5390 905R83003
DCW CHEMICAL COMPANY - MIDLAND PLANT
T/ASTEV/ATER CHARACTERIZATION STUDY
PRELIMINARY
SUMMARY OF RESULTS
MARCH 28, 1983
U.S. ENVIRONMENTAL PROTECTION AGENCY
REGION V
ENVIRONMENTAL SERVICES DIVISION
EASTERN DISTRICT OFFICE
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UNITED STATES
.„ __ 5 ENVIRONMENTAL PROTECTION AGENCY
I fej^£~ 1 REGION V
\ ^AIAZ ° 230 SOUTH DEARBORN ST.
^•^IH^^^ CHICAGO, ILLINOIS 60604
**•* PRO^ REPLY TO ATTENTION OF
March 31, 1983
Re: DOW CHEMICAL COMPANY - MIDLAND PLANT:
WASTEWATER CHARACTERIZATION STUDY
The attached preliminary report presents the results of a study of toxicant
contamination in discharges of the Dow Chemical Company at Midland, Michigan,
and in the waters of the Tittabawassee River near the Dow plant. The study
was performed to assist the State of Michigan in the development of effluent
limitations to be included in a revised NPDES wastewater discharge permit
for Dow. The final report of the study will be completed this summer.*
Samples of Dow's Midland plant wastewater effluents were collected and analyzed
for a wide range of pollutants. In addition, fish were held in cages for 28 days
in the Tittabawassee River at the point where Dow's effluent is discharged as
well as upstream and downstream of the plant. The exposed fish were analyzed
to determine the concentrations of toxicants that had accumulated in their
tissues. Of the pollutants examined in both wastewater and fish, dioxins were
given particular emphasis.
Field work for the study, including all sample collection, was completed in
September 1981. Because of the complexity of the analysis and the need to
perfect methods to analyze samples in the sub-parts per trillion range, the
completion of this report was delayed until now.
More than 40 toxic organic chemicals were identified and quantified in the main
process wastewater outfall, most in the low part per billion range. Discharge
of toxic organic pollutants from the plant is estimated to exceed 6 tons per
year. More than 30 organic chemicals were found in whole fish exposed to the
main outfall plume at levels ranging from a few parts per billion to over 1 part
per million. These chemicals include chlorinated benzenes and phenols, and
certain pesticides.
A number of dioxin isomers were found in the discharges and the caged fish. The
most toxic dioxin isomer, 2,3,7,8-tetrachloro dibenzo-p-dioxin, was found at a
level of 50 parts per quadrillion in the main process effluent and at 100 parts
per trillion in whole fish exposed to the effluent plume. The complete results
from the fish bio-accumulation study are not yet available. The remaining
analyses will be completed this summer.
Valdas V, Adamk
Regional Admini
',, '"' t?,. •'-. t. ' /' -'
(•-' #>.l^ '
0". l-\, ,.,^ I, > , ..»
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TABLE OF CONTENTS
PAGE
I. INTRODUCTION 1
II. OBJECTIVES 4
IIL SCOPE OF WORK 4
IV. FINDINGS AND CONCLUSIONS 5
V. RECOMMENDATIONS 7
VI. DOW CHEMICAL - MIDLAND PLANT 9
VIL FIELD STUDIES 16
A. Tittabawassee Sediment Survey 16
B. Conventional Water Sampling 16
C. Static Bioassay; Algal Assay; Ames Test 23
D. Large Volume Water Sampling for PCDDs and PCDFs 25
E. Bioaccumulation Study 32
APPENDICES
A. Sediment Survey Data
B. Conventional Water Sampling Data
C. PCDDs and PCDFs - Methodology and Quality Control
Large Volume Sampling Study
D. Large Volume Sampling Study Results
E. Bioaccumulation Study Results
F. PCDDs and PCDFs - Methodology and Quality Control
Bioaccumulation Study
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I. INTRODUCTION
In the spring and summer of 1981, the Michigan Department of Natural
Resources (MDNR) and Region V of the U.S. Environmental Protection Agency
cooperated in development of a wastewater characterization study for the
Midland Plant of the Dow Chemical Company USA, Michigan Division. The plant
is located in Midland, Michigan, on the Tittabawassee River in Midland County,
(Figure 1). The MDNR and EPA-Region V conducted this study because of the
nature of the process operations at Dow Chemical, concern over actual and
potential discharges of toxic substances from the Midland Plant, and lack of
cooperation from Dow Chemical to provide requested wastewater discharge and
production process information. The study results, along with other information
being sought from Dow Chemical, will be used to develop a Best Available
Technology (BAT) NPDES permit for the Midland Plant which will effectively
regulate the discharge of toxic pollutants.
The purposes of this summary report are to present a compilation of
currently available data from the study and to present preliminary findings and
conclusions regarding the character of the Dow Chemical discharge. The final
report on this study will include all of the raw data and quality assurance for the
data as well as the sampling and analytical protocols used in this study. The final
report will present comparisons of the available discharge data from this study
with historical discharge data, and, comparisons of the bioaccumulation study
results with results from other bioaccumulation studies and native fish data. The
final report will also identify, at least in part, those operations and production
processes at the Midland Plant recommended for evaluation and further study
and assess compliance with current NPDES permit conditions. The final report
will not assess the potential human health impacts of the discharges from Dow
Chemical as that is beyond the scope of this study. In conducting the study, EPA
and MDNR provided split or duplicate samples to Dow Chemical for its analyses.
Dow Chemical data for these split and duplicate samples will be evaluated by
EPA and MDNR upon receipt.
A major problem with complex field studies is the time required to obtain
the final results. This continues to be a particular problem with this study as a
substantial number of organic chemical analyses of complex sample matrices and
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the development of new sampling and analytical methods were required. The
initial planning for this survey was based, in part, upon the availability of EPA
laboratory resources, specifically for analyses of the large-volume water samples
and bioaccumulation samples for poly chlorinated dibenzo-p-dioxins (PCDDs) and
polychlorinated dibenzofurans (PCDFs). EPA laboratory resources were not
available at the time the field studies were to begin. As a result, Region V was
compelled to secure analytical contractors for virtually the entire project. The
difficulty in obtaining numerous contracts and contract amendments with the
required detection levels and analytical quality assurance; the financial resources
required; and the complexity of the analyses contributed to the delay in obtaining
results. At this writing, not all of the data are available. This report was
prepared in the interest of providing the currently available data.
The planning for this study was completed by the EPA Region V Eastern
District Office in consultation with the then Region V Enforcement Division; the
Region V Central Regional Laboratory; the MDNR Office of Toxic Materials
Control (now the Toxic Chemicals Evaluation Section); the Great Lakes National
Program Office; and, the then Region V Air and Hazardous Materials Division.
The water sampling field work was conducted by the Eastern District Office and
the bioaccumulation study was conducted by the MDNR and Central Regional
Laboratory. The Region V Quality Assurance Office reviewed and approved all
analytical protocols. The Central Regional Laboratory managed all laboratory
contracts and provided quality assurance audits of the analytical contractors.
The term "dioxin" is often used to describe 2,3,7,8-tetrachloro dibenzo-p-
dioxin (2,3,7,8-TCDD). The isomer 2,3,7,8-TCDD is the most toxic of the dioxin
isomers. In this report, the term "PCDDs" means all polychlorinated dibenzo-p-
dioxin isomers and "PCDFs" means all polychlorinated dibenzofuran isomers.
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i
DQW CHEMICAL CO.
i'2
TITTABAWASSEE RIVER BASIN
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II. OBJECTIVES
The primary objective of this study is to quantify the conventional, non-
conventional, toxic organic and toxic inorganic pollutant discharges from the
Dow Chemical - Midland Plant. This information and data will be used to
develop a Best Available Technology (BAT) NPDES permit for Dow Chemical.
The permit conditions are likely to include specific effluent limitations for
certain organic pollutants; the regulation of others through the use of indicator
pollutants; a compliance schedule for additional in-process controls and end-of-
pipe treatment; and, conventional and special monitoring requirements.
Secondary objectives include: (1) a determination of the types and the
extent of bioaccumulation of pollutants discharged by Dow Chemical in fish;
(2) sub-part per trillion analyses of effluent samples for PCDDs and PCDFs;
(3) development of information on contamination of fish, sediment, and water in
the Tittabawassee River; and (4) analyses of native fish from the Grand River for
PCDDs and PCDFs.
IIL SCOPE OF WORK
To accomplish the study objectives, a multi-phased field program was
planned in the spring and summer of 1981 and executed in late summer and early
fall of 1981. Field programs included the following: (1) a sediment survey of the
Tittabawassee River to determine whether significant toxic pollutant contami-
nation of the sediments has occurred; (2) four 24-hour composite samples of Dow
Chemical water intakes and effluent discharges to determine pollutant
discharges at the low parts per billion range; (3) one large-volume 24-hour
composite sample of Dow Chemical water intakes, certain effluent discharges,
and the receiving water to determine discharge rates of dioxin and furan
compounds in the sub-part per trillion range; (4) a static daphnia bioassay and an
algal assay to determine whether or not the Dow Chemical main process
wastewater effluent exhibits acute toxic effects or stimulatory effects on algal
growth; (5) an Ames test of the main process wastewater discharge to determine
whether the effluent exhibits mutagenic properties; (6) a fish bioaccumulation
study to determine the level and rate of bioaccumulation of pollutants discharged
by Dow Chemical; and, (7) analyses of native fish from the Grand River for
organic compounds.
