905R96018
Columbus
Waste-to-Energy
Municipal
incinerator
Dioxin Soil
Sampling Project
U.S. Environmental Protection Agency
Region 5
Chicago, Illinois
April 1996
-------
Disclaimers
Mention of trade names or commercial products does not constitute endorsement or
recommendation for use. This report has been prepared and reviewed by the Office of Research
and Development, and Region 5, of the United States Environmental Protection Agency (EPA).
There has been no external peer review of this report. This report has been cleared for release by
EPA'sRegionS.
-------
TABLE OF CONTENTS
1.0 EXECUTIVE SUMMARY 1
2.0 PROJECT DESCRIPTION 2
2.1 Facility Background and Description 2
3.0 SITE SELECTION AND SAMPLING PROCEDURES 4
3.1. Sampling Strategy 4
3.2 Sample Site Selection 4
3.3 Sample Collection 6
4.0 ANALYTICAL PROCEDURES AND QUALITY ASSURANCE 6
4.1. Quality Assurance Objectives 6
4.2. Summary of Analytical Method 7
4.3. Summary of the Data Analysis and Quality Assurance Results 8
4.3.1. Description of the data set 8
4.3.2. Overall Summary of QA Results 9
4.3.3. Interefences With Two Chlorodibenzofuran (CDF) 9
Congeners and Estimation Procedures
4.3.4. Second Column Analysis of 2,3,7,8-TCDF 11
and Estimation Procedure
4.3.5. Disposition of Samples S20 and S23 11
5.0 SUMMARY OF SOIL SAMPLING RESULTS 12
6.0 REFERENCES 22
-------
THE COLUMBUS DIOXIN SOIL SAMPLING PROJECT
1.0 EXECUTIVE SUMMARY
This report presents interim results of a dioxin soil sampling project conducted in the
vicinity of the Columbus Waste-to-Energy (WTE) facility in Columbus, Ohio. This report
describes the analytical procedures and quality assurance programs, and presents a summary of
the final data set. This project was designed to assess the presence and degree of residual
dioxin/furan soil concentrations in the vicinity of the facility, and specifically to determine whether
surface soils around the incinerator contain dioxin/furans at levels distinguishable from
background. It is part of a cooperative effort with the United States Environmental Protection
Agency's (EPA) Office of Research and Development (ORD) Exposure Assessment and Risk
Characterization Group, the EPA ORD Laboratory in Las Vegas, Nevada, EPA Region 5, the
Agency for Toxic Substances and Disease Registry (ATSDR, Atlanta, GA), the Ohio
Environmental Protection Agency (OEPA), the Ohio Department of Health (ODH), and other
state and local agencies. Funding for the project was obtained under EPA's Regional Applied
Research Effort (RARE) program.
There were a total of 25 samples in the final data set for analysis. This included 4 samples
that were taken on the site of the Columbus WTE, 18 samples taken outside the Columbus WTE
but within the Columbus urban area, and 3 samples taken at a background site 28 miles away. In
general, examination of the data suggested that it could be logically seperated into four groups: 1)
a set of 4 samples taken on the site of the incinerator, 2) a set of 4 samples taken directly off-site
and in the predominant wind direction, 3) a set of 14 samples which were the other samples in the
city of Columbus, and 4) the set of 3 background samples.
Analysis suggests that the cluster of samples on the site of the Columbus WTE are
influenced by activities at the Columbus WTE. The average toxic equivalent concentration (TEQ)
of the four samples is 356 parts per trillion (ppt). The cluster of samples just outside the
Columbus WTE appear as well to have been influenced by the Columbus WTE, although the
evidence for such influence is weaker than the evidence for the on-site samples. The average
TEQ soil concentration is 49 ppt. The 14 samples within the city of Columbus average 10 ppt,
and the background samples have a low average soil concentration of 1 ppt.
Other soil data in America and around the world support the generality that soil
concentrations within urban centers are higher than in rural areas. Sources in urban centers are
more numerous than in rural centers, another generally accepted conclusion which explains this
observation regarding soil concentrations. Limited information summarized in this report
generally place rural, background soil concentrations to be near to or less than 5 ppt, urban soil
concentrations in a range of 10 to 30 ppt, and industrial concentrations exceeding 100 ppt. Based
on emission testing, there can beflttle doubt that the Columbus WTE has been a source of dioxins
in the Columbus urban environment. This study has not attempted to identify other sources, and
particularly to place the Columbus WTE in any perspective with other sources in the city of
-------
Columbus. This study has confirmed that soil concentrations appear to be higher within the city
of Columbus, as compared to background soils. However, except for the two clusters of samples
(on the incinerator site and just outside the property), the 14 samples within the city of Columbus
do not appear to be elevated compared to limited information on urban soils in general, and in
comparison to these two clusters.
2.0 PROJECT DESCRIPTION
This report presents interim results of a dioxin soil sampling project conducted in the
vicinity of the Columbus Waste-to-Energy (WTE) facility in Columbus, Ohio. This report
describes the analytical procedures and quality assurance programs, and presents a summary of
the final data set. The United States Environmental Protection Agency (EPA) will continue to
analyze this data with regard to interpretations and future monitoring activities.
Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (dioxins and furans)
constitute a class of related chemicals formed inadvertantly during various combustion and
chemical processes. Congeners of dioxin differ in the number and position of chlorine atoms
attached to the basic dioxin or furan ring system. These congeners also differ in their degree of
toxicity, with compounds chorinated at the 2,3,7, and 8 positions on the dioxin or furan rings
considered to contribute to some degree to toxicity. EPA has derived relative potency estimates
for the seventeen 2,3,7,8,chlorine-substituted congeners, based on relative potency to 2,3,7,8-
tetrachlorodibenzodiozin (2,3,7,8-TCDD), the most potent chemical in the class (USEPA, 1989).
These measures of relative potency are applied to the concentrations of seventeen congeners to
derive toxicologically equivalent concentrations (TEQ) of 2,3,7,8-TCDD. This document reports
both TEQ concentrations of dioxin, and total dioxin concentration in the results section.
This project was designed to assess the presence and degree of residual dioxin/furan soil
concentrations in the vicinity of the facility, and specifically to determine whether surface soils
around the incinerator contain dioxin/furans at levels distinguishable from background. In
addition, the results of this study may also be used to improve the general understanding about
dioxin fate and transport.
This project is part of a cooperative effort with the EPA's Office of Research and
Development (ORD) Exposure Assessment and Risk Characterization Group, the ORD
Laboratory in Las Vegas, Nevada, EPA Region 5, the Agency for Toxic Substances and Disease
Registry (ATSDR, Atlanta, GA), the Ohio Environmental Protection Agency (OEPA), the Ohio
Department of Health (ODH), and other state and local agencies. Funding for the project was
obtained under EPA's Regional Applied Research Effort (RARE) program.
2.1 Facility Background and Description
The Columbus Municipal Waste-to Energy facility is located on the south side of
2
-------
Columbus, Ohio, adjacent to the Columbus Workhouse. The power generating plant, fueled by
both coal and municipal refuse, began operation in June, 1983 and ceased operation in December,
1994. The facility has six boilers and is equipped with hot-side electrostatic precipitators (ESP).
Wastes from the plant include fly ash which was collected in the ESP hopper, just prior to the
stack discharge, and bottom ash, the residue remaining on the grate after incineration of the fuel.
