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TCDD distribution in the Spring River, Southwestern Missouri
Environmentlnternational, Vol. 9, pp. 249-253, 1983
0160-4120/83 $3.00 + .00 Copyright © 1983 Pergamon Press Ltd.
Printed in the USA. All rights reserved.
TCDD DISTRIBUTION IN THE SPRING RIVER, SOUTHWESTERN MISSOURI Robert D. Kleopfera U.S. Environmental Protection Agency, Region VII Laboratory, Kansas City, Kansas 66115, USA
John Zirschky Department of Agricultural Engineering, Clemson University, Clemson, South Carolina 29631, USA
(Received 9 September 1982; Accepted 18 April 1983) The waste management practices of a now defunct chemical company created several disposal sites containing 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) contaminated materials. A sampling survey of the Spring River, which drains the disposal sites, was conducted to determine if TCDD contamination of this river had occurred. TCDD was found in fish at concentrations of 0.8 to 55 ng/kg (whole fish) and 1.4 to 18. ng/kg (fillet). In addition, TCDD was present in the fish at least as far as 69 mi (111 km) downstream of the disposal sites. The detection limits were generally not sufficient to determine the sediment TCDD concentration in the river. TCDD was only found in the sediments immediately downstream of the former manufacturing facility, at 12 ng/kg.
Introduction
1975). Therefore, a sampling survey was conducted to determine if TCDD contamination of the Spring River had occurred.
Between 1969 and 1972, the waste management practices of the now defunct North Eastern Pharmaceutical and Chemical Company (NEPACCO) created several uncontrolled hazardous waste disposal sites. This facility manufactured hexachlorophene from tetrachlorobenzene with 2,4,5-trichlorophenol (TCP) produced as an intermediate. As a result of the process used for
Numerous investigations have been conducted on the fate of TCDD in aquatic environments. TCDD has a moderately high sediment/water partition coefficient which has been estimated to range from 1.1 x 104 to 3.5 x 104 (Veterans Administration, 1981). TCDD would therefore be expected to be associated primarily with the sediments in an aquatic system.
TCP production, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) was formed as an unwanted trace contaminant
Bioaccumulation of TCDD does occur in aquatic systems. Bioconcentration factors for fish (tissue to water) of 2000 (catfish), 6600 (rainbow trout), and 24,000 (mosquito fish) have been reported (Dow Chemical Company, 1978; Isensee and Jones, 1975).
of the TCP (Esposito et al., 1980). A distillation process was used to purify the TCP, and the distillation residues containing the TCDD were disposed of at several locations in southwestern Missouri (Harris, 1981). The Spring River Basin encompasses most of the
Seasonal fluctuations in the bioaccumulation of TCDD by fish may also occur. Data presented by the National Research Council of Canada (NRCC, 1981) suggests
known TCDD disposal sites used by NEPACCO in southwestern Missouri. TCDD is an extremely toxic substance and thus is of great concern to human and animal life when released to the environment (NRCC, 1981). For example, the distillation residues from this same facility were implicated in the deaths of over 60 horses and numerous other animals when used for dust
that the TCDD tissue concentration can increase from winter to summer; however, sufficient data was not available for a definitive detemination of the variation of TCDD concentration with season. TCDD has been detected in fish from several surface waters in North America, and many investigators believe that dioxins may be ubiquitous in the environment (NRCC, 1981). TCDD concentrations of 15-480
control at several horse arenas in 1971 (Carter et al., aTo whomcorrespondence should be addressed, 249
250
R.D. Kleopfer and J. Zirschky
ng kg-' were detected in fish from the Arkansas River near another former 2,4,5-TCP producer (NRCC, 1981). Concentrations of 2,3,7,8-TCDD from 4 to 695 ng kg-' were detected in fish collected from the Tittabawassee, Saginaw, and Grand rivers and Saginaw Bay in Michigan (Harless et aL, 1982). Fish from the Flint, Cass, and Shiawassee rivers in Michigan have been found to contain 1-104 ng kg-1 of 2,3,7,8-TCDD. Possible sources of the TCDD in the Tittabawassee, Saginaw, Grand, Flint, and Cass rivers include power plants, incinerators, and vehicle emissions. A pesticide plant is also a potential source for the Tittabawassee River. The Shiawassee River, however, is remote from any of the abovementioned sources (Crummett, 1982). Contaminated fish have also been found in the Housatonic River, Lake Ontario, the Niagara River, Lake Erie, and Lake Huron in the ngkg-' range (NRCC, 1981; Stalling et al., 1981). Several safe consumption levels have been suggested for 2,3,7,8-TCDD in fish. The U.S. Food and Drug Administration (FDA) considers 25 ng kg-' a safe 2,3,7,8-TCDD level for human consumption (at 4 oz per meal); however, fish containing less than 50 ng kg-' can be consumed on a limited basis (one meal per week for sport fisherman or two meals per month for individuals who consume contaminated fish year round). The New York State Department of Environmental Conservation
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(NYDEC) considers 10 ng kg-1 a safe level, assuming 6-8-oz portions. Finally, the Canadian government has set a 20 ng kg -1 level, assuming a 4-oz portion (NRCC, 1981). These safe consumption levels are based on the edible tissue concentrations and not the whole fish TCDD concentration.
