of the pesticides, and the interval over
which the C02 trap will remain in contact with the atmosphere in the reaction
vessel between scintillation counts. Mr. Hubbard will make the necessary
calculations after he has had an opportunity to review the initial analytical
results relative to the decay rate of the pesticides, and will submit them to
Dr. Brunker for review.
IMUS CORPORATION
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C-34-8-6-182
Ms. Laura Boornazian
U.S. Environmental Protection Agency, Region III
August 14, 1986 - Page Three
The estimated duration of the radio-isotope study will be about 30 days.
Counts will be made daily for the first week, and the interval between CO?
sample coll lections will be adjusted thereafter based on the data obtained. A
minimum of two replicates of each treatment cell will be configured.
Initiation of the study is anticipated by the week of August 25. With this
late date for initiation of the work, it is recognized that there is some risk
that the study may have to be aborted without final completion near the close
of the REM/FIT contract on September 30.
I understand from our conversation that EPA Region III is interested in having
NUS continue on this project in a design and construction capacity. This was
originally suggested in the context of the EPA "Contractor Continuity" Pilot
Program. In terms of additional work beyond the bench scale treatability
study, we discussed the need to engage in pilot-scale studies of the most
promising treatments, possibly in conjunction with further-refined bench scale
microbial degradation studies. It is possible that the pilot-scale studies
could be initiated this winter. It will be important in scheduling of such
studies, however, for us to be aware of the Superfund Comprehensive
Accomplishments Plan (SCAP) commitments for the Leetown Site regarding design
and construction.
Finally, I would like to take this opportunity to thank you and Dr. Brunker
for taking the time to overview the treatability study set-up and to provide
suggestions on the study.
Very truly yours, Approved for submission by:
John George David E. Maclntyre
Project Manager Regional Manager of Projects
JAG/jag
cc: Ed Shoener, EPA Region III
Richard Brunker, EPA Region III
Lisa Woodson, EPA Headquarters
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IMUS
CXDRPORATON
INTERNAL CORRESPONDENCE
C-34-8-6-384
TO:
FROM:
FILE
ROBERT J. HUBBARD/f^'
MTE: AUGUST 29. 1986
COPIES: D. BRENNEMAN
0. SENOVICH
D. NACIirTYRE
H. HOFFMAN
J. GEORGE
SUBJECT:
LEETOHN PESTICIDE SITE TREATABILITY STUDY - PROGRESS REPORT 12
EPA WORK ASSIGNMENT NUMBER 65-3L52
NUS PROJECT NUMBER S794.14
Reaction vessels were configured from June 25 through June 28, 1986 to study
the blodegradatlon of DDT and DDE by Indigenous soil microorganisms. The
Influence of pH, soil moisture, temperature, and various soil amendments on
the activity of such organisms was considered In devising the experimental
design. Additional details are Included 1n the file memo dated July 9, 1986
(C-34-7-6-113).
A sample was collected from each reaction vessel during the week of July 28,
1986. Samples were extracted and analyzed by Debra M. Schelb, using the gas
chromatograph 1n the mobile laboratory. Holding time requirements for
pesticide/FCB analysis (as specified under the EPA's Contract Laboratory
Program) were satisfied.
Baseline (t«0) concentrations were determined at the time the cells were
generated. The analytical results of the baseline analyses, as well as the
results of the first sampling round (t*30 days) are Included In the
attachments.
Table 1 summarizes average values of the "degradation ratio" for all of the
cell configurations (5 Individual cells comprise each configuration). The
degradation ratio was devised to facilitate a statistical analysis and 1s
simply the concentration of DDT and DDE at time t«30 days divided by the
concentration of the respective analyte at time t*0. Note that some of these
values exceed unity. This 1s considered evidence of the heterogeneous nature
of the pesticide contamination. However, Increases 1n DDE concentrations were
noted in a number of the anaerobic cells, and this 1s not believed to be
result of matrix effects (as discussed further below).
The results were subjected to a statistical treatment (Analysis of Variance)
to confirm or negate the null hypothesis (I.e., to determine 1f variance in
sample means was caused by random fluctuations attributable to sampling and
analysis). The results of the F-test indicated that variance 1n sample means
is significant 1n all of the sets at a minimum level of significance of 0.05.
Variance is significant in a number of the cells at much lower probability
levels (i.e., as low as 0.005). The statistical treatment 1s outlined in
detail in the attached sample calculation package. Table 2 summarizes
experimental F values and literature F values for each of the sample
populations considered.
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Although 1t 1s apparent that non-homogeneity of contamination 1n the soil
atrlx may have had some effect on the results, several trends are evident In
the analytical data that provide Information regarding the applicability of
various treatment techniques at the Leetown Site. Several of the treatment
cells displayed favorable results for the degradation of both DDT and DDE. The
composition of these cells will be used as a basis for configuration of cells
for additional study using radio-labeled pesticides (I.e., ring-labeled DDT
and DDE).
Results at 30 days should be considered an Initial Indication of the success,
or lack thereof, 1n achieving degradation. At this phase of the study only a
qualitative Indication of promising degradation avenues Is necessary.
Quantitative results will be provided by the carbon 14 study through
scintillation counts (1f complete mineralization occurs) or through thin layer
chromatography (If complete breakdown to carbon dioxide and water 1s not
observed).
Figure 1 displays a schematic representation of the experimental design.
Three main branches of the experiment are shown: a fungal degradation branch;
an aerobic bacterial degradation branch; and an anaerobic bacterial
degradation branch. The analytical results for each of these 1s discussed
briefly below.
Fungal Branch (pH«4.5)
Several of the cell configurations for this branch gave favorable results
for the degradation of both DDT and DDE. It was observed that the best
results occurred 1n the cells containing only the natural soil. A possible
hypothesis 1s that the presence of alternate food sources (such as the
organic material In manure) Inhibits the action of the low pH-favoring soil
microorganisms on the pesticide compounds. It appears that Increasing the
temperature of the vessels Is detrimental to the performance of the
organisms in these cells.
Aerobic Bacterial Branch (pH»7)
Favorable results were also observed In several of these cells. In contrast
to the fungal cells, microorganisms operating under these conditions aopear
to perform better 1n the presence of alternate food sources. It 1s
speculated that population growth 1s more pronounced for organisms 1n these
cells, and that they compete for any available organic molecules, including
the pesticides. It should be noted that most of the literature reports that
aerobic bacteria are Incapable of degrading DDT. However, It should be
recognized that these species reside in an area with high background levels
of these organochlorlne pesticides. They are expected to be at least
tolerant of these chemicals and have hopefully developed the capacity to
enzymatically degrade them.
Some indication that degradation 1s favorable at higher temperatures is
offered by the results. However, this evidence is not considered conclusive
at this time. Difficulties were experienced in maintaining the soil
moisture of the Incubated vessels, and deIonized water was added to the
cells on several occasions. Because of the problems with desslcatlon,
results may be less conclusive than those operating under ambient
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conditions. The ambient cells have not required the addition of moisture
during the period of study.
Anaerobic Cells
Degradation of DDT was evident In several of these cells and appears to
occur more rapidly at elevated temperatures. This 1s consistent with
observations 1n the lab. The Incubated anaerobic cells were generating gas
at a much earlier date than the cells at room temperature (most of the
ambient cells are still not evolving gas). DDE concentrations Increased 1n a
number of these cells (when contrasted with the baseline concentrations for
the amended soil matrix). This was also observed for DDT 1n a number of
the cells. For this reason It was considered likely that the baseline
concentrations were somewhat lower than the true values and therefore the
results from the thirty day samples were also contrasted with the baseline
concentrations for the natural soil. Although DDE concentrations were
generally lower when contrasted 1n this manner, they still did not Indicate
that any significant degradation has transpired. Overall, these results are
consistent with other studies that have shown DDE to be a predominant
degradation product of DDT under anaerobic conditions.
