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KEPONE AND THE JAMES RIVER Robert J. Huggett College of William and Mary ABSTRACT The James River in Virginia was contaminated by the pes- ticide kep one when the material entered the river as early as 1968 and continued until its discovery in 1975. The river became so contaminated that commercial fisheries were closed. In 1988, 13 years after closure, all fishing res- trictions were lifted. The contaminated sediments have been diluted and covered enough by uncontaminated material that the Rep one flux back into the water column has diminished. depone concentrations in organisms inhabitating the river are finally below the U.S. Environmental Protection Agency and Food and Drug Administration action levels. Biological, chemical, physical and geological aspects of the contamina- tion indicate that remedial actions to remove kep one would be expensive and environmentally unwise. INTRODUCTION In 1988, there were no restrictions on commercial fishing in the James River. It has been more than a decade since workers at a kepone manufacturing facility in Hopewell, Virginia became ill from occupa- tional exposure to the pesticide. The knowledge of their exposure, the fact that kep one is a mammalian carcinogen, and the subsequent determin- ation that the adjacent river had become contaminated with the compound led Governor Mills Godwin to close the tidal portion of the James and its tributaries to commercial fishing. Kepone (decachlorooctabydro-1,3,4-metheno-2H-cyclobutarcd]-pentalen- 2-one) was produced from hexachlorocyclopentadiene in the presence of sulfur trioxide. A solution of sodium hydroxide was used in the purifi- cation process (Huggett et al., 1980~. The conditions used in the for- mulation of the compound suggest that it should be resistant to chemi- cal degradation under natural environmental conditions, a supposition that has been verified by field observations. If kepone has degraded significantly in the river, it is not obvious even after thousands of chemical observations over 13 years. The fishing restrictions were meets were diluted and covered by relaxed because the contaminated sedi- __ _ ~ uncontaminated materials. Since the kep one flux back into the water column diminished, finfish and shell- fish inhabiting the river contain concentrations below action levels 417
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418 established by the U.S. Environmental Protection Agency (EPA) and Food and Drug Administration (FDA). THE JAMES RIVER The James River extends from its mouth near Norfolk and Newport News, Virginia, to West Virginia (Figure 1~. It is tidal for the first 160 km with the city of Richmond located at ifs fall line. The drain- age basin encompasses approximately 25,600 km and runoff from this area results in it being the third largest tributary of the Chesapeake Bay, delivering approximately 16 percent of the fresh water entering the system. The average discharge over the fall line at Richmond is 212 m /sec. The river is a coastal plain estuary for its first 60 to 80 km with the location of the freshwater-saltwater interface varying depending on rainfall in the drainage basin. Fresh water from upstream flows over more dense saline water creating a two-layer circulation pattern. As the fresh water flows to the sea, there is some mixing between layers, giving rise to a net downstream flow in the surface layer and a net upstream flow on the bottom (Pritchard, 1952~. Suspended particulate matter is carried downstream in the tidal freshwater portion of the river (i.e., above the freshwater-saltwater interface) and downstream in the surface layer of the estuary. If the particles sink into the bottom layer, they are transported upstream toward the interface (Fig- ure 2~. This phenomenon is mainly responsible for the higher sedimenta- tion rate and more turbid water in the interface region of the river, which is appropriately called the "turbidity maximum zone." The circulation pattern and its influence on the movement of partic- ulate matter controls the transport of kep one in the James River. The pesticide entered the river at Hopewell, associated with particulate material, and was transported downstream. Most of the kepone deposited in the turbidity maximum zone. THE KEPONE SOURCE Allied Chemical Corporation began producing kepone in 1966 and intermittently continued until 1974. At this time, Life Science Pro- ducts, Inc., began production and continued until July, 1975 (Huggett et al., 1980; Huggett and Bender, 1980~. During this period over 1.5 x 106 kg of the substance were produced (Batelle Memorial Institute, 1978~. It is likely that kepone entered the James River throughout the period of production. Analyses of oysters (Crassostrea virginica) and bottom sediments collected as early as 1967, but analyzed in 1976, revealed that the James River was contaminated in the 1960s (Huggett et al.9 1980; Huggett and Bender, 1980~. Kep one entered the river at Hopewell via a number of routes. The most significant was the discharge of the local municipal sewage sys- tem.- Kepone-laden industrial waste entered the sewage treatment plant and the pesticide exited with little or no degradation. Other sources
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770100' 76° tOO' 7S3OO' ~ ~ _ __—- I ~~ —T ~ :- ' ~ ~ :~/ . ^~e | ||| ~ BALTIMORE ,~ ~ ~?pS ~ ~ ~ ~ kY~ 1 ~ :~ ~ 1~.~E ~ L'~ Wl,~0 ~ ~ l l :.: :-: HOPE WE Iffy ~ ~ I I ~ . ~ . ~ A,,, .-> _ j HI ~ 3°~ ~ / i!_ ~ ~ ' ~ _. I ~ Quit=., (1°°~ NAUTICAL FILES ~ FORM _ ~ ~ | I . . , ~ ~ I I | ~ ~ ~ 1 T T ~ I ~ ~ . . . 77° GO' 76° GO' 75° 1°° - ^,~. —~ BAR - ^ ~ By'` C, of I i. - ~ ~ ~l-:: FIGI1RE 1 Map of the Chesapeake Bay showing the tidal James River.
