905R96019
FINAL REPORT
PHASE H INVESTIGATION OF DIOXIN/FURAN
EMISSION IMPACT ON SOILS
IN THE VICINITY OF THE COLUMBUS, OHIO
WASTE-TO-ENERGY FACILITY
Submitted to
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Pollution Prevention and Toxics
and
Region V
EPA Contract No. 68-D2-0139
Work Assignment No. 4-6
September 27, 1996
Prepared by
BATTELLE
505 KING AVENUE
COLUMBUS OH 43201
(614)424^911
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TABLE OF CONTENTS
Eage
SUMMARY 1
BACKGROUND INFORMATION 1
Sample Preparation and Analysis 1
Sample Results 4
Quality Control Results 6
Method Blanks 6
Field Blanks 6
Surrogate Internal Standards 7
Matrix Spike/Matrix Spike Duplicate 7
Sample Duplicates 7
Estimated Detection Limit (EDL) Sample 8
APPENDIX A. INITIAL ANALYSIS REPORTING FORMS A-l
APPENDIX B. SECOND COLUMN CONFIRMATION RESULTS B-l
APPENDIX C. QUALITY CONTROL SAMPLE RESULTS C-l
APPENDIX D. MANUAL DETECTION LIMIT CHECKS D-l
APPENDIX E. CHROMATOGRAMS AND BENCH DATA E-l
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PHASE n INVESTIGATION OF DIOXIN/FURAN
EMISSION IMPACT ON SOILS
IN THE VICINITY OF THE COLUMBUS, OHIO
WASTE-TO-ENERGY FACILITY
September 27, 1996
SUMMARY
This report contains analytical results for the seventeen 2,3,7,8-substituted
polychlorinated dibenzo-p-dioxins and polychlorinated dibenzorurans (PCDD/PCDF)
determined in seventeen soil samples and one water sample from the area around the Columbus
municipal waste-to-energy (WTE) incinerator. These samples were analyzed according to the
Environmental Protection Agency (EPA) Method 8290.
BACKGROUND INFORMATION
Phase I data were presented to the public in April, 1996. Data from both phases of this
investigation will be used to ascertain whether PCDD/PCDF concentrations in soils near and at
a distance from the Columbus incinerator, and in several drinking water sources, are above
area background concentrations. The results from this and previous studies will be used to
determine if more comprehensive sampling efforts are required to characterize site
contamination.
Experimental Procedures
The 17 soil samples and 1 water sample were delivered by the field team directly to
Battelle laboratories. All 18 samples were analyzed in one batch consisting of 17 soil samples,
1 water samples plus the associated quality control samples: 2 soil field blanks, 2 soil
duplicates, 1 soil matrix spike, 1 soil matrix spike duplicate, 1 water duplicate, 1 water field
blank, and 1 method blank. In addition to these nine QC samples, one of the soils was spiked
with PCDD/PCDF at 5 times the method detection limits (MDL) specified in the Quality
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Assurance Project Plan (QAPP) to verify that these detection limits were achieved. Method
detection limits are 1, 5, and 10 pg/g for the respective tetra, penta/hexa/hepta, and octa
congeners. This estimated detection limit (EDL) sample was included in the extraction,
cleanup, and analysis of the soil and water samples for Phase II. The samples processed in
Phase II, in order of analysis, are as follows:
lethod Blank
R06, Field Blank
U9, Field Blank
S02, Site 2
S03, Site 3 Top
S04, Site 3 Middle
S07, Site 4
CS08, Site 4 Duplicate
Sll, Site 7
S13, Site 10
S15, Site 11
S24, Site 17 ("'(,
CS17, Site 17 Duplicate -<<*-* -v
S18, Site 20
S21, Site 18 (0-1.5")
S22, Site 18(1.5-3.0")
S25, Site 16
S27, Site 13
S30, Site 9
S10, Site 6
SOI, Site 1
PR03, Water Blank
I SOI, Site 10 Water
lv_S02, Site 10 Water Duplicate
S09, Site 5
Us 15, Site 11 EDL Sample
pS09, Site 5 Matrix Spike
i_S09, Site 5 Matrix Spike Duplicate
Approximately 10 g of each soil sample was used to determine percent solids (percent
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dry weight). Another approximately 10 g of each sample was 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
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for approximately 18 hours with toluene in a Soxhlet apparatus. Extracts were spiked with
37Q4-2,3,7,8-TCDD cleanup standard, partitioned against base and acid solutions, and
processed through acid/base silica, two (2) basic alumina, and Carbopak-C carbon/Celite
cleanup columns. Extracts were spiked with l,2,3,4-TCDD-13C12/l,2,3,7,8,9-HxCDD-13C12
recovery standard and concentrated to a final volume of 20 /xL.