Prior to process modifications completed in June 1994, the emission rate of dioxin/furan TEQs
from the incinerator had been estimated at 3.12*10"5 g TEQ/sec (OEPA, 1994a), which translates
to an annual emission of 984 g TEQ. This estimate is based on emission testing conducted in
1992 which produced concentration measurements and emission gas volumes, and the assumption
that, on a continuous basis, 4.22 of 6 boilers were in operation (OEPA, 1994a).
Although the facility is not currently operating, and therefore most of its potential risk
from exposure to stack emissions no longer exists, there remains the question of potential impacts
to humans and the environment through exposure to soils which contain residual, dioxins as a
result of past emissions.
In May 1994, the Ohio EPA and Department of Health petitioned the ATSDR and the
EPA to investigate the impact of the dioxin emissions on the environment and on the health of the
community. As a result of this petition a multi-agency workgroup was formed to provide study
recommendations. A subgroup on environmental exposure, chaired by EPA but whose members
included OEPA, ODH, ATSDR, local health departments and a citizen's group, came to
consensus on recommending soil sampling to investigate potential impacts.
Of all possible environmental media to sample, the environmental exposure workgroup
concluded that soil best fits the needs of this study. Soil is expected to be a good measure of
cumulative deposition of dioxins because dioxins are tightly bound to soils and are expected to
have a relatively long half-life in soils. USEPA (1994a) has estimated that residues of dioxins in
surface soils may have a 10-year half-life, and Paustenbach, et al (1992) have evaluated the
literature on dioxins and suggests that dioxin residues beneath the surface can have a half-life of
25-100 years. Another issue considered by the workgroup was the ability to relate environmental
measurements of any kind to emissions from the Columbus WTE. Given that dioxins are
ubiquitous in the environment (USEPA, 1994a), any conclusion that an environmental
measurement can be tied to a specific source has to be carefully considered. The workgroup had
established that a principal study objective was to evaluate the impact of the Columbus WTE, to
the extent possible, and not to do a general study of the Columbus area. With this in mind, the
workgroup decided that a focus on environmental measurements physically near the Columbus
WTE would be less ambiguous than measurements taken several kilometers away from the
Columbus WTE. Another consideration for the environmental workgroup was that the Columbus
WTE had ceased operation in December of 1994. Therefore, monitoring of air quality was no
longer an option for consideration for a study conducted in 1995. Finally, it was recognized that
this study was to be a "screening" study. Depending on the results and their interpretation, the
workgroup understood that furthlr study may be warranted.
-------
3.0 SITE SELECTION AND SAMPLING PROCEDURES
3.1. Sampling Strategy
Sampling locations included three types: (1) areas anticipated to be most impacted by
WTE emissions; (2) locations typical of the urban area but expected to be impacted by the WTE
facility to a lesser extent; and (3) areas remote from the WTE (i.e., a control site). Prevailing
winds were considered in targeting locations in the Columbus area most likely to have been
impacted by the WTE.
Figure 1 presents a topological map showing the area surrounding the WTE site; the circle
represents the 1000-meter radii around the incinerator. Figure 2 shows a simple representation of
the stratified random sampling plan. Stratified random sampling involves dividing the study area
into two or more non-overlapping subsets (strata) which cover the entire area to be sampled.
Stratification has been used to ensure that potentially significant areas of a site are represented in
the sample data. Samples within a stratum are assumed to be more similar to each other than to
samples from other strata. Additionally, a stratified random sample may provide more precise
estimates of contaminant levels than those obtained from a simple random sample (USEPA,
1994b).
The four quadrants in Figure 2 can be thought of as four strata for study. Assuming that
the incinerator is represented by the dot in the middle of Figure 2, the predominant wind direction
is the top quadrant. Eight sampling locations were in the top quadrant. More samples were taken
in this quadrant based on the assumption that dioxins would deposit more in the predominant
wind direction than in other directions. As seen in Figure 2, the top quadrant was further divided
into sub-strata. Three background samples were taken approximately 28 miles from the
incinerator, and these locations are not shown in Figures 1 and 2. They are near the sampling
location designated as #5 in the Franklin County Ohio Ambient Air Monitoring Study (OEP A,
1994b).
3.2 Sample Site Selection
Actual sample sites were selected through a series of on-site reconnaissance inspections.
A list of these sites and general location descriptions is given in Attachment A. These locations
were selected to conform to the stratified random sampling grid pattern shown in Figure 2.
Because of the urban industrial Columbus WTE site location, it was impossible to meet all the
criteria specified in the QAPP with respect to all possible dioxin sources. Samples were collected
from sites having a level surface and a minimum potential for run-on/run-off from rain or
snowmelt. Care was taken to sample undisturbed soils. Generally, undisturbed soils are those
soils for which no tillage or other mixing has occurred. Information from mixed soils may be
difficult to interpret with regard fo long term depositions. Sites were also free of immediate tree
cover. Trees may intercept dioxin depositions, and it would less clear how to interpret soil
beneath trees as compared to soils in open settings. No sites were located near wooden structures
-------
11
o
oo
§
en
rt
U
oo
c
a.
E
C
o
'i
o
o
3 3 o
en
o
O
'^
KJ
'•=000
o. — •— o
-------
PREVAILING
WIND DIRECTION
1000 M
Figure 2. Representation of sampling design showing stratified approach.
where the wood may have been pressure treated. This decision was made because
pentachlorophenol, or PCP, is known to be contaminated with dioxins, and soils near pressure
treated wood may be influenced by the gradual leaching of dioxin residues from the treated wood.
Finally, no sites were immediately adjacent to roads, although some of the sites were near roads.
Roadside sampling was avoided so that results could not be attributed to vehicle emissions.
-------
3.3 Sample Collection
Composite soil samples were collected at each of 27 difference sampling sites, on
December 5-7, 1995. Samples were collected using pre-cleaned equipment dedicated to each
sampling location. Each sample site consisted of an area of 5 ft x 5 ft. A grid of 25 sections was
established at each site and used for random selection of aliquot sample sites. Four random
aliquots were collected for each sample. A "sample" for this study was, therefore, a composite of
four aliquots. Aliquots were collected using a stainless steel tulip bulb planting device. This
device removed a plug approximately 3 inches (7.6 cm) in diameter to a depth of about 3 inches
(7.6 cm).
Areas that were recently disturbed or which were in an obvious pathway were avoided.
Before sampling, any plant materials were trimmed to just above the soil surface in the area to be
sampled. The soil plugs were placed in an aluminum foil lined pan and miscellaneous debris (e.g.,
twigs, roots, wood chips, stones, pebbles and other non-soil material that could be distinguished)
was removed by hand. A new set of gloves was used for each sample processed. The remaining
soil was thoroughly mixed and randomly apportioned to sample containers. The sample
containers were clear glass with teflon lids. Region 5 chain of custody procedures were followed.
Samples were immediately tagged with a descriptive and unique label. Sample sites were
permanently marked to allow for identification of sample point and resampling if necessary and
were further documented with Global Positioning System determination of coordinates. Actual
sample locations are shown in Figure 1. Samples were placed in ice chests and delivered directly
to the laboratory the morning following the day of sampling. Samples were stored in the dark at
4 °C prior to analysis.