Sampling Methodology The Spring River Basin drains approximately 3000 mi 2 (4800 km ~) in southwestern Missouri, southeastern Kansas, and northeastern Oklahoma (Fig. 1). The manufacturing facility and the disposal sites are located near the headwaters of this river. Drainage from the former manufacturing facility enters the Spring River at stream mile 2.9 (4.7 km), as measured from the headwaters. Fish and sediment samples were collected from the headwaters of this river to a distance of 96 miles (154 km) downstream in November and December, 1981. Water samples were not collected because of the affinity of TCDD for sediment. The fish were collected by electroshocking and frozen until analysis. During the November sampling, fish and sediment samples were collected from stream miles 0, 0.7, 3.2, 4.3, 5.6, and 11 (0, 1.1, 5.1, 6.9, 9.0, and 17.7 km, respectively). The control sample (stream mile 0) was collected from a
Two d ~ s o , 1 k~at, d ~ o , this point
~.
/=/.
/
~
0 Dec.:1981SomlMing Locations 6 9 Numbers R e m s e n t Strelm Miles o
~
0
Miles 5 Kilometers
Fig. 1. Location of Spring River sampling points.
io
i
TCDD distributionin the SpringRiver
251
trout hatchery which is located at the headwaters of this river. Generally, these sampling locations were selected to isolate known or suspected TCDD sources and for ease of access. The sediment sample container for stream mile 4.3 (6.9 km) was damaged during transport; thus, this sample was not analyzed. Since the results of these samples verified that TCDD was present in the fish flesh, the survey was expanded to determine the extent of contamination. Samples were collected from stream miles 0, 36, 46, 69, and 96 miles (0, 58, 74, 111, and 154 kin, respectively). Accumulation of contaminated sediment was expected to occur at a head dam located at stream mile 46 (74 km). Unfortunately, ice prevented the collection of fish and sediment samples at the dam. Fish samples, however, were collected upstream from the reservoir. The remaining sampling locations were selected for ease of access. The location of all of the sampling points is shown on Fig. 1.
After saponification with ethanol and aqueous potassium hydroxide, the solution was extracted with hexane. The hexane extract was cleaned with concentrated H2SO, prior to extract concentration. Isomer specific analysis was by high resolution gas chromatography/ high resolution mass spectrometry. Detection limits ranged from 1 to 10 ng kg -1. N C T R procedure. Two fish samples were analyzed by the National Center for Toxicological Research (NCTR) (Mitchum et al., 1982). The samples were prepared by the UNL lab by the previously described procedure. Analysis was by combined capillary gas chromatography/atmospheric pressure ionization mass spectrometry. The ions monitored correspond to the 4,5-dichloro-l,2-benzoquinone radical anion. This analytical procedure is selective for TCDD isomers having the 2:2 substitution pattern. This method had a detection limit of 25 ng kg -t.
Analytical P r o c e d u r e s
TCDD in sediment (EPA) Aliquots of sediment (50 g, wet weight) were air dried, dosed with '3C12-TCDD, and mixed with anhydrous sodium sulfate prior to extraction with acetone/hexane using a column, or with toluene using a Soxhlet apparatus. The concentrated extract was cleaned up by liquid chromatography on silica gel, acidified silica gel, and alumina. Analysis was by HRGC/LRMS as previously described for fish analyses (CNFRL and EPA procedures). Detection limits ranged from 5 to 20 ng kg-' (wet).
Due to the need for rapid sample turnaround and the limited availability for low-level TCDD analyses, four laboratories were involved in the analysis of the fish and sediment samples. Different analytical procedures were used at each of these facilities. Several samples were split among at least two laboratories for quality assurance purposes. A brief discussion of the methodologies utilized is presented below.