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IV. FINDINGS AND CONCLUSIONS
A. Based upon the results of this study, the Dow Chemical - Midland Plant
contributes the following discharges to the Tittabawassee River:
Net
Annual Discharge
in Excess of
Total Dissolved Solids 125,000 Tons
Chlorides 60,000 Tons
Sulfates 10,000 Tons
Chemical Oxygen Demand 5,000 Tons
Total Organic Carbon 700 Tons
Total Kjeldahl Nitrogen 275 Tons
Ammonia-Nitrogen 250 Tons
Phosphorus (as P) 40 Tons
Toxic Organic Pollutants 6 Tons
Toxic Metal Pollutants 4 Tons
Phenols (4AAP) 1 Ton
More than 40 toxic organic chemicals were identified and quantified in the main
process wastewater discharge from Outfall 031. Most were found in the low
parts per billion range. A number of organic chemicals were identified but not
quantified. Thus, the total discharge of organic pollutants is probably
considerably higher than the amount listed above. The effluent does not contain
a significant amount of readily biodegradable carbonaceous material. The toxic
metals analyzed were found in the low parts per billion range, generally at
concentrations below most ambient water quality criteria. Dow Chemical did
not report any abnormal operations of the wastewater treatment facilities or
process-related spills during the surveys.
B. The results of the large-volume water sampling for polychlorinated
dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans and the bioaccum-
ulation study demonstrate that the discharge from Dow Chemical is a source of
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PCDDs and PCDFs in the Tittabawassee River/Saginaw Bay system. The isomer
2,3,7,8-TCDD was positively identified in the discharge from Outfall 031 at a
concentration of 50 parts per quadrillion (ppq) and in the plume of Outfall 031 in
the Tittabawassee River at a concentration of 45 ppq. Four tetrachioro dioxin
isomers were found in Outfall 005 at a total concentration of 2300 ppq and two
tetrachioro dioxin isocners were found in Outfall 031 at a total concentration of
80 ppq. The isomer 2,3,7,8-TCDD and other PCDDs detected in both
Outfalls 031 and 005 were not detected in the Tittabawassee River and Lake
Huron water intakes to the Dow Chemical plant. Outfall 031 is the main process
wastewater discharge from the plant and Outfall 005 contains the discharge from
the power house fly ash pond. The isomer 2,3,7,8-TCDF and other PCDFs were
also found in the discharges from Outfalls 005 and 031. The concentrations of all
PCDFs found in both outfalls exceeded 9000 ppq. The specific sources of these
compounds at the Dow Chemical - Midland Plant have not been identified.
If these data represent typical discharge rates, about 1/3 pound of a pound
of PCDDs and 10 pounds of PCDFs are released directly to the Tittabawassee
River on an annual basis by Dow Chemical. The discharges of PCDDs, PCDFs,
and other organic pollutants measured during this survey are probably less than
would have been found in the past owing to process and production changes made
by Dow Chemical prior to this survey.
C. The complete results from the caged fish bioaccumulation study are not
available at this writing. Herbicide analyses for all sampling stations are not
complete, and data for PCDDs and PCDFs are not available for certain stations.
The available data for PCDDs and PCDFs demonstrate that PCDDs and
PCDFs discharged by Dow Chemical concentrate in fish held in a mixture of the
discharge from Outfall 031 and the Tittabawassee River at the point of
discharge. Levels of 2,3,7,8-TCDD reached 100 ppt (0.1 ppb) in whole fish, while
the concentration of all PCDD isomers ranged from 820 to 1280 ppt (0.82 to
1.28 ppb). The FDA guideline for 2,3,7,8-TCDD is 50 ppt in edible portions of
fish. There are, as yet, no guidelines for other PCDD isomers. PCDDs were not
found in fish held at various points upstream of the Dow Chemical plant or in
unexposed fish at concentrations greater than 8 ppt. Data are not yet available
for fish held downstream of the plant. PCDFs were found in the fish exposed to
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the discharge of Outfall 031 at levels ranging from 6480 to 17,200 ppt (6.48 to
17.2 ppb). Upstream control fish showed relatively little contamination by
PCDFs (8 to 290 ppt).
More than 30 other organic chemicals were also found in fish exposed to the
plume of Outfall 031 at levels ranging from a few ppb to over 1 ppm. These
chemicals include chlorinated benzenes and phenols, and certain pesticides.
D. The discharge from Outfall 031 was found not be acutely toxic to
Daphnia magna over one 48-hour static bioassay testing period; and, not acutely
toxic to catfish held continuously for 28 days in a mixture of the discharge and
the Tittabawassee River at the point of discharge. Native fish often have been
observed in the plume of the discharge. The discharge did not exhibit mutagenic
properties in one series of Ames tests (direct test and RLEA test). Based upon
one algal assay, the discharge from Outfall 031 has a higher stimulatory effect
on algal growth than the river intake water. Although the discharge was found
not to be acutely toxic, given the number and type of compounds discharged, the
potential chronic or long term effects of the discharge are still of concern.
E. The current practice at Dow Chemical is to mix and treat large volumes
of cooling water with the process wastewaters, thus diluting the concentrations
of pollutants found in the process wastewaters. Because of the relatively low
concentrations of most of the organic chemicals discharged by Dow Chemical,
the most effective method to achieve further reduction in the mass discharge of
these pollutants is to isolate the contributing sources at the production process
unit and provide, where appropriate, additional process-specific pretreatment
facilities. At this writing, Dow Chemical has not provided sufficient information
and data to EPA and the MDNR for evaluation of alternate pollution control
measures.
V. RECOMMENDATIONS
A. The sources of PCDDs, PCDFs, and the other organic chemicals found
in Outfall 031 should be identified. Likewise, the source of PCDDs and PCDFs
found in Outfall 005 should be determined. Additional testing for PCDDs and
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PCDFs at similar and different industrial and municipal facilities should be
conducted to determine the potential for widespread low-level discharge of these
compounds from other sources. Comprehensive multi-media investigations
covering atmosphere emissions, deposition on soil, solid wastes, and untreated
and treated wastewater should be conducted at selected industrial sites,
including Dow Chemical, to determine the pathways to the environment for
PCDDs and PCDFs.
B. The feasibility of additional in-process, end-of-process, and end-of-pipe
treatment at Dow Chemical should be established where appropriate.
C. The remaining fish data for herbicides, PCDDs, and PCDFs should be
obtained as soon as possible.
D. EPA and MDNR should obtain and evaluate Dow Chemical data for split
samples provided to Dow Chemical from this survey.
E. Dow Chemical should document the effect on the discharge of any
changes in production operations, air pollution control, or wastewater treatment
operations that have occurred since this study was completed.
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VI. DOW CHEMICAL - MIDLAND PLANT
A. General Plant Description
The Dow Chemical - Midland Plant is an operating unit of the Michigan
Division of Dow Chemical USA. The facility is located in Midland, Michigan, and
extends along both banks of the Tittabawassee River (see Figure 2). The Midland
Plant is one of the largest chemical manufacturing complexes in the United
States and is operated continuously. About 5000 people are employed at the
plant. The following types of chemicals are produced:
1. Alkalies and Chlorine
2. Cyclic Intermediates
3. Industrial Organic Chemicals
4. Industrial Inorganic Chemicals
5. Plastic Materials, Synthetic Resins, and Non-Vulcanizable Elastomers
6. Medicinal Chemicals and Botanical Products
7. Surface Active Agents, Finishing Agents, and Sulfonated Oils
8. Pesticides and Agricultural Chemicals
Dow Chemical discharges contact and non-contact cooling waters, storm
water runoff, and treated process and sanitary wastewaters to the Tittabawassee
River through five outfalls. In addition to the wastewaters generated at the
Midland Plant, the company also treats wastewater from other industries. These
include about 1.7 MGD of process wastewaters from the nearby Dow Corning
silicone products facility; about 0.18 MGD of sanitary and laboratory waste-
waters from the Consumers Power Midland Nuclear Plant; about 0.02 MGD of
truck washing wastewaters from the Chemical Leaman and Coastal Trucking
Line at Midland; and, about 500 gallons per day of leachate from the Dow
Chemical Salzburg Road landfill.
According to Dow Chemical's most recent NPDES permit application, the
average daily wastewater flows from these outfalls are as follows:
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FIGURE 2
MIDLAND
LE9CNO
SCOIMCNT *AM^I_IH« STATIONS
WATER SAMPLING STATIONS
10
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Outfall 005 - 3.9 MGD
Outfall 012 - 30.0 MGD
Outfall 01* - 0.7 MGD
Outfall 015 - 0.3 MGD
Outfall 031 - 26.5 MGD
Total - 61.* MGD
The average discharge for Outfall 031 on the sampling dates for this survey was
35.* MGD. Most of the discharge is comprised of Tittabawassee River water
diverted at the Dow Dam into the plant for process and cooling purposes. Other
intake water sources include the city of Midland (1.* MGD) and Lake Huron
(10.5 MGD). Lake Huron water is chlorinated and demineralized prior to use in
various processes. The other intake waters are generally not treated prior to
use.
A description of the sources of effluent discharged through the outfalls
active during the EPA-MDNR survey is presented below:
Outfall 002 - At the time of the survey, the discharge was about 5 MGD
to the Tittabawassee River via Lingie Drain. The discharge has since been
diverted to the wastewater treatment facilities tributary to Outfall 031.
The discharge consisted of untreated non-contact cooling water from coolers
and heat exchangers in the monomer and polymer plastic production area
and various hydrocarbon production processes.
Outfall 005 - The discharge from this outfall is overflow from an ash
pond serving the power house. Cooling water, general use water, and boiler
blowdown are also diverted to the ash pond. The discharge is to the
Tittabawassee River via Ashby Drain.