4.0 ANALYTICAL PROCEDURES
4.1. Quality Assurance Objectives
In order to use information from this project appropriately, the sample results must be
technically sound and of defined and documented quality. To achieve this, and as required by the
EPA for all monitoring and measurement programs, objectives must be established for data
quality based on the proposed end use of the data (Stanley and Verner, 1985). The parameters
generally accepted as indicators of data quality include precision, accuracy/bias,
representativeness, completeness, and comparability. The detection/quantification limits of the
method for the dioxin/furans in soil matrices is also of concern in that the analytical protocol
(combined extraction and analysis) must reliably measure dioxin/furans at concentrations which
will allow the discrimination of blanks, background samples, and routine samples. A Quality
Assurance Project Plan (QAPP) was prepared for this study which specifies data quality objective,
sampling, analytical and associated quality control activities to be performed (USEPA, 1995).
-------
4.2. Summary of Analytical Method
Analytic Method 8290 (USEPA, 1994c) was used for the determination of the
presence/absence and quantification of dioxins/furans (tetra- through octachlorinated
homologues) in the soil samples. It uses high resolution gas chromatography/high resolution mass
spectrometry (HRGC/HRMS) with selected ion monitoring (SIM), matrix-specific extraction, and
analyte-specific cleanup. The target goals for the method detection limits (MDLs) were 1, 5, and
10 ppt or lower for the respective tetra, penta/hexa/hepta, and octa dioxan/furan congeners.
Analysis was conducted on 43 samples in two sets. Included in each set was a method blanks, a
matrix spike, a matrix spike duplicate and a sample duplicate.
Approximately 10 grams of each soil sample were used to determine percent solids
(percent dry weight). Another 10 g of each sample were combined with sodium sulfate for
extraction. All samples were spiked with isotopically labeled analogs of fifteen of the seventeen
2,3,7,8-substituted PCDD/PCDF prior to extraction. The samples were extracted for
approximately 18 hours with toluene in a Soxhlet apparatus. Extracts were spiked with 37C14-
2,3,7,8-TCDD cleanup standard, partitioned against base and acid solutions and processed
through add/base silica, basic alumina, and carbon AX-21/Celite® cleanup columns. Extracts
were spiked with 1,2,3,4-TCDD- 13C12- l,2,3,7,8,9-HxCDD-13C12 recovery standard and
concentrated to a final volume of 20 //L.
The sample extracts were analyzed on a VG AutoSpec® high resolution gas
chromatography/high resolution mass spectrometer (HRGC/HRMS) (Serial #XO88, System
#6744) in the selected ion monitoring mode on a J & W DB-5 capillary column® (Serial
#4499117) at an instrument resolution of approximately 10,000 (10 percent valley). A Hewlett-
Packard 5890 Series II Gas Chromatograph® (C128/83) served as the inlet. Data reduction was
performed on a VAX station 3100, M38, Model ws42A-BC® (Serial #AB11300V6D) using
Opus Quan® software. The criteria used to identify chromatographic peaks were: (1) greater
than 2.5 signal to noise ratio; (2) ion abundance ratios within 15% of the theoretical values; (3)
retention times of native analytes within 2 seconds of 13Cn-labelled internal standards; and (4) no
diphenyl ether interferences. The target range for percent recoveries was 40-120%. Some
samples were diluted to reduce chromatographic interference problems. The dilution factor is
noted on individual analysis data sheets which are included in Attachment B. Because 2,3,7,8-
TCDF is not completely resolved from all other tetrachlorinated isomers on the DB-5 column,
second column confirmation of 2,3,7,8-TCDF levels above 1 pg/g dry weight in the initial analysis
was performed on a J&W DB Dioxin Column® (Serial #2743516) for 14 samples.
The laboratory analysis was conducted by Battelle Laboratories (505 King Avenue,
Columbus, Ohio, 43201-2693) under EPA Contract No. 68-D2-0139, under the supervision of
EPA's ORD Laboratory in Las Vegas.
Attachments B and C sho^ the results in detail. Attachment B gives the results for all 43
samples, and Attachment C summarizes the Quality Assurance data generated in the program.
-------
4.3. Summary of the Data Analysis and Quality Assurance Results
4.3.1. Description of the data set
Forty-three analytical samples were submitted to Battelle for analysis including:
1) 27 field site samples. These included 24 samples taken in the city of Columbus and 3
samples taken 28 miles away in the background setting.
2) 3 field blanks. These field blanks were 500-mL glass jars rinsed with rnethylene
chloride, filled about half full of playsand, and sealed with teflon tape. Prior to producing these
blanks, analysis showed that playsand extract and jar rinsate samples were found to be free of
PCDD/PCDF. These field blanks were put together at the Battelle laboratory. Siamplers treated
these samples in the field as if they were actual samples. Specifically, they opened the sealed jars,
handled the sand as if it were a field soil sample, resealed the jars, and sent them to the laboratory
along with actual samples.
3) 2 method blanks. One was processed with each set of samples. They were 10-g
aliquots of sodium sulfate, which were processed through all extraction, cleanup, and analysis
procedures as if they were actual samples. They were generated by the Battelle laboratory. There
were no detections in the two method blanks.
4) 4 spiked samples. They were created in the lab by adding known amounts of all 17
dioxin congeners into samples taken in the field.
5) 2 laboratory duplicates. They were field samples split into two samples, where the
second sample was analyzed to determine the reproducibility of analyses.
6) 3 field duplicates. These samples are distinct from laboratory duplicates in that a
second field sample was taken from the same grid as the actual field site sample, using different
random aliquots. One of these field duplicates was from the background site, and the two others
were from sampling in the Columbus urban area.
7) 1 reference material. This was a soil standard reference material (Cambridge Isotope
Laboratories #EDF-2513 ®) which was processed along with the first set of samples. Recoveries
of the analytes from this standard reference material was 86.4% to 123.5%.
8) 1 detection-limited spike sample. This was taken from one of the background samples,
and the quantity of each congener added was equal to 5 times the target detection limit.
4.3.2. Overall summary of OA results
a
The field sample collection team and the Battelle laboratory met the requirements of the
Quality Assurance Program Plan (QAPP; USEPA, 1995) for the number of field and method
-------
blanks, duplicates, matrix spikes (MS), and matrix spike duplicates (MSD). The data generally
met or improved upon the desired detection limits of 1, 5, and 10 ppt for tetra-, penta- through
hepta-, and octa-chloro congeners, respectively. Most detection limits were 0.5 ppt or better,
with certain analytes in some cases being in the 1-2 ppt range, as would be expected with real
sample matrices. Results for MS and MSD were generally good, with better recoveries than
required. One recovery of OCDD was slightly above the target range, and some HxCDF
recoveries were skewed by the presence of chlorinated diphenyl ethers (CDPE) interference. The
issue of CDPE intereference is explored in more depth below. The relative percent differences
(RPD) for MS/MSD results were better than required: less than 5% for sample S04, and less than
16% for sample S34. The former sample was a low level background; the latter was a high
concentration field sample (see Attachment B for results of individual samples).
The cleanup procedures were satisfactory, based upon the absence of general chemical
interferences (with the exception of CDPE) in the mass chromatograms, and the recovery of the
cleanup standard. The analytical results on the performance evaluation material were satisfactory,
and better than required recoveries were attained. Specifically, for field samples, they were
generally in the range of 65-95%, which is better than required by the method and QAPP. For
two samples, the recoveries were lower, but well within specifications: S21 had 52-68%
recoveries, and S33 had 46-60%.
Low concentrations (0.2-0.5 ppt) of target analytes were observed in one method blank.
This level reflects the lower limit capabilities of the method, so these levels are not unreasonable,
particularly for a laboratory conducting routine analysis of low to high concentration samples.
