905R81119
A REPORT ON POLYCHLORINATED DIBENZO-P-DIOXINS (PCDDs)
AND POLYCHLORINATED DIBENZOFURANS (PCDFs):
A SUMMARY OF STUDIES CONDUCTED
IN THE GREAT LAKES AREA
U.S. ENVIRONMENTAL PROTECTION AGENCY
REGION V
CHICAGO, ILLINOIS
July 1981
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TABLE OF CONTENTS
List of Tables ii
I. Introduction..- 1
II. Sources of Polychlorinated dibenzo-p-dioxins (PCDDs)
and dibenzofurans (PCDFs) in Commercial Products 2
III. Sources of PCDDs and PCDFs from Pyrolysis, Photolysis,
and Combustion Processes 2
IV. Studies Involving PCDDs and PCDFs Conducted
in the Great Lakes Area 10
V. Current Government Activity on PCDDs and PCDFs 24
References 25
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LIST OF TABLES
Table 1 - Findings on PCDDs and PCDFs in Fly Ash and Other
Combustion Sources 6
Table 2 - Chlorinated Dioxin Content of Particulate Matter
From a Rotary Kiln Incinerator 7
Table 3 - Chlorinated Dioxins in Rotary Kiln Incinerator
Scrubber Water 8
Table 4 - Chlorinated Dioxins in Soils and Dusts 9
Table 5 - Results of 2,3,7,8-Tetrachlorodibenzo-p-dioxin
(TCDD) Fish Monitoring Program Conducted by the
U.S. EPA in Michigan during 1978 14, 15, 16
Table 6 - Residues of Dibenzofurans and Dibenzo-p-dioxins in
Composite Samples of Fish and Gulls from Different
Sites on the Great Lakes 21, 22
Table 7 - Samples Analyzed from Crete Metals, Crete, IL 24
LIST OF FIGURES
Figure 1 - Saginaw River Basin 17
Figure 2 - Dioxin in Gull Eggs 19
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I. Introduction
In the last several years, concern over the environmental and public health
effects from the use of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) and Silvex,
plant herbicides, has increased. Chemical products containing 2,4,5-T
have been shown to contain a highly toxic trace contaminant, 2,3,7,8-tetra-
chlorodibenzo-p-dioxin (2,3,7,8-TCDD), which is considered to be the most
toxic of the 22 possible isomeric forms of TCDD. On February 28, 1979, an
emergency suspension was imposed on certain uses of 2,4,5-T and Silvex based
on extensive animal data showing that exposure to 2,4,5-T, Silvex and/or
2,3,7,8-TCDD resulted in fetotoxic, teratogenic, and carcinogenic effects
and on selected epidemiological data (1,2). TCDDs and other chlorinated
dioxins, technically known as polychlorinated dibenzo-p-dioxins (PCDDs)
and related compounds, polychlorinated dibenzofurans (PCDFs) are found in
certain commercial products. Those compounds which have a broad range of
toxicities, are also receiving considerable attention. Evidence exists
that PCDDs and PCDFs may be released to the environment by combustion
processes. This report summarizes those studies involving PCDDs and PCDFs
in the Great Lakes Area. This report does not address the physical,
chemical, and toxicological properties of these compounds. Several exten-
sive reviews on the properties of PCDDs and PCDFs are available (3,4,5,6).
One of these reviews, "Long Term Hazards of Polychlorinated Dibenzodioxins
and Polychlorinated Dibenzofurans," by Huff, et al is attached at the end
of the report.
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II. Sources of Polychlorinated dibenzo-p-dioxins (PCDDs)
and dibenzofurans (PCDFs) in Commercial Products
A. 2,4,5-T and Silvex (phenoxy herbicides)
2,3,7,8-TCDD is formed in the manufacture of 2,4,5-trichlorophenol from 1,2,4,5-
tetrachlorobenzene, especially if production temperatures exceed 160°C(5).
Drums of Agent Orange, a mixture of 2,4,5-T and 2,4,-D, stored in the USA and in
the Pacific prior to 1970 have been reported to have 2,3,7,8-TCDD levels ranging
from 0.1 to 47 ppm (7). Only trace levels of other PCDDs and PCDFs were found.
In 1978, producers of 2,4,5-T reported that their products contain less than
0.1 ppm of 2,3,7,8-TCDD (5).
B. Chlorinated Phenols
PCDDs and PCDFs have been found in tri, tetra, and pentachlorophenols (4,8,9).
The quantities of these compounds and their isomeric forms depend upon the
reaction process and conditions. In 1978 concentrations of 2,3,7,8-TCDU in
2,4,5-trichlorophenol and its sodium salt were found to be less than 0.1 ppm
(10). Analyses of PCDDs in commercial grade pentachlorophenols (PCP) produced
by various manufacturers during the years 1975 to 1977 found hexa-CDDs (HxCDDs)
(non-detectable (N.D.) to 520 ppm), hepta-CDDs (HpCDDs) (125 to 180 ppm) and
octa-CDDs (OCDDs) (N.D. to 3600 ppm). No TCDDs were found in commercial PCP.
There were several isomeric forms of HxCDD, the major isomers being the
1,2,3,6,8,9; 1,2,3,6,7,8; and 1,2,4,6,7,9. The isomeric forms for HpCDD were
1,2,3,4,6,7,9 and 1,2,3,4,6,7,8(8). PCDFs were also detected in PCP including
hexa-CDFs (HxCDFs) (9 to 90 ppm), HpCDFs (70 to 400 ppm) and OCDFs (55 to 260
ppm).