Outfall 012 - Dow Chemical refers to this outfall as the "H" flume.
Non-contact cooling water from the west power house condensers and excess
river water are discharged directly to the Tittabawassee River.
Outfall 031 - This discharge consists of treated process wastewaters,
cooling water, water softener backwash, cooling tower blowdown, incin-
erator scrubber water, sanitary wastewaters, surface water runoff, and
landfill leachate. Treatment is provided in an end-of-pipe biological
11
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treatment facility followed by a large settling pond called the tertiary pond.
The discharge is from the tertiary pond to the Tittabawassee River. Dow
Chemical has also installed numerous in-process product and by-product
recovery systems and pollution control systems. However, the company has
provided only limited information to EPA and MDNR about the processes
and the treatment systems. According to MDNR records, Dow Chemical
made several process modifications in the period 1978 to 1981 which were
designed to improve the discharge from Outfall 031.
Other active Dow Chemical outfalls not described above include
Outfalls 001, 014, and 015. Outfall 001 serves as a standby for Outfall 031.
Outfalls 014 and 015 convey air conditioner cooling water from the plant
administration building directly to the Tittabawassee River. These outfalls were
not sampled during the EPA-MDNR survey.
B. Waste Management at the Dow Chemical - Midland Plant
Solid and liquid wastes generated at Dow Chemical and wastewaters
received from outside sources are disposed of by one of four methods:
(1) concentrated liquids and burnable solid wastes are incinerated; (2) "biodegrad-
able" dilute liquids and a substantial volume of cooling water are processed in the
wastewater treatment facilities tributary to Outfall 031; (3) non-biodegradable
dilute liquids are injected in one of several deep-wells; and, (4) non-burnable solid
wastes are landfilled.
Wastewater Treatment Plant - "Biodegradable" dilute liquids (process and
sanitary wastewaters) are separated into two categories - phenolic wastewaters
and other organic wastewaters. Figure 3 is a schematic diagram of the biological
treatment systems used to treat these wastewaters. Wastewaters from the
phenolic processes are pumped to the phenolics pretreatment system, where
suspended solids are removed by primary clarification. The wastewaters are then
processed in trickling filters and an activated sludge system operated in series.
After final clarification, the phenolic plant effluent is directed to the larger
biological treatment facility for further treatment with all of the remaining
wastewaters described above.
12
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The wastewaters are collected and directed to primary settling tanks where
suspended solids are removed. Wastewaters high in BOD and toxic wastewaters
can be diverted to a "shot" pond during spills or emergencies and metered into
the treatment system at a controlled rate. The overflow from the primary tanks
is combined with the effluent from the phenolics treatment plant prior to
entering activated sludge aeration basins for biological treatment. From the
aeration basins, the wastewater is fed to secondary clarifiers. Settled activated
sludge is recycled to the aeration basins. Effluent from the secondary clarifier is
pumped to the teritiary pond, which is about 200 acres in area and has a
maximum capacity of about 600 million gallons. The retention time in the pond
provides for temperature equalization and continued biological action. The
effluent from the tertiary pond is discharged to the Tittabawassee River through
Outfall 031.
Primary sludge from the biological treatment facility is pumped to clay pits
located near the intersection of Saginaw and Salzburg Roads and dewatered. The
dewatered sludge is ultimately disposed of at Dow Chemical's Salzburg Road
landfill. The supernatant from the clay pits is returned to the wastewater
treatment plant. Sludge from the phenolic treatment system is either recycled
or processed in the other biological treatment system. Secondary sludge from
the biological treatment system is thickened, filtered and incinerated.
Incineration - The incineration area includes a rotary kiln (refuse burner) and
a tar burner (thermal oxidizer). The tar burner is a standby unit for the rotary
kiln. The tar burner operates at 1000°C in a single combustion chamber with a
retention time of about 2 seconds. Only liquids or gases are incinerated in this
unit. The liquid feed rate is 7.5 gpm. The refuse burner is fed solid and liquid
wastes. The rotary kiln or primary combustion chamber provides about 45
minutes retention at 600-800°C. Exit gases are routed to a secondary
combustion area where they are subjected to 1000°C at a retention time of about
2 seconds. The refuse burner is fired with tars or natural gas. Both units have
qualified for interim status under RCRA.
Incinerator ash is landfilled at the Salzburg Road landfill. Incinerator stack
gases are scrubbed with effluent from the wastewater treatment system. The
scrubber effluent is then returned to the wastewater treatment system.
13
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Landfill - Dow Chemical has been operating a landfill located on Salzburg
Road since January 1981. The landfill was approved by MDNR for hazardous
waste disposal on February 10, 1982, and has qualified for interim status under
RCRA. As noted above, incinerator ash, wastewater treatment sludges,
contaminated soil, and demolition material are currently landfilled at this site.
Leachate collected from the landfill is diverted to the wastewater treatment
plant.
Disposal Wells - Dow Chemical disposes of a small volume of process
wastewaters by deep well injection. These wastewaters cannot be readily
treated by other means. About 18 gpm are passed through sand filters and then
pumped into the receiving underground formation. Dow Chemical had operated
as many as seven deep disposal wells and had disposed of as much as 120 gpm in
this fashion in the past. Wastewaters disposed of by deep well injection contain
several organic compounds and are typically high in dissolved salts. According to
the MDNR critical materials list for the disposal wells submitted by Dow
Chemical, some of the compounds injected are benzenes, dioxins, phenols,
metals, PCBs, styrene, chloroform and others.
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FIGURE 3
- " MICHIGAN DIVISION
WASTE TREATMENT PLANT (UTP)
Phenolic
Severs
Strong
Equalization
Weak Phenol
Recycle
Mixing and
pH Control
General
Sewers
1 -
I"*™* ' r^,
r~-
>
pH
\
j
Shot
Pond
Grit Reraoval and
Bar Screens
rr
incineration
_aod Landfill
Pressure
Filter
f&—
Tittabawassee
River
MIDLAND WASTE WATER TREATMENT PLANT
THE DOH CHEMICAL COMPANY U.S.A.. MICHIGAN DIVISION
15
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VIL FIELD STUDIES
A. Sediment Sampling
A sediment survey of the Tittabawassee River from 0.5 miles upstream of State
Route M-20 downstream to Smith's Crossing Road was conducted on March 18-19, 1981.
River sediment grab samples were obtained for analysis at eight locations shown on
Figure 2. The locations of the sampling sites for the water sampling survey described
below are also presented in Figure 2. Each sediment sampling site is described in Table 1.
Because the stream bottom is mostly sand and gravel, an attempt was made to select sites
which appeared to have accumulations of organic material. For this reason, the samples
do not represent average or typical Tittabawassee River sediment quality. However, the
data obtained do provide an indication of the types of compounds discharged in the area
that accumulate in sediments. The results presented in Appendix A show that more than
40% of the compounds positively identified and quantified were either benzenes or
benzene derivatives. Also, more than 90% of the compounds detected were found in
samples obtained at sampling stations which are near or downstream of Dow Chemical -
Midland Plant discharges. Only one compound, di-n-octylphthalate, was identified
upstream of the Dow Dam. Several unidentified compounds were detected in some of the
sediment samples. Given the nature of the sediments and anticipated discharge levels of
PCDDs and PCDFs from Dow Chemical, the sediment samples were not analyzed for
PCDDs or PCDFs.
B. Conventional Water Sampling Program
During September 1981, four 24-hour composite sampling programs were conducted at
the Dow Chemical - Midland Plant. The sampling dates, the water intakes, and selected
effluent discharges sampled are listed below:
Survey Sampling Stations
Number Date Intakes Outfalls, Other
1
2
3
I_/h*bW *» « fcfcAl^^fcJ ~>^f V» WA^fcAA** J -^ W* <^*
September 1-2, 1981 LH, TR* 002, 005, 012, 031, 031P**, DC***
September 9-10, 1981 LH, TR 005, 031, 03IP, TRSC****
September 15-16, 1981 LH, TR 031, 031P, DC
September 29-30, 1981 LH, TR 031, 03IP
* TR - Tittabawassee River Intake
LH - Lake Huron Intake
** 031P - Plume of Outfall 031 in the Tittabawassee River
*** DC - Untreated Wastewater From Dow Corning
**** TRSC - Tittabawassee River at Smith's Crossing Road
16
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Outfalls 014 and 015 were not sampled since the discharge from these outfalls is office
building air conditioning water. The samples obtained from each of the above listed sites
were analyzed for conventional pollutants, non-conventional pollutants, toxic metal
pollutants, and toxic organic pollutants. Various physical measurements were also made
during each 24-hour sampling period. The gross discharges from Outfall 031 are
summarized below. The complete data will be included in the final report. A summary of
the gross pollutant loadings at each point sampled is presented in Appendix B.
1. Conventional and Non-Conventional Pollutants, Nutrients, Dissolved Salts
Outfall 031
(Gross Discharge in Pounds/Day)
Survey
Pollutants
1
Total Dissolved Solids
Chloride
Fluoride
Sulfate
Total Suspended Solids
Chemical Oxygen Demand
Total Organic Carbon
Total Kjeldahl Nitrogen
Ammonia-N
NO2 and NO3-N
Phosphorus (P)
810,000
340,000
200
87,000
1,450
34,500
4,640
1,860
1,640
115
130
790,000
358,000
200
81,000
2,600
29,200
6,060
1,450
2,070
1,750
104
320
676,000
303,000
160
64,000
3,640
38,500
5,460
1,370
1,700
1,310
11
420
960,000
428,000
190
75,000
7,130
41,300
7,880
1,500
1,630
1,180
41
146
The discharge from Outfall 031 carries high loadings of dissolved salts to the
Tittabawassee River (total dissolved solids concentrations ranging from about 2,800 to
3,000 mg/1; chloride concentrations ranging from about 1,200 mg/1 to 1,300 mg/1; sulfate
concentrations ranging from about 280 to 300 mg/1). The discharge contains relatively low
18
-------
levels of suspended solids and readily biodegradable material. As noted in Section C, the
discharge of nutrients can have a stimulatory effect on algal growth.