TCDD in fish CNFRL and EPA procedures. This procedure was developed at the Columbia National Fisheries Research Laboratory (CNFRL) (Stalling et al., 1981). A ground tissue sample was mixed with anhydrous sodium sulfate and extracted with cyclohexane/methylene chloride 1:1 using column extraction. In this process, the eluate passed through a column containing 1) potassium s i l icate, 2) silica gel, 3) cesium silicate, 4) silica gel, and 5) carbon/glass fiber adsorbent. The TCDD was recovered from the carbon adsorbent by reverse elution with toluene. The concentrated toluene extract was then applied to a second series of adsorbents containing 1) cesium silicate and sulfuric acid-impregnated silica gel, and 2) activated alumina. The desired fraction was reduced in volume and analyzed by high resolution gas chromatography/low resolution mass spectrometrymultiple ion detection (HRGG/LRMS-MID). Quantification was based on the use of isotopically enriched internal standard '3C,2-TCDD which was added to each sample prior to extraction. Typical detection limits were 1 ng kg-'. UNL procedure. This procedure was used by the Midwest Center for Mass Spectrometry at the University of Nebraska--Lincoln (UNL) (Gross et al., 1981). The gound tissue sample was fortified with the isotopically enriched 13C,2-TCDD internal standard,
Results TCDD was detected in the fish from all of the sampiing locations except the stream miles 0 and 96 (0 and 154 km) (Table 1). The highest levels of 2,3,7,8-TCDD detected were at stream mile 3.2 (5.1 km; 37-55 ng kg-'; whole fish). TCDD was also detected upstream from the manufacturing facility at 19-25 ng kg -1 (whole fish) at stream mile 0.7 (1.1 km). TCDD was detected in the sediment only at stream mile 3.2 (5.1 km) at a concentration of 12 ng kg-1. This sampling location is approximately 0.3 (0.5 km) miles downstream of the point where drainage from the former manufacturing facility enters the Spring River. Discussion Fish samples from stream miles 0, 0.7, 3.2, and 5.6 (0, 1.1, 5.1, and 9.0 km, respectively) were split and analyzed by at least two laboratories. In spite of the different analytical techniques, the data obtained by each method appear to be in relative agreement (Table 1). Sufficient data, however, are not available for an extensive comparison of methods. The levels of TCDD detected in the upper reaches of the Spring River (stream mile 0 to 46; 74 km) tend to in-
252
R . D . K l e o p f e r a n d J. Z i r s c h k y
T a b l e 1. F i s h a n d s e d i m e n t 2 , 3 , 7 , 8 - T C D D d a t a ( n g kg-J), a Fish TCDD Concentration Stream Mile (km) 0
Fish Species ( n u m b e r in composite)
CNFRL b
R a i n b o w T r o u t (5) N o v . 81 R a i n b o w T r o u t (5) Dec. 81
Analytical Procedure UNL c NCTR d
< l(w) -
<9(w) < l(w)
19(w) -
15(w) 16(w)
37(w) -
<5
-
25(w) -
< 10
52(w) -
55(w) 18(F)
45(w) -
12
W h i t e S u c k e r (3)
-
15(F)
-
-
-
5.6 (9.0)
W h i t e S u c k e r (5) W h i t e S u c k e r (5)
36(w) -
39(w) 17(F)
-
-
< 20
11 (17.7)
W h i t e S u c k e r (5) H o g S u c k e r (2) C r e e k C h u b (3)
-
6(F) 5(F) < 8(F)
-
-
W h i t e S u c k e r (5) H o g S u c k e r (2)
2.9 (4.7)
Location of NEPACCO
3.2 (5.1)
W h i t e (4) a n d H o g (2) S u c k e r C r e e k C h u b (4)
<25(w) -
Sediment
-
0.7 (1.1)
4.3
EPA e
(6.9)
36 (58)
W h i t e S u c k e r s (4) S m a l l m o u t h B a s s (7)
6.2(w)
< 1.2(w) .
-
46 (74)
S p o t t e d S u c k e r s (6) L a r g e m o u t h B a s s (9)
2.5(w)
< l(w) -
-
-
l.l(w)
-
-
-
-
< l(w)
-
-
0.8(w)
-
-
-
-
< 3(w)
-
-
.
< 10
.
. -
1.4(F)
S h o r t h e a d R e d h o r s e (4) 69 (111) 96
N o r t h e r n H o g s u c k e r s (3) S h o r t h e a d (2) a n d R i v e r (1) Redhorse C a r p (5)
-
-
(154) aw = w h o l e fish; F = fillet; - = n o t a n a l y z e d . b C N F R L = C o l u m b i a N a t i o n a l F i s h e r i e s L a b o r a t o r y (Stalling et al., 1981). c U N L = U n i v e r s i t y o f N e b r a s k a ( G r o s s et aL, 1981). d N C T R = N a t i o n a l C e n t e r f o r T o x i c o l o g i c a l R e s e a r c h ( M i t c h u m et al., 1982). e E P A = U . S . E n v i r o n m e n t a l P r o t e c t i o n A g e n c y ( S t a l l i n g et al., 1981).