Summary
Based on the Initial results of the degradation study, the anaerobic branch
appears unsuitable for degrading both DDT and DDE. Some promise Is evident
for various aerobic configurations. The aerobic branches will be Included 1n
the radio-labeled pesticide study. Pending the concurrence of USEPA Region
III, the following cells will be configured for the second phase of the study:
low pH cells (I.e., pH approximately 4.5) without soil amendments and neutral
pH cells (both amended and unamended cells).
occ: Laura Boornazian (EPA Region III)
Richard Brunker (EPA Region III)
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TABLE 1
Page 1
LEETOWN PESTICIDE SITE, WV
MICROBIAL DEGRADATION TREATABILITY
DEGRADATION RATIO (DR)*
STUDY
Fungal Cells (pH=4.5)
Cell Matrix
Soil
Room Temperature
Soil
T=35°C
Manure (5J by weight)
Room Temperature
Manure (5X by weight)
T=35°C
Manure (10X by weight)
Room Temperature
Manure (10X by weight)
T=35°C
Manure & Wood Chips (51 by weight)
Room Temperature
Manure ft Hood Chips (5X by weight)
T=35°C
Manure & Hood Chips (101 by weight)
Room Temperature
Manure & Wood Chips (10* by weight)
DDT
0.23
0.25
0.48
0.35
0.66
1.31
0.38
0.47
0.54
1.06
DDE
0.10
1.67
0.17
0.35
0.19
1.36
0.11
0.18
0.34
1.23
T=35°C
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Table 1
Page 2
LEETOWN PESTICIDE SITE, HV
MICROBIAL DEGRADATION TREATABILITY STUDY
DEGRADATION RATIO (DR)
Anaerobic Cells (Flooded, pH-7)**
Cell Matrix DDT DDE
Soil 0.71 0.31
Room Temperature
Soil 0.198 0.70
T«35°C
Manure (5X by weight) 2.06 0.98
Room Temperature
Manure (5X by weight) 0.33 1.62
T«35°C
Manure (10* by weight) 2.69 0.97
Room Temperature
Manure (10* by weight) 0.31 1.52
T«35°C
Anaerobic Sewage Sludge 1.06 1.74
(5X by weight)
Room Temperature
Anaerobic Sewage Sludge 0.28 1.59
(5X by weight)
T=35°C
Anaerobic Sewage Sludge 1.16 1.43
(lOt by weight)
Room Temperature
Anaerobic Sewage Sludge 0.65 2.69
(101 by weight)
T=35°C
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Table 1
Page 3
LEETOWN PESTICIDE SITE, WV
MICROBIAL DEGRADATION TREATABILITY STUDY
DEGRADATION RATIO (DR)
Anaerobic Cells (Flooded, pH«7)***
Cell Matrix DDT DDE
Soil 0.71 0.31
Room Temperature
Soil 0.198 0.70
T=35°C
Manure (52 by weight) 0.53 0.3
Room Temperature
Manure (5X by weight) 0.084 0.49
T=35°C
Manure (10% by weight) 0.43 0.32
Room Temperature
Manure (10% by weight) 0.052 0.51
T*35°C
Anaerobic Sewage Sludge 0.22 0.36
(52 by weight)
Room Temperature
Anaerobic Sewage Sludge 0.059 0.33
(51 by weight)
T=35°C
Anaerobic Sewage Sludge 0.25 0.53
(10% by weight)
Room Temperature
Anaerobic Sewage Sludge 0.14 1.00
(10% by weight)
T=35°C
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Cell Matrix
Soil
Room Temperature
Soil
T=35°C
Manure (5X by weight)
Room Temperature
Manure (5X by weight)
T«35°C
Manure (10* by weight)
Room Temperature
Manure (101 by weight)
T*35°C
Table 1
Page 4
LEETOWN PESTICIDE SITE, WV
MICROBIAL DEGRADATION TREATABILITY STUDY
DEGRADATION RATIO (DR)
Aerobic Cells (pH«7)**
DDT
0.159
0.352
0.135
0.679
0.341
0.115
DDE
0.999
0.751
0.073
0.391
0.153^
0.10
Notes:
* - DR=(CODT 9 t * 30 days)/(CDDT 3 t * 0)
** - Results based on baseline concentration of amended soil
*** - Results based on baseline concentration of unamended soil
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TABLE 2
LEETOWN PESTICIDE SITE, HV
MICROBIAL DEGRADATION TREATABILITY STUDY
EXPERIMENTAL VERSUS LITERATURE F VALUES
POPULATION EXPERIMENTAL F LITERATURE F
Fungal Cells
Anaerobic Cellsj
(Amended Cone)
Anaerobic Cells?
(Unamended Cone)
Aerobic Cells
All Cells
(Using 1)
All Cells
(Using 2)
DDT
2.5
7.9
6.5
1.0
5.9
2.9
DDE
3.9
2.8
2.2
8.9
5.0
3.8
O.OS
2.12
2.12
2.12
2.62
1.70
1.70
0.01
2.89
2.89
2.89
3.90
2.12
2.12
0.00!
3.22
3.22
3.22
4.49
2.29
2.29
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PJUS
CXDRPORATOTSI
INTERNAL CORRESPONDENCE
C-34-9-6-43
TO:
FROM:
SUBJECT:
FILE
HUBBARD
LEETONN PESTICIDE S
TREATABILITY STUDY
PROGRESS REPORT 13
EPA WORK ASSIGNMENT NO
NUS PROJECT NO. 794.14
65-3L52
DATE: SEPTEMBER 29, 1986
COPIES: D. BRENNEMAN
D. SENOVICH
D. NACINTYRE
H. ROFFMAN
J. GEORGE
A third round of samples were collected from the Leetown treatablHty study
reaction vessels from September 5, 1986 through September 18, 1986. During
the analysis of these samples, problems were encountered because of
degradation of the chromatographlc column. The column was replaced
approximately halfway through the sampling and analysis program (September 12,
1986). This event extended the period of time necessary to complete the
analytical work. No adverse effects on the analytical results are anticipated
because of this problem.
Table 1 summarizes the analytical results for all samples collected to date.
Included on the table are baseline results, results for the second sampling
round at t » 30 days, and results for the third round at t » 60 days.
During the most recent round, results for some of the cells Indicated that
matrix effects are more severe than anticipated. The concentrations 1n
several samples collected during the third sampling round were noted to be
much higher than those determined during the second sampling round.
Difficulties were especially pronounced In the cells containing 101 manure by
weight (particularly those operating at the higher temperatures). The
problems with these cells are clearly attributable to matrix Interference
effects.
Table 2 presents a summary of the "degradation ratio" for both the t « 30 day
samples and the t 60 day samples. The degradation ratios are simply the
concentrations at t « 30 days and t * 60 days divided by the baseline (t * 0)
concentration. Several points are evident from the degradation ratios
presented 1n the table. It 1s apparent that the most promising results were
obtained from the cells containing no amendments whatsoever. As discussed 1n
Progress Report 12, this Is considered evidence that the best degradation
rates are achieved If alternate carbon sources are not available to the
microorganisms. In addition, 1t 1s also apparent that the cells operating at
ambient conditions also provide more favorable results. Difficulties
encountered In maintaining the moisture levels In the Incubated cells (T *
35°C) were not encountered 1n the cells operating at room temperature. It 1s
felt that more meaningful results will be generated with the cells operating
under ambient conditions. Since temperatures similar to those 1n the
Incubated cells (I.e., T - 35°C) will be difficult to achieve In the field, 1t
1s also felt that the ambient cells will provide results more consistent with
the ultimate field application of the process.