C. Other Chemicals
PCBs have been shown to contain 1-10 ppm of various PCDFs (11). Hexachloro-
phene has been reported to contain traces of TCDDs (4).
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III. Sources of PCDDs and PCDFs from Pyrolysis. Photolysis and Combustion Processes
A. Chlorophenols and Related Compounds
The pyrolysis or combustion of Chlorophenols, chlorophenoxy compounds or
their derivatives has been shown to produce various PCDDs including TCDDs.
The 2,3,7,8 isomer of TCDD has been detected in some experiments although
generally as a minor component of the total TCDDs and PCDDs. Studies con-
ducted on the burning of materials such as grass, leaves or wood chips that
have been treated with Chlorophenols or related compounds have also demon-
strated that PCDDs are formed (7,12-16).
B. Formation of PCDFs by Pyrolysis
1. The pyrolysis of commercial PCBs (Aroclor 1254 and 1260) at temper-
atures of 500-600°C has been shown by Buser and his co-workers to yield
30 major and more than 30 minor PCDFs. From 3 to 25% of the pyrolyzed PCB
was converted to PCDFs. Above 700°C only trace amounts of PCDFs are form-
ed due to the complete destruction of PCB. The formation of PCDFs was
shown to be the result of intermolecular cyclizations of PCB (11).
2. PCDDs and PCDFs are produced from the pyrolysis of tri, tetra, and
pentachlorobenzenes in the presence of air. TCDDs have been found in
pyrolysates of trichlorobenzene. However, the 2,3,7,8-TCDD isomer was
present only as a minor constituent (12).
3. Recently it was reported that soot from the burning of transformer
fluids containing 65% PCB and 35% chlorinated benzenes, mainly trichloro-
benzene and tetrachlorobenzene, contained 3 ppm of 2,3,7,8-TCDD and
273 ppm of 2,3,7,8-TCDF (15).
C. Formation of PCDDs by Photolysis
Dechl on nation of XDD in pentachlorophenol produces tetra, penta, hexa
and hepta chlorinated dioxins (8,17).
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D. PCDDs and PCDFs from Combustion Sources and in Soil and Dust Samples
1. Total amounts of PCDDs and PCDFs In fly ash from a municipal incinerator
in Switzerland were found to be 0.2 ppm and 0.1 ppm respectively. At an
industrial heating facility, the fly ash contained 0.6 ppm PCDD and 0.2 ppm
of PCDF. Only traces of the more toxic PCDDs (2,3,7,8; 1,2,3,7,8;
1,2,3,6,7,8; 1,2,3,7,8,9) were detected (7). More recent comprehensive
studies have shown that PCDDs and PCDFs were present in the fly ash of
35 municipal incinerators in Europe up to 1 ppm amounts (4,14). The for-
mation of PCDDs and PCDFs are thought to be from the combustion of wastes
containing polychlorinated phenates related compounds (15,16).,
2. A study released by Dow Chemical in 1978 and published in 1980 (18)
reported no 2,3,7,8-TCDD (10 ppb detection level) in fly ash from their oil
and coal power plant; however, 38 ppb of other TCDD isomers were found at a
detection limit of 20 ppb. Detectable levels of PCDDs were found in samples
from fireplaces, automobile and truck mufflers and cigarette smoke. The
authors concluded that dioxins have been present since the advent of fire.
The results of their study are presented in Table 1 on page 6. In contrast
to the 1978 report, the authors in their 1980 article tempered their remarks
by stating that some combustion sources may be sources of airborne and
waterborne particulates containing PCDDs. It was theorized that the
formation of PCDDs could be the result of a reaction between inorganic
chloride and organic material and not due to the condensation of
preexisting polychlorinated phenols. The 1980 report also included
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data on emissions from a rotary kiln incinerator operated by Dow Chemical
and analyses of soils and dusts collected between 1976 and 1978. Particu-
late matter collected from the rotary kiln incinerator, operated without
natural gas and burning solid wastes from the facility, had levels of
total TCDD reaching 13,200 ppb (Table 2). Two of the samples collected
had levels of the 2,3,7,8-isomer greater than all other TCDD isomers.
No TCDD emissions were noted when the facility was operated with natural
gas. Other PCDDs were found to be substantially reduced (>95%). Analyses
were also performed on particulates filtered from the scrubber water
(Table 3). Levels of 2,3,7,8-TCDD and other isomers were reduced by 90%
when the kiln was operated with natural gas. Results of soil and dust
samples reported by the authors are presented in Table 4. The highest
levels of PCDDs in soil and dust samples were those collected at the
Midland plant and could be from combustion sources and/or chlorophenolic
production by Dow Chemical. Evaluation of all data reported has been
made by EPA personnel (19,20).
3. The results of Kimble and Gross (21) contrasted with the Dow Chemical
findings. At one coal fired power plant they found no TCDD at a detection
limit of 1.2 ppt in fly ash. Based upon work in their laboratory
Lustenhouwer, et al, (14) have questioned the extraction method used by
Kimble and Gross; however, the method was not exactly duplicated (43,44).