dicate that contamination of this river has resulted from the waste management practices of NEPACCO. This facility and the disposal sites are the only known significant source of TCDD in this portion of the Spring River Basin. Fish migration would account for the presence of TCDD in the fish collected upstream from NEPACCO and the disposal sites at stream mile 0.7 (1.1 km). Suckers have been estimated to have a migratory range of 20-30 mi (32-48 km) in this river (Crunkilton, 1982). It was expected that two dams near Carthage, MO (stream miles 46 and 48; 74 and 77 km) would prevent sediment migration beyond this point and thus limit fish contamination to areas upstream of the dams. Fish were found to be contaminated for a distance of at least 21 mi (77 km) beyond the dams. These dams are not physical barriers to fish movement in either direction; thus, migration may partially account for the extent of TCDD contamination in the Spring River. Bioconcentration of extremely low levels of TCDD from the aqueous phase may also explain the extent of contamination. Although TCDD is primarily associated
with the sediments, a small amount of TCDD would be expected to be present in the aqueous phase. The fish bioconcentration factors presented previously ranged from 2 × 103 to 2.4 x 1 0 4 ; thus, substantially higher concentrations of TCDD would be expected in the fish than in the water. The Spring River discharge generally increases with distance downstream of the headwaters; therefore, dilution of the TCDD in the aqueous phase would be expected. As a result, a general decrease in the fish TCDD concentration with downstream distance would also be expected (assuming a point source), and, indeed, such a general trend is apparent in the data (Table 1). The level of TCDD detected at stream mile 69 (111 km) may also represent background levels for this area of the Spring River basin. The Spring River below stream mile 48 (77 km) receives drainage from several urban areas (Fig. 1). Industrial development in these towns is substantially greater than the development in any of the communities above the Carthage dams. Therefore, the control sample from stream mile 0 may
TCDD distribution in the Spring River n o t be a good reference p o i n t for e v a l u a t i n g the d a t a f r o m the lower p o r t i o n o f the Spring River. Initially, it was h o p e d that it w o u l d be possible to correlate the s e d i m e n t d a t a with the fish data. Since T C D D was o n l y detected in one s e d i m e n t sample, such a c o m p a r i s o n is n o t possible. T h e ratio of fish to sediment T C D D c o n c e n t r a t i o n ranges f r o m 5.7 × 10 -2 to 2.2, based u p o n the b i o c o n c e n t r a t i o n factors a n d s e d i m e n t / water p a r t i t i o n coefficients a l r e a d y discussed. U s i n g the fish a n d s e d i m e n t d a t a f r o m stream mile 3.2 (5.1 km)
(Table 1), a fish-to-sediment concentration ratio of 3.1 t o 4.6 was calculated; this is slightly higher t h a n the r a n g e developed f r o m the literature. C o n s i d e r a b l e a d d i t i o n a l s a m p l i n g over m a n y years will be needed to define the extent a n d possible sources o f the T C D D c o n t a m i n a t i o n . F o r example, it is n o t k n o w n if the past o p e r a t i o n s o f N E P A C C O , o n - g o i n g waste migration from the disposal sites, or another u n i d e n t i f i e d source is responsible for the fish a n d sedim e n t c o n t a m i n a t i o n in the u p p e r p o r t i o n s of the Spring River. U n t i l this work is c o m p l e t e d , the State o f Missouri has r e c o m m e n d e d that residents limit cons u m p t i o n o f fish caught f r o m the entire Spring River, excluding the t r o u t hatchery. T h e fish at the hatchery are captive, a n d T C D D c o n t a m i n a t i o n o f these fish was n o t detected o n two sampling occasions.
Acknowledgements-The authors would like to acknowledge the
substantial analytical contributions by the Columbia National Fisheries Research Lab in Columbia, MO (Dr. David Stalling and Dr. Lawrence Smith), the Midwest Center for Mass Spectrometry at the University of Nebraska-Lincoln (Dr. Michael Gross and Dr. Lal Weerasinghe), and the National Center for Toxicological Research at Jefferson, AR (Dr. Robert Mitchum and Dr. Walter Korfmacher). We also wish to recognize contributions by EPA staff members, including Dr. Ken Yue, William Bunn, Dan Harris, and Bruce Littell. Finally, the authors would like to thank Alvina Laird and Vickie B y k o for preparing the manuscript. At the time this paper was prepared, John Zirschky was with Ecology and Environment, Inc.