2. Toxic Metal Pollutants
Survey
Total Metals
Outfall 031
(Gross Discharge in Pounds/Day)
1
Arsenic
Cadmium
Chromium
Copper
Lead
Zinc
2.30
0.58
18.0
0.87
3.60
1.40
26.8
3.20
23.2
3.75
1.13
39.4
Based upon these data, the discharge of the above toxic metals from Outfall 03 1 does not
appear to be of concern from a water quality standpoint. Typical effluent concentrations
are as follows: arsenic (ND to 3 ppb); cadmium (ND); chromium (8 to 14 ppb); copper (ND
to 5 ppb); lead (ND); and zinc (60 to 100 ppb).
3. Toxic Organic Pollutants
Outfall 031
(Gross Discharge in Pounds/Day)
Survey
a. Volatile Compounds
( B-l , 3 , 4 ) Methylene chloride
1 , 1 -Dichloroethylene
1 , 1 -Dichloroethane
26.12
0.87
1.31
No Sample
1.30
0.70
1.00
45.00
5.25
1.80
19
-------
Survey 1* 2 3 4
(B-1,3,4) Chloroform 2.87 No Sample 3.00 9.38
(3-1,3,4) 1,2-Dichloroethane 2.41 " 2.00 3.75
1,1,1-Trichloroethane 0.92 " 1.02 4.13
Carbon Tetrachloride 3.78 " 2.10 18.77
(B-4) Bromodichloromethane 0.83 " — 1.24
1,2-Dichloropropane 0.55 " 0.90 1.91
Trichloroethylene 0.35 " 0.60 1.39
Dibromochloromethane 1.04 " — 4.88
1,1,2,2-Tetrachloroethane 1.13 " 0.80 7.51
Chlorobenzene — " 1.00
Bromoform --- " — 4.50
* Average of two grab samples for volatile compounds.
(B-1,3,4) Blank Contamination - Surveys 1,3,4
(B-4) Blank Contamination - Survey 4
b. Base/Neutral Compounds
Pyrene —- --- 0.27
2-Chloronaphthalene 0.26 —- • —- —
1,2-Dichiorobenzene Trace Trace Trace —
1,3-Dichlorobenzene 0.41 0.41 0.13 0.71
1,4-Dichlorobenzene 0.64 0.29 0.19 0.75
1,2,4-Trichlorobenzene 1.19 0.58 0.32 1.39
(B-1,4) Di-n-butyl phthalate 0.21 — — 0.21
Butyl benzyl phthalate — — — Trace
(B-2,3) Bis(2-ethylhexyl) phthalate 21.2 60.6 7.1 3.42
Bis(2-chloroethyl) ether 0.04 0.28 0.25 1.28
(B-4) Isophorone — Trace Trace —
Dioctyl phthalate — 2.05 — —
Acenaphthene — — — 0.17
(B-1,4) Blank Contamination - Surveys 1 and 4
(B-2,3) Blank Contamination - Surveys 2 and 3
(B-4) Blank Contamination - Survey 4
20
-------
Survey 1 2 3 4
c. Acid Compounds
2-Chlorophenol 0.28 Trace Trace Trace
Phenol 0.28 — - Trace Trace
2,4-Dichiorophenol 0.35 — 0.26
2,4,6-Trichlorophenol 1.25 — Trace
Pentachlorophenol 4.35 0.55 —- 0.94
d. Herbicides
Dichloroprop —- --- 0.02 0.22
2,4-D 0.01 — 0.30
Silvex — 0.03 . 1.60 2.14
2,4,5-T — — 0.40 0.18
e. Pesticides, PCBs
(B-l) Aldrin 0.06 0.06 —- 0.21
(B-l) 4-4--DDD 0.01* —- — 0.01*
Endosulfan I 0.03*
Endrin aldehyde 0.01* 0.02* — 0.01*
Heptachlor epoxide 0.01 0.01* — 0.02**
B -BHC —- 0.01 -— .
Y-BHC — — — 0.01*
PCB-1242 — — 1.10
PCB-1254 — — 0.09
PCB-1260 — — 0.20
* Not confirmed on second column GC/ECD.
** Not confirmed on second column GC/ECD due to interference.
(B-l) Blank Contamination - Survey 1
21
-------
f. Other Organic Compounds
The concentrations of the compounds listed below were determined by the analyst by
selecting the best fit from a computerized library search program to the mass spectra
obtained for each sample. The quantitation of these compounds was not accomplished
using a pure standard of each compound, but was calculated against the response of an
internal standard. Thus, the pollutant loading data and identification of each compound
presented below are considered tentative.
1) Volatile Compounds
Survey 1* 2 3 4
Methane, dimethoxy 3.77 No Sample 21.90 45.04
Ethane, l,l'-oxy bis 43.52 " 6.60 13.14
Methane, oxy bis 25.63 " — 4.13
* Average of two grab samples for volatile compounds.
2) Extractable Compounds
2-Propanol, l(2-methoxy-l
methylethoxy), or isomers 4.10 2.20 3.40 19.89
2,5-Cyclohexadiene-l ,4-dione,
2,6-Bis( 1,1 -dimethylethyl)
isomers 0.90 — — —
Pentanone, hydroxy methyl — — 1.30 —
2-Propanol, l-(2-methoxy,
propoxy) — 101.30
1-Propanol, 2-(2-hydroxy,
propoxy) — 60.05
Benzamide, N-butyl — — — 2.70
Oxy bis propanol — — — 33.03
22
-------
The discharge from Outfall 031 contains more than 50 organic chemicals including volatile
compounds, base/neutral compounds, acid compounds, pesticides, PCBs, and herbicides.
Most of the compounds were detected at concentrations in the low and sub-ppb range. If
lower levels of detection were available, it is likely more chemicals would have been
found, particularly those found in the untreated wastewaters (such as the Dow Corning
effluent). While the effluent is not acutely toxic (see Section C), the continued net
discharge of more than 35 ibs/day of toxic organic chemicals to the environment is of
concern. Methylene chloride and discharges of those chemicals listed in item f above
were.not included in this estimate. On an annual basis, 35 Ibs/day is equivalent to over
6 tons/year.
• C. Static Daphnia Bioassay, Algal Assay, Ames Test
1. Static Bioassay
Static bioassays, using Daphnia magna, were completed on samples obtained during
the third conventional water survey, September 15-16, 1981. The samples were obtained
from the Dow Chemical Lake Huron and Tittabawassee River Intakes, Outfall 031, and a
field blank. The bioassay was begun on September 22, 1981, and conducted according to
the protocol outlined in "Standard Operating Procedure for Static Bioassay Screening
Test," EPA Region V - Central Regional Laboratory. The results of the bioassay are
presented in Table 2.
The Lake Huron Intake sample produced 100% mortality in both aliquots. The
mortalities are due to the presence of chlorine in the sample which was not removed prior
to testing. The Lake Huron water supply is chlorinated by Dow Chemical at its lake
pumping station. The mortalities observed in the other samples, including the blank and
controls are not considered significant. The discharge from Outfall 031 on September 15-
16, 1981, did not exhibit acute toxic effects to Daphnia magna.
2. Algal Assay
A static algal assay was conducted on the same samples collected for the daphnia
bioassay. The algal assay followed the procedure, "Standard Operating Procedure for
Screening Algal Assay for Determination of Inhibiting or Stimulating Effects of
Effluents," EPA Region V - Central Regional Laboratory. The results, which are based on
a comparison to a control population, are presented below in Table 3.
23
-------
Table 2
Static Daphnla Bioassay
(Number of Survivors and Percent Mortality in Duplicate Test Aliquots)
Aliquot No. of Survivors Percent Mortality
Time (Hours)
Control
Lake Huron Intake
Outfall 031
Tittabawassee River Intake
Field Blank
a.
b.
a.
b.
a.
b.
a.
b.
a.
b.
0
10
10
10
10
10
10
10
10
10
10
24
9
9
0
0
10
10
9
10
8
7
48
9
9
0
0
10
10
9
10
s
0
0
0
0
0
0
0
0
0
0
0
0
24
10
10
100
100
0
0
10
0
20
30
48
10
10
100
100
0
0
10
0
20
100
-------
Table 3
Static Algal Assay
Sample Effect
Lake Huron Intake Inhibition 51.3%
Tittabawassee River Intake Stimulation 63.9%
Outfall 031 Stimulation 191.6%
Field Blank Stimulation 102.8%
The Lake Huron sample inhibited algal growth because of the chlorine present in the
sample. The discharge from Outfall 031 and the field blank showed high stimulatory
effects on algal growth. The effect produced by the discharge from Outfall 031 is about
twice that of the field blank and three times higher than the Tittabawassee River
upstream of Outfall 031. This is due to the level of nutrients in the discharge. The
observed stimulatory effect in the field blank is believed to be a result of low level
nutrient concentrations present in the sample, possibly the result of the bottle preparation
or the distilled water used to make up the blank.
