United States
Environmental Protection
Agency
Region 5
Eastern District Office
25089 Center Ridge Road
Westlake, Ohio 44145
EPA-905/4-88-004
March 1987
vvEPA Michigan Dioxin Studies
Dow Chemical
Building 703 Incinerator Exhaust
and Ambient Air Study
I Ml
X
Air Monitoring Locations
Dow Chsmieal
Company
Bunding 703
Incinerator
-------
DOW CHEMICAL BUILDING 703 INCINERATOR EXHAUST
AND AMBIENT AIR STUDY
MARCH 1987
MARTIN G. TREMBLY
GARY A. AMENDOLA
U.S. ENVIRONMENTAL PROTECTION AGENCY
REGION V
ENVIRONMENTAL SERVICES DIVISION
EASTERN DISTRICT OFFICE
WESTLAKE, OHIO
U.S. Envircnra-^rital Protection Agency
Rsffion 5, Library ("5FL-16)
230 S. Dearborn St-eet, Boom 1670
Chicago, IL 60604
-------
ACKNOWLEDGMENTS
The authors would like to express their appreciation to several individuals
who provided valuable assistance leading toward the completion of this study:
Derivation of study and sample analysis plan - Marcia A. Kuehl , Charles T.
Elly -U.S. Environmental Protection Agency, Region V, Central Regional
Laboratory. Dr. Robert G. Lewis, Dr. Thomas R. Mauser, Dr. John B.
Clements, Dr. Joseph F. Walling- Environmental Monitoring and Support
Laboratory, U.S. Environmental Protection Agency.
Background information about facility and study area - Robert Teoh, Jim
Sygo - Michigan Department of Natural Resources.
Conduct of field work and compilation of data - Mark del and, Mark Conti,
Brian Buckham, Kenneth Radtke, Eric Burneson, David Perko - U.S.
Environmental Protection Agency, Region V, Eastern District Office.
Edward Peduto, John Podlenski, Mark Gollands, Patrick Ford - GCA/Tech-
nol ogy Division. Ronald Agin, Richard Johnson, Jackie Anderson - Dow
Chemical Company.
Laboratory analyses - Dr. Michael Taylor, Dr. Thomas Tiernan - Wright
State University. Bennett Tyson - EAL Corporation. Dr. John Stanley -
Midwest Research Institute. Al Tordini - U.S. Testing Laboratories.
Robert L. Harless, Environmental Monitoring and Support Laboratory,
U.S. Environmental Protection Agency.
Laboratory data review - Francis Thomas, Thomas Bauer - U.S. Environmental
Protection Agency, Region V, Central Regional Laboratory.
Draft report revi-ew - Donald Barnes, Chlorinated Dioxins Work Group, U.S.
Environmental Protection Agency. Edward Lillis, William Kuykendal -
Office of Air Quality Planning and Standards, U.S. Environmental
Protection Agency. David Kee, Larry Fink - U.S. Environmental Pro-
tection Agency, Region V.
Finally, the invaluable assistance of Carol Kopcak, Ellen Harrison, Minnie
Brantley, and Terence Griffin in typing and proofreading this report is
acknowledged.
DISCLAIMER
This document has been reviewed in accordance with U.S. Environmental
Protection Agency policy and approved for publication. Mention of trade names
or commercial products does not constitute endorsement or recommendation for
use.
-------
TABLE OF CONTENTS
ACKNOWLEDGMENTS ................. . ii
LIST OF TABLES .................. 1v
LIST OF FIGURES ................. . vi i
I. INTRODUCTION .................. 1
II. OBJECTIVES ......... . ........ 3
III. SCOPE OF WORK ...... . .......... 4
IV. FINDINGS AND CONCLUSIONS .......... .... 5
V. DOW CHEMICAL MIDLAND PLANT
BUILDING 703 INCINERATOR EMISSIONS STUDY ........ 8
A. Facility Description 8
B. Sampling Strategy 12
C. Conduct of Study 19
D. Analytical Procedures and Quality Assurance Reviews 20
E. Incinerator Operations During Tests 21
F. Results and Discussion 21
VI. AMBIENT AIR STUDY IN VICINITY OF
DOW CHEMICAL COMPANY MIDLAND PLANT ........... 58
A. Monitoring Network Description 59
B. Monitor Descriptions and Sampling Methods 67
C. Conduct of Study 67
D. Analytical Procedures and Quality Assurance 69
E. Results of Study and Discussion 69
REFERENCES .................. 93
APPENDICES
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LIST OF TABLES
Table 1-1 Tier 4 Dioxin Sampling and Analysis Strategy - ... 2
June 1984 Draft
Table V-l Dow Chemical Company Building 703 Incinerator .... 13
Target Compounds in Air
Table V-2 Dow Chemical Company Building 703 Incinerator .... 14
Target Compounds in Water and Solids Discharges
Table V-3 Sampling and Analysis Summary ......... 22
Oow Chemical Company Building 703 Incinerator
Emissions Study 8/28, 8/30, 9/5/84
Table V-4 Volatile Compounds - Precombustion Air ...... 24
Dow Chemical Company Building 703 Incinerator
8/28, 8/30, 9/5/84
Table V-5 Semi-Volatile Compounds - Precombustion Air ..... 25
Dow Chemical Company Building 703 Incinerator
8/28, 8/30, 9/5/84
Table V-6 Incinerator Precombustion Air - PCDD/PCDF Analyses. . . 25
Dow Chemical Company Building 703 Incinerator
8/28, 8/30, 9/5/84
Table V-7 Quantitated Volatile Compounds - Liquid Waste Inputs . . 27
Dow Chemical Company Building 703 Incinerator
8/28, 8/30, 9/5/84
Table V-8 Quantitated Semi-Vol atile Compounds - Liquid Waste Inputs 29
Dow Chemical Company Building 703 Incinerator
8/28, 8/30, 9/5/84
Table V-9 Liquid Waste Inputs - Quantitated Pesticide/PCB Compounds 30
Dow Chemical Company Building 703 Incinerator
8/28, 8/30, 9/5/84
Table V-10 Liquid Waste Inputs - Quantitated PCDD/PCDF 31
Dow Chemical Company Building 703 Incinerator
8/28, 8/30, 9/5/84
Table V-ll Low-BTU Liquid Waste - Volatile Compounds 32
Dow Chemical Company Building 703 Incinerator
8/28 and 9/5/84
IV
-------
LIST OF TABLES (continued)
Page
Table V-12 Low-BTU Liquid Waste - Semi-Volatil e Compounds .... 33
Dow Chemical Company Building 703 Incinerator
8/28 and 9/5/84
Table V-13 Low-BTU Liquid Waste - PCDD/PCDF Analyses ...... 34
Dow Chemical Company Building 703 Incinerator
8/28 and 9/5/84
Table V-14 Approximate Concentrations of Volatile Compounds ... 35
in Incinerator Exhaust 8/28, 8/30, 9/5/84
Table V-15 Approximate Concentration of Semi-Volatile Compounds . . 35
in Incinerator Exhaust 8/30/84
Table V-16 Incinerator Exhaust - PCDD/PCDF Analyses 37
Expressed in Terms of Concentration in Air
Dow Chemical Company Building 703 Incinerator
8/28, 8/30, 9/5/84
Table V-16A Incinerator Exhaust - PCDD/PCDF Analyses 38
Concentration Expressed in ng/dscm, Adjusted
to Standard Temperature and Pressure (68°F, 29.92 in.Hg),
and Normalized to 3% Oxygen Content
Table V-17 Results of Sampling for Vinylidene Chloride 39
Dow Chemical Company Building 703 Incinerator
Table V-18 Incinerator Ash Semi-Vol atil es 40
Dow Chemical Company Building 703 Incinerator
Table V-19 Incinerator Ash - PCDD/PCDF Analyses 41
Dow Chemical Company Building 703 Incinerator
8/28, 8/30, and 9/5/84
Table V-20 Aqueous Influents and Effluents - PCDD/PCDF Analyses . . 43
Dow Chemical Company Building 703 Incinerator
8/28/84
Table V-21 Aqueous Influents and Effluents - PCDD/PCDF Analyses . . 44
Dow Chemical Company Building 703 Incinerator
8/30/84
Table V-22 Aqueous Influents and Effluents - PCDD/PCDF Analyses . . 45
Dow Chemical Company Building 703 Incinerator
9/5/84
Table V-23 Overall Data Completeness 46
Based Upon Analytical Accuracy Criteria
Dow Chemical Company Building 703 Incinerator
-------
LIST OF TABLES (continued)
Table V-24 Adherence to Desired Detection Limits
Dow Chemical Company Building 703 Incinerator
Table VI-1 Midland, Michigan, Ambient Air Sampling Study,
Summary of Sample Types and Sampling Times
Table VI-2 Results of Ambient Air PCDD/PCDF Sampling .......
In Vicinity of Dow Chemical Company, Midland, Michigan
September 1984
Table VI-3 Comparative Analyses for Total and 2378 Isomer of TCDD and TCDF
Midwest Research Institute and EMSL-RTP, EPA
Table VI-4 Comparative Values for Total and 2378 Isomer of TCDD and TCDF
Midwest Research Institute and EMSL-RTP, EPA
Table VI-5 Wind Data - Ambient Air Sampling Program - Midland, Michigan.
September 7-27, 1984
Table VI-6 Results of Ambient Air Sampling for PCDD/PCDF . . . . .
In Vicinity of Dow Chemical, Midland, Michigan
September 1984
Table VI-7 Results of Ambient Air Sampling for Semi-Vol atile Compounds .
in Vicinity of Dow Chemical Company, Midland, Michigan,
September 1984
Table VI-8 Tentatively Identified Semi-Vol atile Compounds Detected In .
Ambient Air Sampling In Vicinity of Dow Chemical Company,
Midland, Michigan, September 1984
Table VI-9 Ranges of Concentrations of Quantitated Semi-Volatile Compounds
In Ambient Air on Nine Sampling Days - Midland, Michigan
9/7/84 - 9/25/84
Table VI-10 Comparative Results of Carbon Molecular Sieve Tube ....
Validation Study
Table VI-11 Results of Ambient Air Sampling for Volatile Compounds. . .
In Vicinity of Dow Chemical Company, Midland, Michigan
September 1984
Table VI-12 Results of Ambient Air Sampling for Formaldehyde.
In Vicinity of Dow Chemical Company, Midland, Michigan
September 1984
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LIST OF FIGURES
Figure V-l
Figure V-2
Figure V-3
Figure V-4
Figure V-5
Figure V-6
Figure V-7
Figure V-8
Figure VI-1
Figure VI-2
Figure VI-3
Figure VI-4
Figure VI-5
Figure VI-6
Dow Chemical Company Building 703 Incinerator
Dow Chemical Company Building 703 Incinerator.
Exhaust Gas Sampling Points
Dow Chemical Company Building 703 Incinerator
Dow Chemical Company Building 703 Incinerator
Dow Chemical Company Building 703 Incinerator
Dow Chemical Company Building 703 Incinerator
Dow Chemical Company - Midland Plant - Building 703. .
Incinerator Distribution of PCDDs and PCDFs Among
Incinerator Ash, Air, and Water Outputs
Dow Chemical Company - Midland Plant - Building 703. .
Incinerator Comparison of PCDD and PCDF Inputs and
Outputs
Midland, Michigan, Ambient Air Monitoring Network . .
Location of Ambient Air Monitoring Site 1 ....
Location of Ambient Air Monitoring Site 2 ....
Location of Ambient Air Monitoring Site 3 ....
Location of Ambient Air Monitoring Site 4 ....
Location of Ambient Air Monitoring Site 7 ....
Page
9
17
50
51
52
53
55
57
60
61
63
64
65
66
(wind monitoring site)
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APPENDICES
Appendix A Detailed Description of Conduct of Study - Michigan Dioxin
Study - Dow Chemical Building 703 Incinerator Emissions Study
Appendix B Extraction Procedure for "High Hazard" Liquid Waste Samples -
Fred C. Hart Associates, Inc.
Appendix C Analytical Procedures for PCDD/PCDF - Brehm Laboratory - Wright
State University
Appendix D Incinerator Exhaust Study Sampling Results
Appendix E Detailed Descriptions of Ambient Air Monitoring Equipment and
Sampling Methods - Michigan Oioxin Studies - Midland, Michigan,
Ambient Air Sampling Study
Appendix F Detailed Description of Conduct of Study - Michigan Dioxin
Studies - Midland, Michigan, Ambient Air Sampling Study
Appendix G Raw Analytical Data - Ambient Air PCDD/PCDF Sampling in Vicinity
of Dow Chemical Company, Midland, Michigan
Appendix H Results of Reanalysis of Selected PCDD/PCDF Samples by USEPA-
EMSL-RTP and Explanatory Information
Appendix J Detailed Discussion of Air Dispersion Modeling to Determine
Point of Maximum Ground-Level Impact
vm
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I. INTRODUCTION
The U.S. Environmental Protection Agency (USEPA) Region V has conducted a
series of comprehensive multi-media studies of dioxins and other toxic pollu-
tants at the Dow Chemical Company Midland Plant, in the Tittabawassee River,
and in and near the city of Midland, Michigan. The purposes of these studies
were to determine current emissions and ambient levels of toxic pollutants and
whether those levels warrant remedial action to minimize or eliminate public
exposure and environmental risks. Soil sampling was conducted in Midland, at
Dow Chemical , and at comparison and background sites during 1983 and 1984.
Results from the soil study were released in April 1985.1 Screening studies of
surface water supplies, potable ground water, and brine operations at the Dow
facility was completed in 1984 and 1985; the results of these studies were
released in December 1985.2 During 1984, samples were collected from Dow
Chemical's waste incinerator; ambient air; Dow Chemical's industrial waste-
waters; and Tittabawassee River sediments. In July 1986, Region V also released
the results of comprehensive testing of Dow Chemical in-plant and effluent
wastewaters, sludges, and Tittabawassee River sediments and native fish.2a
This report presents the results of the hazardous waste incinerator emissions
testing and ambient air monitoring.
On December 1, 1983, EPA published a Dioxin Strategy,3 which provides a
framework under which the Agency is to
- study the nature and extent of contamination of 2,3,7,8-tetrachlorodi-
benzo-p-dioxin (2378-TCDD) and the associated risks to humans and the
environment;
- implement or compel necessary cleanup actions at contaminated sites; and
- further evaluate regulatory alternatives to prevent future contamination,
as well as disposal alternatives to alleviate current problems.
The Dioxin Strategy focuses on seven tiers of sources, ordered by decreasing
potential for 2378-TCDD contamination. Combustion sources, including the Dow
Chemical waste incinerator, comprise Tier 4. EPA published sampling and
analysis plans in February 1985.4 Facilities studied as part of the Tier 4
strategy were sampled at specific fuel and air input points; air, solid, and
water effluent points; and selected surrounding sites for soils. This sampling
and analysis model is reproduced as Table 1-1. The Dow Chemical facility was
studied consistent with the Tier 4 model, but on a separate schedule and with
different field sampling and analytical teams.
In March 1983, the Michigan Department of Natural Resources (MDNR) requested
that EPA conduct studies of the presence of dioxins and other compounds in
various media in the Midland area. Responding to this request, the range of
compounds selected for study in the incinerator emissions and ambient air
studies was expanded from that shown in Table 1-1 to include several which have
estimated risks associated with respiratory exposure (see Tables V-l and V-2).
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TABLE 1-1
Sample
Inputs
Preconfcustion Air
Quench Water
Feed/Fuel
TIER 4 DIOXIN
Method
XAD-2
Grab
Grab (every 4 hours)
SAMPLING AND ANALYSIS STRATEGY
Recommended
(Samples/Day)
0-1
0
Dally Composite
- JUNE 1984 DRAFT
Recommended Analyses
2,3,7,8-TCDD. Homologs. PCBs. TOC1
Cl -phenols. Cl -Benzenes
PCDO scan. Cl -phenols, Cl -benzenes
Total Samples*
for Analysis
1
0.
3b
Outputs
Stack (before control)
MM5T
Stack (after control)
MH5T
2 trains
-Gaseous dally composite
-Condenser rinse
-Adsorbent resin
-Partlculate dally composite
-cyclone catch
-filter
-probe rinse
2 trains
-Gaseous dally composite
-Condenser rinse
-Adsorbent resin
-Partlculate daily composite
-filter catch
-probe rinse
PCBs, TOC1
2,3,7,8-TCDD, Homologs
2,3,7,8-TCDD, Homologs
. Bottom Ash
Ash from Control Device
Quench Mater Effluent
Environmental
Ambient Air
Surface Water
Soil
Grab
Grab
Grab
every 4 hours)
every 4 hours)
every 4 hours)
XAD-2
Grab
Boring
Daily Composite
Daily Composite
Daily Composite
0
0
1
2,3.7,8-TCDD, Homologs 1
2.3.7,8-TCDD, Homologs 1
2,3.7.8-TCOP /
2,3,7,8-TCDD
3-6c
3
0
0
I
TOTAL 23-26
?flased on 3 sampling days.
IT Analysis by contractor.
Hay be combined daily composite.
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II. OBJECTIVES
A. Incinerator Exhaust Study
The purposes of the incinerator emissions study were to
- determine concentrations and mass loadings of polychlorinated
dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs),
chlorobenzenes, chlorophenols, and other chemicals in the exhaust
gas, wastewater, and solid matter (ash and waterborne suspended
solids) discharges from the incinerator, under normal operating
conditions; and
- relate the compounds found in the discharged streams to the
characteristics of liquid and solid wastes incinerated at those
times.
B. Ambient Air Study
A companion study of the ambient air around the Dow Chemical facility was
designed to determine the presence of PCDDs, PCDFs, and other semi-volatile and
volatile compounds; to relate these findings to air emissions from the Building
703 incinerator; and to detect other compounds that may be emitted from other
point sources or fugitive sources at the Midland Plant. It was originally
intended that ambient air samples would be obtained on the same days as incin-
erator exhaust sampling. However, resource requirements of this work dictated
that the monitoring programs be conducted separately.
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III. SCOPE OF WORK
A. Incinerator Exhaust Study
Numerous process vents other than the Building 703 incinerator exist at the
Dow Chemical Company Midland Plant. However, based upon the results of Dow
Chemical self-monitoring of principal process vents in organic chemical
production areas, the incinerator was determined to be the dominant potential
source of PCDO and PCDF emissions in the plant. Therefore, sampling was limited
to the incinerator.
Sampling occurred on August 28, August 30, and September 5, 1984. The
conduct of this work is described in Section V and Appendix A of this report.
A total of 267 samples were collected and analyzed in this portion of the study.
B. Ambient Air Study
For the purposes of the ambient air study, the range of compounds selected
for sampling was expanded beyond PCDOs and PCDFs, to include other compounds
which have demonstrated risks through respiratory exposure; compounds with
chemical structures similar to these; and other compounds which may have been
traceable to emissions from the Dow Chemical Company incinerator. This
selection was based upon an evaluation of information available in files of the
MDNR and USEPA, concerning plant processes, products, intermediates, and wastes
generated. The target compounds included the following:
acryl onitril e chlorinated phenols methyl chloroform
benzene chloroform methylene chloride
biphenyl ethyl ene dibromide perchloroethylene
chl orobenzenes ethyl ene dichloride phenylphenol s
carbon tetrachloride ethyl ene oxide vinyl idene chloride
chlorinated biphenyl s formaldehyde
Constituents such as metals (arsenic, beryllium, etc.) were not included as
the above-referenced file information indicated they were not involved in plant
processes, while others, such as vinyl chloride, were not among the target
compounds as no available sampling methods were applicable to them. However,
compounds not appearing in the above list were reported when they were detected,
subject to quality assurance limitations, as shown in the discussion to follow.
Ambient air was sampled at four locations near the Dow Chemical Midland Plant
on 18 days between September 7 and 27, 1984. The conduct of this study and a
discussion of results appears as Section VI of this report; a total of 353
samples were gathered and analyzed.
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IV. FINDINGS AND CONCLUSIONS
A. Incinerator Exhaust Study
1. Tetra- through octa-CDDs and tetra- through octa-CDFs were detected in
Building 703 incinerator exhaust on two of the three sampling days. On the
third day, only TCDDs, OCDD, TCDFs, and PeCOFs were found in the incinerator
exhaust. TCDDs were detected in the 5 to 45 ng/m3 range, while TCDFs were
found at 80 to 125 ng/m3. Other PCDDs and PCDFs were found at levels typically
lower than 10 ng/m3. 2378-TCDD was not detected in Building 703 incinerator
exhaust at detection levels of approximately 1 ng/m3. A single finding of
2378-TCDD in combustion air drawn into the incinerator is reported.
2. The Modified Method 5 train chosen as the sampling apparatus for PCDDs
and PCDFs and semi-volatile compounds trapped these compounds, frequently at or
near the low detection limits desired in this study. However, the collection
and retention efficiency of the Modified Method 5 sampler for PCDDs, PCDFs, and
other semi-volatile compounds has not been validated. Therefore, the analytical
results stated for PCDDs, PCDFs, and semi-volatile compounds should be
considered minimum values. Analytical accuracy was acceptable for 79% of the
samples obtained for the measurement of tetra- and penta-CDDs, which are of
greatest concern with respect to possible health effects.
3. Comparisons were made of mass inputs of PCDDs and PCDFs in incinerator
feed streams, scrubber and quench waters, and combustion air, with mass outputs
in stack emissions, scrubber and quench waters, and collected ash. A clear
relation between the mass of PCDDs and PCDFs in input streams and discharges
was not discernible; however, higher concentrations of PCDDs and PCDFs in liquid
wastes consumed in the incinerator appeared to translate into higher levels of
PCDDs and PCDFs in incinerator discharge streams. The data suggest limited
destruction in the incinerator of TCDDs and HpCDDs, somewhat higher destruction
of PeCDDs, and mass transfer of HxCDDs and OCDDs from input streams to output
streams. For PCDFs, the data suggest destruction of nearly 90% of the input
TCDFs, and formation of other PCDFs, primarily HxCDFs and OCDF.
4. Analyses for suspected PCDD and PCDF precursors in the influent streams,
such as PCBs and chlorinated benzenes and phenols, were not conclusive in
establishing a relationship between these compounds and emitted PCDDs and
PCDFs. However, the concentrations of certain semi-volatile compounds such as
chlorobenzenes and chlorophenol s in the incinerator exhaust, did appear to
relate directly with emissions of PCDDs and PCDFs.
5. While extensive data on incinerator operating temperatures, pressures,
air pollution control device water, and flow rates were obtained, there was no
discernible relationship between any of these characteristics and exhausted
PCDD and PCDF concentrations within the ranges encountered in this study.
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6. Quality assurance results for semi-volatile and volatile compounds
indicated analytical accuracy and precision problems, such that data for these
compounds were of limited quantitative use.
7. On two of three sampling days, emissions of particulate matter from the
incinerator exhaust were within the standard of 0.08 grain/dscf established for
incinerators burning hazardous waste (40 CFR Part 264.343(c)). Values ranging
from 0.0615 to 0.0842 grain/dscf were measured with a mean value of 0.0747
grain/dscf.
8. Wastes from a nearby Dow Corning Corporation facility were incinerated
on all three sampling days; these wastes contained PCDDs and PCDFs (primarily the
1368 and 1379 TCDD isomers). Ash discharged from the Building 703 incinerator
included silane and siloxane compounds most likely attributable to Dow Corning.
B. Ambient Air Study
1. No 2378-TCDD was detected on a first analysis of ambient air samples by
a contract laboratory. However, reanalysis of two of the 15 sets of sampling
media by the EPA Environmental Monitoring and Support Laboratory, Research
Triangle Park, North Carolina, resulted in detection of 2378-TCDD at an ambient
site near the Dow Chemical Company plant fenceline at a concentration of about
5 pg/m3. Ambient air monitoring by Dow Chemical in 1983 and 1984 showed positive
results for 2378-TCDD up to 0.2 pg/m^. The Dow Chemical data were obtained
with a glass fiber filter in the sampler.
2. Other homologues of PCDD and PCDF were detected with generally acceptable
accuracy in the range of 0.1 to approximately 400 pg/m^. These homologues were
present in proportions similar to those found in previous studies of ambient
air near incineration processes, and in soils sampled by EPA in the Midland,
Michigan, area in 1984.
3. The modified high-volume sampler used for PCDD and PCDF sampling trapped
the full range of PCDD and PCDF homologues. However, the collection and
retention efficiency of the Modified Method 5 sampler for PCDDs and PCDFs has
not been validated. Therefore, the analytical results stated for PCDDs and
PCDFs should be considered minimum values.
It was found that lower-chlorinated homologues generally were trapped in
the second-stage XAD-2 resin trap incorporated into the samplers, while higher-
chlorinated homologues remained in or on the first-stage glass fiber filter.
While no particle size data were obtained at this time, these findings strongly
suggest that both sampling media should be exposed in series to ambient air to
sample for the full range of PCDD and PCDF homologues. Also, it is implied
that lower-chlorinated homologues may either attach to finer, more respirable
particulate matter, or may be air-stripped from larger particles caught in the
glass fiber filter. No particle sizing data were gathered at this time to test
this possibil ity.
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4. A sampler similar to that employed for PCDDs and PCDFs was effective in
sampling for semi-vol atile compounds in ambient air. While analytical precision
was remarkably good in many samples for semi-volatil e compounds, accuracy
problems were frequently encountered.
5. Sources within the Dow Chemical facility, other than the Building 703
incinerator exhaust stack, such as process vents or fugitive emissions sources,
may be responsible for the levels and diversity of semi-vol atile compounds
detected in ambient air around the plant. Principal semi-vol atile compounds
found in this study were trichlorobenzene (three isomers); tetrachlorobenzene
(two isomers); 2,4-dichlorophenol ; and 2,4,6-trichl orophenol , in ranges from
approximately 10 to 1000 ng/m3.
6. Sampling for volatile compounds in ambient air did not yield valid data
due to failure of a contract laboratory to prepare and analyze field samples
within acceptable sample holding times. However, the results obtained have been
reported and interpreted within the limits dictated by quality assurance
results.
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V. DOW CHEMICAL MIDLAND PLANT BUILDING 703 INCINERATOR EMISSIONS STUDY
A. Facility Description
The Dow Chemical Company operates a hazardous waste incinerator at the
Midland Plant identified as Building 703. The incinerator is located in the
southwest quadrant of the facility (see Figure VI-1). Liquid wastes, tars, and
containerized and loose solid wastes are incinerated at this site. Company
records indicate about 200 tons per day of solid and liquid combustible trash
and waste are burned on a typical day. Built as a rotary kiln burner in 1957,
the incinerator has been augmented in succeeding years by addition of an after-
burner section and air pollution control equipment including a quench tower,
venturi scrubber, demister, and a wet electrostatic precipitator. The level of
complexity and expected efficiency of this air pollution control equipment is
generally greater than typically found at other municipal or hazardous waste
incinerators in the United States. A schematic drawing of the incinerator and
associated air pollution control equipment as currently configured appears as
Figure V-l.
1. Waste Feeds and Incinerator Operational Characteristics
Waste feeds to the incinerator are as follows:
a. Liquid Wastes
Liquid wastes are delivered to the incinerator from an adjacent tank farm,
or via direct burn systems in which individual truck or trailer loads of wastes
are consumed. Three wastes may be burned simultaneously in separate feed
nozzles. Two of these nozzles, identified as "BA" and "BB", are located at the
head end of the rotary kiln, and each feeds wastes longitudinally at an average
rate of three to four gallons per minute, atomized with steam. Waste feed
nozzle "C" is placed in the afterburner section. The nozzle is directed
approximately at a right angle to exhaust gas flow to induce turbulence in the
firing zone. These wastes are air-atomized, and typically flow at an average
rate of five to six gallons per minute. Combustion may be supplemented with
natural gas at all three nozzles.
b. Low-BTU Liquid Wastes
Collected rainwater or surface runoff from within the liquid waste tank
farm and handling area, and other contaminated water such as carbon adsorption
bed condensates and runoffs from reaction vessel cleaning, may be fed to the
incinerator as needed to modulate temperature fluctuations. This water flow is
not continuous. As allowed by the MDNR24, surface runoff is directed to the
plant wastewater treatment system if the total organic carbon content is less
than 100 parts per million.
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WASTE FEED-
NOZZLES "8A"
AND BB
LOW BTU
WASTE
QUENCH/SERVICE
AFTERBURNER WATER
VENTURI
WATER
COMBUSTION/
ATOMIZATION
AIR FAN
QUENCH
TOWER
AFTER-
BURNER
VENTURI
SCRUBBER
RUBBISH
AND
BULK
SOLIDS
1000-
IIOO'C
ASH /
TROUGH f-* SERVICE
I 1 WATER
(ASH TROUGH
WATER)
KILN
COMBUSTION
AIR
TO WASTEWATER
TREATMENT
PLANT
CONTAINERIZED
WASTES
(PACKS,DRUMS)
ASH TO
CLASS I
LANDFILL
PRETREATMENT PLANT
AND WASTEWATER
TREATMENT PLANT
FIGURE V-l
SCHEMATIC DIAGRAM
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
-------
c. Containerized Bulk Wastes
Various types of wastes in volumes too small or viscous to be handled in
the liquid waste system, and solid wastes from laboratory operations, facility
demolition and cleanup, are conveyed to the head end of the rotary kiln. One
pack or barrel of containerized waste, weighing a maximum of 200 pounds, is
introduced to the kiln every six minutes from a staging area in which several
packs may be prepared sequentially for incineration. In a typical feed, a pack
is advanced from a conveyor to the outside door of an air lock, the air lock
door opens, the pack is pushed into the lock, and the outside door closes.
Approximately 30 seconds later, the inside air lock door opens and the pack is
dumped into the rotary kiln. At this time, another pack is moved to the outside
air lock door, and the next pack in line is conveyed over a scale for weighing.
d. Miscellaneous Containerized Wastes
On occasion, small quantities, typically less than a few liters, of bottled
liquid or tarry wastes may be introduced directly to the rotary kiln. A small
air lock, or "bottle drop", is provided for this purpose, and company procedures
provide that a person representing the area of the plant generating the waste
be present during this operation.
e. Loose Rubbish
Loose solid waste generated in the Midland Plant is incinerated at Building
703. These wastes, consisting chiefly of paper, plastics, and wood, are dumped
into a holding pit from whence a clamshell deposits batch quantities into a
shredder. Shredded wastes are conveyed at a controlled rate of four to six
tons per hour through an incline to the incinerator.
f. Other Wastes
Wastewater treatment plant solids were formerly fed to the incinerator
along with loose rubbish. However, according to information provided by
plant representatives, this waste stream was redirected to landfill disposal as
of July 1984.
Combustion air is provided through two separate forced-draft fans in the
rotary kiln and afterburner sections. Oxygen concentrations of at least 3
percent, but typically over 10 percent, are maintained in the afterburner
exhaust. Combustion temperatures within the rotary kiln are designed to vary
between 650° and 950°C, and between 1000° and 1100°C in the afterburner. The
temperatures are maintained by cycling the combustion of wastes at the three
nozzles and by selectively adding low-BTU liquid wastes to reduce high tempera-
tures. Thus, temperatures within the rotary kiln may vary over a relatively
large range within short time periods. However, temperatures within the after-
burner fluctuate much more narrowly. Although rotary kiln and afterburner
pressures are held slightly negative, usually between -0.1 and -0.3 inch of
water, violent ignition of waste packs can cause momentary periods in which
positive pressures are experienced.
10
-------
Gas residence times within the incinerator have been calculated by Dow
Chemical as one 'to three seconds in the rotary kiln, and approximately 1.5
seconds in the afterburner.21,22
2. Air Pollution Control Equipment
As indicated previously, the air pollution control system associated with
the Building 703 incinerator consists of several components shown in Figure V-l.
That figure also contains a schematic of water sources through each control
device.
a. Quench Tower
Exhaust gases from the afterburner pass to the quench tower, in which gas
temperature is reduced from about 1000°C to below 100°C. To accomplish this,
a normal water application rate of 650 to 750 gpm is maintained. Secondary
treated wastewater from the plant wastewater treatment system is the primary
water supply. Water pumped from the company's Tittabawassee River intake may
be used to supplement the primary supply. Water effluents from the quench
tower split into two discharges to the plant wastewater treatment system.
b. Venturi Scrubber
Cooled exhaust gases from the quench tower are directed to a variable-throat
venturi scrubber which operates at a pressure differential of 15 to 30 inches
of water. Water application rates are typically between 200 and 275 gpm,
composed of secondary treated wastewater. Venturi effluents combine with the
discharge of the demister tower. This heated water is directed to a portion of
the plant wastewater system in which phenolic wastes are pretreated prior to
mixing with general plant wastewaters.
c. Demister Tower
A water flow of 700. to 1000 gpm of secondary treated wastewater is maintained
through the 12-foot-diameter demister.
d. Wet Electrostatic Precipitator
Exhaust gases from the demister are routed through an induced-draft fan
into a single-field wet electrostatic precipitator. The emitting anodes and
collection plates are arranged concentrically, and are cleaned with a continuous
stream of water taken from the company's river intake, at a volume of 160 to
200 gpm. Effluent waters are directed to the general wastewater treatment
system.
e. Stack
A 200-foot-tall , 12-foot-diameter brick stack vents emissions from the
incinerator. As the gas discharge is usually saturated with water, the stack
has a drain to the general wastewater treatment system, for which Dow Chemical
estimates a flow of 1 gpm.
11
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3. .Other Haste Discharges
The types and volumes of effluent wastewaters from the air pollution control
devices associated with the incinerator were described above. In addition,
bulk solids falling from the rotary kiln are quenched and cooled in an ash
trough through which a flow of 40 to 60 gpm of water drawn from the plant's
Tittabawassee River intake is maintained. In addition, a small stream of
untreated river water, estimated at 10 gpm, flows in a sluice under the rotary
kiln's head end to receive and convey spills of heavy particulate matter
falling from gaps in the seal. The effluent waters from the ash trough
are routed to the general plant wastewater treatment system. About 15 to 20
cubic yards per day of solids are cleaned from the ash trough, and deposited in
Oow Chemical's landfill located on Salzburg Road.
B. Sampling Strategy
1. Background
As indicated previously, the draft project plan for the National Dioxin
Study Tier 4 - Combustion Sources formed the basis for selecting the input and
discharge streams to be sampled in this study. However, that sampling scheme
was formulated for a comparatively simple facility with a single waste input
and a single air pollution control device. To adapt the model to the Dow
Chemical incinerator, with two precombustion air intakes, four liquid waste
feeds, and water effluent discharges from four air pollution control devices,
required the collection of a significant number of samples to assess conditions
during the emissions tests, and to evaluate compounds present in exhaust gases as
they related to wastes incinerated on the test days.
2. Target Compounds
Table 1-1 presents a list of samples and analyses required for a Tier 4
sampling program. The lists of target compounds presented in Tables V-l and
V-2 for air components, water, and solid samples build upon the primary list.
In the case of the latter, the compounds added include several which may be
precursors to formation of polychlorinated dibenzo-p-dioxins (PCDDs) and poly-
chlorinated dibenzofurans (PCDFs) when subjected to elevated temperatures.
These compounds were also selected based upon information about Dow Chemical
manufacturing processes and liquid wastes consumed at the incinerator. For air
components, compounds with known or suspected health effects when respired in
ambient air, such as carbon tetrachloride and trichloroethylene, were added for
the purpose of determining whether significant air emissions, from a public
health standpoint, were occurring from the incinerator.
The compounds listed in Tables V-l and V-2 are arranged by analysis type
(PCDD/PCDF, semi-volatile organic (semi-VOA), and volatile organic (VOA)) to
enable association with the sampling methods presented in the following section.
The Tier 4 sampling and analysis matrix shown in Table 1-1 includes analyses
for total organic chlorine in the two classes of input streams, and for PCDDs.
It was determined that available methods for sampling for total organic chlorine
12
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TABLE V-l
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
TARGET COMPOUNDS IN AIR
Analysis Type
PCDD/PCDF
Semi-volatile
Volatile
2378-TCDD
21 TCDD isomers
Total PeCDD
Total HxCDD
Total HpCDD
OCOD
2378-TCDF
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
OCDF
Polychlorinated biphenyls (as positional isomer classes)
Other chlorinated biphenyls
Chlorinated phenols
Chlorinated benzenes
Diphenyl oxide
Chlorinated diphenyl oxides
Phenol
Phenyl phenol
Biphenyl
Carbon tetrachloride
Ethylene dichloride
Perchloroethylene
Trichloroethylene
Vinylidene chloride
13
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TABLE V-2
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
TARGET COMPOUNDS IN WATER AND SOLIDS DISCHARGES
Analysis Type
PCDD/PCDF
Vol
Semi -
Semi -
Semi -
Vol
Semi -
Semi -
Semi -
Semi-
Semi-
Semi-
Vol
Semi-
Semi-
Vol
Semi-
Semi-
Vol
Semi-
Vol
Semi-
Vol
Vol
atile
volatile
volatile
volatile
atile
volatile
volatile
volatile
volatile
volatile
volatile
atile
volatile
volatile
atile
volatile
volatile
atile
volatile
atile
volatile
atile
atile
2378-TCDD
21 TCDD isomers
Total PeCDD
Total HxCDD
Total HpCDD
OCDD
2378-TCDF
Total TCOF
Total PeCDF
Total HxCDF
Total HpCDF
OCDF
Benzene
Biphenyl
Chlorinated biphenyls (as positional isomer classes)
Biphenyl phenyl ether
Carbon tetrachloride
Chlorinated benzenes
Chlorinated phenols
Diphenyl oxide
Chlorinated diphenyl oxides
Di vinyl benzene
Ethyl benzene
Ethylene dichloride
Hydroxybenzaldehyde
Hydroxybenzoic acid (ortho and para)
Perchloroethylene
Phenol
Phenyl phenols (ortho and para)
Styrene
2,4,5-T and esters
Trichloroethylene
Vinyl toluene (ethenyl methyl benzene)
Vinylidene chloride
Xylene
14
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in liquid streams would not distinguish between organic and inorganic chlorine;
also, the analytical methods were not of sufficient accuracy to be of use in
this study. For this study, analyses for PCDDs and PCDFs were limited to the
tetra-CDO isomers, total tetra- through hepta-CDD and CDF homologues, and OCDD
and OCDF.
In addition to the above analytical work, incinerator emissions were
evaluated with respect to requirements for hazardous waste incinerators
developed pursuant to the Resource Conservation and Recovery Act (RCRA) and
listed at 40 CFR Part 264.343(c). Specifically, particulate emissions for
incinerators consuming hazardous waste are limited to 0.08 grain/dscf. In
accordance with the regulation, the weight of particulate matter caught in the
filter and probe wash portion of the Modified Method 5 train on each sampling
day was reported and compared against the standard. Consistent with the
requirements of EPA Method 5, this analysis did not consider any of the
particulate matter trapped in the "back half" (impinger catch) of the train; in
any event, such an analysis would have disrupted the determination of PCDDs and
PCDFs in this portion of the train, and would likely have added little to the
total catch of particulate matter.
3. Sampling Locations
The following streams and locations were selected for sampling based upon
the unique characteristics of the Building 703 incinerator. These locations
are also described in the quality assurance project plan written by the sampling
contractor, GCA Corporation, in preparation for conducting sampling work.5
a. Precombustion Air
The Tier 4 project plan requires sampling of precombustion air if a
significant source of suspected PCDD precursors is in the vicinity of the
sampling site. It was known that 2,4,5-trichl orophenoxyacetic acid and other
precursor chemicals were manufactured or handled at several locations within
the Dow Chemical facility. Also, previous work by EPA and Dow Chemical
established that surficial soils in the plant were contaminated with 2378-TCDD
and other PCDDs, notably in the immediate area of the incinerator. For these
reasons, precombustion air was sampled.
As indicated earlier, the rotary kiln and afterburner sections each have
combustion air intakes. Given the proximity of these air intakes, it was
estimated that ambient air quality would be similar at either intake; therefore,
only one of the intakes was sampled. Owing to greater accessibility, the
rotary kiln air intake was selected.
b. Liquid Waste Feeds
Each of the three liquid waste feed nozzles, and the low-BTU liquid waste
nozzle, was fitted with an existing valve and spigot for sample collection.
Samples were taken directly into holding containers from these spigots.
15
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c. Incinerator Exhaust
Because a variety of sampling equipment was employed in collecting and
analyzing exhaust gas samples, three separate locations were selected. As shown
in Figure V-2, the sampling locations were between the outlet of the wet
electrostatic precipitator and the stack breeching.
(1) PCDDs, PCDFs, and Semi-Volatile Compounds
An existing pair of four-inch sampling ports spaced 90° apart was used to
operate two Modified Method 5 trains, one dedicated to PCDDs and PCDFs and
the other to semi-volatile pollutants. The trains were operated simul-
taneously in the two ports, such that the probes did not interfere or cause
turbulence with respect to each other. As Figure V-2 indicates, the ports
were sufficiently separated from upstream and downstream bends in the
three-foot-diameter exhaust duct, to comply with the requirements of EPA
test Method 1.
(2) Volatile Compounds
A single four-inch-diameter sample port located about six feet down-
stream of a 90° duct bend was employed for gas sampling utilizing a Volatile
Organic Sampling Train (VOST), described later in this report.
(3) Continuous Emissions Monitoring and Sampling for Vinyl idene Chloride
Continuous emissions monitor (CEM) probes for oxygen, carbon monoxide,
and carbon dioxide were inserted into the exhaust duct at a point about
five feet downstream of the VOST, and three feet upstream of the stack
breeching. In addition, several samples for direct analysis of vinylidene
chloride were drawn through a separate probe inserted at this point.
The exhaust of a carbon-bed adsorbing column is located between the
first and second sampling locations described above. The column is used to
filter airborne hydrocarbon emissions displaced from the loading of liquid
wastes into the incinerator tank farm. These emissions were formerly
vented to the atmosphere. The adsorber was installed in July 1984 and
operates only when liquid transfer to the tank farm occurs. As no other
appropriate sampling locations were available for the VOST, CEM, and Tedlar
bag samplers, it was decided to use those ports. The compounds detected in
the exhaust gas were to be evaluated with respect to the likelihood they
may have arisen from carbon bed operation, as well as combustion within the
incinerator.
(4) Sampling Incinerator Emissions Before Control Devices
The Tier 4 sampling and analysis protocol (see Table 1-1) prescribes that
samples be taken for PCDDs and PCDFs at a point preceding air pollution
control devices. The feasibility of obtaining these samples was evaluated
early in the test planning process; no access to exhaust gases was available
prior to the quench tower, other than a single port at the rear of the
16
-------
I
1
1
I
I
I
f>
I
I
I
i
\
3
\
\
»
t
I
I
I
I
i
fl
fl
fl
MMS
SAMPLING
PORTS
SAMPLING
PLATFORM
T
~8-lOft
1
T
-23'
i
WET
ESP
-10'
VOSTone
amp ling Port
CEM
Sample
Port
200'
FIGURE V-2
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
EXHAUST GAS SArirLING POINTS
17
-------
incinerator afterburner which formerly held temperature monitoring probes.
Because this location did not satisfy the requirements of EPA Method 1 in
terms of separation from flow disturbances, it was rejected.
A second possible test location at the outlet of the quench tower was
considered and rejected as only a single port was provided in a duct bend.
Samples of exhaust gases prior to air pollution control devices were thus not
taken as appropriate test locations were not available.
d. Incinerator Ash
Heavy solids are removed from the incinerator ash trough by a dragout chain
which is operated for about ten minutes per hour. Grab samples were taken of
material conveyed out of the trough by the scraper mechanism associated with
the dragout chain.
e. Influent and Effluent Water and Control Device Ash
(1) Influent Service Water
Samples of the secondary treatment water returned to the incinerator to
serve the quench tower, venturi, and demister were drawn from a one-inch-
diameter spigot at the influent side of the quench tower. Suspended solids
are filtered from this influent water immediately prior to the sampling
point; therefore, separate samples or analyses of the solids portion of
this stream were not specified. Samples of influent water from the Dow
Chemical Tittabawassee River intake, which is directed to the ash trough
and electrostatic precipitator, were not obtained. Previous sampling by
EPA in 1981 showed PCDDs and PCDFs in this stream were not present at
detection levels of 7 to 60 parts per quadrillion.
(2) Quench Tower Effluent
As described previously, waters leave the quench tower through two dis-
charges. The composition of both discharges was expected to be similar;
therefore, one discharge point, referred to as the west discharge, was chosen
for sampl ing.
Advance inspections of the facility indicated the effluent streams from
the quench tower were heavily laden with suspended solids from contact with
incinerator exhaust gases. As the draft Tier 4 project plan specified that
air pollution control device ash was to be analyzed separately, analyses of
the aqueous and filterable solids portions of these samples were performed.
(3) Venturi Scrubber/Demister Effluent
Effluent streams from these devices combine prior to discharge to a sump
located beneath the venturi scrubber, and samples were taken here. Analyses
of aqueous and filterable solids portions were specified.
18
-------
(4) Electrostatic Precipitator Effluent
These samples were obtained from a discharge sump beneath the electro-
static precipitator, and separate analyses of aqueous and filterable solids
portions were requested.
(5) Ash Trough Water Effluent
About 50 gpm of water overflows the ash trough for discharge to the
general wastewater treatment system. Samples were taken of this stream
from a short open discharge flume located near the rotary kiln incinerator.
The aqueous and filterable solids portions of each sample were analyzed
separately.
C. Conduct of Study
Incinerator sampling was planned to include three separate days of
operation, with each day's sampling spanning eight hours. This sampling period
was chosen to assure that sufficient materials would be collected to enable
compound detection, possible replicate analyses, and splitting of sample
extracts between analytical laboratories.
The following influent and effluent streams of the Building 703 incinerator
were sampled, when applicable, during the three-day study period:
Influent Streams
Precombustion Air (incinerator makeup)
Liquid Waste Feeds (maximum of four inlet nozzles)
Influent (service) Water
Effluent Streams
Incinerator Exhaust
Incinerator Ash
Effluent Water (from incinerator and air pollution control devices)
Air Pollution Control Device Ash
Each stream was sampled for the presence of PCDDs and PCDFs and the semi-volatile
and volatile compounds referenced in Tables V-l and V-2. In addition, the
incinerator exhaust was sampled using a specialized analytical method specific
to vinylidene chloride. Detailed information with respect to the conduct of
the study, including sample handling and custody, analytical procedures, and
incinerator operations while samples were obtained, appears in Appendix A of
this report.
Sample collection and other field work were documented by the USEPA's field
contractor (GCA Corporation) and USEPA personnel. Sample documentation included
unique identification numbers and tags or labels; field workbooks; USEPA and
GCA-generated sample custody records; and USEPA Sample Management Office Traffic
Reports and Packing Lists.
19
-------
Samples were gathered and handled according to the protocols outlined in
the USEPA draft study plan? with minor revisions prompted by field conditions.
Generally, the samples were composited over time to represent the entire sampling
period on each day. However, for volatile compounds in aqueous streams (influent
and effluent water) and in liquid waste feeds, single grab samples were taken
as no reliable method was available to composite such samples. In addition,
as discussed in the "Analytical Procedures" section of Appendix A, separate
analyses were provided of the concentrations of the above constituents in the
liquid and in the suspended or settleable solids (filtrate) portions of the
influent and effluent waters. For volatile compound analyses, however,
unfiltered grab samples of influent and effluent waters were analyzed as a
whol e.
The samples collected during this study were identified, packed (cooled as
appropriate), and either shipped via commercial services for next-day arrival
at contract laboratories, or, in the case of certain samples for which holding
times prior to analysis were not of concern, delivered by USEPA personnel.
D. Analytical Procedures and Quality Assurance Reviews
1. Analytical Procedures
Selection of contract laboratories was coordinated by the USEPA Region V
Central Regional Laboratory. Individual contracts were prepared for various
groups of compound analyses, and sent to candidate laboratories for bid. The
laboratories ultimately selected were the EAL Corporation, Richmond, California,
for volatile compounds, semi-volatile compounds, pesticides, and PCBs; and the
Brehm Laboratory, Wright State University, Dayton, Ohio, for PCODs and PCOFs.
For the former, analytical methods are detailed in Appendix A, Section III of
this report. Analytical procedures for PCODs and PCDFs are described in
References 7 and 8, and Appendix C.
Several samples were taken of liquid wastes fed to the Building 703
incinerator. It was known in advance that these wastes were highly concentrated
in single compounds, making them hazardous for analysis without prior extrac-
tion. Procedures for separating and all quoting these waste samples are
presented in Appendix B to this report. This work was carried out by Fred C.
Hart Associates, Inc., Denver, Colorado. The extracts were shipped to EAL
Corporation for analysis.
2. Quality Assurance Reviews
Data returned from the contract laboratories were reviewed for consistency
with contract requirements by the USEPA Sample Management Office (Viar and
Company, Alexandria, Virginia), and for adherence to quality assurance criteria
contained in the Quality Assurance Project Plan developed for the study (see
Reference 7) by the USEPA Region V Central Regional Laboratory. The results of
these reviews are referenced in the discussion of general analytical findings
which follows as Section V.F of this report.
20
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E. Incinerator Operations During Tests
Extensive data concerning the operation of the Building 703 incinerator and
the wastes burned during emissions testing were recorded by Dow Chemical , GCA
Corporation, and USEPA personnel. This information is compiled in Appendix A,
Section IV.
F. Results and Discussion
1. General Findings
Detailed results of sample analyses associated with the Building 703
incinerator emissions study are presented in Appendix D. Table V-3 summarizes
the streams that were sampled and the compound groups analyzed. As indicated
previously, no samples of loose or containerized solid wastes were taken owing
to the unavailability of suitable sampling methods.
Detailed operating and sample analytical data were gathered during this
study to enable association of emissions with such phenomena as incinerator
temperatures, air pollution control device operations, wastes incinerated, and,
if possible, to derive pollutant mass balances around the incinerator. However,
as discussed in Section III.A. of Appendix D to this report, some limitations
were placed on the acceptability of some of the data. For PCDOs and PCDFs,
specifically, the recoveries of surrogate compounds used to assess the accuracy
of analysis for certain homologue groups were not always within the relatively
narrow ranges of acceptability established initially for this study. The ranges
established in the study plan7 were also revised to be consistent with those
normally used by USEPA and others in the conduct of studies of PCDDs and PCDFs.
In any event, overall completeness of PCDD and PCDF analytical data tended to
be best for the tetra- through hexa-CDD homologues, for which health-related
concerns are greatest.
For volatile and semi-volatile compounds, individual analyses were con-
sidered fully acceptable only if the recoveries of all introduced surrogate
compounds were within prescribed ranges. There is no generally accepted
protocol which would permit selective acceptance, compound by compound, based
upon the recovery of specific single surrogates. However, for semi-volatile
compound data, analytical results for an acid compound were considered valid if
the recoveries of all acid surrogates were acceptable; the same was done for
base-neutral compounds. Overall data completeness for semi-vol atil e' compounds
was based upon acceptable recoveries of all six surrogate compounds.
a. Influent Streams
(1) Precombustion Air
As described previously, this stream was sampled at the air intake of
the rotary kiln portion of the Building 703 incinerator, but is taken to
represent the characteristics of all air drawn into the incinerator and
afterburner at any point preceding the combustion process. These data may
also be used to assess the characteristics of ambient air in the immediate
vicinity of the incinerator.
21
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TABLE V-3
ro
ro
Influent Streams
Precombustion Air
Liquid Waste Feeds
Influent (service) Water
Effluent Streams
Incinerator Exhaust
Incinerator Ash
Effluent Water
Air Pollution Control Device Ash3
SAMPLING AND ANALYSIS SUMMARY
iL COMPANY
Volatile
Compounds-
X
X
X
X
X
BUILDING 703 INCINERATOR EMISSIONS STUDY
8/28, 8/30, 9/5/84
Semi -Volatile Pesticides
1 Compounds2 and PCB PCDDs
X
X X
X
X
X
X
X
Vinylidene
and PCDFs Chloride
X
X
X
X X
X
X
X
foiling points less than 100°C.
^Boiling points greater than 100°C.
3Analysis of filterable solids from effluent
wastewater streams from individual air
pollution devices associated with the
incinerator.
-------
Data for volatile pollutants (see Table V-4) showed the possible
presence of the following compounds in the 1 to 100 parts-per-bill ion range:
carbon tetrachloride,
monochlorobenzene,
trichloroethylene, and
ethyl benzene.
However, the stringent quality assurance criteria (see discussion in Section
III.A. of Appendix D) established for accuracy were such that only three
of eight (38%) of the precombustion air volatile compound analyses were
considered acceptable. Also, field duplicate sample analyses, limited
to one of the three sampling days, suggested the quantitation of only
monochl orobenzene to have been reliably established. The semi-volatile
compound 1,4-dichlorobenzene was detected with good precision, and these
data are included in Table V-4 for informational purposes; however, as no
calibration standard for dichl orobenzene was run in the volatile compound
analysis, the analytical method for semi-volatile compounds is more appro-
priate for this compound. Reference is made to Table V-5, where the detected
semi-vol atile compounds are listed.
Of the semi-vol atile compounds (Table V-5), the following were present
in concentrations of approximately 1 ug/m^:
1,2-dichlorobenzene,
1,3-di chl orobenzene,
1,4-dichlorobenzene,
1,2,4-trichlorobenzene, and
naphthalene.
In addition, monochlorobenzene was detected at levels apparently lower than
those indicated by the sampling method for volatile compounds.4 However,
this is not considered a reliable quantitation, as a calibration standard
was not run for this analyte. Tentative findings of low levels of other
benzene-ring compounds are detailed in Appendix 0, Table D-3. All of the
eight samples taken over the three-day period were found to be accurate
within acceptable limits; however, precision criteria were met only for
1,2-dichlorobenzene and 1,2,4-trichlorobenzene.
Levels of PCDD and PCOF (Table V-6) ranging from approximately 10 to over
800 pg/m3 of various homologues were found on all three sampling days, and
about 5 pg/m^ of 2378-TCDO was detected on the second sampling day. The
data appear to show the consistent presence of TCDD, OCDD, TCDF, and OCDF,
along with scattered findings of other homologues. More detailed data
concerning TCDD isomers appear in Appendix D.
(2) Liquid Waste Feeds
The concentrated liquid wastes incinerated on the three sampling days
contained a wide variety of volatile compounds, fully shown in Appendix D,
Table D-10 (and summarized in Table V-7), including several chlorinated and
23
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TABLE V-4
VOLATILE COMPOUNDS - PRE-COM8USTION AIR
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
COMPOUND CONCENTRATION (ug/m3)l
COMPOUNDS DETECTED
SAMPLING DATE
8/28/84
8/28/84
(Field Duplicate)
8/30/84
9/5/84
Precision (RPD)
8/28/84
Samples
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10.63
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93
1 Sample Concentration Less Field Blank Concentration
2 Compound Tentatively Identified
24
-------
TABLE V-5
SEMI-VOLATILE COMPOUNDS - PRE-COMBUSTION AIR
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
COMPOUND CONCENTRATION (ug/m3)!
TARGETED COMPOUNDS
OTHER COMPOUNDS DETECTED
ro
en
SAMPLING DATE
8/28/84
8/30/84
8/30/84
(Field
Duplicate)
9/5/84
Precision (RPD)
8/30/84
Sampl es
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1.42
0.84
1.03
3.73
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c
OJ
rsi
c
O)
J3
O
1-
O
, —
J=
o
o
c
0
3E
3.08
0.53
1.84
—
Ill
O)
. c
0)
R3
x:
4->
.C
CL
m
c
P^.
>•>
j=
^
C
O)
ISI
c
01
-Q
1 , —
^- >>
>>-£=
-C +J
4-> Ol
Ol E
1 1
i-l CM
2.41
i
. — *
,_~
>>
XL
-(->
01
*— '
>^M
-C O)
4-> C.
Ol Ol
e N
^^_^, C
1 CU
t-H JZ
1.92
CM
Ol
c
O)
tsl
C
Ol
-O
^
.c
+->
Ol
•I—
•o
CM
«
i— 1
2.78
CM
Ol
C
Ol
N
C
Ol
J3
^
_C
+-)
01
•1 —
TD
CO
M
I—t
1.26
CM
01
c
Ol
M
C
01
.a
^
c
0>
.c
-t->
0)
•r—
"O
1
CM
9\
I— 1
0.96
t_
Ol
.c
4->
at
^
Ol
JC
a.
•p—
CD
4.74
Sample Concentration Less Field Blank Concentration
Compound Tentatively Identified
-------
TABLE V-6
INCINERATOR PRECOMBUSTION AIR - PCDD/PCDF ANALYSES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
8-28-84
MODIFIED METHOD 5 TRAIN
FIELD DUPLICATE
FIELD BLANK
8-30-84
MODIFIED METHOD 5 TRAIN
FIELD BLANK
9-5-84
MODIFIED METHOD 5 TRAIN
FIELD BLANK
2378-
TCDD
ND
(7.86)
ND
(11.32)
Total
TCDD
58.21
ND
(53.4)
Total
PeCDD
ND
(11.01)
ND
(131)
Total
HxCDD
ND
(6.62)
ND
(125)
Total
HpCDD
ND
(12.02)
ND
(5.43)
OCDD
216.60
335.14
2378-
TCDF
ND
(7.89)
ND
(29.2)
Total
TCDF
391.22
628.02
Total
PeCDF
ND
(6.07)
ND
(6.01)
Total
HxCDF
ND
(16.2)
ND
(4.20)
Total
HpCDF
ND
(27.50)
ND
(8.45)
OCDF
21.18
ND
(30.2)
(Sample analysis not returned from laboratory.)
5.16
ND
(0.77)
ND
(1.48)
ND
(0.55)
17.99
ND
(0.41)
38.90
ND
(0.35)
ND
(2.30)
ND
(2.17)
ND
(0.94)
ND
(0.40)
10.39
ND
(3.67)
ND
(1.46)
ND
(0.85)
235.10
ND
(4.51)
98.14
ND
(2.15)
802.08
ND
(11.85)
306.51
ND
(4.83)
12.93
ND
(1.11)
ND
(1.74)
ND
(0.39)
12.93
ND
(1.20)
206.60
ND
(0.29)
12.50
ND
(1.96)
ND
(1.45)
ND
(0.37)
14.23
ND
(3.28)
ND
1.42
ND
(0.33)
108.48
ND
(5.20)
37.43
ND
(3.08)
113.67
ND
(13.93)
30.95
ND
(4.21)
ro
en
Note: Data expressed In pg/m^.
Detection level indicated in parentheses.
-------
TABLE V-7
QUANTITATED VOLATILE COMPOUNDS - LIQUID WASTE INPUTS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28. 8/30. 9/5/84
TARGET
COMPOUNDS
OTHER
CHLORINATED
COMPOUNDS
BENZENE RING
COMPOUNDS
OTHER
COMPOUNDS
REAGENT BLANK 1
REAGENT BLANK 2
8/28/84
Nozzle BA
Nozzle BA Dilution
Nozzle BB fl
Nozzle BB It
Nozzle BB *2 Dilution
Nozzle C
Nozzle C RERUN
Field Blank
8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB 11
Nozzle BB 11 Field Duplicate
Nozzle BB 12
Nozzle BB 12 Field Duplicate
Nozzle BB ft Meld Duplicate RERUN
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Duplicate RERUN
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BA Dilution
Nozzle BB
Nozzle BB Field Blank
Nozzle C
Nozzle C Dilution
Nozzle C Field Blank
Monochl orobenzene
15300
17700
(St
749C
4340
Carbon tetrachloride
Chloroform
1 BELOW)
446.270
283.000
2970
3260
01
•o
l_
o
J=
0
C_
0
.c
o
144
77200
128.500
137,200
1804
173
2838
2900
Tetrachl oroethyl ene
//UO
04b
«4bO
9180
4400
Benzene
131
192
3ll
Ethyl benzene
1494
2050
35600
2890
2850
44700
1290
1540
96320
IV
c
Ol
i.
>>
4J
>
350
15900
35500
42400
1573
230,400
Toluene
1700
260
2370
2110
1950
43400
210
2440
9920
4620
4340
V)
o>
c
o>
*>,
X
'n
*J
o
\—
2700
1850
2920
1600
176,405
Acetone
393
1478
1700
990
950
65
14
260
2-Butanone
1U5/
1
(SEE 1
2-Hexanone
J4UU
9b3U
9bUO
3tLUW
Bromomethane
4/0
NOTES:
1. Sample extracts were diluted, prior to analysis, five times or more.
were therefore out of acceptable ranges.
2. Data expressed In mg/kg.
Surrogate recoveries
-------
benzene-ring compounds. A complete listing of tentatively identified
volatile compounds appears in Appendix D, Table 0-11. However, nine of the
28 individual • analyses for volatile compounds were judged to be unacceptable
in terms of accuracy (see Appendix D, Table 0-10), as recoveries for all
surrogate compounds were not within the ranges established for the study.
For semi-volatile compounds (Table V-8), 15 of the 29 samples submitted
were analyzed with satisfactory accuracy for all six surrogate compounds.
(see Appendix 0, Table D-12); some chlorinated phenols and other benzene-
ring compounds were qualitatively detected on the first and second sampling
day. A discussion of possible limitations on the use of these semi-vol atile
data may be found in Appendix D, Section III.0.2.
Pesticides in the low ppm range were tentatively found (see Table V-9)
on scattered occasions, but accuracy data were not submitted by the
analytical laboratory, and available precision data appear poor. No PCBs
were found in any liquid waste; however, the detection limit requested of
the analytical laboratory, 5 ppb, was not met, by at least three orders of
magnitude.
When found, PCDDs and PCDFs appeared in liquid wastes fed to the
incinerator through nozzles BB and C. The data in Table V-10 show generally
good precision between duplicate samples from these nozzles on the second
sampling day; accuracy goals were generally met for surrogate compounds
(see Appendix D, Table 0-17). Of the TCDD isomers, the 1368 and 1379 were
most prevalent.
(3) Low-BTU Liquid Waste
A comparison of volatile compounds detected (Table V-ll) reveals, as
expected, concentrations significantly lower in 1 ow-BTU liquid wastes
than in the liquid wastes described above. Concentrations in the range of
10 to 100 ug/L were established on the third sampling day for vinyl idene
chloride, ethyl ene dichloride, and chloroform, within satisfactory limits
for precision and accuracy. Of the semi-volatile compounds (Table V-12)
only 1,2-dichlorobenzene was found, within acceptable quality assurance
1imits.
Analyses for PCDDs and PCDFs were generally successful in achieving
accuracy goals for PCDD surrogates but not for PCDF (see Appendix D, Table
D-17). Therefore, the TCDF data contained in Table V-13 may be suspect.
However, homologue-by-homologue precision on the third sampling day met the
goal established for the study (<50% relative percent difference). Dioxin
homologues were limited to tetra, hepta, and octa, and low-ppq concen-
trations of TCDF were indicated. As with the liquid wastes described
previously, most TCDD was composed of the 1368 and 1379 isomers; no 2378-TCDD
was found.
28
-------
TABLE V-8
QUANTITATED SEMI-VOLATILE COMPOUNDS - LIQUID WASTE INPUTS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
TARGET
COMPOUNDS
BENZENE RING
COMPOUNDS
OTHER
REAGENT BLANK 1
REAGENT BLANK 2
8/28/84
Nozzle BA
Nozzle BA, 5X Dilution
Nozzle BA, 20X Dilution
Nozzle BB #1
Nozzle BB #1, 10X Dilution
Nozzle BB #1, 20X Dilution
Nozzle BB #2
Nozzle BB #2, 10X Dilution
Nozzle C
Field Blank (Nozzles BA & BB)
8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB #1
Nozzle BB #1 Field Duplicate
Nozzle BB #1 Field Duplicate, 5X Dilution
Nozzle BB #2
Nozzle BB #2 Field Duplicate
Nozzle BB #2 Field Duplicate, 10X Dilution
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Duplicate, 10X Dilution
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BA, 10X Dilution
Nozzle BB
Nozzle BB Field Blank
Nozzle C
Nozzle C, 10X Dilution
Nozzle C Field Blank
1,2-dichlorobenzene
1406
1570
1240
o
c
(U
-C
a.
2,4,5-trichlorophenol
4690
1900
4450
2,4,6-trichlorophenol
110
8320
5570
4490
Naphthalene
144
680
34b
fc>2
2-methyl naphthal ene
77
33
2320
1950
27
Anthracene
bbU
41)
Fluorene
190
14b
Diethylphthalate
10500
60800
1390
1130
5930
110
270
NOTE: Data expressed in mg/kg.
29
-------
TABLE V-9
LIQUID WASTE INPUTS - QUANTITATED PESTICIDE/PCB COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, and 9/5/84
PESTICIDES
PCB (AROCLORS)
REAGENT BLANK 1
REAGENT BLANK 2
8/28/84
Nozzle BA
Nozzle BB #1
Nozzle BB #2
Nozzle C
Nozzles BA & BB Field Blank
8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB #1
Nozzle BB #1 Field Duplicate
Nozzle BB #2
Nozzle BB #2 Field Duplicate
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BB
Nozzle BB Field Blank
Nozzle C
Nozzle C Field Blank
c
•1—
c_
~o
<
1.4
3.1
o
:r
CO
i
-------
TABLE V-10
LIQUID WASTE INPUTS - QUANTITATED PCDD/PCDF
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, and 9/5/84
REAGENT BLANK 1
REAGENT BLANK 2
8/28/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB #1
Nozzle BB #2
Nozzle C
8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB #1
Nozzle BB #1 Field Duplicate
Nozzle BB #2
Nozzle BB #2 Field Duplicate
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BB
Nozzle BA Field Blank
Nozzle C
Nozzle C Field Blank
0
O
O
I—
1
00
r--
co
evi
o
Q
0
i—
(O
4->
o
I—
5.8
0.5
33.0
30.7
60.3
21.8
5.9
0.8
o
Q
O
0)
Q_
*
o
i—
11.8
6.3
4.9
3.5
6.1
0.8
(SAM
Q
Q
O
X
in
o
1—
1.2
0.9
0.4
2.6
4.2
>LE AN/
Q
Q
O
Q.