The second method blank did have problems in sample detection limits, and this method blank will
be reanalyzed. In general, blanks and background samples did not appear to have suspiciously
high concentrations of target analytes. High recoveries of OCDD in certain cases suggests a small
background of this may exist in the laboratory. In general, the results of the quality assurance
measures indicate that the Battelle laboratory maintained adequate cleanliness and prevented
sample cross-contamination.
Interference with the analysis of two chlorodibenzofuran congeners, and the lack of a
second column analysis for a third chlorodibenzofuran congener, led EPA to develop estimation
procedures to assign concentrations for a small set of analyses. These estimation procedures are
not part of standard practice for the use of Method 8290. No endorsement of these estimation
procedures is implied by their use in this soil study. EPA concluded that the information learned
from the estimated values justifies their inclusion in the data set examined in this report.
Attachment B identifies all concentrations which were estimated rather than measured. The
following sections describe in detail the situations requiring this estimation, and the procedures
used.
4.3.3. Interefences With Two Chlorodibenzofuran (CDF) Congeners and Estimation
Procedures J
Method 8290 (USEPA, 1994c) describes the possibility of intereferences with some of the
9
-------
dioxin congeners. Chlorinated diphenyl ethers (CDPE) are known to interfere with the CDF
congeners. In this soil study, this compound was found to interfere with two hexa CDF
congeners: 1,2,3,4,7,8-HxCDD and 1,2,3,6,7,8-HxCDF. There were no CDPE interferences in
the method blanks, and only one of the three field blanks showed this interference. This would
suggest that the CDPE was in the soil, or introduced to the soil through its handling, and did not
originate at the laboratory. CDPE is a ubiquotous contaminant and is used as a plasticiser in
various plastics. That is why the Method 8290 raises the possibility that this compound could
interfere with the furan congeners. The precise reason why CDPE was in the soil (or was
introduced into the soil through handling) is not known at this time. All soil samples showed this
interference for 1,2,3,4,7,8-HxCDD, and 3 samples showed this interference for 1,2,3,6,7,8-
HxCDF. Generally, the interference amounted to less than 1 ppt in the background samples and
in the 1 - 10 ppt range in the urban samples.
It was also found that another interference in the samples came from a non-target HxCDF
that eluted just before the 1,2,3,4,7,8-HxCDF. This non-target interference was observable
chromatographically as a fronting shoulder or widened peak.
It was possible to distinguish the concentration of the furan congener from the CPDE.
Specifically, the CPDE concentrations could be estimated using their area counts and the
interference could be subtracted from the HxCDF signal. Also subtracted from the 1,2,3,4,7,8-
HxCDF signal was the interference from the non-target HxCDF that eluted just before
1,2,3,4,7,8-HxCDF. Both these refinements were done to complete the data set. In order to do
so, it was assumed that: 1) all the CDPE signal was in the 1,2,3,4,7,8-HxCDF window, and none
in the 1,2,3,6,7,8-HxCDF retention time window, 2) the CPDE area counts can be subtracted
from the total area, 3) the CPDE signal at m/z 445.8 can be multiplied by a factor to estimate its
contribution to the m/z 374 channel, and 4) the relative peak heights or shoulder and peak heights
of the 1,2,3,4,6,7-HxCDF and 1,2,3,4,7,8-HxCDF can be used to proportion the peak area
between target and non-target isomers.
With regard to the third assumption above, previous work done in USEPA's Las Vegas
Laboratory (Donnelly, 1992) was used. In that project, mass spectra of eighteen chlorinated
diphenyl ether analytical standards showed these compounds have a response ratio for m/z 374:
m/z 446 in the range of 0.35 to 2.0, with an average of 1.23. Therefore, the ether contribution
can be removed by multiplying the ether area at m/z 445.8 by 1.23 and subtracting that product
from the total area.
With regard to the fourth assumption above, the relative peak and shoulder heights were
measured against the relative % Y-axis on the mass chromatogram. The area fraction due to the
target HxCDF is then expressed using the relative peak heights on the mass chromatogram
submitted by Battelle as follows: (1,2,3,4,7,8-HxCDF relative peak height)/(l,2,3,4,6,7-HxCDF
relative peak height + 1,2,3,4,7,8-HxCDF relative peak height). For example, a 1,2,3,4,6,7-
HxCDF shoulder at 60% relativrfo the 1,2,3,4,7,8-HxCDF peak height would result in estimating
the "peak height fraction" due to 1,2,3,4,7,8-HxCDF as being (100/160). The area due to
1,2,3,4,7,8-HxCDF is then, (total area) times (100/160).
10
-------
Attachment B showing all the analytical results includes all these estimated concentrations
for the 2 CDF congeners. The concentrations in all cases are flagged with a footnote indicating
that interferences in the sample required that the concentration be estimated.
4.3.4. Second Column Analysis of 2.3.7.8-TCDF and Estimation Procedure
EPA Method 8290 does require a second column confirmation for 2,3,7,8-TCDF. The
2,3,7,8-TCDF congener is subject to chromatographic interference by a non-2,3,7,8 isomer when
using the DB-5 column. That isomer may be 2,3,4,6, and/or 2,3,4,8-TCDD based upon data
published by Hale, et al. (1985). In order to measure the concentration of 2,3,7,8-TCDF when a
first column shows a positive response is to subject the sample to a second column analysis. In
the Columbus WTE soil study, there were 29 samples which showed a positive response on the
first column: a second column analysis determined the 2,3,7,8-TCDF concentration for 15
samples, but a second column analysis was not conducted on 14 samples. This was done in order
to reserve funds for possible future additional analyses.
For these 14 samples, an estimation procedure was used to assign a value of 2,3,7,8-
TCDF for that sample. Two of those fourteen were from four background samples (as described
above, there were 3 background sample sites and one field duplicate from the background
setting), the remaining 12 were from the city of Columbus. For the 14 samples requiring an
estimated value for 2,3,7,8-TCDF, the following was done.
As noted, two of the four background samples did not have second column analysis, and
two did. For the two which did have second column analysis, the ratios of the second column to
the first column were 0.777 and 0.422, for an average of 0.600. To estimate the concentration of
2,3,7,8-TCDF in the two background samples without the second column, the concentration read
from the first column was multiplied by 0.60. The other 13 samples from the city of Columbus
having both a first and second column analysis for 2,3,7,8-TCDF, the second-to-first column
quantitation ratios ranged from 0.171 to 0.424, with a mean of 0.290 ± 0.037. Therefore,
estimated 2,3,7,8-TCDF values for the 12 samples showing positive on the first column but not
having a second column analysis were calculated as the concentration from the first column times
0.29.
Attachment B which has all the analytical results does identify the concentrations for
2,3,7,8-TCDF which were quantified by the second column and those which required estimation
using the methods described in this section.
4J.5. Disposition of Samples S20 and S23
All 17 congeners of sample S20 had recoveries less than 40%, and 8 of 17 congeners in
sample S23 had recoveries lower than 40%. The QAPP for this project specifies acceptable
recovery ranges of 40-120%. Thjrefore, these samples will not be considered as part of the final
data set for interpretation and analysis. EPA plans to revisit the actual soil sampling locations for
S20 and S23, and take a second sample as near as possible to the first sample to characterize
11
-------
these locations. The results for these two samples are included in Attachment B.