253
References Carter, D. C. et al. (1975) Tetrachlorodibenzodioxin: An accidental poisoning episode in horse arenas, Science 188, 738-740. Crummett, w. B. (1982) Environmental chlorinated dioxins from combustion-The trace chemistries of fire hypothesis, in Chlorinated Dioxins and Related Compounds lmpact on the Environment, o . Hutzinger, R. W. Frei, E. Menan, and F. Poc-
chiari, eds. Pergamon Press, Oxford. Crunkilton, R. (1982) Personal communication. Water Quality Research Biologist, Missouri, Department of Conservation, Columbia, MO. Dow Chemical Company (1978) The trace chemistry of fire-A source of and routes for the entry of chlorinated dioxins into the environment. Chlorinated Dioxin Task Force, Dow Chemical Company, Midland, MI. Esposito, M. P., Tiernan, T. O., and Dryden, F. E. (1980) Dioxins. EPA-600/2-80-197, U.S. Environmental Protection Agency, Cincinnati, OH. Gross, M. L., Sun, Tung, Lyon, B. A., Wejinsk, S. F., and Hiker, D.R. (1981) Method validation of tetrachlorodibenzodioxin at the low part-per-trillion level, A n a l Chem. 53, 1902-1906. Harless, R. L., Oswald, E. O., Lewis, R. G., Dupuy, A. E., McDaniel, D. D., and Tai, Han (1982) Determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin in fresh water fish, Chemosphere 11, 193-198. Harris, D. (1981) Dioxin investigations in southwest missouri, inProceedings o f the National Conference on Management o f UnControlled Hazardous Waste Sites, pp. 322-325. Hazardous Materials
Control Research Institute, Washington, DC. Isensee, A. R. and Jones, G. E. (1975) Distribution of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)in aquatic model ecosystems, Environ. Sci. Technol. 9, 668-672. Mitchum, R. K., Korfmacher, W. A., Moler, G. F., and Stalling, D. L. (1982) Capillary gas chromatography/atmospheric pressure negative chemical ionization mass spectrometry of the 22 isomeric tetrachlorodibenzo-p-dioxins, Anal. Chem. 54, 719-722. National Research Council of Canada (1981) Polychlorinated diobenzo-p-dioxins: Criteria for their effects on man and his environment. NRCCNo. 18574, EnvironmentalSecretariat, Ottawa, Canada. Stalling, D. C., Smith, L. M., Petty, J. D., Hogan, J. W., Johnson, J . L . , Rappe, C., and Buser, H. R. (1981) Residues of polychlorinated dibenzo-p-dioxins and dibenzofurans in Laurentian Great Lakes fish. Second International Conference on TCDD and Related Compounds, Washington, DC. VeteransAdministration (1981) Review o f Literature on Herbicides, Including Phenoxy Herbicides and Associated Dioxins. Volume 1. Analysis o f Literature. Department of Medicine and Surgery, U.S. Veterans Administration, Washington, DC.
0160-4120/83 $3.00 + .00 Copyright © 1983 Pergamon Press Ltd.
Printed in the USA. All rights reserved.
TCDD DISTRIBUTION IN THE SPRING RIVER, SOUTHWESTERN MISSOURI Robert D. Kleopfera U.S. Environmental Protection Agency, Region VII Laboratory, Kansas City, Kansas 66115, USA
John Zirschky Department of Agricultural Engineering, Clemson University, Clemson, South Carolina 29631, USA
(Received 9 September 1982; Accepted 18 April 1983) The waste management practices of a now defunct chemical company created several disposal sites containing 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) contaminated materials. A sampling survey of the Spring River, which drains the disposal sites, was conducted to determine if TCDD contamination of this river had occurred. TCDD was found in fish at concentrations of 0.8 to 55 ng/kg (whole fish) and 1.4 to 18. ng/kg (fillet). In addition, TCDD was present in the fish at least as far as 69 mi (111 km) downstream of the disposal sites. The detection limits were generally not sufficient to determine the sediment TCDD concentration in the river. TCDD was only found in the sediments immediately downstream of the former manufacturing facility, at 12 ng/kg.
Introduction
1975). Therefore, a sampling survey was conducted to determine if TCDD contamination of the Spring River had occurred.
Between 1969 and 1972, the waste management practices of the now defunct North Eastern Pharmaceutical and Chemical Company (NEPACCO) created several uncontrolled hazardous waste disposal sites. This facility manufactured hexachlorophene from tetrachlorobenzene with 2,4,5-trichlorophenol (TCP) produced as an intermediate. As a result of the process used for
Numerous investigations have been conducted on the fate of TCDD in aquatic environments. TCDD has a moderately high sediment/water partition coefficient which has been estimated to range from 1.1 x 104 to 3.5 x 104 (Veterans Administration, 1981). TCDD would therefore be expected to be associated primarily with the sediments in an aquatic system.
TCP production, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) was formed as an unwanted trace contaminant
Bioaccumulation of TCDD does occur in aquatic systems. Bioconcentration factors for fish (tissue to water) of 2000 (catfish), 6600 (rainbow trout), and 24,000 (mosquito fish) have been reported (Dow Chemical Company, 1978; Isensee and Jones, 1975).