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420 0.2 O . 1 ppm FIGURE 2 A. Kep one in the top 2 cm of channel bottom sediments from the James River. B. Hypo- thetical coastal plain estuary with two-layered circulation and turbidity maximum. SOURCE: Hug- gett and Bender (1980), reprinted with permission from the American Chemical Society. A Turbidity Maximum Zone Sou roe /: A,,, \: Chesapeake Bay . . . . . . 140 120 100 80 60 40 20 0 -20 km Dl STA N CE UPST REAM B \ 7one A LTurbidit y—I I Maximu m I F r e s h - So I t Interf ace included runoff from contaminated soils near the manufacturing facili- ties and solid waste dumped into a freshwater marsh on a small tribu- tary of the James River (Huggett et al., 1980~. The material entered the river either as particulates or in solution. In the latter case, it rapidly sorbed to bottom and suspended solids to be transported by the river's currents. CONTAMINATED SEDIMENTS Kepone readily partitions from solution to solids. Dawson (Batelle Memorial Institute, 19784 suggested that a sediment-water partitioning coefficient of 10 to 10 be used. Other laboratory experiments as well as measurements of kepone in suspended sediments and associated waters from The James indicate that the value is between 1.6 x 103 and 7.7 x 10 (Huggett et al., 1980; Strobel et al., 1981~. The partitioning coefficient, as derived in the laboratory, does not appear to be affected by changes in salinity from O to 20 °/oo or by pH values from 6 to 9 (Huggett et al., 1980~. These span both the salin- ity and pH ranges normally found in the contaminated portion of the river. Field investigations verify these findings (Strobe! et al., 1981). The bottom sediments of the James River are contaminated with kepone to varying degrees. The main factors governing the concentra- tions appear to be the makeup of the sediments and the currents of the overlying water. These two factors, in combination, distribute kepone in a nonuniform pattern over an area of approximately 500 km (Hug- gett and Bender, 1980, 1982) . Kepone associates more with the organic portion of the bottom sedi- ments (Huggett et al., 1980) . Sandy or coarse-grained sediments
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421 generally contain less kepone than fine-grained sediments. This is due to the ordinarily high organic content of the latter. The organic content of the sediments can have a dramatic influence on kepone distribution. For instance, the highest sediment concentrations found (except within several kilometers of the Hopewell source) were near the outfall of a sewage treatment facility 75 km downstream (Huggett and Bender, 1982~. The organic content of this sediment was approximately 20 percent. There was no indication that kepone had ever been disposed of by this treatment plant. The distributions of the pesticide in the top 2 cm of bottom sedi- ments in the channel of the river in 1977 and 1979 are given in Figure 2. The highest concentrations in 1977 were found in the vicinity of the turbidity maximum zone. The mass of kepone in the sediments at that time was estimated to be between l x 104 kg and 3 x 104 kg (Huggett and Binder, 1980~. The range was due to the large area contam- inated (500 km ~ and the relatively few samples analyzed at the time. By 1979, surface sediment concentrations were greatly diminished. Analyses of sediment cores with depth showed that kep one was becoming diluted and buried by newly deposited material rather than being trans- ported away or decomposing. This trend has continued, but in areas where the sedimentation rate is low, kep one is most concentrated near the surface. Where the sedimentation rates are high, concentrations increase with depth (Figure 3) (Helz and Huggett, 1987~. As mentioned previously, most of the kepone is deposited in the James' turbidity maximum zone, which has a high sedimentation rate. This has resulted in a continual reduction in the pesticide's concen- tration in surface sediment (Figure 3~. This reduction is reflected in the residue concentrations in edible tissues of male blue crabs (Cal l inectes sapidus) and oysters (Crassostrea virginica) KEPONE ~ mg Kg ~ ) O- 5- - 0- 15- E - I 20 25 FIGURE 3 Kepone concentrations in sediment cores from the James River. Bars indicate the depth interval of the sediments analyzed. SOURCE: Re- printed with permission from Majumdar et al., 1987. 0 0.1 0.2 0.3 _ I I . 1 _; LL 30. cat ~ 35 40- 45- 50- ~ BAILEYS CREEK MOUTH At;, JAMES RIVER TAR BAY