5.0 SUMMARY OF SOIL SAMPLING RESULTS
Table 1 shows the toxic equivalent (commonly abbreviated as TEQ) soil concentrations
calculated with non-detects equal to '/2 detection limit and non-detects equal to 0.00. The "toxic
equivalent" concept is described in USEPA (1989), and generally is a way of describing the
cumulative toxicity of a mixture of dioxin and dioxin-like congeners in relation to the most toxic
dioxin congener, 2,3,7,8-TCDD. Toxic Equivalency Factors (TEFs) have been developed and
adopted internationally which relate the toxicity of each congener to an equivalent toxic amount
of 2,3,7,8-TCDD. In order to calculate a TEQ concentration in soil, the actual concentration of
each of the 17 congeners is multiplied by its TEF and the products are then summed. The TEF
for each congener other than 2,3,7,8-TCDD is a number less than 1.00; the TEF for 2,3,7,8-
TCDD is 1.00. For example, the TEF for OCDD is 0.001, indicating that OCDD has been
evaluated as being 1/1000 as toxic as 2,3,7,8-TCDD. This section of the report will also talk
about "total concentrations". This is simply the sum of the concentrations of all congeners, with
no correction for toxicity. There are 25 sample points listed on Table 1, including three from the
background setting, and 22 from the city of Columbus. As noted above, two samples from the
city of Columbus, S20 and S23, are not considered part of the final data set for analysis because
of problems with analytical quality. As seen from a comparison of the two columns, there is not a
significant difference in soil concentrations in the two ways in which the TEQ concentration is
calculated. Some observations from the data include:
1) The TEQ soil concentrations for background samples S04, SOS, and S06 are in the range of 1.0
to 2.0 ppt TEQ, and are clearly lower than the samples within the city of Columbus. The average
TEQ concentration is 1.4 ppt, and the average total concentration for this cluster is 199 ppt.
2) The TEQ soil concentrations for the cluster on the site of the incinerator, samples S29, S30,
S33, and S34, are substantially higher than the background and are in the range of 50 to 760 ppt.
The average TEQ concentration of those four samples is 356 ppt TEQ, and the average total
concentration is 4834 ppt.
3) There appears to be a second cluster of 4 samples, S25, S26, S27, and S28, which are in the
predominant downwind direction outside the incinerator property, and which appear to have
concentrations that are elevated above all other samples taken in Columbus (except for the
samples on the Columbus WTE site). The TEQ soil concentrations for this cluster range from 31
to 61 ppt. The average TEQ concentration of these four samples is 49 ppt TEQ, and the average
total concentration is 4789 ppt.
4) Not including the cluster of samples on the Columbus WTE site and the cluster of four samples
immediately outside the Columbus WTE site, there are 14 samples in the city of Columbus. The
TEQ soil concentrations for these 14 samples range from 3 to 33 ppt. Except for S14 and SI5,
all these samples are less than 20 ppt TEQ. The average TEQ concentration of these 14 samples
12
-------
is 10 ppt, and the average total concentration is 1095 ppt.
The background soil concentrations in the 1-2 ppt TEQ range is consistent with other
measurements in North America and around the world for background, rural settings. Reed, et al.
(1990) reports on a background soil concentration of 5.2 ppt TEQ in rural Minnesota. Fiedler, et
al. (1995) reports on 36 soil samples taken in 8 counties in Southern Mississippi, in predominantly
rural areas. The TEQ concentration ranged from 0.08 to 22.9 ppt, with 20 samples being less
than 1.0 ppt and a mean concentraiton of 3.1 ppt. A concentration of 5.0 ppt is reported for a
background setting in the British Columbia (BC Environment, 1995). In England, soil
measurements in a rural setting averaged 3.3 ppt TEQ (HMIP, 1995). Dioxin concentration have
also been found to be elevated in urban settings as compared to rural settings, as was the case for
this study. Soil measurements in England showed an urban TEQ concentration of 26 ppt TEQ
(Ball, et al., 1994). A comprehensive soil data base including 1,594 samples from rural, urban and
industrial settings in Germany also shows the difference between urban and rural soils (BLAG,
1992, as reported in Fiedler, et al., 1995). The soil levels in rural settings ranged from 1 to 5 ppt
TEQ, and the range in urban areas was 10 to 30 ppt TEQ. Fiedler, et al. (1995) also reports that
in industrial areas in Germany, concentrations were up to 100 ppt TEQ. Because of the lack of an
extensive US data base of dioxin soil levels, estimates of background are based on a combination
of US and European data.
Another analysis conducted on this data is a comparison of soil congener profiles with
emissions from the 1992 stack emission test. A "congener profile" can be constructed by
summing the concentrations of all the 17 congeners and describing the proportional contribution
of each to the total in terms of fractions. For example, if the sum of the soil concentrations in a
sample is 100, and the OCDD concentration is 65, then the profile contribution of OCDD is 0.65.
In a congener profile, the sum of all fractional contributions from each of the 17 congeners is
1.00. It is important to note that these congener profiles are constructed from the actual
concentrations, not concentrations which are adjusted based on the toxic equivalent factor (TEF)
for that congener.
Figures 3 through 7 show the following, the congener profile for the 1992 emissions test
(Figure 3), the congener profile for the four soil samples taken on-site - S29, S30, S33, and S34
(Figure 4); the congener profile taken on the second cluster of 4 samples which appeared to be
elevated above other samples in the city of Columbus - S25, S26, S27, and S28 (Figure 5); the
congener profile which is constructed as the average of the 14 other soil samples in the city of
Columbus (Figure 6); and the congener profile from the background setting (Figure 7).
From these figures, the following observations are made:
1) The congener profile for the four samples taken at the site of the incinerator appear to be
similar to the congener profile of the emissions from the 1992 stack emission test. Specifically,
nearly all of the congeners show<8ome relative contribution to the total concentration in both the
stack and the soil samples. The three congeners of highest relative contribution to the stack
emission and soil concentrations are 1234678-HpCDD, OCDD, and 1234678-HpCDF.
13
-------
2) The congener profiles for samples S25 through S28 (the cluster immediately outside and
downwind of the Columbus WTE) are dominated by OCDD and 1234678-HpCDD. In fact, all
other clusters of soil samples evaluated, including the others from the city of Columbus and the
background soils, show the same OCDD and HpCDD dominated profile. This OCDD/HpCDD
dominated profile is typical of background rural and urban samples described throughout the
literature. There does appear to be slightly more contributions from the other congeners in this
impacted cluster (S25 through S28) as compared to the 14 other city samples and the background
sample.
From the observations made above regarding concentrations and congener profiles, the
following tentative conclusions/observations are offered. Further analysis of the data may lead to
refinements to these conclusions and the addition of other conclusions or hypotheses:
1) The cluster of samples on the site of the Columbus WTE, S29, S30, S33, and S34, are
influenced by activities at the Columbus WTE. These activities include stack emissions and
possible ash handling. This conclusion is supported by both the high soil concentrations and the
congener profile match.
2) The cluster of samples outside the Columbus WTE, S25 through S28, appears to have been
influenced by the Columbus WTE, although the evidence for such influence is weaker than the
evidence for the influence of the Columbus WTE for the on-site samples (S29, S30, S33, and
S34). The evidence is twofold: the higher soil concentrations (total and TEQ) as compared to
other samples in the city of Columbus and the background samples, and the congener profile for
this cluster which does appear to have slightly higher proportional contributions from congeners
other than the HpCDD and OCDD congeners, as compared to the other samples in Columbus and
the background samples. The total concentration in this cluster, at an average of 4789 ppt, is
similar to the average total concentration for the Columbus WTE site samples, at 4834 ppt.