In addition, the apparently negative results of Kimble and Gross have
subsequently been corroborated by EPA from tests on fly ash obtained from
seven coal-fired power plants (45).
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TABLE 1
PCDDs and PCDFs
In Fly Ash and Other Combustion Sources (Reference #18)
Num-
ber
Sample of
sam-
ples
Apparent dioxin content, ng/g(ppb)
TCDD
Other
isomers 2,3,7,8- Total
HCDD HXCDD OCDD
Incinerators, power-
house
Dow powerhouse 1 38(20)
Dow rotary inciner- 5
ator stack (pre-
sent normal oper-
ation with sup-
plemental fuel)
Dow stationary tar 5 N.D.
burner stack (nor-
mal operation with
supplemental fuel)
U.S. municipal in- 1 7.3
cinerator (elec-
trostatic precipi
tator)(Nashville,
TN)
European municipal
incinerators
N.D.(10) 38(20) 2 4 24
N.D.(2) 1-5 4-100 9,950
N.D.
0.4
N.D.
7.7
1-20 27-160 190-440
14
28
30
2-20
30-200 60-130
40-120
0.100 0.26
0.003-0.01 0.02-0.07
Mufflers
Diesel truck muffler 2 0.02 0.003 0.023 0.020
Auto muffler 4 N.D.-0.004 N.D.-0.004 N.D.-0.008 N.D.
;her sources
tome fireplace soot
tome electrostatic
precipitator
Cigarette smoke
Charcoal-broiled
steak
Mere multiple samples were analyzed from similar sources, the range of observed values is
shown. 2) N.D. indicates that the signal observed was less than 2.5 times noise. Limits of
detection not within these ranges are shown parenthetically after the value reported for sig-
nals between 2.5 and 10 times noise. 3) Data without supplemental fuel is not included here
secause this practice has been eliminated.
2
1
2
4
N.D. -0.3
0.4(0.4)
N.D.
N.D.
N.D. -0.1
0.6
N.D.
N.D.
N.D. -0.4
1.0
N.D.
N.D.
0.2-3
34
0.004-0.008
N.D.
0.7-16
430
0.009
N.D.
0.9-25
1,300
0.02-0.05
0.03(0.03)
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Sam-
ple
R1F1
R1F2
R2FT
R3F1
Fuel
Kiln
T,SW,G
T,SW,G
T,SW,G
T,SW,G
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TABLE 2
Chlorinated Dioxin Content of Parti cul ate Matter
From a Rotary Kiln Incinerator
(Reference #18)
T Apparent dioxins, ng/g (ppb)
Sec-
ond- Other
ary isomers
TCDD
Without
T 1,800
5,000
3,300
12,000
2,3,7,8-
TCDD
supplemental fuel
2,8002
8,2002
110
N.D.(260)3
HxCDD
13,000
65,000
1,300
5,600
HpCDD
110,000
510,000
2,000
37,000
OCDD
180,000
810,000
3,000
59,000
With supplemental fuel
RS
R4
R5
R6
R7
T,SW,G
T,SW,G
T,SW,G
T,SW,G
T,SW,G
0,G N.D.(S.O)
N.D.(7.0)
N.D.(2.0)
T,G N.D.(2.0)
N.D.(2.0)
N.D.(2.0)
N.D.(5.0)
N.D.(2.0)
N.D.(4.0)
N.D.(2.0)
1.4
N.D.(l.O)
N.D.(O.S)
5.0
4.0
13.0
4.0
6.0
27.0
110.0
30.0
9.0
15.0
170.0
950.0
1. T, tars; SW, solid waste; G, gas; 0, oil.
2. The high results reported for the 2,3,7,8-isomer are probably due to analysis
by the nonspecific GC-MS packed-column method. Later results were obtained
with a capillary column specific for 2,3,7,8-TCDD. The TCDD results from run 1
(R-j) are not comparable to those from runs 2 and 3.
3. Numbers in parentheses are limits of detection.
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TABLE 3
Chlorinated Dioxins in Rotary Kiln Incinerator
Scrubber Water
(Reference #18)
Sample
Apparent dioxins, ng/g (ppb)
Other
i somers
TCDD
2,3,7,8-
TCDD
HxCDD HpCDD
OCDO
Participates filtered
from scrubber water
Without supplemental fuel
300
2,200 *
3,400 26,000 42,000
With supplemental fuel
14
32*
200
970 1,200
**
**
Filtered scrubber water 0.0018(0.01) 0.001*(0.0006) 0.005 0.024 0.026
without supplemental fuel
* The analytical method did not separate 2,3,7,8-TCDD from 11 other isomers.
** Numbers in parenthesis are limits of detection.
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TABLE 4
Chlorinated Dioxins in Soils and Dusts (Reference #18):
Apparent dioxin content, ng/g (ppb)
Num-
ber
of
sam- Other
pies isomers 2,3,7,8- Total
TCDD TCDD TCDD
HxCDD HpCDD
OCDD
oil
Rural (Gaylord, MI) 5
Urban (Lansing & 5
East Lansing, MI)
Major metropolitan 8
(Chicago, IL)
Dow Chemical 5
(Midland, MI)
N.D.2
N.D.