Sample extracts were analyzed on a VG AutoSpec high resolution gas
chromatography/high resolution mass spectrometer (HRGC/HRMS) (Serial #X088, System
#6744) in the selected ion monitoring mode on a J&W DB-5 capillary column (Serial
#6124127) 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
OpusQuan software. The criteria used to identify chromatographic peaks were: (1) ^2.5
signal-to-noise ratio; (2) ion abundance ratios within 15% of theoretical values; (3) retention
times of native analytes within ±2 seconds of 13C12-labeled internal standards; and (4) no
diphenyl ether interferences. Because 2,3,7,8-TCDF is not completely resolved from all other
tetra-chlorinated 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. For those samples which were ran on the DB-
Dioxin column, the utility of separating 1,2,3,4,7,8-HxCDF from a non-2,3,7,8-HxCDF was
also investigated.
Per the QAPP for this project, the following deviations to Method 8290, which are part
of routine sample preparation/analysis in Battelle's Dioxin Laboratory, were employed:
Sample Preparation
1. The following additional internal standards were added to the samples prior to extraction
to improve analytical accuracy:
13C12-2,3,4,7,8-PeCDF 13C12-l,2,3,4,7,8-HxCDD
'3C12-l,2,3,6,7,a-HxCDF 13C12-1,2,3,7,8,9-HxCDF
13C,2-2,3,4,6,7,8-HxCDF "C12-l,2,3,4,7,8,9-HpCDF
2. A cleanup standard, 37Cl4-2,3,7,8-TCDD, was added to the samples prior to processing
through cleanup columns to evaluate analyte recovery through cleanup.
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3. A 30-mL volume of acid was used for the first acid wash of the sample extract, rather than
40-mL; 20 mL of acid was used for each successive acid wash instead of 40 mL; and 15
mL of base was used for the base wash.
4. In the acid/base silica column cleanup, a 1-g plug of silica gel was placed between the basic
silica and the acid silica layers. In addition, sodium sulfate was added to the top of the
column. The column is rinsed with 30 mL of hexane instead of 10 mL. The sample was
usually applied in 5 mL of hexane instead of the 2 mL of hexane specified in Method 8290.
The column was eluted with 75 mL of hexane instead of 90 mL.
5. In the alumina column cleanup, Sigma basic alumina, WB-2, activity grade I, was used
instead of acidic or neutral alumina. For the first elution, the alumina column was rinsed
with 15 mL of 3 % methylene chloride/hexane instead of 20 mL of hexane. The second
elution, containing the PCDD/PCDF, consisted of 40 mL of 50% methylene
chloride/hexane instead of 15 mL of 60% methylene chloride/hexane specified in Method
8290.
6. For the carbon column cleanup, procedures similar to those specified in Method T09,
Section 11.3.6, were followed. The column was back eluted with 20 mL of toluene.
Sample Analysis
1. Commercially-prepared calibration standards at concentrations specified in Method 1613
were used instead of calibration concentrations specified in Method 8290. The Method
1613 calibration concentrations cover a wider range and lower limits for some compounds
than the Method 8290 calibration concentrations. In addition, a sixth calibration standard,
at a level approximately '/2 of the lowest Method 1613 calibration standard, was
incorporated into the calibration curve. The concentration of this standard was 0.25, 1.25,
and 2.5 pg /xL for the respective tetra, penta/hexa/hepta, and octa congeners and
corresponded to an LOQ of 0.60, 3.0, and 6.0 pg/g for the respective tetra,
penta/hexa/hepta, and octa congeners in an 8.275-g sample.
SAMPLE RESULTS
Appendix A includes data sheets with analytical results from the initial analysis and
associated quality control results. Data sheets in Appendix B present 2,3,7,8-TCDF
concentrations from second column confirmation analysis of 17 samples. Results for 2,3,7,8-
Jl
TCDF from the second column confirmation analysis have been inserted into the initial
analysis data sheets in appendix A. In addition, because the DB-Dioxin column appeared to
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separate 1,2,3,4,7,8-HxCDF from a co-eluting non-2,3,7,8-HxCDF, the second column data
for 1,2,3,4,7,8-HxCDF was also inserted into initial analysis data sheets in Appendix A.