of the TCP (Esposito et al., 1980). A distillation process was used to purify the TCP, and the distillation residues containing the TCDD were disposed of at several locations in southwestern Missouri (Harris, 1981). The Spring River Basin encompasses most of the
Seasonal fluctuations in the bioaccumulation of TCDD by fish may also occur. Data presented by the National Research Council of Canada (NRCC, 1981) suggests
known TCDD disposal sites used by NEPACCO in southwestern Missouri. TCDD is an extremely toxic substance and thus is of great concern to human and animal life when released to the environment (NRCC, 1981). For example, the distillation residues from this same facility were implicated in the deaths of over 60 horses and numerous other animals when used for dust
that the TCDD tissue concentration can increase from winter to summer; however, sufficient data was not available for a definitive detemination of the variation of TCDD concentration with season. TCDD has been detected in fish from several surface waters in North America, and many investigators believe that dioxins may be ubiquitous in the environment (NRCC, 1981). TCDD concentrations of 15-480
control at several horse arenas in 1971 (Carter et al., aTo whomcorrespondence should be addressed, 249
250
R.D. Kleopfer and J. Zirschky
ng kg-' were detected in fish from the Arkansas River near another former 2,4,5-TCP producer (NRCC, 1981). Concentrations of 2,3,7,8-TCDD from 4 to 695 ng kg-' were detected in fish collected from the Tittabawassee, Saginaw, and Grand rivers and Saginaw Bay in Michigan (Harless et aL, 1982). Fish from the Flint, Cass, and Shiawassee rivers in Michigan have been found to contain 1-104 ng kg-1 of 2,3,7,8-TCDD. Possible sources of the TCDD in the Tittabawassee, Saginaw, Grand, Flint, and Cass rivers include power plants, incinerators, and vehicle emissions. A pesticide plant is also a potential source for the Tittabawassee River. The Shiawassee River, however, is remote from any of the abovementioned sources (Crummett, 1982). Contaminated fish have also been found in the Housatonic River, Lake Ontario, the Niagara River, Lake Erie, and Lake Huron in the ngkg-' range (NRCC, 1981; Stalling et al., 1981). Several safe consumption levels have been suggested for 2,3,7,8-TCDD in fish. The U.S. Food and Drug Administration (FDA) considers 25 ng kg-' a safe 2,3,7,8-TCDD level for human consumption (at 4 oz per meal); however, fish containing less than 50 ng kg-' can be consumed on a limited basis (one meal per week for sport fisherman or two meals per month for individuals who consume contaminated fish year round). The New York State Department of Environmental Conservation
I
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(NYDEC) considers 10 ng kg-1 a safe level, assuming 6-8-oz portions. Finally, the Canadian government has set a 20 ng kg -1 level, assuming a 4-oz portion (NRCC, 1981). These safe consumption levels are based on the edible tissue concentrations and not the whole fish TCDD concentration.
Sampling Methodology The Spring River Basin drains approximately 3000 mi 2 (4800 km ~) in southwestern Missouri, southeastern Kansas, and northeastern Oklahoma (Fig. 1). The manufacturing facility and the disposal sites are located near the headwaters of this river. Drainage from the former manufacturing facility enters the Spring River at stream mile 2.9 (4.7 km), as measured from the headwaters. Fish and sediment samples were collected from the headwaters of this river to a distance of 96 miles (154 km) downstream in November and December, 1981. Water samples were not collected because of the affinity of TCDD for sediment. The fish were collected by electroshocking and frozen until analysis. During the November sampling, fish and sediment samples were collected from stream miles 0, 0.7, 3.2, 4.3, 5.6, and 11 (0, 1.1, 5.1, 6.9, 9.0, and 17.7 km, respectively). The control sample (stream mile 0) was collected from a
Two d ~ s o , 1 k~at, d ~ o , this point
~.
/=/.
/
~
0 Dec.:1981SomlMing Locations 6 9 Numbers R e m s e n t Strelm Miles o
~
0
Miles 5 Kilometers
Fig. 1. Location of Spring River sampling points.
io
i
TCDD distributionin the SpringRiver
251
trout hatchery which is located at the headwaters of this river. Generally, these sampling locations were selected to isolate known or suspected TCDD sources and for ease of access. The sediment sample container for stream mile 4.3 (6.9 km) was damaged during transport; thus, this sample was not analyzed. Since the results of these samples verified that TCDD was present in the fish flesh, the survey was expanded to determine the extent of contamination. Samples were collected from stream miles 0, 36, 46, 69, and 96 miles (0, 58, 74, 111, and 154 kin, respectively). Accumulation of contaminated sediment was expected to occur at a head dam located at stream mile 46 (74 km). Unfortunately, ice prevented the collection of fish and sediment samples at the dam. Fish samples, however, were collected upstream from the reservoir. The remaining sampling locations were selected for ease of access. The location of all of the sampling points is shown on Fig. 1.
After saponification with ethanol and aqueous potassium hydroxide, the solution was extracted with hexane. The hexane extract was cleaned with concentrated H2SO, prior to extract concentration. Isomer specific analysis was by high resolution gas chromatography/ high resolution mass spectrometry. Detection limits ranged from 1 to 10 ng kg -1. N C T R procedure. Two fish samples were analyzed by the National Center for Toxicological Research (NCTR) (Mitchum et al., 1982). The samples were prepared by the UNL lab by the previously described procedure. Analysis was by combined capillary gas chromatography/atmospheric pressure ionization mass spectrometry. The ions monitored correspond to the 4,5-dichloro-l,2-benzoquinone radical anion. This analytical procedure is selective for TCDD isomers having the 2:2 substitution pattern. This method had a detection limit of 25 ng kg -t.
Analytical P r o c e d u r e s
TCDD in sediment (EPA) Aliquots of sediment (50 g, wet weight) were air dried, dosed with '3C12-TCDD, and mixed with anhydrous sodium sulfate prior to extraction with acetone/hexane using a column, or with toluene using a Soxhlet apparatus. The concentrated extract was cleaned up by liquid chromatography on silica gel, acidified silica gel, and alumina. Analysis was by HRGC/LRMS as previously described for fish analyses (CNFRL and EPA procedures). Detection limits ranged from 5 to 20 ng kg-' (wet).