3C
r—
(O
4-J
O
2.8
3.0
2.6
3.8
5.7
Q
Q
0
O
22.0
11.5
12.1
19.8
19.8
1.2
U.YSIS NOT RE1
u_
Q
0
1—
1
oo
r^
oo
CVJ
0.3
1.4
2.1
0.2
Li-
CS
O
I—
fO
4J
0
1—
9.2
0.4
37.0
32.3
36.6
18.0
6.5
LL_
0
{_>
0
1 —
0.8
1.8
5.3
1.5
4.3
0.2
u_
Q
0
X
nr
(O
4->
O
t—
0.7
3.5
7.1
fURNED FROM LABORATORY)
0.2
u_
Q
C_3
Q.
rc
(C
-M
o
1—
0.6
8.1
8.2
Ll_
Q
<_>
O
1.2
0.6
7.4
7.7
NOTES: Data expressed in ng/g.
Where data are not stated, homologue was not detected,
-------
TABLE V-ll
LOW-BTU LIQUID WASTE - VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28 AND 9/5/84
TENTATIVELY
IDENTIFIED
COMPOUNDS
>
8/28/84
COMPOSITE SAMPLE
FIELD BLANK
9/5/84
COMPOSITE SAMPLE
FIELD DUPLICATE
FIELD BLANK
|
r-H
*
i— 1
*
t-H
24
4
O)
C
O)
N
C
0)
_o
^—
>»
_c
+J
0)
14
O)
c
Ol
t_
>»
4J
to
12
O)
-o
(_
o
r—
.C
0
Ol
c
0)
>>
^:
4->
QJ
e
6
170
112?
1241
O)
c
o
4->
d)
u
•r-
^_
>>
C
•r-
>
127
137
0)
TJ
•r—
t_
o
.c
u
•r-
T3
0)
C
0)
r—
>>
^:
+J
(U
86
93
p
{^
o
<4-
o
t_
o
r—
-C
0
12
13
O)
c
0>
>,
-C
-!->
0>
O
c.
0
^:
o
s_
0)
a.
378
O)
c
0)
N
C
0)
^D
O
(_
O
r—
JC
O
260
>
(U
c
0)
>>
X
f«
>a
•u
0
-•->
429
7659
(U
-o
•I-.
c_
o
r™"
JC
0
C-
03
O
2916
(U
c
0)
-C
4->
0)
O
<_
o
J=
o
•^
L
••->
8
i
o
r—
O
>> a
o c
• — «
>> >
^ c
-(-> i-
QJ ••-
E f
(O ••-
x t-
OJ 4-
JC
200
ai
c
>
^:
4->
O)
>>
-4->
(U
E
i
r-«
2791
6222
a>
c
0)
N
C
(U
JD
>,
a.
o
t_
Q.
1160
NOTE: Data expressed in ug/L.
-------
TABLE V-12
LOW-BTU LIQUID WASTE-SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28 AND 9/5/84
CO
co
8/28/84
Composite Sample
Field Blank
9/5/84
Composite Sample
Field Duplicate
leld Blank
QUANTITATED COMPOUNDS
CO
c
Q)
Nl
C
0)
JO
o
c.
o
1 —
-C
o
•^
o
1
CM
i— i
121
9b
CU
c
0)
r—
fO
JC
•M
JC
Q.
(O
C.
r—
>>
.C
4_>
Ol
E
l
CM
1/4
809
CU
•4-}
"0
r~~
.C
CL
**-**
r—
>j
X
OJ
-C
^«—
>^
-d
4-*
0)
1
OJ
*• — *
(/)
•r-
•°
49
96
Ol
c
CO
NJ
c
CU
o
o
L.
o
r—
-C
o
»^-
*u
1
<^"
«*
t— 1
313
r-~
O
c
O)
f~
Q.
0
c_
O
r~*
^:
o
-^
L.
4-)
I
^O
*
•51"
*v
OJ
167
TENTATIVELY - IDENTIFIED COMPOUNDS
c
CU
•^
T5
(O
4_>
Q.
QJ
_C
I
co
•»
CM
1
i—
>^
x:
•M CO
CO C
E >>
•^ 1
"ID LO
1 1
^"
M
OJ
13
0)
c
.
Q.
0
t
Q.
6
CO
c
(O
o
c
•— i fO
1 i —
O HJ
t- ^=
^} f~
-C Q.
•r- CO
"X3 CT
1
^j-
*
r— 1
62
1807
>~- ^
>>
X
o
-C r—
4J 0
CO C
>> O)
1^ , —
1 ^J
CM X
— - o
CM 4->
r-i Ol
t
CM
52
r—
0
•r-
TD
CU
c
CO
[ %
CD
CM
A
I— 1
1
^~
>^
C
CO
Q.
1
i— i
1051
CO
c
CO
c
CO
J3
^.^
^r
01
E
•r—
-o
««3-
A
r-l
461
O)
c
M
C
O)
^
^.^
£—
i \
cu
E
CO
i
>.
c
CU
£•
+•*
CU
1
1— 1
591
"O
0
CO
O
•r—
^_
^.^
X
o
JO l~
(_ CU
CO -t->
O i/)
•i- O)
CO >,
cr t—
CO -(->
N O)
C «=
r_
JO
1— »
M
1— 1
4368
Note: Data expressed in ug/L .
-------
TABLE V-13
LOW-BTU LIQUID WASTE - PCDD/PCDF ANALYSES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28 AND 9/5/84
SAMPLE IDENTIFICATION
8/28/84
COMPOSITE SAMPLE
FIELD BLANK
8/30/84
(NO SAMPLE TAKEN - Low-BTU Ik
9/5/84
COMPOSITE SAMPLE
FIELD DUPLICATE
FIELD BLANK
PRECISION (RPD) -
SAMPLE AND FIELD DUPLICATE
2378-
TCDD
|uid wasl
Total
TCDD
;e was nc
29.3
22.8
25
Total
PeCDD
)t incint
Total
HxCDD
10.4
jrated or
Total
HpCDD
i this d<
181
132
31
OCDD
y)
753
570
28
2378-
TCDF
Total
TCDF
33.9
46.4
31
Total
PeCDF
Total
HxCDF
Total
HpCDF
OCDF
CO
NOTES: 1. All data expressed in pg/g.
2. Blank spaces denote homologue not detected.
Detection limits ranged from 0.2 to 10.2 ppt for
TCDD and TCDF, to 8.9 to 162 ppt for OCDD and OCDF.
-------
b. Effluent Streams
(1) Incinerator Exhaust
Analyses for volatile compounds presented in Appendix D, Tables D-30,
0-31, and D-32, should be evaluated in light of previous comments concerning
the stringency of the accuracy criteria established for this study. Among
the compounds appearing in incinerator exhaust gases were carbon tetra-
chloride, monochlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, per-
chloroethylene, and trichloroethylene. These data are summarized below:
Table V-14
Approximate Concentrations of Volatile Compounds
in Incinerator Exhaust 8/28, 8/30, 9/5/84
Concentration, ug/m^
8/28/84
8/30/84
carbon tetrachloride
monochlorobenzene
1,2-dichlorobenzene
1,4-dichlorobenzene
perchloroethylene
trichloroethylene
ND
0.09-0.13
ND
ND
ND
ND
0.03-0.59
0.01-0.47
0.04-3.81
ND-0.52
0.01-0.07
0.001-0.01
9/5/84
ND
0.06-0.09
ND
ND
0.01-0.04
ND
ND = not detected in concentration higher than in field blanks.
Note that the two dichlorobenzenes detected by the volatile compound
sampling method are considered semi-volatile compounds under the boiling
point definition established previously in this report. With respect to
semi-volatile compounds, only the following were detected on the second
sampling day, August 30, 1984. No semi-volatile compounds were found on
the other sampling days.
Table V-15
Approximate Concentration of Semi-Volatile Compounds
in Incinerator Exhaust 8/30/84
Compound
1,2-di chlorobenzene
1,4-di chlorobenzene
tetrachlorobenzene
naphthalene
Concentration, ug/m3
115
102
25
33
35
-------
However, as shown in Appendix 0, Table D-36, these compounds were detected
in the XAD-2 cartridge portion of the Modified Method 5 train, for which
the recoveries of the three acid surrogates did not meet the accuracy goal
of 20 to 180% established for the study (see Appendix 0, Section III.A.).
The above data should be evaluated in this context.
Table V-16 is a presentation of PCDD and PCDF emissions from the Building
703 incinerator, expressed in ng/m3. These data were developed by summing
the amounts of PCDD and PCDF found in each of the four components of the
Modified Method 5 train. No 2378-TCDD was found, at detection limits of
0.02 to 2 ng/m3.
The data presented in Table V-16A are expressed in units of ng/dscm,
adjusted to standard temperature and pressure, and normalized to a 3% oxygen
content in exhaust gas. This was done to render the data directly comparable
to information presented in the draft Project Summary Report - National
Dioxin Study Tier 4 - Combustion Sources (document EPA-450/4-84-014g, April
1986), in which emissions data for a wide range of sources are presented.
Vinylidene chloride was detected in exhaust gas at concentrations
ranging between 28.1 and 279.8 ppb, as shown in Table V-17.
Prior to analysis, the Modified Method 5 trains used to sample for
PCDDs and PCDFs were disassembled and the filter and probe wash portions
were dried and weighed in a manner conforming to EPA Method 5. The
particulate emissions of the incinerator on the three test days were found
to be 0.0842, 0.0615, and 0.0784 grain/dscf. The arithmetic average of
these data is 0.0747 grain/dscf. The Resource Conservation and Recovery
Act standard for hazardous waste incinerators, appearing at 40 CFR Part
264.343(c), is 0.08 grain/dscf. That standard does not provide for
arithmetic averaging to determine compliance.
To obtain the weights of filter and probe wash residues, these fractions
were desiccated to constant weight. Because of possible losses from
volatilization of PCDDs and PCDFs from the filters and probe washes, the
data presented in Tables V-16 and V-16A may be biased low. However, low
volatilities of PCDDs and PCDFs suggest any losses would not be significant.
(2) Incinerator Ash
Table V-18 includes the results of analyses for semi-volatile compounds
present in incinerator ash sampled on the three test days.
Table V-19 shows the concentrations of PCDD and PCDF found in this ash.
Among the PCDDs, the higher-chlorinated homo! ogues were predominant, at
low parts per billion levels. No 2378-TCDD was detected at the low parts
per trillion range; other isomers, primarily the 1368, 1379, 1237 and
1238, were present at levels of about 0.1 to 1.2 ng/g. Of the PCDFs, the
tetra, hepta, and octa homo! ogues were found at low parts per billion
concentrations.
36
-------
TABLE V-16
INCINERATOR EXHAUST - PCOD/PCDF ANALYSES
EXPRESSED IN TERMS OF CONCENTRATION IN AIR (ng/m3)
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
Modified Method 5 Train
Catches
8/28/84
8/30/84
9/5/84
2378-
TCDD
Total
TCDD
[45.95]
43.75
- 4.92
Total
PeCDD
6.49
1.94
Total
HxCDD
(p. 88)
0.37
Total
HpCDD
0.21
0.84
NOTES -
OCDD
0.93
2.52
0.47
2378-
TCDF
1.51
1.67
Total
TCDF
[81.22]
76.98
124.8
Total
PeCDF
[12.95]
4.28
0.07
Total
HxCDF
[2.47]
1.95
Total
HpCDF
0.26
0.55
OCDF
0.06
0.17
(^) - Data out of control with respect to precision criteria (+50% RPD)
["] - Bracketed data denote homologues detected in filter and probe wash portion
of Modified Method 5 train were deleted owing to unacceptable duplicate
analysis results. Only a small fraction of total concentration detected
was affected (see data in Appendix D, Table D-38).
- Matrix spike analyses indicated recoveries out of control for the following:
Filter and probe wash - PeCDD and HxCDF
XAD-2 cartridge - HpCDD and HpCDF
(
)ther mec
lia in tt
le sampl
ng train showed c
icceptab'
e matri>
, spike r
ecoverie
s.
-------
TABLE V-16A
INCINERATOR EXHAUST - PCDD/PCDF ANALYSES
CONCENTRATION EXPRESSED IN ng/dscw. ADJUSTED TO STANDARD
TEMPERATURE AND PRESSURE (68°F, 29.92 in.Hg). AND NORMALIZED TO 3* OXYGEN CONTENT
8/28. 8/30. 9/5/84
SAMPLE IDENTIFICATION
Modified Method 5 Train
Catches
8/28/84
8/30/84
9/5/84
2378-
TCDD
Total
TCDD
[116.8]
123.8
11.37
Total
PeCDD
16.49
5.49
Total
HxCDD
v'2y
1.05
Total
HpCDD
0.53
2.38
NOTES -
OCDD
2.36
7.13
1.09
2378-
TCDF
3.84
4.72
Total
TCDF
[206.4]
217.8
288.5
Total
PeCDF
[32.91]
12.11
0.17
Total
HxCDF
[6.28]
5.52
Total
HpCDF
0.66
1.56
OCDF
0.15
0.48
O - Data out of control with respect to precision criteria (^50t RPO)
[ ] - Bracketed data denote homologues detected In filter and probe wash portion
of Modified Method 5 train Mere deleted owing to unacceptable duplicate
analysis results. Only a small fraction of total concentration detected
was affected (see data In Appendix 0, Table D-38).
- Matrix spike analyses indicated recoveries out of control for the following:
Filter and probe wash - PeCDD and HxCDF
XAD-2 cartridge - HpCDD and HpCDF
Other media in the sampling train showed acceptable matrix spike recoveries.
1 I 1
I II ! 1 1 I 1
00
-------
TABLE V-17
RESULTS OF SAMPLING FOR VINYLIDENE CHLORIDE
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
DATE
8/28/84
8/30/84
9/5/84
SAMPLE RUN
1
2
3
4
5
6
7
1
2
3
4
5
6
1
2
2 DUPLICATE
3
4
5
6
SAMPLE
COLLECTION TIME (EOT)
1230-1330
1405-1510
1525-1625
1640-1735
1750-1845
1850-1930
1935-2015
1000-1050
1100-1200
1210-1250
1300-1350
1400-1450
1500-1550
1000-1045
1100-1150
1100-1150
1200-1245
1400-1445
1500-1545
1600-1630
VINYLIDENE CHLORIDE
CONCENTRATION (ppbv)
88.6 (83.1, 88.0, 94.7)
68.3 (72.1, 72.3, 60.2)
64.3 (113.0*, 67.5, 61.1)
74.5 (73.9, 74.7, 74.8)
88.9 (94.2, 88.4, 84.1)
112.4 (113.6, 111.2, 138.6*)
104.4 (102.1, 107.8, 103.3)
149.7 (150.0, 154.9, 144.3)
187.6 (180.9, 189.3, 192.7)
241.6 (263.7, 219.5, 402.7*)
279.8 (275.3, 285.9, 278.3)
218.0 (219.6, 216.3)
28.1 (28.9, 27.9, 27.6)
88.7 (94.3, 93.3, 78.5)
70.3 (69.4, 68.9, 72.6)
79.3 (76.7, 81.9, 79.3)
157.8 (156.4, 152.5, 164.4)
154.3 (162.2, 143.5, 157.2)
156.0 (154.7, 161.6, 151.8)
143.5 (146.6, 143.3, 140.6)
STANDARD
DEVIATION
5.8
6.9
4.5
0.5
5.1
1.7
3.0
5.3
6.1
31.3
5.5
2.3
0.7
8.8
2.0
2.6
6.1
9.7
5.0
3.0
* Rejected as greater than one standard deviation from mean of three analyses.
39
-------
TABLE V-18
INCINERATOR ASH SEMI-VOLATILES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
(Results in uy/kg)
8/28/84
8/28/84
Field Blank
8/30/84
8/30/84
Field Pup.
8/30/84
Field Blank
9/5/84
9/5/84
Field Blank
0,
Ol
c
X
L.
0
£:
o
•o
1
t— «
520
HI
Ol
c
Ol
o
.c
0
TJ
1
-
460
1
01
01
N
8
3
C-
o
-C
u
l_
•
-
867
o
a
01
£
jr
°~
•—
4->
jj
•o
433
1933
1733
41
«O
*«
5
-C
,_
.c
*^
T1
01
ia
*io
-C
a.
-^
>.
£
^
*»
4-»
41
CM
'*-"'
JD
.
t-
OJ
0)
•o
201
10.883
^ "
^
2722
41
£
A
,—
.^~
JD
-C
CM
7189 '
C
fl
>»
4)
a
•o
>»
i
52.838
44,757
M
U)
.n
•^
c
^
01
CVJ C
* 01
•— • N
1 Ol
•"•
11,628
5661
-
C
L
41
^^
CM
*—t
•"*
4932
9919
^
41
41
^-,
01
"
•"*
10,792
6245
•^
c
4>
t-
41
^
"
^^
•"-«
11,243
9965
O>
C
^
s
4-*
o
2U06
•—
c
Q.
2
1
—^
O
C
Q.
1
cvj
3681
C
m
*~
^
>»
c
Q.
-O
>>
XT
O>
E
•^
o
0.
^ 01
QJ i —
i x:
CM 4->
"^ '"ci
t/t
-°
(SAMPLE ANALYSIS NOT RETURNED FROM LABORATORY)
363
1110
423
530
170
435
321
1069
(SAMPLE ANALYSIS NOT RETURNED FROM LABORATORY)
-------
TABLE V-19
INCINERATOR ASH - PCDD/PCDF ANALYSES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, AND 9/5/84
SAMPLE IDENTIFICATION
8/28/84
COMPOSITE SAMPLE
FIELD BLANK
8/30/84
COMPOSITE SAMPLE
FIELD DUPLICATE
PRECISION (RPD)
FIELD BLANK
9/5/84
COMPOSITE SAMPLE
FIELD BLANK
2378-
TCDD
ND
(27.7)
ND
(8.2)
ND
(23.1)
ND
(11.8)
ND
(7.1)
ND
(6.9)
Total
TCDD
1170
ND
(9.6)
131
107
20
ND
(3.1)
71
(An<
Total
PeCDD
ND
(19.1)
ND
(35.8)
ND
(13.6)
ND
(15.6)
ND
(15.5)
ND
(16.2)
ilytical
Total
HxCDD
793
ND
(17.5)
129
111
15
ND
(6.1)
ND
(10.9)
data no1
Total
HpCDD
6060
ND
(12.7)
806
498
47
ND
(15.5)
76
; returns
OCDD
32,700
ND
(25.8)
3180
2370
29
ND
(25.8)
266
id from
i
2378-
TCDF
66
ND
(12.6)
17
ND
(11.3)
ND
(4.2)
ND
(6.5)
iborator
Total
TCDF
9160
ND
(12.8)
594
263
77
ND
(5.4)
540
')
Total
PeCDF
68
ND
(21.2)
ND
(5.4)
ND
(7.3)
ND
(7.4)
ND
(7.8)
Total
HxCDF
455
ND
(19.6)
44
37
17
ND
(8.6)
ND
(19.5)
Total
HpCDF
1520
ND
(15.9)
449
248
58
ND
(21.7)
ND
(20.2)
OCDF
2570
ND
(23.4)
573
399
36
ND
(11.3)
78
NOTE: Data expressed in pg/g.
-------
(3) Aqueous Influents and Effluents
Chloroform and carbon tetrachloride were found at low parts per trillion
levels in service water supplied to the incinerator air pollution control
devices. Otherwise, there were no consistent findings of any other volatile
compounds (see Appendix D, Tables D-50, D-51, and 0-52). Other than
scattered detection of phthalate compounds, few semi-volatile compounds
were found in effluent wastewaters. On the second and third sampling days,
various chlorophenols and chlorobenzenes were found in influent service
water, and biphenyls and terphenyls appeared in effluent wastewaters. Any
association between these compounds is speculative.
Tables V-20, V-21, and V-22 are detailed presentations of PCDO and PCDF
data for influent and effluent waters. Of particular interest is the
apparent strong affinity of PCDO and PCDF for the filterable solids present
in these waters. Also, some TCOD, TCDF, HpCDF, and OCDF were detected in
influent service waters. No 2378-TCOD was found at any time, at detection
limits of approximately 1 ng/L for aqueous samples and 10 ng/g for solids
samples. Detailed information with respect to the TCOO isomers detected
appears in Appendix D, Tables D-60, D-61, and 0-62.
2. Quality Assurance Review
As indicated in the Quality Assurance Project Plan for the incinerator
exhaust study (Reference 7), a goal of 90% was established with respect to the
completeness of the analytical data. This measure was devised to assess the
overall suitability of groups of data; individual data points were judged to be
complete if precision and accuracy criteria applicable to a particular type of
sample were met. In retrospect, given the complexity of this study this goal
was overly optimistic.
Field duplicate samples were obtained on one of the three study days for
each sample type. Where calculable, precision data are presented in the data
tables and discussion included in Section V and Appendix D of this report.
Owing to the wide range of compounds sought for analysis in each sample, and
the number of field duplicate samples taken, there were few cases in which the
same compounds were found in both actual samples and the field duplicates. The
quality assurance objective was +_ 50% or +_ the detection limit. Because of the
wide variety of compounds detected and the few opportunities to assess precision,
the following discussion centers on completeness based solely on data accuracy,
as measured by analysis of surrogate compounds introduced to each sample by the
laboratories during analysis. These data are presented in the raw data summary
tables in Appendix D, and, where appropriate, in the data tables in Section V.
Several cases surfaced in which surrogate compounds were not detected or
recovered less than 10%. Laboratory personnel indicated these samples were
generally diluted during analysis such that some of the surrogate peaks were
lost. . • •
Table V-23 is a summary of data completeness for the categories of
samples and compound groups other than PCDDs and PCDFs analyzed in this study.
Generally, the completeness goal of 90%, established in the plan for the study7,
42
-------
TABLE V-20
AQUEOUS INFLUENTS AND EFFLUENTS - PCDD/PCOF ANALYSES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28/84
CO
SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
Venturi/Demister Water
(Water)
Venturi/Demister Hater
(Solids)
ESP Water (Water)
ESP Water (Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water Backup
Field Blank
2378-
TCDD
ND
(.0021)
ND
(.0013)
ND
(15.6)
ND
(.0011)
ND
(2.98)
ND
(.0003)
ND
(19.8)
ND
(.0003)
ND
(.0002)
Total
TCDD
0.0384
NO
(.0010)
432
NO
(.0010)
238
NO
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
Total
PeCDD
ND
(.0043)
ND
(.0010)
54.9
ND
(.0027)
82.0
ND
(.0010)
ND
(171)
ND
(.0016)
ND
(.0054)
Total
HxCDD
ND
(.0086)
ND
(.0042)
43.7
ND
(.0026)
55.1
Total
HpCDD
ND
(.0073)
ND
(.0079)
274
ND
(.0059)
265
OCDD
0.198
ND
( .0206)
1437
NO
(.0147)
1113
2378-
TCDF
ND
(.0011)
ND
(.0005)
11.0
ND
(.0002)
8.52
Total
TCDF
1.26
0.0025
170
0.0393
137
Total
PeCOF
ND
(.0026)
ND
(.0015)
66.4
ND
(.0022)
100
SAMPLE ANALYSIS DATA NOT RETURNED FROM LABORATORY
SAMPLE ANALYSIS DATA NOT RETURNED FROM LABORATORY
ND
(.0027)
ND
(94.3)
ND
(.0026)
ND
(.0115)
ND
(.0058)
ND
(126)
ND
j.0083)
ND
(.0275)
ND
(.0289)
323
ND
(.0130)
NO
(.0447)
ND
(.0003)
ND
(27.4)
ND
(.0002)
ND
(.0003)
ND
(.0010)
189
ND
(.0010)
ND
(.0010)
ND
(.0031)
NO
(45.1)
ND
(.0039)
ND
(.0037)
Total
HxCDF
ND
(.0057)
ND
(.0029)
117
NO
(.0018)
130
ND
(.0012)
ND
(42.5)
ND
(.0014)
NO
(.0075)
Total
HpCDF
0.0558
ND
(.0055)
427
ND
(.0030)
337
ND
(.0066)
ND
(91.5)
ND
(.0055)
NO
(.0167)
Total
OCDF
ND
(.0130)
NO
(.0118)
379
ND
(.0139)
284
ND
(.0121)
NO
(118)
NO
(.0098)
ND
(.0284)
Note - Date expressed in ng/g for solids samples, ng/L for aqueous samples.
-------
TABLE V-21
AQUEOUS INFLUENTS AND EFFLUENTS - PCDD/PCOF ANALYSES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/30/84
SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
ESP Water (Water)
Field
ESP Water (Water) Duplicate
ESP Water (Solids)
Field
ESP Water (Solids) Duplicate
Venturi/Demister Water
(Water)
Venturi/Demister Water
(Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water Backup
Field Blank
2378-
TCDD
NO
(.0027)
ND
(.0007)
ND
(11.1)
ND
(.0009)
ND
( .0028)
ND
(35.3)
ND
(65.5)
ND
(.0006)
ND
(2.08)
ND
(.0010)
NO
(1.08)
ND
(.0005)
ND
(.0005)
Total
TCOD
0.0464
ND
(.0010)
707
.0062
.0189
4212
1864
ND
(.0010)
307
NO
(.0025)
15.9
ND
(.0010)
ND
(.0010)
Total
PeCDO
ND
(.0019)
ND
(.0024)
99.3
NO
(.0011)
NO
(.0019)
885
393
NO
(.0012)
49.2
ND
(.0240)
ND
(3.09)
NO
(.0011)
ND
( .0080)
Total
HxCOD
NO
(.0021)
ND
( .0042)
75.3
NO
( .0028)
ND
( .0029)
147
205
ND
(.0021)
27.6
ND
(.0227)
ND
(3.14)
ND
(.0021)
ND
(.0063)
Total
HpCOD
0.0179
ND
(.0115)
460
ND
(.0057)
NO
( .0044)
417
515
ND
( .0089)
162
NO
(.0292)
21.5
ND
(.0031)
NO
(.0083)
OCDD
0.187
ND
(.0301)
2358
ND .
(.0192)
NO
(.0077)
2199
2530
ND
(.0075)
707
ND
(.0453)
94.9
ND
( .0053)
ND
(.0104)
2378-
TCDF
ND
(.0012)
ND
(.0001)
15.4
ND
(.0004)
NO
(.0004)
45.3
47.7
ND
(.0005)
3.22
ND
(.0022)
ND
(1.71)
ND
(.0006)
NO
(.0014)
Total
TCDF
1.42
0.0223
182
0.287
0.607
539
6574
0.0682
168
ND
( .0038)
114
NO
(.0010)
ND
(.0025)
Total
PeCDF
0.0088
NO
(.0037)
ND
87.5
NO
(.0051)
ND
(.0039)
405
345
ND
(.0021)
64.6
ND
(.0120)
ND
(3.15)
ND
(.0024)
ND
(.0077)
Total
HxCDF
NO
(.0067)
ND
(.0028)
124
ND
(.0037)
ND
(.0017)
75.7
58.6
ND
(.0033)
82.9
ND
(.0110)
ND
(2.93)
NO
(.0017)
NO
(.0128)
Total
HpCDF
0.0167
ND
(.0131)
785
ND
(.0055)
ND
(.0070)
150
161
ND
(.0056)
199
NO
(.0232)
10.0
ND
(.0052)
ND
(.0046)
OCDF
0.0477
NO
(.0168)
641
NO
(.0182)
ND
( .0099)
200
226
ND
j.0164)
283
ND
( .0269)
12.5
NO
(.0037)
NO
(.0127)
Note - Data expressed in ng/g for solids samples, ng/L for aqueous samples.
-------
TABLE V-22
AQUEOUS INFLUENTS AND EFFLUENTS - PCDD/PCDF ANALYSES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
9/5/84
SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
Venturi/Demister Water
(Water)
Venturi/Demister Water
(Solids)
ESP Water (Water)
ESP Water (Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water Backup
Field Blank
2378-
TCOD
ND
(0.341)
ND
(.0004)
ND
(1.10)
NO
( .0008)
ND
(1.29)
ND
(.0014)
ND
(28.2)
ND
(.0003)
ND
(.0013)
ND
(.0003)
Total
TCOD
ND
(0.229)
ND
(.0010)
73.9
ND
(.0010)
56.3
0.0052
247
ND
(.0010)
ND
( .0010]
ND
(.0010)
Total
PeCDD
ND
(0.556)
ND
(.0024)
ND
(7.43)
ND
(.0021)
17.5
ND
(.0104)
61.5
ND
(.0012)
ND
(.0016)
ND
( .0048)
Total
HxCDD
ND
(0.720)
ND
(.0027)
ND
(3.19)
ND
(.0031)
7.35
ND
(.0039)
20.3
ND
(.0017)
Total
HpCDD
ND
(0.318)
ND
(.0018)
69.0
ND
(.0036)
44.3
ND
(.0087)
96.0
ND
( .0029)
OCDD
ND
(0.520)
ND
( .0020)
236
ND
(.0064)
261
ND
(.0051)
423
ND
( .0025)
(SAMPLE ANALYSIS DATA NOT
ND
(.0071)
ND
(.0027)
ND
(.0067)
ND
(.0039)
ND
(.0088)
ND
( .0058)
2378-
TCDF
ND
(0.192)
ND
(.0001)
ND
(1.93)
ND
(.0001)
2.05
ND
(.0015)
9.70
ND
(.0001)
Total
TCOF
ND
(0.517)
0.0058
830
0.0157
723
0.0995
90.0
ND
(.0010)
Total
PeCDF
ND
(0.299)
ND
(.0015)
7.09
ND
(.0010)
22.3
ND
(.0041)
47.0
ND
(.0010)
RETURNED FROM LABORATORY)
ND
(.0023)
ND
( .0002)
ND
(.0022)
ND
(.0010)
ND
( .0080)
NO
(.0025)
Total
HxCDF
ND
(0.351)
ND
(.0015)
16.1
ND
(.0024)
19.7
ND
( .0030)
14.7
ND
(.0010)
ND
(.0025)
ND
( .0027]
Total
HpCDF
ND
(0.627)
ND
(.0012)
125
ND
(.0017)
69.1
ND
(.0026)
68.2
ND
(.0021)
ND
(.0049)
ND
LSS^L
OCDF
ND
(0.396)
ND
(.0011)
103
ND
(.0035)
84.8
ND
(.0061)
82.1
ND
(.0037)
ND
(.0057)
ND
iiOp_39J.
Note - Data expressed in ng/g for solids samples, ng/L for aqueous samples.
-------
TABLE V-23
OVERALL DATA COMPLETENESS
BASED UPON ANALYTICAL ACCURACY CRITERIA
DOM CHEMICAL COMPANY BUILDING 703 INCINERATOR EMISSIONS STUDY
Analysis Type
Type of Sample
Precombustlon Air
Liquid Wastes
Low-BTU Liquid Haste
Incinerator Exhaust
-P» Incinerator Ash
CT>
Aqueous Influents
Volatile
Compounds
38% (3/8)
68t (19/28)
100% (5/5)
13* (2/16)
95% (21/22)
Semi -Volatile
Compounds
88% (7/8)
52% (15/29)
SOX (4/5)
57% (16/28)
71% (5/7)
89% (31/35)
Pesticides/PCB
0% (0/19)1
—
—
—
PCDD/PCDF Internal Standards
and Effluents
"W
71% (5/7)
84% (16/19)
80% (4/5)
79% (19/24)
86% (6/7)
74% (26/35)
37C1 4-2378-
TCDD
86% (6/7)
95% (18/19)
100% (5/5)
83% (20/24)
86% (6/7)
91% (32/35)
13C12-OCDD
29% (2/7)
74% (14/19)
100% (5/5)
75% (18/24)
86% (6/7)
74% (26/35)
37CI4-2378-
TCDF
71% (5/7)
84% (16/19)
20% (1/5)
67% (16/24)
86% (6/7)
60% (21/35)
lowing to dilution effects during analysis, the target detection limit was not met.
-------
was not met, but in many cases was nearly met. In any event, this performance
should be evaluated with respect to comments made previously about the stringency
of the accuracy criteria used to judge the acceptability of volatile and semi-
volatile compound analyses.
Similar data for PCDDs and PCDFs may be found in the tables in Appendix D
in which analytical results are presented. As indicated previously, accuracy
with respect to the TCDD surrogates deemed most important in evaluating potential
health risks, was generally near 80%; for OCDD and PCDFs, accuracy was less
reliable, but these compounds are of less concern regarding health risk
assessment.
The above-referenced study plan also describes desired detection limits for
the types of samples and analytical procedures employed in this study. These
data (Table V-24) indicate detection limits were met or nearly met for volatile
and semi-volatile analyses except those of liquid wastes, where sample
extraction and dilution was necessary. For PCDDs and PCDFs, requested detection
limits were very low, but were met in several cases. Of particular interest is
the demonstrated detection of PCDDs and PCDFs in incinerator exhaust in the
XAD-2 sorbent portion of the Modified Method 5 train, where a significant
portion of PCDDs and PCDFs was trapped.
3. Discussion of Results
The concentrations of PCDDs and PCDFs entering and discharged from the
Building 703 incinerator on the three sampling days, are presented in detail in
Appendix D, Tables D-64 through D-66; Tables D-67 through D-69 of that appendix
show similar data for TCDD isomers. Detailed summaries of incoming and outgoing
loadings of PCDDs and PCDFs, and TCDD isomers, are presented in Appendix D,
Tables D-70 through D-75.
It must be remembered in interpreting these data that a major waste stream
introduced to the incinerator, the loose and containerized solid wastes, could
not be representatively sampled in this study. While no samples of Tittabawassee
River water were taken (this being a component of some waters taken in and
circulated through air pollution control devices), concentrations of PCDDs and
PCDFs were expected to be either not present or not significant in this stream.
Samples obtained by EPA as part of a 1981 water sampling study9 support this
conclusion. At that time, 2378-TCDD and other dioxin homologues were not found
in the Tittabawassee River water intake to the Dow Chemical plant at detection
levels in the parts per quadrillion range.
Total suspended solids (TSS) concentrations used to calculate discharged
PCDD and PCDF loadings in the solid portions of the wastewater streams were
taken from data developed by the analytical laboratory during analysis of
PCDDs and PCDFs. These data are stated below, and compared with data for those
streams gathered on four separate days in 1984 by Dow Chemical20, and during a
sampling program conducted on August 28-29, 1984, by the USEPA Region V Eastern
District Office:
47
-------
TABLE V-24
COMPARISON OF ACTUAL AND DESIRED DETECTION LIMITS
DOM CHEMICAL COMPANY BUILDING 703 INCINERATOR EMISSIONS STUDY
Type of Sample
Precombustion Air
Liquid Wastes
Low-BTU Liquid Wastes
Incinerator Exhaust
Incinerator Ash
Aqueous Influents
and Effluents
Volatile Compounds
Detection Limit
Desired Actual
1 ppb 0.3-0.8 ppb
1 ppb 1 ppm
1 ppb 3 ppt
1 ppb 0.25-
0.50 ppb
...
1 ppb 5 ppb
Semi-Volatile Compounds
Detection Limit
Desired Actual
5 ppb 0.05 ppb
5 ppb 1-10 ppm
5 ppb 6 ppt
5 ppb 1-2 ppb
5 ppb 0.5 ppb
5 ppb 10 ppb
Pestlcldes/PCB
Detection Limit
Desired Actual
5 ppb 100 ppb
...
...
...
...
2378-TCDD
2378-TCOF
Total TCDO
Total TCOF
C15-C18 CDD
C15-C18 CDF
TCDO/TCDF
OCDU/OCDF
TCUD/TCDF
OCDD/OCDF
Impingers
XAD-2 sorbent
TCOO/TCDF
Cl5-C)fj PCDD/PCDF
Water
Solids
PCDD/PCDF
Detection Limit
Desired Actual
2 ny 4.7-94 ny
2 ng 3.3-242 ng
2 ng 3-433 ng
2 ng 2.4-9.3 ng
6 ny 3.4-1038 ny
6 ng 2.8-250 ny
30 ppq 0.25-10.6 ppt
90 ppq 0.77-40.6 ppt
30 ppq 14-714 ppq
90 ppq 230-7940 ppq
30-90 ppq "5-100 ppt
2-6 ny 0.52-126 ny
5 ppt 0.5-1.9 ppt
15 ppt ~0. 3-2.0 ppt
30-90 ppq ->20-1600 ppq
5-15 ppt ~60-6000 ppt
00
-------
TOTAL SUSPENDED SOLIDS (mg/L)
EPA Incinerator Study Dow Chemical EPA
Water Stream 8/28/84 8/30/84 9/5/84 (1984) 8/28-29/84
Quench Tower 71 111 127 106- 488 840
Venturi/Demister 77 132 169 72-1144 276
ESP -- 16 240 42- 444 34
Ash Pit 3 132 156 46- 393 82
These data illustrate the variability of TSS concentrations in the wastewater
streams. Effluent loadings of PCDDs and PCDFs in incinerator ash were calculated
based upon a density of 0.66 ton per cubic yard, as supplied by Dow Chemical 20,
and a disposal rate, as described previously, of 15 to 20 cubic yards per day.
Loadings of discharged PCDDs and PCDFs stated in the tables correspond to
the range of 15 to 20 cubic yards of incinerator ash disposed daily (see
Section V.A. of this report).
Three of the loadings tables (Appendix D, Tables D-70 through D-72) are
averaged over the three days of sampling and summarized in Figure V-3 through V-6
for total TCDD, OCDD, TCDF, and OCDF. In general, the data presented in
these figures indicate loadings in streams discharged from the Building 703
incinerator were comparable to or higher than in those fed to it. There appears
to be a strong tendency for the higher chlorinated homologues (penta- and
higher) to reside in the solid discharges, such as the effluent water solids
portions and incinerator ash.
An objective of this study was to relate air, water, and solids emissions
of PCDDs and PCDFs and other compounds from the Building 703 incinerator to the
operational characteristics and waste materials consumed in the facility. As
the operational characteristics (incinerator temperatures, air pollution control
device water flows, exhaust gas oxygen content, etc.) appeared similar over the
three sampling days, with the exception of an electrostatic precipitator arcing
phenomenon described in Section IV.B.7 of Appendix A, it is thought the
differences in PCDD and PCDF emissions appearing in Tables V-16, V-19, and V-20
through V-22 may have been attributable to waste content.
In exhaust gas, in general, the highest concentrations of penta- and
hexa-CDD and CDF were found on the first sampling day, and of hepta- and octa-
CDD and CDF on the second day. Similar concentrations of TCDO and TCDF were
detected on the first and second days, with the lower concentration of TCDD and
similar concentration of TCDF on the third day. In effluent wastewaters,
highest concentrations of most homologues appeared on the second day.
Incinerated loose and containerized solid wastes were not defined suffi-
ciently to discern any correlations in this area, and the liquid waste feed
from nozzle "BA" was similar on all three days. It was established in the
analytical results that the relative concentrations of most compounds in low-BTU
liquid waste were lower than in any of the concentrated liquid wastes. While
extensive data on incinerator operating temperatures, pressures, air pollution
control device water, and flow rates were obtained (see Appendix A, Table A-3),
49
-------
FIGURE V-3
TCDD LOADINGS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
tour-
en
O
AM HT M4TVA
SOU ft
AMTB4.
Ji
si
NOTE -
S»«pfc
Loadings stated in grams per year,
and calculated as averages of
days
TOTAL LOADINGS OF TCDD
In
Out
2 IS
87.3
-------
e
1
r
.L3T/W
QO
Cvl
in
ro
s
0£
UJ
I
>
LU
o
o
O —I
>ex:
g
o
<:
s
i-
•
9) CO
vt oicvj
i 2^
Iw W CD
J. 0>—'
O) ^
)
*p" (/> Cf> ~S 5
TJ W ? ^
(O -O i. "O * ^
O C .C C J •
_J IB -«J (O J- 5»
i .9 £
-------
FIGURE v-5
TCDF LOADINGS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
M
fc *
£
!!
NOTE - Loadings stated in grams per year,
and calculated as averages of
three sampling days (8/28, 8/30,
and 9/5/84).
TOTAL LOADINGS OF TCDF
In Out
1 872
238
-------
FIGURE V-6
OCDF LOADINGS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
*•»** AMTiet
II
NOTE -
Loadings stated in grams per year,
and calculated as averages of
8/3°'
of
TOTAL LOADINGS OF OCDF
In Out
45.6
72
-------
the ranges of these data frequently overlapped during the three sampling periods,
and no consistent relationship appeared between any of these characteristics
and the PCDD and PCDF concentrations appearing in exhaust air or discharged
wastewaters or solids.
The waste feeds from nozzles "BB" and "C" varied widely over the three
days, and there was no discernible characteristic in any waste which appeared
to have direct bearing on the exhaust gas and wastewater PCDD and PCDF concen-
trations in Tables V-16 and V-20 through V-22. Referring to data appearing in
Tables D-70 through D-72 in Appendix D, however, higher loadings of PCDDs and
PCDFs in liquid wastes appear to translate into higher loadings in discharged
streams. In particular, on the third day, loadings of discharged PCDDs and
PCDFs were markedly lower, corresponding with lower loadings of PCDDs and PCDFs
(and semi-volatile compounds and pesticides; see Tables V-8 and V-9) in liquid
wastes. As indicated above, incinerator operational characteristics were
similar on all three sampling days. For incinerator ash, there is no clear
relation (see Table V-19), as considerably higher concentrations of all PCDD and
PCDF homologues were found on the first day.
Figures V-3 to V-6 present a summary of annualized inputs and outputs of
TCDD, OCDD, TCDF, and OCDF for the Building 703 incinerator. Figures D-l through
D-10 in Appendix D show these loadings for all PCDD and PCDF homologue groups.
These estimates were calculated by averaging the mass inputs and outputs
determined from the three test dates and converting the averages to annual
discharges. Because not all input streams could be sampled (e.g., containerized
waste, and loose refuse), the mass estimates are rough approximations. Nonethe-
less, the data may provide some interesting insights into the fate of PCDDs and
PCDFs in the incinerator.
Figure V-7 compares the mass inputs and mass outputs. Negative values
imply destruction of PCDOs and PCDFs; positive values imply formation in the
incinerator. Values close to 0% change imply mass transfer from input streams
to output streams. Those data suggest only limited destruction of TCDDs,
somewhat higher destruction of PeCDDs (66%), and transfer of HxCDDs and OCDD
from input streams to output streams. For PCDFs, the data suggest destruction
of TCDFs (86%) and formation of HxCDFs and OCDF, and possibly PeCDFs and HpCDFs.
However, a significant portion of some PCDD and PCDF homologue groups discharged
from the incinerator appeared to have entered the incinerator system via the
air pollution control device service water supplied from the Dow Chemical
wastewater treatment facility. These PCDDs and PCDFs would not likely have been
destroyed or altered in the once-through water systems serving the quench tower,
venturi-demister, and ESP, or transferred to the incinerator exhaust gas stream.
Within the bounds of this study, the extent to which PCDDs and PCDFs present in
service water could have been destroyed, transferred to other streams, or
increased with their passage through the incinerator system could not be
evaluated. However, it is acknowledged that a portion of the PCDDs and PCDFs
entering the incinerator air pollution devices may have returned largely
unaltered to the Dow Chemical wastewater treatment system.
54
-------
+200%-i
FIGURE V-7
DOW Chemical Company - Midland Plant
Building 703 Incinerator
Comparison of PCDD and PCDF Inputs and Outputs
+187%
en
en
-100%-^
-87V.
Note. (1) Defined as percent change from estimated mass inputs to estimated mass outputs.
Negative values imply destruction of PCOOs and PCOFs: positive values imply formation.
Values near zero imnlv mass transfer of PCODs and PCDFs from input streams to output streams.
-------
Figure V-8 shows the relative distribution of PCDO and PCDF homo!ogues in
air, water, and ash outputs from the incinerator. In all cases, most PCDDs and
PCOFs were discharged in wastewaters; as indicated above, a significant loading
of many PCDO and PCDF homologue groups entered the incinerator system via
inlet water supplied to the air pollution control devices. Previous data
tables appearing in this report show most of the PCDDs and PCDFs in wastewaters
were found in filterable solids. For each homologue group, if the loadings
found in wastewaters (primarily residing in filterable solids) are combined
with those in discharged ash, it may be concluded that most, in terms of mass,
are discharged along with solid effluents. Lower chlorinated homologues tend
to appear in greater proportion in incinerator air exhausts; however, in this
study, no more than 18% of any homologue group appeared in incinerator exhaust
on a total loading basis.
56
-------
FIGURE V-8
DOW Chemical Company - Midland Plant
Building 703 Incinerator
Distribution of PCDD's and PCDF's Among Incinerator Ash, Air,
And Water Outputs
PCDO's
PCDF's
100%-
75% -
en
c
u>
o
k_
a>
O_
V)
t/>
CO
50%-
25%-
TCDD
| ASH 2%
f AIR 17%
5 WATER 81%
PeCDD
0%
9%
91%
HxCOD
19%
2%
79%
AIR,
"W^iMv^-^."
HpCDD
15%
0.3%
85%
•;H
OCDD
16%
0%
B4%
TCDF
6%
17%
77%
PeCDF
1%
18%
81%
HxCDF
5%
6%
89%
AIR.
AIR,
HpCDF OCDF
3% 6%
0.1% 0.1%
97% 94%
Note: Ash-lncmerator Ash Output
Air^lncmerator Exhaust Output
Water=Ash Pit. Quench Tower, Venturi Scrubber. Oemister and Electrostatic Precipitatar Water Outputs
-------
VI. AMBIENT AIR SAMPLING STUDY IN VICINITY OF DOW CHEMICAL COMPANY MIDLAND PLANT
The Dioxin Strategy referenced in Section I of this report focused on seven
types, or tiers, of locations and sources, ordered by decreasing potential for
2378-TCDD contamination. Combustion sources were grouped into Tier 4, for
which sampling and analysis plans were formulated by EPA and published in
February 1985 in a comprehensive project plan.4 That plan called for limited
ambient air monitoring, only of precombustion air drawn into the combustion
source. The ambient air sampling study in the vicinity of the Dow Chemical
Company Midland Plant encompassed four sites at which monitors were operated to
collect specific target compounds; the scope of the study thus went beyond that
specified in the Tier 4 project plan. This was the only study conducted under
Tier 4 program guidance at which extensive ambient air monitoring was done.
The sites were constructed and operated by a contractor, GCA/Technology
Division, and arranged such that at least one of three sites would frequently
be downwind of the Dow Chemical facility under typical summer wind conditions
in the study area. Two of the downwind monitoring sites were selected as close
as possible to the fenceline of the Dow Chemical plant. The third downwind
site was placed in a residential and recreation area to assess compound concen-
trations to which the local population may be exposed. The fourth site was
selected to be upwind of Dow Chemical under these conditions and would thus
indicate background concentrations of the above compounds. Wind data were
obtained at two sites near the monitoring network. Additional weather data
were taken as needed from facilities maintained locally by Dow Chemical
and from public sources operated by the National Oceanic and Atmospheric
Administration (NOAA).
Monitoring was conducted between September 7 and 27, 1984, and included
18 days of sampling. Analyses of various types of samples were keyed to wind
directions under which appropriate upwind-downwind relationships were experi-
enced between monitoring stations. The site descriptions below include
distances and directions with respect to the Building 703 liquid/solid waste
incinerator as well as references to the Dow plant fenceline as it existed
at the time of the study. While the primary focus of this study was the
incinerator, which was in operation throughout the study period, the results
are also indicative of numerous point source and fugitive emissions from the
Dow Chemical plant.
The sampling network was designed to assess air quality impacts of the Dow
Chemical plant, and was not intended to evaluate or determine the exact location
of maximum effect. Also, the purpose of the network was to monitor the effects
of the entire Midland Plant, rather than the Building 703 incinerator plume in
particular. The frequency of plume impaction or fumigation at the monitoring
sites was not evaluated, and the possible effects of phenomena such as downwash
were not considered. However, two downwind monitoring sites were placed near
the plant fenceline, where dispersion or dilution of plant emissions was likely
to be lowest.
58
-------
No dispersion modeling work was done prior to establishing the network, and
the monitoring sites were, to a large extent, selected based upon the
practicality of locating them on existing structures where physical obstructions
to air flow were absent and adequate deliverable electrical power was available.
These limitations, as well as the short duration of the ambient air study,
should be borne in mind as the study results are evaluated.
Several months after the ambient air study was completed, ground-level
exposure to PCDOs and PCDFs emitted from the stack of the Building 703
incinerator was estimated using the Human Exposure Model developed by USEPA.
This model employed meteorological and population distribution data to determine
the location of maximum impact to the surrounding population of a single point
source. This analysis revealed the point of maximum plume impact to be 1 km
northeast to east-northeast, downwind of the facility, close to sites 2 and 4
described below. A full discussion of this analysis, authored by David Hc
Cleverly of the Pollutant Assessment Branch, Strategies and Air Standards
Division, U.S. Environmental Protection Agency, Research Triangle Park, North
Carolina, appears in Appendix J.
A. Monitoring Network Description
Figure VI-1 shows the locations of each of the monitoring stations described
below.
1. Site 1
As historical data from the Midland area indicated predominant summer winds
to be from the south and southwest, this monitoring site was intended to be the
upwind reference for the three stations located generally downwind the Dow
facility. A two-meter-high equipment scaffold was placed on a low hill at the
west end of Dow property, overlooking a series of Dow brine and wastewater
treatment lagoons. The intersection of Ashby and Poseyville Roads was approxi-
mately 100 meters to the southwest; the Dow Chemical incinerator was located
about 1.1 miles from the site at a heading of about 80°. Looking from the
site, the Dow facility was visible in a sector extending between 0° and 105°;
thus, winds blowing from any direction between 110° and 360° were considered
not to have contacted any portion of the Dow Midland Plant prior to being
sampled.
Site 1 included monitoring equipment for the following distinct groups of
compounds:
PCDDs and PCDFs
Chlorobenzenes (principally Cl2 through Cls)
Semi-volatile and volatile compounds (VOC)
Formaldehyde
Detailed descriptions of each of the above samplers appear later in this report.
In addition to the above, site 1 was equipped with a wind speed and direction
monitor; the sensors were placed at a height of 10 meters above ground. Figure
VI-2 includes a site sketch and information concerning the inlet heights of the
four samplers shown above.
59
-------
Park did* Scb
^ -SLS ITE 7
,
-------
o
IT
Id
(O
O
a
ASHBY RD.
uj x
z
UJ
o
z
UJ
o
Q x
•77 mcttrt
BLOG
ft,
79 mtttrs
i \
DOW CHEMICAL CO.
BRINE POND
W
-*—X-
•X—X—
1. Location - atop scaffolding adjacent to Dow Building No. 1071.
2. Nearest intersection - Poseyville and Ashby Roads, 110 meters to SW.
3. Pollutants monitored at this site - PCDD/PCDF, chlorobenzenes, VOCs, and
formaldehyde.
4. Additional parameters monitored at this site - wind direction and wind
speed.
5. Hi-Vol inlet height - 3.1 meters (PCDD/PCDF, chlorobenzenes).
6. CMS tube inlet height - 3.4 meters (VOCs).
7. Impinger inlet height - 2.6 meters (formaldehyde).
8. Meteorological equipment height - 10 meters (wind speed, wind direction).
9. Obstructions to samplers - none.
10. Orientation to Dow Chemical facility - Dow occupies the sector NE of the
site, 0° N to 100° SE.
11. UTM coordinates - Zone 16; 4,829.9 km N; 722.1 km E.
12. Latitude/longitude - 43°35'25" N, 84°14'48" W.
Figure VI-2
Location of Ambient Air Monitoring Site 1
61
-------
2. Site 2
This site was near the northern fence!ine of the Dow facility, such that
winds between 95° and 285° would pass through the plant before reaching it.
The incinerator was about 0.8 mile from the site, at a bearing of 195°. A
major east-west road, Bay City Road, passed about 16.5 meters to the north of
the site.
Equipment was placed on the flat rooftop of Dow Building 911, a structure
approximately 3.5 meters in height, to monitor the full range of compound groups
as described for site 1. Sampler inlet heights are shown in Figure VI-3.
In general, there were no significant obstructions to free air flow to the
site; Dow Building 566, located about 45 meters southwest, was judged to be
sufficiently distant to preclude significant wind eddying effects.
3. Site 3
To assess concentrations of target compounds in a population center and
recreation area, site 3 was assembled atop the Midland Community Center, a flat-
roofed multistory building about 0.9 mile north of the Dow Chemical fence!ine
and 1.8 miles from the plant incinerator. The incinerator was at a heading of
170° from site 3; however, winds between 135° and 225° were considered upwind
with respect to the entire Dow facility. The site was configured as shown in
Figure VI-4. An airflow obstruction cited in the figure was judged to be minor;
in any event, this low wall was northwest of the monitoring equipment, not in the
direction of emissions from the Dow facility.
4. Site 4
A second site at the fenceline of the Dow plant was established to receive
impacts from the facility under ambient wind conditions between 180° and 285°.
The Building 703 incinerator was located 1.1 miles from the monitoring station,
at a heading of 230°. Monitoring equipment was placed atop a mobile laboratory
trailer parked in a lot located at the east boundary of the Dow Chemical
facility. Sampler inlet heights are shown in Figure VI-5. The site was selected
to deploy field duplicate and field blank samples because of the ease of
servicing this site with equipment stored in the trailer. Periodic weather
data (temperature, relative humidity, and barometric pressure) were obtained
manually at this site.
5. Other Sites
A fifth site, designated as site 7 (Figure VI-6), consisted of a monitoring
trailer operated continuously by the Michigan Department of Natural Resources,
and included wind speed and direction measurement equipment. The Dow Chemical
north fenceline was about 0.3 mile south of this location. Wind data gathered at
the site were considered equivalent to those at sites 2 and 4 and were used as
a check on similar data at site 1.
Sites 5 and 6 were planned as meteorological stations, but were not used and
are not shown in Figure VI-1.
62
-------
I
I
1
1
1
1
^p*
1
1
1
1
BAY CITY Rn
DMI ^ 1 l • r\ \j.
>
<
5
UJ
5
o
MM \f w V
fe "w"
_J
<
CD
1
BLOG. '6.5 mttirt
# 911 1
-1
X
~T
11.5 m«ttr»
i DOW FENCELINE
DOW CHEMICAL FACILITY
1. Location - atop Dow Building No. 911.
2. Nearest intersection - Bay City Road and Ball Street, adjacent to site.
3. Pollutants monitored at this site - PCDD/PCDF, chlorobenzenes, VOCs, and
formaldehyde.
4. Additional parameters monitored at this site —none.
5. Hi-Vol inlet height - 4.9 meters (PCDD/PCDF, chlorobenzenes).
6. CMS tube inlet height - 4.9 meters (VOCs).
1
7. Impinger inlet height - 4.1 meters (formaldehyde).
8. Obstructions to samplers - possible obstruction is building approximately
45 meters SW of sample.
•9. Orientation to Dow Chemical facility - Dow occupies the sector from
95° SE to 285° NW.
10. UTM coordinates - Zone 16; 4,831.4 km N; 724.2 km E.
_~^B
11. Latitude/longitude - 43°36'17"
N, 84°13'14" W.
Figure VI-3
Location of Ambient Air Monitoring Site 2
63
-------
I
I
i
*
*
*
m
MIDLAND
COMMUNITY
CENTER
X X
UJ
UJ
e
-------
I
I
I
I
I
I
I
I
I
I
AUSTIN ROAD
BAY CITY ROAD
I
GCA
MOBILE
LABORATORY
PARKING
LOT
'—X—X—X X X—X—
1. Location - located atop GCA Mobile Laboratory in NE parking lot.
2. Nearest intersection - Bay City Road and S. Saginaw Road.
3. Pollutants monitored at this site - PCDD/PCDF, chlorobenzenes, VOCs,
and formaldehyde.
4. Additional parameters monitored at this site - temperature, barometric
pressure, and relative humidity.
5. Hi-Vol inlet height - 5.1 meters (PCDD/PCDF and chlorobenzenes).
6. CMS tube inlet height - 5.4 meters (VOCs).
7. Impinger inlet height - 4.6 meters (formaldehyde).
8. Obstructions to samplers - none.
9. Orientation to Dow Chemical facility - Dow occupies the sector 180° S to
285° NW.
10. UTM coordinates - Zone 16; 4,831.2 km N; 725.2 km E.
11. Latitude/longitude - 43°36'09" N, 84°12'28" W.
Figure VI-5
Location of Ambient Air Monitoring Site 4
65
-------
•\ 1 1 1 1
UJ
UJ
V)
o
z
i
to
JAMES SAVAGE ROAD
* D
PARKING
LOT
CONSUMERS
POWER BLDG.
r- STATE MET. TRAILER
•SITE 7
PENN CENTRAL R.R.
-i—i—i—i—i—i—i—»—i—H
BARTH STREET
1. Location - Michigan DNR trailer in parking lot of Consumecs Power on
Washington Street.
2. Nearest intersection - James Savage Road and Washington Street.
3. Parameters at this site - wind direction and wind speed.
4. UTM coordinates - Zone 16; 4,832.0 km N; 724.6 km E.
Figure VI-6
Location of Ambient Air Monitoring Site 7 (Wind Monitoring Site)
66
-------
B. Monitor Descriptions and Sampling Methods
All four of the monitoring sites included equipment to monitor four groups
of compounds: PCDDs and PCOFs; higher-substituted chlorobenzenes (Cl2 through
015); a general range of semi-volatile and volatile compounds; and formaldehyde.
The samplers specific to each group are described in detail in Appendix E to this
report.
C. Conduct of Study
1. Sampling Procedures
Field methods for the four types of 24-hour samplers employed in this study
(modified high-volume sampler for PCDDs and PCDFs, and chlorobenzenes and other
semi-volatile compounds; carbon molecular sieve sampler for volatile compounds;
and impinger-type sampler for formaldehyde) were taken from the literature and
modified as necessary according to meteorological conditions encountered, and
the limitations of the selected analytical laboratories. While it would have
been preferable to operate all four sampler types at each site on every day,
practical and resource limitations led to decisions under which some samplers
were run only during periods when meteorology was favorable (good upwind-
downwind relationships existed), or a limited number of exposed samples were
designated for analysis. These decisions are described in the detailed
discussion of sampling methods appearing in Appendix E, and a summary of samples
obtained is presented in Table VI-1. Preparation and assembly of sampler
materials were for the most part coordinated in the GCA sampling trailer also
used as monitoring site 4.
Detailed descriptions of sampling procedures for all of the ambient air
monitors used in this study may be found in Appendix E of this report.
2. Custody, Sample Handling, and Shipping
Samples were obtained and identified using chain-of-custody procedures
described in the Quality Assurance Project Plan developed for the study,I5
and EPA custody forms and GCA data record forms shown in Appendix D of
Reference 16 of this report. In short, standard EPA chain-of-custody protocols
were followed in the conduct of work.
Cleaned and prepared sampling media, with the exception of ONPH reagent for
formaldehyde sampling, were held in a secured trailer (site 4) until use. As
indicated in Appendix E, DNPH reagent was prepared immediately before use and
shipped to the study area for placement in sampling equipment. Exposed sampling
media were kept in secured (locked or sealed) chests, separated from unexposed
media, in the site 4 monitoring trailer before shipping. Subject to appropriate
holding times, samples were shipped under EPA custody procedures and documents
specific to the EPA Special Analytical Services program, to the contract
laboratories selected to perform analyses for various compound classes. For
volatile and semi-volatile compounds, and formaldehyde, analytical services
were provided by United States Testing Company, Hoboken, New Jersey. For PCDD
and PCDF, analyses were conducted by Midwest Research Institute, Kansas City,
Missouri.
67
-------
TABLE VI-1
MIDLAND, MICHIGAN AMBIENT AIR SAMPLING STUDY
SUMMARY OF SAMPLE TYPES AND SAMPLING TIMES
Run Start Chlorobenzenes
Date PCDD/PCDF Semi-Volatlies Volatlies Formaldehyde
9/7/84 X XX
9/8 X X XX
9/9
9/10
9/11 X
9/12 XX XX
9/13 X
9/14 X
9/15 X
9/16 X
9/17 X X
9/18 X XX
9/19 X XX
9/20 X
9/21 X
9/22 XXX
9/23 X X
9/24 X X
9/25 X
9/26 X
NOTE: X denotes sample taken and submitted for analysis
68
-------
D. Analytical Procedures and Quality Assurance
Analytical methods specified for this study appear in References 17 (PCDD/
PCDF) and 18 (semi-volatile compounds, volatile compounds, and formaldehyde),
and are summarized briefly below:
PCDD/PCDF and
Semi-Volatile
Compounds
Volatile Compounds -
Extraction followed by solvent partitioning and liquid
chromatography, analysis by gas chromatography/mass
spectrometry.
Collection on carbon molecular sieves
desorption and analysis by GC/MS.
then thermal
Formaldehyde
- Reverse phase high performance liquid chromatography.
Samples collected during this study were identified, packed (cooled as
appropriate), and shipped via commercial services for next-day arrival at
contract laboratories. Selection of contract laboratories referenced in Section
VI.C was coordinated by the USEPA Region V Central Regional Laboratory.
Analytical data returned from the contract laboratories were reviewed for
consistency with contract requirements by the USEPA Sample Management Office
(Viar and Company, Alexandria, Virginia), and for adherence to quality assurance
criteria contained in the Quality Assurance Project Plan for this study (see
Reference 15) by the USEPA Region V Central Regional Laboratory. The results
of these reviews are referenced in the discussion of general analytical findings
which follows as Section VI.E of this report.
E. Results of Study and Discussion
1. PCDD/PCDF
Consistent with the evaluation of incinerator exhausts, a range of recovery
of analytical surrogate or internal standard compounds of 50% to 150% was
considered acceptable with respect to the suitability of PCDD and PCDF data.
Recoveries of internal standards for PCDDs and PCDFs ranged between 22% and 220%,
with no reportable recovery in a small number of cases.
Four internal standards were used: 13C12 2378-TCDD, 13C12 2378-TCOF, 37C14
1,2,3,4,6,7,8-HpCDD, and Cj? OCDD. Overall performance with respect to
recoveries within the acceptable range of 50% to 150% was as follows for the
45 samples included in these analyses:
13
13
37
13
C12-2378-TCDD
C12-2378-TCDF
Cl4-1,2,3,4,6,7,8-HpCOD
C12-OCDD
Percent of Samples
Within Acceptable Range
82% (37/45)
89% (40/45)
71% (32/45)
80% (36/45).
69
-------
The standard C^p 2378-TCDO is of primary importance as the accuracy determinant
for tetra- through hexa-CDD; those homologue groups are of greatest priority in
assessing potential risks to health. In the above table, satisfactory
recoveries were experienced in 82% of the samples.
Recoveries of the other three standards serve to measure analytical
accuracies for PCDD and PCDF homologues which are of lesser concern with respect
to health risk assessment. In summary, considering the low levels of detection
specified for this study (parts per quadrillion in air), the data presented
below are reasonably complete in terms of accuracy.
Complete results of sampling for PCDD and PCDF for the three selected
sampling days are presented in Table VI-2; these were derived from the raw data
shown in Appendix G, Table G-l, which are as received from the analytical
laboratory. Two of the glass filter (polyurethane foam plug sample pairs (from
sites 2 and 3 on September 8 and 9, 1984) analyzed by Midwest Research Institute
(MRI) were reanalyzed for verification by the Environmental Monitoring and
Support Laboratory (EMSL) of EPA in Research Triangle Park, North Carolina.
The following findings were stated in the EMSL reanalysis and review report:
Standards values were in reasonable agreement,
Quantification of PCDD and PCDF appeared generally accurate,
Most of the TCDF detected in the samples were 1238, 1467, 2468, and
1236 isomers, which were indicated by the EMSL as having been
detected previously in incineration process samples from other
studies,
Similar isomer groups were found in samples of soils which were
analyzed as part of a previous EPA Region V sampling program
conducted in Midland, Michigan, in 1984,
Between 20 and 50% of the concentration of PeCDFs reported in the
samples was attributable to chlorinated diphenylethers (CDEs) which
el ute simultaneously from the capillary column used in analysis
(co-el ution of other CDEs with other PCDFs was not investigated, and
The analytical results should be considered minimum values as
the air sampling method employed in this study was not formally
validated as of the time the study occurred.
Note in Table VI-2 that 2378-TCDD and 2378-TCDF were not detected by MRI in
any sample. In the EMSL reanalyses, however, both isomers were found, as shown
in the raw data in Appendix H. In two of three cases in which the EMSL reported
values where MRI did not, the levels of 2378-TCDO and 2378-TCDF detected by the
EMSL were above the detection limits stated by MRI. These data are presented
in Table VI-3. The single finding of 2378-TCDD, in the sample from site 2 on
9/8-9/84, would result in an ambient air concentration of about 4.8 pg/m3 (ppq).
In Table VI-4, the comparative results of analyses for TCDD and TCDF by MRI
and the EMSL are presented in terms of concentration in air. These data show
generally close agreement. The full text of the EMSL's description of reanalysis
of these samples is presented in Appendix H.
70
-------
TABLE VI-2
RESULTS OF AMBIENT AIR PCOD/PCOF SAMPLING
IN VICINITY OF DOW CHEMICAL COMPANY, MIDLAND, MICHIGAN, SEPTEMBER 1984
(All data stated In picograms per cubic meter.)
Sample Identification
9/8-9/84
Site 1
Average wind Site 2
199°, 6 mph
Site 3
Site 4*
Site 4 duplicate
Precision (RPD)
9/12-13/84
Site 1
Average wind Site 2
191°, 6 mph
Site 3
Site 4
Site 4 duplicate
Precision (RPD)
9/22-23/84
Site 1
Average wind Site 2
212°, 5 mph
Site 3
Site 4
Site 4 duplicate*
Precision (RPD)
2378-
TCDD
NDl
ND(0.85)
N0(0.22)
ND(0.09)
ND(0.15)
—
N0(0.19)
ND(0.24)
ND(1.07)
ND(0.15)
ND(0.17)
—
N0(0.06)
ND(0.05)
ND(0.08)
N0(1.63)
*ND(0.59)
--
•Denotes
Total
TCDD
0.99
44.80
2.40
0.86
0.48
56.7
0.13
NO?
3.27
0.38
NO?