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C-34-9-6-43
MEMO TO: FILE
SEPTEMBER 29, 1986 - PAGE TWO
Based on the results achieved to date, the general conclusion has been reached
that the unamended samples (I.e., natural soil samples) operating at room
temperature display the most promise. Based on these Initial findings, a
decision has been made to focus the remaining study on certain cells rather
than on the entire group. During the fourth sampling round, samples will be
collected from only the unamended (or natural soil) cells. With the exception
of the anaerobic cells, only cells operating at room temperature will be
sampled. Thus a total of 4 sets of cells will be sampled. Because of the
desire to obtain more precise and representative results, 5 samples will be
collected from each of the Individual reaction vessels (5 vessels per
treatment configuration). Thus a total of 100 samples will be collected
during the fourth round. Similar samples will be collected during the 5th
sampling round If funds are available at that time.
Contrast of the results obtained during the 4th and 5th sampling rounds
originally proposed for October and November should provide final, conclusive
evidence that substantial degradation has occurred 1n the selected cells.
Prior to expiration of the REM/FIT contract, the materials for the **C study
were obtained. Labelled pesticides and blometrlc flasks were received from
Pathfinder Laboratories, Inc. and Bellco Glass Company, respectively. This
phase of the study will be Implemented as soon as adequate funds are available
to carry the 1sotop1c study to completion.
RJH/rjh
Att.
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TABLE 2
Page 1
LEETOWN PESTICIDE SITE, WV
MICROBIAL DEGRADATION TREATABILITY STUDY
DEGRADATION RATIO (DR)*
Fungal Cells (pH*4.5)
Cell Matrix
Soil
Room Temperature
Soil
T=35°C
Manure (5* by weight)
Room Temperature
Manure (5* by weight)
T=35°C
Manure (10* by weight)
Room Temperature
Manure (10* by weight)
T-35°C
Manure & Wood Chips
DDT
t=|g
0.23
0.25
0.48
0.35
0.66
1.31
0.38
t=60
7
0.27
0.32
2.12
0.871
5.71
0.28
DDE
0.10
1.67
0.17
0.35
0.19
1.36
0.11
t«60
§J&
0.77
0.36
4.50
0.93
7.87
0.27
(5* by weight)
Room Temperature
Manure & Wood Chips
(5* by weight)
T=35°C
Manure & Wood Chips
(10* by weight)
Room Temperature
0.47 0.71
0.54 0.60
0.18 0.66
0.34 0.60
Manure & Wood Chips
(10* by weight)
T=35°C
1.06 U
1.23 U
-------
Table 2
Page 2
LEETOWN PESTICIDE SITE, WV
MICROS I AL DEGRADATION TREATABILITY STUDY
DEGRADATION RATIO (OR)
Anaerobic Cells (Flooded, pH=7)
Cell Matrix DDT DDE
t=60 t«50 t=60
Soil 0.71 0.11 0.31 0.18
Room Temperature
Soil 0.20 0.08 0.70 0.28
T=35°C
Manure (52 by weight) 2.06 0.34 0.98 1.25
Room Temperature
Manure (5* by weight) 0.33 0.24 1.62 1.81
T=35°C
Manure (10* by weight) 2.69 2.48 0.97 0.93
Room Temperature
Manure (10t by weight) 0.31 0.26 1.52 1.13
A T=35°C
Anaerobic Sewage Sludge 1.06 0.54 1.74 0.55
(55 by weight)
Room Temperature
Anaerobic Sewage Sludge 0.28 0.28 1.59 1.65
(5% by weight)
T*35°C
Anaerobic Sewage Sludge 1.16 0.40 1.43 0.95
(10X by weight)
Room Temperature
Anaerobic Sewage Sludge 0.65 0.27 2.69 1.56
(10* by weight)
T=35°C
-------
Table 2
Page 3
LEETOWN PESTICIDE SITE, WV
MICROBIAL DEGRADATION TREATABILITY STUDY
DEGRADATION RATIO (DR)
Cell Matrix
Soil
Room Temperature
Soil
T=35°C
Manure (5% by weight)
Room Temperature
Manure (5X by weight)
T=35°C
Manure (10X by weight)
Room Temperature
Manure (10% by weight)
T=35°C
Aerobic Cells (pH=7)
DDT
t=30 t=60
0.16 0.20
0.35 0.41
0.75
1.20
2.28
5.81
DDE
t=
0.06
0.75
l.Z-9
t»60
0.25
1.15
0.36
2.06
1.16
7.06
Notes:
* - DR=(CDDT & t 30 days or t = 60 days)/(CDDT § t * 0)
U - results unavailable. Sample extracts Inadvertently destroyed.
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
REGION III
CENTRAL REGIONAL LABORATORY
839 BESTGATE ROAD
ANNAPOLIS, MARYLAND 21401
301-224-2740
FTS-922-3752
DATE ' November 26» 1986
SUBJECT: Leetown Pesticide Treatability Study Data
FROM
TO
THRU
Diana Pickens (3ES23)
Chemist
Laura Boornazian (3HW21)
Site Response Section
Patricia J. Krantz
Chief, Quality Assurance Section
As per your request, I have reviewed the data presented for t=0
to t=60 day from the Leetown Treatability Study. The information
you sent plus verbal input from John Austin is the basis for
this response.
The sample analysis done by NUS is a quick and dirty extraction
with hexane. No cleanup of the extract is done. The identifi-
cation of the pesticides is based on a one column confirmation.
Although cost effective, the risks of relying on this data are:
1. Strongly sorbed compounds may not be detected. DDT and
metabolites are likely to fall into this category. The reported
results may be low estimates of the actual concentration present,
?.. Lack of extract cleanup allows interferences from naturally
occurring organic matter to interfere with both identification
and quantitation of the target compounds.
3. Lack of standardized analytical protocol used in the mobile lab
may introduce extraneous variability into the data set.
The analyses which will be performed by CRL as a lab split may
provide some information to support the original feasibility design.
CRL will utilize an exhaustive soxhlet extraction protocol and any
necessary cleanups. The reported values will contain an estimate of
even highly-sorbed constituents without counting extraneous organic
matter as DDT or metabolites. If necessary, confirmation of the
presence of interferences after routine cleanups may be obtained
using an ion chromatograph at CRL. Since the data from the NUS-CRL
lab split will be obtained through entirely different protocols,
their results may not agree. Keep in mind that the data will be
useful to determine which modifications (if any), are appropriate
for future analytical work for this study.
-------
In addition to analytical comments, I offer the following feedback.
It is very difficult to see trends in the data using a table of
"degredation ratios". Page 4-9 discusses use of ANOVA. I strongly
recommend presenting the data using ANOVA. It is entirely possible
(and likely) that the values which appear to be "creating" DDT and/or
DDE are actually values containing false positives due to the organic
matter in the samples. I do not agree with the proposal to ignore
these study cells based on the information presented.
I recommend two action items to help define the quality of data in
the presented tables:
1. Description of actual methodology and routine QC performed in
the mobile lab; and
2. ANOVA results in tabular form.
These two pieces in addition to the results of the lab split will be
very beneficial in overall interpretation of the treatability data.
It may be appropriate to request ESO assistance in interpretation
once all the additional information is combined.
cc: John Austin (3ES21)
Rosemary Kayser
Deb Scheib , NUS Pittsburgh
DPrwbg
-------
NUS
CORPORATION
=ARK WEST TWO
CLIFF MINE ROAD
EITTSBURBH, PENNSYLVANIA 15275-1071
^wi2)7ae-ioao
December 10, 1986
NUSP/86-0293
NA
Ms. Laura Boornazian (3HW21)
U.S. Environmental Protection Agency
Region III
841 Chestnut Street
Philadelphia, Pennsylvania 19107
Subject: REM III PROGRAM - EPA CONTRACT NO. 68-01-7250
SUMMARY OF REVISIONS TO MICROBIAL INVESTIGATION
TREATABILITY STUDY FROM FINAL WORK PLAN (JUNE 1986)
Dear Laura:
Enclosed please find copies of the three Leetown Pesticide Site Treatability
Study progress reports submitted to date. These enclosures outline, in
detail, the work accomplished with the exception of the most recent round of
sampling and analysis. The attached progress reports present information
relative to the following sampling rounds:
Progress Report No. 1 - One hundred and thirty (130) reaction vessels
were generated from June 25 through 29, 1986. Baseline (t=0) samples
were collected and analyzed.
Progress Report No. 2 - One hundred and thirty (130) reaction vessels
were sampled and DDT/DDE analysis was performed during the week of July
28, 1986.
Progress Report No. 3 - One hundred and thirty (130) reaction vessels
were sampled and DDT/DDE analysis was performed during the period of
September 5 through September 18, 1986.
During the most recent (fourth) sampling round, only four sets of five cells
were sampled, as per our discussion. Five samples were obtained from each of
the following sets of cells (5 cells per set):
Natural soil, pB=7.0, room temperature, aerobic conditions.
Natural soil, pH=4.5, room temperature, aerobic conditions.
Natural soil, pR=7.0, room temperature, anaerobic conditions.
Natural soil, pH=7.0, T=35°C, anaerobic conditions.
Analysis of these samples has been completed. Once the data have been
compiled, an evaluation will be performed, including a complete analysis of
variance (ANOVA), and a progress report will be submitted.
1 A Halliburton Company
-------
December 10, 1986
NUSP/86-0293
Ms. Laura Boornazian
U.S. Environmental Protection Agency
Page 2
Twelve (12) samples were shipped to the EPA Central Regional Laboratory (CKL)
in Annapolis on December 9, 1986 for confirmatory analysis. Ten samples were
submitted for pesticide analysis only. Two samples were submitted for full
Superfund Hazardous Substances List analysis as per your request.
One hundred samples were collected and analyzed during the most recent
sampling round, so that 12% of the samples were submitted for confirmation. A
copy of the NUS field screening extraction and analytical protocol was sent to
the EPA CRL with the samples. I have enclosed two copies of the protocol for
your information.
As per your request I have reviewed the Scope of Work outlined in the Work
Plan for the Leetown Pesticide Site Treatability Study. In addition to the
fourth sampling round, which was not included in the original scope of work,
the following deviations are noted:
The original period of performance was to have been from late June
through mid-September, constrained by the close of the contract period on
September 30, 1986. Sampling was originally to have been done at periods
of approximately 30 days, with three rounds completed by mid-September.
With the concurrence of Mr. Ed Schoener of your office we agreed to
update the progress of the work with technical memoranda following the
conclusion of analysis and quantitation of the results of each of the
sampling tasks. The artificial constraint of the end of the REM/FIT
contract was removed with the understanding that the work would proceed
beyond September, under the present REM III contract.
Two sets of cells consisting of an aerobic sludge/soil mixture were not
configured at the outset of the study. A suitable aerobic sludge could
not be obtained. Two sludges were obtained from local sewage treatment
plants but both were essentially aqueous. An attempt to filter solids
from these aqueous solutions was unsuccessful. Based on the fact that
there is no evidence indicating that aerobic microorganisms are capable
of degrading 4,4'-DDE and because a suitable sludge could not be
obtained, a decision was made to delete these cells from the study.
As per the request of Dr. Richard Brunker of your office, cells were
configured for a photolytic degradation study. These cells consisted of
ultraviolet-transmissive plastic containers. These cells were placed in
-------
December 10, 1986
NUSP/86-0293
Ms. Laura Boornazian
U.S. Environmental Protection Agency
Page 3
an area where they would receive as much sunlight as possible (i.e., on a
roof area with a southern exposure). Unfortunately, these cells were
destroyed during a wind storm several months ago. Only baseline samples
had been collected from these cells prior to the storm.
Please contact Mr. John George or myself if you have any comments or
questions.
Very truly yours,
^£&MM*
Robert J. Hubbard
RJH/cts
Enclosures
cc: L. J. Apoldo (Ebasco) w/encl.
File: Leetown 106-3L52
Daily
NUS CORPORATION
-------
C-34-12-6-387
TO: FILE DATE: DECEMBER 30, 1986
FROM: ROBERT J. HUBBARDy^W- COPIES: A. BOMBERGER
7 r D. BRENNEHAK
SUBJECT: LEETONN PESTICIDE SITE D. MACINTYRE
TREATABILITY STUDY H. ROFFMAN
PROGRESS REPORT *4 J. GEORGE
EPA WORK ASSIGNMENT NO. 106-3L52
NUS PROJECT NO. 372Y.01
A fourth round of samples was obtained from the Leetown Pesticide Site
Treatability Study cells during the period ranging from November 25 through
December 2, 1986. Samples were analyzed using gas chromatography equipment
housed in a mobile laboratory rented from the NUS office in Lansing, Michigan
during the period from December 2 through December 8, 1986. Samples were
refrigerated during the period between sampling and analysis.
As outlined in Progress Report No. 3 (dated September 29, 1986; NUS
Correspondence No. C-34-9-6-43), four sets of five cells each were selected
for sampling and analysis during the fourth sampling round. The decision to
sample only four of the thirteen total cell configurations was based on the
fact that the selected cells had exhibited the most promising results during
the second and third sampling rounds. Some deviation to the original scope of
work was made in this respect. As outlined in the original work plan, it was
intended that all cells be sampled three times during the course of the
Treatability Study. In view of the promising results obtained for the
selected cells and as a result of the desire to collect numerous samples for
statistical analysis, 100 samples were obtained, rather than 130. In the past
only one sample had been obtained from each of the five separate cells
constituting each cell configuration. During the most recent sampling round,
a total of five samples were collected from each of the selected cells. Thus,
25 samples of each of the selected cell configurations were obtained. Split
samples were collected from some cells and submitted to the EPA laboratory in
Annapolis for confirmation analysis. The quantity of soil remaining in the
cells sampled during the fourth round may introduce some limitations on the
amount of sampling that can be conducted in the future.
The cell configurations selected for sampling and analysis were as follows:
Cell Configuration Matrix j>H Temperature Oxygen Conditions
NS-7-R-AN Natural Soil 7.0 20°C Anaerobic
NS-7-I-AN Natural Soil 7.0 35°C Anaerobic
NS-4-R-A Natural Soil 4.5 20°C Aerobic
NS-7-R-A Natural Soil 7.0 20°C Aerobic
The analytical results for each of the 25 samples from each of the above cell
configurations are included in the attached statistical summaries. The
results were subjected to Analysis of Variance (ANOVA) to determine if 1)
there is any statistically significant difference between the various samples
-------
C- 34-12-6- 387
NEMO TO: FILE
DECEMBER 30, 1986 - PAGE TWO
collected from each of the individual treatment cells comprising each cell
configuration (i.e., does the overall average for these samples provide a
representative population mean), and 2) is there a significant difference in
DDT and DDE concentrations from one cell configuration (i.e., treatment) to
the next. To meet these objectives, ANOVA was first performed using the 5
sets of 5 sample results for each individual treatment cell. Matrices with
dimensions of 5 x 5 were generated. The results of the statistical analysis
conducted in this manner are presented on pages 3 through 8 of the attached
computer printouts. A summary of the statistical analysis for this
application is provided in Table 1. An example of one of the statistical
printouts has been included with the attachment, with hand-written notes to
clarify the information presented.
The results obtained from the aforementioned statistical analyses were then
employed to contrast the variations between the individual cell
configurations. The average values calculated from the five samples from each
individual cell in a given configuration were entered as representative
concentrations for that cell. A matrix of dimensions 4x5 was generated and
subjected to ANOVA, as shown on pages 1 and 2 of the attached printouts. The
results of the statistical comparison for the various cell configurations are
provided in Table 2.
It should be noted that during previous sampling rounds it had become evident
that matrix effects (i.e., heterogeneity in the sample cells) had resulted in
highly variable results between each of the 5 cells comprising each
configuration. In view of this difficulty, Ms. Laura Boornazian, the EPA
Regional Project Manager (RPM) at EPA Region III, suggested that a different
sampling approach be used during the fourth sampling round. Ms. Boornazian
suggested that approximately one third of the remaining soil in each cell be
removed and thoroughly mixed prior to analysis. This recommendation was
implemented, and the results obtained for samples obtained in this manner are
more consistent from one cell to the next. It is apparent that replicate
samples taken from the same cell result in a more accurate average value for a
given cell. No statistical statement can be made regarding the accuracy of
results obtained during the second and third sampling rounds because only one
sample was obtained from each cell. The results of the most recent sampling
round and the Implications of these results are discussed in more detail
below.
Table 1 summarizes the statistical results for each of the four cell
configurations sampled and analyzed during the fourth round. The average
concentrations, standard deviations from the average concentration, average
degradation ratio (I.e., the average of the concentrations from the fourth
round divided by the baseline soil concentration), the standard deviation of
the degradation ratios from their population mean, and the F ratio calculated
using ANOVA are presented in the table. Literature values of F values are also
Included on the table for comparative purposes.
-------
C-34-12-6-387
fCMO TO: FILE
DECEMBER 30, 1986 - PAGE THREE
As can be seen from the tabulated values, virtually all of the F values fall
below the literature value provided for the 0.01 level of significance. This
indicates that the results for the five sets of five samples for each cell
configuration do not differ significantly from one set to the next. Hence the
average concentration calculated for each cell configuration is representative
of the population mean. Virtually the only cell in which a significant
difference in the variance between cells versus the variance within cells was
noted was in the DDE results for cell configuration NS-7-R-A. This indicates
that there is a significant difference (at the 0.001 level) between the
average concentrations for each set of 5 samples. It is apparent that some
variance was introduced during generation of these cells.
As shown on Table 2 there is a statistically significant difference between
the various cell configurations. The F Ratios calculated using the average
values for all 25 cells in each configuration are in excess of 10.0 for both
DDT and DDE. This implies that there is only a 0.1% probability that the null
hypothesis (i.e., the various cell configurations are from populations with
the same mean) is true for the different cell configurations.
The statistical results appear consistent with the expected results. The fact
that the individual results for a given cell configuration were generally
consistent validates the sample collection and analytical protocols. In
addition, it was anticipated that significant differences between various cell
configurations would be obtained. Once again, this is evident from the
statistical analysis.
It is apparent from review of the fourth round concentrations and degradation
ratios that certain cell configurations display more promising results than
others.
a DDT degradation appears to be most prounounced under anaerobic
conditions at 35°C.
DDE degradation appears to be most pronounced under aerobic conditions,
at room temperature, 1n the acidic cells.
These results are generally consistent with the anticipated results. The
degradation of DDT under anaerobic conditions is documented in the literature,
whereas the acidic cells were included in the study in an attempt to induce
fungal degradation of the DDE.
Table 3 presents a summary of degradation rate constants calculated using the
baseline soil concentrations. Two values are presented, one based on the
assumption that degradation obeys zeroth order kinetics (i.e., a linear
relationship), and one based on the assumption that degradation obeys first
order kinetics (I.e., a logarithmic relationship). The Intermediate results
for these cells (I.e., those obtained during the second and third sampling
rounds) have not been Included 1n the calculation of these rate constants
because of their questionable accuracy, as previously discussed. The
expressions used to determine the rate constants are as follows:
-------
C-34-12-6-387
NEMO TO: FILE
DECEMBER 30, 1986 - PAGE FOUR
Oth Order Kinetics: k « (CQ - C4)/t (linear)
1st Order Kinetics: k = 1n(C0/C4)/t (logarithmic)
The Oth order rate constant is derived based on the assumption that the
degradation of DDT and DDE are independent of both the substrate (contaminant)
concentration and the concentration of the enzymes (a function of the
microbial population). The 1st order rate constant is derived based on the
assumption that the degradation rate is contingent only upon the
concentrations of DDT and DDE. Although it is likely that the rate constant
depends on both the substrate and enzyme concentrations (e.g., Michaelis-
Menton kinetics), no basis for identifying the enzyme or quantifying their
concentrations is available.
Inspection of the rate constants (for a given analyte) presented in Table 3
indicates that they are remarkably similar from one cell configuration to the
next. Thus, it appears that there may be some phenomenon causing depletion of
the contaminant concentrations other than microbial degradation. Of all the
potential explanations for such a phenomenon, evaporative losses are
considered the most plausible. Although the vapor pressures of DDT and DDE
are low, there can be no doubt that some losses because of evaporation have
occurred. Note, however, that evaporation should be greater in those cells
that are open to the atmosphere than in those that are sealed (i.e., the
anaerobic vessels). The analytical results do not indicate that there is a
substantial difference between the anaerobic cells versus the aerobic cells.
Thus, while evaporative losses are considered possible, there is not
overwhelming evidence of this in the analytical results.
As a result of the review of the most recent round of sampling data it is felt
that the anaerobic vessels operating under incubated conditions represents the
best method of degrading DDT. The DDT and DDE in these cells are less subject
to evaporation, yet there has apparently been substantial degradation of both
contaminants. Although the degradation of DDE in these cells 1s not as
pronounced as in the other cells, 1t is apparent that some degradation of DDE
has occurred. Although the Initial literature review Indicated that
degradation of DDE does not occur under anaerobic conditions, it is apparent
that degradation of DDE by microorganisms indigenous to the contaminated
Leetown soil may be induced.
The treatablHty study thus far has Indicated that both DDT and DDE
degradation may be effected under anaerobic conditions. Robinson property
pesticide action levels (I.e., accepted pesticide residuals 1n soil following
treatment) have been established 1n the Record of Decision (ROD) and are noted
below:
Former Pesticide Pile Area - Total DDT and metabolites = 300 ug/kg.
Former Pesticide Mixing Area - Total DDT and metabolites * 1200 ug/kg.
-------
C-34-12-6-387
NEW TO: FILE
DECEMBER 30, 1986 - PAGE FIVE
Establishment of anaerobic, adlabatic treatment cells may be the most
effective means of reaching the desired action levels for DDT and its
metabolites. At the present time, the best degradation of both analytes has
occurred in the incubated, anaerobic vessel. The average total concentration
of DDT and DDE remaining in the incubated, anaerobic vessel after
approximately 160 days is about 820 ug/kg, based on NUS-analytical results.
Hopefully the results for the most recent round of sampling will be confirmed
in split samples submitted to the EPA Annapolis laboratory. These results
have not been received to date.
If the 1st order rate constants presented 1n table 3 apply to the microbial
degradation of DDT and DDE, and if it is assumed that the composited soil from
the pesticide pile area at Leetown will be roughly similar to the baseline
concentrations of the soil composited from the Robinson property (i.e.,
approximately 7000 ug/kg DDT and 1000 ug/kg DDE) the length of time required
to reach the desired action levels may be estimated using the following
expression:
DDT(t) + DDE(t) Action Level «
7000 ug/kg exp(-1.5xlO"2t) + 1000 ug/kg exp(-8.8x!0'3t) * 300 ug/kg
This expression does not lend itself to a closed-form solution for time (t),
but trial and error can be used to determine that approximately 8 months
(i.e., between 240 and 245 days) will be required to reach the desired action
level. The assumption of a baseline concentration of approximately 8,000
ug/kg may be lower than the actual concentration since the analytical protocol
4s biased towards achieving better results at low concentrations. Previous
analytical results for split samples submitted to the Annapolis lab indicate
that the NUS field screening protocols may underestimate concentrations if
analytes are present at high levels. Thus, the operating period required to
achieve the specified action levels may be greater than that derived above.
At this point, EPA Region III will be consulted regarding the applicability of
the adlabatic, anaerobic treatment configuration, for pilot scale study.
Additional study of this cell configuration, Including further sampling and
analysis of the cells and commencement of the carbon-14 study (using at least
this configuration) may be warranted. Additional sampling of the incubated,
anaerobic cells will confirm or negate the results of the fourth sampling
round. Adequate material (soil) remains for one full laboratory analysis. If
several months are allowed to pass before additional samples are collected, it
may be possible to demonstrate that the desired action level has been achieved
or 1s being approached. In addition, some study of the toxicity of the
metabolites present in the Incubated, anaerobic vessel 1s probably warranted
(I.e., an Ames toxicity test) to demonstrate that the metabolites are less
toxic than the parent compounds. It may be possible to Identify some of the
metabolites through Thin Layer Chromotography (TLC) or Gas Chromotogrpahy/Mass
Spectrometry (GC/MS).
-------
C-34-12-6-387
MEMO TO: FILE
DECEMBER 30, 1986 - PAGE SIX
At this point in the treatability study it is felt that the primary issue
relative to the efficacy of the microbial degradation scheme is the toxicity
and environmental mobility of the metabolites present in the incubated,
anaerobic vessels. Before any additional study of degradation (e.g., the
carbon-14 study) is undertaken, some effort should be made to ensure that the
treatment scheme results in generation of non-toxic (or less toxic, immobile)
species of chlorinated hydrocarbons. If it can be demonstrated that the
metabolites are not hazardous, further study of the degradation rates at the
bench scale will provide the information necessary to devise the pilot scale
study.
-------
TABLE 1
ANOVA BETWEEN CELLS WITHIN EACH CONFIGURATION
TREATABILITY STUDY
LEETOWN PESTICIDE SITE
FOURTH SAMPLING ROUND
CELL
DDT:
NS-7-R-AN
NS-7-I-AN
NS-7-R-A
NS-4-R-A
DDE;
NS-7-R-AN
NS-7-I-AN
NS-7-R-A
NS-4-R-A
AVERAGE
CONCEN.
2600
630
2200
2100
84
190
91
71
STANDARD
DEVIATION
1100
660
750
920
37
100
47
29
AVERAGE
DEGRAD.
0.38
0.092
0.33
0.31
0.11
0.24
0.12
0.092
STANDARD
DEVIATION
0.16
0.097
0.11
0.13
0.048
0.13
0.061
0.037
F RATIO
3.6
1.7
2.4
1.9
0.19
0.65
11
0.59
F VALUES
LEVEL OF SIGNIFICANCE
0.100
0.050
0.025
0.010
0.005
0.001
F VALUE
2.25
2.87
3.29
4.43
5.17
7.10
NOTES:
1. All concentrations presented 1n ug/kg (parts per billion).
2. Average degradation based on average of 25 samples divided by baseline
soil concentrations (DDT 6822 ug/kg; DDE = 772 ug/kg).
3. Standard deviation determined using average concentatlons for all 25
cells.
4. F Values presented are for (k-1) « (5-1) * 4 vertical degrees of freedom,
and k(n-l) » 5(5-1) = 20 horizontal degrees of freedom.
5. Source of F values - Standard Mathematical Tables, 22nd Ed., CRC Press,
Boca Raton, Florida, 1974.
-------
TABLE 2
ANOVA BETWEEN CELL CONFIGURATIONS
TREATABILITY STUDY
LEETOHN PESTICIDE SITE
FOURTH SAMPLING ROUND
AVERAGE
CONCEN.
1900
110
STANDARD
DEVIATION
560
29
AVERAGE
DEGRAD.
0.28
0.14
STANDARD
DEVIATION
0.082
0.038
F RATIO
12
17
F VALUES
NOTES:
LEVEL OF SIGNIFICANCE
0.005
0.001
FTOUE
6.30
9.00
1. All concentrations presented 1n ug/kg (parts per billion).
2. Average degradation based on average of 100 sample concentrations divided
by baseline soil concentrations (DDT = 6822 ug/kg; DDE = 772 ug/kg).
3. Standard deviation derived as square root of average of variances for 4
different cell configurations (25 samples per cell configuration). See
attached printouts for statistical summaries.
4. F Values presented are for (k-1) = (4-1) * 3 vertical degrees of freedom,
and k(n-l) * 4(5-1) * 16 horizontal degrees of freedom.
5. Source of F values - Standard Mathematical Tables, 22nd Ed., CRC Press,
Boca Raton, Florida, 1974.
-------
ANALYTE
DDT:
CELL
NS-7-R-AN
NS-7-I-AN
NS-7-R-A
NS-4-R-A
TABLE 3
DEGRADATION RATE CONSTANTS
TREATABILITY STUDY
LEETOHN PESTICIDE SITE
FOURTH SAMPLING ROUND
______ k (Rate Constant)
OTH ORDER (ug/kg/day)1ST ORDER (dayli)
26 6.0 x 1(T3
39 1.5 x 10"2
29 7.0 x 10"3
30 7.4 x 10'3
DDE:
NS-7-R-AN
NS-7-I-AN
NS-7-R-A
NS-4-R-A
4.3
3.6
4.3
4.4
1.4 X 10'2
8.8 x 10'3
1.5 x 10'2
8.8 x 10"2
NOTES:
1. Rate constants derived using t = 160 days.
2. Results presented to two significant figures.
SAMPLE CALCULATIONS:
1. Oth order kinetics, DDT, NS-7-R-AN:
k = (6,822 ug/kg - 2,603 ug/kg)/160 days « 26 ug/kg/day
2. 1st order kinetics, DDT, NS-7-R-AN:
k * 1n((6,822 ug/kg)/(2,603 ug/kg))/160 days * 6.0 x 10"3 days"1
-------
17
14
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ANALYSIS DF VARjuNCE SPREADSHEET
,rioN RATIOS - LEEiOWN PESTICIDE SITE TREATAEILI
4
5
1
9
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11
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1 -
14
15
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r?
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COL AVERAGE
5IGMA1 SC-
SI 6M A 1 SO AVG
OVERALL AVG
SIGMA2 SQ 1
SIGMA2 SQ 2
SIGMA2 SQ 3
1
. 2584286
.4075051
. 5345940
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. 2739606
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CHEMICAL:
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i
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F RATIO:
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26
27
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CELL: ALL CELLS
1234
77 72 15fc 133
84 71 cO 205
7t. £>t.' 110 189
90 87 G5 235
93. t- <±.f-' e_l 178. 4
IH COL. AVERnGE 84. 1_ /I 9i.'.e 188. OB
]_. SIGMA i SQ 60.272 103.5 1846.7 i404.032
] c. Slf-^lr-il SC1 AVG 853.
17 uVtRALL AVG 1O8.5
IS SI&MA2 SC1 1 bc4c..901
19 SIGMA2 SQ 2 5&861.25
10 ' £.JSM-i2 SC 3 14411.50
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ANnL-i'SIb uF VARIANCE SK-Hi-
r/E£6RHiiA T I uN RMTID^ - LEcfuWN PESriClL'E 31TE TREATAEiILI
LhLMICAL: DDE
CELL: ALL CELLS
1234
1 . i'c/v7409 . i">932t-42 . 204c>e>32 . 1 7*27 9b
2 .1088083 .0919639 . 0". 772O2 . 2o554nO
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11 4 .11&58O3 .112&943 .03419O9 .3044041
1.' 5 .1212431' . 0»4i969 . o79ui55 .2310881
1 _ r
14 COL AVERnGE . K~>89C.37 .091908^ .117olt6 . 243c>269
15 5IGMA1 SQ .OOO1O11 .0'.'01737 . Oi.'3>.'9&6 .0023558
1 c. SIbhA 1 SC' AVG? . OO1 4323
1" OVERALL AVG .14O5440
IS SIGMA2 SQ 1 .0145086.
19 SIGMA2 SO 2 .0987ft31
20 SIGMA2 SQ 3 .0241810
-I _
4^1 .___^_____________
F RATIO: 16.88269
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CELL:
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SI-3MA1 SO AVG
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i i I D i ' t. II F i ! 6 i
,E SPREADSHEET
- LEFT OWN PESTICIDE SITE TRt ATABI t.IT Y' STUD 7
CHEMICAL:
CEt-L :
1
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F RATIO: 3.648712
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A M ' ^ n'_ T r* i c:- i~'" v ' -- - L r -t! « . :r. ct> r ' ^ E. t u r o c t^ !
CONCENTRi-«"i I (ji>ic - i EE-l'wTj F £ ~. . 1 L 1 Dt SITE TKEATHt IL I T i S'lUDi
4 N= 5 CHEMICAL.: DDE
3 ! = 5 CELL: NS-7-R-AN
7 12345
8 1 60 85 80 65 9S
9 2 120 100 45 65 3u
1O 3 110 £>'-> 10O 9^_. 4tf'
1 1 4 50 65 85 140 205
12 5 4b 110 70 85 '--.>
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14 COL AVERAGE: ".'"/ 84 ' 7o 9x> 93. e>
15 SIGPiAi bO 1245 4o7.5 417.5 950 4712.3
16 SIGMA1 Si' AVI-. 1558.4,t.
17 OVERALL AVG 84.12
la SlbMAl1 SO 1 241. OSS
19 SIGM-; SU J 35330.S/
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F R^TIG:
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1 i-< N n._ i 'D I -. i_jF V ni\ I HT>i'..E 6F'Rt_t-iLc'lTt.t.T
iDATlCN RATIOS - LEETOWN PESTICIDE SITE TREATABILIT r' STUD't
4 fJ= 5 CnEMICnL: DDE 7~2
5 r - 5 CELL. : N5-7-R-AU
] 2 3 4 5
8 3 .07772O2 . Ilul03o .103626.9 .0841969 . l^c.9430
2 .1554404 .1295337 .0582902 .0841^69 .033S&01
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11 4 . Gto4766& .03^19,-,? .1101036 .1313472 . 2&55440
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14 COL AVERAGE ,Ov^74o^ . i v£Sud3 .0984456 .1165303 .121243:'.
15 SIGMA1 S& .OO2O59.. . OO'I7o44 .0007005 .0015940 .007
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17 OVERALL. «V3 .1O89.-..37
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F RATIO: . I9337o4
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27
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CHE rl I
CELL:
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2495
1 940
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2T50
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32T.5 141O 1435
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15 SIOjhAi 30 250137.5 337'382.5 832475 814055 1454355
1 o SlG>tr'lMl S.O AVG 737791
17 OVERnl.L AVG 2O96.4
SIOMM2 3C1 1 llOf.421.
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S20rfA2 SO 3 1383027.
1C'.: 1 . b/4551
i: ; , L : ; D i i E ; ; r i ;
',(4f;lHNr£ SPREADSHEET
RATIOS - LEETOWN pESTinr»E SITE TF-EMTAEHL ITI S
5 CHfcrllOiL: DDT
5 CELL: N5-4-R-K
1 . 2L'43242 . 31'">O264 .4771329 . 2Ot>6843 .210346V
2 .3657285 . 5335o"'9 . 1O04104 . 3759394 .5511530
3 .2858399 . 44635OO .2873058 .1443556 ,1421S~0
4 .2330695 .403107& .3156398 .1335224 .1509=21
5 .40384O5 .4851950 . 2:>'9 ,"t,55 . 4i -9t4L . 14O7212
14 r-.CH AVERAGE . 3O85t>O5 .4356494 . 29610O9 . 2571 C 9 4 .2390794
15 SIGhAl SQ .0053753 . OO72494 .0178374 .0174916 .0312605
1 * SI GM A 1 50 A Vl~ . 0 1 58529
1 7 OVERALL AVG . 3072999
18 SIGMA2 SO 1 .0237737
19 SIGMrtZ- SO 2 .4721662
2u SIGMA2 BO 3 .0297171
24 F RATIO: 1.874551
27
-------
6/10
ANA,.. Y SIS OF- V-.R It-it-i^E S
CONCENTRATIONS - LEZETQWN PESTICIDE SITE TREnTAf. IL I 7
N= 5 CHEMICAL: DDE
5 K= 5 CELL: U5-4-R-A
C.' - -
32345
S 1 50 70 4O 45 55
9 2 75 85 4O 12O 55
10 3 95 6O 3O 55 40
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14 C'OL AVERAGE: 72 71 6O 67 cl_'.
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i ANALYSIS; OF VARIANCE SPREADS!-iEtn"
DEGRADATION RATIIOS - LEETOWtJ PESilCIDE SITE TREATMBILI T'r STUL'1!
4 N= 5 CHEMICAL: DDE 7^-2
^ \ -- 5 CEui.. : NS-4-R-A
^^r "
7 1 2 3 4 5
?-. 1 . Uc?4", <±.o8 . i»9il>o736 .0518135 . 05o2'VCjI . o? 12435
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] 0 ";. . 12305" <' . 077", l.11,2 . 038St-01 . 07 1243T- . '.'51 £ 1 35
lj 4 ,i»97i503 .0906730 . Ilo5303 . U7772<"'2 . O34i9o9
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lo 5IGMA1 SO AVG .OO14833
17 OVERALL AVG .0919659
IS SIGMAl SO 1 .OOO694e
19 SIGMA2 SQ 2 .0422914
20 SIGMA2 SO 3 . OOO8t-83
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F RATIO:
. 585407:
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1234
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17 G/EFALL AVG 22 j 5.3
16 ' SIT.MH2 5D 1 5".*2450.S
13 S13nA2 SO 2 246i53c.7
21-' SlC'l^ifM Si"1 3 10905c'4.
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DwN r- EE"i ] r I L'E £'ITE TFi'E1
CHEMICAL: DDT 6622
CEuL : NS-7-R-A
1234 3
1 . 4evo03c. .2052184 .5108477 . 43095S7 . 22Oo0^6
2 .3972442 . 2044S55 .2301378 .3591322 . 24113it
\ <: 3 . 44925 i 7 . 22*4732 . 2 7 9243t> . 1 59777 2 . 3320 1 4 1
li 4 . 332O141 .2704435 . 428O27-0 .4052381 . 43 J 7913
12 5 . 445cl"'l .2719144 . 34O8O91 .120^323 . 30439r.9
14 Co, AVERAGE .4187^11 . 2357O8i.' .357313'J .295^07" .3150555
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17 Cv'EFALL AVG .3252419
j^ SI3MA2 SO 1 . 01874&4
39 :-IuMH2 SD 2 .5239114
2>"' SlL-iMn2 SC1 3 .0234330
24 F RATIO: 2.368959
27
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CHEMILH.: DDE:
CELL: N3-7-R-A
1234
215 £?O 15u SO
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1 1 . 32945
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CHEr-IICAL: DDE
CELL: NS-7-R-A
1234
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F RATIO: 11.32945
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5 f ^ 5 CELL: NS-7-I-AN
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'**
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
REGION III
CENTRAL REGIONAL LABORATORY
839 BESTGATE ROAD
ANNAPOLIS, MARYLAND 21401
301-224-2740
FTS-922-3752
DATE
January 15, 1987
SUBJECT: Pesticide Analysis - Leetown, W. Va.
Superfund-Remedial, (12/11/86 - 1/9/87), 861211-01
FROM
TO
- 12
Chemist
John Austin
Acting Chief, Annapolis Laboratory
Samples were soxhlet extracted and analyzed for pesticides,
Sample Description;
Lab No.
861211-01
OA
-0?
-03
-04
-05
-06
-07
-OR
-09
-10
-11
-12
Check:
Description
Leetown,
Leetown,
Leetown,
Leetown,
Leetown,
Leetown,
Leetown,
Leetown,
Leetown,
Leetown,
Leetown,
Leetown,
W.
W.
W.
W.
W.
W.
W.
W.
W.
W.
W.
W.
Va. NS-4-R-A-2
Va.
Va.
Va.
Va.
Va.
Va.
Va.
Va.
Va.
Va.
Va.
NS-7-R-A-1
NS-7-I-AN-4
NS-4-R-A-5
NS-7-I-AN-1
NS-7-I-AN-5
NS-7-R-A-2
NS-7-R-A-4
NS-7-I-AN-2
NS-4-R-A-4
NS-4-R-A-1
NS-7-R-A-3
Breakdown DDT <10%
Breakdown Endrin <20%
SRKrad
cc: Peggy Zawodnyf^
OCO
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
REGION III
% 1tOs CENTRAL REGIONAL LABORATORY
839 BESTGATE ROAD 301-224-2740
ANNAPOLIS, MARYLAND 21401 FTS-922-3752
DATE : January 16, 1987
SUBJECT: Pesticide Report for Leetown, WV.
FROM : John Austin (3ES21)
Acting Chief, Annapol/s Laboratory
TO : Laura Boornazian (3HW21)
Enclosed is the pesticide report for Leetown, WV. If you have any questions,
you can contact Rosemary Kayser directly.
JArjr
Enclosure
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PESTICIDE/PCBS PRIORITY POLLUTANT COMPOUND DETECTION LIMITS
Parameter
Aldrin
Alpha BHC
Alpha Endosulfan
Beta BHC
Beta Endosulfan
Chlordane
4,4'DDD
4,4'DDE
4,4'DDT
i,4'oon
Delta BHC
Dieldrin
Endosulfan Sulfate
Endrin
Endrin Aldehyde
Gamma BHC (Lindane)
Heptachlor
Heptachlor Epoxide
Toxaphene
PCB 1016
PCB 1221
PCB 1232
PCB 1242
PCB 1248
PCB 1254
PCB 1260
Cas
Number
309-00-2
319-84-6
959-98-8
319-85-7
33213-65-9
57-74-9
72-54-8
72-55-9
50-29-3
319-86-8
60-57-1
1031-07-8
72-20-8
7421-93-4
58-89-9
76-44-8
1024-57-3
8001-35-2
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
Soil /Sediment
mg/kg
0.03
0.02
0.05
0.04
0.1
0.4
0.12
0.06
0.16
0.02
0.04
0.06
0.3
0.09
0.23
0.02
0.02
0.04
4.0
0.4
1.0
1.0
0.5
0.8
0.8
1.5
Page 3 of 3
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IMUS
Park West Two
Cliff Mine Road
Pittsburgh, PA 15275
CXDRPORATON 412-788-1080
January 22, 1987
NUSP/87-0035
NA
Ms. Laura Boornazian
Remedial Project Manager
U.S. Environmental Protection Agency, Region III
814 Chestnut Street
Philadelphia, Pennsylvania 19107
Subject: REM III PROGRAM - EPA CONTRACT NO. 68-01-7250
LEETOWN PESTICIDE SITE, WEST VIRGINIA
EVALUATION OF PRESENT STATUS
Dear Laura:
As we had discussed on January 20, I believe that a meeting
between the EPA, Ebasco Services, and NUS Corporation is required
in the near future to formally evaluate the results of the bench
scale microbial degradation treatability study and to establish
direction to proceed with the studies. We would prefer to
schedule such a meeting in early February, if possible.
As a result of the work done since last June, and particularly
based on the results from the fourth round of sampling in
December 1986, NUS feels that the indigenous microbial
population can be utilized in reducing DDT concentrations in
Leetown soils. While we originally based our evaluation of the
health threats associated with these contaminated soils on
inhalation of fugitive dusts by farmers plowing the soil, we
believe that a toxicity test (e.g., Ames Toxicity Test) and full,
replicate Hazardous Substances List (HSL) scans should be run on
the soils from the anaerobic, incubated cells at this point. If
the soils prove to be non-toxic, and no HSL parameters are found
that could give rise to excess health risk, then we can utilize
the DDT risk-based action levels established in the Remedial
Investigation Risk Assessment as the criterion for evaluating the
success of the microbial degradation.
As you will recall, we did note in our phone conversation that
the formerly incubated cells have been held at room temperature
since mid-December due to a malfunction of the incubator. While
this development may affect the reaction rate in these cells, the
DDT action levels had been achieved through mid-December, and the
fact that the cells are not presently being incubated should not
adversely influence their amenability to further chemical
analysis.
We do not believe that the treated soils will prove to be toxic,
and, indeed, may not have tested so prior to treatment. We also
do not believe that HSL scans of the treated soils will evidence
A Halliburton Company
-------
January 22, 1987
NUSP/87-0035
Ms. Laura Boornazian
U.S. Environmental Protection Agency, Region III
Page 2
any metabolites of DDT that would pose a greater health risk than
that present due to the pesticides. To support this, no peaks
were evident on the chromatograms between DDT and DDE, indicating
few, if any, metabolites present in the samples with similar
molecular weights to DDT and/or DDE.
At the Region's request, we had considered the possibility of
conducting a study using radio-labeled (C-14) pesticides to
assist in determining the degree to which the DDT present in the
original soil is completely mineralized to carbon dioxide and
water. However, the bench scale study has demonstrated the
ability of the microbes to reduce pesticide levels in the soils,
and if the treated soils do not evidence any toxicity we believe
that the C-14 study at this point would be somewhat academic.
The basic premise for the study is that labeled CCU off-gas can
be trapped on an adsorbent medium replaced at periodic intervals.
By counting the activity of the adsorbent material,
quantification of the mineralization can be achieved. We are
aware of several difficulties with conducting this study that may
affect the results. In particular, the study may not be
sensitive to evaporative losses of labeled pesticides from the
soil, resulting in their contaminating the adsorbent material and
artificially elevating activity. It would not be possible to
quantify the degradation via mass balance, since we would be
adding a known quantity of labeled pesticide to an already
contaminated medium, i.e., the Leetown soils. Use of Leetown
soils may be crucial to the success of the degradation, since
indigenous microbes appear to be successful in degrading the DDT.
A calculated quantity of labeled pesticide material must be added
to the soil to ensure that enough mineralization occurs to
produce measurable activity levels. This additional pesticide
contamination may have an adverse impact on the microbes.
We would like the opportunity to discuss the utility of the C-14
Study in the light of the most recent bench scale results. If we
elect to proceed with the toxicity tests and HSL scans, and the
results are as expected, we feel that immediate plans should be
made to establish a more controlled bench scale study, in
parallel with a pilot scale test of the technology at the Leetown
Site. Such a meeting is not presently within our scope of work.
An amendment to our Work Assignment, which would provide the
-------
January 22, 1987
NUSP/87-0035
Ms. Laura Boornazian
U.S. Environmental Protection Agency, Region III
Page 3
funds to develop a Work Plan to pursue the C-14 Study, is
currently pending Ebasco authorization. As we had suggested
during our phone conversation, a portion of these funds would be
better used at this time to conduct a project meeting prior to
further work. You had indicated that you would consider this
approach, and advise Ebasco accordingly. We will await your
direction before proceeding.
Very truly yours,
John A. George
Project Manager
JAG/jag
cc: E. Shoener (EPA Region III)
R. Evans (Ebasco)
W. Mendez (Ebasco)
Pile: Leetown 106-3L52
Daily
NUS CORPORATION
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