Due to the need for rapid sample turnaround and the limited availability for low-level TCDD analyses, four laboratories were involved in the analysis of the fish and sediment samples. Different analytical procedures were used at each of these facilities. Several samples were split among at least two laboratories for quality assurance purposes. A brief discussion of the methodologies utilized is presented below.
TCDD in fish CNFRL and EPA procedures. This procedure was developed at the Columbia National Fisheries Research Laboratory (CNFRL) (Stalling et al., 1981). A ground tissue sample was mixed with anhydrous sodium sulfate and extracted with cyclohexane/methylene chloride 1:1 using column extraction. In this process, the eluate passed through a column containing 1) potassium s i l icate, 2) silica gel, 3) cesium silicate, 4) silica gel, and 5) carbon/glass fiber adsorbent. The TCDD was recovered from the carbon adsorbent by reverse elution with toluene. The concentrated toluene extract was then applied to a second series of adsorbents containing 1) cesium silicate and sulfuric acid-impregnated silica gel, and 2) activated alumina. The desired fraction was reduced in volume and analyzed by high resolution gas chromatography/low resolution mass spectrometrymultiple ion detection (HRGG/LRMS-MID). Quantification was based on the use of isotopically enriched internal standard '3C,2-TCDD which was added to each sample prior to extraction. Typical detection limits were 1 ng kg-'. UNL procedure. This procedure was used by the Midwest Center for Mass Spectrometry at the University of Nebraska--Lincoln (UNL) (Gross et al., 1981). The gound tissue sample was fortified with the isotopically enriched 13C,2-TCDD internal standard,
Results TCDD was detected in the fish from all of the sampiing locations except the stream miles 0 and 96 (0 and 154 km) (Table 1). The highest levels of 2,3,7,8-TCDD detected were at stream mile 3.2 (5.1 km; 37-55 ng kg-'; whole fish). TCDD was also detected upstream from the manufacturing facility at 19-25 ng kg -1 (whole fish) at stream mile 0.7 (1.1 km). TCDD was detected in the sediment only at stream mile 3.2 (5.1 km) at a concentration of 12 ng kg-1. This sampling location is approximately 0.3 (0.5 km) miles downstream of the point where drainage from the former manufacturing facility enters the Spring River. Discussion Fish samples from stream miles 0, 0.7, 3.2, and 5.6 (0, 1.1, 5.1, and 9.0 km, respectively) were split and analyzed by at least two laboratories. In spite of the different analytical techniques, the data obtained by each method appear to be in relative agreement (Table 1). Sufficient data, however, are not available for an extensive comparison of methods. The levels of TCDD detected in the upper reaches of the Spring River (stream mile 0 to 46; 74 km) tend to in-
252
R . D . K l e o p f e r a n d J. Z i r s c h k y
T a b l e 1. F i s h a n d s e d i m e n t 2 , 3 , 7 , 8 - T C D D d a t a ( n g kg-J), a Fish TCDD Concentration Stream Mile (km) 0
Fish Species ( n u m b e r in composite)
CNFRL b
R a i n b o w T r o u t (5) N o v . 81 R a i n b o w T r o u t (5) Dec. 81
Analytical Procedure UNL c NCTR d
< l(w) -
<9(w) < l(w)
19(w) -
15(w) 16(w)
37(w) -
<5
-
25(w) -
< 10
52(w) -
55(w) 18(F)
45(w) -
12
W h i t e S u c k e r (3)
-
15(F)
-
-
-
5.6 (9.0)
W h i t e S u c k e r (5) W h i t e S u c k e r (5)
36(w) -
39(w) 17(F)
-
-
< 20
11 (17.7)
W h i t e S u c k e r (5) H o g S u c k e r (2) C r e e k C h u b (3)
-
6(F) 5(F) < 8(F)
-
-
W h i t e S u c k e r (5) H o g S u c k e r (2)
2.9 (4.7)
Location of NEPACCO
3.2 (5.1)
W h i t e (4) a n d H o g (2) S u c k e r C r e e k C h u b (4)
<25(w) -
Sediment
-
0.7 (1.1)
4.3
EPA e
(6.9)
36 (58)
W h i t e S u c k e r s (4) S m a l l m o u t h B a s s (7)
6.2(w)
< 1.2(w) .
-
46 (74)
S p o t t e d S u c k e r s (6) L a r g e m o u t h B a s s (9)
2.5(w)
< l(w) -
-
-
l.l(w)
-
-
-
-
< l(w)
-
-
0.8(w)
-
-
-
-
< 3(w)
-
-
.
< 10
.