—
NO2
22.35
0.59
74.07
24.28
101.3
analysis o
Total
PeCDD
NDl
9.28
N0(0.46)
ND(0.09)
NDJ0.31)
—
N0(0.38)
ND(0.43)
ND(0.80)
ND(0.15)
NDJ0.64)
—
ND(0.24)
ND(0.32)
N0(0.48)
1.37
ND(1.17)
—
f polyuret
Total
HxCDD
0.95
N0(0.84)
N0(0.32)
0.86
NO(l.ll)
—
ND(1.02)
ND(2.55)
ND(1.19)
2.93
ND(1.39)
—
ND(0.18)
0.55
ND(0.39)
0.28
0.96
109.7
lane foam
Total
HpCDD
0.81
2.08
2.07
1.00
1.54
42.5
0.69
ND{3.51)
0.65
1.48
0.48
102.0
ND(0.69)
2.69
0.55
1.14
1.41
21.2
>lug was n
OCDD
1.15
7.70
7.92
2.69
4.10
41.5
1.66
ND(6.71)
5.10
6.75
5.60
18.6
0.30
14.29
2.73
4.01
4.37
8.6
3t provldec
2378-
TCDF
NO1
ND(0.84)
ND(0.34)
ND(0.12)
ND(0.17)
--
ND(0.18)
NDJ0.24)
ND(0.24)
ND(0.20)
ND(0.17)
—
ND(O.ll)
NOJ0.99)
ND(0.12)
ND(1.63)
ND(1.41)
--
by analyt
Total
TCDF
0.86
249.80
14.72
1.53
2.70
55.3
14.52
14.53
44.95
13.88
11.21
21.2
o
NO'
155.69
2.14
375.37
122.70
101.5
ical labor
Total
PeCDF
ND1
29.80
4.44
1.16
1.41
19.5
ND(2.93)
ND(1.07)
2.22
1.06
3.01
95.8
N0(0.13)
7.45
ND(0.23)
36.73
15.42
81.7
atory.
Calculation of analytical precision should therefore be considered tentative.
"NO" symbol Indicates Isomer or homologue was not detected at method detection limit.
The higher of the two detection limits (for glass fiber filter or PUF plug) is stated.
lOetectlon limit not determined.
^Exposed sample concentration lower than that In field blank. Consider equivalent to
nondetectable.
Total
HxCDF
NDl
4.15
N0(0.37)
ND(0.65)
0.73
•""
ND(0.62)
ND(1.02)
ND(1.31)
ND(1.27)
ND(0.80)
_ —
ND(0.26)
4.52
ND(0.15)
3.00
4.37
37.2
Total
HpCOF
NO1
5.01
ND(0.79)
NOJ0.52)
ND(1.15)
""""
ND(2.16)
ND(1.92)
ND(1.24)
N0(0.90)
ND(5.43)
--
ND(0.83)
2.93
ND(0.80)
3.00
2.70
10.5
OCDF
ND
3.42
1.36
1.66
0.84
65.6
0.99
ND(3.35)
0.81
2.67
ND(3.40)
—
0.13
1.60
0.70
4.64
6.55
34.1
-------
TABLE VI-3
COMPARATIVE ANALYSES FOR TOTAL AND 2378 ISOMER OF TCDD AND TCDF
MIDWEST RESEARCH INSTITUTE AND EMSL-RTP, EPA
Sample Identification
Amount Detected (ng/sample)
MR I
Note: ( ) Detection limit expressed in nanograms.
EMSL
9/8-9/84
9/8-9/84
9/8-9/84
9/8-9/84
, Site 2 Filter 2378-TCDD
Total TCDD
2378-TCDF
Total TCOF
Site 2 PUF 2378-TCDD
Total TCDD
2378-TCDF
Total TCDF
Site 3 Filter 2378-TCDD
Total TCDD
2378-TCDF
Total TCDF
Site 3 PUF 2378-TCDD
Total TCDD
2378-TCDF
Total TCDF
ND (0.10)
3.7
ND (0.69)
36
ND (0.70)
33
ND (0.40)
180
ND (0.18)
1.6
ND (0.20)
7.5
ND (0.12)
1.7
ND (0.28)
3.9
0.4
9.0
0.2
28.0
ND
29.0
ND
131.0
ND
0.8
ND
2.2
ND
1.4
0.4
26.0
72
-------
TABLE VI-4
COMPARATIVE VALUES FOR 2378-TCDD, TOTAL TCDDs, 2378-TCDF, and TOTAL
MIDWEST RESEARCH INSTITUTE AND EMSL-RTP, EPA
EMSL-EPA
Filter
PUF
Total
MRI*
Total
9/8-9/84,
2378-TCDD Total TCDDs
0.49 11.00
ND 35.43
0.49 46.43
ND 44.80
Site 2
2378-TCDF
0.24
ND
0.24
ND
Total TCDFs
34.21
160.06
194.27
249.80
2378-TCDD
ND
ND
ND
ND
9/8-9/84
Total TCDDs
0.97
1.71
2.68
2.40
TCDFs
, Site 3
2378-TCDF
ND
0.49
0.49
ND
Total TCDFs
2.68
31.66
34.34
14.72
*Taken from Table VI-2. Data stated in pg/m3.
-------
Along with the above reanalysis, the data provided by MRI were reviewed by
the EPA Region V Central Regional Laboratory. Following are the principal
findings of that review, as they relate to the quality of these data:
The surrogate compound ^'Cl4-2378-TCDD was not added to any sample, as
required by the analytical specifications for this study. With this
lacking, MRI provided internal standard recovery data by quantitating
one internal standard against another. The recoveries of the surrogate
13C12-TCDF were considered as indication of bias for tetra- and penta-
CDD and CDF; an overall bias of -13% was found.
Based on recoveries of the surrogate 37Cl4-HpCDD, the bias for hexa-
through octa-CDO and CDF was calculated to be +11%. Both of these
biases were considered small with respect to the errors introduced
by taking the recovery of a particular homologue to represent that
of a different homologue.
Field blank samples were spiked to calculate recoveries and precision,
and five of the 42 analyses showed spike recoveries out of control.
However, precision criteria were met in the duplicate blanks.
Since all field blank samples were spiked by MRI, it was not possible to
estimate possible field contamination as planned in the analytical
protocol. However, in the spiked blanks, the levels detected were
close to the spiking levels, suggesting field contamination was not
significant.
While the analytical request called for a laboratory matrix spike for
every ten samples analyzed, this was not provided. This was judged to
be a minor shortfall, and available matrix spike data showed generally
satisfactory performance.
Resolution of 2378-TCDD from neighboring TCDDs ranged between 40 and
60%; the analytical request specified that samples were to have been
rerun if resolution was 25% or greater. As MRI did not detect 2378-TCDD
in any sample, but the EMSL did, this implies that some of that reported
by MRI as total TCDDs may in fact have been 2378-TCDD.
Response factors calculated by MRI for some calibration standards were
not substantiated by verifiable data. Most were provided, however, and
indicated satisfactory performance.
In summary, the Central Regional Laboratory review of the MRI data package
indicated the data were generally suitable for project use, as qualified above.
74
-------
Wind data for the duration of the ambient air sampling study are presented
in Table VI-5. As indicated previously, three of the periods having most
favorable upwind-downwind alignment of monitoring sites with respect to the Dow
Chemical facility were chosen for PCOD and PCOF sample analyses. Wind conditions
averaged over each of these three periods are stated in Table VI-2; Figure VI-1
may be used to relate these wind directions to the findings of PCDD and PCOF
shown in Table VI-2.
From these data, it is apparent that site 1 was upwind of the Dow Chemical
facility on all three days; correspondingly, the lowest concentrations of nearly
all PCDD and PCDF homologues were detected at this site. Higher concentrations
were consistently found at those sites downwind of the Dow facility. For the
first two sampling periods analyzed, these were sites 2 and 3, while on the
third sampling day, sites 2 and 4 were highest in most homologues.
On the first sampling day, highest concentrations were detected at the
north fence! ine of the Dow facility, with considerably less found at the
comparatively distant Midland Community Center site. Under very similar wind
conditions in the second sampling period, however, this pattern reversed, with
concentrations of most PCDD and PCDF homologues in the same range (1 to 10
pg/m3) on both days. With winds shifted 15 to 20 degrees toward the southwest
on the third sampling day, highest concentrations were found exclusively at the
two Dow Chemical fenceline sites. Precision between duplicate samples on all
three days was frequently within the target range of +_ 50% (relative percent
difference).
Overall, these data establish that point and fugitive emissions of PCDD
and PCDF from the Dow Chemical plant may be detected at downwind monitoring
locations. Downwind concentrations were consistently higher than those upwind
of Dow Chemical .
In Table VI-6, the concentration data in Table VI-2 are presented in terms
of the portions of the PCDD and PCDF homologues found in the glass fiber filter
and polyurethane foam plug of the samplers. These data suggest that the lower-
chlorinated homologues, chiefly the tetra- through penta-, tend to reside in the
polyurethane foam plug, while the hexa- through octa- homologues are principally
found on the first-stage glass fiber filter, where more particulate matter is
likely to be caught. These findings imply that
higher-chlorinated homologues of PCDD and PCDF may bind selectively
to particulate matter, while the tetra- and penta- homologues remain
in the gaseous state or bound to finer particul ates. These lower-
chlorinated homologues may not be trapped efficiently by the glass fiber
filter portion of the high-volume sampler, or may be air-stripped from
the filter catch by the action of air moving through the sampler; and
both components of the high-volume sampler should be used in series to
determine the concentration of the full range of PCDD and PCDF
homo!ogues.
75
-------
TABLE VI-5
WIND DATA - AMBIENT AIR SAMPLING PROGRAM
MIDLAND, MICHIGAN - SEPTEMBER 7-27, 1984
Run
29
191
309
331
296
257
212
235
250
334
12
212
197
195
284
293
Oirtction
Std.
deviation
12
14
91
40
32
25
62
38
9
30
44
41
134
15
42
25
25
31
Wind
Mean,
•oh
5.9
6.2
3.8
5.6
3.8
6.6
4.9
3.3
4.1
4.0
4.1
3.7
4.1
4.9
2.6
4.9
6.1
2.7
Sp««d
Std.
deviation
1.5
2.1
0.9
1.3
1.3
1.6
2.8
2.4
1.5
2.0
1.5
2.0
1.7
2.1
l.l
1.4
1.9
1.4
76
-------
TABLE VI-6
RESULTS OF AMBIENT AIR SAMPLING FOR PCDD/PCDF
IN VICINITY OF DOW CHEMICAL, MIDLAND, MICHIGAN, SEPTEMBER 1984
Stated 1n Terms of Concentration (pg/m3) on
Glass Fiber Filter/Polyurethane Foam (PUF) Plug
Date Site
9/8-9/84
Site 1
Average wind Site 2
199°, 6 mph
Site 3
Site 4
Site 4 duplicate
9-12-13/84
Site 1
Average wind Site 2
191°, 6 roph
Site 3
Site 4
Site 4 duplicate
9/22-23/84
Site.l
Average wind Site 2
212°, 5 mph
Site 3
Site 4
Site 4 duplicate
2378-
TCDD
ND/ND
ND/ND
NO/ NO
NO/ND
NO/ND
NO/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/M
Keys to
Total
TCDD
0.30/ 0.69
4.82/39.98
0.67/ 1.73
0.14/ 0.72
0.06/ 0.42
0.13/*
*r
*/ 3.27
0.38/*
*/*
*/*
0.49/21.86
*/ 0.59
10.28/63.79
24.28/M
Symbols
Total
PeCDO
ND/ND
1.95/7.33
ND/ND
ND/ND
NO/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/1.37
ND/ND
Total
HxCDD
0.95/ND
ND/ND
ND/ND
0.86/ND
ND/ND
ND/ND
ND/ND
ND/ND
NO/ 2. 93
ND/ND
ND/ND
0.55/NO
ND/ND
0.28/ND
0.96/ND
Total
HpCDD
0.81/NO
2.08/ND
2.07/ND
1.00/ND
1.54/ND
0.69/ND
NO/ND
0.65/ND
0.22/1.26
0.48/ND
NO/ NO
2.69/ND
0.55/ND
1.14/ND
1.41/NO
OCOO
1.15/*
6.23/1.47
7.31/0.61
2.69/ND
4.10/ND
1.66/ND
ND/ND
5.10/ND
2.67/4.08
5.60/ND
ND/0.30
7.57/6.72
2.73/ND
4.01/ND
4.37/NO
2378-
TCDF
ND/ND
ND/ND
ND/ND
ND/ND
ND/M
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
Total
TCDF
ND/0.86
59.87/219.93
9.98/ 4.74
1.53/M
1.18/ 1.52
7.13/ 7.39
3.51/ 11.02
7.06/ 37.89
2.80/ 11.08
2.55/ 8.66
2.22/ 0.22
65. 33/ 90.36
4.35/ 7.25
84.60/290.77
122. 70/*
Total
PeCDF
ND/ND
10.75/18.33
0.54/ 3.90
1.16/ND
NO/ 1.41
ND/ND
ND/ND
NO/ 2.22
0.74/ 0.32
1.69/ 1.32
ND/ND
2.69/ 4.76
ND/ND
7.90/28.83
15.42/NO
ND-Not found at detection limit (example detection limit ranges: 0.05-0.62 pg/m3 for
2378-TCDF, 0.03-1.62 pg/m3 for 2378-TCDD)
M-Data not provided by analytical laboratory.
*-Exposed sample concentration lower than that of field blank-consider equivalent to
nondetectable.
Total
HxCDF
ND/ND
2.81/1.34
ND/ND
ND/ND
0.73/ND
NO/ND
ND/ND
ND/ND
NO/ND
NO/ND
ND/ND
4.52/ND
ND/ND
3.00/ND
4.37/ND
Total
HpCDF
ND/ND
5.01/ND
ND/ND
ND/ND
ND/ND
NO/NO
NO/ND
ND/ND
ND/ND
ND/ND
NO/ND
2.93/ND
ND/ND
3.00/ND
2.70/ND
OCDF
ND/ND
3.42/ND
0.57/0.79
1.66/ND
0.84/ND
0.99/ND
ND/ND
0.81/ND
ND/2.67
ND/ND
ND/0.13
1.34/0.26
ND/0.70
4.64/ND
6.55/NO
-------
2. Semi-Volatile Compounds
Because of the large number of individual samples and compounds detected in
sampling for semi-volatile compounds, it was decided to limit the full review
of these data to those sampling periods in which consistently favorable relation-
ships existed between monitoring sites upwind and downwind of Dow Chemical.
Nine of the 18 sampling days were evaluated, with southerly to southwesterly
winds having been present in eight of those nine days. These data are presented
in Table VI-7.
Review of these data by the EPA Region V Central Regional Laboratory yielded
the following principal findings:
1. Limited sampling media blank samples were analyzed. A polyurethane
foam blank was found free of contamination. However, method blanks of
XAD-2 resin contained measurable phenol; biphenyl; 2,4-dichlorophenol ;
1,2,4-trichlorobenzene; tetrachlorobenzene, and 2-hydroxybenzaldehyde.
2. Field bias blanks frequently contained phenol, biphenyl, and diphenyl
ether. These were subtracted from the quantities detected in field
samples, as a correction.
3. Problems were observed with interferences or mass spectrum assignment
criteria in some analyses for phenol and biphenyl. These data are
labeled appropriately in Table VI-7.
4. Recoveries of acid and base-neutral surrogate compounds were generally
not within acceptable limits. According to current guidance available
concerning the interpretation of data affected in this way (see Section
V.O. of this report), there is no agreed method to judge acceptability
of compound-by-compound analytical data based on the recovery of
specific surrogates. The semi-volatile compound data presented herein
should be used in that context.
Nonetheless, positive identifications of many semi-volatile compounds were
achieved, and higher concentrations of several semi-volatile compounds were
found at sites downwind of Dow Chemical. For the data reviewed, precision,
compound-by-compound (sample and field duplicate sample from site 4) was within
target criteria for all detected compounds ( + 50% RPD) on four days and the
goal was nearly met on a fifth day. Significantly higher concentrations of
most compounds including
1,2,3-trichlorobenzene
1,2,4-trichlorobenzene
1,3,5-trichlorobenzene
1,2,3,4-tetrachlorobenzene
1,2,4,5-tetrachlorobenzene
phenol
2,4-dichlorophenol
2,4,6-trichlorophenol
biphenyl, and
diphenyl ether (1,1-oxybisbenzene)
78
-------
TABLE VI-7
HESULTS Of AMBIENT AID SAMPLING FOH SEMI-VOLATILE COMPOUNDS
IN VICINITY OF DOM CHEMICAL COMPANf, MIDLAND. MICHIGAN. SEPTEMBER 1984
(Concentration noVa*)
Sampling Period
9/7-8/84
9/8-9/84
9/12-13/84
Site
1
2
3
4
4FD
1
2
3
4
4FO
2
3
4
4FO
Merage
Mind Direction
and Speed
184*. 5.9 «ph
Precision
Detected In blank
199*. 6.2 niph
Precision
Detected In blank
191*. 5.6 «ph
Precision
Detected In blan
j
f,
t.
102
SO. 3
NO
14.8)
NO
ND
(23.0)
41.0
30.2
ND
(17.1)
(17.1)
ND
(17.0
(17.9
37.3
108
NO
(27.4
|
u
(VJ
699
402
26.6
29.2
ND
(23.0)
312
146
23.9
NO
117.1)
5.09*
250
258
855
HO
(27.4
j
U
"I
ND
21.2)
ND
16.8)
'NO
(14.8)
achloro-
S.
i »
296
184
16.2
achloro-
£ »
^
97.4
62.0
ND
(14.8)
1
Pentachl
NO
(21.2)
1S.1*
NO
(14.8)
Hexachlorobenzene
NO
(21.2)
ND
(16.8)
ND
(14.8)
"o
ND
(21.2)
1546
181
(SaMple not analyzed.)
ND
(16.2)
11.4*'
4.86'
ND
(16.2)
ND
(16.2)
492'
2-Chl oroplwnol
ND
(21.2)
ND
(16.8)
ND
(14.8)
ND
(16.2)
o
NO
(21.2)
ND
(16.8)
ND
(14.8)
ND
(34.1)
2.4-Olchloropbeiwl
1693
3S.2
ND
(14.8)
ND
(Site 4 sample not analyzed - precision not calculated.
NO
(23.0)
O**)
fl!%
(17.1)
HlBi
(17.1)
ND
(17.0)
1.79*
ND
(31.1)
(37.2)
TBT
(27.4)
NO
(23.0)
246
70.0
13.7*
ND
(17.1)
ND
(5.1)'
ND
(17.9)
115
409
ND
(27.4)
ND
(23.0)
67.3
49.4
ND
(17.1)
NO
(17.1)
ND
(17.0)
55.5
46.6
141
ND
(27.4)
ND
(23.0)
11. S*
ND
(15.9)
ND
(17.1)
ND
(17.1)
ND
(17.0)
NO
(17.9)
NO
(31.1)
14.9*
ND
(27.4)
NO
(23.0)
ND
(16.4)
ND
(15.9)
ND
(17.1)
ND
(17.1)
ND
(17.0)
NO
' NO '
(31.1)
ND
(37.2)
NO
(27.4)
*
NO
(115)
128
1000
389
I2!
.
84.9
NO
(17.9)
770
35.6
182.3
*
NO
(23.0)
4.92'
ND
(15.9)
ND
(17.1)
ND
(17.1)
ND
(17.0)
ND
(17.9)
NO
(31.1)
ND
(37.2)
ND
(27.4
NO
(23.0)
NO
(16.4)
ND
(15.9)
ND
(17.1)
ND
(17.1)
NO
(17.0)
ND
(17.9)
ND
(31.1)
NO
(37.2)
(27.4)
ND
(23.0)
ND
(16.4)
28.7'
(17.1)
ND
(17.1)
ND
(17.0)
4114
1398
2232
ND
(27.4)
u
"I
NO
(21.2)
ND
(16.8)
ND
(14.8)
ND
(16.2)
e
u
t/i
ND
(21.2)
41.9
ND
(14.8)
ND
(16.2)
NO
(23.0)
NO
(16.4)
ND
(15.9)
(17.1)
NO
(17.1)
NO
(17.0)
ND
(17.9)
ND
(31.1)
ND
(37.2)
ND
(27.4)
NO
(23.0)
123
23.9'
ND
(17.1)
ND
(17.1)
ND
(17.0)
172
ND
(31.1)
ND
(37.2)
ND
(27.4)
Ichlorophenol
IN*
78.3
ND
(16.8)
ND
(14.8)
ND
(16.2)
NO
(23.0)
ND
(72.2)
ND
(15.9)
ND
(17.1)
HD
(17.1)
NO
(17.0)
ND
(17.9)
ND
(31.1)
ND
(37.2)
ND
(27.4)
oroplwnol
Pentachl
ND
(42.3)
ND
(33.5)
ND
(29.5)
ND
(32.5)
ND
(46.0)
ND
(32.8)
ND
(31.8)
ND
(34.1)
NO
(34.1)
ND
(34.0)
ND
(35.8)
ND
(62.1)
ND
(74.4)
ND
(54.8)
1
f
NO
(55.0)
117
NO
(14.8)
ND
(16.2)
ND
(23.0)
NO
(16.4)
191
ND
(17.1)
NO
(17.1)
3.40-
136
ND
(31.1)
78.1
(27.4)
1
|
ND
(21.2)
NO
(16.8)
ND
(14.8)
1.6"
NO
(23.0)
ND
(16.4)
ND
(15.9)
NO
(17.11
NO
(17.1)
6.79*
(17.9)
ND
(31.1)
(37.2)
(27.4)
I
NO
(21.2)
109
249
ND
(16.2)
*
36.8
93.5
97.1
35.8
1.71*
181.8
*
35.7
94.8
ND
(31.1)
338
27.4
172.8
•
ybenzal dehyde
e
I
NO
(21.2)
ND
(16.8)
19.2
ND
(40.6)
NO
(23.0)
(16.4)
ND
(15.9)
ND
(17.1)
ND
(17.1)
NO
(17.0)
(17.9)
ND
(31.1)
(37.2)
(27.4)
4-Hydroxybenzt 1 dehyde
NO
(275)
ND
(16.8)
ND
(14.8)
ND
(16.2)
ND
(23.0)
(16.4)
(15.9)
ND
(17.1)
ND
(17.1)
ND
(17.0)
37.6
74.5
(37.2)
(27.4)
Diphenyl ether
1204
1120
161
117'
*
(')
745
627
17.1
ND
(17.1)
—
•
NO
(17.0)
1789
1025
2194
16.4*
197.0
-------
TABLE VI-; (continued)
(Concentration ng/m*)
CO
O
9/14-15/84
9/17- 18/84
9/18-19/84
Site
1
2
3
4
4FO
,
2
3
4
4FD
1
2
3
4
4FO
Average
and Speed
331*. 6.6 «ph
Precision
Detected In blank
212*. 4.1 mph
Precision
Detected In blank
235*, 4.0 mph
Precision
Detected In blank
1
u
iT
".
-
ND
(15.9)
ND
(21.0)
NO
(14.6)
NO
ND
(37.6)
ND
(16.0)
43.0
10.1*
41.7
31.1
29.1
NO
(22.5)
130
ND
(17.2)
62.6
54.4
14.0
Trtchlorobenzene
•*.
~
20.6
No
(21.0)
NO
(14.6)
ND
(13.8)
ND
(37.6)
NO
(16.0)
362
37.4
233
173
29.6
NO
(22.5)
566
NO
(17.2)
457
429
6.3
Tnchlorobenzene
"I
-
ND
(15.9)
NO
(21.0)
NO
(14.6)
NO
ND
(37.6)
ND
(16.0)
10.3'
ND
(14.4)
NO
<'£,•/>
ND
(17.3)
NO
(22.5)
ND
(17.1)
NO
(17.2)
10.2-
10.0*
4-Tetrachloro-
zene
™.%
-'
7.94*
NO
(21.0)
NO
(14.6)
NO
(13.8)
ND
(37.6)
NO
(16.0)
327
NO*
(21.6)
167
91.5
56.1
NO
(22.5)
823
ND
(17.2)
237
215
9.7
5-Tetrachloro-
zene
-.8
-
NO
(15.9)
NO
(21.0)
NO
(14.6)
NO
(13.8)
NO
(37.6)
NO
(16.0)
126
12.9*
60.0
32.8
52.1
NO
(22.5)
326
ND
(17.2)
110
97.3
12.3
til orobenzene
a
£
NO
(15.9)
ND
(21.0)
NO
(14.6)
ND
(13.8)
ND
(37.6)
ND
(16.0)
NO
NO
(14.4)
5.0*
3.45"
36.7
NO
(22.5)
NO
(17.1)
NO
(17.2)
8.5*
NO
(14.3)
._
1 orobenzene
S
*
ND
(15.9)
ND
(21.0)
NO
(14.6)
NO
(13.8)
NO
(37.6)
NO
(16.0)
NO
C'-2)
ND
NO
('6-')
ND
(17.3)
NO
(22.5)
NO
(17.1)
141
ND
(16.9)
ND
(14.3)
O
ft-
38.1
162
33.6
83.0
NO
(37.6)
84.7
NO
(16.0)
671
NO
(14.4)
112
259
79.2
405
1715
ND
(17.2)
812
601
29.9
*o
c
5
CXI
ND
(15.9)
ND
(21.0)
ND
(14.6)
ND
(13.8)
NO
(37.6)
ND
(16.0)
NO
(»,•*!
NO
(14.4)
ND
NO
(17.3)
NO
(22.5)
No
(17.1)
ND
(17.2)
ND
(16.9)
NO
(14.3)
rophcnol
§
«*>
NO
(15.9)
NO
(21.0)
NO
(14.6)
ND
(13.8)
NO
(37.6)
NO
(16.0)
NO
(17.2)
NO
(14.4)
NO
(16.7)
ND
(17.3)
NO
(22.5)
NO
(17.1)
ND
(17.2)
NO
(16.9)
NO
(14.3)
|
?
CM
ND
(15.9)
NO
(21.0)
ND
(H.6)
ND
(13.8)
NO
(37.6)
NO
(16.0)
112
ND
(14.4)
23.3
NO
(17.3)
NO
(22.5)
NO
(17.1)
NO
117.2)
2538
2003
23.6
Tncnlorophenol
"1
ri
NO
(15.9)
NO
(21.0)
NO
(14.6)
ND
(13.8)
NO
(37.6)
NO
(16.0)
534
NO
(14.4)
ND
(16.7)
ND
(17.3)
ND
(22.5)
NO
(17.1)
NO
(17.2)
NO
(16.9)
ND
(14.3)
Trlcnlorophenol
u>
CM
NO
(15.9)
ND
(21.0)
ND
(14.6)
NO
(13.8)
ND
(37.6)
NO
(16.0)
NO
(17.2)
NO
(14.4)
NO
(16.7)
(17.3)
ND
(22.5)
ND
(17.1)
NO
(17.2)
ND
(16.9)
ND
(14.3)
Trichlorophenol i
">.
~
NO
(15.9)
NO
(21.0)
ND
(14.6)
ND
NO
(37.6)
ND
(16.0)
189
NO
(14.4)
NO
(16.7)
ND
(17.3)
NO
(22.5)
ND
(17.1)
ND
(17.2)
127
104
19.9
hlorophenol
•
S
ND
(31.7)
ND
(21.0)
ND
(29.2)
NO
(27.7)
ND
(75.1)
NO
(32.0)
ND
(34.4)
ND
(28.8)
ND
(33.3)
ND
(34.5)
NO
(45.0)
NO
(34.2)
ND
(34.5)
NO
(33.8)
ND
(28.6)
ylphenol
«
CM
NO
(15.9)
NO
(21.0)
NO
(14.6)
ND
(13.8)
NO
(37.6)
NO
(16.0)
ND
(17.2)
NO
(24.4)
5.0"
NO
(17.3)
NO
(22.5)
ND
(17.1)
ND
(17.2)
40.6
ND
(14.3)
„
ylpnenol
«
4
NO
(15.9)
NO
(21.0)
HO
CI4.6)
NO
(13.8)
NO
(37.6)
NO
(16.0)
ND
(!'. 2)
NO
(14.4)
ND
(16.7)
NO
(17.3)
ND
(22.5)
NO
(17.1)
ND
(17.2)
3.38*
ND
(14.3)
*x
s
tet
28.6
18.9
17.5
19.4
26.3
30.2
36.8
122
104
53.3
ND
(17.3)
.
67.6
92.6
?2.4*»
112'3
104*1
7.4
.
oxybenzaldenyde
CM
ND
(15.9)
ND
(21.0)
ND
(14.6)
ND
(13.8)
ND
(37.6)
4.8*
NO
(17.2)
7.19*
ND
(16.7)
NO
(1'.3)
22.5
NO
(17.1)
NO
(17.2)
ND
(16.9)
NO
(14.3)
oxybenzaldehyde
4
NO
(15.9)
ND
(14.6)
W
(13.8)
ND
(37.6)
NO
(16.0)
KD
(17.2)
NO
(14.4)
NO
(16.7)
ND
(17.3)
NO
(22.5)
NO
(17.1)
NO
(17.2)
NO
(16.9)
NO
1
o
NO
(15.9)
23.1*
ND
(14.6)
NO
(13.8)
NO
(37.6)
3.2-
ND
(17.2)
575
283
157
57.3
ND
(22.5)
2227
ND
(17-2)
1149
1086
5.6
.
-------
IABLE VI-7 (continued)
(Concentration ng/m3)
00
Sampl Ing Period
9/22-23/84
9/23-24/84
9/24-25/84
Site
2
3
4
4FD
1
2
3
4
4FD
1
2
3
4
4FO
Average
Wind Direction
and Speed
212°, 4.9 «ph
Precision
Detected In blank
197'. 2.* niph
Prec Is Ion
Detected In blank
195*. 4.9 inph
Precision
Detected In blank
rrlchlorobenzene
".
57.0
7.16*
61.0
52.8
14.4
3.23*
30.8
10.2*
14.7"
12.3*
17.8
5.57*
38.8
14.2
6.46*
10.8*
50.3
hlorobenzene
~
~:
326
28.6
425
347
20.2
9.71*
199
67.9
101
91.7
9.7
13.0*
254
65.3
51.7
77.1
39.4
hlorobenzene
-
J,
(Incom
NO
(16.3)
NO
(14.3)
3.70*
3.30"
11.4
NO
(16.2)
ND
(18.1)
ND
(17.0)
NO
(18.3)
ND
(17.6)
NO
(18.6)
ND
(18.5)
ND
(14.2)
NO
(16.1)
ND
(17.9)
trachloro-
i*
lete s
151
21.5
296
314
5.9
21.0
181
52.6
75.2
68.8
8.9
24.1
203
75.3
43.6
62.8
36.1
o
o
o
7 £
-"I
mp 1 1 ng
83.0
18.6
107
107
0.0
3.24*
77.8
25.4
25.7
24.7
4.0
NO
(18.6)
83.1
41.2
24.2
37.7
43.6
obenzene
o
1
run --
ND
(16-3)
NO
(14.3)
11. I*
NO
(16.5)
ND
(16.2)
NO
(18.1)
NO
(17.0)
ND
(18.3)
1.76*
__
ND
(18.6)
ND
(18.5)
2.8*
ND
(16.1)
ND
(17.9)
benzene
r_
*J
1
sample
NO
HO
(14.3)
NO
(18.5)
NO
(16.5)
NO
(16.2)
NO
(18.1)
NO
(17.0)
ND
(18.3)
ND
(18.3)
ND
(18.6)
ND
(18.5)
NO
(14.2)
NO
(16.1)
ND
(17.9)
1
not an
6941
1379
956
649
38.3
.
359
6666
1836
224
215
4.1
.
186
1736"
1250
436"
508"
22.4
"o
|
o
<••*
Ijzed.
NO
(1S-3)
Ml
(14.3)
NO
(18.5)
NO
(16.5)
ND
(16.2)
NO
(18.1)
NO
(17.0)
NO
(18.3)
ND
(17.6)
ND
(18.6)
ND
(18.5)
ND
(14.2)
NO
(16.1)
NO
(17.9)
C
o
o
NO
(16.3)
NO
(14.3)
NO
(18.5)
NO
(16.5)
NO
(16.2)
NO
(18.1)
NO
(17.0)
ND
(18.3)
ND
(17.6)
ND
(18.6)
NO
(18.5)
ND
(14.2)
NO
(16.1)
ND
(17.9)
,
|
B
ND
(l«-3)
NO
(14.3)
721
528
30.9
NO
(16.2)
ND
959
ND
(17.0)
NO
(18. J)
NO
(17.6)
NO
(18.6)
ND
(18.5)
ND
(14.2)
ND
(16.1)
ND
(17.9)
1
c
"I
ND
(16.3)
NO
(14.3)
ND
(18.5)
ND
(16.5)
ND
(16.2)
ND
(18.1)
ND
(17.0)
NO
(18.3)
NO
(17.6)
NO
(18.6)
NO
(18.5)
ND
(14.2)
NO
(16.1)
ND
(17.9)
1
1
5
LO
ND
(16.3)
NO
(14.3)
NO
(18.5)
NO
(16.5)
ND
(16.2)
NO
(18.1)
ND
(17.0)
ND
(18.3)
NO
(17.6)
ND
(18.6)
ND
(18.5)
NO
(14.2)
ND
(16.1)
NO
(17.9)
0.
o
u
"I
179
ND
(14.3)
181
162
11.1
ND
(16.2)
ND
(18.1)
30.5
25.7
24.7
4.0
NO
(18.6)
177
31.2
NO
(16.1)
NO
(17.9)
llorophenot
1
ND
(32.6)
NO
(28.6)
ND
(37.0)
ND
(33.0)
NO
(32.4)
NO
(36.2)
ND
(33.9)
NO
(36.7)
ND
(35.3)
ND
(37.1)
ND
(36.9)
NO
(28.4)
ND
(32.3)
NO
(35.9)
1
a.
|
NO
(16.3)
NO
(14.3)
NO
(18.5)
ND
(16.5)
NO
(16.2)
ND
81.5
ND
(17.0)
ND
(18-3)
NO
(17.6)
ND
(18.6)
NO
(18.5)
63.9
NO
(16.1)
ND
(17.9)
"o
I
1
ND
(16.3)
NO
(14.3)
NO
(18.5)
ND
(16.5)
NO
(16.2)
ND
(18.1)
ND
(17.0)
ND
(18.3)
ND
(17.6)
ND
(18.6)
(18.5)
ND
(14.2)
NO
(16.1)
ND
(17.9)
I
111
80.2"
115"3
129*'
11.5
*
64. 7*3
1703
96.7
95. 31
95.2
0.1
16.7
122
115
51.7'
68.2
27.5
i
•
ND
(16.3)
NO
(14.3)
NO
(18.5)
ND
(16.5)
53.4
NO
(18.1)
ND
(17.0)
NO
(18.3)
NO
(17.6)
ND
(18.6)
(18.5)
19.9
ND
(16.1)
ND
(17.9)
4-Hydroxybenzaldehyde
NO
(16.3)
ND
(14.3)
NO
(18.5)
Nb
(16.5)
ND
(16.2)
NO
(18.1)
NO
(17.0)
NO
(18.3)
NO
(17.6)
ND
(18.6)
(18.5)
ND
(14.2)
HO
(16.1)
ND
(17.9)
Diphenylether
1530
286
1128
1090
3.4
ND
(16.2)
1792
594
440
459
4.2
3.7*
720
469
194
251
25.6
-------
TABLE VI-7 (continued)
NOTES: ND = Not detected.
FO = Field duplicate sample.
* = Estimated value.
= Identification and quantitation of dichlorophenol and trichlorophenol suspect.
2 = Concentration in blank higher than in sample.
» Quantitation of blphenyl suspect; all mass spectrum
assignment criteria were not met.
** » Interferences present In mass spectrum;
suspected positive bias.
oo
ro
-------
were detected principally at downwind monitors, in the following sampling
periods:
9/18-19/84
9/22-23/84
9/23-24/84, and
9/24-25/84
with precision achieving the target criterion for many compounds on 9/17-18/84.
As indicated above, southerly to southwesterly wind patterns were considered
most appropriate to judge upwind-downwind relationships. As a control, one
sampling period in which northerly winds were present, 9/14-15/84, was reviewed
to determine whether any of the compounds were present when little or no wind
contacted the Dow Chemical facility prior to collection in the samplers. As
expected, most compounds were not detected. These data demonstrate that
the Dow Chemical facility does emit measurable quantities of semi-volatile
compounds. In addition, the range of tentatively identified compounds (see
Table VI-8) was generally larger at downwind monitoring sites.
Referring to Table V-15 (Section V of this report), the identifiable semi-
volatile compounds measured in Building 703 incinerator exhaust were few, and
were in the range of 10 to 100 ppb. The complement of semi-volatile compounds
presented in Tables VI-7 and VI-9 is much more extensive; further, the single
compound detected in both the incinerator exhaust and ambient air sampling,
tetrachlorobenzene, was found to be present in ambient air at a level con-
siderably higher than expected if the incinerator exhaust were the sole source.
Applying an approximate dilution factor of 105 to account for the distance
and elevation difference of the ambient monitoring sites with respect to
the incinerator stack, to the tetrachlorobenzene concentration presented in
Table V-15, an approximate ground level concentration of tetrachlorobenzene
(1,2,3,4 plus 1,2,4,5 isomer) would be in the range of 0.1 ppt rather than the
maximum concentrations between 100 and 1000 ppt shown in Table VI-9. These
data suggest that sources within the Dow Chemical facility other than the
Building 703 incinerator exhaust stack, such as process vents or fugitive
emissions sources, may be attributable for the levels of semi-volatile compounds
detected in ambient air around the plant. It is known that 2,4-dichlorophenol
is currently produced at the Midland plant. The finding of 2,4,5-trichloro-
phenol is surprising in that Dow Chemical has not produced 2,4,5-trichlorophenol
for some time, nor does the company report any current use of 2,4,5-trichloro-
phenol to any significant extent.23
3. Volatile Compounds
As described previously, these compounds were sampled using traps packed
with carbon molecular sieves (CMS) and a study was conducted to demonstrate the
validity of this sorbent for the compounds to be sampled. Most of the CMS
tubes used in the validation study were not analyzed by the contract laboratory
within required times; results from those tubes analyzed before their expiration
are shown in Table VI-10. Seven of the eight compounds spiked into the tubes
were not detected. The detection of perchloroethylene (tetrachloroethylene),
the remaining spiked compound, was not in consistent agreement with the known
levels spiked.
83
-------
TABLE VI-8
TENTATIVELY IDENTIFIED SEMI-VOLATILE COMPOUNDS DETECTED IN AMBIENT AIR SAMPLING
IN VICINITY OF DOW CHEMICAL COMPANY, MIDLAND. MICHIGAN. SEPTEMBER 1984
Sampling Period Site
9/7-8/84
1
2
3
4
4FD
4FB
Average
Wind Direction
and Speed
184°. 6 mph
Compounds Tentatively Identified
Ethylcyclopentane; methylcyclohexane; xylene; methyl ethyl benzene; dlchlorobenzene; methyl naphthalene
Methyl naphthalene; dlchlorobenzene; benzole acid; 1.2-dlethyl benzene; ethenylmethylbenzene; ethylmethyl-
benzene; ethylmethyl benzene; chlorobenzene; toluene
Methylphenanthrene; phenylblcyclohexyl; terphenyl; methyl naphthalene; b1s(d1methylethylJphenol; xylene; toluene
(Sample not analyzed.)
Ethylbenzene; ethylmethylbenzene; blphenyl
Naphthalene; ethylmethylbenzene; toluene; ethylcyclopentane
9/8-9/84 1 199°, 6 mph Ethylmethylbenzene; propylbenzene; toluene; benzene; benzothlazole; xylene
2 01 ethyl benzene; ethenylethyl benzene; propylbenzene; ethylmethylbenzene; ethylbenzene; toluene
3 Dlchlorobenzene; dlethyl benzene; trlmethylnaphthalene; chlorobenzene; dimethyl benzene; styrene; ethylmethyl-
benzene; ethenylethylbenzene; d1ethenylbenzene; methylbenzaldehyde; ethylbenzene
4 Dlethylbenzene; ethylbenzene; ethenylbenzene; ethylmethylbenzene; 2,3-d1hydro1ndene; ethenylethylbenzene;
dlethenylbenzene
4FD Ethylbenzene; ethenylbenzene; ethylmethylbenzene
4FB Ethylmethylbenzene; trlmethyl benzene; benzene; ethylbenzene; dlethylbenzene
9/12-13/84
00
1 191°. 6 mph
2
3
4
4FD
4FB
Hexanedlolc acid dloctyl ester; dodecanonltrlle; d1-l,2-benzened1carboxyl1c acid; ethylbenzoic acid; 2,6-bls
(l.l-dlmethyl)phenol; l,l'-(l,4-phenylene) B ethanone; benzole acid; 1.2,3-trlmethylbenzene, l-ethyl-2-
ntethylbenzene; ethylbenzene; xylene; acetic acid butylester
1-Methylethylbenzene; 2,3-dihydro 1 H-1ndene; 1,3-dlethylbenzene, l-ethenyl-4-ethylbenzene; l.l'-oxybisbenzene;
hexadecanolc acid methyl ester; 2-methylnaphthalene
3.7-D1methyl-l,6-octad1en-3-ol; l-ethyl-2-methylbenzene; 1-methylethylbenzene; xylene; 2,2-dimethyloctanol;
b1s(2-ethylhexyl) hexanedlolc acid; methyl ethyl benzene; ethylbenzene; 1.2-dlethyl benzene; xylene; 1,4-dihydro-
1.4-methanonaphthalene
Dlethylbenzene; ethylbenzene; xylene; 2,3-dihydro 1 H-lndene; 1-methylethylbenzene
1-Methyl ethyl benzene; 2-ethylhexanolc acid; 2,6-b1s(l,l-d1methylethyl)phenol; 4-methyl-l,3-benzenediamine;
5,7-methylundecane; 2-cyclohexen-l-one
Olmethylbenzene; blcyclo [4.2.0] octa-l,3,5-tr1ene; 1,3,6-octatrlene; 3,7-d1methyl; 1-ethyl-2-methylbenzene;
6,6-d1me blcyclo [3.1.1] heptane; octamethylcyclotetraslloxane; dodecamethylcyclohexaslloxane; 2-methyltrl-
decane; d1-l,2-benzene dlcarboxyllc acid; 2.10-methylundecane; 2,6-b1s(l,l-d1methyl) phenol; 5,7-dimethyl-
undecane; 2-fluorophenol; ethylbenzene; hexanedlolc add dloctylester; 2,7-dlraethyloctane; 1-nltroethyl-
benzene
9/14-15/84
3
4
4FD
4FB
331", 7 mph Xylene; 4-methyl-l-(3)-cyclohexen-l-ol; l-ethyl-2-methylbenzene; ethylmethylbenzene; hexadecanolc acid; ethyl-
benzene methyl ethyl benzene
Xylene; ethylmethylbenzene; 1,2-dlethylbenzene; 1,2,3,4-tetramethylbenzene; 1-ethylnaphthalene; hexadecanoic
acid methyl ester; methyl benzene; ethylmethylbenzene; 1,2,4-trlmethylbenzene; l-ethyl-2,3-d1methylbenzene;
methyl naphthalene; 1.4-d1hydro-l,4-methanonaphthalene
3-Bromodecane; hexadecanolc acid dloctylester; ethylmethylbenzene; xylene
3-Bromodecane; ethylbenzene; 1-methylethylbenzene; 2-propylheptanol, xylene
l-Acetyl-l,2,3.4-tetrapyr1d1ne; 3-bromodecane; ethyl dimethyl benzene; 2-methylpropylbenzene; ethylmethylbenzene
Methylcyclohexane; methyl benzene; d1-l,2-benzened1carboxy!1c acid; 2-propenyl1ndenocyclobutene; methylethyl-
benzene
-------
TABLE VI-8 (continued)
Sampling Period Site
Average
Wind Direction
and Speed
9/17-18/84
00
en
1 212°. 4 mph
2
3
4
4FD
4FB
Compounds Tentatively Identified
2-Methylnaphthalene; 1,1-dlmethylethylbenzene; 4-ethyl-l,2-d1methylbenzene; 1,2,3,4-tetramethylbenzene; ethyl-
benzene; benzole acid; l-methyl-4-propylbenzene; 2-methylnaphthalene; ethylcyclopentane; Il-n1tro-l-undecane;
dimethyl benzene; 1,3.5-cycloheptatHene; 4-methyl-l,3-cyclohexen-l-ol; ethylmethylbenzene; trlmethyl benzene;
ethyl dimethyl benzene; 1,3-dlmethyl benzene
2,4-Hexadfyne; methylbenzene; xylene; 1,3,5,7-cyclooctatetraene; 1-methylethylbenzene; diethylbenzene;
undecane; naphthalene; methyl naphthalene; 3,4,5-trlmethylhexene; dlmethylpentene; 4-ethenylcyclohexene; chloro-
benzene; ethyl benzene
Methyl naphthalene; benzenedlcarbonltrlle; I,l-d1methylethylbenzene; 1-methylpropylbenzene; 1,2.4-trimethyl-
benzene; 1-methylethylbenzene; 1-ethyl-2-methylbenzene; xylene; chlorobenzene; methylcyclohexane; 1,2-dimethyl-
4-ethylbenzene; 2-methyldecahydronaphthalene; propylbenzene
Ethylbenzene; 4-(6-methyl-2-benz) benzamlne; 1-undecane. 11-nltro; o,o-d1ethylphosphoroth1o acid; 2-propyl-l-
heptanol; 1,2-benzenedicarbonltrile; xylene; 1,3,5,7-cyclooctatetraene
2-Methylphenanthrene; l-(2-bromoethyl)-3-fluorobenzene; 2,4-dinitrobenzeneamine; 2.2,7.7-tetra-4,5-octadien-
3-one; 2-ethyl-2H-benzotriazole; l,r-(l,4-phenylene) B-ethanone methylsulfonylbenzene; dichlorobenzene;
1-ethyl-4-methylbenzene; 1-methylethenylbenzene; ethylbenzene; 1,2-diethylbenzene; 1-methylethylbenzene; xylene
1,2,3-Trimethylbenzene; di-l,2-benzenedicarboxyl1c acid; 1-methylethylbenzene; methyl benzene; l-ethyl-2-
methylbenzene
9/18-19/84
9/22-23/84
9/23-24/84
1
2
3
4
4FO
4FB
1
2
3
4
4FD
4FB
1
2
3
4
4FO
4FB
235°. 4 mph Dlmethylbenzene; ethylmethylbenzene; methylbropyl benzene, trlmethylbenzene; benzenedicarbonitrile
Chlorobenzene; ethylbenzene; ethenylbenzene; methylethylbenzene; dichlorobenzene; diethylbenzene; methyl benzo-
furan
Pyrene; dlmethylbenzene; ethylbenzene; ethyldlmethylbenzene; methylethylbenzene; propyl benzene; methylpropyl-
benzene
Dlmethylbenzaldehyde; dimethylbenzene; dichlorobenzene; ethylmethylbenzene; ethenylbenzene; methyl benzaldehyde;
dlethenylbenzene
Methyl benzaldehyde; diethylbenzene; ethylmethylbenzene; dimethylbenzene; dichlorobenzene; ethenylbenzene;
ethylbenzene
Dlmethylbenzaldehyde; dlethenylbenzene; ethenyl ethyl benzene; di ethenylbenzene
212°, 5 mph 1, !'-(!, 4-Phenylene)b1s ethanone; benzoic add; ethylmethylbenzene; dlmethylbenzene
Ethylbenzene; dimethylethylbenzene; phenanthrene, diethylbenzene; dichlorobenzene; ethenylbenzene; chlorobenzene
Ethylmethylbenzene; dichlorobenzene; diethylbenzene; ethyldlmethylbenzene; methyl naphthalene; naphthalene;
dlethenylbenzene; methyl propyl benzene; dlmethylbenzene
Methylethylbenzene; diethylbenzene; ethylbenzene
Ethenyl ethyl benzene; diethylbenzene; methylethylbenzene; ethenylbenzene; ethylbenzene; dlethenylbenzene;
dichlorobenzene; dlmethylbenzene
Dlmethylbenzaldehyde; propyl benzene; ethylmethylbenzene
197", 3 mph Methylnaphthalene; naphthalene; dimethylethylbenzene; methyl propyl benzene; methylethylbenzene; dimethylbenzene
Anthracene; methylethylbenzene; ethenylbenzene; dlmethylbenzene; dichlorobenzene; ethylbenzene; diethylbenzene;
1 ,l'-(l,4-phenylene)b1s ethanone; naphthalene; dlethenylbenzene
Diethylbenzene; ethenyl ethyl benzene; ethylbenzene; l,l'-(l,4-phenylene)bis ethanone; methyl naphthalene;
naphthalene; ethenylethylbenzene; dichlorobenzene; ethenylbenzene; dlmethylbenzene
l,l'-(l,4-Phenylene)bis ethanone; dimethylbenzene; ethenylethylbenzene; di ethenyl benzene; ethyldlmethylbenzene;
diethylbenzene; ethylbenzene; I,l'-oxyb1sbenzene; naphthalene; dichlorobenzene
Dimethylnaphthalene; naphthalene; ethylbenzene; methylethylbenzene; propyl benzene; dlethenylbenzene; dimethyl-
ethylbenzene; diethylbenzene; dlmethylbenzene; dichlorobenzene; ethenylethylbenzene
Propyl benzene; trlmethylbenzene; methyl ethyl benzene; dlmethylbenzene
-------
TABLE VI-8 (continued)
Sampling Period Site
9/24-25/84
1
2
3
4
4FD
4FB
Average
Wind Direction
and Speed
195°. 5 mph
Compounds Tentatively Identified
1.1'-(1,4-Phenylene)b1s ethanone; methyl ethyl benzene; dlmethylbenzene
Ethylbenzene; methyl ethyl benzene; dlethyl benzene; dlethenylbenzene; naphthalene; l.l'-oxybisbenzene; methyl-
benzene; dlraethylbenzene; dlchlorobenzene; methyl naphthalene; 1,l'-(l,4-phenylene)bis ethanone
Methylnaphthalene; dlethylbenzene; methyl ethyl benzene; 1,l'-(l,4-phenylene)b1s ethanone; diethenylbenzene
Dlmethylbenzene; ethylmethylbenzene; dlethylbenzene; ethenylethylbenzene; dlethenylbenzene; naphthalene;
l.l'-oxyblsbenzene; tetramethylbenzene
Dlmethylbenzene; dlethylbenzene; ethenylethylbenzene; dlmethylbenzene; dlethenylbenzene; methylphenylethanone;
l.l'-oxyblsbenzene
Dlethylbenzene; methyl ethyl benzene; dimethylbenzaldehyde
NOTES: FD = Field duplicate sample.
FB = Field blank sample.
00
cn
-------
TABLE VI-9
RANGES OF CONCENTRATIONS OF QUANTITATED SEMI-VOLATILE COMPOUNDS
IN AMBIENT AIR ON NINE SAMPLING DAYS - MIDLAND, MICHIGAN
9/7/84 - 9/25/84
(Data expressed In ng/m3)
Site
1
2
3
4
Maximum
Minimum
Average
Maximum
Minimum
Average
Maximum
Minimum
Average
Maximum
Minimum
Average
2
Ot
c
£
e
0
o
I—
CO
•l
CM
102
ND
13.8
130
ND
43.4
37.3
ND
12.1
108
ND
26.8
%
01
c
0)
o
o
f
o
1
CM
A
699
ND
95.4
566
ND
297
258
ND
70.0
855
ND
194
8
01
N
C
01
o
o
o
f-
o
I—
1
u->
ro
ND
NO
—
10.3
ND
1.34
ND
ND
—
10.2
NO
1.60
1
O
L.
O
-g
«J
01 O>
H- C
1 41
*r isi
* c
CO Ol
CM
*
296
ND
43.6
327
ND
235
115
ND
39.0
409
NO
118
1
O
L.
O
•g
«0
L.
Q) Q)
| (JJ
l/l N
» C
^ fl,
• .o
CM
*
97.4
ND
12.6
326
ND
97.9
49.4
ND
21.6
141
ND
45.4
01
N
C
01
.0
o
o
JC
o
ND
NO
—
ND
ND
—
ND
ND
~
NO
ND
—
8
01
ex
O
C.
O
f
0
o
1
CM
1693
ND
242
4114
ND
580
1398
ND
158
2538
ND
473
8
0)
.c
ex.
o
i.
o
o
t—
t
ro
CM
ND
ND
--
534
NO
59.3
ND
NO
—
ND
ND
—
8
Ol
.C
Q.
O
t_
O
!Z
u
u">
«t
CM
ND
NO
—
172
ND
37.4
239
ND
2.65
ND
ND
—
8
Ol
Q.
O
C-
o
u
c_
K-
1
^
CM
78.3
ND
9.79
189
ND
60.6
31.2
NO
6.86
181
ND
36.7
"o
c
Ol
.c
ex
o
c_
o
u
(O
01
ND
ND
—
ND
ND
—
ND
ND
—
NO
ND
—
,_
8
OJ
£
CL
C
at
a.
i
CM
3.4
NO
—
136
ND
37.2
191
ND
28.3
78.1
NO
7.28
,_
8
01
f~
CL
C
01
ex
1
*
6.79
ND
0.85
NO
ND
—
NO
ND
~
3.38
ND
0.29
C
a>
a.
QO
67.6
NO
35.9
170
18.9
104
249
ND
84.4
358
ND
93.8
01
•a
•o
'a
Nl
c
01
-0
X
o
"O
3:
i
CM
53.4
ND
10.1
ND
ND
--
19.9
NO
5.14
ND
ND
—
01
•a
01
-o
1o
Kl
c
01
.a
X
o
"U
1
"*
ND
ND
—
37.6
ND
4.18
74.5
ND
8.28
NO
NO
—
c_
4-1
ai
ex
Q
1204
ND
151
2227
ND
1105
1025
NO
415
2194
ND
498
00
-------
TABLE VI-10
COMPARATIVE RESULTS OF CARBON MOLECULAR SIEVE TUBE
VALIDATION STUDY
Tube
Identification Compound Amount Spiked (ng) Amount Detected (ng)
4-E perchloroethylene 131 20.0
5-A 1,1,1-trichloroethane (not spiked) 1290
perchloroethylene 26 31.8
5-B 1,1,1-trichloroethane (not spiked) 537
perchloroethylene 26 56.5
5-C (no spiked compounds detected)
88
-------
Also, because of difficulties relating primarily to sample holding times
prior to analysis and possible blank contamination, most CMS tubes were not
analyzed successfully. Therefore, the data for volatile compounds in ambient
air presented in Table VI-11 are presented in qualitative terms.
From these data the following general conclusions appear supportable:
1. On each sampling day, site 1 was considered upwind of Dow Chemical.
A wider range of compounds was usually detected at the downwind sites.
2. Two compounds, 1,1,1-trichloroethane and perchloroethylene, were found
in most samples on the eight days for which analytical data are
available. However, both compounds were frequently found as a blank
contamination. Also, 1,1,1-trichloroethane appeared at high levels in
the method validation study, though it was not spiked.
3. Precision between field duplicate samples was generally poor.
4. On each sampling day, either the low-flow or high-flow set of CMS tubes
was designated the primary set for analysis, based upon ambient
temperature and humidity conditions (see Appendix F, Section III.A).
There was no distinct superiority or consistent pattern in the levels of
compound detection in primary tubes.
5. Acrylonitrile and chloroform, when detected, were found primarily at
monitoring sites downwind of Dow Chemical.
In addition to the six compounds appearing in Table VI-11, three compounds:
monochlorobenzene, 1,3-dichlorobenzene, and 1,4-dichlorobenzene, were not de-
tected in any sample. However, many of the volatile compounds selected for
analysis (see Section II of this report) were not included. Among these
compounds were benzene, ethylene dibromide, ethylene dichloride, ethylene
oxide, methyl chloroform, methylene chloride, and vinylidene chloride. Several
of these compounds were detected in Building 703 incinerator exhaust, as
described in Section V of this report.
Thus, this portion of the ambient air study was not successful in scanning
for the full range of desired compounds, either because of sampling or analytical
method unsuitability, or insurmountable analytical problems. The available
data should be considered qualitative.
4. Formaldehyde
The analytical results appearing in Table VI-12 show higher levels of
formaldehyde in method and field blanks than in any of the 25 exposed field
samples, with two exceptions. These data, evaluated by the EPA Region V
Central Regional Laboratory as acceptable in terms of analytical accuracy,
are not usable for quantifying the presence or absence of formaldehyde in
ambient air during the study period.
89
-------
TABLE VI-11
RESULTS OF AMBIENT AIR SAMPLING FOR VOLATILE COMPOUNDS
IN VICINITY OF DOW CHEMICAL COMPANY, MIDLAND, MICHIGAN, SEPTEMBER 1984
Ol
01
0)
o
oethane
0)
t_ Ol
o c
i— 01
Dates (1984)
Wind Direction
and Average
Speed
Site
High
or
Low Flowl
o
o
c_
o
*""" *O ^H
-------
TABLE VI-11 (continued)
Dates (1984)
,
t_
o
O
C_
O
O O -M
f— -i- OJ
.Ct-.M
U -M
-r- I C
-O r-( O
CVJ
J= •
O r-4
O)
c
(U
0)
O
C-
O
O
C_>
Comments
9/19-20 250° , 4 mph 1 H
2 L
3 H
4 L
4 H
4 H_
9/22-23 212°, 5 mph 1 H_
2 L
2 H
3 L
3 H
4 L
4 L.
9/23-24 197°, 3 mph 1 L
2 I
2 H
3 L
4 L
4 _L
9/24-25 195°, 5 mph 3 L_
4 j.
X
X
X
X
X
X
X
X*
X*
X
X
X*
X
X
X
X
X
X
X
X
X
X
X
X
X
X*
X
X
Field duplicate
sample
Field blank not
analyzed
Field duplicate
sample
Field duplicate
sample
Field blank not
analyzed
Notes: *Denotes compound detected at higher concentration in field blank sample.
IPrimary tubes (high or low flow) are underlined in this category.
91
-------
TABLE VI-12
RESULTS OF AMBIENT AIR SAMPLING FOR FORMALDEHYDE
IN VICINITY OF DOW CHEMICAL COMPANY, MIDLAND, MICHIGAN, SEPTEMBER 1984
Wind Direction Sample Formaldehyde Derivative
Date (1984) and Speed (mph) Identification Detected (ug/sample)
9/7-8 184°, 6 mph Method Blank 5.34
Field Blank 4.78
Site 1 2.04
Site 2 4.09
Site 3 2.68
Site 4 1.89
Site 4 Duplicate 2.15
9/8-9 199°, 6 mph Method Blank 5.24
Field Blank 3.91
Site 1 1.13
Site 2 1.69
Site 3 1.00
Site 4 0.95
Site 4 Duplicate 0.79
9/12-13 191°, 6 mph Method Blank 2.52
Field Blank 2.11
Site 1 1.46
Site 2 0.14
Site 3 0.19
Site 4 0.29
Site 4 Duplicate 0.22
9/18-19 235°, 4 mph Method Blank 2.24
Field Blank 1.80
Site 1 0.51
Site 2 0.90
Site 3 0.55
Site 4 0.36
Site 4 Duplicate 2.91
9/19-20 250°, 4 mph Method Blank 1.42
Field Blank 1.64
Site 1 0.48
Site 2 0.81
Site 3 0.76
Site 4 1.46
Site 4 Duplicate 0.75
92
-------
REFERENCES
1. Amendola, Gary A., Soil Screening Survey at Four Midwestern Sites, Environ-
mental Services Division, Region V, U.S. Environmental Protection Agency,
Westlake, Ohio, EPA 905/4-85-005, June 1985.
2. Michigan Dioxin Studies - Screening Survey of Surface Water Supplies,
Potable Ground Water, and Dow Chemical Brine Operations, EasternDistrict
Office, Environmental Services Division, Region \T, U.S. Environmental
Protection Agency, Westlake, Ohio, December 1985.
2a. Amendola, Gary A. and Barna, David R., Dow Chemical Wastewater Characteri-
zation Study - Tittabawassee River Sediments and Native Fish, Eastern
District Office, Environmental Services Division, Region V, U.S. Environ-
mental Protection Agency, Westlake, Ohio, July 1986.
3. Dioxin Strategy, Office of Water Regulations and Standards, Office of Solid
Waste and Emergency Response, Dioxin Strategy Task Force, U.S. Environmental
Protection Agency, Washington, D.C., October 20, 1983.
4. National Dioxin Strategy Tier 4 - Combustion Sources - Project Plan,
EPA 450/4-84-014a, Air Management Technology Branch,Office of Air and
Radiation, Office of Air Quality Planning and Standards, U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina, Draft, February
1985.
5. Quality Assurance Project Plan - Source Testing of the Dow Chemical Compact
Rotary Kiln Incinerator, Midland, Michigan, Contract No. 68-02-3168, Work
Assignment No.Ill,GCA/TechnologyDivision, GCA Corporation, Bedford,
Massachusetts, July 19, 1984.
6. Riggin, R.M., Compendium of Methods for the Determination of Toxic Organic
Compounds in Ambient Air, ContractHo~.68-02-3745(WA-9),Environmental
Monitoring SystemsLaboratory, Office of Research and Development, U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina.
7. Dow Chemical Company, Midland, Michigan, Incinerator Exhaust Sampling Plan,
Eastern District Office, EnvironmentalServices Division, Region V, U.S.
Environmental Protection Agency, Revision 7, September 24, 1984.
8. Report on Analyses Accomplished Under Special Analytical Services Order No.
1148-E, VolumesI-IV, Brehm Laboratory,Wright State University, Dayton,
Ohio, March 25, 1985.
9. Dow Chemical Company - Midland Plant Wastewater Characterization Study -
Preliminary Summary of Results, U.S. Environmental Protection Agency,
Region5, EnvironmentalServices Division, Eastern District Office,
March 28, 1983, page 26.
93
-------
REFERENCES (continued)
10.
Point Sources and Environmental r
benzo-p-dloxin) on the Midland Plant
Levels of 2378-TCDD (2.3,7,8-Tetrachlorodl-
Dow Chemical Company and
. ,. ' -•• — • •• • — Site of
in the City of Midland, Michigan,Sections
Midland, Michigan, November 5, 1984.
the
A-D, Dow Chemical Company,
13,
11.
Lewis, Robert 6., and MacLeod, Kathryn E., Portable Sampler for Pesticides
and Semi-Volatile Industrial Organic Chemicals in Air, J. Anal Chem., 1982,
54, 310-315 (February 1982).
12. Lewis, Robert, G., Brown, Alan, R., Jackson, D. Merrill, Evaluation of
Polyurethane Foam for Sampling of Pesticides, Polychlorinated Biphenyls and
Polychl orinated Naphthalenes in Ambient Air, Analytical Chemistry, Vol
Page 1668, October 1977.
49,
Lewis, Robert, G.
a High-Volume Air
and Jackson,
Sampler for
Merril 1,0.,
Pesticides
Modification and Evaluation of
andSemi-VolatileIndustrial
Organic Chemicals, Analytical Chemistry, Vol. 54, Pages 592-594, March 1982.
14. IERL-RTP Procedures Manual; Level 1 Environmental Assessment, 2nd Edition,
EPA-600/7-78-201, U.S. Environmental Protection Agency, Research Triangle
Park, North Carolina, October 1978.
15. Dow Chemical Company, Midland, Michigan, Ambient Air Sampling Plan, Eastern
District Office, EnvironmentalServices Division, Region V, U.S. Environ-
mental Protection Agency, Revision 3, June 15, 1984.
16. Qua!ity Assurance Project Plan
Chemical Company Complex, Midland^
Assignment No. Ill, GCA/Technology
Massachusetts, August 7, 1984.
- Ambient Monitoring in
Contract No
and Around the Dow
68-02-3168, Work
Michigan
Division,
GCA Corporation, Bedford,
17. Special Analytical
Management Office,
Virginia.
18. Special Analytical
Management Office,
Virginia.
Services Regional Request No. 1149-E, HWI Sample
U.S. Environmental Protection Agency, Alexandria,
Services Regional Request No. 1151-E,
U.S. Environmental Protection Agency,
HWI Sample
Al exandria,
19. Ambient Monitoring In and Around the Dow Chemical Company Complex, Midland,
Michigan, Contract No. 68-01-6769, Work Assignment No. 84-340, GCA/Tech-
nology Division, GCA Corporation, Bedford, Massachusetts, November 1984.
20. Agin, Ron, Superintendent, Environmental Operations, Dow Chemical Company,
to (Martin G. Trembly, U.S. Environmental Protection Agency, Region V,
Eastern District Office) June 26, 1985, ALS, 1 p.
94
-------
REFERENCES (continued)
21. Veurink, Gary, Dow Chemical Company to (Delbert Rector, Michigan Department
of Natural Resources) February 10, 1985, ALS, Ip.
22. 703 Incinerator: State of Michigan - Observed Experiments for Licensing
Under Michigan Act 64, Dow Chemical Company, Midland, Michigan, undated.
23. Personal communication with Michael Rio, Dow Chemical Company, April 15,
1986.
24. Rector, Delbert, Chief, Hazardous Waste Division, Michigan Department of
Natural Resources, to (James H. Story, Technical Manager, Environmental
Services, Dow Chemical Company) November 29, 1983, ALS, 2 pp.
25. Cleverly, David H., Estimation of the Public Health Risks Associated with
Exposure of CDDs/CDFs Emitted from a Waste Incinerator, and from Ambient
Monitored Concentrations, Office of Air and Radiation, Office of Air Quality
Planning and Standards, Strategies and Air Standards Division, Pollutant
Assessment Branch, U.S. Environmental Protection Agency, Research Triangle
Park, North Carolina, Review Draft, March 7, 1986, pp. 26-30.
95
-------
APPENDIX A
DETAILED DESCRIPTION OF CONDUCT OF STUDY
MICHIGAN DIOXIN STUDIES
DOW CHEMICAL BUILDING 703 INCINERATOR EMISSIONS STUDY
-------
APPENDIX A
I. SAMPLING METHODS
The following sections concern the selection of methods employed to detect
the compounds of interest from the various media that were sampled. Reference
is made to Tables V-l and V-2 of this report, where the compounds are differen-
tiated according to the analytical procedures necessary to detect them.