3) While the congener profiles appear similar for all soil profiles except those at the Columbus
WTE (S29, S30, S33, S34), there is a observable gradient in total and toxic equivalent
concentrations. The TEQ concentrations drop from 356 ppt on the Columbus WTE site to 49 ppt
for the cluster outside the Columbus WTE (S25-S28) to 10 ppt for the other 14 samples in the
city of Columbus to 1 ppt for the background samples (S4, S5, S6). There is a similar gradient in
total concentrations: 4834 ppt at the Columbus WTE, 4789 directly off-site but in the downwind
direction, 1095 ppt in the city of Columbus, and 199 ppt for the background samples.
4) Other soil data in America and around the world support the generality that soil concentrations
within urban centers are higher than in rural areas. Sources in urban centers are thought to be
more numerous than in rural centers, which explains why urban soil concentrations are higher than
rural soil concentrations. There can be little doubt that the Columbus WTE has been a source of
dioxins in the Columbus urban environment. This study has not attempted to identify other
sources, and particularly to place^lhe Columbus WTE in any perspective with other sources in the
city of Columbus. This study has confirmed that soil concentrations, both total and on a TEQ
basis, appear to be higher within the city of Columbus, as compared to background soils.
14
-------
However, except for the two clusters of samples (S25-S28, S29-S34), the 14 samples within the
city of Columbus do not appear to be elevated compared to limited information on urban soils in
general, and in comparison to these two clusters. This tentative conclusion is supported by the
analysis of soil concentrations and congener profiles described above.
15
-------
Table 1. TEQ concentrations in soils calculated with non-detect equal to V-> detection limit and
non-detect equal to 0.0 (concentrations in pg/g, or ppt; LOD = limit of detection).
Sample ID
SO4 - Background
SOS - Background
SO6 - Background
SO7
SOS
SO9
S10
Sll
S12
S13
S14
S15
S18
S19
S21
S22
S24
S25
S26
S27
S28
S29
S30
S33
S34
Non-detect = '/2 LOD
2.0
1.0
1.3
2.8
5.1
4.6
11.0
7.8
5.6
8.6
22.3
33.4
15.4
7.8
4.1
9.0
93
30.9
61.3
42.4
60.9
439.4
759.3
49.8
175.3
Non-detect = 0.0
1.3
0.9
1.1
2.6
5.1
4.5
11.0
7.8
5.6
8.6
22.3
33.3
15.4
7.8
3.9
8.9
8.5
30.9
61.2
41.7
60.9
439.4
759.3
49.8
175.3
Note: Samples S20 and S23 are not included in this table because they fail to meet quality
assurance/quality control criteria. These locations will be resampled.
16
-------
0
I!
CO
M
0)
0)
0
(I
c
0
tt
IA
1
111
O
fi
(0
in
^r
d
10
q
6
ON
ON
O
ao
j*!
o
en
O
1
o
o
cti
•*-*
en
(S
O
I
03
.0
en
O
-------
CO
(0
Q
CO
(0
0)
N
(0
10
T"
6
in
o
CO
s
00
G
O
u
00 ON
r- oo
C5
OO ON --1
OO 00 ON 00
oo co r- r- oo r~-
oo r— r-~ rr \o p- vo
t- w -* m f> fi '*
m cs ci fs rs cs m
-------
oo
00
r-
(S
1/3
vo"
(N
(S
W
£
1
o
•o
I
I
o
T3
T3
U
T3
8
2
a.
o
U
oo
r-
o
OO ON —<
Un UH [t.
00 OO OS 00
oo oo r^ r- oo i^
oo r~- r~ M- \o r— ^o
f~ <^ •"*• m m r^ •*
m r- ^ Q
+3 QQQQDQD
a:
o
Q
3
£
-------An error occurred while trying to OCR this image.
-------
00 ON
r-- oo
in
T-
I
0
10
o
Q
Fl
o
OO ON —'
00 OO O\ OO
oo oo f— r- oo (—
oo r- r- TJ- ^o r- vo
r— m ^~ c*^ co en ^
m CN en CN CN CN en
CN ^- CN •—< —< — CN
— CN
U< UH
(l, P-,
CM
C/5
^
m
on
^^ 00
on 00 oo O\ t-~ r~.
oor^'<3-vot^''f-Q
'^ t^-mcnmmmr-i
mcNCNCNCNCNX
T3CN^-—'—'^ — O
c
o
Ui
DO— (Nm-'tui'or-
^QQQQPQQ
o
t- K
cx.2
u D
CD
O
O
g
Ml
E
-------
6.0 REFERENCES
Ball, D.J., et al. Polychlorinated biphenyls, dioxins and furans in the Pontypool environment.
1994, Research Report No. 21. Report to the Welsh Office. ISBN 1 873933 55 X.
BC Environment 1995. Dioxins and Furans in the British Columbia Environment.
BLAG (1992): BLAG, Bund/Landerarbeitsgruppe DIOXINES, Umweltpolitick: Bericht der
Bund/Lander-Arbeitsgrupe DIOXINE. Rechtsnormen, Richtwerte, Handlungsempfehlunge,
MeBprogramme, MeBwerte und Forschungsprogramme. Bundesminister fur Um
welt, Naturschutz und Reaktorsicherheit (ed.), Bonn, Januar 1992 (as cited in Fiedler, et al.,
1995).
Donnelly, J.R. 1992. Technical Report: Analysis for Chlorinated Dibenzofurans, EPA EMSL-LV
publication TSC-16, June 1992.
Fiedler, H., C. Lau, K. Cooper, R. Andersson, S.-E. Kulp, C. Rappe, F. Howell, and M. Bonner.
1995. PCDD/PCDF in Soil and Pine Needle Samples in a Rural Area in the United States of
America. Presented at, 15th International Symposium on Chlorinated Dioxins arid Related
Compounds. August 21-25, Edmonton, Canada. Abstract in, Organohalogen Compounds,
Volume 24, p. 285-292.
Hale, M.D., F. Hileman, T. Mazer, T. Shell, R. Noble, and J. Brooks. 1985. Mathematical
modeling of temperature program capillary gas chromatographic retention indexes for
polychlorinated dibenzofuran. Analytical Chemistry. Volume 57:640-648.
HMIP 1995. Determination of polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and
polychlorinated dibenzofurans in soils. 2nd Technical Report to Her Majesty's Inspectorate of
Pollution.
OEPA 1994a. Risk Assessment of Potential Health Effects of Dioxins and Dibenzofurans
Emitted from the Columbus Solid Waste Authority's Reduction Facility. The Ohio
Environmental Protection Agency, Division of Air Pollution Control. February 28, 1994.
OEPA. 1994b. Franklin County Ohio Ambient Air Monitoring Study for Dioxins and
Dibenzofurans. Division of Air Pollution Control, Ohio Environmental Protection Agency. July
27, 1994.
Paustenbach, D.J.; Wenning, R.J.; Lau, V.; Harrington, N.W.; Rennix, O.K.; Parsons, A.H.
(1992) Recent developments on the hazards posed by 2,3,7,8-tetrachlorodibenzo-p-dioxin
in soil: implications for setting risk-based cleanup levels at residential and industrial sites.
Journal Toxicology and Envirorypnental Health 36:103-149.
22
-------
Reed, L.W., G.T. Hunt, B.E. Maisel, M. Hoyt, D. Keefe, P. Hackney 1990. Baseline assessment
of PCDDs/PCDFs in the vicinity of the Elk River, Minnesota generating station. Chemosphere
21:1063-1085.