3. Ames Test
The Ames Test was used for the purpose of determining whether the discharge from
Outfall 031 exhibits mutagenic properties. This test was conducted on the samples
described above. For each sample, a concentrated sample extract (100X) was used to
conduct a direct test and a rat liver enzyme activation (RLEA) test for five bacteria test
strains. No mutagenic activity was found in either the direct or the RLEA test.
D. Large Volume Water Sampling for PCDDs and PCDFs
A pilot study was conducted for EPA-Region V by Wright State University to develop
a sampling and analytical method to determine PCDDs and PCDFs in aqueous samples in
the sub-part per trillion range. In short, this method consists of obtaining a large volume
water sample; performing an extraction with a suitable solvent for an extended period;
solvent exchange and clean-up; and HRGC-HRMS analyses of the extract for the desired
25
-------
compounds. After completion of the pilot study, actual effluent and river samples were
obtained. Based upon the quality control completed with the pilot study and with the
analyses of the field samples, all of the data for PCDDs and PCDFs presented below are
considered to be of acceptable quality. Reference is made to Appendix C for a summary
of the analytical methodology and quality control for the large volume sampling study.
One 24-hour composite water sample was taken at each of the following points and
extracted and analyzed for polychlorinated dibenzo-p-dioxins and poiychlorinated dibenzo
furans in accordance with the protocols summarized in Appendix C. Dow Chemical was
provided split samples for its analysis along with the extraction and analytical protocols.
Dow Chemical - Midland Plant
. Lake Huron Water Intake
. Tittabawassee River Intake
. Outfall 005 (Power House Fly Ash Pond)
. Outfall 031 (Main Process Wastewater Discharge)
Tittabawassee River
. Outfall 031 Plume
. At Smith's Crossing
The results from this study are presented graphically in Figures 4 and 5 for dioxins,
and Figures 6 and 7 for furans. The data are presented in Appendix D.
1. Dioxins
Neither 2,3,7,8-TCDD nor any other dioxin isomers were found in the water intakes to
the Dow Chemical Plant at the 10 parts per quadrillion (ppq) level. 2,3,7,8-TCDD was not
detected, but may have been present in Outfall 005. The high levels of other tetrachloro
isomers may have obscured the response of the 2,3,7,8 isomer in that sample. The
combined concentration of five other tetrachloro isomers found in the discharge from
Outfall 005 exceeded 2000 ppq (the mass discharge to the Tittabawassee River was about
7 x 10~ Ibs/day). None of the penta-, hexa-, hepta-, or octachloro isomers were detected
in Outfall 005.
2,3,7,8-TCDD was positively identified in the discharge from Outfall 031 at a level of
50 parts per quadrillion (mass discharge of between 1 and 2 x 10" Ibs/day). The total
26
-------
mass discharge of the two tetrachloro isomers found in Outfaii 031 was in excess of
2 x 10~ Ibs/day. 2,3,7,8-TCDD, an additional tetrachloro isomer, and one pentachloro
dioxin isomer were found in the discharge plume of Outfall 031 in the Tittabawassee River
in the range of 35 to 50 parts per quadrillion. Three tetrachloro isomers, not including
2,3,7,8-TCDD, were found downstream in the Tittabawassee River at Smith's Crossing
Road at a total concentration of '40 parts per quadrillion.
2. Furans
The results for polychiorinated dibenzo furans are similar to those for dioxins
although furans were detected at higher levels. Both the Lake Huron and Tittabawassee
River water intakes contained detectable quantities of 2,3,7,8-TCDF and a few other
isomers at less than 100 ppq, while the discharges from Outfalls 005 and 031 contained
significantly higher concentrations of 2,3,7,8-TCDF (about 1700 ppq and 800 ppq,
respectively) and other tetra- and penta- chloro isomers (several thousand ppq for both
outfalls). The discharge from Outfall 005 may have influenced the results for the
Tittabawassee River intake sample as the outfall empties into the river upstream of the
intake. The mass discharge of all furan isomers from Outfall 005 was about
33 x 10~5 Ibs/day, and nearly 300 x 10~5 Ibs/day from Outfall 031. PCDFs were also found
in the Outfall 031 plume and downstream in the Tittabawassee River at Smith's Crossing.
27
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E. Bioaccumulation Study
A bioaccumuiation study was conducted in the Tittabawassee River around the Dow
Chemical - Midland Plant to determine which toxic organic chemicals discharged by Dow
Chemical bioaccumulate in fish exposed to the effluent. Caged catfish were exposed to
the plume of Dow Chemical's process wastewater effluent (Outfall 031) in the
Tittabawassee River for a period of 28 days. Whole fish were analyzed after various
periods of exposure for PCDDs, PCDFs, and other organic compounds. The caged fish
were fed during the experiment to maintain their body weight and general health. All of
the fish were acclimated in a laboratory prior to the study. Caged fish were also exposed
to the Tittabawassee River both upstream and downstream of Dow Chemical to establish
appropriate controls and reference points. At the request of the MDNR, caged fish were
placed in the Grand River at Jones Road near Grand Ledge, Michigan and analyzed with
native fish from the Grand River.
The original study plan called for exposing the fish directly to Dow Chemical's
process wastewater effluent at the outlet of the tertiary pond just upstream from
Outfall 031 and also analyzing native fish from the tertiary pond. However, Dow
Chemical objected, contending that EPA's legal authority under Section 308 of the Clean
Water Act does not extend to such activities. Rather than engage in lengthy arguments,
and possibly litigation, over this matter, the study plan was modified to place the caged
fish in the plume of Outfall 031 in the Tittabawassee River rather than in the outlet of the
tertiary pond. Based upon conductivity and dissolved solids measurements of the
discharge from Outfall 031 and the plume, the fish in the plume were exposed to the
outfall discharge diluted at or less than 1:1 by river water.
The locations at which caged fish were exposed are listed below and shown on
Figure 8.
Station
Number Location
Control - Central Regional Laboratory
A Tittabawassee River Upstream of Sanford Dam
1 Tittabawassee River at Poseyville Road
2 Tittabawassee River Downstream of Dow
Dam but Upstream of OutfalJ 031
32
-------
Figure 8
Pine River Confluence
2.8 Miles Upsfreom
MIDLAND
DOW-
CHEMICAL
STATI0 N A
Sanford
Lake
Tittabcwassee
River
SANFORD
STATION .B
• Road
6 miles to v
GRAND \
LEDGE
33
Gordonville Rood
-------
3 Tittabawassee River in Outfail 031 Mixing
Zone (Plume)
^ Tittabawassee River Outside of the Outfall 031
Mixing Zone (About 1.98 Miles Downstream
from the Dow Dam)
5 Tittabawassee River About 2.65 Miles
Downstream from the Dow Dam
B Grand River at Jones Road near Grand Ledge,
Michigan
The final report of this study will present a detailed account of the bioaccumulation
study, including the field and analytical protocols followed. The results available at this
writing are summarized in Figures 9 to 15. Because of the high cost for contract analyses
for PCDDs and PCDFs, Region V limited the initial set of analyses to selected samples.
These included the fish food, control fish, and caged fish exposed for 28 days at
Stations A, B, 1, and 3. Based upon the results presented here, analyses for selected
samples at Stations 2, 3, 4, and 5 for dioxins and furans are now being completed.
Analyses for other toxic organic chemicals except herbicides have been completed. The
herbicide analyses should be available in the near future. Except as noted, the data
presented below are considered by EPA to be valid data based upon the quality control
work completed. Reference is made to Appendix E for all of the data available at this
writing from the bioaccumulation study. Reference is made to Appendix F for a summary
of the analytical protocols and quality control for the analyses of PCDDs and PCDFs in
fish.
All of the results presented below are based upon analyses of the whole fish.
Separate analyses of fish filets or fatty tissue were not completed. Dow Chemical was
provided with split samples of the ground fish for its analyses.
1. Dioxins and Furans
Figure 9 illustrates that 2,3,7,8-TCDD was found in fish exposed for 28 days in the
plume of Outfall 031 at levels of about 100 parts per trillion (ppt). The total
concentration of tetrachloro PCDD isomers found was about 800 ppt. Also, three
pentachloro PCDD isomers were found in a duplicate sample (second fish) at a total
-------
concentration of about 500 ppt. 2,3,7,3-TCDD was found at 7 ppt (near the detectable
level of 5 ppt) in the control fish and at 8 ppt in the fish held for 28 days at Station 1
upstream from Dow Chemical. No PCDD's were found in the fish food, a duplicate Day 28
sample from Station 1, and at Station B (Grand River). These data and those from the
large volume sampling study demonstrate that Dow Chemical discharges 2,3,7,8-TCDD
and other dioxin isomers to the Tittabawassee River and that these compounds can
concentrate in fish to levels in excess of the FDA guideline for 2,3,7,8-TCDD of 50 ppt.
The results for furans are similar in that relatively little or no furans were found
except in the fish exposed to the Outfall 031 plume (see Figure 10). The levels of furans
found were about an order of magnitude higher than the levels of dioxins. It is noteworthy
that the caged fish in this study were not exposed to bottom sediments at any station.
Thus, the fish were not able to feed from the bottom as do certain species of native fish.
This should be considered when comparing these data to data obtained from native fish
which may be exposed to dioxins, furans, and other compounds in bottom sediments.
Figures 11 and 12 present PCDDs and PCDFs for native fish obtained from the Grand
River at Jones Road and Francis Road by the MDNR. These data show 2,3,7,8-TCDD was
found in the Jones Road fish at a concentration of 20 ppt and one pentachloro isomer was
found at a concentration of 25 ppt. PCDDs were not found in the fish sample from
Francis Road. 2,3,7,8-TCDF was found at 40 ppt in the Jones Road fish. In all, seven
tetrachloro dibenzo furan isomers were found at a total concentration of 230 ppt; four
pentachloro isomers at 140 ppt; and, two hexachloro isomers at 30 ppt. For the fish
obtained at Francis Road, one tetrachloro isomer other than 2,3,7,8-TCDF was found at a
concentration of 20 ppt.