A. Precombustion Air
A high-volume air sampler modified for the collection of PCDD/PCDF, and
another similar sampler for semi-volatile organic compounds, were placed at
ground level between two and four meters from the rotary kiln combustion air
intake. Each sampler consisted of a glass fiber filter of the type commonly
employed in ambient air monitoring for particulate matter, followed by a
cylindrical trap containing 25 grams of 16/50 mesh Amberlite XAO-2 resin,
configured in a manner based upon that developed by Lewis et.al.12,13
Design flow rates for the two samplers were derived on the basis of
calculated resin breakthrough volumes for the compounds of interest. For
PCDD/PCDF, it was determined that a sampling flow rate of 1.1 to 1.5 m^/min,
and a total sample volume no greater than 720 scm, would be appropriate. For the
other semi-volatile (semi-VOA) compounds a flow rate of 0.6 to 0.8 m^/min was
selected, to result in a final sample volume not to exceed 350 scm. In actual
practice, however, both samplers operated at flow rates of approximately
0.7 m3/min owing to the air flow resistance presented by the tightly-packed
XAD-2 resin columns.
Volatile compounds (for VOA, or volatile organics analysis) were monitored
utilizing a low-volume sampler patterned after that described by Riggin.6
Sampling cartridges containing 1.5 grams of Tenax® GC [poly (2,6-diphenyl
phenylene oxide)] were suspended approximately two meters above ground and
three to four meters from the rotary kiln air intake. Air flow rates of 25 to
35 cm^/min were maintained for eight-hour sampling periods, with a target
sampled gas volume of 14.4 standard liters.
Field blank samples were procured for each of the three samplers on every
sampling day. In addition, a duplicate sample specific to each sampler was
provided on one of the three sampling days.
B. Liquid Waste Feeds
It was known prior to the sampling effort that the sources and composition
of waste delivered to the incinerator through each nozzle were likely to change
every two to four hours on average. Also, because many of the liquid wastes
were described by Dow personnel as containing more than 15 percent of single
compounds, special handling and extraction procedures, involving intermediate
A-l
-------
preparation of extracts by an EPA contractor laboratory prior to analysis by a
second contract laboratory, were required. These procedures are described
fully in Appendix B to this report. As extracts for semi-VOA and VOA analysis
were obtainable from the same samples utilizing these procedures, it was
necessary only to obtain single representative samples of each distinct waste
stream for these compound classes. For PCDO/PCDF, a second sample was required.
In summary, each waste stream was to be represented by a time-composited sample
for PCDO/PCDF, held in a 500-mL hexane-rinsed amber glass bottle, and a pair of
hexane-rinsed 40-mL clear-glass VOA vials with Teflon septa, each containing
composited aliquots of wastes. For VOA, care was taken to avoid agitation of
sampled wastes and minimize possible losses of the volatile compounds to be
analyzed. In any event, no sampling procedure for compositing VOA samples was
available.
For samples to be representative over time, it was planned to obtain portions
of liquid waste every half-hour, avoiding periods in which waste changes were
occurring. Thus, for an eight-hour sampling period, up to 17 individual sets
of grab samples were projected to be composited manually on an equal-volume
basis. However, in some cases few samples were taken where particularly viscous
or fuming wastes were handled.
Field blank samples were obtained on all three test days; a single field
blank represented nozzles "BA" and "BB" as the nozzles were spaced closely
together, while another field blank was taken for nozzle "C". Three field
duplicate samples were drawn, all on the second test day, of two wastes at
nozzle "BB" and a single waste at nozzle "C".
The following sections describe the ways in which the liquid waste sampling
plan was altered at each nozzle.
1. Nozzle "BA"
On all three test days, the origin of the liquid wastes flowing through
this nozzle remained constant throughout the test periods. However, Dow
Chemical personnel indicated the waste originated from a chlorosilane manu-
facturing process at the adjacent Dow Corning Corporation plant, and was a
fuming material which reacted violently with moisture in air. As the contents
of the tank truck connected to nozzle "BA" were reported to be well-mixed and
manual compositing would have presented a hazard to sampling personnel, it was
decided to obtain a single grab sample for PCDD/PCDF, and a pair of VOA samples,
midway through each test day.
2. Nozzle "BB"
During the sampling periods, two distinct wastes were fed through nozzle
"BB" on the first and second sampling days, and a single waste was burned on the
third day. Composites for PCDD/PCDF were manually formulated from the grab
samples taken every half-hour. For semi-VOA and VOA, compositing was also
performed on the first sampling day but was found to be laborious, with a high
risk of spillage of liquids. Therefore, on the second and third days, PCDD/PCDF
composites continued to be created, but to avoid the risks associated with
A-2
-------
compositing the lower-volume semi-VOA and VOA samples, it was decided that the
grab sample (pair of VOA vials) taken midway in time through each run of waste
would be chosen for analysis to represent that waste.
An indicated previously, field blank samples were obtained on all three
days in the vicinity of nozzles "BA" and "88", to apply to both nozzles.
Cleaned 500-mL amber glass bottles and 40-mL clear glass VOA vials were filled
with methanol for this purpose. Field duplicate samples were taken of the two
wastes processed on the second sampling day.
3. Nozzle "C"
On all three sampling days, the wastes fed through nozzle "C" remained
relatively constant throughout the sampling day, so that only a single set of
samples was required to represent each day. For PCDD/PCDF, these samples were
composited from grabs taken every half-hour on the first day and, to accommodate
time constraints, every hour on the third sampling day. Semi-VOA and VOA waste
samples were taken at times approximating the midpoint of these tests.
On the second sampling day, nozzle "C" waste was particularly viscous,
making representative compositing infeasible. Thus, a single set of grab
samples for PCDD/PCDF and semi-VOA/VOA was obtained at the start of the test
run; a field duplicate sample consisted of a second complement of grabs taken
at the same time. Field blank samples for all three days were made up of
methanol-filled sample containers kept closed in the vicinity of the nozzle "C"
sampling area for the duration of the test periods.
C. Low-BTU Liquid Waste
A spigot near waste nozzles "BA" and "BB" was drawn to obtain samples every
half-hour for PCDD/PCDF and semi-VOA. Equal volumes of this liquid were taken
and placed directly into composite bottles at these times. For volatile organic
analyses (VOA), grab samples were obtained every half-hour; however, as no
feasible method of compositing these samples was available, one sample taken
midway through the sampling period was selected for analysis. Field blank
samples, consisting of deionized water-filled sample containers, were taken on
each day.
D. Incinerator Exhaust
1. Modified Method 5 (MM5) Trains for PCDD/PCDF and Semi-Volatiles
Two trains were operated simultaneously in sampling ports placed 90° apart
in the exhaust duct downstream of the electrostatic precipitator. Each sample
train, constructed as shown in Figure A-l, and based on previous designs of the
MM5 train, consisted of a glass-lined, heated probe terminating in a stainless
steel button-hook nozzle and attached thermocouple and pi tot tubes. The probe
outlet was attached to a glass filter holder containing a tared glass fiber
filter (Reeve Angel 934 AH) maintained at a temperature of 248°F +_ 25°F in an
electrically-heated oven. Following the filter, sample gas passed through
A-3
-------
PROBE
REVERSE-TYPE
PITOT TUBE
FLOW
THERMOSTATIC
WATER BATH
UNGREASED-
FITTINGS
HEATED
FILTER
XAO BACKUP
r-THERMOMETER
L f S-VA\
llr^'
CHECK
VALVE
5*?
I
l
2 3 4 i
VACUUM
' LINE
THERMOMETER
BY-PASS
VALVE
ORIFICE^
MANOMETER
TEST\
METER
J
VACUUM
GAUGE
P.
MAIN
VALVE
I \ AIR
^
TIGHT
PUMP
FIGURE A-l
MODIFIED METHOD 5 EXHAUST GAS SAMPLING TRAIN
A-4
-------
flexible Teflon tubing to a water-cooled module containing approximately 25
grams of XAD-2 resin. A thermostatically-controlled water bath maintained the
sorbent temperature at 70°F or below.
Water condensed from the gas stream passing through the XAD-2 module was
retained in an impinger fitted with a short-stem inlet to avoid sample gas
bubbling through collected condensate. The second and third impingers each
held long-stem inlets; the second impinger was filled with 100 ml of deionized
water at the start of sampling, while the third impinger was empty. A backup
sorbent cartridge containing 7.5 grams of XAD-2 was placed between the third
and fourth impinger. The fourth impinger held approximately 200 grams of
indicating silica gel to remove traces of water from the sampled gas. All
connections within the trains were composed of nonreactive materials such as
glass or Teflon, and no sealant greases were employed. Sampled gas flowed
through a check valve, tubing with a vacuum pump connected in parallel with a
bypass valve, a dry gas meter, and an orifice and manometer for instantaneous
flow rate measurement.
As indicated previously, two trains configured as above were operated
simultaneously at a location in which two sampling ports were placed 90° apart.
Initial plans called for a sampling period of eight hours, to obtain sufficient
volumes of sample extracts for replicate analysis, sample splitting, and
archiving. However, on the first sampling day, air flow through both trains
could not be maintained for longer than approximately 6 1/2 hours. Apparently,
the resistance to flow presented by the sorbents in the train and possibly
collected moisture was too great to be overcome by the pump powering the sampling
train. As a result of this experience, the planned sampling period was reduced
to six hours on the second and third sampling days.
Uwing to time delays, and the risk of causing leaks in the sampling trains
by moving them, both trains remained on the same traverse in the exhaust duct
during all three sampling periods. Thus, the trains sampled each point twice on
the same traverse; the traverses were alternated such that one pair of diameters
was employed on the first sampling day, and the other pair of diameters was
used for the PCDD/PCDF and semi-volatile trains on the second and third days.
This was done to avoid unnecessary movement of sampling trains in the limited
space available on the sampling platform, and was not anticipated to have any
significant effect on analytical results.
Two field blank trains were assembled for each sampling day and allowed to
remain undisturbed near the nn5 sampling area. Sorbents and impinger contents
of the sample and blank trains for PCDD/PCDF were removed from the trains by
the analytical laboratory, with the exception of the sampling probe wash, which
was conducted by the field contractor and placed in an amber glass bottle. The
sample and blank trains for semi-volatile compounds were disassembled and rinsed
by the field contractor, and placed in containers for shipment to the analytical
laboratory. Field duplicate samples were not obtained as both sampling ports
were utilized simultaneously.
A-5
-------
2. Volatile Organic Sampling Train (VQST)
The VOST was constructed consistent with configurations developed by Midwest
Research Institute, as shown in Figure A-2. The train was composed of a heated
glass-lined probe with a plug of glass wool placed at the tip to remove
particulate matter. A series of condensers and organic resin traps followed
the probe; the first condenser cooled the sample gas stream to condense water
vapor. Sampled gas and condensed water vapor then passed through a cartridge
containing 1.5 grams of 60/80 mesh Tenax GC®. Condensate was collected in the
first impinger; the second condenser and a trap containing approximately 1 gram
of Tenax and 1 gram of activated charcoal were positioned to retain compounds
having low breakthrough volumes. A second impinger and a drying tube followed
the second sorbent trap, for residual moisture removal.
Sample temperatures were monitored with thermocouples at the outlet of the
probe and the inlet of the first Tenax cartridge. Gas temperatures within the
probe were maintained above 130°C to avoid premature condensation of volatile
compounds; through the resin traps, gases were cooled to 20°C or below.
All of the VOST sampling runs with the exception of two were conducted for
40 minutes at sample gas flow rates of 0.5 liter per minute, resulting in a
total collected volume of 20 liters. For the remaining two runs, a sampling
rate of 1 liter per minute was maintained for 20 minutes; one of these runs was
that in which a field duplicate sample was taken.
Five or six VOST runs were completed on each sampling day. For each run,
the two sorbent tubes were submitted for analysis as single samples. Between
runs, the sorbent cartridges were changed; however, the condensate impingers
remained in place for entire sampling days and thus represented a composite of
all of the runs. The sorbent cartridges were transferred to containers packed
with activated charcoal for shipment to the analytical laboratory, while the
contents of the condensate impingers were placed in 40 mL VGA vials. Head
spaces in these vials were eliminated by the addition of distilled, deionized
water.
In addition to the single field duplicate sample noted above, field blanks
of the VOST were taken on each sampling day. These unexposed sampling materials
remained in the sampling area for complete days while all of the VOSTs for that
day were utilized. The cartridges and condensate impingers were then handled
in the same manner as regular samples.
3. Tedlar Bag Samples for Vinylidene Chloride
Samples were collected for approximately one hour utilizing an apparatus as
shown in Figure A-3. The sampling assembly consisted of a cleaned, evacuated
Tedlar bag placed inside a rigid container. Prior to sampling, each bag was
purged with prepurified nitrogen. The Teflon sampling tubing was attached to
the Tedlar bag container by a quick-disconnect coupling.
A-6
-------
HEATED SAMPLING PROBE
•GLASS WOOL
THERMOCOUPLE
ICC WATER
CONDENSER
THERMOCOUPLE
TENAX
CARTRIDGE
ICE WATER
CONDENSER
TENAX/CHARCOAL
CARTRIDGE
VACUUM
•GAUGE
VALVE
—CXI—i
ROTAMETER
PUMP
MIMET
IMPINttCRS
FIGURE A-2
VOLATILE ORGANIC SAMPLING TRAIN
-------
m M M M
FIGURE A-3
TEDLAR BAG SAMPLING SYSTEM FOR VINYLIDENE CHLORIDE
oo
STAINLESS STEEL
PROBE
TEFLON LINE
GLASS
CONDENSER
UNIT
TO PUMP
ICE BATH
TEDLAR BAG
-------
Within two hours after sampling, filled bags were transported to a field
laboratory in which direct analyses were performed with a gas chromatograph-
electron capture detector (GC-ECD). One field bias blank, consisting of a
bag filled with prepurified nitrogen, was analyzed daily. One collocated field
duplicate sample was obtained on the second day of sampling. A description of
the GC-ECD and its operating conditions are described in Table A-l.
4. Continuous Emissions Monitoring System
Incinerator combustion conditions were monitored utilizing a continuous
emissions monitoring system (CEMS) assembled as shown in Figure A-4, consisting
of a gas conditioning module, monitors for measurement of CO, C02, and 03, and
a data acquisition system. Samples were extracted from the exhaust gas stream
at a point described previously; the effects of the carbon adsorption bed
exhaust, described in Section V of this report, on the measured flue gas
components were expected to be minor.
Sampled gas passed through a glass fiber filter for particulate removal,
and then to a two-stage drier composed of a condenser and permeation drier.
Conditioned gas was analyzed with the instruments detailed in Table A-2.
Exhaust gas was to be monitored for the duration of each Modified Method 5
test run. However, equipment startup problems, and the occasional necessity to
utilize the sampling location for other measurements, prevented the continuous
use of the CEMS. To supplement and check the CEMS, integrated samples were also
obtained and analyzed using an Orsat analyzer.
E. Incinerator Ash
As indicated previously, samples of this material were taken from a dragout
chain serving the ash trough. The chain was known from prior inspections of
the facility to be started manually by an operator, approximately every hour on
the hour. Therefore, a representative of the field contractor was present
every hour to take, or supervise Dow personnel taking, portions of the solid
material lifted out of the ash trough on an appropriate number of flights on
the dragout chain. Typically, this meant samples were taken from three to five
flights per hour; there was insufficient solid material remaining on the dragout
chain to sample more flights than this. On occasion, fewer than three flights
were sampled when ash removal was particularly light. Large pieces of
incompletely-burned wood or fused metal were avoided in sampling owing to their
unrepresentativeness when related to the full sample, and the impossibility
of providing representative split samples to Dow Chemical and EPA contract
laboratories.
Individual grab samples were taken from the chain utilizing a hexane-rinsed
aluminum scoop mounted on a pole, and placed in a hexane-rinsed five-gallon
glass jug to be held for later compositing and sample splitting. Compositing
was performed by later emptying the jug contents on a floor or ground area which
was covered first with a clean sheet of cardboard, in an area well separated
from the incinerator, mixing and quartering them, and apportioning quarters
with a cleaned scoop into separate washed glass containers for Dow and EPA
analysis.
A-9
-------
i
TABLE A-l
GC-ECD OPERATING CONDITIONS FOR VINYLIDENE CHLORIDE ANALYSIS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
m
m
i
Instrument
GC Conditions
Column
Temperature program
Injector temperature
ECD temperature
Carrier flow
Loop Conditions
Volume delivered
Loop temperature
Perkin Elmer 3920
20% SP2100/0.1% carbowax
1500 on 100/120 supelcoport
10' x 1/8" SS Column
Isothermal at 50°C
110°C
325°C
25 ml/rain, argon/methane
1 ml
125°C
A-10
-------
mmmMMMMM
INSTACK
FILTER
O
CALIBRATION
GASES (CO, C02,
°2
t
CONDENSATION/
PUMP ING.SYSTEM
SAMPLE DISTRIBUTION
SYSTEM: SAMPLE. LOCAL
CALIBRATIONS, PROBE
CALIBRATIONS
FIGURE A-4
SCHEMATIC DIAGRAM
CONTINUOUS EMISSIONS MONITORING SYSTEM
HORIBA PIR 2000
CO
MSA 802
°2
HORIBA PIR 2000
CO,
EXHAUST
-------
M ft ft ft M ft ft « B ft fi • 1 1 11
TABLE A-2
CONTINUOUS EMISSIONS MONITORING SYSTEM OPERATING CONDITIONS
Operating
sensitivity
ranges
Operating
temperature
ranges
Analysis method
Linearity
Accuracy
Drift
Horiba
PIR 2000
C02 analyzer
0-5% C02, FS
0-15% C02, FS
0-25% C02, FS
24°F - 122°F
Nondispersive infrared
+ 1% FS
•«• 1% of Full Scale
+ 1% of Full Scale
Horiba
PIR 2000
CO analyzer
0-1000 ppm CO, FS
0-3000 ppm CO, FS
0-5000 ppm CO, FS
24°F - 122°F
Nondispersive infrared
+ 1% FS
+ 1% of Full Scale
+ 1% of Full Scale
MSA
02 analyzer
0-5% 02, FS
0-10% 02> FS
0-25% 02, FS
32°F - 109°F
Paramagnetic wind
+ 1% of Full Scale
+ 1% of Full Scale
<5% Full Scale for
Noise level
in 24 hours in both
zero and span
<0.5% of Full Scale
in most sensitive range
in 24 hours in both
zero and span
<0.5% of Full Scale
in most sensitive range
24 hours in both zero
and span
<.25% of Full Scale
in most sensitive range
-------
Water entrained with sampled ash was allowed to drain, as much as possible,
out of the samples. Ash trough water was sampled separately.
F. Influent and Effluent Water and Control Device Ash
1. Influent Service Water
Grab samples of influent service water (returned secondary treatment water)
for PCDD/PCDF and semi-volatiles were taken taken every half-hour during the
first and second sampling days, and, to accommodate time constraints, every
hour on the third day. Individual samples were obtained in a washed and hexane-
rinsed bottle, the contents of which were placed in a washed and hexane-rinsed
brown glass one-gallon bottle for compositing on an equal-volume basis. For
VOA, a pair of single grab samples was taken directly into washed 40-mL vials
with Teflon septa, midway through each sampling period.
2. Effluent Waters
Effluents, as described previously, arose from the quench tower, venturi
scrubber and demister (combined stream), electrostatic precipitator, and ash
trough. Each of these streams was sampled utilizing ISCO automatic sampling
devices, for PCDD/PCDF and semi-volatiles, and by taking single grab samples
for VOA, as detailed above for influent service water.
The automatic samplers were set to draw a volume of water every half-hour
during the incinerator exhaust sampling period, sufficient to fill to an
appropriate level a five-gallon clear-glass bottle (washed with deionized water,
methanol, and methylene chloride, and oven-dried) held inside it. The bottle
was surrounded with ice for preservation of the sample. At the conclusion of
sampling, portions of this total sample were poured into washed and hexane-rinsed
one-quart brown-glass bottles to be submitted to the analytical laboratories
for PCDD/PCDF and for semi-volatile compounds.
For VOA, each sampling location was represented by filling a single pair of
40-mL vials at a time corresponding closely to the midpoint of each sampling run.
At all four locations, this process necessitated transferring samples from
direct sampling containers, such as a large clear glass bottle, into the vials.
In all cases, care was taken to fill the vials in a quiescent manner such that
the head spaces were devoid of gases.
3. Control Device Ash
The Tier 4 Dioxin Strategy referenced previously required analyses of
control device ash; the control devices at the Dow Chemical incinerator collected
solid particles which were dispersed in water. Therefore, PCDD/PCDF and semi-
volatile compounds in each of the four effluent water streams were analyzed
separately in the aqueous and filterable solid phases. The latter analysis
was estimated to be a reasonable representation of the presence of the analyzed
compounds in the particulate or ash fraction of the control device water
discharges.
A-13
-------
II. SAMPLE IDENTIFICATION, HANDLING, AND CUSTODY
Samples were obtained by employees of the field contractor, GCA/Technology
Division (GCA), and labeled according to a predetermined coding system. Where
multiple grab samples were taken for compositing or transport out of the Dow
Chemical facility, the samples were generally held in closed coolers near the
individual sampling points; these coolers were inspected periodically to guard
against tampering. Incinerator ash samples were stored in closed jars adjacent
to the dragout chain in a location where visual custody was maintained by GCA or
EPA personnel. Likewise, automatic samplers used for effluent water sampling
were set in areas in which they were open to constant view.
As sampling was performed on one day and generally shipped to analytical
laboratories on the next day, it was necessary to hold samples overnight prior
to packing and logging. Two lockable trailers, one near the incinerator and
the second placed on Dow Chemical property immediately outside the plant fence
line, were used for secure storage.
Sample compositing and splitting were performed by or under the direct
control of GCA personnel. After samples were placed into appropriate containers
for shipment, they were relabeled to enable quick identification by contract
analytical laboratories. A master cross-referenced list of samples and their
identifying labels was formulated and maintained by the EPA project manager.
Sample containers were arranged as appropriate in shipping coolers and log
sheets were completed to describe all of the samples in each cooler. On the
first sampling day, the log sheets were written manually on standard EPA manifold
custody forms; on the second and third sampling days, custody forms were created
and reproduced using a computer and printer. Each individual cooler was packed
with coolant and shock-absorbing material, and closed and sealed with custody
tape imprinted with GCA identification. The samples were shipped to the
analytical laboratories via Federal Express.
Information on liquid waste feedstocks was obtained from Dow Chemical prior
to the start of sampling. Dow Chemical indicated that many or most of these
wastes were composed of 15 percent or more of a single constituent. Therefore,
liquid waste samples and blanks (made up of methanol) required special handling
as "high-hazard" materials. These wastes were composited (where compositing
was done) and placed into the smallest appropriate container, in this case
40-mL vials. Specialized tracking records were completed for each distinct
sample, and all such samples were packed consistent with Department of Transpor-
tation regulations for flammable liquids or flammable-corrosive liquids, and
shipped to an intermediary laboratory for extraction.
The above discussion applied to all samples with the exception of the
Modified Method 5 PCDD/PCDF sampling trains, and the liquid waste samples
analyzed for PCDD/PCDF. After sampling, these samples were stored in the
contractor trailer outside Dow Chemical property until the conclusion of the
three days of sampling; appropriately labeled, packed, and logged; and trans-
ported by automobile to the analytical laboratory.
A-14
-------
III. ANALYTICAL PROCEDURES
Procedures for analyzing samples for semi-volatiles and volatiles are
contained in Reference 7 to this report, while PCDD/PCDF methods are indicated
in References 7 and 8. For convenience, the specific analytical procedures and
quality assurance aspects relating to analyses of PCDD/PCDF by the contract
laboratory, the Brehm Laboratory, Wright State University, are excerpted from
Reference 8 and presented as Appendix C to this report.
A. Semi-Volatiles and Volatiles
Volatile pollutants, generally those with boiling points lower than 100°C,
were analyzed according to EPA Method 624. Water samples, including the
incinerator influent and effluents, and VOST impinger liquids, were concentrated
and analyzed directly using this method. However, solid sampling media (Tenax
and charcoal) were desorbed in a Nutech thermal desorption unit at 190°C for 10
minutes at 30 mL/min with helium, directly onto the head of the GC column,
which was held at 20°C.
Semi-volatile pollutants with boiling points above 100°C were analyzed using
EPA Method 625 for base/neutrals and acids. As with volatile component water
samples, impinger washes were concentrated and analyzed. In the Modified
Method 5 train, front half samples (probe washes and filter) samples were
analyzed as a unit. To accomplish this, the probe wash was concentrated and
the filter extracted separately, and the fractions were combined before
analysis. Results were typically reported in ug/L as the relative weight of
probe wash was much greater than that of the filter. The filter, XAD-2 resin
samples, samples of incinerator ash, and the solid filtrates from effluent
waters were Soxhlet extracted with methylene chloride for 16 hours in preparation
for analysis. All analyses were performed in a Finnigan model 4000 GC/MS.
B. PCDD/PCDF
As indicated above, References 7 and 8, and Appendix C to this report
contain descriptions of the methods used to analyze samples for PCDD/PCDF, and
specific TCDD isomers.
C. Tedlar Bag Samples for Vinylidene Chloride
Whole-air samples were analyzed on a Perkin Elmer model 3920 GC/ECD
maintained under the conditions shown in Table A-l. The gas chromatograph was
calibrated prior to each daily run with zero gas and four typical upscale
vinylidene chloride concentrations: 27, 50, 111, and 235 ppb. A fifth
upscale concentration, 531 ppb, was added when measured vinylidene chloride
concentrations exceeded 235 ppb.
A-15
-------
Gas samples were taken for periods of 30 to 65 minutes, such that bags
were filled with a volume sufficient to be analyzed. As each sample was analyzed
in triplicate, the analytical process typically required a longer time than did
sample collection, prompting concerns about the stability of samples while
being held for analysis. Therefore, three bag samples were reanalyzed on the
day following the first and third sampling days. The results of these tests
indicated good sample stability over nearly 24 hours' holding time, and suggested
that reactions, leaks, or other changes occurring in samples being held for one
to four hours before analysis were not significant. Sample bags were used only
once and then discarded, to avoid contamination or wall effects from sample to
sample.
D. Continuous Emissions Monitoring System (CEMS)
The arrangement of the continuous emissions monitoring system employed to
analyze incinerator exhaust gases has been described previously. The specifica-
tions (see Table A-2) of the system show goals for relative accuracy and
zero and span drift. Results of Orsat analyses for oxygen and carbon dioxide
were compared with average data from the CEMS to derive relative accuracy
comparisons; as carbon monoxide concentrations were below the range of sensi-
tivity of the Orsat, it was not possible to evaluate relative accuracy with
respect to CO. Zero and span drift were determined approximately six weeks
after the completion of the study, and the results showed the following:
Instrument Zero Drift (%) Span Drift (%)
MSA 802 02 analyzer 0.00 0.52
Horiba PIR-2000 C02 analyzer 0.00 0.00
Horiba PIR-2000 CO analyzer 0.00 1.09.
These results compared favorably with the criteria shown in Table A-2.
A-16
-------
IV. WASTES INCINERATED AND INCINERATOR OPERATIONS
Dow Chemical provided general information concerning the types of liquid
and solid waste materials incinerated on each sampling day. In addition, basic
descriptions of the chemical composition of each of these wastes were furnished,
as every waste was labeled with a serial number corresponding to an analytical
form filed internally by the company.
A. First Sampling Day - August 28, 1984
Company information indicated the wastes burned on this day consisted of
bulk rubbish; drums and fiber packs (containerized solid wastes); and liquid
wastes fed through all four input nozzles, including that for low-BTU liquid
waste. These wastes are described below:
1. Rubbish
Bulk rubbish consisting of paper, cardboard, plastics, and wood was input
continuously throughout the sampling period, at an average rate indicated by
Dow Chemical to be 19.9 cubic yards per hour, or about 9950 pounds per hour.
2. Containerized Solid Wastes
A total of 84 containers of solid waste were incinerated between 1235 and
2000 EOT; below are general descriptions of each.
Dow ID
Number
1425-04
137-02
1244-01
1202-03
2603-01
Q8-6039-01
8793-01
1552-02
2603-02
2521-06
Number
Fed
6
18
5
1
13
8
21
10
1
1
Total
Weight (Ibs)
267
approx. 3000
381
120
600
1420
2954
1322
90
89
approx.
Primary Constituents
Glass, plastic filters
Latex, plastic wastes, rubber
Acrylamide, acrylonitrile
Glass, toluene, ethanol
Plastic and saran wastes
Filter aids, silicones, hydrocarbons
Miscellaneous Styron wastes
ABS resin
Mineral spirits, methanol, MEK
Glass, PVC, tars
(Total) 84 approx. 10200
3. Nozzle "BA" Feed
A single waste, identified as number Q8-6011-01 and consisting of chloro-
silanes, benzene, chlorobenzene, toluene, and other hydrocarbons, was fed from
a tank truck. The Dow Corning facility located near the Dow Chemical plant was
the source of the waste. The average flow rate of this waste was estimated by
Dow Chemical as 900 pounds per hour.
A-17
-------
4. Nozzle "BB" Feeds
Two liquid waste mixtures were fed. From 1235 until 1606 EOT, wastes from
a storage tank were delivered at an average rate of 1764 pounds per hour.
The components of this mixture were reported by Dow Chemical as follows:
Dow ID Number Primary Constituents
8420-01 Sodium acetate, Dowanol, toluene
8440-03 Amines, Dowanols
8492-06 Polyoxyalkylene ether
8531-01 Alkanolamines, ethyl alcohol
8585-02 Butylene glycol, butylene oxide
From 1606 until the end of sampling at 2000 EOT, 972 pounds per hour of
waste 1450-05 were fed from a direct-burn trailer. Dow's waste description
showed this waste to be composed of 85% methanol and 15% ammonia.
5. Nozzle "C" Feed
Waste 1546-01 was delivered from a tank trailer at an average rate of 2360
pounds per hour. This waste was described by Dow as containing ethanol, toluene,
acetone, and about 2% Probucol in water.
6. Low-BTU Liquid Waste
From 1400 until the end of sampling, approximately eight gallons per minute
(4000 pounds per hour) of collected precipitation were fed to the incinerator.
7. Incinerator Operational Characteristics
No abnormal operating phenomena were cited by Dow personnel. A summary of
incinerator operating data recorded at 15-minute intervals by Dow personnel
throughout the sampling day appears in Table A-3, and in Table A-4 are
exhaust gas oxygen, carbon dioxide, and carbon monoxide data as measured by the
previously-described continuous emissions monitoring system; note that this
system operated only during the second half of the first sampling day.
B. Second Sampling Day - August 30, 1984
Incinerated wastes included bulk rubbish; drums and fiber packs; and liquid
wastes fed through all but the low-BTU liquid waste nozzle.
1. Rubbish
A continuous feed of loose solid waste was provided, at an average rate of
17.1 cubic yards per hour, or about 8550 pounds per hour.
2. Containerized Solid Wastes
Between 1005 and 1630 EOT, 73 containers described below were incinerated.
A-18
-------
Table A-3
Incinerator Operational Data
8/18/84 8/30/84 9/5/84
1235-2000 1005-1630 1010-1630
Rotary Kiln Temperature (°C) 823-1016 851-1089 877-998
Afterburner Temperature (°C) 1038-1106 1013-1096 1013-1121
Quench Water Flow (gpm) 703-717 706-724 719-727
Venturi Scrubber Water Flow (gpm) 265-276 252-264 207-223
Venturi Differential Pressure 26.3-28.7 20.7-25.8 16.6-19.4
(in. H20)
Demister Water Flow (gpm) 961-989 961-985 968-987
ESP Water Flow (gpm) 169-177 172-176 160-181
A-19
-------
Table A-4
Exhaust Gas Data
As Measured by Continuous Emissions Monitor
Oxygen (%) Carbon Dioxide (%) Carbon Monoxide (ppm
Date
8/28/84
8/30/84
9/5/84
Time
Measured
(EOT)
1620-2030
1120-1650
1030-1710
Average*
11.76
12.74
11.28
Std.
Deviation
0.35
0.34
0.82
Average*
6.73
6.00
6.21
Std.
Deviation
0.47
0.49
0.50
Average*
47.5
62.7
32.4
Std.
Deviation
16.7
55.9
22.7
* Arithmetic averages of ten-minute-averaged
data during measurement period cited.
A-20
-------
Dow ID Number Total
Number Fed Weight (Ibs) Primary Constituents
1202-05 19 1159 Wood fiber
8793-01 4 647 Miscellaneous Styron wastes
8893-13 43 4292 Styrene, acrylonitrile, ethylbenzene
1245-05 3 128 Unspecified polymer
1136-01 4 24_ Miscellaneous laboratory wastes
(Total) 73 6250
3. Nozzle "BA" Feed
Approximately 1800 pounds per hour of Dow Chemical waste Q8-6011-01, the
same as burned on the first sampling day, was fed to the rotary kiln through
this nozzle.
4. Nozzle "BB" Feeds
From 1000 until 1415 EOT, wastes from a storage tank, consisting of a
mixture of the following, were fired at a rate of 682 pounds per hour:
Dow ID Number Primary Constituents
8420-01 Sodium acetate, Dowanol, toluene
8440-03 Amines, Dowanols
8440-05 Brake fluids, Dowanols, Dowfroth, polyglycols
8492-01 Acrylamide/acrylic acid copolymer
8492-06 Polyoxyalkylene ether
8531-01 Alkanolamines, ethyl alcohol
8585-02 Butylene glycol, butylene oxide
8769-01 Styrene, benzene, ethylbenzene wastes
From 1415 until the end of sampling, another tank mixture, described below,
was fed to this nozzle at a rate of 1200 pounds per hour:
Dow ID Number Primary Constituents
8052-04 Dimethyl sulfoxide, sodium chloride
8052-07 Dimethyl sulfoxide, dimethyl phthalate, tars.
5. Nozzle "C" Feed
Viscous liquids stored in a stationary tank were fed to the afterburner
section of the incinerator at a rate of 1171 pounds per hour. The tank contents
were a mixture of the following:
Dow ID Number Primary Constituents
9018-03 #2 Diesel oil
9026-01 Phenolic tars, p-phenylphenol.
A-21
-------
6. Low-BTU Liquid Waste
No wastes of this kind were incinerated on this date.
7. Incinerator Operational Characteristics
These data appear in Table A-3. Air pollution control equipment operations
were normal, with the exception of a period from 1515 EOT until the end of
sampling, in which occasional arcing was noted in the electrostatic precipi-
tator, the result of water bridging between the emitting plate and the sidewall
retaining bolts. Facility personnel indicated such arcing would ordinarily have
triggered the shutdown of the incinerator to allow cleaning of the interior of
the precipitator, had it become more severe.
In Table A-4, data concerning exhaust gas characteristics appear. Of
particular interest are the relatively high CO concentrations measured. This
reflects comparatively high peak CO values recorded at intervals corresponding
to the introduction of containerized solid wastes to the incinerator, or approxi-
mately every six minutes. On several occasions, CO measurements exceeded the
scale of the monitor (0 to 1000 ppm); as a result of these sharp peaks, the
standard deviation of these measurements is also high.
C. Third Sampling Day - September 5, 1984
Incinerated wastes included bulk rubbish; drums and fiber packs; and
liquid wastes from all four input nozzles during the sampling period, 1010 to
1630 EOT.
1. Rubbish
Loose rubbish was fed continuously at an average rate of 20.8 cubic yards
per hour, or about 10,400 pounds per hour. Most of these wastes consisted of
cardboard, wood, and plastic; a small portion was described as wet, and some
scrap fiberglass insulation was incinerated.
2. Containerized Solid Wastes
A total of 58 containers of solid waste were incinerated at a uniform rate
between 1010 and 1630 EOT. Their contents are described below:
Dow ID Number Total
Number Fed Weight (Ibs) Primary Constituents
358-07 1 166 Demolition wastes
1586-07 17 812 Dowco 453ME
1250-02 2 143 Miscellaneous laboratory wastes
1223-01 2 approx. 250 Miscellaneous laboratory wastes
1156-01 1 111 Miscellaneous waste solvents
1145-01 1 174 Organic solvents
1224-08 8 409 DMSO, perch!oroethylene
1224-02 1 177 Miscellaneous laboratory wastes
A-22
-------
1407-07
1215-04
1215-02
8428-03
1584-02
10
1
1
12
1
(Total) 58
3. Nozzle "BA" Feed
1459
57
81
3375
106
7320
Polyethyloxazoline
ABS, ethyl benzene, styrene
Styrene, ethyl benzene
Sodium trichloropyridinate
Dursban, methylene chloride
solid sorbent
Dow Corning wastes were incinerated at an average rate of approximately
1726 pounds per hour. As indicated previously, this waste, number Q8-6011-01,
was composed of chlorosilane, benzene, chlorobenzene, toluene, and other
hydrocarbons.
4. Nozzle "BB" Feeds
A mixture of the following liquid wastes was incinerated at an average rate
of 3002 pounds per hour.
Dow ID Number
688-03
8020-01
8420-01
8440-03
8440-05
8492-01
8492-06
8531-01
8585-02
8769-01
5. Nozzle "C" Feed
Primary Constituents
Waste oils, chloroethylene, ethylene glycol
Methyldi ethanolami ne
Sodium acetate, Dowanol, toluene
Amines, Dowanols
Brake fluids, Dowanols, Dowfroth
Acrylamide/acrylic acid copolymer
Polyoxyalkylene ether
Alkanolamines, ethyl alcohol
Butylene glycol, butylene oxide
Styrene, benzene, ethyl benzene wastes
A
truck
Dow Chemical
mixture of wastes referred to as "Canada-02" was delivered from a tank
at a rate of 1758 pounds per hour. Chemical composition data provided by
indicates the waste consisted primarily of styrene, with the
following constituents also present, in descending order: carbon tetrachloride,
4-vinyl cyclohexene, benzene/butadiene, ethyl benzene, isopropyl benzene, and
n-propylbenzene.
6. Low-BTU Liquid Waste
A mixture of aqueous wastes described by Dow Chemical as collected precipi-
tation, condensate from tank storage area carbon bed regeneration, and water
from hydroblasting cleanup, was fed to this nozzle at a steady rate of 4754
pounds per hour between 1130 and 1630. Before this, water flow was intermittent.
A-23
-------
7. Incinerator Operational Characteristics
No operational abnormalities were reported by Dow personnel. Tables A-3
and A-4 contain operational data and exhaust gas measurements obtained through
continuous emissions monitoring.
A-24
-------
APPENDIX B
EXTRACTION PROCEDURE FOR "HIGH-HAZARD" LIQUID WASTE SAMPLES
FRED C. HART ASSOCIATES, INC.
MICHIGAN DIOXIN STUDIES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR EMISSIONS STUDY
-------
Method: RSL-901
Page: 1 of 5
Date: June 1984
Replaces: All previous editions
Separation and Aliquoting High Hazard Waste Samples
1. Scope and Application
This is a general purpose method that provides procedures
for phase separating and aliquoting high hazard waste
samples taken from drums, lagoons, tanks, landfills, and
other uncontrolled hazardous wastes. The method is appli-
cable to a wide range of analyses including volatile organics,
semi-volatile organics, total metals, spot tests,
and strong acid anions.
2. Summary of Method
2.1 Individual phases are separated by decanting and
centrifuging. After separation, phases are weighed to
a tenth of a gram and recomposited by percent weight
(except for compositional analysis). Prior to recom-
position, liquid phases are tested for water misci-
bility.
2.2 Phase separation and recomposition is performed in
order to obtain representative aliquots from the
original sample.
3. Definitions
The characteristics of the samples defined below are the
only descriptions to be used in describing the physical
attributes of the sample:
Phase - A solid (gel or paste), water miscible liquid,
non-water miscible liquid.
Paste - Inseparable solid and liquid.
Viscosity - Non-viscous, similar to water, or viscous.
Color - Colorless, light of the color, medium of the color,
or dark of the color. Use only primary and second-
ary colors.
Texture - Fine grain (powdery), medium grain (sand), or
course grain (large crystals).
Turbidity - Clear, cloudy (transmits light), or opaque.
B-l
-------
June 1984 Page 2 of 5
Method: RSL-901
Minor phase - Phases that represent less than or equal to 5% by
weight for mercury aliquoting. Phases that
represent less than or equal to 2% by weight for
all other aliquoting.
4. Artifacts
Artifacts may occur in samples depenoing on the nature of
the waste and how it is obtained. Aitifacts are not minor
phases but are due to extraneous agents not of the waste.
When excluding a portion of a sample from recompositing
based on the apparent presence of an artifact, the decision
should be fully documented on the laboratory bench sheet.
5. Safety
High hazard samples are expected to contain concentrations
of substances of unknown toxicity and carcinogencity up to
100% by weight. Thus, each sample is to be treated as a
potential health hazard and exposure to these samples is to
be minimized. Each analyst is responsible for maintaining
awareness of safe handling procedures used in this method.
The samples are collected, packaged, and shipped according
to recommended procedures for hazardous wastes and are to be
prepared using the following method in a Regulated Substances
Laboratory prior to analysis.
6. Apparatus and Equipment
6.1 Radiation meter with pancake probe
6.2 Centrifuge, explosion-proof
6.2.1 large process type for 8 oz. jars
6.2.2 small type for vials
6.3 Vials and Jars
6.3.1 2 dram
6.3.2 40 mL
6.3.3 20 mL
6.3.4 8 oz. jar
6.3.5 4 oz. jar
B-2
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June 1984 Page 3 of 5
Method: RSL 901
6.4 Pipets, various sizes
6.5 Balance, four place
6.6 Spatulas, various types
6.7 Miscellaneous
6.7.1 Kimwipes
6.7.2 Soap and water squir; bottles
6.7.3 Methanol squirt bottles
6.7.4 Plastic bags, various sizes
6.7.5 Stainless steel trays
6.7.6 Teflon liners, various sizes
7. Sample Handling
Samples are removed from shipping cans inside a hood and
repackaged after phase separation and aliquoting in the same
manner. Only dilutions, digestions or extractions of a
sample may be removed from the RSL; however, upon special
request small amounts of undiluted samples may be taken from
the regulated area.
8. Procedure
8.1 Traffic Report/Sample Verification
8.1.1 Verify Traffic Report against sample identifi-
cation tag. If custody seal is present, sign and
date where provided. Verify the information on the
sample tag with the phase separation record. If
there are any discrepancies, the sample tag is
checked against the Chain-of-Custody record. The
differences are recorded under sample tag information.
Reconciliation is made bv Sample Control if necessary.
8.2 Place sample can inside small plastic bag. Remove lid
from can and perform radioactivity check. If positive,
replace can lid, remove gloves and vacate lab. Remove
sample from can and record sample condition on Phase
Separation Record and Traffic Report. Wipe down
sample container with a Kimwipe moistened with soapy
water.
B-3
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June 1984 Page 4 of 5
Method: RSL 901
8.3 Open sample container and again perform radioactivity
check and record results. If positive, replace jar
lid, remove gloves ano vacate the lab area.
8.4 Complete any other header information on the phase
separation record.
8.5 Phase Separation
8.5.1 If sample is a single phase liquid, test for
water miscibility by adding several drops of sample
into a 2 dram vial containing 0.5 mL of deionized
water. Record results. Transfer 35 mL of the
liquid to a labeled 40 mL vial or 2 oz. bottle.
Recap original sample.
8.5.2 If sample is a single phase solid, transfer
approximately 35g into a labeled 40 mL vial.
8.5.3 If sample is multi-phase, split sample into
2 jars, place the jars in plastic bags and centri-
fuge at 3000 rpm (50%). Centrifuge sample for not
less than five minutes but no longer than ten minutes.
Check for separation completeness. If incomplete,
centrifuge for an additional five minutes.
8.5.4 Transfer each individual phase to appropriate
tared and labeled vials or jars and record final
weights on separation record. Perform water
miscibility test as described in Section 8.5.1
on each liquid phase.
8.6 Describe and record each phase using phase
descriptions in Definitions (Section 3).
8.7 Remove any material from outside of vials and jars
with Kimwipes and soap and water. (Solvents may be
necessary but use only on SEALED containers) . Place
contained phases in one plastic bag and store for
future aliquoting.
8.8 Aliquot ing
8.8.1 Ascertain whether aliquoting is for compositional
or general charactertization analysis. For
compositional analysis weigh a predetermined amount
of phase into an appropriate test vial. For general
characterization analysis, recomposite each phase
by percent weight into an appropriate test vial.
Refer to extraction and analysis methods for proper
aliquot weights.
B-4
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June 1984
Method: RSL-901
Page 5 of 5
8.8.2 Unless requested, minor phases are not aliquoted.
Minor phases are defined in Section 3.
9. Waste Disposal
9.1 All items listed in the following table will be placed
in the appropriate waste container. The containers
will be either labeled with the DOT classification
from the table or be placed in another container which
will be labeled with the DOT classification (e.g. plastic
bags will be placed in a labeled 55 gallon drum).
Item
Waste Glass
Waste Solvents
Waste Wood
Waste Paper
Gloves, etc.
Waste Liquids
Soapy H20, DDI
Container
5 Gallon can
Reinke
Waste Solvent Can
5 Gallon can
Reinke
Plastic Bag
Waste Solvent Can
Classification (DOT)
Waste Flammable Solid
Waste Flammable Liquid
Waste Flammable Solid
Waste Flammable Solid
Waste Flammable Liquid
Approved by
Reviewed by
Date
Date
B-5
-------
Method: RSL-902
Page: 1 of 10
Date: June 1984
Replaces: All previous editions
Organic Chemical Extraction and Gas Chromatographic Screening o:
High Hazard Waste Samples
1. SCOPE AND APPLICATION
This is a general purpose method that provides procedures
for preparation and screening of organic extracts for
volatile organic (VOA), base/neutral/acid (B/N/A), and
pesticide/PCB. High hazard waste samples include all
chemical wastes both in containers, such as drums or
tanks, and uncontained such as in piles, solid chemical
or pooled liquids.
The method is directed to highly contaminated soil samples
and waste samples that may be solid, aqueous liquid, or
nonaqueous liquid and suspected to contain greater than
0.01% of any one organic chemical component. The method
is not designed for waste samples expected to contain less
than 10 ppm of base/neutral and acid priority pollutants;
for example, as in many sediment samples taken from
leachate streams. That type of sample should be analyzed
using more traditional methods, such as Soxhlet extraction
or homogenization, with larger sediment/soi1 samples.
2. SUMMARY OF METHOD
2.1 One to 1.5 gram aliquots of soil, solid, aqueous
liquid, or nonaqueous liquid are transferred to vials
and diluted with either methanol, hexane, or methylene
chloride. Solid phase aliquots which are not soluble
in the extracting solvent are sonicated for two
minutes. All other aliquots are either shaken by hand
or a mechanical wrist shaker for one minute.
DEFINITIONS
B/N/A - Base/Neutral/Acid
VOA - Volatile Organic analysis
External standard - a known amount of a pure compound that
is analyzed with the same procedures and conditions that
B-6
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June 1984 Page 2 o ' 10
Method: RSL-902
are used to analyze samples containing that compound. From
measured detector responses to known amounts of the external
standard, a concentration of that same compound can be ca '.-
culated from measured detector response to that compound .n a
sample analyzed with the same procedures.
Internal standard - a pure compound added to a sample in 'cnown
amounts and used to calibrate concentration measurements of
other compounds that are sample components. The internal
standard must be a compound that is not a sample component.
NEIC dirt - a loamy soil obtained near the NEIC/Denver wh .ch
has been dried, crushed, and sieved in a #10 sieve.
Laboratory control standard - a solution of analytes prepared
in the laboratory by dissolving known amounts of pure com-
pounds in a known amount of solvent. In this method, the
laboratory control standard is prepared by adding appropr.ate
volumes of the secondary dilution standard solution and the
internal standard/surrogate compound spiking solution to a
known soil/water/oil matrix.
Laboratory replicates - three aliquots of the same sample that
are treated exactly the same throughout laboratory analytical
procedures. Analysis of laboratory replicates indicate pre-
cision associated with laboratory procedures but not with
sample collection, preservation or storage procedures.
Laboratory reagent blank - a portion of reagent solvent pro-
cessed in the same manner as the sample.
Secondary dilution standard - a solution of analytes prepared
in the laboratory from stock standard solutions and diluted
as needed to prepare calibration solutions and laboratory con-
trol standards.
Stock standard solution - a concentrated solution containing a
certified standard that is a method analyte, or a concentrated
solution of an analyte prepared in the laboratory with an
assayed reference compound. Stock standard solutions are used
to prepare secondary standard solutions.
Surrogate compound - a compound that is not expected to be
found in the sample, is added to the original environmental
sample to monitor performance, and is measured with the same
procedures used to measure sample components.
4. LIMITATIONS
The procedure is designed to allow detection limits as low
as 10 ppm for volatile organic priority pollutants. The
procedure is designed to detect extracts at 100 ppm for
base/neutral and acid priority pollutants, 10 ppm for TCDD
and PCB's, and 10 ppm for chlorinated pesticides; lower
B-7
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June 1984 page 3 of 10
Method: RSL-902
limits of detection, tenfold below these values, can be
achieved on relatively clean samples by concentrating the
extracts to 1 mL. Some samples, however, may contain high
concentrations of chemicals that interfere with the analy-
sis of other components at lower levels; the detection
limits in those cases may be significantly higher. These
extraction and preparation procedures were developed for
rapid and safe handling of high concentration chemical
waste samples. The design of the method thus does not
stress efficient recoveries or low limits of detection of
all components. Rather, the procedures were designed to
screen, at moderate recovery and sufficient sensitivity, a
broad spectrum of organic chemicals. The results of the
analyses thus may reflect only a minimum of the amount
actually present in some samples.
5. SAFETY
Potentially carcinogenic, mutagenic, toxic, and other
hazardous materials may be present in these waste samples
at concentrations up to 100 per cent. This procedure is
intended for use in a Regulated Substances Laboratory to
minimize personnel exposure and other hazards relating to
the handling of the samples. In particular, good labora-
tory practices should be used to minimize exposure and
contamination throughout the preparation and analysis
of these types of samples. Each person is responsible
for maintaining awareness of safe handling procedures
used in this method.
6. REAGENTS
6.1 Sodium sulfate (anhydrous). Granular, analytical
reagent grade, pre-extracted with methylene chloride
or muffled at 400°c. for 3 hours before use to remove
interferences.
6.2 Methylene chloride. Pesticide residue analysis grade,
or equivalent.
6.3 Hexane. Pesticide residue analysis grade, or
equivalent.
6.4 Methanol. Pesticide residue analysis grade, free of
purgeable organics. Check by adding 10 uL to 5 mL of
organic free water, and analyzing by GC/MS using the
purge and-trap technique or direct injection by GC/HECD.
7. APPARATUS AND EQUIPMENT
7.1 Glass scintillation vials, at least 20 mL, with screw
cap and aluminum foil liner.
B-8
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June 1984 Page 4 of 10
Method: RSL-902
7.2 Wooden tongue depressors. Dispose of after using to
transfer solid samples.
7.3 Balance capable of weighing 100 gra; is to the nearest
0.01 gram.
7.4 Vials and caps, 2 dram for GC autosampler.
7.5 Disposable pipets, 10 mL. Pasteur pipets.
7.6 Gas chromatograph with a flame ionization detector
and electron capture detector.
7.7 Ultrasonic probe, Braun-Sonic 1510 with intermediate
probe attachment, or equivalent.
7.8 Test tube rack.
7.9 Glass vials with Teflon-lined screw caps, 12 mL for
shipment of extracts.
7.10 VGA bottles, 20 or 40 mL with Teflon-backed septum
and screw cap, for extraction and shipment of VOA samples
7.11 Hamilton 10 ul and 250 ul gas tight syringes.
7.12 Glass wool rinsed with methylene chloride.
8. CALIBRATION
8.1 BASE/NEUTRAL/ACID ANALYSIS
8.1.1 Prepare stock external standard solution
by weighing about 0.025 grams of pure
phenanthrene-dlO. Dissolve the material in
methylene chloride, dilute to volume in a 20
mL volumetric flask. Dilute a portion of the
stock solution (secondary dilution standard)
to achieve a concentration of 25 ug/mL.
Prepare stock internal standard solution by
weighing about 0.050 grams of pure napthalene-
-d8 and phenanthrene-dlO. Dissolve the
material in methylene chloride, dilute to
volume in a 10 mL volumetric flask. Transfer the
stock standard solutions into Teflon sealed screw-
cap bottles. Store at 4° C. Stock standards
should be checked frequently for signs of
degradation or evaporation, especially just
prior to preparing calibration standards from
them.
8.1.2
Using an injection of 2 uL of the external
standard solution, standardize the flame
ionization detector for half-scale response.
B-9
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June 1984 Page 5 of 10
Method: RSL-902
8.1.3 Reconunended operating conditions for the gas
chromatograph are:
Thirty (30) meter X 0.25 mm bended-phase silicone-
coated fused silica capillary column with helium
carrier gas at a flow rate of 30 cm/second. Column
temperature programmed: isothermal, 50° C. for four
minutes, then programmed at 8r C/minute to 300° C.
Hold time, 15 minutes.
8.1.4 Concentrate 10.0 mL of the B/N/A Control and
Reagent Blank extracts under a gentle stream
of purified nitrogen tc 1.0 mL.
8.1.5 Transfer the 1.0 mL extract to a 2 dram vial
and seal.
8.1.6 Immediately prior to analysis, add 10 uL of
the internal standard solution to the extract.
The final concentration of the internal standards
in the extract should be 50 ug/mL.
8.1.7 Surrogate compounds shall be quantified by the
internal standard method. The internal standard
used shall be the one nearest the retention time
to that of a given surrogate.
AT AT
*1 J. O *»W •%
o ...
AIX = Area of Internal standard in standard
AIS = Area of internal standard in sample
ACS = Area of surrogate in sample
ACX = Area of surrogate in standard
Cx = Concentration of surrogate in standard
8.1.8 Each chromatogram shall be clearly identified
with the following information.
(a) Case or Project Number
(b) Sample Identification
(c) Fraction (BNA, V0£, Pesticide/PCB)
(d) Standard, Reagent Blank, Control
(e) GC run number
(f) If sample is a reagent blank or control,
list GC number of Standard used for
quantitation
(g) Date of analysis
(h) Analyst name
(i) Standard Operating Procedure number
(j) Each internal standard and surrogate
identified.
B-10
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June 1984 Page 6 of 10
Method: RSL-902
8.1.9 Report results on QC Bench Sheet
8.2 PESTICIDE/PCB PREPARATION
8.2.1 Prepare stock solution by diluting 1.0 mL
of concentrated Aroclor 1254 (5000 ug/mL)
to 10 mL in acetone. Final concentration
to be 0.5 mg/mL.
8.2.2 Transfer the stock solution into Teflon-
sealed screw-cap bottles. Store at 4°c.
Stock standards should be checked frequently
for signs of degradation or evaporation
especially just prior to preparing calibration
standards from them.
8.2.3 Using an injection of 2 uL of the secondary
dilution standard, standardize the electron
capture detector for half-scale response.
The secondary standard is a lOx dilution of
the stock solution.
8.2.4 Recommended operating conditions for the gas
chromatograph are:
Supelcoport (100/120 mesh) coated with 1.5%
SP-2250/1.95% SP-2401 packed in a 1.8 m long
X 4 mm ID glass column with nitrogen carrier
at a flow rate of 40 mL/minute. Column
temperature, isothermal at 200°c.
8.2.5 Dilute the Pesticide/PCB control and Reagent
Blank extracts by adding 100 uL of extract to
0.9 mL of hexane.
8.2.6 Surrogate compounds shall be quantified by
the external standard method. The integrated
area or peak height for the five largest and
most resolved peaxs are averaged:
AS_ * Cx
As = Average area of peaks in sample
Ax = Average are^ of peaks in standard
Cx = Concentration of surrogate in standard
8.2.7 Reporting (see paragraph 8.1.8)
B-ll
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June 1984 p ? f 1Q
Method: RSL-902
9. QUALITY CONTROL
9.1 Two reagent blanks for each fraction (VOA, Pesticide/
PCB, B/N/A) shall be prepared with each project or
for every 20 samples within a project. One is analyzed
at the RSL while the other is shipped with the sample
extracts to the analysis laboratory.
9.2 One sample from each project or for every 20 samples
within a project is prepared for spiking purposes by
aliquoting six (extra) additional fractions. Three
fractions are spiked at 50 ug/g of sample with PCB
stock solution (Aroclor 1254), three more fractions
are spiked at 100 ug/g of sample with Base, Neutral and
Acid standards (See Table 1.)
9.3 Each B/N/A fraction, blank, and replicate spike shall
be spiked with 150 uL of surrogate Spike.
(see Table 1).
9.4 With each project or 20 samples within a project, the
RSL will prepare two 1.5 gram multi-phase control
samples by mixing 1.0 gram of NEIC "dirt", 0.1 gram of
vegetable oil, and 0.4 gram of tap water. One control
is spike with 150 uL of B/N/A surrogate mix, the second
with 150 uL of PCB mix. The normal extraction procedure
is followed. (See Table 1 for concentrations of these
spike mixes.)
10. PREPARATION PROCEDURE
10.1 Transfer 1.5 + .04 g aliquots (1.0 + .04 g for VOA) to
appropriate test vials (Method RSL-901, Section 8.8)
10.2 Dilute the VOA sample with 10 mL interference-free
methanol. Disrupt insoluble solid samples by ultrasonic
probe for 2 minutes at 100 watts power.
Cap, and shake all o.her samples for one minute. Note:
vials should be capped and removed from the hood prior
to working with methylene chloride or any other solvent
in the hood. They should also be stored in a solvent-
free atmosphere at 4°c.
10.3 Add 150 uL of B/N/A surrogate mix to each of the sample
portions to be extracted with methylene chloride. Add
B-12
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June 1984 Page 8 of 10
Method: RSL-902
the surrogate 50 that it is distributed as uniformly as
possible over the sample; shake the sample to achieve
better mixing Lf appropriate. In addition dilute 100 uL
of B/N/A surrogate mix up to 10 mL in methylene chloride.
This is to be ased as the gc calibration standard for
analyzing blanks and controls.
10.4 Add 15 mL of hsxane to the pesticide/PCB fractions
and 15 mL of mathylene chloride to the B/N/A fractions.
If the pH of the aliquot is less than or equal to five,
or greater thai or equal to eight, an additional B/N/A
extract is prepared with pH adjustment. The pH ad-
justment is prepared by adding the equivalent amount
of acid or bas3 necessary to reach the end point of the
acidity/alkalility determination. Add 6N HC1 to aliquots
whose pH is grsater than or equal to 8. Add 6N NaOH to
aliquots whose pH is less than or equal to five. The
pH adjusted B/M/A aliquot is not prepared when the
addition of acid or base exceeds 2.0 mL.
Calculations for determining required acid or base
additions.
vol. of acid or base = 1.5 X A X NX x Vj
required for adj., mL B X N2
A = dilution volume, mL
B = volume of aliquot, mL
NI = normality of titrant
N2 = 6 (normality of adjusting soln.)
V^ = volume of titrant required, mL
10.5 Add approximately 2.5 g of anhydrous sodium sulfate
to each of the B/N/A and pesticide/PCB extracts to
absorb any water. Additional sodium sulfate may be
required.
10.6 Disrupt insoluble solid samples for 2 minutes using an
ultrasonic probe at 100 watts power. Cap and shake all
other samples for one minute.
10.7 Using a disposable 10 mL pipette, transfer 10 mL of the
extract to a shipping vial. If the sample contains
suspended solids that will not pass through glass wool,
filter enough extract through a pasteur pipet loosely
packed with 2-3 cm of glass wool to yield 10 mL of
filtrate.
10.8 If a pH adjustment extraction was performed, add 5.0 mL
B-13
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June 1984 Page 9 of 10
Method: RSL-902
of each methylene chloride extract together in a shipping
vial; the final volume being 10 mL.
10.9 For all extract vials that are to be shipped, mark
the liquid level on the side of the vial.
11. METHOD PERFORMANCE
11.1 The results of recovery studies presented in Section 11
are from the extraction of 1.0 gram samples with 10 mL
of solvent. It should be noted that during sample ex-
traction preparation, sodium sulfate is added to the
sample prior to the sonication step rather than after
sonication. This change raised recovery of the 50 ug/g
PCB spike into the multi-phase control sample from 50-60
percent to 80-90 percent; recoveries of the B/N/A sur-
rogate compounds were not detectably affected by the
change. The data in Tables 2 through 6 show variability
of recovery due to matrix, pH, solvent, concentration,
and analyst. The B/N/A extracts for these studies were
analyzed on an SE54 capillary column with an FID detector.
The data in Tables 7 through 9 were obtained from capil-
lary column GC/Ms analysis. The GC/MS analysis differed
from that used by contractor laboratories in that only
phenanthrene-dlO was used as an internal standard for
quantitation, and a 15M DBS column with a u urn film
thickness was used rather than a 30M 0.25 urn film thick-
ness column. Section 11.3 presents data showing the
performance of the method for VOA compounds; losses of
very volatile compounds (gases) on the order of 20-40
percent can be expected.
11.2 The data in Tables 7 through 10 were obtained from
analysis of quadruplicate spikes into three matrices.
Matrices 1 and 3 were real samples whose only criterion
for selection for spiking was that the level of chroma-
tographable organics would allow the final extract to be
concentrated to 1 mL. Matrix 2 is the material referred
to as "MEIC dirt" which is described in Section 3.
11.3 A possibility in the use of any extraction method for
VOA compounds is the loss of volatile compounds during
the extraction. In order to investigate the possibility
of losses during the sonication step of this procedure,
replicate portions of standards in methanol were soni-
cated for various lenghts of time. The results indicate
that losses between 20 to 50 percent can be expected,
using this extraction procedure for compounds which are
B-14
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June 1984 Page 10 of 10
Method: RSL-902
gases at room temperature (chloroethane, methyl bromide,
irethyl chloride, vinyl chloride). Losses of other com-
pounds ranged from negligible up to the order of ten
percent for a sonication of two minutes. The developers
of this method suggest that for the assumed application
of this method, losses of ten percent can be considered
negligible. Table 11 presents the results of the percent
recovery as a function of sonication time study. Table 11
lists the average percent recovery and standard deviation
for three determinations at each time. The sonication
study involved six replicate portions of a standard
solution in methanol. Three 10-mL portions were
sonicated for one minute and 1 mL aliquots removed for
analysis. The other three portions were sonicated for
two minutes before removing aliquots. Each group of
three aliquots for analysis after two and four minutes.
This procedure gave aliquots for analysis after sonication
times of one through six minutes. However, the sonication
time for periods greater than two minutes is not continuous,
Solutions had an opportunity to cool before the next
two-minute sonication period; sonicating continuously
for the time periods shown could be expected to produce
lower recoveries because of increased heating of the
solutions. The sonic probe was operated for sufficient
time to bring the tip to a typical operating temperature
before sonicating any of the VOA standards. The
analyses were performed by GC/MS.
Approved by Date
Reviewed by Date
B-15
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APPENDIX C
ANALYTICAL PROCEDURES FOR PCDD/PCDF
BREHM LABORATORY - WRIGHT STATE UNIVERSITY
MICHIGAN DIOXIN STUDIES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR EMISSIONS STUDY
-------
Section 7.0
Revision 0
August 15, 1984
Page 1 of 13
7.0 GENERALIZED BREHM LABORATORY PROCEDURES FOR SAMPLE
EXTRACT CLEAN-UP AND ANALYSES OF ENVIRONMENTAL SAMPLES
FOR CDDs/CDFs
7.1 CLEAN-UP AND PRELIMINARY FRACTIONATION OF SAMPLE EXTRACTS
Extracts of the samples obtained as described in Section 5.0 are
cleaned-up and fractionated using the following procedures.
7.1 ..1 Clean-up and Liquid Chromatographic Separation
a. Add 50 mL of doubly distilled water to the vessel containing the
sample extract, reseal the vessel and agitate for 10 minutes.
Allow the vessel to stand for a period sufficient for the aqueous
and organic layers to separate completely, and remove and discard
the aqueous layer.
b. Using the same procedure as applied in 3a., wash the extract
successively with 50 mL portions of 50% KOH, doubly distilled
water, concentrated H2SOit, and doubly distilled water, in each
case discarding the washing agent. The acid washing procedure
with concentrated sulfuric acid is repeated until the acid layer
is visually colorless.
c. Add 5 g of anhydrous sodium sulfate to the washed extract and
allow to stand in order to remove residual water. Transfer the
extract to a centrifuge tube and concentrate to near dryness by
placing the tube in a water bath at 55°C, and passing a gentle
stream of filtered, prepurified N2 over the solution.
d. Prepare a glass macro-column, 20 mm OD x 230 mm in length,
tapered to 6 mm OD on one end. Pack the column with a plug of
silanized glass wool, followed successively by 1.0 g silica,
2.0 g silica containing 33% (w/w) 1M NaOH, 1.0 g silica,
4.0 g silica containing 44% (w/w) concentrated H^SO^ and 2.0 g
silica. Quantitatively transfer the concentrated extract from
Step c. to the column and elute with 90 mL hexane. Collect the
entire eluent and concentrate to a volume of 1-2 mL in a
centrifuge tube, as before.
e. Construct a disposable liquid chromatography mini-column by
cutting off a Pyrex 10 mL disposable pipette at the 4.0 mL
mark and packing the lower portion of the tube with a small plug
of silanized glass wool, followed by three grams of Woelm basic
alumina, whichhas been previously activated for at least 16 hours
at 600°C in a muffle furnace, and cooled in a dessicator for
30 minutes just prior to use. Quantitatively transfer the
concentrate from Step d. onto the liquid chromatography column,
rinse the centrifuge tube consecutively with two 1 mL portions
of hexane, and also transfer the rinses to the chromatography
column.
C-l
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Section 7.0
Revision 0
August J.5, 1984
Page 2 of 13
f. Elute the column with 15 ml of hexane and discard the
eluent.
g. Elute the column with 10 ml of 8% (v/v) methylene chloride-in-hexane and
discard the eluent.
h. Elute the column with 15 ml 50% (v/v) nethylene chloride-in-hexane and
retain the eluent. Concentrate just to dryness with a
stream of nitrogen, as described above.
i. Take a 9-inch disposable Pasteur pipette and cut off a
0.5 inch section from the constricted tip. Insert a filter
paper disk at the top of the tube, 2.5 cm from the constric-
tion. Add a sufficient quantity of PX-21 Carbon/Celite 545
(Prepared as described in the Reagent section of this
protocol) to the tube to form a 2 cm length of the Carbon-
Celite. Insert a glass wool plug. Pre-elute the column
in sequence with 2 ml of 50% benzene-in-ethyl acetate,
1 ml of 50% methylene chloride-in-cyclohexane and 2 mi of
hexane, and discard these eluates. Load the extract
(reconstituted in 1 ml of hexane) from Step h. onto the
top of the column, along with 1 ml hexane rinse. Elute the
column with 2 ml of 50% methylene chloride-in-hexane and
2 ml of 50% benzene-in-ethyl acetate and discard these
eluates. Invert the column and reverse elute it with 4 ml
of toluene, retaining this eluate for CDD/COF analysis.
j. Concentrate each of the retained fractions to a volume of
approximately 1 ml by heating the tubes in a water bath while
passing a stream of prepurified N* over the solutions, as
described above. Quantitatively transfer the concentrated
fractions into separate micro-reaction vessels for the
appropriate analysis. Evaporate the solutions in each of
the micro-reaction vessels almost to dryness, using the
procedures just mentioned, rinse the walls of each vessel
down with 0.5 ml CH2C12, and reconcentrate just to dryness.