Stanley T.W., and S.S. Verner. 1985. The U.S. Environmental Protection Agency's Quality
Assurance Program, pp. 12-19. In: J.K. Taylor and T.W. Stanley (eds) Quality Assurance For
Environmental Measurements. ASTM, STP 867, American Society for Testing and Materials,
Philadelphia, PA.
USEPA 1995. Quality Assurance Project Plan for the Phase I Investigation of Dioxin/Furan
Emission Impact on Soils in the Vicinity of the Columbus, Ohio Waste-to-Energy Facility. The
US Environmental Protection Agency, Region 5, 77 West Jackson Boulevard, Chicago, IL,
60604-3590. May, 1995.
USEPA. 1994a. Estimating Exposure to Dioxin-Like Compounds. US Environmental
Protection Agency, Office of Research and Development, Washington, B.C. 20460. EPA/60/6-
88/005Ca,b,c. June, 1994. External Review Draft.
USEPA. 1994b. Guidance for the Data Quality Objectives Process. EPAQA/G-4. United
States Environmental Protection Agency Quality Assurance Management Staff, Washington, D.C.
USEPA. 1994c. SW-846 Test Methods for Evaluating Solid Waste, Third Edition. SW-846
Method 8290, Revision 0, September 1994. Polychlorinated Dibenzodioxins (PCDDs) and
Polychlorinated Dibenzofiirans (PCDFs) by High-Resolution Gas Chromatography/High-
Resolution Mass Spectrometry (HRGC/HRMS). Office of Solid Waste and Emergency
Response, United States Environmental Protection Agency, Washington, D.C.
USEPA. 1989. Interim procedures for estimating risks associated with exposures to mixtures of
chlorinated dibenzo-p-dioxins and -dibenzofurans (CDDs and CDFs) and 1989 update. U.S.
Environmental Protection Agency, Risk Assessment Forum, Washington, D.C. EPA/625/3-
89/016.
23
-------
ATTACHMENT A - SOIL SAMPLE SITE DESCRIPTIONS
Site No. Sample No. Site Descriptions
1. S29 Flat grassy area to north of facility buildings
2. S28 Front lawn area of Sheriff training center
3. S27 Covered lagoon area north of American Aggregate's access road and east
of ditch
4. S30 Flat grassy area to east of stacks on facility property
5. S3 3 Front yard area of Columbus Incinerator between the stacks and shredding
operations and east of the creek
6. S34 Front yard of facility slightly north of stacks
7. S25 Behind fenced in area around influent control site for Jackson Pike WWTP
east of Rt. 104
8. S24 North side of Jackson Pike WWTP and just north of the structure covering
Compost Filter 1.
9. S12 Entrance to Roadway Trucking Co property- high grassy knoll to the west
of the entrance drive south of Frank Rd. and east of 1-71
10. S13 West of office area for Agg Rok Materials off of Frank Rd. (711 Frank
Rd.)
11. S14 Scioto River levee approximately 1777 feet upstream of USGS gauging
station on Jackson Pike WWTP property
12. SI 5 Scioto River levee approximately 804 feet downstream of Jackson Pike
WWTP outfall structure.
13 S18 Scioto River Levee at extreme southeast corner of Jackson Pike WWTP
property (access from American Aggregates road)
14 SOS Flat area at top of landfill west of Jackson Pike and south of facility
a
15. S10 Private property south of Dyer Rd.-Tannis Dr.
A-l
-------
16. S11 Private property off Dyer Rd. at end of long tree covered lane
17. S09 Agg Rok Materials property offBrown Rd. opposite 2335 Brown Rd. flat
area above creek valley
18. S07 WMNI Radio tower site off Marlane Dr.
19 S26 Fill area at southwest corner of Jackson Pike WWTP
20. S22 Southwest corner of Berliner Park
21. S23 Berliner Park north of Jackson Pike grit chamber unit high flat grassy area
22. S19 American Aggregate's property off Haul Rd. site south of old quarry train
23. S20 Heritage Temple Baptist Church middle level of open grassy area
24. S21 Scioto Trail School open lawn area behind school
25. S06 Madison Plains School east of new high school high area of lawn to east of
package WWTP behind football practice field
26. 805 Madison Plains School east of new high school high grassy area even with
front of new high school
27. S04 Madison Plains School east of old high school
Quality control sample numbers: S01,S02,S03,S16,S17,S31,& S32
A-2
-------
ATTACHMENT B - LABORATORY ANALYSIS DATA SHEETS
-------
Key for Sample Analysis Data Sheets
Laboratory Identifying Number
47482-6-22
47482-6-16
47482-6-2
47482-6-3
47482-6-4
47482-6-5
47482-6-15
47482-6-6
47482-6-7
47482-6-20
47482-6-18
47482-6-19
47482-6-17
47482-6-8
47482-6-9
47482-6-10
47482-6-11
47482-6-12
47482-6-21
47482-6-23
47482-6-13
47482-6-14
47482-10-2
47482-10-3
47482-10-19
47482-10-20
47482-10-21
47482-10-22
47482-10-4
47482-10-5
47482-10-6
47482-10-7
47482-10-8
47482-10-9
47482-10-10
47482-10-11
47482-10-12
47482-10-13
47482-10-14
47482-10-15
47482-10-16
47482-10-17
47482-10-18
Description
Method Blank
SOI -FieldBlank
S04 - Background Sample
805 - Background Sample
S06 - Background Sample
S07
SI7-FieldBlank
SOS
S09
S09 - Laboratory Duplicate
S03 - Field Duplicate
S03 - Detection Limit Sample
S02 - Soil Reference Material
S10
Sll
S12
S13
S14
S04 - Matrix Spike
S04 - Matrix Spike Duplicate
S15
S16-FieldDuplicate
S18
S19
S34
S34 - Matrix Spike
S34 - Matrix Spike Duplicate
Method Blank
S20
S21
S22
S23
S24
S25
S26
S27
S28
S29
S30
S31 - Field Duplicate
S32 - Field Blank
S33
S3 3 - Laboratory Duplicate
B-2
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------
Ei.
*< *<
S ft
o. 5
HH
oo
E
HH
oo
E
HH
oo
SS 2
II
'22!
g 3 !
S- i 5- i
i o js
S3
5'5
> — K> (
• NJ W I
i D:
> JO JO JO l*>
ItJ U) W ^J
n
» SC E BC o
N. x x x r-i
^ O O O 2
noo oa
a o o a
o
s a?