2. Base Neutral Compounds
Figure 13 summarizes the results for base neutral compounds. These data show that
fish exposed to Outfall 031 readily accumulated several base neutral compounds,
principally chlorinated benzenes (dichioro, trichloro and hexachloro). Aside from
contamination by phthaiate compounds and naphthalene and phenanthrene, the control fish
did not contain the same base neutral compounds as found in the fish exposed to
Outfall 031. 1,2,^—Trichlorobenzene was found in fish from Station 1 upstream of Dow
Chemical at a level 15 to 20 times lower than found in fish exposed to Outfall 031. The
downstream Tittabawassee River fish showed lower levels of most of the chlorinated
35
-------
benzene compounds accumulated in fish exposed to the plume from Outfall 031. The
Day 28 fish and duplicate Day 28 fish from the Grand River showed highly variable levels
of naphthalene. Chlorinated benzenes were not found in the Grand River fish.
3. Acid Compounds
The control fish showed no accumulation of acid compounds (Figure 14). However,
phenol was detected but not confirmed in fish exposed at Station A - Sanford Dam and
Station 1 - Poseyville Road. 2,4,6-Trichiorophenol and pentachlorophenol were found in
caged fish exposed at Poseyville Road for 28 days at levels of 160 and 630 ppb,
respectively. These results may be due to the influence of the Pine River which empties
into the Tittabawassee River via the Chippewa River upstream of Poseyville Road. The
Pine River is known to have contaminated sediments and receives industrial discharges.
Pentachlorophenol was found in fish exposed to the Outfall 031 plume at levels up to
1300 ppb. Phenolic compounds were not found in fish exposed at Stations 4 and 5,
downstream from Dow Chemical.
>i. Pesticides, PCBs
The data summarized in Figure 15 illustrate that the greatest number and highest
levels of pesticides were found in the fish exposed to the plume of Outfall 031. The total
weight of accumulated pesticides generally increased with time of exposure. It is
important to note that -some of the pesticides were detected but not confirmed on a
second GC/ECD column (see Appendix D). While all of the compounds may not have been
confirmed, most probably due to the complex sample matrix of the Outfall 031 discharge,
the data clearly show the discharge from the outfall results in bioaccumulation of more
compounds at higher levels than do background river stations. Some of the pesticides
were also detected but not confirmed at the background stations. Confirmation consists
of analyzing the sample on a second instrument column to positively verify the compound
identification. For purposes of the summary report, the results presented in Figure 15
should be viewed accordingly.
The control fish contained Aldrin; DDD; DDE; Dieldrin; Endosulfan I; Endosulfan
sulfate; and Heptachlor at values ranging from 5 to 34 ppb. DDD, Dieldrin, and
Endosuifan I values were confirmed. Fish exposed at Station A - Sanford Dam contained
most of the same compounds at similar levels and also a -BHC at about 6 ppb. a -BHC,
DDD, DDE, and Dieldrin were confirmed at this site. Slightly higher levels of most of the
36
-------
same compounds were detected in fish from Station 1 - Poseyville Road in addition to a -
BHC (5 to 15 ppb), Endosuifanll (21 ppb), and PC3-1248 (46 ppb). a-BHC, ODD, DDE,
and Endosulfan I were confirmed at Stations 1 and 2. Tne influence of the Pine River may
account for the higher levels and additional compounds. The data obtained at Station 2
(downstream of the Dow Dam but upstream of Outfall 031) show similar levels of most of
the same compounds found at Station 1 in addition to Endrin aldehyde and Heptachlor.
The fish exposed to Outfall 031 contained unconfirmed levels of Aldrin in excess of
200 ppb; a-BHC in excess of 200 ppb; 6 -BHC in excess of 20 ppb; Y-BHC at 16 ppb;
Endosulfan sulfate in excess of 200 ppb; and Endrin at 63 ppb. Confirmed levels of ODD
(as high as 42 ppb); DDE (as high as 65 ppb); DDT (as high as 37 ppb); Dieldrin (as high as
12 ppb); Endrin aldehyde (as high as 26 ppb); and, Heptachlor epoxide (as high as 46 ppb)
were also found in fish exposed to the plume of Outfall 031. Data obtained from fish
exposed at Stations 4 and 5 show lower levels of pesticide accumulation than did the fish
exposed in the plume of Outfall 031. Aidrin, ODD, Dieldrin, and Heptachlor epoxide were
confirmed in fish from Station 4, while a-BHC, ODD, DDE, Dieldrin, Heptachlor epoxide,
and Heptachlor were confirmed at Station 5. PCBs were not detected in any of the caged
fish held in the Tittabawassee River.
The caged fish at Station B (Grand River at Jones Road) contained confirmed levels
of a-BHC, Y-BHC, and ODD at less than 20 ppb, and unconfirmed levels of DDE,
Endosulfan I, Endrin aldehyde, Endosulfan sulfate, and Endosuifan II at less than 23 ppb.
The Grand River native fish contained much higher confirmed levels of pesticides than the
caged fish from the Tittabawassee and Grand Rivers, particularly ODD (18-300 ppb); DDE
(37-330 ppb); and DDT (48-230 ppb). The native Grand River fish also contained PCBs at
confirmed levels ranging from 160 to 1020 ppb (PCB-1254) and 160-1360 ppb (PCB-1260).
5. Other Extractable Compounds
The fish samples from the bioaccumulation study were also analyzed for extractable
organic compounds not included in the toxic (priority) pollutant list. These compounds
were determined by the analyst by selecting the best fit from a computerized library
search program to the mass spectra obtained for each sample. The quantitation of these
compounds was not accomplished using a pure standard of each compound, but was
calculated against the response of an internal standard. Thus, the concentrations
presented are considered estimates. Many of these compounds were found at levels
significantly higher than those noted above. The data are also presented in Appendix E.
37
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APPENDIX C
PCDDs and PCDFs
Methodology and Quality Control
Large Volume Sampling Study
-------
I. DIOXIN METHODOLOGY - WATEPx
The objective of this study was to analyze selected polychlorinated
dibenzofurans (PCDF) and polychlorinated dibenzo-p-dioxins (PCDD) in
water. The detection limits specified for these compounds were parts-
per-quadrillion (1 part in lO1-3 or ppq). Specific compounds which
were selected for identification included: 2,3,7,8-tetrachlorodibenzofuran
(2,3,7,8-TCDF), 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD), and
all tetra through octa chloro furan and dioxin isoraers. High resolution
gas chromatography/high resolution mass spectrometry (HRGC/HRrlS) was used
to identify and quantify these materials at the indicated trace level.
The exact masses used for each isomer class and the expected isotope
ratio used in part for identifying individual compounds, as well as
limits of detection for the water are presented in Table 1. 2,3,7,8-
tetrachlorodibenzo-p-dioxin-l3Ci2 was used as an internal standard for
quantification and recovery determinations. These recovery determinations
are found in Table 2 and were used to estimate the influence of the
matrices on the analytical measurements.
Preparation of Water Samples
The water samples were extracted and cleaned-up using the following
procedure. A ten liter aliquot of water was transferred from the
original sample bottle to a 19 liter glass bottle, and spiked with
2 ng of 2,3,7)8-tetrachlorodibenzo-p-dioxin-13C12 (2,3,7,8-TCDD-13C12).
The water aliquot and internal standard were mixed for 30 minutes
using a magnetic stirring bar. After the initial mixing, the stirring
was discontinued and one liter of hexane was added to the aliquot for
extraction of organics. The stirring was resumed and the aliquot
extracted for 16 hours. After the extraction process, the aliquot
and hexane were allowed to equilibrate for two hours. The hexane was
transferred to a 1000 ml Kuderna-Danish (K-D) flask using a 100 ml •
volumetric pipet. Distilled water was added to the bottle to force
the last 100 nil or less of hexane into the neck of the bottle which
facilitated its transfer. The K-D flasks were placed in a hot water
bath and the extracts were concentrated to a volume of 20 ml. The
extracts were transferred to 250 ml separatory funnels, using three
5 ml hexane rinses of the K-D flask. The hexane extracts were washed
three .times each in t.he following sequence: 50 ml of J.M NaOH, 50 ml
of distilled water, 50 ml of concentrated I^SO^, and finally 50 ml
of distilled water. All base, acid and water washes were collected,
neutralized and discarded. The hexane extracts were transferred to
125 ml K-D flasks, using three 5 ml hexane rinses of 250 separatory
funnels, and concentrated to a volume of 5 ml. The extracts were
introduced onto alumina columns to isolate the furan and dioxin
compound classes. The columns were eluted sequentially with 25 ml
of hexane, 25 ml of 1:1 (V:V) hexane:carbon tetrachloride, and 20 ml
of 1:1 (V:V) hexane:methylene chloride. Decane (20 ul) was added to
the hexane:methylene chloride fraction containing the furans and
dioxins, and the fraction concentrated to 20 ul prior to analyses.
-------
The extracts were analyzed by high resolution gas chromatography/
high resolution mass spectrometry (HRGC/HRMS) at a mass resolution
of 8000-12000 (M&M, 10 percent valley). A VG llodel 7070H mass
spectrometer interfaced to a Carlo Erba Model 4160 gas chromatograph
was used. The chromatographic column was a 3011 D3-5 fused silica
column with helium carrier gas. All HRGC/HRMS data were acquired
in the multiple ion detection mode using a VG Model 2035 Data System
and will be archived on magnetic tape for a period of five years.
II. QUALITY CONTROL
A. Internal Audits
The following quality assurance procedures were employed.
Perfluorokerosene was introduced through a. heated inlet for tuning,
mass calibration and establishing mass resolution. A 2 ul injection
of a test mixture containing 20 pg/ul of 2,3,7,8-TCDD and 95 pg/ul of
2,3,7,8-TCDD- C12 was analyzed. The analysis of this test mixture
provided the following information:
:6rmation concerning sensitivity (absolute response
2,3,7,8-TCDD-13C19)
0 Information
of 2,
0 Accuracy of quantification (native response as compared
to that of its C-13 analogue)
0 Elution within a specific retention time window
0 Chroma tographic peak shape symmetry.
Decane was analyzed to check for dioxin carry over. This
information is used to access performance of the instrument before
the measurement of PCDF and PCDD at trace levels is conducted in
actual samples.
The actual sample analyses were by the following procedure:
four to six samples, a duplicate or spike, an extraction blank, a
test mixture, a decane blank, then the cycle was repeated.
B. External Audits
»
• !• On-site Visit
During September 20-21, 1982, Marcia A. Kuehl , QC Coordinator
for the Central Regional Laboratory, touted the Battelle Columbus dioxin
facilities and audited the chain-of-custody documentation. She spent
a large portion of the time observing the acquisition and reduction of
the dixoin/furan data by HRGC/HRMS.
-------
The objective of this audit was to inspect whether the
analysis of Dow Study samples was conducted according to Contract #68-01-6421,
(Amendment to Work Assignment Specifications #003) and to present and resolve
any anomalous results reported by Battelle for the blind QC samples that
CRL submitted along with the actual samples.
Document Control Study
When the Dow samples arrived at Battelle, the secured shipping
and receiving area contacted the team responsible for the project. An
authorized person signed for the samples and transported them to the
Dioxin Extraction Laboratory. There the samples were unpacked and checked
against the packing list. They were then recorded in the GCA Project File
logbook along with a Battelle number. All logbook entries were of the
form XXYYZZ where XX indicates the logbook number, YY the page of entry
and ZZ the line number of the page.
Only three people had keys to the Dioxin Extraction Laboratory
and sample storage area. As the extraction of the samples proceeded, all
extraction notes were entered in the GCA Project File logbook according
to the format above. When the extracts were ready for HRGC/HRMS, they
were picked up by Dan Aichele, and all HRGC/HRMS work pertaining to the
samples was entered in the HRGC/HRMS logbook, with cross-references
to the extract numbers obtained from the GCA Project File logbook kept
in the locked Dioxin Extraction Laboratory. All computer outputs and
raw HRGC/HRMS data was filed by CRL sample number designation in a
file box kept in the HRGC/HRMS laboratory. The discs containing Dow
sample HRGC/HRMS data were also stored there.
The entire Battelle facility is a security area. In order
for visitors to gain entry, they must fill out a visitors card indicating
their affiliation and Battelle employee to be contacted. A visitor's
badge is typed which indicates that a Battelle escort is required at
all times. Employees wear identification badges and can only gain
entry by a coded keycard or by showing their ID card to a receptionist.
Battelle personnel were careful to not divulge the exact nature of
the analytical work being done on other projects, nor to name any
other clients.
All of the GCA Project File logbook information, relating
HRGC/HRMS logbook information, and raw computer printouts was photocopied
and submitted with the final draft of the report on 12/30/82. The final
report was peer reviewed at Battelle and was sent to GCA (prime Contractor)
as required by the contract. The photocopied logbook and raw data was
sent directly to the CRL on 12/30/82 along with a copy of the final report.
-------
Rattelle QA/QC Protocols
A decane solvent blank and 2,3,7,8-TCDD- 3C^2 standard was run at
least once a day. The area response of the 2,3,7,8-TCDD- CT? standard
must be approximately 4000 and no less than 2000. The ion peak ratio
at m/z of 320 to 322 and 332 to 334 must be 0.77 + 10%. This ion peak
ratio for the native 2,3,7,8-TCDD to 2,3,7,8-TCDD-1 C12 must be within
10% of the expected ratio for the analysis to be acceptable.
A seven-point calibration curve of 2,3,7,8-TCDD is run every 6 months.
Each day, the samples are injected to insure that they are within the
linear range before actual data reduction/quantitation is done. Two
injections of each extract were made to monitor precision of the
2,3,7,8-TCDD-C13 recovery. For all of the Dow Samples, 2,3,7,8-TCDD-C13
was used as the internal standard. No historically based control limits
for 2,3,7,8-TCDD- C12 "recovery from water and fish have been set by
Battelle. Recovery information is found in Table 2.
No splitting of Dow Samples into lab-prepared duplicates was done.
No lab spiking of actual Dow Samples to serve as a matrix spike was
done either. The blind QC samples submitted by CRL served in these
functions.
Quantification Procedure
Before any samples, standards or blanks are injected into the
Carlo Erba HRGC and VG 7070H HRMS system, the instrument is tuned by
the perfluorokerosene lock mass of 319. The response of the MS to this
compound must meet the mass criteria specified before samples are injected.
The VG 7070H electronics were modified by Battelle personnel to allow
more rapid scans over the acquisition time, and thus give greater resolution
and lower detection levels.
All quantitation is done on the basis of a one-point calibration
standard of 2,3,7,8-TCDD-C13. Qualitative identification is done on
the basis of retention time. The correct mass ratio (+ 10%) of the
isomer|s two largest peaks is also used for verification of.identity.
The simplified formulas used are given below:
CONG pg/g = 2000 pg 2,3,7,8-TCDD-C13 x area of analyte in sample
area of 2,3,7,8-^00-^ in sample
ample
Zrl37"!
weight of sample (g)
detection limit = 2.5 x area of analyte in sample x 2000 pg •
area of 2,3,7,8-TCDD-Ci3 in sample
sample weight
-------
2. Blind QC Water Sample Results
QC samples were prepared and originally analyzed by
Dr. Robert Harless, EPA-RTP. They were sent to Curtis Ross, Director CRL,
EPA Region V to use as part of the Quality Assurance program audit of
Battelle Columbus Laboratories for this study. The water QC samples
were received in sealed ampules with benzene as the solvent. These
ampules were opened by CRL personnel at Argonne National Laboratory and
mixed with approximately 25 liters of organic free water to form the blind
QC samples. CRL sample numbers were assigned to the blind QC samples to
further aid in disguising them.
Before any analytical data was generated, a comparison of
EPA 2,3,7,8-TCDD standard (82LS10R05) x*as made with the Battelle prepared
quantitation standard. The EPA standard was previously round robin-tested
and found to contain 10 pg/ul (600 pg in the 60 ul ampule). A variation
of only 4- 10% was allowed between Battelle and this EPA standard. Four
additional standards in benzene were then analyzed for 2,3,7,8-TCDD;
1,3,6,8-TCDD; 1,3,7,9-TCDD; 2,3,7,8-TCDF; OCDD and OCDF.
After these standards were judged acceptable by Dr. Harless,
a blind QC spike (81EH07S09) was analyzed and reported next. After
acceptance of this data, actual sample and other blind analysis began.
Results of all blind standards and samples are given in Table 3.
Recovery Comments
1) 81EH07S23(Spike_QC) - OCDF was reported at a much higher level .
than the spikel the data was re-reduced and the result of 230 ppt was
verified. The problems in OCDD and OCDF recoveries appear to stem from
the lack of a OCDD-C-" standard to check the actual response against
the internal standard.
2) 81EH07S24(Blank QC) - OCDF at a level of 180 ppq was reported.
No OCDF was*present"in"the'QCTampule used to mix this sample. The data
was recalled from disc and the result reverified at 230 ppq. If this
QC sample was mixed after the 81EH07S23 and/or 81EH07S25 QC Samples,
carryover .may have occurred .to account for- this value.
3) 81EH07S25(Spike QC) - Recovery of OCDF was high (750 ppq recovered
vs 160 ppq spiked J"~ Due" to~tfie lack of a C^3 labelled OCDD standard to
judge the relative response against 2,3,7,8-TCDD-C^ quantitation was,
at. best, an estimate. The data was recalled from disc and reverified
at 430 ppq using peak height rather than area.
CONCLUSION:
Due to the imprecise and inaccurate OCDF results discovered by the
three blind audits, any positive OCDF data for water samples should not
be considered usable. All other dioxin/furan sample data should be
considered of an acceptable level of quality.
-------
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TABLE 2. INTERNAL STANDARD RECOVERIES OF
2>3,7,8-TETMaiLORODIBENZO-P-DIOXIM-13C12 IN UATER
Water Recoveries
Sample Name
81EH07S10
81EH07S12
81EH07S22
81EH07S23
81EH07S23
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81EH07S13
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81EH07S88
Internal Standard
Recovery (%)
90
71
81
89
87
94
71
91
83
85
84
83
-------
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APPENDIX D
Large Volume Sampling Study Results
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APPENDIX E
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APPENDIX F
PCDDs and PCDFs
Methodology and Quality Control
Bioaccumulation Study
-------
III. DIOXIN METHODOLOGY AND QUALITY CONTROL
A. Method for Fish Analyses
Battelle Columbus Laboratories, under subcontract 1-453-003-222-01
to GCA; performed the dioxin analyses. The objective of this study was to
analyze selected polychlorinated dibenzofurans (PCDF) and polychlorinated
dibenzo-p-dioxins (PCDD) in fish. The detection limits specified for
these compounds were parts-per-trillion (1 part in 10-^, or ppt) in fish.