0.005-0.03
0.8-18 0.3-100 1-120
N.D. N.D.-0.05 N.D.-0.2
0.03-1.2 0.03-2 0.05-2
0.03-0.3 0.1-3
0.4-22
7-280 70-3,200 490-20,000
ust
Dow Chemical lab. 6 0.5-2 0.7-3 1-4
Midland, Michigan
Metropolitan
(Detroit, MI)
Metropolitan
(St. Louis, MO)
Metropolitan
(Chicago, IL)
2
4
1 0.16 0.12
2
9-35 140-1,200 650-7,500
0.03-0.04(0.02)3 0.2-0.4 2-4 20-30
N.D.-(0.03) N.D.-0.3 0.3-4 0.1-4
0.3
0.04(0.04)
2 34 210
N.D.-0.3 0.6-3 3-8
.. Where multiple samples were analyzed from similar sources, the range of observed values
is shown.
!. N.D. = Not Detectable
. Value in parentheses indicates detection limit.
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IV. Studies Involving PCDDs and PCDFs Conducted in the Great Lakes Area
A. Dow Chemical Monitoring Study, Midland, Michigan (June, 1978)
In June, 1978, Dow Chemical reported results of their monitoring program
to the Michigan Department of Natural Resources (MDNR) as requested by that
agency (22). The data has been summarized below.
1. Tittabawassee River Water and Sediment (1976)
Ten samples (two water and eight sediment) from the Tittabawassee River
and below the plant showed no detectable amounts of TCDDs. The detection
limit (DL) for sediments ranged from 10 to 5Q ppt. Water samples were
analyzed at a DL of 1 ppt.
2. Plant Discharge Stream (1976-1978)
Composite and grab samples of wastewater discharge revealed no detectable
levels of TCDDs in 13 of 14 samples (DL=5 ppt or less). One sample was found
to contain 8 ppt of TCDDs.
3. Bioconcentration Study (1978)
Analyses performed on the edible portions of fish flesh from caged trout
placed six miles downstream of the plant's effluent for periods of 7,14,
and 30 days revealed no detectable level of TCDDs at a DL of 10 to 30 ppt.
Five of six fish placed in the tertiary effluent stream for 7 days were
found to have TCDDs ranging from 20 to 50 ppt at a DL of 10 to 20 ppt.
When analyses were also performed on whole fish, the 30 day trout (downstream)
showed TCDDs ranging from 10 to 20 ppt when analyzed at a DL of 5 ppt.
The fish collected from the tertiary effluent stream showed higher
levels of TCDDs ranging from 50 to 70 ppt at a DL of 20 ppt. Analyses on
the 7 day trout (edible and whole fish) caged along the river bottom
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revealed no TCDDs at a DL of 10 to 40 ppt. No TCDDs were detected in
analyses performed on the edible portions of fish flesh from unexposed
control fish (DL=20 ppt) and those placed in the river at Dow dam (DL=20 ppt),
indicating that TCDDs could be present in the plant's effluent (4).
4. Native Fish Studies
(a) 1976 (Analyses 1978)
TCDDs were detected in 4 of 9 catfish samples, edible portions, at levels
ranging from 70 to 230 ppt. Three of the four samples in which TCDDs were
detected were located downstream of the plant's effluent. OCDDs were found
in 8 of 9 fish, collected both upstream and downstream of the discharge.
The levels ranged from 40 to 150 ppt. One fish sample was positive for
HxCDDs (90 ppt). Detection limits ranged from 10 to 200 ppt.
(b) 1977 (Analyses 1978)
Fish caught downstream of Dow at Smith's Crossing (Figure 1) in the
Tittabawassee River revealed contamination in 9 of 14 fish tested.
Analyses were performed on the edible portions of fish flesh. The levels
of TCDDs ranged from 20 to 244 ppt.
(c) Saginaw Bay 1978
Of three fish collected from Saginaw Bay, one catfish was found to contain
24 ppt TCDDs, at a DL of 10 ppt. The analyses were performed on the edible
portions of fish flesh.
5. Chlorophenols
Chlorophenols were found in the Dow effluent up to levels of 70 ppb.
2,3,4,6-tetrachlorophenol and pentachlorophenol were present at ppb levels
below the dam in sediments of the Tittabawassee River. Chlorophenols
were also found in some fish at ppb levels above the discharge point of
the plant's wastewater effluent.
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Based upon these findings, the Michigan Department of Public Health issued
an advisory on June 28, 1978 against consuming fish caught in the waters
of the Tittabawassee and Saginaw Rivers. This health advisory is still in
effect at this date (23).
B. Dow Chemical Monitoring Study, Midland, Michigan (October, 1978)
Results of PCDD sampling indicated the presence of 2,3,7,8-TCDD in 2,4,5-T
sludge at 10 ppt and in trichlorophenol scrubber fluid at 20 ppt (24). The
2,4,5-T sludge also contained 11 ppt HxCDDs, 4 ppt HpCDDs, and 43 ppt OCDDs
Brine wastes and sludges from 2,4-D processes were negative for PCDDs.