. -
1.4(F)
S h o r t h e a d R e d h o r s e (4) 69 (111) 96
N o r t h e r n H o g s u c k e r s (3) S h o r t h e a d (2) a n d R i v e r (1) Redhorse C a r p (5)
-
-
(154) aw = w h o l e fish; F = fillet; - = n o t a n a l y z e d . b C N F R L = C o l u m b i a N a t i o n a l F i s h e r i e s L a b o r a t o r y (Stalling et al., 1981). c U N L = U n i v e r s i t y o f N e b r a s k a ( G r o s s et aL, 1981). d N C T R = N a t i o n a l C e n t e r f o r T o x i c o l o g i c a l R e s e a r c h ( M i t c h u m et al., 1982). e E P A = U . S . E n v i r o n m e n t a l P r o t e c t i o n A g e n c y ( S t a l l i n g et al., 1981).
dicate that contamination of this river has resulted from the waste management practices of NEPACCO. This facility and the disposal sites are the only known significant source of TCDD in this portion of the Spring River Basin. Fish migration would account for the presence of TCDD in the fish collected upstream from NEPACCO and the disposal sites at stream mile 0.7 (1.1 km). Suckers have been estimated to have a migratory range of 20-30 mi (32-48 km) in this river (Crunkilton, 1982). It was expected that two dams near Carthage, MO (stream miles 46 and 48; 74 and 77 km) would prevent sediment migration beyond this point and thus limit fish contamination to areas upstream of the dams. Fish were found to be contaminated for a distance of at least 21 mi (77 km) beyond the dams. These dams are not physical barriers to fish movement in either direction; thus, migration may partially account for the extent of TCDD contamination in the Spring River. Bioconcentration of extremely low levels of TCDD from the aqueous phase may also explain the extent of contamination. Although TCDD is primarily associated
with the sediments, a small amount of TCDD would be expected to be present in the aqueous phase. The fish bioconcentration factors presented previously ranged from 2 × 103 to 2.4 x 1 0 4 ; thus, substantially higher concentrations of TCDD would be expected in the fish than in the water. The Spring River discharge generally increases with distance downstream of the headwaters; therefore, dilution of the TCDD in the aqueous phase would be expected. As a result, a general decrease in the fish TCDD concentration with downstream distance would also be expected (assuming a point source), and, indeed, such a general trend is apparent in the data (Table 1). The level of TCDD detected at stream mile 69 (111 km) may also represent background levels for this area of the Spring River basin. The Spring River below stream mile 48 (77 km) receives drainage from several urban areas (Fig. 1). Industrial development in these towns is substantially greater than the development in any of the communities above the Carthage dams. Therefore, the control sample from stream mile 0 may
TCDD distribution in the Spring River n o t be a good reference p o i n t for e v a l u a t i n g the d a t a f r o m the lower p o r t i o n o f the Spring River. Initially, it was h o p e d that it w o u l d be possible to correlate the s e d i m e n t d a t a with the fish data. Since T C D D was o n l y detected in one s e d i m e n t sample, such a c o m p a r i s o n is n o t possible. T h e ratio of fish to sediment T C D D c o n c e n t r a t i o n ranges f r o m 5.7 × 10 -2 to 2.2, based u p o n the b i o c o n c e n t r a t i o n factors a n d s e d i m e n t / water p a r t i t i o n coefficients a l r e a d y discussed. U s i n g the fish a n d s e d i m e n t d a t a f r o m stream mile 3.2 (5.1 km)
(Table 1), a fish-to-sediment concentration ratio of 3.1 t o 4.6 was calculated; this is slightly higher t h a n the r a n g e developed f r o m the literature. C o n s i d e r a b l e a d d i t i o n a l s a m p l i n g over m a n y years will be needed to define the extent a n d possible sources o f the T C D D c o n t a m i n a t i o n . F o r example, it is n o t k n o w n if the past o p e r a t i o n s o f N E P A C C O , o n - g o i n g waste migration from the disposal sites, or another u n i d e n t i f i e d source is responsible for the fish a n d sedim e n t c o n t a m i n a t i o n in the u p p e r p o r t i o n s of the Spring River. U n t i l this work is c o m p l e t e d , the State o f Missouri has r e c o m m e n d e d that residents limit cons u m p t i o n o f fish caught f r o m the entire Spring River, excluding the t r o u t hatchery. T h e fish at the hatchery are captive, a n d T C D D c o n t a m i n a t i o n o f these fish was n o t detected o n two sampling occasions.
Acknowledgements-The authors would like to acknowledge the
substantial analytical contributions by the Columbia National Fisheries Research Lab in Columbia, MO (Dr. David Stalling and Dr. Lawrence Smith), the Midwest Center for Mass Spectrometry at the University of Nebraska-Lincoln (Dr. Michael Gross and Dr. Lal Weerasinghe), and the National Center for Toxicological Research at Jefferson, AR (Dr. Robert Mitchum and Dr. Walter Korfmacher). We also wish to recognize contributions by EPA staff members, including Dr. Ken Yue, William Bunn, Dan Harris, and Bruce Littell. Finally, the authors would like to thank Alvina Laird and Vickie B y k o for preparing the manuscript. At the time this paper was prepared, John Zirschky was with Ecology and Environment, Inc.
253
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