Specific compounds which were selected for identification included:
2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF); 2,3,7,8-tetrachlorodibenzo-
p-dioxin (2,3,7,8-TCDD), and all tetra through octa chloro furan and dioxin
isomer classes. High resolution gas chromatography/high resolution mass
spectrometry (HRGC/HRMS) was used to identify and quantify these materials
at the indicated trace level. The exact masses used for each isomer class
and the expected isotope ratio used in part for identifying individual
compounds, as well as limits of detection for the fish are presented
in Table 1. 2,3,7,8-tetrachlorodibenzo-p-dioxin- Cio was used as an
internal standard for quantification and recovery determinations.
These recovery determinations are found in Table 2 and were used to
estimate the influence of the matrices on the analytical measurements.
Preparation of Fish Samples
The fish samples were extracted and cleaned up using the
following procedure. Approximately 5 g portions of fish were placed
in 125 ml round bottom flasks. The fish samples were spiked with 2 ng
of 2,3,7,8-TCDD--L3C12 internal standard followed by the addition of
20 ml of ethanol and 20 ml of 40 percent KOH. The samples were digested
for one hour at 80°C. After cooling, they were extracted three times
each with 10 ml volumes of hexane. The combined hexane extracts weree
transferred to 125 ml separatory funnels and washed three times each
with 10 ml of distilled water. The hexane extracts were concentrated
to 5 ml using K-D apparatus. Each concentrate was transferred to a
multilayered silica column containing the following materials oriented
top to bottom:
0 Activated silica
0 Silica containing 44 percent concentrated sulfuric acid
0 Activated silica
0 Silica containing 33 percent 1M sodium hydroxide
0 Activated silica
These columns were eluted with 30 ml of 1:1 (V:V) benzene:hexane.
The benzene:hexane fraction was exchanged into 5 ml of hexane and transferred
to alumina columns. The alumina column was eluted sequentially with 25 ml
of hexane, 25 ml of 1:1 (V:V) hexane:carbon tetrachloride, and 20 ml of
1:1 (V:V) hexane:me thylene chloride. Decane (20 ul) was added to the
hexane:methylene chloride fraction, and these mixtures were concentrated
to 20 ul prior to their analyses.
-------
The extracts were analyzed by high resolution gas chromatography/
high resolution mass spectrometry (HRGC/HRMS) at a mass resolution of
8000-12000 (M/ M, 10 percent valley). A VG Model 7070H mass spectrometer
interfaced to a Carlo Erba Model 4160 gas chromatograph was used. The
chromatographic column was a 30M DB-5 fused silica column with helium
carrier gas. All HRGC/HRMS data were acquired in the multiple ion
detection mode using a VG Model 2035 Data System and will be archived
on magnetic tape for a period of five years.
B. Quality Control
1. Internal Audits
The following quality assurance procedures were employed.
Perfluorokerosene was introduced through a heated inlet for tuning,
mass calibration and establishing mass resolution. A 2 ul injection
of a test mixture containing 20 pg/ul of 2,3,7,8-TCDD and 95 pg/ul
of 2,3,7,8-TCDD-13Cl2 was analyzed. The analysis of this test
mixture provided the following information:
0 Information concerning sensitivity (absolute response
of 2,3,7,8-TCDD-13C,2)
0 Accuracy of quantification (native response as compared
to that of its C-13 analogue)
0 Elution within a specific retention time window
0 Chromatographic peak shape symmetry.
Decane was analyzed to check for dioxin carry over. This
information is used to access performance of the instrument before the
measurement of PCDF and PCDD at trace levels is conducted in actual samples.
The actual sample analyses were by the following procedure:
four to six samples, a duplicate or spike, an extraction blank, a test
mixture, a decane blank, then the cycle was repeated.
2. External Audits
A. On-site Visit
See Part 2, B.I.
B. Blind QC Fish Sample Results
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Blanks
Along with the actual fish samples two grinding blanks and two
dioxin-free fish filet samples were analyzed. Battelle also extracted and
analyzed a solvent blank. The only reported levels of furans in any blank
were 10 pg in the grinding blank (dry ice) prepared before fish sample
grinding and 95 ppt in the blank perch filet EPA-V-17. The source of
the 10 pg tetrachlorinated dibenzofuran in the grinding blank is not known.
The concentration of 10 pg per sample jar rinse cannot be converted to
ppt, so data is uncorrected.
1) 82LS1QR02
Originally, only five grams of the filet was taken for analysis.
95 ppt 2,3,7,8-TCDF was reported for this first run. A suppression at the
prefluorokerosene lock mass appeared, creating an artifically low
2,3,7,8-TCDD-cl3 signal. This suppression caused all quantitation to be
biased high. The remaining 5 grams of filet were extracted and put through
an additional florisil clean-up and the suppression disappeared.
No 2,3,7,8-TCDF was reported for this aliquot.
Four spiked fish filets were obtained from Dr. Harless at RTF
and sent as "blinds" to Battelle for analysis. However, since the appearance
of the samples EPA-V-21-2, EPA-V-20, EPA-V-21, and EPA-V-22 differed from
the actual sample catfish pastes, they were not actually "blinds".
Battelle, however, did not know which filets, if any, were blanks and
they did not know the isomers or levels used in spiking.
A nearly consistent lack of recovery of OCDF and OCDD at
levels of 100-200 ppt occurred. This may be due to the fact that the
spike levels used were near or at the detection limit. In conversations
with Battelle, it was discovered that OCDD and OCDF have varying response
factors relative to C^-TCDD. These results are therefore estimated
against 2,3,7,8-TCDD-C-^ as no pure certified OCDD and OCDF standards
were available. Such quantitation may be biased low for the sample
results. No OCDD or OCDF was reported above the contract detection
limit of 90 ppt in any of the samples.
820IS22 (EPA-V-22)
This spiked filet QC sample yielded high (277%) recovery of
2,3,7,8-TCDF and low 2,3,7,8-TCDD recovery (54%). The spectral data
was recalled off of the disc and the results recalculated. A suppression
of the 2,3,7,8-Cl3 signal occurred. The usual Battelle procedure is
to go back and rerun the extract through an additional florisil column.
This was.done and the unsuppressed signals yielded 168% recovery for
2,3,7,8-TCDF and 92% recovery 2,3,7,8-TCDD. The recovery for
2,3,7,8-TCDF was still high due to reappearing mass interference at
mass 304 of TCDF.
-------
CONCLUSION
Due to the imprecise and low biased OCDD and OCDF recovery discovered in
blind spike audits, any positive OCDD and OCDF data for fish samples should
not be considered valid. All other dioxin/furan sample data should be
considered of an acceptable level of quality.
-------
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-------
TABLE 2. INTERNAL STANDARD RECOVERIES OF
2,3,7,8-TETRACHLORODIBENZO-P-DIOXIN-13C12
IN FISH
Fish Recoveries
Sample Name Internal Standard
Recovery (%)
82LS10R04 52
82LS10R02 50
82LS10R01 56
82LS05S01 93
82LS05S02 89
81LS15S08 56
81LS11S01 59
81LS17S01 86
81LS17S03 57
81LS17S06 , 72
81LS17S07 47
t
82LS07S05 49
82LS07506 51
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TABLE 3. DOW FISH BLANK RESULTS
UNITS: ppt
ISOMER
2,3,7,8-TCDF
2,3,7,8-TCDD
Tetra CDF
Tetra CDD
Penta CDF
Penta CDD
Hexa CDF
Hexa CDD
Hepta CDF
Hepta CDD
Octa CDF
Octa CDD
Battelle I Dry Ice**
Solvent I Before
Blank I82L205S02
<(7) | < 5
<(4) | < 5
<(4) I 10
<(4) I < (2)
<(1) I <(11)
<(1) 1 <(20)
<(2) 1 < (7)
<(5) I <(12)
<(1) 1 <(17)
<(2) 1 < (6)
<(4) I <(25)
<(3) 1 <(11)
(Dry Ice**| 82L510R02
(After | EPA-V-17
|82L505S02|Run 1
1 < 5 |95
1 < 5 |< 7
1 < (4) |95/(1)
1 < (2) |< 7
1 <(19) |<20
1 <(37) |<10
1 <(19) |<20
1 < (9) |<20
I <(12) |<40
1 < (4) |<40
1 <(16) |<90
1 < (4) |<90
[Run 2
l< 7
l< 7
!< 7
l< 7
|<20
|<14
|<20
|<20
l<40
1<40
!<90
|<90
820I07R15
< 5
< 5
< 5
< 5
<10
<10
<20
<20
<40
<40
<90
<90
** Units - total pg per sample jar rinse.
(X) " (detection limit Battelle); other < values are based on contract
detection limits.
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TABLE 4. DOW FISH SPIKE RESULTS
UNITS: % recovery
IEPA-V-21-2IEPA-V-20 lEPA-V-21 lEPA-V-22 |Spike (ppt)
ISOMER I82LS10R04 J82LS10R01I820I07S20|820I07S22|Levels
2,3,7,8-TCDDl
2,3,7,8-TCDFl
1,3,6,8-TCDDl
1,3,7,9-TCDDl
OCDD |
OCDF |
173 |
70 I
105* |
105* |
0 I
0 I
80 I
125 I
92* |
92* I
75 I
64 |
103
154
60
115
0
0
54
"277
88
130
0
0
10- 30
20- 40
10- 33
3- 10
100-200
100-200
*Isomers not quantified spearately.
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