Please note the following when reviewing these results:
(1) The "*" on the data sheets indicates that the analyte was not detected.
(2) The HRGC/HRMS instrumentation was calibrated in the ranges corresponding
to analyte levels in the samples of 0.60 to 483 pg/g dry weight for tetra
compounds, 3.0 to 1250 pg/g dry weight for penta through hepta compounds,
and 6.0 to 4834 pg/g dry weight for octa compounds. These calibration ranges
are based on an average sample dry weight of 8.275 g and a l-/xL injection
volume. Concentrations below these calibration ranges have been reported;
however, accuracy of concentrations outside the calibration range cannot be
guaranteed.
(3) Of the samples analyzed, only the three field blanks and soil sample S13 did not
require second column confirmation analysis. Because sample S13 did not /
require a second column confirmation analysis, data from the separation of
1,2,3,4,7,8-HxCDF from a non-2,3,7,8-HxCDF were not available. The
concentration reported on the initial analysis data sheet was calculated as an
estimated maximum possible concentration (EMPC), per Method 8290, Section
7.9.5.2.1.
(4) Where data from the DB-Dioxin confirmation run have been inserted into the
initial analysis data sheets, the total TCDDs and total HxCDFs have been
adjusted accordingly.
/
(5) Sample SOI soil, taken from a Phase II resampling of Site 1, had very poor /
chromatography and significant quantitation interferences. (The same results/
were noticed in Phase I analysis of this samplel [Therefore, this sample did not
go through a second column confirmation due to the high level of quantitation
""f
interferences.^ Sample S10, taken from a Phase n resampling^of Site 6, showed
much better chromatography in Phase H than it did in Phased^ perhaps the
result of better cleanup through the two alumina columns used in Phase n.
(6) In some instances an analyte concentration which is slightly below the
instrument limit of quantitation (LOQ) has been reported. In these cases, the
analyst judged the analyte met Method 8290 identification criteria and so the
concentration determined has been reported along with the sample limit of
detection (LOD^and the instrument limit of quantitation (LOQ).
(7) The sample limits of detection shown on the data sheets were calculated by the
OpusQuan data system according to Method 8290, Section 7.9.5.1.1. Appendix
D shows a detailed comparison of manual method detection limit calculations
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with those generated by the OpusQuan data system for four runs. In addition,
the OpusQuan-generated limits of detection were checked randomly by manual
calculation throughout the analyses. In general, there was very good agreement
between the OpusQuan-generated detection limits and the manually-calculated
detection limits. Also, for all analyses (except sample SOI, Site 1), the
OpusQuan-generated LODs were well below the method detection limits
outlined in Method 8290 of 1, 5, and 10 pg/g for tetra, penta/hexa/hepta, and
octa congeners.
(8) Due to incomplete separation of 13CI2- 2,3,7,8-TCDD and 13CI2- 1,2,3,4-TCDD
on the DB-Dioxin column, recovery data for 13C,j- 2,3,7,8-TCDF is not given in
the second column run. The recovery of 2,3,7,8-TCDF is shown for each
sample on the initial data analysis sheet for that sample.
QUALITY CONTROL RESULTS
Appendix A contains initial analysis data sheets for the method blank, water blank, and soil
field blanks. Appendix C contains summary tables of quality control results for matrix spike,
matrix spike duplicate, sample duplicates, and the estimated detection limit (EDL) sample.
Method Blanks: One method blank and one water blank were processed with this batch of
samples to demonstrate freedom from contamination in the laboratory processing and analysis
procedures. For the method blank, a 10-g aliquot of sodium sulfate was processed through all
extraction, cleanup, and analysis procedures as if it were an actual sample. PCDD/PCDF
were not detected at levels above the instrument LOQ or the method detection limits. The
water blank was received along with Phase II samples from the field sampling team. It was
processed through the same extraction, cleanup, and analysis procedures as the two water
samples, samples SOI and S02. Again, no PCDD/PCDF were detected at levels above the
instrument LOQ or the method detection limits.
Field Blanks: The play sand used for preparing soil field blanks in Phase I was muffled
again at 450 C immediately prior to Phase II. Two Phase II field blank samples were prepared
by rinsing new 500-mL jars with methylene chloride, filling about lh. full with play sand, and
sealing jars with lids and teflon tape.