C. U.S. EPA TCDD Fish Monitoring Program (December. 1978)
In response to Dow's first monitoring report, which indicated incidental
contamination of fish from the lower Tittabawassee River, fish were collected
and analyzed from the Tittabawassee, Grand and Saginaw Rivers (25). In 26
out of 35 skinless fillet fish samples, detectable levels of 2,3,7,8-TCDD
were found and ranged from 4 to 695 ppt. Eleven of these fish samples
contained TCDD levels greater than 40 ppt. All but two of these samples
were from locations downstream of Midland. Four out of 6 samples collected
upstream were found to be negative for 2,3,7,8-TCDD. Data is presented in
Table 2 on pages 14 and 15. Analyses of spiked blind controls, which
consisted of various known levels of 2,3,7,8-TCDD, indicated that the
positive results were within +_ 20% of the values reported. Responding to a
request from the Governor of Michigan, the FDA recommended that fish contain-
ing TCDD (2,3,7,8-TCDD) at a level of more than 100 ppt not be consumed.
Where 2,3,7,8-TCDD had been found in fish below 100 ppt, it was recommended
that no more than one average size portion of fish be consumed per week (2fa).
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D. U.S. EPA-Michigan Monitoring Study of Dow Chemical, Midland, Michigan
(April. 1979)
Results of TCDO analysis of samples taken from Dow's 2,4,5-Trichlorophenol
injection well (DL30.06 ppt), phenol treatment system (DL=82 ppt), plant
effluent (DL=0.002 ppt) and upstream Tittabawassee River (DL=5.0 x 10~5 ppt),
were found to be negative. However, the carbon filter concentration system
utilized was believed to be unsuitable for concentrating contaminants found
in water (27).
E. Dow Chemical Study on Fish. April 1979
As part of Dow's study on dioxin the company reported finding the following
ranges of dioxins in parts per trillion (ppt) in fish collected from other
tributaries of the Saginaw River (28).
OCDDs
NO-20
ND-44
ND
Number
of
Samples
Flint Fiver 6
Cass River 6
Shiawasse River 6
Number of
Positive
Results TCDDs
5
4
1
ND-11
ND-104
ND-9
HxCDDs HpCDDs
ND-6
ND-1
ND
ND-5
1 ND-11
ND
ND=not detected
F. Composite Fish
Sample
from the
Tittabawassee
River
(December 1980)
A single composite whole fish sample of five carp, supplied by the MDNR,
(collected downstream of Midland) and analyzed by Columbia National Pesticide
Laboratories, yielded positive results for various PCDDs and PCDFs (29). The
2,3,7,8-isomer of TCDD constituted >90% of the TCDDs found (30,31). The
results are shown below:
TCDDs 81 TCDFs 37
PCDDs 31 PCDFs 73
HxCDDs 44 HxCDFs 145
HpCDDs 53 HpCDFs 31
QCDDs 14 CCDFs 4
Total PCDDs 223 ppt Total PCDFs 290 ppt
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TABLE 5
RESULTS OF 2,3,7,8-TETRACHLORODIBENZO-P-DIOXIN
(TCDD) FISH MONITORING PROGRAM CONDUCTED BY
THE U.S. ENVIRONMENTAL PROTECTION AGENCY
IN MICHIGAN DURING 1978
LOCATION
Tittabawassee River
Tittabawassee Road
Free!and Road
Smith's Crossing Road
Above Dow Dam
Dublin Road
FISH
SPECIES
Carp
Yellow Perch
Carp
Carp
Yellow Perch
Channel Catfish
Carp
Channel Catfish
Carp
Sucker
Sucker
Channel Catfish
Carp
Carp
Channel Catfish
Yellow Perch
Carp
FISH
LENGTH
(cm)
42.2
16.2
11. Ob
39.7
40.0
16.8
12.3
50.3
38.0
38.2
23.1
35.6
38.1
30.9
34.6
33.0
38.1
19.3
52.2
* TCDD
LEVEL
(ppt)a
52
20
93
32
10
273
22
695
49
8"
21
42
NDC
ND
28
ND
ND
TCDD
DETECTION
LIMITS
(ppt)
8
8
6
4
5
6
11
60
1
4
4
9
5
9
2
4
9
* Skinless Fillets
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TABLE 5 (cont'd)
LOCATION
Saginaw River
Wickes Park
Block's Marina
Mouth
Grand River
Jones Road near Eagle
Near Ionia
Saginaw Bay
Lat. 43 40' 16"
Long. 83 50' 21'
FISH
SPECIES
Carp
Yellow Perch
Channel Catfish
Channel Catfish
Carp
Channel Catfish
Carp
Yellow Perch
Carp
Carp
Channel Catfish
Small mouth Bass
Small mouth Bass
Carp
Sucker
Sucker
Yellow Perch
FISH
LENGTH
(cm)
46.0
11.9 __
11.4
69.0
48.5
51.8
46.0
45.0
16.0
16.0
39.0
39.0
35
38.0
50.8
48.3
28.2
31.0
24.2
26.8
* TCDD
LEVEL
(ppt)a
62
ND
105
52
28
30
153
11
20
41
29
7
8
ND
ND
4
ND
TCDD
DETECTION
LIMITS
(ppt)
13
11 _
7
8
4
6
13
4
4
8
6
6
6
2
2
2
3
* Skinless Fillets
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TABLE 5 (cont'd)
TCDD
FISH * TCDD DECTECTION
-- FISH LENGTH LEVEL LIMITS -
Location SPECIES (cm) (ppt)A (ppt)
Lake Michigan
Off Saugatuck Lake Trout 50.8 ND 7
a ppt indicates parts per trillion which is equivalent to ng/kg.
b signifies composite fish sample.
c ND indicates that TCDD was not detected in the fish sample at the
corresponding detection limit.
* Skinless Fillets
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FIGURE 1:
SAG1NAW RIVER BASIN
>uMnRo*d*
SAGINAW
BAY
Direction of rivw flow
* Aponumatdv 3 rivtr mries uonream from
confluence of Chiopewi and Tmabawasaee Riven
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-18-
G. Canadian Study on Gull Eggs from the Great Lakes
Dr. Douglass Hal let of the Canadian Wildlife Service reported finding
2,3,7,8-TCDD in Herring gull eggs, collected in 1980, at 12 different
locations within the Great Lakes (32). The highest levels of 2,3,7,8-TCDD
were found in Saginaw Bay eggs (43-90 ppt). Levels in Lake Ontario eggs were
slightly lower and ranged from 44-64 ppt. Lowec-levels (approximately
3-10 ppt)_were found in eggs collected at other Great Lakes sites. The
2,3,7,8-TCDD isomer was found to predominate (>90%). These results are
graphically presented in Figure 2. There have been no reports of abnor-
malities in gull chicks or mature birds. Eg_g: samples collected from Lake
Ontario in 1971 and preserved until analysis in 1980 had 2,3,7,8-TCDD
levels of 800 ppt. It was conjectured that the decrease in 2,3,7,8-TCDD
levels since 1971 (Figure 2) might be attributed to the discontinuation of
2,4,5-trichlorophenol production by Hooker Chemical at Niagara Falls,
New York in 1971. Confirmational analyses of gull egg samples are now
underway in U.S. laboratories.
H. Gull Flesh Analyses From the Great Lakes (December 1980)
Two flesh samples from gulls in the Saginaw Bay were recently analyzed by-
Dr. David Stalling of the Columbia National Fisheries Research Laboratory (30),
In the two samples, the 2,3,7,8-TCDD isomer predominated (>90%) and was found
at levels of 70 and 160 ppt (31). HxCDDs and OCDDs were also found resulting
in a total PCDD level of 186 and 196 ppt. Total PCDFs were found at 117 and
121 ppt with the PnCDFs and HxCDFs being the predominate furans.
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-19-
01
a
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-20-
I. PCDD and PCDF Analyses on Great Lakes Fish (April 1981)
1. The Columbia National Fisheries Research Laboratory has obtained positive
results for TCDDs and TCDFs on composite whole fish samples from the Great
Lakes (29). This fish sampling is being conducted under the National
Pesticides Monitoring Program. Huron and Ontario fish samples ranged in
TCDD concentrations from 33 to 94 ppt. The highest values were reported
in fish collected from Saginaw Bay in 1978. Data collected to date is
presented in Table 6. Tittabawassee fish data (see E. above) is included
for comparison. The predominate (>90%) isomeric form of TCDD discovered
has been 2,3,7,8-TCDD (30,31). The majority (>90%) of the other chlorinated
X
dioxins and furans found in fish appear to have the 2,3,7,8 ring positions
chlorinated (30,31). Therefore, the potential toxicity of these dioxins
and furans may approach that of 2,3,7,8-TCDD (3). Very preliminary data
indicates that the isomeric distribution of PCDDs and PCDFs in river
sediments do not reflect those found in fish (31,33). Differences in
solubilities of PCDDs and PCDFs, absorption or retention of these chemicals
could account for the observed difference in distribution (33).
2. The FDA has also reported finding TCDDs in fish from Saginaw Bay.
Analyses performed by FDA on edible fillets from 27 fish collected from
Saginaw Bay in 1979, determined four to be positive for TCDDs (21 to 45
ppt). FDA recommended that fish having TCDD residues above 100 ppt
should not be consumed and even lower levels, down to 50 ppt, consumption
should be limited. FDA stated that no adverse health consequences would
be anticipated from the moderate consumption of fish containing TCDD
residues below 50 ppt (34).
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-23-
3. The New York State Department of Health is currently screening Lake
Ontario fish for contamination. Previous analyses conducted on twa fish
determined dioxin contamination at 4.6 and 6.5 ppt (35). A potential :
source of contamination may be from landfills in the Niagara River area
where 2,4,5-trichlorophenol wastes were dumped (36). Sediment samples
from streams which drain into the Niagara River have been reported to
contain dioxin (37).
J. NIEHS Analyses of a Michigan Dairy Herd Tissue Samples and Michigan's
Study on Pentachlorophenol Treated Wood (1978-1979)
Studies by NIEHS of a dairy herd in Michigan, presumed to be contaminated by
contact with PCP treated wood, revealed fat and liver contamination, re-
spectively, with OCDDs at 7 and 15 ppb; HpCDDs at 6 and 15 ppb; and HxCDUs
at 1 and 9 ppb (6). The presence of these contaminants was suspected of
causing the illnesses noted in the cattle. Analyses conducted for PCDDs,
by the State of Michigan, on the PCP treated wood in barns established the
link between the wood and the presence of PCDDs in the cattle samples (38).
OCDDs ranged from 289-5000 ppb, HpCDDs from 9-1161 ppb, and HxCDDs from
non-detectable to 3.7 ppb in the wood.
K. U.S. EPA Assessment of Environmental Contamination in the Area of Hemlock
Michigan (October, 1980)
As a result of numerous health complaints involving humans and domestic
animals, the U.S. EPA conducted an environmental assessment in 1980 of the-
Hemlock, Michigan area, located 14 miles south of Midland (39). Citizens
were dissatisfied with previous health and environmental studies (negative
findings) conducted by county and state agencies. Residents were concerned
that potable groundwater had been contaminated from a brine reinjection
-------
-24-
system operated by Dow Chemical in that area. A study of TCDDs in 40
environmental and biological samples yielded only one positive result at
a detection limit of low ppt levels. Several fish, downspout soils, house
dusts, a well sediment sample, a septic tank sludge, and sediment samples
from Dow's injection systems were found to be negative for TCDDs at detection
levels ranging from 1-43 ppt (40). The one positive sample was a caged
fish collected from the Tittabawassee River, downstream of Midland, which
contained 23 ppt TCDDs.
L. Crete Metals. Crete. Illinois (December. 1980) "
TCDDs and TCDFs analyses were performed in 1980 on environmental and bio-
logical samples as a result of health complaints and the death of several
horses near a wire reclamation facility (41). In the reclamation process,
insulating and other materials were burned off wires, x-ray plates and
transformer cables and other unknown metal containing products.
Samples analyzed and results obtained are presented below in Table 7.
TABLE 7
TCDDs (ppt) TCDFs (ppt)
Stack #2 (Scrapping) 410 11,600
Furnace #2 (Scrapping) 58 730
Soil (on site) 21 230
Adipose (dead horse) 45 165
A variety of isomeric forms of TCDDs and TCDFs were detected, however, the
analytical technique utilized could not adequately discriminate and quan-
tify the isomers.
V. Current Government Activity
Except for disposal requirements for chlorophenolic wastes containing
2,3,7,8-TCDD, no other regulations exist for controlling PCDDs and PCDFs
release to the environment (42). The implications of these data on the
consumption of dioxin contaminated fish are currently undergoing review
by various government agencies in this country and Canada.
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-25-
REFERENCES
1. EPA, "Notice of Intent to Cancel Forestry, Rights of Way, and Pasture
Registrations of Pesticide Products Containing 2,4,5-T," February 28, 1979.
2. EPA, Epidemiologic Studies Program, Human Effects Monitoring Branch, "Report
of Assessment of a Field Investigation of Six-Year Spontaneous Abortion
Rates in Three Oregon Areas in Relation to Forest 2,4,5-T Spray Practices,"
February 28, 1979.
3. Huff, J.E. et al "Long Term Hazards of Polychlorinated Dibenzodioxins and
Polychlorinated Dibenzofurans," Environmental Health Perspectives 36, 221,
1980. ~~
4. Espisito, M.P., et al, "Dioxins", U.S. EPA, Cincinnati, Ohio, 1980.
5. EPA, "Rebuttable Presumption Against Registration and Continued Registration
of Pesticide Products Containing 2,4,5-T," Federal Register. Vol. 43, No. 78,
April 21, 1978.
6. Joint NIEHS/IARC Working Group, "Long Term Hazards of Polychlorinated
Dibenzo dioxins and Polychlorinated Dibenzofurans," June, 1978.
7. Rappe, C., H. R. Buser and H. P. Bosshart, "Polychlorinated Dibenzo-p-Dioxins
(PCDDs) and Dibenzo Furans (PCDFs): Occurrence, Formation and Analysis of
Environmentally Hazardous Compounds," CIPAC Symposium, Baltimore, Maryland,
June, 1979.
8. EPA, Environmental Health Advisory Committee, "Report of the Ad Hoc Study
Group on Pentachlorophenol Contaminants," December 29, 1978.
9. Creosote, Inorganic Arsenicals, Pentachlorophenol, EPA, Position Document
No. 2/3, January 1981.
10. EPA, "Rebuttable Presumption Against Registration and Continued Registration
of Pesticide Products Containing 2,4,5-Trichlorophenol and its Salts,"
Federal Register, Vol. 43, No. 149, August 2, 1978.
11. Buser, H. R., H. P. Bosshardt and C. Rappe, "Formation of Polychlorinated
Dibenzo Furans (PCDFs) from the Pyrolysis of Individual PCB Isomers,
Chemosphere. 3^, 157, 1979.
12. Buser, H. R., "Formation of Polychlorinated Dibenzo Furans (PCDFs) and
Dibenzo-p-Dioxins )PCDDs) from the Pyrolysis of Chlorobenzenes,"
Chemosphere. £, 415, 1979.
13. Ah!ing, B., et al, "Formation of Polychlorinated Dibenzo-p-Dioxins and
Dibenzofurans during Combustion of a 2,4,5-T Formulation," Chemosphere.
8, 461, 1979.
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-26-
14. Lustenhouwer, J., et al, "Chlorinated Dibenzo-p-dioxins and Related
Compounds in Incinerator Effluents," Chemosphere, 2> 501» 1980.
15. Buser, H. R., "Identification of Polychlorinated Dibenzo-p-dioxin Isomers
Found in Fly Ash," Chemosphere. 7_, 165, 1978.
16. Rappe, C., et al, "Formation of Polychlorinated Dibenzo-p-dioxins (PCDDs)
and Polychlorinated Dibenzo-p-furans (PCDFs) by Burning or by Heating
Chlorophenates," Chemosphere, _7, 269, 1978.