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422 ~ 0.8 it, 0.6- - ~5 tic 0.4 o Q Y 0.2- O 76 7'7 7'8 79 8'0 8'1 8'2 8'3 8'4 8'5 0 Year FIGURE 4 Kepone concentrations in blue crabs and oysters. SOURCE: Majumdar et al., 1987. Yearly Mean of James River Kepone Residues _ (X - Blue Crab on) (O -Oysters)— o X "` \~\ O \ \\ \ X~ X \N "a of" ~~~ O —_~( rO.2 _ , -A collected from 1976 to 1985 (Figure 4~. The data are interesting in that they show similar rates of concentration decrease for both species although crabs obtain most of their kep one from food, while oysters obtain kepone both from solution and from suspended particles (Schimmel and Wilson, 1977; Morales-Alamo and Haven, 1983; Bender and Huggett, 1987~. Apparently the equilibration times between sediments and water, sediments and food are relatively short. DISCUSSION AND CONCLUSION Kep one concentrations in the Jades River are much lower now than in the past, therefore the biota are at less risk from the toxicant now than during the period of production. A comparison of existing toxic- ity data and kepone concentrations in solution or in tissues of the biota indicates that there has been little or no biological impact due to the contamination (Bender and Huggett, 1984~. The impact has been economic; commercial fishermen couldn't harvest the seafood and con- sumers couldn't buy it. Any consideration of mitigation must balance the benefits of clean- up, which would be solely economic, with the costs, which are not only economic (e.g., the cost of dredging) but also ecological. Any clean- up effort will have detrimental biological impact relative to doing nothing. Natural forces, such as sedimentation, are cleansing the river and the time frame for this cleanup is on the order of decades. Studies have been conducted, however, to assess the feasibility of mitigating the kepone contamination of the James (Batelle Memorial Institute, 1978~. Options ranged from dredging, at an estimated cost of $3 x 109 not including the cost of disposal, to stabilizing the
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423 sediments with molten sulfur (often called "the Yellow Brick Road theory". None of these options were feasible, either economically or environmentally; therefore, nothing has been done. Kepone concentrations in finfish and shellfish are now low enough to again allow commercial harvesting in the river. The pesticide is buried under a veneer of clean sediments. A major hurricane could stir up these sediments and recontaminate the river (Huggett and Bender, 1980~. Such a storm has not occurred in the area since the 1950s. An- other complicating factor is that the channels of the James River will need to be dredged in the near future. In the past, dredged material was disposed by placing it on the flanks of the river, adjacent to the channel being dredged. Such a practice now would place buried kepone- contaminated sediments back on the surface. The biota would again be exposed to the pesticide. The resulting body burdens could result in fisheries closures. Given the uncertainties involved in predicting the transport and fate of kepone under the conditions mentioned above, deciding whether or not to dredge the James River will be difficult. The benefits of continued shipping on the James River by allowing dredging will have to be compared to the potential costs of fisheries closures due to kep one contamination. One solution to the dilemma may be to bear the expense of upland disposal and containment of the dredged materials rather than pumping them back overboard. (VIMS Publication Number 1502.) REFERENCES Battelle Memorial Institute. 1978. The Feasibility of Mitigating Kepone Contamination of the James River Basin'. Final Report to the U.S. Environmental Protection Agency. Washington, D.C.: Battelle. Bender, M. E. and R. J. Huggett. 1987. Contaminant effects on Chesa- peake Bay shellfish. In Contaminant Problems and Management of Living Chesapeake Bay Resources, S. K. Majumdar, L. W. Hall, and H. M. Austin, eds. Penn. Acad. of Sci. Pub. Pp. 373-393. Bender, M. A. and R. J. Huggett. 1984. Fate and effects of kepone in the James River estuary. In Reviews in Environmental Toxicology, E. Hodgaon, ed. New York: Elsevier Science Publishers. Pp. 5-50. Helz, G. R. and R. J. Huggett. 1987. Contaminants in Chesapeake Bay. In Contaminant Problems and Management of Living Chesapeake Bay Resources, S. K. Majumdar, L. W. Hall, Jr. and H. M. Austin, eds. Penn. Acad. of Sci. Pub., pp. 270-297. Huggett, R. J., M. M. Nichols, and M. E. Bender. 1980. Kepone contam- ination in the James River estuary. In Contaminants and Sediments, R. A. Baker, ed. Ann Arbor, Mich.: Ann Arbor Science Publishers. 1:33-52. Huggett, R. J. and M. E. Bender. 1982. Scientific sessons taught by Kepone. In Proceedings of a Symposium on Agrichemicals and Estu- arine Productivity. Beaufort, N.C.: Duke University Marine Lab- oratory. Pp. 53-61. Huggett, R. J. and M. E. Bender. 1980. Kepone in the James River. Environ. Sci. Tech. 14~8~:918-923.
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424 Morales-Alamo, R. and D. S. Haven. 1983. Uptake of kepone from sediment suspensions and subsequent loss by the oyster Crassostrea vir- ginica . Mar . Biol . 74: 187 - 201. S. K. Majumdar, L. W. Hall, Jr., and H. M. Austin, eds. 1987. Contami nant Problems and Management of Living Chesapeake Bay Resources, Penn. Acad. of Sci. Pub. Pritchard, D. W. 1952. Salinity distribution and circulation in the Chesapeake Bay estuarine system. J. Mar. Res. 11:106-123. Schimmel, S. C. and A. S. Wilson. 1977. Acute toxicity of Kep one to four estuarine animals. Chesapeake Sci. 18:224-227. Strobel, C. J., R. E. Croonenberghs, and R. J. Huggett. 1981. The sus pended sediment-water partitioning coefficient for kepone in the James River, Virginia. Environ. Poll. 2:367-372. -
Representative terms from entire chapter: