NCD980602163_19950321_Warren County PCB Landfill_SERB C_Eco Report & Fee Review - Pauline Ewald, 1994 - 1995-OCR

State of North Carolina
Department of Environment,
Health and Natural Resources
Division of Epidemiology
James B. Hunt. Jr., Governor
Jonathan B. Howes, Secretary
March 21, 1995
MEMORANDUM
TO: William L. Meyer, Director
Division of Solid Waste Management
THROUGH: John I. Freeman, D.V.M., M.P.H., Ch'
Environmental Epidemiology Section
FROM: Kenneth Rudo, Ph.D., Toxicologist
Environmental Epidemiology Section
SUBJECT: Response to ECO Final Sample Analysis Report
I have reviewed the "Final Sample Analysis Report" written by the
Environmental Compliance Organization (ECO) for the Joint Warren
County and State PCB Landfill Working Group (February, 1995).
With the exception of the following statement concerning the ECO
review of the State Laboratory of Public Health (SLPH), I will
confine my comments to the dioxin/furan groundwater data, the
review of which has been the extent of my involvement at the PCB
landfill site.
I find myself completely in agreement with the response of Roger
McDaniel, the Chief of the Environmental Sciences Section, to the
ECO report. The SLPH has been subjected to a totally
inappropriate attack in this review. Dr. McDaniel's response
addressed very well the specifics of ECO's misstatements. The
SLPH is one of, if not the best analytical laboratory in North
Carolina. SLPH maintains a level of quality control that is
routinely of the finest caliber, producing analytical reports of
groundwater samples that are consistently reproducible and in
instances where split samples are analyzed at other labs, very
consistent with other lab reports. If the reporting format was
not up to the detailed level that ECO wanted, the quality of the
results were extremely accurate. SLPH is a high -volume lab,
analyzing well water samples that are instrumental in protecting
the drinking water supplies in North Carolina. As the state's
risk assessor in charge of evaluating both public and private
water supplies, I do not know of a single instance where SLPH has
erred in an analysis.
P.O. Box 27687, Raleigh, North Carolina 27611-7687
An Equal Opportunity Affirmative Action Employer 50% recycled/ 10% post-consumer paper
Mr. William L. Meyer
Page 2
March 21, 1995
As I have discussed with the residents in Warren County, I find
myself agreeing with the ECO report in identifying dioxins and
furans in monitoring wells at the site. The levels in the
samples exceed the laboratory blanks and appear to indicate the
presence of dioxins and furans in these samples. However, the
s ource of this contamination cannot be scientifically determined
at this time because inadequate or non-existent controls were
utilized at the time the sampling was done. Indeed, part per
quadrillion (ppq) dioxin and furan levels may be ubiquitous in
groundwater. We simply do not have an existing data base for
these compounds at ppq levels. Until resampling is done with
proper controls, as we have discussed on several occasions, any
statements about probable sources for these compounds in
groundwater are hypothetical at best. Therefore, the ECO
statement on page 35 of the report is just their opinion,
completely unsupported by scientific data. The statement on page
37 of the report about the rarity of detecting these compounds in
water is also a supposition. Until a data base exists for ppq
levels of dioxins and furans, their rarity in groundwater is not
factually established. The additive levels of dioxins and furans
in several monitor well samples exceed EPA's MCL of 30 ppq for
2,3,7,8-TCDD. From a public health standpoint, this may pose a
slightly increased lifetime cancer risk if this water was
consumed over many years. At this time, it is evident that
groundwater from this site may contain dioxins and furans.
Further evidence of their presence and possible link to a source
can only be determined by sampling this site again with proper
controls. The ECO report completely fails to address this fact,
and their findings of dioxins and furans in groundwater related
to a possible source (the landfill) is a scientifically-invalid
statement. Because the groundwater presence of dioxins and
furans appears to be the only public health concern outside the
landfill at this time, the ECO report should have supported an
attempt to acquire reliable, scientific data on the groundwater,
with proper control samples. Regrettably, they failed to do so.
KR:td
TCI
.2..-!..::,_ ..... : .·: .... •-·-·-.... . ........... .., ..... .
March 9, 1995
Sharron E. Rogers
North Carolina Department of Environment, Health and Natural Resources
401 Oberlin Road, Suite 27605
Raleigh, North Carolina 27611-7687
Dear Ms. Rogers:
In reviewing the Joint Warren County and State PCB Landfill Working Group Final Sample
Analysis Report prepared by ECO, I found several areas of concern. Those concerns
involve lack of specificity in reporting the analytical methods used, inconsistent sample IDs.
errors made in changing the reporting units for the summary table, disparity in the report
units for the water samples, and evaluation of holding times for dioxin samples.
The ECO report does not specifically state which method was used by either laboratory
performing the dioxin analyses. I have reviewed the original reports issued by Triangle
laboratories, and know that that wori< utilized SW-846 Method 8290. I do not know what
method was used by Pace. The use of different methods could make the data from two
labs difficult to compare.
The sample IDs listed in the sampling locations section of the ECO report do not match the
sample IDs received by Triangle. Triangle received the following samples: WL-001-GW,
WL-002-GW, WL-003--GW, WL-004-GW, WL-002-LC, WL-001-LE and WL-002-LE. The
last two samples listed (WL-001-LE and WL-002-LE) are not included in the sampling
location section of the ECO report; however, that section of the report lists two other sample
IDs ('Nl.-005-GW and WL-001-LC) which were not received by Triangle. I do not know if
these two sets of IDs are related in any manner.
A serious error was made in converting the Triangle data for sample WL-002-LC to parts
per quadrillion (ppq) for the ECO report. The units in the original Triangle report for this
sample were parts per trillion. The conversion for the ECO report treated this data as
though it had been reported in parts per thousand. That error resulted in a 1 million fold
error. The data for sample WL-002-LC (analyzed by Triangle) and IC-002-LC (analyzed by
Pace) actually compare reasonably well when evaluated property (see attached comparison
table). Toe units for the water samples were property presented and the data in the ECO
report matches the original reports issued by Triangle. However, sample WL-001-SW in
the ECO report is actually sample WL-001-GW in the original Triangle report.
The data for the water samples which were analyzed by both labs cannot be compared
because of the disparity in the report units. While data in the parts per quadrillion range
was reported by Triangle, the Pace data was reported in parts per billion and no reportable
levels were found. I was unable to determine if the same analytical method was used by
both labs.
Environmental Division
801 Capitola Drive P.O. Box 13485 _ ..
Durham, NC 27713-4411 Research Triangle Park, NC 2, 709·3•-•o~
919-544-5729 Fax# [phone]
... · ttt-=,F·-~(3-1 '3'35 15: 3'3 FF'OM TF: I At~C:iLE LAB'::; CIF FffF' TO
With regard to the comment on holding times for the dioxin samples, the waste sample WL-
002-LC was extracted twice by Triangle--8/16/94 and 8/26/94. Both extractions were within
the thirty (30) day holding time specified in Method 8290. The results for the two analyses
are very reproducible. Only data from the second extraction was reported because of sligh t
contamination in the blank for the first extract.
On a positive note, the internal and surrogate standards in the original Triangle data were
well within the control limit<; and I did not find anything in that data Which indicated a
problem. The samples did exhibit a quantitative interference affecting the pentas, but that
fact was duely noted in the case narrative and the affected data was flagged.
If additional information is needed or I can be of further assistance, please call me at
[phone].
Sincerely,
~/4~.
Patty L. Ragsdale
Quality Assurance Manager
F'.C3
TD F'. [1..:;
Comparison of Triangle and Pace data for
duplicate "wet landfill contents" sample
WL-002-LC IC-003-LC % Relative
ppt ppb Difference
2378-TCDD 0.0%
12378-PeCDD 0.0%
1234 78-HxCDD 0.0%
123678-HxCDD 0.0%
123789-HxCDD 0.0%
1234678-HpCDD 28.1 200.0%
12346789-OCDO 1970 0.3237 143.5%
0.0%
2379-TCDF 80.8 0.1133 -33.5%
12378-PeCDF 25.1 0.0329 -26.9%
23478-PeCDF 73.8 0.1188 -46.7%
1234 78-HxCOF 802 4.7059 -141.8%
123678-HxCDF 78.7 0.5958 -153.3%
234678-HxCDF 66.7 0.3657 -138.3%
123789-HxCDF 55.8 200.0%
1234678-HpCDF 701 3.0825 -125.9%
1234 789-HpCDF 669 200.0°/o
12346789-OCDD 4720 14.435 -101.4%
.. '. . .,
FROM: Phil Albro, 75452, 1665
TO: Yves Tondeur. 7 4552.1350
DATE: 3/06/1995 10:35 AM
Re: Chapter 11 Comments
(1) Hydrophobic adsorption occurs in the presence of water _only_, and is _not_ synonymous
with 'lipophilicity', which doesn't require water (p.31 ).
(2) Lipophilicity is not involved in binding of PCBs or Dioxins to soil. Soil is not lipid. Binding
to soil Itself involves things like salt formation, chelation, bridging; none of these occur with
PCBs or Dioxins. The main force would be hydrogen bonding. There is a big difference
between binding to _sediment_ and binding to soil. The former would depend on hydrophobic
bonding and hydrogen bonding primarily, While binding to soil will involve _primarily_ binding
to the humic components.
(3) pp.33-34: The transport of PCBs and dioxins/furans in groundwater is associated to an
insignificant extent with solubility in the water -this aspect of the discussion is almost
irrelevant. Transport in groundwater involves binding of PCBs and dioxins/furans to humic
and fulvic materials, which are fairly water soluble. The binding involves hydrogen bonding to
some extent, but also charge transfer complex formation to the high percentage of aromatic
rings in the humic/fulvic materials. Both PCBs and dioxin/furans can bind strongly, such that
they move with the dissolved humiclfulvic materials. This binding can be strong enough that
passing ground water through C18-SPE cartridges.-will not break it. The strength of such
binding depends on the exact isomer/congener involved for all three classes, and there is
class overlap. This is not simply theoretical information -it has been studied (mainly at UNC
SPH Dept. of Environmental Science and Engineering.)
Post-W Fax Note 7671
Co./Dept,
Phone It Phone II
Fax# Fax#
State of North Carolina
Department of ·Environment.
Health and Natural Resources
Division of Laboratory Services
Jomes B. Hunt. Jr., Governor
Jonathon 8. Howes, Secretary
Samuel N. Merritt, Dr. PH, Director
MEMORANDUM:
TO: William L. Meyer, Director
Division of Solid Waste Management
...;...J□l(.J....J r .l(.Jc;.
AVA .·
DEHNR
FROM: Roger L. McDaniel. Ph.D., Chicf(i31l
Environmental Sciences Section ~
THROUGH: Samuel N. Menitt, Dr. PH, Director Jr 1,
Division of Laboratory Services
DATE: March 1, 1995
SUBJECT: Response to the ECO Final Sample Analysis Report
I have reviewed the Final Sample Analysis Report written by the Environmental Compliance
. Organization (ECO) for the Joint Warren County and State PCB Landfill Working Group (dated
February 1995). I am outraged by the misstatements and innuendoes contained in this document
regarding the quality of the work performed at the State Laboratory of Public Health (SLPH).
1bis document is laced with comments apparently intended to discredit the State by impeaching
the validity of the analytical results. The State Laboratory of Public Health firmly stands behind
the data regarding the Warren County PCB Landfill as being timely, complete, and accurate;
The recurring complaint in ECO's review of work perfonned at the SLPH is the reporting format
used to present the data. ECO stated (at every opportunity) that because the State Laboratory of
Public Health did not follow the Contract Laboratory Program (CLP) reporting format, all results
were considered unreliable and therefore W1usable. ECO then contradicts its own conclusions by
using SLPH data throughout the report.
There are several valid reasons why the SLPH does not report results using CLP format. First of
all, SLPH chemists perform the final review of all raw and finished data generated by this
laboratory. Since the programs do not routinely review raw data from this laboratory, inclusion
of volumes of instrument tuning, calibration, and quality control documents (as required under
CLP) would not be particularly beneficial. Secondly, UP fonnat is extremely labor intensive and
requires a tremendous amount of clerical work to assemble the packages. For a high volume
laboratory, such the SLPH, productivity would be greatly' reduced. For example, a typical two
page summary report, if reported under CLP format, would fill a 2 inch notebook. 'This would
impose a great burden on this laboratory, increasing both the cost and turnaround
... '} i~''
P.O. Box 28047. Rdeigh. North Carolino 27611-8047
~ :.< \'.~i} ·. ·::
An Equol Opportunity Atfrrmotive Action EmployQr 50'I, recycled/ I O'I. post-cons.imer poper
WUliam L. Meyer
' March 1, 1995
Page2
time, without providing any additional benefit to the supported programs. Contrary to ECO' s
·Fin.al Analysis Sample R~port, the SLPH did not agree (nor were we asked) to report results
from the Warren PCB Landfill in CLP fonnat. Although the SLPH does not routinely report
results in CLP format, all standard quality assurance / quality control procedures are strictly
followed.
Overall, the ECO report was poorly written and contained numerous misstatements, omissions,
and significant erro~. For example, ECO devoted seven pages of this report to illustm.e a
calculational error in a PCB calibration from a SLPH worksheet. This analysis, in fact, was a
rough qualitative confirmation of PCB used as part of a degradation study. These results were for
internal use only, and did not undergo a standard final review by a SLPH chemist. It should have
been obvious to ECO's reviewer that these calculations were not used in the final results. The
ECO narrative and comments regarding this particular analysis are therefore totally irrelevant.
Other errors are addressed in Attachment 1.
I can understand the difficulty that the ECO reviewer must have experienced in trying to interpret
another laboratory's raw data. However, I must point out that no effort was made on the part of
ECO to contact the SLPH to request additional infonnatio~ to ask for an explanation, or to
request help in interpreting any of the raw data or quality control measures. Several statements
regarding missing quality control data were made throughout the report. 1be ECO reviewe.r
apparently failed to recognize, or chose to ignore, the many quality assurance / quality control
measures that were apparent in the raw data. For these reasons, I question ECO' s sincerity in
. pcrf onning an accurate and impartial evaluation.
The SLPH has been in the business of environmental analysis for 90 years. It tw been continually
certified by the USEPA since the inception of the certification program in 1978. The latest EPA
on-site evaluation (perfonned in May 1994) included a review of all personnel, equipment,
analytical methods, records, and quality control procedures. No deficiencies were found. The
attack on the credibility of this laboratory by the ECO report is totally unfounded.
In appendix A, I have responded to many of the errors, misstatements, and omissions that were
contained in the ECO report which are relative to work performed at the SLPH. Pl~ contact
me at 3-7308 if you need additional information or have questions.
'\.
W...JU~W I eLl"'"t
ATTACHMENT 1
Response to errors, misstatements, and omissions in the ECO Final Sample Analysis Report of
the Warren County PCB Landfill (February 1995).
Section 6.0 Metals Analysis.
Page 11. Table titled DETECTION LEVELS should be titled LOWEST REPORTING
VALUES.
Page 11. Since some barium w~ found in the soil samples and TCLP extracts, inclusion of a
detection limit is not particularly relevant.
Page 11. The report stated that "mercury detection limits differ by greater than 1 OX,
indicating an error." The report, however, failed to take into account the dilution
factor of 20X prior to digestion and analysis. There was no error in the mercw:y
analysis.
Page 11. Holding times for samples (from Field Collection to TCLP extraction) are 28 days
for mercury and 180 days for other metals.
Page 12. Response to the second paragraph under the heading Calibration. Calibration of
the atomic absorption spectrophotometer for graphite furnace analyses is
accomplished using a blank, two standards, and checking a third standard (at the
less than reporting value concentration). A quality control standard is then
analyzed along with a reagent blank (unspiked) and a fortified blank (spiked).
Samples are analyzed only if these values are within acceptable range.
Page 12.
All samples are tested using methods of additions (spiked recoveries) for the
graphite furnace metals. Quality control samples are checked initially, every 20
samples, and at the end of the run.
Calibration of the inductively coupled plasma spectrophotometer utilizes a blank
and one standard. A quality control standard is analyzed along with blanks. If the
results are within acceptable limits, the samples are analyzed. Quality control
samples are checked initially, every 20 samples, and at the end of the run. Ten
percent of samples are analyzed as duplicates or spikes.
On both instruments, calibration is performed according to the instrument
manufacturer's specifications. These procedures have met EPA's approval as
indicated by the many satisfactory site visits and examinations of laboratory data
and procedures.
Concentrations of standards were mostly above the sample concentrations. Most
sample data was reported as less than values.
Section 7.0 Volatile Organks
Page 17. Response to paragraph titled Calibration. For the record, the gas chromatograph
mass spectrometers are tuned, and initial and continuing calibrations performed
with external standards. An internal standard (bromochloromethanet 40 ppb) is
used with every sample. Field blanks, and laboratory blanks are also analyzed.
Page 19. Table 2 omitted 48 ppb lA dichlorobenzene reported by the SLPH for sample WL
002LC.
Section 8.0 Semi-Volatile Organics
Page 20. Calibration. For the record, three recovery checks were made on each sample.
Also, each sample contained an internal standard (d-10 anthracene).
Page 23. Titled PCB Calibration Error (also includes Appendix A, Figures 1-5). This
example was addressed in the cover letter. This calibration data was not used in
any fmal results.
Page 21. Table 3 is incomplete. Values for 1,3-dichlorobcmene and 1,4-dichlorobenzene
for sample WL 002 LC should be followed by the letter "k" (indicates amount
present is less than stated value). Also sample WL 004 BL that contained 6333
ppb phthalate, also contained 22000 ppb dibutylphthalate. This contamination
probably occurred during the sampling procedure.
Page 25. Table 4. Sample WL 004 BL also contained .0042 ppm PCB 1260. Samples \VL
028 SS which contained 1.45 ppm PCB 1260 is erroneously listed in the table as
PCB 1248. Similarly, sample WL 029 SS, which contained 0.22 ppm PCB 1260
erroneously appears in the table as PCB 1248. The units of the table are in Parts
Per Million (ppm) not Parts Per Billion (ppb).
,
JOINT WARREN COUNTY AND ST ATE PCB
LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
E C 0
.,
REPORT CONTENTS
1.0 SUMMARY
2.0 CASE NARRATIVE
3.0 SAMPLING PARAMETERS
4.0 SAMPLING LOCATIONS
4.1 State Sample Collection
4.2 Split Sample Locations
5.0 FIELD CHANGES TO SAMPLING PLAN
6.0 METALS ANALYSIS
6.1 Summary
6.2 NC State Laboratory Analysis
6.3 Split Sample Analysis
7.0 VOLATILE ORGANICS
7.1 Summary
8.0 SEMI-VOLATILE ORGANICS
8.1 Summary
9.0 PESTICIDES/PCBs
9.1 Summary
10.0 PCDD/PCDFs
10.1 Summary
11.0 DISCUSSION OF ISSUES RELATED TO SAMPLE RESULTS
11.1 Relative Solubilities of PCDD vs . PCBs
11.1.1 Properties of PCBs
11. 1.2 Properties of Dioxins
11.1.3 Transport and fate in water systems
11.2 Evaluating PCDD/PCDF Concentrations
12.0 SCIENCE ADVISOR OPINIONS AND CONCLUSIONS
LIST OF TABLES, FIGURES AND APPENDICES
TABLES
TABLE 1-COMPILATION OF METALS AND EXTRACTABLE
DETECTIONS
TABLE 2-COMPILATIONS OF VOLATILE ORGANIC
DETECTIONS
TABLE 3 -COMPILATION OF SEMI-VOLATILE ORGANIC
DETECTIONS
TABLE 4-COMPILATION OF PCB DETECTIONS
TABLE 5-COMPILATION OF PCDD/PCDF DETECTIONS
TABLE 6-TOXICITY EQUIVALENCE FACTORS (TEFs)
FIGURES
FIGURE 1-WATER SOLUBILITY OF PCDD/PCDF/PCBs
APPENDICES
APPENDIX A -FIGURES 1 -5
PCB CALIBRATION EXHIBITS
APPENDIX B -WORKSHEETS -
•
1.0 SUMMARY
This report is a presentation of validated data resulting from a joint sampling effort
completed at the Warren county PCB Landfill in July, 1994. The data reported
reflect results from samples collected by the North Carolina Division of Solid
Waste, and splits of approximately twenty percent (20%) of all samples collected
which were handled by ECO, an independent contractor working on behalf of the
Joint State and Warren County PCB Landfill Working Group.
2.0 CASE NARRATIVE
Pursuant to a request from the Working Group, ECO participated in a field
sampling event at the PCB landfill located in Warren County on July 27 and 28,
1994. ECO staff were on-site during all field activities, and video taped and/or
photographed random sample collections and recorded field notes regarding all
split sample collections. Sample collection, preservation and handling by
NCDEHNR personnel was to have proceeded according to a written Quality
Assurance Plan, and the pre-approved Sampling Plan. ECO has not received
information from the state indicating significant deviation from sample collection
guidelines.
..
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
In addition, ECO received sample splits from pre-selected sample locations. These
splits were delivered directly to ECO staff, immediately cooled and packed as per
protocol, and maintained under constant surveillance by ECO staff until
relinquished to the overnight courier service for shipment to the laboratory.
The majority of samples were analyzed by the State laboratory in Raleigh, North
Carolina, with PCB and PCDD/PCDF samples analyzed by
Triangle Laboratories Incorporated (TLI). All split samples were analyzed by
independent, out of state facilities with State of North Carolina and EPA
certification.
Analytical results from the State laboratory and TLI were reported to ECO along
with requested QA/QC documentation. It was represented to the Joint Working
Group and ECO that all available QA/QC documentation regarding the full sample
set had been copied to ECO for analysis and review.
Analytical results for split samples were reported directly to ECO. A duplicate
data package, containing all reporting sheets, and raw and QA/QC data was sent to
the North Carolina Division of Solid Waste directly from the laboratory.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
3.0 SAMPLING PARAMETERS
As agreed to by the Working Group, all splits collected ( except as noted in
Section 5.0 -Field Changes) were analyzed for a broad range of contaminants
including Volatiles, Semi-Volatiles, Metals, BNAs, Pesticides, PCBs, PCDD and
PCDFs (Dioxins and Furans), as well as for Toxicity Characteristic Leaching
Procedure or TCLP which determines whether a sample may be classified as a
regulatory hazardous waste.
All analyses were performed using EPA approved methodologies and protocols in
accordance with Standard Methods 17th Edition; the Solid Waste Manual SW-846
and /or 40 CFR part 136 as follows :
ANALYTE
Volatile Organics
Pesticides
BNAs
PCBs
PCDD/PCDFs
METHOD
8240
8141
8270
8081
8280
E NVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
It was agreed that all laboratories employed in the analysis of samples from the
PCB landfill would perform EPA CLP equivalent analytical work. However, the
parameters tested, methodology and data validation package submitted from the
NC State Laboratory (NCSL) failed to meet even minimal CLP criteria, with
significant deficits to include a truncated parameters list and failure to report even
basic QNQC data. The data generated by NCSL was unsupported by quality
control information and is not usable to characterize the samples. ECO data
validaters consider it to be suitable at best only as "estimated" quantitations.
E NVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
4.0 SAMPLING LOCATIONS
4.1 -State Sample Collection
The following samples were collected in the noted media at the indicated
locations at the Warren County PCB Landfill:
SAMPLE SAMPLE
LOCATION NUMBER
Landfill air vent WL-001-AR
WL-006-SS
Surface soil near through
air vent* WL-0015-SS
Duplicate of one
of above samples WL-026-SS
WL-016-SS
Surface soil near through
pump house WL-025-SS
Duplicate of one
of above samples WL-027-SS
Seep on slope* WL-005-SS
Monitoring well WL-001-GW
#1
Monitoring WL-002-GW
well #2 *
SAMPLE MEDIA ANALYSES
arr
soil
soil
soil
soil
soil
water
water
ORDERED
PCB
PCB
PCB
PCB
PCB
PCB
VOC/SVOC/
PEST/HERB/
PCB/INORG/
DIOXIN
VOC/SVOC/
PEST/HERB/
PCB/INORG/
DIOXIN
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
SAMPLE SAMPLE
LOCATION NUMBER
Monitoring well WL-003-GW
#3
Monitoring WL-004-GW
well #4 *
Duplicate of
WL-004-GW WL-005-GW
Landfill air vent * WL-001-LC
landfill air vent * WL-002-LC
Richneck creek,
upstream WL-001-SW
Richneck creek,
upstream WL-001-SD
Richneck creek,
downstream WL-002-SW
Richneck creek,
downstream * WL-002-SD
Unnamed
Tributary,
upstream WL-003-SW
SAMPLE MEDIA ANALYSES
water
water
water
dry
landfill contents
wet landfill
contents
surface water
sediment
surface water
sediment
surface water
ORDERED
VOC/SVOC/
PEST/HERB/
PCB/INORG/
DIOXIN
VOC/SVOC/
PEST/HERB/
PCB/INORG/
DIOXIN
VOC/SVOC/
PEST/HERB/
PCB/INORG/
DIOXIN
VOC/SVOC/
PEST/HERB/
PCB/INORG/
DIOXIN
VOC/SVOC/
PEST/HERB/
PCB/INORG/
DIOXIN
PCB
PCB
PCB
PCB
PCB
E NVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
SAMPLE SAMPLE SAMPLE MEDIA ANALYSES
LOCATION NUMBER
Unnamed
Tributary,
upstream WL-003-SD sediment
Unnamed
Tributary,
downstream WL-004-SW surface water
Unnamed
Tributary,
upstream WL-004-SD sediment
Duplicate of
WL-004-SW WL-005-SW surface water
Duplicate Of
WL-004-SD WL-005-SD sediment
* DENOTES SAMPLE SPLIT WITH ECO FOR
INDEPENDENT ANALYSIS
ORDERED
PCB
PCB
PCB
PCB
PCB
E NVIRONMENT AL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
4.2 -Split Sample Locations
The following samples were split with ECO for analysis at an independent CLP
laboratory:
SAMPLE
LOCATION
Surface soil near
air vent
Surface soil from
seep
Monitoring
well# 2
Monitoring
well #4
Dry landfill
contents
Duplicate dty
landfill contents
Wet landfill
contents
Richneck creek,
downstream
sediment
Sediment basin
outlet ravine
Filter system inlet
SAMPLE
NUMBER
IC-001-SS
IC-002-SS
IC-001-GW
IC-002-GW
IC-001-LC
IC-002-LC
IC-003-LC
IC-001-SED
IC-003-SS
IC-001-LCH
ANALYSES ORDERED
VOC/SVOC/PEST /HERB/PCB/
INORG/DIOXIN
VOC/SVOC/PEST/HERB/PCB/
INORG/DIOXIN
VOC/SVOC/PEST /HERB/PCB/
INORG/DIOXIN
VOC/SVOC/PEST /HERB/PCB/
INORG/DIOXIN
VOC/SVOC/PEST /HERB/PCB/
INORG/DIOXIN
VOC/SVOC/PEST /HERB/PCB/
INORG/DIOXIN
VOC/SVOC/PEST/HERB/PCB/
INORG/DIOXIN
VOC/SVOC/PEST /HERB/PCB/
INORG/DIOXIN
VOC/SVOC/PEST /HERB/PCB/
INORG/DIOXIN
VOC/SVOC/PEST /HERB/PCB/
INORG/DIOXIN
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
5.0 FIELD CHANGES TO SAMPLING PLAN
Several changes to originally planned sampling order were necessitated by field
conditions. The following changes/additions to the scheduled sampling effort
were made in the field:
ECO SAMPLE SAMPLE LOCATION FIELD CHANGES
NUMBER
IC -00 I-LC diy landfill contents only enough diy material
recovered for VOC and PCB
analysis
IC-002 -LC
IC-003 -GW
duplicate diy landfill
contents
Limmer well
sample duplicate of wet landfil)
contents because not
enough diy material recovered for
analysis
added sample -PCB analysis only
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
6.0 METALS ANALYSIS
6 .1 - S wnmaiy
Metals results are swnmarized in Table 1. Blanks and non-listed analytes were
non-detects. Analytical detection limits vaiy between the laboratories and the
samples were low concentration. Detections were inconsistent. The NC State
Laboratory data does not show strong adherence to minimal QC requirements and
those results are therefore estimated. Because concentrations are low, no impact
on the detection of risk to human health and the environment is expected because
the samples are below TCLP limits. If MCLs for compliance with SDW A are the
limits, a reevaluation of the data quality is necessaiy.
6.2 -NC State Laboratory Results
Five soil and ten water samples were sent for analysis of total and (TCLP)
leachable hazardous metals.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
DETECTION LEVELS:
METAL SOIL (mg/kg) TCLP (mg/L) WATER (mg/L)
Arsenic 2.0 0.01 0.01
Barium ? ? 0.01
Cadmium 9.8 0.05 0.002
Chromium 9.8 0.05 0.01
Lead 20 0.1 0.005
Mercury 0.09 0.01 0.0005
Selenium 1.0 .005 0.005
Silver 9.8 .05 0.05
The sample size and dilution used to determine the leachable metals by the TCLP
(EPA Method 1311) should result in a 200 X difference between the two analyses.
No where in the NC State Laboratory report is the detection limit for barium given.
Mercury detection limits differ by greater than lOX, indicating an error.
Holding Times: Although water holding times are often applied, there are no
required holding times for soil samples. Water holding times are 180 day except
for mercury which is 28 days for properly preserved samples. No holding times
exceeded these limits.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
Calibration: Proper calibration for samples analyzed by atomic absorption are a
minimum of three standard concentrations and a blank. The standards need to span
the range of the sample concentrations. Calibrations for mercury and silver in
water and mercury and lead in soil appear to have been carefully executed, and
that data appears to be usable.
Calculation algorithms and factors are not given for any results. It is not possible
to verify the connection between raw and final data except through stated
recoveries on control samples. Although laboratory control samples showed good
recovery, the NCSL analytical calibrations were mostly above the samples, and the
remainder of the data must be qualified as estimated.
6.3 -Split Sample Analysis
Six soil and three water samples were sent to ETC, an independently contracted
laboratory, for analysis of total and leachable (TCLP) metals.
E NVIRONMENT AL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
DETECTION LEVELS:
METAL SOIL (mg/kg) TCLP (mg/L) WATER (mg/L)
Arsenic 12.5 0.050 0.050
Barium 0.20 0.002 0.002
Cadmium 1.0 0.004 0.004
Chromium 3.50 0.007 0.007
Lead 11.3 0.045 0.045
Mercmy 0.020 0.001 0.007
Selenium 18.8 0.075 0.075
Silver 1.75 0.007 0.007
Detection limits for most elements for the two methods are slightly different from
the 200X expected factor. Chromium and mercmy are the most extreme. No
significant impact on data quality is evident, except that it makes comparison of
results from the two laboratories for low concentration samples unreliable. TCLP
detection limits for the extract are also different, but do not affect the detection of
samples that fail the regulatory limits.
Holding Time: No holding time problems occurred.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
Calibration: The ETC laborat01y QC report maintains that calibrations met all
criteria. No calibration results or criteria are given to verify this. Laboratory
control samples (method blank, matrix spike and duplicate) are all presented as
within limits. The limits given are appropriate for the analytical method.
Recoveries of spiked amounts indicate accurate analyses for the samples.
The method of calculation of the duplicate percent difference is unclear. Because
a different spike amount is reported in each duplicate, the standard calculation
does not work. Attempts to check the calculation and reproduce the presented
result were unsuccessful.
E NVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP FINAL SAMPLE ANALYSIS REPORT FEBRUARY 1995 SAMPLE# LAB As Ba WL 001 LE NCSL 0.23 IC 001 LCH ETC 0.224/0.21 6 WL 002 LE NCSL 0.07 WL 002 BL NCSL WL 003 BL NCSL WL 004 BL NCSL 0.06 NCSL 0.05 WL 002 GW NCSL IC 001 GW ETC 0.034/0.17 6 WL 003 GW NCSL WL 004 GW NCSL 0.08 IC 002 GW ETC 0.045/0.15 8 WL 005 GW NCSL 0.08 WL 002 LC NCSL 2 23/0.42 IC 002 LC ETC 28.8/0.385 IC 003 LC ETC 26.7/0.335 WL 002 SD NCSL 16/0.38 IC 001 SED ETC 12.3/0.419 WL 001 SS NCSL 88/0.46 IC 003 SS ETC 122/0.420 WL 005 SS NCSL 2 94/0.58 WL 006 SS NCSL 72/0. 70 IC 001 SS ETC 81.4/0.768 IC 002 SS ETC 136/0.519 Cr /0.010 I 0.008 12 15.6/0.170 17/0.167 14.7/0.008 12 23.7 12 16 26.7 24.4 Hg Pb 0.041 35/0.12 0.026 61.8/0.170 0.025 46.9/0.167 /0.048 0.041 0.04 26.4 0.018 ENVIRONMENTAL C OMPLIANCE 0 RGANIZATION NITS LISTED PPM) Se 1 1.4
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
7.0 VOLATILE ORGANICS
Sample results for volatile organic constituents are summarized in Table 2. Only
quantifiable detections are listed. The modifier "j" indicates that a detectable
quantity for the target substance is readily identifiable, but the quantity is below
the lowest standard used in the calibration, and the quantitation is estimated. The
modifier "b" indicates some presence in the laboratory processing blank of the
relevant constituent. The determination of whether blank contamination is
creating a "detection" in environmental samples is controlled by EPA Functional
Guidelines. The guidelines provide that for common laboratory solvents such as
acetone, methylene chloride and 2-butanone, the level of concern for original
samples concentrations must meet or exceed a factor of ten. For all other blank
contaminants, the threshold level of concern is raised by a factor of 5 or greater.
7.1 -Summary
Seventeen samples were sent to the NC State laboratory for analysis of target
compound list (TCL) volatile organic substances. The target compound list for the
analysis of volatile organics contains about 33 compounds. The raw data analyte
list used by NC State laboratory contains only 22 compounds (and the report sheet
contains compounds that are not analyzed for on the raw data). The analyte list
used by ETC had 18 more compounds than the TCL. NC State laboratory did not
meet TCL criteria for the waste characterization. Although the presence of these
contaminants may be detected in the tentatively identified compound search,
detection and quantitation do not meet the criteria for an adequate characterization.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
Detection limits for CLP work are the contract required quantitation limits of the
EPA Statement Of Work. For the TCL these are 10 ppb for all compounds. NC
State Laboratory in general, met or exceeded these on its report sheet, but because
the report sheet does not correlate with the raw data sheet, actual limits are
indeterminate. ETC met or exceeded these limits for all except for some ketones
and methylene chloride. No significant levels of these were detected by either
laboratory. No impact on data quality for detection levels are likely. Of greatest
note is the shortened analytes list.
Holding Time: The maximum holding times for analysis of volatile organics in
properly preserved ( acidified to Ph<2, and held at 4 deg. C) waters is 14 days. Soil
samples for volatiles should meet the same criteria, although none is mandated. No
exceedances were noted for VOA by either laboratory.
Calibration: No GC-MS tuning or initial calibration data was submitted by NC
State laboratory to meet CLP criteria. Continuing calibration data was not
supplied. No indication of what standards were used, or whether QC criteria was
met was submitted. No laboratory quality control sample data for method blanks,
spikes, duplicates, laboratory check samples or surrogate recoveries were included.
Data must be considered as unsupported and unusable.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
The data package submitted by the independent laboratory, ETC contained QC
data sufficient to assess data usability. Initial and continuing calibration was
correctly perlormed and submitted. 12 hour tuning checks met criteria.
Standardization met all QC criteria. MS/MSD spike recoveries were low for waters
for benzene and 1,2-dichloroethene on a sample from another matrix. Surrogate
recoveries for samples from the Warren County group within the analytical batch
were all within QC limits indicating accurate identification and quantitation of
target analytes.
TCLP extract analysis was done on samples sent to ETC. Three samples identified
PCE at the detection level in the extracts. The three samples (IC 001 LCH, IC 001
GW, IC 001 GW) did not have detectable levels in the original samples. It is likely
that these samples were contaminated in the laboratory.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP FINAL SAMPLE ANALYSIS REPORT FEBRUARY 1995 TABLE 2 -COMPILATION OF VOLATILE ORGANIC DETECTIONS SAMPLE# VOA LAB MethCl Cloro 2-Buta.none form WL 001 LE NCSL IC 001 LCH ETC WL 002 LE NCSL WL 002 BL NCSL 2jb WL 003 BL NCSL 15jb 2j WL 004 BL NCSL 14 2j WL 001 GW NCSL WL 002 GW NCSL IC 001 GW ETC WL 003 GW NCSL WL 004 GW NCSL IC 002 GW ETC WL 005 GW NCSL WL 002 LC NCSL Sj IC 002 LC ETC IC 003 LC ETC WL 002 SD NCSL Sjb IC 001 SED ETC WL 001 SS NCSL IC 003 SS ETC WL 005 SS NCSL Bjb WL 006 SS NCSL Bjb IC 001 SS ETC IC 002 SS ETC WL 001 LC NCSL IC 001 LC ETC WL 001 BL NCSL 3jb ALL UNITS LISTED IN PPB Acetone Bnz ClBnz l,2di ClBnz 2j 2.58j 2j 60 82. 7j 252 132 62 4j 76.3j l.98j 108 10.6 E NVIRONMENTAL COMPLIANCE 0 RGANIZATION l,3di l,4di ClBnz ClBnz 23.9 420 12.3 211 23 25.3 63.1 PCE Toluene Xyl lj 2j /0.005 4.76j /0.005 /0.005 1. 89j 4.08j
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
8.0 SEMI-VOLATILE ORGANICS
8.1 -Summary
Fourteen samples were sent to NC State laboratory for semi-volatile analysis. Nine
of the samples were also duplicated and sent to ETC for analysis of total and
extractable semi-volatiles. Detections are summarized in Table 3.
Holding Time: Method holding time for semi-volatile analyses require
completion of extraction within seven days of collection for water samples ( 14-
days for non-aqueous) and analysis within 40 days of extraction. Both NC State
laboratory and ETC completed extraction and analysis within these criteria.
Calibration: The analytical data for GC-MS analysis of semi-volatile organics by
NC State laboratory is unsupported with QC information. The data can not be
characterized as to accuracy or precision.
ETC data reports were supported with QC results including tuning checks,
calibrations, method blanks, MS/MSD results, and surrogate recoveries.
Calibrations were correctly done. Some low surrogate recoveries indicate that
quantitation of semi-volatiles for samples IC 002 LC and IC 003 LC are likely
greater than reported. TCLP acid extractables might have been greater than
reported based on some low surrogate recovery. However, no level of acid
extractables were present in the original material (IC 001 SED) and no impact on
data usability is indicated.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP FINAL SAMPLE ANALYSIS REPORT FEBRUARY 1995 TABLE 3 -COMPILATION OF SEMI-VOLATILE ORGANIC DETECTIONS SAMPLE# LAB WL 001 LE NCSL IC 001 LCH ETC WL 002 LE NCSL WL 002 BL NCSL WL 003 BL NCSL WL 004 BL NCSL WL 001 GW NCSL WL 002 GW NCSL IC 001 GW ETC WL 003 GW NCSL WL 004 GW NCSL IC 002 GW ETC WL 005 GW NCSL WL 002 LC NCSL IC 002 LC ETC IC 003 LC ETC WL 002 SD NCSL IC 001 SED ETC WL 001 SS NCSL IC 003 SS ETC WL 005 SS NCSL WL 006 SS NCSL IC 001 SS ETC IC 002 SS ETC ALL UNITS LISTED JN PPB l,3diC1Bnz 330 l,4diC1Bnz Phth 330 474 388 E NVIRONMENTAL COMPLIANCE 0 RGANIZATION 6333
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
9.0 PESTICIDES /PCBS
9.1 -Summary
Fifty-three water and non-aqueous samples were sent to NC State laboratory for
analysis. Eleven of these were duplicated and sent to ETC which sent them on to
Weston (WST) for analysis of chlorinated pesticides and PCBs. Detections are
summarized in Table 4. In addition to the chlorinated pesticides, ETC also
analyzed for TCLP extractable chlorinated and total and extractable herbicides and
phosphorus compounds. No detections of any pesticides were found, only PCBs.
Holding Times: As noted previously, all holding times were reported as met for
water and non-aqueous extractions and analyses by all laboratories.
Calibrations: NC State laboratory supplied as supporting QC documentation with
the results, the GC chromatograms. There appears to be data indicating calibration
and accurate quantitation. The format of the documentation is not summarized in
such a manner as to track the calibration algorithm. Some supplied calculations
show errors in quantitation. Results must be considered estimated, and not
conclusive of analysis.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
ETC and WST documentation met all criteria for support of calibration and
quantitation. Data included method blanks, initial and continuing calibrations,
laboratory control samples, and MS/MSD results. Where duplicate samples
contained PCBs (WL 001 LC and WL 002 LC) NC State laboratory results were
about 1/2 those of the independently contracted laboratory.
9 .2 -PCB Calibration Error
A five page set of documents is attached as Appendix A -Figures 1-5 to illustrate
an example of a calibration error problem with the data submitted to support the
analysis of samples from Warren County PCB Landfill (NC), for PCBS by the NC
State laboratory.
Appendix A -Figure 1 is the Gas Chromatograph report sheet showing the
calibration data for a series of three concentrations (300, 1500, 3000) of Aroclor
1260 and the analytical results for six samples.
E NVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
The columns are headed by a series of retention times ranging from 45.733 to
59 .50 with a final column labeled "T". The number in each column is the area of a
compound peak exiting the GC column at that time from resolution/separation of
the 1500 ng/mL standard mixture of PCB compounds found in Aroclor 1260. The
chromatogram itself is shown as Appendix A-Figure 2, and in greater detail in
Appendix A-Figure 3, with each peak marked at the exit time. Because of slight
differences in samples, the key peaks may not exit exactly at the expected time.
For example the first two calibration peaks exited about 0-017 minutes after the
expected time 47.750 versus 47.733 minutes. There is a "window" of acceptable
performance that is part of the calibration procedure. This calibration is within
that window, and later peaks exit right on time.
Appendix A-Figure 4 is a print out of the retention times and areas and heights of
the individual peaks. The key peaks areas are transferred to the calibration sheet.
The total area of these compounds is summed under "T". The problem occurs
with the 49.667 peak which comes out at +0.017 minutes at 49.683 with an area of
1969183. However the sheet contains the area of 113 7724 which is the area of the
peak at 45.750 minutes. This leads to a different total from the listed 10,893,238
to 20,042,929.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP FINAL SAMPLE ANALYSIS REPORT FEBRUARY 1995 TABLE 4 -COMPILATION OF PCB DETECTIONS SAMPLE# LAB WL 004 BL NCSL WL 002 LC NCSL IC 002 LC WST IC 003 LC WST IC 001 SS WST IC 002 SS WST WL 003 SS NCSL WL 004 SS NCSL WL 028 SS NCSL WL 029 SS NCSL WL 001 LC NCSL IC 001 LC WST ALL UNITS LISTED IN PPB 1248 63 60 1.45 0.22 E NVIRONMENTAL COMPLIANCE 0 RGANIZATION 1260 151.8 303 303 0.008j 0.004j 0.53 1.15 301.4 880
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
10.0 PCDD/PCDFs
10.1 -Summary
Nineteen samples were collected for analysis of dioxin and furan contents. Eight
went to Triangle Laboratories and eleven to PACE. Detections are compiled in
Table 5. It is important in comparing data to note the units. The units ppb and
ppq differ by a factor of 1,000,000. This makes most of the data from the two
laboratories difficult to compare. However, one sample by TLI (WL 001 LC) was
done at the higher DL and confirms the levels found by PACE in other samples.
The presence of dioxins/furans is often ubiquitous. At ppq levels the laboratory
processing is often a source of detectable levels. The "j" and "b" modifiers are as
noted above indicating concentrations below reliable quantitation limits, and the
presence of a an analyte in the method blank. Two of the TLI water method
blanks are included in the table adjacent to relative TLI samples to show the
contribution of laboratory contamination. Levels in the samples exceed blank
levels well in excess of the 5X factor elevation to account for blank contribution.
The samples had significant levels before processing, and if other laboratory
blanks do not show the levels detected here, the source for this contamination may
be the samples themselves which were processed with the blank.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
Holding Times: No extraction or analysis holding time problems were observed.
The extreme stability of dioxin and furans makes minor delays negligible. TLI and
PACE exceeded extraction times for some waters by 2-5 days, and for the solid
sample WL-002-LC, TLI exceeded the 14 day limit by 16 days. The data usability
from that analysis may not be equal to the others. This may have caused the lower
concentrations found compared to those from duplicates IC 002 LC and IC 003 LC
analyzed by PACE.
Calibration: Both laboratories supplied CLP quality data packages with QC
documentation supporting accurate tuning and calibrations. QC data included
method blanks and laboratory control samples all reporting recoveries with
acceptable limits.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
TABLE 5-COMPILATION OF PCDD/PCDF DETECTIONS
SAMPLE# LAB UNITS 2378-TCDD
TLIWB TLI ppq
WL00lLE TLI ppq 9.0
IC00lLCH PACE oob
WL002LE TLI 000 8.3
IC00lGW PACE oob
WL002GW TLI 000 13.2
WL003GW TLI 000 16.7
WL004GW TLI 000 10.9
IC002GW PACE oob
WL00lSW TLI 000
TLIWB TLI ppq
WL002BL TLI ppq
WL002LC TLI ppq
IC002LC PACE oob
IC003LC PACE oob
IC00ILC PACE NA
IC00lSED PACE oob
IC003SS PACE oob
IC00lSS PACE nob
IC002SS PACE nob
IC003GW PACE NA
12378-
PeCDD
11.1
10.5
20.5
27.9
15.4j
123478-123678-123789-
HxCDD HxCDD HxCDD
3. lj
4.2j 8.8 8.lj
6.2 8.lj 8.lb
19.0 24.7 26.3b
22.7 29.8 31.5b
12.2 16.7 18.2b
10.5 14.2j l l.6jb
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
TABLE 5-CONTINUED COMPILATION OF PDCC/PCDF DETECTIONS
SAMPLE# LAB UNITS 1234678-
HoCDD
TLIWB TLI ODO 4.2
WL00lLE TLI ODO 38.2
IC00ILCH PACE nob
WL002LE TLI ODO 54.3
IC00lGW PACE nob
WL002GW TLI ppq 134
WL003GW TLI nna 203
WL004GW TLI ODO 104i
IC002GW PACE oob
WL00lSW TLI nna 82.6b
TLIWB TLI ODO 13.8
WL002BL TLI D00 13.5b
WL002LC TLI ODO 0.028
IC002LC PACE nob
IC003LC PACE nob
IC00lLC PACE NA
IC00lSED PACE oob
IC003SS PACE ppb
IC00lSS PACE oob
IC002SS PACE oob
IC003GW PACE NA
OCDD
12.3
26.3
24.7
606
1050
559
397
30.0j
69.7b
1.970
0.3237
0.2774
1.1889
2.9478
0.5782
2378-12378-23478
TCDF PeCDF PeCDF
3.7J
49.9 13.4b 21.1
56.9 14.lb 17.9
70.4 47.0 43.6
93 .1 92.2 79.5
65.3 20.2ib 7.9
58.7 50.4
7.9i
0.079 0.0328 0.0808
0.5214 0.1171 0.4418
0.1133 0.0329 0.1188
E NVIRONMENTAL
C OMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
TABLE 5-CONTINUED COMPILATION OF PCDD/PCDF DETECTIONS
SAMPLE# LAB UNITS 123478-123678-
HxCDF HxCDF
TLIWB TLI PPQ 4.0 3.7
WL00lLE TLI noa 31.lb 11.6b
IC00lLCH PACE nnb
WL002LE TLI PPQ 39.6b 11.4b
IC00lGW PACE nnb
WL002GW TLI noa 85.1 30.5b
WL003GW TLI PPQ 114 40.lb
WL004GW TLI PPQ 70.6b 19.9b
IC002GW PACE nnb
WL00lSW TLI ppq 54.5b 18.7jb
TLIWB TLI noa 6.3
WL002BL TLI noa
WL002LC TLI D00 0.753
IC002LC . PACE oob 4.7059 0.5958
IC003LC PACE oob 1.1452 0.1712
IC00lLC PACE NA
IC00lSED PACE ppb
IC003SS PACE oob
234678-
HxCDF
7.9
17.lb
21.7b
40.lb
57.8
36.9b
30.3b
16.0j
18.0b
0.0658
0.3657
0.1010
123789-1234678-123478-
HxCDF HpCDF HpCDF
3.9 4.9 4.2j
4.0ib 41.2b 5.7b
5.9b 53.3b
12.0ib 118 14.2b
17.9b 160 21.5jb
7.6ib 99.3
72.6b
9.5j 11.8
5.6b
0.673 0.628
3.0825
0.8958
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
OCDF
61.1
46.8
115
205
105
66.9
28.8j
12.9ib
4.630
14.435
4.2072
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
11.0 DISCUSSION OF ISSUES RELATED TO SAMPLE RESULTS
11.1 -Relative Solubilities of PCDD versus PCBs
11 .1.1 -Properties of PCBs
PCBs are extremely stable and persistent environmental contaminants.
PCBs exhibit strong lipophilic affinity. Solubility in water is directly related
to degree of chlorination; i.e., isomers or isomeric mixtures with increasing
chlorination show a decrease in water solubility. PCBs vary from
approximately 12 to 68 % chlorine. The degree of chlorination in PCB
isomeric mixtures may be identified by their designation, e.g., Arochlor
1242 (42% chlorination), Arochlor 1254 (54% chlorination, Arochlor 1260
(60% chlorination). PCBs appear to be slightly less soluble than dioxins
based on 1994 EPA chart graphed as Figure 1. Studies have also indicated
that this strong hydrophobic (i.e. lipophilic) absorption of PCBs onto soil is
a function of organic matter in the soil, and that once absorbed, such
compounds do not readily desorb. Reports indicate that in aquatic
environments, PCBs show a partition coefficient between sediment and
water of approximately 10,000 time more affinity for sediment than water,
although this ratio could be significantly affected by the presence of other
constituents like salt, hydrocarbons ( oil) or other organic chemical
contaminants.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
0.01 0.001 I .....] ti) E 0.0001 -+-coo 5 ---COF i:o ---Jlr-PCB 0.00001 ~ ~ __._ ~ ~ ~ ~ 0.000001 ~ ~ ~ '-.... I 0.0000001 + ~ 0.00000001 4 5 6 7 8 CHLORINE NUMBER COPIED FROM EPN606/6-88/005Cb June, 1994
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
Correspondingly, their behavior in soil absorption should be the rough
inverse of their aqueous solubility; that is, the more chlorinated the
compound, the greater its affinity to become bound to soil. It also follows
that the more organic in nature the soil is, the more tightly bound the PCBs
become. Compounds exhibiting such properties would not be expected to
readily leach or diffuse in the soil, nor would they be expected to readily
transport through groundwater. Displacement through erosion of
contaminated soil particulates, or sedimentation, is the usual and more
probable mechanism of diffusion. Or, in simple terms, once in place on soil
containing a high level of organic matter, the PCBs would be expected to
remain in the soil rather than readily partitioning and transporting through
groundwater.
11.1.2 -Properties of Dioxins
Like PCBs, the properties of dioxins may be related to the degree of
chlorination of isomeric forms; 75 possible chlorinated isomers of dibenzo-
p-dioxin can be formed. Chemical solubility theory predicts that chlorinated
dioxins will behave similarly to PCBs, i.e., the more highly chlorinated, the
more hydrophobic in character (less water soluble).
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
The greater observed solubility of dioxins in water over PCBs is related to
several factors occurring in interactions of the respective molecules with
water at the molecular level -chlorinated dioxins are more likely to be
soluble or form azeotropic forms with water because the molecule is
slightly more polar than PCB. The dioxin's oxygen atoms and hydrogen
atoms are slightly more susceptible to interaction through van der Waals
forces or weak hydrogen bonding with the water's hydrogens. Information
also suggests that dioxins are not as resistant to desorption from soils as the
PCBs are, and being slightly less lipophilic would be expected to have a
lower partition coefficient than a PCB of corresponding chlorine number
(i.e., more likely to move from soil into water).
11 .1.3 -Transport and fate in water systems
Dioxin has been reported in the literature to be a contaminant of Arochlor
1254, and under certain conditions involving partially burned PCBs or the
presence of unreacted chlorophenol contaminants in Arochlor mixtures, it is
not unreasonable to assume dioxin contamination of PCBs. Information
currently available suggests that dioxins show somewhat greater solubility
in water than PCBs. Furthermore, literature indicates that PCBs have a
tendency to strongly absorb to soils with high organic content, are highly
resistant to desorption, and in an aqueous environment show a low
likelihood of partitioning into the aqueous phase from sediments.
E NVIRONMENT AL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
In an environment where the PCB concentration is significantly higher than
the corresponding dioxin concentration, and the PCBs, having a high
affinity for soil and relatively low affinity for water compared to dioxins, it
is not unreasonable to expect the dioxins to be "forced out" of the soil and
into the aqueous phase. Any PCBs released from the soil into an aqueous
phase would be expected to readily reabsorb back into the PCB/soil
conglomerate rather than remain in solution, operating on the "like
dissolves like" principle, which states simply that the PCBs would be more
likely to dissolve in a medium more like the PCBs themselves rather than
water. Dioxin, however, would be less likely to readily reabsorb into the
PCB/soil mix, and despite its relatively low solubility in water, would be
more likely to be transported through the aqueous medium (groundwater).
Having discounted through this sampling effort any other overwhelming
evidence of possible dioxin sources, including contamination from other
aquifers, dioxin contamination from off-site use of pesticide sources or
laboratory error, release of dioxin from the PCB landfill is the most likely
source for the demonstrated dioxin and furan contamination in on-site
monitoring wells.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
11.2 -Evaluating PCDD/PCDF Concentrations
As demonstrated by Table 5, a number of samples from the Warren County
landfill revealed contamination with various congeners of dioxins and
furans. Although the research on the toxicity of dioxins and furans is
incomplete, EPA has created a method for weighting the relative toxicity of
various forms of dioxin and furan based on the standard of 2378 TCDD.
The weighting scale reports Toxicity Equivalence Factors or TEFs. The
EPA TEF chart is shown at Table 6.
The TEF weighting factors are multiplied against concentrations of the
various dioxins and furans detected in samples. The sum of all the TEFs
for a particular sample is then totaled to yield a TCDD Equivalent (TEQ).
The formula for TEQs is as follows:
TEQs = { C congener X TEF congener }
TEFs as summed into a TEQ are an evaluation tool in judging contaminant
concentrations and relative toxicity.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
It should noted that many of the congeners detected in the Warren County
PCB landfill are given zero value or weight in the TEF table, while other
congeners have weighting values that are a fraction of the 2378 TCDD
value of one, depending on relative observed toxicity. It is important to
factor all weighted congeners into a consideration of whether or not the
contaminant hits in a particular sample are cause for concern.
The detection of dioxins and furans in three groundwater and one surface
water sample from the PCB landfill are of particular concern. As
discussed, dioxins and furans are relatively insoluble in water, although
more soluble in general than the PCBs that are co-located at this site.
Therefore it is rare to detect any dioxin/furan contamination in water.
Additionally, these detections are of concern because the federal Safe
Drinking Water Maximum Contaminant Level (MCL) is an extremely
minute 30 parts per quadrillion for 2378 TCDD.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
Several of the water samples have 2378 TCDD concentrations that alone
approach the federal standard. When a TEQ is calculated for these
samples, three of the four exceed the 30 ppq benchmark.
SAMPLE NUMBER
WL-002-GW
WL-003-GW
WL-004-GW
WL-001-SW
TEQ
40.211 ppq
71.63 ppq
23 .05 ppq
31.53
DENOTES TEQ EXCEEDING MCL FOR 2378 TCDD
It is apparent that the contaminant concentrations detected in the on-site
monitoring wells are at, or above the level deemed safe for human
consumption, and the use of on-site water for drinking, cooking and bathing
would be considered a potential human health risk under EPA risk exposure
criteria.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
Of additional concern is the potential impact of this contamination on
environmental receptors such as wildlife and fish, and the probability that
such contaminations will create further human exposure through the food
chain. A recent EPA risk assessment cited in the EPA Dioxin Fact Sheet
has found that the amount of 2378 TCDD in surface waters that would be
associated with one additional cancer in a population of 100,000 could be
as low as O .13 parts per quadrillion based on the consumption of
contaminated water or fish.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
TABLE 6 -TOXICITY EQUIVALENCE FACTORS (TEFs)
COMPOUND
Mono-,Di-, and Tri-DDs
2,3,7,8 -TCDD
Other TCDDs
2,3,7,8 -PeCDD
Other PeCDDs
2,3,7,8-HxCDD
Other HxCDDs
2,3,7,8 -HpCDD
Other HpCDDs
OCDD
Mono-, Di-, and Tri CDFs
2,3,7,8-TCDF
OtherTCDFs
1,2,3,7,8 -PeCDF
2,3,4, 7,8-PeCDF
Other PeCDFs
2,3,7,8 -HxCDF
Other HxCDFs
2,3,7,8-HpCDF
Other HpCDFs
OCDF
TEF
0
0
0.5
0
0.1
0
0.01
0
0.001
0
0.1
0
0.05
0.5
0
0.1
0
0.01
0
0.001
E NVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
12.0 SCIENCE ADVISOR OPINIONS AND CONCLUSIONS
• Dioxins and Furans are demonstrated co-contaminants of PCBs
• Although neither PCDD/PCDF or PCB are extremely soluble in water,
PCDD/PCDF appear to be slightly more soluble than PCBs with
their strong soil binding tendency
• Dioxins and furans were detected in the groundwater monitoring wells located
on the site
• Dioxins and furans in the groundwater cannot be attributed to background
contamination due to the absence of any other chlorinated contaminants in
water and soil samples
• Contamination of the samples during handling in the field and laboratory does
not account for the concentrations detected in the water samples when
evaluated according to EPA criteria
• The TCDD Equivalents (TEQs) for several water samples exceed the federal
standard for safe drinking water which is set at 30 parts per quadrillion
• In the absence of other likely sources of chlorinated contamination, it is likely
that the PCB landfill is the source for the dioxin and furan contamination noted
at the site
• This site is appropriate for remediation based on these sampling results and the
presence in the landfill of one million plus gallons of unintended water that
could adversely impact the containment safeguards engineered into the design
of the facility
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
FINAL SAMPLE ANALYSIS REPORT
FEBRUARY 1995
• ECO does not recommend proceeding to a involved study of remedial
alternatives for cleaning up this site. As previously noted, Base Catalyzed
Decomposition (BCD) is the only non-thermal treatment technology that has
been demonstrated to be effective in destroying PCBs, dioxins and furans, and
which has received official EPA Region IV endorsement.
• ECO advises that plans be immediately commenced to begin full scale pilot
testing of BCD at the Warren County Landfill, with a target testing date in
summer 1995
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
APPENDIX A
FIGURES 1-5
PCB CALIBRATION EXHIBITS
COMPANY: SAMPLE# l/S. 71J ~n,, ~T/1 !ol "i--, J J 1lJ'1 1510~1 ~"J n Io 3Dllb "..f 1 j/'f()s-'-tf' 1f .215z.. -'Y'1,7J) ;i3tdtf 1 ll Z-75 ( 5" 3 1;4 f, q'{ Z-711,,--1ttz7 'If> Jlf 7/'J7Z,, 'f'I,...., q1 .\J. l/2.270 \ '-"1,Jt.-~ ~W\ D&IINR 3068 (Rev. 4/92) Laboratory Services DRPAll'rMBNT OP l!.NVHONHENT, UEAL'l.'8, ANO NATURAL RESOURCES Division of Laboratory Senices Knvironme~tal Organic Chemistry Branch G C REPORT SHEET DATK OF ANALYSIS: TOTAL HILLIGI\AMS L( l,,o.rl) 41,,, 7 S7'.0 8 'J P-1, ?')-a ,t';pi t, 7 rf.s () -r Jf'f•.:.?'5' '1? 4167 /au. r/t 7 /7 5'11 (,, If ttJlJ 172. I.ft Z. SI{ t Sf7<n77 7//f// Ii 1.nz Y ). a 'I 11.f'li 3J''f1.JJ7 1 t>'l'-17 lrt-,1 n JbH1t}~ /2.4 H5"r ?n1tn J t;'7?1[ t.14~11,J 1 Dl77JZ. JJ1 gJ71 JI 31.'f1 31 'I I 'fv-·¥;. 31,J '' n J" t ' f11 ()() J () 5' ftJ 313t3ft 2 707'{!( 51DZ 11 l.YiS.,i 87'11,7< 'f /,8'f 3> :n, i.2J 7'3"37'(' r-1·v,1 J ;.ol.JDoo1 ,1f /fV'l I 7f1JnJ'f L/1../i>l,f/-'{ Hl..o5"9t> /1i1~3t? ----JJ '>f JY -}<ffl.f 17 Jlll{Z/6]'( l'i' 'I) I> 1o'l-;i.1 zf/.1S'Z-/t>1,71?7 J11/t'l,'f? roq 1 Jq.r.rz. I it, {,07-1, I !/ /J lf Jt/1f 3h1r1f f J/, ,;-ti{~ .2. t i,7JtJ 1 12. ff/I 7 ).0 7f 'I I O J 1-Q \ LC... i-t)19r'Z_Lc.. rJ.,z •o ~ # L. J,O ~t:J,j @/Oc> @/tJt7 Lo <-I en-c. H1.i ~ S"fv a, ;,-,5 > ~ z ~ ~ > I ~ ~ § ~ ~
C:\EZCHROM\CHROM\PCB1260.B26. Chann&I A C·.4..-----------------------------------~0.4 Retention Time > ~ I h.s ~ C.31 ~ z t:, ~ 0100 t ~ > V ·1 fr .,.m , V ~ D D ~ I I ~ t I ~ 9 s ~ N ... ·8~t.a1 · 481r 0.11 I 111 111 n 1n.1 o.o~ 1M'# 'TB WClll I It' 1 q ' stHB3 2S fill""" l!LJ1.UNM I\A~nJlfd-lYYo,o Minutes
C:\EZCHROM\CHR0M\PCB1260.826, Channel A 0.4►.-----------------------------------~.4 Retention Tlma > '"'d '"'d 0.31 ~ ln_3 t'.":I z t:, ~ V •-~ 0 l~ r17 I II t I s V > 0 ~ 6,7.267 0,2 I I ~ s ~ 0 ~ ~ 0.11 48.7'' .. 111~33 5,4.,~7 n ! 1111 s.db~I I i I I II r·1 3,9.783 d6.067 4. 760 1,1133 0 4-6
Area Report --Channel A File C:\EZCHROM\CHROl>\\PCB1260.826 Method 1 Ci\EZCHROM\METHc;DS\508.MET Sample ID 1 pcb standard 15Q0 ng/ml Acquired : Aug 26, 1994 0Q:15138 User : John Neal =~•na=~=sm•a~•a•:maaam~-=m-a~~a==----------------------------~~--c~~=~#a•======zma=a=~~=== Pkno Ret. Time Are~ Areat Height Height\ Flags --------------------------------------------------------------------1 1.850 6.f.8157 1.981 20655 0.778 .av 2 2.367 415291 1.2n 18306 0,690 YS 3 2.600 22527] 0,689 17802 0,671 av > 4 2.883 436234 1.334 17553 0,661 'TV ~ 5 3.533 52732~ 1.612 17038 0.642 YV ~ 6 3.983 56204~ 1,718 16593 0.625 'TV trj 7 4,900 84771G 2.592 15587 0.587 'TV z 8 5.283 18014~ O.SSL 15160 0.571 'TS ~ -9 5.533 35164~ 1.075 16078 0.606 av ~ 10 5,950 30258~ 0.925 16051 0.605 YV > 11 6.217 418451 l.279 15550 0.586 'TV 12 6,?0C 31086~ 0.95D 13701 0.516 'TV 13 7.233 23416~ 0. 716 12!H7 0.487 'TS ~ 14 7.S0C 671533 2.053 17585 0.663 SV -~ 15 8.267 370814 1.134 12203 0.460 'TS ~ 16 8.66, 135847 · 0.415 11480 0.433 BV ,:i 17 9.033 175574 0.537 10969 0.413 'TS 18 9.217 151464 0.463 10844 0.409 sv trj l9 9,483 168996 0,517 10561 0.398 'TS .&;. 20 9.833 257718 0.788 10437 0.393 8S 21 10.050 168076 0.514 10068 0.379 .av 22 10.483 196592 0.601 9692 0.365 'TV 23 10.983 24581S 0.751 8778 0.331 'TS 24 11.917 49420'1 1.511 7785 0.293 8V 25 12.550 28751S 0.879 7098 0.267 'TV 26 12.950 11392? 0.34B 6724 0.253 'TS 27 13.150 114953 0.351 6493 0,245 8V 28 ll.933 24444E 0,747 5582 0.210 'TV 29 14,21') 14901E 0 .456 5272 0.199 YV 30 14. 633 10569'1 0.323 4726 0.178 'TV 3l 15,367 214234 0,655 3877 0.146 YV 32 17.2B3 11447] 0,350 1819 0.069 av
33 39.783 548252 1.676 69169 2.607 vv 34 41.833 122124 0.373 7349 0.277 vs 35 45.750 635310 1.942 67494 2.543 vv 36 46.067 711811 2.176 79792 3,007 vv 37 48.217 148625 0.45-l 16056 0.605 vv 38 48.750 1137724 3.478 1234'13 4.653 vv 39 49.250 911270 2.786 41380 1.559 vv 40 49.683 1969103 6.020 214055 8.066 w 41 50.100 2099447 6.-ll.8 242392 9.134 w 42 51.133 728224 2.226 87863 3 .311 sv 43 51.833 730815 2,234 101967 3,843 BS 44 52. 317 2826061 8.639 213289 8.038 sv > 45 52.817 611642 1.870 72672 2. 739 VS ~ 46 53.500 155803 0.476 17435 0.657 vv ~ 47 54,317 1612150 4.928 130393 4,914 vv ~ 48 54.733 737932 2,256 76198 2.871 vs :;,z 49 54.967 35-l2317 10.829 3B0867 14. 353 SB i::, 50 56.850 740707 2.264 64774 2.441 vv ~ 51 57.267 1881617 5.75.2 179544 6.766 vv 52 59.500 885012 2.706 78794 2.969 sv > 53 61.233 134210 0,410 13700 0.516 SIC I ~ Totals 32711044 100.000 :.1653641 100.000 Jo,,,( ~ ~ (!; u.
APPENDIXB
WORKSHEETS
Inorganics Technical Initial Blank ICP Interfemce Laboratory Duplicate Matrix Furnace ICP Serial Sample Result Holding Times Calibration Check Samole Control Samole Samole Analvsis Spikes Atomic Adsorp Dilution Verification Form IIA X Form III X Form IV X Form V X Form VI X Form VII X Form IX X EPA Sample X Traffic Report raw data X X X X X X X X X digestion/ X X distillation leas ICP analysis X AA analysis X Hg analysis X Cyanide X analysis calibration X verification Furnace AA raw X data RSD X instrument X printouts strip charts X sample field sheet QA/QC criteria
SemiVOC Technical GC/MS Initial Continui Blank Surroga Matrix Laborator QNQ Internal Target Holding Instrwnent Calibrati ng te Spikes/D y Control C Standard Compow1d Times Perfonnance Oil Calibrati Spikes up Sample Identificatio Check on n mass listing X LCS X chromatogram traffic report & X raw data for Regional QC samples mass spectra X sample prep sheets case narrative sample cleanup sheets library search printout & spectra for 3 TIC candidates entire data packa_ge data review results QaPjP if available Sampling & analvsis plan
SemiVOC Technical GC/MS Initial Continui Blank Surroga Matrix Laborator QNQ Internal Target Holding Instrument Calibrati ng te Spikes/D y Control C Standard Compound Times Performance on Calibrati Spikes up Sample Identificatio Check on n Form I SV-1 X X X X Form I SV-2 X X X X Form II SV-1 X Form II SV-2 X Form III SV-1 X Form III SV-2 X Fonn IV SV X Form V SV X Form VI SV-1 X Form VI SV-2 X Fonn VII SV-1 X Form VII SV-2 X Form VIII SV-1 X Fonn VIII SV-2 X Form I SY-TIC Form III LVC X chromatogram X X X X X X X X quantitation report X X X X X X X X X EPA Sample X Traffic Report chain of custody X raw data X SDG narrative X DFTPP mass X spectra
voe Teohnical GC/MS Initial Continuing Blank System Matrix Laboratory Q,A/QJ: Internal Target CQRLo Tent Holding Instrument Calibration Calibration Monitoring Spikeo/Dup contro,l Standard Compound Iden Times Perform. Compound Sample ID Comp Check Form I VOA X X X X X Form II VOA X Form III VOA-1 X X Form III VOA<~ X Form IV VOA X Form V VOA X Form VI VOA X Form VII VOA X Form VI I I VOA Form I VOA-TIC X Form III LVC-1 X chromatogram X X X X X X X X X X cruantitation rePort X X X X X X X X X X EPA Sample Traffic X Report chain of cuetndv X raw data X S00 narrative X X BFB mass eDeotra X maao listing X LCS chromatoqram X maoe ooectra X oaffl'Dle Dreo sheets X Technical GC/HS Initial Continuing Blank syotem Matrix Laboratory Q,A/QJ: Internal Target CQRLa Tent Holding Instrument Calibration Calibration Monitoring Spikeo/Dup Contro,l Standard Compound Ider, Times Perform. Compound Sample ID Comp Check 1 ibrary oearch X printout & opectra for 3 TIC candidates entire data package data review results OaPi P if available Sampling & analyeio plan
TEQ WORKSHEETS
SAMPLE NUMBER WL-002-GW
8.3 ppq 2378-TCDD X 1.0 = 8.3 ppq
606 ppq OCDD X .001 = 0.606 ppq
70.4 ppq 2378-TCDF X 0.1 = 7.04 ppq
47.0 ppq 12378 PeCDF X 0.05 = 2.35 ppq
43.6 ppq 23478 PeCDF X 0.5 = 21.8 ppq
115 ppq OCDF X 0.001 = 0.115
TEQ 40.21 ppq
SAMPLE NUMBER WL-003-GW
16.7 ppq 2378 TCDD X 1.0 = 16.7 ppq
1050 ppq OCDD X 0.001 = 1.05 ppq
93.1 ppq 2378 TCDF X 0.1 = 9.31
92.2 ppq 12378 PeCDF X 0.05 = 4.61 ppq
79.5 ppq 23478 PeCDF X 0.5 = 39.75 ppq
205 ppq OCDF X 0.001 = 0.205
TEQ 71.63 ppq
SAMPLE NUMBER
WL-004-GW
10.9 ppq 2378 TCDD X 1.0 = 10.9 ppq
559 ppq OCDD X 0.001 = 0.559 ppq
65.3 ppq 2378 TCDF X 0.1 = 6.53 ppq
20.2 ppq 12378 PeCDF X 0.05 = 1.01 ppq
7.9 ppq 23478 PeCDF X 0.5 = 3.95 ppq
105 ppq OCDF X 0.001 = 0.105 ppq
TEQ 23.05 ppq
SAMPLE NUMBER
WL-001-SW
397 ppq OCDD X 0.001 = .397 ppq
58.7 ppq 2378 TCDF X 0.1 = 5.87 ppq
50.4 ppq 23478 PeCDF X 0.5 = 25.2 ppq
66.9 ppq OCDF X 0.001 = 0.0669 ppq
TEQ 31.53 ppq
·-·02.'1?7 /95 17: 22 !!'919 541 0239 MRDDIAREAL,RTP
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
ATMOSPHERIC RESEARCH AND EXPOSURE ASSESSMENT LABORATORY
RESEARCH TRIANGLE PARK
NORTH CAROLINA 27711
February 27, 1995
MEMORANDUM
SUBJECT:
FROM:
TO:
Review of ECO Final Analysis Report -Warren County PCB Landfill
Robert G. Lewis, Ph.DE~---
Senior Science Advisoil1vfRDD (!\ID-77)
Sharon E. Rogers
Assistant Director for Policy, Planning, and Development
Solid waste Management Division
N. C. Department of Environment, Health and Narural Resow-ces
40 J Oberlin Road
P.O. Box 27687
Raleigh, NC 27611-7687
~0021005
I have reviewed the Joint Warren County and State PCB Landfill Working Group's Final
Sample Analysis Report dated February 1995 . This report was apparently prepared by ECO, who
recommends immediate remediation of the land.fill by the BCD method. I have passed the report
on to Robert L. Harless, who is our resident expert on PCDD/PCDF analytical chemistry, for
possible further comment.
Without complete sample location identification, I cannot tell where all the samples were
taken, what samples (if any) were spikes or field blanks, or, in many cases, what were duplicates.
Therefore, I cannot provide much comment on the quality of the data. However, I am familiar
with Triangle Laboratories, Inc. (TLn, and have a great deal of coofidence in the quality of their
data. The report is poorly prepared and is obviously not intended to be readily interpreted by an
individual who is not intimately familiar with the monitoring and analysis efforts.
As you know, I was intimately involved with the PCB spill cleanup, was responsible for
monitoring potential air emissions from the landfill shortly after it was closed, and served on
Governor Hunt's first commission to study detoxification of the landfill. Therefore, I do have
some appreciation of the subject. I am an expert on PCBs and semivolatile organics and am
somewhat knowledgeable concerning PCDDs/PCDFs. I am not an expert in hydrogeology or
ground water translocation of chemicals, but have seen a lot of data on movemeot of chemicals
leaking from landfills through soil and water. With those qualifications, I have the following
comments:
~003/005
General Comments
Ihe __!.epon is highly critical of the State Laboratory for allegedly poor OAIOC practices,
which are not documented, yet it uses data provided by the state as the basis of its · ~
recommendations. Had it relied on its the ECO results obr.ained from PACE, there would be no
basjs for the recommendation that the landfill be immediately remediated .
The r~ort is very poorly 'Written and structured. The several unnumbered tables on the
pages you have hand-numbered 5 through 8 and the tables of detection "levels" on pages 11 and
13 need headings; units arc missing in the text (e.g., for PCB concentrations on p. 23 and
retention times on p. 24); "Aroclor'' is usually misspelled; there are typographical errors; and
entries such as "Ph" for "pH'', the redundant "GC chromatograms", use of the term "isomer" to
refer to "congener", the criterion "extremely stable" (rather than "very") to characterize PCBs,
and the omission of I: from the TEQ equation suggest that the author of this report critiquing
chemical analytical results was not a chemist or even a careful scientist. The report also contains
serious errors in scientific deductions presented in the Discussion of Issues section.
Analytical Results ·
It is difficult to interpret the analytical results since they are not presented in any logical
fashion and there are several sample identifications that do not appear in the section on Sampling
· Locations. Even those that are identified cannot be precisely located -without a map or
coordinates indicating direction and distance from the landfiU, etc. I will confine my comments to
semivolatile organic chemicals (SVOCs), PCBs, and PCDDs/PCDFs.
SVOCs. It is difficult to believe the lack of detection of SVOCs in the samples listed.
Apparently, the target analyte list was very short and the detection limits high. The two
chlorobenzenes are, of course, residual solvent from the A.roclor mixture deposited in the landfill.
The results obtained by the N. C. State Laboratory (NCSL) and unidentified laboratory "ETC" for
I, 4-dichlorobenzene agree very well in the case of wet landfill contents (3 3 0 ppb for WL 002 LC
and 388 ppb for IC 003 LC, respectively). ETC reported 474 ppb for this analyte in the dry
landfill contents (IC 002 LC), but the corresponding State sample (WL 001 LC) is missing from
the table. No other comparison is possible. The samples ending in "LE" and "BL" and sample
WL 001 SS are not identified on pp . 5-8 . They were negative except for \VL 004 BL, which
contained a very high concentration of "Phth", presumably phthalates, probably representing
laboratory contamination. Was this a blank?
PCBs. The results obtained by NCSL for the landfill contents (wet, 151. 8 ppb and dry,
301 .4 ppb) are consistent "\.Vith previous analyses with which I am familiar and with expectations
based on original soil concentrations. The unidentified laboratory 'WST" obtained 303 ppb and
880 ppb for duplicate dry samples and 303 ppb for the wet sample. Samples WL 003, 004, 028,
and 029 SS are not identified on pp. 5-8. The results indicate no significant translocation of PCBs
from the landfill.
2
·-.02 ,,.'!7195 1 i: 23 e'919 541 0239 11:RDD/AREAL,RTP ~ 0041005
PCDDs. Results are presented for seven specific PCDD congeners in Table 5. Except for
one sample, all positive results were obtained only by 1LI. One split sample shared with PACE
was positive for OCDD. Three groundwater samples and two unidentified samples (WL 001 LE
and WL 002 LE) [leachate?] were positive for 23 78-TCDD and several higher-chlorinated CDDs,
with the former showing levels about twice those of the latter (l 1-17 ppq of 23 78-TCDD and up
to I 050 ppq of OCDD). These samples appear to be taken from three of the four monitoring
wells closely surrounding thP. landfi]] Results for the fourth well arc missing. TLI also found
higher-chlorinated CDDs in Richneck Creek at SO to 400 ppq and in the landfill contents at much
lower levels(0.03 to 2 ppq, wet). Several other samples were found positive by TLI at levels
ranging from 4 to 57 ppq, but the sites from which these samples were taken were not identified
in the report. he lone positive result from PACE was for one of a du licate set of d samples
taken from within the landfill 002 LC and IC 003 LC). PACE reported 0.3237 ppb
(a323,700 ppq) for one of these and nothing in the othe.L/fiie PACE results should be
discounted due to the large variance in duplicate results. From the TL! results, coupled with the
fact that the dumped Aroclor was negative for PCDD (USEP A and NIEHS, 1978-79), suggests
that the landfill is not the source of the PCDDs found in the groundwater and R.ichneck Creek . ......
PCDFs. The majority of the data contained in the report is on PCDFs. Ten samples of
various types were found by TRI to contain up to ten PCDF congeners. PACE found PCDFs
only in the duplicate dry landfill samples. Again, many of the samples are not identified on pp. 5-
. 8. 2378-TCDF was found at 65-93 ppq in the three groundwater (monitoring well) samples,
along with similar concentrations of several other PCDFs. 1LI also found 59 ppq of 23 78-TCDF
and 19-73 ppq of higher CDFs in Richneck Creek, but only traces of PCDFs in the landfiU itself
(0.08 ppq 2378 and 0.3-4.6 ppq higher). Once more, PACE found PCDFs only in th.e duplicate
dry landfill samplers, but their results are rather strange. The PACE results are reported in ppb at
five signincant figures and correspond to 33,000 to 14,000,000 ppq. The duplicate results differ
by 3-5. While the PACE landfill results (of0.1-14 ppb) would not seem unreasonable in light of
the PCB concentrations (up to 40 ppb of higher-chlorinated PCDFs were found in the soil before
the spill was excavated), the poor precision of their analyses and their failure to detect PCDFs in
other samples cast doubt on their .findings. I would be inclined to believe TLI, which has a
worldwide reputation of excellence for these type of analyses. As was the case for PCDDs, the
TL! results suggest that the landfill is not the source of the off-site PCDFs.
Discussion of Issues. This section of the report is filled with improper terminology,
misspellipgs, and technical errors. The authors consistently misspell "Aroclor", misuse the terms
"lipophilic" (fat-loving) and "absorption" to describe PCB adsorption by soil particles, and the
term "azeotropic" to describe PCDD water solubility . .I,he principal error made, however, is the
statement that PCDDs and PCDFs are more water-soluble than PCBs and that this property
accounts for their preferentially leaking out of the landfill. Despite the fact that PCDDs and
PCDFs contain oxygen (in ether bonds that are low in h dro hilici ) the are in fact less water
~oluble t~an s. or example, at 25DC the solubilities of 2378 TCDD and of2'.378~TCDF are
2 x 1 O"" mg/L and 4 x 10-4 mg/L, respectively1 compared to 1.14 x 10·3 mg/L for the structurally
corresponding PCB, 33'44' TeCB (cf MacKay et al., Illustrated Handbook of Physical-Chemical
3
DDD.t AREAL, RTP Ill 0051005
Properties and Environmental Fate for Organic Chemicals. Vols. I and II, 1992, the "bible" for
such information). Other tctrachlorobiphenyls have water solubilities as high as 10·1 to 10·2 .mgJ1,.
The fully-chlorinated OCDD and OCDF exhibit a thousand-fold solubility advantage over
octachlorobiphenyls (e.g., 2 x 10""' mg.IL for 22'33'551661-OCB vs. 10·7 to 10·• mg/L for
OCDD/OCDF). Data on the other congeners likewise show that PCDDs and PCDFs are always
more water soluble. PCDDs and PCDFs arc also known to strongly adsorb to soil particles,
perhaps more strongly than PCBs, due their generally more planar structure and electron-rich
oxygen orbitals.
Even if PCDDS and PCDFs were more water soluble and more mobile thao PCBs, it is
entirely unreasonable in the light of the fact that the latter are present in the landfill at thousands
of times higher concentrations that no PCBs would leak out with them. In the event oflcakage,
PCB concentrations in the monitoring wells and surface waters would be higher even if
PCDD/PCDFs were leaching out at 1000 times higher rates. Furthermore, the second law of
thermodynamics dictates that the concentrations of PCDD/PCDFs must be higher inside than
·those<>utside the landfill if the landfill is the source. Therefore, the report's conclusion that "the
PCB landfill is the most likely source for the demonstrated dioxin and furan contamination io the
on-site monitoring wells" is absolutely without support and contrary the principles of science .
. cc. RL Harless
4
t '
• I
SPECIAL SAMPLING ANALYSES REPORT
WARREN COUNTY NORTH CAROLINA PCB LANDFILL
NOVEMBER 1994
E C 0
LO-SUMMARY
This report has been prepared for the information of the Joint Warren
County and State PCB Landfill Working Group, and is not intended to represent
final work product for the technical reporting of sample analyses. ECO intends to
prepare a final, technical document containing data validation and QA/QC analysis
as soon as necessary raw data is provided by the Division of Solid Waste to allow
completion of this task.
2.0-CASE NARRATIVE
Pursuant to a request from the working group, ECO participated in a field
sampling event at the PCB landfill located in Warren County on July 27 and 28,
1994. ECO staff were on-site during all field activities, and video taped and/or
photographed random sample collections and recorded field notes regarding all
split sample collections. In addition, ECO received sample splits from pre-
selected sample locations. These splits were delivered directly to ECO staff,
immediately cooled and packed as per protocol, and maintained under constant
surveillance by ECO staff until relinquished to the overnight courier service for
shipment to the laborato:ry. All samples were analyzed by independent, out of
state facilities with State of North Carolina and EPA certification.
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
SPECIAL SAMPLE ANALYSIS REPORT
NOVEMBER 1994
Analytical results were reported directly to ECO. A duplicate data package,
containing all reporting sheets, and raw and QA/QC data was sent to the North
Carolina Division of Solid Waste directly from the laboratory.
3.0 -SAMPLING PARAMETERS
As agreed to by the Working Group, all splits collected ( except as noted in Section
6.0 -Field Changes) were analyzed for a broad range of contaminants including
Volatiles, Semi-Volatiles, Metals, BNAs, Pesticides, PCBs, PCDD and PCDFs
(Dioxins and Furans), as well as for Toxicity Characteristic Leaching Procedure or
TCLP which determines whether a sample may be classified as a regulatory
hazardous waste.
All analyses were performed using EPA approved methodologies and protocols in
accordance with Standard Methods 17th Edition; the Solid Waste Manual SW-846
and /or 40 CFR part 136 as follows :
ANALYTE
Volatile Organics
Pesticides
BNAs
PCBs
PCDD/PCDFs
METHOD
8240
8141
8270
8081
8280
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFIU WORKING GROUP
SPECIAL SAMPLE ANALYSIS REPORT
NOVEMBER 1994
4.0-ECO SAMPLING RESULTS FOR ROUTINE PARAMETERS
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
ECO SAMPLE NUMBER SAMPLE MEDIA SAMPLE LOCATION IC -001-SS SOIL surface soil near air vent SAMPLE CONTAMINANTS DETECTED bariwn -81.4 ppm chromiwn -26. 7 ppm lead -26.4 ppm tetrachloroethene -l.89J ppm l2t1J.;;\B11!~li~--~-lfl~1IIB~t.~ll■-,t'#f\l%~W~lt~~w.~~;*~~W~W\~~~'%~t\1ll~i--ll■A111l~ iilii<i IC -002-SS SOIL surface soil from seep on slope bariwn -136 ppm chromiwn -24.4 ppm mercwy-0.018 tetrachloroethene -4.08J ppm lllti~1l~lt{■w-lJ~--~t·¾}j11Bla1t,_lllla1■ll~-illi■fB1~11{i•1~~;~[1~~-IC-001-GW GROUNDWATER water from monitoring well #2 bariwn -0.034 ppm tetrachloroethene -0.005 ppm ( regulatory level= 0.70 ppm) TCLP at non-detect or well below regulatory limits
ECO SAMPLE NUMBER SAMPLE MEDIA SAMPLE LOCATION IC-002-GW GROUNDWATER water from monitoring well# 4 SAMPLE CONTAMINANTS DETECTED barium -0.045 ppm chromium -0.008 ppm tetrachloroethene -0.005 ppm lw01]iiliffilt~l1;it1i~l■i!*li!lt~!ill~1tfl:fli■~:,t,J~~}~mt,~?-~iw11ifj}il,l!jljw,-1:■•1111■•••1■-!Sil~ll,11■111■ IC-001-LC SOIL diy landfill contents acetone -76.3J ppb benzene -1. 98J ppb chlorobenzene - l 08 ppb 1,2 dichlorobenzene -10.6 ppb 1,3 dichlorobenzene -25.3 ppb 1,4 dichlorobenzene -63. l ppb :Mi:-,J.itifaiJ-¼,L-k~wi::'«"M~L{;,,~i1:~,;,i;M~~ti•tt~Eiib~i:i,1Mk:~~~;-,~i~aatik±~isi~i~:awlili:~i~ IC -002-LC SOIL duplicate diy landfill contents barium -28.8 ppm chromium -15.6 ppm lead -61.8 ppm acetone -82.7 J ppm chlorobenzene -252 ppm 1,3 dichlorobenzene -23.9 ppm 1,4 dichlorobenzene -420 ppm 1,4 dichlorobenzene -474 ppm
ECO SAMPLE NUMBER SAMPLE MEDIA SAMPLE LOCATION IC-003-LC SOIL wet landfill contents SAMPLE CONTAMINANTS DETECTED barium -26. 7 ppm chromium -17.0 ppm lead-46.9 ppm chlorobenzene -132 ppm 1,3 -dichlorobenzene -12.3 ppm 1,4 dichlorobenzene -211 ppm 1,4 dichlorobenzene -388 ppm llttl1~,tillfl1ill&.■ll■lll~~f-tll~•-c;M;.¥'ilr%A?.~WWf~~~~{i:1~1-1m~■1fl\*-111111\11111!.Blf;■■llilllnlll IC-001-SED SEDIMENT downstream sediment Richneck Creek barium -12.3 ppm chromium -14.7 ppm TCLP at either non-detect or well below regulatory levels ■~l\llllmilm~ill■l~~K¥i1~1l1n~wt~~~irw='.*twit11'-t.£Mt1mi11il~lllt.~~iltl~i1!8~iTt,~itff:1~fi,M■~iwll§IJjJ]fillffm■l■1 IC-003-SS SOIL sediment basin outlet ravme barium -122 ppm chromium -23. 7 ppm mercury-0.041 ppm TCLP at either non-detect or well below regulatory levels
ECO SAMPLE NUMBER SAMPLE MEDIA SAMPLE LOCATION IC -001-LCH LEACHATE filter system inlet SAMPLE CONTAMINANTS DETECTED barium -0.224 ppm benzene -2.581 ppm xylenes -4.761 ppm tetrachloroethene -0.005 ppm ~it~11~l@M~Jil~ll'.tJJ:~t~\!1t.tl■filiB-lll<i~~-~l~■f'.11'l~l~llllrli;~J■tlBl!■l■IB\l~lmti@ll■1i~ IC-003-GW WATER water sample from Limmer well only analyzed for PCBs
JOINT WARREN COUNTY AND STATE PCB LANDFIU WORKING GROUP
SPECIAL SAMPLE ANALYSIS REPORT
NOVEMBER 1994
5.0 -ECO SAMPLING RESULTS FOR PCBs -PCDD/PCDFs
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
ECO SAMPLE NUMBER SAMPLE MEDIA SAMPLE LOCATION IC -001-SS SOIL surface soil near air vent SAMPLE CONTAMINANTS DETECTED AROCLOR 1260-0.008 J ppm OCDD -2.9478 J ppb ~-i~--~lllr~ww-~❖;;wlif~~~'WMW,¥% .,,;;111111■ IC -002-SS 1t!i&wiil1l~f11~·· IC-001-GW SOIL surface soil from seep on AROCLOR 1260 -0.004 J ppm ~,=,xmg:~1::r1~W&ffl}'fD'W¾JJ···--Jl\~\i~f in, GROUNDWATER water from monitoring well #2 PCB/PESTICIDES -NON-DETECT t;iuwiil¾lltw;~l■m:ilr,~1*:a11111~-~-•-1•;•f1r•\~TIA-IIl11A■i■l~l~~~iii■I•·~-IC-002-GW GROUNDWATER water from monitoring well# 4 PCB/PESTICIDES -NON-DETECT rn~t~ll~1~~1w.tl~lllil~J!frlllt1li$-~f.~~<5~~t~~{P,f.M¥1-■l-lJt\W~t~iBll~-,-•i¥Iillilllll%~ID.~i,111tl{~iJ;'I~-IC-001-LC SOIL my landfill contents AROCLOR 1248-146 ppm AROCLOR 1260 -880E ppm
ECO SAMPLE NUMBER SAMPLE MEDIA SAMPLE LOCATION SAMPLE CONTAMINANTS DETECTED IC -002-LC SOIL duplicate chy landfill contents AROCLOR 1248 -63 ppm AROCLOR 1260-303 ppm 2378 TCDF - 0.5214 J ppb 12378 PeCDF -0.1171 J ppb 23478 PeCDF -0.4418 J ppb 123478 HxCDF - 4.7069 ppb 123678 HxCDF -0.5958 J ppb 234678 HxCDF - 0.3657J ppb 1234678 HpCDF -3.0825 ppb 1234789 HpCDF -1.7253 J ppb OCDF -14.4435 ppb
ECO SAMPLE NUMBER SAMPLE MEDIA SAMPLE LOCATION SAMPLE CONT AMIN ANTS DETECTED IC-003-LC SOIL IC-001-SED SEDIMENT wet landfill contents downstream sediment Richneck Creek AROCLOR 1248 -60 ppm AROCLOR 1260 -303 ppm 2378 TCDF -0.1133 J ppb 12378 PeCDF -0.0329 J ppb 23478 PeCDF -O. l 188J ppb 123478 HxCDF -1.1452 J ppb 123678 HxCDF -0.1712 234678 HxCDF -0.1010 J ppb 1234678 HpCDF -0.8958J ppb 1234789 HpCDF -0.5491 J ppb OCDD -0.3237 J ppb OCDF -4.2072 J ppb PCB/PESTICIDES -NON-DETECT OCDD - 0.2774 J ppb
ECO SAMPLE NUMBER SAMPLE MEDIA SAMPLE LOCATION IC-003-SS SOIL sediment basin outlet ravine SAMPLE CONTAMINANTS DETECTED PCB/PESTICIDES -NON-DETECT OCDD -1.1889 J ppb i~i&::~::::2i;:z:~2:b~1L2i:~:;z:U:t!:;ii&f£1kf&taamJ1mi•ttmiE&r~tmlitI1xttZittlttt'.~~tl1m:2ztlittltwE,J IC -001-LCH LEACHATE filter system inlet PCB/PESTICIDES -NON-DETECT t11uilltti1@f.a1;;mi11■•~1•~i-~j~wai}i\11im1tit.lj~~•w•-~•~ri~~a1:11il,w1tf~@1tm@1fffii~~r11%ri~~11w~~ IC -003-GW WATER water sample from Limmer well PCB/PESTICIDES -NON-DETECT
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
SPECIAL SAMPLE ANALYSIS REPORT
NOVEMBER 1994
6.0-FIELD CHANGES TO SAMPLING PLAN
Several changes to originally planned sampling order were necessitated by field
conditions. The following changes/additions to the scheduled sampling effort
were made in the field:
ECO SAMPLE SAMPLE LOCATION FIELD CHANGES
NUMBER
IC -00 I -LC dry landfill contents only enough dry material
recovered for VOC and PCB
analysis
IC-002 -LC duplicate dry landfill sample duplicate of wet landfill
contents contents because not enough dry
material recovered for analysis
IC -003 -GW Limmer well added sample -PCB analysis only
E NVIRONMENT AL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
SPECIAL SAMPLE ANALYSIS REPORT
NOVEMBER 1994
7.0-DATA INTERPRETATION
Analytical results reported by laboratories are subject to a set of notations known
as data qualifiers. Data qualifiers consist of a numeric or letter notation
immediately following a reported value, and give added information regarding the
data reported that may influence how information should be used in decision
making. In the data sets reported by ECO, the only data qualifier present is the
notation J. The J data flag denotes an estimated value due to the result being
outside the calibration limit for the analytical equipment.
8.0 -QUALITY ASSURANCE /QUALITY CONTROL
As noted earlier, a complete technical report will be prepared discussing and
documenting data validation and QA/QC concerns in detail. General quality
parameters affecting validity of the data reported here, including holding time
limits for sample extraction and analysis, and initial and continuing calibration of
analytical equipment were met. Additionally, matrix spike and matrix duplicate
recoveries were generally within EPA specified quality control limits. No target
analytes were detected in method blanks and all laboratory control sample criteria
were met.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
SPECIAL SAMPLE ANALYSIS REPORT
NOVEMBER 1994
9.0-SAMPLE RESULTS
The general analysis of both soil and water revealed no significant contamination
with volatile organics, BNAs or pesticides. With the exception of borderline
significant lead contamination in samples IC -002-LC and IC-003-LC, there were
no metals detected in soil or water at levels of regulatory concern. Likewise, no
pesticides were detected via EPA method 8081 which revealed AROCLOR 1248
and 1260 (PCBs) in samples IC-001-SS, IC-002-SS, IC-001-LC, IC-002-LC, IC-
003-LC, with reported levels ranging from 0.008 ppm to 303 ppm. Numerous
congeners of dioxins and furans were detected in all samples of landfill contents.
The less toxic octa congeners of dioxins and furans were also detected in samples
taken from the surface soils located outside the landfill and sediment sampled
downstream from Richneck creek.
10.0-DISCUSSION OF DATA AND RECOMMENDATIONS
The purpose of this field event was, in part, to perform comprehensive
characterization of the landfill contents. Fewer metals and organic contaminants
than expected were detected in this sampling event, but in accordance with
expectations, numerous congeners of PCDD/PCDFs were found to be co-located
with the PCBs originally demonstrated as the Constituents of Interest (COis).
E NVIRONMENTAL
COMPLIANCE
0 RGANIZATION
JOINT WARREN COUNTY AND STATE PCB LANDFILL WORKING GROUP
SPECIAL SAMPLE ANALYSIS REPORT
NOVEMBER 1994
The presence of dioxins and furans in, and around the landfill elevates the level of
concern about this containment facility, due to the generally accepted belief that
dioxins and furans are considerably more potentially toxic to human health and the
environment than even the toxic PCBs. The recent EPA draft reassessment of
dioxin toxicology confirms previous data indicating that even trace amounts of
dioxins can be detrimental to human health and the environment, and are capable
of producing numerous health difficulties and abnormalities in addition to being
suspected carcinogens.
Dioxins are of further concern because of their ability to persist in the environment
and resist degradation for very long periods of time. This chemical property has
implications for the long term storage and/or disposal of dioxin contaminated
wastes, and requires the implementation of permanent containment and/or
destruction technologies for successful outcome. The Superfund Amendment and
Reauthorization Act (SARA), the most comprehensive site remediation regulation,
creates a statutory preference for on-site, permanent destruction technologies for
the treatment of dioxins and other wastes wherever possible. This scientific and
statutory imperative for the on-site, complete destruction of dioxins and other
wastes is crucial to preventing continual monit~ring and liability of potential off-
site contaminant migration at all sites, including the Warren County PCB landfill.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION
I. JOINT WARREN COUNTY AND STATE PCB LANDFIU WORKING GROUP
SPECIAL SAMPLE ANALYSIS REPORT
NOVEMBER 1994
Several technologies are suggested by the particular waste stream of the Warren
County PCB facility, but only Base Catalyzed Decomposition (BCD), or some
closed loop treatment train employing BCD, would meet the criteria of being EPA
demonstrated as effective on similar waste streams on North Carolina sites, EPA
and State approved and most importantly, acceptable to the community.
Therefore, it our ECO's recommendation that the Joint Warren County and State
PCB Landfill Working Group immediately begin the process of formally soliciting
proposals for the complete remediation of the Warren County PCB landfill from
all relevant vendors of BCD technologies and treatment processes. We further
suggest that ECO staff, integral to use of BCD at Morrisville and Statesville North
Carolina sites be utilized in the formulation of Requests For Proposal, bid
specifications, remedial specifications and the interviewing and selection of an
appropriate vendor, in order to ensure that all technical and regulatory
requirements are satisfied or exceeded.
ENVIRONMENTAL
COMPLIANCE
0 RGANIZATION