§11
3 « -
C» y""V «
, •• w
to n
'» r
fo en
>fl
n
a
i)
>
00
O
n
a
"8
PI
I
IX
m
\O VO I—
Ni U» OO
pop
*-4 ^ QQ
# O <-ft L/»
p p
Lri k)
•a TI _
•5.0Q
O * N> Lfl #
(_/» \O p p
^j lu '^ ui
• ON O '-'i tO
pppppppppO
UJCOO^-tO^-SiWhJOJ
LASJ^t>J4^^4hJU>ON'-/i
p O O O O
^- ui l»j 'ro io
ex a\ bJ ^- oo
Cd
i
en
\ ON O\ Ov *-•
K) Ni K> N> K> to
L ON O\ ON ON ON '-ft
0. H
• tn
•— h- N- H- O O
O i— i—
H-^-^J^OOOO oo.,oro
•^JOO *<_«OO'— SO *OOO
PPr r r P >;
•UlON§-JON**NO "<'
n
tn
>
H D
8g
D 6
r r 9 9 9 9 C C r 9 9 C
JO JO JO — — — ,-j Q — JO — —(-)„
"u» "w "oj "to "to "to ^ ^ UJ w jo JO ^ w
"~J ON ON "-J ON V "^ \^ JO ON ON J^ "w J°
00 "-J "-J 00 "-) *-J Vj '^j ^ — .--1 .-1 ."•" "~J -W
TlTlTi'Tl'-n'n'nTi'nOODDGD
toiotototototototo-^-tototototo
r
OB
p
§
o
o
I
D
t/5
<
'nfl
"-E.pt
1 » 2. 3
» — - b_4 N— ^3
sffll
s ^ I s; I
§0>g^
^r
w O oo
^1 LO o
00 00
I-1" ^
£•2. S
eu
s'<-
=•2-0
3 -1 S
O NO 5J
e oo S
ft * to
01 ON
g
^C 8
NO 3 Ui
"B
OS ^
§5;
pm
p p p p p p >— '—
li
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------
— — — — oo — •
i O O O O O O
04
£§
8£
vi -. S 0 CO < '
^2 a S.Q «
oo o oj ** 5? S
i?2°!$ i
.. ^ § < ..^
-> eg7:'
Ji "S r9 " S
|^g g it
« Jii £ o .
« g.73 5 O
•9 i 1 I «
,j w £ £ O c
5 a
isS
n °
CL, O
oo u
S
Z
I
I
O
I
S
C-) (N (N (S
Q Q
QQ
U U
Q Q
QQ
\ eN
,U,U,U,U,U.U.tt,U,
IQQQQQQQQ
IUUOUUOUU
-) X X X X Q. Q.
' S3 S ffi EC 33 EC
'££.
(^ xf 00 00_ CO ,
y - en en Tt
en i M es en
- O -T -T es
2 6 6 -7
en en r \
*i oo oo i
\ 00 OO ^
" oo" r-" r~" oo"
es
I Q
Q H
Z oo
I en ,
T ™ rJ eN^ es' en' en en
O O »--' •-< »H" cs" ts
•
88888888888888888
I
03
O (N OO
Tt en —_
O O O
8
O
tu
>•
<
<
a
Q Q Q Q
Q p y
U* U.
H, a. u. uu Q Q
Q Q Q Q
H oo t
'
h* oo OG
* "
rs ri fs fS oi U rn rs m r{ rN CM" m* fN r^f O
— <' V-H' — ' — T —T O CN' — *
-------An error occurred while trying to OCR this image.
-------
Z p so
00 &
$:
CO
Q
z
I
8
Q
3
w
ca
Q Q
QQ
U U
QQ
QQ
Qft
Q Q
"u
UH fTi UM UN [Ti f.Ti ITi QM
QQQQQQQQ
UOUUUCJUU
V4>XXXXO.O.
(V^aaaaaa
°°. °° 00 00 CT\ 00 00 ON
- U _" « J2 — — 2 tj cj
Q Q
at Q
5".
u
^Hr— oo
O* —
• — — * o
o — -. — — -. o —•
•H -H O O
o o — — — — —
I
OQ
d o o d o
i oo oo in o en
i d d d d d
e 3
3,2
o x
ed
1 °
u
on
I
<
u.
Q
Q
Q
<
CO -4 '
O
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------
l
-^ — d d d d d d
CO
Q
1
O
u
g
Q Q Q
Q QQ
U U U
E-H D X
-S1?
'-"£"-
m ^ •-.
* en -+
f :
--UUUU7T
2 « 2 2 u u
^
< U
Q t;
u
J
CO
«E;»;
IS
CM
CM
I
CQ
—; S; —; oo vq
'
<
Q
a a Q Q
Q QQ U
O U CJ £•
cu oo oo os
oo r~" r-" oo" v
en en
" r-f ri «
i.Q '
i u i
tu tu
it. CL, u, a, Q Q
....QQQQUCJ
ft Q u u u u £•.§•
CjCL(a*obooo\oor*-"od"
c™1 oo oo r^ t^- oo r^ ^o t^
i oo t~~ r^ ^t" *o r^ *o ^ ^f ri
CN m c^ r^ c~i m fN c^ u
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------
d -- — ,j _;
-- -< oooood
8
; —> — — (S p p oq
'
oo
CN
I
OQ
z *
o 2
UJ
en
Q
23
55
IL,
Q
Q
Q
U « *od
3 5 5"
w SsS
. U
S
= o
,-v
g
Q Q
Q Q
u u
Q
Q Q
Q U
u £•
X K
SB afa
j
(Li (b
QQ
UU
XX
as x
00 Ov
U-
IL, O I
QU
U £•
U.
Q
U
•
sgg
£ 5 £
ag
H oo oo i
. oo r-T r-' •
IS^.S^Q
r^ r^ CN cs^ (N^ O c^ fs r^ r^ rs^ r| r^ rs^ r-4
—" —' —' —• —• O (N ~" (N —" —«" —*
-------An error occurred while trying to OCR this image.
-------
O es en en •
oo r^ oo as i
—< oo
it f-
Sen (N -^
oo oo oo
en en _ i
CO
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------
^ —• d d d d d d
iOOooosi~*r^oo^\oooor^oooot^-i^
S
Q Q
Q Q
U U
P
^
33
m i
— u
QQQQU«PUU«te.U,tt*U-cU-.U<
QQQQQQQQQQQQQ
uuuuuuuuuuuuu
x x O.X Huuxxxxo.a,
M M >i* *-'lCLlCUHrl*TlhT''TINtNT'
ffiffiffi'oo^:L******
oo oo oo X r-"
q Q
2Q
< O
Q f-
r- r^ r-^
Tt" ^o vcT
n' c^" T}-*
ri r^ en
—r'-«" rs'
! u U -f
2^0
--r^1
- m •
, oo oo o\ oo oo o\
•, i-" r{ oo i-~" f-" oo
"
oo r- oo
' oo' r-' vo r-'
" * '
K o ^ .2 c O
[2 5 a. c>
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------
o —• — _<_oo — ~ o o o o o o
o|
§1
w u
g o
co U
z
1
o
u
Q
3
w
3
8
I
CQ
Ui
[: °S
^^ ii *~^
a m
a'*
^^
S5.S
31,
ta
IB
to
M ** ' I 3
aSSii?
I U
?
r^
VD "!
OS o O
y (N .- 0)
<-^s
•• 2: j ,3,0
oo 3 u ^
Mil
•- t g e
S. u -i .9
ti-ii
< w £"Q
g
i ^? ~H >/-) o *o r- ~- i
Q
Q Q Q Q
QQQQy
« u uu £•
a x « x >B
U ffi K 35 oi
cu oo oo ON r-
1 oo r- t^-" oo" \o~
**.
U.
Q
u
H ob ob r-'
U- U,
U. ft, it, U, Q Q
Q Q Q a
U UU
U
, op '
i(Nrv4fN(NOJCJfri(1Nf*^r^(N(Nr^(SCNCJ
a
-s
Ij ". I I jrt rt
<3 2 cs ro iJ i-J
oooooooo
d
etf
O
u
c
3
o
o
•a
o
o
u
o
£
-------An error occurred while trying to OCR this image.
-------
ATTACHMENT C - SUMMARY OF LABORATORY QUALITY CONTROL RESULTS
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
-------An error occurred while trying to OCR this image.
------- |