*
k. Approximately 1 hour before gas chromatographic-mass
spectrometric (GC-MS) analysis, dilute the residue in each
micro-reaction vessel with an appropriate quantity of
tridecane (depending upon the anticipated quantities of
analytes in each vessel) and gently swirl the solvent in
the vessel to ensure dissolution of CDDs/CDFs.
Inject an appropriate aliquot of this solution into tne
GC-MS instrument.
C-2
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Section 7.0
Revision 0
August 15, 1984
Page 3 of 13
7.2 ANALYSIS OF SAMPLE EXTRACTS FOR PCDD/PCDF USING COUPLED GAS
CHROMATOGRAPHY-MASS SPECTROMETRY (GC-MS)
Sample extracts prepared by the procedures described in the foregoing are
analyzed by GC-MS utilizing the following instrumental parameters. Typically,
1 to 5 yl portions of the extract are injected into the GC. Sample extracts
are analyzed for the concentrations of total tetra- through octa-CDDs and CDFs,
and for 2,3,7,8-TCDD, and 2,3,7,8-TCDF.
7.2.1. Gas Chromatograph
a. Injector: Configured for capillary column, splitless/split
injection (split flow on 60 seconds following injection), injector
temperature, 250°C.
b. Carrier gas: Hydrogen, 30 Ib head pressure
c. Capillary Column: For total tetra- through octa- CDDs/CDFs and
2,3,7,8-TCDD, 60 M x 0.25 mm I.D. fused silica DB-5; temperature,
programmed, see Table 1 for temperature program.
d. Interface Temperature: 250°C
7.2.2. Mass Spectrometer
a. lom'zation Mode: Electron impact (70 eV)
b. Static Resolution: 1:600 (10% valley) or 1:10,000 depending upon
requirements.
c. Source Temperature: 250°C
d. Ions Monitored: Computer-Controlled Selected-Ion-Monitoring, See
Table 1for list of ion masses monitored and time intervals
during which ions characteristic of each class of PCDD and PCDF
are monitored.
7.Z2 Calibration Procedures
a. Calibrating the MS Mass Scale: Perfluoro Kerosene is introduced
into the MS, in order to calibrate the mass scale through at
least m/z 500. The mass calibration is rechecked at least at
8 hr. operating intervals.
b. Table 1A shows the GC temperature program typically used to resolve each
chlorinated class of PCDD and PCDF from the other chlorinated classes,
and indicates the corresponding time intervals during which ions
indicative of each chlorinated class are monitored by the MS. This
- temperature program and ion monitoring time cycle were established by
injecting aliquots of Standard Mixtures A and B. (See below for list
03
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sectxon /.u
Revision 0
August 15, 1984
Page 4 cf 12
of calibration standard mixtures). Corresponding data was established
for the PCBs by injecting Standard Mixture D.
c. Checking GC Column Resolution for 2,3,7,8-TCDD. Utilize the column-
resolution TCDD isomer mixtures (Standard Mixture C) to verify that
2,3,7,8-TCDD is separated from the other TCDD isomers. A 20% valley or
less must be obtained between the mass chromatographic peak observed for
2,3,7,8-TCDD and adjacent peaks arising from other TCDD isomers.
d. Calibration of the GC-MS-DS system to accomplish quantitative analysis
of 2,3,7,8-TCDD and 2,3,7,8-TCDF, and of the total tetra- through octa-
CDDs and CDFs contained in the sample extract is accomplished by
analyzing a series of at least three working calibration standards.
Each of these standards is prepared to contain the same concentration of
each of the stable-isotopically labelled internal standards used here
(Standard Mixture A) but a different concentration of native PCDD/PCDF
(Standard Mixture B). Typically, mixtures will be prepared so that the
ratio of native PCDD and PCDF to isotopically-labelled PCDD and PCDF
will be on the order of 0.1, 0.5 and 1.0 in the three working calibration
mixtures. The actual concentrations of both native and isotopically-
labelled PCDD and PCDF in the working calibration standards will be
selected on the basis of the concentrations to be measured in the
actual sample extracts. Equations for calculating relative response
factors from the calibration data derived from the calibration
standard analyses, and for calculating the recovery of the
13C12-2,3,7,8-TCDD and the other isotopically-labelled PCDD and PCDF,
and the concentration of native PCDD and PCDF in the sample (from
the extract analysis) are summarized below. In these calculations, as can
be seen, 2,3,7,8-TCDD is employed as the illustrative model. However,
the calculations for each of the other native dioxins and furans in the
sample analyzed are accomplished in an analogous manner. It should be
noted that in view of the fact that stable-isotopically labelled internal
standards corresponding to each tetra- through octachlorinated class are
not used here (owing to limited availability at this time) the
following approach is adopted: For quantisation of tetrachlorinated
dibenzofurans 13d2-2,3,7,8-TCDF is used as the internal standard.
For quantisation of tetrachlorodibenzo-p-dioxins, 13Ci2-2,3,7,8-TCDD
is used as the internal standard. For quantitation of PeCDD,
HxCDD, PeCDF, and HxCDF, the labelled TCDD and TCDF standards,
respectively, are used. For quantitation of HpCDD, OCDD, and
HpCDF, OCDF, the isotopically-labelled OCDD is used. Inherent
in this approach is the assumption that the response factors for each
of the isomers of each chlorinated class are equal.
7.2.4. Calibration Standard Mixtures
a. Standard Mixture A: 0.4ng/yl 37CU-2,3,7,8-TCDD
0.4ng/ul 37CU-2,3,7,8-TCDF
l.Ong/yl 13C12-2,3,7,8-TCDD
l.Ong/yl 13C12-OCDD
b. Standard Mixture B: i) 10 ng/yl of each of: 2,3,7,8-TCDD
1,2,3,7,8-PeCDD
_ 1,2,3,4,7,8-HxCDD
1,2,3,4,6,7,8-HpCDD
\^ *" T"
-------
Section 7.0
Revision 0
August 15, 1984
Page 5 of 13
OCDD
2,3,7,8-TCDF
2,3,4,7,8-PeCDF
1,2,3,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCOF
OCDF
ii) 2ng/ul of each of same isomers as in 4.b.
iii) 0.4ng/yl of each of same isomers as in 4.
c. Standard Mixture C: EPA TCDD Column Performance Mixture
•7.2.5 Equations for Calculating Response Factors. Concentration of 2,3,7,8-TCDD
In An Unknown Sample, and Recoveries of Internal Standards
Equation 1: Response Factor (RRF) for native 2, 3, 7, 8-TCDO using
l3Ci2-2,3,7,8-TCDD as an internal standard.
RRFd= (ASC.S/A1SCS)
where: AS » SIM response for 2,3,7,8-TCDD ion- at m/z 320 + 322
A. = SIM response for lsCi2-2,3,7,8-TCDD internal standard
.
15
ion at m/z 332
C. 3 Concentration of the internal standard (pg./yL.)
C = Concentration of the 2,3,7,8-TCDD (pg./uL.)
C-5
-------
Section 7.0
Revision 0
August 15, 1984
Page 6 of 13
Equation 2: Response Factor (RRF) for37C\ -2,3,7,8-TCOD, the co-injected
external standard
RRFf * (AisCes^A C' ^
where: A. = SIM response for 13Ci2-2,3,7,8-TCDD internal
standard ion at m/z 332
A = SIM response for co-injected 37CU-2,3,7,S-TCDD external
standard at m/z 328 - 0.009 (SIM response for native
2,3,7,8-TCDD at m/z 322)
C^ - Concentration of the internal standard (pg./ul.)
I e
Cgs = Concentration of the external standard (pg./pL.)
Equation 3: Calculation of concentration of native 2,3,7,8-TCDD using
-l3Ci2-2,3,7,8-TCDD as internal standard
Concentration, pg./g. = (Ag) (Is)/(Ais)(RRFd)(W)
where: A = SIM response for 2,3,7,8-TCDD ion at m/z 320 + 322
A- = SIM response for the 13Ci2-2,3,7,8-TCDD internal
standard ion at m/z 332
I = Amount of internal standard added to each sample (pg.)
W = Weight of soil or waste in grams
RRFd = Relative response factor from Equation 1
Equation 4: Calculation of % recovery of 13CL2-2,3,7,8-TCDD internal standard
% Recovery = 100(A1s)(Es)/(Aes)(Ii)(RRFf)
A. = SIM response for 13Ci2-2,3,7,8-TCDD internal standard
15 ion at m/z 332
A = SIM response for 37CU-2,3,7,8-TCDD external standard
ion at m/z 328 - 0.009 (SIM Response for native
2,3,7,8-TCDD at m/z 322)
E = Amount of 37CU-2,3,7,8-TCDD external standard
co-injected with sample extract (ng.)
I. » Theoretical amount of 13Ci2-2,3,7,8-TCDD internal
standard in injection
RRFf * Relative response factor from Equation 2
C-6
-------
Section 7.0
Revision 0
August 15, 1984
Page 7 of 13
As noted above, procedures similar to these are applied to calculate
analytical results for all of the other PCDD/PCDF determined
in this method.
7.2.f Criteria Which GC-MS Data Must Satisfy for Identification of PCB and
PCDD/PCDF in Samples Analyzed and Additional Details of Calculation"
Procedures.
In order to identify specific PCDD/PCDF and PCB in samples analyzed,
the GC-MS data obtained must satisfy the following criteria:
a. Mass spectral responses must be observed at both the molecular and
fragment ion masses corresponding to the ions indicative of each
chlorinated class of PCDD/PCDF and PCB identified (see Tables 1A
& IB) and intensities of these ions must maximize essentially
simultaneously (within +^ 1 second). In addition, the chromatographic
retention times observed for each PCDD/PCDF e-signal must be
correct relative to the appropriate stable-isotopically labelled
internal standard and must be consistent with the retention time
windows established for the chlorinated group to which the particular
PCDD/PCDF is assigned.
b. The ratio of the intensity of the molecular ion (M)+ signal to that of
the (M+2)+ signal must be within + 10% of the theoretically expected
ratio (for example, 0.77 in the case of TCDD; therefore the
acceptable range for this ratio is 0.62 to 0.92).
c. The intensities of the ion signals are considered to be detected
if each exceeds the baseline noise by a factor of at least 3:1.
The ion intensities are considred to be quantitatively measurable
if each ion intensity exceeds the baseline noise by a factor of at
least 5:13 .
d. For reliable detection and quantitation of PCDF it is also desirable
to monitor signals arising from chlorinated diphenyl ethers which,
if present could give rise to fragment ions yielding ion masses
identical to those monitored as indicators of the PCDF. Accordingly,
in Table 1A, appropriate chlorinated diphenyl ether masses are
specified which must be monitored simultaneously with the PCDF
ion-masses. Only when the rasponse for the diphenyl ether ion mass
is not detected at the same time as the PCDF ion mass can the signal
obtained for an apparent PCDF be considered unique.
a' In practice, the analyst can estimate the baseline noise by measuring
the extension of the baseline immediately prior to each of the two mass
chromatographic peaks attributed to a given PCDO/PCDF. Spurious
signals may arise either from electronic noise or from other organic compounds
in the extract. Since it may be desirable to evaluate the judgement of the
analyst in this respect, copies of original mass chromatograms must be
included in the report of analytical results.
C-7
-------
oeu I_-LUU / . w
Revision 0
August 15, 1984
Page 8 of 13
e. Measurement of the concentration of the congeners in a
chlorinated class using the methods described herein is based on the
assumption that all of the congeners are identical to the calibration
standards employed in terms of their respective chemical and separation
properties and in terms of their respective gas chromatographic and mass
spectrometric responses. Using these'assumptions, for example, the
13Ci2-2,3,7,8-TCDD internal standard is utilized as the internal
calibration standard for all of the 22 TCDD isomers or congeners.
Furthermore, the concentration of the total TCDD present in a sample
extract is determined by calculating, on the basis of the standard
procedure outlined above, the concentration of each TCDD isomer peak
(or peaks for multiple TCDD isomers, where these coelute) and these
individual concentrations are subsequently summed to obtain the concen-
tration of "total" TCDD. Similar procedures are applied, of course for
all tne other PCDD/PCDF.
f. Frequently, during the analysis of actual sample extracts,
extraneous compounds which are present in the extract (those organic
compounds not completely removed during the clean-up phase of the analysis)
can cause changes in the liquid and gas chromatographic elution characteristics
of the PCDD/PCDF (typically retention times for the PCDO/PCDF are prolonged).
Such extraneous organic compounds, when introduced into the mass spectro-
meter source may also result in a decrease in the sensitivity of the MS
because of suppression of ionization, and other affects such as charge
transfer phenomena. The shifts in chromatographic retention times are
usually general shifts, that is, the relative retention times for the
PCDO/PCDF are not changed, although the entire elution time scale is
prolonged. The analyst's intervention in the GC-MS operating sequence
can correct for the lengthened GC retention times which are sometimes
observed due to the presence of extraneous organics in the sample
extract. For example, using the program outlined in Table 1, if the
retention time observed for 2,3,7,8-TCDD (which normally is 19.5 minutes)
is lengthened by 30 seconds or more, appropriate adjustments in the
programming sequence outlined in Table 1 can be made, that is, each
selected ion-monitoring program is delayed by a length of time propor-
tionate to the lengthening of the retention time for the 2,3,7,8-TCDO
isomer. In the case of ionization suppression, this phenomenon is
• inherently counteracted by the internal standard approach. However,
if loss of sensitivity due to ionization suppression is severe,
additional clean-up of the sample extract may be required in order to
achieve the desired detection limits.
7.2.7 Quality Assurance/Quality Control
Quality assurance and quality control are ensured by the following
provisions:
C-8
-------
Section 7.0
Revision 0
Aug'ist 15, 1984
Page 9 of 13
.a. Each sample analyzed is spiked with stable isotopically labelled
internal standards, prior to extraction and analysis. Recoveries
obtained for each of these standards should typically be in the
range from 60-90%. Since these compounds are used as true internal
standards however, lower recoveries do not necessarily invalidate
the analytical results for native PCOD/PCDF or PCB but may result
in higher detection limits that are desired.
b. Processing and analysis of at least one method blank sample is
accomplished for each set of samples (a set being defined as 20
samples or less). Analyses of field and travel blanks may also be
desirable.
7,3 REAGENTS AND CHEMICALS
The following reagents and chemicals are appropriate for use in the
procedures described above. In all cases, equivalent materials from
other suppliers may also be used.
7.3.1 Sources of Chemicals, Procedures Employed for Preparing Reagents
a. Potassium Hydroxide, Anhydrous, Granular Sodium Sulfate and
Sulfuric Acid (all Reagent Grade): J.T. Baker Chemical Co. or
Fisher Scientific Co. The granular sodium sulfate is purified
prior to use by placing a beaker containing the sodium sulfate
in a 400°C oven for four hours, then removing the beaker and
allowing it to cool in a desiccator. Store the purified sodium
sulfate in a bottle equipped with a Teflon-lined screw cap.
b. Hexane, Methylene Chloride, Benzene, Methanol, Toluene, Isooctane:
"Distilled in Glass" Burdick and Jackson.
c. Tridecane (Reagent Grade): Sigma Chemical Co.
d. Basic Alumina (Activity Grade 1, 100 - 200 mesh): ICN Pharmaceuticals,
Immediately prior to use, the alumina is activated by heating
for at least 16 hours at 600°C in a muffle furnace and then
allowed to cool in a dessicator for at least 30 minutes prior
to use. Store preconditioned alumina in a desiccator.
C-9
-------
Section 7.0
Revision 0
August 15, 1984
Page 10 of 13
e. Silica (Bio-Sil A, 100/200 mesh): Bio-Rad. The following procedure
is recommended for conditioning the Bio-Sil A prior to use. Place
an appropriate quantity of Bio-Sil A in a 30 mm x 300 mm long glass
tube (the silica gel is held in place by glass wool plugs) which
is placed in a tube furnace. The glass tube is connected to a pre-
purified nitrogen cylinder, through a series of four traps (stainless
steel tubes, 1.0 cm O.D. x 10 cm long)5: 1) Trap No. 1 - Mixture
comprised of Chromosorb W/AW (60/80 mesh coated with 5% Apiezon L),
Graphite (UCP-1-100), Activated Carbon (50 to 200 mesh) in a 7:1.5:1.5
ratio (Chromosorb W/AW, Apiezon L obtained from Supelco, Inc., Graphite
obtained from Ultracarbon Corporation, 100 mesh, 1-M-USP; Activated
Carbon obtained from Fisher Scientific Co.; 2) Trap No. 2'- Molecular
Sieve 13 X (60/80 mesh), Supelco, Inc.; 3) Trap No. 3 - Carbosieve S
(80/100 mesh), obtained from Supelco, Inc.; 4) The Bio-Sil A is heated
in the tube for 30 minutes at 180°C while purging with nitrogen (flow
rate 50-100 ml/minute), and the tube is then removed from the furnace
and allowed to cool to room temperature. Methanol (175 ml) is then
passed through the tube, followed by 175 ml methylene chloride. The
tube containing the silica is then returned to the furnace, the nitrogen
purge is again established (50-100 ml flow) and the tube is heated at
50°C for 10 minutes, then the temperature is gradually increased to
180°C over 25 minutes and then maintained at 180°C for 90 minutes. Heating
is then discontinued but the nitrogen purge is continued until the tube
cools to room temperature. Finally, the silica is transferred to a
clean, dry, glass bottle and capped with a Teflon-lined screw cap
for storage.
f. Silica Gel Impregnated With Sulfuric Acid: Concentrated sulfuric
acid (44 g) is combined with 100 g Bio-Sil A (conditioned as
described above) in a screw capped bottle and agitated to mix
thoroughly. Aggregates are dispersed with a stirring rod until a
uniform mixture is obtained. The HLSO.-silica gel is stored in a
screw-capped bottle (Teflon-lined cap).
g. Silica Gel Impregnated with Sodium Hydroxide: IN Sodium hydroxide
(39 g) is combined with 100 g Bio-Sil A (conditioned as described
above) in a screw capped bottle and agitated to mix throughly.
Aggregates are dispersed with a stirring rod until a uniform mixture
is obtained. The NaOH-silica gel is stored in a screw-capped bottle
(Teflon-lined cap).
h. Carbon/Celite: Comb:ne Amoco PX-21 carbon (10.7 g) with Celite 545
(Fisher Scientific Co.) (124 g) in a 250 mL glass bottle fitted with
a Teflon-lined cap. Agitate the mixture to combine thoroughly.
Store in the screw-capped bottle.
i. Nitrogen and Hydrogen (Ultra High Purity): Matheson Scientific
j. Fused Silica Capillary Gas Chromatographic Column: 60 M fused
silica (0.25 mm I.D.) capillary column coated with DB-5 (0.25 y
film thickness), J & S Scientific, Inc., Crystal Lake, IL.
C-10
-------
Section 7.0
Revision 0
August IS, 1984
Pr.ge 11 of 13
k. Chlorinated Dibenzo-p-dioxins and Dibenzofurans Used As Calibration
Standards: 37CU-2,3,7,8-TCDD (SSY-6-123) and 37CU-2,3,7,8-TCDF
(DF-14) were obtained from KOR, Inc. 13C12-2,3,7,8-TCDO (AWN
1203-65) and 13Ci2-OCDD (SSY-8-78) were obtained from Cambridge
Isotope Laboratores. The 22 TCDD standards and all other CDDs/
CDFs employed in the study were synthesized in the Brehm Laboratory.
A column performance check standard was obtained from USEPA (Check
Standard Mixture #2) which contained 1,4,7,8-TCOD; 2,3,7,8-TCDD;
1,2,3,4-TCOD; 1,2,3,7/1,2,3,8-TCDD; 1,2,7,8-TCDO and 1,2,6,7-TCDO.
C-ll
-------
TABLE 1
Sequence of Operations in GC-HS-DS_ Quant i tat ion of
o
i—•
ro
Elapsed
Time
(nun) Event
00
00
00
00
00
14.00
22.00
22.60
23.00
26.00
32.00
32.50
Injection, splitless
Turn on split valve
Gegin temp, program to 220°C
Open column flow to mass spectrometer
Column temperature hold
Start Tetra Program; sweep *
350 ppm; time/mass = 0.08 sec.
Stop Tetra Program
Start Penta Program; sweep -
350 ppm; time/mass • 0.12 sec.
Begin temp, program to 235"
Column temperature hold
Stop Penta Program
Start Hcxa Program; sweep *
350 ppm; time/mass • 0.20 sec.
LODs/CDfs
GC Column
Temperature*
(°C)
190
190
190
215
220
220
220
235
235
in Extracts of Environmental Samples
Ions Monitored
Temperature by Mass
Program Rate Spectrometer Identity of
(°C/min) (m/z) Fragment Ion
5
5
240.936
258.930
303.902
305.699
315.942
319.697
321.894
327.805
331.937
'H-COC11*
M-COC1J+
H]*
M»2]+
M]*
MJ*
H»2]*
M]»
M]'
373.840 [MJ*
274.899
290.894
337.863
5 339.860
353.858
355.855
407.801
310.857
326.852
373.021
375.02)
385.861
389.816
391.813
411.856
443.759
M-COCI1*
H-COC1J*
M]*
M'2]*
•H]*
Mf2]f
[M]*
,M-cocn*
M-COC1J*
M]*
M»Z]*
M]*
Ml*
Mt2]*
M]*
H]*
Compounds
Monitored
TCDF
TCOO
TCDF
TCOF
"CU-TCDF
TCOO
TCCH
"CK-TCDO
"CU-TCOO
HxDPEa-
PeCDF
I'eCOO
I'cCOF
PeCDF
PeCDO
PeCOD
HpDPE8-
llxCDF
HxCOD
HxCOF
llxCOF
1>C,,-IUCOF
HxCOO
llxCDD
"Cu-HxCOO
ODP£»-
Ihcoret ical
Pa 110
0.77
0.77
1.54
1.54
1.23
1.23
V > fO on
w c m IB
OQ TO < O
(D C H- rt
W en H-
(— rt p. o
K) O O
t- 3
O tn -v4
00
-------
I
TABLE 1 (continued)
o
CO
tlapsed
Time
(win) Event
33.00
36.00
42.50
43.00
53.00
53.50
54.00
58. bO
6s. 00
65.00
71.00
75.00
*-|UHI
Begin temp, program to 250°C
Column temperature hold
Stop Ilex a Program
Start Hepta Program; sweep *
350 ppm; time/mass * 0.30 sec.
Stop Hepta Program
Start Octa Program; sweep -
350 ppm; time/mass = 0.30 sec.
Begin temp, program to 270°
Column temperature hold
Stop Octa Program
•
Ucijin temp. |iro $0 C/i
P> c it n>
OQ OP r»
0) W H-
W O 3
H- O
t-h • O •
di-l J< hlorod i|ili< iiyl cllici i.
•Ihc
•livi-n liciv JIG ,i|i|ilu.ilili; for « 60-nx'ter fused silica capillary GC column co.ited with DD-5.
U)
oo
-------
APPENDIX D
INCINERATOR EXHAUST
STUDY SAMPLING RESULTS
-------
APPENDIX D
I. ORGANIZATION OF DATA
The analytical results of the Dow Chemical Company Midland Plant Building
703 incinerator emissions study encompass a wide variety of influent and effluent
streams, analyzed for the following generalized categories of compounds:
- Volatile compounds, or those with boiling points generally below
100°C,
- Semi-volatile compounds, with boiling points greater than 100°C, and
- PCDD/PCDF. These were analyzed separately from other semi-volatile
compounds, as described below.
In addition, incinerator exhaust gases were sampled for vinylidene chloride
using a direct capture method with immediate instrumental analysis, as the
analytical methods for other volatile compounds were not amenable to vinylidene
chloride. Further detail concerning these analyses are contained in Appendix A,
Section III.C. of this report.
In general, the data are presented below individually for each type of
stream, and in terms of volatile compounds, semi-volatile compounds, and
PCDD/PCDF, in that order. Discussion of quality assurance aspects relating to
each category of stream and compound group is presented to highlight the
information contained in the data tables.
II. ANALYTICAL LABORATORIES
As indicated above, PCDD/PCDF analyses were performed by an analytical
laboratory other than that involved with volatile and semi-volatile compounds,
owing to the comparatively limited number of capable laboratories. The Brehm
Laboratory of Wright State University, Fairborn, Ohio, completed these analyses,
while the EAL Corporation of Richmond, California, was selected to analyze the
samples for volatile and semi-volatile compounds.
III. ANALYTICAL RESULTS
A. Acceptability
In the sections to follow, data are generally presented in tables which are
based on concentration, with accompanying tables showing raw data as presented
by the analytical laboratories. Either of these tables may include quality
assurance data relating to accuracy (% recovery of known surrogate compounds
introduced to the analyzed matrix by the laboratory).
D-l
-------
1. PCDD/PCDF
For PCOD/PCDF, the ranges of acceptability defined in the Quality Assurance
Project Plan7 for the study were 70 to 130% recoveery for two isotopically
labeled analogs (13Cio 2378-TCDD and 37C14 2378-TCDF) and 50 to 150% for two
others (37C1^ 2378-TCTjD and 1 C12 OCDD). However, in comparing these acceptance
criteria to those commonly usecf in other current work involving analyses for
PCDO/PCDF, they were found to be overly stringent. In judging the acceptability
of PCDD/PCDF data, therefore, a range of recoveries of 50 to 150% was considered
acceptable.
The internal standard ^^12 2378-TCDD is a primary importance as the accuracy
determinant for tetra- througn hexa-CDD; those homologue groups are of greatest
priority in assessing potential risks to health. Recoveries of the second 2378-
TCDD surrogate, 37C14 2378-TCDD, serves to confirm the recoveries of Ci^ 2378-
TCDO. In summary, if both 2378-TCDD surrogates are recovered witnin the
acceptable range of 50 to 150%,, the analytical data are defined as acceptable
for the homologues of greatest concern.
Recoveries of the internal standard Ci£ OCDD were frequently poorer than
for the other standards. However, this internal standard measures analytical
accuracy for hepta- and octa-CDD and CDF homologues, which are of comparatively
low concern in terms of risk assessment. Recoveries of 37C14 2378-TCDF are
used to judge the accuracy of tetra- through hexa-CDF data, which, with respect
to risk, are of lower priority than the corresponding PCDDs.
In the PCDD/PCDF data in this Appendix, completeness is calculated and
presented individually by standard. According to the above discussion, the
value of the PCDD/PCDF data should be judged primarily by the accuracy of
recovery of the two labeled 2378-TCDD compounds. Completeness in this area was
generally near or above 80%; this performance confirms the overall validity of
the analytical data in calculating general mass balances and risk assessment.
2. Other Compounds
The Quality Assurance Project Plan references ranges of acceptable surrogate
recovery of 20 to 180% for semi-volatile compounds, and 80 to 125% for volatile
compounds. For semi-volatile compounds, six surrogates were used — three acid
and three base-neutral, while for volatile compounds three or four surrogates
were used, depending upon the type of sample. There is no currently accepted
guidance relating specific surrogates to particular analytes. However, the
evaluate the acceptability of semi-volatile compound analyses, if the recovery
of all three acid surrogates was acceptable, then the analysis of any detected
acid compound was considered valid; the same was done for base-neutral compounds.
On the semi-volatile compound data tables to follow in this section and in
Appendix D of this report, data which were treated in this way are appropriately
labeled. To assess overall completeness, however, data were defined as valid
only if all of the semi-volatile surrogate compounds were analyzed within range.
0-2
-------
For volatile compounds, as there was no available summary of the ranges of
compounds to which particular surrogates are associated, data points were
considered acceptable only if the recoveries of all three or four surrogates
were within the target range of 80 to 125%. Detailed inspection of the volatile
compound data tables which include surrogate recovery information reveal many
cases in which the recoveries of most surrogates were very close to the target
range. Therefore, the volatile compound data are probably more reliable than a
strict interpretation of the accuracy data would indicate.
B. Precombustion Air
1. Volatile Compounds
These data appear in Table 0-1 in terms of concentration. The raw analytical
data used to derive them are presented in Table 0-2.
The method blank, which was comprised of 1.5 grams of Tenax GC sorbent sent
directly from GCA to the analytical laboratory, EAL Corporation, showed the
presence of measurable amounts of chloroform, perchloroethylene, methylcyclo-
hexane, and 1,3-dichlorobenzene. The last two compounds were not detected in
any exposed sample. However, chloroform and perchloroethylene were found at
higher concentrations than in any exposed sample, indicating that both compounds
were present as laboratory contamination.
Two of the eight sample sets were acceptable in terms of accuracy (%
surrogate recovery, see Table 0-2). Of the target volatile compounds shown in
Table D-l, three,
- carbon tetrachloride (days 1 and 3)
- monochlorobenzene (days 1 and 3), and
- trichloroethylene (day 1 only),
were detected in the concentrations indicated. However, target precision
criteria of £50% RPD (between day 1 sample and field duplicate results) were
met only for monochlorobenzene. Accuracy (surrogate recovery) data were
unacceptable for samples taken on the second sampling day. Other compounds of
possible interest detected only on the first sampling day included ethylbenzene
and xylene (total xylenes); however, precision criteria were not met for either
compound. Benzene and toluene were noted on the third sampling day, but as
there was no duplicate sample taken on this day, this result is considered
tentative.
Detection limit objectives of 1 ppb in air were achieved for all of the
above-listed detected compounds as shown in Table D-l. Actual detection limits
were in the range of 0.3 to 0.8 ppb for the compounds detected above.
These samples were obtained with a 14-day target limit for holding time
prior to analysis. Samples were actually held for periods of 19 to 27 days
before analysis. Thus, the results presented are considered to be conservative
it is possible that some compounds may have been lost or altered due to decay
or reaction in the time between sampling and analysis.
D-3
-------
TABLE D-l
VOLATILE COMPOUNDS - PRE-COMBUSTION AIR
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
COMPOUND CONCENTRATION (ug/m3)1
COMPOUNDS DETECTED
ACCURACY (% SURROGATE RECOVERY)
(SAMPLE TUBE/FIELD BLANK TUBE)
APPROXIMATE
DETECTION LIMIT
IN AIR (ug/m3)
SAMPLING DATE
8/28/84
8/28/84 (Field
Duplicate)
8/30/84
9/5/84
Precision (RPD)
8/28/84
Samples
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t_
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15.35
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222.50
26.69
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O)
N
C
01
j^
o
t_
o
3
p.
<*-
o
E
O
i_
CO
154/108
110/108
0*/86
92/116
i
Ol
c
fO
.C
4->
01
o
t_
o
r— «d"
JC Q
O
•r—
"O
1
C\J
r— 1
58/86
54/86
0*/60
87/78
0
i— •
Q
1
O)
c
O)
N
C
O)
.a
>»
_c
LU
186*/108
106/108
oviio
112/104
CO
LU
_l
OQ
<
1—
Q-
UJ
CJ
C__3
<
N/Y
N/Y
N/N
Y/N
0.40 - 0.80
0.37 - 0.74
0.37 - 0.74
0.32 - 0.64
a
i
Notes:
1
2
3
Sample concentration less field blank concentration.
Compound tentatively identified.
All surrogate recoveries within target range (80-125%)
established in Quality Assurance Project Plan.
Recovery outside of acceptable range of 80-125%
-------
TABLE 0-2
QUANTITATED AND TENTATIVELY-IDENTIFIED VOLATILE COMPOUNDS DETECTED IN PKECOMBOSTION
DOW CHEMICAL COMPANY BOILD1NG 703 INCINERATOR
O
oi
8/28/84 Sample
Field Duplicate
Field Blank
8/30/84 Sample
FTeld Blank
9/5/84 Sample
Field Blank
Tenax GC« Method Blank
QUANTITATED COMPOUNDS
TENTATIVELY-IDENTIFIED COMPOUNDS
ACCURACY (% SURROGATE
RECOVERY)
C/1
h-
2
r
»
•
9
E
O
Chloro
88
194
b4
645
tetrachloride
o
301
8/2
109
3373
347
84i
424
sroethylene
.c
0
L
t—
22
b3
14
290
b9
41
jroethylene
.c
o
t.
at
O-
m
182
'44
36
138
b2
403
orobenzene
Monoch
l&l
2b/
4b6
auazu;
.0
!>
-4->
LU
186
419
b3
22
29b
t/)
Ol
c
Oi
^
(O
4->
o
I—
786
1302
80
84bb
112
343
trichloro-
;thane
i
8/b
1^06
c
c
o
*o
4->
3
O
1
CVJ
Benzen
90
57
1182
756
:hl orobenzene
•o
i
«*
1137
984
231
1192
81
1420
708
3PO-
sroraethane
i — 3
-C r—
0 <4-
L I_
1— *->
6481
:yclopentane
>>
£;
+-»
^
bb90
thylcyclo-
sxane
X -t-
,
JC
+-»
£
124
:hl orobenzene
T3
ro
f—«
4084
^1 pentane
3-methj
1390
7000
:hl orobenzene
T3
1
C\J
6b/
97
^1-1-pentane
jz
4-»
0)
e
i
C^J
700
>
.c
O>
03
H
C
01
CO
470
05
D
1
C
,
.c
4->
UJ
186
106
108
0
110
112
104
62
UJ
_l
CO
ACCEPT
No
No
Yes
No
No
Yes
No
No
Note:
surrogate recoveries within target range (80-125%)
established in Quality Assurance Project Plan.
COMPLETENESS - 25% (2/8)
-------
2. Semi-Volatile Compounds
The results of these analyses are reported in Tables D-3 and 0-4.
The method blank, composed of 75 grams of XAD-2 sorbent, was analyzed and
found free of contamination (see Table 0-4). However, this sample was extracted
and diluted prior to analysis, such that surrogate compounds added to the matrix
were poorly detected. Since the field blank samples showed the presence
only of ubiquitous phthalate compounds commonly considered laboratory-related,
and these analyses were satisfactory with respect to surrogate recoveries
(accuracy), it was determined that the sorbents employed in sampling were free
of background quantities of several compounds of interest detected in sampled
air.
As the data presented in Tables D-3 and 0-4 indicate, 1,2-dichlorobenzene
and 1,2,4-trichlorobenzene were found on all three sampling days; field dupli-
cate sampling on the second day indicated precision was within the objectives of
the study for these two compounds. Another dichlorobenzene, the 1,4 isomer, was
also detected on all three days, but precision could not be judged as it was
not found in the field duplicate. Low concentrations of 1,3-dichlorobenzene
were detected on the first and third sampling days, but none on the second day,
when a field duplicate was obtained.
Other target compounds were detected, as follows:
- 1-1 biphenyl (day 1),
- biphenyl (day 2, but not in field duplicate), and
- monochlorobenzene (days 1 and 2).
The latter is a volatile compound for which the previously described volatile
air sampler was considered more appropriate. The precision of the analytical
method for volatile compounds appeared better than that for semi-volatiles in
the case of monochlorobenzene. In any event, the concentrations of monochloro-
benzene measured by both methods were comparable within an order of magnitude.
Naphthalene was detected on all three sampling days, but satisfactory
precision was not achieved, as measured in the field duplicate sample on the
second day. Several substituted benzenes were seen on all three days, with a
host of isomers in comparatively high concentrations observed on the first day.
The target detection limit criterion of 5 ppb in air for semi-volatile
compounds was achieved; actual detection limits, for 1,2,4-trichlorobenzene, for
example, were on the order of 0.05 ppb. Accuracy criteria (20 to 180% surrogate
recovery) were met for seven of the eight samples, including field and method
blanks and duplicates (see Tables D-3 and D-5).
A summary assessment of these data indicates that while a wide variety of
semi-volatile compounds were detected, the presence of only two, 1,2-dichloro-
benzene, and 1,2,4-trichlorobenzene, could be established and supported by
acceptable measures of accuracy. The presence of other compounds should be
considered a tentative finding.
D-6
-------
TABLE D-3
SEMI-VOLATILE COMPOUNDS - PRE-COMBUSTION AIR
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28. 8/30, 9/5/84
COMPOUND CONCENTRATION (ug/m3)1
SAMPLING DATE
8/28/84
8/30/84
8/30/84
Field Duplicat
9/5/84
Precision (RPD)
8/30/84
Samples
ACCURACY (% SURROGATE RECOVERY)
TARGETED COMPOUNDS OTHER COMPOUNDS DETECTED (SAMPLE TUBE/FIELD BLANK TUBE)
•obenzene
Monochlo
3.UB
O.b3
1.84
e
--
111
orobenzene
a
•o
i
CM
•— t
1.42
0.84
1.03
J./3
21
orobenzene
u
i
ro
O.lb
—
--
O.O/
—
orobenzene
JC
0
•o
1.41
0./4
--
3.24
—
chloro-
zene
i- t>
t-> -O
CM
l.bH
0.86
1.19
2.59
32
Naphthalene
0.44
U.UU
0.64
1.23
l&b
I,l'-biphenyl2
2.22
—
--
—
Biphenyl
—
0.90
--
—
c
01
ro
JC
JC
CL
ro
C
1
CM
0.25
1.65
Ethyl benzene?
2.19
0.50
1-ethyl -
2-methyl benzene2
2.41
Ol
<-> c
Ol Ol
E N
V Ol
-H J3
1.92
CM
Ol
C
Ol
c
Ol
Ol
•5
1
CM
2.78
Ol
c
Ol
1
01
1
1.26
CM
O>
C
0*
N
C
0)
.c
*
0.96
Diphenyl ether
4.74
Base-Neutrals
Nitrobenzene - D5
94/63
67/85
96/85
104/98
2-fluorobiphenyl
95/76
59/74
65/74
61/58
Terphenyl - D14
142/148
112/116
122/116
58/98
Acids
Ut
Q
1
O
C
-------
TABLE D-4
QIMNTITATED ABD T£NTATIVEL»-IDENTIFIEO SEHI-VOLAI1LE COMPOUNDS DETECTED IN PRECOMBUST10N AIR
DOM CHEMICAL COMPANV BUILDING 703 INCINERATOR
l,2-d1chlorobenzene
~5BBJ
J-3fzd
I I"" '
I l,3-d1chlorobenzene
[m
\m\
Wi
jjjj-
H
limn I
1, 2, 4-tr1chl orobenzene
KS4T
#&
win
rrrr
Naphthalene
THTO
7741
4711
nrr
JDIecthylpnthalate 1
STJ
1 Anthracene I
TW
raar
Dt -n-butyl -
pnthalate
T75T
TW
WT
TWT
W7T
nrr
0*-n-octyl-
phthalate
7747
BWTT
mr
WiT
nmr
Twnr
Phenanthrene 1
m
TW
7S7
rr
Bis (2-etnylheiyl)-
1 phthal ate |
1T77
-im
TT7T
WSK
2««etnyl naphthal ene
STW
T-Tffll
TJ
5
o
il
iS
TI52T
LE|
Monochl orobenzene
T7777
TITO
itm
1
«->
uJ
904T
4£
l,3,S,7-cycloocta-
tet raene
T5555
l-(Mthylethyl)'
benzene
75W
7WJ1
l-ethyl-2-nethyl-
benzene
999S
3
£
T47W
TJ777
Octanethyl -
cyclotetrasilonane
H91B7
l.2-d1*thylD«iz*ne
TT52T
l,3-d4ethylbenzene
5207
1 ,2-d1ethenylbenzene
3978
1,1-blphenyl
9209
01 pnenyl ether
15647
~JOTT
now
Bis(2-aiethylpropyl)
pnthalate
23914
Ui
i
*
im
U- , . . 1
|
wre"
J,4-d1«ethyl-
2,3-hcptad1ene-
5-yne
TJTJT
TDBH
I 01 ethyl benzene
929
|
SOT
2-ethy!-l,4-d1nethyl-
benzene
~~B9T
TJBS7
!
Ik
.
n
1
1
i
7197
I*
|
*>.
I
2T
4t
[tt
ButylBethyl-
propylphthalate
TTO
*J
4-t
mm
|2-ethyl-l,l'-
1 blphenvl
^B7
2-butoiy-
dthanol
157T
2,6-d1iMthyl-
octane
2978"
Tndecane
T37SO"
Pentadecane
^500"
8/28/64
Sample
Field (lank
8/30/84
Sample
field Duplicate
Field Blink
9/5/84
Sample
Field (lank
Netnod Blank
00
NOTE - Results stated In m/>».
-------
TABLE D-5
QUALITY ASSURANCE DATA - PRECOMBUSTION AIR SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
ACCURACY (% SURROGATE RECOVERY)
8/28/84
SAMPLE
FIELD BLANK
8/30/84
SAMPLE
FIELD DUPLICATE
FIELD BLANK
9/5/84
SAMPLE
FIELD BLANK
METHOD BLANK
Base-Neutrals
Lf)
0
1
O)
c
z
94
63
67
96
85
104
98
12
>>
c
O)
.c
Q.
•r~
.0
O
t_
o
3
^«
M-
CM
95
76
59
65
74
61
58
0
«s-
i— i
Q
|
f_>
>,
O)
.G
CL
t_
Ol
142
148
112
122
116
58
98
6
Acids
Lft
Q
1
f—
0
C
OJ
JZ
Q.
87
84
36
49
33
88
79
100
^—
o
c
OJ
-C
Q.
O
c_
o
3
r_
<^
1
CM
101
80
31
45
34
90
85
28
o
c
CJ
CL
O
1=
O
t_
ja
•r—
t_
4->
|
^O
A
*3-
•V
C\J
75
41
53
59
55
80
48
0
f— i
'jj
_i
22
-------
3. PCDD/PCDF
a. All Homologues
In Table 0-7 analytical data are presented in terms of weight per sample;
these data are expressed in units of concentration in Table D-6. The data are
self-explanatory; note that for the two homologues detected in both samples
(actual and field duplicate) on August 28, the precision criterion (50% RPD or
less) was met for both. However, accuracy criteria were met for only one of
the four surrogates. Field blank samples were free of detectable PCDD/PCDF,
with accuracies as shown.
In summary, while OCDD and TCDF were detected on the first sampling day,
the accuracy of quantification is questionable as the recovery of surrogate
compounds was unacceptable. These and other homologues were found on the other
sampling days, but accuracy was unacceptable on the second sampling day, and
precision was not determined on the third sampling day. Accuracy criteria,
however, were met on the third sampling day.
b. TCDD Isomers
These data are shown in raw form in Table 0-9, and expressed as concentra-
tions in Table 0-8. On the first sample day, TCDD was found only as the 1368 and
1379 isomers, while on the second day a wider diversity of isomers was detected,
including the only finding of the 2378 isomer in any sample obtained in this
study. The third sample day also showed a comparatively diverse range of
isomers.
As for all of the TCDO isomer analyses conducted during this study, no
accuracy data are stated, as no surrogate isomers were added to the analyzed
matrices. The precision and accuracy limitations stated above for the analyses
of all homologues should also be applied to these data.
C. Liquid Waste Feeds
1. Concentrated Liquid Wastes
a. Volatile Compounds
These data are shown in Table D-10. Substantial analytical problems were
encountered with these samples; some of these are apparent in scanning the
surrogate recovery data shown in these tables. Other problems with individual
data are described in the notes included in the tables. Generally, however,
internal quality assurance review of the volatile pollutant data revealed that
they should be used with caution, as they showed a high level of contamination
of column degradation material. As a result of delays in preparing sample
extracts, volatile organic analyses were not performed until at least four
months after the samples were first obtained. Surrogate recoveries for four
data points (see above-referenced table) were out of acceptable ranges owing to
dilutions necessary to respond to peak saturation problems. Calibration checks
D-10
-------
TABLE D-6
INCINERATOR PRECOMBUSTION AIR - PCDD/PCOF ANALYSES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
8/28/84
MODIFIED METHOD 5 TRAIN
FIELD DUPLICATE
FIELD BLANK
8/30/84
MODIFIED METHOD 5 TRAIN
FIELD BLANK
9/5/84
MODIFIED METHOD 5 TRAIN
FIELD BLANK
2378-
TCDD
NO
(7.86)
NO
(11.32)
5.16
ND
(1.48)
ND
(0.55)
Total
TCDD
58.21
ND
(53.4)
17.99
38.90
ND
(0.35)
Total
PeCDD
ND
(11.01)
ND
(131)
ND
(2.30)
ND
(0.94)
ND
(0.40)
Total
HxCOD
ND
(6.62)
ND.
(125)
(Sample
10.39
ND
(1.46)
ND
(0.85)
Total
HpCDD
ND
(12.02)
ND
(5.43)
analyst:
235.10
98.14
ND
(2.15)
OCDD
216.60
335.14
not ret
802.08
306.51
NO
(4.83)
2378-
TCDF
ND
(7.89)
NO
(29.2)
urned fn
12.93
ND
(1.74)
ND
(0.39)
Total
TCDF
391.22
628.02
m labor.
12.93
206.60
ND
(0.29)
Total
PeCOF
ND
(6.07)
ND
(6.01)
tory.)
12.50
ND
(1.45)
ND
(0.37)
Total
HxCDF
ND
(16.2)
NO
(4.20)
14.23
ND
(1.42)
NO
(0.33)
HpCDF
ND
(27.50)
ND
(8.45)
108.48
37.43
ND
(3.08)
Accuracy
Total
OCOF
21.18
ND
(30.2)
113.67
30.95
ND
(4.21)
COMPLETENESS BY SURROGATE
1
00 O
r*. o
ro o
CM »—
f-4
o
no
84
2
99
100
89
77
71%
(^Surrogate Recovery
i
00 Q
r-~ o
m o
(M h-
*r
o
i^-
CO
85
125
92
90
92
97
86%
0
o
8
CM
O
CO
i—*
17
22
35
27
61
59
29%
i
CO U_
r~ o
M O
Cvj f-
«3-
CJ
r~-
n
100
100
100
48
100
76
71%
a
i
Notes: Data expressed In pg/m^.
1 All surrogate recoveries within target ranges of 50-150%.
-------
TABLE D-7
INCINERATOR PRECOMBUSTION AIR - PCDD/PCDF ANALYSES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
8/28/84
HI-Vol Filter + XAD-2 sorbent
Field Blank
Field Duplicate
8/30/84
Hi-Vol Filter + XAD-2 sorbent
Field Blank
9/5/84
Hi-Vol Filter + XAD-2 sorbent
Field Blank
:
2378-
TCDD
ND(2.47)
ND(3.75)
1.59
ND(0.237)
ND(O.SOl)
ND(0.187)
TOTAL
TCDD
18.3
ND(17.7)
5.54
ND(0.129)
13.2
ND(0.120)
TOTAL
PeCDD
N0(3.46)
ND(43.4)
ND(0.709)
NO(0.66B)
ND(0.318)
ND(0.135)
TOTAL
HxCOD
ND(2.08)
(Sample .
ND(41.5)
3.20
ND(1.13)
N0(0.496)
ND(0.287)
TOTAL
HpCDO
ND(3.78)
nalysis m
N0(1.80)
72.4
ND(1.39)
33.3
N0(0.725)
OCDD
68.1
t returne
111
247
ND(3.65)
104
N0(1.63)
2378-
TCDF
N0(2.48)
d from labc
ND(9.67)
3.98
ND(0.342)
ND(0.590)
ND(0.132)
TOTAL
TCDF
123
iratory.)
208
3.98
ND(0.371)
70.1
ND(0.0973)
TOTAL
PeCOF
ND(1.60)
ND(1.99)
3.85
ND(0.603)
ND(0.492)
ND{0.124)
TOTAL
HxCDF
ND(4.27)
ND(1.39)
4.38
ND(l.Ol)
ND(0.483)
ND(O.llO)
TOTAL
HpCDF
ND(7.25)
ND(2.80)
33.4
ND(1.60)
12.7
ND(1.04)
OCDF
6.66
ND(IO.O)
35.0
ND(4.29)
10.5
ND(1.42)
a
i—'
ro
NOTE: Data expressed in ng/g.
-------
TABLE 0-8
INCINERATOR PRECOMBUSTION AIR - TCOD ISOMER ANALYSES
OOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
8/28/84
MODIFIED METHOD 5 TRAIN
FIELD DUPLICATE
8/30/84
MODIFIED METHOD 5 TRAIN
9/5/84
MODIFIED METHOD 5 TRAIN
1368
44.21
23.96
1379
13.99
4.32
7.57
1369
1247
1248
1378
1469
1.62
2.45
1246
1249
1268
1278
1478
1268
1279
0.97
1234
1236
1269
0.81
0.98
1237
1238
5.03
3.92
2378
5.16
1239
1278
1279
1267
1289
00
Note - Data expressed in
-------
TABLE D-9
INCINERATOR PRECOMBUSTION AIR - TCDD ISOMERS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30. 9/5/84
SAMPLE IDENTIFICATION
8/28/84
Hi-Vol Filter + XAD-2 Sorbent
Field Blank
Field Duplicate
8/30/84
HI-Vol Filter + XAD-2 Sorbent
Field Blank
9/5/84
Hf-Vol Filter + XAD-2 Sorbent
Field Blank
1368
13.9
ND(247)
ND(0.204)
ND(0.129)
8.13
ND(0.120)
1379
4.40
ND(212)
1.33
ND(0.129)
2.57
ND(0.120)
1369
N0(2.31)
ND(141)
ND(0.204)
ND(0.129)
ND(0.611)
ND(0.120)
1247
1248
1378
1469
ND(2.70)
(San
ND(70.7)
0.500
ND(0.129)
0.830
ND(0.120)
1246
1249
ND(2.70)
pie analy
ND(17.7)
ND(0.204)
ND(0.129)
ND(0.611)
ND(0.120)
1268
1278
ND(2.70)
Is not re
ND(17.7)
ND(0.204)
ND(0.129)
ND(0.611)
N0(0.120)
1478
ND(2.70)
urned fron
ND(17.7)
ND( 0.204)
ND(0.129)
ND(0.611)
ND(0.120)
1268
1279
ND(1.16)
i laborator
ND(17.7)
0.300
ND(0.129)
ND(0.611)
ND(0.120)
1234
1236
1269
N0(2.70)
y.l
ND(17.7)
0.250
ND(0.129)
0.332
ND(0.120)
1237
1238
ND(2.70)
ND(17.7)
1.55
ND(0.129)
1.33
ND(0.120)
2378
ND(2.44)
ND(3.75)
1.59
ND(0.237)
ND(0.501)
ND(0.187)
1239
ND(1.54)
ND(17.7)
ND(0.163)
ND(0.129)
ND(0.611)
ND(0.120)
1278
1279
ND(1.54)
ND(17.7)
ND(0.196)
ND(0.129)
ND(0.611)
ND(0.120)
1267
N0(1.54)
ND(17.7)
ND(0.244)
ND(0.129)
ND(0.611)
ND(0.120)
1289
ND(1.54)
ND(17.7)
ND(0.204)
ND(0.129)
ND(0.611)
ND(0.145)
D NOTE: Data expressed In ng/g.
-------
TABLE D-10
QUANTITATED VOLATILE COMPOUNDS - LIQUID WASTE INPUTS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
OTHER
TARGET CHLORINATED BENZENE RING OTHER
COMPOUNDS COMPOUNDS COMPOUNDS COMPOUNDS
REAGENT BLANK 1
REAGENT BLANK 2
8/28/84
Nozzle BA
Nozzle BA Dilution
Nozzle BB ll
Nozzle BB *2
Nozzle BB *2 Dilution
Nozzle C
Nozzle C RERUN
Field Blank
8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB 11
Nozzle BB 11 Field Duplicate
Nozzle BB *2
Nozzle BB *2 Field Duplicate
Nozzle BB 12 Field Duplicate RERUN
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Duplicate RERUN
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BA Dilution
Nozzle BB
Nozzle BB Field Blank
Nozzle C
Nozzle C Dilution
Nozzle C Field Blank
Monochlorobenzene
15300
17700
(St
7490
4340
o
1 BELO
446,270
283,000
Chloroform
'I
2970
3260
Methylene chloride
11
50
4136
3400
-------
of the GC column revealed sporadic outliers, according to EPA review of these
laboratory data. On this basis, quality assurance review suggested strongly
that the analytical results presented here are biased low by an amount which
cannot be reliably quantitated.
If these data are used for qualitative purposes, some tentative trends or
conclusions may be supportable:
- Some of the liquid waste incinerated appeared to contain detectable
quantities of benzene ring compounds such as ethyl benzene, styrene,
toluene, and xylenes.
- Chlorinated compounds were detected primarily on the third sampling
day; however, these findings were largely affected by the surrogate
recovery problems highlighted above.
- Of the chlorinated ring compounds, only monochlorobenzene was
detected.
A listing of tentatively identified compounds and their concentrations are
presented in Table D-ll. These data are included for information only, as no
support can be offered for their accuracy. Hexamethylcyclotrisiloxane was
found in nearly all of the samples and thus appeared to be a laboratory
contaminant.
b. Semi-Volatile Compounds
Table D-12 includes data for all quantitated semi-volatile compounds;
several target and benzene ring compounds were detected, and accuracy criteria
(80-125% surrogate recovery) were met for 15 of the 29 sample runs shown in the
table. Note that problems in surrogate recovery occurred chiefly with the acid
surrogates. Therefore, the findings of the following compounds may be supported
as the surrogate compounds corresponding to their pH range were recovered within
acceptable limits:
Waste Nozzle Sampling Day Compounds Detected
BB (first feed) 1 2,4,5-trichlorophenol (A)
naphthalene (BN)
2-methylnaphthalene (BN)
BA BA 2 2-methylnaphthalene (BN)
BB (first feed) 2 1,2-dichlorobenzene (BN)
2-methylnaphthalene (BN)
anthracene (BN)
C 2 1,2-dichlorobenzene (BN)
2,4,5-trichlorophenol (A)
2,4,6-trichlorophenol (A)
naphthalene (BN)
anthracene (BN)
fluorene (BN).
D-16
-------
TABLE 0-11
LIQUID WASTE INPUTS - TENTATIVELY IDENTIFIED VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, and 9/5/84
REAfiENT BLANK I
RECENT BLANK 2
8/28/84
Nozzle 3A
Nozzle BA Dilution
Nozzle 88 11
Nozzle 88 »2
Nozzle BB 12 Dilution
Nozzle C
Nozzle C REftUN
Held Blank
8/30/84
Nozzle 3A
Nozzle BA Field Blank
Nozzle 88 11
Nozzle 3B fl Field Duplicate
Nozzle 36 *2
Nozzle 88 »2 Field Duplicate
Nozzle BB 12 Field Duplicate RERUN
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Duplicate RERUN
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle 3A Dilution
Nozzle 58
Nozzle 38 Field Blank
Nozzle C
Nozzle C Dilution
Nozzle C Field Blank
Hexamethylcyclo-
trlsUoxane
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
' n.?
'0.?
0.?
1 rr.71
Dlethoxydimethyl-
silane
821
18816
96079
7655
4637
5375
4213
2333
4212
4375
27216
6250
2649
55492
13d9
WW
IHiM
1????
?3lO
?MM
2330
2 -methyl butane
14884
34518
?ft44fi
Cyclohexane
20464
7561
"2875T
8630
Methoxytrlmethyl-
silane
17452
66477
cu
c
n
*j
J
I
4j
1
•S
1
-------
TABLE 0-12
QUANTIFIED SEM1-VOLAMLE COMPOUNUS - LIQUID WASTE INPUTS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
TARGET BENZENE KING
COMPOUNDS COMPOUNDS OTHER
URGENT BLANK 1
REAGENT BLANK 2
8/28/84
Nozzle BA
Nozzle BA, 5X Dilution
Nozzle DA, 20X Dilution
Nozzle BB 11
Noizle BB fl. 16X Dilution
Nozzle BB 11! 20X Dilution
Nozzle BB 12
Nozzle BB 12. 10X Dilution
Nozzle C
Field Blank (Nozzles BA i BB)
8/30/84 1
Nozzle BA 1
Nozzle BA Field Blank I
Nozzle BB il 1
Nozzle BB il Field Duplicate I
Nozzle BB 11 Field Duplicate. 5X Dilution |
Nozzle BB 12
Nozzle BB 2 Field Duplicate
Nozzle BB 12 Field Duplicate. IflX Dilution)
Nozzle C
Nozzle C F eld Duplicate
NbTTle C F eld Duplicate. IPX Dilution
Jjozz _§_C F eld BlSnk
9/57 4
Nozz e BA
Nozz e BA, 10X Dilution
Nozz e BB
Nozz e BB Field Blank
Nozz e C
Nb"iz e C. IPX Dilution
Nolz e C Field Blank
1,2-dichlorobenzene
1406
Tim
1240
o
c
01
c
a.
o
c
a>
c.
a.
o
i_
o
c
o
t_
*j
1
ift
**
c\*
4640
1900
44M1
2,4,6-trichlorophenol
110
fl.VO
is;*)
4490
Naphthalene
144
6BU
'MS
~W
2-methyl naphthalene
77
3;J
n^
ItbU
~TT
Anthracene
b6(J
~40
Fluorene
190
T4T
0
10SOO
£3800
1390
1130
5930
— rro
~T70~
ACCURACY (% SURROGATE
RECOVERY)
Base-Neutrals
N1trobenzene-D5
44
25
45
110
40
20
' To"
20
Tfi
85
40
50
68
132
65
60
76
10
58
~4T
~ro
52
~nr
2-fluorobiphenyl
60
120
40
122
30
20
75
35
84
Bff
40
^5
BO
?8
3~5
64
~2TT
35
70
3D
~~5T
^*
o
1
">,
c
0)
c
0.
(_
*->
A3
Ol
o
t_
i_
3
t/1
ID
5
(T
N~
IP
T
N
N
V
N
Y
<
V
Y
Y
IT
IT
T
N
N
V
V
N
V
N
N
Y
Y
y
N
V
b2
Base-Neutrals
Y
»
Y
Y
V
y
N
I/
y
N
N
y
y
N
y
Y
N
y
Y
y
y
Y
83
Overall2
N
N
IT
1
N
N
¥
N
Y
Y
Y
1
i
N
N
I/
N
N
y
y
N
y
N
N
y
Y
y
N
y
52
a
i
oo
NOTES: Data expressed In ing/kg.
IA|| surrogate recoveries within target range (20-180X) established
In Quality Assurance Project Plan. N=No, Y*Yes
?Based on all surrogate recoveries for both acids and base-neutrals within target range.
of surrogates and overall.
a inittratP that althnuuh accnr»e\t for all <;iirrn.i;«l-<^ ua<; nnt arronf^hfo the
-------
In the above summary, "A" in parentheses denotes an acid compound while "BN"
denotes a base-neutral compound. The detection of 2,4,6-trichlorophenol, an
acid, in the first nozzle 88 feed on the second sampling day is not confirmed
as the recoveries of all acid surrogates in those samples was not within the
acceptable range. Note that diethyl phthalate, a common analytical contaminant,
was detected on occasion, and that analytical precision between sample dilutions
appeared generally poor.
In Tables 0-13, 0-14, and D-15 listings of tentatively identified semi-
volatile compounds are presented sample by sample.Inadditionto" these
tentatively identified compounds, a number of peaks labeled "unknown" were
listed.
c. Pesticides and Polychlorinated Biphenyls (PCBs)
These data are presented in Table D-16. Most pesticides were detected on
the first and second sampling days, with no PCB found in any sample. However,
detection limits for the PCBs and for chlordane and toxaphene were in the range
of 1 to 10 mg/kg (ppm), much higher than the 5 ppb detection limit specified
for this study. Also, as shown in Table D-16, no surrogate recovery data were
submitted by the analytical laboratory. Therefore, no judgments can be made
concerning the accuracy of these results.
d. PCDD/PCDF
(1) All Homologues
These data, presented with accuracy information in Table 0-17 and with
detection limit data in Table 0-18, show the presence of a wide range of
PCDO and PCDF homologues in waste feeds from nozzles BB (first waste fed on
the second sampling day) and C. Precision data indicate generally good
agreement between the two field duplicate samples obtained on that day.
Detection limit goals of 30 ppq for TCDO and TCDF, and 90 ppq for other
homologues, were generally met for the latter; however, more frequent
problems appeared on the second sampling day, where higher detection limits
were common. The completeness criterion of 90%, based upon successful
recoveries of all four surrogate compounds, was not met (see Table D-17).
(2) TCDD Isomers
These data are self-explanatory, and are shown in Table 0-20, with
detection limit data included. Table 0-19 is an abridged version of this
table, indicating only those isomers which were detected, and rounding the
data as appropriate.
2. Low-STU Liquid Waste (Dike Water)
Dilute wastewaters composed of collected precipitation, condensates from
tank farm carbon adsorption system regeneration, and collected runoff from
hydroblasting operations in the Dow facility, were incinerated on the first and
third sampling days.
D-19
-------
TABLE D-13
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
REAGENT BLANK
! . . <*^/-oc-
-------
TABLE D-13 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOU CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID HASTE NOZZLE BA
8/28/84 LABORATORY RERUN
D-21
-------
TABLE D-13 (contl)
LIQUID '-/ASTE INPUTS - TENTATIVELY-IDENTIFIED SEM1 -VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID HASTE NOZZLE BA
8/28/84 SECOND LABORATORY RERUN
CAS
Compound Nwrw
Fraction
Torcaijy
NumSST
ErtJnvat»d
Conc«ntntion
(ug/l
fLflAr*1
i jjy/-Pjj-7-
-triyrt
4.
e.
9._
n.
-7*70
is.
77?
l 113.
ia..
\MH-TH?
D-22
-------
TABLE D-13 (cont,-)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE BB (1145-1606 EOT)
R/28/84
TABLE D-13 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE BB (1145-1606 EDT) LABORATORY RERUN
E>timai»d
Cooc»ntratJon
(«•/»
D-23
-------
D-13 Icont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID HASTE NOZZLE BR (1145-1606 EOT) - 8/28/84 SECOND LABORATORY RERUN
TABLE D-13 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE BR (1606-2020 EDT)
8/28/84
1U
1 K
I .
19
21 1
23
2S
I
\f
A6M
\
vK
3/
73£>
7*3
121
•2*/O
ZZ3
977
?$7
/OO?
(Oft,
/O3O
/O'jG
/06ff
113-2-
tSb£
D-24
-------
TABLE D-13 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE BB (1606-2020 EOT)
8/28/84 LABORATORY RERUN
CAS
Wumb«f
Compound
Fraction
-ass
Estimated
Concentration
t&^^
46N
2..
4..
6..
6..
/etc,-?
\/_
TABLE D-13 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE C
8/28/84
10.
D-25
-------
LIQUID WASTE INPUTS - TmY-DENTFED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE FIELD BLANK - 8/28/84
10..
'11..
112..
TABLE D-14
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE BA - 8/30/84
-------
lnDLC 3-14 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHE-1ICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE BB (1000-1415 EOT) FIELD DUPLICATE SAMPLE
8/30/84
30.
ff
D-27
-------
TABLE D-14 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE BB (1000-1415 EDT) FIELD DUPLICATE SAMPLE LABORATORY RERUN
8/30/84
CAS
Numb*
Compound MMTW
Fraction
Estimated
Cooe*ntr«tjfln
^31- /j«3j3-
2.
4.
5.
7. q?-<.
8
9
10
ll«5V*5X-
0>Htb
77 Z.
10 /f
-k
- /./'-jt+t4*uj
/Y7.S"
- /. i ' ': ?' t "
IB..
it
TABLE D-14 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CH01ICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE BA FIELD BLANK - 8/30/84
A6N
15.1
(.
-------
TABLE
D-14 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOU CHEHCAL COMPANY BUILDING 703 INCINERATOR
LIQUID HASTE NOZZLE BB (1000-1415 EPT) - 3/30/84
CAS
Mumbw
Compound MMTM
M^nSSr
Estinvitvd
SAJ
1-
TABLE D-14 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE BB (1415-1700 EOT) - 8/30/84
D-29
-------
TABLE D-H (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID HASTE NOZZLE C - 8/30/84
TABLE 0-14 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SB'! I-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE C - 3/30/84 FIELD BLANK
7
' 5
5
10
1 1
1?.
L(^rLSZ*a-*+3~>~1 —
A&l
5-73
D-30
-------
TABLE D-14 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE C - 8/30/84 FIELD DUPLICATE SAMPLE
0.
D-31
-------
TABLE D_14 (cont>)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE C - 8/30/84 FIELD DUPLICATE SAMPLE LABORATORY RERUH
TABLE D-14 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE BB (1415-1700 EDT) FIELH DUPLICATE SAMPLE
8/30/84
-------
TABLE D-14 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOU CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE BB (1415-1700 EOT) FIELD DUPLICATE SAMPLE LABORATORY RERUN
8/30/84
D-33
-------
TABLE D-15
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID HASTE NOZZLE BA
9/5/84
TABLE D-15 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SB-11-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE BA LABORATORY RERUN - 9/5/84
D-34
-------
TABLE D-15 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE BB FIELH CLANK
9/5/84
IV
12
• **
14
IS
1S . ...
/hs&tts <£&***<*/,
,/
t.tbl.Soo
397-
1.^12.7.00
16.
7/0
713
20
?i/fr/-gy-g
22
- A / '-
TABLE D-15 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
DOW CHE1ICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE C
9/5/84
CAS
Compound
Fnctkm
1..
2._
4..
5..
6..
7..
3..
2.2.7
V
37/
-/V7
D-35
-------
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
D'J5 DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
(cont.)
HASTE NOZZLE C LABORATORY RERUN - 9/5/84
TABLE D-15 (cont.)
LIQUID WASTE INPUTS - TENTATIVELY-IDENTIFIED SEMI-VOLATILE COMPOUNDS
OOW CHE'IICAL COMPANY BUILDING 703 INCINERATOR
LIQUID WASTE NOZZLE C FIELD BLANK
9/5/84
1V-
12..
•»3.
14..
15..
IS..