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The field blanks for Phase II sampling effort were samples R06 and R19. In each case,
PCDD/PCDF were not detected or were detected at levels well below both the instrument
LOQ or method detection limits. These results suggest that the field blanks were not exposed
to PCDD/PCDF background contamination in the field sampling activities.
Surrogate Internal Standards: Each sample was spiked with l3C12-labeled analogs of fifteen
of the seventeen 2,3,7,8-PCDD/PCDF prior to extraction. Recovery of these internal
standards gives an indication of method performance. All internal standard recoveries were
within the 40-135 percent limit stated in Method 8290 except for 1) 1,2,3,4,7,8,9-HpCDF-
13C12 in samples S30 (38 percent) and sample S02 (water duplicate) (39 percent); 2) 2,3,4,7,8-
PeCDF-13C,2 in sample S25 (38 percent); and 3) several internal standards in soil sample SOI.
Recovery losses in sample SOI appear to be attributed to column overload during sample
cleanup. The generally good recovery of surrogate internal standards indicates that laboratory
extraction procedures are sufficient to remove PCDD/PCDF from the matrix and cleanup
procedures are not contributing to excessive losses of PCDD/PCDF.
Matrix Spike/Matrix Spike Duplicate: A matrix spike (MS) and matrix spike duplicate
(MSD), samples S09 MS and S09 MSD, were processed with this batch of samples by spiking
both samples with the seventeen 2,3,7,8-PCDD/PCDF and processing through all extraction,
cleanup, and analysis procedures.
Spike recoveries for these two quality control samples were 60.7 to 112.1 percent.
Required control limits for matrix spike/matrix spike duplicate agreement were ±25% relative
percent difference (RPD). This control limit was met for all 2,3,7,8-substituted PCDD/PCDF
congeners and is an indication of good laboratory precision.
Sample Duplicates: Two soil duplicates, for Site 4 and Site 17, and one water duplicate,
for Site 10, were received with the Phase II samples. Required control limits for duplicates
>3
were less than 25% RPD. The control limit was met for most analytes in the three samples
with the exception of a few analytes that were detected below the instrument LOQ. Again, the
low RPD is an indication of good laboratory precision.
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Estimated Detection Limit (EDLt Sample: One of the soils (S15), chosen by the field
sampling team, was used to verify that method detection limits were achieved. Two aliquots of
SI 5, one spiked with PCDD/PCDF at about 5 times the method detection limit (MDL) and one
unspiked to serve as its background, were extracted with this set of samples. The recoveries of
the analytes ranged from 87.6% to 114.8%. The percent recovery for OCDD was calculated
using the following equation (a):
Percent Recovery = 100 (Cone. found)/(Spike cone. + Background cone.)
This equation was used for the OCDD recovery calculation due to the very high background
level of OCDD, which "swamps" the relatively small spike.
(a) L. P. Provost and R. S. Elder, "Interpretation of Percent Recovery Data," Amer. Lab., 15(12), pg. 57, 1983.
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APPENDIX A
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COMPLETE ANALYSIS DATA SHEETS FOR
INITIAL ANALYSIS OF PHASE n SAMPLES
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Phase II Sample Analyses
Lab Record Book #
47482-20-26
47482-20-6
47482-20-19
47482-20-3
47482-20-*
47482-20-5
47482-20-7
47482-20-8
47482-20-12
47482-20-13
47482-20-14
47482-20-16
47482-20-17
47482-20-18
47482-20-20
47482-20-21
47482-20-22
47482-20-23
47482-20-24
47482-20-25
47482-20-2
47482-20-29
47482-20-27
47482-20-28
47482-20-9
47482-20-15
47482-20-10
47482-20-11
Sample ID
Method Blank
R06, Field Blank
R19, Field Blank
-. S02, Site 2 >
^ S03, Site 3 Top
2 S04, Site 3 Middle
S07, Site 4
SOS, Site 4 Duplicate
SI 1, Site 7
S13, Site 10
S15, Site 11
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APPENDIX B
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ANALYSIS DATA SHEETS FOR
2.3.7.8-TCDF SECOND COLUMN CONFIRMATION
OF PHASE II SAMPLES
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APPENDIX C
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QUALITY CONTROL SAMPLE RESULTS
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