17. Nestrick, T. J. , et al, "Indentification of Tetrachlorodibenzo-p-dioxin
Isomers at the one ng Level by Photolytic Degradation and Pattern Recogni-
tion Techniques, Analytical Chemistry, 52, 1865, 1980.
18. Bumb, R. R., et al, "Trace Chemistries of Fire: A Source of Chlorinated
Dioxins," Science. 210. 385, 1980.
19. August 8, 1978, communication to Joseph J. Merenda, Director, Assessment
Division, OTE/OTS, "Interim Status Report 8EHQ-0778-0209," from Frank D.
Kover, OTE/OTS.
20. September 6, 1978, communication to Etcyl H. Blair, Dow Chemical, "EPA
Document Control No. 8EHQ-0778-0209," from Warren R. Muir, OTS, EPA.
21. Kimble, B. J. and M. C. Gross, "Tetrachlorodibenzo-p-Dioxin Quantification
in Stack-Collected Coal Fly Ash," Science, 207, 50, 1980.
22. June 27, 1978, communication to John Hesse, Office of Toxic Materials Control,
Michigan Department of Natural Resources, from John Gledhill, Dow Chemical.
23. Forney, J., "Summary of Dioxin Contamination in Michigan," Office of Toxic
Materials Control, Michigan Department of Natural Resources, December 9, 1980.
24. January 15, 1979, communication to Mr. G. Amendola, EPA, EDO, "Results of
October Samples from Dow Midland Plant Production Facilities," from H. B.
Frodge, Dow Chemical Company.
25. December 20, 1978, communication to K. Bremer, EPA, "Summary of Results for
Analyses of Samples of Fish from Michigan," from E. 0. Oswald, ETD, HERL.
26. October 17, 1978, communication to Michigan Governor William G. Mil liken
from Sherwin Gardner, Acting Commissioner of Food and Drugs.
27. April 9, 1978, communication to Karl Bremer, "Results of Analysis of Environ-
mental Samples from Michigan for TCDD," from E. 0. Oswald, ETD, HERL.
28. April 12, 1979, communication to John Hesse, Office of Toxic Materials Control,
Michigan Department of Natural Resources from John Gledhill, Dow Chemical.
29. Stalling, D., "Residues of Dibenzofurans and Dibenzo-p-dioxins in Composite
Samples of Fish and Gulls from Different Sites on the Great Lakes," Presented
at the Association of Analytical Chemists, Ottawa, Canada, May 12, 1981.
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-27-
30. January 12, 1981, communication to David Stalling, Columbia National Fisheries
Laboratory, from Milt Clark, Office of Toxic Substances, EPA, Region V.
31. July 1, 1981, communication to Milt Clark, Office of Toxic Substances,
EPA, Region V, from David Stalling, Columbia National Fisheries Laboratory.
32. Hal let, D. J. and R. Norstom, "TCDD in Great Lakes Herring Gulls," December 2,
1980 Report of the Canadian Wildlife Service, National Wildlife Service.
33. April 16, 1981, communication to Charles Fink, Connecticut Agriculture ""
Experiment Station, from David Stalling, Columbia National Fisheries
Laboratory.
34. April 20, 1981, communication to Dr. Burton Cardwell, Toxic Substance and
Emergency Office, Michigan Department of Agriculture From Alan L. Hoeting,
District Director, FDA.
35. April 24, 1979, Press Release, New York Department of Public Health.
36. "Hooker Dumpsites May Pose Dioxin Threat," Chemical Week. 124. 16, 1979.
37. May 2, 1979, Press Release, New York Department of Public Health.
38. August 13, 1978, communication to G. Marsh, Pesticides Branch, EPA Region V,
from Thomas 0. Tiernan, Wright State University.
39. EPA Region V, "Evaluation of Suspected Environmental Contamination of the
Hemlock, Michigan Area," September 1980.
40. April 25, 1980, communication to Mike Dellarco, Special Pesticides Review,
EPA, from Michael Gross, Department of Chemistry, University of Nebraska.
41. Gross, M., "Analysis of Tetrachlorodioxin and Tetrachlorodibenzofuran in
Three Environmental Samples and One Biological Sample," Department of
Chemistry, University of Nebraska, December 12, 1980.
42. EPA, "Storage and Disposal of Waste Material: Prohibition of Disposal of
Tetrachlorodibenzo-p-Dioxin," Federal Register. Vol. 45, No. 98, May 19, 1980.
43. August 19, 1980, communication to 0. Hutzinger from B. J. Kimble,
Letter Exhibit #1500, EPA, 2,4,5-T/Silvex Cancellation Proceedings,
Inre: Dow Chemical Company, et al, FIFRA #415, et al.
44. Testimony of 0. Hutzinger, November 18, 1980, Transcript pages 17,466 - 17,471,
EPA, 2,4,5-T/Silvex Cancellation Proceedings, Inre: Dow Chemical Company,
et al, FIFRA #415, et al.
45. Harless, R.L. and R. G. Lewis "Quantitative Determination of 2,3,7,8-Tetra-
chlorodibenzo-p-dioxin by Gas Chromatography and Mass Spectroscopy,"
October 1980, Letter Exhibit #1501, EPA, 2,4,5-T/Silvex Cancellation
Proceedings, Inre: Dow Chemical Company, et al, FIFRA #415, et al.
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