D-36
-------
TABLE D-16
LIQUID HASTE INPUTS - QUANTITATED PESTICIDE/PCB COMPOUNDS
DOH CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, and 9/5/84
PESTICIDES PCB (AROCLORS)
REAGENT BLANK 1
REAGENT BLANK 2
8/28/84
Nozzle BA
Nozzle BB li
Nozzle BB »2
Nozzle C
Nozzles BA i BB Field Blank
8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB *1
Nozzle BB ll Field Duplicate
Nozzle BB |2
Nozzle BB |2 Field Duplicate
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BB
Nozzle BB Field Blank
Nozzle C
Nozzle C Field Blank
Aldrin
1 4
1.1
O
X
CO
1
«o
7.1
11.7
O
DC
CD
1
Ol
CO
0.2
0
a:
CO —
a
1 C
1C
ID T:
g c
csC
0.1
0.3
n.A
0.1
Chlordane
o
o
a
fl.4
1.2
i—
o
o
1
O.fi
0.3
Oieldrin
2.5
3.1
Endosulfan II
n.4
1.4
Heptachlor
II. 1
1.2
Toxaphene
vo
1—4
O
1—t
CM
CM
CM
CM
CM
CM
00
CM
If)
CM
O
CM
ACCURACY (X SURROGATE RECOVERY)
(ACCURACY
BMIl
~TiAl
A N
1
'TED BY
I 1
ANALYTICAL
1
LABORATORY . )
1
O
OJ
NOTE: Data expressed in mg/kg.
Where data are not stated, compound was not detected.
-------
TABLE D-17
LIQUID WASTE INPUTS - QUANTITATED PCDD/PCDPI
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, and 9/5/84
ACCURACY
(% RECOVERY)
REAGENT BLANK 1
REAGENT BLANK 2
8/28/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB #1
Nozzle BB #2
Nozzle C
8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB #1
Nozzle BB #1 Field Duplicate
Nozzle BB #2
Nozzle BB #2 Field Duplicate
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BB
Nozzle BA Field Blank
Nozzle C
Nozzle C Field Blank
Q
Q
O
1—
1
oo
r^
OO
CM
Q
Q
O
t—
o
H-
1.2
0.9
0.4
2.6
4.2
Q
Q
0
Q.
:r
O
9.2
0.4
37.0
32.3
36.6
18.0
6.5
U-
Q
O
O)
O
f—
0.8
1.8
5.3
1.5
4.3
0.2
U-
Q
O
X
n:
0
O./
3.b
I.I
u_
o
C_J
Q-
(O
4->
O
0.6
8.1
8.2
u_
Q
0
0
1.2
0.6
/.4
/./
\NALYSIS NOT RETURNED FROM LABORATORY)
0.2
COMPLETENESS BY SURROGATE
Q
Q
O
00
r-
co
CM
i
CM
i-H
0
OO
.— «
35
100
38
88
9b
88
100
100
100
//
57
75
97
100
100
100
99
75
84%
Q
Q
O
t—
1
OO
r~
oo
CM
1
*d-
o
r^
oo
119
90
118
112
105
96
91
90
113
88
94
98
9/
93
93
91
92
99
9b%
Q
Q
O
O
t
CM
i— 1
O
OO
t— 1
100
89
100
100
100
100
34
87
92
83
100
b3
23
49
75
53
40
64
/4%
Ll-
Ci
O
(—
1
OO
r~-
oo
CM
1
<3-
o
r^-
oo
44
61
39
75
81
84
82
75
85
75
60
100
100
57
50
90
100
56
84%
I
CO
CO
NOTES: 1. Data expressed in ng/g.
o mi . *• ~ -
-------
TABLE D-18
LIQUID WASTE INPUTS - PCOD/PCDF ANALYSES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30. 9/5/84
SAMPLE IDENTIFICATION
8/28/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB ll
Nozzle 66 12
Nozzle C
8/30/84
Nozzle BA
Nozzle ^A Field Blank
Nozzle BB 11
Nozzle BB 11 Field Duplicate
Nozzle BB |2
Nozzle BB 12 Field Duplicate
Nozzle C
Nozzle C Fleld^lant
Nozzle C Field Duplicate
9/5/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB
Nozzle C
Nozzle C Field Blank
2378-
TCDD
ND
ND
RTJ
Nb
ND
0.0066
0.0199
0.110)
0.0128
O156
ND
Nb
Nb
ND"
ND"
0.0035,
0.0117
0.0416
0.0603
0.0349'
ND:o.oi2Z
ND
ND"
TO"
0.152)
0.0396)
0.108)
ND( O.OOM)
NDf"
ND]
"ND
U.0<:44
0.0796
0.0096
TOTAL
TCDD
NU
NU
1
i
0.0419
0.0322!
>.79
).548
ND 0.0173)
NU
NU
0.0098
0.0044
~~33.0
30.7
ND(0.0208)
0.716
60.3
NDI0.0394)
21.8
ND 0.0013)
T.88
0.835
ND O.OOZ7)
TOTAL
PeCDO
ND
Nb
0.295
0.183
11.8
ND
Nb
0.371)
0.0398)
ND
NU
0.0289
0.0188
6.27
4.85
ND
Nb
0.0319
0.0661
3.45
ND(0.109I
6.13
ND(0.0084)
0.808
ND
ND
0.235
0.004
TOTAL
HxCDD
NU
Nu
ND
NU
NU
ND
0.399
'd.107
1.19
0.0782
0.0294
0.0757
0.0094'
~D.895
0.375
ND
NU
t
NU
i
0.135
0.309
?.61
0.0693)
1.24
ND; 0.0046)
NU
NU
NU
0.0892
0.217
0.003
TOTAL
HpCDO
NU
No
ND
NU
NU
ND
ND
TJV3ZT
0.557
2.79 "
0.265
0.126
0.122)'
0.0389
3.00'
2.64
0.266)
ND;0.0567)
3.80
ND;
-------
TABLE D-19
LIQUID WASTE INPUTS - TCDO ISOMER ANALYSES
DOU CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28. 8/30, 9/5/84
SAMPLE IDENTIFICATION
8/28/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB ll
Nozzle BB |2
Nozzle BB 12 Lab Duplicate
Nozzle C
8/30/84
Nozzle BA
Nozzle BA Lab Duplicate
Nozzle BA Field Duplicate
Nozzle BB 11
Nozzle BB 11 Field Duplicate
Nozzle BB 12
Nozzle BB 12 Field Duplicate
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB
Nozzle BB Lab Duplicate
Nozzle C
Nozzle C Field Blank
1368
1.2
0.3
21.8
19.3
39.9
8.8
4.1
4.2
0.6
1379
4.1
0.3
10.3
11.4
20.4
10.8
1.8
1.6
0.2
1369
1247
1248
1378
1469
0.4
0.4
0.1
1246
1249
1268
1278
1478
1268
1279
1234
1236
1269
1237
1238
0.5
0.4
1.4
0.1
2378
1239
0.3
1278
1279
*
o
I
O
* GC retention time exceeded; therefore, this Isomer could not be quantltated.
NOTE: Data expressed In ng/g.
Blank spaces denote isomer was not detected (see Table D-20).
-------
TABLE 0-20
LIQUID WASTE INPUTS - TCDO ISOMERS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
8/28/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB ll
Nozzle BB |2
Nozzle BB 12 Lab Duplicate
Nozzle !T
8/30/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB 11
Nozzle BB ll Field Duplicate
Nozzle BB 12
Nozzle BB 12 Field Duplicate
Nozzle C
Nozzle C Field Duplicate
Nozzle C Field Blank
9/5/84
Nozzle BA
Nozzle BA Field Blank
Nozzle BB
Nozzle BB Lab Duplicate
Nozzle C
Nozzle C Field Blank
1368
TO IF. 0415"
TO
(
Nb
NU
NU
NU
i
TT.OJ2T
.19
i.276
0.0077,
0.0173
0.0098
0.0044
'1.8
9.3
ND(0.0450)
0.510
39.9
fiYBT
W 0.0394)
WO. 0015)
^4.05
4.16
0.636
1379
Nb
Nb
I
0.0419
0.0322'
.11
~0.272
NO"
Nb
Nb
NU
0.0033
0.0173
0.0098
0.0044
0.3
.1.4
ND(0.0277)
0.186
20.4
10.8
Nb(0.0394)
ND" 0.0013)
1.84
1.55
0.199
1369
m
Nb
ND
ND
ND
NU
0.0419)
0.0322)
0.206
0.031!
>
0.0033
0.0173
ND( 0.0098
ND"
ND
ND
ND
NU
NU
NU
NU
0.0044
0.537
0.346
0.0277
0.0258,
1.00)
0.270
0.0391
Nb(0.0013)
ND"
NU
NU
0.200
0.101
0.0660)
1247
1248
1378
1469
ND"
ND
ND
Nb
ND
NU
NU
NU
(
ND
Nb
0.0419
6.0322'
0.206)
6.0315
0.0033
5.0414
0.0098
0.0044
i.437
0.946)
0.0277)
0.0206
ND(2.01)
0.431
Nb(6.0334)
N0(0.0013)
ND(0.200)
0.084
ND(0.0660)
1246
1249
Nb(0.04l9
ND"
Nb
070322
0.206)
ND" 0.0315
ND"
NU
NU
NU
ND
Nb
ND
NU
NU
NU
ND
0.0033
0.0173
0.0098)
0.0044)
0.537
0.346
0.0277
0.0258
2.01)
0.270)
0.0394)
N0(0.0013)
ND
NU
Nb
0.200)
0.101)
0.0660)
1268
1278
ND"
Nb
ND
Nb
NU
NU
0.0419
0.0322
0.206)
0.0315
0.0033
0.0173
ND"
NU
ND
ND
ND
Nb
Nb
NU
Nb
0.0098
0.0044
0.537'
0.346
0.0277)
0.0129)
2.01)
0.270)
0.0394)
ND(0.0013)
NO
NU
Nb
l>.<>00)
0.101)
0.0660)
1478
NO
Nb
Nb
NU
NU
Nb
0.0419)
0.0322)
0.206)
0.0315)
0.0033
0.0207
ND
Nb
Nu
Nb
Nb
Nu
NU
NU
Nb
0.0098
0.0044
0.537
0.946
0.0277
0.0129,
2.01)
0.270)
0.0394)
Nb(0.0013)
ND
NU
0.200
0.101'
N0~(0.0660)
1268
1279
NO"
NU
ND
NO'
NU
Nb
0.0419)
0.0322)
0.206
0.03H
)
0.0033:
0.0173
ND"
Nb
Nb
ND
ND
Nb
NU
Nb
0.0098
0.0044
0.537
0.946
0.0277
0.0129
1.00)
0.270
ND~;0.039'
ND(0.0013)
ND
NU
0.200
0.101
N0(0.066(
J)
1234
1236
1269
ND
NU
ND
NU
Nb
Nb
Nb
NU
Nb
ND
ND
NU
NU
NU
NU
0.0419
0.0322
0.206
0.031
>
0.0033
0.0173
0.0098)
0.0044)
0.537
0.946
0.027
r
0.0129
1.00)
0.270
0.033
i
ND(0.0013)
ND
NU
NU
0.200
0.101
0.066
J)
1237
1238
Nb"
NU
0.0419
0.0322
0.493
NO"
NU
0.0315
0.0033
ND(0.0345
Nb"
Nb
I
Nb
Nb
Nb
NU
0.0098
0.0044
i.437
1.42)
0.0277)
0.0361)
2.01)
.40
NO 0.0394)
Nb(0.0013)
ND(0.200)
0.064
ND(0.0660)
2378
ND
NU
ND
Nb
Nb
Nu
0.0066
0.0199
0.110)
0.0129
0.0106
0.0156
ND(0.0035)
ND
Nb
ND
Nb
NU
NU
NU
0.0107)
0.0416)
0.0603'
0.0344'
0.0122)
0.152
0.180
1239
ND(0.0419
Nb 0.0322
Nb
Nb
NO
Nb
0.110)
0.0315
0.0033'
0.0173
ND
NU
ND
Nb
Nb
NU
ND
0.0098
0.0044
0.0416
1.42)
0.0208
0.0258
2.01)
1.323
TO; 0.0394) N0(0.0394)
!
ND(0.0034) Nb(0.0013)
ND
ND
Nb
0.0224
0.0214'
0.0796
NO
1 ND
1 NU
0.200)
0.202)
0.0660)
1278
1279
ND"
NO
Nb
ND
Nb
NU
0.0419
0.0322
0.206)
0.0315
0.0101
0.0173'
ND"
Nb
Nb
Nb
ND
Nb
Nb
0.0098
0.0044
1.07)
1.42)
0.0277)
0.0361)
2.01)
*
ND(0.0394)
ND(0.0013)
NO
NO
NU
0.200)
0.202}
0.0660)
1267
ND(0.0419
ND(0.0322
ND
ND
ND
0.206)
0.0315
0.0033
NDTff.0173
Nb"
Nb
ND
Nb
ND
Nb
0.0098)
0.0044)
0.537)
0.946)
0.0277
0.0258
ND(2.01)
*
Nb(0.0394)
N0(0.0013)
ND
Nb
NU
0.200)
0.101)
0.0660)
1289
ND"
ND
NO
NU
ND
Nb
0.0419
0.0322
0.206)
0.0315
0.0397
0.0173
ND
NU
Nb
0.0098)
0.0044)
0.537)
*
*
ND
Nb
0.0258)
2.01)
*
Nb(0.0394)
Nb(0.0013)
-
ND
Nb
O.ZOO)
0.101)
ND(0.0660)
NOTE: Data expressed In ng/g.
O
-------
a. Volatile Compounds
Field blank samples were found to contain relatively low levels of compounds
not generally found in samples of wastewater. As with semi-volatile compounds,
no volatiles were detected in first-day samples at levels higher than those in
the field blank. On the third sampling day, however, several target compounds
were detected, though not all were found in both actual and field duplicate
samples. A summary of these data appears below:
Table D-21
Low-BTU Liquid Waste
Target Volatile Compounds Detected
9/5/84
Concentration (ug/L)
Field Precision
Compound Sample Dupl icate (RPD)
1,1-dichloroethylene (vinylidene chloride) 127 137 3.8
1,1-dichloroethane (ethylene dichloride) 86 93 7.8
Chloroform 12 13 8.0
Tetrachloroethylene (perch!oroethylene) 378 ND*
Monochlorobenzene 260 ND
Carbon tetrachloride ND 2916
Trichl oroethylene ND 8
* ND = Not detected.
As shown in detail in Table D-23, other compounds were found in dike water
samples from the third sampling day, summarized as follows:
Table D-22
Low-BTU Liquid Waste
Other Volatile Compounds Detected
9/5/84
Concentration (ug/L)
Field Precision
Compound Sampl e Duplicate (RPD)
Methylene chloride 1127 1241 9.6
Acetone 1163 1302 11.3
l-(methylethyl)-benzene 2791 6222 76.1
The first two compounds commonly appear as contaminants in laboratory
analyses; therefore, their presence in dike water may be questionable.
Accuracy criteria were met for all five samples (see Table D-23).
D-42
-------
• -» x
-j ti
O T
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•o -..
— 3
•n
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~
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1
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00
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ro
t—>
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o-
-n
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3
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2
A
i
w
*o
w
o
Ui
X
3^
CD
rv
no
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«_i
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2
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i— i
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t/1
COMPOSITE SAMPLE
v
y
£
X
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a
ro
3
3
ro
•».
K^
t-^
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i— •
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MJ
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8/28/84
1,1,1-trichloroethane
benzene
toluene
ethyl benzene
styrene
methylene chloride
acetone
vinyl idene chloride
ethylene dichloride
chloroform
perchloroethylene
chlorobenzene
total xylenes
carbon tetrachloride
trichloroethylene
hexamethylcyclo-
trisiloxane
l-(methylethyl )-benzene
propyl benzene
toluene - 08
bromofluorobenzene
1,2 - dichloroethane - D4
ACCEPTABLE1
TENTATIVELY
IDENTIFIED ACCURACY
COMPOUNDS (% SURROGATE RECOVERY)
o z:
z i
m cc
8 =
i5
CO "
-~
re-
CO •
VO O «= I
— « O ro
. ID >
CO —I
z o
<-> 2
~- "O
z o
-------
b. Semi-Volatile Compounds
Field blank samples taken on both days on which dike water was fed to the
incinerator were generally free of detectable contamination; a phthalate was
noted in one of the blanks. No detectable semi-volatile compounds were found
in the composite water sample taken on the first day. On the third day, 1,2-
dichlorobenzene, 2-methylnaphthalene, 1,4-dichlorobenzene, and 2,4,6-trichloro-
phenol were detected, but only in the field duplicate sample in the case of the
latter two. Following is a summary of these results:
Table D-24
Low-BTU Liquid Waste
Semi-Volatile Compounds Detected
9/5/84
Concentration (ug/L)
Field Precision
Compound Sample Duplicate (RPD)
1,2-dichlorobenzene 121 95 24.1
2-methylnaphthalene 174 809 129.2
1,4-dichlorobenzene ND* 313
2,4,6-trichlorophenol ND 167
* ND = Not detected.
The presence of 1,2-dichlorobenzene in this wastewater stream on the third day
is affirmed within satisfactory bounds of precision. At the flow rate described
above, this concentration corresponds to a mass flow of 0.34 to 0.44 milligram
per day of 1,2-dichlorobenzene to the incinerator on the third sampling day.
While 2-methylnaphthalene was present, the analytical data failed to meet
established limits for precision.
Other tentatively identified compounds (Table D-25), some of them possibly
of interest as they are ring compounds, were detected in the sample but not the
field duplicate, and vice versa, on the third day. In the single case in which
a compound was found in both (a substituted naphthalene), quality assurance
criteria for precision were not met. Accuracy goals, as measured by recovery
of base-neutral and acid surrogate compounds, were met for four of the five
samples in this category, resulting in completeness of 80% (see Table D-25).
Recovery of an acid surrogate was outside of the acceptable range in the
sample not meeting the accuracy criterion.
c. PCDD/PCDF
(1) All Homologues
These data are presented in Tables D-26 and D-27. When compared to the
liquid waste feeds data in Section B.l.d., the concentrations of PCDD/PCDF
D-44
-------
TABLE 0-25
LOW-BTU LIQUID WASTE - SEMI-VOLATILE COMPOUNDSl
DOM CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28 AND 9/5/84
8/28/84
Composite Sample
Field Blank
975/84
Composite Sample
Field Duplicate
Field Blank
QUANTITATED COMPOUNDS
«U
c
a;
N
C
01
£)
o
O
u
•o
I
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121
95
OJ
c
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313
o
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167
TENTATIVELY - IDENTIFIED COMPOUNDS
0)
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COMPLETENESS3
ACCURACY
(% SURROGATE RECOVERY
BASE-NEUTRALS
o
i
Ol
c
ai
c
Ol
a
o
i.
£
c
/9
58
56
79
49
c
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1
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80
70
48
45
48
0
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c
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C
a.
ai
124
86
53
50
53
Base-Neutrals
100%
ACIDS
in
o
i
o
c
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^
58
16
56
29
31
o
c
01
J=
a.
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76
50
63
75
54
r—
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c
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9/
97
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27
55
Acids
80%
CM
UJ
CO
t—
Q.
UJ
0
^
YES
NO
YES
YES
YES
Overall
80% (4/5)
O
I
-pi
c_n
Notes: iData expressed In ug/L.
?A11 surrogate recoveries within target range (20-180%)
established in Quality Assurance Project Plan.
3By class of surrogates (acids and base-neutrals) and
overall (combined).
-------
TABLE 0-26
LOW-BTU LIQUID WASTE - PCDD/PCOF ANALYSES1
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28 AND 9/5/84
Accuracy (X Surrogate Recovery)
SAMPLE IDENTIFICATION
8/28/84
COMPOSITE SAMPLE
FIELD BLANK
87 30/84
(NO SAMPLE TAKEN - Low-BTU lie
4/5/84
COMPOSITE SAMPLE
FIELD DUPLICATE
FIELD BLANK
PRECISION(RPD) - SAMPLE AND
FIELD DUPLICATE
2378-
TCDD
luid was
Total
TCDD
e was nc
29.3
22.8
25
Total
PeCDD
t Inclru
Total
HxCDD
10.4
irated or
Total
HpCDD
i this dc
181
132
31
OCDD
y)
753
570
28
2378-
TCOF
Total
TCDF
33.9
46.4
31
Total
PeCDF
Total
HxCDF
Total
HpCDF
OCOF
COMPLETENESS BY SURROGATE
i
00 O
r~ o
ro o
C\J 1—
C\J
0
0")
t-H
60
62
45
84
100
80%
i
oo o
r~ o
m o
CVJ (—
«»
0
r^
n
114
93
93
78
108
100%
o
o
8
CM
t— t
O
n
100
100
100
100
96
100*
i
00 U.
r- o
n o
C\J H-
«•
0
1 —
n
39
43
37
63
46
20 1
o
cr>
NOTES: 1. All data expressed in pg/g.
2. All surrogate recoveries within target range of 50-15051.
3. Blank spaces denotes homologue not detected. Detection limits ranged from 0.3-3 ppq for
TCDD and TCDF. to 14-28 ppq for OCDD and OCDF.
-------
TABLE D-27
LOW-BTU LIQUID WASTE - PCDD/PCDF ANALYSES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28 AND 9/5/84
SAMPLE IDENTIFICATION
8/28/84
COMPOSITE SAMPLE
FIELD BLANK
9/5/85
COMPOSITE SAMPLE
FIELD DUPLICATE
FIELD BLANK
2378-
TCDD
ND
( .0008)
ND
(.0009)
ND
(.0102)
ND
(.0027)
ND
(.0002)
Total
TCDD
ND
(.0010)
ND
(.0010)
0.0293
0.0228
ND
(.0010)
Total
PeCDD
ND
(.0024)
ND
(.0026)
ND
(.0024)
ND
(.0035)
ND
(.0010)
Total
HxCDD
ND
(.0031)
ND
(.0027)
ND
(.0028)
ND
(.0055)
ND
(.0029)
Total
HpCDD
0.0104
ND
( .0068)
0.181
0.132
ND
(.0067)
OCDD
ND
(0.162)
ND
(.0089)
0.753
0.570
ND
(.0138)
2378-
TCDF
ND
(.0003)
ND
(.0005)
ND
(.0007)
ND
(.0009)
ND
(.0003)
Total
TCDF
ND
(.0010)
ND
(.0010)
0.0339
0.0464
ND
(.0010)
Total
PeCDF
ND
(.0011)
ND
(.0013)
ND
(.0016)
ND
(.0036)
ND
(.0046)
Total
HxCDF
ND
(.0016)
ND
(.0051)
ND
(.0015)
ND
(.0081)
ND
(.0025)
Total
HpCDF
ND
(.0061)
ND
(.0036)
ND
(.0040)
ND
(.0143)
ND
(.0013)
OCDF
ND
(.0098)
ND
(.0104)
ND
(.0047)
ND
(.0280)
ND
(.0166)
o
I
Notes: Data expressed in ng/g.
Accuracy data appear in Table D-26.
-------
are low, as may be expected, and limited to the tetra-, hepta-, and octa-
CDD, and tetra-CDF homologues. On the third sampling day, OCDD comprised
approximately 78% by weight of the PCDD detected.
Note, however, that none of the five sample analyses met the accuracy
criteria established for the four surrogate compounds. These data are
therefore not suitable for quantitative purposes, despite the good precision
observed (see Table D-26).
(2) TCDD Isomers
No 2378-TCDD or 2378-TCDF were detected. The isomers found (see Tables
D-28 and D-29) were limited to 1368, 1378, and 1237/1238.
D. Incinerator Exhaust
1. Volatile Compounds
Method blanks of the Tenax and charcoal adsorbents appeared to contain
measurable amounts of several contaminants; however, the analytical accuracy
may be questionable as none of the four surrogates was recovered. Analytical
problems traceable to poor fit of the VOST tubes in the thermal desorbing unit
were frequently cited by the laboratory. This phenomenon usually first affected
the recovery of the surrogate l,2-dichloroethane-D4, but not of the other three
surrogates. The data summaries (Tables 0-30, D-31, and D-32) indicate the data
points which were affected in this way.
On the three sampling days, five or six sets of VOSTs were exposed, usually
for 40 minutes, with single field blanks for the sorbents and condensates on
each day covering the time period in which all five or six sets were operated.
Thus, where compounds were detected in the field blank, the amounts trapped
were apportioned to each exposed sample according to the length of sampling
time. For example, if six VOSTs were employed for 40 minutes each, resulting
in a total sampling time of 240 minutes, one-sixth of the amount of a compound
in the field blank was subtracted from that in each exposed sample.
In Tables D-30, D-31, D-32, no data are stated for compounds trapped in the
collected condensates, which were pooled in the field and analyzed as composites
of all of the sample runs on each day. With few exceptions (see raw data,
Tables D-33, D-34, 0-35), no compounds other than methylene chloride and acetone
were detected, and it is suspected that these findings may be the result of
typical laboratory contamination.
The data tables present the compounds detected in terms of those specifically
targeted, other chlorinated compounds, benzene ring compounds, and other ring
compounds. While the materials consumed in the 703 Building incinerator varied
from day to day, it is apparent that carbon tetrachloride and 1,4-dichlorobenzene
were present in exhaust gas almost continuously. Other compounds, such as
1,2-dichlorobenzenes, ethylbenzene, 1,1,1-trichloroethane, and toluene, were
found in measurable concentrations but not on all three sampling days.
D-48
-------
TABLE D-28
LOW-BTU LIQUID WASTE - TCDO ISOMERS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28 AND 9/5/84
SAMPLE IDENTIFICATION
8/28/84
COMPOSITE SAMPLE
FIELD BLANK
8/30/84
(NO SAMPLE TAKEN -
975/84
COMPOSITE SAMPLE
FIELD DUPLICATE
FIELD BLANK
PRECISION(RPD) - SAMPLE AND
FIELD DUPLICATE
1368
Low-BTU
16.2
12.0
29.8
1379
liquid v
5.3
6.0
12.4
1369
tfaste was
1247
1248
1378
1469
not 1m
1246
1249
.ineratec
1268
1278
on thli
1478
day.)
1268
1279
1234
1236
1269
1237
1238
3.4
2.0
51.9
2378
1239
1278
1279
1267
1289
Notes: Data expressed in pg/g.
Blank spaces denote isomer was not detected.
-------
TABLE 0-29
LOW-BTU LIQUID WASTE - TCOD ISOMERS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28 AND 9/5/84
SAMPLE IDENTIFICATION
8/28/84
COMPOSITE SAMPLE
FIELD BLANK
9/5/64
COMPOSITE
FIELD DUPLICATE
FIELD BLANK
1368
ND
(.0017)
ND
(.0010)
0.0162
0.0120
ND
(.0010)
1379
ND
(.0010)
NO
(.0010)
0.0053
0.0050
ND
(.0010)
1369
ND
(.0010)
ND
(.0010)
ND
(.0011)
ND
(.0010)
NO
(.0010)
1247
1248
1378
1469
ND
(.0010)
ND
(.0010)
ND
(.0011)
ND
(.0010)
ND
(.0010)
1246
1249
ND
(.0010)
ND
(.0010)
ND
(.0010)
ND
(.0010)
ND
(.0010)
1268
1278
ND
(.0010)
ND
(.0010)
ND
(.0011)
ND
(.0010)
ND
(.0010)
1478
ND
(.0010)
ND
(.0010)
ND
(.0011)
ND
(.0010)
ND
(.0010)
1268
1279
ND
(.0010)
ND
(.0010)
NO
(.0010)
ND
(.0010)
ND
(.0010)
1234
1236
1269
ND
(.0010)
NO
(.0010)
ND
(.0010)
ND
(.0010)
ND
(.0010)
1237
1238
ND
(.0010)
NO
(.0010)
0.0034
0.0020
ND
(.0010)
2378
NO
(.0008)
ND
(.0009)
ND
(.0102)
ND
(.0027)
ND
(.0002)
1239
ND
(.0010)
NO
(.0010)
ND
(.0011)
NO
(.0010)
ND
(.0010)
1278
1279
ND
(.0010)
NO
(.0010)
ND
(.0011)
ND
(.0010)
ND
(.0010)
1267
ND
(.0010)
ND
(.0010)
ND
(.0010)
ND
(.0010)
ND
(.0010)
1289
ND
(.0010)
ND
(.0010)
NO
(.0011)
NO
(.0010)
ND
(.0010)
c_n
O
NOTE: Data expressed In ng/g.
-------
TABLE 0-30
INCINERATOR EXHAUST VOLATILE COMPOUNDS AS MEASURED
USING VOLATILE ORGANIC SAMPLING TRAIN, IN TERMS OF CONCENTRATION IN AIR
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28/84
SAMPLE ID
FIRST FRONT TUBE
FIRST BACk TUBE
FIELD DUPLICATE FRONT TUBE
FIELD DUPLICATE BACk TUBE
SECOND FRONT TUBE
SECOND BACk TUBE
THIRD FRONT TUBE
THlWlACK TUBE
FOURTH FRONT TUBE
FOURTH BACK TUBE
FIFTH FRONT TUBE
FIFTH BACk TufiE
SIM PROMT TUBE
SIXTH BACK TUBE
FIELD BLANK
:RONT TUBE
BACK TUBE
UNITS
ug/m3
ug/m-5
ug/ra^
ug/mi
ug/rn3
ug/m3
ug/mj
ug/m-i
ug/rn3
ug/nv
ug/n\J
ug/m*
ug/mi
r ug/mj
ng
ng
TARGET COMPOUNDS
UJ
O
Of
o
_l
1
Of
t—
UJ
t—
X
o
CO
DC
<
O
~T6T
-^T
~rrc
~nr
TW
11
-ZTC
1676
135
UJ
z
UJ
M
Z
UJ
CO
o
DC
O
_J
1
o
JC
~97
(Sam
(Sam
Tinl
TOT
"T31
(Sam
*
UJ
z
UJ
M
Z
UJ
CO
o
cc
o
_J
oc
o
o
ile ar
lie ar
>le ar
*
fe1
UJ
fsj
Z
Ul
§
QC
O
0
O
1
CM
•>
~IW
lalys
talys
277
522
HIT
alys
42J1
*
UJ
z
Ul
M
z
UJ
s
s
I
o
o
ro
s no
s not
s noi
*
Ul
z
Ul
hsl
z
Ul
g
oc
o
_j
DC
O
O
1
^-
"TOT
55
. reti
reti
njFri
~37r
-295
~T7T
~B5
reti
462 /
*
1
£
oe
o
_t
DC
(T
~T7"
rned
rned
pf7!
25
"~T2"
TIT
HIT
rned
Bi»0
i!0
UJ
z
UJ
_l
0
Ul
o
O£
O
_J
ac
o
tx
Ul
~w
from
from
riVi
— 3"
~TS
~T5"
from
62
UJ
z
Ul
_l
>-
X
t—
Ul
o
oc
o
_l
3:
0
Of
labor
labor
r^rr
— T
?
~TTT
labor
80
OTHER CHLORINATED
COMPOUNDS
Ji jjojo J 1,1,1-TRICHLOROETHYLENE
~33T
190
atory
/by
102
UJ
z
«t
I
1—
UJ
o
or
o
_i
ac
o
a:
^-
i
cu
*— 1
~HT
Is
1
UJ
Z
<<
CL
0
QC
a.
0
§
x
c_>
Q
1
CM
~5T
~Tff
~T7
Tff
*
Ul
Z
-
DC
1—
Ul
51
t-^-
~^T
"~S7
^fi
"W
T
HO?
iJOrt
Ul
z
UJ
Of
V-
f-
00
1/1
?
Ul
UJ
Z3
_J
0
»—
104
17
m
^TT
nft
174
ND
10fl<)
?^fi
OTHER RING
COMPOUNDS
*
Ul
<
1—
z
UJ
a.
o
_i
o
>-
0
_l
>-
3T
t—
Ul
z:
*
UJ
Ul
o
•t
*—
z
UJ
%
o
>-
o
1
<0
#
UJ
z
UJ
t^r
»—
<:
»—
Q_
UJ
§
_J
0
>-
u
IT)
CO
f— •
*
Ul
<
X
Ul
g
_J
o
>-
0
_J
>-
DC
f—
Ul
^
ACCURACY
(% SURROGATE RECOVERY)
CD
a
i
Ul
z
Ul
ID
-J
O
t—
lift
fto
%
104
100
114
ftfl
7ft
fi7
7?
44
4?
UJ
Z
Ul
r-j
z
Ul
00
o
a:
o
Z3
_J
U_
o
§
en
CO
114
h«
ft?
flfll
fto
-
DZ
t—
Ul
4?
~T?2"
10?
-------
TABLE 0-31
INCINERATOR EXHAUST VOLATILE COMPOUNDS AS MEASURED
USING VOLATILE ORGANIC SAMPLING TRAIN, IN TERMS OF CONCENTRATION IN AIR
OOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/30/84
SAMPLE ID
FIRST FRONT TUBE
FIRST BACk TUBE
FIELD DUPLICATE FRONT TUBE
FIELD DUPLICATE BACk TUBE
SECOND FRONT TUBE
SECOND BACk TUBE
THIRD FRONT TUBE
THIRD BACK TUBE
FOURTH FRONT TUBE
rUUKIH BALK 1 Uot 1
FIFTH FRONT TUBE
FIFTH BACK TUBE
SIXTH FRONT TUBE
SIXTH BACk TUBE
FIELD BLANK
FRONT TUBE
BACK TUBE
UNITS
ug/m^
ug/m3
ug/mj
ug/m^
uQ/in
UQ/ITI
ug/m^
ug/rn^
ug/rn^
ug/m^
ug/m'
ug/m'
ug/m^
ng
ng
TARGET COMPOUNDS
CARBON TETRACHLORIDE
--
34
2b8
—
--
201
85
532
323
262
375
—
MONOCHLOROBENZENE
15
—
—
--
Ob
—
64
465
—
b
—
DICHLOROBENZENE*
—
10
b
—
--
--
—
--
—
--
—
1,2-DICHLOROBENZENE*
—
38
—
~
—
725
422
3517
~
—
1,3-DlCHLOROBENZENE*
—
56
—
—
--
—
--
—
--
—
1,4-DICHLOROBENZENE*
1234
59
ND
284
284
—
250
767T
303
7
2058
CHLOROFORM**
—
—
—
--
lol
b
9
5"
--
—
5
PERCHLOROETHYLENE
b
—
—
—
28
—
.... >
~5B"
--
—
TRICHLOROETHYLENE
- 1
—
1
11
—
—
5
6
14
— 6"
9
6
—
OTHER CHLORINATED
COMPOUNDS
1
—
1,1,2-TRICHLOROETHANE
—
—
11
—
—
--
1,2-DICHLOROPROPANE
—
—
bb
—
—
--
2J
—
/I
~W
—
14
—
1,2, 3-TR I CHLOROPROPANE*
DIBROMOCHLOROMETHANE
—
34
--
--
—
BENZENE RING
COMPOUNDS
BENZENE
—
—
--
—
--
—
92
~NTT
—
37
—
1238
ETHYLBENZENE
U
6
--
1
--
b/
bl
—
30
4
ND
210
STYRENE
—
--
—
^
--
—
--
~^~
—
--
—
TOLUENE
—
41
--
ND
ND
256
115
545
225
--
ND
548
1385
OTHER RING
COMPOUNDS
METHYLCYCLOPENTANE*
9
--
-•
--
--
--
2041
3757
—
--
--
2476
1,3-CYCLOPENTADIENE*
1,3,5-CYCLOHEPTATRIENE*
--
—
--
—
--
METHYLCYCLOHEXANE*
—
113
--
--
ACCURACY
(% SURROGATE RECOVERY)
00
0
UJ
UJ
•=1
—t
o
1—
ion
82
104
6T
9T
122
116
97
TJ
~~G
0"
58
70
BROMOFLUOROBENZENE
112
82
nroo"
9
-------
TABLE D-32
INCINERATOR EXHAUST VOLATILE COMPOUNDS AS MEASURED
USING VOLATILE ORGANIC SAMPLING TRAIN, IN TERMS OF CONCENTRATION IN AIR
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
9/5/84
SAMPLE ID
FIRST FRONT TUBE
FIRST BACk TUBE
FIELD DUPLICATE FRONT TUBE
FIELD DUPLICATE BACK TUBE
SECOND FRONT TUBE
SECOND BACk TUBE
THtRD FRONT TUBE
THIRD BACK TUBE
FOURTH FRONT TUBE
FOURTH BACK TUBE
FIFTH FRONT TUBE
FIFTH BACk TUBE
SIXTH FRONT TUBE
SIXTH BACK TUBE
FIELD BLANK
FRONT TUBE
BACk TUBE
UNITS
ug/m3
ug/ni3
u Q/fn
u Q/rn
ug/m3
ug/n)3
ug/m3
ug/m3
ug/m3
ug/m3
ug/n)3
ug/m3
ug/n)3
ug/m3
ng
ng
TARGET COMPOUNDS
CARBON TETRACHLORIDE
120
—
142
28
--
226
—
128
--
97
1160
SRI
MONOCHLOROBENZENE
94
—
—
—
—
—
—
—
--
56
HLOROBENZENE*
.r.
--
—
—
22
--
--
—
—
—
—
-DICHLOROBENZENE*
.
98
—
—
—
—
196
—
—
«
333
556
-DICHLOROBENZENE*
.
—
—
—
—
--
34
—
—
—
—
669
-DICHLOROBENZENE*
.
57
14
225
1089
202
282
78
--
192
21
2513
OROFORM**
3C
64
—
—
—
--
b
--
9
--
4
tCHLOROETHYLENE
UJ
36
—
38
—
--
--
—
15
--
14
CHLOROETHYLENE
ce
10
—
8
--
--
--
—
4
--
4
79
OTHER CHLORINATED
COMPOUNDS
,1-TRICHLOROETHYLENE
•
.-
—
—
—
—
—
—
—
—
—
,2-TRICHLOROETHANE
-
>-DICHLOROPROPANE
-
21
--
4;
—
--
--
68
—
28
--
11
—
',3-TRICHLOROPROPANE*
•
HBROMOCHLOROMETHANE
BENZENE RING
COMPOUNDS
BENZENE
--
—
—
—
--
40
—
—
—
18
--
—
419
237
ETHYLBENZENE
26
--
4b
—
—
44
38
--
—
--
45
--
747
216
STYRENE
123
—
--
--
--
—
--
—
--
--
—
--
TOLUENE
--
—
—
--
--
--
—
—
—
--
NO
1840
306
OTHER RING
COMPOUNDS
METHYLCYCLOPENTANE*
1,3-CYCLOPENTADIENE*
6
--
1,3,5-CYCLOHEPTATRIENE*
METHYLCYCLOHEXANE*
ACCURACY
(% SURROGATE RECOVERY)
CO
a
i
Ul
z
UJ
o
(—
73
94
74
78
90
86
106
100
110
94
94
82
86
76
BROMOFLUOROBENZENE
bb
94
66
82
100
92
76
94
108
90
84
92
104
1,2-DICHLOROETHANE - D4
1U1
72
/4
127
136
28
16
86
J2
96
36
32
0
82
ETHYLBENZENE - DIO
4U
78
lib
124
124
82
146
146
88
10
106
92
64
84
ACCEPTABLE1
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
on
CO
Notes - 1 All surrogate recoveries within taryet range (80-125%)
established in Quality Assurance Project Plan.
* Tentatively-identified compound.
** Breakthrough volume exceeded during sampling.
ND Compounds present on blank tubes In higher concentrations
than on exposed sample.
COMPLETENESS = 0/16 = Ot
-------
TABLE 0-33
INCINERATOR EXHAUST VOLATILE COMPOUNDS AS MEASURED
USING VOLATILE ORGANIC SAMPLING TRAIN
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28/84
UNITS
METHOD BLANKS
VOST TENAX/TENAX-Charcoal
VOST CONDENSER
VOST TUBES
FIRST FRONT TUBE
FIRST BACk TUBE
SECOND FRONT TuBE
SECOND BACK TUBE
THIRD FRONT TUBE
THIRD BACK TUBE
FOURTH FRONT TUBE
FOURTH BACK TuBE
FIFTH FRONT TUBE
FIFTH BACK TUBE
FIELD BLANK (Composite
of 5 Runs)
VOST CONDENSER
COMPOSITE SAMPLE (5 Runs)
FIELD BLANK
ng
ug/L
ng
ng
ng
ng
ng
ng
ng
ng
ng
ng
ng
ug/L
ug/L
QUANTITATED COMPOUNDS
METHYLENE CHLORIDE
18000
3518
11
55
157
14Z7
1??
49
TOLUENE
428
2152
857
2524
1791
2766
3478
28
1089
ETHYLBENZENE
344
1191
105
1256
1337
909
2334
276
802
?nn
STYRENE
264
3144
44
UJ
z:
UJ
-J
X
t~
O
295
1016
482
714
11925
731
1360
1511
9482
811
CHLOROFORM*
282
514
blO
280
97
66
820
?0
UJ
CD
(\J
1115
440
UJ
Z
-------
99-Q
1
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UJ O
D "^
-J fc*j|
r\j O CD
* O rsa
•^ O GO
9 O *
cc
V/l
^ a - -
— n so ;o
3D O J ro wi o
g 5 CHLOROFORK*
«* 0=
2 2-BUTANONE
o
J S S CARBON TETRACHLORIDE*
S SI, 2-OICHLOROPROPANE
S 1,1,2-TRICHLOROETHANE
BENZENE
S « TETRACHLOROETHYLENE*
i £ CHLOROBENZENE*
3 rv>2 TRICHLOROETHYLENE*
n uj LJ
ACETONE
£ DIBROHOCHLOROMETHANE
00
S BROMOFORM
rg
-d "« 1,4-DICHLOROBENZENE*
w ~3 o
Ch «-M O
1,2-DICHLOROBENZENE*
a
I HEXANE
g i HEXAMETHYLCYCLOTRISILOXANE
o
S DIBROMOMETHANE
^
- METHVLCrCLOPENTANE
CO
U)
5 TRICHLOROFLUOROMETHANE
UJ
S 3-METHYLPENTANE
w BENZOFURAN
C S OICHLOROBENZENE*
U) -«J
^ g 1,3,5-CYCLOHEPTATRIENE
CO A
1,3-OICHLOROBENZENE*
S METHYLCYCLOHEXANE
o(
,0
?
^
o
0
13
o
c
z
o~.
— 1
m
z
-4
<
m
i—
c
m
z
Tn
pn
f)
i
"O
c
z
o
LO
S-H3.
»— * CO
%3
-------
TABLE D-35
INCINERATOR EXHAUST VOLATILE COMPOUNDS AS MEASURED
USING VOLATILE ORGANIC SAMPLING TRAIN
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
9/5/84
UNITS
VOST Tubes
First Front Tube
First Back Tube
Second Front Tube
Second Back Tube
Third Front Tube
Third Back Tube
Fourth Front Tube
Fourth Back Tube
Fifth Front Tube
Fifth Back Tube
Sixth Front Tube
Sixth Back Tube
Field Blank
(Composite of 6 Runs)
VOST Condenser
Composite Sample (6 Runs)
Field Blank
ng
ng
ng
ng
ng
ng
ng
ng
ng
ng
ng
ng
ng
ug/L
ug/L
QUANTITATED COMPOUNDS
ne chloride
1?
4-*
2
61
2t)
140
c
01
3
"o
t—
192
1840
306
nzene
.0
1?
+j
UJ
638
1000
1036
866
1016
92
747
216
c
at
i_
>>
+j
>
24b3
in
S
a>
">.
10
4-1
o
t—
463
b/4
4855
bU
1083
!>26
1033
300
*
o
o
c_
o
!c
o
12/2
100
1/4
77
o
2btt6
29lb
b4b
4532
J14
2/62
2104
1160
351
1,2 - dichloropropane
412
H96
905
bM
220
91
C
OJ
c
01
on
36
967
44
561
91
419
237
III
762
Mb
280
>robenzene*
JC
CJ
lt)63
1136
hloroethylene*
i_
t—
i!0b
16b
48
98
79
o>
c
o
o>
£
1354
39U
950
TENTATIVELY IDENTIFIED COMPOUNDS
1,4 - dichlorobenzene*
1557
278
4728
20560
3735
4165
1944
4195
410
2513
1,2 - dichlorobenzene*
1944
4173
6550
556
Hex ane
810
Hexamethyl cyclotri si 1 oxane
200
200
200
200
200
200
200
Oxi sane
16
2 - (methoxyethyl ) -
trimethylsilane
14
Trlchlorofluoromethane
96b«
3 - methyl pentane
100
9711
50
8/J
1150
1100
Hexamethy Idi si 1 oxane
500
Dichlorobenzene*
429
Fluorotrimethyl s i 1 ane
1500
2,4 - dimethyl -1-pentene
500
/Ob
1,3 - dichlorobenzene*
J13/
669
2 - methyl pentene
1850
1,3 - cyclopentadiene
117
o
en
* Target Volatile Compound
-------
The distribution of these compounds appeared generally random between the
front and back detection tubes when measurable quantities were found in each.
Also, several cases appear in which the same compound was detected only in the
front tube during one run, and only in the back tube in another. Field duplicate
samples taken during the first of six runs on the second sampling day were not
comparable for any compound, and no evaluation of precision could be made.
Field blank samples showed no clear, consistent pattern of blank contamination;
in some cases, denoted by the label "NO", compounds were present in higher
concentrations on blanks than on exposed samples.
For screening purposes, these data, despite their variability, appear to
suggest strongly that several compounds were regularly present in exhausts from
the 703 Building incinerator stack. However, any contributions of organics
resulting from the venting of gases from the activated carbon bed filter serving
the liquid waste tank storage area cannot be assessed from these data.
Therefore, emissions of the above compounds cannot be differentiated according
to their source.
A detection limit goal of 1 ppb was set with respect to collection of
volatile compounds using the VOST. Actual method sensitivities were 0.25 to
0.50 microgram/cubic meter, and indicated the objective was met. However, the
completeness goal of 90% was not met, as only 5% of the samples submitted were
analyzed such that surrogate recoveries were within the acceptable range of 80
to 125% (see Tables D-30, D-31, and D-32).
2. Semi-Volatile Compounds
Method blanks of the glass fiber filter, XAD-2 sorbent, and impinger catch
(distilled, deionized water) were found free of contaminants other than two
phthalates commonly considered ubiquitous in laboratory analyses.
The physical limitations of the sampling site at the incinerator outlet,
and the need to sample simultaneously at the same location for PCDD/PCDF,
precluded taking field duplicate samples to judge precision. In any event,
sampling of incinerator exhaust gases for semi-volatiles revealed few compounds
in detectable concentrations, with the exception of three base-neutral chloro-
benzenes and naphthalene found only on the second day of sampling. As the
recovery of the base-neutral surrogates in the XAD-2 sample was within the
acceptable range (see Table D-36), these findings are supportable; however, it
is suspected that breakthrough volumes for dichlorobenzenes on XAD-2 were
exceeded in this sample. Therefore these data may be biased low. None of
these compounds was found in any component of the Modified Method 5 train other
than the primary XAD-2 sorbent cartridge. However, the presence of several
substituted benzene, naphthalene, and phenyl compounds in the field blank
sample on this day may point to contamination during sampling.
The chlorobenzene concentrations found on the second day of sampling, shown
below, correspond to daily emissions of the following quantities of the listed
compounds:
D-57
-------
OUANTITATED AND TENTATIVELY IDENTIFIED SEMI-VOLATILE COMPOUNDS DETECTED IN INCINERATOR EXHAUST
DOM CHEMICAL COMPANY BUILDING 703 INCINERATOR - 8/28, R/30, and 9/5/04
8/28/B4
Filter • Probe Mash
Field Blank
XAD-2 Cartridges
Field Blank
Inplngers 1 Rinses
Field Blank
Backup XAD-2
Field Blink
8/30/84
Filter « Probe Mash
Field Blank
XAD-2 Cartridges
Implngers I Rinses
Field Blank
Backup XAD-2
Field Blank
9/S/B4
Filter « Probe Mash
Field Blank
UD-2 Cartridges
Field Blank
[•plngers 1 Rinses
Field Blank
Backup XAD-2
Field Blank
METHOD BLANKS
Filter
Probe Wash
XAO-2 Cartridges
laiplnger
1.2-OICHLOROBENZENE
27540
219
1,4-DICHLOROBENZENE
24140
NAPHTHALENE
7820
BENZOIC ACID
1600
ISOPHORONE
3120
BIS(2-ETHYLHEXYL)
PHTHALATE
24
859
6.5
11
67
9010
30
428
~T7B
44
40
330
117
69
OI-N-OCTYL
PHTHALATE
4375
476
OI-N-BUTYL
PHTHALATE
14J
422
1537
330
1047
470
2/44
1466
-t 4
X <
t- X
5(0
TETRACHLORO-
BENZENE
5500
BIPHENYL
1875
1,4-DIMETHOXY-
BENZENE
4592
3.5-DIMETHOXY-2-
CYCLOHEXENE-1-ONE
4353
o
X
O
633
2-ETHYL-
1-HEXANOL
2300
27
625
BUTYL-2-METHYL
PROPYLPHTHALATE
IB
1,3,5-TRITHIANE
3
1.4-OIHYDRO-1.4-
ETHANONAPHTHALENE
11027
2-ETHYL-l,!'-
BIPHENYL
5125
METHYL-
DIPHENYLSILAHE
14(80
1,1'-(1,2-ETHENOIYL)-
BIS(Z)BENZENE
7511
r-f
r-j ix
4403
TERPHENYL
5026
1-NONANOL
1795
'
3-METHYL-6- ( 1-METHYLENE I -1
DENE)-2-CYCLOHEXENE-l-ONE
5058
'All surrogate recoveries within target range (20-1801)
established In Quality Assurance Project Plan.
By class of surrogates (acids and base-neutrals) and overall (combined).
7.7'-OICHLORO-BICYCLO-
(4,1.0) HEPTANE
"T4T3
BIS-2-METHYL-
PROPYLPHTHALATE
2020
i
ug/L
uij/L
ug/kg
ug/kg
ug/L
ug/L
ug/kg
ug/kg
ug/L
ug/L
ug/kg
ug/kg
ug/L
ug/L
ug/kg
ug/kg
us/L
ug/L
ug/kg
ug/kg
ug/L
ug/L
ug/kg
ug/kg
ug/kg
uq/L
I COMPLE1ENESS?
ACCURACY (I SURROGATE RECOVERY)
Base-Neutrals
UJ
ae
UJ
i
58
47
0
110
101
70
61
32
2240
36
57
78
56
110
55
(1
31
0
50
43
42
64
91
67
10
71
91
§UJ
X
CNJ
89
80
0
273
81
51
85
37
120
55
68
74
85
86
64
80
34
71
0
30
58
58
97
111
(2
5
77
68
TERPHENYL-D14
54
15
0.2
133
43
25
38
23
204
21
85
fifl
" 47
75
52
77
56
71
1
84
75
65
42
44
84
0
122
106
Base-Neutrals
791
Acids
0
i
Ui
46
nl
0.1
51
50
101
52
40
2
27
8
7!
48
46
35
40
0
0
0
0
0
0
56
51
52
0
71
64
2-FLUORO-
PHENOL
24
44
(1
2(1
6J
25
^
29
0
22
0
96
41
41
75
85
0
0
0
0
0
0
85
43
51
0
57
71
Acids
5/1
2,4,6-TRIBROMO-
PHENOL
104
6(1
(1
(1
22
2(1
0
72
0
53
0
41
56
65
46
48
0
0
0
0
0
0
25
20
48
0
86
100
ACCEPTABLE1
YES
VFS
HO
m
VE5
VFS
NO
VES
NO
VES
NO
YES
YFT
VES
YTS"
YFS
NO
"10
NO
NO
NO
NO
VES
VFS
VES
(0
'ES
rffS
Overall
571 (16/28)
en
CO
-------
Table D-37
Incinerator Exhaust
Semi-Volatile Compounds
8/30/84
Concentration Daily Emissions
Compound (ug/m3) (grams)
1,2-dichlorobenzene 115 141-150
1,4-dichlorobenzene 102 125-133
Tetrachlorobenzene 25 31-33
In addition, 40 to 43 grams per day of naphthalene (33 ug/m3) were emitted from
the incinerator at the operational level of the second sampling day.
Raw analytical data are presented in Table D-36; these show the presence of
compounds not appearing on the target list (Table V-l). In the table, it is
shown in completeness data that generally better accuracy (% surrogate recovery)
was achieved for base-neutral compounds than for acid compounds. Phthalate
compounds, considered to be common laboratory contaminants, were also frequently
found. Also, substantial contamination by several compounds appeared in field
blank samples, particularly on the second sampling day; however, though the
surrogate recovery performance for those samples were generally acceptable
for both acids and base-neutrals, those contaminants rarely appeared in the
corresponding exposed samples. The detection limit objective of 5 ppb in air
was achieved, with actual sensitivities on the order of 1 to 2 ug/m3, or
generally less than 1 ppb.
As indicated previously, recoveries of acid surrogates during analysis was
frequently poor, especially from handling solid sorbent media or mixtures of
solids and liquids. The recognized strong affinities to water exhibited by
the phenolic (acid) surrogates may have been a factor in the poor observed
recoveries, as the exhaust gases that passed through the sorbents were nearly
saturated with moisture. In any event, overall completeness for this category
of samples was 57% (16 of 28), including method blank samples (see Table D-36).
3. PCDD/PCDF
a. All Homologues
In Table D-40, these data show a full range of homologues were present in
incinerator exhaust gases, particularly on the second sampling day. Tetra-
homologues appeared to be present universally, while octa-homologues were also
found frequently. Also of interest is the apparent tendency of most collected
constituents to reside in the XAD-2 cartridge; however, the backup XAD-2
cartridges on the second and third sampling days were not analyzed successfully,
and an evaluation of breakthrough was thus not possible on these days.
Particularly high concentrations of TCDD and TCDF were found on the third day;
however, accuracy measurements indicated these data to be questionable.
D-59
-------
Overall completeness (see Table D-38), taking into account satisfactory
accuracy and availability of data, did not meet the 90% goal established for
this study. Detection limit criteria of 5 ppt for tetra-homologues and 15 ppt
for other homologues, were met. The data in Table D-38 are restated in terms
of concentration in air in Table D-39; also included is information with respect
to the conditions placed on the summed data for the entire Modified Method 5
train, when precision, duplicate analysis, and spike analysis problems are
considered. The analytical data presented in Table D-39 represent the total
emissions of PCDD/PCDF homologues; these data were calculated by summing the
homologues caught in each portion of the Modified Method 5 trains. Note from
Table D-38 that some of these individual analyses were acceptable in terms of
accuracy, while other analyses were marked by unacceptable surrogate recoveries.
b. TCDD Isomers
These data, presented in Table D-43 and in abridged form in Table D-41, are
largely self-explanatory. When TCDD was present, the 1368 isomer was most
common, followed by the 1379 and 1237/1238 isomers. No 2378-TCDD was detected
in any of these samples. These data are restated in Table D-42 in terms of
concentration in air.
4. Vinylidene Chloride
The results of instrumental (GC-ECD) analysis of Tedlar bag samples for
vinylidene chloride are presented in Table D-44. Of the 20 samples obtained,
all but one was analyzed in triplicate. Three individual data points were
rejected as being much more than one standard deviation from the mean.
These data suggest that vinylidene chloride was present in exhaust gas
continuously throughout the three sampling periods. However, analyses of the
same samples by Dow Chemical using GC-MS indicated those peaks identified as
vinylidene chloride were attributable to other compounds.
As with the VOST samples, the vent of the incinerator liquid waste tank
farm activated carbon bed filter system was located upstream of the bag sampling
location. Therefore, the compounds identified above may not be traceable
entirely to emissions from the incinerator.
Table D-45 presents the results of a series of replicate analyses for
vinylidene chloride carried out on the contents of the same Tedlar bags,
approximately 24 hours apart. These data were intended to demonstrate possible
changes in bag contents from the time of sampling until later analysis. The
results appear to show random differences which are sufficiently small to
indicate that delays between sampling and analysis did not cause significant
errors.
D-60
-------
TABLE D-38
INCINEKATOR EXHAUST - PCDO/PCDF ANALYSESi
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
8/28/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Impingers
Field Blank
Backup XAD-2
Field Blank
8/30/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Impingers
Field Blank
Backup XAD-2
Field Blank
9/5/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Impingers
Field Blank
Backup XAD-2
Field Blank
2378-
TCDD
Total
TCDD
10.2
283
16.6
1.4
19.0
206
24.4
Samp
Total
PeCDD
42.5
3.0
8.1
Total
HxCDD
5.8
1.2
0.9
Total
HpCDD
1.4
3.5
1.3
OCDD
2.8
1.3
2.3
2.2
11.4
1.5
1.5
2378-
TCDF
0.6
9.3
0.5
8.3
0.7
.
Total
TCDF
29.2
21'
1.2
287
32. d
264
33.8
,14:
e analysis not returned from laboratory.
Sample analysis not returned from laboratory.
10.2
0.4
15,9
2.1
Samp
4.3
1.7
0.3
191
6.0
313
36.1
e analysis not returned from laboratory.
Sample analysis not returned from laboratory.
Total
PeCDF
4.0
84.8
6.2
11.8
6.3
1.0
Total
HxCDF
1.1
16.2
2.8
3.2
5.1
Total
HpCDF
1.7
1.8
1.4
Accuracy (% Surrogate Recovery
OCDF
0.4
1.0
COMPLETENESS BY SURROGATE
oo o
ro o
OJ h-
CJ
,— *
o
ro
100
100
2T
55"
100
IUO"
65
80
67
78
63
100
58
100
100
57
100
100
100
72
79%
i
00 O
r- o
ro o
CJt—
i
o
ro
96
92
54"
54
53
53
55
91
96
94
93
88
96
57
95
94
§2
93
90
108
83%
o
o
%,
0
ro
95
44
100
100
49
61
100
100
100
loo
53
82
150
54
89
100
57
64
33
100
75%
1
GO U_
r-- o
ro o
e\j t—
O
ro
84
65
55
94
90
55
78
37
51
1(50
57
51
P
90
35
98
62
87
44
67%
o
01
Notes:
1. Data expressed in nanograms per total sample. Detection limit data appear
in Table 0-40.
2. All surrogate recoveries within target range of 50-150%.
-------
TABLE D-39
INCINERATOR EXHAUST - PCDD/PCDF ANALYSES
EXPRESSED IN TERMS OF CONCENTRATION IN AIR (ng/m3)
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
Modified Method 5 Train
Catches
8/28/84
8/30/84
9/5/84
2378-
TCDD
Total
TCDD
[45.95]
43.75
4.92
NOTES
0 -
[ ] -
Total
PeCDD
6.49
1.94
Total
HxCDD
(p.88J
0.37
Total
HpCDD
0.21
0.84
OCDD
0.93
2.52
0.47
2378-
TCDF
1.51
1.67
Total
TCDF
[81.22]
76.98
94.53
Total
PeCDF
[12.95]
4.28
0.17
Total
HxCDF
[2.47]
1.95
Total
HpCDF
0.26
0.55
OCDF
0.06
0.17
Data out of control with respect to precision criteria (+50% RPD)
Bracketed data denote homologues detected in filter and probe wash portion
of Modified Method 5 train were deleted owing to unacceptable duplicate
analysis results. Only a small fraction of total concentration detected
was affected (see data in Table 0-38).
Matrix s
Fil
XAD
Other me
pike ana
ter and
-2 cartr
dia in t
lyses in
probe wa
idge - H
he sampl
dicated recoverie
sh - PeCDD and Hx
pCDD and HpCDF
ing train showed
II
s out of
CDF
acceptab
control
le matri
for the
x spike
followi
recoveri
ng
es.
cr>
-------
TABLE D-40
INCINERATOR EXHAUST - PCDD/PCDF ANALYSES
FROM MODIFIED METHOD 5 TRAINS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
O
i
CTl
CO
SAMPLE IDENTIFICATION
8/28/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Impingers
Field Blank
Backup XAD-2
Field Blank
8/30/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Impingers
Field Blank
Backup XAD-2
Field Blank
9/5/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Impingers
Field Blank
Backup XAD-2
Field Blank
2378-
TCDD
ND
(0.638)
ND
(0.107)
ND
(3.63)
ND
(.0630)
ND
(0.436)
ND
(0.236)
ND
(0.135)
ND
(.0862)
ND
(0.597)
ND
(.0736)
ND
(16.6)
ND
(0.132)
ND
(0.374)
ND
(0.137)
ND
(0.324)
ND
(0.109)
ND
(0.198)
ND
(0.801)
ND
(0.442)
ND
(0.153)
Total
TCDD
10.2
No
(0.111)
283
ND
.0209)
16.6
ND
(0.162)
1.35
ND
.0542)
19.0
ND
.0150)
206
ND
(0.154)
24.4
ND
(0.280)
10.2
0.369
15.9
ND
(1.04)
2.11
ND
(0.111)
Total
PeCDD
ND
(0.160)
ND
(0.276)
42.5
ND
(0.143)
ND
(0.430)
ND
(0.613)
ND
(0.146)
ND
(0.340)
2.96
ND
(.0558)
8.10
ND
(0.421)
ND
(0.274)
ND
1.30)
ND
(0.160)
ND
(.0769)
ND
(.0787)
NO
(1.86)
ND
(4.60)
ND
(0.558)
Total
HxCDD
ND
(0.301)
ND
(0.191)
5.75
ND
(0.119)
ND
(0.470)
ND
(0.485J
ND
(.0768)
ND
(0.180)
1.22
ND
(.0425)
ND
(0.339)
ND
(0.411)
0.878
ND
(0.790)
ND
(0.109)
ND
(.0483)
ND
(.0616)
ND
(1-74)
Nb
(3.90)
ND
(0.447)
Total
HpCDD
ND
(0.431)
ND
(1.27)
1.36
ND
(0.127)
ND
(0.709)
ND
(0.898)
ND
(.0605)
ND
(0.216)
3.52
ND
0.119)
ND
(0.358)
ND
(0.345)
1.26
ND
(5.02)
ND
(0.443)
ND
(0.129)
ND
(0.371)
ND
(2.73)
ND
(278)
ND
(0.753)
OCDD
2.80
ND
(5.49)
1.33
0.341
2.29
2.19
ND
(0.441)
ND
(0.338)
11.4
ND
(0.271)
1.46
ND
(0.369)
1.52
ND
(3.81)
4.30
1.65
ND
(0.281)
NO
(2.69)
ND
(16.2)
ND
(1.89)
2378-
TCDF
0.584
ND
(0.138)
9.32
ND
(0.297)
ND
(0.463)
ND
(0.180)
ND
(0.481)
ND
(.0704)
0.532
ND
.0433)
8.26
ND
(0.170)
0.712
ND
(0.259)
ND
(0.379)
ND
.0264)
ND
(0.322)
ND
(0.847)
ND
(0.488)
ND
(0.138)
Total
TCDF
29.2
ND
(0.186)
213
1.23
287
ND
(0.169)
32.0
ND
(.0649)
264
ND
(.0171)
33.8
ND
(0.175)
141
ND
(0.302)
191
5.98
313
ND
(0.905)
36.1
ND
(0.173)
Total
PeCDF
3.95
ND
(0.154)
84.8
ND
(0.357)
ND
(0.680)
NO
(0.471)
ND
(.0778)
ND
(0.148)
6.23
ND
(.0623)
11.8
ND
(0.230)
6.34
ND
(0.661)
0.967
ND
(.0555)
ND
(.0734)
ND
(1.28)
ND
(0.823)
ND
(0.413)
Total
HxCDF
1.09
ND
(0.223)
16.2
ND
(0.470)
ND
(0.469)
ND
(0.364)
ND
(.0742)
ND
(0.130)
2.79
ND
(.0663)
3.23
ND
(0.333)
5.11
ND
(1.12)
ND
(0.124)
ND
(.0939)
ND
(.0566)
ND
(1.93)
ND
(2.54)
ND
(0.456)
Total
HpCDF
ND
(0.428)
ND
(0.662)
1.70
ND
(.0707)
ND
(0.968)
ND
(0.495)
ND
(0.112)
ND
(0.301)
1.76
ND
(.0833)
ND
(0.360)
ND
(0.345)
1.39
ND
(1.57)
ND
(0.771)
ND
(0.132)
ND
(0.340)
ND
(3.24)
ND
(3.82)
ND
(0.819)
OCDF
ND
(0.592)
ND
(3.56)
0.400
ND
(0.122)
ND
(0.830)
ND
(0.694)
ND
(0.105)
NO
(0.326)
0.967
ND
(0.218)
ND
(0.646)
ND
(0.368)
ND
(0.207)
ND
(2.39)
ND
(0.220)
NO
(0.125)
ND
(0.556)
ND
(2.00)
ND
(25.0)
ND
(0.621)
NOTES: Data expressed in nanograms per total sample. Accuracy (surrogate recovery) data appear in Table D-38.
-------
TABLE D-41
INCINERATOR EXHAUST - TCDD ISOMERS
DOM CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, 9/5/84
SAMPLE IDENTIFICATION
8/28/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Implngers
Field Blank*
Backup XAD-2
Field Blank
8/30/B4
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Implngers
Field Blank
Backup XAD-2*
Field Blank*
9/5 /b4
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Implngers
Field Blank
Backup XAD-2*
Field Blank*
1368
0.69
122 ~
B.94
0.88
8.70
74.8
12.3
4.51
0.81
8.67
2.11
1379
3.74
75.9
4.51
0.37
4.96
60.6
6.65
2.82
0.07
4.68
1369
1247
1248
1378
1469
11.0
0.52
0.62
0.32
0.52
1246
1249
1268
1278
1478
1268
1279
1234
1236
1269
1237
1238
5.29
73.5
3.16
0.10
4.79
64.3
4.81
2.50
0.12
1.99
2378
1239
1278
1279
1267
1289
a
i
NOTE: Data expressed In nanograms per total sample.
* Sample analysis not returned from laboratory
-------
TABLE D-42
INCINERATOR EXHAUST- TCDO ISOMERS
EXPRESSED IN TERMS OF CONCENTRATION IN AIR
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30. 9/5/84
SAMPLE IDENTIFICATION
Notified Method 5 Train
Catches
8/28/84
8/30/84
9/5/84
1368
20
17
2.9
1379
13
13
1.3
NOTE -
1369
lata exp
1247
1248
1378
1469
1.8
0.2
0.2
•essed 1
1246
1249
i ng/m3
1268
1278
1478
1268
1279
1234
1236
1269
123?
1238
12.5
13
0.8
2378
1239
1278
1279
1267
1289
a
i
CTl
Ol
-------
TABLE 0-43
INCINERATOR EXHAUST - TCDO ISOHERS
AS MEASURED USING MODIFIED METHOD 5 TRAINS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28. 8/30. AND 9/5/84
(All data expressed in nanograms per total sample.)
SAMPLE IDENTIFICATION
8/28/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Implngers
Field Blank
Backup XAD-2
Field Blank
8/30/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Implngers
Field Blank
Backup XAD-2
Field Blank
9/5/84
Filter + Probe Wash
Field Blank
XAD-2 Cartridge
Field Blank
Implngers
Field Blank
Backup XAD-2
Field Blank
1368
0.694
ND
(0.111)
122
ND
( .0209)
8.94
NO
(0.162)
0.879
ND
(.0867)
8.70
ND
(.0150)
74.8
ND
(0.165)
12.3
ND
(0.280)
(S
{£
4.51
0.176
8.67
ND
(1-39)
2.11
ND
(0.111)
(S<
1379
3.74
ND
(0.111)
75.9
ND
( .0209)
4.51
ND
(0.162)
0.372
ND
(.0542)
4.96
ND
(.0150)
60.6
ND
(0.154)
6.65
ND
(0.280)
ample an
ample ar
2.82
0.0732
4.68
ND
(1.04)
ND
(0.581)
ND
(0.111)
mple an;
1369
NO
(0.258)
ND
(0.111)
ND
(3.09)
ND
(.0209)
ND
(0.434)
ND
(0.162)
ND
(.0431)
ND
(.136)
ND
(0.217)
ND
(.0150)
ND
(3.78)
NO
(.154)
ND
(0.307)
ND
(0.280)
ilysls r
ilysls r
ND
(0.231)
ND
(.0272)
ND
(0.428)
ND
(1.04)
ND
(0.581)
ND
(0.111)
lysis n<
1247
1248
1378
1469
0.980
ND
(0.111)
11.0
NO
( .0209)
ND
(0.651)
ND
(0.162)
NO
(.0647)
ND
(.0542)
0.522
ND
(.0150)
ND
(3.78)
ND
(0.154)
0.616
ND
(0.280)
)t retur
at retur
0.319
NO
(.0272)
0.520
NO
(1.04)
ND
(0.581)
NO
(0.111)
it returr
1246
1249
NO
(0.258)
ND
(0.111)
ND
(3.09)
ND
(.0209)
ND
(0.434)
ND
(0.162)
NO
(.0647)
ND
(.0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
NO
(0.614)
ND
(0.280)
led fron
led frorr
ND
(0.231)
ND
( .0272)
ND
(0.428)
ND
(1.04)
ND
(0.581)
ND
(0.111)
ed from
1268
1278
ND
(0.258)
ND
(0.111)
ND
(3.09)
ND
(.0209)
ND
(0.434)
NO
(0.162)
ND
(0.108)
ND
(.0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
ND
(0.307)
ND
(0.280)
laborat
laborat
NO
(0.231)
ND
(.0272)
ND
(0.428)
ND
(1.04)
ND
(0.581)
ND
(0.111)
laboratc
1478
ND
(0.258)
ND
0.111)
ND
(3.09)
ND
(.0209)
ND
(0.434)
ND
(0.162)
ND
(.0518)
ND
(.0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
ND
(0.307)
ND
(0.280)
>ry.)
>ry.)
ND
(0.231)
ND
(0.127)
NO
(0.428)
ND
(1.04)
ND
(0.581)
ND
(0.111)
ry.)
1 1
(Sample analysts not returned from laboratory.)
1268
1279
ND
(0.258)
ND
(0.111)
ND
(3.09)
ND
(.0290)
ND
(0.434)
ND
(0.162)
ND
(.0431)
ND
(.0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
NO
(0.307)
ND
(0.280)
ND
(0.231)
ND
(0.272)
ND
(0.428)
NO
(1.04)
ND
(0.581)
ND
(0.111)
1234
1236
1269
NO
(0.258)
ND
(0.111)
ND
(3.09)
ND
(.0290)
ND
(0.651)
ND
(0.162)
ND
(0.431)
No
( .0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
NO
(0.307)
ND
(0.280)
NO
(0.231)
ND
(.0363)
ND
(0.428)
ND
(1.04)
ND
(0.581)
NO
(0.111)
1237
1238
5.29
ND
(0.111)
73.5
NO
(.0290)
3.16
ND
(0.288)
0.0997
ND
(.0542)
4.79
ND
(.0150)
64.3
ND
(0.154)
4.81
ND
(0.5601
2.50
0.121
1.99
'ND
(1.04)
ND
(0.697)
ND
(0.111)
2378
NO
(0.638)
ND
(0.107^
ND
(3.63)
ND
(.0630)
ND
(0.436)
NO
(0.236)
ND
(0.135)
ND
(.0862)
ND
(0.597)
ND
(.0736)
ND
(16.6)
ND
(0.132)
ND
(0.374)
ND
(0.137)
ND
(0.324)
NO
(0.109)
NO
(0.198)
ND
(0.801)
ND
(0.442)
NO
(0.153)
1239
NO
(0.258)
ND
(0.111)
ND
(3.09)
NO
(.0290)
ND
(0.434)
ND
(0.162)
NO
(.0431)
ND
(.0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
ND
(0.307)
ND
(0.350)
ND
(0.231)
ND
(0-272)
ND
(0428)
ND
(1.04)
ND
(0581)
ND
(0.111)
1278
1279
ND
(0.258)
NO
(0.111)
NO
(6.17)
ON
( .0290)
ND
(0.434)
ND
(0.162)
ND
(.0431)
ND
(.0542)
NO
(0.217)
ND
(.0150)
NO
(3.78)
ND
(0.154)
ND
(0.307)
ND
(0.350)
NO
(0.231)
ND
(0.272)
ND
(0.428)
ND
(1.04)
ND
(0.581)
ND
(0.111)
1267
NO
( .0258)
ND
(0.111)
ND
(3.09)
ND
( .0290)
ND
(0.434)
ND
(0.162)
NO
(.0431)
ND
(.0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
ND
(0.307)
ND
(0.350)
ND
(0.231)
ND
(0272)
ND
(0.428)
ND
(1.04)
ND
(0581)
ND
(0.111)
1289
ND
(0.258)
NO
(0.111)
ND
(6.17)
ND
(.0290)
ND
(0.434)
ND
(0.162)
NO
(.0431)
NO
(.0542)
ND
(0.217)
ND
(.0150)
ND
(3.78)
ND
(0.154)
ND
(0.307)
ND
(0.350)
NO
(0.231)
ND
(0.272)
ND
(0.428)
ND
(1.04)
NO
(1-16)
ND
(0.111)
a
i
CTi
CTl
-------
TABLE D-44
RESULTS OF SAMPLING FOR VINYLIDENE CHLORIDE
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
DATE
8/28/84
8/30/84
9/5/84
SAMPLE RUN
1
2
3
4
5
6
7
1
2
3
4
5
6
1
2
2 DUPLICATE
3
4
5
6
SAMPLE
COLLECTION TIME (EOT)
1230-1330
1405-1510
1525-1625
1640-1735
1750-1845
1850-1930
1935-2015
1000-1050
1100-1200
1210-1250
1300-1350
1400-1450
1500-1550
1000-1045
1100-1150
1100-1150
1200-1245
1400-1445
1500-1545
1600-1630
VINYLIDENE CHLORIDE
CONCENTRATION (ppbv)
88.6 (83.1, 88.0, 94.7)
68.3 (72.1, 72.3, 60.2)
64.3 (113.0*, 67.5, 61.1)
74.5 (73.9, 74.7, 74.8)
88.9 (94.2, 88.4, 84.1)
112.4 (113.6, 111.2, 138.6*)
104.4 (102.1, 107.8, 103.3)
149.7 (150.0, 154.9, 144.3)
187.6 (180.9, 189.3, 192.7)
241.6 (263.7, 219.5, 402.7*)
279.8 (275.3, 285.9, 278.3)
218.0 (219.6, 216.3)
28.1 (28.9, 27.9, 27.6)
88.7 (94.3, 93.3, 78.5)
70.3 (69.4, 68.9, 72.6)
79.3 (76.7, 81.9, 79.3)
157.8 (156.4, 152.5, 164.4)
154.3 (162.2, 143.5, 157.2)
156.0 (154.7, 161.6, 151.8)
143.5 (146.6, 143.3, 140.6)
STANDARD
DEVIATION
5.8
6.9
4.5
0.5
5.1
1.7
3.0
5.3
6.1
31.3
5.5
2.3
0.7
8.8
2.0
2.6
6.1
9.7
5.0
3.0
* Rejected as greater than one standard deviation from mean of three analyses,
D-67
-------
TABLE D-45
RESULTS OF SAMPLE AND BAG STABILITY TESTS
FOR VINYLIDENE CHLORIDE SAMPLES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28 AND 9/5/84
DATE
8/28/84
9/5/84
SAMPLE RUN
5
6
7
1
5
6
COMPARATIVE CONCENTRATION
ANALYSIS DAY
88.9
112.4
104.4
88.7
156.0
143.5
FOLLOWING DAY
63.5 (47.6*, 65.6, 61.4)
104.7 (108.4, 102.8, 103.0)
105.4 (112.2, 100.9, 103.2)
84.8 (single value only)
178.4 (182.5, 183.9, 168.8)
179.1 (171.1, 183.2, 183.1)
DIFFERENCE (%)
-28.6
-6.9
+1.0
-4.4
+14.4
+24.8
* Rejected as greater than one standard deviation from mean of three analyses.
D-68
-------
E. Incinerator Ash
1. Semi-Volatiles
Analyses of incinerator ash (see Table 0-46) revealed the presence of
1,2- and 1,4-dichlorobenzene; 1,2,4-trichlorobenzene; phenol; and biphenyl,
among the targeted compounds. However, the first three compounds wera found
only in the field duplicate sample on the second sampling day, in the low ppm
range. Phenol and biphenyl were detected at the 0.5 ppm level on the third
sampling day. Tentatively identified in the ash collected on the second sampling
day, in the sample and field duplicate, were the following ring compounds:
Table D-47
Semi-Volatile Compounds
Incinerator Ash
8/30/84
Concentration
(mg/kg)
Compound
Methyldi phenylsi 1ane
l,l'-(l,2-ethendiyl)bis(z)benzene
1,1':2',l-terphenyl
1,1':3',l-terphenyl
1,1':4',1-terphenyl
Sample
52.838
11.628
4.932
10.792
11.243
Field
Duplicate
44.757
5.661
9.919
6.245
9.965
Precision
(RPD)
16.6
69.0
67.2
53.4
12.1
Quality assurance criteria with respect to accuracy (surrogate recovery)
were met for all of the samples analyzed. However, two of the seven samples,
field blanks for the second and third sampling days, were lost prior to analysis
by the laboratory.
2. PCDD/PCDF
a. All Homologues
These data, presented in Table D-48, appear to indicate that among the
PCDDs, the homologues were detected in concentrations increasing according to
their chlorine substitution; OCDD was most common. With PCDF, this relationship
did not hold; total TCDF were generally most prevalent, followed by OCDF and
hepta-CDF.
Accuracy criteria for the four surrogate compounds were not met for two of
the six completed analyses; the seventh analysis was not accomplished, resulting
in 57% completeness for the incinerator ash PCDD/PCDF analyses. Note, however,
that the surrogate recovery criteria for 1-3C]_22378-TCDD and •37C142378-TCDF
(70-130%) were missed by only 5 to 6%. The precision goal of +50% was achieved
for most homologues detected in the field duplicate samples obtained on the
D-69
-------
TABLE D-46
o
8/28/84
8/28/84
field blank
8/30/84
8/30/84
field dup.
8/30/84
field blank
9/5/84
9/5/84
field blank
01
4->
(D
OJ .C
c *J a;
aj a> .c c
0) a» N •*-* o. at
c c c ia M
01 a; Of •— a/ c
N N £* to -*-> 'T Ol
CCO -C (O O1 JO
ai a) i. <-> •— 5; i
^3 ^) O -C 10 ^ *t
00.- CL J=. ;f -r-
i- 1- -C 4-* ^ XI
0 0 U r- .C JT> 1
r— r— -r- >, O- fj >,
-c -c «- <-> % x
U U •»-* 3 •— y O
"O T3 ** O 1 -C .^ . ^H
1 1 C C +J "
i-i t-l t-H O-TJT3^1^H
433 201
1933
520 460 867 1733 (0663
(SAMPLE ANALYSIS NOT RETURNED
363 1110 423530
(SAMPLE ANALYSIS NOT RETURNED
INCINERATOR ASH SEMI-VOLATILES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
(Results in fig/kg )
~ ACCURACY (% SURROGATE RECOVERY)
IO >i
QJ XI C Ol QJ --^
r->, C C C O '*- f— Ct
•f- -t- a> - o
r— irt T3 XTXIXI-r- | t/ll_
>,r-C O-D-Cin- ^-d
c:>>o» c (. i. -i- f-* >i r—
QJ C -C O) QJ QJ U - C >, QJ
d x: OJ ^>^O.QJr—
^ XI -r- CM 0) - - *X:X'«-Era
>t^-X) *N- - - 4->O-C IX:
1_ C >-1r-£-tCC\JO->«3- QJ C »— eg -p
3O*x: v,;Taj E> — -c
3-i-lQJ » »*»OlQJ-r-
t/>XICMGr-t i-Ht-Hf-HOfMEXl
2722
TltS 5UJ9 11624 4932 W792 11243
44757 M«l MM CMS JX5 tO« 3«l
FROM LABORATORY)
170 435 321 1069
FROM LABORATORY)
1
QJ
M
C
QJ
Xt
O
•r-
C
10?
65
96
30
63
Com
c.
-------
TABLE D-48
INCINERATOR ASH - PCOD/PCDF ANALYSES1
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30. AND 9/5/84
SAMPLE IDENTIFICATION
8/28/84 '
COMPOSITE SAMPLE
FIELD BLANK
8/30/84
COMPOSITE SAMPLE
FIELD DUPLICATE
PRECISION (RPD)
FIELD BLANK
9/5/84
COMPOSITE SAMPLE
FIELD BLANK
2378-
TCDD
ND
(27.7)
ND
(8.2)
ND
(23.1)
NO
(11.8)
ND
(6.9)
Total
TCDD
1170
NO
(9-6)
131
107
20
71
(Ani
Total
PeCDD
ND
(19.1)
ND
(35.8)
ND
(13.6)
ND
(15.6)
ND
(16.2)
lytical
Total
HxCDD
793
ND
(17.5)
129
111
15
ND
(10.9)
data noi
Total
HpCDD
6060
NO
(12.7)
806
498
47
76
returns
OCOD
32,700
ND
(25.8)
3180
2370
29
266
d from 1
2378-
TCDF
66
ND
(12.6)
17
ND
(11.3)
NO
(6.5)
aboratory
1 J
Total
TCDF
9160
ND
(12.8)
594
263
77
540
.)
Total
PeCDF
68
ND
(21.2)
NO
(5.4)
ND
(7.3)
ND
(7.8)
Total
HxCDF
455
NO
(19.6)
44
37
17
ND
(19.5)
Total
HpCOF
1520
NO
(15.9)
449
248
58
NO
(20.2)
OCDF
2570
ND
(23.4)
573
399
36
78
COMPLETENESS BY SURROGATE
Accuracy (%Surrogate Recovery
i
CO o
r-~ Q
CO O
CM h-
C\J
O
ro
88
74
65
64
100
84
86*
i
OO O
r- O
ro o
CM (—
«»
<->
i —
ro
97
91
92
95
97
98
86%
o
o
8
CM
LJ
CO
100
100
100
100
78
100
86%
00 U.
r- o
ro o
CM I—
*3-
<3
r-~
ro
80
70
73
65
93
78
86%
O
I
NOTES: Iflata expressed In pg/g.
2A11 surrogate recoveries within target range of 50-1502.
-------
second day. Detection limit goals of 5 ppt for TCDD and TCDF, and 15 ppt for
other homologues, were generally met; detection limits of 0.5 to 1.9 ppt were
achieved for TCDD and TCDF, and about 0.3 to 2.0 ppt for higher homologue
groups.
b. TCDD Isomers
The 1368, 1379, and 1237/1238 isomers appeared in all samples; no 2378
isomer was found. Duplicate samples from the second day yielded satisfactory
results for precision (see Table D-49).
F. Aqueous Influents and Effluents
This category of samples refers to those water streams circulated on a
once-through basis in air pollution control equipment associated with the
Building 703 incinerator, and the returned treated wastewaters ("service water")
used to make up the bulk of water supplied to these devices (except the ESP,
see Section V.A.2.d, and the ash pit, see Section V.A.3 of this report).
1. Volatile Compounds
Owing to the small volume of water samples taken (40 ml for volatiles
compared to one gallon for semi-volatiles) and the correspondingly small
fraction of solid matter in these samples, data with respect to volatile
compounds in influent and effluent waters were reported in terms of micrograms
per liter. Quality assurance criteria for accuracy (percent recovery of
surrogates) were met for all but two of the 22 samples analyzed in this category;
however, the analytical procedures did not achieve the target detection limit
of 1 ppb, as the detection limit for most of the compounds of interest was 5 ppb.
The behavior of volatile compounds in air pollution control equipment waters
appeared similar to that of the semi-volatiles discussed previously. That is,
many compounds present in influent (service) water appeared to have been
volatilized in contact with scrubbed exhaust gases from the incinerator. This
phenomenon (see Tables 0-50, D-51, and D-52) was observed in the cases of
chloroform, carbon tetrachloride, and some other compounds.
The data revealed the regular presence of no distinct compounds. However,
on the second sampling day, a number of compounds were found in ash pit effluent,
among them the target compounds 'perch!oroethylene and monochlorobenzene, and
other constituents of interest, such as chloroethane, chloromethane, and
ethylbenzene. This corresponds to a previously described finding of several
semi-volatile compounds in ash pit solid matter on the second sampling day.
Field duplicate samples were obtained only of the ESP water stream on the
second sampling day. Analytical results could be compared only for methylene
chloride and dimethoxymethane; precision appeared good for the former but poor
for the latter.
D-72
-------
TABLE D-49
INCINERATOR ASH - TCOI) ISOMERS
OOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28, 8/30, AND 9/5/84
i
^~j
CO
SAMPLE IDENTIFICATION
8/26/84
COMPOSITE SAMPLE
FIELD BLANK
/JO/84
COMPOSITE SAMPLE
FIELD DUPLICATE
PRECISION (RPD)
FIELD BLANK
9/5/84
COMPOSITE SAMPLE
FIELD BLANK
1368
620
65
57
13
35
1379
248
35
31
12
23
(An,
1369
lytical
1247
1248
1378
1469
37
8
data noi
1246
1249
returm
1268
1278
d from :
1478
aborator
1268
1279
y.)
1234
1236
1269
1237
1238
267
23
19
19
14
2378
1239
1278
1279
1267
1289
NOTE: Data expressed in pg/g.
-------
IA6LE D-50
AQUEOUS INFLUENIS AND EFFLUENTS - VOLATILE COMPOUNOSl
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/2H/84
SAMPLE IDENTIFICATION
INFLUENT
SERVICE WATER
EFFLUENTS
QUENCH WATER
VENTURI/DEM1STER
UATEK
ESP UMER
ESP UATER
FIELD DUPLICATE
ASH PIT UATER
FIELD BUHV5
EFFLUENT MATER
EFFLUENT UATER
DUPLICATE
TARGET COMPOUNDS
t
o
o
£
U
4'
t'
16
lo simp
c
1
fe
L.
e taker
|
|
e
I
•j
OTHER VOLATILE COMPOUNDS
S
O
I
\
41
6
232
169
V
w
I
£
o
"c
u
t-
-i
c
2
O
O
5
~.
6
•1
*
1
I
|
L.
0
U
|
•^t
O
JC
u
g
4->
E
C
c
1
«u
i
&
o
f
tl
a
"o
*j
TENTATlV£iy IDENTlflfO
COMPOUNDS
£
1
t
ts
289
73
173
S
O
L.
a
o
o
u
t
tsi
ft*
x
I
1
I
".
_
4,
IB
M
ACCURACY
(t SURROGATE RECOVERY
S
i
3
"o
111
111
104
104
103
102
102
I
1
|
91
99
103
111
103
n;
111
s
1
g
0
c
(M
84
103
91
97
102
103
103
Note - ID«U expressed In uj/l. Completeness «
established tn Quality Assurance Project Plan.
• Estimated value.
ACCEPTABLE?
YES
YES
YES
YES
—
YES
YES
YES
O
I
--J
-O
-------
TABLE D-51
AQUEOUS INHUENIS ANU EFFLUENTS - VOLATILE COMPOUNDS!
DOH CHEMICAL COMPANY BUILUING 703 INCINERATOR
8/30/84
SAMPLE IDENTIFICATION
INFLUENT
SERVICE WATER
EFFLUENTS
QUENCH WATER
VENTODI/DEMIsTEK
MATER
ESP WATER
ESP WATER
FIELD DUPLICATE
ASH PIT MATER
FIELD BLANKS
EFFLUENT HATER
EFFLUENT WATER
DUPLICATE
TARGET COMPOUNDS
r
chlorofo
7
*
etrachlor
*>
o
71
oethylene
perchlor
218
|
1
Note - lOata expressed
?AI1 surrogate
OlHtH VOtAMIE COMPOUNDS
«
o
5
ftt
1
*
68
5
8
,.
S
20
19
acetone
19
30
33
15
S
c
Ichloroet
-;
9
£
1
O
O
•5
(V)
benzene
11
7
I
chloronte
94
I
chloroet
37
2-butano
41
«
eth/lDen
96
j
o
4-1
117
toluene
184
TENIATIVELV IDENTIFIED
COMPOUNDS
I
S
3
S
o
Ichlorop
~:
17
S
1
*
thylbuta
I
Ol
c
X
o
ylcyclot
M
41
32
ACCURACY
(1 SURROGATE RECOVERY)
§
toluene
96
90
93
89
94
97
91
S
S
1
o
bromofli
80
104
88
94
99
95
84
t
£
|
o
u
84
104
108
96
10S
106
112
In uq/L Completeness -
recoveries xlthln target range (80-1251) "8 ' 88t
established In Quality Assurance Project Plan.
* Estimated value.
ACCEPTABLE2
YES
YES
YES
YES
YES
YES
YES
o
c_n
-------
1ABLE D-52
AQUEOUS INFLUENTS AND EFFlUENtS - VOLATILE COMPOUNDS'
DOM CHEMICAL COMPANY BUILDING 703 INCINERATOR
9/5/84
SAMPLE IDENTIFICATION
INFLUENT
SERVICE MATER
EFFLUENTS
QUENCH UATER
VENTURl/OEHISTER
MATER
ESP MATER
ESP UATER
FIELD DUPLICATE
ASH PIT MATER
FIELD BLANKS
EFFLUENT MATER ,
EFFLUENT MATER
DUPLICATE
TARGET COMPOUNDS
chlorofona
21
(
110
o samp
g
perchloroetnyl
4
e take
!
o
. )
1
OTHER VOLATILE COMPOUNDS
•ethylene chlo
55
24
2600
16
70
26
acetone
1198
„
44
~
6
5
c
o
u
r*j
16
}
4
5
,
7
4
4
chl oroKthane
chloroethene
I
J
ethylbenzene
o
5
|
3
*O
1.6*
TENTATIVELY IDENTIFIED
COMPOUNDS
c
dlmcthoxyiKth
225
C
3.
O
O
O
£
l_
*J
ro
CM
S
41
O
g
4-)
E
4->
I!
7
f*l
1
200
200
hexane
ACCURACY
(I SURROGATE RECOVERY
toluene-08
97
99
99
99
98
93
101
¥
brow)fluorobe
99
100
107
98
118
108
91
S
c
m
1,2-dlchloroe
80
91
92
81
96
115
96
Not. - lOata expressed In ug/L. C°»J""?OW "
established In Quality Assurance Project Plan.
* Estimated value.
ACCEP1A8LE*
YES
YES
YES
YES
YES
YES
YES
a\
-------
2. Semi-Volatile Compounds
Quality assurance criteria with respect to accuracy (surrogate recoveries)
were generally met for the analyses of aqueous samples and solid filtrates.
However, detection limit goals of 5 ppb in liquids and solids were not achieved,
actual detection limits being on the order of 10 ppb. The analytical data,
Tables D-53, D-54, and D-55, show that few semi-volatile compounds were detected
in any of the wastewater liquid and solid streams at levels higher than those in
influent service waters. This appears to indicate that such compounds present
in influent waters may have volatilized out of the liquids as they passed
through the incinerator air pollution control devices.
Effluent waters were found to contain only the following targeted compounds
on the sampling days indicated:
Concentration
Compound Sampling Day (ug/L) Effluent Stream
Tetrachlorophenol 2 13 Venturi/Demister
Monochlorobenzene 2 157 Ash Pit
l,l'-biphenyl 2 285 Ash Pit
However, surrogate recoveries from the sample from which the last two compounds
were analyzed did not meet the quality assurance goals established for the
study, and these data should therefore be considered tentative.
Little was detected in the filtered solids portions of the effluent streams.
As the data in Tables 0-53, D-54, and D-55 indicate, several phthalates were
found regularly, and many effluent streams contained solid elemental sulfur.
Of possible interest is the finding of biphenyls in electrostatic precipitator
and ash pit effluent solids on the third sampling day, and a variety of benzene,
biphenyl, and terphenyl compounds in ash pit effluent solids on the second
sampling day. Note that several of these compounds also appeared in incinerator
ash on that day.
3. PCDD/PCDF
a. All Homologues
It will be recalled from previous descriptions of the Dow facility that
service water circulated in most incinerator air pollution control devices is
composed of a stream of wastewater from the plant's wastewater treatment
system. Low concentrations of tetra- and octa-CDD and CDF were detected on the
first and second sampling days, along with traces of other homologues on the
latter day; no PCDD or PCDF were found on the third day (see Tables D-56, D-57,
and D-58).
Effluent water stream concentrations of all homologues appear several orders
of magnitude higher than in service water. However, note that PCDD and PCDF
reside almost exclusively in the suspended (filterable) solids present in these
D-77
-------
TABU 0-53
AQUEOUS INFLUENIS AND EFFLUENTS - SEHI-VuLAIlLE CONFOUNDS
00* CHEHICAL COMPANY BUILDING 703 INCINEKAKW
«/28/84
SAMPLE IDEHIIFICA1IOH
Service Hater
Quench Hater
(Deter Portion)
Quench Hater
(Solids Portion)
Venturl/Denlster Hater
(Deter Portion)
Venturl/DCMlster Deter
(Solids Portion)
ESP Heter
(Hater Portion)
ESP Hater
Deter Field Oupllcete
ESP Heter
(Solids Portion)
ESP Deter
Solids Field Duplicate
Ash Pit Hater
(Deter Portion)
Ash Pit Hater
(Solids Portion)
Effluent Heter Field Blank
Effluent Heter Backup
Field Blenk
uHiis
"%
u%
"%,
•%,
u,/t
"%
u,/L
"%,
"'/k,
""/I
"'/kg
»%
U,/L
IARGEI COHPOUNOS
*o
1
tetrechlorophenol
(No
(No
2,3,4,6-tetrachloroohenol
a»pl
r
amp)
pefttachlorophenol*
tak
tak
1
a
n.)
n.)
1
J
I
\
5
,
18
21
100
34.750
dtethyl pnthalete
132
D1s(2-«thylhexyl)pht halite*
82.725
di-n-octyl pnthelate*
bi s ( 2-chl oroethyl ) ether*
benzole acid*
S
S
28
107.155
3
35
32
242.536
bts(2-ecthylpropyl ) pnthilate
336
36,212
butyl -2-avnhyl propyl
phthalite
f
2-ethyl-l,l'-elpMnyl
•ethyldlphenylstlane
l,2-ethendtyl)b1S'(2)-
zene
:•*
l.l':2',l-t«rpHe»iyl
j
1.1-dlpMnrllMfJtene
5
*>,
bu ty 1 octadeca noa te
2,2l-oxyt>1setn*nol
1.3-41.Mthylbenzene
l-butoxy-2-propanol
£3 Ull surrogate recoveries within terget range (20-1801) established In
o
c
eV
O
i
1,1.3-trltjethylcyclopentane
l-(2-butOKyethoxy) ethenol
COUPLE IENESS2
Accuracy
(1 SurroQete Recoverv)
Base-Neutrals
nitrobenzene-OS
57
72
57
72
24
83
72
54
32
61
46
J
i
1
60
59
67
63
30
70
04
48
38
66
50
1
77
9,
98
81
44
95
46
58
22
96
66
1001
Acids
phenol -05
69
37
37
82
22
26
43
2H
31
21
17
"o
S
3
51
35
73
84
26
101
J7
61
38
39
49
2,4,6-trlbromooheno!
54
67
71
68
32
90
67
51
52
0]
85
91»
ACCEPTABLE'
YES
IES
YES
YES
IES
YES
YES
US
,ES
IES
NO
Hi
10/11)
-^J
CO
2B, ,
s) and overall (combined).
-------
AQUEOUS INFIUCNIS Mil EFflUENIS - SEHI-YOIMIIE COMPOUNDS
DON CHEM1I AL COMPANY BUILDING JUJ INC I NERAIOR
8/30/8*
O
I
SAMPLE t«*r tf ic*ftG*r
Service Water
Quench Miter
(Mater Portion)
Quench Miter
(Soltdi Portion)
(Miter Portion)
(Soltd> Portion)
ESP Meter
(H*tir Portion)
Mater Field Ow»)tc*te
ESP Miter
(SoHdi Portion)
ESP Miter
iollai Field Duplicate
Aih Pit Miter
(Mater Portion)
AlF> Pit M»ter
(Solldl Portion)
Effluent Meter Field •link
Field I lint
MOltS - All co»pounOUNOS
I
I
19
I
S
11
a
1
tMtltlv.lv l'
ecqterf)
Acldt
e
It,
86
»
44
86
»
10
ins
I.
44
52
j
a
68
36
52
»
99
6]
H2
187
101
96
in
921 J
i
3
ffS
«s
YES
»;
,E,
If S
IES
MO
US
IfS
TES
U 11
(ll/IJJ
-------
08-Q
Ifffs
f=l?5
isz.£i
itjij
I-
ill
Hi
ll!
I!
1=.
il
If
sz
• 3
I
i
a
i
a
1
i
s
s
"S 31
i
I
1
re tentittvtli Identified imleti Indicated by «« *il«rlit
j
|
1
i
I
f
~
E
1
C
*
S
J
*
"i
i
•»
s
i
~
i
[f
J
s
*
i
i
i
S.
S
(^ Hitrr
Solid! Field Duplicate
^
f
i
r
s~
g
5
i
I
i
i ~
fSP H«ttr
ISolttfl Portion)
c
I
is
a
p
>
1
^r
t
1
£
-
«
S
o
•j
£
i !
(IV Uttr
IIMtcr Portion)
jf
s
>
I
c
*•
1
o
9
ll
n
j
8
i
1
~
s
\
"c
i
Ifcnturt/Dmtiter Vitcr
c
*
s
jf
i *
c
1
s
s
1
1
s
s
;f
i!
c
I
1
;
J
~
=
i-
-
«
2
SMPIE IDCNIIFICAIKW
!
!,'.<•
-trlchloropftenol*
mr.UI.-MMi.)
2.3,4
, 6-tet r «cM oropn«no 1
D»«t«hloropn«»ot*
klpM
i.r-
nyl
blpnwyl
•~C""K~"""«
l.!H)(ck).r«».n,«.-
1 .2 , 4-t rl ch) aroMnzttw*
1.2,4
, 5~ tit r*ch 1 oroocn z*n«
1-"""-Z-""""""""
41-fl-
Butyl iffrthilKc*
dtetnyl phth*lit*
t>U(2-«thy)h«jiyl IpntniUte'
— «" ^^
61s(2-en)oroethyn ether"
bcnzoi c *ciO*
n«iadecino-trlBethylcyclopent*nc
oo*nieie-Di ?
Uoro0,p«n,l »
htmi -an |
Ol-Oi
uoropnenol -
6-tr10r.«pnen0l !
\f
f s . s ' s : s ' : s's|~ s s ! ACCEPTABLE' '
1-
l!
U» m
-------
TABLE D-56
AQUEOUS INFLUENTS AND EFFLUENTS - PCDD/PCDF ANALYSESl
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28/84
Accurac
SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
Venturl/Demlster Water
(Water)
Venturi/Demister Water
(Solids)
ESP Water (Water)
ESP Water (Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water
Backup Field Blank
2378-
TCDD
ND
(.0021)
NO
(.0013)
NO
(15.6)
ND
(.0011)
ND
(2.98)
NO
(.0003)
ND
(19.8)
ND
(.0003)
NO
(.0002)
Total
TCDD
0.0384
ND
(.0010)
432
ND
(.0010)
238
(Samp It
(Sampli
ND
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
Total
PeCDD
NO
(.0043)
NO
(.0010)
54.9
NO
(.0027)
82.0
analys
: analys
ND
(.0010)
ND
(171)
ND
(.0016)
ND
(.0054)
Total
HxCDD
ND
.0086)
NO
(.0042)
43.7
ND
(.0026)
55.1
s data r
s data r
ND
(.0027)
ND
(94.3)
ND
(.0026)
ND
(.0115)
Total
HpCDD
ND
.0073)
ND
.0079)
274
ND
(.0059)
265
ot retur
tot retut
ND
(.0058)
ND
(126)
ND
(.0083)
ND
(.0275)
OCOD
0.198
ND
(.0206)
1437
ND
(.0147)
1113
•ned from
1
1
•ned from
ND
(.0289)
323
NO
(.0130)
ND
(.0447)
2378-
TCDF
ND
.0011)
NO
.0005)
11.0
ND
(.0002)
8.52
laboratc
1
1
laborati
ND
(.0003)
ND
(27.4)
ND
(.0002)
NO
(.0003)
Total
TCDF
1.26
0.0025
170
0.0393
137
>ry.)
iry.)
ND
(.0010)
189
ND
(.0010)
ND
(.0010)
Total
PeCDF
ND
(.0026)
NO
(.0015)
66.4
ND
(.0022)
100
ND
(.0031)
ND
(45.1)
ND
(.0039)
ND
(.0037)
Total
HxCOF
ND
(.0057)
ND
(.0029)
117
ND
(.0018)
130
NO
(.0012)
ND
(42.5)
ND
(.0014)
ND
(.0075)
Total
HpCDF
0.0558
ND
(.00551
427
ND
(.0030)
337
ND
(.0066)
NO
(91.5)
ND
(.0055)
ND
(.0167)
Total
OCDF
ND
(.0130)
NO
(.0118)
379
ND
(.0139)
284
ND
(.0121)
ND
(118)
ND
(.0098)
ND
(.0284)
COMPLETENESS BY SURROGATE
i
OO Q
P~ Q
CO CJ
(VJ t-~
Csj
r- 1
0
ro
100
100
93
62
47
100
46
100
30
55%
1
00 O
r- Q
ro O
CVJ t—
«3-
(_>
r-.
m
91
81
94
89
95
90
95
84
80
82%
o
o
o
O
OJ
r-t
O
m
r-*
63
87
84
100
100
98
100
43
10
64%
1
OO U_
r- O
CO O
00 K-
*r
G
r*.
m
81
62
100
57
49
59
55
62
20
64%
(% Surrogate Recovery)
o
i
oo
Notes - lOata expressed In ng/g.
^Al 1 surrogate recoveries within range of 50-150%.
-------
TABLE D-57
AQUEOUS INFLUENTS AND EFFLUENTS - PCDD/PCDF ANALYSESl
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/30/84
SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
ESP Water (Water)
Field
ESP Water (Water) Duplicate
ESP Water (Solids)
Field
ESP Water (Solids) Duplicate
Venturl/Demlster Water
(Water)
Venturl/Demlster Water
(Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water
Backup Field Blank
2378-
TCDD
NO
(.0027)
ND
(.0007)
ND
(11.1)
ND
(.0009)
ND
(.0028)
ND
(35.3)
ND
(65.5)
ND
(.0006)
ND
(2.08)
ND
(.0010)
ND
(1.08)
ND
(.0005)
ND
(.0005)
Total
TCDO
0.0464
ND
(.0010)
707
.0062
.0189
4212
1864
ND
(.0010)
307
ND
(.0025)
ND
15.9
ND
(.0010)
ND
(.0010)
Total
PeCDD
ND
(.0019)
ND
(.0024)
99.3
ND
(.0011)
ND
(.0019)
885
393
ND
(.0012)
49.2
NO
(.0240)
ND
(3.09)
ND
(.0011)
ND
(.0080)
Total
HxCDD
ND
(.0021)
ND
(.0042)
75.3
ND
(.0028)
ND
(.0029)
147
205
ND
(.0021)
27.6
NO
(.0227)
ND
(3.14)
ND
(.0021)
ND
(.0063)
Total
HpCOD
0.0179
NO
(.0115)
460
ND
(.0057)
NO
(.0044)
417
515
ND
(.0089)
162
NO
(.0292)
21.5
ND
(.0031)
ND
(.0083)
OCDD
0.187
ND
(.0301)
2358
NO
(.0192)
ND
(.0077)
2199
2530
ND
(.0075)
707
NO
(.0453)
94.9
ND
(.0053)
ND
(.0104)
2378-
TCOF
ND
(.0012)
ND
(.0001)
15.4
ND
(.0004)
ND
(.0004)
45.3
47.7
ND
(.0005)
3.22
NO
(.0022)
ND
(1.71)
NO
(.0006)
NO
(.0014)
Total
TCDF
1.42
0.0223
182
0.287
0.607
539
6574
0.0682
168
NO
(.0038)
114
ND
(.0010)
ND
(.0025)
Total
PeCDF
0.0088
NO
(.0037)
NO
87.5
ND
(.0051)
ND
(.0039)
405
345
ND
(.0021)
64.6
ND
(.0120)
ND
(3.15)
NO
(.0024)
ND
(.0077)
Total
HxCDF
ND
(.0067)
ND
(.0028)
124
ND
(.0037)
ND
(.0017)
75.7
58.6
ND
(.0033)
82.9
ND
(.0110)
ND
(2.93)
ND
(.0017)
ND
(.0128)
Total
HpCDF
0.0167
ND
(.0131)
785
ND
(.0055)
ND
(.0070)
150
161
ND
(.0056)
199
ND
(.0232)
10.0
ND
(.0052)
ND
(.0046)
OCDF
0.0477
ND
(.0168J
641
ND
(.0182)
ND
(.0099)
200
226
ND
(.0164)
283
ND
(.0269)
12.5
NO
(.0037)
NO
(.0127)
COMPLETENESS BY SURROGATE
Accuracy (% Surrogate Recovery
CO 0
r- O
CO O
o
tM I-
*f
0
l-~
ro
66
57
100
44
73
95
27
46
57
29
65
36
17
54%
O
I
00
ro
NOTES - !Data expressed In ng/g.
surrnaatc rt»r
-------
TABLE D-58
AQUEOUS INFLUENTS AND EFFLUENTS - PCOO/PCDF ANALYSES1
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
9/5/84
SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
Venturl/Demlster Water
(Water)
Venturl/Demlster Water
(Solids)
ESP Water (Water)
ESP Water (Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water
Backup Field Blank
2378-
TCDD
ND
(0.341)
ND
(.0004)
ND
(1.10)
ND
(.0008)
ND
(1.29)
ND
(.0014)
ND
(28.2)
ND
(.0003)
ND
(.0013)
ND
(.0003)
Total
TCOO
ND
(0.229)
ND
(.0010)
73.9
ND
(.0010)
56.3
0.0052
247
ND
(.0010)
(Sam|
ND
(.00101
NO
(.0010)
Total
PeCDD
ND
(0.556)
ND
.0024)
ND
(7.43)
NP
(.0021)
17.5
ND
(.0104)
61.5
ND
(.0012)
ile anal.
ND
(.0016)
NO
(.0048)
Total
HxCDD
ND
(0.720)
ND
(.0027)
ND
(3.19)
ND
(.0031)
7.35
ND
(.0039)
20.3
ND
(.0017)
•sis dati
ND
(.0071)
NO
(.0027)
Total
HpCDD
ND
(0.318)
ND
.0018)
69.0
ND
(.0036)
44.3
ND
(.0087)
96.0
ND
(.0029)
not re
ND
(.0067)
ND
(.0039)
OCDD
NO
(0.520)
ND
(.0020)
236
ND
(.0064)
261
ND
(.0051)
423
NO
(.0025)
.urned fr
NO
(.0088)
NO
(.0058)
2378-
TCDF
ND
(0.192)
ND
(.0001)
ND
(1.93)
ND
(.0001)
2.05
ND
(.0015)
9.70
ND
(.0001)
om labor.
ND
(.0023)
NO
(.0002)
Total
TCDF
ND
(0.517)
0.0058
830
0.0157
723
0.0995
90.0
ND
(.0010)
tory.)
ND
(.0022)
NO
(.0010)
Total
PeCDF
ND
(0.299)
ND
(.0015)
7.09
ND
(.0010)
22.3
ND
(.0041)
47.0
ND
(.0010)
ND
(.0080)
NO
(.0025)
Total
HxCDF
ND
(0.351)
ND
(.0015)
16.1
ND
(.0024)
19.7
ND
(.0030)
14.7
ND
(.0010)
ND
(.0025)
NO
(.0027)
Total
HpCDF
ND
(0.627)
NO
(.0012)
125
ND
(.0017)
69.1
ND
(.0026)
68.2
ND
(.0021)
ND
(.0049)
NO
(.0026)
OCDF
ND
(0.396)
ND
(.0011)
103
ND
(.0035)
84.8
ND
(.0061)
82.1
ND
(.0037)
ND
(.0057)
ND
(.0039)
COMPLETENESS BY SURR OGATE
Accuracy (% Surrogate Recovery)
i
co a
r— a
fO {_>
CM h-
C\J
f-4
CJ
ro
r~t
100
53
81
84
100
53
70
100
70
48
82%
1
CO O
r- a
ro o
CM 1—
«*
o
r-.
ro
93
107
96
89
92
97
91
110
93
94
91%
0
a
8
CM
f— i
O
CO
r-4
58
100
48
53
94
35
39
48
100
100
55%
i
00 U-
r- O
<"•> O
C\J (—
-»•
o
r-
n
82
30
100
53
100
54
100
89
17
26
64%
a
i
oo
OJ
NOTES - iflata expressed In ng/g.
2A11 surrogate recoveries within range of 50-150%.
-------
once-through effluents. A full range of homologues was found on all three
sampling days, though from these data it did not appear that PCDD and PCDF
appear consistently in any particular wastewater stream.
No 2378-TCDD was detected on any day, but 2378-TCDF was found on three days.
In general, the range and concentrations of all homologues was greater by one
to two orders of magnitude on the second sampling day than on the other days.
Particularly high concentrations of tetra- and octa-CDD and CDF were present in
the solids fractions of the wastewaters.
Complete data sets covering all wastewater streams were not returned from
the analytical laboratory for any but the second sampling day. Overall
completeness, taking accuracy criteria into account, was 17% (6 of 35). Twenty-
six of the 29 data sets were incomplete because of unsatisfactory accuracy.
Field duplicate samples were taken only on the second day, of the ESP water
stream. Calculations shown in Table D-59 reveal mixed precision between these
sample data; generally good precision was achieved with higher homologues.
Detection limit criteria:
2378- and Total Tetras Penta- through Octa-
Waters 30 ppq 90 ppq
Solids 5 ppt 15 ppt,
were not met for water fraction analyses, with actual detection limits in the
range of about 20 to 1600 ppq, nor for solids analyses, where detection limits
were in the 0.6 to 6.0 ppb range (see Tables D-56, D-57, and 0-58).
b. TCDO Isomers
As indicated previously, no 2378-TCDD was detected at any time in influent
or effluent water streams. The data presented in Tables D-60, D-61, and D-62
indicate most TCDD appeared as the 1368, 1237/1238, and 1379 isomers. Occa-
sionally, the 1369 isomer was observed, and on the second day, when the highest
concentrations of PCDD/PCDF appeared, the 1247/1248/1378/1469 combination was
noted.
Precision data obtained for the second day's samples are presented in Table
D-63 and indicate generally poor performance in this area. The detection limit
goals of 30 and 90 ppq, respectively, for water and solids fractions, were not
achieved for the latter, with actual sensitivities one to two orders of magnitude
lower.
D-84
-------
TABLE D-59
AQUEOUS INFLUENT AND EFFLUENT WASTEWATER SAMPLE PRECISION
PCDD/PCDF MONOLOGUES
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/30/84
SAMPLE IDENTIFICATION
WATER FRACTION
ESP Water
ESP Water
Field Duplicate
Precision (RPD)
FILTERABLE SOLIDS FRACTION
ESP Water
ESP Water
Field Duplicate
Precision (RPD)
2378-
TCDD
Total
TCDD
0.0062
0.0189
101
4212
1864
65
Total
PeCDD
885
393
77
Total
HxCDD
147
205
33
Total
HpCDD
417
515
21
OCDD
2199
2530
14
2378-
TCDF
45.3
47.7
5
Total
TCDF
0.287
0.607
56
539
6574
170
Total
PeCDF
405
345
16
Total
HxCDF
75.7
58.6
25
Total
HpCDF
150
161
7
OCDF
200
226
12
CO
in
NOTE - Concentration data in ng/g.
-------
TABLE D-60
AQUEOUS INFLUENTS AND EFFLUENTS - TCOO ISOMERS
DOM CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28/84
SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
Venturi/Demlster Water
(Water)
Venturi/Demlster Water
(Solids)
ESP Water (Water)
ESP Water (Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water
Backup Field Blank
1368
0.0172
NO
( .0010)
183
NO
(.0013)
113
ND
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
1379
0.0095
ND
( .0010)
113
ND
(.0011)
ND
(3.91)
ND
( .0010)
ND
(23.3)
ND
( .0010)
ND
(.0010)
1369
ND
(.0022)
ND
( .0010)
ND
(4.57)
ND
( .0010)
7.83
( Sampl i
( Sampl
ND
(.0010)
ND
(23.3)
ND
( .0010)
ND
( .0010)
1247
1248
1378
1469
ND
(.0012)
ND
( .0010)
7.32
ND
( .0010)
ND
(3.91)
: analys
? analys
ND
( .0010)
ND
(23.3)
ND
( .0010)
ND
(.0010)
1246
1249
ND
(.0010)
ND
(.0010)
ND
(4.57)
ND
(.0010)
ND
(3.91)
s data
s data
ND
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
1268
1278
ND
(.0010)
ND
( .0010)
ND
(4.57)
ND
( .0010)
ND
(3.91)
lot retu
lot retu
ND
( .0010)
ND
(23.3)
ND
( .0010)
ND
(.0010)
1478
NO
.0010)
ND
(.0010)
ND
(9.14)
ND
(.0010)
ND
(3.91)
*ned fra
•ned froi
ND
(.0010)
ND
(23.3)
ND
( .0010)
ND
(.0010)
1268
1279
NO
(.0010)
ND
(.0010)
ND
(4.57)
ND
(.0010)
ND
(3.91)
i labora
i labora
ND
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
1234
1236
1269
ND
.0010)
ND
(.0010)
ND
(4.57)
ND
( .0010)
ND
(3.91)
:ory)
:ory)
ND
(.0010)
ND
(23.3)
ND
( .0010)
ND
(.0010)
1237
1238
0.0100
ND
(.0010)
128
ND
( .0010)
117
ND
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
2378
ND
(.0021)
ND
(.0013)
ND
(15.6)
ND
(.0011)
ND
(2.98)
ND
(.0003)
ND
(19.8)
ND
(.0003)
ND
( .0002)
1239
ND
(.0010)
ND
(.0010)
ND
(4.57)
ND
( .0010)
ND
(3.91)
ND
( .0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
1278
1279
ND
(.0010)
ND
(.0010)
ND
(4.57)
ND
(.0010)
ND
(3.91)
NO
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
1267
ND
(.0010)
ND
(.0010)
ND
(4.57)
ND
( .0010)
ND
(3.91)
ND
(.0010)
ND
(23.3)
ND
(.0010)
ND
(.0010)
1289
ND
(.0010)
ND
( .0010)
ND
(4.57)
ND
( .0010)
ND
(3.91)
ND
(.0010)
ND
(23.3)
NO
(.0010)
ND
(.0010)
o
I
oo
1
Data expressed In ng/g.
-------
TABLE p-61
AQUEOUS INFLUENTS AND EFFLUENTS - TCDD ISOMERS1
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/30/84
SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
ESP Water (Water)
Field
ESP Water (Water) Duplicate
ESP Water (Solids)
Field
ESP Water (Solids) Duplicate
Venturl/Demister Water
(Water)
Venturl/Demister Water
(Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water
Backuo Field Blank
1368
0.0198
ND
( .0010)
290
0 .0038
0 .0074
1968
486
ND
(.0010)
130
ND
(.0025)
74.7
ND
(.0010)
ND
(.0010)
1379
0.0154
ND
( .0010)
183
0.0025
0.0057
945
ND
(32.8)
ND
( .0010)
85.5
ND
(.0025)
3.97
ND
(.0010)
ND
(.0010)
1369
ND
(.0010)
ND
(.0010)
ND
(7.23)
ND
(.0010)
ND
(.0010)
ND
(48.4)
65.6
ND
(.0010)
ND
(3.23)
ND
(.0025)
ND
(0.998)
ND
(.0010)
ND
(.0010)
1247
1248
1378
1469
ND
(.0016)
ND
( .0010)
14.5
ND
(.0010)
ND
(.0010)
59.0
ND
(32.8)
ND
(.0010)
7.77
ND
(.0025)
0.934
ND
(.0010)
ND
(.0010)
1246
1249
ND
(.0010)
ND
( .0010)
ND
(7.23)
ND
(.0010)
ND
(.0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
ND
(.0025)
ND
(.998)
ND
(.0010)
ND
(.0010)
1268
1278
ND
(.0010)
ND
(.0010)
ND
(7.23)
ND
(.0010)
ND
( .0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
ND
(.0025)
NO
(.998)
ND
(.0010)
ND
(.0010)
1478
ND
(.0010)
ND
( .0010)
ND
(7.23)
ND
(.0010)
NO
(.0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
ND
(.0025)
ND
(.998)
ND
( .0010)
ND
(.0010)
1268
1279
ND
(.0010)
ND
( .0010)
ND
(7.23)
ND
(.0010)
ND
( .0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
NO
( .0025)
ND
(.998)
ND
(.0010)
ND
(.0010)
1234
1236
1269
ND
(.0010)
ND
( .0010)
ND
(7.23)
ND
(.0010)
ND
(.0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
ND
(.0025)
ND
( .998)
ND
(.0010)
ND
(.0010)
1237
1238
0.0093
ND
(.0010)
220
ND
(.0031)
0.0058
1240
1313
ND
(.0010)
84.2
ND
(.0025)
3.50
ND
(.0010)
ND
(.0010)
2378
ND
(.0027)
ND
(.0007)
ND
(11.1)
ND
(.0009)
ND
(.0028)
ND
(35.3)
ND
(65.5)
ND
(.0006)
ND
(2.08)
ND
(.0010)
ND
(1.08)
ND
(.0005)
ND
(.0005)
1239
NO
(.0010)
ND
(.0010)
ND
(7.23)
ND
( .0010)
ND
(.0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
ND
(.0025)
NO
(0.998)
ND
(.0010)
ND
(.0010)
1278
1279
ND
(.0010)
ND
(.0010)
ND
(7.23)
ND
(.0010)
ND
(.0010)
ND
(48.4)
NO
(32.8)
ND
(.0010)
ND
(3.23)
ND
(.0025)
ND
(0.998)
ND
( .0010)
NO
(.0010)
1267
ND
(.0010)
ND
(.0010)
ND
(7.23)
ND
( .0010)
ND
(.0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
NO
(.0025)
NO
(0.998)
ND
(.0010)
ND
(.0011)
1289
ND
(.0010)
ND
( .0010)
ND
(7.23)
ND
(.0010)
ND
(.0010)
ND
(48.4)
ND
(32.8)
ND
(.0010)
ND
(3.23)
*
ND
(1.20)
*
*
o
CO
Data expressed In ng/g.
* Denotes data not reported by laboratory.
-------
TABLE p-62
AQUEOUS INFLUENTS AND EFFLUENTS - TCDD ISOMERSJ
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
9/5/84
SAMPLE IDENTIFICATION
Service Water
Quench Water (Water)
Quench Water (Solids)
Venturl/Demister Water
(Water)
Venturl/Demister Water
(Solids)
ESP Water (Water)
ESP Water (Solids)
Ash Pit Water (Water)
Ash Pit Water (Solids)
Effluent Water Field Blank
Effluent Water
Backup Field Blank
1368
NO
( .0229)
NO
( .0010)
26.9
NO
( .0010)
28.2
ND
(.0033)
15.8
NO
( .0010)
NO
(.0010)
ND
(.0010)
1379
ND
(0.229)
ND
( .0010)
24.7
ND
( .0010)
ND
(0.985)
ND
( .0048)
ND
(5.66)
ND
( .0010)
ND
( .0010)
ND
(.0010)
1369
ND
(0.229)
NO
(.0010)
ND
(1.31)
ND
(.0010)
2.01
ND
( .0032)
6.79
NO
( .0010)
(Sampli
ND
( .0010)
ND
( .0010)
1247
1248
1378
1469
ND
(0.229)
ND
(.0010)
ND
(2.62)
ND
(.0010)
NO
(0.985)
ND
(.0018)
NO
(5.66)
ND
(.0010)
analys
ND
( .0010)
ND
.0010)
1246
1249
ND
(0.229)
ND
(.0010)
NO
(1.97)
ND
( .0010)
ND
(0.985)
ND
( .0032)
ND
(5.66)
ND
( .0010)
s data i
ND
(.0010)
ND
(.0010)
1268
1278
ND
(0.229)
ND
( .0010)
ND
(1.97)
ND
(.0010)
ND
(0.985)
ND
(.0032)
ND
(5.66)
NO
(.0010)
ot retui
ND
(.0010)
ND
.0010)
1478
NO
(0.229)
ND
( .0010)
ND
(1.97)
ND
( .0010)
ND
(0.985)
ND
( .0032)
ND
(5.66)
ND
( .0010)
ned froc
ND
( .0010)
ND
.0010)
1268
1279
NO
(0.229)
ND
( .0010)
ND
(1.97)
ND
(.0010)
ND
(0.985)
ND
(.0032)
ND
(5.66)
ND
(.0010)
i laboral
ND
(.0010)
ND
.0010)
1234
1236
1269
ND
(0.229)
ND
(.0010)
NO
(1.97)
ND
(.0010)
ND
(0.985)
ND
(.0013)
NO
(5.66)
ND
(.0010)
ory)
ND
( .0010)
ND
.0010)
1237
1238
ND
(0.229)
ND
( .0010)
22.2
ND
( .0010)
26.1
0.0052
224
ND
( .0010)
NO
(.0010)
ND
( .0010)
2378
ND
(0.341)
ND
( .0004)
ND
(1.10)
ND
( .0008)
ND
(1.29)
NO
(.0014)
ND
(28.2)
ND
( .0003)
ND
(.0013)
ND
( .0003)
1239
ND
(0.229)
ND
( .0010)
ND
(1.97)
ND
( .0010)
NO
(0.985)
NO
( .0025)
ND
(5.66)
ND
(.0010)
ND
(.0010)
ND
(.0010)
1278
1279
ND
(0.229)
ND
(.0010)
ND
(1.97)
ND
( .0010)
ND
(0.985)
NO
(.0013)
ND
(5.66)
NO
(.0010)
NO
( .0010)
ND
( .0010)
1267
ND
(0.229)
ND
(.0010)
ND
(1.97)
ND
(.0010)
ND
(0.985)
ND
(.0019)
ND
(5.66)
ND
( .0010)
ND
(.0010)
NO
( .0010)
1289
ND
(0.229)
ND
( .0010)
NO
(1.97)
*
ND
(0.985)
ND
(.0032)
ND
(5.66)
ND
(.0010)
*
*
o
00
00
1 Data expressed in ng/g.
* Denotes data not reported by laboratory.
-------
TABLE D-63
AQUEOUS INFLUENT AND EFFLUENT WASTEWATER SAMPLE PRECISION
TCDD ISOMERS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/30/84
(Data expressed in ng/g.)
WATER FRACTION
tbr water
ESP Water
Field Duplicate
Precision ^Kruj^
FILTERABLE SOLIDS FRACTION
tbr water
ESP Water
Me i u uu pn cate
Precision \Kru;
1368
Onn^s
.UU JO
Or\r\~! A
• UU/4
CA
O't
1 Q£Q
lyoo
AQK
too
1237/1238
Onnt\8
.UU So
1 940
1^'tU
1 -31 -3
1 01 J
f.
D
ISOMERS
1379
n nn?^
n nn^7
U .UUD /
70
/ o
Q^C
y+o
1247/12W
1378/1469
CQ n
oy «u
1369
fit; fi
*Re1ative percent difference,
D-89
-------
IV. SUMMARY OF RESULTS FOR PCDDs AND PCDFs
The analytical data for PCDDs and PCDFs, and for TCDD isomers, are presented
in Tables D-64 through D-69, to show the concentrations of these compounds in
influent and effluent streams around the Building 703 incinerator on the three
sampling days. Those data were combined with the flow rate information appearing
in Tables D-64 through D-66, to derive the loadings, in grams per year, of each
PCDD and PCDF homologue and TCDD isomer, which are presented in Tables D-70
through D-75. The data for PCDDs and PCDFs were averaged by homologue over the
three sampling days and summarized in Figures D-l through D-10, illustrating
the probable destruction, transfer, or formation of each homologue in the
incineration process. As described previously, data for loose solid wastes fed
to the incinerator could not be gathered as no representative sampling method
was available. Figures D-l through D-10 should be interpreted accordingly.
D-90
-------
TABLE 0-64
INFIUEN1 AND EFFLUENT PCDO/PCF1F CONCENTRATIONS
UOM CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28/84
Sample Identification
INFLUENTS
~ TTK
Service Hater (Sec. Frtd.)
TlUabiwtsstt River Uattr
Liquid UasU Mottle B»
Liquid UasU HoiiU BB1
Liquid Uastt Nozzle C
Low-BTU Liquid Waste
SOLID
Loose and Containerized
Solid Hastes
EfHU£»7S
THR
Incinerator Exhaust
LIQUID —
jencn lower Mater
jench Tower Sol Ids
enturl/Oenlster Mater
venturl/uenlstcr solids
E
5r Mater '
sti Pit U.t.T
Ash Pit Solids
237B-
TCDO
(Mi
(N01
Total
TCDO
58.3/HO*
lO
5M6/S4B
SAMPLED)
4Z.fi
432
2M
Total
PeCDD
11800/NO
P. MS
54.9
82.0
Total
HxCOO
1190/ND
0.88
43.7
55.1
1
Total
HpCDD
2790/NO
TF?
0.21
274
265
OCDO
217/335*
198
22000/ND
0 93
1437
1113
~?n ~
2378-
TCDF
1.51
11.0
8.5
Total
TCDF
391/628*
1260
imm
" 86.1
25.0
170
39.3
"13) -•
' 189
lotal
PeCOF
845/ND
13.6
66.4
160
Total
HxCDF
?,64
117
Uo
Total
HpCDF
55,9
0.26
427
33?
OCOF
21.2/ND*
1240/WD
0.06
3)9
284
UNITS
pq/m3
T^T~
nq/L
nail
nq/L
nu/L
"1/mj
nq/L
nq/L
nq/q
nq/L
nq/4
nq/L
ng/g
"9/9
FLOW KATE
30.4?8 dscfm
5.33 * 10" L/dav
9 80 x 10? L/dav
1.92 x lO'/l.oe x 10* L/dav
2.57 x IP' L/dav
4,35 x 10' L/dav
30.478 dscfm
3.86 x 10b L/dav
1.47 x 10° L/dav
0.95 x 106 L/day
•Field duplicate sample result
aSt" *re Stit'd
|0lnonhUn7n'l S"M>le analysis not returned from laboratory
Loadings (Table 0-70) were calculated based on the length of time each waste was
burned during the emissions test NO denotes homologue was not detected.
-------
TABLE 0-65
ItirillfNI AND EFFLUFNT PCDD/PCDF CONCENTRAIIONS
OOU CHEMICAL COHPANT BUILDING 703 INCINERATOR
8/30/84
Sample Identification
INFLUENTS
AIR
LIQUID ••"•*" '"'
Service Uater (Sec. Md.)
Tlttabaoassee Pl.er Water
Liquid Uaste Nouli U
Liquid Uaste Nonle B>l
Liquid Uaste Motile C
— loJ-BTU Liquid" Uatte '
501 ID !CJ
Loose and Containerised
Solid Mattel
EfFLUE
~nun
Ven
ESP
ESP
— KK
Ash
NTS
IB ~
nch To«
nch Towe
turl/0e«l
turl/Oe.i.1
Nater
Solids
Ister Uater
stcr Solid!
Solids
Pit Uater
Pit Solids
SOLID
TGK
23/8-
TCDO
Total
TCDD
/NOT SAMI
60300/21800*
(NOT SAMF
43.8
"707
lOl
6.2/18.9*
J2|2/1B64*
TO
Total
PeCDO
TOT
3450/6130*
EO)
~ T94
99.3
"TO
885/393*
Total
HiCDO
2610/4240^
—07
^-751
147/205*
0.13/0.11*
Total
HpCOO
38QQ/569Q*
1 O4
162
417/515*
— fT5
0. 81/0. 50
OCDO
187
19800/19800*
2.52
7358
"To?
2199/2530*
$4.9
3.2/2.4*
2378-
ICOF
NO/2100*
j 1.67 |
JM_
45.3/47.7*
Q.02/ND*
Total
TCDF
12.9
36600/18000*
77.0
22.3
287/607*
539/6574*
114
Total
PeCDF
12,5
8'8
17BO/ND
1510/4320*
4.28
87.5
64 6
405/345*
Total
HxCOF
14.2
749/HD
3510/7130*
1.95
124
82 9
75. 7/58. S'
Total
HpCOF
108-5
16.7
593/NO
8070/8160*
0.55
785
199
150/161*
10.0
OCOF
6Z5/HD
7430/7680*
0.17
641
283
200/22S*
12.5
UNITS
P
-------
IA11E 0-66
InfllllNI AND EFFIUEN1 PCOO/PCOF CONCENIRAIIONS
DOM CHEMICAL COMPAIK 10IIOIMC 10) INCINEMlOft
9/S/B4
mriucms
'Ml
Stoic* Water (J*c. Trtd.)
P TlttakwMiM llw Vttw
lljl.1 Uaitl hill. II
loi-ItU liquid U4»U
5H.1D
loon and CofltalMHlerf
IFFl
11
11
I
1
nclncrator Eihaust
miiB
jtnch Towvr Hat«r
itnch Towtr Solldt
Kiturl/Dmlitir Hater
tSf Uattr
t5l> Solid.
»ik Pit Uater
Ath Ml Sol Ml 1
MHO
Inclntrator Ask
237a-
ICOO
local
ICOO
\\
UM
(HQf j
i«
73.9
'
0.07
Iota)
PtCDO
*>»I-H>1
toe
J
lotal
HuCDO
2Q-3
lolil
HpCDO
98.1
p^
69,0
. 86. Q
. 0,08
ocoo
_^^_
1210
047
236
J2J
4,27
ICOf
J37
2.05
9.70
lotal
ICOF
206.6
•il^JJ
^
OB
436
90.0
lOtil
•eCOF
Ui
7.09
it 3
lotal
M«COf
. 3.M
"19 )
lotal
HpCOF
37.1
125
69 T~~
OCOF
3o.a
103
34. B
or
UNI IS
j^L
'3/1-
nq/l,
rw/q
nq/q
nq/C
nq/q
nq/q
FLOU KAIE
I3.5S1 dSf'-
^.m . 100 L/dax
I.Z7 A 1C L/Sy
51 K 18' L/da,
5.17 « 10" L/da»
33.599 dscfm
3.91 » 100 i/da»
1 19 x To^lj-daj
0 95 » Id* I/da,
0 5J « lO6 l/dsy
I
VO
CO
•field duplicate simple reiult
analysts not returned frOM laboratory.
-------
TABLE D-67
INFLUENT AND EFFLUENT TCDO ISOMER CONCENTRATIONS
UOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28/84
Sample Identification
INFLUENTS
AIR
Precanbgs.ttgn. A.1r
LI
quiu
Service Mater (Sec. Trtd.)
Tlttabawassee River Water
Liquid Waste Nozzle BA
•Liquid Waste Nozzle BB~
Uquia Haste Nozzle C
Low-BTU Liquid Waste
SOLID
Loose and Containerized
Solid Wastes
EFFLUENTS
AIR
Incinerator Exhaust
LIQUID
(
(
\
jench Tower Hater
mnch Tower Sot Ids
inturl/Dealster Uater
Venturl/DeMlster SoHds
ESP Water
ESP Solids
Ash Pit Uater
Ash Pit Solids
SOLID
Incinerator Ash
1368
44.2
lfl.0
1189/276
20.4
183
113
0.62
1379
14.0
9.9
TNOT SAI
4108/272
{NOT SA*
13.0
113
7.8J
0.25
1369
PLED)
PLED)
1247
1248
1378
1469
1.69
7.32
0.04
1246
1249
1268
1278
1478
1268
1279
1234
1236
1269
1237
1238
10.5
493/ND
12.6
J28
117
0.27
2378
1239
1278
1279
1267
1289
UNITS
pg/m3
ng/L
ng/L
ng/L
ng/L
ng/L
ng/L
nq/ni-1
nq/X
pq/q
ng/L
nq/q
nq/L
nq/q
na/L
nq/q
nq/q
o
i
10
*Two distinct wastes Incinerated. Analytical results for both wastes are
stated In a manner similar to that In Table 0-64.
-------
TABLE 0-68
INFLUENT AND EFFLUENT TCDD ISOMER CONCENTRATIONS
DOM CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/30/84
Sample Identification
INFLUENTS
AIR
1
'recombustlon Air
'QUID
Service water (Sec. Trtd.l
Tutabawassee River Water
Liquid Haste Nozzle BA
Liquid Haste Nozzle BB *
I
1368
20.6
WLK'WL'MI
1379
04—
16.1
(NOT SAMPL
IBHSHMl
1369
:o)
Lt nt'm.t m •, 'j««u »^^^» pmili7/:l:l[iL' K
cn
'Field duplicate sample.
Two distinct wastes Incinerated. Analytical
results for both wastes are stated, in
similar manner as in Table 0-65.
No waste incinerated.
-------
TABLE D-69
INFLUENT AND EFFLUENT TCOO 1SOHER CONCENTRATIONS
DOU CHEMICAL COMPANY BUILDING 703 INCINERATOR
9/5/84
Sample Identification
INFLUENTS
AIR
"T
'recombustion Air
Service Uater (Sec. Trtd.)
Tlttabawassee River Hater
Liquid Uaste Nozzle BA
Liquid Uaste Nozzle BB
— i
.{quid Uaste Nozzle C
.ow-BTU Liquid Uaste
5H.IO
Loose and Containerized
Solid Hastes
EFFLUENTS
AIR
— T
•i
1
'
nclnerator Exhaust
QUID
uench Tower Hater
jtnch Tower Solids
enturl/Denlster Uater
VenturlVDenlster Solids
:SP Uater
ISP Solids
Ash Pit Uater
Ash Pit Sol Ids 1
SOLID
Incinerator Ash
1368
24.6
4050
19. 1m. 4'
129
26.9
26.2
15.8
0.04
1379
7.58
(NOT
1940
199
6.23/6.00*
(NOT
70.7
24.7
0.02
1369
SAMPLED)
AMPLED)
2.01
6.79
1247
1248
1378
1469
2.45
O.Qfi
1246
1249
1268
1278
1478
1268
1279
1234
1236
1269
Q.9B
1237
1238
3.92
4.PO/2.40*
0.46
22.2
26.1
&. 2
224
0.01
2378
1239
1278
1279
1267
1289
UNITS
pq/m-1
nq/L
ng/L
ng/L
ng/L
ng/L
ng/L
ng/mJ
ng/L
na/a
nq/L
ng/g
ng/L
ng/q
ng/L
ng/g
ng/g
I
ID
•Field duplicate sample results.
Sample analysis not returned from laboratory.
-------
TABLE D-70
INFLUENT AND EFFLUENT PCDD/PCDF LOADINGS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/28/84
(in grams per year)
Sample Identification
INFLUENTS
AIR
Precombustion Air
LIQUID
Service Water (Sec. Trtd.)
Tlttabawassee River Utter
1
1
I
(quid Uaste Nozzle BA
(quid Uaste Nozzle BB '
iquid Uaste Nozzle C
Low-BTU Liquid U«ste
SOLID
Loose and Containerized
Solid Wastes
TOTAL INFLUENTS (grams/year)
EFFL
UENTS
AIR
Incinerator Exhaust
LIQUID
t
<
v
jench Tower Water
jench Tower Sol ids
enturi/Demister Utter
Venturi/uemisier >onas
1 ESP Utter ?
1 ESP Solids^
Ash Pit Utter
Ash Pit Solids
SOLID
Incinerator Ash
TOTAL EFFLUENTS (grains year
2378-
TCDO
Tottl
TCDD
0,026
74.8
(NOT S
42.7
(NOT S
117.5
21.6
4.32
9.83
3.84-5.12
40.2
Total
PeCDD
MPLEO)
82.7
WLED)
82.7
2.94
5.50
3.33
11.8
Total
HxCOD
8.32
8.32
0.40
4.37
2.26
2.60-3.47
10.1
Total
HpCDD
195
0.16
195
0.09
27.4
1Q-9
19.9-26.5
61.6
OCDD
0.099
385
154
539
0.44
144
46.0
O2
107-143
316
2378-
TCDF
0.69
1.10
^13
0.22-0.29
2.41
Total
TCDF
0.18
2451
65.6
2517
38.9
35.2
17.0
21.1
3.0°
0.07
30.0-40.1
153
Total
PeCDF
5.92
5.92
6.14
6.65
q.in
0.22-0.30
17.2
Total
HxCDF
1,20
11.7
c 17
1.49-1.99
20.0
Total
HpCDF
106
108
0.12
42.7
11 Q
4.99-6.65
62.5
OCOF
0.003
8.69
8.69
0.03
37,9
11 7
8.43-11.2
59.4
UNITS
'Total of two wastes incinerated. 2Sample analysis not returned from laboratory.
o
-------
TABLE D-71
INFLUENT AND EFFLUENT PCDD/PCOF LOADINGS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/30/84
(in grams per year)
o
IO
00
Sample Identification
INFLUENTS
AIR
Precombustlon Air
LIQUID
Service Water (Sec. Trtd.)
Tittabawassee Rtver Water
Liquid Waste Nozzle BA
Liquid Waste Nozzle BB *
Liquid Waste Nozzle C
Low-BTU Liquid Waste z
SOLID
Loose and Containerized
Solid Wastes
TOTAL INFLUENTS (grams/year)
EFFLUENTS
AIR
Incinerator Exhaust
LIQUID
Quench Tower Water
Quench Tower Solids
VentuH/Deaister Uaier
Venturl/Denister Solids
ESP Uater
ESP Solids
Ash Pit Uater
Ash Pit Solids
SOLID
Incinerator Ash
TOTAL EFFLUENTS (grams/year)
2378-
TCOO
0.002
Total
TCDD
0.008
89.8
(NOT
89.4
280
(NOT
459
20.8
111
20.9
2.15
23.4
0.20
0.43-0.57
179
Total
PeCDD
SAMPLED)
17.0
16.0
iAMPLED)
33
0.92
15.6
3.35
4.89
24.6
Total
HxCOO
2.42
12.1
14.5
0.17
11.8
1.87
0.82
0.42-0.56
15.2
Total
HpCDO
34.7
8.14
17.6
60.4
0.40
72.5
10.98
2.31
0.31
2.65-3.53
89.6
OCDD
362
31.1
91.8
485
1.20
371
48.0
12.2
1.46
10.4-13.9
446
2378-
TCOF
0.006
0.77
0.78
0.79
2,41
0.22
0.25
0.05-0.07
3.73
Total
TCOF
0.006
2748
100
171
3019
36.6
31.7
28,7
35.1
11.4
99.5
2.99
1.78
1.95-2.60
250
Total
PeCDF
0.006
17.2
4.82
7.01
29.0
2.03
13.8
4.42
2.25
22.5
Total
HxCDF
0.007
2.03
16.3
18.3
0.93
19.6
5.63
0.42
0.15-0.19
26.8
Total
HpCDF
0.005
32.5
1.61
37.4
71.5
0.26
124
13.5
0.83
0.14
1.47-1.97
140
OCDF
0.065
92.3
1.69
34.5
128
0.08
101
19.2
1.11
0.20
1.88-2.51
124
UNITS
•Field duplicate sample result. *Total of two wastes Incinerated. No waste incinerated.
-------
TABLE D-72
INFLUENT AND EFFLUENT PCOD/PCDF LOADINGS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
9/5/84
(in grams per year)
Sample Identification
INFLUENTS
Alft
Precombustlon Air
LIQUID
Service Water (Sec. TrtdY
Tittabawassee River Water
Liquid Waste Nozzle BA
Liquid Waste Nozzle BB
Liquid Waste Nozzle C
Low-BTU Liquid Waste
SOLID
Loose and Containerized
Solid Wastes
TOTAL INFLUENTS (grams/year)
EFFLUENTS
AIR
Incinerator Exhaust
LIQUID
tench Tower Water
ench Tower Solids
nturi/Demister Water
Venturi/Demister Solids
ESP Water" "
ESP Solids
Ash Pit Water 1
Ash Pit Solids 1
SOLID
Incinerator Ash
TOTAL EFFLUENTS (grams/year)
2378-
TCDD
Total
TCDD
0,019
(NOT
70.2
5.82
0.55
(NOT S
76.6
2.46
13.4
4.10
1.80
20.7
0.23-0.31
42.7
Total
PeCDD
SAMPLED)
9.64.
WPLED)
9.64
1.29
5.22
6.51
Total
HxCOD
0.54
1.69
2.23
Total
HpCDD
0.047
3.40
3.40
11.1
3.26
7.98
0.25-0.33
22.6
OCOD
0.153
14.5
14.1
28.8
0.23
42.8
19.1
31.7
0.87-1.16
94.6
2378-
TCDF
2.83
2.83
0.14
0.78
0.92
Total
TCDF
0.102
77.3
1.26
0.62
79.3
47.2
8.28
151
6.82
53.0
34.5
7.48
1.77-2.36
310
Total
PiCOF
2.12
2.12
0.09
1.27
1.61
3.95
6.92
Total
HxCDF
2.94
1.46
1.27
5.7
Total
HpCDF
0.019
0.019
22.6
5.05
5.65
33.3
OCOF
0.015
0.015
18.7
6.24
6.78
0.26-0.34
32.0
UNITS
Sample analysis not returned from laboratory.
-------
TABLE D-73
INFLUENT AND EFFLUENT TCDD ISOMER LOADINGS (In grams per year)
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
3/28/84
Sample Identification
INFLUENTS
AIR
Precombustlon Air
LIQUID
Service Water (Sec. Trtd.)
Tlttabawassee River Water
Liquid Waste Nozzle BA
1 Liquid Waste Nozzle BB
Liquid Waste Nozzle C
Low-BTU Liquid Waste
SOLID
Loose and Containerized
Solid Wastes
TOTAL INFLUENTS (grams/year
EFFLUENTS
AIR
Incinerator Exhaust
LIQUID '
tench Tower Water
ench Tower Solids
nturl/Demlster Water
Venturl/Demlster Solids
ESP Water
ESP Solids
Ash Pit Water
Ash Pit Solids
SOLID
Incinerator Ash
TOTAL EFFLUENTS (grams/year
1368
0.02
35.1
9.39
44.5
9.18
18.2
4.68
2.03-2.71
34.5
1379
0.01
19.3
(N01
29.9
(NOT
49.2
5.85
11.3
0.81-1.09
18.1
1369
SAMPLED)
SAMPLED)
0.32
0.32
1247
1248
1378
1469
6.80
0.74
0.12-0.16
1.68
1246
1249
1268
1278
1478
1268
1279
1234
1236
1269
1237
1238
20.5
3.45
24.0
5.68
ii;.au
4.84
0.37-1.17
24.3
2378
1239
1278
1279
1267
1289
o
o
Total of two wastes Incinerated.
-------
TABLE 0-74
INFLUENT AND EFFLUENT TCOD ISOMER LOADINGS (in grams per year)
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
8/30/84
Sample Identification
INFLUENTS
Precombustion Air
LIQUID
Service Water (Sec. Trtd.)
ittabawassee River Water
. Liquid Waste Nozzle BA
1 Liquid Waste Nozzle BB
Liquid Waste Nozzle C
Low-BTU Liquid Waste '
SOLID
Loose and Containerized
Solid Wastes
TOTAL INFLUENTS (grams/year)
EFFLUENTS
• yfc —
AIR
incinerator Exhaust
LI
^
IJUIU
uench Tower Water
j encn Tower Solids
entu rl/Demlster Water
Veniuri/uemister ion as
ESP water
SP Solids
Asn IMt Water
Ash Pit Solids
— tn\ ii\ '
SOLID
Incinerator Ash
TOTAL EFFLUENTS (grams/year;
1368
45.0
59.1
185
289
7.98
45.7
8.83
I73T
10.9
0.11
). 21-0. 28
75.1
1379
0.002
35.6
(NO'
27.3
94.6
(NOT
158
6.02
28.9
5.81
0.87
572?
Q.Q«
0.11-0.15
47.1
1369
SAMPLED)
SAMPLED)
— IH7
1248
1378
1469
0.0008
1.18
1.18
0.10
2.28
0.53
0.33
0.01
0.03-0.03
3.30
1246
1249
1268
1278
0.0005
0.0005
1478
1268
1279
1234
1236
1269
0.0004
0.0004
1237
1238
0.002
9.78
1.18
11.0
6.16
34.6
5.72
" 6.87
0.06
0.03-0.10
53.5
2378
0.002
0.002
1239
1278
1279
1267
1289
o
I—1
o
Total of two wastes incinerated.
No waste incinerated.
-------
TABLE 0-75
INFLUENT AND EFFLUENT TCDD ISOMER LOADINGS (in grams per year)
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
9/5/34
Sample Identification
INFLUENTS
AIR
i tP«hiCJ?mbMSt1on ^1r
LIQUID
Service Tfeter (Sec. Trtd.)
Tlttabawtssee River Hater
Liquid Waste Nozzle BX
Liquid Waste Nozzle BB
Liquid Waste Nozzle C
Low-BTU Liquid Waste
SOLID
Loose and Containerized
Solid Wastes
TOTAL INFLUENTS (grams/year!
EFFLUENTS
AIR
Incinerator Exhaust
LIQUID
Quench Tower Water
Quench Tower Sol Ids
Venturl/Demlster Water
Venturl/Demlster Solids
ESP Water
ESP Solids
Ash Pit Water l
Ash Pit Sol Ids l
SOLID
Incinerator Ash
TOTAL EFFLUENTS (grams/year)
1368
0.012
48.3
4.43
0.36
53.1
64.3
4.90
2.07
1.34
0.11-0.15
72.7
1379
0.004
(NOT 5
22.0
1.39
0.12
(NOT S
23.5
35.3
4.46
0.08-0.10
39.9
1369
0.001
\MPLEb)
WPLED)
0.001
0.14
0.56
0.70
1247
1248
1378
1469
0.03
0.03
1246
1249
1268
1278
1478
1268
1279
1234
1236
1269
0.0005
0.0005
1237
1238
0.002
0.07
0.073
0.21
4.03
1.92
1.80
18.6
0.05-0.06
26.6
2378
1239
1278
1279
1267
1289
o
ro
Sample analysis not returned from laboratory.
-------
FIGURE D-i
TCDD LOADINGS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
NOTE - Loadings stated in grams per year,
and calculated as averages of
Sdmpic
o«c of
11
ii
TOTAL LOADINGS OF TCDD
In
Out
218
-------
FIGURE D-?
PeCDD LOADINGS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
NOTE - Loadings stated in grams per year
and calculated as averages of '
Aw*. 4*704.
r
*M
6 5
al
TOTAL LOADINGS OF PeCDD
In Out
-------
6URE D-3
DOW CHEMICAL
703 INCINERATOR
NOTE - Loadings stated In grams per year,
and calculated as averages of
three sampling days (8/28, 8/30,
and 9/5/84).
TflTAL LQADIMSS OF HxCDD
In
7.6
-------
FIGURE D.-4
HpCDD LOADINGS .„
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
NOTE - Loadings stated 1n grams per year,
and calculated as averages of
three sampling days (8/28. 8/30,
and 9/5/84).
TOTAL LOADINGS OF HpCDP
In Out
86
58
-------
FIGURE n-5
OCOD LOADINGS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
NOTE -
Loadings stated in grams per year
and calculated as averages of
8/3°'
TOTAL LOADINGS OF PC DP
*" Out
351
-------
1
S
-L3/M
u.
o
o
oo
CM
CSJ
-------
FIGURE D-7
PeCDF LOADINGS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
7Xco*o trrtu+rr Mwrat
if
£
II
(2.8
NOTE -
Loadings stated 1n grams per year.
and calculated as averages of
thr«« sampling days (8/28. 8/30.
and 9/5/84).
Staple *»*lys«* r»
««««f
TOTAL LOADINGS OF PeCDF
In Out
12.3 (%) 15,5
-------
FIGURE iw*.
HxCDF LOADINGS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
NOTE -
Loadings stated 1n grains per year.
and calculated as averages of
three sampling days (8/28, 8/30.
and 9/5/84).
TOTAL LOADINGS OF HxCDF
In _ Out
6.1 (%)
17.5
-------
FIGURE D-9
HpCDF LOADINGS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
NOTE - Loadings stated In grams per year,
and calculated as averages of
three sampling days (8/28. 8/30.
and 9/5/84).
TOTAL LOADINGS OF HpCDF
In Out.
~—'
60
79
-------
FIGURE D-1CJ
OCDF LOADINGS
DOW CHEMICAL COMPANY BUILDING 703 INCINERATOR
NOTE -
S»«|»l«
Loadings stated in grams per year
and calculated as averages of
th*;ee sampling days (8/28, 8/30,
and 9/5/84).
<"« of -tAw.
TOTAL LOADINGS OF QCDF
In Out
45.6
72
-------
APPENDIX E
DETAILED DESCRIPTIONS OF AMBIENT AIR MONITORING EQUIPMENT
AND SAMPLING METHODS
MICHIGAN DIOXIN STUDIES
MIDLAND, MICHIGAN, AMBIENT AIR SAMPLING STUDY
-------
APPENDIX E
In the following narrative, each individual type of sampling device used in
the ambient air study is described in terms of its components.
I. HIGH-VOLUME SAMPLER FOR PCDD/PCDF
Previous studiesll»12,13 snowec| the applicability of a modified high-volume
sampler in the collection of pesticides and other semi -volatile compounds in
air. More recently, the use of this sampler was extended to apply to PCOD and
PCDF. The modified sampler, shown in an exploded view in Figure E-l, consisted
of a high-volume sampler with a shelter, motor, timer, and flow controller
arranged in a manner similar to that described in the April 30, 1971, Federal
Register (Vol. 36, Number 84). However, an extended throat section was inserted
between the glass fiber filter and the motor, to hold a cylindrical polyurethane
foam (PUF) plug.
Standard glass fiber filters (Whatman 934-AH) of the type specified in the
above Federal Register were used; that is, they were at least 99% efficient in
trapping particles of 0.3-micron average diameter. Filters were used as
supplied, and were not subjected to any precleaning steps. The PUF plugs were
manually cut from 3-inch stock of open-cell polyether-type material, into
cylindrical shapes 10 to 11 centimeters in diameter. Initial cleanup of the
PUF plugs was accomplished by the field contractor, GCA/Technology Division, by
Soxhlet extraction for 14 to 24 hours at four cycles per hour, three times,
using 95:5 V/V hexane/ethyl ether. Extracted PUF was placed in a vacuum oven
evacuated by a water aspirator, and dried at room temperature for two to four
hours until a solvent odor was absent. Each plug was then placed in a cleaned,
labeled hexane-rinsed sample container, using hexane-rinsed forceps, for trans-
port to the sampling sites. A representative sample of every lot of cleaned
PUF was analyzed at GCA for background levels of contaminants. The results of
these tests are presented in Table E-l.
II. HIGH-VOLUME SAMPLER FOR CHLOROBENZENES AND OTHER SEMI-VOLATILE COMPOUNDS
Lewis and MacLeod cite data indicating the collection efficiency of a
sampler with PUF alone as the sorbent decreases dramatically for chlorobenzenes
below Cls. On this basis it was decided that, to sample for semi-volatile
compounds, a backup sorbent would be employed in a separate set of samplers
constructed similarly to the PCDD/PCDF samplers described above. The extended
throat beneath the glass-fiber filter was packed with a sorbent "sandwich"
consisting of two PUF plugs of the same size as in the PCDD/PCDF sampler,
surrounding a layer of 75 grams of 16/50 mesh Amberlite XAD-2 (Rohm & Haas,
Philadelphia, Pennsylvania) resin. To facilitate handling of this finely
divided sorbent, it was contained in a Teflon cup, as shown in Figure E-2. The
E-l
-------
Filter holder support
Teflon gasket
Teflon gasket
Aluminum throat extension
and foam plug
Aluminum flange & motor
support
Hi-Vol motor
Sheet metal adaptor for
exhaust duct
Flow controller & sensor
Power cords
Exhaust duct
FIGURE E-l
EXPLODED VIEW OF AMBIENT AIR SAMPLER FOR PCDD/PCDF
E-2
-------
TABLE E-l
RESULTS
OF QUALITY CONTROL
CHECKS ON UNEXPOSED POLYURETHANE
FOAM PLUGS
Concentration (ug)*
Sample
QC 365
QC 366
QC 367
QC 368
QC 369
Die thy 1
Phthalate
0
120.05
231.78
53.44
220.23
Bis 2-Ethyl
Hexyl Phthalate
ND
24
ND
ND
ND
Adipate
Alkyl Ester
ND
Found
ND
ND
ND
Phenolics
ND
ND
ND
ND
ND
PCDDS and
Biphenyls
ND
ND
ND
ND
ND
c6-c8
Hydrocarbons
100 - 500
ND
ND
ND
ND
Higher
Boiling Point
Hydrocarbons
ND
ND
ND
ND
100
71 *Detection Limits
Phenolics: ND = <50 ug
TCDD: ND = <100 ug
Biphenyls: ND - <100 ug
Priority pollutants - <10 - 50 yg
1 Identity of quality control samples:
QC 365 - Laboratory blank. Solvent KD concentrated to 10 mL.
QC 366 - Two PUF plugs from Lot //I ("Old PUF")
QC 367 - Two PUF plugs from Lot #1 ("Old PUF")
QC 368 - Two PUF plugs fr.om Lot #7 ("New PUF")
QC 369 - Two PUF plugs from Lot //7 ("New PUF")
-------
1
I
1
I
I
I
i
I
1
I
I
TEFLON CUP <
ALUMINUM
THROAT
StCOND PUF PLUG
75 9- XAD-2
FINE MESH SS SCREEN
SNUG FIT BETWEEN TEFLON CUP
AND ALUMINUM THROAT
FIRST PUF PLUG
NE MESH SS SCREEN
FIGURE E-2
HIGH-VOLUME SAMPLER ATTACHMENT
TO SAMPLE FOR CHLOROBENZENES AND OTHER SEMI-VOLATILE COMPOUNDS
E-4
-------
cup included a 40-mesh stainless steel screen bottom, and was filled in the
field with preweighed aliquots of XAD-2 delivered from containers sealed at the
GCA laboratory. The sampling assembly was constructed by placing a PUF plug in
the aluminum throat, a Teflon cup containing XAD-2 atop the plug, and a second
PUF plug into the top of the cup. The prefilter head was secured to the top of
the extended throat, forming a tightly-packed sorbent assembly.
A representative sample of every lot of XAD-2 used in this study was analyzed
by the supplier, Supelco, Inc. These data are shown in Table E-2, and show the
sorbent to have met requirements established by EPA for the maximum content of
contaminants in unexposed sorbent. 14
III. LOW-VOLUME SAMPLER FOR VOLATILE COMPOUNDS
As the compounds selected to be sampled in this study included several with
boiling points lower than 100°C, a sampling method appropriate to the collection
of these more volatile pollutants was found in the work of Riggin.6 Carbon
molecular sieve (CMS) adsorbents were determined to be appropriate to collect
selected volatile organic compounds, specifically, certain nonpolar organics
with boiling points between -15° and 120°C. The performance of CMS adsorbents
was described by Riggin as superior to and more sensitive than other sorbents,
such as Tenax GC, for a wider range of compounds. With the guidance of the
document cited above, a low-volume sampler incorporating Spherocarb® adsorbent
was constructed, as shown in Figure E-3.
The sampling system consisted of a pair of sorbent cartridges, each
approximately three inches long, constructed of 1/4-inch O.D. stainless steel
tubing. Each tube was loosely packed with 0.4 gram of 60/80 mesh Spherocarb
held in place with precleaned glass wool plugs; the direction of sampled air
flow was engraved on the body of the tubes to assure that the tubes were
assembled correctly in sampling and analysis. The tubes were equipped with
Swagelok fittings at both ends, and were prelabeled such that one tube was
designated an inlet or primary tube. The primary tube was mated with a secondary
or backup tube to evaluate penetration of compounds through the primary tube.
The tube pair was connected by a length of Teflon tubing to a duPont model
P-125 or Alpha 2 constant flow pump capable of maintaining accurately the low
flow rates required (approximately 30 to 70 mL/min).
In field use, the cartridge pair was hung vertically from a support built
onto one of the high-volume samplers described above. It was found that during
heavy rains, water was drawn into the unprotected inlet of the primary tube.
A funnel formed of aluminum foil attached to the lower end of the cartridges was
successful in eliminating this problem.
To guard against the battery-powered sample pumps becoming discharged during
use, they were operated while connected to battery chargers at all times. This
procedure was effective in assuring reasonably constant air flows through the
samplers over entire sampling periods.
E-5
-------
TABLE £-2
QUALITY ASSURANCE ANALYSES
XAD-2 RESIN LOTS USED IN AMBIENT AIR SAMPLING
XAD-2 Lot Number
Residual
Organics (ug/g)
Total Chromatographable
Organics (ug/mL)
221
222
223
224
225
226
227
228
229
230
29.14
39.40
84.50
97.20
69.30
77.50
64.70
87.30
69.30
62.30
0.00
0.00
0.00
0.83
3.66
8.27
0.00
0.00
0.32
7.87
NOTE Guidelines established by EPA allow for the presence of a
maximum of 1000 ug/g of residual organics, and 20 ug/mL of
total Chromatographable organics in unexposed sorbent media.
(IERL-RTP Procedures Manual: Level 1 Environmental Assessment,
2nd Edition, EPA 600/7-78-201. U.S. Environmental Protection
Agency, Research Triangle Park, NC, October 1978).
E-6
-------
TO DUPONT
PUMP
(LOW FLOW)
TEFLON TUBING
FOIL TUBE SHELTER
CMS TUBES
BACKUP TUBES
SWAGED UNIONS
PRIMARY TUBES
FOIL FUNNELS
SHELTER SUPPORTS
TO DUPONT
PUMP
(HIGH FLOW)
FIGURE E-3
AMBIENT AIR SAMPLER FOR VOLATILE COMPOUNDS
-------
IV. LOW-VOLUME LIQUID IMPINGER SAMPLER FOR FORMALDEHYDE
In selecting the methods to be used in sampling for the compounds of interest
in ambient air, it was discovered that the solid sorbent method described above
for volatile compounds was not appropriate to sample for formaldehyde, owing to
apparent problems with retention on the sorbent and artifact formation. A wet
chemical method involving bubbling ambient air through a mixture of 2N HC1/0.05%
2,4-dinitrophenylhydrazine (DNPH) and isooctane was chosen. Reference 6 to this
report describes this method as applicable to detect aldehydes and ketones.
Samples were analyzed by high-performance liquid chromatography.
The samplers (see Figure E-4) consisted of a short length of Teflon tubing
connected to a pair of midget impingers, each containing the DNPH-isooctane
absorbing reagent. The system was powered by a duPont constant flow sampling
pump similar to that employed in the low-flow CMS sampler. The pump was joined
to the impinger system by Tygon tubing. Like the CMS samplers, the inlet of
the sampler was protected from rain by wrapping in a short funnel of aluminum
foil.
E-8
-------
TYGON TUBING
FOIL
FUNNEL
i
UD
TEFLON
TUBING
DNPH
ABSORBING
SOLUTION
DUPONT P-125
PUMP
MINI IMPINGERS
SILICA GEL
STYROFOAM
BASE
FIGURE E-4
AMBIENT AIR SAMPLER FOR FORMALDEHYDE
-------
APPENDIX F
DETAILED DESCRIPTION OF CONDUCT OF STUDY
AND CARBON MOLECULAR SIEVE METHOD VALIDATION STUDY
MICHIGAN DIOXIN STUDIES
MIDLAND, MICHIGAN, AMBIENT AIR SAMPLING STUDY
-------
APPENDIX F
I. HIGH-VOLUME SAMPLER FOR PCDD/PCDF
As indicated previously in the description of this sampler, the polyurethane
foam (PUF) plugs were preextracted in the GCA laboratory, dried, and placed in
a cleaned, labeled sample jar for transport to the study area. At the beginning
of each sampling day, the filter supports, Teflon gaskets, and extended throats
were cleaned, rinsed with hexane, and dried in a resistance-heated oven at
approximately 150°C. These parts were assembled and wrapped at both ends with
hexane-rinsed aluminum foil for transport to the monitoring sites. The serial
numbers of the glass fiber filters were associated with the appropriate
monitoring sites and recorded in a field log book maintained by the GCA field
team coordinator. As the PUF plug was removed from its container and placed
into the sampling assembly with hexane-rinsed forceps, the identity of the site,
run number, and date of sampling was written on the exterior of the plug
container.
Completed sampling assemblies were transported to the monitoring sites,
where the protective foil covers were removed, and screwed tightly onto the
appropriate high-volume samplers. The sampler timers were then activated and
the flow controllers set to provide a target flow rate of 20 cubic feet per
minute (0.57 m3/min). In practice, however, the resistance to air flow presented
by the PUF plug occasionally overcame the capacity of the sampler motor to
provide this flow rate. In this case, the flow controller was set for the
highest flow rate attainable. Prior to leaving each site, time, and ambient
temperature, pressure, and relative humidity were recorded by the field team
coordinator.
At the conclusion of each sampling run, about 24 hours later, final flow
rate data were taken, the samplers were disassembled and the filter portions
of the assembly were covered with hexane-rinsed aluminum foil. The samplers
were then reassembled and restarted for the next sampling period. As the four
monitoring sites were serviced in sequence, the sampling periods at each site
were necessarily slightly different.
After each sampler was serviced, the exposed samples were returned to the
mobile laboratory, where the glass-fiber filter was removed, folded inward
lengthwise, and placed in a wrapper of hexane-rinsed aluminum foil. This foil
was folded twice to form an envelope, labeled by filter, site, and run number,
and stored flat in the mobile laboratory.
The PUF plugs were removed from the sampler assembly and returned to their
original labeled container using hexane-rinsed forceps. Filter supports and
the interior of the extended throats were rinsed with hexane into the PUF plug
containers, and the containers were sealed for shipping to the analytical
laboratory.
F-l
-------
. Sites 1, 2, and 3 were equipped with single samplers for PCDD/PCDF. On
every sampling day, field blank and field duplicate samples were obtained at
site 4, this being the site expected to be downwind of Dow Chemical most
frequently. Method blanks, one each for the filter and the PUF, were submitted
separately to the analytical laboratory; neither of these blanks was exposed to
ambient air in Midland at any time with the exception of the brief period between
removal of a random filter from the stock of unexposed filter media and its
immediate wrapping in aluminum foil for shipment.
It was initially intended in this study to obtain PCDD/PCDF samples daily
and to submit most for analysis. However, analytical cost and laboratory
scheduling limitations were such that samples from three of the 18 total sampling
days were analyzed. The selection was based upon examination of ambient wind
data for direction and probable persistence on each sampling day. By these
measures, samples from runs 4, 6, and 16 were forwarded for analysis.
II. HIGH-VOLUME SAMPLER FOR CHLOROBENZENES AND OTHER SEMI-VOLATILES
These samplers were assembled in a manner similar to that of the PCDD/PCDF
units, with exceptions owing to the insertion of XAD-2 sorbent and an additional
PUF plug in the high-volume sampler's extended throat (see Figure IV-7). To
accomplish this, the first PUF plug was placed in the throat; its container was
labeled as with the PCDD/PCDF samplers. A prewashed Teflon cup was inserted
atop the first plug in the throat and filled with 75 grams of XAD-2 resin from
a preweighed container; that container was also labeled appropriately according
to site, run number, and date. The second PUF plug was then fitted into the
top of the Teflon cup with hexane-washed forceps, and the assembly pressed
together. As with the PCDD/PCDF samplers, both ends of the filter assembly
were wrapped in hexane-rinsed aluminum foil for transport to the monitoring
sites.
At the sites, sampler assembly was completed similarly to the PCOO/PCDF
samplers. A target sampling flow rate of 20 cfm was again selected; however,
this rate was achieved or exceeded during only two of the 86 successful sampler
runs, because of the severe resistance to air penetration presented by the
tightly-packed sorbent materials. Moreover, on some days, perhaps due to
humidity, much less than the target sample volume of 800 cubic meters was
collected. While runs of this kind would not have been of concern with respect
to sorbent breakthrough, the sensitivity of the analytical method could have
been reduced.
Following each run at each site, the sampler assembly, covered with
hexane-rinsed aluminum foil at its inlet end, was dismantled, with the exposed
sorbents returned to their original containers. The granular XAD-2 sorbent was
poured quiescently from the Teflon cup into its container. The filter supports
and throat assemblies were rinsed into the container holding both PUF plugs.
Each container was then sealed for shipping.
F-2
-------
As for PCDD/PCOF, sites 1, 2, and 3 were equipped with single samplers.
Field blank and field duplicate samples were taken daily at site 4. Method
blanks, one each for the filter and PDF, and of two of the ten lots of XAD-2
used in the study, were submitted for analysis for the components of interest.
Samples from each site, along with field blanks- and field duplicates from
site 4, were shipped for analysis for all 18 sampling days regardless of wind
or other meteorological conditions.
III. LOW-VOLUME SAMPLER FOR SEMI-VOLATILES AND VOLATILES
A. CMS Field Methods
The CMS sorbent cartridges described previously were preconditioned and
packed at the GCA laboratory according to the following procedure:
Swagelok plugs, ferrules, unions, and empty stainless steel tubes were
washed, rinsed with methylene chloride, and heated at 250° +_ 20°C for
one hour. The hardware was then assembled (see Figure IV-8).
Each tube was packed with approximately 0.4 gram of 60/80 mesh
Spherocarb and glass wool end plugs.
Tubes were conditioned in bulk at 400°C for 16 hours under a purified
nitrogen purge flow of 100 cc/min. The exit end of each cartridge was
capped and the entire cartridge was removed from the flow line and the
other end cap immediately installed. Sealed cartridges were then
placed in a metal friction-top can containing two inches of granulated
activated charcoal beneath a retaining screen. Paper tissues were
placed in the can to avoid damage to the cartridges during shipment.
Tubes were conditioned in this manner no more than 30 days prior to their use
in sampling.
Prior to each sampling day, two pairs of CMS tubes per sampling site were
joined together by Swagelok unions. As indicated previously, the direction of
air flow through the tubes was clearly labeled; thus, primary and backup tubes
were designated in each pair. Sampling site identifications and run numbers
were written on metal tags fastened on each individual tube. Assembled tube
pairs were carried to the sampling sites in metal cans.
Each site included two low-volume samplers operating at flow rates of
30 mL/min (low-flow) and 70 mL/min (high-flow). These flow rates were selected
out of concern that sorbent breakthrough volumes may have been exceeded at high
sampling rates on days in which high ambient temperature and/or humidity were
experienced. Prior to each sampling run, pumps were calibrated to yield sampling
flow rates corresponding to the above.
F-3
-------
At each monitoring site, a low- and high-flow pump and tube pair were
assembled as shown in Figure IV-8. Pumps were started, times and meteorological
data were taken, and the samplers allowed to run for about 24 hours.
At the conclusion of each run, a final flow rate check of each pump was
performed; those varying by more than +_5% from initial flow rates were flagged
and the sampling runs were considered invalid. Exposed CMS tube pairs were
removed, their ends closed with Swagelok caps, and placed in a can for transport
back to the mobile laboratory. At the laboratory, the primary and backup tubes
were separated and open ends were closed tightly with Swagelok caps. Individual
tubes were then placed in a can containing a two-inch bed of activated charcoal
and stored in a cooler packed with ice.
Sites 1, 2, and 3 were equipped with a low- and high-flow CMS sampler on
selected sampling days. Site 4 included these in addition to field duplicate
samplers operating in both flow rate ranges. A single field blank, made up
from an individual unexposed CMS tube, was supplied from site 4. Thus, on each
sampling day 21 tubes (primary, backup, and blank) were exposed.
Analytical laboratory resources to analyze these samples were limited such
that only 180 tubes could be analyzed. Thirty of these analyses were to be
associated with the method validation study to be described in the Section
III.B of this appendix. A reasonable analytical scheme incorporating 150 total
analyses was devised, based upon ambient temperature, humidity, and wind
direction on the sampling days.
Sampling days were first selected on the basis of weather forecasts available
locally. If persistent winds were expected in directions likely to establish
good upwind-downwind relationships between two or more sampling sites, then the
CMS samplers were activated. At the conclusion of the run, if winds were
favorable, 15 of the 21 tubes utilized that day were selected for analysis
based on temperature and humidity conditions. If the high temperature in the
sampling period exceeded 80°F, with associated high humidity, the following CMS
tubes were submitted for analysis:
- All primary low-flow samples
- All backup low-flow samples
- Field blank
- Primary and backup low-flow field duplicates (site 4)
- Primary and backup high-flow samples from the two
sites most closely downwind of Dow Chemical
On cooler days with lower humidity, the following tubes were to be analyzed:
- All primary high-flow samples
- All backup high-flow samples
- Field blank
- Primary and backup high-flow field duplicates (site 4)
- Primary and backup low-flow samples from the two
sites most closely downwind of Dow Chemical
Samples were shipped from runs 3, 4, 6, 10, 11, 12, 15, 16, and 17, resulting
in a total of 135 samples submitted for analysis.
F-4
-------
B. CMS Method Validation Study
Because the range of compounds projected to be determined using the low-
volume sampler was wide, and sufficient information concerning spiking and
recovery efficiencies and breakthrough volumes on Spherocarb was not available
from any previous source, a short-term laboratory validation study was conducted
to test the procedure. Eight volatile compounds, as shown in Table F-l, were
selected to span a range of boiling points from 37° to 173°C. The validation
study consisted of two segments: determination of spiking and recovery
efficiency, and validation of sampling procedures and breakthrough volumes.
Spiking and ambient conditioning of prepared CMS tubes was performed by GCA,
while sample analysis was conducted by a contract laboratory.
To conduct the determination of spiking efficiency, each of the compounds
of interest was combined in the liquid phase in a spiking carrier matrix. A
known volume was drawn with a micro liter syringe and injected into the inlet
of a sorbent tube by way of a heated gas chromatography injector assembly. A
total of 20 carbon molecular sieve sorbent tubes were spiked at an approximate
level of 100 ng per compound of interest (concentration range - 54-82 mg/L) and
analyzed by the laboratory. Five CMS tubes were spiked at an approximate level
of 20 ng of each compound of interest (concentration range - 5.4-8.2 mg/L) per
tube.
For validation of sampling procedures and breakthrough volumes, a system
was configured to provide scrubbed (organic free), humidified air at 86°F (30°C)
and 85 percent relative humidity to spiked CMS tubes attached to duPont constant
flow pumps. A schematic of this system is shown in Figure F-l. These validation
conditions were selected to represent the worst-case ambient temperature and
humidity conditions expected to be encountered in the field during the sampling
program.
A total of 30 CMS tubes were used in the validation study, allowing for a
range of spiking quantities, sampling rates, and total sample volumes. These
data are presented in Table F-2, and show that the tubes were divided into
seven distinct sets, five of which contained five tubes each, and two of which
included three and two tubes, respectively. Set 1 was spiked but not subjected
to the simulated ambient sampling conditions described above; this set was
intended to provide a measure of spiking and recovery efficiency alone, without
considering breakthrough volumes. Sets 2 through 5 were spiked prior to being
conditioned, at the air flow rates shown, for various sample volumes. Set 6,
including three tubes, was conditioned but not spiked, while the two tubes in
Set 7 were neither spiked nor conditioned, and were thus considered to be
method blank samples.
As described in Section VI.E.3 of the report of which this appendix is a
part, only four of the 30 CMS tubes in the validation study were analyzed by the
contract laboratory within desired holding times. Analytical results for those
four tubes showed that seven of the eight compounds shown in Table F-l were not
detected. The last compound, perchloroethylene (tetrachloroethylene), was
detected, but not in consistent agreement with the known levels spiked (see
Table VI-10 of report).
F-5
-------
TABLE F-l
COMPOUNDS USED FOR VALIDATION STUDY
Compound
Boiling Point (°C)
1,1-Dichioroethylene (Vinylidene Chloride)
Chloroform
Carbon Tetrachloride
Aerylonitrile
Benzene
Tetrachloroethylene
Chlorobenzene
o-Dichlorobenzene
37
61.7
76.5
77.5
80.1
121
132
173
F-6
-------
HG.
THERMOMETER
ERLENMEYER FLASK
2-HOLEO STOPPER
(EXCESS MOISTURE
KNOCK-OUT FLASK)
FLOW
METER
5.5 LITER MANIFOLD
(AT ELEVATED
TEMPERATURE)
FLOW
METER
ERLENMEYER FLASK
3-HOLED STOPPER
HOT PLATE (AIR HEATER,
HUMIDIFIER)
DIGITAL
PYROMETER
COMPRESSED,
PURIFIED AIR
(CARRIER)
LOW VOLUME,OUPONT CONSTANT
FLOW PUMPS
FIGURE F-l
SIMULATED AMBIENT AIR GENERATION SYSTEM
CMS TUBE VALIDATION STUDY
-------
Table F-2
CMS Tube Validation Study
Tube Run Flow Rate
Set Duration Average Sample Volume
Number (min.) (L/min., std.) (Liters, std.) Comments
1 NA NA NA No carrier air
NA NA NA Spiking level - 100 ng
NA NA NA
NA NA NA
NA NA NA
2 1,440 0.0283 40.701 Spiking level - 100 ng
1,440 0.0271 38.980
1,440 0.0272 39.163
1,440 0.0274 39.391
1,440 0.0280 40.365
3 1,440 0.0626 90.070 Spiking level - 100 ng
1,440 0.0649 93.451
1,440 0.0657 94.644
1,440 0.0667 96.066
1,440 0.0642 92.462
4 420 0.0658 27.654 7 hour run
420 0.0623 26.162 Spiking level - 100 ng
420 0.0629 26.410
420 0.0635 26.647
420 0.0643 26.999
f -*
5 1,440 0.0280 40.314 Spiking level - 20 ng
1,440 0.0276 39.723
1,440 0.0276 39.767
1,440 0.0270 38.820
1,440 0.0281 40.491
6 1,440 0.0655 94.369 Blank with carrier air
1,440 0.0646 92.980
1,440 0.0650 93.609
7 NA NA NA Blanks without carrier air
NA NA NA
F-8
-------
IV. LOW-VOLUME LIQUID IMPINGER FOR FORMALDEHYDE
Sampling trains composed of the parts described in Section IV of Appendix £
were assembled as shown in Figure E-4. Samples were collected and handled
according to the protocols outlined in pages 40 to 43 of Reference 19 to this
report. Owing to limitations on the number of samples that could be analyzed
by the contract laboratory, and the requirement that DNPH absorbing reagent be
used for sampling within 48 hours of its initial preparation, it was determined
that samples for formaldehyde would be obtained on six of the 18 sampling
days which encompassed the ambient air study period. The DNPH reagent was
prepared in the GCA laboratory and air-shipped to the Midland sampling sites by
commercial carrier, when requested by field contractor representatives based
upon predictions of favorable wind directions.
F-9
-------
APPENDIX G
RAW ANALYTICAL DATA
AMBIENT AIR PCDD/PCDF SAMPLING
IN VICINITY OF DOW CHEMICAL COMPANY, MIDLAND, MICHIGAN
ANALYTICAL LABORATORY - MIDWEST RESEARCH INSTITUTE
KANSAS CITY, MISSOURI
-------
TABLE G-l
Raw PCDD/PCDF Analytical Data
Ambient Air Study in Vicinity of
Dow Chemical Company, Midland, Michigan
UK I Sample Ho.
1149E-1-NFA-1
I149E-2-NPA-2
M49E-3-FA-3
1149E-4-PA-4
1149E-5-FA-5
1149E-6-PA-6
1149E-7-FA-7
11A9E-8-PA-B
1149E-9-FA-9
1149E-10-PA-10
1149E-11-FA-11
1149E-12-PA-12
11A9E-13-FA-13
11A9E-14-PA-14
I149E-MB1-15
1149E-39-HNF-16
1149E-15-FB-17
1149E-16-FB-18
1149E-18-FB-19
11A9E-19-FB-20
1149E-20-FB-21
11A9E-AO-NMP-22
11A9E-15-PB-23
1IA9E-16-PB-24
1149E-17-PB-25
1149E-18-PB-26
HA9E-19-PB-27
11A9E-20-PB-28
11A9E-17-FB-29
11A9E-MB2-30
I149E-A1-NMF-31
liA'JE-21-FC-32
11A9E-22-FC-33
11A9E-23-FC-3A
I1A9E-2A-FC-35
SAS
Sample
No.
11A9E-1
11A9E-2
11A9E-3
1IA9E-A
11A9E-5
11A9E-6
1149E-7
11A9E-8
11A9E-9
11A9E-10
11A9E-11
11A9E-12
1149E-13
11A9E-1A
11A9E-39
11A9E-15
11A9E-19
11A9E-21
11A9E-23
11A9E-25
11A9E-AO
11A9E-16
11A9E-18
1149E-20
11A9E-22
11A9E-2A
11A9E-26
11A9E-17
1IA9E-A1
11A9E-27
1IA9E-29
11A9E-31
1IA9E-33
Total TCDF
1.0
1.0
ND (0.11)
0.65
36
180
7.5
3.9
1.2
d
ND (0.03)
ND (0.03)
0.92
A.O
ND (0.09)
1.0
5.6
5. A
2.2
ND (0.05)
1.5
0.82
5.8
6.9
29
8.7
ND (O.A1)
5.1
2.2
ND (0.04)
0.9A
3.0
58
4.6
72
2.3.7.8-TCUF
'•°b
i.ob
ND (0.11)
ND (0.06)
ND (0.69)
ND (0.40)
ND (0.20)
ND (0.28)
NO (0.09)
d
NO (0.03)
ND (0.03)
ND (0.06)
ND (0.13)
ND (0.09)
1.0b
ND (0.10)
ND (0.11)
ND (0.11)
ND (0.03)
ND (0,05)
O.B26
ND (0.1A)
ND (0.15)
ND (0.18)
ND (0.16)
ND (0.10)
ND (0.10)
ND (0.04)
ND (0.04)
0.94b
Nl) (0.06)
Nl) (0.81)
ND (0.10)
ND (1.1)
Total
TCDD
1.3
1.5
0.88
0.80
3.7
33
1.6
1.7
0.76
0.84
0.65
0.28
0.70
0.61
0.84
1.5
1.1
0.94
1.3
1.0
0.66
1.3
0.77
1.8
6.0
D.7A
3.5
0.57
0.43
0.26
1.3
0.29
4.5
0.71
9.3
2.3.7,8-TCDD
0.75b
0.93b
ND (0.10)
ND (0.10)
ND (0.10)
ND (0.70)
ND (0.18)
ND (0.12)
ND (0.07)
ND (0.02)
ND (0.05)
ND (0.08)
ND (0.08)
ND (0.12)
ND (0.02)
0.85b
ND (0.06)
ND (0.06)
ND (0.13)
ND (0.08)
ND (0,08)
0.836
ND (0.15)
ND (0.15)
ND (0.82)
ND (0.12)
ND (0.61)
ND (0.10)
' ND (0.03)
ND (0.03)
0.87b
ND (0.03)
ND (0.03)
ND (0.07)
ND (0.20)
Total
PSCDF
ND (0.20)c
ND (0.46)
ND (0.09)
NO (2.0)
4.0
28
0.25
3.2
0.91
ND (0.12)
ND (0.07)
ND (0.10)
ND (0.67)
1.1
ND (0.12)
ND (0.09)
ND (0.06)
ND (0.36)
0.58
ND (0.06)
1.0
ND (0.03)
ND (2.3)
ND (0.67)
1.7
0.25
ND (0.79)
0.78
ND (0.03)
ND (0.18)
ND (0.04)
ND (0.09)
2.2
ND (0.09)
6.3
Total
P6CDI)
0.42b
0.56b
ND (0.16)
ND (0.29)
ND (0.48)
6.0
ND (0.38)
ND (0.25)
ND (0.07)
ND (0.03)
ND (0.11)
ND (0.13)
ND (0.24)
ND (0.20)
ND (0.03)
0.36b
ND (0.11)
ND (0.61)
ND (0.24)
ND (0.05)
ND (0.38)
l.O6
ND (0.30)
ND (0.27)
ND (0.39)
ND (0.12)
ND (0.10)
ND (0.25)
ND (0.09)
ND (0.21)
0.55b
ND (0.22)
ND (0.25)
ND, (0.29)
ND (0.45)
Total '
HxCDF
ND (0.19)
ND (0.18)
ND (0.13)
ND (0.30)
2.3
ND (1.1)
ND (0.30)
ND (0.25)
ND (0.51)
ND (0.18)
ND (0.48)
ND (0.16)
0.57
ND (0.11)
ND (0.04)
ND (0.11)
ND (0.49)
ND (0.19)
ND (0.14)
ND (0.01)
ND (0.23)
ND (0.09)
ND (0.20)
ND (0.64)
ND (1.0)
ND (1.0)
ND (0.31)
ND (0.47)
ND (0.60)
ND (0.35)
ND (0.14)
ND (0.24)
3.7
NO (0.13)
2.4
Total
llxCUD
a.s:
7.3
0.72
ND (0.64)
ND (0.69)
ND (0.51)
ND (0.26)
ND (0.20)
0.67
ND (0.15)
ND (0.35)
ND (0.11)
ND (0.24)
ND (0.87)
ND (0.06)
6.2e
ND (0.80)
NU (0.13)
ND (0.12)
NO (0.01)
ND (0.82)
3.4e
ND (0.45)
ND (0.48)
ND (0.91)
2.3
ND (0.89)
ND (0.08)
ND (1.6)
ND (0.28)
5.1e
ND (0.17)
0.45
ND (0.33)
0.22
Total
HpCDF
ND (0.74)
ND (0.73)
ND (0.52)
ND (0.66)
4.1
ND (0.74)
ND (0.65)
ND (0.45)
ND (0.28)
ND (0.41)
NO (0.85)
ND (0.70)
ND (0.43)
ND (0.90)
ND (0.21)
Nl) (0.38)
ND (0.09)
ND (0.16)
ND (0.13)
ND (0.07)
ND (0.08)
ND (0.12)
ND (1.7)
ND (1.2)
ND (0.95)
ND (0.71)
ND (0.77)
ND (3.2)
ND (0.96)
ND (0.51)
ND (0.35)
ND (0.53)
2. A
ND (0.46)
2.4
Total
HpCDD
5-°:
4.7
0.61
ND (0.41)
1.7
ND (0.36)
1.7
ND (0.35)
0.78
ND (0.46)
ND (0.88)
ND (0.32)
1.2
ND (0.16)
ND (0.26)
4.9e
2.3
0.50
0.18
ND (0.05)
0.28
3.1e
ND (0.22)
ND (2.2)
ND (0.91)
1.7
0.71
ND (0.96)
ND (1.2)
ND (0.56)
4.6e
ND (0.64)
2.2
0.46
0.91
Total
OCDF
*6|
5.2
0.75
ND (0.51)
2.8
ND (0.49)
0.47
0.65
1.3
ND (0.43)
ND (0.98)
ND (0.21)
Nl) (0.66)
ND (0.98)
ND (0.17)
7.8f
0.78
0.62
ND (0.42)
ND (0.10)
ND (0..25)
A. 1
ND (0.72)
ND (1.4)
ND (1.2)
3.6
1.5
ND (2.0)
ND (2.1)
ND (0.59)
7.3f
ND (1.0)
1.1
ND (0.53)
3.7
Total
OCDD
5.8}
6.) *•
. 2
0.87
0.53
5. 1
1.2
6.0
1.2
2. 1
ND (1.5)
ND (1.6)
0.70
3.2
ND (0.26)
ND (0.40)
7.0f
1.3
3.9
2. 1
ND (0.20)
3.3
7* !•
. 1
ND (2. A)
ND (4.2)
ND (4.0)
5.4
2.2
ND (2.3)
ND (2.1)
ND (0.67)
8.2f
ND (2.3)
6.2
2.3
3.2
-------
TABLE G-l (continued)
SAS
Sample Total
Mill Sample No. No. Total TCDF 2,3,7,8-TCDF TCDD
1149E-25-FC-36 1149E-35 4.5 ND (0.10) 1.1
1149E-26-FC-37 1149E-37 100 ND (1.1) ?0
1149E-21-PC-39 1149E-28 3.8 ND (0.10) 0.78
1149E-22-PC-40 1149E-30 82 ND (0.10) 19
1149E-23-PC-41 1149E-32 9.7 ND (0.04) 1.6
1149E-42-NMP-38 1I49E-42 3.6 0.92b 1.7
1149E-24-PC-42 1149E-34 240 ND (1.3) 52
1149E-25-PC-43 1149E-36 8.0 ND (0.15) 1.1
1149E-26-PC-44 1149E-38 5.1 ND (0.25) g
1149E-MB3-45 - ND (0.02) ND (0.02) 0.44
, a All data reported as nanograms (ng)/sample.
b Sample originally spiked with 1 ng of this compound.
c Value in parenthesis reflects estimated detection limit.
„ d Sample analyzed after additional cleanup by carbon column.
I e Sample originally spiked with 5 ng of a single isomer.
ro f Sample originally spiked with 10 ng of a single isomer.
g The 2,3,7,B-TCDD-13C,2 internal standard was not recovered
2,3.7,8-TCDD
ND (0.12)
ND (0.46)
ND (0.06)
ND (0.04)
ND (0.06)
1.2b
ND (1. 3)
NO (0.07)
g
ND (0.04)
TCDD and TCDF
Calculations
Total
PECDF
ND (0.10)
U
ND (0.12)
3.9
ND (0.19)
ND (0.06)
23
ND (0.07)
ND (0.30)
ND (0.03)
internal'
for TCDF,
Total
PSCDD
ND (0.36)
ND (0.91)
ND (0.12)
ND (0.26)
ND (0.40)
0.4?
1.09
ND (0.12)
ND (0.30)
ND (0.05)
Total
HxCDF
ND (0.10)
3.4
ND (0.16)
ND (0.40)
ND (0.06)
ND (0.06)
ND (1.8)
ND (0.46)
ND (0.19)
ND (1.0)
*
Total
HxCDD
ND
0
ND
ND
ND
4
ND
ND
ND
ND
(0.
.75
(0.
(0.
(0.
.le
(3.
(0.
(0.
(2.
25)
12)
09)
12)
4)
70)
3D
0)
Total
HpCDF
ND (0.69)
2.1
ND (0.32)
ND (0.56)
ND (0.67)
ND (0.29)
ND (0.74)
ND (2.4)
ND (1.0)
ND (0.61)
Total
llpCDO
ND (0.33)
1.1
ND (0.37)
ND (0.32)
ND (0.09)
5.4e
ND (1.3)
ND (1.5)
ND (1.0)
ND (1.4)
Total
OCDF
ND (0.58)
5.1
0.12
0.21
0.59
7.5f
ND (0.96)
ND (0.60)
ND (0.98)
ND (1.3)
Total
OCDD
ND (0.72)
3.4
0.28
5.5
ND (0.77)
8.0f
ND (1.2)
ND (1.7)
ND (2.5)
ND (3.0)
standards not recovered.
*
P6CDF and
PgCDD based
on
2,3
,7,8-TCDF-13C,2.
-------
TABLE G-2
Key to Sample Identification
Ambient Air PCDD/PCDF Sampling
In Vicinity of Dow Chemical Company, Midland, Michigan
SAS
Sample Number
(1149E-
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
Sample Identity
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/8-9/84;
9/12-13/84
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APPENDIX H
RESULTS OF REANALYSIS OF SELECTED
PCDD/PCDF SAMPLES BY USEPA-EMSL-RTP
AND EXPLANATORY INFORMATION
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UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
DATE: MAY 2, 1985
SUBJECT: ANALYSIS FOR CDDs AND CDFs IN EXTRACTS OF AMBIENT AIR
HxOr.. ROBERT L. HARLESS, RESEARCH CHEMIST
METHODS DEVELOPMENT BRANCH/EMSL-RTP (MD-77)
TO: Dr. NORBERT JAWORSKI, DIRECTOR.
ENVIRONMENTAL RESEARCH CENTER-DULUTH and
HO LIASION FOR NATIONAL DIOXIN STUDY
Background information regarding these analyses is brie-fly
summarized. Ambient air samples were collected in Region V
utilizing high volume air samplers. The samples were subjected to
Midwest Research Institute "*:'1/1985. HRGC-HRMS analyses were per-formed on the standards
and extracts utilizing a 60m SP-2330 fused silica capillary
column -for resolution o-f components. The concentrations o-f MRI
analytical standards were compared with EMSL-RTP and ECL
«.-. r-.l •/1 i cal standards. Four extracts specified by Region V were
subjected to analysis for TCDDs*, TCDFs and penta-CDFs as
requested. Preliminary analytical results were discussed with
Frank Thomas, Region V, in mid March at which time I indicated
that this report would not be written until a TCDF isomer that
was needed for identification purposes was received. The work is
now complete. Analytical results are shown in Table 1, and
summarized below.
# The stated concentration of labeled and native 237S-TCDD
and TCDF in MRI standards are in reasonable agreement with
concentrations of ECL and EMSL-RTP standards.
* MRI standards were used for quantification purposes.
Comparisons of MRI and EMSL-RTP results indicate that in general
most values agree from the standpoint of low or high amounts in
each extract. ./'
' * The high amounts of TCDF in the extracts is due to one or
more of the following isomers, 1238-,1467-,2468-,1236-TCDF that
elute simultaneously from a 60m SP-233O fused silica capillary
column. A 2468-TCDF isomer was obtained for identification
purposes. The retention time is within acceptable agreement, one
H-l
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second, with the isomer or- isomers in the extracts. The TCDFs in
the extracts by themselves are unusual. Dr. Rappe's work in ES
and T, Vol. 18, no. 3, 1984 was used -for reference purposes since I
do not have these •four individual isomers. Many isomers including
these are -found in effluents -from incineration processes. Also,
some are present in chemical products. For example, 2468-TCDF is
an impurity in 246-trichlorophenol.
* Several extracts o-f soil -from the study performed last year
were analyzed again to determine if this speci-fic TCDF or TCDF
isomers were present. The analyses o-f 13394 indicates that the
same i somer or group o-f isomers is also present in the soil
extract.
* The distribution o-f TCDD isomers in the extracts o-f ambient
air is also similar to those -found in e-f-fluents -from incineration
processes and the extracts o-f soil that were analyzed in the
study last year. However, there are some di-f-f erences in the ratio
o-f various isomers in the extracts o-f ambient air.
* Chlorinated diphenyl ethers are responsible -for some (20 to
50%) o-f the concentration reported as penta-CDFs in the extracts.
Region V did not request or instruct MRI to perform this analysis
required to di-f f erenti ate CDFs -from chlorinated di phenylethers.
It should be done in future studies.
In summary, the TCDFs,TCDDs,and F'CDFs present in extracts of
ambient air were also present in the extracts of soil from the
general area that were analyzed in the study last year. The
distribution of TCDD isomers is similar to those found in
effluents from incineration processes. The TCDF isomer or isomers
by themselves are not similar to those found in incineration
processes. However they were present in the extracts of soil that
were analyzed last year. The amounts of 2378-TCDD and 237S-TCDF
in the ambient air extracts are very low and or not detected in
most cases. Evaluation of the data indicates that the
TCDFs,TCDDs, and PCDFs in the ambient air extracts may be due to:
(1) airborne particulate matter from incineration processes on a
daily basis or (2) contaminated soil in the area that became
airborne during the time that the air sampler was in operation.
The air sampler collection and retention efficiency for CDDs and
CDFs has not been validated. Therefore, results should be
considered as minimum values and actual maximum values are
unknown.
The MRI extracts and analytical standards are stored for
reference. Please call me if you have any questions.
CC:C.ROSS
'M.DELLARCO
N.WILSON
J.CLEMENTS
R.LEWIS
H-2
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TABLE 1. ANALYTICAL RESULTS FOR TCDFs AND TCDDs IN EXTRACTS OF
AMBIENT AIR • ...-..,,.- -.
COMPOUNDS SAMPLE ID AND ESTIMATED AMOUNTS (ng) IN THE EXTRACTS
'1V-''»1';-'- - 1149E-5 1149E-6 1149E-7* 1149E-8 -"" . IT . . L ,* ,
a .
2378-TCDF"RT" O.2 - - 0.4
b
TOTAL TCDFs 28.0 131.0 2.2 26.0
2378-TCDD 0.4
TOTAL TCDDs 9.0 29.0 0.8 1.4
a The concentrations shown above for 2378-TCDF are for the
specific time window exhibited by 2378-TCDF analytical
standard. However, NOTE, conclusive assignment of 2378-TCDF
in these extracts can not be made because the other two
TCDF isomers required for conclusive identification purposes
are not available.
b Average of two analyses performed on separate days.
Refer to text for comments regarding these analyses.
H-3
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APPENDIX J
DETAILED DISCUSSION OF AIR DISPERSION
MODELING TO DETERMINE POINT OF
MAXIMUM GROUND-LEVEL IMPACT
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Possible Association of Stack Emissions and Ambient. Monitored
Concentrations of CDDs/CDPs
A fundalmental question arises as to the possible orlqln of the ambient
monitored concentrations of COOs/CDFs 1n Midland, *1ch1qan. flow Chemical
Company has concluded that, "dispersion of ashes and vent stack oartlculates
from historical Incineration operations are the probable source of the
trace TCOO levels now found 1n the local (Midland) environment (Dow, 19*41."
This qualitative conclusion was reached by comoarlno current emissions of
2379-TCOD with levels measured In the ambient air and 1n Midland soil. An
Independent panel of experts reviewed the Oow report and concluded: "The
major Identified source of 2373-TCDD Into the air and soil of the Midland
area 1s the waste Incinerator stack with an estimated release of 0.33
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the concentration of COOs/COFs measured with ambient monitors. The EPA's
Human Exposure Model predicted the maximum annual averaqt concentration of
2378-TCOO equivalence emitted from the waste Incinerator stack to occur
approximately one kilometer northeast and east-northeast downwind of the
facility. This agrees qualitatively with the placement of samollng Stations
2 and 4 for ambient air sampling 1n Midland, Michigan. Station 2 1s
aoproxlmatelv 1.3 km northeast of the Incinerator, and Station 4 1s
approximately 1.8 km east-northeast of the Incinerator. Station 2 measured
approximately 3.5 og 2378-TCOO equlvalence/m^ of air, and Station 4 measured
about 2 pq 2378-TCOO equlvalence/m^ of air. The dlsoerslon model predicted
about 0.10 oq 2378-TCOO equlvalence/m2 of air, however, this concentration
reflected five years of average meteorology. In addition, the mass emission
rate of 2378-TCOO equivalence was an average emission rate over three days
of stack sampHnq. The ambient monitoring was not conducted 1n concert
with the stack testing, therefore, 1t 1s likely there would be no perfect
correlation between the relative maanltude of the predicted concentration
and the ambient monitored concentration. The aonarent aqreement. with the
predicted fallout area using dispersion wode!1n
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TABLE *. Average Percent Distribution of COOs and CHFs 1n
Both Stack Emissions o* the Dow Incinerator anH
Ambient Monitored Concentrations 1n Midland, MI.
Pollutant
2378-TCOO
TotalTCOO
PentaCOO
HexaCOO
HeotaCDO
OctaCDO
2378-TCOF
Total TCOF
PentaCDF
HexaCDF
HeotaCOF
OctaCOF
Incinerator^
Emissions
(Percent)
86.06
7.72
1.15
1.03
3.10
1.70
86.37
9.04
2.41
0.45
0.13
Station
Ambient
Ion* toH nq
(Percent)
0.38
37.00
Mot Reoorted
13.88
10.01
34.41
0.78
71.57
14.13
0.24
0.24
13.07
HOTE: Percent distribution 1s determined by CDO, and COF
TotaTTDO TbTTl COF.
Incinerator distribution was determined as an average o* EPA stack
tests on 8/28 and 8/30.
Averaqe distribution of 3 sampling days at Station 4.
J-3
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emissions, does suggest that the Incinerator emissions may be contributing
to the COOs and COFs measured by the monitor. For examole, 237R-TCr»n 1s
less than 1% of total COO emissions 1n both Incinerator emissions and 1n
ambient measured concentrations. Total TCOO Isomers oredom^nate 1n both
sampling regimes (Incinerator emissions and ambient monitoring. OctaCOO
1s about 34* of COO concentration measured 1n the ambient, whereas OctaCOO
1s only about 5% of Incinerator emissions of COOs. This mav suggest
atmosoheHc transformation 1n the Isomer ratios of the Incinerator emissions
as the COOs are dispersed from the stack to the ground. However, this 1s
only speculation since such phenomena are currently poorly understood, and
have only recently been hypothesized (Czucwa, 1986). In any case, given the
fact that ambient sampling and stack testing occurred over different time
periods, there 1s relatively good agreement 1n the homologue distribution
patterns of the two sampling regimes. A similarity 1n distribution of COFs
can also he seen. For example, 2378-T.OF 1s a minor constituent (£ 1%) of
the total COFs measured 1n Incinerator stack emissions and 1n ambient
monitoring. The predominant COF 1n both measurements 1s total TCOF 1 sowers.
PentaCDF Isomers constitute the second most frequent Isomers 1n emissions
of COFs 1n both Incinerator emissions and 1n the a"*l«nt concentrations.
Althouqh there 1s not a perfect comparison 1n the distribution pattern
of COFs/COOs, there appears to be relatively good agreement between the two
sampling regimes to sugaest a continued cpntrlbutlon of the waste Incinerator
to ambient concentrations of COOs/COFs 1n the Midland, Michigan, envlronnwnt.
The measured ambient concentrations confirm the significance of even low
levels of emissions from stationary combustors, 1f these levels are a daily
occurrence, and continue over a long period of time.
J-4
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This "fingerprint" analysis 1n which the area of maximum fallout from
Incinerator emissions, and the oercent distribution of COOs/CDFs 1n
Incinerator emissions 1s compared with the ambient measured concentrations,
can only suggest an association between the Incinerator and ambient levels
of COOs/COFs 1n Midland. Perhaos a riaorous analysis o* emissions using
mlcrometeorology recorded for the nearby nuclear nower plant project woul*
helo resolve a quantitative association. In addition, mornholoqlcal
*
comoarlsons of particulate matter emitted from the waste Incinerator to
narticulate matter captured 1n ambient samplers could also help resolve a
quantltate association between emissions and ambient levels 1n lidland.
Electron microscopy could aid such an analysis.
This report cannot rule out the possibility that sources other than,
or In addition to, COO/CDF emissions from the waste incinerator may be
contributing to COOs/COFs measured at ambient wonitorimi stations in lidlanH,
These possibilities include: fugitive process emissions durina chemical
manufacturing at Oow; fugitive emissions at both the electrical powerhouse
and waste incinerator at Dow, and re-entra1nwent of contaminated soil and
dust particles.
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